WO2012169909A1 - Triaminocyclopropenium salts - Google Patents

Triaminocyclopropenium salts Download PDF

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WO2012169909A1
WO2012169909A1 PCT/NZ2012/000090 NZ2012000090W WO2012169909A1 WO 2012169909 A1 WO2012169909 A1 WO 2012169909A1 NZ 2012000090 W NZ2012000090 W NZ 2012000090W WO 2012169909 A1 WO2012169909 A1 WO 2012169909A1
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bis
cyclopropenium
substituted
alkyl
diethylamino
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PCT/NZ2012/000090
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French (fr)
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Owen John CURNOW
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Curnow Owen John
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/14—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by amino groups
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C211/39—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of an unsaturated carbon skeleton
    • C07C211/40—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of an unsaturated carbon skeleton containing only non-condensed rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/53—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having the nitrogen atom of at least one of the amino groups further bound to a hydrocarbon radical substituted by amino groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/22—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C305/00—Esters of sulfuric acids
    • C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
    • C07C305/06—Hydrogenosulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to salts comprising triaminocyclopropenium cations, to processes for the preparation of these salts, and to the use of these salts as ionic liquids.
  • Ionic liquids comprise ions and short-lived ion pairs, in contrast to conventional organic or aqueous solvents. They generally do not contain neutral molecules and usually have melting points below 373 K. These substances are also known as liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses.
  • Ionic liquids have developed significantly over the past 10 years, particularly as they become available on industrial scales. The great attraction of these liquids stems from their properties of almost zero vapour pressure, low flammability and ease of recycling. For these reasons, they are frequently considered as potential green alternatives to classical organic solvents. Additionally, most classes of ionic liquid can be readily tuned to provide unique solvent environments in which to carry out reactions, extractions and other processes.
  • ionic liquids for example melting point, thermal and electrochemical stability and viscosity, are affected by the nature of both the cation and the anion. Similarly, the selection of cation and anion can affect the polarity and hydrophilicity/hydrophobicity of the resulting ionic liquid.
  • Triaminocyclopropenium salts were first identified in 1971 (Z. Yoshida and Y. Tawara, J. Am. Chem. Soc , 1971 , 93, 2573). There have, however, been no investigations of their properties as ionic liquids, and no viscosity data is available for any triaminocyclopropenium salt.
  • Triaminocyclopropenium salts are particularly stable due to a combination of the aromaticity of the three- membered ring and ⁇ donation from the three planar amino groups which consequently disperse the charge from the C 3 ring. These cations are sufficiently electron rich to be considered as "donor" species.
  • triaminocyclopropenium salts that are preferably suitable for use as ionic liquids; and/or to at least provide the public with a useful choice.
  • the present invention provides a compound of formula [Y ⁇ q PC " ] wherein q is 1, 2 or 3;
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Cuo alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C 2 _ 2 o alkenyl, C 2 . 2 o alkynyl, substituted C 2 . 2 o alkynyl, C3.10 cycloalkyl, substituted C 3- i 0 cycloalkyl, C3.10 cycloalkenyl, substituted C3_io cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;
  • R 4 and R 6 are each independently selected from C 2 . 20 alkyl, substituted C ⁇ o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C 2 _ 20 alkynyl, substituted C 2 . 2 o alkynyl, C 3- i 0 cycloalkyl, substituted C3.10 cycloalkyl, C3.10 cycloalkenyl, substituted C3.10 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or
  • R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl, substituted heterocyclyl, heteroaryl or substituted heteroaryl, wherein heteroaryl is imidazolyl, pyrazolyl, pyrrolyl or azepinyl; and
  • anion, X q ⁇ is selected from the group consisting of:
  • R A is a side chain of a natural or non-natural alpha-amino acid
  • R B is H, Ci_6 alkyl, Ci_ 6 alkenyl, Ci_6 perfluoroalkyl, Ci_ 6 perfluoroalkenyl or Si(C ]-6 alkyl) 3 ;
  • R c is H, methyl, CI or Br;
  • R is Ci_ 20 alkyl or C 2 _ 2 o alkenyl, wherein one or two non-adjacent carbon atoms in R D which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S0 2 -, or -NR J -, and wherein R D is optionally substituted by one or more R E ; or
  • R D is C 3 _io cycloalkyl, C 3 _io cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of Ci_ 6 alkyl, C 2 -6 alkenyl, and R E ;
  • R E at each instance is independently selected from halo, cyano, Q_6 alkoxy, Si(Cj_6 alkyl) 3 , C 3 _io cycloalkyl optionally substituted by one or more R H* , C 3 _i 0 cycloalkenyl optionally substituted by one or more R E* , aryl optionally substituted by one or more R E* , heteroaryl optionally substituted by one or more R E* , and heterocyclyl optionally substituted by one or more R E* ;
  • R E* at each instance is independently selected from halo, d_6 alkyl, Ci_ 6 alkoxy, and oxycarbonyl;
  • X B is CI or Br
  • R F at each instance is independently selected from perfluoro Ci_ 20 alkyl, perfluoro C 2 _ 20 alkenyl having one or more double bonds, perfluoro C 2 . 2 o alkynyl having one or more triple bonds, perfluoro C 3 _i 0 cycloalkyl optionally substituted by one or more perfluoro Q.6 alkyl, perfluoro C 3 .i 0 cycloalkenyl optionally substituted by one or more perfluoro Ci_ 6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro C ]-6 alkyl, wherein any two R F may be connected by a single or double bond, wherein when R F is perfluoro C ⁇ o alkyl, perfluoro C 2 _ 2 o alkenyl, or perfluoro C 2 _ 20 alkynyl one or two non-adjacent carbon atoms in R F which are not in the alpha-
  • R G at each instance is independently selected from perfluoro C 2 _ 20 alkyl, perfluoro C 2 _ 2 o alkenyl having one or more double bonds, perfluoro C 2 . 20 alkynyl having one or more triple bonds, perfluoro C 3 _i 0 cycloalkyl optionally substituted by one or more perfluoro Ci -6 alkyl, perfluoro C 3 .i 0 cycloalkenyl optionally substituted by one or more perfluoro Cj.6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci_ 6 alkyl, wherein any two R G may be connected by a single or double bond, wherein when R G is perfluoro C1.20 alkyl, perfluoro C2-20 alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms in R G which are not in the alpha-position to a hetero
  • R J at each instance is independently selected from Ci_ 6 alkyl, fluoro Ci -6 alkyl, perfluoro Ci_ 6 alkyl, C3.10 cycloalkyl, phenyl optionally substituted by one or more R K , heteroaryl optionally substituted by one or more R K , and heterocyclyl optionally substituted by one or more R K ;
  • R K at each instance is independently selected from Ci_ 6 alkyl, Ci-6 alkenyl, nitro, halo, hydroxyl, Ci-e alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
  • alkyl)amino -C0 2 H, -C(0)NR L , -S0 2 OR L , -S0 2 X D , -S0 2 NR L 2 , -S0 3 H, and -NHC(0)R L ;
  • R L at each instance is independently selected from Ci_ 6 alkyl, fluoro Ci -6 alkyl, perfluoro Ci_ 6 alkyl, and C3.10 cycloalkyl;
  • X D at each instance is independently selected from F, CI, and Br;
  • n 1 to 20;
  • n 0, 1, 2, or 3;
  • y is 1 , 2, 3, or 4;
  • z 0, 1, 2, or 3;
  • k is 1, 2, 3, or 4; and p is 1 , or 2.
  • the present invention provides a compound of formula [ ⁇ ⁇ ⁇ 1" ] wherein q is 1 ; wherein the cation, Y ⁇ is selected from
  • anion, X q ⁇ is selected from CT, Br “ , [BF 4 ] ⁇ , [N0 3 ] “ , ⁇ PF 6 Y, [SCN] “ , [CF 3 S0 3 ] “ , [CH 3 OS0 3 ] “ , [C 2 H 5 OS0 3 ]- [(CF 3 S0 2 ) 2 N]-, [(FS0 2 ) 2 N]-, [C 2 F 5 S0 3 ]-, [(C 2 F 5 S0 2 ) 2 N)]- and [N(CN) 2 ]-.
  • the present invention provides a compound of formula [Y ⁇ tX" 1" ] wherein q is 1 ;
  • Y is tris(diethylamino)cyclopropenium
  • anion, X q ⁇ is selected from ⁇ , [BF 4 ] ⁇ [N0 3 ] _ , [PF 6 ] “ , [SCNf, [CF 3 S0 3 ] “ , [CH 3 OS0 3 ] "
  • the present invention provides a compound of formula [Y f ] q [X q ] wherein q is 1 ;
  • anion, X q" is selected from [BF 4 ] ⁇ , [PF 6 ] “ , [CF 3 S0 3 ] " , [CH 3 OS0 3 ]- [C 2 H 5 OS0 3 ] ⁇
  • the present invention provides a compound of formula [Y + ] q [X q ⁇ ] wherein q is 1 or 2 wherein the cation, Y ⁇ is a triaminocyclopropenium ion of the formula (II):
  • anion, X q ⁇ is selected from [SCN] ⁇ , [CF 3 S0 3 ] " , [FHO(C 1-6 alkyl)]-, [(C,. 6 alkyl)OS0 3 ]- [C 6 F 5 S0 3 ]- [(C 1-6 alkyl)(C,. 6 alkyl)P(0)0]-, [CH 3 C 6 H 4 S0 3 r, [Co(C 2 B 9 H u ) 2 r, [C 2 B 9 H I2 ]-, [B 10 C1 10 ] 2 - [B 12 C1 12 ] 2 -, [CB u H 12 r, [B 12 H conflictN(C,.
  • the present invention provides a compound of formula wherein q is 1 or 2 wherein the cation, Y -1" , is a triaminocyclopropenium ion of the formula (III):
  • R ? is methyl and R 8 is selected from C2-20 alkyl, substituted C 1.20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C 2 _ 2 o alkynyl, substituted C2-20 alkynyl, C3.10 cycloalkyl, substituted C3 - ] 0 cycloalkyl, C 3 .i 0 cycloalkenyl, substituted C3.10 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or
  • R 7 and R 8 are each independently selected from C2-20 alkyl, substituted C1.20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C2-20 alkynyl, C3-10 cycloalkyl, substituted C3-10 cycloalkyl, C3.10 cycloalkenyl, substituted C 3 .io cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;
  • X q ⁇ is selected from [SCNf, [CF 3 COO] “ , [SeCNf, [CF 3 S0 3 ] “ , [FHO(d-6 alkyl)] " , [(C,_6 alkyI)OS0 3 ]-, [C ⁇ SO,] " [(C,.
  • R B , R c , R D , X B , R F , R G , n, m, y, z, -Z-, and -Y- are as defined for the compounds of the first aspect.
  • the present invention provides a compound selected from the group consisting of: (2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
  • the present invention provides an ionic liquid comprising a triaminocyclopropenium cation and an anion.
  • the present invention provides an ionic liquid comprising a compound of the invention.
  • the present invention provides use of a compound of the invention as a solvent.
  • the present invention provides use of a compound of the invention as an electrolyte.
  • the present invention provides use of a compound of the invention for gas storage.
  • This invention may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which this invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.
  • the compounds of the invention may form or exist as hydrates or solvates with various solvents.
  • the present invention contemplates such hydrates and solvates as well as the corresponding unsolvated forms.
  • the compounds of the invention when used as ionic liquids, are unsolvated and, in particular, unhydrated.
  • Some of the compounds of the invention include cations or anions or both that have asymmetric carbon atoms. Therefore, stereoisomers (both enantiomers and diastereomers) of such cations or anions can exist.
  • the present invention contemplates the pure stereoisomers (including geometric isomers) and any mixture of the isomers. For example, a pure enantiomer of a cation can be isolated from a mixture of enantiomers of the cation using conventional optical resolution techniques. Enol forms and tautomers are also contemplated, where appropriate.
  • alkyl groups comprise 1 to 20 carbon atoms. In some embodiments, alkyl groups comprise 1 to 6 carbon atoms.
  • the alkyl group is methyl, ethyl, w-propyl, wopropyl, n-butyl, wo-butyl, sec-butyl, or tert-butyl;
  • substituted alkyl alone or in combination with other terms means an alkyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, substituted alkynyloxy, substituted alkynyl; substituted alkyny
  • cycloalkyl groups comprise 3 to 10 ring carbon atoms. In some embodiments, cycloalkyl groups comprise 3 to 8 ring carbon atoms. In some embodiments, the cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; the term "substituted cycloalkyl" alone or in combination with other terms means a cycloalkyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, substituted substituted cycloalkenyloxy, substituted
  • alkenyl groups comprise 2 to 20 carbon atoms. In some embodiments, alkenyl groups comprise 2 to 6 carbon atoms. In some embodiments, the alkenyl group is vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl- 1-propenyl, 2-methyl-2-propenyl, 1 -methyl- 1 -propenyl, 1 -methyl-2-propenyl, 1 -methyl vinyl, 1 -ethyl vinyl, or 1,3-butadienyl; the term "substituted alkenyl" alone or in combination with other terms means an alkenyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted
  • cycloalkenyloxy alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "cycloalkenyl" alone or in combination with other terms means a cyclic
  • cycloalkenyl groups comprise 3 to 20 ring carbon atoms. In some embodiments, cycloalkenyl groups comprise 3 to 8 carbon atoms. In some embodiments, the cycloalkenyl group is cyclopropen-l-yl, cyclopropen-3-yl, cyclobuten- 1-yl, cyclobuten-3-yl, cyclohexen-l-yl, cyclohexen-3-yl, cyclohexen-4-yl, 1 ,3-cyclooctadien-l-yl, l ,3-cyclooctadien-2-yl, l ,3-cyclooctadien-5-yl, l,3-cyclooctadien-6-yl, 1,5-cyclooctadien-l-yl, or 1 ,5-cyclooctadien-3-yl; the term "substituted
  • alkynyl groups comprise 2 to 20 carbon atoms. In some embodiments, alkynyl groups comprise 2 to 6 carbon atoms. In some embodiments, the alkynyl group is ethynyl, propargyl, 3-butynyl, 4-pentynyl, 5-hexynyl, or 3,5-hexadiynyl; the term "substituted alkynyl" alone or in combination with other terms means an alkynyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted substituted alken
  • alkyl-O- group wherein "substituted alkyl” is as defined herein;
  • cycloalkoxy alone or in combination with other terms means a cycloalkyl-O- group;
  • substituted cycloalkoxy alone or in combination with other terms means a substituted cycloalkyl-O- group, wherein "substituted cycloalkyl” is as defined herein;
  • alkenyloxy alone or in combination with other terms means an alkenyl-O- group, wherein "alkenyl” is as defined herein;
  • substituted alkenyloxy alone or in combination with other terms means a substituted alkenyl-O- group, wherein "substituted alkenyl” is as defined herein;
  • cycloalkenyloxy alone or in combination with other terms means a cycloalkenyl-O- group, wherein "cycloalkenyl” is as as
  • aryl is phenyl, naphthyl, indanyl, biphenyl, anthracenyl, phenanthryl, or terphenyl, and the like. In some embodiments, aryl is phenyl, naphthyl, anthracenyl, phenanthryl, biphenyl, or terphenyl. In some embodiments, aryl is phenyl, naphthyl, biphenyl, or terphenyl.
  • aryl is phenyl; the term "substituted aryl" alone or in combination with other terms means, unless otherwise stated, an aryl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyl, heterocycly
  • cycloalkyloxy substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryloxy, substituted
  • heterocyclyl substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy
  • acylamino alone or in combination with other terms means an acyl-NR 105 - group, wherein R 105 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl;
  • substituted acylamino alone or in combination with other terms means a substituted acyl-NR 106 - group or acyl-NR 107 - group, wherein "substituted acyl” is as defined herein, R 106 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl,
  • R 108 C(S)NR 109 - group wherein R 108 is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl and R 109 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted thioamide" alone or in combination with other terms means a substituted amino-C(S)- group or R 1 10 C(S)NR n i - group, wherein "substituted amino" is as defined herein, R 110 is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl
  • R U3 C(0)S- group wherein R 112 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl, and R 113 is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl;
  • substituted thioester alone or in combination with other terms means a R 114 SC(0)- group or R 115 C(0)S- group, wherein R 114 and R 115 are each independently selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl;
  • carbarbamate alone or in combination with other terms means an amino-C(0)0- group or oxycarbonyl-NR 116 - group, wherein R 116 is selected from the group consisting of hydrogen,
  • amino-C(0)NR 120 - group or amino-C(0)NR 121 - group wherein "substituted amino" is as defined herein, and R 120 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R 121 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "dithiocarbamate" alone or in combination with other terms means an amino-C(S)S- group or R SC(S)NR - group, wherein R and R are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalken
  • R 26 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl;
  • substituted dithiooxaamide alone or in combination with other terms means a substituted amino-C(S)C(S)NR 127 - group or amino-C(S)C(S)NR 128 - group, wherein "substituted amino” is as defined herein, R 127 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R 128 is selected from the group consisting of substituted alkyl, substituted cycloalky
  • aryl-O- group wherein "substituted aryl” is as defined herein; the term “heteroaryl” alone or in combination with other terms means a monocyclic, bicyclic or tricyclic heteroaromatic radical comprising 5 to 14 ring atoms.
  • heteroaryl is pyrrolyl, furyl, thiophenyl, pyridyl, bipyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, pyrrodiazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, indolyl, isoindolyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, benzotriazolyl, benztetrazolyl, indazolyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benz
  • heteroaryl is pyrrolyl, furyl, thiophenyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, pyrrodiazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, or triazinyl;
  • substituted heteroaryl alone or in combination with other terms means a heteroaryl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl
  • heterocyclyl is piperidinyl, pyrrolidinyl, piperazinyl, 1 ,4-dioxanyl, tetrahydrofuryl, tetrahydrothiophenyl, morpholinyl, or azepanyl.
  • heterocyclyl is tetrahydrofuryl or 1 ,4-dioxanyl; the term "substituted heterocyclyl” alone or in combination with other terms means an heterocyclyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy,
  • R 161 , R 162 , R 163 , and R 164 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R 161 and R 162 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl and at least one of R 163 and R 164 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted substituted
  • substituted means that one or more hydrogen atoms (or halo atoms for perhalo groups, such as perfluoroalkyl, perfluoroalkenyl, perfluoroalkynyl, perfluorocycloalkyl and
  • perfluorophenyl in the group indicated is replaced with one or more independently selected suitable substituents, provided that the normal valency of each atom to which the substituent/s are attached is not exceeded, and that the substitution results in a stable compound.
  • substituted alkyl substituted alkenyl
  • substituted alkynyl substituted cycloalkyl
  • substituted cycloalkenyl substituted heterocyclyl
  • substituted heteroaryl substituted heteroaryl
  • substituted aryl alone or in combination with other terms include their “halo”, including “monohalo-”, “dihalo-” and “polyhalo-” , including “perhalo-”, equivalents.
  • haloalkyl alone or in combination with other terms means an alkyl group as defined herein wherein one or more hydrogen atoms in the group is replaced with one or more halo.
  • haloalkyl includes monohaloalkyl, dihaloalkyl and polyhaloalkyl, including perhaloalkyl, groups.
  • perhaloalkyl alone or in combination with other terms means an alkyl group as defined herein wherein all hydrogen atoms in the group are replaced with one or more halo.
  • Each "halo" in any dihaloalkyl and polyhaloalkyl group is independently selected.
  • haloalkyl examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoropropyl, difluorochloromethyl, dichlorofluoromethyl, difluoroethyl, difluoropropyl, dichloroethyl and dichloropropyl.
  • perhaloalkyl includes “perfluoroalkyl”. Examples of “perfluoroalkyl” include trifluoromethyl and pentafluoroethyl.
  • alkyl alone or in combination with other terms, where appropriate, also include divalent and polyvalent radicals derived from each respective group, such as alkylene (alkanediyl), alkenylene, heterocyclylene, heteroarylene, and arylene.
  • alkylene alkanediyl
  • alkenylene alkenylene
  • heterocyclylene heteroarylene
  • arylene arylene
  • side chain of a natural or non-natural alpha-amino acid includes the group R A in a natural or non-natural amino acid of general formula NH 2 -CH(R A )-C0 2 H.
  • the term also includes, for example, side chains that link to the alpha-amino group such as the pyrrolidinyl ring of proline.
  • R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 together with the nitrogen atom to which they are attached are -pyrrolidinyl-2-C0 2 H.
  • X q" is [pyrrolidinyl-2-COO] " .
  • natural alpha-amino acid includes the 20 L-amino acids (or a residue thereof) which commonly comprise most polypeptides in living systems, that is: alanine (Ala); arginine (Arg); asparagine (Asn); aspartic acid (Asp); cysteine (Cys); glutamine (Gin); glutamic acid (Glu); glycine (Gly); histidine (His); isoleucine (lieu); leucine (Leu); lysine (Lys); methionine (Met); phenylalanine
  • proline Pro
  • serine Ser
  • Thr tryptophan
  • Trp tryptophan
  • Trp tyrosine
  • Val valine
  • the term also includes rarer amino acids found in fibrous proteins (for example, 4-hydroxyproline,
  • 5-hydroxylysine, N-methyllysine and 3-methylhistidine 5-hydroxylysine, N-methyllysine and 3-methylhistidine
  • naturally occurring amino acids not found in proteins for example, homocysteine, homoserine, citrulline, ornithine, canavanine, djenkolic acid and beta-cyanoalanine.
  • Natural alpha-amino acids which contain functional substituents, for example amino, carboxyl, hydroxy, mercapto, guanidyl, imidazolyl or indolyl groups in their characteristic side chains include arginine, lysine, glutamic acid, aspartic acid, tryptophan, histidine, serine, threonine, tyrosine and cysteine.
  • R 1 to R 6 in the compounds of the invention is -CH(R A )-C0 2 H
  • R A is a side chain of an alpha-amino acid that includes a functional substituent, such as a side chain of one of those natural alpha-amino acids or a side chain of a non-natural alpha-amino acid
  • the functional substituent may optionally be protected.
  • the carboxyl substituent in -CH(R A )-C0 2 H may optionally be protected.
  • R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C0 2 H
  • the carboxyl substituent may optionally be protected.
  • Protecting groups may be added and removed in accordance with techniques that are well known to those persons skilled in the art. The use of protecting groups is described in, for example, P. G. M. Wuts and T. W. Greene, Greene 's Protective Groups in Organic Synthesis, 4 th edition, Wiley, New York, 2006 and P. J. Kocienski, Protecting Groups, 3 rd edition, Georg Thieme Verlag, Stuttgart, 2005.
  • the carboxyl substituent is protected as a Ci_ 6 alkyl ester.
  • non-natural alpha-amino acid includes any alpha-amino acid (or residue thereof) other than the natural amino acids listed above.
  • Non-natural amino acids include the D-isomers of the natural L-amino acids.
  • Non-natural amino acids also include, but are not limited to:
  • D-phenylalanine norleucine
  • hydroxyproline carboxyglutamic acid
  • pyroglutamic acid D-phenylalanine
  • D- or L- indicate an alpha-amino acid of D- or L-configuration respectively.
  • a “D.L-” prefix indicates a racemic mixture of amino acids of the two configurations.
  • the present invention provides a compound of formula [Y ⁇ q PC " ] wherein q is 1 , 2 or 3;
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, C1.20 alkyl, substituted Ci_ 2 o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C 2 - 2 o alkynyl, substituted C2-20 alkynyl, C 3 _io cycloalkyl, substituted C 3 . ]0 cycloalkyl, C 3 _i 0 cycloalkenyl, substituted C3.10 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;
  • R 4 and R 6 are each independently selected from C2-20 alkyl, substituted Ci_ 20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C2-20 alkynyl, C3.10 cycloalkyl, substituted C 3 _i 0 cycloalkyl, C3-io cycloalkenyl, substituted C 3 .
  • R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl, substituted heterocyclyl, heteroaryl or substituted heteroaryl, wherein heteroaryl is imidazolyl, pyrazolyl, pyrrolyl or azepinyl; and
  • anion, X q ⁇ is selected from the group consisting of:
  • R A is a side chain of a natural or non-natural alpha-amino acid; [CF3COO]-, [SeCN]-, [HSO 4 ]-, [H 2 P0 4 ] ' , [(MeO)(H)P0 2 ]- [CF 3 SO 3 ]- [CF 3 OSO 3 ]- [FHO(C,. 6 alkyl)]-, [(C 2 alkyi SOjF, [(C,., 2 alkyl)S0 3 ]-, [(C 2 H 5 ) 2 N(CH 2 ) 4 S0 3 ;r, [C ⁇ SO ⁇ , [(C M2 alkyl)(C,_ 12
  • R B is H, Ci_ 6 alkyl, C]_ 6 alkenyl, Ci_ 6 perfluoroalkyl, C]_ 6 perfluoroalkenyl or Si(Ci_ 6 alkyl) 3 ;
  • R c is H, methyl, CI or Br;
  • R D is Ci_ 20 alkyl or C 2 _ 20 alkenyl, wherein one or two non-adjacent carbon atoms in R D which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S0 2 -, or -NR J -, and wherein R D is optionally substituted by one or more R E ; or
  • R D is C 3 _io cycloalkyl, C 3 _i 0 cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of C ⁇ . 6 alkyl, C 2 -6 alkenyl, and R E ;
  • R E at each instance is independently selected from halo, cyano, Ci_ 6 alkoxy, Si(Ci_ 6 alkyl) 3 , C 3 _i 0 cycloalkyl optionally substituted by one or more R E* , C3-10 cycloalkenyl optionally substituted by one or more R E* , aryl optionally substituted by one or more R E* , heteroaryl optionally substituted by one or more R E* , and heterocyclyl optionally substituted by one or more R E *;
  • R E* at each instance is independently selected from halo, Ci_6 alkyl, Ci geometry 6 alkoxy, and oxycarbonyl;
  • X B is CI or Br
  • R F 4 . Z [BF Z R F 4 . Z ]-, [BF Z (CN) 4 . Z ]-, [Me 3 SiC 2 H 4 0CH 2 BF 3 ]- [N(CF 3 ) 2 ] " [N(CN) 2 ] " , [C(CN) 3 ]- and wherein R F at each instance is independently selected from perfiuoro Ci. 2 o alkyl, perfluoro C 2 . 20 alkenyl having one or more double bonds, perfluoro C 2 _ 20 alkynyl having one or more triple bonds, perfluoro C 3 .
  • R G at each instance is independently selected from perfluoro C 2 _2o alkyl, perfluoro C 2 _2o alkenyl having one or more double bonds, perfluoro C 2 _2o alkynyl having one or more triple bonds, perfluoro C3.10 cycloalkyl optionally substituted by one or more perfluoro Cue alkyl, perfluoro C 3 .
  • R J at each instance is independently selected from C alkyl, fluoro Ci_ 6 alkyl, perfluoro Ci_ 6 alkyl, C3.10 cycloalkyl, phenyl optionally substituted by one or more R K , heteroaryl optionally substituted by one or more R K , and heterocyclyl optionally substituted by one or more R K ;
  • R K at each instance is independently selected from Ci_ 6 alkyl, C 6 alkenyl, nitro, halo, hydroxyl, Ci_ 6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
  • Ci- alkoxycarbonyl Ci- alkoxycarbonyl
  • Ci_ 6 alkylamino di(Ci_6
  • alkyl)amino -C0 2 H, -C(0)NR L , -S0 2 OR L , -S0 2 X D , -S0 2 NR L 2 , -SO3H, and -NHC(0)R L ;
  • R L at each instance is independently selected from Cue alkyl, fluoro C 6 alkyl, perfluoro C ]-6 alkyl, and
  • X D at each instance is independently selected from F, CI, and Br;
  • n 1 to 20;
  • n 0, 1, 2, or 3;
  • y is 1, 2, 3, or 4;
  • z 0, 1, 2, or 3;
  • k is 1 , 2, 3, or 4;
  • p 1 , or 2.
  • the anion, X q ⁇ is selected from the group consisting of:
  • R A is a side chain of a natural or non-natural alpha-amino acid
  • R B is H, Ci_ 6 alkyl, Ci_ 6 alkenyl, Ci_6 perfluoroalkyl, Ci_6 perfluoroalkenyl or Si(Ci_ 6 alkyl) 3 ;
  • R c is H, methyl, CI or Br;
  • R D is Ci_ 2 o alkyl or C 2 _ 20 alkenyl, wherein one or two non-adjacent carbon atoms in R D which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S0 2 -, or -NR J -, and wherein R D is optionally substituted by one or more R E ; or
  • R D is C 3 _io cycloalkyl, C 3 _io cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of Ci-6 alkyl, C 2 -6 alkenyl, and R E ;
  • R E at each instance is independently selected from halo, cyano, Cj_6 alkoxy, Si(Ci_6 alkyl) 3 , C 3 _ ! o cycloalkyl optionally substituted by one or more R E* , C 3 _io cycloalkenyl optionally substituted by one or more R E* , aryl optionally substituted by one or more R E *, heteroaryl optionally substituted by one or more R E ⁇ and heterocyclyl optionally substituted by one or more R E *;
  • R E* at each instance is independently selected from halo, Ci_6 alkyl, Ci_6 alkoxy, and oxycarbonyl;
  • X B is CI or Br
  • R F at each instance is independently selected from perfluoro Ci_ 20 alkyl, perfluoro C 2 _ 20 alkenyl having one or more double bonds, perfluoro C 2 .
  • one or two non-adjacent carbon atoms in R F which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S0 -, or -NR J -, and wherein a terminal carbon atom in R F , if present, may be replaced by -S0 2 X D ;
  • R G at each instance is independently selected from perfluoro C 2-20 alkyl, perfluoro C 2 . 20 alkenyl having one or more double bonds, perfluoro C 2 . 2 o alkynyl having one or more triple bonds, perfluoro C 3- i 0 cycloalkyl optionally substituted by one or more perfluoro C ⁇ .
  • one or two non-adjacent carbon atoms in R G which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S0 2 -, or -NR J -, and wherein a terminal carbon atom in R°, if present, may be replaced by -S0 2 X D ;
  • R J at each instance is independently selected from Ci -6 alkyl, fluoro Ci. 6 alkyl, perfluoro Ci_ 6 alkyl, C 3 . ] 0 cycloalkyl, phenyl optionally substituted by one or more R K , heteroaryl optionally substituted by one or more R , and heterocyclyl optionally substituted by one or more R K ;
  • R K at each instance is independently selected from Ci -6 alkyl, Ci -6 alkenyl, nitro, halo, hydroxyl, C]. 6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
  • Ci_ 6 alkoxycarbonyl -NH 2
  • Ci -6 alkylamino di(Ci -6
  • alkyl)amino -C0 2 H, -C(0)NR L , -S0 2 OR L , -S0 2 X D , -S0 2 NR L 2 , -S0 3 H, and -NHC(0)R L ;
  • R L at each instance is independently selected from Ci -6 alkyl, fluoro C 6 alkyl, perfluoro Ci -6 alkyl, and C 3 _io cycloalkyl;
  • X D at each instance is independently selected from F, CI, and Br;
  • n 1 to 20;
  • n 0, 1, 2, or 3;
  • y is 1, 2, 3, or 4;
  • k is 1, 2, 3, or 4;
  • p 1, or 2.
  • the anion, X q is selected from the group consisting of:
  • R A is a side chain of a natural or non-natural alpha-amino acid. This group is referred to herein as "Group 1".
  • the anion, X q ⁇ is selected from the group consisting of:
  • R B is H, Ci_ 6 alkyl, Ci_ 6 alkenyl, Ci_ 6 perfluoroalkyl, Ci_ 6 perfluoroalkenyl or Si(Ci -6 alkyl) 3 ;
  • R c is H, methyl, CI or Br;
  • R D is C-20 alkyl or C 2 _ 2 o alkenyl, wherein one or two non-adjacent carbon atoms in R D which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S0 2 -, or -NR J -, and wherein R D is optionally substituted by one or more R E ; or
  • R D is C 3 _io cycloalkyl, C3_io cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of Q. 6 alkyl, C 2 - 6 alkenyl, and R E ;
  • R E at each instance is independently selected from halo, cyano, C)_ 6 alkoxy, Si(Ci_ 6 alkyl) 3 , C 3 _io cycloalkyl optionally substituted by one or more R E* , C 3 _i 0 cycloalkenyl optionally substituted by one or more R E* , aryl optionally substituted by one or more R E* , heteroaryl optionally substituted by one or more R E* , and heterocyclyl optionally substituted by one or more R E* ;
  • R E* at each instance is independently selected from halo, Ci_ 6 alkyl, Ci_ 6 alkoxy, and oxycarbonyl;
  • R J at each instance is independently selected from Ci -6 alkyl, fluoro Ci_ 6 alkyl, perfluoro Ci -6 alkyl, C 3 _io cycloalkyl, phenyl optionally substituted by one or more R K , heteroaryl optionally substituted by one or more R K , and heterocyclyl optionally substituted by one or more R K ;
  • R K at each instance is independently selected from Ci. 6 alkyl, C]_ 6 alkenyl, nitro, halo, hydroxyl, C]. 6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
  • alkyl)amino -C0 2 H, -C(0)NR L , -S0 2 OR L , -S0 2 X D , -S0 2 NR L 2 , -S0 3 H, and -NHC(0)R L ;
  • R L at each instance is independently selected from Ci_ 6 alkyl, fluoro Ci- 6 alkyl, perfluoro Ci_e alkyl, and C 3 .io cycloalkyl;
  • X B is CI or Br
  • X D at each instance is independently selected from F, CI, and Br. This group is referred to herein as
  • the anion, X q is selected from the group consisting of: [Al(OCH 2 R F ) 4 ] ,
  • any two R F may be connected by a single or double bond, wherein when R F is perfluoro Ci_ 20 alkyl, perfluoro C 2 . 20 alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO2-, or -NR J -, and wherein a terminal carbon atom in R F , if present, may be replaced by -S0 2 X D ; and
  • R G at each instance is independently selected from perfluoro C2-20 alkyl, perfluoro C2-20 alkenyl having one or more double bonds, perfluoro C2-20 alkynyl having one or more triple bonds, perfluoro C3.10 cycloalkyl optionally substituted by one or more perfluoro Ci-e alkyl, perfluoro C3.10 cycloalkenyl optionally substituted by one or more perfluoro C t .
  • R G perfluorophenyl optionally substituted by one or more perfluoro Ci.6 alkyl, wherein any two R G may be connected by a single or double bond, wherein when R G is perfluoro Ci_ 2 o alkyl, perfluoro C 2 _ 20 alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO2-, or -NR J -, and wherein a terminal carbon atom in R G , if present, may be replaced by -S0 2 X D ;
  • R J at each instance is independently selected from Ci -6 alkyl, fluoro d. 6 alkyl, perfluoro Ci -6 alkyl, C 3 _i 0 cycloalkyl, phenyl optionally substituted by one or more R K , heteroaryl optionally substituted by one or more R K , and heterocyclyl optionally substituted by one or more R ;
  • R K at each instance is independently selected from Ci.6 alkyl, Ci -6 alkenyl, nitro, halo, hydroxyl, Ci. 6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
  • Ci_ 6 alkoxycarbonyl -NH 2
  • Ci -6 alkylamino di(C]. 6
  • alkyl)amino -C0 2 H, -C(0)NR L , -S0 2 OR L , -S0 2 X D , -S0 2 NR L 2 , -S0 3 H, and -NHC(0)R L ;
  • R L at each instance is independently selected from C]. 6 alkyl, fluoro Ci-6 alkyl, perfluoro Ci. 6 alkyl, and
  • X D at each instance is independently selected from F, CI, and Br;
  • n 1 to 20;
  • n 0, 1, 2, or 3;
  • y is 1, 2, 3, or 4;
  • z 0, 1, 2, or 3;
  • k is 1 , 2, 3, or 4;
  • Group 3 is 1 , or 2. This group is referred to herein as "Group 3”.
  • the Group 3 anion, X q is selected from the group consisting of: [(CF 3 S02)2N] ⁇ , [(CF 3 S0 2 )NC(0)CF 3 ]-, [(FS0 2 ) 2 N]- [R F CF 2 S0 3 j-, [R F CF 2 OS0 3 ]-, [(R G S0 2 ) 2 N)]-, [(R G S0 2 ) 3 Cr,
  • R F at each instance is independently selected from perfluoro Ci_ 2 o alkyl, perfluoro C 2 -2o alkenyl having one or more double bonds, perfluoro C2- 2 o alkynyl having one or more triple bonds, perfluoro C 3 _i 0 cycloalkyl optionally substituted by one or more perfluoro Cj.6 alkyl, perfluoro C 3 _i 0 cycloalkenyl optionally substituted by one or more perfluoro Ci_6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci -6 alkyl, wherein any two R F may be connected by a single or double bond, wherein when R F is perfluoro Ci.
  • R G at each instance is independently selected from perfluoro C 2 . 20 alkyl, perfluoro C 2 . 2 o alkenyl having one or more double bonds, perfluoro C2-20 alkynyl having one or more triple bonds, perfluoro C 3 _io cycloalkyl optionally substituted by one or more perfluoro Ci_ 6 alkyl, perfluoro C 3 .i 0 cycloalkenyl optionally substituted by one or more perfluoro C e alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci_ 6 alkyl, wherein any two R G may be connected by a single or double bond, wherein when R G is perfluoro Ci_ 2 o alkyl, perfluoro C2-20 alkenyl, or perfluoro C2-2 0 alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced
  • R J at each instance is independently selected from Ci_ 6 alkyl, fluoro Ci_ 6 alkyl, perfluoro C ]-6 alkyl, C 3 _io cycloalkyl, phenyl optionally substituted by one or more R K , heteroaryl optionally substituted by one or more R K , and heterocyclyl optionally substituted by one or more R K ;
  • R K at each instance is independently selected from Ci_6 alkyl, Ci_6 alkenyl, nitro, halo, hydroxyl, Ci_6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
  • Ci -6 alkoxycarbonyl -NH 2
  • Ci_ 6 alkylamino di(Ci_ 6
  • alkyl)amino -C0 2 H, -C(0)NR L , -S0 2 OR L , -S0 2 X D , -S0 2 NR L 2 , -SO 3 H, and -NHC(0)R L ;
  • R L at each instance is independently selected from Ci.6 alkyl, fluoro Ci-6 alkyl, perfluoro Ci-e alkyl, and C3-10 cycloalkyl;
  • X D at each instance is independently selected from F, CI, and Br;
  • n 1 to 20;
  • n 0, 1, 2, or 3;
  • y is 1 , 2, 3, or 4;
  • z 0, 1, 2, or 3;
  • k is 1 , 2, 3, or 4;
  • p 1 , or 2.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C 2 -2o alkynyl, aryl, and substituted aryl; and
  • R 4 and R 6 are each independently selected from C 2 . 2 o alkyl, substituted Ci -2 o alkyl, C 2-2 o alkenyl, substituted C 2-2 o alkenyl, C 2 _ 20 alkynyl, substituted C 2 _ 2 o alkynyl, aryl, and substituted aryl; or one or more of R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 20 alkyl, substituted Ci_ 20 alkyl, C 2 _ 2 o alkenyl, substituted C 2 . 2 o alkenyl, C 2-2 o alkynyl, and substituted C 2 - 2 o alkynyl; and R 4 and R 6 are each independently selected from C 2 _ 2 o alkyl, substituted Ci_ 2 o alkyl, C 2 _ 20 alkenyl, substituted C 2 . 2 o alkenyl, C 2 - 2 o alkynyl, and substituted C 2 . 20 alkynyl; or
  • R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 20 alkyl, substituted Ci_2o alkyl, C 2-2 o alkenyl, substituted C 2 _ 20 alkenyl, aryl, and substituted aryl; and
  • R 4 and R 6 are each independently selected from C 2 - 2 o alkyl, substituted Ci_ 2 o alkyl, C 2 . 20 alkenyl, substituted C 2 - 2 o alkenyl, aryl, and substituted aryl; or
  • R 1 and R 2 , R 3 and R 4 , or R 5 and R 6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 20 alkyl, substituted C]. 2 o alkyl, C 2 - 2 o alkenyl, and substituted C 2 . 2 o alkenyl; and
  • R 4 and R 6 are each independently selected from C 2 . 20 alkyl, substituted Ci_ 20 alkyl, C 2 . 20 alkenyl, and substituted C 2-2 o alkenyl; or
  • R 1 and R 2 , R 3 and R 4 , or R 5 and R 6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci_ 2 o alkyl, C 2 . 2 o alkenyl, substituted C 2 . 2 o alkenyl, aryl, and substituted aryl; and R 4 and R 6 are each independently selected from C 2 .2o alkyl, substituted C ⁇ o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; or
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, C1.20 alkyl, substituted Ci-20 alkyl, C 2 . 2 o alkenyl, and aryl; and
  • R 4 and R 6 are each independently selected from C2-20 alkyl, substituted Ci_ 20 alkyl, C2-20 alkenyl, and aryl; or
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci-6 alkyl, C 2 . 6 alkenyl, and aryl; and
  • R 4 and R 6 are each independently selected from C 2 . 20 alkyl, substituted alkyl, C 2- 6 alkenyl, and aryl; or
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl.
  • R 1 , R 2 and R 3 are each independently selected from -H, Ci. 0 alkyl, substituted Ci-20 alkyl, C 2- 2o alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and
  • R 4 is selected from C2-20 alkyl, substituted C1.20 alkyl, C2- 2 o alkenyl, substituted C 2 _ 20 alkenyl, aryl, and substituted aryl;
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 , R 2 and R 3 are each independently selected from -H, Ci -2 o alkyl, substituted Ci_ 20 alkyl, C 2 . 2 o alkenyl, and aryl; and
  • R 4 is selected from C 2 . 2 o alkyl, substituted C1.20 alkyl, C 2 . 2 o alkenyl, and aryl;
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 , R 2 and R 3 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci_ 6 alkyl, C2-6 alkenyl, and aryl; and
  • R 4 is selected from C 2 . 20 alkyl, substituted Ci_6 alkyl, C 2 _6 alkenyl, and aryl;
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci-20 alkyl, C 2-2 o alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and R 2 , R 4 and R 6 are each independently selected from C2-20 alkyl, substituted Ci_ 2 o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; or
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, and aryl; and
  • R 2 , R 4 and R 6 are each independently selected from C2-20 alkyl, substituted Ci_ 2 o alkyl, C2-20 alkenyl, and aryl; or
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 and R 3 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C 2 .2o alkenyl, aryl, and substituted aryl; and
  • R 2 and R 4 are each independently selected from C2-20 alkyl, substituted C )-2 o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 and R 3 are each independently selected from -H, Ci_ 2 o alkyl, substituted C1.20 alkyl, C2-20 alkenyl, and aryl; and
  • R 2 and R 4 are each independently selected from C2-20 alkyl, substituted C 1-2 o alkyl, C2-20 alkenyl, and aryl;
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 and R 3 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci.6 alkyl, C 2 -e alkenyl, and aryl; and
  • R 2 and R 4 are each independently selected from C2-20 alkyl, substituted Ci-e alkyl, C 2 -6 alkenyl, and aryl;
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
  • R 1 and R 3 are each independently selected from -H, Ci -2 o alkyl, hydroxy ⁇ . 6 alkyl, carboxyl C 6 alkyl, Ci_ 6 alkoxycarbonyl Ci_ 6 alkyl, Ci_ 6 alkoxy Ci -6 alkyl, Ci_6 alkyl-NH 2 , Ci_ 6 alkylamino Ci_ 6 alkyl, carboxyl hydroxy Ci_ 6 alkyl, C 2 _6 alkenyl, and aryl; and
  • R 2 and R 4 are each independently selected from C2-20 alkyl, hydroxy Ci. 6 alkyl, carboxyl Ci. 6 alkyl, Ci_6 alkoxycarbonyl Ci_ 6 alkyl, C1-5 alkoxy Ci_ 6 alkyl, Ci_ 6 alkyl-NH 2 , ⁇ . 6 alkylamino Ci -6 alkyl, carboxyl hydroxy Cj.6 alkyl, C 2 _ 6 alkenyl, and aryl; and R 5 and R 6 form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl.
  • R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl
  • the heterocyclyl or substituted heterocyclyl is pyrrolidinyl, substituted pyrrolidinyl, piperidinyl, substituted piperidinyl, morpholinyl, substituted morpholinyl, azepanyl, or substituted azepanyl.
  • the heterocyclyl or substituted heterocyclyl is pyrrolidinyl or substituted pyrrolidinyl.
  • R 1 and R 3 are each independently selected from -H, Ci_ 2 o alkyl, hydroxy Ci_ 6 alkyl, carboxyl Ci -6 alkyl, Ci_ 6 alkoxycarbonyl Cj -6 alkyl, Ci -6 alkoxy Ci -6 alkyl, Ci -6 alkyl-NH 2 , C 1-6 alkylamino Ci -6 alkyl, carboxyl hydroxy Ci_6 alkyl, C 2 _6 alkenyl, and aryl; and
  • R 2 and R 4 are each independently selected from C 2 . 20 alkyl, hydroxy Ci_ 6 alkyl, carboxyl C]. 6 alkyl, Ci-e alkoxycarbonyl Ci -6 alkyl, Ci_ 6 alkoxy Ci- ⁇ alkyl, Ci -6 alkyl-NH 2 , Ci_ 6 alkylamino C]. 6 alkyl, carboxyl hydroxy C
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a substituted pyrrolidinyl.
  • the heterocyclyl is substituted by one or more carboxyl groups.
  • R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 independently form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl
  • the heterocyclyl is substituted by one or more substituents independently selected from Cj. 6 alkyl, C 1 .6 alkoxy and C a alkoxy C b alkyl wherein a and b are independently 1 , 2, 3, 4, or 5 and the sum (a + b) is 2, 3, 4, 5, or 6.
  • R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 independently form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl
  • the heterocyclyl is substituted by one or more substituents independently selected from Ci_ 6 alkyl and C a alkoxy C b alkyl wherein a and b are independently 1 , 2, 3, 4, or 5 and the sum (a + b) is 2, 3, 4, 5, or 6.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, C]_ 2 o alkyl, substituted Cue alkyl, C 2-2 o alkenyl, substituted C 2 . 20 alkenyl, aryl, and substituted aryl; and
  • R 4 and R 6 are each independently selected from C 2 . 2 o alkyl, substituted Cuo alkyl, C 2-20 alkenyl, substituted C 2 _ 2 o alkenyl, aryl, and substituted aryl.
  • R 1 , R 3 and R 5 are each independently selected from -H, Ci_ 20 alkyl, substituted Ci_2o alkyl, C 2-2 o alkenyl, substituted C 2 - 2 o alkenyl, aryl, and substituted aryl; and
  • R 2 , R 4 and R 6 are each independently selected from C2-20 alkyl, substituted C i_ 2 o alkyl, C 2 _2o alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, and substituted C2-20 alkenyl; and
  • R 4 and R 6 are each independently selected from C2-20 alkyl, substituted Ci_ 2 o alkyl, C2-20 alkenyl, and substituted C2-20 alkenyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, C t .20 alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, and aryl; and
  • R 4 and R 6 are each independently selected from C 2 _2o alkyl, substituted C ⁇ o alkyl, C2-20 alkenyl, and aryl.
  • R 1 , R 3 and R 5 are each independently selected from -H, C ]. 2 o alkyl, substituted C
  • R 2 , R 4 and R 6 are each independently selected from C2-20 alkyl, substituted C i -2 o alkyl, C 2 _2o alkenyl, and aryl.
  • R 1 , R 3 and R 5 are each independently selected from -H, C1.20 alkyl, substituted Ci-20 alkyl, and C2-20 alkenyl;
  • R 2 is selected from -H, Ci. 2 o alkyl, substituted Ci_ 2 o alkyl, C2-20 alkenyl, and aryl;
  • R 4 and R 6 are each independently selected from C 2 _2o alkyl, substituted C ⁇ o alkyl, C2-20 alkenyl, and aryl.
  • R 1 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci-20 alkyl, and C2-20 alkenyl;
  • R 2 , R 4 and R 6 are each independently selected from C2-20 alkyl, substituted Ci -2 o alkyl, C2-20 alkenyl, and aryl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci-20 alkyl, and C2-20 alkenyl; and
  • R 4 and R 6 are each independently selected from C 2 _2o alkyl, substituted Ci_ 2 o alkyl, and C2-20 alkenyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, C1.20 alkyl, substituted Ci-6 alkyl, C 2 -6 alkenyl, and aryl; and
  • R 4 and R 6 are each independently selected from C2-20 alkyl, substituted Ci_ 6 alkyl, C2- alkenyl, and aryl.
  • R 1 , R 3 and R 5 are each independently selected from -H, C1.20 alkyl, substituted Ci. « alkyl, and C 2- 6 alkenyl;
  • R 2 is selected from -H, Ci -2 o alkyl, substituted C,_ 6 alkyl, C 2- 6 alkenyl, and aryl;
  • R 4 and R 6 are each independently selected from C2-20 alkyl, substituted Ci_ 6 alkyl, C 2 . 6 alkenyl, and aryl.
  • R 1 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci_ 6 alkyl, and C2-6 alkenyl;
  • R 2 , R 4 and R 6 are each independently selected from C2-20 alkyl, substituted Ci. 6 alkyl, C 2 . 6 alkenyl, and aryl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci -2 o alkyl, substituted Ci_6 alkyl, and C 2 _6 alkenyl; and
  • R 4 and R 6 are each independently selected from C 2 _2o alkyl, substituted C1.6 alkyl, and C 2 -6 alkenyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, C1.20 alkyl, hydroxy Ci-6 alkyl, carboxyl Ci -6 alkyl, C 1-6 alkoxycarbonyl Ci -6 alkyl, C ⁇ . 6 alkoxy Ci_ 6 alkyl, d -6 alkyl-NH 2 , Ci -6 alkylamino Ci_ 6 alkyl, carboxyl hydroxy Ci -6 alkyl, C 2 -6 alkenyl, and aryl; and
  • R 4 and R 6 are each independently selected from C2-20 alkyl, hydroxy Ci_ 6 alkyl, carboxyl Ci.6 alkyl, C]_ 6 alkoxycarbonyl Ci_ 6 alkyl, Ci -6 alkoxy C ⁇ . 6 alkyl, C]. 6 alkyl-NH 2 , Ci -6 alkylamino Ci -6 alkyl, carboxyl hydroxy C ⁇ .(, alkyl, C2-6 alkenyl, and aryl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, hydroxy Ci.6 alkyl, carboxyl Ci -6 alkyl, Ci_ 6 alkoxycarbonyl Ci_ 6 alkyl, C ⁇ . 6 alkoxy Ci_ 6 alkyl, C]. 6 alkyl-NH 2 , Ci -6 alkylamino Ci.6 alkyl and C2-6 alkenyl; and
  • R 4 and R 6 are each independently selected from C2-20 alkyl, hydroxy Ci -6 alkyl, carboxyl Ci. 6 alkyl, C ⁇ . 6 alkoxycarbonyl Ci_ 6 alkyl, Ci-6 alkoxy Ci_ 6 alkyl, Ci_ 6 alkyl-NH 2 , Ci_ 6 alkylamino Ci_ 6 alkyl and C 2 -6 alkenyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, hydroxy Ci_6 alkyl, carboxyl C e alkyl, carboxyl hydroxy Ci -6 alkyl, C 2 _6 alkenyl, and aryl; and
  • R 4 and R 6 are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl Ci_6 alkyl, carboxyl hydroxy Ci rating 6 alkyl, C 2 -e alkenyl, and aryl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci -2 o alkyl, hydroxy Ci-6 alkyl, carboxyl C ⁇ .e alkyl, and C 2 -6 alkenyl; and
  • R 4 and R 6 are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl Ci.6 alkyl, and C 2 -6 alkenyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, C]. 2 o alkyl, hydroxy Ci_e alkyl, and C 2-6 alkenyl; and
  • R 4 and R 6 are each independently selected from C2-20 alkyl, hydroxy Ci_ 6 alkyl, carboxyl Ci_6 alkyl, carboxyl hydroxy Ci_6 alkyl, and C 2 -6 alkenyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, hydroxy Ci-6 alkyl, and C2-6 alkenyl; and R 4 and R 6 are each independently selected from C2-20 alkyl, hydroxy Ci_ 6 alkyl, carboxyl Ci. 6 alkyl, and C2-6 alkenyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, methyl, ethyl,
  • R 4 and R 6 are each independently selected from ethyl, «-propyl, /so-propyl, n-butyl, w-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, 1-carboxylethyl, 1 -carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl; or
  • R 5 and R 6 together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, methyl, ethyl,
  • R 4 and R 6 are each independently selected from ethyl, n-propyl, z ' so-propyl, «-butyl, «-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, methyl, ethyl, «-propyl, « ⁇ -propyl, «-butyl, «-hexyl, stearyl, 2-hydroxyethyl, and allyl; and
  • R 4 and R 6 are each independently selected from ethyl, n-propyl, wo-propyl, «-butyl, n-hexyl, stearyl, 2-hydroxyethyl, 1-carboxylethyl, and allyl.
  • R'-R 6 are identical.
  • R ] -R 6 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, or C 2 .e alkenyl.
  • R l -R 6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl.
  • R'-R 6 are identical and are pentyl, hexyl, or decyl.
  • R ] -R 6 are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl.
  • R'-R 6 are identical and are 2-hydroxyethyl.
  • each of R'-R 6 comprise 2- 10 non-hydrogen atoms. In some embodiments, wherein R'-R 6 are identical, each of R'-R 6 comprise 2-6 non-hydrogen atoms.
  • the anion, X q ⁇ is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.
  • R 1 , R 3 and R 5 are identical. In some embodiments, R 1 , R 3 and R 5 are identical and are -H, C1.20 alkyl, substituted Ci_6 alkyl, or C 2 -6 alkenyl. In some embodiments, R 1 , R 3 and R 5 are identical and are C1.20 alkyl, substituted Ci_e alkyl, or C 2 -6 alkenyl. In some embodiments, R 1 , R 3 and R 5 are identical and are C2-20 alkyl, substituted C e alkyl, or C 2 -6 alkenyl.
  • R 4 , R 5 and R 6 are identical.
  • R 2 , R 4 and R 6 are identical and are C2-20 alkyl, substituted Ci_ 6 alkyl, C 2 -e alkenyl, or aryl.
  • R 2 , R 4 and R 6 are identical and are C2-20 alkyl, substituted Ci_ 6 alkyl, C 2 -6 alkenyl, or phenyl.
  • R 1 , R 3 and R 5 are identical, R 2 , R 4 and R 6 are identical, and R 1 and R 2 are different.
  • R 1 , R 3 and R 5 are identical and are -H, Ci_ 2 o alkyl, substituted Ci -6 alkyl, or C 2 -e alkenyl, and R 2 , R 4 and R 6 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, C2-6 alkenyl, or aryl, and R' and R 2 are different.
  • R 1 , R 3 and R 5 are identical and are -H, C1.20 alkyl, substituted Ci_ 6 alkyl, or C 2 -e alkenyl
  • R 2 , R 4 and R 6 are identical and are C 2 _2o alkyl, substituted Ci_ 6 alkyl, C2-6 alkenyl, or phenyl, and R 1 and R 2 are different.
  • R 1 , R 3 and R 5 are identical and are Ci_ 2 o alkyl, substituted Ci_ 6 alkyl, or C 2 -6 alkenyl, and R 2 , R 4 and R 6 are identical and are C2-20 alkyl, substituted Ci_ 6 alkyl, or C 2 -e alkenyl, and R 1 and R 2 are different.
  • R 1 , R 3 and R 5 are identical and are C2-20 alkyl, substituted Ci_ 6 alkyl, or C 2 -6 alkenyl, and R 2 , R 4 and R 6 are identical and are C2-20 alkyl, substituted Ci_ 6 alkyl, or C 2 _ 6 alkenyl, and R 1 and R 2 are different.
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl.
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl.
  • R 1 , R 3 and R 5 are -H and R 2 , R 4 and R 6 are phenyl.
  • R 1 , R 3 and R 5 are identical, R 2 , R 4 and R 6 are identical, and R 1 and R 2 are different, R 1 and R 2 together comprise 2-10 non-hydrogen atoms.
  • R 1 is not -H.
  • the anion, X q ⁇ is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • the anion, X q ⁇ is selected from Group 3.
  • R 1 , R 2 , R 3 and R 4 are identical.
  • R 1 , R 2 , R 3 and R 4 are identical and are C 2 _2o alkyl, substituted Q-e alkyl, or C 2 _6 alkenyl.
  • R 3 , R 4 , R 5 and R 6 are identical. In some embodiments, R 3 , R 4 , R 5 and R 6 are identical and are C 2 - 2 o alkyl, substituted Ci -6 alkyl, or C 2 -6 alkenyl.
  • R 1 , R 2 , R 3 and R 4 are identical, R 5 and R 6 are identical, and R 1 and R 5 are different.
  • R 1 , R 2 , R 3 and R 4 are identical and are C 2 _2o alkyl, substituted C 1-6 alkyl, or C 2-6 alkenyl
  • R 5 and R 6 are identical and are C2-20 alkyl, substituted Ci -6 alkyl, or C 2- e alkenyl
  • R 1 and R 5 are different.
  • R 3 , R 4 , R 5 and R 6 are identical, R 1 and R 2 are identical, and R 1 and R 3 are different.
  • R 3 , R 4 , R 5 and R 6 are identical and are Ci -2 o alkyl, substituted Ci -6 alkyl, or C 2- alkenyl
  • R 1 and R 2 are identical and are -H, C 2-20 alkyl, substituted Ci_ 6 alkyl, or C 2 _ 6 alkenyl, and R 1 and R 3 are different.
  • R 3 , R 4 , R 5 and R 6 are identical and are Ci-20 alkyl, substituted Ci_ alkyl, or C 2 - 6 alkenyl, R 1 and R 2 are identical and are C 2 _2o alkyl, substituted Ci -6 alkyl, or C 2 . 6 alkenyl, and R 1 and R 3 are different.
  • R 3 , R 4 , R 5 and R 6 are identical and are C2-20 alkyl, substituted Ci. 6 alkyl, or C2-6 alkenyl, R 1 and R 2 are identical and are -H, C2-20 alkyl, substituted C ]-6 alkyl, or C 2 . 6 alkenyl, and R 1 and R 3 are different.
  • R 3 , R 4 , R 5 and R 6 are identical and are C 2 . 2 o alkyl, substituted Ci_ 6 alkyl, or C 2 . 6 alkenyl
  • R 1 and R 2 are identical and are C2-20 alkyl, substituted Ci_ 6 alkyl, or C2-6 alkenyl, and R 1 and R 3 are different.
  • R 1 , R 2 , R 3 and R 4 are identical, R 5 and R 6 are identical, and R 1 and R 5 are different, R 1 , R 2 , R 3 and R 4 are ethyl.
  • R 5 and R 6 together comprise 2-8 non- hydrogen atoms.
  • the anion, X q ⁇ is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.
  • R 3 , R 4 , R 5 and R 6 are identical, R 1 and R 2 are identical, and R 1 and R 3 are different, R 3 , R 4 , R 5 and R 6 are ethyl.
  • R 1 and R 2 together comprise 2-8 non- hydrogen atoms.
  • the anion, X q ⁇ is selected from Group 2 or 3.
  • the anion is selected from Group 3.
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are j ' so-propyl.
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl.
  • R ⁇ R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl.
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl.
  • R 1 , R 2 , R 3 and R 4 are wo-propyl and R 5 and R 6 are butyl. In some embodiments, R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl.
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl.
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are hydrogen.
  • R 1 , R 2 , R 3 and R 4 are identical, R 5 and R 6 are identical, and R 1 and R 5 are different, R 5 and R 6 together comprise 2-8 non-hydrogen atoms.
  • the anion, X q ⁇ is selected from Group 2 or 3.
  • R 3 , R 4 , R 5 and R 6 are identical, R 1 and R 2 are identical, and R 1 and R 3 are different, R 1 and R 2 together comprise 2-8 non-hydrogen atoms.
  • the anion, X q" is selected from Group 2 or 3.
  • the anion, X q" is selected from Group 2 or 3.
  • R 3 , R 4 , R 5 and R 6 are identical, R 1 and R 2 are identical, and R 1 and R 3 are different, R 3 and R 4 together comprise 2-8 non-hydrogen atoms.
  • the anion, X ⁇ is selected from Group 2 or 3.
  • R 1 , R 2 , R 3 and R 4 are identical, R 5 and R 6 are different and R 1 , R 5 and R 6 are different.
  • R 1 , R 2 , R 3 and R 4 are identical and are C 2 - 20 alkyl, substituted Ci_ 6 alkyl, or C 2 -6 alkenyl
  • R 5 is H, Ci_ 2 o alkyl, substituted Q.6 alkyl, or C 2- 6 alkenyl
  • R 6 is C 2 - 20 alkyl, substituted Ci_ 6 alkyl, or C 2 . 6 alkenyl
  • R 1 , R 5 and R 6 are different.
  • R 3 , R 4 , R 5 and R 6 are identical, R 1 and R 2 are different and R 1 , R 2 and R 3 are different. In some embodiments, R 3 , R 4 , R 5 and R 6 are identical and are C 2 . 2 o alkyl, substituted C ⁇ . e alkyl, or C 2 -6 alkenyl, R 1 and R 2 are each independently H, Ci_ 2 o alkyl, substituted C]_ 6 alkyl, or C 2 -6 alkenyl, and R 1 , R 2 and R 3 are different.
  • R 5 and R 6 are different and R 1 , R 5 and R 6 are different, R 1 , R 2 , R 3 and R 4 are ethyl.
  • R 5 and R 6 together comprise 1 -6 non- hydrogen atoms.
  • the anion, X q ⁇ is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.
  • R 1 and R 2 are different and R 1 , R 2 and R 3 are different, R 3 , R 4 , R 5 and R 6 are ethyl.
  • R 1 and R 2 together comprise 1-6 non- hydrogen atoms.
  • the anion, X q is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl.
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl. In some embodiments, R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl.
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is hexyl.
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1-carboxylethyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxyl-2-hydroxypropyl, or 1 -carboxyl-2-methylpropyl. In some embodiments, R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl. In some embodiments,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is (S)- 1-carboxylethyl, (S)-l -carboxyl-2-hydroxypropyl, or (S)-l -carboxyl-2-methylpropyl.
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is (S)-l -carboxyl-2-hydroxypropyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is (S)-l -carboxylethyl. In some embodiments,
  • R'-R 6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
  • R 1 , R 3 and R 5 are -H and R 2 , R 4 and R 6 are phenyl,
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are wo-propyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are /so-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are -H,
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxyl-2-hydroxypropyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxyl-2-methylpropyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, and R 5 and R 6 , together with the nitrogen atom to which they are attached, are
  • R 1 , R 3 and R 5 are -H and R 2 , R 4 and R 6 are phenyl,
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are iso-propyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are wo-propyl and R 5 and R 6 are butyl, R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl,
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are -H,
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl
  • R 5 is hydrogen and R 6 is 1 -carboxyl-2-hydroxypropyl
  • R 1 , R 2 , R 3 and R 4 are ethyl
  • R 5 is hydrogen and R 6 is 1 -carboxyl-2-methylpropyl.
  • R'-R 6 are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are wo-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl.
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are wo-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl, R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are chiral.
  • one or more of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is (S)-l -carboxylethyl
  • R 1 or R 2 together comprise 3-7 non-hydrogen atoms
  • R 3 and R 4 together comprise 3-7 non-hydrogen atoms
  • R 1 or R 2 together comprise 3-7 non-hydrogen atoms
  • R 3 and R 4 together comprise 3-7 non-hydrogen atoms
  • R 5 or R 6 is (S)-l -carboxylethyl, (S)-l-carboxyl-2-hydroxypropyl, or
  • one or more of R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 , together with the nitrogen atom to which they are attached, is independently -NH-CH(R A )-C0 2 H, wherein R A is a side chain of a natural or non-natural alpha-amino acid.
  • one or more of R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C0 2 H.
  • R 1 , R 2 , R 3 and R 4 are ethyl, and R 5 and R 6 , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C0 2 H. In some embodiments, R 1 , R 2 , R 3 and R 4 are ethyl, and R 5 and R 6 , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-(S)-2-C0 2 H.
  • one or more of R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C0 2 H, -NH(CH(CH 3 )C0 2 H),
  • one or more of R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-(S)-2-C0 2 H, -NH((5)-CH(CH 3 )C0 2 H),
  • one or more of R 1 - R 6 is independently -CH(R A )-C0 2 H, wherein R A is a side chain of a natural or non-natural alpha-amino acid, provided that the side chain does not link to the alpha-amino group.
  • one or more of R 1 - R 6 is independently -CH(CH 3 )C0 2 H,
  • one or more of R 1 - R 6 is independently -(S)-CH(CH 3 )C0 2 H,
  • R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 are independently
  • R A is a side chain of a natural or non-natural alpha-amino acid, provided that the side chain does not link to the alpha-amino group.
  • one or more of R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 , together with the nitrogen atom to which they are attached, are independently -N(Ci_6 alkyl)-CH(R A )-C0 2 H, wherein R A is a side chain of a natural or non-natural alpha-amino acid, provided that the side chain does not link to the alpha-amino group.
  • R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 together with the nitrogen atom to which they are attached, are independently -NH-CH(R A )-C0 2 (Ci_6 alkyl), wherein R A is a side chain of a natural or non-natural alpha-amino acid.
  • one or more of R 1 and R 2 , R 3 and R 4 , and R 5 and R 6 , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C0 2 (Ci. 6 alkyl).
  • R 1 and R 2 are identical
  • R 3 and R 4 are identical
  • R 5 and R 6 are identical
  • R 1 , R 3 and R 5 are different.
  • R 1 and R 2 are different, R 3 and R 4 are different, and R 5 and R 6 are different, R 1 , R 3 and R 5 are identical, and R 2 , R 4 and R 6 are different.
  • R 1 and R 2 are different, R 3 and R 4 are different, and R 5 and R 6 are identical, R 1 and R 3 are identical, R 1 and R 5 are different, R 2 and R 4 are identical, and R 2 and R 6 are different.
  • R 1 and R 2 are different, R 3 and R 4 are different, and R 5 and R 6 are identical, R 1 and R 3 are identical, R 1 and R 5 are different, R 2 and R 4 are identical, and R 2 and R 6 are different, R 1 is butyl and R 2 is methyl.
  • R 5 and R 6 together comprise 1 -6 non- hydrogen atoms.
  • R 1 and R 2 are different, R 3 and R 4 are different, and R 5 and R 6 are different, R 1 , R 3 and R 5 are identical, R 2 and R 4 are identical, and R 2 and R 6 are different.
  • R 1 and R 2 are different, R 3 and R 4 are different, and R 5 and R 6 are different, R 1 and R 3 are identical, R 1 and R 5 are different, R 2 and R 4 are identical, and R 2 and R 6 are different.
  • R 1 and R 2 are different, R 3 and R 4 are different, and R 5 and R 6 are different, R 1 and R 3 are identical, R 1 and R 5 are different, R 2 and R 4 are identical, and R 2 and R 6 are different, R 1 and R 2 together comprise 3-7 non-hydrogen atoms.
  • R 1 is butyl and R 2 is methyl.
  • R 1 and R 2 are different, R 3 and R 4 are different, R 5 and R 6 are different, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are different.
  • R 1 , R 2 , R 3 , R 4 and R 5 are identical and R 1 and R 6 are different.
  • R 1 , R 2 and R 3 are identical, R 3 and R 4 are different, and R 4 , R 5 and R 6 are identical.
  • R 1 , R 2 and R 3 are identical, R 3 and R 4 are different, R 5 and R 6 are identical, and R 2 , R 4 and R 6 are different.
  • R 1 and R 2 are identical, R 3 and R 4 are identical, and R 1 , R 3 , R 5 and R 6 are different.
  • R D is (4-methylpiperazinyl)methyl, 2,3-difluoro-4-pyridyl, 3-fluoropyridyl, 5-methyl-2-furyl, [2-(trimethylsilyl)ethoxy]methyl, or bromomethyl.
  • R F is perfluoro C 1 . 1 2 alkyl.
  • R F is perfluoro C 2 _i2 alkenyl having one or more double bonds or perfluoro C 2 -n alkynyl having one or more triple bonds.
  • R F is selected from pentafluoroallyl, heptafluorobut-2-enyl, heptafluorobut-3-enyl, wo-heptafluorobutenyl, sec-heptafluorobutenyl, nonafluoropent-4-enyl, wo-nonafluoropentenyl, and -C 6 Fi i .
  • R F is selected from fluoroethynyl, trifluoropropyn-l -yl, trifluoroprop-2-ynyl, pentafluorobut-2-ynyl, pentafluorobut-3-ynyl, heptafluoropent-3-ynyl, heptafluoropent-4-ynyl, and nonafluorohexynyl.
  • R F is selected from trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, -C(CF 3 ) 3 , -CF 2 N(CF 3 )CF 3 , -CF 2 OCF 3 , -CF 2 S(0)CF 3 ,
  • -CF CFN(CF 3 )CF 3
  • -C(CF 3 ) CFCF 3
  • -CF 2 CF CFCF 3
  • -CF CFN(CF 3 )CF 3 .
  • R F is trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.
  • R F is perfluorophenyl optionally substituted by one or more perfluoro C,. 6 alkyl.
  • R G is perfluoro C 2 _i 2 alkyl.
  • R° is perfluoro C 2 . ]2 alkenyl having one or more double bonds or perfluoro C 2 _i 2 alkynyl having one or more triple bonds.
  • R G is selected from pentafluoroallyl, heptafluorobut-2-enyl, heptafluorobut-3-enyl, wo-heptafluorobutenyl, seoheptafluorobutenyl, nonafluoropent-4-enyl, wo-nonafluoropentenyl, and -C 6 F u .
  • R G is selected from fluoroethynyl, trifluoroprop-l-ynyl, trifluoroprop-2-ynyl, pentafluorobut-2-ynyl, pentafluorobut-3-ynyl, heptafluoropent-3-ynyl, heptafluoropent-4-ynyl, and nonafluorohexynyl.
  • R G is selected from pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, — C(CF 3 ) 3 , -CF 2 N(CF 3 )CF 3 , -CF 2 OCF 3 , -CF 2 S(0)CF 3 , -CF 2 S0 2 CF 3 ,
  • R G is pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.
  • R G is perfluorophenyl optionally substituted by one or more perfluoro Ci_ 6 alkyl.
  • any two or more R F or any two or more R G may be connected by a single or a double bond to form a cyclic, bicyclic or polycyclic anion.
  • R J is phenyl substituted with methyl, ethyl, propyl, « ⁇ -propyl, tert-butyl, nitro, fluoro, chloro, bromo, iodo, hydroxyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy,
  • R J is phenyl disubstituted with methyl, fluoro, chloro, bromo, hydroxyl, or methoxy.
  • R J is 5-fluoro-2-methylphenyl, 3,4,5-trimethoxyphenyl, or 2,4,5-trimethylphenyl.
  • R is perfluorophenyl.
  • R J is heteroaryl or heterocyclyl optionally substituted by one or more R K , wherein the heteroaryl or heterocyclyl is acridinyl, benz-2, 1 ,3 -oxadiazolyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzofuryl, benzopyrazolyl, benzothiazolyl, benzothienyl, benzoxazolyl, carbazolyl, cinnolinyl, furyl, imidazolyl, IH-indolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrroly
  • the anion, X q ⁇ is selected from [(CF 3 S0 2 ) 2 N] “ , [(CF 3 S0 2 )NC(0)CF 3 ] " ,
  • the anion, X q is selected from [P(C n F 2 n + i- m H m ) y F 6 -y] , [BF Z R F 4 _ Z ] a d
  • n 1 to 12.
  • the anion, X q ⁇ is [B(CN) 4 ] ⁇ , [(C 2 F 5 ) 3 PF 3 ] " , [(C 2 F 5 )2PF 4 ] " , [(C 4 F 9 ) 3 PF 3 ] ⁇
  • the anion is [B(CN) 4 ] " , [(C 2 F 5 ) 3 PF 3 ] " , or [B(C 2 F 5 )F 3 ] .
  • the anion, X q ⁇ is a group 1 anion selected from F ⁇ , Br ⁇ , ⁇ , [HF 2 ] " , [SCN] ⁇ ,
  • the anion, X q ⁇ is the group 1 anion [SnCl 3 ] ⁇ .
  • the anion, X q ⁇ is a group 1 anion selected from F-, Br ⁇ , ⁇ , [HF 2 ]-, [SCN] ⁇ ,
  • the anion, X q_ is a group 2 anion selected from [SeCN]-, [CF 3 SO 3 ]-, [FHOMe]-, [FHOEtr, [FHOPr]-, [MeOS0 3 ] ⁇ [EtOS0 3 ] " , [(BuO) 2 P(0)0]-, [CH 3 C 6 H 4 S0 3 ] " ,
  • the anion, X q" is a group 2 anion selected from [SeCN] “ , [CF 3 S0 3 ] “ , [FHOMe] “ , [FHOEt] “ [FHOPr] " [MeOS0 3 ] “ , [EtOS0 3 ] “ , [(BuO) 2 P(0)0] “ , and [CH 3 C 6 H 4 S0 3 ] " .
  • the anion, X q" is a group 3 anion selected from [(CF 3 S0 2 )2N] ⁇ ,
  • the anion, X q" is selected from F “ , Br “ , ⁇ , [HF 2 ] ⁇ , [SCN] “ , [NCO] “ , [N0 3 ] “ , [A1C1 4 ]-, [A1 2 C1 7 ]- [PF 6 ]-, [SnCl 3 ] " ,
  • the anion, X q ⁇ is selected from F “ , Br ⁇ , ⁇ , [HF 2 ] ⁇ [SCN] “ , [NCO] ⁇ , [N0 3 ] ⁇ , [A1C1 4 ] " , [A1 2 C1 7 ]-, [PF 6 ]-,
  • the anion, X q" is selected from F ⁇ , Br “ , ⁇ , [HF 2 ] “ , [SCN] “ , [NCO] “ , [N0 3 ] “ , [A1C1 4 ]-, [A1 2 C1 7 ]-, [PF 6 ] “ , [SnCl 3 ] "
  • the anion, X q" is selected from F ⁇ , Br-, ⁇ , [HF 2 ] ⁇ , [SCN]-, [NCO] " , [N0 3 ]- [AICI4]- [A1 2 C1 7 ]-, [PF 6 ]-
  • the anion, X q ⁇ is [NH 2 -CH(R A )C(0)0] " .
  • the anion, X q ⁇ is [pyrrolidinyl-2-COO] ⁇ .
  • the anion, X q" is selected from F-, Br- ⁇ , [N0 3 ] " , [PF 6 ]- [SnCl 3 ] ⁇ [SCN] " , [NCO] , [CF 3 S0 3 r, [CH3OSO3]-, [CJHSOSOJ]- [C 6 F 5 S0 3 ]-, [(BuO) 2 P(0)0]- [CH 3 C 6 H 4 S03] " ,
  • the anion, X q" is selected from F ⁇ , Br-, ⁇ , [N0 3 ]- [SnCl 3 ]-, [SCN]-, [NCO]-, [CF 3 SO3]- [CH 3 OSO 3 ]-, [(BuO) 2 P(0)0]-, [CH 3 C 6 H 4 S0 3 ]-, [(CF 3 S0 2 ) 2 N]-, [P(C 2 F 5 )3F 3 ]-, [B(CN) 4 ]-, and [N(CN) 2 ]-.
  • the anion, X q- is selected from F-, ⁇ , [N0 3 ]-, [PF 6 ]-, [SCN]- [CF 3 S0 3 ]-,
  • the anion, X q- is selected from Br " , ⁇ , [N0 3 ]- [PF 6 ]-, [SnCl 3 ]-, [SCN]-, [NCO]- [CF3SO 3 ]- [CH3OSO3]- [C 2 H 5 OS0 3 ]- [C 6 F 5 S0 3 r, [(BuO) 2 P(0)0]- [CH 3 C 6 H 4 S0 3 ]-, [(CF 3 S0 2 ) 2 N]-, [(FS0 2 ) 2 N]-, [C 2 F 5 S0 3 r, [(C 2 F 5 S0 2 ) 2 N)]-, [P(C 2 F 5 ) 3 F 3 ]-, [B(CN) 4 ]-, and [N(CN) 2 ]-.
  • the anion, X q- is selected from Br-, [N0 3 ]-, [PF 6 ]-, [SCN]-, [CF 3 SO 3 ]-,
  • the anion, X q- is selected from [N0 3 ]- [PF 6 ]- [SnCl 3 ]-, [SCN]-, [NCO]-,
  • the anion, X q- is selected from [N0 3 ]-, [PF 6 ]-, [SCN] , [CF 3 S0 3 ]-, [CH 3 OS0 3 ]-, [C 2 H 5 OS0 3 ]-, [C 6 F 5 S0 3 ]- [CH J C ⁇ SO J F, [(CF 3 S0 2 ) 2 N]- [(FS0 2 ) 2 N]- [C 2 F 5 S0 3 ]-, [(C 2 F 5 S0 2 ) 2 N)]- and [N(CN) 2 ]-.
  • the anion, X q ⁇ is selected from [PF 6 ] ⁇ , [CF 3 S0 3 ] “ , [CH 3 OS0 3 ] “ , [C 2 H 5 OS0 3 ] “ , [CeFsSO,]-, [CH ⁇ SO,] " , [(CF 3 S0 2 ) 2 N] " , [(FS0 2 ) 2 N]-, [C 2 F 5 S0 3 ]-, [(C 2 F 5 S0 2 ) 2 N)] " and [N(CN) 2 ] "
  • the anion, X q" is F ⁇ .
  • the invention also contemplates embodiments in which the cation, Y ⁇ , is as identified in any of the embodiments disclosed above and the anion, X " , is as identified in any of the embodiments disclosed above.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, C 2 o alkyl, substituted Ci_2o alkyl, C 2 . 2 o alkenyl, substituted C 2 . 20 alkenyl, aryl, and substituted aryl; and
  • R 4 and R 6 are each independently selected from C -2 o alkyl, substituted Ci. 2 o alkyl, C 2 . 2 o alkenyl, substituted C 2 . 20 alkenyl, aryl, and substituted aryl; or
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl;
  • X q is selected from F “ , Br “ , ⁇ , [HF 2 ] “ , [SCN] “ , [NCO] “ , [N0 3 ] ⁇ , [AICL,] " [A1 2 C1 7 ] ⁇ [PF 6 ] “ , [SnCl 3 ]- [SeCN]-, [CF 3 S0 3 ] " , [FHOMef, [FHOEt] " , [FHOPr] " , [MeOS0 3 ] “ , [EtOS0 3 ] “ , [(BuO) 2 P(0)0] " ,
  • R 1 , R 2 and R 3 are each independently selected from -H, Ci. 2 o alkyl, substituted Ci_ 20 alkyl, C 2 . 2 o alkenyl, substituted C 2 . 2 o alkenyl, aryl, and substituted aryl; and
  • R 4 is selected from C 2 - 2 o alkyl, substituted Ci-20 alkyl, C 2 . 20 alkenyl, substituted C 2 . 20 alkenyl, aryl, and substituted aryl; and
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl;
  • X q is selected from F “ , Br “ , ⁇ , [HF,] “ [SCN] “ , [NCO] “ , [NO 3 ] “ , [AICI 4 ] “ , [AI2CI7] “ , [PF 6 ] “ [SnCl 3 ] “ ,
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci.20 alkyl, C 2 _ 20 alkenyl, and aryl;
  • R 4 and R 6 are each independently selected from C 2-2 o alkyl, substituted Ci_ 2 o alkyl, C2-20 alkenyl, and aryl;
  • X q is selected from F “ , Br “ , ⁇ , [HF 2 ] “ , [SCN] “ , [NCO] “ , [N0 3 ] ' , [AICU] “” , [A1 2 C1 7 ] ⁇ , [PF 6 ] “ ,
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci. 20 alkyl, and C2-20 alkenyl;
  • R 4 and R 6 are each independently selected from C 2 . 20 alkyl, substituted C]. 2 o alkyl, and C 2 . 2 o alkenyl; and the anion, X q" is selected from F , Br “ , ⁇ , [HF 2 ] ⁇ , [SCN] , [NCO] “ [N0 3 ] [AICU] " , [A1 2 C1 7 ] " , [PF 6 ] “ , [SeCN] “ , [CF 3 S0 3 ] " [FHOMe]-, [FHOEt] " , [FHOPr] " , [MeOS0 3 ] “ , [EtOS0 3 ] “ , [(BuO) 2 P(0)0] " ,
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted C1.6 alkyl, C 2 . 6 alkenyl, and aryl;
  • R 4 and R 6 are each independently selected from C2-20 alkyl, substituted Ci_ 6 alkyl, C 2 _6 alkenyl, and aryl;
  • X q is selected from F “ , Br “ , ⁇ , [HF 2 ] “ , [SCN]-, [NCO] “ [N0 3 ] " [AICU] “ , [A1 2 C1 7 ] “ , [PF 6 ] “ , [SnCl 3 ] “ ,
  • R 4 and R 6 are each independently selected from C 2 . 20 alkyl, substituted Ci_ 6 alkyl, and C 2 . 6 alkenyl; and the anion, X q_ , is selected from F “ , Br “ , ⁇ , [HF 2 ] “ , [SCN] “ , [NCO]-, [N0 3 T, [A1C ] ⁇ [A1 2 C1 7 ]-, [PF 6 ] ⁇ , [SeCN]-, [CF 3 S0 3 r, [FHOMe] " , [FHOEt] " , [FHOPrf, [MeOS0 3 ] " [EtOS0 3 ] ⁇ [(BuO) 2 P(0)0]
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, hydroxy Ci- alkyl, carboxyl Q-6 alkyl, Ci_6 alkoxycarbonyl C
  • R 4 and R 6 are each independently selected from C 2-20 alkyl, hydroxy Ci_ 6 alkyl, carboxyl C]_ 6 alkyl, Ci_6 alkoxycarbonyl Cue alkyl, Ci_6 alkoxy Ci.e alkyl, d_ 6 alkyl-NH 2 , C[. 6 alkylamino ue alkyl, carboxyl hydroxy C e alkyl, C 2 -e alkenyl, and aryl; and
  • X q ⁇ is selected from F “ , ⁇ , ⁇ , [HF 2 ] “ , [SCN]-, [NCO] “ [N0 3 ] _ , [AICL,]-, [A1 2 C1 7 ] ⁇ [PF 6 ] “ [SnCl 3 ]-,
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, hydroxy Cj.6 alkyl, carboxyl Ci.e alkyl, Ci_ 6 alkoxycarbonyl Ci -6 alkyl, Cue alkoxy Cj. 6 alkyl, C]. 6 alkyl-NH 2 , C ]-6 alkylamino C,.
  • R 4 and R 6 are each independently selected from C 2 - 2 0 alkyl, hydroxy Ci_ 6 alkyl, carboxyl Ci_6 alkyl, Ci -6 alkoxycarbonyl Ci -6 alkyl, Ci -6 alkoxy Ci -6 alkyl, Ci configuration 6 alkyl-NH 2 , C,. 6 alkylamino Ci -6 alkyl and C 2 . 6 alkenyl; and
  • the anion, X q_ is selected from F, Br “ , ⁇ , [HF 2 ] ⁇ , [SCN] ⁇ , [NCO]-, [N0 3 ] “ , [AICI 4 ] “ , [A1 2 C1 7 ] “ .
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci- 20 alkyl, hydroxy Ci-6 alkyl, carboxyl Ci_6 alkyl, carboxyl hydroxy Ci. 6 alkyl, C 2-6 alkenyl, and aryl; and
  • R 4 and R 6 are each independently selected from C 2-2 o alkyl, hydroxy Ci_ 6 alkyl, carboxyl Ci -6 alkyl, carboxyl hydroxy C 1-6 alkyl, C 2- 6 alkenyl, and aryl; and
  • X q_ is selected from F “ , Br “ , ⁇ , [HF 2 ] “ , [SCN] “ , [NCO] “ , [ ⁇ 0 3 ⁇ , [AIC ] “ , [A1 2 C1 7 ]-, [PF 6 ] “ , [SnCl 3 ]-
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci. 2 o alkyl, hydroxy Ci-6 alkyl, carboxyl Ci_6 alkyl, and C 2 . 6 alkenyl;
  • R 4 and R 6 are each independently selected from C 2-20 alkyl, hydroxy Ci -6 alkyl, carboxyl Ci_ 6 alkyl, and C2-6 alkenyl;
  • the anion, X q ⁇ is selected from F “ , Br “ , ⁇ , [HF 2 ] ⁇ [SCN] “ [NCO] “ , [N0 3 ] _ , [AICI 4 ] “ , [Al 2 Cl 7 r, [PF 6 ] “ [SeCN] [CF3SO3] , [FHOMe] [FHOEt] [FHOPr] " , [MeOSO,] " , [EtOS0 3 ] “ , [(BuO) 2 P(0)0] ,
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, hydroxy C]-6 alkyl, and C2-6 alkenyl;
  • R 4 and R 6 are each independently selected from C2-20 alkyl, hydroxy Ci_ 6 alkyl, carboxyl C ]-6 alkyl, and C 2 -6 alkenyl;
  • the anion, X q" is selected from F ⁇ , Br , ⁇ , [HF 2 ] ⁇ [SCN] “ , [NCO] “ [N0 3 ] ⁇ , [AICU] " , [A1 2 C1 7 ] “ , [PF 6 ] “ , [SeCN] “ , [CF3SO3] “ , [FHOMe] “ , [FHOEt] “ , [FHOPr] " , [MeOS0 3 ] “ , [EtOS0 3 ] ⁇ , [(BuO) 2 P(0)0] " ,
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 20 alkyl, substituted Ci-20 alkyl, C 2 . 20 alkenyl, and aryl;
  • R 4 and R 6 are each independently selected from C 2 - 2 o alkyl, substituted Ci. 2 o alkyl, C 2 . 2 o alkenyl, and aryl; or
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl;
  • X q is selected from IT, Br “ , ⁇ , [N0 3 ] “ [PF 6 ] “ , [SnCl 3 ] “ , [SCN] ' , [NCO] “ , [CF 3 S0 3 ] "
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci_ 20 alkyl, C 2 . 20 alkenyl, and aryl;
  • R 4 and R 6 are each independently selected from C 2 . 2 o alkyl, substituted Ci -2 o alkyl, C 2-20 alkenyl, and aryl; and
  • X q is selected from F “ , Br “ , ⁇ , [N0 3 ] _ , [PF 6 ] “ , [SnCl 3 ] “ , [SCN] “ , [NCO] “ , [CF 3 S0 3 ] “ ,
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 20 alkyl, substituted Ci. 20 alkyl, C 2-20 alkenyl, and aryl;
  • R 4 and R 6 are each independently selected from C 2 . 2 o alkyl, substituted Ci_ 2 o alkyl, C 2 _2o alkenyl, and aryl; or
  • R 5 and R 6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl; and the anion, X q_ , is selected from Br “ , ⁇ , [ ⁇ 0 3 ] ⁇ , [PF 6 ] “ [SnCl 3 ] ⁇ , [SCN] " , [NCOf, [CF 3 S0 3 ] _ , [CH 3 OS0 3 ] _ , [C 2 H 5 OS0 3 ]-, [CeFjSOa]-, [(BuO) 2 P(0)0] " [CH 3 C 6 H 4 S0 3 ] " , [(CF 3 S0 2 ) 2 N]-, [(FS0 2 ) 2 N] ⁇ [C 2 F 5 S0 3 ]- [(C 2 F 5 S0 2 ) 2 N)]-, [P(C 2 F 5 ) 3 F 3 ]- [B(CN) 4 ]-, and [N(CN) 2
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ o alkyl, substituted Ci-20 alkyl, C 2 . 20 alkenyl, and aryl;
  • R 4 and R 6 are each independently selected from C 2 . 2 o alkyl, substituted C io alkyl, C 2 _ 2 o alkenyl, and aryl;
  • the anion, X q_ is selected from Br “ , ⁇ , [N0 3 ] ⁇ , [PF 6 ] _ , [SnCl 3 ] “ , [SCN] “ , [NCO]-, [CF 3 S0 3 ]-, [CH 3 OS0 3 ] “ , [C2H5OSO3]-, [CeFjSOj] " , [(BuO) 2 P(0)0]-, [(CF 3 S0 2 ) 2 N]-, [(FS0 2 ) 2 Nr, [C 2 F 5 S0 3 ] , [(C 2 F 5 S0 2 ) 2 N)]-, [P(C 2 F 5 ) 3 F 3 ]-, [B(CN) 4 ] " , and [N(CN) 2 ] " .
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 2 o alkyl, substituted Ci_ 20 alkyl, and C 2 . 20 alkenyl;
  • R 4 and R 6 are each independently selected from C 2 - 20 alkyl, substituted Ci_ 20 alkyl, and C 2 _ 20 alkenyl; and the anion, X q , is selected from Br , [N0 3 ] “ , [PF 6 ] “ , [SCN] ⁇ , [CF 3 S0 3 ] , [CH 3 OS0 3 ] " , [C 2 H 5 OS0 3 ]-,
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 20 alkyl, substituted Ci -6 alkyl, and C 2-6 alkenyl;
  • R 4 and R 6 are each independently selected from C 2 - 2 o alkyl, substituted Ci_ 6 alkyl, and C 2-6 alkenyl; and the anion, X q ⁇ , is selected from Br “ , [N0 3 ] " , [PF 6 ] “ , [SCN] ⁇ , [CF 3 S0 3 ] ⁇ , [CH 3 OS0 3 ] " , [C 2 H 5 OS0 3 ]- [C 6 F 5 S0 3 ]- [CH 3 C6H 4 S03]-, [(CF 3 S0 2 ) 2 N]-, [(FS0 2 ) 2 N]-, [C 2 F 5 S0 3 ]-, [(C 2 F 5 S0 2 ) 2 N)]- and rN(CN) 2 r.
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci_ 20 alkyl, hydroxy C e alkyl, carboxyl Ci. 6 alkyl, and C 2 .e alkenyl;
  • R 4 and R 6 are each independently selected from C 2 . 2 o alkyl, hydroxy Ci_ 6 alkyl, carboxyl Ci_ 6 alkyl, and C2-6 alkenyl;
  • X q_ is selected from Br “ , [N0 3 ] “ , [PF 6 ] “ , [SCN] “ [CF 3 S0 3 ] “ , [CH 3 OS0 3 ] “ [C 2 H 5 OS0 3 ]-,
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, Ci -20 alkyl, hydroxy Ci-6 alkyl, and C 2 . 6 alkenyl;
  • R 4 and R 6 are each independently selected from C 2-2 o alkyl, hydroxy Ci -6 alkyl, carboxyl Ci_ 6 alkyl, and C 2 -6 alkenyl;
  • X q ⁇ is selected from Br “ , [N0 3 ] “ , [PF 6 ] _ , [SCN] “ , [CF 3 S0 3 ] “ , [CH 3 OS0 3 ] “ , [C 2 H 5 OS0 3 ] ⁇
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, methyl, ethyl, w-propyl, wo-propyl, w-butyl, n-pentyl, n-hexyl, decyl, stearyl, 2-hydroxyethyl, allyl, and phenyl; and R 4 and R 6 are each independently selected from ethyl, w-propyl, wo-propyl, w-butyl, «-pentyl, ra-hexyl, decyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, l-carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl; or
  • R 5 and R 6 together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl; and the anion, X q" , is selected from F “ , Br “ , I “ , [N0 3 ] ⁇ [SnCl 3 ] " , [SCN] , [NCO] _ , [CF 3 S0 3 ] " , [CH 3 OS0 3 ] " , [(BuO) 2 P(0)0]- s [CH 3 C 6 H 4 S0 3 ]-, [(CF 3 S0 2 ) 2 N]-, [P(C 2 F 5 ) 3 F 3 ] " , [B(CN) 4 ]- and [N(CN) 2 ] " .
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, methyl, ethyl, w-propyl, zjo-propyl, «-butyl, «-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, allyl, and phenyl; and R 4 and R 6 are each independently selected from ethyl, n-propyl, zjo-propyl, H-butyl, «-pentyl, rc-hexyl, decyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, 1 -carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl; and
  • the anion, X _ is selected from F “ , Br “ , ⁇ , [N0 3 ] “ , [SnCl 3 ] ⁇ , [SCN] “ , [NCO]-, [CF 3 S0 3 ] _ , [CH 3 OS0 3 ] ⁇ [(BuO) 2 P(0)0]-, [CH 3 C 6 H 4 S0 3 ]-, [(CF 3 S0 2 ) 2 N]- [P(C 2 F 5 ) 3 F 3 ] [B(CN) 4 ] , and [N(CN) 2 ] " .
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, methyl, ethyl, n-propyl, wo-propyl, «-butyl, «-hexyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, and allyl; and
  • R 4 and R 6 are each independently selected from ethyl, «-propyl, wo-propyl, H-butyl, «-hexyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, and allyl; and
  • X q ⁇ is selected from F “ , Br “ , [N0 3 ] ⁇ , [SCN] “ , [CF 3 S0 3 ] “ , [CH 3 OS0 3 ] _ , [CH 3 C 6 H 4 S0 3 ] " ,
  • R 1 , R 2 , R 3 and R 5 are each independently selected from -H, methyl, ethyl, n-propyl, zjo-propyl, «-butyl, «-hexyl, stearyl, 2-hydroxyethyl, and allyl; and
  • R 4 and R 6 are each independently selected from ethyl, ⁇ -propyl, wo-propyl, «-butyl, n-hexyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, and allyl; and
  • X q ⁇ is selected from F ⁇ , Br “ , [N0 3 ] “ , [SCN] “ [CF 3 S0 3 ] “ , [CH 3 OS0 3 ] ⁇ , [CH 3 C 6 H 4 S0 3 ] " ,
  • R'-R 6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
  • R 1 , R 3 and R 5 are -H and R 2 , R 4 and R 6 are phenyl,
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are z ' sopropyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl, R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl,
  • R 1 , R 2 , R 3 and R 4 are wo-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are -H,
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl,
  • R', R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxyl-2-hydroxypropyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxyl-2-methylpropyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, and R 5 and R 6 , together with the nitrogen atom to which they are attached, are
  • X q ⁇ is selected from F “ , Br “ , ⁇ , [HF 2 ] ⁇ , [SCN] “ , [NCOf, [N0 3 ] [AIC ] “ , [A1 2 C1 7 ] ⁇ [PF 6 ] ⁇
  • R'-R 6 are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are z ' so-propyl and R 5 and R 6 are butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl
  • R 5 is hydrogen and R 6 is butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl
  • R 5 is hydrogen and R 6 is 1 -carboxylethyl
  • X q " is selected from IT, Br " , ⁇ , [HF 2 ] ⁇ , [SCN] ⁇ , [NCO] " [N0 3 ] “ , [AICU]-, [AI2CI7] " , [PF 6 ] “ , [SeCN] “ , [CF3SO3] " , [FHOMe] “ , [FHOEt] “ , [FHOPr] " , [MeOS0 3 ] “ , [EtOS0 3 ] “ , [(BuO) 2 P(0)0] “ , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
  • R'-R 6 are 2-hydroxyethyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are ⁇ -propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl, and
  • X q is selected from F “ , Br “ , ⁇ , [HF 2 ] ⁇ [SCN]-, [NCO] “ , [N0 3 ] “ , [AICU] “ , [AI2CI7] “ , [PF 6 ] “ , [SeCN] “ , [CF 3 S0 3 ] “ , [FHOMe] “ , [FHOEt] “ , [FHOPr] " , [MeOS0 3 ] ⁇ , [EtOS0 3 ] “ , [(BuO) 2 P(0)0] " , [CH 3 C6H 4 S03] ⁇ , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
  • R'-R 6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
  • R 1 , R 3 and R 5 are -H and R 2 , R 4 and R 6 are phenyl,
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are iso-propyl, R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R ⁇ R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are wo-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are -H,
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R L , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is l-carboxyl-2-hydroxypropyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is l-carboxyl-2-methylpropyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, and R 5 and R 6 , together with the nitrogen atom to which they are attached, are
  • the anion, X q ⁇ is selected from Br “ , ⁇ , [N0 3 ] “ , [PF 6 ] ⁇ , [SnCl 3 ] ⁇ , [SCN] " , [NCO]-, [CF 3 S0 3 ] ⁇ , [CH 3 OS0 3 r, [C 2 H 5 OS0 3 ]- [CeFsSO,]- [(BuO) 2 P(0)0] , [CH 3 C 6 H 4 S0 3 ] ' [(CF 3 S0 2 ) 2 N] , [(FS0 2 ) 2 N] , [C 2 F 5 S0 3 ] ⁇ , [(C 2 F 5 S0 2 ) 2 N)]- [P(C 2 F 5 ) 3 F 3 ]-, [B(CN) 4 r, and [N(CN) 2 ] ⁇ .
  • X q ⁇ is selected from Br “ , ⁇ , [N0 3 ] “ , [PF 6 ]
  • R'-R 6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
  • R 1 , R 3 and R 5 are -H and R 2 , R 4 and R 6 are phenyl,
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are zso-propyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are wo-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are -H,
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl
  • R 5 is hydrogen and R 6 is hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl
  • R 5 is hydrogen and R 6 is 1-carboxylethyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxyl-2-hydroxypropyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxyl-2-methylpropyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, and R 5 and R 6 , together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl, and
  • the anion, X" ' is selected from ⁇ , [N0 3 ] “ , [PF 6 ] “ , [SCNf, [CF 3 S0 3 ] “ , [CH 3 OS0 3 ] ⁇ , [C 2 H 5 OS0 3 ] _ , [C 6 F 5 S0 3 ]-, [CH 3 C6H 4 S0 3 ]-, [(CF 3 S0 2 ) 2 N]-, [(FS0 2 ) 2 N] " [C 2 F 5 S0 3 ] " , [(C 2 F 5 S0 2 ) 2 N)r and [N(CN) 2 ] ' .
  • R'-R 6 are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are fso-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl, and
  • the anion, X q" is selected from Br “ , [ ⁇ 0 3 ⁇ , [PF 6 ] ⁇ [SCN] ⁇ [CF 3 SO,] " , [CH 3 OS0 3 ] _ , [C 2 H 5 OS0 3 ] ⁇ , [C 6 F 5 S0 3 ]-, [CH 3 C 6 H 4 S0 3 ]- [(CF 3 S0 2 ) 2 N]- [(FS0 2 ) 2 N] " [C 2 F 5 S0 3 ]- [(C 2 F 5 S0 2 ) 2 N)]- and [N(CN) 2 ] " .
  • R'-R 6 are 2-hydroxyethyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are wo-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1-carboxylethyl, and the anion, X q" is selected from Br-, [NOj] " , [PF 6 ] ' , [SCN] " , [CF 3 SO 3 ] " , [CH 3 OSO 3 ] " , [C 2 H 5 OSO 3 ]-, [C 6 F 5 S0 3 ]-, [CH J C ⁇ SO J ]-, [(CF 3 S0 2 ) 2 N]-, [(FS0 2 ) 2 N] " [C 2 F 5 S0 3 ]- [(C 2 F 5 S0 2 ) 2 N)]- and [N(CN) 2 ] " .
  • R'-R 6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
  • R 1 , R 3 and R 5 are -H and R 2 , R 4 and R 6 are phenyl,
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are wo-propyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are wo-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are -H,
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxyl-2-hydroxypropyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxyl-2-methylpropyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, and R 5 and R 6 , together with the nitrogen atom to which they are attached, are
  • X q is selected from F “ , Br “ , ⁇ , [ ⁇ 0 3 ⁇ , [SnCl 3 ] “ , [SCN] “ , [NCO] “ , [CF 3 SO 3 ] , [CH 3 OS0 3 ] " ,
  • R'-R 6 are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R 1 , R 2 , R 3 and R 4 are wo-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl, R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is butyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl, or
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1-carboxylethyl, and
  • X" " is selected from F “ , Br “ , [N0 3 ] “ , [SCN] ⁇ , [CF 3 S0 3 ] ⁇ , [CH 3 OS0 3 ] ⁇ ,
  • R'-R 6 are 2-hydroxyethyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are butyl
  • R 1 , R 3 and R 5 are methyl and R 2 , R 4 and R 6 are stearyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are hexyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are allyl
  • R', R 2 , R 3 and R 4 are iso-propyl and R 5 and R 6 are butyl
  • R 1 , R 2 , R 3 and R 4 are ethyl and R 5 and R 6 are 2-hydroxyethyl
  • R 3 , R 4 , R 5 and R 6 are ethyl and R 1 and R 2 are methyl
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is methyl and R 6 is hexyl,
  • R 1 , R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is butyl, or
  • R', R 2 , R 3 and R 4 are ethyl, R 5 is hydrogen and R 6 is 1 -carboxylethyl, and
  • X q " is selected from F “ , Br-, [N0 3 ] “ , [SCN] “ , [CF 3 S0 3 ] “ , [CH 3 OS0 3 ] “ , [CH 3 C 6 H 4 S0 3 ] " ,
  • the compound is selected from the group consisting of:
  • (21) tris(dibutylamino)cyclopropenium dicyanoamide; (22) tris(dibutylamino)cyclopropenium nitrate;

Abstract

Disclosed are salts comprising triaminocyclopropenium cations and various anions, and ionic liquids comprising the salts. Also disclosed are intermediates and methods of preparing the salts. The ionic liquids are useful as, for example, solvents and electrolytes, and for gas storage.

Description

TRIAMINOCYCLOPROPENIUM SALTS TECHNICAL FIELD
The present invention relates to salts comprising triaminocyclopropenium cations, to processes for the preparation of these salts, and to the use of these salts as ionic liquids.
BACKGROUND ART
Ionic liquids comprise ions and short-lived ion pairs, in contrast to conventional organic or aqueous solvents. They generally do not contain neutral molecules and usually have melting points below 373 K. These substances are also known as liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses.
Ionic liquids have developed significantly over the past 10 years, particularly as they become available on industrial scales. The great attraction of these liquids stems from their properties of almost zero vapour pressure, low flammability and ease of recycling. For these reasons, they are frequently considered as potential green alternatives to classical organic solvents. Additionally, most classes of ionic liquid can be readily tuned to provide unique solvent environments in which to carry out reactions, extractions and other processes.
Currently, there are four major classes of ionic liquids (based on pyridinium, imidazolium, phosphonium and ammonium cations). Guanidinium salts have also been recently investigated.
The properties of ionic liquids, for example melting point, thermal and electrochemical stability and viscosity, are affected by the nature of both the cation and the anion. Similarly, the selection of cation and anion can affect the polarity and hydrophilicity/hydrophobicity of the resulting ionic liquid.
Triaminocyclopropenium salts were first identified in 1971 (Z. Yoshida and Y. Tawara, J. Am. Chem. Soc , 1971 , 93, 2573). There have, however, been no investigations of their properties as ionic liquids, and no viscosity data is available for any triaminocyclopropenium salt.
Triaminocyclopropenium salts are particularly stable due to a combination of the aromaticity of the three- membered ring and τ donation from the three planar amino groups which consequently disperse the charge from the C3 ring. These cations are sufficiently electron rich to be considered as "donor" species.
Accordingly, it is an object of the present invention to provide triaminocyclopropenium salts that are preferably suitable for use as ionic liquids; and/or to at least provide the public with a useful choice.
Other objects of the invention may become apparent from the following description which is given by way of example only. Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is solely for the purpose of providing a context for the present invention. It is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date. SUMMARY OF THE INVENTION
In a first aspect, the present invention provides a compound of formula [Y^qPC"] wherein q is 1, 2 or 3; and
wherein the cation, Y*, is a triamino l formula (I):
Figure imgf000003_0001
wherein
R1, R2, R3 and R5 are each independently selected from -H, Cuo alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C2_2o alkenyl, C2.2o alkynyl, substituted C2.2o alkynyl, C3.10 cycloalkyl, substituted C3-i0 cycloalkyl, C3.10 cycloalkenyl, substituted C3_io cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;
R4 and R6 are each independently selected from C2.20 alkyl, substituted C^o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2_20 alkynyl, substituted C2.2o alkynyl, C3-i0 cycloalkyl, substituted C3.10 cycloalkyl, C3.10 cycloalkenyl, substituted C3.10 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or
one or more of R1 and R2, R3 and R4, and R5 and R6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl, substituted heterocyclyl, heteroaryl or substituted heteroaryl, wherein heteroaryl is imidazolyl, pyrazolyl, pyrrolyl or azepinyl; and
wherein the anion, Xq~, is selected from the group consisting of:
F", Br" Γ, [I3]-, [HF2]-, [CN]" [SCNf, [NCO]", [CH3C(0)0]", [(C2.6 alkyl)C(0)0]",
[NH2-CH(RA)C(0)0] [SiF6]2- [S04]2" [Ν03Γ, [C03]2", [BPiy, [AsF6]", [SbF6] ~, [A1C ]", [A12C17]- [Gad,]-, [SOeF]-, [PFgf, [A1F4]- [A1F6]3-, [CuCy, [SnClj]", [GeCy, [ZnCL,]" [FeCl,]", [FeC ]2", [C0CI4]", [CoC ]2", and [Co(CO)4]";
wherein RA is a side chain of a natural or non-natural alpha-amino acid;
[CF3COO]-, [SeCN]-, [HSO4]- [H2P04]- [(MeO)(H)P02]- [CF3S03]- [CF3OSO3]- [FHO(C,.6 alkyl)]" [(C 2 alkyl)OS03]- [(CM2 alkylJSOj]",
Figure imgf000003_0002
[C6F5S03]- [(C,_12 alkyl)(C,.12 alkyl)P(0)0]-, [(CM2 alkyl)(C,.12 alkyl-0)P(0)0]', [(C,.I2 alkyl-0)(CM2 alkyl-0)P(0)0]-, [CH3C6H4S03]", [C12H25C6H4S03]", [CH2(COO)2]2", [Co(C2B9H„)2]-, [C2B9H12]" [B10C110]2', [B12C112]2- [CB„H12]- [Bi2HiiN(Ci_6 alkyl)3]-, [(C,.6 alkyl)SnBnHu]- [RBCBURC 5XB6]", and [R°BF3]";
wherein RB is H, Ci_6 alkyl, Ci_6 alkenyl, Ci_6 perfluoroalkyl, Ci_6 perfluoroalkenyl or Si(C]-6 alkyl)3; Rc is H, methyl, CI or Br;
R is Ci_20 alkyl or C2_2o alkenyl, wherein one or two non-adjacent carbon atoms in RD which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S02-, or -NRJ-, and wherein RD is optionally substituted by one or more RE; or
RD is C3_io cycloalkyl, C3_io cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of Ci_6 alkyl, C2-6 alkenyl, and RE;
RE at each instance is independently selected from halo, cyano, Q_6 alkoxy, Si(Cj_6 alkyl)3, C3_io cycloalkyl optionally substituted by one or more RH*, C3_i0 cycloalkenyl optionally substituted by one or more RE*, aryl optionally substituted by one or more RE*, heteroaryl optionally substituted by one or more RE*, and heterocyclyl optionally substituted by one or more RE*;
RE* at each instance is independently selected from halo, d_6 alkyl, Ci_6 alkoxy, and oxycarbonyl;
XB is CI or Br;
[Al(OCH2RF)4r, [(CF3S02)2N]-, [(CF3S02)NC(0)CF3]" [(FS02)2N]-, [RFCF2S03]- [RFCF2OS03]~
[(RGS02)2N)] - [(RGS02)3C]- [(CF3S02)3C]-, [(FS02)3C]", [RFCF2C(0)0]\ [P(CnF2n+1_mHm)yF6.y]- [P(C6F5)yF6.y]-, [RF 2P(0)0]-, [RFP(0)02]2-, [(RF0)2P(0)0]", [(RF0)(RF)P(0)0]", [(RF0)P(0)02]2"
[BFZRF4.Z]-, [BFZ(CN)4.Z]- [Me3SiC2H4OCH2BF3]-, [N(CF3)2]", [N(CN)2]" [C(CN)3]" and
.
Figure imgf000004_0001
. . J
wherein RF at each instance is independently selected from perfluoro Ci_20 alkyl, perfluoro C2_20 alkenyl having one or more double bonds, perfluoro C2.2o alkynyl having one or more triple bonds, perfluoro C3_i0 cycloalkyl optionally substituted by one or more perfluoro Q.6 alkyl, perfluoro C3.i0 cycloalkenyl optionally substituted by one or more perfluoro Ci_6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro C]-6 alkyl, wherein any two RF may be connected by a single or double bond, wherein when RF is perfluoro C^o alkyl, perfluoro C2_2o alkenyl, or perfluoro C2_20 alkynyl one or two non-adjacent carbon atoms in RF which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S02-, or -NRJ-, and wherein a terminal carbon atom in RF if present, may be replaced by -S02XD; and
RG at each instance is independently selected from perfluoro C2_20 alkyl, perfluoro C2_2o alkenyl having one or more double bonds, perfluoro C2.20 alkynyl having one or more triple bonds, perfluoro C3_i0 cycloalkyl optionally substituted by one or more perfluoro Ci-6 alkyl, perfluoro C3.i0 cycloalkenyl optionally substituted by one or more perfluoro Cj.6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci_6 alkyl, wherein any two RG may be connected by a single or double bond, wherein when RG is perfluoro C1.20 alkyl, perfluoro C2-20 alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms in RG which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO2-, or -NRJ-, and wherein a terminal carbon atom in RG, if present, may be replaced by -S02XD;
RJ at each instance is independently selected from Ci_6 alkyl, fluoro Ci-6 alkyl, perfluoro Ci_6 alkyl, C3.10 cycloalkyl, phenyl optionally substituted by one or more RK, heteroaryl optionally substituted by one or more RK, and heterocyclyl optionally substituted by one or more RK;
RK at each instance is independently selected from Ci_6 alkyl, Ci-6 alkenyl, nitro, halo, hydroxyl, Ci-e alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
trifluoromethylsulfonyl, Ci_6 alkoxycarbonyl, -NH2, C].6 alkylamino, di(Ci_6
alkyl)amino, -C02H, -C(0)NRL, -S02ORL, -S02XD, -S02NRL 2, -S03H, and -NHC(0)RL;
RL at each instance is independently selected from Ci_6 alkyl, fluoro Ci-6 alkyl, perfluoro Ci_6 alkyl, and C3.10 cycloalkyl;
XD at each instance is independently selected from F, CI, and Br;
n is 1 to 20;
m is 0, 1, 2, or 3;
y is 1 , 2, 3, or 4; and
z is 0, 1, 2, or 3; and
-Z- and -Y- are independently selected from -C(0)C(0)-, -C(0)(CH2)4C(0)-, -C(0)(CF2)qC(0)- wherein q = l, 2 or 3, -C(CF3)2C(CF3)2-,
Figure imgf000005_0001
k is 1, 2, 3, or 4; and p is 1 , or 2.
In a second aspect, the present invention provides a compound of formula [Υ^ςΓ 1"] wherein q is 1 ; wherein the cation, Y\ is selected from
tris(dipropylamino)cyclopropenium,
tris(dibutylamino)cyclopropenium,
tris(dipentylamino)cyclopropenium,
tris(dihexylamino)cyclopropenium,
tris(didecylamino)cyclopropenium,
tris(diallylamino)cyclopropenium,
tris(butylmethylamino)cyclopropenium,
tris(hexylmethylamino)cyclopropenium,
tris(octadecylmethylamino)cyclopropenium,
bis(diwo-propylamino)dibutylaminocyclopropenium,
bis(diethylamino)dipropylaminocyclopropenium,
bis(diethylamino)diwo-propylaminocyclopropenium,
bis(diethylamino)dibutylaminocyclopropenium,
bis(diethylamino)dihexylaminocyclopropenium,
bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)butylmethylaminocyclopropenium,
bis(diethylamino)hexylmethylaminocyclopropenium,
bis(diethylamino)octadecylmethylaminocyclopropenium,
bis(diethylamino)dimethylaminocyclopropenium, and
bis(diethylamino)di(2-methoxyethyl)aminocyclopropenium; and
wherein the anion, Xq~ is selected from CT, Br", [BF4]~, [N03]", {PF6Y, [SCN]", [CF3S03]", [CH3OS03]", [C2H5OS03]-
Figure imgf000006_0001
[(CF3S02)2N]-, [(FS02)2N]-, [C2F5S03]-, [(C2F5S02)2N)]- and [N(CN)2]-.
In a third aspect, the present invention provides a compound of formula [Y^tX"1"] wherein q is 1 ;
wherein the cation, Y is tris(diethylamino)cyclopropenium; and
wherein the anion, Xq~, is selected from Γ, [BF4]~ [N03]_, [PF6]", [SCNf, [CF3S03]", [CH3OS03]"
[C2H5OS03] - [CeFsSO,]", [CH3C6H4S03] [(CF3S02)2N] , [(FS02)2N]-, [C2F5S03]-, [(C2F5S02)2N)] and [N(CN)2]-.
In a fourth aspect, the present invention provides a compound of formula [Yf]q[Xq ] wherein q is 1 ;
wherein the cation, Y1", is selected from
bis(diethylamino)aminocyclopropenium,
bis(diethylamino)butylaminocyclopropenium, bis(diethylamino)hexylaminocyclopropenium,
bis(diethylamino)diethanolaminocyclopropenium,
tris(diethanolamino)cyclopropenium,
trisanilinocyclopropenium,
bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium,
bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropeniuni,
bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropeniuni, and
bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino))cyclopropenium; and
wherein the anion, Xq", is selected from [BF4]~, [PF6]", [CF3S03]", [CH3OS03]- [C2H5OS03]\
[CH3C6H4S03r, [(CF3S02)2N]-, [(FS02)2Nr, [C2F5S03]-, [(C2F5S02)2N)r and [N(CN)2]
In a fifth aspect, the present invention provides a compound of formula [Y+]q[Xq~] wherein q is 1 or 2 wherein the cation, Y\ is a triaminocyclopropenium ion of the formula (II):
Figure imgf000007_0001
wherein the anion, Xq~, is selected from [SCN]^, [CF3S03]", [FHO(C1-6 alkyl)]-, [(C,.6 alkyl)OS03]- [C6F5S03]- [(C1-6 alkyl)(C,.6 alkyl)P(0)0]-, [CH3C6H4S03r, [Co(C2B9Hu)2r, [C2B9HI2]-, [B10C110]2- [B12C112]2-, [CBuH12r, [B12H„N(C,.6 alkyl)3r, [(C1-6 alkyl)SnBnHur, [RBCB„Rc 5XB6r, [R°BF3]", [(CF3S02)2N]- [(CF3S02)NC(0)CF3]-, [(FS02)2N]", [RFCF2S03]" [(RGS02)2N)]- [(RGS02)3C]-, [(FS02)3C]-, [RFCF2C(0)0]-, [P(CnF2n+1.mHm)yF6.y]- [P(C6F5)yF6. -, [RF 2P(0)0]-, [RFP(0)02]2"
[BFZRF4.Z]-, [BFz(CN)4.zr, [N(CF3)2]-, [N(CN)2]", [C(CN)3r and
Figure imgf000007_0002
j ; and wherein RB, Rc, RD, XB, RF, RG, n, m, y, z, -Z-, and -Y- are as defined for the compounds of the first aspect.
In a sixth aspect, the present invention provides a compound of formula
Figure imgf000007_0003
wherein q is 1 or 2 wherein the cation, Y-1", is a triaminocyclopropenium ion of the formula (III):
Figure imgf000008_0001
wherein R? is methyl and R8 is selected from C2-20 alkyl, substituted C 1.20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2_2o alkynyl, substituted C2-20 alkynyl, C3.10 cycloalkyl, substituted C3- ] 0 cycloalkyl, C3.i0 cycloalkenyl, substituted C3.10 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or
R7 and R8 are each independently selected from C2-20 alkyl, substituted C1.20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C2-20 alkynyl, C3-10 cycloalkyl, substituted C3-10 cycloalkyl, C3.10 cycloalkenyl, substituted C3.io cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;
wherein the anion, Xq ~ is selected from [SCNf, [CF3COO]", [SeCNf, [CF3S03]", [FHO(d-6 alkyl)]", [(C,_6 alkyI)OS03]-, [C^SO,]" [(C,.6 alkyl)(C1-6 alkyl)P(0)0]-, [CI^C^SO^, [Co(C2B9Hn)2]", [C2B9H12r, tB,oCl10]2 [B12C112]2- [CB„H12r, [Bi2HnN(Ci-6 alkyl)3]", [(C,.6 alkyl)SnB„H„r,
[RBCB„Rc 5XB6r, [RDBF3]~, [(CF3S02)2N]- [(CF3S02)NC(0)CF3]-, [(FS02)2N]-, [RFCF2S03]-,
[(RGS02)2N)]- [(RGS02)3C]-, [(FS02)3C]- [RFCF2C(0)0]-, [P(CnF2„+1.mHm)yF6.y]- [P(C6F5)yF6.y]-, [RF P(0)0]^, [RFP(0)02]2- [BFZRF4.Z]-, [BFZ(CN)4-Z]-, [N(CF3)2]-, [N(CN)2]~, [C(CN)3]- and
Figure imgf000008_0002
wherein RB, Rc, RD, XB, RF, RG, n, m, y, z, -Z-, and -Y- are as defined for the compounds of the first aspect.
In a seventh aspect, the present invention provides a compound selected from the group consisting of: (2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium >-toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate; (Π) tris(dipropylamino)cyclopropenium chloride;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(14) tris(dipropylamino)cyclopropenium fluoride diethanol;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(18) tris(dibutylamino)cyclopropenium chloride;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(26) tris(diethanolamino)cyclopropenium fluoride;
(27) tris(diallylamino)cyclopropenium chloride;
(28) tris(diallylamino)cyclopropenium bromide;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(49) bis(diethylamino)diethanolaminocyclopropenium iodide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;
(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate;
(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride;
(67) tris(dipentylamino)cyclopropenium chloride;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(69) tris(dipentylamino)cyclopropenium dicyanoamide;
(70) tris(dihexylamino)cyclopropenium chloride;
(71 ) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide;
(73) tris(didecylamino)cyclopropenium chloride;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;
(78) bis(diethylamino)hexylaminocyclopropenium methylsulfate;
(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(80) bis(diethylamino)aminocyclopropenium methylsulfate;
(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;
(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide; (86) bis(diethylamino)dihexylaminocyclopropenium iodide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide;
(88) tris(dimethylamino)cyclopropenium thiocyanate;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;
(91) tris(dihexylamino)cyclopropenium dibutylphosphate;
(92) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(95) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;
(96) bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;
(98) bis(diethylamino)-S-(l-carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(99) tris(dibutylamino)cyclopropenium isocyanate;
(100) tris(dibutylamino)cyclopropenium trichlorostannate;
(101 ) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;
( 102) bis(diethylamino)diwo-propylaminocyclopropenium methylsulfate;
(103) bis(diethylamino)dii5o-propylaminocyclopropenium dicyanoamide;
(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
( 107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In an eighth aspect, the present invention provides an ionic liquid comprising a triaminocyclopropenium cation and an anion.
In a ninth aspect, the present invention provides an ionic liquid comprising a compound of the invention.
In a tenth aspect, the present invention provides use of a compound of the invention as a solvent.
In an eleventh aspect, the present invention provides use of a compound of the invention as an electrolyte.
In a twelfth aspect, the present invention provides use of a compound of the invention for gas storage.
This invention may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which this invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.
The compounds of the invention may form or exist as hydrates or solvates with various solvents. The present invention contemplates such hydrates and solvates as well as the corresponding unsolvated forms. In some embodiments, when used as ionic liquids, the compounds of the invention are unsolvated and, in particular, unhydrated.
Some of the compounds of the invention include cations or anions or both that have asymmetric carbon atoms. Therefore, stereoisomers (both enantiomers and diastereomers) of such cations or anions can exist. The present invention contemplates the pure stereoisomers (including geometric isomers) and any mixture of the isomers. For example, a pure enantiomer of a cation can be isolated from a mixture of enantiomers of the cation using conventional optical resolution techniques. Enol forms and tautomers are also contemplated, where appropriate.
It is intended that reference to a range of numbers disclosed herein (for example, 1 to 10) also
incorporates reference to all rational numbers within that range (for example, 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9 and 10) and also any range of rational numbers within that range (for example, 2 to 8, 1.5 to 5.5 and 3.1 to 4.7) and, therefore, all sub-ranges of all ranges expressly disclosed herein are hereby expressly disclosed. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. Although the present invention is broadly as defined above, those persons skilled in the art will appreciate that the invention is not limited thereto and that the invention also includes embodiments of which the following description gives examples.
DETAILED DESCRIPTION OF THE INVENTION
Definitions The term "comprising" as used in this specification means "consisting at least in part of. When interpreting each statement in this specification that includes the term "comprising", features other than that or those prefaced by the term may also be present. Related terms such as "comprise" and
"comprises" are to be interpreted in the same manner.
As used herein, the term "and/or" means "and" or "or", or both.
The general chemical terms used in the formulae herein have their usual meanings. As used herein, and unless otherwise stated: the terra "alkyl" alone or in combination with other terms means a straight chain or branched chain saturated hydrocarbon group. In some embodiments, alkyl groups comprise 1 to 20 carbon atoms. In some embodiments, alkyl groups comprise 1 to 6 carbon atoms. In some embodiments, the alkyl group is methyl, ethyl, w-propyl, wopropyl, n-butyl, wo-butyl, sec-butyl, or tert-butyl; the term "substituted alkyl" alone or in combination with other terms means an alkyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl,
cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "cycloalkyl" alone or in combination with other terms means a cyclic saturated hydrocarbon group. In some embodiments, cycloalkyl groups comprise 3 to 10 ring carbon atoms. In some embodiments, cycloalkyl groups comprise 3 to 8 ring carbon atoms. In some embodiments, the cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; the term "substituted cycloalkyl" alone or in combination with other terms means a cycloalkyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted
cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted carboxyl, oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "alkenyl" alone or in combination with other terms means a straight chain or branched chain unsaturated hydrocarbon group including at least one carbon-carbon double bond. In some embodiments, alkenyl groups comprise 2 to 20 carbon atoms. In some embodiments, alkenyl groups comprise 2 to 6 carbon atoms. In some embodiments, the alkenyl group is vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl- 1-propenyl, 2-methyl-2-propenyl, 1 -methyl- 1 -propenyl, 1 -methyl-2-propenyl, 1 -methyl vinyl, 1 -ethyl vinyl, or 1,3-butadienyl; the term "substituted alkenyl" alone or in combination with other terms means an alkenyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyloxy, cycloalkenyl,
cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "cycloalkenyl" alone or in combination with other terms means a cyclic unsaturated hydrocarbon group including at least one carbon-carbon double bond. In some embodiments, cycloalkenyl groups comprise 3 to 20 ring carbon atoms. In some embodiments, cycloalkenyl groups comprise 3 to 8 carbon atoms. In some embodiments, the cycloalkenyl group is cyclopropen-l-yl, cyclopropen-3-yl, cyclobuten- 1-yl, cyclobuten-3-yl, cyclohexen-l-yl, cyclohexen-3-yl, cyclohexen-4-yl, 1 ,3-cyclooctadien-l-yl, l ,3-cyclooctadien-2-yl, l ,3-cyclooctadien-5-yl, l,3-cyclooctadien-6-yl, 1,5-cyclooctadien-l-yl, or 1 ,5-cyclooctadien-3-yl; the term "substituted cycloalkenyl" alone or in combination with other terms means a cycloalkenyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "alkynyl" alone or in combination with other terms means a straight chain or branched chain hydrocarbon group including at least one carbon-carbon triple bond. In some embodiments, alkynyl groups comprise 2 to 20 carbon atoms. In some embodiments, alkynyl groups comprise 2 to 6 carbon atoms. In some embodiments, the alkynyl group is ethynyl, propargyl, 3-butynyl, 4-pentynyl, 5-hexynyl, or 3,5-hexadiynyl; the term "substituted alkynyl" alone or in combination with other terms means an alkynyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "alkoxy" alone or in combination with other terms means an alkyl-O- group; the term "substituted alkoxy" alone or in combination with other terms means a substituted
alkyl-O- group, wherein "substituted alkyl" is as defined herein; the term "cycloalkoxy" alone or in combination with other terms means a cycloalkyl-O- group; the term "substituted cycloalkoxy" alone or in combination with other terms means a substituted cycloalkyl-O- group, wherein "substituted cycloalkyl" is as defined herein; the term "alkenyloxy" alone or in combination with other terms means an alkenyl-O- group, wherein "alkenyl" is as defined herein; the term "substituted alkenyloxy" alone or in combination with other terms means a substituted alkenyl-O- group, wherein "substituted alkenyl" is as defined herein; the term "cycloalkenyloxy" alone or in combination with other terms means a cycloalkenyl-O- group, wherein "cycloalkenyl" is as defined herein; the term "substituted cycloalkenyloxy" alone or in combination with other terms means a substituted cycloalkenyl-O- group, wherein "substituted cycloalkenyl" is as defined herein; the term "alkynyloxy" alone or in combination with other terms means a alkynyl-O- group, wherein "alkynyl" is as defined herein; the term "substituted alkynyloxy" alone or in combination with other terms means a substituted alkynyl-O- group, wherein "substituted alkynyl" is as defined herein; the term "aryl" alone or in combination with other terms means a monocylic, bicyclic or tricyclic aromatic radical comprising only carbon and hydrogen atoms and 4 to 18 ring carbon atoms. In some embodiments, aryl is phenyl, naphthyl, indanyl, biphenyl, anthracenyl, phenanthryl, or terphenyl, and the like. In some embodiments, aryl is phenyl, naphthyl, anthracenyl, phenanthryl, biphenyl, or terphenyl. In some embodiments, aryl is phenyl, naphthyl, biphenyl, or terphenyl. In some embodiments, aryl is phenyl; the term "substituted aryl" alone or in combination with other terms means, unless otherwise stated, an aryl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted
cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryloxy, substituted
heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy, alkynyl, alkynyloxy, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "amino" alone or in combination with other terms means a - 101 102 group, wherein R101 and R102 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted amino" alone or in combination with other terms means a -NR103R104 group, wherein R103 and R104 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that least one of R103 and R104 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "amido" alone or in combination with other terms means an amino-C(O)- group; the term "substituted amido" alone or in combination with other terms means a substituted
amino-C(O)- group, wherein "substituted amino" is as defined herein; the term "acylamino" alone or in combination with other terms means an acyl-NR105- group, wherein R105 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted acylamino" alone or in combination with other terms means a substituted acyl-NR106- group or acyl-NR107- group, wherein "substituted acyl" is as defined herein, R106 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R107 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "thioamide" alone or in combination with other terms means an amino-C(S)- group or
R108C(S)NR109- group, wherein R108 is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl and R109 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted thioamide" alone or in combination with other terms means a substituted amino-C(S)- group or R1 10C(S)NRn i- group, wherein "substituted amino" is as defined herein, R110 is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R111 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R110 and Rni is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "thioester" alone or in combination with other terms means a R112SC(0)- group or
RU3C(0)S- group, wherein R112 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl, and R113 is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted thioester" alone or in combination with other terms means a R114SC(0)- group or R115C(0)S- group, wherein R114 and R115 are each independently selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "carbamate" alone or in combination with other terms means an amino-C(0)0- group or oxycarbonyl-NR116- group, wherein R116 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted carbamate" alone or in combination with other terms means a substituted amino-C(0)0- group, substituted oxycarbonyl-NR117- group, or oxycarbonyl-NR118- group, wherein "substituted amino" and "substituted oxycarbonyl" are as defined herein, R117 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R118 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "urea" alone or in combination with other terms means an amino-C(0)NR119- group, wherein R119 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted urea" alone or in combination with other terms means a substituted
amino-C(0)NR120- group or amino-C(0)NR121- group, wherein "substituted amino" is as defined herein, and R120 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R121 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "dithiocarbamate" alone or in combination with other terms means an amino-C(S)S- group or R SC(S)NR - group, wherein R and R are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted dithiocarbamate" alone or in combination with other terms means a substituted amino-C(S)S- group or R124SC(S)NR125- group, wherein "substituted amino" is as defined herein, and R124 and R125 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R124 and R125 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "dithiooxaamide" alone or in combination with other terms means an
amino-C(S)C(S)NR126- group, wherein R26 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted dithiooxaamide" alone or in combination with other terms means a substituted amino-C(S)C(S)NR127- group or amino-C(S)C(S)NR128- group, wherein "substituted amino" is as defined herein, R127 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R128 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "imino" alone or in combination with other terms means a =NR group, wherein R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted imino" alone or in combination with other terms means a =NR130 group, wherein R130 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "aryloxy" alone or in combination with other terms means an aryl-O- group; the term "substituted aryloxy" alone or in combination with other terms means a substituted
aryl-O- group, wherein "substituted aryl" is as defined herein; the term "heteroaryl" alone or in combination with other terms means a monocyclic, bicyclic or tricyclic heteroaromatic radical comprising 5 to 14 ring atoms. In some embodiments, heteroaryl is pyrrolyl, furyl, thiophenyl, pyridyl, bipyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, pyrrodiazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, indolyl, isoindolyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, benzotriazolyl, benztetrazolyl, indazolyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxadiazolyl, benzoxazolyl, cinnolinyl, indolizinyl, triazinyl, naphthyridinyl, phthalazinyl, pteridinyl, purinyl, oxazolopyridinyl, thiazolopyridinyl, imidazopyridinyl, furopyridinyl, thienopyridinyl, pyridopyrimidinyl, pyridopyrazinyl, pyridopyridazinyl, thienothiazolyl, thienoxazolyl, thienoimidazolyl, or phenazinyl. In some embodiments, heteroaryl is pyrrolyl, furyl, thiophenyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, pyrrodiazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, or triazinyl; the term "substituted heteroaryl" alone or in combination with other terms means a heteroaryl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "heteroaryloxy" alone or in combination with other terms means a heteroaryl-O- group; the term "substituted heteroaryloxy" alone or in combination with other terms means a substituted heteroaryl-O- group, wherein "substituted heteroaryl" is as defined herein; the term "heterocyclyl" alone or in combination with other terms means a monocyclic non-aromatic saturated or unsaturated heterocyclic radical comprising 3 to 7 ring atoms. In some embodiments, heterocyclyl is piperidinyl, pyrrolidinyl, piperazinyl, 1 ,4-dioxanyl, tetrahydrofuryl, tetrahydrothiophenyl, morpholinyl, or azepanyl. In some embodiments, heterocyclyl is tetrahydrofuryl or 1 ,4-dioxanyl; the term "substituted heterocyclyl" alone or in combination with other terms means an heterocyclyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyloxy, substituted
heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "heterocyclyloxy" alone or in combination with other terms means an heterocyclyl-O- group; the term "substituted heterocyclyloxy" alone or in combination with other terms means a substituted heterocyclyl-O- group, wherein "substituted heterocyclyl" is as defined herein; the term "acyl" alone or in combination with other terms means a -C(0)R131 group, wherein R131 is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted acyl" alone or in combination with other terms means a -C(0)R132 group, wherein R132 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "carboxyl" alone or in combination with other terms means a -C(0)OH group; the term "oxycarbonyl" alone or in combination with other terms means a -C(0)OR133 group, wherein R133 is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted oxycarbonyl" alone or in combination with other terms means a -C(0)OR134 group, wherein R134 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "carbonyloxy" alone or in combination with other terms means a -OC(0)R135 group, wherein R135 is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted carbonyloxy" alone or in combination with other terms means a -OC(0)R136 group, wherein R136 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "halo" alone or in combination with other terms means chloro, bromo, fluoro, or iodo; the term "oxo" alone or in combination with other terms means a =0 group; the term "oxy" alone or in combination with other terms means a -O- group; the term "phosphate" alone or in combination with other terms means a -OP(0)(OR137)(OR138) group, wherein R137 and R138 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphate" alone or in combination with other terms means a -OP(0)(OR139)(OR140) group, wherein R139 and R140 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R139 and R140 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "phosphinate" alone or in combination with other terms means a -OP(0)R141R142 group or -P(0)(OR143)R144 group, wherein R141, R142, R143, and R144 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphinate" alone or in combination with other terms means a -OP(0)R145R146 group or -P(0)(OR147)R148 group, wherein R145, R146, R147, and R148 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R145 and R146 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl and at least one of R147 and R148 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "phosphine" alone or in combination with other terms means a -PR149R150 group, wherein R149 and R150 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphine" alone or in combination with other terms means a -PR151R152 group, wherein R151 and R152 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R151 and R152 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "phosphite" alone or in combination with other terms means a -OP(OR153)(OR154) group, wherein R153 and R154 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphite" alone or in combination with other terms means a -OP(OR155)(OR156) group, wherein R155 and R156 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R155 and R156 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "phosphonate" alone or in combination with other terms means a -P(0)(OR157)(OR158) and -OP(0)(OR159)R160 group, wherein R157, R158, R159, and R160 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphonate" alone or in combination with other terms means
a -P(0)(OR16I)(OR162) group or -OP(0)(OR163)R164 group, wherein R161, R162, R163, and R164 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R161 and R162 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl and at least one of R163 and R164 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "phosphine oxide" alone or in combination with other terms means a -P(0)Rl83R184 group, wherein R183 and R184 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphine oxide" alone or in combination with other terms means a -P(0)R,85R186 group, wherein R185 and R186 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R185 and R186 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "silane" alone or in combination with other terms means a -SiR187R188R189 group, wherein R187, R , and R are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted silane" alone or in combination with other terms means a -SiRI66R167R168 group, wherein R166, R167, and R168 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R166, R167, and R168 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "siloxane" alone or in combination with other terms means a -Si(0)R169 group, wherein R169 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted siloxane" alone or in combination with other terms means a -Si(0)R170 group, wherein R170 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "sulfate" alone or in combination with other terms means a -OS(0)2OR171 group, wherein R171 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted sulfate" alone or in combination with other terms means a -OS(0)2OR172 group, wherein R172 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "sulfenyl" alone or in combination with other terms means a -SR173 group, wherein R173 is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted sulfenyl" alone or in combination with other terms means a -SR190 group, wherein R190 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "sulfonyl" alone or in combination with other terms means a -S(0)2R174 group, wherein R174 is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted sulfonyl" alone or in combination with other terms means a -S(0)2R175 group, wherein R175 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "sulfonamide" alone or in combination with other terms means an amino-S(0)2- group or sulfonyl-NR176- group, wherein R176 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted sulfonamide" alone or in combination with other terms means a substituted amino-S(0)2- group, sulfonyl-NR177- group, or substituted sulfonyl-NR178- group, wherein "substituted amino" and "substituted sulfonyl" are as defined herein, R177 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl, and R178 is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl; the term "sulfonate" alone or in combination with other terms means a -S(0)2OR179 group, wherein R179 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted sulfonate" alone or in combination with other terms means a -S(0)2OR180 group, wherein R180 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "sulfoxide" alone or in combination with other terms means a -S(0)R181 group, wherein R181 is alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; and the term "substituted sulfoxide" alone or in combination with other terms means a -S(0)R182 group, wherein R182 is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl.
As used herein, the term "substituted" means that one or more hydrogen atoms (or halo atoms for perhalo groups, such as perfluoroalkyl, perfluoroalkenyl, perfluoroalkynyl, perfluorocycloalkyl and
perfluorophenyl) in the group indicated is replaced with one or more independently selected suitable substituents, provided that the normal valency of each atom to which the substituent/s are attached is not exceeded, and that the substitution results in a stable compound.
The term "substituted alkyl", "substituted alkenyl", "substituted alkynyl", "substituted cycloalkyl", "substituted cycloalkenyl", "substituted heterocyclyl", "substituted heteroaryl", and "substituted aryl" alone or in combination with other terms include their "halo", including "monohalo-", "dihalo-" and "polyhalo-" , including "perhalo-", equivalents.
For example, the term "haloalkyl" alone or in combination with other terms means an alkyl group as defined herein wherein one or more hydrogen atoms in the group is replaced with one or more halo. The term "haloalkyl" includes monohaloalkyl, dihaloalkyl and polyhaloalkyl, including perhaloalkyl, groups. The term "perhaloalkyl" alone or in combination with other terms means an alkyl group as defined herein wherein all hydrogen atoms in the group are replaced with one or more halo. Each "halo" in any dihaloalkyl and polyhaloalkyl group is independently selected. Examples of "haloalkyl" include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoropropyl, difluorochloromethyl, dichlorofluoromethyl, difluoroethyl, difluoropropyl, dichloroethyl and dichloropropyl. The term "perhaloalkyl" includes "perfluoroalkyl". Examples of "perfluoroalkyl" include trifluoromethyl and pentafluoroethyl. The terms "alkyl", "alkenyl", "alkynyl", "cycloalkyl", "cycloalkenyl", "heterocyclyl", "heteroaryl", and "aryl" alone or in combination with other terms, where appropriate, also include divalent and polyvalent radicals derived from each respective group, such as alkylene (alkanediyl), alkenylene, heterocyclylene, heteroarylene, and arylene. For example, where a "heteroaryl" may be substituted with up to two substituents, the "heteroaryl" may represent a monovalent heteroaryl or a divalent heteroarylene.
As used herein, the term "side chain of a natural or non-natural alpha-amino acid" includes the group RA in a natural or non-natural amino acid of general formula NH2-CH(RA)-C02H. The term also includes, for example, side chains that link to the alpha-amino group such as the pyrrolidinyl ring of proline.
Accordingly, in some embodiments, one or more of R1 and R2, R3 and R4, and R5 and R6, together with the nitrogen atom to which they are attached are -pyrrolidinyl-2-C02H. In some embodiments, Xq" is [pyrrolidinyl-2-COO]".
As used herein, the term "natural alpha-amino acid" includes the 20 L-amino acids (or a residue thereof) which commonly comprise most polypeptides in living systems, that is: alanine (Ala); arginine (Arg); asparagine (Asn); aspartic acid (Asp); cysteine (Cys); glutamine (Gin); glutamic acid (Glu); glycine (Gly); histidine (His); isoleucine (lieu); leucine (Leu); lysine (Lys); methionine (Met); phenylalanine
(Phe); proline (Pro); serine (Ser); threonine (Thr); tryptophan (Trp); tyrosine (Tyr); and valine (Val). The term also includes rarer amino acids found in fibrous proteins (for example, 4-hydroxyproline,
5-hydroxylysine, N-methyllysine and 3-methylhistidine), and naturally occurring amino acids not found in proteins (for example, homocysteine, homoserine, citrulline, ornithine, canavanine, djenkolic acid and beta-cyanoalanine).
Natural alpha-amino acids which contain functional substituents, for example amino, carboxyl, hydroxy, mercapto, guanidyl, imidazolyl or indolyl groups in their characteristic side chains include arginine, lysine, glutamic acid, aspartic acid, tryptophan, histidine, serine, threonine, tyrosine and cysteine. When any one of R1 to R6 in the compounds of the invention is -CH(RA)-C02H, wherein RA is a side chain of an alpha-amino acid that includes a functional substituent, such as a side chain of one of those natural alpha-amino acids or a side chain of a non-natural alpha-amino acid, the functional substituent may optionally be protected. Similarly, the carboxyl substituent in -CH(RA)-C02H may optionally be protected. Further, when one or more of R1 and R2, R3 and R4, and R5 and R6, together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C02H, the carboxyl substituent may optionally be protected. Protecting groups may be added and removed in accordance with techniques that are well known to those persons skilled in the art. The use of protecting groups is described in, for example, P. G. M. Wuts and T. W. Greene, Greene 's Protective Groups in Organic Synthesis, 4th edition, Wiley, New York, 2006 and P. J. Kocienski, Protecting Groups, 3rd edition, Georg Thieme Verlag, Stuttgart, 2005.
In some embodiments, the carboxyl substituent is protected as a Ci_6 alkyl ester. As used herein, the term "non-natural alpha-amino acid" includes any alpha-amino acid (or residue thereof) other than the natural amino acids listed above. Non-natural amino acids include the D-isomers of the natural L-amino acids. Non-natural amino acids also include, but are not limited to:
D-phenylalanine; norleucine; hydroxyproline; carboxyglutamic acid; and pyroglutamic acid.
The prefixes "D-" or "L-" indicate an alpha-amino acid of D- or L-configuration respectively. A "D.L-" prefix indicates a racemic mixture of amino acids of the two configurations.
Triaminocyclopropenium salts
In a first aspect, the present invention provides a compound of formula [Y^qPC"] wherein q is 1 , 2 or 3; and
wherein the cation, Y1", is a formula (I):
Figure imgf000031_0001
wherein
R1, R2, R3 and R5 are each independently selected from -H, C1.20 alkyl, substituted Ci_2o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-2o alkynyl, substituted C2-20 alkynyl, C3_io cycloalkyl, substituted C3.]0 cycloalkyl, C3_i0 cycloalkenyl, substituted C3.10 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci_20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C2-20 alkynyl, C3.10 cycloalkyl, substituted C3_i0 cycloalkyl, C3-io cycloalkenyl, substituted C3.|0 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or
one or more of R1 and R2, R3 and R4, and R5 and R6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl, substituted heterocyclyl, heteroaryl or substituted heteroaryl, wherein heteroaryl is imidazolyl, pyrazolyl, pyrrolyl or azepinyl; and
wherein the anion, Xq~, is selected from the group consisting of:
F, Br" I" [Ι3Γ, [HF2]~, [CN]" [SCN]", [NCO]", [CH3C(0)0]-, [(C2.6 alkyl)C(0)0]-
[NH2-CH(RA)C(0)0]-, [SiF6]2-, [S04]2", [N03]~ [C03]2-, [BPI14]-, [AsF6]", [SbF6]", [AIC ]" [A12C17]- [GaCU]", [S06F]-, [PF6]-, [A1F4]-, [A1F6]3" [CuCl2]-, [SnCl,]", [GeCl,]", [ZnC ]" [FeC ]", [FeC ]2", [C0CI4]", [CoCL,]2", and [Co(CO)4]";
wherein RA is a side chain of a natural or non-natural alpha-amino acid; [CF3COO]-, [SeCN]-, [HSO4]-, [H2P04]', [(MeO)(H)P02]- [CF3SO3]- [CF3OSO3]- [FHO(C,.6 alkyl)]-, [(C 2 alkyi SOjF, [(C,.,2 alkyl)S03]-, [(C2H5)2N(CH2)4S03;r, [C^SO^, [(CM2 alkyl)(C,_12
alkyl)P(0)0]-, [(C,.12 alkyl)(CM2 alkyl-0)P(0)0]-, [(CM2 alkyl-0)(C 2 alkyl-0)P(0)Or,
[CH3C6H4S03]", [Cl2H25C6H4S03]", [CH2(COO)2]2", [Co(C2B9Hu)2r, [C2B9H12r, [B10C110]2-, [B12C1I2]2 ~, [CB„H12]-, [BnHuNid-e alkyljj]" [(C,.6 alkyl)SnBuHn]", [RBCB„RC 5XB6]", and [RDBF3]~;
wherein RB is H, Ci_6 alkyl, C]_6 alkenyl, Ci_6 perfluoroalkyl, C]_6 perfluoroalkenyl or Si(Ci_6 alkyl)3; Rc is H, methyl, CI or Br;
RD is Ci_20 alkyl or C2_20 alkenyl, wherein one or two non-adjacent carbon atoms in RD which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S02-, or -NRJ-, and wherein RD is optionally substituted by one or more RE; or
RD is C3_io cycloalkyl, C3_i0 cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of C{.6 alkyl, C2-6 alkenyl, and RE;
RE at each instance is independently selected from halo, cyano, Ci_6 alkoxy, Si(Ci_6 alkyl)3, C3_i0 cycloalkyl optionally substituted by one or more RE*, C3-10 cycloalkenyl optionally substituted by one or more RE*, aryl optionally substituted by one or more RE*, heteroaryl optionally substituted by one or more RE*, and heterocyclyl optionally substituted by one or more RE*;
RE* at each instance is independently selected from halo, Ci_6 alkyl, Ci„6 alkoxy, and oxycarbonyl;
XB is CI or Br;
[Al(OCH2RF)4]-, [(CF3S02)2N]- [(CF3S02)NC(0)CF3]", [(FS02)2N]" [RFCF2S03]", [RFCF2OS03]-,
[(RGS02)2N)] -, [(RGS02)3Cr, [(CF3S02)3C]-, [(FS02)3C]", [RFCF2C(0)0]", [P(CnF2n+1.mHm)yF6.yy]j >
[P(C6F5)YF6_Y]-, [RF 2P(0)0]-, [RFP(0)02]2-, [(RFO)2P(0)0]" [(RF0)(RF)P(0)0]" [(RF0)P(0)02]2"
[BFZRF 4.Z]-, [BFZ(CN)4.Z]-, [Me3SiC2H40CH2BF3]- [N(CF3)2]" [N(CN)2]", [C(CN)3]- and
Figure imgf000032_0001
wherein RF at each instance is independently selected from perfiuoro Ci.2o alkyl, perfluoro C2.20 alkenyl having one or more double bonds, perfluoro C2_20 alkynyl having one or more triple bonds, perfluoro C3.10 cycloalkyl optionally substituted by one or more perfluoro Ci_6 alkyl, perfluoro C3.10 cycloalkenyl optionally substituted by one or more perfluoro Ci.6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci-6 alkyl, wherein any two RF may be connected by a single or double bond, wherein when RF is perfluoro Ci. 0 alkyl, perfluoro C2_20 alkenyl, or perfluoro C2.2o alkynyl one or two non-adjacent carbon atoms in RF which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S02-, or -NRJ-, and wherein a terminal carbon atom in RF, if present, may be replaced by -S02XD; and RG at each instance is independently selected from perfluoro C2_2o alkyl, perfluoro C2_2o alkenyl having one or more double bonds, perfluoro C2_2o alkynyl having one or more triple bonds, perfluoro C3.10 cycloalkyl optionally substituted by one or more perfluoro Cue alkyl, perfluoro C3.10 cycloalkenyl optionally substituted by one or more perfluoro Ci_6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci-6 alkyl, wherein any two RG may be connected by a single or double bond, wherein when RG is perfluoro Ci_20 alkyl, perfluoro C2.2o alkenyl, or perfluoro C2-2o alkynyl one or two non-adjacent carbon atoms in RG which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S02-, or -NR.1-, and wherein a terminal carbon atom in RG, if present, may be replaced by -S02XD;
RJ at each instance is independently selected from C alkyl, fluoro Ci_6 alkyl, perfluoro Ci_6 alkyl, C3.10 cycloalkyl, phenyl optionally substituted by one or more RK, heteroaryl optionally substituted by one or more RK, and heterocyclyl optionally substituted by one or more RK;
RK at each instance is independently selected from Ci_6 alkyl, C 6 alkenyl, nitro, halo, hydroxyl, Ci_6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
trifluoromethylsulfonyl, Ci- alkoxycarbonyl, -NH2, Ci_6 alkylamino, di(Ci_6
alkyl)amino, -C02H, -C(0)NRL, -S02ORL, -S02XD, -S02NRL 2, -SO3H, and -NHC(0)RL;
RL at each instance is independently selected from Cue alkyl, fluoro C 6 alkyl, perfluoro C]-6 alkyl, and
C3-10 cycloalkyl;
XD at each instance is independently selected from F, CI, and Br;
n is 1 to 20;
m is 0, 1, 2, or 3;
y is 1, 2, 3, or 4; and
z is 0, 1, 2, or 3; and
-Z- and -Y- are independently selected from -C(0)C(0)-, -C(0)(CH2)4C(0)-, -C(0)(CF2)qC(0)- wherein q = 1 , 2 or 3, -C(CF3)2C(CF3)2-,
Figure imgf000033_0001
Figure imgf000034_0001
k is 1 , 2, 3, or 4; and
p is 1 , or 2.
In some embodiments, the anion, Xq~, is selected from the group consisting of:
F-, Br , Γ, [Is]", [HF2]-, [CN]", [SCN]", [NCO]", [CH3C(0)0]-, [(C2.6 alkyl)C(0)0] ,
[NH2-CH(RA)C(0)0]-, [SiF6]2- [S04]2-, [Ν03]", [CO,]2", [ΒΡη,Γ, [AsF6]-, [SbF6]", [AIC ]", [A12C17]-, [GaC ]", [SO^f, [PF6]- [A1F4]-, [A1F6]3" [CuCl2]", [SnClj]" [GeCl,]" [ZnC ]" [FeCl,]", [FeC ]2", [CoC r, [CoC ]2", and [Co(CO)4]";
wherein RA is a side chain of a natural or non-natural alpha-amino acid;
[CF3COO]-, [SeCN]-, [HS04] ~, [H2P04]", [(MeO)(H)P02]", [CF3S03]", [CF3OS03]~, [FHO(d_6 alkyl)]-, [(C., 2 alkyl)OS03]- [(CM2 alkyl)S03]-, [(C2H5)2N(CH2)4S03]- [C^SO,]", [(C1-12 alkyl)(CM2 alkyl)P(0)0]- [(CM2 alkyl)(C 2 alkyl-0)P(0)0]-, [(C,.12 alkyl-0)(C1-12 alkyl-0)P(0)0]',
[CH3C6H4S03]- [C12H25C6H4S03]-, [CH2(COO)2]2 ~ [Co(C2B9H„)2]- [C2B9H12]" [B10C110]2 [B12C112]2 , [CB„H12]-, [Bi2HuN(Ci_6 alkyl),]", [(C,.6 alkyl)SnB„H„]- [RBCBuRc 5XB6]", and [RDBF3]_;
wherein RB is H, Ci_6 alkyl, Ci_6 alkenyl, Ci_6 perfluoroalkyl, Ci_6 perfluoroalkenyl or Si(Ci_6 alkyl)3; Rc is H, methyl, CI or Br;
RD is Ci_2o alkyl or C2_20 alkenyl, wherein one or two non-adjacent carbon atoms in RD which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S02-, or -NRJ-, and wherein RD is optionally substituted by one or more RE; or
RD is C3_io cycloalkyl, C3_io cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of Ci-6 alkyl, C2-6 alkenyl, and RE;
RE at each instance is independently selected from halo, cyano, Cj_6 alkoxy, Si(Ci_6 alkyl)3, C3_!o cycloalkyl optionally substituted by one or more RE*, C3_io cycloalkenyl optionally substituted by one or more RE*, aryl optionally substituted by one or more RE*, heteroaryl optionally substituted by one or more RE\ and heterocyclyl optionally substituted by one or more RE*;
RE* at each instance is independently selected from halo, Ci_6 alkyl, Ci_6 alkoxy, and oxycarbonyl;
XB is CI or Br;
[(CF3S02)2N] - [(CF3S02)NC(0)CF3]- [(FS02)2N] , [RFCF2S03]-, [RFCF2OS03]", [(RGS02)2N)] ,
[(RGS02)3C]-, [(CF3S02)3C]- [(FS02)3C]", [RFCF2C(0)0]", [P(CnF2n+1.mHm)yF6.y]-, [PCC^ ^]- [RF 2P(0)0]-, [RFP(0)02]2- [(RF0)2P(0)0]-, [(RF0)(RF)P(0)0]" [(RF0)P(0)02]2-, [BF2RF 4.Z] , [BFZ(CN)4.J- [Me3SiC2H40CH2BF3]-, [N(CF3)2]", [N(CN)2]~, [C(CN)3]" and
Figure imgf000035_0001
wherein RF at each instance is independently selected from perfluoro Ci_20 alkyl, perfluoro C2_20 alkenyl having one or more double bonds, perfluoro C2.2o alkynyl having one or more triple bonds, perfluoro C3_io cycloalkyl optionally substituted by one or more perfluoro Ci_6 alkyl, perfluoro C3_io cycloalkenyl optionally substituted by one or more perfluoro Ci-6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci_6 alkyl, wherein any two RF may be connected by a single or double bond, wherein when RF is perfluoro C1.20 alkyl, perfluoro C2. 0 alkenyl, or perfluoro C2.20 alkynyl one or two non-adjacent carbon atoms in RF which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S0 -, or -NRJ-, and wherein a terminal carbon atom in RF, if present, may be replaced by -S02XD; and
RG at each instance is independently selected from perfluoro C2-20 alkyl, perfluoro C2.20 alkenyl having one or more double bonds, perfluoro C2.2o alkynyl having one or more triple bonds, perfluoro C3-i0 cycloalkyl optionally substituted by one or more perfluoro C\.6 alkyl, perfluoro C3-i0 cycloalkenyl optionally substituted by one or more perfluoro Ci-6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci-6 alkyl, wherein any two RG may be connected by a single or double bond, wherein when RG is perfluoro Ci_20 alkyl, perfluoro C2-20 alkenyl, or perfluoro C2.20 alkynyl one or two non-adjacent carbon atoms in RG which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S02-, or -NRJ-, and wherein a terminal carbon atom in R°, if present, may be replaced by -S02XD;
RJ at each instance is independently selected from Ci-6 alkyl, fluoro Ci.6 alkyl, perfluoro Ci_6 alkyl, C3.] 0 cycloalkyl, phenyl optionally substituted by one or more RK, heteroaryl optionally substituted by one or more R , and heterocyclyl optionally substituted by one or more RK;
RK at each instance is independently selected from Ci-6 alkyl, Ci-6 alkenyl, nitro, halo, hydroxyl, C].6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
trifluoromethylsulfonyl, Ci_6 alkoxycarbonyl, -NH2, Ci-6 alkylamino, di(Ci-6
alkyl)amino, -C02H, -C(0)NRL, -S02ORL, -S02XD, -S02NRL 2, -S03H, and -NHC(0)RL;
RL at each instance is independently selected from Ci-6 alkyl, fluoro C 6 alkyl, perfluoro Ci-6 alkyl, and C3_io cycloalkyl;
XD at each instance is independently selected from F, CI, and Br;
n is 1 to 20;
m is 0, 1, 2, or 3;
y is 1, 2, 3, or 4; and
z is 0, 1, 2, or 3; and -Z- and -Y- are independently selected from -C(0)C(0 , -C(0)(CH2)4C(0)-, -C(0)(CF2)qC(0)- wherein q = 1, 2 or 3, -C(CF3)2C(CF3)2-,
Figure imgf000036_0001
k is 1, 2, 3, or 4; and
p is 1, or 2.
In some embodiments, the anion, Xq , is selected from the group consisting of:
F-, Br" Γ, [I3]-, [HF2]- [CN]", [SCNT, [NCO]" [CH3C(0)0]- [(C2.6 alkyl)C(0)0]- [NH2-CH(RA)C(0)0]", [SiF6]2-, [S04]2 ~, [ΝΟ,Γ, [C03]2", [BPh,]" [AsF6]-, [SbF6]", [AICL,]", [A12C17]- [GaC r, [S06F]- [PF6]- [A1F4]" [A1F6]3- [CuCy, [SnClj]", [GeCl3]~ [ZnCl4]~, [FeCl4]" [FeC ]2", [CoCl4]-, [CoC ]2", and [Co(CO)4]";
wherein RA is a side chain of a natural or non-natural alpha-amino acid. This group is referred to herein as "Group 1".
In some embodiments, the anion, Xq~, is selected from the group consisting of:
[CF3COOr, [SeCN]- [HS04]" [H2P04]" [(MeO)(H)P02]" [CF3S03]", [CF3OS03]", [FHO(C1-6 alkyl)]" [(Ci.,2 alkyl)OS03]-, [(C 2 alkyl)S03r, [(C2H5)2N(CH2)4S03r, [C^SO,]" [(C,.12 alkyl)(C,.12 alkyl)P(0)0]-, [(CM2 alkyl)(CM2 alkyl-0)P(0)0]-, [(C,_12 alkyl-0)(C,_12 alkyl-0)P(0)Or,
[CH3C6H4S03]", [C12H25C6H4S03]-, [CH2(COO)2]2", [Co(C2B9H, ,)2]", [C2B9H12]-, [B10C110]2- [B12C112]2-, [CBnH12]- [Bi2HiiN(Ci_6 alkyl),]", [(C1-6 alky SnBnHn]" [RBCB„RC 5XB 6]-, and [R°BF3]-;
wherein RB is H, Ci_6 alkyl, Ci_6 alkenyl, Ci_6 perfluoroalkyl, Ci_6 perfluoroalkenyl or Si(Ci-6 alkyl)3; Rc is H, methyl, CI or Br; RD is C-20 alkyl or C2_2o alkenyl, wherein one or two non-adjacent carbon atoms in RD which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S02-, or -NRJ-, and wherein RD is optionally substituted by one or more RE; or
RD is C3_io cycloalkyl, C3_io cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of Q.6 alkyl, C2-6 alkenyl, and RE;
RE at each instance is independently selected from halo, cyano, C)_6 alkoxy, Si(Ci_6 alkyl)3, C3_io cycloalkyl optionally substituted by one or more RE*, C3_i0 cycloalkenyl optionally substituted by one or more RE*, aryl optionally substituted by one or more RE*, heteroaryl optionally substituted by one or more RE*, and heterocyclyl optionally substituted by one or more RE*;
RE* at each instance is independently selected from halo, Ci_6 alkyl, Ci_6 alkoxy, and oxycarbonyl;
RJ at each instance is independently selected from Ci-6 alkyl, fluoro Ci_6 alkyl, perfluoro Ci-6 alkyl, C3_io cycloalkyl, phenyl optionally substituted by one or more RK, heteroaryl optionally substituted by one or more RK, and heterocyclyl optionally substituted by one or more RK;
RK at each instance is independently selected from Ci.6 alkyl, C]_6 alkenyl, nitro, halo, hydroxyl, C].6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
trifluoromethylsulfonyl, C\.6 alkoxycarbonyl, -NH2, Ci_6 alkylamino, di(Ci-6
alkyl)amino, -C02H, -C(0)NRL, -S02ORL, -S02XD, -S02NRL 2, -S03H, and -NHC(0)RL;
RL at each instance is independently selected from Ci_6 alkyl, fluoro Ci-6 alkyl, perfluoro Ci_e alkyl, and C3.io cycloalkyl;
XB is CI or Br; and
XD at each instance is independently selected from F, CI, and Br. This group is referred to herein as
"Group 2".
In some embodiments, the anion, Xq , is selected from the group consisting of: [Al(OCH2RF)4] ,
[(CF3S02)2N]-, [(CF3S02)NC(0)CF3]- [(FS02)2N]~ [RFCF2S03]" [RFCF2OS03] ~, [(RGS02)2N)]",
[(RGS02)3C]-, [(CF3S02)3C]-, [(FS02)3C]-, [RFCF2C(0)0]", [P(CnF2n+1.mHm)yF6.yr, [P(C6F5)yF6.y]- [RF 2P(0)0]- [RFP(0)02]2-, [(RF0)2P(0)0]- [(RF0)(RF)P(0)0]', [(RFO)P(0)02]2", [BFZRF 4-Z]-,
[BFz(CN)4-z] [Me3SiC2H4OCH2BF3r, [N(CF3)2]-, [N(CN)2]", [C(CN)3]" and
Figure imgf000037_0001
one or more perfluoro Ci-6 alkyl, wherein any two RF may be connected by a single or double bond, wherein when RF is perfluoro Ci_20 alkyl, perfluoro C2.20 alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO2-, or -NRJ-, and wherein a terminal carbon atom in RF, if present, may be replaced by -S02XD; and
RG at each instance is independently selected from perfluoro C2-20 alkyl, perfluoro C2-20 alkenyl having one or more double bonds, perfluoro C2-20 alkynyl having one or more triple bonds, perfluoro C3.10 cycloalkyl optionally substituted by one or more perfluoro Ci-e alkyl, perfluoro C3.10 cycloalkenyl optionally substituted by one or more perfluoro Ct.6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci.6 alkyl, wherein any two RG may be connected by a single or double bond, wherein when RG is perfluoro Ci_2o alkyl, perfluoro C2_20 alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO2-, or -NRJ-, and wherein a terminal carbon atom in RG, if present, may be replaced by -S02XD;
RJ at each instance is independently selected from Ci-6 alkyl, fluoro d.6 alkyl, perfluoro Ci-6 alkyl, C3_i0 cycloalkyl, phenyl optionally substituted by one or more RK, heteroaryl optionally substituted by one or more RK, and heterocyclyl optionally substituted by one or more R ;
RK at each instance is independently selected from Ci.6 alkyl, Ci-6 alkenyl, nitro, halo, hydroxyl, Ci.6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
trifluoromethylsulfonyl, Ci_6 alkoxycarbonyl, -NH2, Ci-6 alkylamino, di(C].6
alkyl)amino, -C02H, -C(0)NRL, -S02ORL, -S02XD, -S02NRL 2, -S03H, and -NHC(0)RL;
RL at each instance is independently selected from C].6 alkyl, fluoro Ci-6 alkyl, perfluoro Ci.6 alkyl, and
C3.10 cycloalkyl;
XD at each instance is independently selected from F, CI, and Br;
n is 1 to 20;
m is 0, 1, 2, or 3;
y is 1, 2, 3, or 4; and
z is 0, 1, 2, or 3; and
-Z- and -Y- are independently selected from -C(0)C(0)-, -C(0)(CH2)4C(0)-, -C(0)(CF2)qC(0)- wherein q = 1, 2 or 3, -C(CF3)2C(CF3)2-,
Figure imgf000039_0001
k is 1 , 2, 3, or 4; and
p is 1 , or 2. This group is referred to herein as "Group 3".
In some embodiments, the Group 3 anion, Xq , is selected from the group consisting of: [(CF3S02)2N]~, [(CF3S02)NC(0)CF3]-, [(FS02)2N]- [RFCF2S03j-, [RFCF2OS03]-, [(RGS02)2N)]-, [(RGS02)3Cr,
[(CF3S02)3Cr, [(FS02)3C] -
Figure imgf000039_0002
[RF 2P(0)0]"
[RFP(0)02]2-, [(RF0)2P(0)Or, [(RF0)(RF)P(0)0]-, [(RF0)P(0)02]2-, [BFZRF 4.J- [BFZ(CN)4.Z]-
Figure imgf000039_0003
[Me3SiC2H4OCH2BF3]~ [N(CF3)2]", [N(CN)2] , [C(CN)3r and
wherein RF at each instance is independently selected from perfluoro Ci_2o alkyl, perfluoro C2-2o alkenyl having one or more double bonds, perfluoro C2-2o alkynyl having one or more triple bonds, perfluoro C3_i0 cycloalkyl optionally substituted by one or more perfluoro Cj.6 alkyl, perfluoro C3_i0 cycloalkenyl optionally substituted by one or more perfluoro Ci_6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci-6 alkyl, wherein any two RF may be connected by a single or double bond, wherein when RF is perfluoro Ci.2o alkyl, perfluoro C2_2o alkenyl, or perfluoro C2_2o alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S02-, or -NRJ-, and wherein a terminal carbon atom in RF, if present, may be replaced by -S02XD; and
RG at each instance is independently selected from perfluoro C2.20 alkyl, perfluoro C2.2o alkenyl having one or more double bonds, perfluoro C2-20 alkynyl having one or more triple bonds, perfluoro C3_io cycloalkyl optionally substituted by one or more perfluoro Ci_6 alkyl, perfluoro C3.i0 cycloalkenyl optionally substituted by one or more perfluoro C e alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci_6 alkyl, wherein any two RG may be connected by a single or double bond, wherein when RG is perfluoro Ci_2o alkyl, perfluoro C2-20 alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO2-, or -NRJ-, and wherein a terminal carbon atom in R°, if present, may be replaced by -S02XD;
RJ at each instance is independently selected from Ci_6 alkyl, fluoro Ci_6 alkyl, perfluoro C]-6 alkyl, C3_io cycloalkyl, phenyl optionally substituted by one or more RK, heteroaryl optionally substituted by one or more RK, and heterocyclyl optionally substituted by one or more RK;
RK at each instance is independently selected from Ci_6 alkyl, Ci_6 alkenyl, nitro, halo, hydroxyl, Ci_6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
trifluoromethylsulfonyl, Ci-6 alkoxycarbonyl, -NH2, Ci_6 alkylamino, di(Ci_6
alkyl)amino, -C02H, -C(0)NRL, -S02ORL, -S02XD, -S02NRL 2, -SO3H, and -NHC(0)RL;
RL at each instance is independently selected from Ci.6 alkyl, fluoro Ci-6 alkyl, perfluoro Ci-e alkyl, and C3-10 cycloalkyl;
XD at each instance is independently selected from F, CI, and Br;
n is 1 to 20;
m is 0, 1, 2, or 3;
y is 1 , 2, 3, or 4; and
z is 0, 1, 2, or 3; and
-Z- and -Y- are independently selected from -C(0)C(0)-, -C(0)(CH2)4C(0)-, -C(0)(CF2)qC(0)- wherein q = l, 2 or 3, -C(CF3)2C(CF3)2-,
Figure imgf000040_0001
Figure imgf000041_0001
k is 1 , 2, 3, or 4; and
p is 1 , or 2.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C2-2o alkynyl, aryl, and substituted aryl; and
R4 and R6 are each independently selected from C2.2o alkyl, substituted Ci-2o alkyl, C2-2o alkenyl, substituted C2-2o alkenyl, C2_20 alkynyl, substituted C2_2o alkynyl, aryl, and substituted aryl; or one or more of R1 and R2, R3 and R4, and R5 and R6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_20 alkyl, substituted Ci_20 alkyl, C2_2o alkenyl, substituted C2.2o alkenyl, C2-2o alkynyl, and substituted C2-2o alkynyl; and R4 and R6 are each independently selected from C2_2o alkyl, substituted Ci_2o alkyl, C2_20 alkenyl, substituted C2.2o alkenyl, C2-2o alkynyl, and substituted C2.20 alkynyl; or
one or more of R1 and R2, R3 and R4, and R5 and R6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_20 alkyl, substituted Ci_2o alkyl, C2-2o alkenyl, substituted C2_20 alkenyl, aryl, and substituted aryl; and
R4 and R6 are each independently selected from C2-2o alkyl, substituted Ci_2o alkyl, C2.20 alkenyl, substituted C2-2o alkenyl, aryl, and substituted aryl; or
R1 and R2, R3 and R4, or R5 and R6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_20 alkyl, substituted C].2o alkyl, C2-2o alkenyl, and substituted C2.2o alkenyl; and
R4 and R6 are each independently selected from C2.20 alkyl, substituted Ci_20 alkyl, C2.20 alkenyl, and substituted C2-2o alkenyl; or
R1 and R2, R3 and R4, or R5 and R6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci_2o alkyl, C2.2o alkenyl, substituted C2.2o alkenyl, aryl, and substituted aryl; and R4 and R6 are each independently selected from C2.2o alkyl, substituted C^o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl. In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, C1.20 alkyl, substituted Ci-20 alkyl, C2.2o alkenyl, and aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci_20 alkyl, C2-20 alkenyl, and aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci-6 alkyl, C2.6 alkenyl, and aryl; and
R4 and R6 are each independently selected from C2.20 alkyl, substituted alkyl, C2-6 alkenyl, and aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl.
In some embodiments, R1, R2 and R3 are each independently selected from -H, Ci. 0 alkyl, substituted Ci-20 alkyl, C2-2o alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and
R4 is selected from C2-20 alkyl, substituted C1.20 alkyl, C2-2o alkenyl, substituted C2_20 alkenyl, aryl, and substituted aryl; and
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1, R2 and R3 are each independently selected from -H, Ci-2o alkyl, substituted Ci_20 alkyl, C2.2o alkenyl, and aryl; and
R4 is selected from C2.2o alkyl, substituted C1.20 alkyl, C2.2o alkenyl, and aryl; and
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1, R2 and R3 are each independently selected from -H, Ci_2o alkyl, substituted Ci_6 alkyl, C2-6 alkenyl, and aryl; and
R4 is selected from C2.20 alkyl, substituted Ci_6 alkyl, C2_6 alkenyl, and aryl; and
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci-20 alkyl, C2-2o alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and R2, R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci_2o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl. In some embodiments, R1, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, and aryl; and
R2, R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci_2o alkyl, C2-20 alkenyl, and aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1 and R3 are each independently selected from -H, Ci_2o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C2.2o alkenyl, aryl, and substituted aryl; and
R2 and R4 are each independently selected from C2-20 alkyl, substituted C)-2o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1 and R3 are each independently selected from -H, Ci_2o alkyl, substituted C1.20 alkyl, C2-20 alkenyl, and aryl; and
R2 and R4 are each independently selected from C2-20 alkyl, substituted C1-2o alkyl, C2-20 alkenyl, and aryl; and
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1 and R3 are each independently selected from -H, Ci_2o alkyl, substituted Ci.6 alkyl, C2-e alkenyl, and aryl; and
R2 and R4 are each independently selected from C2-20 alkyl, substituted Ci-e alkyl, C2-6 alkenyl, and aryl; and
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
In some embodiments, R1 and R3 are each independently selected from -H, Ci-2o alkyl, hydroxy \.6 alkyl, carboxyl C 6 alkyl, Ci_6 alkoxycarbonyl Ci_6 alkyl, Ci_6 alkoxy Ci-6 alkyl, Ci_6 alkyl-NH2, Ci_6 alkylamino Ci_6 alkyl, carboxyl hydroxy Ci_6 alkyl, C2_6 alkenyl, and aryl; and
R2 and R4 are each independently selected from C2-20 alkyl, hydroxy Ci.6 alkyl, carboxyl Ci.6 alkyl, Ci_6 alkoxycarbonyl Ci_6 alkyl, C1-5 alkoxy Ci_6 alkyl, Ci_6 alkyl-NH2, \.6 alkylamino Ci-6 alkyl, carboxyl hydroxy Cj.6 alkyl, C2_6 alkenyl, and aryl; and R5 and R6 form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl.
In some embodiments, wherein one or more of R1 and R2, R3 and R4, and R5 and R6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl, the heterocyclyl or substituted heterocyclyl is pyrrolidinyl, substituted pyrrolidinyl, piperidinyl, substituted piperidinyl, morpholinyl, substituted morpholinyl, azepanyl, or substituted azepanyl.
In some embodiments, the heterocyclyl or substituted heterocyclyl is pyrrolidinyl or substituted pyrrolidinyl.
In some embodiments, R1 and R3 are each independently selected from -H, Ci_2o alkyl, hydroxy Ci_6 alkyl, carboxyl Ci-6 alkyl, Ci_6 alkoxycarbonyl Cj-6 alkyl, Ci-6 alkoxy Ci-6 alkyl, Ci-6 alkyl-NH2, C1-6 alkylamino Ci-6 alkyl, carboxyl hydroxy Ci_6 alkyl, C2_6 alkenyl, and aryl; and
R2 and R4 are each independently selected from C2.20 alkyl, hydroxy Ci_6 alkyl, carboxyl C].6 alkyl, Ci-e alkoxycarbonyl Ci-6 alkyl, Ci_6 alkoxy Ci-β alkyl, Ci-6 alkyl-NH2, Ci_6 alkylamino C].6 alkyl, carboxyl hydroxy C|-6 alkyl, C2_6 alkenyl, and aryl; and
R5 and R6 form, together with the nitrogen atom to which they are attached, a substituted pyrrolidinyl. In some embodiments, wherein one or more of R1 and R2, R3 and R4, and R5 and R6 independently form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl, the heterocyclyl is substituted by one or more carboxyl groups.
In some embodiments, wherein one or more of R1 and R2, R3 and R4, and R5 and R6 independently form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl, the heterocyclyl is substituted by one or more substituents independently selected from Cj.6 alkyl, C1.6 alkoxy and Ca alkoxy Cb alkyl wherein a and b are independently 1 , 2, 3, 4, or 5 and the sum (a + b) is 2, 3, 4, 5, or 6.
In some embodiments, wherein one or more of R1 and R2, R3 and R4, and R5 and R6 independently form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl, the heterocyclyl is substituted by one or more substituents independently selected from Ci_6 alkyl and Ca alkoxy Cb alkyl wherein a and b are independently 1 , 2, 3, 4, or 5 and the sum (a + b) is 2, 3, 4, 5, or 6.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, C]_2o alkyl, substituted Cue alkyl, C2-2o alkenyl, substituted C2.20 alkenyl, aryl, and substituted aryl; and
R4 and R6 are each independently selected from C2.2o alkyl, substituted Cuo alkyl, C2-20 alkenyl, substituted C2_2o alkenyl, aryl, and substituted aryl. In some embodiments, R1, R3 and R5 are each independently selected from -H, Ci_20 alkyl, substituted Ci_2o alkyl, C2-2o alkenyl, substituted C2-2o alkenyl, aryl, and substituted aryl; and R2, R4 and R6 are each independently selected from C2-20 alkyl, substituted C i_2o alkyl, C2_2o alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, and substituted C2-20 alkenyl; and
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci_2o alkyl, C2-20 alkenyl, and substituted C2-20 alkenyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ct.20 alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, and aryl; and
R4 and R6 are each independently selected from C2_2o alkyl, substituted C^o alkyl, C2-20 alkenyl, and aryl. In some embodiments, R1, R3 and R5 are each independently selected from -H, C ].2o alkyl, substituted C |.2o alkyl, and C2-20 alkenyl; and
R2, R4 and R6 are each independently selected from C2-20 alkyl, substituted C i-2o alkyl, C2_2o alkenyl, and aryl.
In some embodiments, R1, R3 and R5 are each independently selected from -H, C1.20 alkyl, substituted Ci-20 alkyl, and C2-20 alkenyl;
R2 is selected from -H, Ci.2o alkyl, substituted Ci_2o alkyl, C2-20 alkenyl, and aryl; and
R4 and R6 are each independently selected from C2_2o alkyl, substituted C^o alkyl, C2-20 alkenyl, and aryl.
In some embodiments, R1, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci-20 alkyl, and C2-20 alkenyl; and
R2, R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci-2o alkyl, C2-20 alkenyl, and aryl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci-20 alkyl, and C2-20 alkenyl; and
R4 and R6 are each independently selected from C2_2o alkyl, substituted Ci_2o alkyl, and C2-20 alkenyl. In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, C1.20 alkyl, substituted Ci-6 alkyl, C2-6 alkenyl, and aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci_6 alkyl, C2- alkenyl, and aryl.
In some embodiments, R1, R3 and R5 are each independently selected from -H, C1.20 alkyl, substituted Ci.« alkyl, and C2-6 alkenyl;
R2 is selected from -H, Ci-2o alkyl, substituted C,_6 alkyl, C2-6 alkenyl, and aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci_6 alkyl, C2.6 alkenyl, and aryl. In some embodiments, R1, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci_6 alkyl, and C2-6 alkenyl; and
R2, R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci.6 alkyl, C2.6 alkenyl, and aryl. In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci-2o alkyl, substituted Ci_6 alkyl, and C2_6 alkenyl; and
R4 and R6 are each independently selected from C2_2o alkyl, substituted C1.6 alkyl, and C2-6 alkenyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, C1.20 alkyl, hydroxy Ci-6 alkyl, carboxyl Ci-6 alkyl, C1-6 alkoxycarbonyl Ci-6 alkyl, C\.6 alkoxy Ci_6 alkyl, d-6 alkyl-NH2, Ci-6 alkylamino Ci_6 alkyl, carboxyl hydroxy Ci-6 alkyl, C2-6 alkenyl, and aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl Ci.6 alkyl, C]_6 alkoxycarbonyl Ci_6 alkyl, Ci-6 alkoxy C\.6 alkyl, C].6 alkyl-NH2, Ci-6 alkylamino Ci-6 alkyl, carboxyl hydroxy C\.(, alkyl, C2-6 alkenyl, and aryl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, hydroxy Ci.6 alkyl, carboxyl Ci-6 alkyl, Ci_6 alkoxycarbonyl Ci_6 alkyl, C\.6 alkoxy Ci_6 alkyl, C].6 alkyl-NH2, Ci-6 alkylamino Ci.6 alkyl and C2-6 alkenyl; and
R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Ci-6 alkyl, carboxyl Ci.6 alkyl, C\.6 alkoxycarbonyl Ci_6 alkyl, Ci-6 alkoxy Ci_6 alkyl, Ci_6 alkyl-NH2, Ci_6 alkylamino Ci_6 alkyl and C2-6 alkenyl. In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, hydroxy Ci_6 alkyl, carboxyl C e alkyl, carboxyl hydroxy Ci-6 alkyl, C2_6 alkenyl, and aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl Ci_6 alkyl, carboxyl hydroxy Ci„6 alkyl, C2-e alkenyl, and aryl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci-2o alkyl, hydroxy Ci-6 alkyl, carboxyl C\.e alkyl, and C2-6 alkenyl; and
R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl Ci.6 alkyl, and C2-6 alkenyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, C].2o alkyl, hydroxy Ci_e alkyl, and C2-6 alkenyl; and
R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl Ci_6 alkyl, carboxyl hydroxy Ci_6 alkyl, and C2-6 alkenyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, hydroxy Ci-6 alkyl, and C2-6 alkenyl; and R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl Ci.6 alkyl, and C2-6 alkenyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, methyl, ethyl,
H-propyl, wo-propyl, n-butyl, w-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, allyl, and phenyl; and R4 and R6 are each independently selected from ethyl, «-propyl, /so-propyl, n-butyl, w-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, 1-carboxylethyl, 1 -carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl; or
R5 and R6, together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, methyl, ethyl,
M-propyl, wo-propyl, «-butyl, «-pentyl, n-hexyl, decyl, stearyl, 2-hydroxyethyl, allyl, and phenyl; and R4 and R6 are each independently selected from ethyl, n-propyl, z'so-propyl, «-butyl, «-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, 1 -carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, methyl, ethyl, «-propyl, «ο-propyl, «-butyl, «-hexyl, stearyl, 2-hydroxyethyl, and allyl; and
R4 and R6 are each independently selected from ethyl, n-propyl, wo-propyl, «-butyl, n-hexyl, stearyl, 2-hydroxyethyl, 1-carboxylethyl, and allyl.
In some embodiments, R'-R6 are identical. In some embodiments, R]-R6 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, or C2.e alkenyl. In some embodiments, Rl-R6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl. In some embodiments, R'-R6 are identical and are pentyl, hexyl, or decyl. In some embodiments, R]-R6 are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl. In some embodiments, R'-R6 are identical and are 2-hydroxyethyl.
In some embodiments, wherein R'-R6 are identical, each of R'-R6 comprise 2- 10 non-hydrogen atoms. In some embodiments, wherein R'-R6 are identical, each of R'-R6 comprise 2-6 non-hydrogen atoms. In some embodiments, the anion, Xq~, is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.
In some embodiments, R1, R3 and R5 are identical. In some embodiments, R1, R3 and R5 are identical and are -H, C1.20 alkyl, substituted Ci_6 alkyl, or C2-6 alkenyl. In some embodiments, R1, R3 and R5 are identical and are C1.20 alkyl, substituted Ci_e alkyl, or C2-6 alkenyl. In some embodiments, R1, R3 and R5 are identical and are C2-20 alkyl, substituted C e alkyl, or C2-6 alkenyl.
In some embodiments, R4, R5 and R6 are identical. In some embodiments, R2, R4 and R6 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, C2-e alkenyl, or aryl. In some embodiments, R2, R4 and R6 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, C2-6 alkenyl, or phenyl. In some embodiments, R1, R3 and R5 are identical, R2, R4 and R6 are identical, and R1 and R2 are different. In some embodiments, R1, R3 and R5 are identical and are -H, Ci_2o alkyl, substituted Ci-6 alkyl, or C2-e alkenyl, and R2, R4 and R6 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, C2-6 alkenyl, or aryl, and R' and R2 are different. In some embodiments, R1, R3 and R5 are identical and are -H, C1.20 alkyl, substituted Ci_6 alkyl, or C2-e alkenyl, and R2, R4 and R6 are identical and are C2_2o alkyl, substituted Ci_6 alkyl, C2-6 alkenyl, or phenyl, and R1 and R2 are different. In some embodiments, R1, R3 and R5 are identical and are Ci_2o alkyl, substituted Ci_6 alkyl, or C2-6 alkenyl, and R2, R4 and R6 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, or C2-e alkenyl, and R1 and R2 are different. In some embodiments, R1, R3 and R5 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, or C2-6 alkenyl, and R2, R4 and R6 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, or C2_6 alkenyl, and R1 and R2 are different.
In some embodiments, R1, R3 and R5 are methyl and R2, R4 and R6 are butyl.
In some embodiments, R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl.
In some embodiments, R1, R3 and R5 are -H and R2, R4 and R6 are phenyl.
In some embodiments, wherein R1, R3 and R5 are identical, R2, R4 and R6 are identical, and R1 and R2 are different, R1 and R2 together comprise 2-10 non-hydrogen atoms. In some embodiments, R1 is not -H. In some embodiments, the anion, Xq~, is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.
In some embodiments, wherein R1, R3 and R5 are methyl and R2, R4 and R6 are butyl, the anion, Xq~, is selected from Group 3. In some embodiments, R1, R2, R3 and R4 are identical. In some embodiments, R1, R2, R3 and R4 are identical and are C2_2o alkyl, substituted Q-e alkyl, or C2_6 alkenyl.
In some embodiments, R3, R4, R5 and R6 are identical. In some embodiments, R3, R4, R5 and R6 are identical and are C2-2o alkyl, substituted Ci-6 alkyl, or C2-6 alkenyl.
In some embodiments, R1, R2, R3 and R4 are identical, R5 and R6 are identical, and R1 and R5 are different. In some embodiments, R1, R2, R3 and R4 are identical and are C2_2o alkyl, substituted C1-6 alkyl, or C2-6 alkenyl, R5 and R6 are identical and are C2-20 alkyl, substituted Ci-6 alkyl, or C2-e alkenyl, and R1 and R5 are different.
In some embodiments, R3, R4, R5 and R6 are identical, R1 and R2 are identical, and R1 and R3 are different. In some embodiments, R3, R4, R5 and R6 are identical and are Ci-2o alkyl, substituted Ci-6 alkyl, or C2- alkenyl, R1 and R2 are identical and are -H, C2-20 alkyl, substituted Ci_6 alkyl, or C2_6 alkenyl, and R1 and R3 are different. In some embodiments, R3, R4, R5 and R6 are identical and are Ci-20 alkyl, substituted Ci_ alkyl, or C2-6 alkenyl, R1 and R2 are identical and are C2_2o alkyl, substituted Ci-6 alkyl, or C2.6 alkenyl, and R1 and R3 are different. In some embodiments, R3, R4, R5 and R6 are identical and are C2-20 alkyl, substituted Ci.6 alkyl, or C2-6 alkenyl, R1 and R2 are identical and are -H, C2-20 alkyl, substituted C]-6 alkyl, or C2.6 alkenyl, and R1 and R3 are different. In some embodiments, R3, R4, R5 and R6 are identical and are C2.2o alkyl, substituted Ci_6 alkyl, or C2.6 alkenyl, R1 and R2 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, or C2-6 alkenyl, and R1 and R3 are different.
In some embodiments, wherein R1, R2, R3 and R4 are identical, R5 and R6 are identical, and R1 and R5 are different, R1, R2, R3 and R4 are ethyl. In some embodiments, R5 and R6 together comprise 2-8 non- hydrogen atoms. In some embodiments, the anion, Xq~, is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.
In some embodiments, wherein R3, R4, R5 and R6 are identical, R1 and R2 are identical, and R1 and R3 are different, R3, R4, R5 and R6 are ethyl. In some embodiments, R1 and R2 together comprise 2-8 non- hydrogen atoms. In some embodiments, the anion, Xq~, is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3. In some embodiments, R1, R2, R3 and R4 are ethyl and R5 and R6 are j'so-propyl.
In some embodiments, R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl.
In some embodiments, R\ R2, R3 and R4 are ethyl and R5 and R6 are hexyl.
In some embodiments, R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl.
In some embodiments, R1, R2, R3 and R4 are wo-propyl and R 5 and R6 are butyl. In some embodiments, R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl.
In some embodiments, R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl.
In some embodiments, R3, R4, R5 and R6 are ethyl and R1 and R2 are hydrogen.
In some embodiments, wherein R1, R2, R3 and R4 are identical, R5 and R6 are identical, and R1 and R5 are different, R5 and R6 together comprise 2-8 non-hydrogen atoms. In some embodiments, the anion, Xq~, is selected from Group 2 or 3.
In some embodiments, wherein R3, R4, R5 and R6 are identical, R1 and R2 are identical, and R1 and R3 are different, R1 and R2 together comprise 2-8 non-hydrogen atoms. In some embodiments, the anion, Xq", is selected from Group 2 or 3. In some embodiments,' wherein R1, R2, R3 and R4 are identical, R5 and R6 are identical, and R1 and R5 are different, R1 and R2 together comprise 2-8 non-hydrogen atoms. In some embodiments, the anion, Xq", is selected from Group 2 or 3.
In some embodiments, wherein R3, R4, R5 and R6 are identical, R1 and R2 are identical, and R1 and R3 are different, R3 and R4 together comprise 2-8 non-hydrogen atoms. In some embodiments, the anion, X ~, is selected from Group 2 or 3.
In some embodiments, R1, R2, R3 and R4 are identical, R5 and R6 are different and R1, R5 and R6 are different. In some embodiments, R1, R2, R3 and R4 are identical and are C2-20 alkyl, substituted Ci_6 alkyl, or C2-6 alkenyl, R5 is H, Ci_2o alkyl, substituted Q.6 alkyl, or C2-6 alkenyl, R6 is C2-20 alkyl, substituted Ci_6 alkyl, or C2.6 alkenyl, and R1 , R5 and R6 are different.
In some embodiments, R3, R4, R5 and R6 are identical, R1 and R2 are different and R1, R2 and R3 are different. In some embodiments, R3, R4, R5 and R6 are identical and are C2.2o alkyl, substituted C}.e alkyl, or C2-6 alkenyl, R1 and R2 are each independently H, Ci_2o alkyl, substituted C]_6 alkyl, or C2-6 alkenyl, and R1, R2 and R3 are different. In some embodiments, wherein R1, R2, R3 and R4 are identical, R5 and R6 are different and R1, R5 and R6 are different, R1, R2, R3 and R4 are ethyl. In some embodiments, R5 and R6 together comprise 1 -6 non- hydrogen atoms. In some embodiments, the anion, Xq~, is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.
In some embodiments, wherein R3, R4, R5 and R6 are identical, R1 and R2 are different and R1, R2 and R3 are different, R3, R4, R5 and R6 are ethyl. In some embodiments, R1 and R2 together comprise 1-6 non- hydrogen atoms. In some embodiments, the anion, Xq , is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.
In some embodiments, R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl.
In some embodiments, R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl. In some embodiments, R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl.
In some embodiments, R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is hexyl.
In some embodiments, R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1-carboxylethyl,
1 -carboxyl-2-hydroxypropyl, or l-carboxyl-2-methylpropyl. In some embodiments, R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-hydroxypropyl, or 1 -carboxyl-2-methylpropyl. In some embodiments, R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl. In some
embodiments, R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is (S)- 1-carboxylethyl, (S)-l -carboxyl-2-hydroxypropyl, or (S)-l -carboxyl-2-methylpropyl. In some embodiments, R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is (S)-l -carboxyl-2-hydroxypropyl, or
(S)-l -carboxyl-2-methylpropyl. In some embodiments, R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is (S)-l -carboxylethyl. In some embodiments,
R'-R6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
R1, R3 and R5 are -H and R2, R4 and R6 are phenyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are wo-propyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are /so-propyl and R5 and R6 are butyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are -H,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-hydroxypropyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-methylpropyl, or
R1, R2, R3 and R4 are ethyl, and R5 and R6, together with the nitrogen atom to which they are attached, are
2-carboxylpyrrolidinyl.
In some embodiments,
are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
R1, R3 and R5 are -H and R2, R4 and R6 are phenyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are iso-propyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are wo-propyl and R5 and R6 are butyl, R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are -H,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1 , R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-hydroxypropyl, or R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-methylpropyl.
In some embodiments,
R'-R6 are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are wo-propyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl, or
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl. In some embodiments,
are 2-hydroxyethyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are wo-propyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl, R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl, or
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl.
In some embodiments, one or more of R1, R2, R3, R4, R5 and R6 are chiral.
In some embodiments, one or more of R1, R2, R3, R4, R5 and R6 is (S)-l -carboxylethyl,
(S)- 1 -carboxyl-2-hydroxypropyl, or (S)- 1 -carboxyl-2-methylpropyl; or (S)- 1 -carboxyl-2-hydroxypropyl or (S)-l -carboxyl-2-methylpropyl; or (S)-l -carboxylethyl.
In some embodiments, R1 or R2 together comprise 3-7 non-hydrogen atoms, R3 and R4 together comprise 3-7 non-hydrogen atoms and R5 or R6 is chiral.
In some embodiments, R1 or R2 together comprise 3-7 non-hydrogen atoms, R3 and R4 together comprise 3-7 non-hydrogen atoms and R5 or R6 is (S)-l -carboxylethyl, (S)-l-carboxyl-2-hydroxypropyl, or
(S)-l -carboxyl-2-methylpropyl; or (S)-l-carboxyl-2-hydroxypropyl or (S)-l -carboxyl-2-methylpropyl; or (S)- 1 -carboxylethyl.
In some embodiments, one or more of R1 and R2, R3 and R4, and R5 and R6, together with the nitrogen atom to which they are attached, is independently -NH-CH(RA)-C02H, wherein RA is a side chain of a natural or non-natural alpha-amino acid.
Accordingly, in some embodiments, one or more of R1 and R2, R3 and R4, and R5 and R6, together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C02H.
In some embodiments, R1, R2, R3 and R4 are ethyl, and R5 and R6, together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C02H. In some embodiments, R1, R2, R3 and R4 are ethyl, and R5 and R6, together with the nitrogen atom to which they are attached, is -pyrrolidinyl-(S)-2-C02H.
In some embodiments, one or more of R1 and R2, R3 and R4, and R5 and R6, together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C02H, -NH(CH(CH3)C02H),
-NH(CH(CH(OH)CH3)C02H), or -NH(CH(CH(CH3)2)C02H); or - H(CH(CH3)C02H),
-NH(CH(CH(OH)CH3)C02H), or -NH(CH(CH(CH3)2)C02H); or -pyrrolidinyl-2-C02H,
-NH(CH(CH(OH)CH3)C02H) or -NH(CH(CH(CH3)2)C02H); or -NH(CH(CH(OH)CH3)C02H) or -NH(CH(CH(CH3)2)C02H); or -NH(CH(CH3)C02H).
In some embodiments, one or more of R1 and R2, R3 and R4, and R5 and R6, together with the nitrogen atom to which they are attached, is -pyrrolidinyl-(S)-2-C02H, -NH((5)-CH(CH3)C02H),
-NH(CH((S)-CH(OH)CH3)C02H), or -NH((S)-CH(CH3)C02H); or -NH((S)-CH(CH3)C02H),
-NH(CH((S)-CH(OH)CH3)C02H) or -NH((S)-CH(CH(CH3)2)C02H); or -pyrrolidinyl-(S)-2-C02H, -NH(CH((S)-CH(OH)CH3)C02H) or -NH((S)-CH(CH(CH3)2)C02H);
or -NH(CH((S)-CH(OH)CH3)C02H) or -NH((5)-CH(CH(CH3)2)C02H); or -NH((S)-CH(CH3)C02H).
In some embodiments, one or more of R1 - R6 is independently -CH(RA)-C02H, wherein RA is a side chain of a natural or non-natural alpha-amino acid, provided that the side chain does not link to the alpha-amino group.
In some embodiments, one or more of R1 - R6 is independently -CH(CH3)C02H,
-CH(CH(OH)CH3)C02H, or -CH(CH(CH3)2)C02H; or -CH(CH(OH)CH3)C02H
or - CH(CH(CH3)2)C02H; or -CH(CH3)C02H.
In some embodiments, one or more of R1 - R6 is independently -(S)-CH(CH3)C02H,
-CH((S)-CH(OH)CH3)C02H, or -(S)-CH(CH(CH3)2)C02H; or -CH((5)-CH(OH)CH3)C02H
or -(S)-CH(CH(CH3)2)C02H; or -(S)-CH(CH3)C02H.
In some embodiments, one or more of R1 and R2, R3 and R4, and R5 and R6, together with the nitrogen atom to which they are attached, are independently
-N(Ci_6 alkyl)-CH(RA)-C02(Ci.6 alkyl), wherein RA is a side chain of a natural or non-natural alpha-amino acid, provided that the side chain does not link to the alpha-amino group.
In some embodiments, one or more of R1 and R2, R3 and R4, and R5 and R6, together with the nitrogen atom to which they are attached, are independently -N(Ci_6 alkyl)-CH(RA)-C02H, wherein RA is a side chain of a natural or non-natural alpha-amino acid, provided that the side chain does not link to the alpha-amino group. In some embodiments, one or more of R1 and R2, R3 and R4, and R5 and R6, together with the nitrogen atom to which they are attached, are independently -NH-CH(RA)-C02(Ci_6 alkyl), wherein RA is a side chain of a natural or non-natural alpha-amino acid.
Accordingly, in some embodiments, one or more of R1 and R2, R3 and R4, and R5 and R6, together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C02(Ci.6 alkyl). In some embodiments, R1 and R2 are identical, R3 and R4 are identical, and R5 and R6 are identical, and R1, R3 and R5 are different.
In some embodiments, R1 and R2 are different, R3 and R4 are different, and R5 and R6 are different, R1, R3 and R5 are identical, and R2, R4 and R6 are different.
In some embodiments, R1 and R2 are different, R3 and R4 are different, and R5 and R6 are identical, R1 and R3 are identical, R1 and R5 are different, R2 and R4 are identical, and R2 and R6 are different. In some embodiments, wherein R1 and R2 are different, R3 and R4 are different, and R5 and R6 are identical, R1 and R3 are identical, R1 and R5 are different, R2 and R4 are identical, and R2 and R6 are different, R1 is butyl and R2 is methyl. In some embodiments, R5 and R6 together comprise 1 -6 non- hydrogen atoms.
In some embodiments, R1 and R2 are different, R3 and R4 are different, and R5 and R6 are different, R1, R3 and R5 are identical, R2 and R4 are identical, and R2 and R6 are different.
In some embodiments, R1 and R2 are different, R3 and R4 are different, and R5 and R6 are different, R1 and R3 are identical, R1 and R5 are different, R2 and R4 are identical, and R2 and R6 are different.
In some embodiments, wherein R1 and R2 are different, R3 and R4 are different, and R5 and R6 are different, R1 and R3 are identical, R1 and R5 are different, R2 and R4 are identical, and R2 and R6 are different, R1 and R2 together comprise 3-7 non-hydrogen atoms. In some embodiments, R1 is butyl and R2 is methyl.
In some embodiments, R1 and R2 are different, R3 and R4 are different, R5 and R6 are different, and R1, R2, R3, R4, R5 and R6 are different.
In some embodiments, R1, R2, R3, R4 and R5 are identical and R1 and R6 are different.
In some embodiments, R1, R2 and R3 are identical, R3 and R4 are different, and R4, R5 and R6 are identical.
In some embodiments, R1, R2 and R3 are identical, R3 and R4 are different, R5 and R6 are identical, and R2, R4 and R6 are different.
In some embodiments, R1 and R2 are identical, R3 and R4 are identical, and R1, R3, R5 and R6 are different.
In some embodiments, RD is (4-methylpiperazinyl)methyl, 2,3-difluoro-4-pyridyl, 3-fluoropyridyl, 5-methyl-2-furyl, [2-(trimethylsilyl)ethoxy]methyl, or bromomethyl.
In some embodiments, RF is perfluoro C1.12 alkyl.
In some embodiments, RF is perfluoro C2_i2 alkenyl having one or more double bonds or perfluoro C2-n alkynyl having one or more triple bonds.
In some embodiments, RF is selected from pentafluoroallyl, heptafluorobut-2-enyl, heptafluorobut-3-enyl, wo-heptafluorobutenyl, sec-heptafluorobutenyl, nonafluoropent-4-enyl, wo-nonafluoropentenyl, and -C6Fi i . In some embodiments, RF is selected from fluoroethynyl, trifluoropropyn-l -yl, trifluoroprop-2-ynyl, pentafluorobut-2-ynyl, pentafluorobut-3-ynyl, heptafluoropent-3-ynyl, heptafluoropent-4-ynyl, and nonafluorohexynyl.
In some embodiments, RF is selected from trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, -C(CF3)3, -CF2N(CF3)CF3, -CF2OCF3, -CF2S(0)CF3,
-CF2S02CF3, -C2F4N(C2F5)C2F5, -CF=CF2, -C(CF3)=CFCF3, -CF2CF=CFCF3,
-CF=CFN(CF3)CF3, -CF2S02F, -C(CF3)=CFCF3, -CF2CF=CFCF3, and -CF=CFN(CF3)CF3.
In some embodiments, RF is trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.
In some embodiments, RF is perfluorophenyl optionally substituted by one or more perfluoro C,.6 alkyl. In some embodiments, RG is perfluoro C2_i2 alkyl.
In some embodiments, R° is perfluoro C2.]2 alkenyl having one or more double bonds or perfluoro C2_i2 alkynyl having one or more triple bonds.
In some embodiments, RG is selected from pentafluoroallyl, heptafluorobut-2-enyl, heptafluorobut-3-enyl, wo-heptafluorobutenyl, seoheptafluorobutenyl, nonafluoropent-4-enyl, wo-nonafluoropentenyl, and -C6Fu.
In some embodiments, RG is selected from fluoroethynyl, trifluoroprop-l-ynyl, trifluoroprop-2-ynyl, pentafluorobut-2-ynyl, pentafluorobut-3-ynyl, heptafluoropent-3-ynyl, heptafluoropent-4-ynyl, and nonafluorohexynyl.
In some embodiments, RG is selected from pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, — C(CF3)3, -CF2N(CF3)CF3, -CF2OCF3, -CF2S(0)CF3, -CF2S02CF3,
-C2F4N(C2F5)C2F5, -CF=CF2, -C(CF3)=CFCF3, -CF2CF=CFCF3, -CF=CFN(CF3)CF3,
-CF2S02F, -C(CF3)=CFCF3, -CF2CF=CFCF3 or -CF=CFN(CF3)CF3.
In some embodiments, RG is pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.
In some embodiments, RG is perfluorophenyl optionally substituted by one or more perfluoro Ci_6 alkyl. In some embodiments, wherein two or more RF or two or more RG are present in the anion, Xq~, any two or more RF or any two or more RG may be connected by a single or a double bond to form a cyclic, bicyclic or polycyclic anion.
In some embodiments, RJ is phenyl substituted with methyl, ethyl, propyl, «ο-propyl, tert-butyl, nitro, fluoro, chloro, bromo, iodo, hydroxyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy,
trifluoromethylsulfonyl, -NH2, or -N(CH3)2. In some embodiments, RJ is phenyl disubstituted with methyl, fluoro, chloro, bromo, hydroxyl, or methoxy.
In some embodiments, RJ is 5-fluoro-2-methylphenyl, 3,4,5-trimethoxyphenyl, or 2,4,5-trimethylphenyl.
In some embodiments, R is perfluorophenyl. In some embodiments, RJ is heteroaryl or heterocyclyl optionally substituted by one or more RK, wherein the heteroaryl or heterocyclyl is acridinyl, benz-2, 1 ,3 -oxadiazolyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzofuryl, benzopyrazolyl, benzothiazolyl, benzothienyl, benzoxazolyl, carbazolyl, cinnolinyl, furyl, imidazolyl, IH-indolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolyl, quinazolinyl, quinolinyl, tetrazolyl, thiadiazolyl, thiazolyl, thienyl, 2H-thiopyranyl, 4H-thiopyranyl, or triazolyl.
In some embodiments, the anion, Xq~ is selected from [(CF3S02)2N]", [(CF3S02)NC(0)CF3]",
[(FS02)2N]- [CF3CF2S03]", [(C2F5S02)2N]", [(C2F5S02)3C]-, [(FS02)3C]", [CF3CF2C(0)C>r,
[P(C2F5)3F3]-, [P(CF3)3F3]-, [P(C2F4H)(CF3)2F3] , [P(C2F3H2)3F3] , [P(C2F5)(CF3)2F3] ~, [P(C6F5)3F3] , [P(C3F7)3F3]-, [P(C4F9)3F3]-, [P(C2F5)2F4]-, [(C2F5)2P(0)Or, [(C2F5)P(0)02]2- [P(C6F5)2F4]- [(CF3)2P(0)Or, [(C4F9)2P(0)0]-, [CF3P(0)02]2 [BF3(CF3)]', [BF2(C2F5)2r, [BF3(C2F5)F, [BF2(CF3)2]", [B(C2F5)4]", [BF3(CN)]^, [BF2(CN)2r, [B(CN) ~, [B(CF3)4]", [N(CF3)2]", [N(CN2)2]",
Figure imgf000057_0001
Figure imgf000058_0001
In some embodiments, the anion, Xq , is selected from [P(CnF2n+i-mHm)yF6-y] , [BFZRF 4_Z] a d
[BF2(CN)4-Z]~, wherein n is 1 to 20; m is 0, 1, 2, or 3; y is 1, 2, 3, or 4; and z is 0, 1, 2, or 3.
In some embodiments, n is 1 to 12.
In some embodiments, the anion, Xq~ is [B(CN)4]~, [(C2F5)3PF3]", [(C2F5)2PF4]", [(C4F9)3PF3]~
[(C3F7)3PF3]", [B(C2F5)F3]", or [B(CF3)4]". In some embodiments, the anion is [B(CN)4]", [(C2F5)3PF3]", or [B(C2F5)F3] . In some embodiments, the anion, Xq~ is a group 1 anion selected from F~, Br~, Γ, [HF2]", [SCN]~,
[NCO]- [ΝΟ3Γ, [AlC r, [A12C17]-, [PF6]-, and [SnCl3]-
In some embodiments, the anion, Xq~, is the group 1 anion [SnCl3]~.
In some embodiments, the anion, Xq~, is a group 1 anion selected from F-, Br~, Γ, [HF2]-, [SCN]~,
[NCO]" [NO3]- [A1C14]- [A12C17]-, and [PF6]". In some embodiments, the anion, Xq_, is a group 2 anion selected from [SeCN]-, [CF3SO3]-, [FHOMe]-, [FHOEtr, [FHOPr]-, [MeOS03]~ [EtOS03]", [(BuO)2P(0)0]-, [CH3C6H4S03]",
((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4- trifluoroborate, 5-methylfuran-2-trifluoroborate, [2-(trimethylsilyl)ethoxy]methyltrifluoroborate, and [BrCH2BF3]".
In some embodiments, the anion, Xq", is a group 2 anion selected from [SeCN]", [CF3S03]", [FHOMe]", [FHOEt]" [FHOPr]" [MeOS03]", [EtOS03]", [(BuO)2P(0)0]", and [CH3C6H4S03]". In some embodiments, the anion, Xq", is a group 3 anion selected from [(CF3S02)2N]~,
[(CF3S02)NC(0)CF3r, [(FS02)2N]-, [CF3CF2S03]" [C^SO,]", [(CF3CF2S02)2N)]" [(CF3S02)3C]-, [(FS02)3C]-, [P(C2F5)3F3]-, [(CF3)2P(0)0]-, [(C2F5)2P(0)0]-, [(CF30)2P(0)0]", [(C2F50)2P(0)0]" [BF3(CF3)3]" [BF3(C2F5)3]" [BF3(CN)]", [B(CN)4]", [N(CN)2]" and [C(CN)3]".
In some embodiments, the anion, Xq", is selected from F", Br", Γ, [HF2]~, [SCN]", [NCO]", [N03]", [A1C14]-, [A12C17]- [PF6]-, [SnCl3]",
[SeCN] ", [CF3S03]", [FHOMe]", [FHOEt] ", [FHOPr] , [MeOS03]" [EtOS03]", [(BuO)2P(0)0]"
[CH3C6H4S03]", ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate,
3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]~,
[(CF3S02)2N]-, [(CF3S02)NC(0)CF3]-, [(FS02)2N]", [CF3CF2S03]-, [C4F9S03]-, [(CF3CF2S02)2N)]-,
[(CF3S02)3C] - [(FS02)3C] - [P(C2F5)3F3]-, [(CF3)2P(0)0]", [(C2F5)2P(0)0]", [(CF30)2P(0)0] ,
[(C2F50)2P(0)0]- [BF3(CF3)3]- [BF3(C2F5)3]-, [BF3(CN)]" [B(CN)4]", [N(CN)2]", and [C(CN)3]".
In some embodiments, the anion, Xq~, is selected from F", Br~, Γ, [HF2]~ [SCN]", [NCO]~, [N03]~, [A1C14]", [A12C17]-, [PF6]-,
[SeCN]", [CF3S03]", [FHOMe]', [FHOEt]" [FHOPr]" [MeOS03]" [EtOS03]", [(BuO)2P(0)0]"
[CH3C6H4S03]", ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2N]", [(CF3S02)NC(0)CF3]", [(FS02)2N]" [CF3CF2S03]" [C4F9S03]" [(CF3CF2S02)2N)]" [(CF3S02)3Cr, [(FS02)3C]-, [P(C2F5)3F3]" [(CF3)2P(0)0]", [(C2F5)2P(0)0]" [(CF30)2P(0)0]-,
[(C2F50)2P(0)0]", [BF3(CF3)3] , [BF3(C2F5)3]" [BF3(CN)]", [B(CN)4]", [N(CN)2r, and [C(CN)3]-.
In some embodiments, the anion, Xq", is selected from F~, Br", Γ, [HF2]", [SCN]", [NCO]", [N03]", [A1C14]-, [A12C17]-, [PF6]", [SnCl3]"
[SeCN]", [CF3S03]~, [FHOMe]", [FHOEt]", [FHOPr]", [MeOS03]", [EtOS03]", [(BuO)2P(0)0]",
Figure imgf000059_0001
[(CF3S02)2N]- [(CF3S02)NC(0)CF3r, [(FS02)2N]", [CF3CF2S03]", [C^SO,]", [(CF3CF2S02)2N)]" [(CF3S02)3C]" [(FS02)3C]", [P(C2F5)3F3]", [(CF3)2P(0)0]", [(C2F5)2P(0)0]-, [(CF30)2P(0)0]~
[(C2F50)2P(0)0]", [BF3(CF3)3]", [BF3(C2F5)3]" [BF3(CN)]" [B(CN)4]", [N(CN)2]", and [C(CN)3]". In some embodiments, the anion, Xq", is selected from F~, Br-, Γ, [HF2]~, [SCN]-, [NCO]", [N03]- [AICI4]- [A12C17]-, [PF6]-
[SeCN]-, [CF3SO3]", [FHOMe]-, [FHOEt]", [FHOPr]- [MeOS03]-, [EtOS03]-, [(BuO)2P(0)0]',
[CF^C^SO,]-,
[(CF3S02)2N]-, [(CF3S02)NC(0)CF3r, [(FS02)2N]-, [CF3CF2S03]-, [C^SO,]-, [(CF3CF2S02)2N)]-, [(CF3S02)3Cr, [(FS02)3C]- [P(C2F5)3F3]-, [(CF3)2P(0)0]-, [(C2F5)2P(0)0]-, [(CF30)2P(0)0]- [(C2F50)2P(0)0]- [BF3(CF3)3]-, [BF3(C2F5)3]-, [BF3(CN)]-, [B(CN)4]- [N(CN)2] , and [C(CN)3]-
In some embodiments, the anion, Xq~, is [NH2-CH(RA)C(0)0]".
Accordingly, in some embodiments, the anion, Xq~, is [pyrrolidinyl-2-COO]~. In some embodiments, the anion, Xq", is selected from F-, Br- Γ, [N03]", [PF6]- [SnCl3] ~ [SCN]", [NCO] , [CF3S03r, [CH3OSO3]-, [CJHSOSOJ]- [C6F5S03]-, [(BuO)2P(0)0]- [CH3C6H4S03]",
[(CF3S02)2N]-, [(FS02)2N]-, [C2F5S03]-, [(C2F5S02)2N)]" [P(C2F5)3F3]- [B(CN)4]- and [N(CN)2]".
In some embodiments, the anion, Xq", is selected from F~, Br-, Γ, [N03]- [SnCl3]-, [SCN]-, [NCO]-, [CF3SO3]- [CH3OSO3]-, [(BuO)2P(0)0]-, [CH3C6H4S03]-, [(CF3S02)2N]-, [P(C2F5)3F3]-, [B(CN)4]-, and [N(CN)2]-.
In some embodiments, the anion, Xq-, is selected from F-, Β , [N03]-, [PF6]-, [SCN]- [CF3S03]-,
[CH3OSO3]-, [C2H5OS03]- [C6F5S03]-, [CH3C6H S03]-, [(CF3S02)2N]-, [(FS02)2N]-, [C2F5S03]-, [(C2F5S02)2N)]- and [N(CN)2]-.
In some embodiments, the anion, Xq- is selected from Br", Γ, [N03]- [PF6]-, [SnCl3]-, [SCN]-, [NCO]- [CF3SO3]- [CH3OSO3]- [C2H5OS03]- [C6F5S03r, [(BuO)2P(0)0]- [CH3C6H4S03]-, [(CF3S02)2N]-, [(FS02)2N]-, [C2F5S03r, [(C2F5S02)2N)]-, [P(C2F5)3F3]-, [B(CN)4]-, and [N(CN)2]-.
In some embodiments, the anion, Xq-, is selected from Br-, [N03]-, [PF6]-, [SCN]-, [CF3SO3]-,
[CH3OSO3]-, [C2H5OS03]- [C6F5S03]-, [CH3C6H4S03]", [(CF3S02)2N]-, [(FS02)2N]-, [C2F5S03]- [(C2F5S02)2N)]- and [N(CN)2]-. In some embodiments, the anion, Xq- is selected from [N03]- [PF6]- [SnCl3]-, [SCN]-, [NCO]-,
[CF3S03r, [CH3OS03]-, [C2H5OS03]-, [C6F5S03]- [(BuO)2P(0)0]-, [CHJC^SOJ]-, [(CF3S02)2N]- [(FS02)2N]-, [C2F5S03]-, [(C2F5S02)2N)]-, [P(C2F5)3F3]-, [B(CN)4]-, and [N(CN)2]-.
In some embodiments, the anion, Xq-, is selected from [N03]-, [PF6]-, [SCN] , [CF3S03]-, [CH3OS03]-, [C2H5OS03]-, [C6F5S03]- [CHJC^SOJF, [(CF3S02)2N]- [(FS02)2N]- [C2F5S03]-, [(C2F5S02)2N)]- and [N(CN)2]-. In some embodiments, the anion, Xq~ is selected from [PF6]~, [CF3S03]", [CH3OS03]", [C2H5OS03]", [CeFsSO,]-, [CH^^SO,]", [(CF3S02)2N]", [(FS02)2N]-, [C2F5S03]-, [(C2F5S02)2N)]" and [N(CN)2]"
In some embodiments, the anion, Xq", is F~.
The invention also contemplates embodiments in which the cation, Y^, is as identified in any of the embodiments disclosed above and the anion, X ", is as identified in any of the embodiments disclosed above.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, C 2o alkyl, substituted Ci_2o alkyl, C2.2o alkenyl, substituted C2.20 alkenyl, aryl, and substituted aryl; and
R4 and R6 are each independently selected from C -2o alkyl, substituted Ci.2o alkyl, C2.2o alkenyl, substituted C2.20 alkenyl, aryl, and substituted aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl; and
the anion, Xq" is selected from F", Br", Γ, [HF2]", [SCN]", [NCO] ", [N03]~, [AICL,]" [A12C17]~ [PF6]", [SnCl3]- [SeCN]-, [CF3S03]", [FHOMef, [FHOEt]", [FHOPr]", [MeOS03]", [EtOS03]", [(BuO)2P(0)0]",
[CH3C6H4S03] , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifIuoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2N]", [(CF3S02)NC(0)CF3r, [(FS02)2N]~ [CF3CF2S03] ", [C4F9SO3]- [(CF3CF2S02)2N)]" [(CF3S02)3C]-, [(FS02)3C]-, [P(C2F5)3F3]", [(CF3)2P(0)0]- [(C2F5)2P(0)0]" [(CF30)2P(0)0]-
[(C2F50)2P(0)0]-, [BF3(CF3)3]^, [BF3(C2F5)3]-, [BF3(CN)]" [B(CN)4]-, [ (C )2]-, and [C(CN)3] .
In some embodiments, R1, R2 and R3 are each independently selected from -H, Ci.2o alkyl, substituted Ci_20 alkyl, C2.2o alkenyl, substituted C2.2o alkenyl, aryl, and substituted aryl; and
R4 is selected from C2-2o alkyl, substituted Ci-20 alkyl, C2.20 alkenyl, substituted C2.20 alkenyl, aryl, and substituted aryl; and
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl; and
the anion, Xq", is selected from F", Br", Γ, [HF,]" [SCN]", [NCO]", [NO3]", [AICI4]", [AI2CI7]", [PF6]" [SnCl3]",
[SeCN]' [CF3S03]-, [FHOMe]", [FHOEt]", [FHOPr]", [MeOS03]", [EtOS03]", [(BuO)2P(0)0]",
[CH3C6H4S03]", ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2N]", [(CF3S02)NC(0)CF3]", [(FS02)2N]", [CF3CF2S03]", [C4F9S03]", [(CF3CF2S02)2N)]", [(CF3S02)3C]" [(FS02)3C]- [P(C2F5)3F3]", [(CF3)2P(0)0]", [(C2F5)2P(0)0]-, [(CF30)2P(0)0]"
[(C2F50)2P(0)0]-, [BF3(CF3)3]-, [BF3(C2F5)3]", [BF3(CN)r, [B(CN)4]-, [ (CN)2]-, and [C(CN)3]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci.20 alkyl, C2_20 alkenyl, and aryl;
R4 and R6 are each independently selected from C2-2o alkyl, substituted Ci_2o alkyl, C2-20 alkenyl, and aryl; and
the anion, Xq", is selected from F", Br", Γ, [HF2]", [SCN]", [NCO]", [N03]', [AICU]"", [A12C17]~, [PF6]",
[Sncy-,
[SeCN]", [CF3S03]", [FHOMe]", [FHOEt]", [FHOPr]", [MeOS03]-, [EtOS03]", [(BuO)2P(0)0]",
[CH3C6H4S03]~, ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]~,
[(CF3S02)2N]- [(CF3S02)NC(0)CF3]-, [(FS02)2N]", [CF3CF2S03]" [C4F9S03]", [(CF3CF2S02)2N)]", [(CF3S02)3C]- [(FS02)3C]- [P(C2F5)3F3]- [(CF3)2P(0)0]" [(C2F5)2P(0)0]", [(CF30)2P(0)0]",
[(C2F50)2P(0)0]-, [BF3(CF3)3]- [BF3(C2F5)3]-, [BF3(CN)]", [B(CN)4]~, [N(CN)2]", and [C(CN)3]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci.20 alkyl, and C2-20 alkenyl;
R4 and R6 are each independently selected from C2.20 alkyl, substituted C].2o alkyl, and C2.2o alkenyl; and the anion, Xq" is selected from F , Br", Γ, [HF2]~, [SCN] , [NCO]" [N03] [AICU]", [A12C17]", [PF6]", [SeCN]", [CF3S03] " [FHOMe]-, [FHOEt]", [FHOPr]", [MeOS03]", [EtOS03]", [(BuO)2P(0)0]",
[CH3C6H4S03]~, ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2N]", [(CF3S02)NC(0)CF3]", [(FS02)2N]" [CF3CF2S03]", [C4F9S03]", [(CF3CF2S02)2N)]", [(CF3S02)3Cr, [(FS02)3C]", [P(C2F5)3F3]", [(CF3)2P(0)0]", [(C2F5)2P(0)0]-, [(CF30)2P(0)Or,
[(C2F50)2P(0)0]-, [BF3(CF3)3]-, [BF3(C2F5)3]-, [BF3(CN)]" [B(CN)4]", [N(CN)2]-, and [C(C )3]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted C1.6 alkyl, C2.6 alkenyl, and aryl;
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci_6 alkyl, C2_6 alkenyl, and aryl; and
the anion, Xq", is selected from F", Br", Γ, [HF2]", [SCN]-, [NCO]" [N03]" [AICU]", [A12C17]", [PF6]", [SnCl3]",
[SeCN]", [CF3S03]- [FHOMe]", [FHOEt]", [FHOPr]", [MeOS03]", [EtOS03]", [(BuO)2P(0)0]",
[CH3CeH4S03]", ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate, [2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]~,
[(CF3S02)2N]", [(CF3S02)NC(0)CF3r, [(FS02)2N]", [CF3CF2S03r, [C4F9S03]-, [(CF3CF2S02)2N)]-, [(CF3S02)3C]-, [(FS02)3C]-, [P(C2F5)3F3]-, [(CF3)2P(0)0]" [(C2F5)2P(0)0]- [(CF30)2P(0)0]- [(C2F50)2P(0)0]- [BF3(CF3)3]-, [BF3(C2F5)3]-, [BF3(CN)]", [B(CN)4]", [N(CN)2]", and [C(CN)3]" In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci-2o alkyl, substituted Ci_6 alkyl, and C2.<, alkenyl;
R4 and R6 are each independently selected from C2.20 alkyl, substituted Ci_6 alkyl, and C2.6 alkenyl; and the anion, Xq_, is selected from F", Br", Γ, [HF2]", [SCN]", [NCO]-, [N03T, [A1C ]~ [A12C17]-, [PF6]~, [SeCN]-, [CF3S03r, [FHOMe]", [FHOEt]", [FHOPrf, [MeOS03]" [EtOS03] ~ [(BuO)2P(0)0]
[CH3C6H4S03]~, ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3] ,
[(CF3S02)2N]-, [(CF3S02)NC(0)CF3]- [(FS02)2N]", [CF3CF2S03]", [C^SO,]", [(CF3CF2S02)2N)]", [(CF3S02)3C]-, [(FS02)3C]- [P(C2F5)3F3]-, [(CF3)2P(0)0]", [(C2FS)2P(0)0]- [(CF30)2P(0)0]",
[(C2F50)2P(0)0]-, [BF3(CF3)3]- [BF3(C2F5)3] ~, [BF3(CN)]" [B(CN)4]-, [N(CN)2]", and [C(CN)3]"
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, hydroxy Ci- alkyl, carboxyl Q-6 alkyl, Ci_6 alkoxycarbonyl C|.6 alkyl, C .e alkoxy C e alkyl, Q-e alkyl-NH2, Ci-6 alkylamino Ci_6 alkyl, carboxyl hydroxy Ci-6 alkyl, C2-e alkenyl, and aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl C]_6 alkyl, Ci_6 alkoxycarbonyl Cue alkyl, Ci_6 alkoxy Ci.e alkyl, d_6 alkyl-NH2, C[.6 alkylamino ue alkyl, carboxyl hydroxy C e alkyl, C2-e alkenyl, and aryl; and
the anion, Xq~ is selected from F", ΒΓ, Γ, [HF2]", [SCN]-, [NCO] " [N03]_, [AICL,]-, [A12C17]~ [PF6]" [SnCl3]-,
[SeCN]", [CF3S03]-, [FHOMe]" [FHOEt]", [FHOPr]", [MeOS03]", [EtOS03]", [(BuO)2P(0)0]",
[CH3CeH4S03] , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy] methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2N]", [(CF3S02)NC(0)CF3]", [(FS02)2N]", [CF3CF2S03]", [C4F9S03]", [(CF3CF2S02)2N)]", [(CF3S02)3C]-, [(FS02)3C]- [P(C2F5)3F3]-, [(CF3)2P(0)0]-, [(C2F5)2P(0)0]-, [(CF30)2P(0)0]"
[(C2F50)2P(0)0] , [BF3(CF3)3]-, [BF3(C2F5)3]-, [BF3(CN)]", [B(CN)4]", [N(CN)2]", and [C(CN)3]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, hydroxy Cj.6 alkyl, carboxyl Ci.e alkyl, Ci_6 alkoxycarbonyl Ci-6 alkyl, Cue alkoxy Cj.6 alkyl, C].6 alkyl-NH2, C]-6 alkylamino C,.6 alkyl and C2-6 alkenyl; and R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl Ci_6 alkyl, Ci-6 alkoxycarbonyl Ci-6 alkyl, Ci-6 alkoxy Ci-6 alkyl, Ci„6 alkyl-NH2, C,.6 alkylamino Ci-6 alkyl and C2.6 alkenyl; and
the anion, Xq_, is selected from F, Br", Γ, [HF2]~, [SCN]~, [NCO]-, [N03]", [AICI4]", [A12C17]". [PF6r, [SeCN]- [CF3SO3]- [FHOMe]", [FHOEt]-, [FHOPr] , [MeOS03]", [EtOS03]", [(BuO)2P(0)0]',
[CH3C6H SO3]", ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2N]- [(CF3S02)NC(0)CF3]-, [(FS02)2N]", [CF3CF2S03]- [C^SOa]" [(CF3CF2S02)2N)]-, [(CF3S02)3C]-, [(FS02)3C]-, [P(C2F5)3F3]-, [(CF3)2P(0)0] , [(C2F5)2P(0)0] -, [(CF30)2P(0)0]-,
[(C2F50)2P(0)0]-, [BF3(CF3)3]- [BF3(C2F5)3]-, [BF3(CN)]", [B(CN)4]-, [N(CN)2]- and [C(CN)3]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci-20 alkyl, hydroxy Ci-6 alkyl, carboxyl Ci_6 alkyl, carboxyl hydroxy Ci.6 alkyl, C2-6 alkenyl, and aryl; and
R4 and R6 are each independently selected from C2-2o alkyl, hydroxy Ci_6 alkyl, carboxyl Ci-6 alkyl, carboxyl hydroxy C1-6 alkyl, C2-6 alkenyl, and aryl; and
the anion, Xq_, is selected from F", Br", Γ, [HF2]", [SCN]", [NCO]", [Ν03Γ, [AIC ]", [A12C17]-, [PF6]", [SnCl3]-
[SeCN]- [CF3SO3]", [FHOMe]" [FHOEt]-, [FHOPr] " [MeOS03]", [EtOS03]", [(BuO)2P(0)0]- [CH3C6H4SO3]-, ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]~,
[(CF3S02)2N]-, [(CF3S02)NC(0)CF3]-, [(FS02)2N]", [CF3CF2S03]", [C4F9S03]- [(CF3CF2S02)2N)]" [(CF3S02)3C]- [(FS02)3C]-, [P(C2F5)3F3]-, [(CF3)2P(0)0]" [(C2F5)2P(0)0] , [(CF30)2P(0)0]"
[(C2F50)2P(0)0]- [BF3(CF3)3]- [BF3(C2F5)3]", [BF3(CN)r, [B(CN)4]" [N(CN)2]-, and [C(CN)3]". In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci.2o alkyl, hydroxy Ci-6 alkyl, carboxyl Ci_6 alkyl, and C2.6 alkenyl;
R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Ci-6 alkyl, carboxyl Ci_6 alkyl, and C2-6 alkenyl; and
the anion, Xq~, is selected from F", Br", Γ, [HF2]~ [SCN]" [NCO]", [N03]_, [AICI4]", [Al2Cl7r, [PF6]" [SeCN] [CF3SO3] , [FHOMe] [FHOEt] [FHOPr]", [MeOSO,]", [EtOS03]", [(BuO)2P(0)0] ,
[CH3C6H4S03]", ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]~,
[(CF3S02)2N]-, [(CF3S02)NC(0)CF3]- [(FS02)2N]~ [CF3CF2S03r, [C^SO,]", [(CF3CF2S02)2N)]- [(CF3S02)3C]- [(FS02)3C]-, [P(C2F5)3F3]-, [(CF3)2P(0)0]- [(C2F5)2P(0)0]- [(CF30)2P(0)Or,
[(C2F50)2P(0)0]- [BF3(CF3)3]- [BF3(C2F5)3]- [BF3(CN)]", [B(CN)4]" [N(CN)2r, and [C(CN)3]- In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, hydroxy C]-6 alkyl, and C2-6 alkenyl;
R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl C]-6 alkyl, and C2-6 alkenyl; and
the anion, Xq", is selected from F~, Br , Γ, [HF2]~ [SCN]", [NCO]" [N03]~~, [AICU]", [A12C17]", [PF6]", [SeCN]", [CF3SO3]", [FHOMe]", [FHOEt]", [FHOPr]", [MeOS03]", [EtOS03]~, [(BuO)2P(0)0]",
[CH3C6H4S03]~, ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2N] - [(CF3S02)NC(0)CF3]-, [(FS02)2N]" [CF3CF2S03] , [C4F9S03]-, [(CF3CF2S02)2N)]~ [(CF3S02)3C]-, [(FS02)3Cr, [P(C2F5)3F3]-, [(CF3)2P(0)0]-, [(C2F5)2P(0)0]-, [(CF30)2P(0)0]"
[(C2F50)2P(0)0]- [BF3(CF3)3]" [BF3(C2F5)3]-, [BF3(CN)]~, [B(CN)4]-, [N(CN)2]" and [C(CN)3]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_20 alkyl, substituted Ci-20 alkyl, C2.20 alkenyl, and aryl;
R4 and R6 are each independently selected from C2-2o alkyl, substituted Ci.2o alkyl, C2.2o alkenyl, and aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl; and
the anion, Xq", is selected from IT, Br", Γ, [N03]" [PF6]", [SnCl3]", [SCN]', [NCO]", [CF3S03]"
[CH3OS03]-, [C2H5OS03]-, [C6F5S03r, [(BuO)2P(0)0] , [CI^C^SO,]", [(CF3S02)2N] [(FS02)2N]~ [C2F5S03]-, [(C2F5S02)2N)]-, [P(C2F5)3F3]-, [B(CN)4]" and [N(CN)2]-.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci_20 alkyl, C2.20 alkenyl, and aryl;
R4 and R6 are each independently selected from C2.2o alkyl, substituted Ci-2o alkyl, C2-20 alkenyl, and aryl; and
the anion, Xq" is selected from F", Br", Γ, [N03]_, [PF6]", [SnCl3]", [SCN]", [NCO]", [CF3S03]",
[CH3OS03]-, [C2H5OS03]", [CeFjSO,]" [(BuO)2P(0)0]" [CH.C^SO,]" [(CF3S02)2N] , [(FS02)2N]" [C2F5S03]", [(C2F5S02)2N)]-, [P(C2F5)3F3]", [B(CN)4]", and [N(CN)2]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_20 alkyl, substituted Ci.20 alkyl, C2-20 alkenyl, and aryl;
R4 and R6 are each independently selected from C2.2o alkyl, substituted Ci_2o alkyl, C2_2o alkenyl, and aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl; and the anion, Xq_, is selected from Br", Γ, [Ν03]~, [PF6]" [SnCl3]~, [SCN]", [NCOf, [CF3S03]_, [CH3OS03]_, [C2H5OS03]-, [CeFjSOa]-, [(BuO)2P(0)0]" [CH3C6H4S03] ", [(CF3S02)2N]-, [(FS02)2N]~ [C2F5S03]- [(C2F5S02)2N)]-, [P(C2F5)3F3]- [B(CN)4]-, and [N(CN)2]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_ o alkyl, substituted Ci-20 alkyl, C2.20 alkenyl, and aryl;
R4 and R6 are each independently selected from C2.2o alkyl, substituted C io alkyl, C2_2o alkenyl, and aryl; and
the anion, Xq_, is selected from Br", Γ, [N03]~, [PF6]_, [SnCl3]", [SCN]", [NCO]-, [CF3S03]-, [CH3OS03]", [C2H5OSO3]-, [CeFjSOj]", [(BuO)2P(0)0]-,
Figure imgf000066_0001
[(CF3S02)2N]-, [(FS02)2Nr, [C2F5S03] , [(C2F5S02)2N)]-, [P(C2F5)3F3]-, [B(CN)4]", and [N(CN)2]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci_20 alkyl, and C2.20 alkenyl;
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci_20 alkyl, and C2_20 alkenyl; and the anion, Xq , is selected from Br , [N03]", [PF6]", [SCN]^, [CF3S03] , [CH3OS03]", [C2H5OS03]-,
[C6F5S03]-, [CH3C6H4S03]-, [(CF3S02)2N]-, [(FS02)2N]-, [C2F5S03]- [(C2F5S02)2N)]- and [N(CN)2]"
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_20 alkyl, substituted Ci-6 alkyl, and C2-6 alkenyl;
R4 and R6 are each independently selected from C2-2o alkyl, substituted Ci_6 alkyl, and C2-6 alkenyl; and the anion, Xq~, is selected from Br", [N03]", [PF6]", [SCN]~, [CF3S03] ~, [CH3OS03]", [C2H5OS03]- [C6F5S03]- [CH3C6H4S03]-, [(CF3S02)2N]-, [(FS02)2N]-, [C2F5S03]-, [(C2F5S02)2N)]- and rN(CN)2r.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci_20 alkyl, hydroxy C e alkyl, carboxyl Ci.6 alkyl, and C2.e alkenyl;
R4 and R6 are each independently selected from C2.2o alkyl, hydroxy Ci_6 alkyl, carboxyl Ci_6 alkyl, and C2-6 alkenyl; and
the anion, Xq_, is selected from Br", [N03]", [PF6]", [SCN]" [CF3S03]", [CH3OS03]" [C2H5OS03]-,
[C6F5S03]- [CH3C6H4S03]-, [(CF3S02)2N]-, [(FS02)2N]" [C2F5S03r, [(C2F5S02)2N)]- and [N(CN)2]-.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, Ci-20 alkyl, hydroxy Ci-6 alkyl, and C2.6 alkenyl;
R4 and R6 are each independently selected from C2-2o alkyl, hydroxy Ci-6 alkyl, carboxyl Ci_6 alkyl, and C2-6 alkenyl; and
the anion, Xq~, is selected from Br", [N03]", [PF6]_, [SCN]", [CF3S03]", [CH3OS03]", [C2H5OS03] ~
[C6F5S03]-, [CH3C6H4S03]-, [(CF3S02)2N]" [(FS02)2N]", [C2F5S03]-, [(C2F5S02)2N)]" and [N(CN)2]-. In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, methyl, ethyl, w-propyl, wo-propyl, w-butyl, n-pentyl, n-hexyl, decyl, stearyl, 2-hydroxyethyl, allyl, and phenyl; and R4 and R6 are each independently selected from ethyl, w-propyl, wo-propyl, w-butyl, «-pentyl, ra-hexyl, decyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, l-carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl; or
R5 and R6, together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl; and the anion, Xq", is selected from F", Br", I", [N03]~ [SnCl3]", [SCN] , [NCO] _, [CF3S03]", [CH3OS03]", [(BuO)2P(0)0]-s [CH3C6H4S03]-, [(CF3S02)2N]-, [P(C2F5)3F3]", [B(CN)4]- and [N(CN)2]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, methyl, ethyl, w-propyl, zjo-propyl, «-butyl, «-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, allyl, and phenyl; and R4 and R6 are each independently selected from ethyl, n-propyl, zjo-propyl, H-butyl, «-pentyl, rc-hexyl, decyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, 1 -carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl; and
the anion, X _, is selected from F", Br", Γ, [N03]", [SnCl3]~, [SCN]", [NCO]-, [CF3S03]_, [CH3OS03] ~ [(BuO)2P(0)0]-, [CH3C6H4S03]-, [(CF3S02)2N]- [P(C2F5)3F3] [B(CN)4] , and [N(CN)2]".
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, methyl, ethyl, n-propyl, wo-propyl, «-butyl, «-hexyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, and allyl; and
R4 and R6 are each independently selected from ethyl, «-propyl, wo-propyl, H-butyl, «-hexyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, and allyl; and
the anion, Xq ~ is selected from F", Br", [N03]~, [SCN]", [CF3S03]", [CH3OS03]_, [CH3C6H4S03]",
[(CF3S02)2N]_ and [N(CN)2]_.
In some embodiments, R1, R2, R3 and R5 are each independently selected from -H, methyl, ethyl, n-propyl, zjo-propyl, «-butyl, «-hexyl, stearyl, 2-hydroxyethyl, and allyl; and
R4 and R6 are each independently selected from ethyl, ^-propyl, wo-propyl, «-butyl, n-hexyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, and allyl; and
the anion, Xq~, is selected from F~, Br", [N03]", [SCN]" [CF3S03]", [CH3OS03]~, [CH3C6H4S03]",
[(CF3S02)2N]- and [N(CN)2]".
In some embodiments,
R'-R6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
R1, R3 and R5 are -H and R2, R4 and R6 are phenyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are z'sopropyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl, R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are wo-propyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are -H,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl,
R', R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-hydroxypropyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-methylpropyl, or
R1, R2, R3 and R4 are ethyl, and R5 and R6, together with the nitrogen atom to which they are attached, are
2- carboxylpyrrolidinyl, and
the anion, Xq~ is selected from F", Br", Γ, [HF2]~, [SCN]", [NCOf, [N03] [AIC ]", [A12C17] ~ [PF6]~
[SeCN]", [CF3SO3]", [FHOMef, [FHOEt]", [FHOPr]", [MeOS03]~, [EtOS03]", [(BuO)2P(0)Or,
[CH3C6H4S03]~, ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate,
3- fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2Nr, [(CF3S02)NC(0)CF3]- [(FS02)2N]" [CF3CF2S03r, [C4F9S03]-, [(CF3CF2S02)2N)]- [(CF3S02)3C]- [(FS02)3C]- [P(C2F5)3F3]-, [(CF3)2P(0)Or, [(C2F5)2P(0)0]-, [(CF30)2P(0)0]- [(C2F50)2P(0)0]- [BF3(CF3)3]-, [BF3(C2F5)3]- [BF3(CN)r, [B(CN)4]-, [N(CN)2]" and [C(CN)3]-.
In some embodiments,
R'-R6 are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are z'so-propyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1 , R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl, or R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl, and
the anion, Xq " is selected from IT, Br", Γ, [HF2]~, [SCN]~, [NCO]" [N03]", [AICU]-, [AI2CI7]", [PF6]", [SeCN]", [CF3SO3]", [FHOMe]", [FHOEt]", [FHOPr]", [MeOS03]", [EtOS03]", [(BuO)2P(0)0]",
Figure imgf000069_0001
((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2N]" [(CF3S02)NC(0)CF3]-, [(FS02)2N]", [CF3CF2S03r, [C^SO,]-, [(CF3CF2S02)2N)] ", [(CF3S02)3C]", [(FS02)3C]-, [P(C2F5)3F3]", [(CF3)2P(0)0]", [(C2F5)2P(0)0]" ; [(CF30)2P(0)0]"
[(C2F50)2P(0)0]- [BF3(CF3)3]-, [BF3(C2F5)3]-, [BF3(CN)]", [B(CN)4]-, [N(CN)2r, and [C(CN)3]" In some embodiments,
R'-R6 are 2-hydroxyethyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are ώο-propyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl, or
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl, and
the anion, Xq" is selected from F", Br", Γ, [HF2]~ [SCN]-, [NCO]", [N03]", [AICU]", [AI2CI7]", [PF6]", [SeCN]", [CF3S03]", [FHOMe]", [FHOEt]", [FHOPr]", [MeOS03]~, [EtOS03]", [(BuO)2P(0)0]", [CH3C6H4S03]~, ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2Nr, [(CF3S02)NC(0)CF3] , [(FS02)2N]", [CF3CF2S03]", [C^SO,]", [(CF3CF2S02)2N)]", [(CF3S02)3C]-, [(FS02)3C]", [P(C2F5)3F3]", [(CF3)2P(0)0]", [(C2F5)2P(0)0]", [(CF30)2P(0)0]-,
[(C2F50)2P(0)0]", [BF3(CF3)3]", [BF3(C2F5)3]", [BF3(CN)]", [B(CN)4]", [N(CN)2]", and [C(CN)3]".
In some embodiments,
R'-R6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
R1, R3 and R5 are -H and R2, R4 and R6 are phenyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are iso-propyl, R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R\ R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are wo-propyl and R5 and R6 are butyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are -H,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
RL, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is l-carboxyl-2-hydroxypropyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is l-carboxyl-2-methylpropyl, or
R1, R2, R3 and R4 are ethyl, and R5 and R6, together with the nitrogen atom to which they are attached, are
2-carboxylpyrrolidinyl, and
the anion, Xq~, is selected from Br", Γ, [N03]", [PF6]~, [SnCl3]~, [SCN]", [NCO]-, [CF3S03]~, [CH3OS03r, [C2H5OS03]- [CeFsSO,]- [(BuO)2P(0)0] , [CH3C6H4S03] ' [(CF3S02)2N] , [(FS02)2N] , [C2F5S03] ~, [(C2F5S02)2N)]- [P(C2F5)3F3]-, [B(CN)4r, and [N(CN)2]~. In some embodiments,
R'-R6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
R1, R3 and R5 are -H and R2, R4 and R6 are phenyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are zso-propyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are wo-propyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are -H,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is hexyl, R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1-carboxylethyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-hydroxypropyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-methylpropyl, or
R1, R2, R3 and R4 are ethyl, and R5 and R6, together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl, and
the anion, X"', is selected from ΒΓ, [N03]", [PF6]", [SCNf, [CF3S03]", [CH3OS03]~, [C2H5OS03]_, [C6F5S03]-, [CH3C6H4S03]-, [(CF3S02)2N]-, [(FS02)2N]" [C2F5S03]", [(C2F5S02)2N)r and [N(CN)2]'.
In some embodiments,
R'-R6 are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,
R1 , R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1 , R2, R3 and R4 are fso-propyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl, or
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl, and
the anion, Xq", is selected from Br", [Ν03Γ, [PF6]~ [SCN]~ [CF3SO,]", [CH3OS03]_, [C2H5OS03]~, [C6F5S03]-, [CH3C6H4S03]- [(CF3S02)2N]- [(FS02)2N]" [C2F5S03]- [(C2F5S02)2N)]- and [N(CN)2]".
In some embodiments,
R'-R6 are 2-hydroxyethyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are wo-propyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl, or
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1-carboxylethyl, and the anion, Xq" is selected from Br-, [NOj]", [PF6]', [SCN]", [CF3SO3]", [CH3OSO3]", [C2H5OSO3]-, [C6F5S03]-, [CHJC^SOJ]-, [(CF3S02)2N]-, [(FS02)2N]" [C2F5S03]- [(C2F5S02)2N)]- and [N(CN)2]".
In some embodiments,
R'-R6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,
R1, R3 and R5 are -H and R2, R4 and R6 are phenyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are wo-propyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are wo-propyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are -H,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-hydroxypropyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-methylpropyl, or
R1, R2, R3 and R4 are ethyl, and R5 and R6, together with the nitrogen atom to which they are attached, are
2-carboxylpyrrolidinyl, and
the anion, Xq", is selected from F", Br", Γ, [Ν03Γ, [SnCl3]", [SCN]", [NCO]", [CF3SO3] , [CH3OS03]",
[(BuO)2P(0)0]" [CH3C6H4S03]-, [(CF3S02)2N]-, [P(C2F5)3F3]-, [B(CN)4]-, and [N(CN)2]".
In some embodiments,
R'-R6 are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are wo-propyl and R5 and R6 are butyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl, R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl, or
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1-carboxylethyl, and
the anion, X"" is selected from F", Br", [N03]", [SCN] ~, [CF3S03] ~, [CH3OS03]~,
Figure imgf000073_0001
[(CF3S02)2N]- and [N(CN)2]".
In some embodiments,
R'-R6 are 2-hydroxyethyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1 , R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R', R2, R3 and R4 are iso-propyl and R5 and R6 are butyl,
R1 , R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl, or
R', R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl, and
the anion, Xq " is selected from F", Br-, [N03]", [SCN]", [CF3S03]", [CH3OS03]", [CH3C6H4S03]",
[(CF3S02)2N]" and [N(CN)2]_.
In some embodiments, the compound is selected from the group consisting of:
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethyIamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium/>-toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(14) tris(dipropylamino)cyclopropenium fluoride diethanol;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide; (22) tris(dibutylamino)cyclopropenium nitrate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(26) tris(diethanolamino)cyclopropenium fluoride;
(28) tris(diallylamino)cyclopropenium bromide;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(41 ) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(49) bis(diethylamino)diethanolaminocyclopropenium iodide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;
(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate; (68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(69) tris(dipentylamino)cyclopropeniuni dicyanoamide;
(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(76) bis(di 5o-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;
(78) bis(diethylamino)hexylaminocyclopropenium methylsulfate;
(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(80) bis(diethylamino)aminocyclopropenium methylsulfate;
(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide;
(86) bis(diethylamino)dihexylaminocyclopropenium iodide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide;
(88) tris(dimethylamino)cyclopropenium thiocyanate;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;
(91) tris(dihexylamino)cyclopropenium dibutylphosphate;
(92) bis(diethylamino)-5-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(95) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;
(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;
(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(99) tris(dibutylamino)cyclopropenium isocyanate;
(100) tris(dibutylamino)cyclopropenium trichlorostannate;
(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;
(102) bis(diethylamino)di 0-propylaminocyclopropenium methylsulfate;
(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;
(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the compound is selected from the group consisting of compounds (4)-(6), (8)-(10), (12)-(16), (19)-(22), (24), (26), (28)-(30), (32)-(34), (36), and (38)-(64). In one embodiment, the compound is selected from the group consisting of compounds (68), (69), (71), (72), (74)-(82), (84)-(103), and (105)-(107).
In some embodiments, the compound is selected from the group consisting of:
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium/?-toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(14) tris(dipropylamino)cyclopropenium fluoride diethanol;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(20) tris(dibutylamino)cyclopropenium bromide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(26) tris(diethanolamino)cyclopropenium fluoride;
(28) tris(diallylamino)cyclopropenium bromide;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(44) bis(diethylamino)dibutylarm^ocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide; (46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(49) bis(diethylamino)diethanolaminocyclopropenium iodide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;
(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide; and
(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate.
In a second aspect, the present invention provides a compound of formula [Y+]q[Xq"] wherein q is 1 ; wherein the cation, is selected from
tris(dipropylamino)cyclopropenium,
tris(dibutylamino)cyclopropenium,
tris(dipentylamino)cyclopropenium,
tris(dihexylamino)cyclopropenium,
tris(didecylamino)cyclopropenium,
tris(diallylamino)cyclopropenium,
tris(butylmethylamino)cyclopropenium,
tris(hexylmethylamino)cyclopropenium,
tris(octadecylmethylamino)cyclopropenium,
bis(diwo-propylamino)dibutylaminocyclopropenium,
bis(diethylamino)dipropylaminocyclopropenium,
bis(diethylamino)diiio-propylaminocyclopropenium,
bis(diethylamino)dibutylaminocyclopropenium,
bis(diethylamino)dihexylaminocyclopropenium,
bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)butylmethylaminocyclopropenium, bis(diethylamino)hexylmethylaminocyclopropenium,
bis(diethylamino)octadecylmethylaminocyclopropenium,
bis(diethylamino)dimethylaminocyclopropenium, and
bis(diethylamino)di(2-methoxyethyl)aminocyclopropenium; and
wherein the anion, Xq~ is selected from CI" Br" [BF4]", [N03]", ( F6]", [SCN]", [CF3S03]", [CH3OS03]", [C2H5OS03]-, [C^sSO,]-, [CH3C6H4S03]-, [(CF3S02)2N]-, [(FS02)2N]", [C2F5S03]- [(C2F5S02)2N)]" and [N(CN)2]-.
In some embodiments, the cation, Y1", is selected from
tris(dipropylamino)cyclopropenium,
tris(dibutylamino)cyclopropenium,
tris(dipentylamino)cyclopropenium,
tris(dihexylamino)cyclopropenium,
tris(didecylamino)cyclopropenium,
tris(diallylamino)cyclopropenium,
tris(butylmethylamino)cyclopropenium,
tris(octadecylmethylamino)cyclopropenium,
bis(diwo-propylamino)dibutylaminocyclopropenium,
bis(diethylamino)diwo-propylaminocyclopropenium,
bis(diethylamino)dibutylaminocyclopropenium,
bis(diethylamino)dihexylaminocyclopropenium,
bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)butylmethylaminocyclopropenium,
bis(diethylamino)hexylmethylaminocyclopropenium, and
bis(diethylamino)dimethylaminocyclopropenium. In some embodiments, the cation, Y1", is selected from
tris(dipropylamino)cyclopropenium,
tris(dibutylamino)cyclopropenium,
tris(dihexylamino)cyclopropenium,
tris(diallylamino)cyclopropenium,
tris(butylmethylamino)cyclopropenium,
tris(hexylmethylamino)cyclopropenium,
tris(octadecylmethylamino)cyclopropenium,
bis(dii5O-propylamino)dibutylaminocyclopropenium,
bis(diethylamino)dipropylaminocyclopropenium,
bis(diethylamino)diwo-propylaminocyclopropenium,
bis(diethylamino)dibutylaminocyclopropenium, bis(diethylamino)dihexylaminocyclopropenium, bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)butylmethylaminocyclopropenium, bis(diethylamino)hexylmethylaminocyclopropenium, bis(diethylamino)octadecylmethylaminocyclopropenium, bis(diethylamino)dimethylaminocyclopropenium, and bis(diethylamino)di(2-methoxyethyl)aminocyclopropenium.
In some embodiments, the cation, Y^, is selected from tris(dipropylamino)cyclopropenium,
tris(dibutylamino)cyclopropenium,
tris(diallylamino)cyclopropenium,
tris(butylmethylamino)cyclopropenium,
tris(octadecylmethylamino)cyclopropenium,
bis(diwo-propylamino)dibutylaminocyclopropenium, bis(diethylamino)dibutylaminocyclopropenium, bis(diethylamino)dihexylaminocyclopropenium, bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)butylmethylaminocyclopropenium, bis(diethylamino)hexylmethylaminocyclopropenium, and bis(diethylamino)dimethylaminocyclopropenium.
In some embodiments, the cation, Y , is selected from tris(dipropylamino)cyclopropenium,
tris(dibutylamino)cyclopropenium,
tris(dihexylamino)cyclopropenium,
tris(diallylamino)cyclopropenium,
tris(butylmethylamino)cyclopropenium,
tris(hexylmethylamino)cyclopropenium,
bis(diethylamino)dipropylaminocyclopropenium, bis(diethylamino)dibutylaminocyclopropenium, bis(diethylamino)dihexylaminocyclopropenium, bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)butylmethylaminocyclopropenium, bis(diethylamino)hexylmethylaminocyclopropenium, bis(diethylamino)octadecylmethylaminocyclopropenium, bis(diethylamino)dimethylaminocyclopropenium, and bis(diethylamino)di(2-methoxyethyl)aminocyclopropenium. In some embodiments, the cation, is selected from
tris(dipropylamino)cyclopropenium,
tris(dibutylamino)cyclopropenium,
tris(diallylamino)cyclopropenium,
tris(butylmethylamino)cyclopropenium,
bis(diethylamino)dibutylaminocyclopropenium,
bis(diethylamino)dihexylaminocyclopropenium,
bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)butylmethylaminocyclopropenium,
bis(diethylamino)hexylmethylaminocyclopropenium, and
bis(diethylamino)dimethylaminocyclopropenium.
In some embodiments, the cation, is selected from
tris(butylmethylamino)cyclopropenium,
tris(octadecylmethylamino)cyclopropenium,
bis(diwo-propylamino)dibutylaminocyclopropenium,
bis(diethylamino)dibutylaminocyclopropenium,
bis(diethylamino)dihexylaminocyclopropenium,
bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)butylmethylaminocyclopropenium,
bis(diethylamino)hexylmethylaminocyclopropenium, and
bis(diethylamino)dimethylaminocyclopropenium; and
the anion, Xq~, is selected from CI', Br", [BF4]~, [Ν03Γ, [PF6]" [SCNf, [CF3S03]", [CH3OS03]",
[C2H5OS03] - [C6F5S03]-, [CH3C6H4SO3]", [(CF3S02)2Nr, [(FS02)2N] , [C2F5S03] , [(C2F5S02)2N)r and [N(CN)2]-. In some embodiments, the cation, Y\ is selected from
tris(diallylamino)cyclopropenium,
tris(butylmethylamino)cyclopropenium,
tris(octadecylmethylamino)cyclopropenium,
bis(di 5O-propylamino)dibutylaminocyclopropenium,
bis(diethylamino)dibutylaminocyclopropenium,
bis(diethylamino)dihexylaminocyclopropenium,
bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)hexylmethylaminocyclopropenium, and
bis(diethylamino)dimethylaminocyclopropenium; and the anion, Xq" is selected from CI", Br", [BF4]~, [N03]", [PF6]", [SCN]", [CF3SO3]", [CH3OSO3]",
[C2H5OSO3]-, [C6F5SO3]- [CH3C6H4S03]", [(CF3S02)2N]-, [(FS02)2N]", [C2F5S03r, [(C2F5S02)2N)r and [N(CN)2]-.
In some embodiments, the cation, Y"1", is selected from
tris(butylmethylamino)cyclopropenium,
tris(octadecylmethylamino)cyclopropenium,
bis(diwo-propylamino)dibutylaminocyclopropenium,
bis(diethylamino)dibutylaminocyclopropenium,
bis(diethylamino)dihexylaminocyclopropenium,
bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)hexylmethylaminocyclopropenium, and
bis(diethylamino)dimethylaminocyclopropenium; and
the anion, Xq" is selected from CI", Br", [BF4]", [N03]", [PF6]", [SCN]", [CF3SO3]", [CH3OSO3]",
[C2H5OS03]", [C^SC^]", [CH3C6H4S03]", [(CF3S02)2N]", [(FS02)2N]", [C2F5S03r, [(C2F5S02)2N)]" and [N(CN)2]".
In some embodiments, the cation, Y"\' is selected from
tris(dipentylamino)cyclopropenium,
tris(didecylamino)cyclopropenium,
tris(butylmethylamino)cyclopropenium,
tris(octadecylmethylamino)cyclopropenium,
bis(dit5o-propylamino)dibutylaminocyclopropenium,
bis(diethylamino)dibutylaminocyclopropenium,
bis(diethylamino)diwo-propylaminocyclopropenium,
bis(diethylamino)dihexylaminocyclopropenium,
bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)hexylmethylaminocyclopropenium, and
bis(diethylamino)dimethylaminocyclopropenium; and
the anion, Xq" is selected from CI", Br", [BF4]", [N03]", [PF6]", [SCN]", [CF3SO3]", [CH3OSO3]",
[C2H5OS03]", [C6F5S03]",
Figure imgf000081_0001
[(CF3S02)2N]", [(FS02)2N]", [C2F5S03]", [(C2F5S02)2N)]" and [N(CN)2]".
In a third aspect, the present invention provides a compound of formula [Y+]q[Xq ] wherein q is 1 ;
wherein the cation, is tris(diethylamino)cyclopropenium; and
wherein the anion, Xq" is selected from Γ, [BF4]" [N03]", [PF6]", [SCN]", [CF3SO3]", [CHJOSOJ]",
[C2H5OS03]" [C6F5S03]-
Figure imgf000081_0002
[(CF3S02)2N]", [(FS02)2N]", [C2F5S03]" [(C2F5S02)2N)]" and [ (CN)2]-. In some embodiments, the anion, Xq", is selected from [BF4]~, [N03]_, [PF6]~, [SCN]", [CF3S03]~,
[CH3OS03r, [C2H5OS03]-, [C6F5S03]- [CH.C^SO,]" [(CF3S02)2N]-, [(FS02)2N]~ [C2F5S03]-,
[(C2F5S02)2N)]- and [N(CN)2]-.
In a fourth aspect, the present invention provides a compound of formula [Y^qfX11"] wherein q is 1 ;
wherein the cation, Y1", is selected from
bis(diethylamino)aminocyclopropenium,
bis(diethylamino)butylaminocyclopropenium,
bis(diethylamino)hexylaminocyclopropenium,
bis(diethylamino)diethanolaminocyclopropenium,
tris(diethanolamino)cyclopropenium,
trisanilinocyclopropenium,
bis(diethylamino)-iS'-(l -carboxylethylamino)cyclopropenium,
bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,
bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium, and
bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium; and
wherein the anion, Xq", is selected from [BF4]~, [PF6]", [CF3S03]", [CH3OS03]", [C2H5OS03]", [C6F5S03]\ [CH^^SO,]" [(CF3S02)2N]- [(FS02)2N]", [C2F5S03r, [(C2F5S02)2N)]- and [N(CN)2]"
In some embodiments, the cation, Y1", is selected from
bis(diethylamino)aminocyclopropenium,
bis(diethylamino)butylaminocyclopropenium,
bis(diethylamirio)hexylaminocyclopropenium,
trisanilinocyclopropenium,
bis(diethylamino)-5-( 1 -carboxylethylamino)cyclopropenium,
bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,
bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium, and
bis(diethylamino)-5-(l -carboxy-2-hydroxylpropylamino))cyclopropenium.
In some embodiments, the cation, Y1", is selected from
bis(diethylamino)butylaminocyclopropenium,
bis(diethylamino)hexylaminocyclopropenium,
trisanilinocyclopropenium,
bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium,
bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,
bis(diethylamino)-S-(l-carboxy-2-methylpropylamino)cyclopropenium, and
bis(diethylamino)-S-(l-carboxy-2-hydroxylpropylamino))cyclopropenium. In some embodiments, the cation, Y"1", is selected from
bis(diethylamino)-S-(l-carboxylethylamino)cyclopropenium,
bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,
bis(diethylamino)-S-(l-carboxy-2-methylpropylamino)cyclopropenium, and
bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium.
In some embodiments, the cation, Y^, is selected from
bis(diethylamino)aminocyclopropenium,
trisanilinocyclopropenium,
bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,
bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium, and
bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium.
In some embodiments, the cation, Y^, is selected from
bis(diethylamino)aminocyclopropenium,
bis(diethylamino)hexylaminocyclopropenium,
trisanilinocyclopropenium,
bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,
bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium, and
bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium.
In some embodiments, the cation, Y"1", is selected from
bis(diethylamino)butylaminocyclopropenium,
bis(diethylamino)hexylaminocyclopropenium,
bis(diethylamino)diethanolaminocyclopropenium,
tris(diethanolamino)cyclopropenium, and
bis(diethylamino)-5-( 1 -carboxylethylamino)cyclopropenium. In some embodiments, the cation, Y^, is selected from
bis(diethylamino)butylaminocyclopropenium,
bis(diethylamino)diethanolaminocyclopropenium,
tris(diethanolamino)cyclopropenium, and
bis(diethylamino)-5-( 1 -carboxy lethylamino)cyclopropenium. In some embodiments, the cation, Y+, is bis(diethylamino)aminocyclopropenium.
In some embodiments, the cation, Y is trisanilinocyclopropenium.
In a fifth aspect, the present invention provides a compound of formula [Y+]q[Xq"] wherein q is 1 or 2; wherein the cation, Y\ is a triaminocyclopropenium ion of the formula (II):
Figure imgf000084_0001
wherein the anion, Xq~, is selected from [SCN]~, [CF3SO3]-, [FHO(C,_6 alkyl)]", [(C,.6 alkyl)OS03]", [C6F5S03]-, [(C,.6 alkyl)(C,.6 alkyl)P(0)Or, [CH^^SCy", [Co(C2B9H„)2r, [C2B9H12]-, [B10Cl10 [B12C112]2- [CB„H12r, P12H„N(CW alkyl),]" [(C,_6 alkyl)SnB„H„r, [RBCB„Rc 5XB6r, [R°BF3] , [(CF3S02)2N]- [(CF3S02)NC(0)CF3]- [(FS02)2N]-, [RFCF2S03r, [(RGS02)2N)]" [(RGS02)3C]',
[(FS02)3Cr [RFCF2C(0)0]-, [P(CnF2n+1.mHm)yF6-y]-, [PiC^)^.^, [RF 2P(0)0]", [RFP(0)02]2"
[BF,RF4_J-,
Figure imgf000084_0002
J ; and wherein RB, Rc, RD, XB, RF, R°, n, m, y, z, -Z-, and -Y- are as defined for the compounds of the first aspect.
In some embodiments, wherein the cation, is tris(dimethylamino)cyclopropenium, the anion, Xq~, selected from [SCN]" [CF3S03]", [CH3OS03] , [C2H5OS03] , [C6F5S03] , [CH3C6H4S03]~
[(CF3S02)2N]-, [(FS02)2N]-, [C2F5S03]-, [(C2F5S02)2N)]- and [N(CN)2]-.
In another embodiment, the compound is selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide
(87) tris(dimethylamino)cyclopropenium dicyanoamide; and
(88) tris(dimethylamino)cyclopropenium thiocyanate.
In one embodiment, the compound is compound (2). In another embodiment, the compound is compound (87) or (88).
In a sixth aspect, the present invention provides a compound of formula [Y+]q[Xq"] wherein q is 1 or 2; wherein the cation, Y*, is a triaminocyclopropenium ion of the formula (III):
Figure imgf000085_0001
wherein R7 is methyl and R8 is selected from C2-20 alkyl, substituted Ci.20 alkyl, C2.20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C2.2o alkynyl, C3.i0 cycloalkyl, substituted C3.10 cycloalkyl, C3.i0 cycloalkenyl, substituted C3-i0 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or
R7 and R8 are each independently selected from C2-2o alkyl, substituted Cj_2o alkyl, C2.2o alkenyl, substituted C2-2o alkenyl, C2-20 alkynyl, substituted C2-20 alkynyl, C3_i0 cycloalkyl, substituted C3_io cycloalkyl, C3.10 cycloalkenyl, substituted C3.|0 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;
wherein the anion, Xq~~, is selected from [SCN]-, [CF3COO]_, [SeCN]-, [CF3S03r, [FHO(C,.6 alkyl)]", [(C1-6 alkyl)OS03]-, [C^SO,]', [(C,_6 alkyl)(C,_6 alkyl)P(0)0]- [CH3C6H4S03]-, [Co(C2B9Hn)2]", [C2B9H12r, [B10C110]2', [B12C112]2- [CBuH12r,
Figure imgf000085_0002
alkyl),]", [(C,_6 alkyl)SnB„H„r,
[RBCB„Rc 5XB6r, [RDBF3]~, [(CF3S02)2N]-, [(CF3S02)NC(0)CF3]- [(FS02)2Nr, [RFCF2S03r,
[(RGS02)2N)]- [(RGS02)3C]-, [(FS02)3C]-, [RFCF2C(0)0]- [P(CnF2n+1.mHm)yF6.y]-, [P(C6F5)yF6.y]- [RF P(0)0] - [RFP(0)02]2-, [BFzRF4-z]- [BF2(CN)4.Z]- [N(CF3)2] ~, [N(CN)2]", [C(CN)3]" and
Figure imgf000085_0003
wherein RB, Rc, RD, XB, RF, RG, n, m, y, z, -Z-, and -Y- are as defined for the compounds of the first aspect.
In some embodiments, R7 is methyl and R8 is butyl, R7 is methyl and R8 is hexyl, R7 is methyl and R8 is stearyl, R7 and R8 are ethyl, R7 and R8 are propyl, R7 and R8 are butyl, or R7 and R8 are hexyl.
In some embodiments, the cation, Y ", is selected from
bis(dimethylamino)hexylmethylaminocyclopropenium,
bis(dimethylamino)dihexylaminocyclopropenium, and
bis(dimethylamino)dibutylaminocyclopropenium. In some embodiments, the cation, Y4, is selected from bis(dimethylamino)hexylmethylaminocyclopropenium,
bis(dimethylamino)dihexylaminocyclopropenium,
bis(dimethylamino)dibutylaminocyclopropenium; and
the anion, Xq" is selected from [SCN]", [CF3SO3]", [CH3OS03]", [C2H5OS03]-, [CeFsSOa]-,
[CH3C6H4S03]-, [(CF3S02)2N]- [(FS02)2N]", [C2F5S03] , [(C2F5S02)2N)]" and [N(CN)2]"
In another embodiment, the compound is selected from the group consisting of:
(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In a seventh aspect, the present invention provides a compound selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium p-toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(11) tris(dipropylamino)cyclopropenium chloride;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(14) tris(dipropylamino)cyclopropenium fluoride diethanol;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(18) tris(dibutylamino)cyclopropenium chloride;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(26) tris(diethanolamino)cyclopropenium fluoride;
(27) tris(diallylamino)cyclopropenium chloride;
(28) tris(diallylamino)cyclopropenium bromide; (29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)arriide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(49) bis(diethylamino)diethanolaminocyclopropenium iodide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;
(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61 ) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-(l-carboxylethylamino)cyclopropenium methylsulfate;
(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride; (67) tris(dipentylamino)cyclopropenium chloride;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(69) tris(dipentylamino)cyclopropenium dicyanoamide;
(70) tris(dihexylamino)cyclopropenium chloride;
(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide;
(73) tris(didecylamino)cyclopropenium chloride;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(76) bis(diwo-propylarruno)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;
(78) bis(diethylamino)hexylaminocyclopropenium methylsulfate;
(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(80) bis(diethylamino)aminocyclopropenium methylsulfate;
(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;
(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide;
(86) bis(diethylamino)dihexylaminocyclopropenium iodide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide;
(88) tris(dimethylamino)cyclopropenium thiocyanate;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;
(91) tris(dihexylamino)cyclopropenium dibutylphosphate;
(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(95) bis(diethylamino)-5-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;
(96) bis(diethylamino)-S-(l-carboxy-2-methylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(97) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;
(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(99) tris(dibutylamino)cyclopropenium isocyanate;
(100) tris(dibutylamino)cyclopropenium trichlorostannate;
(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate; 102) bis(diethylamino)diwo-propylaminocyclopropenium methylsulfate;
103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;
105) bis(dimethylannno)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
106) bis(dimethylarnino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide. n one embodiment, the compound is selected from the group consisting of compounds (2), and (4)-(65). n one embodiment, the compound is selected from the group consisting of compounds (67)-(103), and 105)-(107). n one embodiment, the compound is selected from the group consisting of:
2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
5) tris(diethylamino)cyclopropenium dicyanoamide;
6) tris(diethylamino)cyclopropenium nitrate;
7) tris(diethylamino)cyclopropenium tetrafluoroborate;
8) tris(diethylamino)cyclopropenium thiocyanate;
9) tris(diethylamino)cyclopropenium p-toluenesulfonate;
10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
13) tris(dipropylamino)cyclopropenium dicyanoamide;
14) tris(dipropylamino)cyclopropenium fluoride diethanol;
15) tris(dipropylamino)cyclopropenium fluoride ethanol;
16) tris(dipropylamino)cyclopropenium nitrate;
17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
20) tris(dibutylamino)cyclopropenium bromide;
21) tris(dibutylamino)cyclopropenium dicyanoamide;
22) tris(dibutylamino)cyclopropenium nitrate;
23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
25) tris(diethanolamino)cyclopropenium chloride;
26) tris(diethanolamino)cyclopropenium fluoride;
28) tris(diallylamino)cyclopropenium bromide;
29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
30) tris(diallylamino)cyclopropenium dicyanoamide;
31) tris(butylmethylamino)cyclopropenium chloride;
32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; (33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)arnide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(49) bis(diethylamino)diethanolaminocyclopropenium iodide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;
(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate; and
(65) bis(dii5o-propylamino)dibutylaminocyclopropenium chloride.
In another embodiment, the compound is selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; (5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium/?-toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(14) tris(dipropylamino)cyclopropenium fluoride diethanol;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(20) tris(dibutylamino)cyclopropenium bromide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(26) tris(diethanolamino)cyclopropenium fluoride;
(27) tris(diallylamino)cyclopropenium chloride;
(28) tris(diallylamino)cyclopropenium bromide;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(49) bis(diethylamino)diethanolaminocyclopropenium iodide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;
(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifiuoromethanesulfonyl)amide;
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate; and
(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride.
In another embodiment, the compound is selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(?) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium/ toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(14) tris(dipropylamino)cyclopropenium fluoride diethanol;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(20) tris(dibutylamino)cyclopropenium bromide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(26) tris(diethanolamino)cyclopropenium fluoride; (28) tris(diallylamino)cyclopropenium bromide;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(49) bis(diethylamino)diethanolaminocyclopropenium iodide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;
(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S- ( 1 -carboxylethylamino)cyclopropenium methylsulfate; and
(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride. In another embodiment, the compound is selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(44) bis(diethylamino)dibutylaminocyclopropemum bis(trifluoromethanesulfonyl)amide;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(71 ) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;
(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(94) bis(diethylamino)-5-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the compound is selected from the group consisting of compounds (2), (4), (12), (19), (29), (32), (38), (41), (44), (47), (50), (54), (56), (59), and (62). In another embodiment, the compound is selected from the group consisting of compounds (68), (71 ), (74), (76), (79), (81 ), (82), (92), (94), (96), (98), (105), (106), and (107). In another embodiment, the compound is selected from the group consisting of:
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(69) tris(dipentylamino)cyclopropenium dicyanoamide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(77) bis(di/5o-propylamino)dibutylaminocyclopropenium dicyanoamide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide; and
(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide.
In one embodiment, the compound is selected from the group consisting of compounds (5), (13), (21), (30), (33), (39), (42), (45), (48), (57), (60), and (63). In another embodiment, the compound is selected from the group consisting of compounds (69), (72), (75), (77), (87), and (103).
In another embodiment, the compound is selected from the group consisting of:
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate; and
(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate.
In one embodiment, the compound is selected from the group consisting of compounds (7), (17), (23), and (35). In another embodiment, the compound is compound (83).
In another embodiment, the compound is selected from the group consisting of:
(6) tris(diethylamino)cyclopropenium nitrate;
(16) tr is(dipropylamino)cyclopropenium nitrate;
(22) tris(dibutylamino)cyclopropenium nitrate; and
(34) tris(butylmethylamino)cyclopropenium nitrate. In another embodiment, the compound is selected from the group consisting of:
(1 1 ) tris(dipropylamino)cyclopropenium chloride;
(18) tris(dibutylamino)cyclopropenium chloride;
(25) tris(diethanolamino)cyclopropenium chloride;
(27) tris(diallylamino)cyclopropenium chloride;
(31) tris(butylmethylamino)cyclopropenium chloride;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(65) bis(diwo-propylarnino)dibutylaminocyclopropenium chloride;
(67) tris(dipentylamino)cyclopropenium chloride;
(70) tris(dihexylamino)cyclopropenium chloride; and
(73) tris(didecylamino)cyclopropenium chloride.
In one embodiment, the compound is selected from the group consisting of compounds (1 1), (18), (25), (27), (31), (37), and (65). In another embodiment, the compound is selected from the group consisting of compounds (67), (70), and (73).
In another embodiment, the compound is selected from the group consisting of:
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;
(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate;
(78) bis(diethylamino)hexylaminocyclopropenium methylsulfate;
(80) bis(diethylamino)aminocyclopropenium methylsulfate;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(95) bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;
(97) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate; and
(102) bis(diethylamino)diwo-propylaminocyclopropenium methylsulfate.
In one embodiment, the compound is selected from the group consisting of compounds (40), (43), (46), (52), (53), (55), (58), (61), and (64). In another embodiment, the compound is selected from the group consisting of compounds (78), (80), (93), (95), (97), and (102).
In another embodiment, the compound is selected from the group consisting of: (14) tris(dipropylamino)cyclopropenium fluoride diethanol;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(26) tris(diethanolamino)cyclopropenium fluoride; and
(51 ) bis(diethylamino)diethanolaminocyclopropenium fluoride. In another embodiment, the compound is selected from the group consisting of:
(8) tris(diethylamino)cyclopropenium thiocyanate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate; and
(88) tris(dimethylamino)cyclopropenium thiocyanate.
In one embodiment, the compound is compound (8) or (36). In another embodiment, the compound is compound (88).
In another embodiment, the compound is (20) tris(dibutylamino)cyclopropenium bromide or (28) tris(diallylamino)cyclopropenium bromide.
In another embodiment, the compound is selected from the group consisting of:
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate; and
(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate.
In one embodiment, the compound is compound (10) or (24). In another embodiment, the compound is compound (101).
In another embodiment, the compound is (9) tris(diethylamino)cyclopropenium /?-toluenesulfonate. In another embodiment, the compound is selected from the group consisting of:
(49) bis(diethylamino)diethanolamino-cyclopropenium iodide;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide; and
(86) bis(diethylamino)dihexylaminocyclopropenium iodide. In one embodiment, the compound is compound (49). In another embodiment, the compound is selected from the group consisting of compounds (84), (85), and (86).
In another embodiment, the compound is (89) tris(dibutylamino)cyclopropenium tetracyanoborate.
In another embodiment, the compound is (90) tris(dibutylamino)cyclopropenium
tris(pentafluoroethyl)trifluorophosphate.
In another embodiment, the compound is (91) tris(dihexylamino)cyclopropenium dibutylphosphate. In another embodiment, the compound is (99) tris(dibutylamino)cyclopropenium isocyanate.
In another embodiment, the compound is (100) tris(dibutylamino)cyclopropenium trichlorostannate.
In another embodiment, the compound is selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide; and
(88) tris(dimethylamino)cyclopropeniuni thiocyanate.
In one embodiment, the compound is compound (2). In another embodiment, the compound is compound (87) or (88).
In another embodiment, the compound is selected from the group consisting of:
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium /?-toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate; and
(85) tris(diethylamino)cyclopropenium iodide.
In one embodiment, the compound is selected from the group consisting of compounds (4)-(10). In another embodiment, the compound is compound (85).
In another embodiment, the compound is selected from the group consisting of:
(1 1) tris(dipropylamino)cyclopropenium chloride;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(14) tris(dipropylamino)cyclopropenium fluoride diethanol;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate; and
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate.
In another embodiment, the compound is selected from the group consisting of:
(18) tris(dibutylamino)cyclopropenium chloride;
( 19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(22) tris(dibutylamino)cyclopropenium nitrate; (23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate
(99) tris(dibutylamino)cyclopropenium isocyanate; and
(100) tris(dibutylamino)cyclopropenium trichlorostannate.
In one embodiment, the compound is selected from the group consisting of compounds (18)-(24). In another embodiment, the compound is selected from the group consisting of compounds (89), (90), (99), and (100).
In another embodiment, the compound is (25) tris(diethanolamino)cyclopropenium chloride or (26) tris(diethanolamino)cyclopropenium fluoride.
In another embodiment, the compound is selected from the group consisting of:
(27) tris(diallylamino)cyclopropenium chloride;
(28) tris(diallylamino)cyclopropenium bromide;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; and
(30) tris(diallylamino)cyclopropenium dicyanoamide.
In another embodiment, the compound is selected from the group consisting of:
(67) tris(dipentylamino)cyclopropenium chloride;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; and
(69) tris(dipentylamino)cyclopropenium dicyanoamide.
In another embodiment, the compound is selected from the group consisting of:
(70) tris(dihexylamino)cyclopropenium chloride;
(71 ) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide; and
(91) tris(dihexylamino)cyclopropenium dibutylphosphate.
In another embodiment, the compound is selected from the group consisting of:
(73) tris(didecylamino)cyclopropenium chloride;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; and
(75) tris(didecylamino)cyclopropenium dicyanoamide.
In another embodiment, the compound is (82) trisanilinocyclopropenium
bis(trifluoromethanesulfonyl)amide.
In another embodiment, the compound is selected from the group consisting of: (31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)arnide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate; and
(36) tris(butylmethylamino)cyclopropenium thiocyanate.
In another embodiment, the compound is selected from the group consisting of:
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; and
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide.
In another embodiment, the compound is selected from the group consisting of:
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide.
In another embodiment, the compound is selected from the group consisting of:
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide; and
(84) bis(diethylamino)dibutylaminocyclopropenium iodide.
In one embodiment, the compound is selected from the group consisting of compounds (43)-(45). In another embodiment, the compound is compound (84).
In another embodiment, the compound is selected from the group consisting of:
(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(86) bis(diethylamino)dihexylaminocyclopropenium iodide; and
(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate.
In one embodiment, the compound is selected from the group consisting of compounds (46)-(48). In another embodiment, the compound is compound (86) or (101).
In another embodiment, the compound is selected from the group consisting of:
(49) bis(diethylamino)diethanolaminocyclopropenium iodide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (51) bis(diethylamino)diethanolaminocyclopropenium fluoride; and
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate.
In another embodiment, the compound is (53) bis(diethylamino)diallylaminocyclopropenium
methylsulfate or (54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In another embodiment, the compound is selected from the group consisting of:
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide.
In another embodiment, the compound is selected from the group consisting of:
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide.
In another embodiment, the compound is selected from the group consisting of:
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide; and
(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate.
In one embodiment, the compound is selected from the group consisting of compounds (61 )-(63). In another embodiment, the compound is compound (83).
In another embodiment, the compound is (64) bis(diethylamino)-S-(l -carboxylethylamino)- cyclopropenium methylsulfate or (92) bis(diethylamino)-S-(l-carboxylethylamino)-cyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the compound is compound (64). In another embodiment, the compound is compound (92).
In another embodiment, the compound is selected from the group consisting of:
(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride;
(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(77) bis(di/50-propylamino)dibutylaminocyclopropenium dicyanoamide.
In one embodiment, the compound is compound (65). In another embodiment, the compound is compound (76) or (77). In one embodiment, the compound is (78) bis(diethylamino)hexylaminocyclopropenium methylsulfate or (79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the compound is (80) bis(diethylamino)aminocyclopropenium methylsulfate or (81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the compound is (93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate or (94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium
bis(trifluoromethanesulfonyl)amide.
In one embodiment, the compound is (95) bis(diethylamino)-S-(l-carboxy-2- methylpropylamino)cyclopropenium methylsulfate or (96) bis(diethylamino)-S-(l-carboxy-2- methylpropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the compound is (97) bis(diethylamino)-S-(l-carboxy-2- hydroxylpropylamino)cyclopropenium methylsulfate or (98) bis(diethylamino)-S-(l-carboxy-2- hydroxylpropylamino))cyclopropemum bis(trifluoromethanesulfonyl)amide.
In one embodiment, the compound is (102) bis(diethylamino)diz'so-propylamino-cyclopropenium methylsulfate or (103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide.
In one embodiment, the compound is (105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the compound is (106) bis(dimethylamino)dihexylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide.
In one embodiment, the compound is (107) bis(dimethylamino)dibutylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide.
Preparation
Triaminocyclopropenium chloride salts wherein all six substituents are identical (R6 = R5 = R4 = R3 = R2 = R1), or wherein all three amino groups are identical (R5 = R3 = R1 and R6 = R4 = R2), can be synthesised from the appropriate secondary amine and either tetrachlorocyclopropene (Z. Yoshida and Y. Tawara, J. Am. Chem. Soc., 1971, 93, 2573, which is incorporated herein in its entirety by reference) or
pentachlorocyclopropane (M. J. Taylor, P. W. J. Surman and G. R. Clark, J. Chem. Soc, Chem.
Commun., 1994, 21, 2517, which is incorporated herein in its entirety by reference). Generally, a larger amount of the amine is required for those reactions using pentachlorocyclopropane. An excess of amine may be used as a base to remove the HC1 generated during the reaction. These synthetic methods are particularly useful to prepare salts with hydrophobic anions, such as
[CF3SO3]", Γ, [I3] and [BF4]~, but are not limited thereto, because the salt can be extracted into an organic layer with the ammonium salt byproduct remaining in the aqueous layer.
In some embodiments, up to four equivalents of the secondary amine may be replaced by triethylamine or another suitable base. This variation may be particularly useful if the secondary ammonium salt byproduct is hard to separate.
Other suitable bases include tertiary amines and non-nucleophilic bases, including, but not limited to: carbonate salts, such as K2C03 and CS2CO3; Ν,Ν-diwo-propylethylamine (DIPEA, also known as Hunig 's Base); and l,8-diazabicycloundec-7-ene (DBU). The triaminocyclopropenium chloride product may be isolated by crystallisation from
CH2Cl2/diethylether.
In some embodiments, the formation of secondary ammonium salt may be avoided by reacting tetrachlorocyclopropene with an aminosilane (R. Weiss and K. Schloter, Tetrahedron Lett. , 1975, 40, 3491, which is incorporated herein in its entirety by reference). The triaminocyclopropenium chloride may be purified by a number of techniques including:
(i) extracting the triaminocyclopropenium chloride from an aqueous solution using CH2C12 or CHCI3 then removing the organic solvent;
(ii) adding a 1 :2 mixture of acetonitrile:toluene to the dried triaminocyclopropenium chloride and secondary ammonium chloride. The solution can be cooled to precipitate out the secondary ammonium chloride, which may be filtered off;
(iii) adding acetone to precipitate the secondary ammonium chloride, which may be filtered from the solution comprising the triaminocyclopropenium chloride; and
(iv) adding aqueous NaOH to convert the secondary ammonium chloride to the corresponding secondary amine which may removed by washing with petroleum ether or diethyl ether. In those embodiments wherein the secondary amine is volatile, extraction may be unnecessary. The aqueous solution comprising the triaminocyclopropenium chloride may be neutralized with HCl before removing water. Acetone may be added to precipitate NaCl, which may be filtered off. Alternatively, the NaCl may be removed by washing a chloroform or dichloromethane solution of the triaminocyclopropenium chloride with water. In some embodiments, a combination of any two or more of the methods (i)-(iv) may be used, depending on the absolute and relative solubility properties of the triaminocyclopropenium chloride, secondary ammonium chloride and secondary amine. Other purification methods may also be used, for example ion exchange chromatography and selective absorption using molecular sieves.
The triaminocyclopropenium chloride salts are also useful as intermediates in the preparation of other triaminocyclopropenium salts by anion metathesis. Anion metathesis can be carried out by a variety of standard techniques known to those persons skilled in the art. Such techniques include, but are not limited to:
(i) addition of an aqueous solution of a strong acid, for example H2S04, HBF4, HBr, HN03 or HPF6, followed by extraction with an organic solvent such as dichloromethane or diethylether;
(ii) addition of an aqueous solution of a group 1 metal or ammonium salt of a hydrophobic anion, for example LiCF3S03, followed by extraction with an organic solvent such as dichloromethane or diethylether;
(iii) addition of a silver salt, for example AgCF3S03, AgDCA, AgN03 or Ag[CBnHi2], to precipitate AgCl that can then be removed by filtration (this can be carried out in aqueous solution as well as in organic solvents such as methanol);
(iv) use of ion chromatography to exchange chloride for OFT followed by addition of a weak acid, for example CF3COOH or HF;
(v) use of an ion-exchange resin containing pre-loaded anion, for example [CH2=CHS03]";
(vi) exchange of halide ions, for example chloride, bromide or iodide, by reaction with alkylating agents, for example Me2S04, MeOTs, [Me30]BF4 or [Et30][PF6] (P. D. Vu, A. J. Boydston, C. W.
Bielawski, Green Chem. 2007, 9, 1158-9, which is incorporated herein in its entirety by reference); and
(vii) exchange of chloride for iodide by reaction with iodoethane.
A person skilled in the art can select the appropriate method, taking into account factors such as the relative solubility and miscibility properties of the reagents and products, the degree of purity required and the scale of the reaction. For example, water immiscible products are most easily prepared by methods (i) and (ii) whereas water miscible salts are generally better prepared using methods (iii), (iv) or (v). The use of silver salts provides products with low halide residues. Such products may, however, contain traces of silver.
Triaminocyclopropenium salts wherein two amino groups are the same (R5 = R1 and R6 = R2 or R6 = R5 = R = R ) can be synthesised by converting a triaminocyclopropenium salt wherein R = R = R = R = R = R1, or wherein R5 = R3 = R1 and R6 = R4 = R2, to the corresponding cyclopropenone, alkylating the cyclopropenone to a diaminoalkoxycyclopropemum salt, and reacting with a primary or secondary amine to give the desired product, as illustrated in Scheme 1. odide
HNR3R4 Alkyl-OH
Figure imgf000105_0001
Scheme 1
The first step, in which the cyclopropenone is formed, also forms an amine which is typically removed prior to the alkylation, to prevent it being alkylated to an ammonium salt. The amine may be removed, for example, under reduced pressure or by washing with diethyl ether or another suitable non-polar solvent.
A number of alkylating agents are suitable for use in the alkylation step. In some embodiments, and as illustrated in Scheme 1 , the alkylating agent is an alkyl iodide. Advantageously, the use of alkyl iodides results in triaminocyclopropenium iodide salts that are suitable for conversion to the corresponding triaminocyclopropenium fluoride salts. The use of dimethylsulfate results in triaminocyclopropenium methylsulfate salts, and the methylsulfate anion may be readily exchanged to form other salts. Other reactive alkylating reagents may also be used. For example, methyl trifluoromethanesulfonate provides the trifluoromethanesulfonate salt directly, and [Me30]BF4 provides the tetrafluoroborate salt directly.
In some embodiments, wherein the alkylating agent is an alkyl iodide, the alkyl iodide is preferably methyl iodide or ethyl iodide. Advantageously, methyl iodide and ethyl iodide, and the corresponding alcohols formed during the alkylation (methanol and ethanol, respectively), are volatile and may be conveniently removed under reduced pressure. The invention also contemplates embodiments in which a triaminocyclopropenium salt having three different amino groups is prepared from a triaminocyclopropenium salt wherein two amino groups are the same, as illustrated in Scheme 2.
Figure imgf000106_0001
Scheme 2
A number of alkylating agents (RX) are suitable for use in the alkylation step. In some embodiments, the alkylating agent is an alkyl iodide. Advantageously, the use of alkyl iodides results in
triaminocyclopropenium iodide salts that are suitable for conversion to the corresponding
triaminocyclopropenium fluoride salts. The use of dimethylsulfate results in triaminocyclopropenium methylsulfate salts, and the methylsulfate anion may be readily exchanged to form other salts. Other reactive alkylating reagents may also be used, for example, methyl trifluoromethanesulfonate provides the trifluoromethanesulfonate salt directly, and [Me30]BF4 provides the tetrafluoroborate salt directly.
The invention also contemplates embodiments in which the product obtained following the alkylation step shown in Scheme 2 is reacted with a natural or non-natural alpha-amino acid, as illustrated in Scheme 3. Reaction of the initial product, in which R5 is H and R6 is -CH(RA)-C02H, with 2 equivalents of butyllithium generates the anion [C3(R1R2)(R3R4)=N(CH(RA)COO)]_. Reaction of
[C3(R'R2)(R3R4)=N(CH(RA)COO)]- with an alkylating agent (R'X') provides a doubly alkylated product, in which R5 is R' and R6 is -CH(RA)-C02R'. Those persons skilled in the art will appreciate that various other bases, including alkyl- and aryllithium reagents, for example, may be used instead of butyllithium to generate the anion.
Figure imgf000107_0001
Scheme 3
A number of alkylating agents ( 'X') are suitable for use in the alkylation step. In some embodiments, the alkylating agent is dimethylsulfate. The use of dimethylsulfate results in triaminocyclopropenium methylsulfate salts, and the methylsulfate anion may be readily exchanged to form other salts. Other reactive alkylating reagents may also be used, for example, alkyl iodides provide the iodide salt directly, methyl trifluoromethanesulfonate provides the trifluoromethanesulfonate salt directly, and [Me30]BF4 provides the tetrafluoroborate salt directly.
Advantageously, the doubly alkylated products are non-protic and would, therefore, be expected to have lower viscosities.
In some embodiments, the doubly alkylated product, in which R5 is R' and R6 is -CH(RA)-C02R', in Scheme 3 is unstable to hydrolysis under acid and/or basic conditions. Accordingly, the invention also contemplates embodiments in which the product obtained following the alkylation step shown in Scheme 2 is reacted with a natural or non-natural alpha-amino acid, as illustrated in Scheme 4. In some of these embodiments, the product in which R5 is H and R6 is -CH(RA)-C02H, may be isolated with significant amounts of the corresponding zwitterionic species in which R5 is H and R6 is -CH(RA)-C02 ". The amount of zwitterion formed generally increases with the hydrophilicity of the anion.
Figure imgf000108_0001
Scheme 4
The invention contemplates embodiments in which a triaminocyclopropenium salt wherein R6 is alkyl is prepared from a protic triaminocyclopropenium salt, wherein R6 is H, as illustrated in Scheme 5.
Figure imgf000108_0002
Scheme 5
The protic triaminocyclopropenium salt, wherein R6 is H, is first reacted with a base, which in Scheme 5 is illustrated as butyllithium. Those persons skilled in the art will appreciate that various other bases, including other alkyl- and aryllithium reagents, sodium hydroxide and other bases, for example, may be used instead of butyllithium. A number of alkylating agents are suitable for use in the alkylation step. In some embodiments, the alkylating agent is dimethylsulfate. The use of dimethylsulfate results in triaminocyclopropenium methylsulfate salts, and the methylsulfate anion may be readily exchanged to form other salts. Other reactive alkylating reagents may also be used, for example, alkyl iodides provide the iodide salt directly, methyl trifluoromethanesulfonate provides the trifluoromethanesulfonate salt directly, and [Me30]BF4 provides the tetrafluoroborate salt directly. Accordingly, in some embodiments, the present invention provides a method for preparing a compound of the invention substantially as herein described. In some embodiments, the present invention provides a method for preparing a compound of the invention substantially as herein described with reference to Scheme 1, Scheme 2, Scheme 3, Scheme 4, or Scheme 5. Triaminocyclopropenium salts comprising basic anions, for example carboxylates and fluoride, can be water sensitive. The formation of hydroxide can lead to cyclopropenone formation at elevated temperatures or with significant hydroxide ion concentration. Accordingly, in some embodiments, the triaminocyclopropenium salts are azeotrope dried in vacuo with benzene or ethanol, for example, at ambient temperature, and stored under anhydrous conditions. Other techniques may be used to dry the triaminocyclopropenium salts, for example: drying in vacuo at 70 °C; addition of ethanol or propanol and removal of the alcohol/water azeotrope in vacuo; and bubbling dry dinitrogen gas through the liquid triaminocyclopropenium salt.
Ionic liquids
The triaminocyclopropenium salts are suitable for use as ionic liquids. The term "ionic liquid", as used herein, means an organic salt or hydrate or solvate thereof that is in liquid form at or below about 100 °C.
Accordingly, in an eighth aspect, the present invention provides an ionic liquid comprising a
triaminocyclopropenium cation and an anion.
Some embodiments provide a compound comprising a triaminocyclopropenium cation and an anion, wherein the compound is in liquid form at or below about 100 °C.
In a ninth aspect, the present invention provides an ionic liquid comprising a compound of the invention.
In some embodiments, the ionic liquid consists essentially of a compound of the invention.
The anion (Xq~) of the ionic liquid of the invention is any anion which, when associated with the selected triaminocyclopropenium cation, results in a salt that behaves as an ionic liquid. As is known in the art, the composition and structure of the cation and the anion may significantly affect the chemical and physical properties, for example melting point, volatility, stability, viscosity and hydrophobicity, of the resulting ionic liquid.
Compared to the ammonium, phosphonium, and guanidinium cations, triaminocyclopropenium cations have a greater dispersion of the positive charge (that is, reduced charge density) while compared to the imidazolium, pyridinium and triazonium cations, they have reduced hydrogen bond donor capabilities. Consequently, triaminocyclopropenium salts generally exhibit weak ion-pair interactions.
The strength of the ion-pair interaction can be further influenced by selecting weakly interacting anions, which generally have low charge density and moderate size.
The melting point is typically reduced in triaminocyclopropenium salts that have low symmetry in the cation and/or anion, and in salts in which the Ri-R.6 groups have higher conformational flexibility. For example, the melting point generally decreases in the alkyl series wherein Ri-R.6 are identical: methyl > ethyl > propyl > butyl. Similarly, the melting point for triaminocyclopropenium salts in which Ri-Re are w-propyl is generally lower than that for the corresponding salts in which R1-R6 are wo-propyl; and the melting point for triaminocyclopropenium salts in which R1-R6 are ethyl is generally lower than that for the corresponding salts of the cyclic analogue in which NRjR2, NR3R4, and NR5R2 are pyrrolidinyl.
Larger triaminocyclopropenium cations generally result in reduced ion-pair interactions and lower melting points. However, for particularly large cations, van der Waals interactions can become more significant as the cation size increases, resulting in increased melting points and viscosities.
Smaller Ri-Re groups and smaller anions tend to lower viscosities.
Protic substituents tend to increase melting points and viscosities via hydrogen bonding, whereas non- interacting substituents, such as alkyl and alkoxyalkyl (for example CH3OCH2-) groups, tend to lower melting points and viscosities. Aryl groups tend to increase melting points and viscosities due to ττ-τ stacking between aromatic rings. Accordingly, in some embodiments, the triaminocyclopropenium cation comprises a limited number of aryl groups, preferably three or fewer, more preferably two or fewer.
Fluorinated anions interact weakly with cations, which typically results in low melting points and low viscosities. Charge delocalisation on the cation and/or anion also reduces anion/cation interactions and typically results in lower melting points and viscosities.
The triaminocyclopropenium salts may be compared to analogous guanidinium salts, since both cations are stabilised by three electron-donating amino groups and have Z) 3h symmetry.
Figure imgf000110_0001
melts at 41 °C whereas a melting point of 147 °C has been reported for the guanidinium analogue; [C(NBu2)3]Cl.
In one embodiment, the ionic liquid comprises a compound selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate; (8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium -toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(Π) tris(dipropylamino)cyclopropenium chloride;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(18) tris(dibutylamino)cyclopropenium chloride;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(26) tris(diethanolamino)cyclopropenium fluoride;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride; - I l l -
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate;
(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(69) tris(dipentylamino)cyclopropenium dicyanoamide;
(70) tris(dihexylamino)cyclopropenium chloride;
(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(76) bis(diwo-propylarnino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(77) bis(diz'io-propylamino)dibutylaminocyclopropenium dicyanoamide;
(79) bis(diethylamino)hexylannnocyclopropenium bis(trifluoromethanesulfonyl)amide;
(80) bis(diethylamino)aminocyclopropenium methylsulfate;
(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;
(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide;
(86) bis(diethylamino)dihexylaminocyclopropenium iodide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide;
(88) tris(dimethylamino)cyclopropenium thiocyanate;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;
(91 ) tris(dihexylamino)cyclopropenium dibutylphosphate;
(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(95) bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;
(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(97) bis(diethylamino)-5-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;
(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(99) tris(dibutylamino)cyclopropenium isocyanate;
( 100) tris(dibutylamino)cyclopropenium trichlorostannate;
(101 ) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;
(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;
( 105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(106) bis(diniethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (2), (4)-(13), (15)-(26), (29)-(39), (41), (42), (44), (45), (47), (48), (50), (51), (54), (56), (57), and (59)-(65).
In another embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (68)-(72), (74)-(77), (79)-(101), (103), and (105)-(107).
In one embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of:
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium )-toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(1 1) tris(dipropylamino)cyclopropenium chloride;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(18) tris(dibutylamino)cyclopropenium chloride;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide; (22) tris(dibutylaraino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(26) tris(diethanolamino)cyclopropenium fluoride;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
• (38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(69) tris(dipentylamino)cyclopropenium dicyanoamide;
(70) tris(dihexylamino)cyclopropenium chloride; - -
(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; (72) tris(dihexylamino)cyclopropeniura dicyanoamide;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(76) bis(di/50-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;
(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(80) bis(diethylamino)aminocyclopropenium methylsulfate;
(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide;
(86) bis(diethylamino)dihexylaminocyclopropenium iodide;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;
(91 ) tris(dihexylamino)cyclopropenium dibutylphosphate;
(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(95) bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;
(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;
(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(99) tris(dibutylamino)cyclopropenium isocyanate;
(100) tris(dibutylamino)cyclopropenium trichlorostannate;
(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;
(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;
(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (4)-(13), (15)-(26), (29)-(39), (41), (42), (44), (45), (47), (48), (50), (51), (54), (56), (57), and (59)-(64). In another embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (68)-(72), (74)-(77), (79)-(88), (83)-(86), (89)-(101), (103), and (105)-(107). In another embodiment, the ionic liquid comprises a compound selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium -toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(11) tris(dipropylamino)cyclopropenium chloride;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(18) tris(dibutylamino)cyclopropenium chloride;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)aniide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-(l-carboxylethylamino)cyclopropenium methylsulfate;
(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(69) tris(dipentylamino)cyclopropenium dicyanoamide;
(70) tris(dihexylamino)cyclopropenium chloride;
(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;
(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide;
(86) bis(diethylamino)dihexylaminocyclopropenium iodide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide;
(88) tris(dimethylamino)cyclopropenium thiocyanate;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;
(91) tris(dihexylamino)cyclopropenium dibutylphosphate;
(92) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(95) bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium methylsulfate; (96) bis(diethylamino)-5-(l -carboxy-2-methylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;
(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(99) tris(dibutylamino)cyclopropenium isocyanate;
(100) tris(dibutylamino)cyclopropenium trichlorostannate;
(101 ) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;
(103) bis(diethylamino)dii50-propylaminocyclopropenium dicyanoamide;
(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
( 107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (2), (4)-(9), (1 1)-(13), (15)-(19), (21)-(25), (29)-(36), (38), (39), (41), (42), (44), (45), (47), (48), (50), (54), (56), (57), and (59)-(65).
In one embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (2), (4)-(13), (15)-(25), (29)-(38), (39), (41), (42), (44), (45), (47), (48), (50), (54), (56), (57), and (59)-(65).
In another embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (10), (20), (37), (68)-(72), (74)-(77), (79), (82), (84)-(101), (103), and (105)-(107).
In another embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (68)-(72), (74)-(77), (79), (82), (84)-(101 ), (103), and (105)-(107).
In another embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of:
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium /?-toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(11) tris(dipropylamino)cyclopropenium chloride;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide; (15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(18) tris(dibutylamino)cyclopropenium chloride;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(44) bis(diethylamino)dibutylannnocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide; (64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(69) tris(dipentylamino)cyclopropenium dicyanoamide;
(70) tris(dihexylamino)cyclopropenium chloride;
(71 ) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide;
(74) tris(didecylarnino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;
(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide;
(86) bis(diethylamino)dihexylaminocyclopropenium iodide;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;
(91) tris(dihexylamino)cyclopropenium dibutylphosphate;
(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(95) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;
(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;
(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(99) tris(dibutylamino)cyclopropenium isocyanate;
(100) tris(dibutylamino)cyclopropenium trichlorostannate;
(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;
(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;
(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
In one embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (4)-(9), (1 1)-(13), (15)-(19), (21)-(25), (29)-(36), (38), (39), (41), (42), (44), (45), (47), (48), (50), (54), (56), (57), and (59)-(64). In one embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (4)-(13), (15)-(25), (29)-(38), (39), (41), (42), (44), (45), (47), (48), (50), (54), (56), (57), and (59)-(64).
In another embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (10), (20), (37), (68)-(72), (74)-(77), (79), (84)-(86), (89)-(101), (103), and (105)-(107).
In another embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (68)-(72), (74)-(77), (79), (84)-(86), (89)-(101), (103), and (105)-(107).
In another embodiment, the ionic liquid comprises a compound selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium -toluenesulfonate;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; (39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-(l-carboxylethylamino)cyclopropenium methylsulfate; and
(65) bis(diz o-propylamino)dibutylaminocyclopropenium chloride.
In another preferred embodiment, the ionic liquid comprises a compound selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium/?-toluenesulfonate;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide; (31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)arnide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(38) tris(octadecylmethylannno)cyclopropenium bis(trifluorornethanesulfonyl)amide;
(39) tris(octadecylraethylamino)cyclopropenium dicyanoamide;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate; and
(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride.
In another embodiment, the ionic liquid comprises a compound selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium /?-toluenesulfonate;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(22) tris(dibutylamino)cyclopropenium nitrate; (23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31 ) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(41 ) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate; and
(65) bis(diz.yo-propylamino)dibutylaminocyclopropenium chloride. In some embodiments, the ionic liquid comprises a compound selected from any of the compounds identified in the embodiments of the first to the seventh aspects of the invention disclosed above.
The ionic liquid of the invention is in liquid form at or below about 100 °C. In some embodiments, the ionic liquid is in liquid form at or below about 50 °C. In some embodiments, the ionic liquid is in liquid form at or below room temperature, for example in liquid form at or less than about 15, 20, 25, or 30 °C. In other embodiments, the ionic liquid is in liquid form at or below about 0 °C, -5 °C, -10 °C, -20 °C, or -30 °C. The invention also contemplates ionic liquids that are solid or semi-solid at about room temperature or above, but which can be melted at a higher temperature.
The conductivity of the ionic liquid of the invention is preferably at least 0.01 mS/cm at a temperature between about 20 °C and about 100 °C. In some embodiments, the conductivity of the ionic liquid is at least Ο.Οί, 0.05, 0.1, 0.5, 1, 5, or 10.
Viscosity is typically an important property of ionic liquids as lower viscosities lead to higher conductivities as well as greater ease of processibility. However, higher viscosities may be useful in some embodiments, for example those embodiments wherein the ionic liquid is for use in or as a lubricant. The viscosity of the ionic liquid of the invention is preferably less than 50,000 mPa.s at a temperature between about 20 °C and about 100 °C. In some embodiments, the viscosity of the ionic liquid is less than about 25,000 mPa.s, 10,000 mPa.s, 5,000 mPa.s, 2,000 mPa.s, 1,000 mPa.s, 800 mPa.s, or 700 mPa.s, 600 mPa.s, 500 mPa.s, 400 mPa.s, 300 mPa.s, 200 mPa.s, 100 mPa.s, 50 mPa.s, or 25 mPa.s.
The ionic liquid of the invention can be of any suitable purity level. In some embodiments, the ionic liquid has a purity at least about 95%, 96%, 97%, 98%, 99%, 99.5%, or 99.9% by weight. In some embodiments, the ionic liquid is substantially free of salt byproducts (for example, secondary ammonium salts) that may be produced during synthesis of the triaminocyclopropenium salt. In some embodiments, the ionic liquid contains less than about 1% by weight of salt byproducts, preferably less than about 0.5%, 0.1%, 0.01%, or even 0.001% by weight of salt byproducts. The ionic liquids of the invention may be used as solvents, for example as reaction media or for extractions.
In some embodiments, the ionic liquid comprises a chiral triaminocyclopropenium cation and is useful as a solvent for synthesis.
Accordingly, in a tenth aspect, the present invention provides use of a compound of the invention as a solvent. The invention also provides a compound of the invention that is in liquid form at or below about 100 °C for use as a solvent.
The ionic liquids of the invention may be used as electrolytes, for example in batteries, capacitors, and electrochemical cells.
Accordingly, in an eleventh aspect, the present invention provides use of a compound of the invention as an electrolyte. The invention also provides a compound of the invention that is in liquid form at or below about 100 °C for use as an electrolyte. In some embodiments, the ionic liquids of the invention may be mixed with other ionic liquids and/or other additives.
For example, the invention contemplates embodiments in which dimethylformamide and/or
dimethylsulfoxide are used as additives to aid the dissolution of cellulose in the ionic liquid. In some embodiments, the ionic liquids of the invention comprise fluoride anions. Accordingly, in some embodiments, the present invention provides an ionic liquid comprising a triaminocyclopropenium cation as defined for any of the embodiments of the first to the sixth aspects of the invention disclosed above and a fluoride anion. In some embodiments, the present invention provides an ionic liquid consisting essentially of a triaminocyclopropenium cation as defined for any of the embodiments of the first to the sixth aspects of the invention disclosed above and a fluoride anion.
While many organic fluoride salts are known, these materials are generally thermally unstable when pure due to the high basicity of the "naked" fluoride anion. [Bu4N]F, for example, is only available commercially as a hydrate, in tetrahydrofuran or water solution, or supported on silica gel or alumina. Organic fluoride salts are also typically not stable as liquids, and decompose before melting. Common ionic liquid cations, such as ammonium, phosphonium, pyridinium and imidazolium, are all well-known to decompose with fluoride because they have acidic hydrogen atoms on the carbon atoms alpha to nitrogen or phosphorus. In comparison, the triaminocyclopropenium cation has low acidity because there are no aromatic C-H groups and the charge is delocalised over three nitrogen and three carbon atoms.
In some preferred embodiments, the triaminocyclopropenium cation in the ionic liquid fluorides of the invention comprises at least one hydroxyl or amino functional group. In some preferred embodiments, the triaminocyclopropenium cation in the ionic liquid fluorides of the invention comprises at least one hydroxyl functional group. In some embodiments, at least one of Ri-Re is Ci_6 alkyl-OH, Ci.e alkyl-NH2 or Ci-6 alkyl-NH-Ci_6 alkyl. In some embodiments, at least one of Ri-Re is Ci_6 alkyl-OH. In some embodiments, at least one of Ri-R.6 is -CH2CH2OH or -CH2CH2NH2. In some embodiments, at least one of R1-R6 is -CH2CH2OH. The hydroxyl or amino functional group reduces the basicity of the fluoride anion when it is associated with the triaminocyclopropenium cation.
In some embodiments, when used as ionic liquids, the compounds of the invention are unsolvated and, in particular, unhydrated.
In some embodiments, the ionic liquids of the invention comprise solvated triaminocyclopropenium salts. In some embodiments, solvation may increase the stability of the triaminocyclopropenium salt.
Advantageously, moderate proton donor solvates reduce the nucleophilicity and basicity of the fluoride anion, which hinders decomposition routes. In some embodiments, the solvate comprises an alcohol, or primary or secondary amine. In some embodiments, the solvate comprises methanol, ethanol, propanol, wo-propanol, H-butanol, wo-butanol, sec-butanol, tert-butanol, ethylamine, monoethanolamine, or diethanolamine. In some embodiments, the solvate comprises ethanol.
In a twelfth aspect, the present invention provides use of a compound of the invention for gas storage. The invention also provides a compound of the invention that is in liquid form at or below about 100 °C for use in gas storage.
In some embodiments, the stored gas is a weak to moderate proton donor. Such gases include NH3, MeNH2, H2S, CH and C2H6.
The fluoride-containing ionic liquids of the invention are particularly suitable for use as electrolytes. The invention also contemplates their application in pharmaceutical synthesis and for gas storage applications. The application of the fluoride-containing ionic liquids of the invention for hydrogen storage, in particular, is also contemplated.
The following non-limiting examples are provided to illustrate the present invention and in no way limit the scope thereof.
EXAMPLES
Abbreviations
Bu -(CH2)3CH3
DCA dicyanoamide
Dec -(CH2)9CH3
DSC differential scanning calorimetry
Et -CH2CH3
EI electron impact ionisation
ES electrospray ionisation
FAP tris(pentafluoroethyl)trifluorophosphate
Hex -(CH2)5CH3
Me -CH3
MS mass spectrometry
NMR nuclear magnetic resonance
OTf trifiuoromethanesulfonate
Pent -(CH2)4CH3
Ph phenyl
Pr -(CH2)2CH3
i-Pr -CH(CH3)2
St -(CH2)17CH3 TFSA bis(trifluoromethanesulfonyl)amide
TGA thermogravimetric analysis
General procedures
All reagents and solvents were obtained from commercial sources. Liquid reagents and solvents were typically distilled under a dinitrogen atmosphere prior to use.
All operations were performed using standard Schlenk techniques with a dinitrogen atmosphere in order to reduce exposure to water.
Ή- and 13C {'H} -NMR spectra were collected on a Varian Unity-300 operating at 300 and 75 MHz respectively, or on a Varian INOVA-500 operating at 500 and 126 MHz respectively, in CDC13, referenced to residual solvent peaks unless otherwise indicated.
DSC was performed on a Perkin Elmer Q100. Samples of mass 5-20 mg were sealed in a vented aluminium pan and placed in the furnace with a 50 mL/min nitrogen stream; the temperature was raised at
10 °C/min.
Viscosities were measured on an Anton Parr AMVn falling-ball viscometer or a Brookfield- Wells cone- and-plate viscometer operating at 0.005 - 0.2 s_1 rotation speed range.
TGA data were collected on dried samples using a TA Instruments SDT Q600 at 10 °C/min after further drying at 100 °C for one hour in the instrument.
AC Impedance Spectroscopy was performed on a Hewlett Packard 4284A precision LCR meter, with a range of 20 Hz to 1 MHz. Samples were tested in a cylindrical cell with a "gun barrel" design, where 6 sample wells surround a heating element in the centre. Measurements were calibrated using a 0.001 M
KC1 standard solution. Samples were prepared for analysis by melting into a sample well. While samples were molten, a counter electrode was plunged into the sample, with a Teflon sleeve around the counter electrode making a seal. Measurements were run in a copper Faraday cage, using liquid nitrogen to cool the cell and vermiculite to insulate the cell. Electrospray mass spectrometry was carried out on a Micromass LCT, with samples dissolved in acetonitrile.
Water contents were determined by Karl Fischer titration using a Metrohm 831 KF coulometer.
Chloride contents were determined using a AutolabEco Chemie, with associated GPES software, under a dinitrogen atmosphere. The electrodes were either a glassy carbon (3 mm diameter) or platinum (1 mm diameter) working electrode, a platinum wire counter electrode and a silver reference electrode. Microanalysis was performed by the Campbell Microanalytical Laboratory, Department of Chemistry, University of Otago, Dunedin, New Zealand.
Trisanilmocyclopropenium chloride ([C3(NPhH)3]Cl) was prepared according to the procedure described in Weiss, R.; Hertel, M. J. Chem. Soc, Chem. Comm. 1980, 223-4, which is incorporated herein in its entirety by reference.
Bis(dimethylamino)cyclopropenone was prepared by the route described in Wilcox, C; Bresloti, R. Tetrahedron Lett. 1980, 21, 3241-2, which is incorporated herein in its entirety by reference.
Preparation of triaminocyclopropenium chloride salts from pentachlorocyclopropane
Pentachlorocyclopropane was added to freshly distilled CH2CI2 (from CaH2). This was stirred at 0 °C under a dinitrogen atmosphere. A 7-8 fold excess of amine was added over 1 h and the solution stirred at 0 °C for a further 4 h and then at ambient temperature for 18 h, before heating to reflux (65 °C) for 5 h. The solution, usually yellow/orange in colour, was then placed under vacuum to remove the solvent.
The order of addition of pentachlorocyclopropane and amine can be reversed and, in some reactions, this resulted in products that were less coloured. In some reactions, four equivalents of the secondary amine was replaced by triethylamine. This modification may be useful if the secondary ammonium salt byproduct is hard to separate.
Removal of the secondary ammonium salts was carried out in several ways. Four options are outlined below. For some reactions, it was advantageous to use a combination of methods, which were selected depending on the solubilities of the species involved. (i) The triaminocyclopropenium salt was extracted from an aqueous solution using chloroform or dichloromethane. The organic solvent was removed under vacuum.
(ii) A 1 :2 mixture of acetonitrile:toluene was added to the dried triaminocyclopropenium and secondary ammonium salts. The solution was cooled in the freezer to precipitate out the secondary ammonium salt, which was then filtered off. (iii) Dichloromethane was removed in vacuo. Acetone was added to precipitate the secondary ammonium salt, which was then filtered from the solution comprising the triaminocyclopropenium salt.
(iv) Dichloromethane was removed in vacuo. Aqueous NaOH was added to convert the secondary ammonium salt to the amine which was then removed by washing with petroleum ether or diethyl ether. The aqueous solution was then neutralized with HC1 before removing the water in vacuo. Addition of acetone precipitated NaCl, which was filtered off. NaCl could also be removed by washing a chloroform or dichloromethane solution of the triaminocyclopropenium salt with water. Preparation of methylsulfate triaminocyclopropenium salts from cyclopropenone
Various triaminocyclopropenium methylsulfate salts were prepared from the respective
diaminocyclopropenone. The cyclopropenone was dried, typically by using an wo-propanol or ethanol azetrope. Dimethylsulfate was added while under a dry, inert atmosphere, and the solution was then stirred for approximately 1 h. An excess of a primary or secondary amine was then added, and the mixture was stirred for a further 1 h. Excess amine was removed by washing with diethylether or petroleum ether and ammonium salts were removed by water-chloroform extractions.
(1) Tris(dimethylamino)cycIopropenium chloride, [C3(NMe2)3]Cl
C3CI5H (3.53 g, 16.5 mmol) and HNMe2 (10.2 g, 226 mmol) gave an orange solid (1.81 g, 54% yield) after separation from dimethylammonium chloride using option (ii) twice. Ή NMR (500 MHz, CDC13): δ 3.16 (s, NCH3). 13C NMR (126 MHz, CDC13): δ 116.76 (C3), 42.11 (N H3). ES-MS+: m/z 168 (100%, M+).
(2) Tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide,
[C3(NMe2)3]TFSA [C3(NMe2)3]Cl (3.5 g, 17.2 mmol) was stirred with LiTFSA (15.0 g, 52.3 mmol) in H20 (200 mL). The product was extracted with dichloromethane:diethyl ether (1:3, 200 mL), washed with H20 (3 x 100 mL) and dried in vacuo to yield colourless crystals (1.5 g, 19.5%). Ή, 13C NMR and MS+ as for
[C3(NMe2)3]Cl with an additional peak at 119.8 ppm in the I3C NMR spectrum due to TFSA.
(3) Tris(diethylamino)cyclopropenium chloride, [C3(NEt2)3]Cl C3CI5H (66.7g, 311 mmol) and HNEt2 (213 g, 2910 mmol) gave an orange liquid (77.0 g, 86.0% yield), that slowly solidified after separation from diethylammonium chloride using options (iii), (iv) and then (i). Ή NMR (CDCI3, 300 MHz): 8 3.36 (q, 3JHH= 7.3 Hz, 12H, NC¾), 1.22 (t, 3JHH = 7.4 Hz, 18H, NCH2C¾). 13C NMR (CDCI3, 75 MHz): b 115.99 (C3), 47.07 (CH2), 14.24 (CH3). ES-MS+: m/z 252 (100%, M+). (4) Tris(diethylamino)cyclopropenium bis(trifluoromethanesuIfonyl)amide, [C3(NEt2)3]TFSA
[C3(NEt2)3]Cl (7.30 g, 25.4 mmol) was stirred with LiTFSA (21.8 g, 76.0 mmol) in H20 (200 mL). The product was extracted with chloroform (200 mL), washed with H20 (3 x 200 mL) and dried in vacuo to yield an orange liquid (11.5 g, 85.2%). Ή, 13C NMR and MS+ as for [C3(NEt2)3]Cl with an additional peak at 119.8 ppm in the 13C NMR spectrum due to TFSA. (5) Tris(diethylamino)cyclopropenium dicyanoamide, [C3(NEt2)3]DCA
[[C3(NEt2)3]Cl (8.30 g, 28.3 mmol) was stirred with NaDCA (9.50 g, 107 mmol) in H20 (100 mL). The product was extracted with chloroform (150 mL), washed with H20 (3x 100 mL) and dried in vacuo to yield an orange liquid (7.88 g, 85.8%). Ή, 13C NMR and MS+ as for [C3(NEt2)3]Cl. (6) Tris(diethylamino)cyclopropenium nitrate, [C3(NEt2)3]N03
[C3(NEt2)3]Cl (4.74 g, 16.5 mmol) was stirred with HN03 (5 mL, 69%, 77 mmol) in H20 (50 mL). The product was extracted with dichloromethane (50 mL), washed with HN03 (5 mL, 69%, 77 mmol), washed with H20 (3 x 50 mL) until the pH was neutral, and then dried in vacuo to yield an orange liquid (4.13 g, 79.6%). Ή, 13C NMR and MS+ as for [C3(NEt2)3]Cl. (7) Tris(diethylamino)cyclopropenium tetrafluoroborate, [C3(NEt2)3]BF4
[C3(NEt2)3]Cl (5.77 g, 20.1 mmol) was stirred with aqueous HBF4 (11 mL, 35%, 60 mmol) in H20 (50 mL). The product was extracted with dichloromethane (50 mL) and washed again with aqueous HBF4 (1 1 mL, 35%, 60 mmol). The product was then washed with H20 (3 x 50 mL), until the pH was neutral, and dried in vacuo, yielding an orange liquid (5.3 g, 78.4%). Ή, 13C NMR and MS+ as for [C3(NEt2)3]Cl. (8) Tris(diethylamino)cyclopropenium thiocyanate, [C3(NEt2)3]SCN
[C3(NEt2)3]Cl (5.03 g, 17.5 mmol) was stirred with NaSCN (1.43 g, 17.6 mmol) in H20 (20 mL). The product was extracted with dichloromethane (10 mL) and the solvent removed in vacuo. This product was washed twice with NaSCN (1.43 g, 17.6 mmol) in H20 (20 mL), then with H20 (3 x 20 mL), and then dried in vacuo to yield a dark orange liquid (4.05 g, 74.7%). 'H, 13C NMR and MS+ as for
[C3(NEt2)3]Cl.
(9) Tris(diethylamino)cycIopropenium 7-toluenesuIfonate, [C3(NEt2)3] Jp-MeC6H4S03]
[C3(NEt2)3]Cl (4.99 g, 17.3 mmol) was stirred with para-toluenesulfonic acid (29.88 g, 173 mmol) in H20 (200 mL). The product was extracted with chloroform (100 mL), washed with H20 (3 x 100 mL) and dried in vacuo to yield an orange liquid (6.59 g, 90.0%). Ή, 13C NMR and MS+ as for [C3(NEt2)3]Cl. Additional peaks due to anion: Ή NMR (500 MHz, CDC13): δ 7.70 (d, 3JHH = 1.5 Hz, 2H, CH), 6.98 (d, 3JHH = 8.5 Hz, 2H, CH), 2.20 (s, 3H, C6H4CH3). 13C NMR (126 MHz, CDC13): δ 144.46 (CS03), 137.38 (CH), 127.39 (CH), 125.52 (CCH3).
(10) Tris(diethylamino)cyclopropenium trifluoromethanesulfonate, [C3(NEt2)3]OTf
[C3(NEt2)3]Cl (3.58 g, 12.5 mmol) was stirred with LiOTf (5.83 g, 37.4 mmol) in H20 (200 mL). The product was extracted with dichloromethane (100 mL), washed with H20 (3 x 100 mL) and dried in vacuo to yield a yellow solid (4.51 g, 90.2%). Ή, 13C NMR and MS+ as for [C3(NEt2)3]Cl. Additional peaks due to anion: 13C NMR (126 MHz, CDC13): δ 120.39 (q, JCT = 322 Hz, CF3).
(11) Tris(diprop lamino)cyclopropenium chloride, [C3(NPr2)3]Cl
HNPr2 (88.6 g, 0.875 mol) was dissolved in CH2C12 (250 mL) and cooled to 0 °C. C3C15H (25.0 g, 0.117 mol) was added dropwise and the solution stirred overnight. The solution was refluxed for 3 h, before CH2CI2 and excess amine were removed in vacuo. Acetone (200 mL) was added and the [H2NPr2]Cl precipitate was filtered off. After removal of acetone under vacuum, the residual [H2NPr2]Cl was removed by washing a CH2C12 solution (250 mL) with H20 (3 x 150 mL). Removal of CH2C12 in vacuo yielded an orange liquid, which solidified overnight (36.9 g, 84.9%). Ή NMR (500 MHz, CDC13): b 3.25 (t, 3JHH= 8.0 Hz, 12H, NCH2), 1.65 (m, 12Η, NCH2CH2), 0.92 (t, 3JHH = 7.3 Hz, 18H, NCH2CH2CH3). I3C NMR (126 MHz, CDC13): 8 1 15.98 (C3), 52.22 (NCH2), 21.81 (NCH2 H2), 10.52 (CH3). ES-MS+: m/z 336 (100%, M+).
(12) Tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide, [C3(NPr2)3]TFSA
Metathesis to the TFSA salt was carried out by mixing [C3(NPr2)3]Cl (17.5 g, 47.1 mmol) with 3 equivalents of LiTFSA in H20 (100 mL), followed by addition of CHC13 (100 mL) and washing with H20 (3 x 100 mL). Removal of CHC13 in vacuo yielded an orange liquid (24 g, 83%). Ή, 13C NMR and MS+ as for [C3(NPr2)3]Cl with an additional peak in the 13C NMR due to TFSA. Water content: 100 ppm.
(13) Tris(dipropylamino)cyclopropenium dicyanoamide, [C3(NPr2)3]DCA
[C3(NPr2)3]Cl (7.69 g, 20.7 mmol) was stirred with aqueous NaDCA (3.73 g, 41.9 mmol) in water (100 mL). The product was extracted with dichloromethane (50 mL) and washed with H20 (3 x 100 mL).
Additional aqueous NaDCA (1.85 g, 20.8 mmol) was added and the organic layer was then washed with H20 (4 x 100 mL) and dried in vacuo to yield a yellow liquid (11.5 g, 85.2%), which slowly crystallised. Ή, ,3C NMR and MS+ as for [C3(NPr2)3]Cl with an additional peak in the 13C NMR due to DC A.
(14) Tris(dipropylamino)cyclopropenium fluoride diethanol, [C3(NPr2)3]F.2EtOH [C3(NPr2)3]Cl (10.6 g, 28.5 mmol) was stirred in H20 (450 mL), in a blacked-out flask, to which Ag20 (6.7 g, 28.9 mmol) was added and stirring continued for 3 h. AgCl formed and was removed by filtering through Celite, before the solution was neutralized to pH 7.1 with aqueous HF. The solution was reduced in volume to 100 mL in vacuo, with drying being completed with ethanol azetrope drying (3 x 500 mL) to yield an orange liquid (12.4 g, 97.1 %). 2200 ppm H20. A fluoride selective electrode showed 44300 ppm fluoride. Ή NMR (300 MHz, CDC13): δ 3.68 (q, JHH = 7.03 Hz, 4H, CH3CH2OH), 3.27 (t, JHH = 7.91 Hz, 12H, NG¾), 1.67 (m, 12H, NCH2CH2), 1.21 (t, 3JHH = 7.03 Hz, 6H, CH3CH2OH), 0.94 (t, JHH = 7.33 Hz, 18H, NCH2CH2CH3). 19F NMR (282 MHz, D20, C6H5F reference): δ 122.03 (s). (15) Tris(dipropylamino)cyclopropenium fluoride ethanol, [C3(NPr2)3]F.EtOH
To remove one EtOH solvated molecule from [C3(NPr2)3]F.2EtOH (2.5 g, 5.6 mmol), a benzene azetrope was used (20 mL, then 10 mL). This yielded a brown liquid (2.02 g, 90.4%). Ή NMR (300 MHz, CDC13): δ 3.67 (q, 3JHH = 7.03 Hz, 2H, CH3CH2OH), 3.26 (t, 3JHH = 7.91 Hz, 12H, NCH2CH2CH3), 1.66 (m, 12H, NCH2CH2CH3), 1.20 (t, 3JHH = 7.03 Hz, 3H, CHjCH2OH), 0.93 (t, VHH = 7.33 Hz, 18H,
NCH2CH2CH5). 13C NMR and MS+ as for cation of [C3(NPr2)3]Cl. 19F NMR as for [C3(NPr2)3]F.2EtOH.
(16) Tris(dipropylamino)cyclopropenium nitrate, [C3(NPr2)3]N03
[C3(NPr2)3]Cl (7.49 g, 20.1 mmol) was dissolved in 20 mL of water. HNO3 (> 90%, 5.0 mL) was added to the solution, stirred and the [C3(NPr2)3]N03 was extracted with chloroform. HN03 (> 90%, 5.0 mL) was added to the chloroform extract, stirred and washed with 20 mL of water. The previous step was repeated. The resulting solution was washed with water until the pH was neutral. The solvent was removed under vacuum and the product formed an orange-brown solid (7.70 g, 96%). Ή, I3C NMR and MS+ as for [C3(NPr2)3]Cl.
(17) Tris(dipropylamino)cyclopropenium tetrafluoroborate, [C3(NPr2)3]BF4 [C3(NPr2)3]Cl (7.49 g, 20.1 mmol) was dissolved in water (20 mL). HBF4 (35%, 10 mL) was added to the solution, stirred and the [C3(NPr2)3]BF4 was then extracted with chloroform. HBF4 (35%, 10 mL) was added to the chloroform extract, stirred and washed with 20 mL of water. The previous step was repeated. The resulting solution was washed with water until the pH was neutral. The solvent was removed under vacuum and the product formed a white solid (7.96 g, 93%). Ή, 1 C NMR and MS+ as for [C3(NPr2)3]Cl.
(18) Tris(dibutylamino)cycIopropenium chloride, [C3(NBu2)3]Cl
C3C15H (25.0g, 1 17 mmol) and HNBu2 (123 g, 950 mmol) gave a light brown liquid (50.8 g, 95.5% yield) that slowly solidified. The product was separated from dibutylammonium chloride using option (iii) and then (i) with dichloromethane. This was followed by washing with petroleum ether (4 x 50 mL) to remove residual amine. Ή NMR (300 MHz, CDC13): δ 3.27 (t, 3JHH = 7.91 Hz, 12H, NCH2), 1.57 (m,
12H, NCH2G¾), 1.29 (m, 12H, NCH2CH2CH2), 0.91 (t, 3JHH = 7.03 Hz, 18H, CH3). ,3C NMR (75MHz, CDCI3): δ 116.2 (C3), 52.6 (N H2), 30.7 (NCH2 H2), 19.6 (NCH2CH2CH2), 13.5 (CH3). ES-MS+: m/z 420 (100%, M+).
(19) Tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyI)amide, [C3(NBu2)3lTFSA [C3(NBu2)3]Cl (10.74 g, 23.6 mmol) was stirred with aqueous LiTFSA (7.8 g, 27.2 mmol) in water (100 mL). The product was extracted with dichloromethane (40 mL) and washed with H20 (2 x 40 mL). Additional aqueous LiTFSA (7.7 g, 26.8 mmol) was added, and the solution was then washed with H20 (3 x 30 mL) and dried in vacuo to yield an orange liquid (12.9 g, 78.0%). Ή, 13C NMR and MS+ as for [C3(NBu2)3]Cl with an additional peak in the 13C NMR due to TFSA.
(20) Tris(dibutylamino)cyclopropenium bromide, [C3(NBu2)3]Br [C3(NBu2)3]Cl (0.86 g, 1.9 mmol) was stirred with HBr (20 mL, 38%, 140 mmol). The product was extracted with chloroform (20 mL) and washed again with HBr (20 mL, 38%, 140 mmol). It was then washed with H20 (3 x 20 mL) until the pH was neutral and dried in vacuo to yield a dark brown solid (0.5 g, 52%). Ή, l3C NMR and MS+ as for [C3(NBu2)3]Cl.
(21) Tris(dibutylamino)cyclopropenium dicyanoamide, [C3(NBu2)3]DCA [C3(NBu2)3]Cl (6.00 g, 13.2 mmol) was stirred with AgDCA (7.8 g, 27.2 mmol) in H20 (100 mL).
Dichloromethane (150 mL) was added to form a separate layer containing the traiminocyclopropenium salt. A fine filter was used to remove solid AgCl and the solution was washed with H20 (2 x 100 mL). The organic layer was concentrated and filtered again. It was then dried in vacuo to yield a yellow liquid (5.06 g, 79.0%). 'H, ,3C NMR and MS+ as for [C3(NBu2)3]Cl with an additional peak in the ,3C NMR due to DC A.
(22) Tris(diburylamino)cyclopropenium nitrate, [C3(NBu2)3]N03
[C3(NBu2)3]Cl (5.24 g, 1 1.5 mmol) was stirred with HN03 (10 mL, 69%, 153 mmol) in H20 (20 mL). The product was extracted with dichloromethane (75 mL) and washed again with HN03 (10 mL, 69%, 153 mmol). The organic layer was then washed with H20 (3 x 75 mL) until the pH was neutral and dried in vacuo to yield an orange liquid (4.16 g, 75.2%). ¾, 13C NMR and MS+ as for [C3(NBu2)3]Cl.
(23) Tris(dibutylamino)cycIopropenium tetrafluoroborate, [C3(NBu2)3]BF4
[C3(NBu2)3]Cl (6.17 g, 13.6 mmol) was stirred with HBF4 (20 mL, 35%, 110 mmol) in H20 (50 mL). The product was extracted with dichloromethane (75 mL) and washed again with HBF4 (20 mL, 35%, 110 mmol). The organic layer was then washed with H20 (3 x 50 mL) until the pH was neutral and dried in vacuo to yield an orange liquid (4.13 g, 79.6%). Ή, , C NMR and MS+ as for [C3(NBu2)3]Cl.
(24) Tris(dibutylamino)cyclopropenium trifiuoromethanesulfonate, [C3(NBu2)3]OTf
[C3(NBu2)3]Cl (6.00 g, 13.2 mmol) was stirred with LiOTf (2.25 g, 14.5 mmol) in H20 (100 mL). The product was extracted with dichloromethane (75 mL), washed with H20 (5 x 100 mL), and dried in vacuo to yield a yellow solid (5.95 g, 79.4%). Ή, 13C NMR and MS+ as for [C3(NBu2)3]Cl with an additional peak in the 13C NMR due to OTf. (25) Tris(diethanolamino)cyclopropenium chloride, [C3(N(CH2CH2OH)2)3]Cl
HN(CH2CH2OH)2 (97.1 g, 0.925 mol) was mixed with CH2C12 (250 mL), and the suspension was cooled to 0 °C. C3CI5H (24.7 g, 0.115 mol) was added dropwise and the solution stirred overnight. The mixture was heated to reflux for 24 h. CH2C12 was then removed in vacuo. The mixture was dissolved into ethanol (150 mL) and molecular sieves (13X, 10 A pore size) were added slowly until the solution was completely absorbed into the sieves. Two further portions of ethanol (100 mL), were added and then soaked up by more molecular sieves. The molecular sieves were soaked in ethanol for 3 h, then overnight in ethanol. This was repeated twice, soaking overnight in methanol. Alcohol was removed in vacuo, yielding a pale yellow viscous liquid (24 g in total). All four fractions were approximately 90% tris(diethanolamino)cyclopropenium chloride, with 10% [H2N(CH2CH20H)2]C1. Molecular sieves were washed with excess H20, and the process was repeated to remove [H2N(CH2CH20H)2]C1, which gave a pale yellow viscous liquid (7 g, 15.8%). Ή NMR (D20, 300 MHz) δ 3.81 (t, 3Jm = 5.3 Hz, 12H, NCH2), 3.61 ppm (t, 3JHH = 5.3 Hz, 12H, NCH2CH2).
(26) Tris(diethanolamino)c clopropenium fluoride, [C3(N(CH2CH2OH)2)3]F The sample of [C3(N(CH2CH2OH)2)3]Cl, prepared as described above, was dissolved into water (250 mL), and Ag20 (7.0 g, 0.030 mol) added and stirred for 3 h in a blacked out flask. AgCl was removed by filtration through Celite. The solution was then neutralized to pH 7.5 with aqueous HF. H20 was partially (200 mL) removed in vacuo. Complete drying was achieved with additions (3 x 150 mL, 3 x 50 mL) of ethanol and wo-propanol, followed by extended drying under a high vacuum, with stirring and mild heat (40 °C). 19F NMR (282 MHz, D20) δ 122.05 (s). 13C NMR (75 MHz, D20, acetonitrile added as reference): δ 1 18.18 (C3), 59.38 (NCH2CH2OH), 54.29 (N H2CH2OH).
(27) Tris(diaUylamino)cyclopropenium chloride, [C3(N(CH2CHCH2)2)3]CI
C3C15H (6.67 g, 31.1 mmol) and HN(CH2CHCH2)2 (23.6 g, 243 mmol) gave a yellow liquid (9.95 g, 88.9% yield) after separation from diallylammonium chloride using option (i) with chloroform. ]H NMR (500 MHz, CDC13): δ 5.58 (m, 6H, NCH2CHCH2), 5.04 (m, 12H, NCH2CHCH2), 3.76 (d, 3JHH = 5.14 Hz, 13H, NCH2CHG¾). 13C NMR (126 MHz, CDC13): δ 130.81 (NCH2 HCH2), 1 18.39 (NCH2CH H2), 116.36 (C3), 54.03 (NC¾CHCH2). ES-MS+: m/z 324 (100%, M+).
(28) Tris(diallylamino)cyclopropeiiium bromide, [C3(N(CH2CHCH2)2)3]Br
[C3(N(CH2CHCH2)2)3]C1 (1.07 g, 2.98 mmol) was stirred with HBr (7 mL, 38%, 44 mmol). The product was extracted with dichloromethane (2 x 25 mL), washed twice more with HBr (5 mL, 38%, 33 mmol), washed with H20 (4 x 50 mL) until the pH was neutral, and then dried in vacuo to yield a dark brown solid (0.8 g, 66.6%). I3C NMR and MS+ as for [C3(N(CH2CHCH2)2)3]C1. (29) Tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide,
[C3( (CH2CHCH2)2)3]TFSA
[C3(N(CH2CHCH2)2)3]C1 (4.11 g, 11.4 mmol) was stirred with LiTFSA (7.00 g, 24.4 mmol) in H20 (100 mL). The product was extracted with chloroform (2 x 100 mL), washed with H20 (3 x 100 mL), and then dried in vacuo to yield a light yellow liquid (5.00 g, 72.4%). Ή, 13C NMR and MS+ as for
[C3(N(CH2CHCH2)2)3]C1 with an additional peak in the 1 C NMR due to TFSA.
(30) Tris(diallylamino)cyclopropenium dicyanoamide, [C3( (CH2CHCH2)2)3]DCA
[C3(N(CH2CHCH2)2)3]C1 (5.19 g, 14.4 mmol) was stirred with NaDCA (2.84 g, 31.9 mmol) in H20 (100 mL). The product was extracted with chloroform (2 x 100 mL), washed with H20 (3 x 100 mL), and then dried in vacuo to yield a light yellow liquid (5.06 g, 89.9%). Ή, 13C NMR and MS+ as for
[C3(N(CH2CHCH2)2)3]C1 with an additional peak in the 13C NMR due to DC A.
(31) Tris(butylmethylamino)cyclopropenium chloride, [C3(NBuMe)3]Cl
C3C15H (25.0 g, 117 mmol) and HNBuMe2 (81.0 g, 929 mmol) gave a light yellow liquid (35.0 g, 90.9% yield) after separation of butylmethylammonium chloride using option (iii) then (i) with chloroform. It was then washed with diethyl ether (2 x 100 mL) and petroleum ether (2 x 75 mL) to remove residual amine. Ή NMR (500 MHz, CDC13): 5 3.29 (t, 3JHH= 7.8 Hz, 6H, NG¾), 3.12 (s, 9H, NCH3), 1.56 (m, 6H, NCH2C¾), 1.27 (m, 6H, NCH2CH2CH2), 0.88 (t, 3JHH = 7.5 Hz, 9H, CH2CH3). 13C NMR (126 MHz, CDC13): δ 1 16.75 (C3), 55.32 (NCH2), 40.18 (NCH3), 29.89 (NCH2 H2), 19.71 (NCH2CH2 H2), 13.64 (CH2 H3). ES-MS+: m/z 294.29 (100%, M+). (32) Tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide,
[C3(NBuMe)3]TFSA
[C3(NBuMe)3]Cl (3.00 g, 9.10 mmol) was stirred with LiTFSA (5.00 g, 17.4 mmol) in H20 (100 mL). The product was extracted with chloroform (50 mL), washed with H20 (3 x 50 mL) and was dried in vacuo to yield a yellow liquid (3.90 g, 74.6%). Ή, 13C NMR and MS+ as for [C3(NBuMe)3]Cl with an additional peak in the 13C NMR due to TFSA.
(33) Tris(burylmethylamino)cyclopropenium dicyanoamide, [C3(NBuMe)3]DCA
[C3(NBuMe)3]Cl (5.30 g, 16.1 mmol) was stirred with NaDCA (3.65 g, 41.0 mmol) in H20 (100 mL). The product was extracted with chloroform (50 mL), washed with H20 (3 x 50 mL) and dried in vacuo to yield a yellow liquid (5.40 g, 93.3%). Ή, 13C NMR and MS+ as for [C3(NBuMe)3]Cl with an additional peak in the 13C NMR due to DCA. (34) Tris(butylmethylamino)cyclopropenium nitrate, [C3(NBuMe)3]N03
[C3(NBuMe)3]Cl (3.49 g, 10.6 mmol) was stirred with HN03 (0.8 mL, 69%, 12.3 mmol) in H20 (20 mL). The product was extracted with chloroform (3 x 20 mL), washed twice more with HN03 (0.8 mL, 69%, 12.3 mmol) in H20 (20 mL), washed with H20 (6 x 30 mL) until the pH was neutral, and was dried in vacuo to yield a brown liquid (3.51 g, 93.0%). Ή, l3C NMR and MS+ as for [C3(NBuMe)3]Cl.
(35) Tris(butylmethylamino)cyclopropenium tetrafluoroborate, [C3(NBuMe)3]BF4
[C3(NBuMe)3]Cl (2.02 g, 6.13 mmol) was stirred with HBF4 (1.3 mL, 35%, 7.23 mmol) in H20 (15 mL). The product was extracted with chloroform (3 x 10 mL), and washed twice more with HBF4 (1.3 mL, 35%, 7.23 mmol) in H20 (15 mL). It was then washed with H 0 (3 x 30 mL) until the pH was neutral and was dried in vacuo to yield a brown liquid (2.19 g, 93.9%). Ή, 13C NMR and MS+ as for
[C3(NBuMe)3]Cl.
(36) Tris(butylmethylamino)cyclopropeniuni thiocyanate, [C3(NBuMe)3]SCN
[C3(NBuMe)3]Cl (3.50 g, 10.6 mmol) was stirred with NaSCN (0.86 g, 10.6 mmol) in H20 (20 mL). The product was extracted with chloroform (20 mL), washed twice with additional NaSCN (0.86 g, 10.6 mmol) and H20 (20 mL), washed with H20 (4 x 30 mL), and dried in vacuo to yield a brown liquid (3.97 g, 95.5%). Ή, 13C NMR and MS+ as for [C3(NBuMe)3]Cl with an additional peak in the 13C NMR due to SCN.
(37) Tris(octadecylmethylamino)cycIopropenium chloride, [C3(NStMe)3]Cl
C3C15H (2.92 g, 13.6 mmol), HNMe(C18H37) (11.6 g, 40.9 mmol) and NEt3 (14.5 g, 143 mmol) gave a light yellow solid (10.2 g, 81.4% yield) after separation from methyloctadecylammonium chloride using option (i) with chloroform. The product was washed with petroleum ether (2 x 50 mL) to remove residual amine and dried in vacuo. ¾ NMR (300 MHz, CDC13): δ 3.33 (t, 3/HH = 7.6 Hz, 6H, NCH2C17H35), 3.17 (s, 9H, NCH , 1.60 (m, 6Η, NCH2CH C16H33), 1.12-34 (m, 90H, NC2H4Ci5H50CH3), 0.85 (t, 3JHH = 6.5 Hz, 9H, NC17H34CH3). 13C NMR (75 MHz, CDC13): δ 116.99 (C3), 55.70 (NCH2), 40.31 (NCH3), 31.90, 28.72-30.42, 28.05, 26.66, 22.66, 14.10 (CH3). ES-MS+: m/z 882.95 (100%, M+).
(38) Tris(octadecylmethylamino)cyclopropeniuni bis(trifluoromethanesulfonyl)amide,
[C3(NStMe)3]TFSA
[C3(NStMe)3]Cl (4.00 g, 4.35 mmol) was stirred with LiTFSA (5.00 g, 17.4 mmol) in H20 (100 mL). The product was extracted with chloroform (100 mL), washed with H20 (3 x 50 mL) and dried in vacuo to yield a yellow liquid (4.30 g, 84.9%). Ή, 13C NMR and MS+ as for [C3(NStMe)3]Cl with an additional peak in the 13C NMR due to TFSA. (39) Tris(octadecylmethylamino)cyclopropenium dicyanoaraide, [C3(NStMe)3]DCA
[C3(NStMe)3]Cl (3.00 g, 3.38 mmol) was stirred with NaDCA (1.20 g, 13.5 mmol) in H20 (100 mL). The product was extracted with dichloromethane (100 mL), washed with H20 (3 x 100 mL) and dried in vacuo to yield a yellow solid (2.20 g, 68.5%). Ή, ,3C NMR and MS+ as for [C3(NStMe)3]Cl with an additional peak in the 13C NMR due to DC A.
(40) Bis(diethylamino)dimethylaminocyclopropenium methylsulfate, [C3(NEt2)2(NMe2)]MeS04
Cyclopropenone (Et2N)2C30 (8.91 g, 45.5 mmol), Me2S04 (8.60 g, 68.2 mmol) and HNMe2 (6.80 g, 150 mmol) were reacted as described in the general synthetic procedure and gave a yellow liquid (5.72 g, 37.6%). Ή NMR (300 MHz, CDC13): δ 3.68 (s, 3H, MeS04), 3.40 (q, 3JHH = 7.3 Hz, 8H, NC¾CH3), 3.17 (s, 6H, NC¾), 1.27 (t, 3JHH= 7.2 Hz, 12H, NCH2CH?). 13C NMR (126 MHz, CDC13): δ 117.83 (CO, 1 16.31 (C2), 54.02 (CH3S04), 47.28 (NCH2CH3), 42.07 (CH3), 14.07 (NCH2CH3).
(41) Bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide,
[C3(NEt2)2(NMe2)]TFSA
[C3(NEt2)2(NMe2)]MeS04 (2.74 g, 8.18 mmol) was stirred with LiTFSA (8.0 g, 28.0 mmol) in H20 (200 mL). The product was extracted with Et20 (200 mL), washed with H20 (3 x 200 mL) and dried in vacuo to yield a pale yellow liquid (2.63 g, 63.7%). ES-MS+: m/z 224.21 (100%, M+). Ή and 13C NMR as for [C3(NEt2)2(NMe2)]MeS04 with an alternative peak in the 13C NMR due to TFSA replacing MeS04.
(42) Bis(diethylamino)dimethyIaminocyclopropenium dicyanoamide, [C3(NEt2)2(NMe2)]DCA
[C3(NEt2)2(NMe2)]MeS04 (4.34 g, 13.0 mmol) was stirred with NaDCA (5.60 g, 62.9 mmol) in H20 (100 mL). The product was extracted with chloroform (100 mL), washed with H20 (3 x 100 mL) and dried in vacuo to yield a pale yellow liquid (3.24 g, 86.0%). Ή and 13C NMR as for [C3(NEt2)2(NMe2)]MeS04 but with no peaks due to MeS04 and an additional peak in the 13C NMR due to DC A. MS+ as for
[C3(NEt2)2(NMe2)]TFSA.
(43) Bis(diethylamino)dibutylaminocycIopropenium methylsulfate, [C3(NEt2)2(NBu2)]MeS04 Cyclopropenone (Et2N)2C30 (6.23 g, 31.8 mmol), Me2S04 (4.40 g, 34.9 mmol) and HNBu2 (4.91 g, 38.0 mmol) were reacted as described in the general synthetic procedure and gave a dark orange liquid (6.31 g, 47.4%). Ή NMR (300 MHz, CDC13): δ 3.69 (s, 3H, MeS04), 3.40 (q, JHH = 7.1 Hz, 8H, NC¾CH3), 3.28 (t, 3JHH = 7.91 Hz, 4H, NCH2CH2), 1.60 (m, 4H, NCH2G¾), 1.19-39 (m, 16H, NCH2CH2C¾ and NCH2CH), 0.93 (t, 3JHH = 7.33 Hz, 6H, CH2CH2CHj). 13C NMR (126 MHz, CDC13): δ 116.76 (Q), 116.64 (C2), 54.35 (CH3S04), 53.17 (NCH2CH2), 47.35 (NCH2CH3), 31.28 (NCH2CH2), 20.10
(NCH2CH2CH2), 14.54 (NCH2CH3), 14.00 (CH2CH2CH3). (44) Bis(diethylamino)diburylaminocyclopropenium bis(trifluoromerhanesulfonyl)amide,
[C3(NEt2)2(NBu2)]TFSA
[C3(NEt2)2(NBu2)]MeS04 (7.35 g, 17.5 mmol) was stirred with LiTFSA (10.0 g, 34.8 mmol) in H20 (150 niL). The product was extracted with chloroform (150 mL), washed with H20 (3 x 150 mL) and dried in vacuo to yield a dark orange liquid (6.71 g, 65.2%). ¾ and 13C NMR as for [C3(NEt2)2(NBu2)]MeS04 but with no peaks due to MeS04 and an additional peak in the 13C NMR due to TFSA.
(45) Bis(diethylamino)dibuty]aminocyclopropenium dicyanoamide, [C3(NEt2)2(NBu2)]DCA
[C3(NEt2)2(NBu2)]MeS04 (6.31 g, 15.0 mmol) was stirred with NaDCA (4.00 g, 44.9 mmol) in H20 (150 mL). The product was extracted with chloroform (150 mL), washed with H20 (3 x 150 mL) and dried in vacuo to yield a dark orange liquid (5.05 g, 90.0%). Ή and 13C NMR as for [C3(NEt2)2(NBu2)]MeS04 but with no peaks due to MeS04 and an additional peak in the 13C NMR due to DC A.
(46) Bis(diethylamino)dihexyIaminocyclopropenium methylsulfate, [C3(NEt2)2(NHex2)]MeS04
Cyclopropenone (Et2N)2C30 (5.53 g, 28.2 mmol), Me2S04 (5.33 g, 42.3 mmol) and HNHex2 (9.03 g, 48.7 mmol) were reacted as described in the general synthetic procedure and gave an orange liquid (10.9 g, 81.1 %). ¾ NMR (300 MHz, CDC13): δ 3.69 (s, 3H, MeS04), 3.41 (q, VHH = 7.3 Hz, 8H, NC¾CH3), 3.27 (t, 3JHH = 8.5 Hz, 4H, NCH2C5H„), 1.60 (m, 4H, NCH2CH2C4H9), 1.19-35 (m, 24H,
N(CH2)2(CH2)3CH3 and NCH2CH)), 0.86 (t, 3JHH = 6.5 Hz, 6H, -N(C5UW)CH3). I C NMR (75 MHz, CDC13): δ 116.45 (C,), 116.38 (C2), 54.26 (CH3S04), 53.17 (NCH2C5HU), 47.10 (N H2CH3), 31.39 (NCH2CH2C4H9), 29.02 (NC2H4CH2C3H7), 26.25 (NC3H6 H2C2H5), 22.47
Figure imgf000139_0001
14.29 (NCH2CH3), 13.91 (NC5H10CH3).
(47) Bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide,
[C3(NEt2)2(NHex2)]TFSA
[C3(NEt2)2(NHex2)]I samples contaminated with (Et2N)2C30, prepared by treatment of (Et2N)2C30 with excess Etl followed by removal of Etl by washing with diethylether, addition of HNHex2, and further washing with diethylether, were combined and a large excess of LiTFSA (20 g, 69.7 mmol) in H20 (300 mL) was added. The product was extracted with chloroform (300 mL) and washed with H20 (2 x 300 mL). (Et2N)2C30 was removed by washing with petroleum ether : diethylether (1 : 1 , 3 x 100 mL) and the product was dried in vacuo to yield a dark brown liquid (4 g). Ή and 13C NMR as for
[C3(NEt2)2(NHex2)]MeS0 but with no peaks due to MeS04 and an additional peak in the 13C NMR due to TFSA. (48) Bis(diethylamino)dihexylaminocyclopropenium dicyanoamide, [C3(NEt2)2(NHex2)]DCA
[C3(NEt2)2(NHex2)]MeS04 (10.9 g, 22.9 mmol) was stirred with NaDCA (7.50 g, 84.2 mmol) in H20 (150 mL). The product was extracted with chloroform (150 mL), washed with H20 (4 x 100 mL) and dried in vacuo to yield an orange liquid (8.86 g, 90%). Ή and 13C NMR as for
[C3(NEt2)2(NHex2)]MeS04 but with no peaks due to MeS04 and an additional peak in the 1 C NMR due to DC A.
(49) Bis(diethylamino)diethanolaminocyclopropenium iodide, [C3(NEt2)2(N(CH2CH20H)2)]I
Cyclopropenone (Et2N)2C30 (7.68 g, 39.2 mmol) was dried using ethanol azetropes (5 x 50 mL).
Iodoethane (97.5 g, 625 mmol) was added and the solution was heated to reflux for 18 h. It was then cooled to ambient temperature and HN(C2H4OH)2 (8.44 g, 80.3 mmol) was added and stirred at ambient temperature 48 h. Excess iodoethane was removed in vacuo and H20 (100 mL) added. Cyclopropenone was extracted with dichloromethane (100 mL and 50 mL) and the combined extracts were washed with H20 (2 x 100 mL). The H20 washings were combined with the main product H20 layer and were then extracted with dichloromethane (3 x 100 mL) to yield a yellow liquid (3.50 g, 21.7%). Ή NMR (300 MHz, D20): δ 3.73 (t, VHH = 5.3 Hz, 4H, NCH2C¾OH), 3.47 (t, VHH = 5.3 Hz, 4H, NCH2CH2OH), 3.37 (q, 3JHH = 7.1 Hz, 8H, NCH2CH3), 1.17 (t, VHH = 7.1 Hz, 12H, NCH2C¾). 13C NMR (75 MHz, D20, methanol added as reference): δ 1 17.89 (C,), 117.26 (C2), 59.46 (NCH2CH2OH), 54.38 (NCH2CH2OH), 47.20 (N H2CH3), 13.98 (NCH2 H3). MS+ as for [C3(NEt2)2(N(CH2CH2OH)2)]MeS04.
(50) Bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide, [C3(NEt2)2(N(CH2CH2OH)2)]TFSA
[C3(NEt2)2(N(CH2CH2OH)2)]I (3.50 g, 8.52 mmol) was stirred with LiTFSA (5.0 g, 17 mmol) in H20 (150 mL). The product was extracted with chloroform (150 mL), washed with H20 (4 x 150 mL) and dried in vacuo to yield a yellow liquid (3.5 g, 73%). Ή and 13C NMR as for
[C3(NEt2)2(N(CH2CH2OH)2)]I with an additional peak at 119.8 in the 13C NMR spectrum due to TFSA. MS+ as for [C3(NEt2)2(N(CH2CH2OH)2)]MeS04.
(51) Bis(diethylamino)diethanolaminocyclopropenium fluoride, [C3(NEt2)2(N(CH2CH2OH)2)]F
[C3(NEt2)2(N(CH2CH2OH)2)]I (3.50 g, 8.52 mmol) was stirred in H20 (250 mL), in a blacked-out flask, to which Ag20 (3.0 g, 13 mmol) was added. After stirring for 3 h, AgCl precipitated and was removed by filtration through Celite. The solution was then neutralized to pH 7.5 with aqueous HF and reduced in volume to 20 mL in vacuo, with drying being completed with ethanol azetrope drying (3 x 200 mL) to yield a viscous yellow liquid (2.5 g, 96%). 19F NMR (282 MHz, D20, C6H5F reference): δ 121.94 (s). (52) Bis(diethylamino)diethanolaminocyclopropenium methyls ulfate,
[C3(NEt2)2(N(CH2CH2OH)2)]MeS04
Cyclopropenone (Et2N)2C30 (8.88 g, 45.3 mmol), Me2S04 (8.53 g, 67.6 mmol) and HN(C2H4OH)2 (8.10 g, 77.0 mmol) were reacted as described in the general synthetic procedure and gave a yellow liquid (6.40 g, 35.8%). Separation from the ammonium species and cyclopropenone was carried out by dissolution into H20 (75 mL), and extraction of cyclopropenone and [C3(NEt2)2(N(CH2CH2OH)2)]MeS04with dichloromethane (8 x 75 mL). [C3(NEt2)2(N(CH2CH2OH)2)]MeS04 was then extracted using H20 (3 x 50 mL). Ή NMR (500 MHz, CDC13): δ 3.82 (t, 3JHH = 4.9 Hz, 4H, NCH2CH2OH), 3.66 (s, 3H, MeS04), 3.51 (t, 3JHH = 4.9 Hz, 4H, NCH2CH2OH), 3.42 (q, VHH = 7.1 Hz, 8H, NC¾CH3), 1.25 (t, 3JHH = 7.1 Hz, 12H, NCH2CH3). 13C NMR as for [C3(NEt2)2(N(CH2CH2OH)2)]I with an additional peak in the 13C NMR spectrum due to MeS04. ES-MS+: m/z 284.23 (M+, 100%).
(53) Bis(diethylamino)diallylaminocyclopropeniuni methyls ulfate,
[C3(NEt2)2(N(CH2CHCH2)2)]MeS04
Cyclopropenone (Et2N)2C30 (7.54 g, 38.5 mmol), Me2S04 (6.27 g, 49.7 mmol) and HN(CH2CHCH2)2 (6.30 g, 64.8 mmol) were reacted as described in the general synthetic procedure and gave an orange liquid (7.44 g, 50%). Ή NMR (CDC13, 500 MHz): 8 5.81 (m, 2H, NCH2CH=CH2), 5.28 (d, 3JHH = 10.5 Hz, 2H, NCH2CH=CH2), 5.25 (d, 3JHH= 17 Hz, 2H, NCH2CH=CH2), 3.92 (d, 3JHH= 5.5 Hz ,4H,
NCH2CH=CH2), 3.68 (s, 3H, CH5S04), 3.35 (q, 3JHH = 7 Hz, 8H, NCH2CH3), 1.23 (t, 3JHH = 7 Hz,12H, NCH2CH3). '¾{Ή} NMR (CDC13, 126 MHz): δ 131.34 (NCH2 HCH2), 1 18.60 (NCH2CH H2), 1 16.48 (ring C), 116.15 (ring C), 54.34 (NCH2CHCH2), 54.04 (MeS04), 46.95 (NCH2CH3), 13.97 (NCH2 H3)2. ES-MS+: m/z 276.245 (M+, 100%).
(54) Bis(diethylamino)diallylaminocyclopropeiiium bis(trifluoromethanesulfonyl)amide,
[C3(NEt2)2(N(CH2CHCH2)2)]TFSA
[C3(NEt2)2(N(CH2CHCH2)2)]MeS04 (7.44 g, 19.2 mmol) was stirred with LiTFSA (3 equivalents) in H20 (100 mL). The product was extracted with chloroform (100 mL), washed with H20 (3 x 100 mL) and dried in vacuo to yield an orange liquid (7.0 g, 84%). ¾, 13C NMR and MS+ as for
[C3(NEt2)2(N(CH2CHCH2)2)]MeS04 but with no peaks due to MeS04 and an additional peak in the 13C NMR due to TFSA.
(55) Bis(diethylamino)butylmethylaminocyclopropenium methyls ulfate,
[C3(NEt2)2(NBuMe)]MeS04
Cyclopropenone (Et2N)2C30 (6.41 g, 32.7 mmol), Me2S04 (8.26 g, 65.5 mmol) and HNBuMe (7.14 g, 81.9 mmol) were reacted as described in the general synthetic procedure and gave an orange liquid (9.70 g, 78.6%). Using an alternative route, to a stirred solution of [C3(NEt2)2(NHBu]MeS04 (1.0 g, 2.8 mmol) in dry THF at -78 °C was slowly added n-BuLi (1.89 mL, 3.03 mmol). The reaction was then stirred for 6 h and brought to room temperature. Me2S04 (0.33 mL, 2.76 mmol) was added to this solution and stirred for 1 h. The solvent was removed in vacuo, the oil was washed with dry diethyl ether several times, the product was then dissolved in chloroform and filtered to remove LiMeS04. Removal of solvent in vacuo gave an orange oil (0.90 g, 87%).
Ή NMR (300 MHz, CDC13): δ 3.66 (s, 3H, MeS04), 3.39 (q, 3JHH = 7.3 Hz, 8H, NCH2CH3), 3.30 (t, 3JHH = 7.9 Hz, 2H, NC¾CH2), 3.13 (s, 3H, NCHj), 1.59 (m, 2Η, NCH2G¾), 1.19-38 (m, 14H, NCH2CH2CH2 and NCH2G¾), 0.92 (t, VHH = 7.3 Hz, 3H, CH2CH3). 13C NMR (126 MHz, CDC13): δ 117.20 (C,), 116.14 (C2), 55.16 (N H2CH2), 54.04 (CH3S04), 47.18 (N H2CH3), 39.53 (NCH3), 30.01 (NCH2 H2), 19.72 (NCH2CH2 H2), 14.14 (NCH2 H3), 13.68 (CH2CH2C¾).
(56) Bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide, [C3(NEt2)2(NBuMe)] TFS A
[C3(NEt2)2(NBuMe)]MeS04 (3.90 g, 10.3 mmol) was stirred with LiTFSA (10 g, 34.8 mmol) in H20 (100 mL). The product was extracted with chloroform (150 mL), washed with H20 (3 x 100 mL) and dried in vacuo to yield an orange liquid (4.48 g, 79.3%). Ή and 13C NMR as for [C3(NEt2)2(NBuMe)]MeS04 but with no peaks due to MeS04 and an additional peak in the 13C NMR due to TFS A.
(57) Bis(diethylamino)buty lmethylaminocyclopropenium dicyanoamide,
[C3(NEt2)2(NBuMe)]DCA [C3(NEt2)2(NBuMe)]MeS04 (5.50 g, 14.6 mmol) was stirred with NaDCA (4.00 g, 44.9 mmol) in H20 (100 mL). The product was extracted with chloroform (100 mL), washed with H20 (3 x 100 mL) and dried in vacuo to yield an orange liquid (4.10 g, 84.6%). Ή and l3C NMR as for
[C3(NEt2)2(NBuMe)]MeS04 but with no peaks due to MeS04 and an additional peak in the 13C NMR due to DC A. (58) Bis(diethyIamino)hexylmeth\ aminocyclopropenium methyls ulf ate,
[C3(NEt2)2(NHexMe)]MeS04
Cyclopropenone (Et2N)2C30 (4.77 g, 24.3 mmol) and dimethylsulfate (3.68 g, 29.1 mmol) were mixed at ambient temperature for 30 min. Hexylmethylamine (3.45 g, 29.9 mmol) was added and the solution stirred at ambient temperature for 30 min. The product was washed with pentane (3 x 75 mL), to remove excess hexylmethylamine, and then with diethylether (3 x 75 mL), to remove residual
bis(diethylamino)cyclopropenone. The product was then dissolved in CHC13 (100 mL) and washed with H20 (3 x 100 mL). CHC13 was removed in vacuo to yield an orange liquid (7.70 g, 78.2%). !H NMR (300 MHz, CDC13): δ 3.67 (s, 3H, MeSQ4), 3.40 (q, 3JHH = 7.2 Hz, NCH2CH3), 3.30 (t, 3JHH = 7.8 Hz, NCH2(CH2)4CH3), 3.14 (s, NG¾), 1.55-69 (m, NCH2CH (CH2)3CH3), 1.19-36 (m, NCH2C¾ and N(CH2)2(CH2)3CH3), 0.85 (t, 3JHH = 6.9 Hz, NCH2(CH2)4CH3). 13C NMR (75 MHz, CDC13): δ 117.36 (C), 116.40 (C2), 55.73 (N H2C5H„), 54.04 (MeS04), 47.39 (N H2CH3), 39.66 (NCH3), 31.63
(NCH2 H2C4H9), 28.21 (N(C2H4) H2C3H7), 26.45 (NC3H6 H2C2H5), 22.72 (NC4H8 H2CH3), 14.25 (NCH2 H3), 14.16 (NC5H10 H3).
(59) Bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide, [C3(NEt2)2(NHexMe)]TFSA
[C3(NEt2)2(NHexMe)]MeS04 (3.10 g, 7.65 mmol) was stirred with LiTFSA (7.20 g, 25.08 mmol) in H20 (150 mL). The product was extracted with chloroform (150 mL), washed with H20 (3 x 150 mL) and dried in vacuo to yield a yellow liquid (3.60 g, 82.0%). Water content: 173.1 ppm. Ή and 13C NMR as for [C3(NEt2)2(NHexMe)]MeS04 but with no peaks due to MeS04 and an additional peak in the 13C NMR at 119.85 (q, 'JcF = 321.6 Hz, CF3), due to TFSA.
(60) Bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide,
[C3(NEt2)2(NHexMe)]DCA [C3(NEt2)2(NHexMe)]MeS04 (4.60 g, 11.4 mmol) was stirred with NaDCA (3.40 g, 38.2 mmol) in H20 (150 mL). The product was extracted with chloroform (150 mL), washed with H20 (3 x 150 mL) and dried in vacuo to yield a yellow liquid (3.75 g, 91.6%). Ή and 1 C NMR as for
[C3(NEt2)2(NHexMe)]MeS04 but with no peaks due to MeS04 and an additional peak in the 13C NMR due to DC A. (61) Bis(diethylamino)butylaminocyclopropenium methylsulfate, [C3(NEt2)2(NHBu)]MeS04
Cyclopropenone (Et2N)2C30 (9.00 g, 45.9 mmol), Me2S04 (8.70 g, 69.0 mmol) and H2NBu (4.37 g, 59.7 mmol) were reacted as described in the general synthetic procedure and gave an orange liquid (10.46 g, 62.7%). Before H2NBu was added, the product was washed with dry diethyl ether (5 x 20 mL) to remove unreacted Me2S04. Ή NMR (500 MHz, CDC13): δ 8.14 (br, 1H, NH), 3.67 (s, 3H, CH3S04), 3.35 (q, HH = 7.16 Hz, 2H, NCH2CH3), 3.20 (t, 3JHH = 6.83 Hz, 2H, NCH2CH2), 1.61 (m, 2H, NCH2CH2), 1.33 ( m, 2Η, NCH2CH2CH2), 1.21 (t, 3JHH = 7.25 Hz, 3H, NCH2CH3), 0.87 (t, 3JHH = 7.25 Hz, 3H,
CH2CH2CH3). 13C NMR (126 MHz, CDC13): δ 115.94 (equivalent C3 atoms), 1 14.65 (br, unique C3 atom), 53.92 (CH3S04), 46.79 (N H2CH2), 46.27 (NCH2CH3), 32.044 (NCH2CH2), 19.46
(NCH2CH2CH2), 13.95 (NCH2CH3), 13.34 (CH2CH2 H3). (62) Bis(diethylamino)burylaminocyclopropenium bis(trifluoromethanesulfonyl)amide,
[C3(NEt2)2(NHBu)]TFSA
[C3(NEt2)2(NHBu)]MeS04 (3.40 g, 9.37 mmol) was stirred with LiTFSA (8.10 g, 28.2 mmol) in H20 (150 mL). The product was extracted with chloroform (150 mL), washed with H20 (2 x 100 mL) and dried in vacuo to yield an orange liquid (3.67 g, 73.7%). Ή and 13C NMR similar to
[C3(NEt2)2(NHBu)]MeS04 with some differences: Ή NMR NH resonance at 6.22 ppm. 13C NMR resonance for TFSA at 119.79 ppm (q, 'JcF = 322 Hz, CF3), C3 ring resonances at 115.40 (equivalent C3 atoms) and 1 15.37 (unique C3 atom) ppm.
(63) Bis(diethylamino)burylaminocyclopropenium dicyanoamide, [C3(NEt2)2(NHBu)]DCA [C3(NEt2)2(NHBu)]MeS04 (5.92 g, 16.3 mmol) was stirred with NaDCA (4.37 g, 49.1 mmol) in H20
(150 mL). The product was extracted with chloroform (2 x 100 mL), washed with H20 (4 x 100 mL) and dried in vacuo to yield an orange liquid (3.36 g, 64.8%). Ή and 1 C NMR similar to
[C3(NEt2)2(NHBu)]MeS04 with some differences: Ή NMR resonance for NH at 7.92 ppm. ,3C NMR resonance for DCA at 1 19.39 ppm, C3 ring resonances at 1 15.54 (equivalent C3 atoms) and 114.81 (slightly br, unique C3 atom) ppm.
(64) Bis(diethylamino)-iS'-(l-carboxylethylamino)cyclopropenium methylsulfate,
[C3(NEt2)2(NH((S)-CHMeCOOH))]MeS04
Dried bis(diethylamino)cyclopropenone (21.13 g, 108 mmol) was stirred with Me2S04 (13.3 mL, 140 mmol) for 30 minutes. The mixture was washed with dry diethyl ether several times to remove excess Me2S04 and cyclopropenone. This gave [C3(NEt2)(OMe)]MeS04 as an orange viscous oil (24.2 g, 70%). [C3(NEt2)2(OMe)]MeS04 (11.37 g, 35.31 mmol) was stirred with L-alanine (4.1 g, 46 mmol) and NEt3 (17 mL, 106 mmol) in water (20 mL) overnight. Water was removed in vacuo and the product was dissolved in acetone (20 mL) and filtered to remove unreacted L-alanine. The solvent was removed in vacuo and NEt3 was removed by washing with dry diethylether (5 x 50 mL) to yield an orange oil (10.4 g, 75.7%). Ή NMR (500MHz, CDC13): δ 8.36 (d, 3JHH = 7 Hz, 1H, NH), 5.65 (br, 1H, COOH), 4.01 (dq, 3JHH = 7 Hz, JHH = 7 Hz, 1H, CH), 3.71 (s, 3H, MeS04), 3.38 (q, 3JHH = 6.6 Hz, 8H, NCH2CH3), 1.58 (d, 3JHH = 7 Hz, 3H, Me), 1.24 (t, 3JHH = 6.6 Hz, 12H, NCH2CH3). 13C NMR (CDC13, 126 MHz) δ 175.37 (COOH), 1 15.75 (unique ring C), 115.18 (equivalent ring C), 56.54 (CHMe), 54.74 (MeS04), 46.54 (N H2CH3), 18.34 (CH H3), 14.22 (NCH2 H3). EI-MS: m/z 268.93 (M+). (65) Bis(dus0-propylamino)dibutylaimnocydopropenium chloride, [C3(N(i-Pr)2)2(NBu2)]Cl
C3C15H (5.00 g, 23.4 mmol) was stirred at 0 °C in dry dichloromethane (75 mL). HN(i-Pr)2 (11.9 g, 1 18 mmol) added dropwise over 1 h followed by stirring for 2 h at 0 °C and then overnight at ambient temperature. HNBu2 (12.3 g, 95.0 mmol) was added dropwise over 1 h, followed by stirring for 2 h at 0 °C, then overnight at ambient temperature. The product was separated from ammonium chloride salts using option (iv) and then (i) using dichloromethane. Drying in vacuo yielded a colourless solid (5.77 g, 61.9%). Ή NMR (300 MHz, CDC13): δ 3.79 (spt, 3JHH = 13.8 Hz, 4H, NCH(CH3)2), 3.36 (t, 3JHH = 7.9 Hz, 4H, NCH2), 1.53 (m, 4Η, NCH2CH2), 1.30 (d, VHH = 7.0 Hz, 24H, NCH(CH 2), 1.23 (m, 4Η, NCH2CH2CH2), 0.89 (t, 3JHH = 7.90 Hz, 6H, CH2CHj). I C NMR (75 MHz, CDC13): & 118.46 (d), 1 17.49 (C2), 51.57 (N H2), 51.50 (N H(CH3)2), 30.77 (NCH2CH2), 21.99 (NCH(CH3)2), 19.44
(CH2CH3), 13.67 (CH2CH3).
(66) Bis(diethylamino)cyclopropenone, (Et2N)2C30
KOH (300 g) was dissolved into water (4 L). Tris(diethylamino)cyclopropenium chloride (42 g, 0.15 mol) was added to the solution, and heated to 70 °C for 18 h. Organic compounds were extracted from aqueous solution using CH2C12 (3 x 250 mL). CH2C12 removed in vacuo and neutralized using a small amount of HCl. Ethanol (25 mL) added to allow filtering to remove an insoluble impurity, followed by removal of the ethanol in vacuo. Addition of acetone (75 mL) precipitated KC1, which was filtered off. Acetone was removed in vacuo, yielding a dark orange liquid (22 g, 77%). Ή NMR (300 MHz, CDC13): δ 3.21 (q, 3JHH = 7.2 Hz, 8H, NCH2CH3), 1.20 (t, 37HH = 7.2 Hz, 12H, NCH2CH3). 13C NMR (75 MHz, CDC13): δ 133.74 (CO), 119.32 (C2), 46.01 (NCH2CH3), 14.18 (NCH2CH3).
(67) Tris(dipentylamino)cyclopropenium chloride, [C3(NPent2)3]Cl
Dipentylamine (11.9 g, 75.9 mmol) and NEt3 (25 mL, 179 mmol) were added to CH2C12 (100 mL) and cooled to 0 °C. C3C15H (4.84 g, 22.6 mmol) was added dropwise and the solution stirred overnight at ambient temperature. The solution was heated to reflux for 4 h, and then H20 (200 mL) was added. The solution was acidified with aqueous HCl. The CH2C12 was separated and washed with H20 (3 x 150 mL). Removal of CH2C12 in vacuo yielded a viscous orange liquid (10.6 g, 90.4% yield). Ή NMR (500 MHz, CDC13): δ 3.25 (t, 3JHH= 7.70 Hz, 12 H, NCH2), 1.57 (m, 12 Η, NCH2CH2), 1.30 (m, 12 Η,
NCH2CH2CH2), 1.21 (m, 12 Η, NCH2CH2CH2CH2), 0.85 (t, 3JHH = 7.15 Hz, 18 H,
NCH2CH2CH2CH2CH3). , C NMR (126 MHz, CDC13): 8 1 16.30 (C3), 52.86 (N H2), 28.50 (NCH2CH2), 28.45 (NCH2CH2CH2), 22.16 (NCH2CH2CH2 H2), 13.67 (NCH2CH2CH2CH2 H3). ES-MS+: m/z 504.5265 (100%, M+).
(68) Tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide,
[C3(NPent2)3]TFSA
[C3(NPent2)3]Cl (3.09 g, 5.73 mmol) was stirred with aqueous LiTFSA (4.9 g, 19.9 mmol) in water (100 mL). The product was extracted with Et20 (200 mL), and additional LiTFSA (6.1 g, 21.3 mmol) and H20 (100 mL) were added. The Et20 was then washed was H20 (3 x 100 mL) and dried in vacuo to yield an orange liquid (4.30 g, 95.7%). Ή, 13C NMR and MS+ as for [C3(NPent2)3]Cl with additional peaks in the 1 C NMR due to TFSA.
(69) Tris(dipentylaniino)cyclopropenium dicyanoamide, [Cj(NPent2)3]DCA
[C3(NPent2)3]Cl (4.13 g, 7.66 mmol) was stirred with aqueous NaDCA (3.8 g, 43.1 mmol) in water (100 mL). The product was extracted with Et20 (200 mL), and additional NaDCA (6.1 g, 44.9 mmol) and H20 (100 mL) were added. The Et20 was then washed was H20 (3 x 100 mL) and dried in vacuo to yield an orange liquid (3.69 g, 84.5%). Ή, 13C NMR and MS+ as for [C3(NPent2)3]Cl with additional peaks in the 13C NMR due to DC A.
(70) Tris(dihexyIamino)cyclopropenium chloride, [C3(NHex2)3]Cl Dihexylamine (20.8 g, 112 mmol) and NEt3 (45 mL, 323 mmol) were added to CH2C12 (200 mL) and cooled to 0 °C. C3C15H (4.84 g, 22.6 mmol) was added dropwise and the solution stirred overnight at ambient temperature. The solution was heated to reflux for 4 h, then washed with H20 (4 x 200 mL). The solution was acidified with aqueous HC1. The CH2C12 was separated and washed with H20 (4 x 200 mL). Removal of CH2C12 in vacuo gave a viscous orange liquid (11.8 g, 83.4% yield). Ή NMR (500 MHz, CDC13): δ 3.29 (t, 3JHH= 8.07 Hz, 12 H, NCH2), 1.60 (m, 12 Η, NCH2CH2), 1.28 (m, 36 Η,
NCH2CH2(CH2)3), 0.86 (t,
Figure imgf000146_0001
6.60 Hz, 18 H, N(CH2)5CH3). 13C NMR (126 MHz, CDC13): δ 1 16.55 (C3), 53.14 (NCH2), 31.46 (NCH2 H2), 28.98 (N(CH2)2CH2), 26.34 (N(CH2)3CH2), 22.50 (N(CH2)4 H2), 13.88 (N(CH2)5CH3). MS+ as for [C3(NHex2)3]TFSA.
(71) Tris(dihexylamino)cyclopropenium bis(trifluoromethanesuIfonyl)amide, [C3(NHex2)3]TFSA [C3(NHex2)3]Cl (3.12 g, 5.00 mmol) was stirred with LiTFSA (4.0 g, 14.0 mmol) in water (50 mL). The product was extracted with CH2C12 (25 mL) and washed with H20 (50 mL). Additional LiTFSA (4.0 g,
14.0 mmol) and H20 (100 mL) were added. The product was extracted with Et20 (100 mL), washed with H20 (4 x 100 mL) and dried in vacuo to yield an orange liquid (3.91 g, 89.9%). Ή and 13C NMR as for [C3(NHex2)3]Cl with additional peaks in the l3C NMR due to TFSA. ES-MS+: m/z 588.6 (100%, M+). (72) Tris(dihexylamino)cyclopropenium dicyanoamide, [C3(NHex2)3]DCA
[C3(NHex2)3]Cl (3.85 g, 6.16 mmol) was stirred with NaDCA (2.5 g, 28.1 mmol) in water (50 mL). The product was extracted with CH2C12 (25 mL) and washed with H20 (50 mL). Additional NaDCA (2.5 g,
28.1 mmol) and H20 (100 mL) were added. The product was extracted with Et20 (100 mL), washed with H20 (4 x 100 mL) and dried in vacuo to yield an orange liquid (3.61 g, 89.4%). Ή, 13C NMR and MS+ as for [C3(NHex2)3]Cl with additional peaks in the 13C NMR due to DC A. (73) Tris(didecylamino)cyclopropenium chloride, [C3(NDec2)3]Cl
Didecylamine (13.8 g, 46.3 mmol) and Et3 (15 mL, 108 mmol) were added to CH2C12 (100 mL) and cooled to 0 °C. C3C15H (2.84 g, 13.2 mmol) was added dropwise and the solution stirred overnight at ambient temperature. The solution was heated to reflux for 6 h, then H20 was added (200 mL). The solution was acidified with aqueous HC1, separated and washed again with dilute aqueous HC1. The CH2C12 was separated and washed with H20 (3 x 150 mL). Removal of CH2C12 in vacuo yielded a viscous orange liquid and white precipitate. After addition of acetone and cooling in the freezer, the precipitate was removed by filtration through silica gel three times. Removal of acetone in vacuo yielded an orange liquid (9.46 g, 74.5% yield). Ή NMR (500 MHz, CDC13): δ 3.26 (t, 3JHH= 7.70 Hz, 12 H, NCH2), 1.57 (m, 12 Η, NCH2CH2), 1.23 (m, 84 Η, N(CH2)2(CH2)7), 0.83 (t, 3JHH= 6.97 Hz, 18 H,
N(CH2)9CH3). 13C NMR (126 MHz, CDC13): δ 1 16.49 (C3), 53.1 1 (NC¾), 31.78 (NCH2 H2), 29.50 (N(CH2)2CH2), 29.44 (N(CH2)3CH2), 29.34 (N(CH2)4 H2), 29.21 (N(CH2)5 H2), 29.01 (N(CH2)6 H2), 26.66 (N(CH2)7 H2), 22.57 (N(CH2)8CH2), 14.00 (N(CH2)9CH3). ES-MS+: m/z 924.9965 (100%, M+).
(74) Tris(didecylamino)cyclopropenium bis(rrifluoromethanesulfonyl)amide, [C3(NDec2)3]TFSA [C3(NDec2)3]Cl (3.05 g, 3.18 mmol) was stirred with LiTFSA (4.0 g, 14.0 mmol). H20 (100 mL) was added and product extracted with Et20 (200 mL). Additional LiTFSA (4.0 g, 14.0 mmol) and H20 (100 mL) were added. The solution was again extracted with Et20 and washed with H20 (3 x 100 mL) before drying in vacuo to yield an orange liquid (3.18 g, 83.0%). Ή, 13C NMR and MS+ as for [C3(NDec2)3]Cl with additional peaks in the 13C NMR due to TFSA. (75) Tris(didecylamino)cyclopropenium dicyanoamide, [C3(NDec2)3]DCA
[C3(NDec2)3]Cl (3.10 g, 3.23 mmol) was stirred with aDCA (2.0 g, 22.5 mmol). H20 (100 mL) was added and the product was extracted with Et20 (200 mL). Additional NaDCA (2.0 g, 22.5 mmol) and H20 (100 mL) were added. The solution was again extracted with Et20 and then washed with H20 (3 x 100 mL) and dried in vacuo to yield an orange liquid (3.10 g, 96.8%). Ή, 13C NMR and MS+ as for [C3(NDec2)3]Cl with additional peaks in the ,3C NMR due to DC A.
(76) Bis(di .w-propylamino)dibutylaminocyclopropeniuni bis(trifluoromethanesulfonyl)amide, [C3(N(i-Pr)2)2(NBu2)]TFSA
[C3(N(i-Pr)2)2(NBu2)]Cl (0.302 g, 0.755 mmol) was stirred with LiTFSA (0.650 g, 2.27 mmol) in water (50 mL). The product was extracted with CHC13 (50 mL). Additional LiTFSA (0.804 g, 2.81 mmol) in H20 (50 mL) was added. The CHC13 solution was separated and then washed with H20 (3 x 50 mL) and dried in vacuo to yield a colourless solid (0.30 g, 61.7%). Ή and 13C NMR as for [C3(N'Pr2)2(NBu2)]Cl with additional peaks in the 1 C NMR due to TFSA. (77) Bis(dif.sO-propylaraino)dibur> aminocyclopropeniura dicyanoamide,
[C3(N(i-Pr)2)2(NBu2))DCA
[C3(N(i-Pr)2)2(NBu2)]Cl (0.300 g, 0.750 mmol) was stirred with NaDCA (0.350 g, 3.93 mmol) in water (50 mL). The product was extracted with CHC13 (50 mL). Additional NaDCA (0.519 g, 5.83 mmol) in H20 (50 mL) was added. The CHC13 solution was separated and then washed with H20 (3 x 50 mL) and dried in vacuo to yield a colourless solid (0.25 g, 77.5%). Ή and l 3C NMR as for
[C3(N(i-Pr)2)2(NBu2)]Cl with additional peaks in the ,3C NMR due to DC A.
(78) Bis(diethylamino)hexylaminocyclopropenium methylsulfate, [C3(NEt2)2(NHHex)]MeS04
Dried cyclopropenone (Et2N)2C30 (4.61 g, 23.5 mmol) and dimethylsulfate (5.93 g, 47.0 mmol) were mixed at ambient temperature for 1 h. Hexylamine (15.32 g, 151 mmol) was added and the solution was stirred at ambient temperature for 3 h. The product was washed with diethyl ether :petroleum ether (1 :1, 3 x 75 mL). The product was then dissolved in H20 (50 mL), acidified with aqueous HC1, extracted with CH2C12 (50 mL) and washed with H20 (3 x 75 mL). CH2C12 was removed in vacuo, and the product was then washed with diethyl ether (4 x 50 mL). Aqueous NaOH (200 mL, 0.38 mol/L) was added, and the product was washed with pet ether (4 x 100 mL) and diethyl ether (3 x 100 mL). The product was acidified with aqueous HC1 and H20 removed in vacuo. Addition of acetone caused precipitation of NaCl, which was filtered off. Removal of acetone in vacuo yielded a yellow liquid (2.64 g, 33.9%). Ή NMR (500 MHz, CDC13): δ 9.04 (br. s, 1H, NH), 3.69 (s, (CH3)S04), 3.39 (br. q, H = 7.0 Hz,
NCH2CH3), 3.19 (q, 3JHH = 7.0 Hz, NCH2(CH2)4CH3), 1.65 (m, NCH2CH2(CH2)3CH3), 1.18-35 (m, NCH2CH5 and N(CH2)2(CH2)3CH3), 0.82 (t, VHH = 6.8 Hz, NCH2(CH2)4C¾). 13C NMR (125 MHz, CDC13): 1 16.93 (d and C2), 54.61 (CH3S04), 47.64 (NCH2C5Hn), 46.82 (NCH2CH3), 31.65
(NCH2CH2C4H9), 30.67 (N(C2H4)CH2C3H7), 26.69 (NC3H6CH2C2H5), 22.74
Figure imgf000148_0001
14.53 (NCH2CH3), 14.123(NC5H10CH3). MS+ as for [C3(NEt2)2(NHHex)]TFSA.
(79) Bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide,
[C3(NEt2)2(NHHex)]TFSA
[C3(NEt2)2(NHHex)]MeS04 (2.64 g, 7.97 mmol) was stirred with LiTFSA (6.9 g, 24.1 mmol) in H20 (200 mL) for 30 min. The product was extracted with diethyl ether (200 mL). Additional LiTFSA (6.3 g, 22.0 mmol) and H20 (200 mL) were added and the mixture stirred for 1.5 h. The organic layer was washed with H20 (4 x 75 mL) and dried in vacuo to yield a yellow liquid (3.50 g, 78.4%). Ή and 13C NMR as for [C3(NEt2)2(NHHex)]MeS04 but with no peaks due to MeS04 and additional peaks in the 13C NMR due to TFSA. ES-MS+: m/z 280.3 (100%, M+). (80) Bis(diethylamino)aminocyclopropenium methyls ulfate, [C3(NEt2)2(NHz)]MeS0
NH3(g) (excess) was passed through a rapidly stirred sample of [C3(NEt2)2(OMe)]MeS04 (3 g, 9 mmol) for 2 h. Excess NH3 was removed in vacuo to yield an orange viscous oil (2.86 g, 100%). Ή NMR (500 MHz, D20): δ 3.60 (s, 3H, CH3S04), 3.24 (q, 3JHH = 7.3 Hz , 8H, NCH2CH3), 1.08 (t, 3JHH = 7.3 Hz, 12H, NCH2CH3). Ή NMR (500 MHz, CDC13): δ 7.18 (s, 2H, NH), 3.77 (s, 3Η, CH3S04), 3.39 (q, 3JHH = 7 Hz , 8H, NCH2CH3), 1.23 (t, 3JHH = 7 Hz, 12H, NCH2CH3). ,3C NMR (126 MHz, D20) δ 116.57 (equivalent ring C), 113.97 (unique ring C), 55.55 (CH3S04), 46.42 (NCH2CH3), 13.80 (NCH2 H3). EI-MS: m/z 196.18 (M+).
(81) Bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide,
[C3(NEt2)2(NH2)]TFSA
[C3(NEt2)2(NH2)]MeS04 (2.35 g, 8 mmol) was stirred with LiTFSA (6.58 g, 24 mmol) in water (10 mL) for 30 min. The product was extracted with chloroform (3 x 10 mL) to yield a yellow oil (2.83 g, 78%). Ή NMR (500 MHz, CDC13): 8 5.83 (s, 2H, NH), 3.36 (q, 3JHH = 7 Hz , 8H, NCH2CH3), 1.25 (t, 3JHH = 7 Hz, 12H, NCH2CH3). l C NMR (126 MHz, CDC13) δ 120.74 (q, = 299 Hz, CF3), 116.23 (equivalent ring C), 114.18 (unique ring C), 46.80 (N H2CH3), 14.40 (NCH2 H3). EI-MS: m/z 196.18 (M+).
(82) Trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide, [C3(NPhH)3]TFSA
[C3(NPhH)3]Cl (2 g, 6 mmol) was stirred with LiTFSA (4.95 g, 18 mmol) in water (10 mL) for 1 h. The product was extracted with dichloromethane (3 x 10 mL) to yield yellow crystals (3 g, 88%). Ή NMR (500 MHz, CDCN3): δ 8.8 (br, 1H, NH), 7.52 (dt, 3JHH = 8Hz, 2H, Ph), 7.32 (t, 3JHH = 8 Hz, 1H, Ph), 7.28 (dd, 3JHH = 8 Hz, 2H, Ph). 13C NMR (126 MHz, CD3CN): δ 138.44 (ipso-P ), 130.32 (m-Ph), 125.30 (p- Ph), 118.45 (o-Ph), 113.05 (C3). EI-MS: m/z 312.15 (M+).
(83) Bis(diethylamino)butylaminocyclopropenium tetrafluoroborate, [C3(NEt2)2(NHBu)]BF4
Dried bis(diethylamino)cyclopropenone (1.03 g, 5 mmol) was stirred with [Me30]BF4 (1.01 mL, 6.5 mmol) for 4 h to yield [C3(NEt2)2(OMe)]BF4 as a yellow oil (1.3 g, 83%). Butylamine (0.56 mL, 5.67 mmol) was then added and the mixture was stirred for 2 h. The product was washed several times with diethyl ether to remove unreacted amine. This yielded a yellow oil (1.2 g, 82%). Ή and 13C NMR spectra as for [C3(NEt2)2(NHBu)]MeS04 but with no peaks due to MeS04 and an NH peak at 6.81 ppm.
(84) Bis(diethyIamino)dibutylaminocyclopropenium iodide, [C3(N£t2)2(NBu2)]I
Dried bis(diethylamino)cyclopropenone (4.19 g, 21 mmol) and ethyl iodide (43 mL, 530 mmol) were heated to reflux for 20 h. Unreacted ethyl iodide was distilled out and the residue was washed with diethyl ether to yield [C3(NEt2)2(OEt)]I as a yellow solid (3.44 g, 45.65%). Dichloromethane (10 mL) and dibutylamine (2.14 mL, 13 mmol) were then added and the solution was stirred for 2 h. Dichloromethane was then removed in vacuo. The product was washed several times with diethyl ether to remove unreacted amine. This yielded a yellow solid (3 g, 71%). Ή NMR and 13C NMR spectra as for [C3(NEt2)2(NBu2)]MeS04 but with no peaks due to MeS04. (85) Tris(diethylamino)cyclopropenium iodide, [C3(NEt2)3]I
[C3(NEt2)3]Cl (1.15 g, 4 mmol) was heated to reflux with ethyl iodide (6.43 mL, 80 mmol) for 20 h. Unreacted ethyl iodide was distilled out and the residue was dissolved in dichloromethane (20 mL) and washed with water (3 x 10 mL). Dichloromethane was removed in vacuo to yield orange crystals (1.2 g, 79%). ¾ 13C NMR and MS+ as for [C3(NEt2)3]Cl. Anal, calcd for C15H30N3I: I, 33.45. Found (ion chromatography): I, 32.35. Chloride content was determined by ion chromatography to be 14 ppm.
(86) Bis(diethyIamino)dihexylaminocyclopropenium iodide, [C3(NEt2)2(NHex2)]I
Dihexylamine (1.72 mL, 7 mmol) was added to a solution of [C3(NEt2)2(OEt)]I (2 g, 5.6 mmol) (prepared as described above for [C3(NEt2)2(NBu2)]I) in dichloromethane (10 mL) and stirred for 2 h.
Dichloromethane was removed in vacuo. The product was washed several times with diethyl ether to remove unreacted amine. This gave a yellow liquid (2.5 g, 87%). Ή and I3C NMR as for
[C3(NEt2)2(NHex2)]MeS04 with no peaks due to MeS04.
(87) Tris(dimethylamino)cyclopropenium dicyanoamide, [C3(NMe2)3]DCA
[C3(NMe2)3]Cl (4.35 g, 21 mmol) was stirred with NaDCA (5.68g, 64 mmol) in water (50 mL) at 40 °C overnight. The product was extracted with chloroform (3 x 10 mL). The solvent was removed in vacuo to yield a yellow solid (2.7g, 54%). Ή, 13C NMR and MS+ as for [C3(NMe2)3]Cl with an additional peak in the 13C NMR due to DC A.
(88) Tris(dimethylamino)cyclopropenium thiocyanate, [C3(NMe2)3]SCN
[C3(NMe2)3]Cl (4.5 g, 22 mmol) was stirred with NH4SCN (5.68 g, 66 mmol) in water (50 mL) overnight. The product was extracted with chloroform (3 x 10 mL) and the solvent was removed in vacuo to yield a yellow solid (2.6 g, 52%). ¾, 13C NMR and MS+ as for [C3(NMe2)3]Cl with an additional peak in the 13C NMR due to SCN.
(89) Tris(dibutylamino)cyclopropeniuni tetracyanoborate, [C3(NBu2)3]B(CN)4 l-Ethyl-3-methylimidazolium tetracyanoborate (2.43 g, 1 1 mmol) was stirred with [C3(NBu2)3]Cl (5.62 g, 12 mmol) in water (50 mL) at 60 °C overnight. The product was extracted with diethyl ether (3 x 10 mL) and then washed with water. The solvent was removed in vacuo to yield a yellow liquid (4.86g, 81%). ¾, 13C NMR and MS+ as for [C3(NBu2)3]Cl with additional peaks in the 1 C NMR due to IB(CN)4]" at 122.66 ppm (q, 'jCB = 71.6 Hz).
(90) Tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate,
[C3(NBu2)3]FAP l-Ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate (3.85 g, 7 mmol) was stirred with [C3(NBu2)3]Cl (3.48 g, 8 mmol) in 50 mL of water at 60 °C overnight. The product was extracted with diethyl ether (3 x 10 mL) and then washed with water. The solvent was removed in vacuo to yield a yellow liquid (5.26 g, 88%). Ή, 13C NMR and MS+ as for [C3(NBu2)3]Cl.
(91) Tris(dihexylamino)cycIopropenium dibutylphosphate, [C3(NHex2)3](BuO)2P02 NaOH (2.56 g, 64.1 mmol) was dissolved in H20 (200 mL) and dibutylphosphate (12.4 mL, 62.5 mmol) was added. [C3(NHex2)3]Cl (6.44 g, 10.3 mmol) was stirred with half of this solution for 30 min. The product was extracted with diethyl ether (200 mL), and the diethyl ether solution was then stirred with the remainder of the sodium dibutylphosphate solution for 30 min. The diethyl ether layer was separated and washed with H20 (3 x 100 mL). The solution was dried in vacuo to yield an orange liquid (7.64 g, 93.1%). Ή NMR (CDC13, 500 MHz): δ 3.25 (t, 12H, NCH2), 3.25 (t, 4Η, PCH2), 1.57 (m, 12Η, NC¾CH2), 1.57 (m, 4Η, PCH2CH2), 1.34 (m, 4Η, PCH2CH2CH2), 1.26 (s, 36Η,
NCH2CH2CH2CH2CH2CH2), 0.85 (m, 18Η, NCH2CH2CH2CH2CH2CH3), 0.85 (m, 6Η,
PCH2CH2CH2CH3). ,3C NMR (CDC13, 125 MHz): <5 116.52 (s, ring C), 64.61 (d, 'jpc = 5.65 Hz, P H2), 53.09 (N H2), 33.10 (d, 2JPC = 7.63 Hz, PCH2 H2), 31.46 (NCH2 H2), 28.98 (NCH2CH2 H2), 26.33 (NCH2CH2CH2 H2), 22.50 (NCH2CH2CH2CH2 H2), 19.1 (PCH2CH2C¾), 13.93 (PCH2CH2CH2 H3), 13.87 (NCH2CH2CH2CH2CH2CH3). EI-MS: m/z 588.62 (M+).
(92) Bis(diethylamino)-5-(l-carboxylethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide, [C3(NEt2)2(NH((£)-CHMeCOOH))]TFSA
[C3(NEt2)2(NH((5)-CHMeCOOH))]MeS04 (2.1 g, 5 mmol) was stirred with LiTFSA (4.71 g, 16 mmol) in 10 mL of water. Extraction with chloroform (3 x 10 mL) yielded the product (2.57 g, 86%). 'H and 13C NMR spectra similar to [C3(NEt2)2(NH((5)-CHMeCOOH))]MeS04 with no peaks due to MeS04 and additional peaks in the 13C NMR due to TFSA. ES-MS+ as for [C3(NEt2)2(NH((S)- CHMeCOOH))]MeS04.
(93) Bis(diethylamino)-5'-(2-carboxypyrrolidino)cyclopropenium methylsulfate,
[C3(NEt2)2(N(C4H7COOH))]MeS04
[C3(NEt2)2(OMe)]MeS04 (5.65 g, 18 mmol) was stirred with L-proline (2.62 g, 23 mmol) and NEt3 (3.64 mL, 23 mmol) in water (20 mL) overnight. Water was removed in vacuo and the product was dissolved in acetone (20 mL) and filtered to remove unreacted L-proline. The mixture was dissolved in ice cold water and the product was extracted with chloroform: ethanol (2:1) (3 x 30 mL). The solvent was removed in vacuo to yield an orange oil (5.53 g, 78%). Ή NMR (400 MHz, CDC13): δ 7.37 (br, 1H, COOH), 4.42 (dd, 3JHH= 3.6Hz, , 3JHH= 8Hz, 1H, CH), 3.72 (m, 1H, NCH2), 3.68 (s, 3Η, CH3S04), 3.60 (ddd, 3JHH = 7.9Hz, 1H, NCH2), 3.34 (m, 8Η, NCH2CH3), 2.31 (m, 2H, NCH2CH2CH2), 2.01 (m, 2Η, NCH2CH2), 1.21 (t, 3JHH = 6.6 Hz, 12H, NCH2CH3). 13C NMR (100 MHz, CDC13) δ 174.09 (COOH), 116.08 (equivalent ring C), 114.80 (unique ring C), 64.60 (NCH), 54.26 (CH3S04), 51.89 (NCH2), 46.77 (NCH2CH3), 31.13 (NCHCH2), 24.32 (NCH2CH2CH2), 13.94 (NCH2CH3). EI-MS: m/z 295.00 (M+).
(94) Bis(diethylamino)-5-(2-carboxypyrrolidino)cyclopropenium
bis(trifluoromethanesulfonyl)amide, [C3(NEt2)2(N(C4H7COOH))]TFSA
[C3(NEt2)2(N(C4H7COOH))]MeS04 (2.1 g, 5 mmol) was stirred with LiTFSA (4.71 g, 16 mmol) in 10 mL of water. Extraction with chloroform (3 x 10 mL) yielded the product (2.57 g, 86%). ¾ and 13C NMR similar to [C3(NEt2)2(N(C4H7COOH))]MeS04 but with no peaks due to MeS04 and additional peaks in the 13C NMR due to TFSA. ES-MS+ as for [C3(NEt2)2(N(C4H7COOH))]MeS04. (95) Bis(diethylamino)-5-(l-carboxy-2-methylpropylamino)cyclopropenium methylsulfate, [C3(NEt2)2(NH(C4H8COOH))]MeS04
[C3(NEt2)2(OMe)]MeS04 (15 g, 47 mmol) was stirred with L-valine (7.09 g, 61 mmol) and NEt3 (9.67 mL, 61 mmol) in water (50 mL) overnight. Water was removed in vacuo and the product was dissolved in acetone (20 mL) and filtered to remove unreacted L-valine. The mixture was dissolved in ice cold water and the product was extracted with chloroform: ethanol (2: 1) (3 x 30 mL). The solvent was removed in vacuo to yield a yellow solid (10.00 g, 55%). Ή NMR (400MHz, CDC13): δ 8.44 (br, 1H, NH), 3.67 (s, 3Η, CH3S04), 3.62 (d, 3JHH= 6.4Hz, 1H, CH), 3.38 (m, 8Η, NCH2CH3), 2.23 (m, 1H, CH), 1.22 (t, 3JHH= 7.2 Hz, 12H, NCH2CH3), 1.03 (d, 3JHH= 6.8 Hz, 3H, CH3), 0.98 (d, 3JHH= 6.8 Hz, 3H, CH3). 13C NMR (100 MHz, CDC13) δ 174.25 (COOH), 1 15.87 (equivalent ring C), 1 15.46 (unique ring C), 68.82 (CHNH), 54.27 (CH3S04), 46.62 (NCH2CH3), 31.00 (CH(CH3)2), 19.28 (C¾), 18.80 (C¾), 14.27 (NCH2CH3). EI-MS: m/z 296.233 (M+).
(96) Bis(diethylamino)-1S'-(l-carboxy-2-methylpropylamino)cyclopropeniuiii
bis(trifluoromethanesulfonyl)amide, [C3(NEt2)2(NH(C4H8COOH))]TFSA
[C3(NEt2)2(NH(C4H8COOH))]MeS04 (2.1 g, 5 mmol) was stirred with LiTFSA (4.71 g, 16 mmol) in 10 mL of water. Extraction with chloroform (3 x 10 mL) yielded the product (2.57 g, 86%). 'H and 13C NMR spectra similar to [C3(NEt2)2(NH(C4H8COOH))]MeS04 but with no peaks due to MeS04 and additional peaks in the 1 C NMR due to TFSA. ES-MS+ as for [C3(NEt2)2(NH(C4H8COOH))]MeS04. (97) Bis(diethylamino)-5'-(l-carboxy-2-hydroxylpropylamino)cyclopropenium methyls ulf ate, [C3(NEt2)2(NH(C3H5OHCOOH))]MeS04
[C3(NEt2)2(OMe)]MeS04 (10 g, 31 mmol) was stirred with L-threonine (4.8 g, 40 mmol) and NEt3 (6.45 mL, 40 mmol) in water (50 mL) overnight. Water was removed in vacuo and the product was dissolved in acetone (20 mL) and filtered to remove unreacted L-threonine. The mixture was dissolved in ice cold water and the product was extracted with chloroform:ethanol (2:1) (3 x 30 mL). The solvent was removed in vacuo to yield a yellow solid (9.30 g, 76%). Ή NMR (500 MHz, CDC13): δ 8.04 (br, 1H, NH), 5.27 (br, 2Η, OH+H20), 4.08 (m,lH, NCH), 3.69 (m, 1Η, CHOH), 3.67 (s, 3H, CH3S04), 3.37 (q, 3JHH= 7.16 Hz , 8H, NCH2CH3), 1.23 (d, 3JHH= 7.5 Hz, 3H, CH3), 1.21 (t, 3JHH= 7.25 Hz, 12H,
NCH2CH3).,3C NMR (126 MHz, CDC13) b 173.37 (COOH), 115.98 (equivalent ring C), 115.35 (unique ring C), 67.78 ( HCH3), 67.20 (CHNH), 54.31 (CH3S04), 46.49 (NCH2CH3), 19.42 (C¾), 14.20 (NCH2 H3). EI-MS: m/z 298.87 (M+).
(98) Bis(diethylamino)-i_>-(l-carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide, [C3(NEt2)2(NH(C3H5OHCOOH))]TFSA [C3(NEt2)2(NH(C3H6OCOOH))]MeS04 (2.1 g, 5 mmol) was stirred with LiTFSA (4.71 g, 16 mmol) in 10 mL of water. Extraction with chloroform (3 x 10 mL) yielded the product (2.57 g, 86%). Ή and 13C NMR spectra similar to [C3(NEt2)2(NH(C3H6OCOOH))]MeS04 but with no peaks due to MeS04 and additional peaks in the 13C NMR due to TFSA. MS+ as for [C3(NEt2)2(NH(C3H6OCOOH))]MeS04.
(99) Tris(dibutylamino)cyclopropenium isocyanate, [C3(NBii2)3]NCO [C3(NBu2)3]Cl (4.92 g, 10.8 mmol) was stirred overnight with NaNCO (2.13 g, 32.8 mmol) in H20 (15 mL). The product was extracted with CHC13 (3 x 20 mL) and dried in vacuo to yield a brown liquid (3.16 g, 63%). Ή, 13C NMR and MS+ as for [C3(NBu2)3]Cl with an additional peak in the 13C NMR due to NCO.
(100) Tris(diburylamino)cyclopropenium trichlorostannate, [C3(NBu2)3]SnCl3 [C3(NBu2)3]Cl (3.53 g, 7.74 mmol) and SnCl2.H20 (1.75 g, 8.43 mmol) were each dissolved in 0.5N HCl (10 mL) and were separately heated to 50 °C. These solutions were then combined and kept at 50 °C for 2 h. An aqueous solution (20 mL) was then extracted with dichloromethane (3 x 10 mL) and dried in vacuo to yield a yellow product (3.12 g, 62%). Ή, 13C NMR and MS+ as for [C3(NBu2)3]Cl. (101) Bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate,
[C3(NEt2)2(NHex2)]OTf
Dried bis(diethylamino)cyclopropenone (1.14 g, 6 mmol) was stirred with MeCF3S03 (0.8 mL, 8 mmol) in dry dichloromethane for 2 h. Solvent was removed in vacuo. The mixture was washed with dry diethyl ether several times to remove excess MeCF3S03 and cyclopropenone. This gave an orange viscous oil of [C3(NEt2)(OMe)]CF3S03, which was then stirred with Hex2NH (1.23 mL, 5.2 mmol) for 2 h. The mixture was dissolved in chloroform: ethanol (2: 1 , 30 mL) and the product was washed with water (3 x 30 mL) to remove ammonium salts. Solvent was removed in vacuo to yield a brown oil (1.6 g, 77%). Ή, 13C NMR and MS+ as for [C3(NEt2)2NHex2]MeS04 but with no peaks in the Ή and 13C NMR due to MeS04 and an additional peak in the 13C NMR due to OTf.
(102) Bis(diethylamino)diiso-propylaminocyclopropemum methylsulfate,
[C3(NEt2)2(N(i-Pr)2)]MeS04
[C3(NEt2)2(OMe)]MeS04 (7.0 g, 33 mmol), prepared by stirring bis(diethylamino)cyclopropenone with Me2S04 as described for [C3(NEt2)2(NH((S)-CHMeCOOH))]MeS04, was stirred with distilled (i-Pr)2NH (33.93 g, 335 mmol) in an ice bath and then at ambient temperature for 18 h. The mixture was then heated to reflux for 3 h. Excess reagent was removed in vacuo. The mixture was dissolved in water (30 mL) and the product was extracted with dichloromethane (3 x 30 mL). Solvent was removed in vacuo and the product was washed with diethylether: dichloromethane (95:5, 3 x 15 mL) to yield an orange liquid (4.45 g, 33%). Ή, 13C NMR and MS+ as for [[C3(NEt2)2(N(i-Pr)2)]DCA but with no peaks in the 13C NMR due to DCA and additional peaks in the Ή and 13C NMR due to MeS04.
(103) Bis(diethylamino)diis0-propylaminocyclopropenium dicyanoamide,
[C3(NEt2)2(N(i-Pr)2)]DCA
[C3(NEt2)2(N(i-Pr)2)]MeS04 (4.45 g, 11.4 mmol) was stirred with NaDCA (6.02 g, 68 mmol) in H20 (200 mL) for 40 minutes. The product was extracted with dichloromethane (3 x 20 mL), washed with H20 (3 x 20 mL) and dried in vacuo to yield an orange liquid (3.67 g, 93%). Ή NMR (500 MHz,
CDC13): δ 3.75 (sept, 3JHH = 7.0 Hz, 2H, NCH(CH3)2), 3.70 (s, 3H, CH3SO4), 3.50 (q, 3JHH = 7.2 Hz, 8H, NCH2), 1.34 (d, 3JHH = 7.0 Hz, 12H, CH(CH3)2), 1.29 (t, 3JHH = 7.2 Hz, 12H, CH2CH3). 13C NMR (126 MHz, CDCI3) δ 117.99 (C3), other C3 peak n.o., 54.46 (CH3S04), 51.59 ( H(CH3)2), 49.67 (NCH2), 22.10 (CH(CH3)2), 14.55 (CH2CH3). EI-MS: m/z 280.2752 (M+). (104) Bis(dimethylamino)methoxycyclopropenium methylsulphate, [C3(NMe2)(OMe)]MeS04
Dried bis(dimethylamino)cyclopropenone (2.69 g, 19.2 mmol) was stirred with Me2S04 (2.36 mL, 25 mmol) for 2 h. The mixture was washed with dry diethyl ether several times to remove methanol and excess dimethylsulfate. This gave an orange viscous oil (4.57 g, 90%). !H NMR (500 MHz, CDC13): δ 4.15 (s, 3H, OCH3), 3.63 (s, 3Η, CH3SO4), 3.16 (s, 12Η, NCH3). 13C NMR (126 MHz, CDC13) δ 122.76 (equivalent ring C), 119.89 (unique ring C), 63.87 (O H3), 54.17 (CH3SO4), 41.13 (NCH3). EI-MS: m z 155.12 (M+).
(105) Bis(dimethylamino)hexylmeth laniinocyclopropenium bis(trifluoromethanesulfony )amide, [C3(NMe2)2(NHexMe)]TFSA
[C3(NMe2)2(OMe)]MeS04 (4.11 g, 15 mmol) was stirred with HexMeNH (2.88 mL, 19 mmol) in dry dichloromethane (10 mL) for 2 h. Dichloromethane was removed in vacuo. The mixture was dissolved in ice cold water and the product was extracted with chloroform: ethanol (2:1 , 3 x 30 mL). The solvent was removed in vacuo to yield [C3(KMe2)2(NHexMe)]MeS04 as a light yellow oil, which was stirred with LiTFSA (9.85g, 34 mmol) in H20 (50 mL) for 30 min. The solvent was then removed in vacuo.
The mixture was dissolved in chloroform:ethanol (2:1 , 30 mL) and the product was washed with ice cold water (3 x 30 mL) to remove ammonium salts. Solvent was removed in vacuo and the product was dissolved in CHC13 (50 mL) and washed with water (3 x 50 mL). The solvent was removed in vacuo to yield a light yellow oil (5.62 g, 95%). Ή NMR (400 MHz, CDC13): δ 3.29 (t, 3JHH = 7.6 Hz, 2H, NCH2), 3.12 (s, 12Η, NCH3), 3.10 (s, 3Η, NCH3), 1.63 (m, 2Η, NCH2CH2), 1.29 (m, 6Η,
NCH2CH2CH2CH2 H2 H2), 0.88 (t, 3JHH= 6.8Hz, 6H, NCH2 CH2CH2CH2CH2CH3). 13C NMR (100 MHz, CDCI3): δ 1 19.91 (q, = 347 Hz, F3), 117.73 (equivalent ring C), 117.45 (unique ring C), 55.55 (N H2), 42.25 (N H3), 40.07 (N H3), 31.33 (NCH2 H2), 27.64 (NCH2CH2 H2), 26.21
(NCH2CH2CH2 H2), 22.42(NCH2CH2CH2CH2 H2), 13.88 (NCH2CH2CH2CH2CH2 H3). EI-MS: m/z 238.22 (M+).
(106) Bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide, [C3(NMe2)2(NHex2)]TFSA
[C3(NMe2)2(OMe)]MeS04 (2 g, 8 mmol) was stirred with Hex2NH (2.3 mL, 10 mmol) in dry
dichloromethane (5 mL) for 2 h. Dichloromethane was removed in vacuo, the mixture was dissolved in ice cold water, and the product was extracted with chloroform:ethanol (2: 1 , 3 x 30 mL). The solvent was removed in vacuo to yield [C3(NMe2)2(NHex2)]MeS04 as a light yellow oil, which was then stirred with LiTFSA (5.22g, 18 mmol) in H20 (10 mL). The solvent was removed in vacuo, the mixture was dissolved in chloroform:ethanol (2:1 , 30 mL), and the product was washed with ice cold water (3 x 30 mL) to remove ammonium salts. The solvent was removed in vacuo to yield a light yellow oil (3 g, 80%). Ή NMR (400 MHz, CDC13): δ 3.28 (t, 3JHH = 8Hz, 4H, NCH2), 3.11 (s, 12Η, NCH3), 1.61 (m, 4Η, NCH2CH2), 1.29 (m, 12Η, NCH2 CH2CH2CH2 H2 H2), 0.88 (t,
Figure imgf000155_0001
6.8Hz, 6H, NCH2
CH2CH2CH2CH2CH3). 13C NMR (100 MHz, CDC13): δ 120.06 ( q, lJCF = 347 Hz, CF3), 1 17.69
(equivalent ring C), 1 16.73 (unique ring C), 53.52 (NCH2), 42.18 (N H3), 31.32 (NCH2 H2), 28.55 (NCH2CH2 H2), 26.23 (NCH2CH2CH2 H2), 26.23 (NCH2CH2CH2CH2CH2), 26.23 (NCH2CH2CH2 CH2CH2 H3). EI-MS: m/z 308.31 (M+). (107) Bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide, [C3(NMe2)2(NBu2)]TFSA
[C3(NMe2)2(OMe)]MeS04 (2.4 g, 9 mmol) was stirred with Bu2NH (1.97 mL, 12 mmol) in dry dichloromethane (5 mL) for 2 h. Dichloromethane was removed in vacuo and excess amine was removed by washing several times with dry diethylether to yield [C3(NMe2)2(NBu2)]MeS04 as a light yellow oil, which was then stirred with LiTFSA (6.92 g, 24 mmol) in H20 (10 mL). The solvent was removed in vacuo, the mixture was dissolved in chloroform: ethanol (2:1, 30 mL), and the product was washed with ice cold water (3 x 30 mL) to remove ammonium salts. The solvent was then removed in vacuo to yield a light yellow oil (3.4 g, 80%). Ή NMR (400 MHz, CDC13): δ 3.28 (t, 3JHH= 7.6Hz, 4H, NCH2), 3.11 (s, 12Η, NCH3), 1.60 (m, 4Η, NCH2CH2), 1.32 (m, 4Η, NCH2CH2CH2), 0.94 (t, 3JHH= 7.6Hz, 6H, NCH2 CH2CH2CH3). 13C NMR (126 MHz, CDC13): δ 119.89 ( q, F = 322 Hz, CF3), 117.59 (equivalent ring C), 116.66 (unique ring C), 53.22 (N H2), 42.17 (NCH3), 30.56 (NCH2 H2), 19.79 (NCH2 CH2CH2), 13.65 (NCH2CH2CH2 H3). EI-MS: m/z 252.24 (M+).
DSC, TGA and viscosity data for various of the triaminocyclopropenium salts discussed above are shown in Table 1 , in which Tg is the glass transition temperature, Tm the melting point, and Td the thermal decomposition onset temperature. Microanalytical data are shown in Table 2, in which the first line in each row is the calculated value and the second line the value obtained on analysis. Conductivity data are shown in Table 3.
Table 1 : DSC, TGA and viscosity data
Compound Tm Td Viscosity Viscosity
(°C)fl (°C)a (°C)* (mPa.s (mPa.s at at 20°C) 60°C)
(1) [C3(NMe2)3]Cl 32.5 78.3 221 - -
(2) [C3(NMe2)3]TFSA n.o. 105.2 339 - -
(3) [C3(NEt2)3]Cl n.o. 102.5 306 - -
(4) [C3(NEt2)3]TFSA n.o. 17.7 393 143.5 21.8
(5) [C3(NEt2)3]DCA n.o. 8.6 330 64.2 14.6
(6) [C3(NEt2)3]N03 -66.1 40.7 330 395.4 46.9
(7) [C3(NEt2)3]BF4 n.o. 26.9 377 207.4 28
(8) [C3(NEt2)3]SCN -77.8 23.1 31 1 132.4 20.7
(9) [C3(NEt2)3] ^-MeC6H4S03 8 77.7 214 764.2 57.4 Compound T T„ Viscosity Viscosity
(°C)e (°C)e (°C)* (mPa.s (mPa.s at at 20°C) 60°C)
(10) [C3(NEt2)3]OTf -0.2 50.3 345 -
(l l) [C3(NPr2)3]Cl -30 80.9° 308 - . -
(12) [C3(NPr2)3]TFSA -71.7 33.7 409 219.7 32.3
(13) [C3(NPr2)3]DCA n.o. 52.9 317 - 14.6
(15) [C3(NPr2)3]F.EtOH 49.6 14
(16) [C3(NPr2)3]N03 -55.5 n.o. 311 - 141.4
(17) [C3(NPr2)3]BF4 n.o. 80.9 397 - -
(18) [C3(NBu2)3]Cl -28.0 41 303 - 674.3
(19) [C3(NBu2)3]TFSA -74.5 6.7 400 230.4 38.3
(20) [C3(NBu2)3]Br -32 n.o. 318
(21) [C3(NBu2)3]DCA -61.8 17.3 335 292.8 41
(22) [C3(NBu2)3]N03 -61.7 n.o. 234 - 149.6
(23) [C3(NBu2)3]BF4 -50.9 33.5 373 - 89.9
(24) [C3(NBu2)3]OTf -58.3 44.5 388 - 24.9
(25) [C3(N(CH2CH2OH)2)3]Cl -41.7 n.o. 227
(26) [C3(N(CH2CH2OH)2)3]F 158
(29) [C3(N(CH2CHCH2)2)3]TFSA -81.5 8.8 306 125.7 21.1
(30) [C3(N(CH2CHCH2)2)3]DCA -67.8 23.7 270 210.5 27.2
(31) [C3(NBuMe)3]Cl n.o. 87.9 293 - -
(32) [C3(NBuMe)3]TFSA -81.4 n.o. 386 104.4 19.4
(33) [C3(NBuMe)3]DCA -72.9 n.o. 338 101.2 16.9
(34) [C3(NBuMe)3]N03 -55 24 315 - 68.3
(35) [C3(NBuMe)3]BF4 -61.5 n.o. 374 659 22.1
(36) [C3(NBuMe)3]SCN -69 n.o. 313 279.9 30.9
(37) [C3(NStMe)3]Cl n.o. 51.7 278 Compound T Td Viscosity Viscosity
(°C)a (°C)° (°C)* (mPa.s (mPa.s at at 20°C) 60°C)
(38) [C3(NStMe)3]TFSA n.o. 64.7 384
(39) [C3(NStMe)3]DCA n.o. 52.3 279
(41) [C3(NEt2)2(NMe2)]TFSA n.o. 17.0 379 83.6 17.9
(42) [C3(NEt2)2(NMe2)]DCA -85 32.1 322 58.4 13.2
(44) [C3(NEt2)2(NBu2)]TFSA -85.9 -4.3 403 125.7 23.1
(45) [C3(NEt2)2(NBu2)]DCA -81.8 30.2 334 105 19.4
(47) [C3(NEt2)2(NHex2)]TFSA -81.4 n.o. 396 182.1 30.2
(48) [C3(NEt2)2(NHex2)]DCA -79.8 n.o. 348 131 22.2
(50) [C3(NEt2)2(N(CH2CH2OH)2)]TFSA -62.1 n.o.
(51) [C3(NEt2)2(N(CH2CH2OH)2)]F 174
(54) [C3(NEt2)2(N(CH2CHCH2)2)]TFSA -87.3 -26.4 358 111.4 20.9
(56) [C3(NEt2)2(NBuMe)]TFSA -88.2 n.o. 384 106.2 21.1
(57) [C3(NEt2)2(NBuMe)]DCA -83 8.1 332 73.7 15.3
(59) [C3(NEt2)2(NHexMe)]TFSA -84 n.o. 396 82.1 16.7
(60) [C3(NEt2)2(NHexMe)]DCA -82 n.o. 348 69 14.3
(61) [C3(NEt2)2(NHBu)]MeS04 -67.9 n.o. 242 344.3 45
(62) [C3(NEt2)2(NHBu)]TFSA -80.1 n.o. 301 175.7 25.5
(63) [C3(NEt2)2(NHBu)]DCA -69.7 n.o. 233 251.3 31.6
(64) [C3(NEt2)2(NH((S)-CHMeCOOH))]MeS04 -7.9 n.o. 214 - 1006 (65°C)
(65) [C3(N(i-Pr)2)2(NBu2)]Cl n.o. 118 292 - -
(68) [C3(NPent2)3]TFSA -73 4 395 268.7 41.9
(69) [C3(NPent2)3]DCA -64 n.o. 321 307.5 40.0
(70) [C3(NHex2)3]Cl -53.7 n.o.
(71) [C3(NHex2)3]TFSA -70.6 3.1 406 273.0 44.9
(72) [C3(NHex2)3]DCA -64.1 n.o. 321 332.3 46.9 Compound T Viscosity Viscosity
(°C)" (°C)" (°C)* (mPa.s (mPa.s at at 20°C) 60°C)
(74) [C3(NDec2)3]TFSA n.o. 8 401 407.6 56.0
(75) [C3(NDec2)3]DCA n.o. -13 321 553.7 62.3
(76) [C3(N(i-Pr)2)2(NBu2)]TFSA n.o. 51.8 342
(77) [C3(N(i-Pr)2)2(NBu2)]DCA -52.3 46.7 332
(79) [C3(NEt2)2(NHHex)]TFSA -82 n.o. 371 170.6 27.9
(80) [C3(NEt2)2(NH2)]MeS04 230 - -
(81) [C3(NEt2)2(NH2)]TFSA 334 - -
(82) [C3(NPhH)3]TFSA 16.7 149 295 - -
(83) [C3(NEt2)2(NHBu)]BF4 228
(84) [C3(NEt2)2(NBu2)]I 74.0 319 - -
(85) [C3(NEt2)3]I 46.2 299 - -
(86) [C3(NEt2)2(NHex2)]I 292 - 127
(87) [C3(NMe2)3]DCA 1 17 285 - -
(88) [C3(NMe2)3]SCN 148 270 - -
(89) [C3(NBu2)3]B(CN)4 275 187 27
(90) [C3(NBu2)3]FAP 303 334 41
(91) [C3(NHex2)3](BuO)2P02 232 227 30.2
(92) [C3(NEt2)2(NH((S)-CHMeCOOH))]TFSA -30.1 n.o. 253 - 838 (75°C)
(93) [C3(NEt2)2(N(C4H7COOH))]MeS04 -15.7 n.o. 228 - 834 (75°C)
(94) [C3(NEt2)2(N(C4H7COOH))]TFSA -22.2 n.o. 275 - 564
(95) [C3(NEt2)2(NH(C4H8COOH))]MeS04 -50.4 20.9 214 - -
(96) [C3(NEt2)2(NH(C4H8COOH))]TFSA -40.7 n.o. 247 - 791 (70°C)
(97) [C3(NEt2)2(NH(C3H5OHCOOH))]MeS04 n.o. 43.6 197 - -
(98) [C3(NEt2)2(NH(C3H5OHCOOH))]TFSA -22.1 n.o. 176 - 884 (75°C)
(99) [C3(NBu2)3]NCO 236 397 Compound T Viscosity Viscosity
(0C)" (°C)e (°C)* (mPa.s (mPa.s at at 20°C) 60°C)
(100) [C3(NBu2)3]SnCl3 -44.4 n.o. 279
(101) [C3(NEt2)2(NHex2)]OTf 314 • 444 54.7
(103) [C3(NEt2)2(N(i-Pr)2)]DCA 289 164.5 24.9
(105) [C3(NMe2)2(NHexMe)]TFSA 295 65.9 13.0
(106) [C3(NMe2)2(NHex2)]TFSA 335 162.4 22.5
(107) [C3(NMe2)2(NBu2)]TFSA 297 53.1 9.6 a Determined by DSC at 10 °C/min. * Determined by TGA at 10 °C/min. 0 Also a solid-solid transition at 66.0 °C. n.o. = not observed.
Table 2: Microanalytical data
Compound C H N CI F S
(1) [C3(NMe2)3]Cl 46.49 9.19 18.07
46.92 9.47 16.49
(2) [C3(NMe2)3]TFSA 29.46 4.05 12.49
29.58 4.10 12.28
(3) [C,(NEt2)3]C1.1.6H20 56.89 10.57 13.27 11.19
56.96 10.12 12.66 11.93
(4) [C3(NEt2)3]TFSA 38.34 5.68 10.52
38.80 5.81 10.60
(5) [C3(NEt2)3]DCA 64.12 9.50 26.39
63.99 9.77 26.59
(6) [C3(NEt2)3]NO3.0.5H2O 55.70 9.66 17.32
55.63 9.80 17.41
(7) [C3(NEt2)3]BF4 53.11 8.91 12.39
52.91 9.10 12.36
(8) [C3(NEt2)3]SCN.0.24H2O 61.05 9.76 17.80
61.08 9.99 17.82 Compound C H N CI F S
(9) [C3(NEt2)3][p-MeC6H4S03] 61.72 8.82 9.81
61.73 9.23 9.83
(10) [C3(NEt2)3]OTf 47.87 7.53 10.47
48.03 7.65 10.44
(l l) [C3(NPr2)3]C1.2H20 61.81 11.36 10.30 8.69
62.01 10.77 8.93 9.56
(12) [C3(NPr2)3]TFSA 44.79 6.86 9.08
44.95 6.99 9.11
(13) [C3(NPr2)3]DCA.0.6H2O 66.82 10.53 20.33
67.19 10.57 19.77
(14) [C3(NPr2)3]F.2EtOH.2H20 62.07 12.08 8.69
61.95 12.48 8.77
(16) [C3(NPr2)3]N03.1.4H20 59.62 10.65 13.24
59.80 10.76 13.10
(17) [C3(NPr2)3]BF4 59.57 10.00 9.92
59.85 10.25 10.05
(18) [C3(NBu2)3]C1.0.72H2O 69.12 11.91 8.96 7.55
69.09 11.38 9.06 7.99
(19) [C3(NBu2)3]TFSA 49.70 7.77 7.99
49.43 7.92 8.07
(20) [C3(NBu2)3]Br.l.35H20 61.77 10.89 8.00
61.82 10.37 7.63
(21) [C3(NBu2)3]DCA.0.4H2O 70.51 11.18 17.01
70.31 11.20 17.28
(22) [C3(NBu2)3]NO3.0.6H2O 65.71 11.27 11.35
65.49 11.42 11.80
(23) [C3(NBu2)3]BF4 63.89 10.72 8.28
63.88 10.50 8.14
(24) [C3(NBu2)3]OTf 59.02 9.55 7.37
59.33 9.83 7.41 Compound C H N CI F S
(26) [C3(N(CH2CH2OH)2)3]F.0.16H2O 48.65 8.25 11.34
48.73 8.07 11.05
(27) [C3(N(CH2CHCH2)2)3]C1.0.9H2O 67.05 8.52 11.17 9.43
67. 22 8.51 10.82 9.17
(28) [C3(N(CH2CHCH2)2)3]Br .0.41 H20 61.25 7.54 10.20
61.47 7.58 9.81
(29) [C3(N(CH2CHCH2)2)3]TFSA 45.68 5.00 9.27
45.95 5.22 9.56
(30) [C3(N(CH2CHCH2)2)3]DCA.0.5H2O 69.14 7.82 21.03
69.11 7.71 21.06
(31) [C3(NBuMe)3]C1.1.24H20 61.37 10.87 11.93
61.32 10.94 11.99
(32) [C3(NBuMe)3]TFSA 41.80 6.31 9.75
41.52 6.30 9.88
(33) [C3(NBuMe)3]DCA 66.63 10.06 23.31
66.38 10.22 23.39
(34) [C3(NBuMe)3]NO3.0.45H2O 59.29 10.20 15.36
59.29 10.33 15.49
(35) [C3(NBuMe)3]BF40.19H2O 56.20 9.53 10.92
56.18 9.36 11.00
(36) [C3(NBuMe)3]SCN.0.33H2O 63.66 10.31 15.63
63.66 10.37 15.73
(37) [C3(NStMe)3]C1.2.2H20 75.17 13.08 4.38
75.18 12.86 4.56
(38) [C3(NStMe)3]TFSA.1.5H20 62.54 10.41 4.71
62.54 10.24 4.87
(39) [C3(NStMe)3]DCA.0.7H2O 77.39 12.72 8.73
77.31 12.90 9.10
(41) [C3(NEt2)2(NMe2)]TFSA 35.71 5.19 11.11
36.38 5.48 11.13 Compound C H N CI F S
(42) [C3(NEt2)2(NMe2)]DCA.lH20 58.41 9.15 27.25
58.91 8.90 26.66
(44) [C3(NEt2)2(NBu2)]TFSA 42.85 6.51 9.52 19.36 10.89
42.95 6.72 9.60 19.42 10.79
(45) [C3(NEt2)2(NBu2)]DCA 67.34 10.23 22.44
64.93 9.68 21.85
(47) [C3(NEt2)2(NHex2)]TFSA 46.57 7.19 8.69 17.68
47.35 7.58 8.78 14.87
(48) [C3(NEt2)2(NHex2)]DCA.0.85H2O 67.33 10.78 18.84
67.43 10.62 18.71
(54) [C3(NEt2)2(N(CH2CHCH2)2)]TFSA 41.00 5.43 10.07
41.03 5.47 10.04
(56) [C3(NEt2)2(NBuMe)]TFSA 39.55 5.90 10.25 20.85
40.41 5.87 10.28 17.08
(57) [C3(NEt2)2(NBuMe)]DCA.0.5H2O 63.31 9.74 24.61
63.08 9.86 24.78
(59) [C3(NEt2)2(NHexMe)]TFSA 41.80 6.31 9.75 19.84 11.16
42.78 6.35 9.75 17.29 10.07
(60) [C3(NEt2)2(NHexMe)]DCA 66.63 10.06 23.31
64.61 9.95 21.89
(61) [C3(NEt2)2( HBu)]MeS04 52.87 9.15 11.56
52.27 9.25 11.49
(62) [C3(NEt2)2(NHBu)]TFSA 64.12 9.50 26.40
63.91 9.93 25.96
(63) [C3(NEt2)2(NHBu)]DCA 64.12 9.50 25.96
63.91 9.93 25.96
(64) [C3(NEt2)2(NH((5)-CHMeCOOH))]MeS04 51.33 8.13 12.23
(25% zwitterion) 51.70 8.34 11.82
(65) [C3(Ni-Pr2)2(NBu2)]C1.0.4H2O 67.83 11.58 10.32
67.83 11.48 10.50 Compound C H N CI F S
(67) [C3(NPent2)3]Cl.l.lH20 70.76 12.27 7.50
70.76 12.22 7.65
(68) [C3(NPent2)3]TFSA 53.55 8.47 7.14
54.43 8.57 7.23
(69) [C3(NPent2)3]DCA.0.16H2O 73.26 11.65 14.65
73.26 11.58 14.64
(71) [C3(NHex2)3]TFSA 56.66 9.04 6.45
57.30 9.22 6.48
(72) [C3(NHex2)3]DCA 75.17 12.00 12.83
75.31 12.25 12.72
(73) [C3(NDec2)3]C1.0.59H2O 77.86 13.19 4.32
77.86 13.23 4.43
(74) [C3(NDec2)3]TFSA 64.74 10.53 4.65
64.80 10.57 4.84
(75) [C3(NDec2)3]DCA 78.72 12.81 8.47
78.61 12.88 8.51
(76) [C3(N(i-Pr)2)2(NBu2)]TFSA 46.57 7.19 8.69
(4.4% [C3(N(i-Pr)2)2(NBu2)]Cl) 47.23 7.26 8.62
(77) [C3(N(i-Pr)2)2(NBu2)]DCA 69.72 10.77 19.51
69.67 10.76 19.64
(79) [C3(NEt2)2(NHHex)]TFSA 40.71 6.11 9.99
41.43 6.26 10.07
(80) [C3(NEt2)2(NH2)]MeS04.1.5H20 43.10 8.43 12.56
42.78 8.29 12.84
(81) [C3(NEt2)2(NH2)]TFSA 34.51 4.87 11.86
(4% cyclopropenone) 34.15 4.94 11.89
(82) [C3(NPhH)3]TFSA 46.62 3.06 9.45
46.66 3.21 9.35
(83) [C3(NEt2)2(NHBu)]BF4.0.25H2O 52.31 9.23 12.22
52.41 8.94 12.22 Compound C H N CI F S
(84) [C3(NEt2)2(NBu2)]I 52.41 8.97 9.65
52.87 8.95 9.65
(85) [C3(NEt2)3]I 47.49 7.97 11.07
48.44 8.35 10.72
(86) [C3(NEt2)2(NHex2)]I.0.25H2O 55.69 9.44 8.47
55.62 9.53 8.52
(87) [C3(NMe2)3]DCA 55.89 7.92 33.58
(15% [C3(NMe2)3]Cl) 55.64 7.93 33.63
(88) [C3( Me2)3]SCN 53.07 8.15 24.13
53.87 8.29 23.40
(89) [C3(NBu2)3]B(CN)4 69.51 10.16 18.30
69.75 10.30 18.48
(90) [C3(NBu2)3]FAP 45.79 6.28 4.85
46.72 6.48 4.77
(91) [C3(NHex2)3](BuO)2PO2.0.5H2O 69.84 12.22 5.20
69.50 12.27 5.26
(92) [C3(NEt2)2(NH((S)-CHMeCOOH))]TFSA 36.15 4.96 10.43
(4% zwitterion) 36.14 5.31 10.40
(93) [C3(NEt2)2(N(C4H7COOH))]MeS04 54.47 8.38 11.52
(38% zwitterions, 3% water) 54.57 8.89 11.59
(94) [C3(NEt2)2(N(C4H7COOH))]TFSA 40.59 5.73 10.13
(15% zwitterions, 3% water) 40.41 5.69 10.24
(95) [C3(NEt2)2(NH(C4H8COOH))]MeS04 57.01 9.05 12.15
(50% zwitterion, 1% water) 57.10 9.01 12.08
(96) [C3(NEt2)2(NH(C4H8COOH))]TFSA 41.49 6.27 10.27
(19% zwitterion, 3% water) 41.38 6.46 10.56
(97) [C3(NEt2)2(NH(C3H6OCOOH))]MeS04 54.44 8.47 12.39
(55% zwitterion) 54.43 8.46 12.38
(98) [C3(NEt2)2(NH(C3H6OCOOH))]TFSA 38.51 5.39 10.36
(8% zwitterion) 38.57 5.51 10.52 Compound C H N CI Γ s
(99) [C3(NBu2)3]NC0.2.4H20 66.46 11.71 1 1.07
66.85 1 1.68 10.67
(100) [C3(NBu2)3][SnCl3].0.2H2O 49.94 8.44 6.47
49.97 8.57 6.48
(103) [C3(NEt2)2(N(i-Pr)2)]DCA.0.35H2O 64.68 9.91 23.82
64.35 9.81 24.12
Table 3: Conductivity data
Conductivity (mS/cm)
Compound
20 °C 30 °C 40 °C 50 °C 60 °C 70 °C 80 °C 90 °C
(4) [C3(NEt2)3]TFSA 1.387 1.983 2.755 3.681 4.752 5.972 7.349 8.857
(5) [C3(NEt2)3]DCA 4.688 6.797 9.199 11.97 15.14 18.63 22.40 26.33
(9) [C3( Et2)3][ -MeC6H4S03] 0.090 0.217 0.446 0.828 1.394 2.180 3.220 4.51
(12) [C3(NPr2)3]TFSA 0.498 0.862 1.323 1.904 2.629 3.491 4.498 5.642
(13) [C3(NPr2)3]DCA 0.634 5.871 8.016 10.481 13.246
(16) [C3( Pr2)3]N03 0.069 0.181 0.365 0.678 1.060 1.352 1.944 2.664
(18) [C3(NBu2)3]Cl 0.014 0.035 0.081 0.164 0.306 0.528 0.857
(19) [C3(NBu2)3]TFSA 0.428 0.694 1.057 1.535 2.144 2.915 3.819 4.870
(21) [C3( Bu2)3]DCA 1.158 1.892 2.886 4.161 5.732 7.576 9.684
(22) [C3(NBu2)3]N03 0.071 0.161 0.323 0.590 0.965 1.567 2.340
(23) [C3(NBu2)3]BF4 0.084 0.173 0.315 0.532 0.841 1.262 1.795 2.453
(24) [C3(NBu2)3]OTf 0.299 0.531 0.868 1.342 1.965 2.749 3.714
(29) [C3( (CH2CHCH2)2)3]TFSA 0.927 1.472 2.192 3.099 4.164 5.424 6.826 8.397
(30) [C3(N(CH2CHCH2)2)3]DCA 0.879 1.562 2.525 3.818 5.424 7.349 9.235
(32) [C3(NBuMe)3]TFSA 0.939 1.451 2.074 2.825 3.711 4.723 5.869 7.124
(33) [C3(NBuMe)3]DCA 2.160 3.507 5.445
(35) [C3(NBuMe)3]BF4 0.252 0.529 0.928 1.492 2.252 3.196 4.363 5.691
(41) [C3(NEt2)2(NMe2)TFSA 1.572 2.250 3.101 4.106 5.264 6.547 7.933 9.374
(42) [C3(NEt2)2(NMe2)DCA 4.643 6.969 9.537 12.44 15.70 19.25 23.13 27.21 Conductivity (mS/cm)
Compound
20 °C 30 °C 40 °C 50 °C 60 °C 70 °C 80 °C 90 °C
(44) [C3(NEt2)2(NBu2)]TFSA 0.850 1.288 1.847 2.532 3.346 4.284 5.348 6.522
(45) [C3(NEt2)2(NBu2)]DCA 2.203 3.424 4.912 6.703 8.794 11.16 13.82 16.71
(48) [C3(NEt2)2(NHex2)]DCA 1.028 1.710 2.572 3.641 4.939 6.463 8.210 10.164
(50) [C3(NEt2)2(N(CH2CH2OH)2)]TFSA 0.168 0.317 0.545 0.873 1.311 1.844 2.498 3.283
(56) [C3(NEt2)2(NBuMe)TFSA 1.225 1.839 2.512 3.346 4.322 5.413 6.630 7.964
(57) [C3(NEt2)2(NBuMe)DCA 3.501 5.119 7.134 9.503 12.20 15.24 18.60 22.16
(59) [C3(NEt2)2(NHexMe)TFSA 1.176 1.818 2.650 3.690 4.940 6.380 8.030
(60) [C3(NEt2)2(NHexMe)DCA 2.770 4.340 6.340 8.820 11.75 15.13 18.88
(68) [C3(NPent2)3]TFSA 0.245 0.420 0.670 1.011 1.453 2.000 2.670 3.450
(69) [C3(NPent2)3]DCA 0.295 0.543 0.914 1.439 2.140 3.030 4.120 5.400
(71) [C3(NHex2)3]TFSA 0.141 0.226 0.349 0.508 0.710 0.965 1.257 1.602
(72) [C3(NHex2)3]DCA 0.161 0.260 0.414 0.620 0.891 1.228 1.644 2.129
(74) [C3(NDec2)3]TFSA 0.027 0.048 0.082 0.131 0.198 0.288 0.404
(75) [C3(NDec2)3]DCA 0.022 0.043 0.078 0.130 0.205 0.307 0.440
Reaction using triaminocyclopropenium salt as a solvent
Sodium /3-naphthoxide (0.210 g, 1.26 mmol) was dissolved in [C3(NBu2)3]BF4 (1.71 g, 3.3 mmol) over 1 h. Benzyl chloride (0.160 g, 1.25 mmol) was added and the solution stirred at 25 °C for 24 h. Addition of 10 mL of 1 :2 water:ethanol dissolved the [C3(NBu2)3]BF4 and precipitated the organic products. The organic products were then analysed by Ή NMR to determine the ratio of O-alkylation: C-alkylation.
In order to investigate potential solvent effects using triaminocyclopropenium salts as ionic liquids, a benzylation of sodium- 3-napthoxide was carried out in [C3(NBu2)3]BF4. In phosphonium, ammonium and imidazolium ionic liquids, 92-99% O-alkylation occurs (M. Badri, J. J. Brunet and R. Perron, Tetrahedron Lett., 1992, 33, 4435, which is incorporated herein in its entirety by reference). Using similar conditions with [C3(NBu2)3]BF4, no products of C-alkylation were able to be observed. This illustrates that triaminocyclopropenium salts have similar polar solvent effects to conventional ionic liquids. It is not the intention to limit the scope of the invention to the abovementioned examples only. As would be appreciated by a skilled person in the art, many variations are possible without departing from the scope of the invention as set out in the accompanying claims.
In addition, where features or aspects of the invention are described in terms of a Markush group, those skilled in the art will recognise that the invention is also thereby described in terms of any individual member or subgroup of members of the Markush group.

Claims

1. A compound of formula [Y ]q[Xq"] wherein q is 1 , 2 or 3; and
wherein the cation, Y1", is a triaminocyclopropenium ion of the general formula (I):
Figure imgf000169_0001
wherein
R1, R2, R3 and R5 are each independently selected from -H, C1.20 alkyl, substituted C1.20 alkyl,
C2-20 alkenyl, substituted C2-20 alkenyl, C2_2o alkynyl, substituted C2-20 alkynyl, C3.10 cycloalkyl, substituted C3.10 cycloalkyl, C3.10 cycloalkenyl, substituted C3.10 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;
R4 and R6 are each independently selected from C2-20 alkyl, substituted C1-2o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C2-20 alkynyl, C3.i 0 cycloalkyl, substituted C3.K cycloalkyl, C3-10 cycloalkenyl, substituted C3.i0 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or
one or more of R1 and R2, R3 and R4, and R5 and R6 independently form, together with the nitrogen atom to which they are attached, a heterocyclyl, substituted heterocyclyl, heteroaryl or substituted heteroaryl, wherein heteroaryl is imidazolyl, pyrazolyl, pyrrolyl or azepinyl; and wherein the anion, Xq_, is selected from the group consisting of:
F-, Br" Γ, [Ι3Γ, [HF2]~, [CN]", [SCN]" [NCO]-, [CH3C(0)0]- [(C2.6 alkyl)C(0)0]-
[NH2-CH(RA)C(0)0]-, [SiF6]2", [SOJ2", [N03]", [C03] , [ΒΡη,Γ, [AsF6r, [SbF6]~, [AlC r,
[A12C17]- [GaC ]- [SOiF]-, [PF6r, [A1F4]', [A1F6]3-, [CuCl2]-, [SnCl3r, [GeClj]", [ZnCl4]-
[FeCUr, [FeCl4]2', [CoCU]~, [CoCU]2", and [Co(CO)4]";
wherein RA is a side chain of a natural or non-natural alpha-amino acid;
[CF3COO]-, [SeCNT, [HSO4]-, [H2P04]-, [(MeO)(H)P02]- [CF3SO3]-, [CF3OSO3]-, [FHO(C,_6 alkyl)]" [(CM2 alkyl)OS03r, [(C,.,2 alkyl)S03r, [(C2H5)2N(CH2)4S03r, [C^SCy, [(C,.,2 alkyl)(C,.,2 alkyl)P(0)Or, [(C,.,2 alkyl)(CM2 alkyl-0)P(0)0]", [(C,.,2 alkyl-0)(CM2 alkyl- 0)P(0)0]- [CH3C6H4S03r, [C12H25C6H4S03]", [CH2(COO)2]2-, [Co(C2B9Hn)2]- [C2B9H12]~ [B10Cl,o]2-, [BI2C112]2- [CB„H12]- [B12H„N(C,.6 alkyl)3r, [(C,.6 alkyl)SnBuH„r,
[RBCBnRc 5XB6]~, and [RDBF3]~;
wherein RB is H, Ci_6 alkyl, Ci_6 alkenyl, Ci_6 perfluoroalkyl, Ci_6 perfluoroalkenyl or Si(Ci-6 alkyl)3; Rc is H, methyl, CI or Br;
RD is C]_2o alkyl or C2_2o alkenyl, wherein one or two non-adjacent carbon atoms in RD which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S02-, or -NRJ-, and wherein RD is optionally substituted by one or more RE; or
RD is C3_]o cycloalkyl, C3_10 cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of C].6 alkyl, C2-6 alkenyl, and RE;
RE at each instance is independently selected from halo, cyano, Ci_6 alkoxy, Si(Ci_6 alkyl)3, C3_10 cycloalkyl optionally substituted by one or more RE*, C3_io cycloalkenyl optionally substituted by one or more RE\ aryl optionally substituted by one or more RE*, heteroaryl optionally substituted by one or more RE*, and heterocyclyl optionally substituted by one or more RE*;
RE* at each instance is independently selected from halo, Ci_6 alkyl, Ci 6 alkoxy, and
oxycarbonyl;
XB is CI or Br;
[Al(OCH2RF)4]- [(CF3S02)2N]-, [(CF3S02)NC(0)CF3]-, [(FS02)2N]-, [RFCF2S03]-,
[RFCF2OS03]- [(RGS02)2N)]-, [(RGS02)3C]-, [(CF3S02)3Cr, [(FS02)3C]- [RFCF2C(0)0]\
[P(CnF2„+1-mHm)yF6.y]-, [P(C6F5)yF6.y]-, [RF 2P(0)Or, [RFP(0)02]2-, [(RF0)2P(0)Or,
F0)(RF)P(0)0]- [(RFO)P(0)02]2-, [BFZRF 4.Z]-, [BFZ(CN)4_2]- [Me3SiC2H4OCH2BF3]-
Figure imgf000170_0001
wherein RF at each instance is independently selected from perfluoro Ci_2o alkyl, perfluoro C2-2o alkenyl having one or more double bonds, perfluoro C2.2o alkynyl having one or more triple bonds, perfluoro C3_io cycloalkyl optionally substituted by one or more perfluoro Ci-6 alkyl, perfluoro C3.io cycloalkenyl optionally substituted by one or more perfluoro Cj.6 alkyl, and per fluorophenyl optionally substituted by one or more perfluoro Ci_6 alkyl, wherein any two RF may be connected by a single or double bond, wherein when RF is perfluoro Ci_20 alkyl, perfluoro
C2-2o alkenyl, or perfluoro C2-2o alkynyl one or two non-adjacent carbon atoms in RF which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S02-, or -NRJ-, and wherein a terminal carbon atom in RF, if present, may be replaced by -S02XD; and
RG at each instance is independently selected from perfluoro C2.20 alkyl, perfluoro C2-20 alkenyl having one or more double bonds, perfluoro C2.20 alkynyl having one or more triple bonds, perfluoro C3.io cycloalkyl optionally substituted by one or more perfluoro Ci_6 alkyl, perfluoro C -1o cycloalkenyl optionally substituted by one or more perfluoro Cj.6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci-6 alkyl, wherein any two RG may be connected by a single or double bond, wherein when RG is perfluoro Ci_2o alkyl, perfluoro C2.20 alkenyl, or perfluoro C2-2o alkynyl one or two non-adjacent carbon atoms in RG which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S02-, or -NRJ-, and wherein a terminal carbon atom in RG, if present, may be replaced by -S02XD;
RJ at each instance is independently selected from C]_ alkyl, fluoro C alkyl, perfluoro Ci_6 alkyl, C3.i0 cycloalkyl, phenyl optionally substituted by one or more RK, heteroaryl optionally substituted by one or more R , and heterocyclyl optionally substituted by one or more RK;
RK at each instance is independently selected from Ci-6 alkyl, C]-6 alkenyl, nitro, halo, hydroxyl, Ci_6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfonyl, C].6 alkoxycarbonyl, -NH2, Ci-6 alkylamino, di(Ci_6 alkyl)amino, -C02H, -C(0)NRL, -S02ORL, -S02XD, -S02NRL 2, -S03H, and -NHC(0)RL;
RL at each instance is independently selected from Ci-6 alkyl, fluoro Q-e alkyl, perfluoro C].6 alkyl, and C3.10 cycloalkyl;
XD at each instance is independently selected from F, CI, and Br;
n is 1 to 20;
m is 0, 1 , 2, or 3;
y is 1 , 2, 3, or 4; and
z is 0, 1 , 2, or 3; and
-Z- and -Y- are independently selected
from -C(0)C(0)-, -C(0)(CH2)4C(0)-, -C(0)(CF2)qC(0)- wherein q = 1 , 2 or 3, -C(CF3)2C(CF3)2-,
Figure imgf000171_0001
is 1 , 2, 3, or 4; and
is 1 , or 2.
2. A compound as claimed in claim 1, wherein the anion, Xq", is selected from the group consisting of:
F- Br", Γ, [I3r, [HF2]- [C ]" [SCN]" [NCO]' [CH3C(0)0]- [(C2.6 alkyl)C(0)0]-,
[NH2-CH(RA)C(0)0]- [SiF6]2", [S04]2", [NO,]", [C03]2-, [ΒΡη,Γ, [AsF6r, [SbF6]" [AICL,]", [A12C17]-, [GaC ]", [S06F]^, [PF6]", [A1F4]", [A1F6]3-, [CuCl2]-, [SnCl3]- [GeCl,]", [ZnC ]",
[FeCl4]~ [FeCl4]2~, [CoC T, [CoC ]2", and [Co(CO)4]";
wherein RA is a side chain of a natural or non-natural alpha-amino acid;
[CFjCOO]- [SeCN]-, [HSO,]", [H2P04]" [(MeO)(H)P02]" [CF3S03]', [CF3OS03]", [FHO(C,.6 alkyl)]-, [(C 2 alkyl)OS03]-, [(CM2 alkyl)S03r, [(C2H5)2N(CH2)4S03r, [C^SO,]", [(C,-12 alkyl)(C,.12 alkyl)P(0)Or, [(C1-12 alkyl)(C,_12 alkyl-0)P(0)0]-, [(d_12 alkyl-0)(CM2 alkyl-
0)P(0)0]- [CH3C6H4S03]- [C12H25C6H4S03]-, [CH2(COO)2]2-, [Co(C2B9H„)2r, [C2B9H12]-, [B10Cl,o]2-, [B12C112]2- [CB„H12]- [ΒπΗπΝ^ alkyl)3]-, [(C,_6 alkyl)SnB„Hn]- [RBCB„Rc 5XB6r, and [RDBF3]~;
wherein RB is H, Ci_6 alkyl, Ci_6 alkenyl, C]_6 perfluoroalkyl, Ci_6 perfluoroalkenyl or Si(Ci-6 alkyl)3;
Rc is H, methyl, CI or Br;
Ru is Ci_2o alkyl or C2^2o alkenyl, wherein one or two non-adjacent carbon atoms in RD which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S02-, or -NRJ-, and wherein RD is optionally substituted by one or more RE; or
Ru is C3_io cycloalkyl, C3_io cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of C alkyl, C2.6 alkenyl, and RE;
RE at each instance is independently selected from halo, cyano, C]_6 alkoxy, Si(Ci_6 alkyl)3, C3_i0 cycloalkyl optionally substituted by one or more RE*, C3_io cycloalkenyl optionally substituted by one or more RE*, aryl optionally substituted by one or more RE*, heteroaryl optionally substituted by one or more RE*, and heterocyclyl optionally substituted by one or more RE*;
RE* at each instance is independently selected from halo, Ci_6 alkyl, C[_6 alkoxy, and oxycarbonyl;
XB is CI or Br;
[Al(OCH2RF)4]-, [(CF3S02)2N]- [(CF3S02)NC(0)CF3r, [(FS02)2N]", [RFCF2S03]-,
[RFCF2OS03]-, [(RGS02)2N)]-, [(R°S02)3C]-, [(CF3S02)3C]" [(FS02)3C] ~, [RFCF2C(0)0]-, [P(CnF2n+1.mHm)yF6.y]-, [P(C6F5)yF6-y]-, [RF 2P(0)0]-, [RFP(0)02]2" [(RF0)2P(0)Or,
F0)(RF)P(0)Or, [(RF0)P(0)02]2-, [BFZRF 4.Z]-, [BFZ(CN)4.Z]-, [Me3SiC2H4OCH2BF3]-,
Figure imgf000172_0001
wherein RF at each instance is independently selected from perfluoro C^o alkyl, perfluoro C2-20 alkenyl having one or more double bonds, perfluoro C2-20 alkynyl having one or more triple bonds, perfluoro C3-10 cycloalkyl optionally substituted by one or more perfluoro Ci_6 alkyl, perfluoro C3.10 cycloalkenyl optionally substituted by one or more perfluoro Ci_6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci-6 alkyl, wherein any two RF may be connected by a single or double bond, wherein when RF is perfluoro Ci-2o alkyl, perfluoro C2-20 alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms in RF which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO2-, or -NRJ-, and wherein a terminal carbon atom in RF, if present, may be replaced by -S02XD; and
RG at each instance is independently selected from perfluoro C2-20 alkyl, perfluoro C2-20 alkenyl having one or more double bonds, perfluoro C2-20 alkynyl having one or more triple bonds, perfluoro€3.10 cycloalkyl optionally substituted by one or more perfluoro C]_6 alkyl, perfluoro C3.10 cycloalkenyl optionally substituted by one or more perfluoro C)-6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci-β alkyl, wherein any two RG may be connected by a single or double bond, wherein when RG is perfluoro Ci_2o alkyl, perfluoro C2-2o alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms in RG which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S02-, or -NRJ-, and wherein a terminal carbon atom in RG, if present, may be replaced by -S02XD;
RJ at each instance is independently selected from C e alkyl, fluoro C e alkyl, perfluoro Cj.6 alkyl, C3.i0 cycloalkyl, phenyl optionally substituted by one or more R , heteroaryl optionally substituted by one or more RK, and heterocyclyl optionally substituted by one or more RK;
RK at each instance is independently selected from Ci_6 alkyl, Ci_6 alkenyl, nitro, halo, hydroxyl,
Ci-6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifiuoromethoxy, trifluoromethylthio, trifluoromethylsulfonyl, Ci-6 alkoxycarbonyl, -NH2, Ci_6 alkylamino, di(C|.g alkyl)amino,
-C02H, -C(0)NRL, -S02ORL, -S02X , -S02NRL 2, -S03H, and -NHC(0)RL;
RL at each instance is independently selected from Ci_ alkyl, fluoro Ci-6 alkyl, perfluoro Ci_6 alkyl, and C3.10 cycloalkyl;
XD at each instance is independently selected from F, CI, and Br;
n is 1 to 20;
m is 0, 1, 2, or 3;
y is 1 , 2, 3, or 4; and
z is 0, 1, 2, or 3; and
-Z- and -Y- are independently selected
from -C(0)C(0)-, -C(0)(CH2)4C(0)-, -C(0)(CF2)qC(0)- wherein q = 1, 2 or 3, -C(CF3)2C(CF3)2-,
Figure imgf000174_0001
k is 1 , 2, 3, or 4; and
p is 1 , or 2.
3. A compound as claimed in claim 1 , wherein R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci_2o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
4. A compound as claimed in claim 1 , wherein R1, R3 and R5 are each independently selected from -H, C1.20 alkyl, substituted C1.20 alkyl, C2-20 alkenyl, and aryl; and
R2, R4 and R6 are each independently selected from C2-20 alkyl, substituted C\.2o alkyl, C2-20 alkenyl, and aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.
5. A compound as claimed in claim 1 , wherein R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci-2o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C2.20 alkenyl, aryl, and substituted aryl.
6. A compound as claimed in claim 1 , wherein R1, R2, R3 and R5 are each independently selected from -H, C]_2o alkyl, substituted Ci-6 alkyl, C2-6 alkenyl, and aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci_6 alkyl, C2-6 alkenyl, and aryl. 7. A compound as claimed in claim 1, wherein R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, substituted Ci_6 alkyl, C2-e alkenyl, and aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, substituted Ci-e alkyl, C2-6 alkenyl, and aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl.
8. A compound as claimed in claim 1 , wherein R1, R2, R3 and R5 are each independently selected from -H, Ci_2o alkyl, hydroxy Ci_6 alkyl, C2-6 alkenyl, and aryl; and
R4 and R6 are each independently selected from C2-20 alkyl, hydroxy Q_6 alkyl, carboxyl Ci_6 alkyl, carboxyl hydroxy Ci_6 alkyl, C2-e alkenyl, and aryl. 9. A compound as claimed in claim 1, wherein R1, R2, R3 and R5 are each independently selected from -H, methyl, ethyl, «-propyl, wo-propyl, n-butyl, n-pentyl, w-hexyl, decyl, stearyl,
2-hydroxyethyl, allyl, and phenyl; and
R4 and R6 are each independently selected from ethyl, ^-propyl, wo-propyl, «-butyl, w-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, 1-carboxylethyl, l-carboxyl-2-hydroxypropyl,
1 -carboxyl-2-methylpropyl, allyl, and phenyl.
10. A compound as claimed in claim 1 , wherein R1, R2, R3 and R5 are each independently selected from -H, methyl, ethyl, n-propyl, wo-propyl, rc-butyl, w-pentyl, «-hexyl, decyl, stearyl,
2-hydroxyethyl, allyl, and phenyl; and
R4 and R6 are each independently selected from ethyl, «-propyl, wo-propyl, «-butyl, n-pentyl, n-hexyl, decyl, stearyl, 2-hydroxyethyl, 1-carboxylethyl, l-carboxyl-2-hydroxypropyl,
1 -carboxyl-2-methylpropyl, allyl, and phenyl; or
R5 and R6, together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl.
11. A compound as claimed in claim 1 , wherein
R'-R6 are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl, R1, R3 and R5 are -H and R2, R4 and R6 are phenyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are butyl,
R1, R3 and R5 are methyl and R2, R4 and R6 are stearyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are wo-propyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are butyl, R1, R2, R3 and R4 are ethyl and R5 and R6 are hexyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are allyl,
R1, R2, R3 and R4 are iso-propyl and R5 and R6 are butyl,
R1, R2, R3 and R4 are ethyl and R5 and R6 are 2-hydroxyethyl,
R3, R4, R5 and R6 are ethyl and R' and R2 are -H,
R3, R4, R5 and R6 are ethyl and R1 and R2 are methyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is methyl and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is butyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is hexyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxylethyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-hydroxypropyl,
R1, R2, R3 and R4 are ethyl, R5 is hydrogen and R6 is 1 -carboxyl-2-methylpropyl, or
R1, R2, R3 and R4 are ethyl, and R5 and R6, together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl.
12. A compound as claimed in claim 1 , wherein the anion, Xq~, is selected from F~, Br~, Γ, [HF2]~, [SCN]-, [ CO]-, [Ν03]', [AlC f, [Al2Cl7r, [PF6]", [SnCl,]',
[SeCN] [CFjSOjf, [FHOMe] [FHOEt]", [FHOPr]", [MeOSOsf, [EtOS03]", [(BuO)2P(0)0]", [CH3C6H S03]-, ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4- trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]_,
[(CF3S02)2N]-, [(CF3S02)NC(0)CF3]-, [(FS02)2N]- [CF3CF2S03]", [C4F9S03r,
[(CF3CF2S02)2N)]-, [(CF3S02)3C]- [(FS02)3C]" [P(C2F5)3F3]-, [(CF3)2P(0)0]", [(C2F5)2P(0)0]- [(CF30)2P(0)0]-, [(C2F50)2P(0)0]-, [BF3(CF3)3r, [BF3(C2F5)3]-, [BF3(CN)]', [B(CN)4]-, [ (CN)2]", and [C(CN)3]".
13. A compound as claimed in claim 1, wherein the anion, Xq~, is selected from Br~, Γ, [N03]~ [PF6r, [SnCl3]- [SCN]", [NCO]" [CF3S03]" [CH3OS03]", [C2H5OS03]- [C6F5S03]-,
[(BuO)2P(0)0]- [CH3C6H4S03]-, [(CF3S02)2N]-, [(FS02)2N]" [C2F5S03]-, [(C2F5S02)2N)]-, [P(C2F5)3F3]-, [B(CN)4]-, and [ (CN)J-.
A compound as claimed in claim 1 , wherein the anion, Xq , is selected from Br , [N03] , [PF¾] [SCN]", [CF3S03r, [CH3OS03r, [C2H5OS03]- [C6F5S03]-, [CftQH^O.,]-, [(CF3S02)2N]-, [(FS02)2N]-, [C2F5S03]-, [(C2F5S02)2N)]- and [N(CN)2]".
15. A compound as claimed in claim 1, wherein R1, R2, R3 and R5 are each independently selected from -H, Ci-2o alkyl, substituted Ci-20 alkyl, C2.20 alkenyl, and aryl;
R4 and R6 are each independently selected from C2.20 alkyl, substituted Ci_20 alkyl, C2.20 alkenyl, and aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl; and
the anion, Xq~, is selected from F', Br", Γ, [HF2]~, [SCNf, [NCO]~, [Ν03Γ, [AlC r, [A12C17]", [PF6]- [SnCl3]-
[SeCNf, [CF3SO3]", [FHOMe]', [FHOEt]~ [FHOPr]", [MeOS03]', [EtOSOjf, [(BuO)2P(0)0]", [CH3C6H4S03]~, ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4- trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]_,
[(CF3S02)2Nr, [(CF3S02)NC(0)CF3]-, [(FS02)2N] [CF3CF2S03]', [C^SO,]"
[(CF3CF2S02)2N)]- [(CF3S02)3C]-, [(FS02)3C]-, [P(C2F5)3F3r, [(CF3)2P(0)0]-, [(C2F5)2P(0)0]- [(CF30)2P(0)0]-, t(C2F50)2P(0)0]-, [BF3(CF3)3]" [BF3(C2F5)3]-, [BF3(CN)] , [B(CN)4]",
[N(CN)2]- and [C(CN)3]".
16. A compound as claimed in claim 1 , wherein R1, R2, R3 and R5 are each independently selected from -H, Ci_20 alkyl, substituted Ci_6 alkyl, C2_6 alkenyl, and aryl;
R4 and R6 are each independently selected from C2_2o alkyl, substituted C alkyl, C2_6 alkenyl, and aryl; or
R5 and R6 form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl; and
the anion, Xq_, is selected from F, Br", Γ, [HF2] ~, [SCNf, [NCO]~ [N03] " [AIC F, [A12C17]", [PF6]-, [SnCl3]',
[SeCN]", [CF3S03]", [FHOMe]~, [FHOEt]", [FHOPr] ~ [MeOS03] [EtOS03]", [(BuO)2P(0)0]", [CH3C6H4S03]", ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4- trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,
[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH2BF3]",
[(CF3S02)2N]-, f(CF3S02)NC(0)CF3]-, [(FS02)2N] ~, [CF3CF2S03]" [C4F9S03]-,
[(CF3CF2S02)2N)]-, [(CF3S02)3C]-, [(FS02)3Cr, [P(C2F5)3F3]-, [(CF3)2P(0)0]" [(C2F5)2P(0)0] ~ [(CF30)2P(0)0]-, [(C2F50)2P(0)0]-, [BF3(CF3)3] [BF3(C2F5)3]- [BF3(CN)r, fB(CN)4]-,
[N(CN)2]-, and [C(CN)3]-.
17. A compound as claimed in claim 1 , wherein R1, R2, R3 and R5 are each independently selected from -H, methyl, ethyl, «-propyl, z'so-propyl, H-butyl, n-pentyl, «-hexyl, decyl, stearyl,
2-hydroxyethyl, allyl, and phenyl; and
R4 and R6 are each independently selected from ethyl, w-propyl, wo-propyl, «-butyl, R-pentyl, -hexyl, decyl, stearyl, 2-hydroxyethyl, 1 -carboxyl-2-hydroxypropyl, l-carboxyl-2-methylpropyl, 1 -carboxylethyl, allyl, and phenyl; or
R5 and R6, together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl; and
the anion, Xq", is selected from F~, Br , Γ, [N03]~ [SnCl3]~ [SCN]", [NCO]", [CF3S03r, [CH3OS03]-, [(BuO)2P(0)0]-; [CH3C6H4S03]", [(CF3S02)2N]", [P(C2F5)3F3]-, [B(CN)4r, and [N(CN)2]-. 18. A compound as claimed in claim 1, selected from the group consisting of:
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium -toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(14) tris(dipropylamino)cyclopropenium fluoride diethanol;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(26) tris(diethanolamino)cyclopropenium fluoride;
(28) tris(diallylamino)cyclopropenium bromide;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(49) bis(diethylamino)diethanolaminocyclopropenium iodide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;
(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(69) tris(dipentylamino)cyclopropenium dicyanoamide;
(71 ) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(76) bis(dii5o-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(77) bis(diw -propylamino)dibutylaminocyclopropenium dicyanoamide;
(78) bis(diethylamino)hexylaminocyclopropenium methylsulfate;
(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(80) bis(diethylamino)aminocyclopropenium methylsulfate;
(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide;
(86) bis(diethylamino)dihexylaminocyclopropenium iodide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide; (88) tris(dimethylamino)cyclopropenium thiocyanate;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;
(91) tris(dihexylamino)cyclopropenium dibutylphosphate;
(92) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(95) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;
(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;
(98) bis(diethylamino)-S-(l-carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(99) tris(dibutylamino)cyclopropenium isocyanate;
( 100) tris(dibutylamino)cyclopropenium trichlorostannate;
(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;
( 102) bis(diethylamino)diwo-propylaminocyclopropenium methylsulfate;
(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;
(105) bis(dimethylamino)hexylmethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide;
( 106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
19. A compound of formula [Y^qtX"1"] wherein q is 1 ;
wherein the cation, Y1", is selected from
tris(dipropylamino)cyclopropenium,
tris(dipentylamino)cyclopropenium,
tris(dibutylamino)cyclopropenium,
tris(dihexylamino)cyclopropenium,
tris(didecylamino)cyclopropenium,
tris(diallylamino)cyclopropenium,
tris(butylmethylamino)cyclopropenium,
tris(hexylmethylamino)cyclopropenium,
tris(octadecylmethylamino)cyclopropenium, bis(diwo-propylamino)dibutylaminocyclopropenium,
bis(diethylamino)dipropylaminocyclopropenium,
bis(diethylamino)diwo-propylaminocyclopropenium,
bis(diethylamino)dibutylaminocyclopropenium,
bis(diethylamino)dihexylaminocyclopropenium,
bis(diethylamino)diallylaminocyclopropenium,
bis(diethylamino)butylmethylaminocyclopropenium,
bis(diethylamino)hexylmethylaminocyclopropenium,
bis(diethylamino)octadecylmethylaminocyclopropenium,
bis(diethylamino)dimethylaminocyclopropenium, and
bis(diethylamino)di(2-methoxyethyl)aminocyclopropenium; and
wherein the anion, Xq~, is selected from CI", Br", [BF4]", [N03]~, [PF6]~, [SCN]~, [CF3S03]\ [CH3OSO3]- [C2H5OS03]-, [C6F5SO3]-, [CH3C6H4S03]-, f(CF3S02)2Nr, [(FS02)2N]-,
[C2F5S03]-, [(C2F5S02)2N)]- and [N(C )2]". 20. A compound of formula
Figure imgf000181_0001
wherein q is 1 ;
wherein the cation, Y1', is tris(diethylamino)cyclopropenium; and
wherein the anion, Xq_, is selected from Γ, [BF4]", [ 03]", [PF6]", [SCN]~ [CF3S03r,
[CH3OS03]", [C2H5OS03]~, [C6F5S03]-, [CH3C6H4S03]-, [(CF3S02)2N]-, [(FS02)2N]- [C2F5S03]-, [(C2F5S02)2N)]- and [N(CN)2]-. 21. A compound of formula [Y^qPC1"] wherein q is 1 ;
wherein the cation, Y , is selected from
bis(diethylamino)aminocyclopropenium,
bis(diethylamino)butylaminocyclopropenium,
bis(diethylamino)hexylaminocyclopropenium,
bis(diethylamino)diethanolaminocyclopropenium,
tris(diethanolamino)cyclopropenium,
trisanilinocyclopropenium,
bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium,
bis(diethylamino)-5-(2-carboxypyrrolidino)cyclopropenium,
bis(diethylamino)-5-(l -carboxy-2-methylpropylamino)cyclopropenium, and
bis(diethylamino)-5-(l-carboxy-2-hydroxylpropylamino))cyclopropenium; and
wherein the anion, Xq", is selected from [BF4]_, [PF6]", [CF3S03]", [CH3OS03]~, [C2H5OS03]~,
[C6F5S03]-, [CH3C6H4S03]-, [(CF3S02)2N]", [(FS02)2N]- [C2F5S03r, [(C2F5S02)2N)r and
[N(CN)2]-.
22. A compound of formula POqiX'1"] wherein q is 1 or 2; wherein the cation, Y1", is a triaminocyclopropenium ion of the formula (II):
Figure imgf000182_0001
wherein the anion, Xq~, is selected from [SCN]", [CF3SO3]", [FHO(C,.6 alkyl)]~, [(Cw alkyl)OS03r,
Figure imgf000182_0002
[(CI-6 alkyl)(Cw alkyl)P(0)Or, [Co(C2B9H, ,)2Γ, [C2B9H12r, [B,oCl10]2- [B12C112]2-, [CB„H12]", [B12HnN(C,.6 alkyl)3r, [(Cu6 alkyl)SnB„H„r, [RBCB„RC5XB 6]- [RDBF3]- [(CF3S02)2N]- t(CF3S02)NC(0)CF3]" [(FS02)2N]-, [RFCF2S03] ~ [(RGS02)2N)]-, [(RGS02)3Cr, [(FS02)3C]- [RFCF2C(0)0]-, [P(CnF2n+I.mHm)yF6.yr,
-, [RF 2P(0)0]-, [RFP(0)02]2 [BFzRF 4.zr, [BFz(CN)4-zr, [N(CF3)2]-, [N(CN)2]-
Figure imgf000182_0003
wherein RB, Rc, RD, XB, RF, RG, n, m, y, z, -Z-, and -Y- are as defined in claim 1.
23. A compound as claimed in claim 22, wherein the anion, Xq , is selected from [SCN] , [CF3S03] ,
[CH3OSO3]-, [C2H5OS03r, [C6F5S03]-, [OfcCeHiSOj]-, [(CF3S02)2N]-, [(FS02)2N]-,
[C2F5S03]-, [(C2F5S02)2N)]- and [N(CN)2]-.
24. A compound as claimed in claim 22 or 23, selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide; and
(88) tris(dimethylamino)cyclopropenium thiocyanate.
25. A compound of formula [Y+]q[Xq~] wherein q is 1 or 2;
wherein the cation, Y1", is a triaminocyclopropenium ion of the formula (III):
H3C^ ^CH3
' (HI) wherein R7 is methyl and R8 is selected from C2.2o alkyl, substituted Ci-2o alkyl, C2-2o alkenyl, substituted C2-20 alkenyl, C2_20 alkynyl, substituted C2-20 alkynyl, C3.i0 cycloalkyl, substituted C3.i0 cycloalkyl, C3.i0 cycloalkenyl, substituted C3_i0 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or
R7 and R8 are each independently selected from C2.20 alkyl, substituted Ci.20 alkyl, C2.20 alkenyl, substituted C2-2o alkenyl, C2.20 alkynyl, substituted C2-2o alkynyl, C3-10 cycloalkyl, substituted C3.i0 cycloalkyl, C3_i0 cycloalkenyl, substituted C3-io cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;
wherein the anion, X"~, is selected from [SCN]~ [CF3COO]~ [SeCNf, [CF3S03]',
[FHO(C,.6 alkyl)r, [(C,.6 alkyl)OS03r, fC6F5S03r, [(C,,6 alkyl)(C,_6 alkyl)P(0)0]",
[CH3C6H4S03]-, [Co(C2B9Hn)2r, [C2B9H12]', [B10C110]2^ [B12C112]2-, [CB„H12r, [B12HnN(C,.6 alkyl),]" [(C,.6 alky^SnBnHn]-, [RBCB„Rc 5XB6r, [RDBF3]~, [(CF3S02)2N]",
[(CF3S02)NC(0)CF3r, [(FS02)2N]-, [RFCF2S03] ~, [(RGS02)2N)]" [(RGS02)3C]- [(FS02)3C]" [RFCF2C(0)0]-, [P(CnF2n+l.mHm)yF6.y]-, P(C6F5)yF6.y]-, [RF 2P(0)0]- [RFP(0)02]2-, [BF2RF4.Z]-,
[BF2(CN)4-J-, [N(CF3)2]-, [N(CN)J-,
Figure imgf000183_0001
J ; and wherein RB, Rc, RD, XB, RF, RG, n, m, y, z, -Z-, and -Y- are as defined in claim 1.
26. A compound as claimed in claim 25, wherein R7 is methyl and R8 is butyl, R7 is methyl and Rg is hexyl, R7 is methyl and Rg is stearyl, R7 and R8 are ethyl, R7 and R8 are propyl, R7 and R8 are butyl, or R7 and Rg are hexyl.
27. A compound as claimed in claim 25 or 26 wherein the cation, Y1", is selected from
bis(dimethylamino)hexylmethylaminocyclopropenium,
bis(dimethylamino)dihexylaminocyclopropenium,
bis(dimethylamino)dibutylaminocyclopropenium; and
the anion, Xq", is selected from [SCNf, [CF3SO3]", [CH3OS03]", fC2HsOS03]", [CeFsSOjf, [CH3C6H4S03]-, [(CF3S02)2N]- [(FS02)2N]" [C2F5S03]-, [(C2F5S02)2N)r and [N(CN)2]".
28. A compound as claimed in any one of claims 25 to 27, selected from the group consisting of:
(105) bis(dimethylarnino)hexylmethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide;
( 106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
29. A compound selected from the group consisting of:
(2) tris(dimethylarnino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium -toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(11) tris(dipropylamino)cyclopropenium chloride;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(14) tris(dipropylamino)cyclopropenium fluoride diethanol;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(18) tris(dibutylamino)cyclopropenium chloride;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(26) tris(diethanolamino)cyclopropenium fluoride;
(27) tris(diallylamino)cyclopropenium chloride;
(28) tris(diallylamino)cyclopropenium bromide;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; (39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(49) bis(diethylamino)diethanolaminocyclopropenium iodide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;
(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61 ) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate;
(65) bis(di 5o-propylamino)dibutylaminocyclopropenium chloride;
(67) tris(dipentylamino)cyclopropenium chloride;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(69) tris(dipentylamino)cyclopropenium dicyanoamide;
(70) tris(dihexylamino)cyclopropenium chloride;
(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide;
(73) tris(didecylamino)cyclopropenium chloride;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(76) bis(dii50-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (77) bis(di 50-propylamino)dibutylaminocyclopropenium dicyanoamide;
(78) bis(diethylamino)hexylaminocyclopropenium methylsulfate;
(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(80) bis(diethylamino)aminocyclopropenium methylsulfate;
(81 ) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;
(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide;
(86) bis(diethylamino)dihexylaminocyclopropenium iodide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide;
(88) tris(dimethylamino)cyclopropenium thiocyanate;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;
(91) tris(dihexylamino)cyclopropenium dibutylphosphate;
(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(94) bis(diethylamino)-5-(2-carboxypyrrolidino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(95) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;
(96) bis(diethylamino)-5-(l -carboxy-2-methylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(97) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;
(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(99) tris(dibutylamino)cyclopropenium isocyanate;
(100) tris(dibutylamino)cyclopropenium trichlorostannate;
(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;
( 102) bis(diethylamino)diz'so-propylaminocyclopropenium methylsulfate;
(103) bis(diethylamino)dii'so-propylaminocyclopropenium dicyanoamide;
(105) bis(dimethylamino)hexylmethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide;
(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
30. An ionic liquid comprising a triaminocyclopropenium cation and an anion.
31. An ionic liquid as claimed in claim 30 wherein the ionic liquid comprises a compound selected from the group consisting of:
(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(5) tris(diethylamino)cyclopropenium dicyanoamide;
(6) tris(diethylamino)cyclopropenium nitrate;
(7) tris(diethylamino)cyclopropenium tetrafluoroborate;
(8) tris(diethylamino)cyclopropenium thiocyanate;
(9) tris(diethylamino)cyclopropenium >-toluenesulfonate;
(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;
(11) tris(dipropylamino)cyclopropenium chloride;
(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(13) tris(dipropylamino)cyclopropenium dicyanoamide;
(15) tris(dipropylamino)cyclopropenium fluoride ethanol;
(16) tris(dipropylamino)cyclopropenium nitrate;
(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;
(18) tris(dibutylamino)cyclopropenium chloride;
(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(20) tris(dibutylamino)cyclopropenium bromide;
(21) tris(dibutylamino)cyclopropenium dicyanoamide;
(22) tris(dibutylamino)cyclopropenium nitrate;
(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;
(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;
(25) tris(diethanolamino)cyclopropenium chloride;
(26) tris(diethanolamino)cyclopropenium fluoride;
(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(30) tris(diallylamino)cyclopropenium dicyanoamide;
(31) tris(butylmethylamino)cyclopropenium chloride;
(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(33) tris(butylmethylamino)cyclopropenium dicyanoamide;
(34) tris(butylmethylamino)cyclopropenium nitrate;
(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;
(36) tris(butylmethylamino)cyclopropenium thiocyanate;
(37) tris(octadecylmethylamino)cyclopropenium chloride;
(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; (39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;
(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;
(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;
(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;
(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;
(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;
(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;
(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;
(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;
(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate;
(65) bis(diw0-propylamino)dibutylaminocyclopropenium chloride;
(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(69) tris(dipentylamino)cyclopropenium dicyanoamide;
(70) tris(dihexylamino)cyclopropenium chloride;
(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(72) tris(dihexylamino)cyclopropenium dicyanoamide;
(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;
(75) tris(didecylamino)cyclopropenium dicyanoamide;
(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;
(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(80) bis(diethylamino)aminocyclopropenium methylsulfate;
(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;
(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;
(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate;
(84) bis(diethylamino)dibutylaminocyclopropenium iodide;
(85) tris(diethylamino)cyclopropenium iodide;
(86) bis(diethylamino)dihexylaminocyclopropenium iodide;
(87) tris(dimethylamino)cyclopropenium dicyanoamide; (88) tris(dimethylamino)cyclopropenium thiocyanate;
(89) tris(dibutylamino)cyclopropenium tetracyanoborate;
(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;
(91) tris(dihexylamino)cyclopropenium dibutylphosphate;
(92) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;
(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(95) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;
(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;
(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium
bis(trifluoromethanesulfonyl)amide;
(99) tris(dibutylamino)cyclopropenium isocyanate;
(100) tris(dibutylamino)cyclopropenium trichlorostannate;
(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;
(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;
(105) bis(dimethylamino)hexylmethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide;
( 106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and
(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.
32. An ionic liquid comprising a compound of any one of claims 1 to 29.
33. Use of a compound of any one of claims 1 to 29 as a solvent.
34. Use of a compound of any one of claims 1 to 29 as an electrolyte.
35. Use of a compound of any one of claims 1 to 29 for gas storage.
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