EP2786135A1 - Benzyl-pyridinium and -imidazolinium ionic liquid salts for use in planar chromatography - Google Patents

Benzyl-pyridinium and -imidazolinium ionic liquid salts for use in planar chromatography

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Publication number
EP2786135A1
EP2786135A1 EP12798677.6A EP12798677A EP2786135A1 EP 2786135 A1 EP2786135 A1 EP 2786135A1 EP 12798677 A EP12798677 A EP 12798677A EP 2786135 A1 EP2786135 A1 EP 2786135A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
group
halo
alkoxy
haloci
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP12798677.6A
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German (de)
French (fr)
Inventor
Olivier Lavastre
Audrey CABROL
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TotalEnergies One Tech Belgium SA
Centre National de la Recherche Scientifique CNRS
Original Assignee
Total Research and Technology Feluy SA
Centre National de la Recherche Scientifique CNRS
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Priority to EP12798677.6A priority Critical patent/EP2786135A1/en
Publication of EP2786135A1 publication Critical patent/EP2786135A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/90—Plate chromatography, e.g. thin layer or paper chromatography

Definitions

  • the present invention is in the field of ionic liquids, chromatography, and polymers technology.
  • ILs ionic liquids
  • Ionic liquids are generally defined as organic salts that are liquid at ambient temperatures, preferably at room temperature.
  • Ionic liquids are composed of large organic cations and small inorganic or organic anions.
  • Room temperature ionic liquids (sometimes abbreviated as RTILs) have emerged as a new class of solvents for practical applications due to their unique combination of low volatility because of their negligible vapor pressure at near ambient temperatures, chemical stability, high thermal stability, high conductivity, wide electrochemical window, wide liquid ranges, ability to dissolve organic and inorganic solutes and gases, and tunable solvent properties.
  • Ionic liquids are actively investigated as alternative solvent media in many industrial applications such as synthesis, catalysis, separation, electrochemistry, or nanoparticles stabilization.
  • ILs may offer some advantage for the processes which require removal of by-products at relatively high temperatures such as polycondensation processes.
  • Another property of ILs is their ability to dissolve several inorganic or organometallic compounds that are used as catalysts in polymerization processes. This offers at least two advantages. Polymerizations in ILs may be conducted under homogeneous conditions otherwise difficult to achieve (an example is a solubility of ATRP catalysts in ILs). Other advantage is a possibility of recycling and reusing solutions of catalyst in I Ls, especially when expensive catalysts (e.g. those based on noble metals) are used.
  • ionic liquids in polymer science is not limited to their application as solvents. Ionic liquids are also used as additives to polymers (plasticizers, components of polymer electrolytes, porogenic agents).
  • ILs Due to the unique properties inherent to ILs, they have also been widely used in various analytical applications including gas chromatography (GC), high-performance liquid chromatography (HPLC), gel permeation chromatography (GPC), liquid-liquid extraction, microextraction, mass spectrometry, and electrophoresis.
  • GC gas chromatography
  • HPLC high-performance liquid chromatography
  • GPC gel permeation chromatography
  • liquid-liquid extraction microextraction
  • mass spectrometry mass spectrometry
  • electrophoresis electrophoresis
  • each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium; each group being optionally substituted with one, two, or three substituents selected from Ci_i 2 alkyl and Ci-i 2 alkoxy;
  • L 1 is Ci-i 2 alkylene; preferably Ci -6 alkylene; more preferably Ci -2 alkylene;
  • L 2 is Ci-i 2 alkylene; preferably Ci -6 alkylene; more preferably Ci -2 alkylene; L 3 is a single bond or Ci-i 2 alkylene; wherein one carbon of the Ci-i 2 alkylene is optionally replaced by one or more heteroatoms; preferably L 3 is a single bond or d. i 2 alkylene;
  • Y 1 is C 6- i 2 aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • Y 2 is C 6- i 2 aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [N(S0 2 CF 3 ) 2 ], [BF 4 ], [CF3SO3], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I], and [AIR 1 4-n R 2 n ];
  • R 1 is halo or Ci_i 2 alkyl
  • R 2 is halo
  • n is an integer selected from 0, 1 , 2, 3, or 4.
  • These compounds possesses attractive properties as a solvent, in particular as solvent for polymers such as polyolefins. They are suitable as solvent in chemical reactions such as polymerizations as well as for various analytical applications including thin-layer chromatography (TLC), gas chromatography (GC), high-performance liquid chromatography (HPLC), gel permeation chromatography (GPC), liquid-liquid extraction, microextraction, mass spectrometry, and electrophoresis.
  • TLC thin-layer chromatography
  • GC gas chromatography
  • HPLC high-performance liquid chromatography
  • GPC gel permeation chromatography
  • liquid-liquid extraction microextraction
  • mass spectrometry mass spectrometry
  • electrophoresis electrophoresis.
  • halo or halogen as a group or part of a group is generic for fluoro, chloro, bromo or iodo.
  • Ci- 6 alkyl as a group or part of a group defines straight and branched chained saturated hydrocarbon radicals having from 1 to 6 carbon atoms such as, for example, methyl, ethyl, propyl, butyl, 2-methyl-propyl, pentyl, hexyl, 2-methylbutyl, 3-methylpentyl and the like.
  • Ci-i 2 alkyl as a group or part of a group defines straight and branched chained saturated hydrocarbon radicals having from 1 to 12 carbon atoms, such as, those defined for Ci -6 alkyl and heptyl, octyl, 2-methyl-hetyl, 3-ethyl-hexyl, nonyl, decyl, undecanyl, dodecanyl, and the like.
  • Ci-i 2 alkylene as a group or part of a group defines bivalent straight and branched chained saturated hydrocarbon radicals having from 1 to 12 carbon atoms such as, for example, methylene, ethan-1 ,2-diyl, propan-1 ,3-diyl, propan-1 ,2-diyl, butan-1 ,4- diyl, pentan-1 ,5-diyl, hexan-1 ,6-diyl, 2-methylbutan-1 ,4-diyl, 3-methylpentan-1 ,5-diyl, octan-1 ,8-diyl, undecan-1 ,9-diyl, dodecan-1 ,12-diyl, and the like.
  • C 6 -i 2 aryl refers to a polyunsaturated, aromatic hydrocarbyl group having a single ring (i.e. phenyl) or multiple aromatic rings fused together (e.g. naphthyl), or linked covalently, typically containing 6 to 12 atoms; wherein at least one ring is aromatic.
  • Non-limiting examples of C 6- i 2 aryl comprise phenyl, biphenylyl, biphenylenyl, indanyl, or 1 ,2,3,4-tetrahydronaphthyl, or 1 -or 2-naphthanelyl, each of which may be optionally substituted with one, two or three substituents selected from halo, Ci_ 6 alkyl, polyhaloCi -6 alkyl, hydroxy, Ci -6 alkoxy, polyhaloCi -6 alkoxy, Ci- 6 alkoxyCi- 6 alkyl, carboxyl, Ci -6 alkylcarbonyl, Ci -6 alkoxycarbonyl, cyano, nitro, amino, mono- or diCi_ 6 alkylamino, aminocarbonyl, mono- or diCi -6 alkylaminocarbonyl, azido, mercapto.
  • C 1-6 alkoxy or "C 1-6 alkyloxy” as used herein refers to a radical having the Formula -OR a wherein R a is Ci -6 alkyl as defined herein.
  • suitable alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert- butoxy, pentyloxy and hexyloxy.
  • haloCi- 6 alkyl refers to an Ci -6 alkyl as defined herein wherein one or more hydrogens are replaced with a halogen, preferably, chloro or fluoro atoms, more preferably fluoro atoms.
  • haloCi -6 alkyl radicals include chloromethyl, 1 -bromoethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 ,1 - trifluoroethyl, 1 -bromopropyl, 2-fluorobutyl, 3,4-difluoropentyl, 3,4,4-trifluoropentyl, 1 ,1 ,1 - trifluorohexyl, and the like.
  • haloCi -6 alkoxy or "haloCi -6 alkyloxy” as used herein refers to a radical having the Formula -OR b wherein R b is haloCi -6 alkyl as defined herein.
  • suitable alkoxys include chloromethoxy, 1 -bromoethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 ,1 -trifluoroethoxy, 1 -bromopropoxy, 2-fluorobutoxy, 3,4- difluoropentyloxy, 3,4,4-trifluoropentyloxy, 1 ,1 ,1 -trifluorohexyloxy, and the like.
  • substituted is used in defining the compounds of the present invention, it is meant to indicate that one or more hydrogens on the atom indicated in the expression using “substituted” is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a chemically stable compound, i.e. a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture.
  • chromatography refers to a physical method of separation in which the components to be separated are distributed between two phases, one of which is stationary (stationary phase) while the other (the mobile phase) moves in a definite direction.
  • chromatography includes, among others, the techniques of thin-layer chromatography (TLC), gas chromatography (GC), gel permeation chromatography (GPC), and high-performance liquid chromatography (HPLC).
  • planar chromatography refers to a separation technique in which the stationary phase is present as or on a plane (planar stationary phase).
  • the plane can be a paper, used as such or impregnated by a substrate as the stationary bed (paper chromatography, PC) or a layer of solid particles spread on a support e.g. a glass or metal plate.
  • support or "plate” or “support plate” refers to the plate that supports the stationary phase, such as the thin layer in thin-layer chromatography.
  • TLC thin-layer chromatography
  • stationary phase or “stationary bed” or “sorbent bed” or “absorbent” are used interchangeably and refer to an immobile phase or non-fluid phase employed in the chromatography method.
  • the expression chromatographic bed or sorbent bed may be used as a general term to denote any of the different forms in which the stationary phase is used.
  • the stationary phases used are typically the base sorbents known for chromatographic purposes. These are, for example, silica gel, aluminium oxide, cellulose, kieselguhr or other organic or inorganic polymers or organic/inorganic hybrid polymers.
  • the base sorbents may furthermore be derivatized with functional groups which modify their separation properties.
  • RP phases in which, for example, silica gel has been derivatized with ligands which have C8 or C18 chains (reversed phase material).
  • ligands which have C8 or C18 chains
  • CN or diol-modified phases Suitable common sorbent phases for planar chromatography are described in Klaus K. Unger, Packings and Stationary Phases in Chromatographic Techniques, M. Decker, New York 1990.
  • mobile phase refers to a fluid which migrates through or along the stationary bed, in a definite direction, carrying thereby the sample through the stationary phase. It may be a liquid or a supercritical fluid.
  • exent is also used for the mobile phase.
  • co-eluent refers to a second fluid which migrates through or along the stationary bed, in a definite direction.
  • the co-eluent accompanies the eluent, both forming the mobile phase.
  • additive when referred to polymers means a plasticizer, a component of polymer electrolytes, a porogenic agent, and the like.
  • the present invention relates to a compound formula (I) or (II)
  • each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium, each group being optionally substituted with one, two, or three substituents selected from Ci_i 2 alkyl and Ci-i 2 alkoxy; preferably each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, pyrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium, each group being optionally substituted with one, two, or three substituents selected from Ci_i 2 alkyl and Ci-i 2 alkoxy, preferably optionally substituted with one, two, or three substituent
  • Ci-i 2 alkylene preferably L 1 is Ci -6 alkylene; more preferably L 1 is Ci -3 alkylene; also preferably L 1 is Ci -2 alkylene;
  • Ci-i 2 alkylene preferably L 2 is Ci -6 alkylene; more preferably L 2 is Ci -3 alkylene; also preferably L 2 is Ci -2 alkylene;
  • Ci-i 2 alkylene wherein one carbon of the Ci-i 2 alkylene is optionally replaced by one or more heteroatoms; preferably L 3 is a single bond or Ci -6 alkylene; wherein one carbon of the Ci -6 alkylene is optionally replaced by one or two heteroatoms selected from O, N or S; preferably L 3 is a single bond or Ci -3 alkylene; wherein one carbon of the Ci -3 alkylene is optionally replaced by one heteroatoms selected from O, N or S; preferably L 3 is a single bond or Ci -2 alkylene;
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [N(S0 2 CF 3 ) 2 ], [BF 4 ], [CF3SO3], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I], and [AIR 1 4-n R 2 n ]; preferably A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ],
  • A is selected from the group consisting of [Br], [PF 6 ], [BF 4 ], [CI], [CF 3 SO 3 ], and [I]; preferably A is selected from the group consisting of [Br], [PF 6 ], [BF 4 ];
  • R 1 is halo or Ci-i 2 alkyl; preferably R 1 is halo or Ci -6 alkyl; preferably R 1 is bromo, chloro, iodo, or Ci -4 alkyl;
  • R 2 is halo; preferably R 1 is bromo, or chloro, and
  • n is an integer selected from 0, 1 , 2, 3, or 4.
  • the present invention relates to the compound of formula (I) or (II) as depicted above, preferably of formula (I) wherein
  • each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, imidazolium, pyrazinium, pyrrolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium; each group being optionally substituted with one, two, or three substituents selected from Ci-i 2 alkyl and Ci-i 2 alkoxy, preferably each group being optionally substituted with one, two, or three substituents selected from Ci -6 alkyl and Ci -6 alkoxy;
  • L 1 is Ci -6 alkylene
  • L 2 is Ci -6 alkylene
  • L 3 is a single bond, or Ci -6 alkylene; wherein one carbon of the Ci -6 alkylene is optionally replaced by one or two heteroatoms;
  • Y 1 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • Y 2 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [N(S0 2 CF 3 ) 2 ], [BF 4 ], [CF3SO3], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I], and [AIR 1 4-n R 2 n ];
  • R 1 is halo or Ci-i 2 alkyl
  • R 2 is halo
  • n is an integer selected from 0, 1 , 2, 3, or 4.
  • the present invention relates to the compound of formula (I) or (II) as depicted above, preferably (I), wherein
  • each ring comprising the nitrogen atom is independently selected from pyridinium, imidazolium; pyrazinium, and pyrrolium, each being optionally substituted with one, two, or three substituents selected from Ci -6 alkyl and Ci -6 alkoxy, preferably each optionally substituted with one, two, or three substituents selected from Ci -4 alkyl and Ci -4 alkoxy;
  • L 1 is Ci -2 alkylene
  • L 2 is Ci -2 alkylene
  • L 3 is a single bond, or Ci -2 alkylene
  • Y 1 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy; preferably halo;
  • Y 2 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy; preferably halo;
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [N(S0 2 CF 3 ) 2 ], [BF 4 ], [CF 3 S0 3 ], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I], and [AIR 1 4-n R 2 n ];
  • R 1 is halo or Ci-i 2 alkyl
  • R 2 is halo
  • n is an integer selected from 0, 1 , 2, 3, and 4.
  • the compound of formula (I) as depicted above is a compound of formula (la), or (lb),
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [N(S0 2 CF 3 ) 2 ], [BF 4 ], [CF3SO3], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I], and [AIR 1 4-n R 2 n ]; and
  • R 1 is halo or Ci-i 2 alkyl; preferably halo or Ci -6 alkyl;
  • R 2 is halo
  • n is an integer selected from 0, 1 , 2, 3, or 4;
  • L 1 is Ci -6 alkylene; preferably L 1 is Ci -4 alkylene; preferably L 1 is Ci -2 alkylene; preferably - CH 2 -;
  • each R 3 is independently selected from hydrogen, Ci -6 alkyl and Ci -6 alkoxy;
  • each R 4 is independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • R 5 is independently selected from Ci -6 alkyl or hydrogen; preferably Ci -6 alkyl;
  • p is an integer selected from 1 , 2, or 3;
  • q is an integer selected from 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein A is selected from the group consisting of [Br], [CI], [PF 6 ], [AsF 6 ], [SbF 6 ], [BF 4 ], [CH 3 C0 2 ], [CF 3 S0 2 ], [N0 2 ], [N0 3 ], [CI0 4 ], [I];
  • L 1 is Ci -6 alkylene; preferably L 1 is Ci -4 alkylene; more preferably L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is independently selected from hydrogen, Ci -6 alkyl and Ci -6 alkoxy;
  • each R 4 is independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • R 5 is independently selected from Ci -6 alkyl or hydrogen; preferably Ci -6 alkyl;
  • p is an integer selected from 1 , 2, or 3;
  • q is an integer selected from 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], [BF 4 ], [CH 3 C0 2 ], [CF 3 S0 2 ], [I];
  • L 1 is Ci -4 alkylene; more preferably L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is independently selected from hydrogen, Ci -6 alkyl and Ci -6 alkoxy;
  • each R 4 is independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • R 5 is independently selected from Ci -6 alkyl or hydrogen; preferably Ci -6 alkyl;
  • p is an integer selected from 1 , 2, or 3;
  • q is an integer selected from 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein
  • A is selected from the group consisting of [Br], [CI], [PF 6 ], and [BF 4 ];
  • L 1 is Ci -4 alkylene; more preferably L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is independently selected from hydrogen, Ci -6 alkyl and Ci -6 alkoxy;
  • each R 4 is independently selected from the group consisting of halo, haloCi -6 alkyl, and haloCi -6 alkoxy;
  • R 5 is independently selected from Ci -6 alkyl or hydrogen; preferably Ci -6 alkyl;
  • p is an integer selected from 1 , 2, or 3; and q is an integer selected from 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein
  • A is [Br], [PF 6 ], [BF 4 ];
  • L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is independently selected from hydrogen, Ci -4 alkyl and Ci -4 alkoxy; preferably hydrogen
  • each R 4 is independently selected from chloro, fluoro, and bromo, preferably chloro or, bromo,
  • R 5 is independently selected from Ci -4 alkyl or hydrogen; preferably Ci -2 alkyl;
  • p 1 , 2 or 3
  • q is 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb) as depicted above, wherein
  • A is Br], [PF 6 ], or [BF 4 ],
  • L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is hydrogen, or Ci -4 alkyl
  • each R 4 is independently selected from chloro or bromo, and
  • R 5 is independently selected from Ci -2 alkyl or hydrogen ;
  • p 1 , 2 or 3
  • q is 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb) as depicted above, wherein
  • A is [Br], [PF 6 ], [BF 4 ];
  • L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is hydrogen, or Ci -4 alkyl; preferably hydrogen
  • each R 4 is independently selected from chloro, and bromo,
  • R 5 is independently selected from Ci -2 alkyl or hydrogen ; preferably Ci -2 alkyl; p is 1 , or 2, and
  • q is 1 , 2, or 3.
  • the ionic liquid is a compound of formula (la), or (lb) as depicted above, wherein
  • A is [Br], [PF 6 ], [BF 4 ];
  • L 1 is Ci -2 alkylene; preferably -CH 2 -;
  • each R 3 is hydrogen
  • each R 4 is independently selected from chloro, and bromo,
  • R 5 is independently selected from Ci -2 alkyl or hydrogen ; preferably Ci -2 alkyl;
  • the ionic liquid is a compound as listed in Table 1 .
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as a solvent; preferably as a solvent for polymers.
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as an eluent; preferably as an eluent for polymers.
  • the polymers are selected from the group comprising polyolefins, polyamides, polycarbonates, poly(hydroxy carboxylic acid) , polystyrenes, polyesters, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethylmethacrylate (PMMA), poly(methyl acrylate) (PMA), vinyl polymers, proteins, and polysaccharides, or blends thereof.
  • the compound of formula (I), (II), (la), or (lb), is particularly useful as a solvent or as an eluent for polyolefins.
  • the polyolefins may be any olefin homopolymer or any copolymer of an olefin and one or more comonomers.
  • the polyolefins may be atactic, syndiotactic or isotactic.
  • the olefin can for example be ethylene, propylene, 1 -butene, 1 -pentene, 1 -hexene, 4-methyl-1 -pentene or 1 -octene, but also cycloolefins such as for example cyclopentene, cyclohexene, cyclooctene or norbornene.
  • the comonomer may be different from the olefin and chosen such that it is suited for copolymerization with the olefin.
  • the comonomer may be an olefin as defined above.
  • olefin copolymers that can be analyzed, separated, or characterized in the present invention are random copolymers of propylene and ethylene, random copolymers of propylene and 1 -butene, heterophasic copolymers of propylene and ethylene, ethylene- butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and vinyl alcohol (EVOH).
  • polyolefins are olefin homopolymers and copolymers of an olefin and optionally one or more comonomers, wherein said olefin and said one or more comonomer are different.
  • said olefin is ethylene or propylene.
  • the term "comonomer” refers to olefin comonomers which are suitable for being polymerized with olefin monomers, preferably ethylene or propylene monomers.
  • Comonomers may comprise but are not limited to aliphatic C 2 -C 2 o alpha-olefins.
  • Suitable aliphatic C 2 -C 20 alpha-olefins include ethylene, propylene, 1 -butene, 4-methyl-1 -pentene, 1 -hexene, 1 -octene, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene and 1 -eicosene.
  • Preferred polyolefins for use in the present invention are propylene and ethylene polymers.
  • the terms "propylene polymer” and “polypropylene” as well as the terms "ethylene polymer” and “polyethylene” are used interchangeably.
  • the polyolefin is selected from polyethylene and polypropylene homo- and copolymers.
  • the present invention further relates to a chromatographic stationary phase impregnated with the ionic liquid compound of formula (I), (II), (la), or (lb), according to any one of the embodiments presented herein.
  • the present invention also encompasses a composition for use in chromatography comprising a substrate impregnated with an ionic liquid of formula (I), (II), (la), or (lb).
  • the impregnation of the stationary phase with an ionic liquid of formula (I), (II), (la), or (lb) may be performed by simply pouring, mixing or spraying the ionic liquid pure or in solution onto the stationary phase, and optionally allowing the stationary phase to dry.
  • the impregnation may be performed by covalent anchoring of non- coordinating anions on mineral supports to prepare supported ionic liquids as described in US201 1/0178258.
  • the substrate comprises silica based normal and reverse-phase resin optionally derivatized with alkyl groups or aromatic groups, preferably silica gel 60F254.
  • One embodiment of the present invention relates to the use of a composition according to the present invention as a stationary phase in chromatography.
  • One embodiment of the present invention relates to a method of performing chromatography characterized in that the stationary phase is a composition according to the present invention.
  • the chromatography is a planar chromatography.
  • One embodiment of the present invention relates to a method of performing chromatography characterized in that the stationary phase is a composition according to the present invention, in a method for analyzing, separating, or characterizing chemical compounds, preferably polymers selected from polyolefins, polyamides, polycarbonates, poly(hydroxy carboxylic acid) like polylactic acid, polystyrenes, polyesters polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethylmethacrylate (PMMA), poly(methyl acrylate) (PMA), vinyl polymers, proteins, and polysaccharides; or blends thereof.
  • the present invention also relates to a method of performing planar chromatography characterized in that the planar stationary phase is impregnated with an ionic liquid of formula (I), (II), (la), or (lb) .
  • the present invention also relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a mobile phase in chromatography.
  • the present invention also relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as an eluent in chromatography.
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a co-eluent in chromatography.
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a solvent in a chemical reaction.
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a solvent in a chemical separation such as liquid-liquid extraction, microextraction, and electrophoresis, or in mass spectrometry.
  • the chemical reaction is selected from a polycondensation, a polymerization, a radical polymerization, and an ionic polymerization.
  • the present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as an additive to polymers.
  • the additive to polymers is selected from a plasticizer, a component of polymer electrolytes, and a porogenic agent.
  • the present invention further relates to a method for the preparation of the ionic liquid compound of formula (I) or (II) as defined in any one of the embodiments presented herein, comprising contacting a compound of formula (Ig) with a compound of formula (Ih) thereby forming the compound of formula (I)
  • X 1 is halo
  • the nitrogen-containing ring is selected from the group consisting of pyridine, imidazole, pyrazine, pyrrole, pyrazole, thiazole, triazole, indole, tetrazole, pyrimidine, pyridazine, piperazine, and piperidine; each group being optionally substituted with one, two, or three substituents selected from Ci_i 2 alkyl and Ci-i 2 alkoxy; and L 1 , and Y 1 are as defined in any one of the embodiments presented herein.
  • the contacting step can be done at room temperature in a suitable solvent such as ethyl acetate.
  • the two solutions were mixed and a white precipitate was immediately formed.
  • the aqueous solution containing the precipitate was extracted several times with dichloromethane.
  • the organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate.
  • the dichloromethane was removed under vacuum and 94 mg (yield:45%) of a white solid was obtained having a melting point of 139.48°C.
  • the two solutions were mixed and a white precipitate was immediately formed.
  • the aqueous solution containing the precipitate was extracted several times with dichloromethane.
  • the organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate.
  • the dichloromethane was removed under vacuum and 231 mg (yield:17%) of a white solid was obtained having a melting point of 164°C.
  • the two solutions were mixed and a white precipitate was immediately formed.
  • the aqueous solution containing the precipitate was extracted several times with dichloromethane.
  • the organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate.
  • the dichloromethane was removed under vacuum and 3.28 g (yield:91 %) of a white solid was obtained having a melting point of 163.92°C.
  • Ionic liquid 7 Two solutions were prepared:
  • the two solutions were mixed and a white precipitate was immediately formed.
  • the aqueous solution containing the precipitate was extracted several times with dichloromethane.
  • the organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate.
  • the dichloromethane was removed under vacuum and a white solid was obtained having a melting point of 180°C.
  • the ionic liquids as listed in Table 2 have been tested as solvent for polyethylene.
  • the polyethylenes were dissolved in all the tested ionic liquids (results not shown).

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Abstract

The invention relates to an ionic liquid compound of formula (I)or (II) wherein each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, imidazolium, pyrazinium, pyrrolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium; each group being optionally substituted with one, two, or three substituents selected from C1-12alkyl and C1-12alkoxy; L1 is C1-12alkylene; L2 is C1-12alkylene; L3 is a single bond or C1-12alkylene; wherein one carbon of the C1-12alkylene is optionally replaced by one or more heteroatoms; Y1 is C6-12aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloC1-6alkyl, and haloC1-6alkoxy; Y2 is C6-12aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloC1-6alkyl, and haloC1-6alkoxy; A is selected from the group consisting of [Br], [Cl], [PF6], [AsF6], [SbF6], [N(SO2CF3)2], [BF4], [CF3SO3], [CH3CO2], [CF3SO2], [NO2], [NO3], [ClO4], [I], and [AlR1 4-nR2n]; R1 is halo or C1-12alkyl; R2 is halo; and n is an integer selected from 0, 1, 2, 3, or 4. The invention further relates to uses of the ionic liquid compounds of the invention as well as to methods for their preparation.

Description

BENZYL-PYRIDINIUM AND -IMIDAZOLINIUM IONIC LIQUID SALTS FOR USE
IN PLANAR CHROMATOGRAPHY
Field of the invention
The present invention is in the field of ionic liquids, chromatography, and polymers technology.
Background of the invention
The field of ionic liquids (ILs) has received an increasing amount of attention in the past decade largely due to their unique and tuneable physicochemical properties and their versatility in various applications. ILs are generally defined as organic salts that are liquid at ambient temperatures, preferably at room temperature. Ionic liquids are composed of large organic cations and small inorganic or organic anions.
Room temperature ionic liquids (sometimes abbreviated as RTILs) have emerged as a new class of solvents for practical applications due to their unique combination of low volatility because of their negligible vapor pressure at near ambient temperatures, chemical stability, high thermal stability, high conductivity, wide electrochemical window, wide liquid ranges, ability to dissolve organic and inorganic solutes and gases, and tunable solvent properties.
The first RTIL, ethyl ammonium nitrate, was discovered during World War I in 1914 (P. Wasserscheid, W. Keim, Angew. Chem. Int. Ed., 39 (2000), p. 3772). In 1982, Wilkes et al. first reported the ionic liquids based on the 1 -alkyl-3-methylimidazolium cation (J.S. Wilkes, J.A. Levisky, R.A. Wilson, C.L. Hussey. Inorg. Chem., 21 (1982), p. 1263). From then on, different varieties of ILs with various cation and anion combinations have been synthesized and applied in different fields of science and engineering.
Ionic liquids are actively investigated as alternative solvent media in many industrial applications such as synthesis, catalysis, separation, electrochemistry, or nanoparticles stabilization.
Good thermal stability and non-volatility may offer some advantage for the processes which require removal of by-products at relatively high temperatures such as polycondensation processes. Another property of ILs is their ability to dissolve several inorganic or organometallic compounds that are used as catalysts in polymerization processes. This offers at least two advantages. Polymerizations in ILs may be conducted under homogeneous conditions otherwise difficult to achieve (an example is a solubility of ATRP catalysts in ILs). Other advantage is a possibility of recycling and reusing solutions of catalyst in I Ls, especially when expensive catalysts (e.g. those based on noble metals) are used.
Nevertheless, the use of ionic liquids in polymer science is not limited to their application as solvents. Ionic liquids are also used as additives to polymers (plasticizers, components of polymer electrolytes, porogenic agents).
Due to the unique properties inherent to ILs, they have also been widely used in various analytical applications including gas chromatography (GC), high-performance liquid chromatography (HPLC), gel permeation chromatography (GPC), liquid-liquid extraction, microextraction, mass spectrometry, and electrophoresis.
However, there remains a need for ionic liquids with minimal risks for humans and the environment.
Summary of the invention
The present inventors have surprisingly found ionic liquid compounds of formula (I) or (I I)
(I) (I I)
wherein,
each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium; each group being optionally substituted with one, two, or three substituents selected from Ci_i2alkyl and Ci-i2alkoxy;
L1 is Ci-i2alkylene; preferably Ci-6alkylene; more preferably Ci-2alkylene;
L2 is Ci-i2alkylene; preferably Ci-6alkylene; more preferably Ci-2alkylene; L3 is a single bond or Ci-i2alkylene; wherein one carbon of the Ci-i2alkylene is optionally replaced by one or more heteroatoms; preferably L3 is a single bond or d. i2alkylene;
Y1 is C6-i2aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
Y2 is C6-i2aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [N(S02CF3)2], [BF4], [CF3SO3], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I], and [AIR1 4-nR2 n];
R1 is halo or Ci_i2alkyl;
R2 is halo; and
n is an integer selected from 0, 1 , 2, 3, or 4.
These compounds possesses attractive properties as a solvent, in particular as solvent for polymers such as polyolefins. They are suitable as solvent in chemical reactions such as polymerizations as well as for various analytical applications including thin-layer chromatography (TLC), gas chromatography (GC), high-performance liquid chromatography (HPLC), gel permeation chromatography (GPC), liquid-liquid extraction, microextraction, mass spectrometry, and electrophoresis.
The independent and dependent claims set out particular and preferred features of the invention. Features from the dependent claims may be combined with features of the independent or other dependent claims as appropriate.
In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
Description of the invention
Before the present products and uses of the invention are described, it is to be understood that this invention is not limited to particular methods, components, products or combinations described, as such methods, components, products and combinations may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.
As used herein, the singular forms "a", "an", and "the" include both singular and plural referents unless the context clearly dictates otherwise.
The terms "comprising", "comprises" and "comprised of" as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. It will be appreciated that the terms "comprising", "comprises" and "comprised of" as used herein comprise the terms "consisting of", "consists" and "consists of".
The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within the respective ranges, as well as the recited endpoints.
All documents cited in the present specification are hereby incorporated by reference in their entirety.
As used herein, the term "halo" or "halogen" as a group or part of a group is generic for fluoro, chloro, bromo or iodo.
The term "Ci-6alkyl" as a group or part of a group defines straight and branched chained saturated hydrocarbon radicals having from 1 to 6 carbon atoms such as, for example, methyl, ethyl, propyl, butyl, 2-methyl-propyl, pentyl, hexyl, 2-methylbutyl, 3-methylpentyl and the like.
The term "Ci-i2alkyl" as a group or part of a group defines straight and branched chained saturated hydrocarbon radicals having from 1 to 12 carbon atoms, such as, those defined for Ci-6alkyl and heptyl, octyl, 2-methyl-hetyl, 3-ethyl-hexyl, nonyl, decyl, undecanyl, dodecanyl, and the like.
The term "Ci-i2alkylene" as a group or part of a group defines bivalent straight and branched chained saturated hydrocarbon radicals having from 1 to 12 carbon atoms such as, for example, methylene, ethan-1 ,2-diyl, propan-1 ,3-diyl, propan-1 ,2-diyl, butan-1 ,4- diyl, pentan-1 ,5-diyl, hexan-1 ,6-diyl, 2-methylbutan-1 ,4-diyl, 3-methylpentan-1 ,5-diyl, octan-1 ,8-diyl, undecan-1 ,9-diyl, dodecan-1 ,12-diyl, and the like.
The term "C6-i2aryl", as a group or part of a group, refers to a polyunsaturated, aromatic hydrocarbyl group having a single ring (i.e. phenyl) or multiple aromatic rings fused together (e.g. naphthyl), or linked covalently, typically containing 6 to 12 atoms; wherein at least one ring is aromatic. Non-limiting examples of C6-i2aryl comprise phenyl, biphenylyl, biphenylenyl, indanyl, or 1 ,2,3,4-tetrahydronaphthyl, or 1 -or 2-naphthanelyl, each of which may be optionally substituted with one, two or three substituents selected from halo, Ci_ 6alkyl, polyhaloCi-6alkyl, hydroxy, Ci-6alkoxy, polyhaloCi-6alkoxy, Ci-6alkoxyCi-6alkyl, carboxyl, Ci-6alkylcarbonyl, Ci-6alkoxycarbonyl, cyano, nitro, amino, mono- or diCi_ 6alkylamino, aminocarbonyl, mono- or diCi-6alkylaminocarbonyl, azido, mercapto.
The term "C1-6alkoxy" or "C1-6alkyloxy" as used herein refers to a radical having the Formula -ORa wherein Ra is Ci-6alkyl as defined herein. Non-limiting examples of suitable alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert- butoxy, pentyloxy and hexyloxy.
The term "haloCi-6alkyl" as used herein refers to an Ci-6alkyl as defined herein wherein one or more hydrogens are replaced with a halogen, preferably, chloro or fluoro atoms, more preferably fluoro atoms. Examples of such haloCi-6alkyl radicals include chloromethyl, 1 -bromoethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 ,1 - trifluoroethyl, 1 -bromopropyl, 2-fluorobutyl, 3,4-difluoropentyl, 3,4,4-trifluoropentyl, 1 ,1 ,1 - trifluorohexyl, and the like.
The term "haloCi-6alkoxy" or "haloCi-6alkyloxy" as used herein refers to a radical having the Formula -ORb wherein Rb is haloCi-6alkyl as defined herein. Non-limiting examples of suitable alkoxys include chloromethoxy, 1 -bromoethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 ,1 -trifluoroethoxy, 1 -bromopropoxy, 2-fluorobutoxy, 3,4- difluoropentyloxy, 3,4,4-trifluoropentyloxy, 1 ,1 ,1 -trifluorohexyloxy, and the like.
Although different authors use different abbreviations for ionic liquids, most commonly abbreviations for cation and anion structure are given in square brackets (without charges). As such, the substituents listed for A, like [PF6] denotes hexafluorophosphate, [CI] denotes chloride, etc.
Whenever the term "substituted" is used in defining the compounds of the present invention, it is meant to indicate that one or more hydrogens on the atom indicated in the expression using "substituted" is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a chemically stable compound, i.e. a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture.
The term "chromatography" refers to a physical method of separation in which the components to be separated are distributed between two phases, one of which is stationary (stationary phase) while the other (the mobile phase) moves in a definite direction. The term chromatography includes, among others, the techniques of thin-layer chromatography (TLC), gas chromatography (GC), gel permeation chromatography (GPC), and high-performance liquid chromatography (HPLC).
The term "planar chromatography" refers to a separation technique in which the stationary phase is present as or on a plane (planar stationary phase). The plane can be a paper, used as such or impregnated by a substrate as the stationary bed (paper chromatography, PC) or a layer of solid particles spread on a support e.g. a glass or metal plate.
The term "support" or "plate" or "support plate" refers to the plate that supports the stationary phase, such as the thin layer in thin-layer chromatography.
The term "thin-layer chromatography" or TLC refers to a chromatography carried out in a thin layer of adsorbent spread on a support e.g. a glass or metal plate.
The terms "stationary phase" or "stationary bed" or "sorbent bed" or "absorbent" are used interchangeably and refer to an immobile phase or non-fluid phase employed in the chromatography method. The expression chromatographic bed or sorbent bed may be used as a general term to denote any of the different forms in which the stationary phase is used. The stationary phases used are typically the base sorbents known for chromatographic purposes. These are, for example, silica gel, aluminium oxide, cellulose, kieselguhr or other organic or inorganic polymers or organic/inorganic hybrid polymers. The base sorbents may furthermore be derivatized with functional groups which modify their separation properties. Examples thereof are RP phases, in which, for example, silica gel has been derivatized with ligands which have C8 or C18 chains (reversed phase material). Other examples are CN or diol-modified phases. Suitable common sorbent phases for planar chromatography are described in Klaus K. Unger, Packings and Stationary Phases in Chromatographic Techniques, M. Decker, New York 1990.
The term "mobile phase" refers to a fluid which migrates through or along the stationary bed, in a definite direction, carrying thereby the sample through the stationary phase. It may be a liquid or a supercritical fluid. The term "eluent" is also used for the mobile phase.
The term "co-eluent" refers to a second fluid which migrates through or along the stationary bed, in a definite direction. The co-eluent accompanies the eluent, both forming the mobile phase.
The term "additive" when referred to polymers means a plasticizer, a component of polymer electrolytes, a porogenic agent, and the like. The present invention relates to a compound formula (I) or (II)
(I) (II)
wherein
each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium, each group being optionally substituted with one, two, or three substituents selected from Ci_i2alkyl and Ci-i2alkoxy; preferably each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, pyrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium, each group being optionally substituted with one, two, or three substituents selected from Ci_i2alkyl and Ci-i2alkoxy, preferably optionally substituted with one, two, or three substituents selected from Ci-6alkyl and Ci-6alkoxy; more preferably each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, pyrazolium, pyrimidinium, and pyridazinium, each group being optionally substituted with one, two, or three substituents selected from Ci-i2alkyl and Ci-i2alkoxy, preferably optionally substituted with one, two, or three substituents selected from Ci-6alkyl and Ci-6alkoxy; even more preferably each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, imidazolium, and pyrazolium, each group being optionally substituted with one, two, or three substituents selected from Ci-i2alkyl and Ci-i2alkoxy, preferably optionally substituted with one, two, or three substituents selected from Ci-6alkyl and Ci-6alkoxy; also preferably each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, pyrazinium, pyrrolium, and imidazolium, each group being optionally substituted with one, two, or three substituents selected from Ci_i2alkyl and Ci-i2alkoxy, preferably optionally substituted with one, two, or three substituents selected from Ci-6alkyl and Ci_ 6alkoxy; also preferably each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, imidazolium, pyrazinium, and pyrrolium, each group being optionally substituted with one, two, or three substituents selected from Ci_i2alkyl and Ci-i2alkoxy, preferably optionally substituted with one, two, or three substituents selected from Ci-6alkyl and Ci_ 6alkoxy; most preferably each ring comprising the nitrogen atom is pyridinium, or imidazolium, each being optionally substituted with one, two, or three substituents selected from Ci_i2alkyl and Ci-i2alkoxy, preferably optionally substituted with one, two, or three substituents selected from Ci-6alkyl and Ci-6alkoxy; preferably optionally substituted with one, two, or three Ci-6alkyl substituents;
Ci-i2alkylene; preferably L1 is Ci-6alkylene; more preferably L1 is Ci-3alkylene; also preferably L1 is Ci-2alkylene;
Ci-i2alkylene; preferably L2 is Ci-6alkylene; more preferably L2 is Ci-3alkylene; also preferably L2 is Ci-2alkylene;
a single bond or Ci-i2alkylene; wherein one carbon of the Ci-i2alkylene is optionally replaced by one or more heteroatoms; preferably L3 is a single bond or Ci-6alkylene; wherein one carbon of the Ci-6alkylene is optionally replaced by one or two heteroatoms selected from O, N or S; preferably L3 is a single bond or Ci-3alkylene; wherein one carbon of the Ci-3alkylene is optionally replaced by one heteroatoms selected from O, N or S; preferably L3 is a single bond or Ci-2alkylene;
C6-i2aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy; preferably Y1 is C6-ioaryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy; preferably Y1 is phenyl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy; preferably Y1 is phenyl substituted with one, two, or three halo substituents; more preferably Y1 is phenyl substituted with one, two, or three substituents independently selected from fluoro, chloro or bromo; more preferably Y1 is phenyl substituted with one, two, or three substituents independently selected from bromo, fluoro, or chloro; more preferably Y1 is phenyl substituted with one, two, or three bromo or chloro substituents; Y2 is C6-i2aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy; preferably Y2 is C6-ioaryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy; preferably Y2 is phenyl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy; preferably Y2 is phenyl substituted with one, two, or three halo substituents; more preferably Y2 is phenyl substituted with one, two, or three substituents independently selected from fluoro, chloro or bromo; more preferably Y2 is phenyl substituted with one, two, or three substituents independently selected from bromo, fluoro, or chloro; more preferably Y2 is phenyl substituted with one, two, or three bromo or chloro substituents;
A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [N(S02CF3)2], [BF4], [CF3SO3], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I], and [AIR1 4-nR2 n]; preferably A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6],
[BF4], [CF3SO3], [CH3C02], [CF3S02], and [I]; preferably A is selected from the group consisting of [Br], [PF6], [BF4], [CI], [CF3SO3], and [I]; preferably A is selected from the group consisting of [Br], [PF6], [BF4];
R1 is halo or Ci-i2alkyl; preferably R1 is halo or Ci-6alkyl; preferably R1 is bromo, chloro, iodo, or Ci-4alkyl;
R2 is halo; preferably R1 is bromo, or chloro, and
n is an integer selected from 0, 1 , 2, 3, or 4.
In one embodiment, the present invention relates to the compound of formula (I) or (II) as depicted above, preferably of formula (I) wherein
each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, imidazolium, pyrazinium, pyrrolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium; each group being optionally substituted with one, two, or three substituents selected from Ci-i2alkyl and Ci-i2alkoxy, preferably each group being optionally substituted with one, two, or three substituents selected from Ci-6alkyl and Ci-6alkoxy;
L1 is Ci-6alkylene;
L2 is Ci-6alkylene; L3 is a single bond, or Ci-6alkylene; wherein one carbon of the Ci-6alkylene is optionally replaced by one or two heteroatoms;
Y1 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
Y2 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [N(S02CF3)2], [BF4], [CF3SO3], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I], and [AIR1 4-nR2 n];
R1 is halo or Ci-i2alkyl;
R2 is halo; and
n is an integer selected from 0, 1 , 2, 3, or 4.
In another embodiment, the present invention relates to the compound of formula (I) or (II) as depicted above, preferably (I), wherein
each ring comprising the nitrogen atom is independently selected from pyridinium, imidazolium; pyrazinium, and pyrrolium, each being optionally substituted with one, two, or three substituents selected from Ci-6alkyl and Ci-6alkoxy, preferably each optionally substituted with one, two, or three substituents selected from Ci-4alkyl and Ci-4alkoxy;
L1 is Ci-2alkylene;
L2 is Ci-2alkylene;
L3 is a single bond, or Ci-2alkylene;
Y1 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy; preferably halo;
Y2 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy; preferably halo;
A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [N(S02CF3)2], [BF4], [CF3S03], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I], and [AIR1 4-nR2 n];
R1 is halo or Ci-i2alkyl;
R2 is halo; and
n is an integer selected from 0, 1 , 2, 3, and 4. Preferably the compound of formula (I) as depicted above, is a compound of formula (la), or (lb),
wherein
A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [N(S02CF3)2], [BF4], [CF3SO3], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I], and [AIR1 4-nR2 n]; and
R1 is halo or Ci-i2alkyl; preferably halo or Ci-6alkyl;
R2 is halo;
n is an integer selected from 0, 1 , 2, 3, or 4;
L1 is Ci-6alkylene; preferably L1 is Ci-4alkylene; preferably L1 is Ci-2alkylene; preferably - CH2-;
each R3 is independently selected from hydrogen, Ci-6alkyl and Ci-6alkoxy;
each R4 is independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
R5 is independently selected from Ci-6alkyl or hydrogen; preferably Ci-6alkyl;
p is an integer selected from 1 , 2, or 3; and
q is an integer selected from 1 , 2, or 3.
In a preferred embodiment, the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [BF4], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I];
L1 is Ci-6alkylene; preferably L1 is Ci-4alkylene; more preferably L1 is Ci-2alkylene; preferably -CH2-;
each R3 is independently selected from hydrogen, Ci-6alkyl and Ci-6alkoxy;
each R4 is independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
R5 is independently selected from Ci-6alkyl or hydrogen; preferably Ci-6alkyl;
p is an integer selected from 1 , 2, or 3; and
q is an integer selected from 1 , 2, or 3.
In a further embodiment, the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein
A is selected from the group consisting of [Br], [CI], [PF6], [BF4], [CH3C02], [CF3S02], [I];
L1 is Ci-4alkylene; more preferably L1 is Ci-2alkylene; preferably -CH2-;
each R3 is independently selected from hydrogen, Ci-6alkyl and Ci-6alkoxy;
each R4 is independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
R5 is independently selected from Ci-6alkyl or hydrogen; preferably Ci-6alkyl;
p is an integer selected from 1 , 2, or 3; and
q is an integer selected from 1 , 2, or 3.
In a further embodiment, the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein
A is selected from the group consisting of [Br], [CI], [PF6], and [BF4]; and
L1 is Ci-4alkylene; more preferably L1 is Ci-2alkylene; preferably -CH2-;
each R3 is independently selected from hydrogen, Ci-6alkyl and Ci-6alkoxy;
each R4 is independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
R5 is independently selected from Ci-6alkyl or hydrogen; preferably Ci-6alkyl;
p is an integer selected from 1 , 2, or 3; and q is an integer selected from 1 , 2, or 3.
In a further embodiment, the ionic liquid is a compound of formula (la), or (lb), as depicted above, wherein
A is [Br], [PF6], [BF4];
L1 is Ci-2alkylene; preferably -CH2-;
each R3 is independently selected from hydrogen, Ci-4alkyl and Ci-4alkoxy; preferably hydrogen
each R4 is independently selected from chloro, fluoro, and bromo, preferably chloro or, bromo,
R5 is independently selected from Ci-4alkyl or hydrogen; preferably Ci-2alkyl;
p is 1 , 2 or 3, and
q is 1 , 2, or 3.
In a further embodiment, the ionic liquid is a compound of formula (la), or (lb) as depicted above, wherein
A is Br], [PF6], or [BF4],
L1 is Ci-2alkylene; preferably -CH2-;
each R3 is hydrogen, or Ci-4alkyl;
each R4 is independently selected from chloro or bromo, and
R5 is independently selected from Ci-2alkyl or hydrogen ;
p is 1 , 2 or 3, and
q is 1 , 2, or 3.
Preferably, the ionic liquid is a compound of formula (la), or (lb) as depicted above, wherein
A is [Br], [PF6], [BF4];,
L1 is Ci-2alkylene; preferably -CH2-;
each R3 is hydrogen, or Ci-4alkyl; preferably hydrogen
each R4 is independently selected from chloro, and bromo,
R5 is independently selected from Ci-2alkyl or hydrogen ; preferably Ci-2alkyl; p is 1 , or 2, and
q is 1 , 2, or 3.
In a further embodiment, the ionic liquid is a compound of formula (la), or (lb) as depicted above, wherein
A is [Br], [PF6], [BF4];,
L1 is Ci-2alkylene; preferably -CH2-;
each R3 is hydrogen,
each R4 is independently selected from chloro, and bromo,
R5 is independently selected from Ci-2alkyl or hydrogen ; preferably Ci-2alkyl;
p is 1 , and
q is 2, or 3.
Preferably, the ionic liquid is a compound as listed in Table 1 .
Table 1
Ionic liquid structure
1
BF4 Br
-N
Br" The present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as a solvent; preferably as a solvent for polymers.
The present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as an eluent; preferably as an eluent for polymers.
Preferably, the polymers are selected from the group comprising polyolefins, polyamides, polycarbonates, poly(hydroxy carboxylic acid) , polystyrenes, polyesters, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethylmethacrylate (PMMA), poly(methyl acrylate) (PMA), vinyl polymers, proteins, and polysaccharides, or blends thereof.
In a preferred embodiment, the compound of formula (I), (II), (la), or (lb), is particularly useful as a solvent or as an eluent for polyolefins. The polyolefins may be any olefin homopolymer or any copolymer of an olefin and one or more comonomers. The polyolefins may be atactic, syndiotactic or isotactic. The olefin can for example be ethylene, propylene, 1 -butene, 1 -pentene, 1 -hexene, 4-methyl-1 -pentene or 1 -octene, but also cycloolefins such as for example cyclopentene, cyclohexene, cyclooctene or norbornene. The comonomer may be different from the olefin and chosen such that it is suited for copolymerization with the olefin. The comonomer may be an olefin as defined above. Further examples of suitable comonomers are vinyl acetate (H3C-C(=0)0- CH=CH2) or vinyl alcohol ("HOCH=CH2"), acrylate, methacrylate or styrene. Examples of olefin copolymers that can be analyzed, separated, or characterized in the present invention are random copolymers of propylene and ethylene, random copolymers of propylene and 1 -butene, heterophasic copolymers of propylene and ethylene, ethylene- butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and vinyl alcohol (EVOH).
Most preferred polyolefins are olefin homopolymers and copolymers of an olefin and optionally one or more comonomers, wherein said olefin and said one or more comonomer are different. Preferably, said olefin is ethylene or propylene. The term "comonomer" refers to olefin comonomers which are suitable for being polymerized with olefin monomers, preferably ethylene or propylene monomers. Comonomers may comprise but are not limited to aliphatic C2-C2o alpha-olefins. Examples of suitable aliphatic C2-C20 alpha-olefins include ethylene, propylene, 1 -butene, 4-methyl-1 -pentene, 1 -hexene, 1 -octene, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene and 1 -eicosene. Preferred polyolefins for use in the present invention are propylene and ethylene polymers. As used herein, the terms "propylene polymer" and "polypropylene" as well as the terms "ethylene polymer" and "polyethylene" are used interchangeably. Preferably, the polyolefin is selected from polyethylene and polypropylene homo- and copolymers.
The present invention further relates to a chromatographic stationary phase impregnated with the ionic liquid compound of formula (I), (II), (la), or (lb), according to any one of the embodiments presented herein.
The present invention also encompasses a composition for use in chromatography comprising a substrate impregnated with an ionic liquid of formula (I), (II), (la), or (lb). The impregnation of the stationary phase with an ionic liquid of formula (I), (II), (la), or (lb) may be performed by simply pouring, mixing or spraying the ionic liquid pure or in solution onto the stationary phase, and optionally allowing the stationary phase to dry. Alternatively, the impregnation may be performed by covalent anchoring of non- coordinating anions on mineral supports to prepare supported ionic liquids as described in US201 1/0178258.
In one embodiment of the present invention, the substrate comprises silica based normal and reverse-phase resin optionally derivatized with alkyl groups or aromatic groups, preferably silica gel 60F254.
One embodiment of the present invention relates to the use of a composition according to the present invention as a stationary phase in chromatography.
One embodiment of the present invention relates to a method of performing chromatography characterized in that the stationary phase is a composition according to the present invention. In an embodiment the chromatography, is a planar chromatography.
One embodiment of the present invention relates to a method of performing chromatography characterized in that the stationary phase is a composition according to the present invention, in a method for analyzing, separating, or characterizing chemical compounds, preferably polymers selected from polyolefins, polyamides, polycarbonates, poly(hydroxy carboxylic acid) like polylactic acid, polystyrenes, polyesters polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethylmethacrylate (PMMA), poly(methyl acrylate) (PMA), vinyl polymers, proteins, and polysaccharides; or blends thereof. In an embodiment, the present invention also relates to a method of performing planar chromatography characterized in that the planar stationary phase is impregnated with an ionic liquid of formula (I), (II), (la), or (lb) .
The present invention also relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a mobile phase in chromatography.
The present invention also relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as an eluent in chromatography.
The present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a co-eluent in chromatography.
The present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a solvent in a chemical reaction.
The present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as a solvent in a chemical separation such as liquid-liquid extraction, microextraction, and electrophoresis, or in mass spectrometry.
In one embodiment, the chemical reaction is selected from a polycondensation, a polymerization, a radical polymerization, and an ionic polymerization.
The present invention further relates to the use of a compound of formula (I), (II), (la), or (lb) as defined in any one of the embodiments presented herein, as an additive to polymers.
In one embodiment, the additive to polymers is selected from a plasticizer, a component of polymer electrolytes, and a porogenic agent.
The present invention further relates to a method for the preparation of the ionic liquid compound of formula (I) or (II) as defined in any one of the embodiments presented herein, comprising contacting a compound of formula (Ig) with a compound of formula (Ih) thereby forming the compound of formula (I)
(ig) (In) wherein X1 is halo, and the nitrogen-containing ring is selected from the group consisting of pyridine, imidazole, pyrazine, pyrrole, pyrazole, thiazole, triazole, indole, tetrazole, pyrimidine, pyridazine, piperazine, and piperidine; each group being optionally substituted with one, two, or three substituents selected from Ci_i2alkyl and Ci-i2alkoxy; and L1, and Y1 are as defined in any one of the embodiments presented herein.
The contacting step can be done at room temperature in a suitable solvent such as ethyl acetate.
Once compound of formula (I) is prepared, different counter ion A, can be substituted with each other, by contacting the compound of formula (I) with the desired salt of said counter ion.
The present invention can be further illustrated by the following examples, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.
Examples
The ionic liquids according to the invention have been prepared as described below:
The structures of the compounds are listed in Table 2.
Table 2
Ionic liquid structure Melting point
1 18°C
Br CI
Ionic liquid structure Melting point
10 231 °C
Br"
CI
Ionic liquid 1 :
242μΙ of N-methyl-imidazole have been added to a round bottom flask. 1 g of 2,3,6- trichlorobenzylbromide dissolved in 3ml_ of ethyl acetate was subsequently added to the round bottom flask at room temperature. After few minutes, a precipitate was obtained which was filtrated and washed several times with ethyl acetate. 594 mg (yield:55%) of a white solid was obtained having a melting point of 1 17.85°C.
Ionic liquid 2:
Two solutions were prepared:
1 ) 200mg of ionic liquid 1 was dissolved in 3ml of distilled water.
2) 74 mg of sodium tetrafluoroborate was dissolved in 2 ml of distilled water.
The two solutions were mixed and a white precipitate was immediately formed. The aqueous solution containing the precipitate was extracted several times with dichloromethane. The organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate. The dichloromethane was removed under vacuum and 94 mg (yield:45%) of a white solid was obtained having a melting point of 139.48°C.
Ionic liquid 3:
Two solutions were prepared:
1 ) 3.22g of ionic liquid 9 was dissolved in 4ml of distilled water.
2) 1 .318 g of sodium tetrafluoroborate was dissolved in 20 ml of distilled water.
The two solutions were mixed and a white precipitate was immediately formed. The aqueous solution containing the precipitate was extracted several times with dichloromethane. The organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate. The dichloromethane was removed under vacuum and 1 .91 g (yield:58.6%) of a white solid was obtained having a melting point of 125.71 °C. Ionic liquid 4:
Two solutions were prepared:
1 ) 2g of ionic liquid 8 was dissolved in 5ml of distilled water.
2) 826 mg of sodium tetrafluoroborate was dissolved in 4 ml of distilled water.
The two solutions were mixed and a white precipitate was immediately formed. The aqueous solution containing the precipitate was extracted several times with dichloromethane. The organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate. The dichloromethane was removed under vacuum and 231 mg (yield:17%) of a white solid was obtained having a melting point of 164°C.
Ionic liquid 4:
Two solutions were prepared:
1 ) 3g of ionic liquid 9 was dissolved in 4ml of distilled water.
2) 1 .2 g of potassium hexafluorophosphate was dissolved in 20 ml of distilled water.
The two solutions were mixed and a white precipitate was immediately formed. The aqueous solution containing the precipitate was extracted several times with dichloromethane. The organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate. The dichloromethane was removed under vacuum and 3.28 g (yield:91 %) of a white solid was obtained having a melting point of 163.92°C.
Ionic liquid 6:
Two solutions were prepared:
1 ) 200mg of ionic liquid 1 was dissolved in 4ml of distilled water.
2) 123.9mg of potassium hexafluorophosphate was dissolved in 5 ml of distilled water. The two solutions were mixed and a white precipitate was immediately formed. The aqueous solution containing the precipitate was extracted several times with dichloromethane. The organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate. The dichloromethane was removed under vacuum and 203mg (yield:86%) of a white solid was obtained having a melting point of 164.62°C.
Ionic liquid 7: Two solutions were prepared:
1 ) 10Omg of ionic liquid 10 was dissolved in 3ml of distilled water.
2) 37.27mg of sodium tetrafluoroborate was dissolved in 2 ml of distilled water.
The two solutions were mixed and a white precipitate was immediately formed. The aqueous solution containing the precipitate was extracted several times with dichloromethane. The organic phases were combined, washed several time with water and subsequently dried using magnesium sulfate. The dichloromethane was removed under vacuum and a white solid was obtained having a melting point of 180°C.
Ionic liquid 8:
1 .535ml of pyridine have been added to a round bottom flask. 5.5g of 2,6- dibromobenzylbromide dissolved in 5ml_ of ethyl acetate was subsequently added to the round bottom flask at room temperature. A precipitate was obtained which was filtrated and subsequently washed several times with ethyl acetate. 4.662 g (yield:77.6%) of a white solid was obtained having a melting point of 223°C.
Ionic liquid 9:
1 .45ml of N-methyl-imidazole have been added to a round bottom flask. 5.3g of 2,6- dibromobenzylbromide dissolved in 4ml_ of ethyl acetate was subsequently added to the round bottom flask at room temperature. After a few minutes, a precipitate was obtained which was filtrated and subsequently washed several times with ethyl acetate. 5.792 g (yield:49%) of a white solid was obtained having a melting point of 224.86°C.
Ionic liquid 10:
245μΙ of pyridine have been added to a round bottom flask. 1 g of 2,3,6- trichlorobenzylbromide dissolved in 4ml_ of ethyl acetate was subsequently added to the round bottom flask at room temperature. A precipitate was obtained which was filtrated and subsequently washed several times with ethyl acetate. 350 mg (yield:33%) of a white solid was obtained having a melting point of 231 °C.
Polyolefin dissolution tests:
The ionic liquids as listed in Table 2 have been tested as solvent for polyethylene.
Two linear polyethylenes insoluble in classical solvent (cold or hot) have been tested: 200 mg of the ionic liquid have been added to a test tube. The tube was heated until liquefaction of the liquid. 5 mg of the tested polyethylene was added. Visual observation of the dissolution of the polyethylene was performed.
The polyethylenes were dissolved in all the tested ionic liquids (results not shown).

Claims

Claims
A compound of formula (I) or (II)
(I) (II)
wherein
each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, imidazolium, pyrazinium, pyrrolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium; each group being optionally substituted with one, two, or three substituents selected from Ci_i2alkyl and Ci-i2alkoxy;
L1 is Ci-i2alkylene;
L2 is Ci-i2alkylene;
L3 is a single bond or Ci-i2alkylene; wherein one carbon of the Ci-i2alkylene is optionally replaced by one or more heteroatoms;
Y1 is C6-i2aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
Y2 is C6-i2aryl substituted with one, two, or three substituents each independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [N(S02CF3)2], [BF4], [CF3SO3], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I], and [AIR1 4-nR2 n];
R1 is halo or Ci-i2alkyl;
R2 is halo; and n is an integer selected from 0, 1 , 2, 3, or 4.
The compound according to claim 1 , wherein
each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, imidazolium, pyrazinium, pyrrolium, pyrazolium, thiazolium, triazolium, indolium, tetrazolium, pyrimidinium, pyridazinium, piperazinium, and piperidinium; each group being optionally substituted with one, two, or three substituents selected from Ci_i2alkyl and Ci-i2alkoxy;
L1 is Ci-6alkylene;
L2 is Ci-6alkylene;
L3 is a single bond, or Ci-6alkylene; wherein one carbon of the Ci-6alkylene is optionally replaced by one or two heteroatoms;
Y1 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
Y2 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [N(S02CF3)2], [BF4], [CF3SO3], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I], and [AIR1 4-nR2 n];
R1 is halo or Ci-i2alkyl;
R2 is halo; and
n is an integer selected from 0, 1 , 2, 3, or 4.
The compound according to claim 1 or 2, wherein
each ring comprising the nitrogen atom is independently selected from the group consisting of pyridinium, imidazolium, pyrazinium, and pyrrolium; each group being optionally substituted with one, two, or three substituents selected from Ci-6alkyl and Ci-6alkoxy;
L1 is Ci-2alkylene;
L2 is Ci-2alkylene;
L3 is a single bond, or Ci-2alkylene; Y1 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
Y2 is phenyl substituted with one, two, or three substituents selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [N(S02CF3)2], [BF4], [CF3SO3], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I], and [AIR1 4-nR2 n];
R1 is halo or Ci-i2alkyl;
R2 is halo; and
n is an integer selected from 0, 1 ,
2,
3, or 4.
4. The compound according to any of claims 1 to 3, wherein said compound has formula (la), or (lb),
wherein
A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [N(S02CF3)2], [BF4], [CF3S03], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I], and [AIR1 4-nR2 n];
R1 is halo or Ci-i2alkyl;
R2 is halo;
n is an integer selected from 0, 1 , 2, 3, or 4; L1 is Ci-6alkylene;
each R3 is independently selected from hydrogen, Ci-6alkyl and Ci-6alkoxy;
each R4 is independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
R5 is independently selected from Ci-6alkyl or hydrogen;
p is an integer selected from 1 , 2, or 3; and
q is an integer selected from 1 , 2, or 3.
5. The compound according to claim 4, wherein
A is selected from the group consisting of [Br], [CI], [PF6], [AsF6], [SbF6], [BF4], [CH3C02], [CF3S02], [N02], [N03], [CI04], [I];
L1 is Ci-6alkylene;
each R3 is independently selected from hydrogen, Ci-6alkyl and Ci-6alkoxy;
each R4 is independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
R5 is independently selected from Ci-6alkyl or hydrogen;
p is an integer selected from 1 , 2, or 3; and
q is an integer selected from 1 , 2, or 3.
6. The compound according to claim 4 or 5, wherein
A is selected from the group consisting of [Br], [CI], [PF6], and [BF4]; and
L1 is Ci-4alkylene;
each R3 is independently selected from hydrogen, Ci-6alkyl and Ci-6alkoxy;
each R4 is independently selected from the group consisting of halo, haloCi-6alkyl, and haloCi-6alkoxy;
R5 is independently selected from Ci-6alkyl or hydrogen;
p is an integer selected from 1 , 2, or 3; and
q is an integer selected from 1 , 2, or 3.
7. Use of a compound as defined in any one of claims 1 to 6 as a solvent.
8. Use of a compound as defined in any one of claims 1 to 6 as a solvent for polymers.
9. A chromatographic stationary phase impregnated with the compound according to any one of claims 1 to 6.
10. Use of a compound as defined in any one of claims 1 to 6 as a mobile phase in chromatography.
1 1 . Use of a compound as defined in any one of claims 1 to 6 as an eluent in chromatography.
12. The use of a compound as defined in any one of claims 1 to 6, as a solvent in a chemical reaction wherein the chemical reaction is selected from a polycondensation, a polymerization, a radical polymerization, and an ionic polymerization.
13. Use of a compound as defined in any one of claims 1 to 6 as an additive to polymers.
14. The use of a compound according to claim 13, wherein the additive to polymers is selected from a plasticizer, a component of polymer electrolytes, and a porogenic agent.
15. A method for the preparation of the compound as defined in any one of claims 1 to 6, comprising contacting a compound of formula (Ig) with a compound of formula (Ih) thereby forming the compound of formula (I) or (II),
(ig) (in) wherein X1 is halo, and the nitrogen-containing ring is selected from the group consisting of pyridine, imidazole, pyrazine, pyrrole, pyrazole, thiazole, triazole, indole, tetrazole, pyrimidine, pyridazine, piperazine, and piperidine; each group being optionally substituted with one, two, or three substituents selected from d. i2alkyl and Ci-i2alkoxy; and L1, and Y1 are as defined in any one of claims 1 to 6.
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