Patent Application
20090253905
The invention relates to a process for the preparation of onium salts with alkyl- or arylsultfonate anions or alkyl- or arylcarboxylate anions by reaction of an onium halide with an alkyl or trialkylsilyl ester of an alkyl- or aryl-sulfonic acid or alkyl- or arylcarboxylic acid or anhydrides thereof.
A large number of onium salts, in particular alkyl- or arylsulfonates or alkyl- or arylcarboxylates, are ionic liquids. Owing to their properties, ionic liquids represent an effective alternative to traditional volatile organic solvents for organic synthesis in modern research. The use of ionic liquids as novel reaction medium could furthermore be a practical solution both for solvent emission and also for problems in the reprocessing of catalysts.
Ionic liquids or liquid salts are ionic species which consist of an organic cation and a generally inorganic anion. They do not contain any neutral molecules and usually have melting points below 373 K. However, the melting point may also be higher without restricting the usability of the salts in all areas of application. Examples of organic cations are, inter alia, tetraalkylammonium, tetraalkylphosphonium, N-alkylpyridinium, 1,3-dialkylimidazolium or trialkylsulfonium. Amongst a multiplicity of suitable anions, mention may be made, for example, of BF4−, PF6−, SbF6−, NO3—, CF3SO3—, (CF3SO2)2N−, arylSO3−, CF3CO2−, CH3CO2− or Al2Cl7−.
A general method for the preparation of onium sulfonates or carboxylates is alkylation of the organic base, i.e., for example, the amine, phosphine, guanidine or heterocyclic base, using alkyl esters of an alkyl- or arylsulfonic acid, for example alkyl p-toluenesulfonate (alkyl tosylate), or of an alkyl- or arylcarboxylic acid, for example alkyl trifluoroacetate, also disclosed by (Richard C. Larock, Comprehensive Organic Transformations, 2nd Edition, Wiley-VCH, New York, 1999, or P. Wasserscheid and T. Welton (Eds), Ionic Liquids in Synthesis, Wiley-VCH, 2003).
A disadvantage of this method is, however, that a substituent of the onium cation formed always corresponds to the corresponding alkyl group of the alkyl ester. If, for example, 1-butylimidazolium is reacted with methyl p-toluenesulfonate, 1-butyl-3-methylimidazolium p-toluenesulfonate is formed. However, asymmetrically substituted onium salts, i.e. salts in which the alkyl group of the ester employed is not a substituent of the onium salt formed, are desired.
Asymmetrical onium salts with alkyl- or arylsulfonate anions or alkyl- or arylcarboxylate anions, as defined above, can also be prepared by a metathesis by reacting an onium halide with a corresponding alkali metal salt of the corresponding acid. However, the alkali metal halide formed, for example sodium chloride, has to be removed by an additional purification method. The contamination by halide ions, for example chloride ions, greater than 1000 ppm (0.1%), reduces the usability of the ionic liquid, in particular in the use for electrochemical processes. The technology is therefore of crucial importance in processes for the preparation of onium salts, in particular ionic liquids, in order that they can be synthesised with low impurity levels by the reaction per se or by the reaction procedure, and thus further expensive additional process steps during the synthesis are superfluous.
The object of the present invention was accordingly to provide an alternative process for the preparation of onium salts with alkyl- or arylsulfonate anions or alkyl- or arylcarboxylate anions having a low halide content which results in salts, preferably of asymmetrically substituted onium salts, of high purity in good yield and is also suitable for large-scale industrial production.
A process of this type is of course then also suitable for the preparation of symmetrically substituted onium sulfates.
The object is achieved by the process according to the invention since the alkyl or trialkylsilyl ester of the sulfonic or carboxylic acid employed or the corresponding anhydride alkylates or acylates the anion of the onium halide employed and not the organic onium cation. The alkyl, trialkylsilyl or acyl halides formed as by-product are generally gases or very volatile compounds which can be removed from the reaction mixture without major engineering effort. Some of these by-products are themselves valuable materials for organic syntheses.
The invention therefore relates to a process for the preparation of onium salts with alkyl- or arylsulfonate anions or alkyl- or arylcarboxylate anions by reaction of an onium halide with an alkyl or trialkylsilyl ester of an alkyl- or arylsulfonic acid or alkyl- or arylcarboxylic acid or anhydrides thereof. In accordance with the invention, the reaction of the onium halide with an alkyl ester of a sulfonic acid is carried out at room temperature.
U.S. Pat. No. 2,585,979 discloses the preparation of quaternary sulfonates of pyrimidylaminoquinoline derivatives
by reaction of the corresponding pyrimidylaminoquinoline halide with a lower-alkyl ester of a sulfonic acid. However, the reaction with methyl methanesulfonate, in contrast to the process according to the invention, is carried out at temperatures of 130° to 140° C. in the presence of a solvent, for example a mixture of nitrobenzene and toluene. The reaction with methyl p-toluenesulfonate is carried out without addition of solvent, likewise at high temperatures of 130° to 135° C. Surprisingly, however, the reaction according to the invention with the alkyl esters of sulfonic acids succeeds at room temperature, i.e. at temperatures between 10° and 30° C., without the use of a solvent, in approximately quantitative yield.
U.S. Pat. No. 2,585,979 contains no indication that trialkylsilyl esters of the sulfonic or carboxylic acid or an anhydride of the sulfonic or carboxylic acid could be employed.
However, the process is particularly distinguished on use of trialkylsilyl esters of alkyl- or arylsulfonic or -carboxylic acids since these compounds have low toxicity.
The trialkylsilyl esters of alkyl- or arylsulfonic acids are preferably suitable for the preparation of the onium salts with alkyl- or arylsulfonate anions by the process according to the invention.
The anhydrides of alkyl- or arylcarboxylic acids are preferably suitable for the preparation of the onium salts with alkyl- or arylcarboxylate anions by the process according to the invention.
Suitable onium halides are ammonium halides, phosphonium halides, thiouronium halides, guanidinium halides or halides with a heterocyclic cation, where the halides can be selected from the group chlorides, bromides or iodides. Chlorides or bromides are preferably employed in the process according to the invention. Iodides are preferably employed for the synthesis of the thiouronium salts.
The onium halides are generally commercially available or can be prepared by synthetic methods as known from the literature, for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart, Richard C. Larock, Comprehensive Organic Transformations, 2nd Edition, Wiley-VCH, New York, 1999, or P. Wasserscheid, T. Welton (Eds), Ionic Liquids in Synthesis, Wiley-VCH, 2003. Use can also be made here of variants known per se which are not mentioned here in greater detail.
Ammonium halides can be described, for example, by the formula (1)
[NR4]+Hal− (1),
phosphonium halides can be described, for example, by the formula (2)
[PR4]+Hal− (2),
where
Hal denotes Cl, Br or I and
R in each case, independently of one another, denotes
H, where all substituents R cannot simultaneously be H,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms,
which may be substituted by alkyl groups having 1-6 C atoms,
where one or more R may be partially or fully substituted by —F, but where all four or three R must not be fully substituted by F,
and where, in the R, one or two non-adjacent carbon atoms which are not in the α- or ω-position may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)— or —SO2—.
However, compounds of the formulae (1) and (2) in which all four or three substituents R are fully substituted by halogens, for example tris(trifluoromethyl)methylammonium chloride, tetra(trifluoromethyl)ammonium chloride or tetra(nonafluorobutyl)ammonium chloride, are excluded.
Thiouronium halides can be described, for example, by the formula (3)
[(R1R2N)—C(═SR7)(NR3R4)]+Hal− (3)
and guanidinium halides can be described, for example, by the formula (4)
[C(NR1R2)(NR3R4)(NR5R6)]+Hal− (4),
where
Hal denotes Cl, Br or I and
R1 to R7 each, independently of one another, denote
hydrogen or CN, where hydrogen is excluded for R7,
straight-chain or branched alkyl having 1 to 20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms,
which may be substituted by alkyl groups having 1-6 C atoms,
where one or more of the substituents R1 to R7 may be partially or fully substituted by —F, but where all substituents on an N atom must not be fully substituted by F,
where the substituents R1 to R7 may be connected to one another in pairs by a single or double bond
and where, in the substituents R1 to R7, one or two non-adjacent carbon atoms which are not bonded directly to the heteroatom and are not in the ω-position may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)— or —SO2—.
Halides with a heterocyclic cation can be described, for example, by the formula (5)
[HetN]+Hal− (5),
where
Hal denotes Cl, Br or I and
HetN+ denotes a heterocyclic cation selected from the group
where the substituents
R1′ to R4′ each, independently of one another, denote
hydrogen or CN,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
dialkylamino having alkyl groups having 1-4 C atoms, but which is not bonded to the heteroatom of the heterocycle,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms,
which may be substituted by alkyl groups having 1-6 C atoms, or aryl-C1-C6-alkyl,
where the substituents R1′ and R4′ may be partially or fully substituted by F, but where R1′ and R4′ are not simultaneously CN or must not simultaneously be fully substituted by F,
where the substituents R2′ and R3′ may be partially or fully substituted by halogens or partially substituted by NO2 or CN
and where, in the substituents R1′ to R4′, one or two non-adjacent carbon atoms which are not bonded directly to the heteroatom and are not in the ω-position may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)— or —SO2—.
For the purposes of the present invention, fully unsaturated substituents are also taken to mean aromatic substituents.
In accordance with the invention, suitable substituents R and R1 to R7 of the compounds of the formulae (1) to (4), besides hydrogen, are preferably: C1- to C20-, in particular C1- to C14-alkyl groups, and saturated or unsaturated, i.e. also aromatic, C3- to C7-cycloalkyl groups, which may be substituted by C1- to C6-alkyl groups, in particular phenyl. However, the substituents R and R1 to R7 may likewise be substituted by further functional groups, for example by CN, SO2R′, SO2OR′ or COOR′. R′ denotes non- or partially fluorinated C1- to C6-alkyl, C3- to C7-cycloalkyl, unsubstituted or substituted phenyl.
The substituents R in the compounds of the formula (1) or (2) may be identical or different here. Preferably, three substituents in the formulae (1) and (2) are identical and one substituent is different.
The substituent R is particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl or tetradecyl.
Up to four substituents of the guanidinium cation [C(NR1R2)(NR3R4)(NR5R6)]+ may also be connected in pairs in such a way that mono-, bi- or polycyclic cations are formed.
Without restricting generality, examples of such guanidinium cations are:
where the substituents R1 to R3 and R6 may have an above-mentioned or particularly preferred meaning.
The carbocycles or heterocycles of the above-mentioned guanidinium cations may optionally also be substituted by C1- to C6-alkyl, C1- to C6-alkenyl, NO2, F, Cl, Br, I, C1-C6-alkoxy, SCF3, SO2CF3, SO2CH3, CN, COOR″, SO2NR″2, SO2X′ or SO3R″, where X′ denotes F, Cl or Br and R″ denotes a non- or partially fluorinated C1- to C6-alkyl or C3- to C7-cycloalkyl as defined for R′, or by substituted or unsubstituted phenyl.
Up to four substituents of the thiouronium cation [(R1R2N)—C(═SR7)—(NR3R4)]+ may also be connected in pairs in such a way that mono-, bi- or polycyclic cations are formed.
Without restricting generality, examples of such cations are indicated below:
where the substituents R1, R3 and R7 may have an above-mentioned or particularly preferred meaning. The carbocycles or heterocycles of the above-mentioned thiouronium cations may optionally also be substituted by C1- to C6-alkyl, C1- to C6-alkenyl, NO2, F, Cl, Br, I, C1-C6-alkoxy, SCF3, SO2CF3, SO2CH3, CN, COOR″, SO2NR″2, SO2X′ or SO3R″, where X′ denotes F, Cl or Br and R″ denotes a non- or partially fluorinated C1- to C6-alkyl or C3- to C7-cycloalkyl as defined for R′, or by substituted or unsubstituted phenyl.
The C1-C14-alkyl group is, for example, methyl, ethyl, isopropyl, propyl, butyl or sec-butyl, furthermore also pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl, optionally perfluorinated, for example as difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.
A straight-chain or branched alkenyl having 2 to 20 C atoms, where a plurality of double bonds may also be present, is, for example, vinyl, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, —C9H17, —C10H19 to —C20H39, preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore preferably 4-pentenyl, isopentenyl or hexenyl.
A straight-chain or branched alkynyl having 2 to 20 C atoms, where a plurality of triple bonds may also be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3-pentynyl, hexynyl, heptynyl, octynyl, —C9H15, —C10H17 to —C20H37, preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3-pentynyl or hexynyl.
Aryl-C1-C6-alkyl denotes, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, where both the phenyl ring and also the alkylene chain may be partially or fully substituted as described above by —F, particularly preferably benzyl or phenylpropyl. However, the phenyl ring or also the alkylene chain may likewise be substituted by further functional groups, for example by CN, SO2R′, SO2OR′ or COOR′. R′ here has a meaning defined above.
Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopenta-1,3-dienyl, cyclohexenyl, cyclohexa-1,3-dienyl, cyclohexa-1,4-dienyl, phenyl, cycloheptenyl, cyclohepta-1,3-dienyl, cyclohepta-1,4-dienyl or cyclohepta-1,5-dienyl, each of which may be substituted by C1- to C6-alkyl groups, where the cycloalkyl group or the C1- to C6-alkyl-substituted cycloalkyl group may in turn also be substituted by F. However, the cycloalkyl groups may likewise be substituted by further functional groups, for example by CN, SO2R′, SO2OR′ or COOR′. R′ here has a meaning defined above.
In the substituents R, R1 to R6 or R1′ to R4′, one or two non-adjacent carbon atoms which are not bonded in the α-position to the heteroatom or in the ω-position may also be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)— or —SO2—.
Without restricting generality, examples of substituents R, R1 to R6 and R1′ to R4′ modified in this way are:
—OCH3, —OCH(CH3)2, —CH2OCH3, —CH2—CH2—O—CH3, —C2H4OCH(CH3)2, —C2H4SC2H5, —C2H4SCH(CH3)2, —S(O)CH3, —SO2CH3, —SO2C6H5, —SO2C3H7, —SO2CH(CH3)2, —SO2CH2CF3, —CH2SO2CH3, —O—C4H8—O—C4H9, —CF31—C2F6, —C3F7, —C4F9, —CF2CF2H, —CF2CHFCF3, —CF2CH(CF3)2, —C2F4N(C2F5)C2F5, —CHF2, —CH2CF3, —C2F2H3, —C3H6, —CH2C3F7, —CH2C(O)OCH3, —CH2C6H5 or —C(O)C6H5.
R′ is C3- to C7-cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
In R′, substituted phenyl denotes phenyl which is substituted by C1- to C6-alkyl, C1- to C6-alkenyl, NO2, F, Cl, Br, I, C1-C6-alkoxy, SCF3, SO2CF3, SO2CH3, COOR″, SO2X′, SO2NR″2 or SO3R″, where X′ denotes F, Cl or Br and R″ denotes a non- or partially fluorinated C1- to C6-alkyl or C3- to C7-cycloalkyl as defined for R′, for example o-, m- or p-methylphenyl, o-, m- or p-ethylphenyl, o-, m- or p-propylphenyl, o-, m- or p-isopropylphenyl, o-, m- or p-nitrophenyl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m-, p-(trifluoromethyl)phenyl, o-, m-, p-(trifluoromethoxy)phenyl, o-, m-, p-(trifluoromethylsulfonyl)phenyl, o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, o-, m- or p-iodophenyl, further preferably 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl, 2,3-, 2,4-, 2,6-, 2,6-, 3,4- or 3,5-difluorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dibromophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethoxyphenyl, 5-fluoro-2-methylphenyl, 3,4,5-trimethoxyphenyl or 2,4,5-trimethylphenyl.
The substituents R1 to R7 are each, independently of one another, preferably a straight-chain or branched alkyl group having 1 to 10 C atoms. The substituents R1 and R2, R3 and R4 and R5 and R6 in compounds of the formulae (3) and (4) may be identical or different here.
R1 to R7 are particularly preferably each, independently of one another, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, phenyl or cyclohexyl, very particularly preferably methyl, ethyl, n-propyl, isopropyl or n-butyl.
In accordance with the invention, suitable substituents R1′ to R4′ of compounds of the formula (5), besides hydrogen, are preferably: CN, C1- to C20-, in particular C1- to C12-alkyl groups, and saturated or unsaturated, i.e. also aromatic, C3- to C7-cycloalkyl groups, which may be substituted by C1- to C6-alkyl groups, in particular phenyl or aryl-C1-C6-alkyl.
However, the substituents R1′ to R4′ may likewise be substituted by further functional groups, for example by CN, SO2R′, SO2OR′ or COOP′. R′ denotes non- or partially fluorinated C1- to C6-alkyl, C3- to C7-cycloalkyl, un-substituted or substituted phenyl.
The substituents R1′ and R4′ are each, independently of one another, particularly preferably CN, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl, phenylpropyl or benzyl. They are very particularly preferably methyl, CN, ethyl, n-butyl or hexyl. In pyrrolidinium or piperidinium compounds, the two substituents R1′ and R4′ are preferably different.
The substituent R1′ or R4′ is in each case, independently of one another, in particular hydrogen, dimethylamino, diethylamino, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, cyclohexyl, phenyl or benzyl. R2′ is particularly preferably hydrogen, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or dimethylamino. R2′ and R3′ are very particularly preferably hydrogen.
The alkyl groups as substituents R and R1 to R6 and R1′ and R4′ of the heterocyclic cations of the formula (5) are preferably different from the alkyl group of the alkyl ester of the alkyl- or arylsulfonic acid or alkyl- or arylcarboxylic acid employed.
The onium sulfonate or carboxylate prepared in accordance with the invention may, however, also have alkyl groups in the cation which are identical with the alkyl group in the ester, but were not introduced in accordance with the invention by alkylation. The focus is then on the simple reaction procedure and the particularly low halide content in the end product, as is important for the reaction according to the invention with trialkylsilyl esters of the alkyl or arylsulfonic acids or alkyl- or arylcarboxylic acids or anhydrides thereof.
HetN+ of the formula (5) is preferably
where the substituents R1′ to R4′ each, independently of one another, have a meaning described above.
HetN+ is particularly preferably imidazolium, pyrrolidinium or pyridinium, as defined above, where the substituents R1′ to R4′ each, independently of one another, have a meaning described above.
The alkyl ester of an alkyl- or arylsulfonic acid employed is preferably an alkyl ester having a straight-chain or branched alkyl group having 1-8 C atoms, preferably having 1-4 C atoms, where the alkyl group may also contain Cl or F atoms. Examples of alkyl esters of sulfonic acids are, for example, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, propyl trifluoromethanesulfonate, butyl trifluoromethanesulfonate, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, methyl ethanesulfonate, ethyl ethanesulfonate, propyl ethanesulfonate, butyl ethanesulfonate, methyl benzenesulfonate, ethyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, methyl p-nitrobenzenesulfonate or ethyl p-nitrobenzenesulfonate.
Particular preference is given to the use of methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, methyl methanesulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate or ethyl p-toluenesulfonate. Very particular preference is given to the use of methyl trifluoromethanesulfonate or ethyl trifluoromethanesulfonate.
Alkyl esters or trialkylsilyl esters of chlorosulfonic acid can also be used in the process according to the invention, for example methyl chlorosulfonate or trimethylsilyl chlorosulfonate.
The trialkylsilyl ester of an alkyl- or arylsulfonic acid employed is preferably a trialkylsilyl ester having a straight-chain or branched alkyl group having 1-8 C atoms, preferably having 1-4 C atoms, where each alkyl group is independent of one another. The alkyl groups on the silicon are preferably identical. Trialkylsilyl esters of sulfonic acids are, for example, CF3—SO2—O—Si(CH3)3, CF3—SO2—O—Si(CH3)2(t-C4H9), CF3—SO2—O—Si(C2H5)2(i-C3H7), CF3—SO2—O—Si(C2H6)3, CF3—SO2—O—Si(i-C3H7)3, CF3—SO2—O—Si-(n-C4H9)3, CH3SO2—O—Si(CH3)3, CH3—SO2—O—Si(CH3)2(n-C4H9), (C2H5)—SO2—O—Si—(CH3)3, (C2H5)—SO2—O—Si(C2H5)3, C2F5—SO2—O—Si(CH3)3, C4F9SO2—O—Si(CH3)3, C4F9—SO2—O—Si(C2H5)3, C4F9—SO2—O—Si(CH3)2(n-C4H9), C4F9—SO2—O—Si(CH3)(n-C4H9)2, C8F17—SO2—O—Si(CH3)3, C6F5—SO2—O—Si(CH3)3 or (p-CH3)C6H4—SO2—O—Si(CH3)3. Particular preference is given to the use of CF3—SO2—O—Si(CH3)3, CH3SO2—O—Si(CH3)3, (C2H5)—SO2—O—Si(C2H5)3, C4F9SO2—O—Si(CH3)3, C8F17—SO2—O—Si(CH3)3, C6F5—SO2—O—Si(CH3)3 or (p-CH3)C6H4—SO2—O—Si(CH3)3, very particular preference is given to the use of trimethylsilyl methanesulfonate (CH3SO2—O—Si(CH3)3), trimethylsilyl pentafluorobenzenesulfonate (C6F5SO2—O—Si(CH3)3), trimethylsilyl toluenesulfonate ((p-CH3)C6H4—SO2—O—Si(CH3)3) or trimethylsilyl trifluoromethanesulfonate (CF3SO2—O—Si(CH3)3).
The alkyl ester of an alkyl- or arylcarboxylic acid employed is preferably an alkyl ester having a straight-chain or branched alkyl group having 1-8 C atoms, preferably having 1-4 C atoms. Alkyl esters of carboxylic acids are, for example, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, butyl trifluoroacetate, tert-butyl acetate, tert-butyl propionate, isopropyl benzoate, tert-butyl benzoate, methyl 4-nitrobenzoate or methyl pentafluorobenzoate. Particular preference is given to the use of methyl trifluoroacetate or ethyl trifluoroacetate.
The trialkylsilyl ester of an alkyl- or arylcarboxylic acid employed is preferably a trialkylsilyl ester having a straight-chain or branched alkyl group having 1-8 C atoms, preferably having 1-4 C atoms, where each alkyl group is independent of one another. The alkyl groups on the silicon are preferably identical. Trialkylsilyl esters of carboxylic acids are, for example, CF3—C(O)—O—Si(CH3)3, CF3—C(O)—O—Si(CH3)2(t-C4H9), CF3—C(O)—O—Si(C2H5)2(i-C3H7), CF3—C(O)—O—Si(C2H5)3, CF3—C(O)—O—Si(i-C3H7)3, CF3—C(O)—O—Si-(n-C4H9)3, CH3—C(O)—O—Si(CH3)3, CH3—C(O)—O—Si(CH3)2(n-C4H9), (C2H5)—C(O)—O—Si—(CH3)3, (C2H5)—C(O)—O—Si(C2H5)3, C2F5—C(O)—O—Si(CH3)3, C4F9—C(O)—O—Si(CH3)3, C4F9—C(O)—O—Si(C2H5)3, C4F9—C(O)—O—Si(CH3)2(n-C4H9), C4F9—C(O)—O—Si(CH3)(n-C4H9)2, C8F17—C(O)—O—Si(CH3)3, C6H5—C(O)—O—Si(CH3)3 or (p-NO2)C6H4—C(O)—O—Si(CH3)3. Particular preference is given to the use of CF3—C(O)—O—Si(CH3)3, C4F9—C(O)—O—Si(CH3)3, C8F17—C(O)—O—Si(CH3)3, C6F5—C(O)—O—Si(CH3)3 or (p-NO2)C6H4—C(O)—O—Si(CH3)3, very particular preference is given to the use of trimethylsilyl pentafluorobenzoate (C6F5—C(O)—O—Si(CH3)3) or trimethylsilyl trifluoroacetate (CF3—C(O)—O—Si(CH3)3).
The acid anhydride employed is preferably the anhydride of a straight-chain or branched alkylcarboxylic acid having 1-8 C atoms in the alkyl group, preferably having 1-4 C atoms in the alkyl group, the anhydride of an aromatic carboxylic acid, the anhydride of a sulfonic acid or the mixed anhydride of a carboxylic acid and a sulfonic acid. Suitable anhydrides are trifluoroacetic anhydride, succinic anhydride, pentafluoropropanoic anhydride, trifluoromethanesulfonic anhydride or mixed anhydrides of trifluoroacetic acid, acetic acid, propionic acid, tartaric acid, malonic acid, nicotinic acid, aminoacetic acid or benzoic acid. Particular preference is given to the use of trifluoroacetic anhydride.
Likewise suitable for use in the process according to the invention are alkyl or trialkylsilyl esters of 2,4,6-trinitrophenol (picric acid) or 2,4-dinitrophenol.
The esters or anhydrides employed are generally commercially available or can be prepared by synthetic methods as known from the literature, for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart, or Richard C. Larock, Comprehensive Organic Transformations, 2nd Edition, Wiley-VCH, New York, 1999. Use can also be made here of variants known per se which are not mentioned here in greater detail.
A general scheme summarises the process according to the invention:
The substituents R, R1 to R7 and HetN+ of the compounds of the formulae (1) to (10) correspond to the meanings as described above.
The reaction with alkyl esters of alkyl- or arylsulfonic acids is carried out in accordance with the invention at room temperature, i.e. generally at temperatures between 10° and 30° C. The reaction with alkyl esters of alkyl- or arylcarboxylic acids, trialkylsilyl esters of alkyl or arylsulfonic acids or alkyl- or arylcarboxylic acids is generally carried out at temperatures between 0° and 50° C., preferably 100 to 30° C., particularly preferably at room temperature. The reaction with acid anhydrides is carried out at temperatures between 20° and 180° C., preferably between 50° and 100° C. However, it can also be carried out at room temperature.
A solvent is not required. However, it is also possible to employ solvents, for example dimethoxyethane, acetonitrile, acetone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, propionitrile or mixtures with one another.
The reaction is carried out with an excess or equimolar amount of alkyl or trialkylsilyl esters of an alkyl- or arylsulfonic acid or an alkyl- or arylcarboxylic acid or the corresponding anhydride.
The method described is also suitable for the purification of the onium salts. This means that a corresponding ester according to the invention or an anhydride of the acid of the anion, for example trimethylsilyl trifluoromethanesulfonate, is added to the ionic liquid contaminated by halide ions, for example 1-butyl-3-methylimidazolium trifluoromethanesulfonate contaminated with 1-butyl-3-methylimidazolium chloride. The contaminant reacts away, and the halide-reduced ionic liquid is obtained.
The synthesis is also particularly suitable for heterocyclic trifluoromethanesulfonates, where a positive nitrogen in the heterocycle carries a CN group. Such compounds are excellent cyanation reagents. Exchange of the known anion tetrafluoroborate to give trifluoromethanesulfonate results in morestable compounds.
The invention therefore likewise relates to triflates of the formula (11)
HetN+[CF3SO3]− (11),
where
HetN+ denotes a heterocyclic cation selected from the group
where
R1′ or R4′ denotes CN and the other substituents
R1′ to R4′ each, independently of one another, denote
hydrogen,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
dialkylamino having alkyl groups having 1-4 C atoms, but which is not bonded to the heteroatom of the heterocycle,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms,
which may be substituted by alkyl groups having 1-6 C atoms, or aryl-C1-C6-alkyl,
where one or more substituents R2′ and R3′ may be partially or fully substituted by —F,
but where R1′ and R4′ are not simultaneously CN,
and where, in the substituents R1∝ to R4′, one or two non-adjacent carbon atoms which are not bonded directly to the heteroatom and are not in the ω-position may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)— or —SO2—.
In accordance with the invention, suitable substituents R1′ to R4′ of compounds of the formula (5), besides hydrogen, are preferably: CN, C1- to C20-, in particular C1- to C12-alkyl groups, and saturated or unsaturated, i.e. also aromatic, C3- to C7-cycloalkyl groups, which may be substituted by C1- to C6-alkyl groups, in particular phenyl or aryl-C1-C6-alkyl.
One substituent R1′ or R4′ is by definition CN. The second substituent R1′ or R4′ is particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl, phenylpropyl or benzyl, very particularly preferably methyl, ethyl, n-butyl or hexyl.
The substituent R2′ or R3′ is in each case, independently of one another, in particular hydrogen, dimethylamino, diethylamino, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, cyclohexyl, phenyl or benzyl. R2′ is particularly preferably hydrogen, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or dimethylamino. R2′ and R3′ are very particularly preferably each, independently of one another, hydrogen.
HetN+ of the formula (11) is preferably
where the substituents R1′ to R4′ each, independently of one another, have a meaning described above.
HetN+ is particularly preferably imidazolium, pyrrolidinium or pyridinium, as defined above, where the substituents R1′ to R4′ each, independently of one another, have a meaning described above, very particularly preferably pyridinium.
Even without further comments, it is assumed that a person skilled in the art will be able to utilise the above description in the broadest scope. The preferred embodiments and examples should therefore merely be regarded as descriptive disclosure which is absolutely not limiting in any way.
It goes without saying for the person skilled in the art that substituents in the compounds mentioned above and below, such as, for example, H, N, O, Cl or F, can be replaced by the corresponding isotopes.
The NMR spectra were measured on solutions in deuterated solvents at 20° C. on a Bruker ARX 400 spectrometer with a 5 mm 1H/BB broadband head with deuterium lock, unless indicated in the examples. The measurement frequencies of the various nuclei are: 1H: 400.13 MHz and 19F: 276.50 MHz. The referencing method is indicated separately for each spectrum or each data set.
A mixture of 1.80 g (8.88 mmol) of 1-hexyl-3-methylimidazolium chloride and 1.52 g (9.26 mmol) of methyl triflate, CF3SO2OCH3, is stirred at room temperature for 30 minutes. NMR measurements show the completeness of the reaction. The residue is dried for 30 minutes in vacuo at 13.3 Pa and 120° C. (oil-bath temperature), giving 2.80 g of 1-hexyl-3-methylimidazolium triflate in approximately quantitative yield.
1H NMR (reference: TMS; CD3CN), ppm: 0.87 m (CH3); 1.29 m (3CH2); 1.81 m (CH2); 3.82 s (CH3); 4.11 t (CH2); 7.35 d,d (CH); 7.39 d,d (CH); 8.55 br. s. (CH); 3JH,H=6.9 Hz; JH,H=1.5 Hz.
19F NMR (reference: CCl3F—internal; CD3CN), ppm: −78.1 s (CF3).
1.04 g (5.95 mmol) of 1-butyl-3-methylimidazolium chloride are reacted with 1.67 g (10.2 mmol) of methyl triflate analogously to Example 1, giving 1.71 g of 1-butyl-3-methylimidazolium triflate in approximately quantitative yield.
1H NMR (reference: TMS; CD3CN), ppm: 0.92 t (CH3); 1.31 m (CH2);
1.80 m (CH2); 3.82 S(CH3); 4.12 t (CH2); 7.34 d,d (CH); 7.38 d,d (CH); 8.51 br. s. (CH); 3JH,H=7.4 Hz; 3JH,H=7.1 Hz; JH,H=1.7 Hz.
19F NMR (reference: CCl3F—internal; CD3CN), ppm: −78.11 s (CF3).
1.56 g (8.29 mmol) of 1-ethylpyridinium bromide are reacted with 1.67 g (10.2 mmol) of methyl triflate analogously to Example 1, giving 2.13 g of 1-ethylpyridinium triflate in approximately quantitative yield.
1H NMR (reference: TMS; CD3CN), ppm: 1.58 t (CH3); 4.59 q (CH2); 8.02 m (2CH); 8.49 t,t (CH); 8.78 d (2CH); 3JH,H=7.3 Hz; 3JH,H=7.6 Hz; 3JH,H=6.1 Hz; 4JH,H=1.2 Hz.
19F NMR (reference: CCl3F—internal; CD3CN), ppm: −78.0 s (CF3).
4.31 g (19.9 mmol) of 1-butylpyridinium bromide are reacted with 4.41 g (26.9 mmol) of methyl triflate analogously to Example 1, giving 5.68 g of 1-butylpyridinium triflate in approximately quantitative yield.
1H NMR (reference: TMS; CD3CN), ppm: 0.93 t (CH3); 1.35 m (CH2);
1.93 m (CH2); 4.53 t (CH2); 8.02 m (2CH); 8.50 t (CH); 8.74 d (20H); 3JH,H=7.4 Hz; 3JH,H=7.6 Hz; 3JH,H=7.9 Hz; 3JH,H=6.1 Hz.
19F NMR (reference: CCl3F—internal; CD3CN), ppm: −78.0 s (CF3).
1.75 g (3.37 mmol) of trihexyltetradecylphosphonium chloride are reacted with 2.59 g (15.8 mmol) of methyl triflate for 30 minutes analogously to Example 1, giving 2.13 g of trihexyltetradecylphosphonium triflate in approximately quantitative yield.
1H NMR (reference: TMS; CD3CN), ppm: 0.84-0.94 m (4CH3), 1.24-1.37 m (16CH2), 1.37-1.57 m (8CH2), 1.99-2.09 m (4CH2).
19F NMR (reference: CCl3F—internal; CD3CN), ppm: −78.0 s (CF3).
31P {1H} NMR (reference: 85% H3PO4—external; CD3CN), ppm: 33.5.
A mixture of 1.85 g (9.84 mmol) of 1-ethylpyridinium bromide and 2.54 g (11.4 mmol) of trimethylsilyl triflate, CF3SO2OSi(CH3)3, is stirred at room temperature for 4 hours. NMR measurements show the completeness of the reaction. The residue is dried for 30 minutes in vacuo at 13.3 Pa and 120° C. (oil-bath temperature), giving 2.53 g of 1-ethylpyridinium triflate in approximately quantitative yield.
The NMR spectra correspond to those from Example 3.
1.42 g (6.57 mmol) of 1-butylpyridinium bromide are reacted with 1.73 g (7.78 mmol) of trimethylsilyl triflate analogously to Example 6, giving 1.87 g of 1-butylpyridinium triflate in approximately quantitative yield.
The NMR spectra correspond to those from Example 4.
1.67 g (9.56 mmol) of 1-butyl-3-methylimidazolium chloride are reacted with 2.36 g (10.6 mmol) of trimethylsilyl triflate analogously to Example 6, giving 2.75 g of 1-butyl-3-methylimidazolium triflate in approximately quantitative yield.
The NMR spectra correspond to those from Example 2.
1.81 g (8.93 mmol) of 1-hexyl-3-methylimidazolium chloride are reacted with 2.62 g (11.79 mmol) of trimethylsilyl triflate analogously to Example 6, giving 2.81 g of 1-hexyl-3-methylimidazolium triflate in approximately quantitative yield.
The NMR spectra correspond to those from Example 1.
1.64 g (3.16 mmol) of trihexyltetradecylphosphonium chloride are reacted with 0.91 g (4.09 mmol) of trimethylsilyl triflate analogously to Example 6, giving 2.00 g of trihexyltetradecylphosphonium triflate in approximately quantitative yield.
The NMR spectra correspond to those from Example 5.
Analogously to Example 6,
1-methylimidazolium chloride is reacted with trimethylsilyl triflate to give
2.06 g (11.8 mmol) of 1-butyl-3-methylimidazolium chloride are reacted with 1.99 g (11.8 mmol) of trimethylsilyl methanesulfonate, CH3SO3Si(CH3)3, analogously to Example 6, giving 2.72 g of 1-butyl-3-methylimidazolium methylsulfonate in approximately quantitative yield.
1H NMR (reference: TMS; CD3CN), ppm: 0.91 t (CH3); 1.30 m (CH2);
1.80 m (CH2); 2.47 s (CH3); 3.87 S(CH3); 4.18 t (CH2); 7.48 d,d (CH); 7.51 d,d (CH); 9.23 br. s. (CH); 3JH,H=7.4 Hz; JH,H=7.2 Hz; JH,H=1.7 Hz.
1.57 g (8.99 mmol) of 1-butyl-3-methylimidazolium chloride are reacted with 2.09 g (9.07 mmol) of trimethylsilyl benzenesulfonate, C6H5SO3Si(CH3)3, analogously to Example 6. Drying in vacuo at an oilbath temperature of 60° C. gives 2.66 g of 1-butyl-3-methylimidazolium benzenesulfonate in approximately quantitative yield.
1H NMR (reference: TMS; CD3CN), ppm: 0.89 t (CH3); 1.27 m (Ch2);
1.76 m (CH2); 3.82 s (CH3); 4.12 t (CH2); 7.32-7.39 (3H, C6H5); 7.39 d,d (CH); 7.43 d,d (CH); 7.70-7.79 (2H, C6H5); 9.01 br. s. (CH); 3JH,H=7.4 Hz; 3JH,H=7.3 Hz; JH,H=1.8 Hz.
A mixture of 2.42 g (13.85 mmol) of 1-butyl-3-methylimidazolium chloride and 3.21 g (15.28 mmol) of trifluoroacetic anhydride, CF3C(O)OC(O)CF3, is stirred at room temperature for 3 hours. NMR measurements show the completeness of the reaction. The residue is dried for 30 minutes in vacuo at 13.3 Pa and 60° C. (oil-bath temperature), giving 3.49 g of 1-butyl-3-methylimidazolium trifluoroacetate in approximately quantitative yield.
1H NMR (reference: TMS; CD3CN), ppm: 0.89 t (CH3); 1.27 m (CH2);
1.78 m (CH2); 3.34 s (CH3); 4.15 t (CH2); 7.44 d,d (CH); 7.49 d,d (CH), 9.24 br. s. (CH); 3JH,H=7.4 Hz; JH,H=1.7 Hz.
19F NMR (reference: CCl3F—internal; CD3CN), ppm: −74.4 s (CF3).
Analogously to Example 14,
1,3-dimethylimidazolium chloride is reacted with trifluoroacetic anhydride to give
1,3-dimethylimidazolium trifluoroacetate;
1-butyl-1-methylpyrrolidinium chloride is reacted with trifluoroacetic anhydride to give
111.43 g (1.36 mol) of methylimidazole and 160 g (1.47 mot) of bromoethane are mixed, and 400 ml of isopropanol are subsequently added. The reaction mixture is heated for 72 hours with stirring, during which the oil-bath temperature is 80° C. Isopropanol is then removed by distillation, and the residue is dried for two hours in vacuo at 13.3 Pa and an oil-bath temperature of 100° C., giving 258.6 g of 1-ethyl-3-methylimidazolium bromide, corresponding to a yield of 99.7%.
M.p.: 73-74° C.
1H NMR (reference: TMS; CD3CN), ppm: 1.44 t (CH3); 3.88 s (CH3); 4.23 q (CH2); 7.49 m (CH); 7.56 m (CH); 9.45 br. s. (CH); 3JH,H=7.2 Hz.
45.5 g (0.227 mol) of molten ethyl tosylate (p-CH3C6H4SO2OC2H5, m.p. 32-34° C.) are added to 43.41 g (0.227 mol) of 1-ethyl-3-methylimidazolium bromide. The reaction mixture is stirred at room temperature for 24 hours until the bromide salt has completely dissolved. The liquid product is subsequently dried for one hour in vacuo at 13.3 Pa and an oil-bath temperature of 60° C., giving 64.1 g of 1-ethyl-3-methylimidazolium tosylate, corresponding to an approximately quantitative yield.
1H NMR (reference: TMS; CD3CN), ppm: 1.35 t (CH3); 2.29 s (CH3); 3.78 s (CH3); 4.11 q (CH2); 7.13 d (2CH, A); 7.60 d (2CH, B); 7.42 m (CH); 7.49 m (CH); 9.10 br. s. (CH); 3JH,H=7.3 Hz; 3JH(A),H(B)=8.1 Hz.
Analogously to Example 16,
1-methylimidazolium chloride is reacted with trimethylsilyl (p-toluene)sulfonate to give
A mixture of 2.38 g (10.62 mmol) of N,N,N′N′-tetramethyl-N″-ethylguanidinium bromide and 1.95 g (10.95 mmol) of ethyl trifluoromethanesulfonate is stirred at room temperature for one hour. An NMR measurement shows the completeness of the reaction. The residue is subsequently dried for 2 hours in a vacuum of 13.3 Pa and at an oil-bath temperature of 60° C., giving 3.11 g of N,N,N′,N′-tetramethyl-N″-ethylguanidinium trifluoromethanesultfonate as a liquid, corresponding to an approximately quantitative yield.
1H NMR (reference: TMS; CD3CN), ppm: 1.13 t (CH3); 2.87 br.s; 2.89 br.s;
2.92 S (4CH3); 3.22 m (CH2); 6.42 br.s (NH); 3JH,H=7.1 Hz.
19F NMR (reference: CCl3F—internal; CD3CN), ppm: −78.0 s (CF3).
Analogously thereto,
N,N,N′,N′,N″-pentamethyl-N″-propylguanidinium chloride is reacted with methyl or ethyl triflate to give
A mixture of 1.88 g (8.24 mmol) of 1-cyano-4-dimethylaminopyridinium bromide and 1.93 g (10.83 mmol) of ethyl trifluoromethanesulfonate is stirred at room temperature for 5 hours. The volatile compounds are subsequently removed in vacuo, and the residue is dried for 2 hours at room temperature in a vacuum of 13.3 Pa, giving 2.40 g of 1-cyano-4-dimethylaminopyridinium trifluoromethanesulfonate, corresponding to a yield of 98%.
M.p.: 75-77° C.
1H NMR (reference: TMS; CD3CN), ppm: 3.33 s (2CH3); 7.02 d,m (2CH, A);
8.09 d,m (2CH, B); 3JH(A),H(B)=8.1 Hz.
19F NMR (reference: CCl3F—internal; CD3CN), ppm: −78.02 s (CF3).
13C NMR (reference: TMS; CD3CN), ppm: 42.2 q,q [N(CH3)2]; 107.6 m (CN); 109.8 d,m (2CH); 141.5 d,m (2CH); 158.0 m (C); 1JC,H=195 Hz; 1JC,H=175 Hz; 1JC,H=142 Hz; 3JC,H=3.3 Hz.
Raman spectrum: 2272.9 cm−1 (CN).
Elemental analysis C9H10F3N3O3S (molecular weight 297.25):
found: C, 36.00%; H, 3.22%; N, 13.92%; S, 9.84%.
calculated: C, 36.37%; H 3.39%; N, 14.14%; S, 10.79%.
2.65 g (13.23 mmol) of molten ethyl tosylate (melting point 32-34° C.) are added to 2.08 g (12.95 mmol) of 1-ethyl-2,3-dimethylimidazolium bromide. The reaction mixture is stirred at room temperature for 1 hour and dried in vacuo at 13.3 Pa and an oil-bath temperature of 110-112° C., giving 3.83 g of 1-ethyl-2,3-dimethylimidazolium p-toluenesulfonate. The yield is approximately quantitative.
1H NMR (reference: TMS; CD3CN), ppm: 1.33 t (CH3); 2.32 s (CH3); 2.48 s (CH3); 3.68 s (CH3); 4.07 q (CH2); 7.13 d (2CH, A); 7.47 d (2CH, B); 7.36 m (2CH); 3JH,H=7.3 Hz; 3JH(A),H(B)=8.0 Hz.
A mixture of 2.36 g (12.15 mmol) of 1-ethyl-1-methylpyrrolidinium bromide and 2.70 g (12.15 mmol) of trimethylsilyl triflate is stirred at room temperature for 3 hours. All volatile products are removed over the course of one hour in vacuo at 13.3 Pa and 60° G, giving 3.19 g of 1-ethyl-1-methylpyrrolidinium triflate. The yield is approximately quantitative.
M.p.: 94-95° C.
1H NMR (reference: TMS; CD3CN), ppm: 1.32 μm (CH3); 2.15 m (2CH2);
2.95 s (CH3); 3.35 q (CH2); 3.42 m (2CH2); 3JH,H=7.3 Hz.
19F NMR (reference: CCl3F-internal; CD3CN), ppm: −78.03 s (CF3).
Analogously thereto,
1-butyl-1-methylpyrrolidinium chloride is reacted with trimethylsilyl triflate to give
A mixture of 2.23 g (18.80 mmol) of 1-methylimidazolium chloride and 4.61 g (20.74 mmol) of trimethylsilyl triflate is stirred at room temperature for 2 hours. NMR measurements show the completeness of the reaction. The residue is dried for 1 hour in vacuo at 13.3 Pa and an oil-bath temperature of 60° C., giving 4.36 g of 1-methylimidazolium triflate. The yield is approximately quantitative.
M.p.: 90-91° C.
1H NMR (reference: TMS; CD3CN), ppm: 3.86 s (CH3); 7.38 br.s (2CH); 8.54 br.s (CH); 12.30 br. s (NH).
19F NMR (reference: CCl3F—internal; CD3CN), ppm: —78.1 s (CF3).
A mixture of 19.14 g (131 mmol) of 1-ethyl-3-methylimidazolium chloride and 72.62 g (390 mmol) of trimethylsilyl trifluoroacetate, CF3C(O)OSi(CH3)3, is heated and refluxed for three hours. Trimethylchlorosilane, (CH3)3SiCl, which forms during the reaction and excess trimethylsilyl trifluoroacetate are removed by distillation over a column. The residue is pumped over within 30 minutes at 13.3 Pa and at a bath temperature of 80° C., giving 29.25 g of 1-ethyl-3-methylimidazolium trifluoroacetate. The yield is virtually quantitative.
1H NMR (reference: TMS; CD3CN), ppm: 1.41 t (CH3); 3.82 s (CH3); 4.16 q (CH2); 7.38 d,d (CH); 7.44 d,d (CH); 8.79 br. s. (CH); 3JH,H=7.3 Hz; JH,H=1.7 Hz.
19F NMR (reference: CCl3F—internal; CD3CN), ppm: −74.5 s (CF3).
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2004 060 076.7 | Dec 2004 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP05/12401 | 11/18/2005 | WO | 00 | 6/13/2007 |
