Classifications

• • 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
• • 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
  • C07D207/06—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 radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • 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
  • C07D213/18—Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • 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
  • 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
  • C07D233/56—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 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
  • C07D277/62—Benzothiazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
  • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
  • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms

Definitions

• the present invention relates to salts of bis (trifluoromethyl) imide anions and saturated, partially or completely unsaturated, heterocyclic cations, a process for their preparation and their use as ionic liquids.
• Ionic liquids or liquid salts are ionic species, which consist of an organic cation and a usually inorganic anion exist. They contain no neutral molecules and have melting points below 373 K. A large number of compounds are known in the prior art which are called ionic
• Hurley and Wier first disclosed solvent-free ionic liquids in a number of US patents (US 2,446,331, US 2,446,339 and US 2,446,350). These "salts melted at room temperature" contained AICI 3 and a large number of n-alkylpyridinium halides.
• EP 1 081 129 discloses stable N (CF 3 ) 2 " salts with tetraalkylammonium and comparable cations. Neither heterocyclic cations nor the use of the disclosed compounds as ionic liquids are described.
• ionic liquids e.g. Melting point, thermal and electrochemical stability, viscosity
• properties of ionic liquids are strongly influenced by the nature of the anion.
• the polarity and the hydrophilicity or lipophilicity can be varied by the appropriate choice of the cation / anion pair.
• the object of the present invention is to provide new stable compounds with valuable properties which can be used as ionic liquids, and a process for their preparation.
• A is a saturated, partially or completely unsaturated 3- to 8-membered
• Hydrocarbon chain in which all but one carbon atom is replaced by identical or different heteroatoms selected from N, P, O and S. where the carbon atoms of the hydrocarbon chain and the heteroatoms therein are saturated with substituents R 2 in accordance with their bond value,
• R, R 2 -H with the proviso that there is no bond to the positively charged heteroatom, straight-chain or branched alkyl having 1-20 carbon atoms straight-chain or branched alkenyl having 2-20 carbon atoms and one or more double bonds straight-chain or branched alkynyl having 2-20 Carbon atoms and one or more triple bonds saturated, partially or completely unsaturated cycloalkyl with 3-7 carbon atoms halogen, in particular fluorine or chlorine, with the proviso that for
• Hetero atom is present, -CN with the proviso that there is no bond to the positively charged hetero atom,
• R 2 and / or R 1 can be connected in pairs by single or double bond
• R 2 and / or R 1 partially or completely with halogens, in particular -F and / or -Cl, or partially with -CN or
• R 1 and / or R 2 are selected from the group by heteroatoms and / or atomic groups
• the atomic bond value is the number of bonds that originate from a neutral atom or the number of electron pairs that a neutral atom in a molecule shares with other atoms and that are represented in a simplified representation of the electron formulas as valence lines , Roger that.
• nitrogen and phosphorus atoms therefore have a bond value of 3
• oxygen and sulfur atoms have a bond value of 2
• carbon atoms have a bond value of 4.
• Phosphorus atoms, if they are neutral atoms of the cation, can also have a bond value of 5.
• the compounds according to the invention are salts which have an N (CF 3 ) 2 " anion and, as the cation, a heterocyclic 4- to 9-membered ring which is saturated or unsaturated. N, P, O or S.
• the heterocyclic ring can also contain further, identical or different hetero atoms selected from the group consisting of N, P, O and S. However, the ring contains at least one carbon atom.
• Suitable cations according to the invention are heterocyclic compounds which are stable, in particular those which can be isolated.
• Binding value are saturated.
• the number of substituents corresponds to the bond value increased by 1.
• a substituent is simply attached to the cyclic ring by oxygen or sulfur atoms with a positive charge and by double bond to the cyclic ring nitrogen or phosphorus atoms bound by a positive charge and simply bound to the cyclic ring by nitrogen or phosphorus atoms without a positive charge.
• the substituents R 1 , R 2 of the heterocyclic ring according to the invention are: C * - to C 20 -, in particular d- to C 2 -alkyl groups, C 2 - to C 2 o-, in particular C 2 - to C 12 -, alkenyl or alkynyl groups, saturated or unsaturated, ie also aromatic, C 3 - to C 7 -cycloalkyl groups, NO 2 , CN or halogens.
• a limitation of the halogens is that they only appear as substituents on carbon atoms or on phosphorus atoms of the heterocyclic ring, but not on the heteroatoms N, O, S. H, NO 2 and CN do not appear as substituents on the positively charged heteroatom.
• the substituents R 1 , R 2 can also be connected in pairs in such a way that bi- or polycyclic cations are formed.
• the substituents can be partially or completely substituted with halogen atoms, in particular with F and / or Cl, or partially with CN or N0 2 and one or two heteroatoms or
• Atomic groups selected from the group O, C (O), C (O) 0, S, S (O), SO 2 ( SO 2 O, N, P, NH, PH, NR ', PR', included In the case of complete halogenation, however, not all of the substituents R 1 and R 2 present must be fully halogenated, ie at least one R 1 and / or R 2 is not perhalogenated.
• the [N (CF 3 ) 2 ] " anion has a van der Waals radius of 90.90 A 3 and is therefore relatively small compared to the anions of ionic liquids known from the prior art.
• the salts according to the invention are not hydrophobic, i.e. at least to a certain extent they mix with water.
• the salts according to the invention are advantageously very readily soluble in organic solvents.
• the salts according to the invention surprisingly have a low viscosity.
• the salts according to the invention are advantageously stable. They can be isolated and stored at room temperature. Furthermore, the salts according to the invention are relatively easy to prepare, while in particular the [N (S0 2 CF 3 ) 2 ] ⁇ anion known from the prior art is difficult to access and in particular very expensive.
• the cation has a heterocyclic, saturated or unsaturated five, six or seven ring.
• An example of a five-membered ring with only one carbon atom according to the invention is the tetrazolium cation, e.g. in
• the heterocyclic ring of the cation contains a maximum of 3 heteroatoms selected from N, P, O or S. Very particularly preferably, in the case of a plurality of heteroatoms, only a maximum of 2 heteroatoms are arranged directly adjacent.
• preferred substituents for the heterocyclic ring are halogens, in particular fluorine, provided that these are not bonded to a heteroatom with the exception of phosphorus, straight-chain or branched C 1 -C 6 -alkyl groups, in particular -CH 3 , -C 2 H 5 , - ⁇ -C 3 H, -CH (CH 3 ) 2 »- ⁇ -C 4 H9, -n- C 6 H * t 3 and straight-chain or branched, partially or perfluorinated C * - to CQ-alkyl groups , in particular -CF 3 , -C 2 F 5 , -C 4 F 9 .
• halogens in particular fluorine
• a preferred embodiment of the invention are salts in which the saturated, partially or completely unsaturated heterocyclic cation is a five- or six-membered ring with the following structure:
• Y are each independently selected from the group C, N, P, O and S, where at least one Y is a carbon atom, while the remaining three or four Y can be carbon or heteroatoms.
• the number n of substituents R 1 on the positively charged heteroatom X corresponds to the bond value increased by 1, ie unsaturated oxygen or sulfur atoms have no substituents, saturated oxygen and sulfur atoms as well as unsaturated nitrogen and phosphorus atoms have a substituent R 1 and saturated nitrogen - and phosphorus atoms have two substituents R 1 .
• the remaining atoms (Y) of the heterocyclic ring each have so many (m) identical or different substituents R 2 that they are saturated according to their bond value.
• DH saturated oxygen and sulfur atoms as well as unsaturated nitrogen and phosphorus atoms have no substituents
• sp 2 -hybridized carbon atoms have a substituent R 2 and saturated
• sp 3 -hybridized carbon atoms have two substituents R 2 .
• the number n, m of the substituents R 1 , R 2 on the positively charged heteroatom X or The remaining atoms of the heterocyclic ring are defined according to the general formulas for the five- and six-ring cations.
• the substituents R 1 and R 2 are defined as in the general formula (1).
• the atoms of the heterocyclic ring each have so many identical or different substituents R 1 that they are saturated in accordance with their bond value, where n is increased by 1 for the heteroatom X which carries the positive charge.
• a ' has the meaning of a saturated, partially or completely unsaturated 2- to 7-membered hydrocarbon chain, the carbon atoms of the hydrocarbon chain being saturated with substituents R 2 in accordance with their bond value.
• the substituents R 1 and R 2 are defined as in the general formula (1), but the substituents R 1 in the ⁇ -position to the positively charged hetero atom do not have a methylene group directly adjacent to the heterocyclic ring.
• salts are preferred according to the invention in which the saturated, partially or completely unsaturated heterocyclic cation has the following structure:
• the number n of the substituents R 1 on the hetero atom Y is 0 in the case of an oxygen or sulfur atom and is 1 in the case of a nitrogen or phosphorus atom.
• a ' has the meaning of a 2- to 7-membered, B' that of a 1- to 6-membered hydrocarbon chain, the hydrocarbon chains being saturated, partially or completely unsaturated and in which all but one carbon atom is selected by identical or different heteroatoms from N, P, O and S, can be replaced and the carbon atoms of the hydrocarbon chains A 'and B' are saturated with substituents R 2 according to their bond value.
• the present invention also relates to salts of the general formula (2)
• X, Y are each independently N, P, O or S.
• n, m is an integer selected from 0, 1 or 2, such that X, Y are each saturated according to their binding valency, increased by 1,
• a “, B” saturated, partially or completely unsaturated 0- to 4-membered hydrocarbon chain, in which the carbon atoms can be replaced by identical or different heteroatoms selected from N, P, O and S, where in the chains A “and B “together contains at least one carbon atom and the carbon atoms of the hydrocarbon chains A” and B “and the heteroatoms therein are saturated with substituents R 2 in accordance with their bond value,
• R 1 , R 2 and / or R 3 can be connected in pairs by single or double bond
• R 1 , R 2 and / or R 3 can be partially or completely substituted with halogens, in particular -F and / or -Cl, or partially with -CN or -NO 2 , with the proviso that not all R 1 , R 2 and R 3 are completely halogenated,
• heterocyclic dication is a 4-, 5-, 6-, 7-, 8- or 9-membered ring.
• the dication has a heterocyclic, saturated or unsaturated five, six or seven ring.
• the present invention furthermore relates to salts of the general formula (3)
• X, Y are each independently N, P, O or S.
• n is an integer selected from 0, 1 or 2 such that X is saturated according to its binding valency, increased by 1,
• n is an integer selected from 0, 1 or 2 such that Y is saturated according to its binding value
• R 1 , R 2 -H with the proviso that there is no bond to the positively charged heteroatom, straight-chain or branched alkyl with 1-20 carbon atoms straight-chain or branched alkenyl with 2-20 carbon atoms and one or more double bonds straight-chain or branched alkynyl with 2- 20 carbon atoms and one or more triple bonds saturated, partially or completely unsaturated cycloalkyl with 3-7 carbon atoms halogen, in particular fluorine or chlorine, with the proviso that for
• the position of the heterocyclic ring are in each case the same or different,
• R 2 and / or R 1 can be connected in pairs by single or double bond
• Formula (4) and (5) are defined as those in general formulas (1) and (2).
• fluoroalkylated bis (trifluoromethyl) amide is preferably used for the reaction with the alkali metal fluoride.
• the process is carried out as a one-pot reaction, i.e. the intermediate product of alkali fluoride and fluoroalkylated sulfonic acid bis (trifluoromethyl) amide or acyl bis (trifluoromethyl) amide is not isolated, but is reacted directly with the salt of the general formula (4) or (5).
• the reactants are preferably used in an approximately equimolar amount, the acylbis (trifluoromethyl) amide being used in a double equimolar amount.
• the reaction according to the invention can be carried out directly in a one-pot reaction and without added alkali metal fluoride DF.
• Volatile by-products can arise, which are then removed under vacuum. Usually, however, insoluble by-products are formed in the solvents used, which are separated off by filtration. The solvent is optionally removed together with volatile by-products under reduced pressure.
• the salts according to the invention can generally be isolated in yields above 80%.
• the salt according to the invention can be dissolved in a polar organic solvent and be treated with rubidiumimide Rb + N (CF 3 ) 2 " .
• the precipitated rubidium salt which forms is then filtered off and the solvent is removed in vacuo.
• potassium or rubidium fluoride is preferably used as the alkali fluoride, particularly preferably the less expensive potassium fluoride.
• the polar organic solvent preferred according to the invention is selected from the group consisting of acetonitrile, dimethoxyethane, dimethylformamide and propionitrile.
• the reaction according to the invention is preferably carried out at temperatures between -40 ° C. and 80 ° C., in particular between 0 ° C. and 40 ° C. and very particularly preferably at room temperature.
• All compounds according to the invention have a salt-like character, relatively low melting points (usually below 100 ° C.) and can be used as ionic liquids.
• the salts according to the invention can be used as solvents for many synthetic or catalytic reactions, e.g. Friedel-Crafts acylation and alkylation, Diels-Alder cycloadditions, hydrogenation and
• fluorinated solvents for secondary and primary batteries can be synthesized, for example.
• N (CF 3 ) 2 groups are suitable as reagents for the introduction of N (CF 3 ) 2 groups.
• N (CF 3 ) 2 groups in organic halogen compounds can substitute the halogen atoms.
• the salts according to the invention are of interest as precursors for the production of liquid crystal compounds and of active substances, inter alia for medicinal and crop protection agents.
• Electrolyte optionally in combination with other electrolytes known to the person skilled in the art is possible.
• salts according to the invention can be used as non-aqueous, polar substances in suitable reactions as a phase transfer catalyst or as
• N-methyl-N-ethylpyrrolidinium-bis (trifluoromethyl) imide [C 7 H 6 N] + N (CF 3 ) 2 ⁇ is 93.4%.
• the salt is dissolved in 10 cm 3 of dry acetonitrile and treated with a solution of 1.35 g (5.7 mmol) of Rb + N (CF) 2 " in 8 cm 3 of dry acetonitrile at room temperature.
• the precipitated RbBF 4 is filtered off and washed with dry acetonitrile (5 cm 3 )
• the acetonitrile is removed at 30-35 ° C. in a vacuum of 1.3 Pa. 7.8 g of 1-ethyl-3-methylimidazolium bis (trifluoromethyl) imide, [C 6 HnN 2 ] + N (CF 3 ) 2 " with a purity of 98%.

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