RU2575352C2 - Method of producing perfluoroalkylcyano- or perfluoroalkylcyanofluoroborates - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing salts of formula M^a+[B(R_f)(CN)_x(F)_y]_a ^- (I), which can be used as ionic liquids. The method includes reaction of an alkali metal salt of formula Me⁺[B(R_f)F₃]^- (II) with trialkylsilyl cyanide to obtain a salt of formula Me⁺[B(R_f)(CN)_x(F)_y]^- (III) and a salt exchange reaction of a salt of formula III with a salt formula MA (IV). In formula I M^a+ is a silver, copper (I) or copper (II) cation or an organic cation, R_f is a straight or branched perfluorinated alkyl group containing 1-4 C atoms, C₆F₅, C₆H₅, a partially fluorinated phenyl or a phenyl which is mono- or disubstituted with a perfluoroalkyl group containing 1-4 C atoms, where the perfluoroalkyl group is independently selected, a equals 1 or 2, x equals 1, 2 or 3, y equals 0, 1 or 2, where 0 is excluded if R_f=C₆H₅, and x+y=3. In formula II Me⁺ is a lithium, potassium, sodium, caesium or rubidium cation, and R_f has a value given above. In formula III Me⁺, R_f, x and y have values given above. The alkyl group in trialkylsilyl cyanide is in each case, independently, a straight or branched alkyl group containing 1-4 C atoms. In formula IV M has a value given for M^a+, and A is selected from a group of anions F^-, Cl^-, Br^-, I^-, OH^-, [HF₂]^-, [CN]^-, [SCN]^- etc. The invention also relates to a method of producing compounds of formula III, certain lithium salts of formula III, as well as to an electrolyte and an electrochemical cell including said salts.

EFFECT: method enables to obtain salts of formula I with good output from readily available raw materials.

14 cl, 38 ex

Description

The invention relates to a method for producing salts containing perfluoroalkyl tricyano or perfluoroalkyl cyano fluoroborate anions, ((per) fluoro) phenyl tricyano or ((per) fluoro) phenyl cyano fluoroborate anions, phenyl tricyano borate anions which are mono or disubstituted with perfluoro groups 1-4 or phenylcyanofluoroborate anions that are mono- or disubstituted with perfluoroalkyl groups containing 1-4 C atoms by the reaction of an alkali metal trifluoroperfluoroalkyl borate with a trialkylsilyl cyanide followed by a salt exchange or by direct reaction of an organic trifluoroperfluoroalkyl borate with a trialkylsilyl cyanide.

Salts of the formula M ^{a +} [B (R _f ) _4-xy (CN) _x (F) _y ] _a , where M ^{a +} may be an inorganic or organic cation and a = 1 or 2, x = 1, 2 or 3, y = 0 or 1 and x + y≤4 are known from WO 2006/045405, where, however, only potassium tris (trifluoromethyl) cyanoborate, guanidinium tris (trifluoromethyl) cyanoborate and trityl tris (trifluoromethyl) cyanoborate are disclosed. WO 2006/045405 describes that these salts of this formula containing organic cations and anions are ionic liquids.

Under the ionic liquid should be understood salts, which usually consist of an organic cation and an inorganic anion. They do not contain any neutral molecules and usually have melting points below 373 K [Wasserscheid P, Keim W, 2000, Angew. Chem. 112: 3926]. Due to their salt character, ionic liquids have unique properties, such as, for example, low vapor pressure, a liquid state in a wide temperature range, fire resistance, show high electrical conductivity and high electrochemical and temperature stability.

Surprisingly, ionic liquids containing borate anions, which include both perfluoroalkyl groups and cyano groups, exhibit lower viscosity than ionic liquids containing borate anions that include perfluoroalkyl groups and fluorine groups, such as, for example, perfluoroalkyl trifluoroborate, or more lower viscosity than ionic liquids containing tetracyanoborate anions. Viscosity is an important property of a substance when considering the use of salts containing perfluoroalkylcyanofluoroborate anions, in particular in electrochemistry.

In particular, salts containing perfluoroalkyltricyanoborate, perfluoroalkylcyanodifluoroborate or perfluoroalkyldicyanofluoroborate anions exhibit dynamic viscosities, for example of the order of 13-17 cP at 25 ° C. Salts of this type containing these selected anions are new, and in particular a selective invention relative to WO 2006/045405.

The synthesis of borate anions [B (R _f ) 4 _-xy (CN) _x (F) _y ] where x = 1, 2 or 3, y = 0 or 1 and x + y <4 succeeds, in accordance with the description of the published description inventions WO 2006/045405, by isomerization of the corresponding isocyanoborate salts at temperatures between 150 ° and 300 ° C. Isocyanoborate salts are formed by the reaction of isocyanoboric acid with a strong base and differ in that the nitrogen atom binds to the boron atom. For comparison, cyanide in the salts of WO 2006/045405 binds to a boron atom via C.

E. Bernhard et al., Chemistry A European J. 2001, 7, No.21, 4696-4705) describe the NMR data of the anions [(CF ₃ ) BF ₂ (CN)] ^- and [(CF ₃ ) BF (CN) ₂ ] ^- , which were obtained during the fluorination of lithium, silver or ammonium tetracyanoborate (NH ₄ [B (CN) ₄ ]) using CIF ₃ , but which were not isolated. The final product of this fluorination was salts containing tetratrifluoromethyl borate anion ([B (CF ₃ ) ₄ ] ^- ). The synthesis of alkali metal tetracyanoborates by reaction of a solid alkali metal tetrafluoroborate in the presence of potassium cyanide / lithium chloride is described, for example, in WO 2004/072089.

The synthesis of borate anions in the absence of a perfluoroalkyl group [B (CN) _x (F) _y ], where x = 2 or 3, y = 1 or 2, and x + y = 4 succeeds, as described by E. Bernhard et al. , Z.fur Anorg. Allg. Chem. 2003, 629, 677-685, by reaction of lithium tetrafluoroborate or potassium tetrafluoroborate with trimethylsilyl cyanide. In addition, this reference describes that the reaction rate is very slow, the reaction time is from several hours to several weeks, and that mixtures of dicyanodifluoroborate anions and tricyanofluoroborate anions are usually formed. The synthesis and isolation of trifluoromonocyanoborate anions was not possible using this method.

However, there remains a demand for economical alternative synthetic methods for producing this interesting class of salts containing perfluoroalkylcyanofluoroborate anions, perfluorophenylcyanofluoroborate anions or perfluorophenyltricyanoborate anionic, fluorophenylcyanofluoroboroborate-anionic, or be mono- or disubstituted with perfluoroalkyl groups containing 1-4 C atoms.

Therefore, it is an object of the present invention to provide an alternative preparation process that provides the desired salts in good yield and based on readily available starting materials.

Surprisingly, alkali metal trifluoroperfluoroalkyl borates have been found to be excellent starting materials for the synthesis of the desired mixed borates, which are readily available.

Therefore, the invention relates to a method for producing salts of the formula I

,

,

Where

или органический катион,M ^{a +} means a cation of silver, magnesium, copper (I), copper (II), zinc (II), calcium,

or organic cation,

R _f means a linear or branched perforated alkyl group containing from 1 to 4 C, C ₆ F ₅ , C ₆ H ₅ atoms, partially fluorinated phenyl, or phenyl which is mono- or disubstituted with a perfluoroalkyl group containing from 1 to 4 C atoms where the perfluoroalkyl group is independently selected,

a means 1 or 2,

x means 1, 2 or 3,

y means 0, 1 or 2 and

x + y = 3,

by reaction of an alkali metal salt of formula II

,

,

Where

Me ⁺ means a salt of lithium, potassium, sodium, cesium or rubidium and R _f has the meaning indicated above,

with trialkylsilyl cyanide to give a salt of formula III

,

,

where Me ⁺ , R _f , x and y are as defined above and the alkyl group of the trialkylsilyl cyanide is, in each case, independently, a linear or branched alkyl group containing from 1 to 4 C atoms,

and the subsequent salt-exchange reaction of salts of formula III with a salt of formula IV,

,

,

Where

M has the meaning indicated for M ^{a +} , and

A is selected from the group of anions:

F ^- Cl ^- , Br ^- , I ^- , OH ^- , [HF ₂ ] ^- , [CN] ^- [SCN] ^- , [R ₁ COO] ^- , [R ₁ SO ₃ ] ^- [R ₂ COO] ^- , [R ₂ SO ₃ ] ^- , [R ₁ OSO ₃ ] ^- , [SiF ₆ ] ^2- , [BF ₄ ] ^- , [SO ₄ ] ^2- , [HSO ₄ ] ^1- , [NO ₃ ] ^- , [ (R ₁ ) ₂ P (O) O] ^- , [R ₁ P (O) O ₂ ] ^2- , [(R ₁ O) ₂ P (O) O] ^- , [(R ₁ O) P (O ) O ₂ ] ^2- , [(R ₂ ) ₂ P (O) O] ^- , [R ₂ P (O) O ₂ ] ^2- , tosylate, benzoate, oxalate, succinate, suerate, ascorbate, sorbate, tartrate, citrate, malate, malonate, malonates, which are optionally substituted with alkyl groups containing from 1 to 4 C atoms, or [CO ₃ ] ^2- ,

where R ₁ in each case, independently of one another, means H and / or a linear or branched alkyl group containing from 1 to 12 C atoms,

R ₂ in each case, independently of one another, means a partially fluorinated or perforated linear or branched alkyl group containing from 1 to 12 C atoms, or pentafluorophenyl, and where electroneutrality must be ensured in the MA salt formula.

A perfluorinated linear or branched alkyl group containing 1-4 C atoms means, for example, trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl, isoheptafluoropropyl, n-nonafluorobutyl, sec-nonafluorobutyl or tert-nonafluorobutyl. R2 is defined similarly as a linear or branched perforated alkyl group containing 1-12 C atoms, containing the above perfluoroalkyl groups, and, for example, perfluorinated n-hexyl, perforated n-heptyl, perforated n-octyl, perfluorinated ethylhexyl, perfluorinated n-nonyl perfluorinated n-decyl, perfluorinated n-undecyl or perfluorinated n-dodecyl.

Rf is preferably trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, perfluorohexyl, C ₆ F ₅ , p-PC ₆ H ₄ , 3,5- (CF ₃ ) ₂ C ₆ H ₃ or C ₆ H ₅ ; particularly preferred is a linear or branched perforated alkyl group containing 1-4 C or C ₆ F ₅ atoms, even more preferably trifluoromethyl or pentafluoroethyl, extremely preferably pentafluoroethyl.

Accordingly, the preferred salts of formula I, wherein the borate anion is selected from the group consisting triftormetiltritsianoborat, pentaftoretiltritsianoborat, geptaftorpropiltritsianoborat, triftormetilditsianoftorborat, pentaftoretilditsianoftorborat, geptaftorpropilditsianoftorborat, triftormetilmonotsianodiftorborat, pentaftormetilmonotsianodiftorborat, geptaftorpropilmonotsianodiftorborat, nonaftorbutilmonotsianodiftorborat,

pentaftorfeniltritsianoborat, pentaftorfenilditsianoftorborat, pentaftorfenilmonotsianodiftorborat, feniltritsianoborat, fenilditsianoftorborat, fenilmonotsianodiftorborat, p-ftorfeniltritsianoborat, p-ftorfenilditsianoftorborat, p-ftorfenilmonotsianodiftorborat, 3,5-bis (trifluoromethyl) feniltritsianoborat, 3,5-bis (trifluoromethyl) fenilditsianoftorborat or 3,5-bis ( trifluoromethyl) phenylmonocyanodifluoroborate.

R ₂ means particularly preferably trifluoromethyl, pentafluoroethyl or nonafluorobutyl, even more preferably trifluoromethyl or pentafluoroethyl.

A linear or branched alkyl group containing 1-4 C atoms means, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

R _{1 is} defined similarly as a linear or branched alkyl group containing 1-12 C atoms, including the above-mentioned alkyl groups and, for example, n-hexyl, n-heptyl, n-octyl, ethylhexyl, n-nonyl, n-decyl, n undecyl or n-dodecyl.

R ₁ means particularly preferably methyl, ethyl, n-butyl, n-hexyl or n-octyl, even more preferably methyl or ethyl.

Substituted malonates mean, for example, methyl malonate or ethyl malonate compounds.

M ^{a +} preferably means an organic cation selected from ammonium cations, sulfonium cations, oxonium cations, phosphonium cations, uronium cations, thiuronium cations, guanidinium cations or heterocyclic cations, as described below, in particular by formulas (1) to (8), and preferred their meanings.

The alkyl groups of the trialkylsilyl cyanide may be the same or different. Alkyl groups are preferably the same. Examples of trialkylsilyl cyanides are therefore trimethylsilyl cyanide, triethylsilyl cyanide, triisopropylsilyl cyanide, tripropylsilyl cyanide or tributylsilyl cyanide. Particular preference is given to the use of trimethylsilyl cyanide, which is commercially available or can also be obtained in situ.

Preference is given to the use of compounds of formula II in which the alkali metal is lithium, sodium or potassium, particularly preferably potassium.

The most preferred compounds of formula II for the synthesis of compounds of formula I described above are therefore compounds selected from potassium trifluoromethyl trifluoroborate, potassium pentafluoroethyl trifluoroborate, potassium heptafluoropropyl trifluoroborate or pentafluorophenyl trifluoroborate.

It is possible to select the reaction conditions of this reaction in such a way that, in particular in the case of the conversion of compounds of formula II to compounds of formula III, as described above, a specific borate anion is specially obtained in high yield. Without specific temperature control, a mixture of salts having various borate anions is usually formed, as defined above, or as described as a preferred embodiment. Temperature control is mainly carried out by means of microwave radiation.

Compounds of formula II can be prepared by conventional methods known to one skilled in the art, for example, based on the description in US 7,208,626 B2; WO 2003/087020 (A1) and WO 2003/087113 (A1) or in R. D. Chambers et al., J. of the American Chemical Society, 82 (1960), pp. 5296-5301; H.-J-Frohn and V. V. Bardin, Z. fur Anorganische und Allgemeine Chemie, 627 (2001), pp. 15-16; G.A. Molander and G.P. Hoag, Organometallics, 22 (2003), p. 3313-3315; Zhi-Bin Zhou et al., J. of Fluorine Chem., 123 (2003), p. 127-131].

If the reaction of the compounds of formula II

,

,

Where

Me ⁺ means a salt of lithium, potassium, sodium, cesium or rubidium and R _f has the meaning indicated above

with trialkylsilyl cyanide, as described above, at temperatures between 10 ° C and 110 ° C or under microwave irradiation with a power of 100 W, in particular, compounds of the formula III are formed

,

,

where Me ⁺ , R _f , have the meanings as indicated for the compounds of formula II and x = 1 and y = 2, that is, the fluorine atom is replaced by a cyano group. Thus, in a high yield, compounds of formula III are formed having an anion of formula Ia

If the group R _f means trifluoromethyl, the corresponding salt containing trifluoromethyl monocyanodifluoroborate anion is preferably formed at room temperature or under 100 W microwave radiation. The reaction time can be observed within a few hours. Details in this regard are described in the examples. If the group R _f means pentafluoroethyl, the corresponding salt is preferably formed at temperatures of 100 ° C with a reaction time of the order of one hour or with microwave power of 100 watts. If the group R _f means phenyl, partially fluorinated phenyl, phenyl or perfluorophenyl, each of which is mono- or disubstituted with perfluoroalkyl groups containing 1-4 C atoms, the corresponding monocyanodifluoroborate salt is preferably formed at room temperature with a reaction time of several days. A preferred embodiment for the preparation of salts of formula I which have anions of formula Ia is therefore characterized in that the reaction of formula II with trialkylsilyl cyanide, as described above, is carried out at temperatures between 10 ° C and 110 ° C, preferably in the range between room temperature ( 25 ° C) and 100 ° C, or under microwave irradiation with a power of 100 watts.

If the reaction of the compounds of formula II

,

,

Where

Me ⁺ means a salt of lithium, potassium, sodium, cesium or rubidium and R _f has the meaning indicated above,

with trialkylsilyl cyanide, as described above, at temperatures between 115 ° C and 200 ° C or under microwave irradiation with a power of 200 W, in particular, compounds of the formula III are formed

,

,

where Me ⁺ , R _f , have the meanings as indicated for the compounds of formula H and x = 2 and y = 1, that is, two fluorine atoms are replaced by cyano groups. Thus, compounds of formula III containing an anion of formula Ib are formed in high yield

.

.

If the group R _f means, for example, trifluoromethyl, the corresponding salt containing trifluoromethyldicyanofluoroborate anion is preferably formed at 130 ° C or under microwave irradiation with a power of 200 watts. The reaction time is about 5 hours. Details in this regard are described in the examples. If the group R _f means, for example, pentafluoroethyl, the corresponding salt of formula Ib is preferably formed at temperatures of 180 ° C with a reaction time of about 6 hours or with microwave irradiation with a power of 200 W with a reaction time of about several minutes. A preferred embodiment for the preparation of salts of formula I which have anions of formula Ib is therefore characterized in that the reaction of formula II with trialkylsilyl cyanide as described above is carried out at temperatures between 115 ° C and 200 ° C, preferably between 130 ° C and 180 ° C, or under microwave irradiation with a power of 200 watts.

If the reaction of the compounds of formula II

,

,

Where

Me ⁺ means a salt of lithium, potassium, sodium, cesium or rubidium and R _f has the meaning indicated above

with trialkylsilyl cyanide, as described above, under microwave irradiation with a power of more than 200 W, in particular 300 W, in particular, compounds of formula III are formed

,

,

where Me ⁺ and R _f have the meanings as indicated for the compound of formula II and x = 3 and y = 0, that is, all three fluorine atoms are replaced by cyano groups. Thus, compounds of formula III containing an anion of formula Ic are formed in high yield.

.

.

A preferred embodiment for the preparation of salts of formula I which have anions of formula Ic, therefore, is characterized in that the reaction of formula II with trialkylsilyl cyanide is carried out as described above with microwave irradiation with a power of more than 200 watts, preferably with microwave irradiation of 300 watts.

If the group R _f means, for example, trifluoromethyl, the corresponding salt containing trifluoromethyltricyanofluoroborate anion is preferably formed by microwave radiation with a power of 300 watts. The reaction time is about one to two hours. Details in this regard are described in the examples. If the group R _f means, for example, pentafluoroethyl, the corresponding salt is preferably formed by microwave irradiation with a power of 300 W at a reaction time of the order of one hour.

It was impossible to predict that the compounds of formula II, as described above, are suitable as starting materials for the preparation of compounds of the formula III and, after a salt exchange reaction, for the preparation of compounds of the formula I. In contrast to the reaction described by Bernhard et al. (Z. fur Anorg. Allg. Chem. 2003, 629, 677-685), an alkali metal tetrafluoroborate with trimethylsilyl cyanide, it cannot be expected that the reactivity in the presence of a bulky group R _f , for example in the presence of a perfluoroalkyl group, is sufficient to facilitate the replacement of fluorine atoms by ianogruppy. In addition, it is unexpected that the reaction rate even increases relatively. Replacement of three fluorine atoms is not possible in the link mentioned above, whereas precisely such a replacement occurs in the method in accordance with the invention with a 300 W microwave radiation. Microwave radiation as a heat source is not described in these references. Unexpectedly and unexpectedly, trimethylsilyl cyanide selectively attacks only fluorine atoms bound to boron, and not fluorine atoms in the perfluoroalkyl chain.

The reaction of the compound of formula II with trialkylsilyl cyanide can be carried out in the absence of a protective gas atmosphere. However, the reaction is preferably carried out in dry air or in an inert gas atmosphere.

The reaction of the compound of formula II with trialkylsilyl cyanide is preferably carried out in the absence of solvents. However, a reaction in the presence of an organic solvent, for example tetrahydrofuran or acetonitrile, is also possible.

In a further embodiment, the trialkylsilyl cyanide used is prepared in situ from alkali metal cyanide and trialkylsilyl chloride in the presence of alkali metal iodide or fluoride, and optionally iodine, before reacting with a compound of formula II as described above. In this case, sodium cyanide and sodium iodide or potassium cyanide and potassium iodide are preferably used, where the alkali metal iodide is preferably added in a molar amount of 0.1 mol / L in terms of 1 mol / L of alkali metal cyanide and trialkylsilyl chloride. Details of this preparation method are given in the examples. In general, this preparation method is based on the description of M.T. Reetz, I. Chatziiosifidis, Synthesis, 1982, p. 330; J.K. Rasmussen, S.M. Heilmann and L.R. Krepski, The Chemistry of Cyanotrimethylsilane in G.L. Larson (Pefl.) "Advances in Silicon Chemistry", v. 1, pp. 65-187, JAI Press Inc., 1991 or WO 2008/102661 A1.

The invention therefore also relates to a process for preparing compounds of formula I as described above, characterized in that the trialkylsilyl cyanide is prepared in situ from alkali metal cyanide and trialkylsilyl chloride in the presence or catalysis of alkali metal iodide and optionally iodine, before reacting with the compound of formula II.

If the preparation of compounds of formula I according to the invention is carried out as described above, it is possible to purify the obtained compounds of formula III in the first reaction step and use them in the form of isolated, pure compounds in the second stage of a salt exchange reaction or metathesis reaction.

However, in a further embodiment, it is advantageous not to isolate the intermediate compound of formula III to obtain a pure substance, but instead to only separate by-products that are insoluble in organic solvents or are volatile, such as, for example, trialkylsilyl fluoride or excess trimethylsilyl cyanide, and react the compound of formula III without further purification to obtain a pure substance with a compound of formula IV, as described above.

Alternatively, the synthesis of compounds of formula I, as described above, can also be carried out by reacting a compound of formula II, as described above, with an alkali metal cyanide in the presence of an alkali metal chloride, as described, for example, in Example 5C. The resulting compounds can be isolated by crystallization. If a mixture is used in the salt exchange reaction to produce compounds containing the corresponding organic cations, salts containing organic cations can be isolated, for example, using extraction methods. This alternative method is preferably suitable for the preparation of (pentafluoroethyl) alkali metal difluoromonocyanoborates and the corresponding organic salts or alternative metal salts after salt exchange. A preferred alkali metal chloride is lithium chloride. The reaction is a sintering reaction, in particular at temperatures between 160 ° C and 200 ° C.

Examples of organic cations of formulas (1) to (8) can be selected from the group:

ammonium cations of the formula (1), sulfonium cations of the formula (2) or oxonium cations of the formula (3)

,

или

,

or

Where

R in each case, independently of one another, means

- H, where all the substituents R cannot simultaneously mean H,

- straight or branched chain alkyl,

containing 1-20 C atoms,

- straight chain or branched alkenyl,

containing 2-20 C atoms and one or more double bonds,

- straight or branched chain alkynyl,

containing 2-20 C atoms and one or more triple bonds,

- saturated, partially or completely unsaturated

cycloalkyl containing 3-7 C atoms, which may be substituted by alkyl groups containing 1-6 C atoms,

, -CN,

или

, и где один или два не расположенных рядом атома углерода, которые не расположены в α-положении радикала R, могут быть заменены атомами и/или группами атомов, выбранными из группы -О-, -S-, -S(O)-, -SO₂-, -N⁺R¹ ₂-, -C(O)NR¹-, -SO₂NR¹- или -P(O)R¹-; или катионы фосфония формулы (4)where one or two R can be fully substituted and / or one or more R can be partially substituted with halogens or partially with -OR ¹ ,

, -CN,

or

, and where one or two non-adjacent carbon atoms that are not located in the α-position of the radical R can be replaced by atoms and / or groups of atoms selected from the group —O—, —S—, —S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ - or -P (O) R ¹ -; or phosphonium cations of the formula (4)

,

,

Where

R ² in each case independently of one another, means

,- H,

,

- straight or branched chain alkyl,

containing 1-20 C atoms,

- straight chain or branched alkenyl,

containing 2-20 C atoms and one or more double bonds,

- straight or branched chain alkynyl,

containing 2-20 C atoms and one or more triple bonds,

- saturated, partially or completely unsaturated

cycloalkyl containing 3-7 C atoms, which may be substituted by alkyl groups containing 1-6 C atoms,

,

, и где один или два не расположенных рядом атома углерода, которые не расположены в α-положении R², могут быть заменены атомами и/или группами атомов, выбранными из группы -О-, -S-, -S(O)-, -SO₂-, -N⁺R¹ ₂-, -C(O)NR¹-, -SO₂NR¹-, или -P(O)R¹-; или катионы урония формулы (5) или катионы тиурония формулы (6)where one or two R ² can be fully substituted and / or one or more R ² can be partially substituted with halogens, or partially with -OR ¹ , -CN,

,

, and where one or two non-adjacent carbon atoms that are not located in the α-position of R ² can be replaced by atoms and / or groups of atoms selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ -, or -P (O) R ¹ -; or uronium cations of formula (5) or thiuronium cations of formula (6)

or

,

,

Where

R ³ -R ⁷ each, independently of one another, means

,- H,

,

- straight or branched chain alkyl containing 1-20 C atoms,

- straight-chain or branched alkenyl containing 2-20 C atoms and one or more double bonds,

- straight or branched chain alkynyl containing 2-20 C atoms and one or more triple bonds,

- saturated, partially or completely unsaturated cycloalkyl containing 3-7 C atoms, which may be substituted by alkyl groups containing 1-6 C atoms,

where one or more substituents R ³ -R ⁷ can be partially or completely substituted with halogens, or partially with -OH, -OR ¹ , -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ¹ ₂ ,

and where one or two non-adjacent carbon atoms that are not located at the α-position of R ³ -R ⁷ can be replaced by atoms and / or groups of atoms selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ -, or -P (O) R ¹ -; or guanidinium cations of the formula (7)

Where

R ⁸ -R ¹³ each, independently of one another, means

,- H,

,

- straight or branched chain alkyl,

containing 1-20 C atoms,

- straight-chain or branched alkenyl containing 2-20 C atoms and one or more double bonds,

- straight or branched chain alkynyl containing 2-20 C atoms and one or more triple bonds,

- saturated, partially or completely unsaturated cycloalkyl containing 3-7 C atoms, which may be substituted by alkyl groups containing 1-6 C atoms,

,

,where one or more substituents R ⁸ -R ¹³ can be partially or completely substituted with halogens or partially with -OR ¹ , -CN,

,

,

and where one or two non-adjacent carbon atoms that are not located at the α-position of R ⁸ -R ¹³ can be replaced by atoms and / or groups of atoms selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ - or -P (O) R ¹ -; or heterocyclic cations of the formula (8)

,

,

where [HetN] ⁺ means a heterocyclic cation selected from the group including

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

и

,

,

,

,

and

where the substituents R ¹ -R ⁴ each, independently from each other, mean - H, with the restriction that R ¹ 'and R ⁴ cannot simultaneously mean H,

- straight or branched chain alkyl containing 1-20 C atoms, which may also be fluorinated or perforated,

- straight chain or branched alkenyl containing 2-20 C atoms and one or more double bonds, which may also be fluorinated or perforated,

- straight or branched chain alkynyl containing 2-20 C atoms and one or more triple bonds, which may also be fluorinated or perforated,

- saturated, partially or completely unsaturated cycloalkyl containing 3-7 C atoms, which may be substituted by alkyl groups containing 1-6 C atoms,

- saturated, partially or completely unsaturated heteroaryl, heteroaryl-C ₁ -C ₆ -alkyl or aryl-C ₁ -C ₆ -alkyl, where the substituents R ^{1 '} , R ^2' , R ^{3 '} and / or R ⁴ together can form a ring system where one or more substituents R ^{1 '} -R ^4' can be partially or completely substituted with halogens or partially with -OR ¹ , -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ¹ ₂ , but wherein R ¹ and R ⁴ can not simultaneously be fully substituted by halogens, and where one or two non-adjacent carbon atoms which are not bonded to the heteroatom substituents R ^{1 '-R 4} may be replaced by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) - , -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ - or -P (O) R ¹ -;

where R ¹ means H, non-, partially or perfluorinated C ₁ -C ₆ -alkyl, C ₃ -C ₇ -cycloalkyl, unsubstituted or substituted phenyl and R ^{1 *} means non-, partially or perfluorinated C ₁ -C ₆ -alkyl C ₃ -C ₇ cycloalkyl, unsubstituted or substituted phenyl.

Cations of formulas (1), (2), (3) and (4) in which all four or three of the substituents R and R ^{2 are} completely substituted with halogens, for example, the tris (trifluoromethyl) methylammonium cation, the tetrakis (trifluoromethyl) ammonium cation or the tetrakis cation (nonafluorobutyl) ammonium is therefore excluded.

Fully unsaturated substituents in the sense of the present invention should also be understood as aromatic substituents. Suitable substituents R and R ² -R ^{13 of the} compounds of formulas (1) to (7) according to the invention are, in addition to H, preferably: C ₁ -C ₂₀ -, in particular C ₁ -C ₁₄ -alkyl groups, and saturated or unsaturated, i.e. also aromatic, C ₃ -C ₇ cycloalkyl groups which may be substituted with C ₁ -C ₆ alkyl groups, in particular phenyl.

The substituents R and R ² in the compounds of formula (1), (2), (3) or (4) in this case may be the same or different. In the compounds of formulas (1), three or four R substituents are preferably the same. In the compounds of formulas (2), all R substituents are preferably the same or two are the same and one substituent is different. In the compounds of formula (3), all R substituents are preferably the same. In the compounds of formula (3), three or four R ² substituents are preferably the same.

The substituents R and R ^{2 are} particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl or tetradecyl.

Up to four substituents of the guanidinium cation [C (NR ⁸ R ⁹ ) (NR ¹⁰ R ¹¹ ) (NR ¹² R ¹³ )] ⁺ can also be paired in such a way that mono-, bi- or polycyclic molecules are formed.

Without limiting the general nature, examples of guanidinium cations of this type are:

,

,

,

,

,

,

,

или

,

,

,

,

,

,

,

or

where the substituents R ⁸ -R ¹⁰ and R ¹³ may have the above or particularly preferred meaning.

, F, Cl, Br, I, C₁-C₆-алкокси, SCF₃, SO₂CF₃ или

, где R¹ имеет упомянутое выше значение, замещенным или незамещенным фенилом или незамещенным или замещенным гетероциклом.Carbocycles or heterocycles of the aforementioned guanidinium cations may optionally also be substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, CN,

, F, Cl, Br, I, C ₁ -C ₆ alkoxy, SCF ₃ , SO ₂ CF ₃ or

where R ¹ has the above meaning, substituted or unsubstituted phenyl or unsubstituted or substituted heterocycle.

Up to four substituents of the thiuronium cation [C (NR ³ R ⁴ ) (SR ⁵ ) (NR ⁶ R ⁷ )] ⁺ can also be paired in such a way that mono-, bi- or polycyclic molecules are formed.

Without limiting the general nature, examples of thiuronium cations of this type are the following cations:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

or

in which Y = S

and where the substituents R ³ , R ⁵ and R ⁶ may have the above or particularly preferred meanings.

, F, Cl, Br, I, C₁-C₆-алкокси, SCF₃, SO₂CF₃ или

, или замещенным или незамещенным фенилом или незамещенным или замещенным гетероциклом, где R¹ имеет упомянутое выше значение.The carbocycles or heterocycles of the above molecules may optionally also be substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, CN,

, F, Cl, Br, I, C ₁ -C ₆ alkoxy, SCF ₃ , SO ₂ CF ₃ or

or substituted or unsubstituted phenyl or unsubstituted or substituted heterocycle, where R ¹ has the above meaning.

The substituents R ³ -R ¹³ each independently of one another preferably means a straight or branched chain alkyl group containing 1-10 C atoms. The substituents R ³ and R ⁴ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ¹⁰ and R ¹¹ and R ¹² and R ¹³ in the compounds of formulas (5) to (7) in this case may be the same or different. R ³ -R ^{13 is} particularly preferably each independently of one another, meaning methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, phenyl or cyclohexyl, even more preferably methyl, ethyl, n- propyl, isopropyl or n-butyl.

Suitable substituents R ¹ -R ^{4 of the} compounds of formula (8) according to the invention are, in addition to H, preferably: C ₁ -C ₂₀ , in particular C ₁ -C ₁₂ -alkyl groups, and saturated or unsaturated, i.e. also aromatic, C ₃ -C ₇ cycloalkyl groups which may be substituted with C ₁ -C ₆ alkyl groups, in particular phenyl.

The substituents R ^{1 '} and R ^4' each, particularly preferably independently, are methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl or benzyl. They are even more preferably methyl, ethyl, n-butyl or hexyl. In pyrrolidine, piperidine, indoline, pyrrolidinium, piperidinium or indolinium compounds, the two substituents R ^{1 '} and R ^4' are preferably different.

The substituent R ^{2 '} or R ^3' means in each case, independently of one another, in particular H, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, tert-butyl, cyclohexyl, phenyl or benzyl. R ^{2 ′} is particularly preferably H, methyl, ethyl, isopropyl, propyl, butyl or sec-butyl. R ^{2 '} and R ^3' even more preferably mean H.

C ₁ -C ₁₂ -alkyl group means, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, in addition also pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. Optional difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.

A straight or branched chain alkenyl containing 2-20 C atoms, where many double bonds may also be present, is, for example, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, in addition 4-pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, -C ₉ H ₁₇ , -C ₁₀ H ₁₉ to -C ₂₀ H ₃₉ ; preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl; in addition, 4-pentenyl, isopentenyl or hexenyl is further preferred. If the compounds are partially fluorinated, at least one H atom is replaced by an F. atom. If the compounds are perfluorinated, all H atoms of the corresponding alkyl group are replaced by F. atoms.

Branched or branched alkynyl containing 2 to 20 C atoms, where many triple bonds may also be present, means, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, in addition 4-pentynyl, 3- pentynyl, hexynyl, heptinyl, octynyl, -C ₉ H ₁₅ , -C ₁₀ H ₁₇ to -C ₂₀ H ₃₇ , preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3- pentinyl or hexynyl. If the compounds are partially fluorinated, at least one H atom is replaced by an F. atom. If the compounds are perfluorinated, all H atoms of the corresponding alkyl group are replaced by F. atoms.

, -CN,

, -

.Aryl-C ₁ -C ₆ -alkyl means, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, where both fragments, and the phenyl ring and alkylene chain, can be partially or completely substituted, as described above, with halogens, in particular -F and / or -Cl, or partially with -OR ¹ , -

, -CN,

, -

.

, -

.Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups containing 3-7 C atoms mean therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, phenyl, cycloheptenyl, each of which may be substituted with C ₁ -C ₆ - alkyl groups, where a cycloalkyl group or a cycloalkyl group which is substituted with C ₁ -C ₆ alkyl groups can in turn also be substituted with halogen atoms such as F, Cl, Br or I, in particular F or Cl, or -OR ¹ , -CN,

, -

.

In the substituents R, R ² -R ¹³ or R ¹ -R ⁴ , one or two non-adjacent carbon atoms that are not attached at the α-position to the heteroatom can also be replaced by atoms and / or groups of atoms selected from the group - O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ - or -P (O) R ¹ -, where R ¹ = non-, partially or perfluorinated C ₁ -C ₆ -alkyl, C ₃ -C ₇ -cycloalkyl, unsubstituted or substituted phenyl.

Without limiting the general nature, examples of the substituents R, R ² -R ¹³ and R ^{1 '} -R ^4' , modified in this way are: -OCH ₃ , -OCH (CH ₃ ) ₂ , -CH ₂ OCH ₃ , -CH ₂ -CH ₂ -O-CH ₃ , -C ₂ H ₄ OCH (CH ₃ ) ₂ , -C ₂ H ₄ SC ₂ H ₅ , -C ₂ H ₄ SCH (CH ₃ ) ₂ , -S (O) CH ₃ , -SO ₂ CH ₃ , -SO ₂ C ₆ H ₅ , -SO ₂ C ₃ H ₇ , -SO ₂ CH (CH ₃ ) ₂ , -SO ₂ CH ₂ CF ₃ , -CH ₂ SO ₂ CH ₃ , - OC ₄ H ₈ -OC ₄ H ₉ , -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , -C (CF ₃ ) ₃ , -CF ₂ SO ₂ CF ₃ , -C ₂ F ₄ N (C ₂ F ₅ ) C ₂ F ₅ , -CHF ₂ , -CH ₂ CF ₃ , -C ₂ F ₂ H ₃ , -C ₃ FH ₆ , -CH ₂ C ₃ F ₇ , -C ( CFH ₂ ) ₃ , -CH ₂ C ₆ H ₅ or P (O) (C ₂ H ₅ ) ₂ .

In R ¹ or R ^{1 *} , C ₃ -C ₇ cycloalkyl means, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

, F, Cl, Вr, I, C₁-C₆-алкокси, SCF₃, SO₂CF₃ или

, где R^* означает не-, частично или перфторированный C₁-С₆-алкил или С₃-С₇-циклоалкил, как определено для R¹, например, о-, м- или п-метилфенил, о-, м- или п-этилфенил, о-, м- или п-пропилфенил, о-, м- или п-изопропилфенил, о-, м- или п-трет-бутилфенил, о-, м- или п-метоксифенил, о-, м- или п-этоксифенил, о-, м-, п-(трифторметил)фенил, о-, м-, п-(трифторметокси)фенил, о-, м-, п-(трифторметилсульфонил)фенил, о-, м- или п-фторфенил, о-, м- или п-хлорфенил, о-, м- или п-бромфенил, о-, м- или п-йодфенил, более предпочтительно 2,3-, 2,4-, 2,5-, 2,6-, 3,4- или 3,5-диметилфенил, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- или 3,5-дигидроксифенил, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- или 3,5-дифторфенил, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- или 3,5-дихлорфенил, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- или 3,5-дибромфенил, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- или 3,5-диметоксифенил, 5-фтор-2-метилфенил, 3,4,5-триметоксифенил или 2,4,5-триметилфенил.In R ¹ or R1 *, substituted phenyl means phenyl which is substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, CN,

, F, Cl, Br, I, C ₁ -C ₆ alkoxy, SCF ₃ , SO ₂ CF ₃ or

where R ^* means non-, partially or perfluorinated C ₁ -C ₆ -alkyl or C ₃ -C ₇ -cycloalkyl as defined for R ¹ , 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-tert-butylphenyl, 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, more preferably 2,3-, 2,4-, 2, 5-, 2,6-, 3,4- or 3,5-dimethylphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3 5-dihydroxyphenyl, 2,3-, 2,4-, 2,5-, 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.

, F, Cl, Br, I, C₁-C₆-алкокси, SCF₃, SO₂CF₃ или

, где R¹ имеет упомянутое выше значение.In R ^{1 '} -R ^4' , heteroaryl is understood to mean a saturated or unsaturated mono- or bicyclic heterocyclic radical containing from 5 to 13 ring members where 1, 2 or 3 N atoms and / or 1 or 2 S atoms or O, and the heterocyclic radical may be mono- or polysubstituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, CN,

, F, Cl, Br, I, C ₁ -C ₆ alkoxy, SCF ₃ , SO ₂ CF ₃ or

where R ¹ has the above meaning.

Heterocyclic radical means preferably substituted or unsubstituted 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidine, in addition, preferably 1,2,3-triazol-1-, -4- or -5-yl, 1,2,4-triazol-1- , -4- or -5-yl, 1- or 5-tetrazolyl, 1,2,3-oxadiazol-4- or -5-yl, 1,2,4-oxadiazol-3- or -5-yl, 1 , 3,4-thiadiazol-2- or -5-yl, 1,2,4-thiadiazol-3- or -5-yl, 1,2,3-thiadiazol-4- or -5-yl, 2-, 3-, 4-, 5- or 6-2H-thiopyranyl, 2-, 3- or 4-4 -thiopyranyl, 3- or 4-pyridazinyl, pyrazinyl, 2-, 3-, 4-, 5-, 6- or 7-benzofuryl, 2-, 3-, 4-, 5-, 6- or 7 benzothienyl, 1 -, 2-, 3-, 4-, 5-, 6- or 7-1Н-indolyl, 1-, 2-, 4- or 5-benzimidazolyl, 1-, 3-, 4-, 5-, 6- or 7-benzopyrazolyl, 2-, 4-, 5-, 6- or 7-benzoxazolyl, 3-, 4-, 5-, 6- or 7-benzisoxazolyl, 2-, 4-, 5-, 6-or 7 -benzothiazolyl, 2-, 4-, 5-, 6- or 7-benzisothiazolyl, 4-, 5-, 6- or 7-benz-2,1,3-oxadiazolyl, 1-, 2-, 3-, 4 -, 5-, 6-, 7- or 8-quinolinyl, 1-, 3-, 4-, 5-, 6-, 7- or 8-isoquinolinyl, 1-, 2-, 3-, 4- or 9 -carbazolyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-acridinyl, 3-, 4-, 5-, 6-, 7- or 8-cinnolinyl, 2-, 4-, 5-, 6-, 7- or 8-quinazolinyl; or 1-, 2- or 3-pyrrolidinyl.

Heteroaryl-C ₁ -C ₆ -alkyl at the moment should be understood analogously to the term aryl-C ₁ -C ₆ -alkyl, for example, in the meaning of pyridinylmethyl, pyridinylethyl, pyridinylpropyl, pyridinylbutyl, pyridinylpentyl, pyridinylhexyl, and in this way the heterocycles described above can be attached to an alkylene chain.

HetN * means preferably

pyridinium pyrimidinium

imidazolium pyrazolium pyrrolidinium

,

,

,

,

,

,

или

,

,

,

,

,

,

or

where the substituents R ^{1 '} -R ^4' each, independently of one another, have the meanings described above.

The organic cation [Kt] ^{x + is} particularly preferably selected from the group consisting of cations of imidazolium, pyridinium, pyrrolidinium, ammonium or phosphonium, as defined above.

Particularly suitable cations are selected from the group of tetraalkylammonium, 1,1-dialkylpyrrolidinium, 1-alkyl-1-alkoxyalkylpyrrolidinium or 1,3-dialkylimidazolium, where the alkyl groups or alkoxy group in the alkoxyalkyl group can each contain 1-10 atoms independently C. Alkyl groups even more preferably contain 1-6 C atoms, and an alkoxy group even more preferably contains 1-3 C atoms. The alkyl groups in tetraalkylammonium can therefore be the same or different. Preferably, the three alkyl groups are the same and one alkyl group is the other or the two alkyl groups are the same and the remaining two alkyl groups are different. Preferred tetraalkylammonium cations are, for example, trimethyl (ethyl) ammonium, triethyl (methyl) ammonium, tripropyl (methyl) ammonium, tributyl (methyl) ammonium, tripentyl (methyl) ammonium, trihexyl (methyl) ammonium, triheptyl (methyl) ammonium, trioctyl (methyl) ammonium, trinonyl (methyl) ammonium, tridecyl (methyl) ammonium, trihexyl (ethyl) ammonium, ethyl (trioctyl) ammonium, propyl (dimethyl) ethylammonium, butyl (dimethyl) ethylammonium, methoxyethyl (dimethyl) ethylammonium, methoxyethyl (diethyl) ) methylammonium, methoxyethyl (dimethyl) propylammonium, ethoxyethyl (dimethyl) ethylammo s. Particularly preferred quaternary ammonium cations are propyl (dimethyl) ethylammonium and / or methoxyethyl (dimethyl) ethylammonium.

Preferred 1,1-dialkylpyrrolidinium cations are, for example, 1,1-dimethylpyrrolidinium, 1-methyl-1-ethylpyrrolidinium, 1-methyl-1-propylpyrrolidinium, 1-methyl-1-butylpyrrolidinium, 1-methyl-1-pentyl pyrrolidinium, 1-methyl-1-hexyl pyrrolidinium, 1-methyl-1-heptyl pyrrolidinium, 1-methyl-1-octylpyrrolidinium, 1-methyl-1-nonylpyrrolidinium, 1-methyl-1-decylpyrrolidinium, 1,1-diethylpyrrolidinium, 1- Ethyl-1-propylpyrrolidinium, 1-ethyl-1! Butylpyrrolidinium, 1-ethyl-1-pentylpyrrolidinium, 1-ethyl-1-hexylpyrrolidinium, 1-ethyl-1-heptylpyrrolidinium, 1-ethyl-1-octylpyrrolidinium, 1-ethyl one- nonylpyrrolidinium, 1-ethyl-1-decylpyrrolidinium, 1,1-dipropylpyrrolidinium, 1-propyl-1-methylpyrrolidinium, 1-propyl-1-butylpyrrolidinium, 1-propyl-1-pentylpyrrolidinium, 1-propyl-1-hexylpyrrolidinium propyl-1-heptylpyrrolidinium, 1-propyl-1-octylpyrrolidinium, 1-propyl-1-nonylpyrrolidinium, 1-propyl-1-decylpyrrolidinium, 1,1-dibutylpyrrolidinium, 1-butyl-1-methylpyrrolidinium, 1-butyl-1- pentylpyrrolidinium, 1-butyl-1-hexylpyrrolidinium, 1-butyl-1-heptylpyrrolidinium, 1-butyl-1-octylpyrrolidinium, 1-butyl-1-nonylpyrrolidinium, 1-butyl-1-decylpyrrolidinyl, 1,1-d idinium, 1-pentyl-1-hexylpyrrolidinium, 1-pentyl-1-heptylpyrrolidinium, 1-pentyl-1-octylpyrrolidinium, 1-pentyl-1-nonylpyrrolidinium, 1-pentyl-1-decylpyrrolidinium, 1,1-di-pyrrolidinium 1-hexyl-1-heptylpyrrolidinium, 1-hexyl-1-octylpyrrolidinium, 1-hexyl-1-nonylpyrrolidinium, 1-hexyl-1-decylpyrrolidinium, 1,1-dihexylpyrrolidinium, 1-hexyl-1-heptylpyrrolidinium, 1-octylpyrrolidinium, 1-hexyl-1-nonylpyrrolidinium, 1-hexyl-1-decylpyrrolidinium, 1,1-diheptylpyrrolidinium, 1-heptyl-1-octylpyrrolidinium, 1-heptyl-1-nonylpyrrolidinium, 1-heptyl-pyrrolidinium inium, 1,1-dioctylpyrrolidine, 1-octyl-1-glgtdpyrrolidinium, 1-octyl-1-decylpyrrolidinium, 1-1-dinonylpyrrolidine, 1-nonyl-1-decylpyrrolidinium or 1,1-didecylpyrrolidinium. Particular preference is given to 1-butyl-1-methylpyrrolidinium or 1-propyl-1-methylpyrrolidinium.

Preferred 1-alkyl-1-alkoxyalkylpyrrolidinium cations are, for example, 1- (2-methoxyethyl) -1-methylpyrrolidinium, 1- (2-methoxyethyl) -1-ethyl pyrrolidinium, 1- (2-methoxyethyl) -1-propylpyrrolidinium , 1- (2-methoxyethyl) -1-butylpyrrolidinium, 1- (2-ethoxyethyl) -1-methyl pyrrole idinium, 1-ethoxymethyl-1-methylpyrrolidinium. Particular preference is given to 1- (2-methoxyethyl) -1-methylpyrrolidinium.

Preferred 1,3-dialkylimidazolium cations are, for example, 1-ethyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1-methyl-3-pentylimidazolium, 1-ethyl-3-propylimidazolium , 1-butyl-3-ethylimidazolium, 1-ethyl-3-pentylimidazolium, 1-butyl-3-propylimidazolium, 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1,3-dipropylimidazolium, 1,3-dibutylimidazolium, 1 , 3-dipentylimidazolium, 1,3-dihexylimidazolium, 1,3-diheptylimidazolium, 1,3-dioctylimidazolium, 1,3-dinonylimidazolium, 1,3-didecylimidazolium, 1-hexyl-3-methylimidazolium, 1-heptyl-3-methylimidazolium olium, 1-methyl-3-octylimidazolium, 1-methyl-3-nonylimidazolium, 1-decyl-3-methylimidazolium, 1-ethyl-3-hexylimidazolium, 1-ethyl-3-heptylimidazolium, 1-ethyl-3-octylimidazolium 1-ethyl-3-nonylimidazolium or 1-decyl-3-ethylimidazolium.

Particularly preferred cations are 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium or 1-methyl-3-propylimidazolium.

Particularly preferred 1-alkenyl-3-alkylimidazolium cations are 1-allyl-3-methylimidazolium or 1-allyl-2,3-dimethylimidazolium.

The organic cations of the compounds of formula I are preferably heterocyclic cations of the formula (8), where HetN ^{z +} is imidazolium, pyrrolidinium or pyridinium, with substituents R ^{1 'to} R ^4' , each of which has, independently of one another, the indicated value or as preferred. The organic cation of the compounds of formula I is particularly preferably imidazolium, where the substituents R ^{1 'to} R ^4' have the meanings indicated above or the meanings indicated as preferred or they have the meanings chosen from meanings preferably given for 1,1-dialkylpyrrolidinium, 1-alkyl-1-alkoxyalkylalkylpyrrolidinium, 1,3-dialkylimidazolium, 1-alkenyl-3-alkylimidazolium or 1-alkoxyalkyl-3-alkylimidazolium as described above.

Particularly preferred organic cations of formula I, respectively, are 1-butyl-1-methylpyrrolidinium, 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (2-methoxyethyl) -3-methylimidazolium, 1- butyl-3-methylimidazolium, tributylmethylammonium, tetra-n-butylammonium, tributylmethylphosphonium, tetraphenylphosphonium, diethylmethylsulfonium, S-ethyl-N, N, N ', N'-tetramethylisothiouronium, 1-allyl-3-allyl-3-allyl-3 3-dimethylimidazolium, 1-cyanomethyl-3-methylimidazolium, 1-methyl-3-propynyl imidazolium, 1,1-dimethylpyrrolidinium or trimethylsulfonium.

In one embodiment, compounds of formula I are synthesized from compounds of formula III by a subsequent salt exchange reaction with compounds of formula IV, as described above. The anion of formula (IV) preferably means OH ^- , Cl ^- , Br ^- , I ^- , [CH ₃ SO ₃ ] ^- [CH ₃ OSO ₃ ] ^- , [CF ³ COO] ^- , [CF ₃ SO ₃ ] ^- , [ (C ₂ F ₅ ) 2P (O) O] ^- or [CO ₃ ] ² -, particularly preferably OH ^- , Cl ^- , Br ^- , [CH ₃ OSO ₃ ] ^- , [CF ₃ OSO ₃ ] ^- , [CH ₃ SO ₃ ] ^- or [(C ₂ F ₅ ) ₂ P (O) O] ^- .

The reaction is preferably carried out in water, with temperatures in the range of 0-100 ° C, preferably 15-60 ° C, being suitable. The reaction is particularly preferably carried out at room temperature (25 ° C).

However, the reaction can alternatively also be carried out in organic solvents at temperatures between -30 and 100 ° C. Suitable solvents in this case are acetonitrile, dioxane, dichloromethane, dimethoxyethane, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or an alcohol, for example methanol, ethanol or isopropanol.

In an alternative embodiment, depending on a suitably desired organic cation of a compound of formula I, a compound of formula II containing an organic cation desired for a compound of formula I can also be reacted with trialkylsilyl cyanide as described above. This synthesis is particularly suitable for ammonium or phosphonium cations.

The object of the main claim, that is, the method for producing compounds of formula I, as described above, is thus essentially new and has an inventive step, since compounds of formula III can be obtained economically for the first time.

The invention, therefore, similarly relates to a method for producing compounds of formula III

,

,

where Me ⁺ means a salt of lithium, potassium, sodium, cesium or rubidium, R _f means a linear or branched perforated alkyl group containing from 1 to 4 atoms C, C6F ₅ , C ₆ H5, partially fluorinated phenyl, or phenyl, which is mono- or disubstituted with a perfluoroalkyl group containing from 1 to 4 C atoms, where the perfluoroalkyl group is independently selected, and means 1 or 2, x means 1, 2 or 3, y means 0,1 or 2 and x + y = 3,

by reaction of an alkali metal salt of formula II

,

,

Where

Me ⁺ and R _f have the above meanings, with a trialkylsilyl cyanide, where the alkyl group of the trialkylsilyl cyanide is, in each case, independently, a linear or branched alkyl group containing from 1 to 4 C.

As also described above, this method in accordance with the invention is also characterized in that the reaction for producing compounds of formula III where x = 1, y = 2 is carried out at temperatures between 10 ° C and 110 ° C or under microwave irradiation with a power of 100 W or that the reaction for the preparation of compounds of formula III where x = 2 and y = 1 is carried out at temperatures between 115 ° C and 200 ° C or under microwave irradiation with a power of 200 W or the reaction for the preparation of compounds of formula III where x = 3 and y = 0 is carried out under microwave irradiation with a power of more than 200 W, preferably at 300 t.

The same detailed descriptions also apply to this method, which includes a partial step from the method in accordance with the invention according to the main claim.

The invention also relates to salts of the formula III,

where Me ⁺ means a salt of lithium, potassium, sodium, cesium or rubidium, R _f means a linear or branched perforated alkyl group containing from 1 to 4 atoms C, C ₆ F ₅ , C ₆ H ₅ , partially fluorinated phenyl, or phenyl, which is mono- or disubstituted with a perfluoroalkyl group containing from 1 to 4 C atoms, where the perfluoroalkyl group is independently selected, and means 1 or 2, x means 1, 2 or 3,

y means 0, 1 or 2, where 0 is excluded in the case of R _f = C ₆ H ₆ , and x + y = 3.

The invention also relates to salts of the formula III,

,

,

where Me ⁺ is a salt of lithium, potassium, sodium, cesium or rubidium, Rf is a linear or branched perfluorinated alkyl group containing from 1 to 4 C atoms, CeFs, C ₆ H ₅ , partially fluorinated phenyl, or phenyl, which is mono- or disubstituted with a perfluoroalkyl group containing from 1 to 4 C atoms, where the perfluoroalkyl group is independently selected, and means 1 or 2,

x means 1, 2 or 3,

y means 0,1 or 2, where 0 is excluded in the case of R _f = C ₆ H ₆ ,

and x + y = 3,

where lithium trifluoromethyl difluoromonocyanoborate, lithium trifluoromethyl fluorodicyanoborate, potassium trifluoromethyl difluoromonocyanoborate and potassium trifluoromethyl fluorodicyanoborate are excluded.

Potassium and sodium salts are particularly suitable according to the invention for preparing compounds of formula I as described above.

The lithium salts of the compounds of formula III are particularly suitable for the preparation of electrolyte compositions, in particular for electrochemical or optoelectronic devices. The lithium salts of formula III are particularly suitable as a conductive salt for electrochemical batteries, in particular lithium-ion batteries, lithium-ion capacitors or lithium batteries. The difference from known lithium salts containing borate anions, such as, for example, lithium tetrafluoroborate or lithium tetracyanoborate, is that lithium salts of formula III are capable of dissolving in high concentrations in carbonate-containing solvents. Thus, for example, it was found that the lithium salt of Example 37 dissolves in diethyl carbonate to give a 2 molar solution and has high electrochemical stability. The use of lithium salts of formula III in lithium ion batteries, lithium ion capacitors or lithium batteries would therefore be extremely beneficial.

Therefore, the present invention particularly preferably relates to a lithium salt of the formula III.

Are preferred in this case, the following salts, and lithium salts are particularly preferred: triftormetiltritsianoborat potassium, potassium pentaftoretiltritsianoborat, geptaftorpropiltritsianoborat potassium triftormetilditsianoftorborat potassium pentaftoretilditsianoftorborat potassium geptaftorpropilditsianoftorborat potassium triftormetilmonotsianodiftorborat, potassium pentaftormetilmonotsianodiftorborat, geptaftorpropilmonotsianodiftorborat, potassium nonaftorbutilmonotsianodiftorborat, pentaftorfeniltritsianoborat potassium pentaftorfenilditsianoftorborat, potassium pentaftorfenilmonotsianodiftorborat, fenilditsianoftorborat, potassium fenilmonotsianodiftorborat, p-ftorfeniltritsianoborat potassium ftorfenilditsianoftorborat potassium p-n-ftorfenilmonotsianodiftorborat potassium 3,5-bis (trifluoromethyl) potassium feniltritsianoborat, 3,5-bis (trifluoromethyl) fenilditsianoftorborat potassium or potassium 3,5-bis (trifluoromethyl) phenylmonocyanodifluoroborate, lithium trifluoromethyltricyanoborate, lithium pentafluoroethyltricyanoborate, lithium heptafluoropropyltricyanoborate, trifluoromethyldicyano lithium fluoroborate, lithium pentaftoretilditsianoftorborat, geptaftorpropilditsianoftorborat lithium triftormetilmonotsianodiftorborat lithium pentaftormetilmonotsianodiftorborat lithium geptaftorpropilmonotsianodiftorborat lithium nonaftorbutilmonotsianodiftorborat lithium pentaftorfeniltritsianoborat lithium pentaftorfenilditsianoftorborat lithium pentaftorfenilmonotsianodiftorborat lithium fenilditsianoftorborat lithium fenilmonotsianodiftorborat lithium, n-ftorfeniltritsianoborat lithium, n-ftorfenilditsianoftorborat lithium, n-ftorfenilmonotsian lithium difluoroborate, lithium 3,5-bis (trifluoromethyl) phenyltricyanoborate, lithium 3,5-bis (trifluoromethyl) phenyldicyanofluoroborate or lithium 3,5-bis (trifluoromethyl) phenylmonocyanodifluoroborate, sodium trifluoromethyltetorifluorobenzyl trifluorobutyl fluoride , sodium heptafluoropropyl dicyanofluoroborate, sodium trifluoromethyl monocyanodifluoroborate, sodium pentafluoromethyl monocyanodifluoroborate, sodium heptafluoropropyl monocyanodifluoroborate, nonaft orbutilmonotsianodiftorborat sodium, sodium pentaftorfeniltritsianoborat sodium pentaftorfenilditsianoftorborat sodium pentaftorfenilmonotsianodiftorborat sodium fenilditsianoftorborat sodium fenilmonotsianodiftorborat, sodium n-ftorfeniltritsianoborat, sodium p-ftorfenilditsianoftorborat sodium ftorfenilmonotsianodiftorborat-l, 3,5-bis (trifluoromethyl) sodium feniltritsianoborat, 3,5-bis ( sodium trifluoromethyl) phenyldicyanofluoroborate or sodium 3,5-bis (trifluoromethyl) phenylmonocyanodifluoroborate, cesium trifluoromethyltricyanoborate, pentafluoroethyl cesium tritsianoborat, geptaftorpropiltritsianoborat cesium triftormetilditsianoftorborat cesium pentaftoretilditsianoftorborat cesium geptaftorpropilditsianoftorborat cesium triftormetilmonotsianodiftorborat cesium pentaftormetilmonotsianodiftorborat cesium geptaftorpropilmonotsianodiftorborat cesium nonaftorbutilmonotsianodiftorborat cesium pentaftorfeniltritsianoborat cesium pentaftorfenilditsianoftorborat cesium pentaftorfenilmonotsianodiftorborat cesium fenilditsianoftorborat cesium fenilmonotsianodiftorborat cesium, n-ftorfen cesium tritium cyanoborate, cesium p-fluorophenyl dicyanofluoroborate, cesium p-fluorophenyl monocyanodifluoroborate, cesium 3,5-bis (trifluoromethyl) phenyltricyanoborate, cesium 3,5-bis (trifluoromethyl) phenyldicyanofluoroborate cesium or 3,5-trifluorobenzodifluorobenzo rubidium, rubidium heptafluoropropyl tricyanoborate, rubidium trifluoromethyldicyanofluoroborate, rubidium pentafluoroethyl dicyanofluoroborate, rubidium heptafluoropropyl dicyanofluoroborate, rubidium trifluoromethyl monocyanodifluoroborate, pentafluorome etilmonotsianodiftorborat rubidium geptaftorpropilmonotsianodiftorborat rubidium nonaftorbutilmonotsianodiftorborat rubidium pentaftorfeniltritsianoborat rubidium pentaftorfenilditsianoftorborat rubidium pentaftorfenilmonotsianodiftorborat rubidium fenilditsianoftorborat rubidium fenilmonotsianodiftorborat rubidium, rubidium ftorfeniltritsianoborat l-p-ftorfenilditsianoftorborat rubidium, rubidium p-ftorfenilmonotsianodiftorborat, 3,5-bis (trifluoromethyl) feniltritsianoborat rubidium Rubidium 3,5-bis (trifluoromethyl) phenyldicyanofluoroborate or 3,5- rubidium bis (trifluoromethyl) phenylmonocyanodifluoroborate.

The invention, respectively, also relates to an electrolyte comprising a compound of the formula

,

,

where Me ⁺ means a salt of lithium, potassium, sodium, cesium or rubidium, R _f means a linear or branched perforated alkyl group containing from 1 to 4 atoms C, C ₆ F ₅ , C ₆ H ₅ , partially fluorinated phenyl or phenyl, which mono- or disubstituted with a perfluoroalkyl group containing from 1 to 4 C atoms, where the perfluoroalkyl group is independently selected,

a means 1 or 2,

x means 1, 2 or 3,

y means 0, 1 or 2, and x + y = 3,

or a compound described as preferred.

The invention accordingly also relates to an electrochemical cell containing a compound of formula III, as described above, as an electrolyte component, or a compound described as preferred, or to an electrolyte including these compounds.

In particular, a lithium ion battery, a lithium ion capacitor or a lithium battery are extremely preferred as an electrochemical cell.

The following working examples are intended to clarify the invention without limiting it. The invention can be carried out accordingly throughout the claimed scope. Based on the examples, possible variants can also be obtained. In particular, the features and conditions of the reactions described in the examples can also be applied to other reactions that are not shown in detail, but are within the scope of legal protection defined by the claims.

Examples

The obtained substances are characterized using Raman spectroscopy, elemental analysis and NMR spectroscopy. NMR spectra are measured in solutions in deuterated acetone-De on a Bruker Avance III spectrometer with deuterium stabilization. Measuring the frequency characteristics of the frequencies of different cores: ¹ H: 400.17 MHz, ¹⁹ F: 376.54 MHz, ¹¹ B: 128.39 MHz, ³¹ P: 161.99 MHz and ¹³ C: 100.61 MHz. The reference signal is formed using the internal standard: TMS for ¹ H and ¹³ C spectra; CCl ₃ F for ¹⁹ F and BF ₃ Et ₂ O for ¹¹ B spectra.

For the anions in the compounds, the following values for ¹³ C-NMR spectra described below, found (solvent: acetone-De and reference substance: TMS):

[C ₂ F ₅ BF ₂ (CN)] ^-

¹³ C-NMR: δ, ppm = 129.66 q, t (CN, 1C); 120.80 q, t (CF ₃ , 1C); 116.90 m (CF _2l 1C).

[C ₂ F ₅ BF (CN) 2] ^-

¹³ C-NMR: δ, ppm = 128.18 q, t (2CN, 2C); 121.88 q, t (CF _3, 1C); 117.60 m (CF ₂ , 1C).

[C ₂ F ₅ B (CN) ₃ ] ^-

¹³ C-NMR: δ, ppm = 123.46 q (3CN, 3C); 121.10 q, t (CF ₃ , 1C); 118.20 m (CF ₂ , 1C).

[CF ₃ B (CN) ₃ ] ^-

¹³ C-NMR: δ, ppm = 123.62 q (3CN, 3C); 130.33 q, q (CF ₃ , 1C).

Example 1

Potassium trifluoropentafluoroethyl borate - K [C ₂ F ₅ BF ₃ ]

Pentafluoroethyl iodide C ₂ F ₅ I (1.5 g, 6.1 mmol) was condensed into a 100 ml reaction vessel with a glass faucet and a PTFE rod (Young, London) and an armature of a magnetic stir bar, and then dissolved in 50 ml of diethyl ether and reacted at -78 ° C with a solution of ethyl magnesium bromide in diethyl ether (2.0 ml, 6.1 mmol, 3 mol L ^-1 ) and stirred at -78 ° C for 1 hour. The reaction mixture was then added at -78 ° C to trimethoxyborane (1.2 ml, 10.8 mmol). The mixture was slowly warmed to room temperature. Spray dried KF (1.3 g, 22.4 mmol) was added to the suspension, and it was stirred at room temperature for an additional hour. The reaction mixture was then washed with 50 ml of THF in a PFA flask and all volatile components were distilled off. 10 ml of anhydrous HF was added to the solid, and the mixture was stirred at room temperature for several hours. HF is removed in vacuo and the solid is taken up in 15 ml of acetonitrile and filtered. The resulting solution of K [C ₂ F ₅ BF ₃ ] in acetonitrile (about 0.29 mol L ^-1 ) can be used directly to prepare compounds of formula III or, after solvent removal, convert to K [C2F ₅ BF ₂ (CN)], K [C ₂ F ₅ BF (CN) ₂ ] or K [C ₂ F ₅ B (CN) ₃ ] in accordance with Example 5, 6 or 7 .

Example 2. Potassium cyanodifluorotrifluoromethylborate - K [CF ₃ BF ₂ (CN)]

Potassium trifluorotrifluoromethyl borate, K [CF ₃ BF ₃ ] (3.0 g, 17.0 mmol), is weighed into a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and an armature of a magnetic stirrer. Trimethylsilyl cyanide (6.0 ml, 45.0 mmol) was added under argon. The reaction mixture was stirred at room temperature for 20 hours. All volatile components were removed in vacuo, and most of the unreacted trimethylsilyl cyanide (3.0 ml, 22.5 mmol) was recovered by fractional distillation. The solid residue was taken up in THF (3 ml) and K [CF ₃ BF ₂ CN] was precipitated by adding CH ₂ Cl (150 ml) and then filtered. The colorless solid was dried in vacuo. Yield, calculated on the potassium trifluorotrifluoromethylborate used: 3.0 g (16.4 mmol, 96%).

Decomposition from 200 ° C

.Raman spectroscopy:

.

^elevenB NMR: δ, ppm = - 3.8 tq (1B),^oneJ_F, in = 49.0 Hz,²J_F,_at= 34.5 Hz.

¹⁹ F-NMR: δ, ppm = - 77.4 q (CF ₃ , 3F), ² J _{F, B} = 34.5 Hz; -169.1 q (BF ₂ , 2F), ¹ J _F , _B = 49.3r4

Elemental analysis: found,%, C 13.29, N 7.62; calculated for C ₂ BF ₅ KN,%, C 13.13, N 7.66.

Example 3. Potassium Dicyanofluorotrifluoromethylborate - K [CF ₃ BF (CN) ₂ ]

microwave radiation 200 W, 15 min

Potassium trifluorotrifluoromethyl borate, K [CF ₃ BF ₃ ] (6.0 g, 34.1 mmol), is weighed into a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and an armature of a magnetic stirrer. Trimethylsilyl cyanide (17.1 ml, 127.5 mmol) was added under argon. The reaction mixture was stirred at room temperature for 12 days. Most of the trimethylsilyl fluoride formed is removed in vacuo. The reaction mixture was then irradiated in a microwave oven (CEM Discover) (200 W, T _max = 90 ° C, 20 minutes). All volatile components are removed in vacuo and most of the unreacted trimethylsilyl cyanide (6.3 ml, 47.2 mmol) is recovered by fractional distillation. The residue was taken up in aqueous H ₂ 0 ₂ (30%, 50 ml) and stirred for one hour. The pH of the solution is set to 1 using 37% hydrochloric acid. N (C ₃ H ₇ ) ₃ (7.0 ml, 36.8 mmol) was added to the reaction mixture, and the tripropylammonium salt was extracted with CH ₂ Cl ₂ (3 × 50 ml). The combined organic phases were dried using MgS0 ₄ , filtered, and an aqueous solution of potassium hydroxide (6 g, 30 ml) was added. The organic phase is decanted, a second portion of an aqueous KOH solution (6 g, 30 ml) is added, and the organic phase is decanted again. The aqueous phases are extracted with THF (3 × 50 ml). The collected tetrahydrofuran fractions were dried using K ₂ CO ₃ , filtered and evaporated. K [CF ₃ BF (CN) ₂ ] was precipitated by adding CHG ₂ Cl ₂ (150 ml) and dried in vacuo. Yield, calculated on the potassium trifluorotrifluoromethylborate used: 5.0 g (26.3 mmol, 77%). Decomposition from 260 ° C;

.Raman spectroscopy:

.

¹¹ B-NMR: δ, ppm = - 12.8 dq (1B), ¹ J _F , _B = 49.3 Hz, ² J _F , _B = 35.7 Hz.

¹⁹ F-NMR: δ, ppm = - 74.0 qd (CF ₃ , 3F), ² J _{F, B} = 35.7 Hz, ³ J _{F, F} = 8.3 Hz; -219.7 qq (BF, 1F), ¹ J _{F, B} = 49.2 Hz, ³ J _{F, F} = 8.0 Hz

Example 4. Potassium Tricyanotrifluoromethylborate - K [CF ₃ B (CN) ₃ ]

microwave radiation 300 W, 95 min

Potassium trifluorotrifluoromethyl borate, K [CF ₃ BF ₃ ] (0.5 g, 2.8 mmol), is weighed into a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and an armature of a magnetic stirrer. In an argon atmosphere, trimethylsilyl cyanide (10.0 ml, 74.9 mmol) was added. The reaction mixture was stirred at 100 ° C for 2 hours. Most of the trimethylsilyl fluoride formed is then removed in vacuo and the reaction mixture is irradiated in a microwave oven (CEM Discover) (300 W, T _max = 120 ° C, 95 minutes). All volatile components are then removed under reduced pressure, and most of the unreacted trimethylsilyl cyanide (8.0 ml, 59.9 mmol) is recovered by fractional distillation. The residue was dissolved in 30% aqueous H ₂ O ₂ (5 ml). K ₂ CO _{3 is} added to the solution, which is then stirred for one hour. The mixture was evaporated to dryness using a rotary evaporator and the residue was extracted with diethyl ether (3 × 50 ml). The volume of the combined ether phases was reduced to 5 ml, and the addition of CH ₂ Cl ₂ (100 ml) gave colorless K [CF ₃ B (CN) ₃ ]. The potassium salt is filtered off and dried in vacuo. Yield, calculated on the potassium trifluorotrifluoromethyl borate used: 0.53 g (2.74 mmol, 95%).

.Decomposition from 320 ° C Raman spectroscopy:

.

¹¹ B-NMR: δ, ppm = - 32.0 q (1B), ² J _{F, B} = 36.3 Hz.

¹⁹ F-NMR: δ, ppm = - 66.4 q (CF ₃ , 3F), ² J _{F, B} = 36.3 Hz

Example 5. Potassium cyanodifluoropentafluoroethyl borate - K [C ₂ F ₅ BF ₂ (CN)]

A.

Potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (10.4 g, 46.0 mmol), is weighed into a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and a magnetic stir bar anchor. The flask was closed and trimethylsilyl cyanide (70.0 ml, 524.9 mmol) was added under argon atmosphere. The reaction mixture was stirred at 100 ° C. for 45 minutes, and the trimethylsilyl fluoride thus formed was continuously distilled off. All volatile components are then removed in vacuo. Most of the unreacted trimethylsilyl cyanide (58.1 ml, 159.9. Mmol) was recovered by fractional distillation. The residue was washed with CH ₂ Cl ₂ (200 ml), filtered and dried in vacuo. Potassium cyanodifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₂ (CN)], is obtained as a colorless solid. Yield, calculated on the potassium trifluoropentafluoroethyl borate used: 9.8 g (42.1 mmol, 92%).

.Decomposition from 260 ° C; Raman spectroscopy:

.

¹¹ B-NMR: δ, ppm = - 2.7 tt (1B), ¹ J _F , _B = 51.0 Hz, ² J _F , _B = 25.3 Hz

¹⁹ F-NMR: δ, ppm = - 83.31 (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F),

² J _{F, B} = 23.3 Hz; -167.2 qq (BF ₂ , 2F), ¹ J _F , _B = 51.1 Hz, ⁴ J _F , _F = 5.1 Hz

B.

A cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and an armature of a magnetic stirrer is filled with potassium trifluoropentafluoroethyl borate, K [F ₂ F ₅ BF ₃ ] (15.8 g, 69.9 mmol). Trimethylsilyl cyanide (35.0 ml, 262.5 mmol) is added in a shielding gas atmosphere. The reaction mixture was stirred at 100 ° C for 1 hour, and the formed trimethylsilyl fluoride was continuously distilled off. All volatile components are then removed in vacuo. Most of the unreacted trimethylsilyl cyanide (21.3 ml, 159.9 mmol) was recovered by fractional distillation. The residue was dissolved in THF (5 ml), and colorless potassium cyanodifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₂ (CN)], precipitated by adding CH ₂ Cl ₂ (200 ml), then was filtered and dried in vacuo. Yield, calculated on the potassium trifluoropentafluoroethyl borate used: 15.8 g (67.8 mmol, 97%). ¹¹ B and ¹⁹ F NMR spectra correspond to the values indicated in Example 5, A.

Elemental analysis: found,%, C 15.24, N 5.78; calculated for C ₃ BF ₇ KN,%, C 15.47, N 6.01.

C.

In a dry box, finely ground together K [C ₂ F ₅ BF ₃ ] (100 mg, 0.44 mmol), LiCI (180 mg, 4.2 mmol) and KCN (260 mg, 3.99 mmol), and introduced into a cylindrical reaction vessel with a glass faucet and PTFE rod (Young, London). The reaction mixture was heated at 180 ° C for 20 hours in vacuo.

¹¹ B-NMR spectroscopic analysis showed that the reaction mixture contains the following borate anions:

Anion δ ( ¹¹ B) [ppm] Content in% [C ₂ F ₅ BF ₂ (CN) ^- -2.8 82 [BF ₂ (CN) ₂ ] ^- -7.3 5 [BF (CN) ₃ ] ^- -17.8 four unknown -20.5 one [B (CN) ₄ ] ^- -38.5 6

Example 6. Potassium Dicyanofluoropentafluoroethylborate - K [C ₂ F ₅ BF (CN) ₂ ]

A.

Potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (1.0 g, 4.4 mmol), was dissolved in trimethylsilyl cyanide (10.0 ml, 74.9 mmol) in an argon atmosphere in a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and an anchor magnetic stirrer. The reaction mixture was stirred at 110 ° C for 1 hour, and the resulting trimethylsilyl fluoride was continuously distilled off. The reaction mixture was then stirred at 180 ° C for 10 intervals of about 30 minutes each, cooled, and most of the formed trimethyl silt fluoride was removed. All volatile components were then removed in vacuo. Most of the unreacted trimethylsilyl cyanide (7.1 ml, 53.0 mmol) was purified by fractional distillation. The residue was dissolved in THF (3 ml), and colorless K [C ₂ F ₅ BF (CN) ₂ ] was precipitated by adding CH ₂ Cl ₂ (100 ml). The salt is filtered off and dried in vacuo. Yield, calculated on the potassium trifluoropentafluoroethyl borate used: 0.97 g (4.0 mmol, 92%).

.Decomposition from 260 ° C; Raman spectroscopy:

.

¹¹ B-NMR: δ, ppm = - 12.0 dt (1B), ¹ J _F , _B = 51.6 Hz, ² J _F , _B = 25.2 Hz.

¹⁹ F-NMR: δ, ppm = - 82.6 dt (CF ₃ , 3F), ³ J _F , _F = 1.0 Hz, ⁴ J _F , _F = 6.3 Hz;

-132.0 qd (CF ₂ , 2F), ³ J _{F, F} = 5.0 Hz, ² J _F , _B = 25.3 Hz; -219.1 qqt (BF, 1F),

¹ J _{F, B} = 52 Hz, ³ J _F , _F = 5-6 Hz, ⁴ J _F , _F = 5-6 Hz.

B.

To potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (1.0 g, 4.4 mmol), in a cylindrical reaction vessel with a glass tap and a PTFE rod (Young, London) and an armature of a magnetic stir bar, trimethylsilyl cyanide (10.0 ml, 74.9 mmol). The reaction mixture was stirred at 150 ° C for 52 hours with regular evacuation. All volatile components are then removed in vacuo. Most of the unreacted trimethylsilyl cyanide (7.1 ml, 53.0 mmol) was recovered by fractional distillation. Colorless K [C ₂ F ₅ BF (CN) ₂ ] is precipitated from THF (3 ml) using CH ₂ Cl ₂ (100 ml), filtered and dried in vacuo. Yield, calculated on the potassium trifluoropentafluoroethyl borate used: 0.95 g (3.9 mmol, 90%). ¹¹ B and ¹⁹ F NMR spectra correspond to the values indicated in Example 6, A.

C.

microwave radiation 200 W, 15 min

Potassium trifluoropentafluoroethyl borate, K [C₂F₅Bf₃] (5.0 g, 22.1 mmol), weighed into a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and the armature of a magnetic stirrer. The flask was evacuated and trimethylsilyl cyanide (10.0 ml, 74.9 mmol) was condensed into it. The reaction mixture is irradiated in a microwave oven (CEM Discover) (200 W, T_max ⁼70 ° C) for 15 minutes All volatile components are removed in vacuo, and most of the unreacted trimethylsilyl cyanide (3.1 ml, 23.1 mmol) is recovered by fractional distillation. The residue is dissolved in 30% aqueousH ₂ O ₂ (200 ml), and the pH of the solution was adjusted to 1 by adding 37% hydrochloric acid with stirring. Then add N (C₃H₇)₃ (7.0 ml, 36.8 mmol). The mixture is extracted with CH₂Cl₂ (2 × 100 and 1 × 50 ml). The combined organic phases are dried using MgSO._four, filtered, and aqueous KOH solution (6 g, 30 ml) was added. The organic phase is decanted and a second portion of an aqueous KOH solution (10 g, 40 ml) is added and the mixture is stirred for one hour. The organic phase is then separated and the aqueous phase is extracted with Et₂O (3 × 100 ml). At each of the three stages of extraction, an additional amount of K is added to the aqueous phase.₂CO₃. The collected ether phases are dried using K₂CO₃, filtered and evaporated to dryness. The resulting residue was suspended in CH₂Cl₂ (50 ml), filtered and dried in vacuo. The yield of potassium dicyanofluoropentafluoroethyl borate, K [C₂F₅BF (CN)₂], is 3.4 g (14.3 mmol, 65%), calculated on the potassium trifluoropentafluoroethyl borate used.

¹¹ B and ¹⁹ F NMR spectra correspond to the values indicated in Example 6, A.

D.

microwave radiation 200 W, 15 min

To potassium trifluoropentafluoroethyl borate, K [C₂F₅Bf₃] (8.0 g, 35.4 mmol), trimethylsilyl cyanide (25.0 ml, 187.5 mmol) is added in a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and an armature of a magnetic stirrer in an argon atmosphere. The reaction mixture was stirred at room temperature for 3 days. The mixture is evacuated and then irradiated in a microwave oven (CEM Discover) (200 W, T_max= 78 ° C) for 15 minutes. All volatile components are removed in vacuo, and most of the unreacted trimethylsilyl cyanide (13.5 ml, 101.5 mmol) is recovered by fractional distillation. The residue is dissolved in 30%H ₂ O ₂ (20 ml) and add K₂CO₃ (5 g). The mixture was stirred at room temperature for 1 hour. The solution was evaporated to dryness at 70 ° C. on a rotary evaporator, and the resulting solid was extracted with Et₂O (7 × 50 ml). The combined organic phases are dried over K₂CO₃, filtered and evaporated to dryness. The residue was dissolved in acetone (5 ml). Colorless potassium dicyanofluoropentafluoroethyl borate, K [C₂F₅BF (CN)₂], obtained by adding CH₂Cl₂ (150 ml), filtered and dried in vacuo. Yield, calculated on the potassium trifluoropentafluoroethyl borate used: 7.8 g (32.5 mmol, 92%).

¹¹ B and ¹⁹ F NMR spectra correspond to the values indicated in Example 6, A.

EXAMPLE 7 Tritsianopentaftoretilborat potassium - K [C ₂ F _5, B (CN) _3]

microwave radiation 300 W, 60 min

Potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (0.5 g, 2.2 mmol), is weighed into a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and a magnetic stir bar anchor. The flask was closed and trimethylsilyl cyanide (10.0 ml, 74.9 mmol) was added under argon atmosphere. The reaction mixture was stirred at room temperature for 2 days and then irradiated in a microwave oven (CEM Discover) (300 W, T _max = 120 ° C, 60 min). All volatile components were removed in vacuo and most of the unreacted trimethylsilyl cyanide (6.9 ml, 52.0 mmol) was recovered by fractional distillation. The residue was dissolved in 30% aqueous H ₂ Og (10 ml), and K ₂ CO ₃ (2 g) was added. The mixture was stirred at room temperature for 1 hour. The solution was evaporated to dryness at 80 ° C using a rotary evaporator. The remaining solid is extracted with Et ₂ O (4 × 50 ml). The combined organic phases are dried using K ₂ CO ₃ , filtered and evaporated to a residual volume of 5 ml. A colorless precipitate was obtained by slowly adding CH ₂ Cl ₂ (150 ml). The colorless K [C ₂ F ₅ B (CN) ₃ ] is filtered off and dried in vacuo. Yield, calculated on the potassium trifluoropentafluoroethyl borate used: 480 mg (1.9 mmol, 88%).

.Decomposition from 350 ° C; Raman spectroscopy:

.

¹¹ B-NMR: δ, ppm = - 31.91 (1B), ² J _F , _B = 25.2 Hz.

¹⁹ F-NMR: δ, ppm = - 82.3 s (CF ₃ , 3F); -124.2 q (CF ₂ , 2F), ² J _F , _B = 25.2 Hz.

Elemental analysis: found,%, C 24.10, N 16.06; calculated for C ₅ BF ₅ KN ₃ ,%, C 24.32, N 17.01.

EXAMPLE 8 Potassium Tsianodiftorpentaftorfenilborat - K [C ₆ F ₅ BF ₂ (CN)]

Potassium trifluoropentafluorophenylborate, K [C ₆ F ₅ BF ₃ ] (2.5 g, 9.3 mmol), is weighed into a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and a magnetic stir bar anchor. Trimethylsilyl cyanide (10.0 ml, 74.9 mmol) was added under a protective gas atmosphere. The reaction mixture was stirred at room temperature for 7 days. All volatile components are removed in vacuo, and most of the unreacted trimethylsilyl cyanide (7.7 ml, 57.9 mmol) is recovered by fractional distillation. The residue was dissolved in acetone (5 ml). Colorless K [C ₆ F ₅ BF ₂ CN] precipitated by adding CHCl ₃ (25 ml). Yield, calculated on the potassium trifluoropentafluorophenylphenyl borate used: 2.1 g (7.5 mmol, 82%).

.Decomposition from 190 ° C; Raman spectroscopy:

.

¹¹ B-NMR: δ, ppm = - 1.3 t, ¹ J _{F, B} = 52 Hz.

¹⁹ F-NMR: δ, ppm = - 136.4 m (2F), -151.1 tq (2F, BF2), ¹ J _{B, F} = 52 Hz, ⁴ J _F , _F = 14 Hz; -161.91 (1F), ³ J _F , _F = 19 Hz; -167.2 m (2F).

Example 9. Potassium tricyanopentafluorophenylborate - K [C ₆ F ₅ B (CN) ₃ ]

A suspension of potassium trifluoropentafluorophenylphenyl borate, K [C ₆ F ₅ BF3] (2.0 g, 7.3 mmol), in trimethylsilyl cyanide (15.0 ml, 112.5 mmol) was introduced into a 50 ml two-necked flask with an arm of a magnetic stirrer and with a reflux condenser in a counter flow of argon. The reaction mixture was refluxed for 3 days, and all volatile components were distilled off, and most of the unreacted trimethylsilyl cyanide (10.8 ml, 81.1 mmol) was recovered by fractional distillation. The residue was taken up in THF (80 ml) with the addition of K ₂ CO ₃ and filtered. The filtrate was evaporated to a volume of 10 ml, and virtually colorless K [C ₆ F ₅ B (CN) ₃ ] precipitated by the slow addition of CHCl ₃ (100 ml). The precipitate was filtered and dried in vacuo. The yield of potassium tricyanopentafluorophenylphenyl borate, K [C ₆ F ₅ B (CN) ₃ ], is 1.7 g (5.9 mmol), 81% based on the potassium trifluoropentafluorophenyl phenate used. Decomposition from 280 ° C.

¹¹ B-NMR: δ, ppm = - 33.81t, ³ J _F , _B = 7 Hz.

¹⁹ F-NMR: δ, ppm = - 132.0 m (1F), -158.7 t (2F), ³ J _F , _F = 19 Hz; -165.4 m (2F).

Example 10. Cyanodifluorotrifluoromethyl borate tetra-n-butylammonium - [(n-C ₄ H ₉ ) ₄ N] [CF ₃ BF ₂ (CN)]

A.

Potassium cyanodifluorotrifluoromethyl borate, K [CF ₃ BF ₂ CN] (0.5 g, 2.7 mmol), obtained as described in Example 2, was dissolved in deionized water (20 ml), and an aqueous solution of [H-Bu ₄ N] was added slowly with stirring. Br (1.7 g, 5.4 mmol, 20 ml). The colorless precipitate formed is filtered off and dried in vacuo. The yield of tetra-n-butylammonium cyanodifluorotrifluoromethyl borate is 0.7 g (1.9 mmol), 67% in terms of the potassium cyanodifluorotrifluoromethyl borate used.

.Melting point: 73 ° C; Raman spectroscopy:

.

¹ H-NMR: δ, ppm = 1.0 t (4CH ₃ , 12 N), ³ J _{H, .H} = 7 Hz; 1.4 m (4CH ₂ , 8 H), ³ J _{H, H} = 7 Hz, 1.7-1.8 m (4CH ₂ , 8 N); 3.3-3.5 m, (4CH ₂ , 8 N).

¹³ C { ¹ H}-NMR (cation): δ, ppm = 59.3 s (4 C), 24.3 s (4 C), 20.2 s (4 C), 13.7 s (4 C).

¹¹ B-NMR: δ, ppm = - 3.8 tq (1B), ¹ J _{F, B} = 49.0 Hz, ² J _F , _B = 34.5 Hz.

¹⁹ F-NMR: δ, ppm = - 77.4 q (CF ₃ , 3F), ² J _F , _B = 34.5 Hz; -169.1 q (BF ₂ , 2F), ¹ J _F , _B = 49.3r4

Elemental analysis: found,%, C 57.19, H 9.36, N 7.44; calculated for C ₁₈ H ₃₆ BF ₅ N ₂ ,%, C 55.97, H 9.39, N 7.25.

B.

Sodium cyanide (13.1 g, 267.3 mmol) and sodium iodide (3.8 g, 25.4 mmol) are dried at 130 ° C in vacuum for 4 hours in a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and an armature of a magnetic stirrer. Then acetonitrile (15 ml) and trimethylsilyl chloride (30.0 ml, 25.8 g, 237.5 mmol) are added.

The suspension is stirred at 50 ° C for 24 hours and at room temperature for 3 days. K [CF₃Bf₃] (0.5 g, 2.8 mmol) is then added in a counter flow of argon, and the reaction mixture is stirred at 50 ° C for 24 hours and then at 80 ° C for 4 days. All volatile components are removed at room temperature in vacuo. Trimethylsilyl cyanide (28.2 ml, 211.2 mmol) is isolated as a by-product from the condensed phase by fractional distillation and used in further reactions. The solid residue obtained is taken up in deionized water (15 ml). 30% waterH ₂ O ₂ (25 ml) and K₂ CO ₃ add to the resulting solution with stirring, and the mixture is stirred for one hour. The solution was evaporated to dryness in vacuo, and the residue was extracted with acetone (3 × 50 ml). Deionized water (30 ml) was added to the combined organic phases, and acetone was removed in vacuo. Clean [n-Bu_fourN] [CF₃Bf₂(CN)] is obtained by adding a solution of [n-Bu_fourN] Br (1.0 g, 3.1 mmol) in deionized water (20 ml). The yield of tetra-n-butylammonium cyanodifluorotrifluoromethyl borate is 0.9 g (2.4 mmol), 86% in terms of the potassium cyanodifluorotrifluoromethyl borate used.

¹ H and ¹³ C NMR spectra correspond to the values indicated in Example 10, A.

Example 11. 1-Ethyl-3-methylimidazolium cyanodifluorotrifluoromethylborate - [C ₆ H ₁₁ N ₂ ] [CF ₃ BF ₂ (CN)]

K [CF ₃ BF ₂ (CN)] (5.9 g, 32.5 mmol) obtained as described in Example 2 was added with vigorous stirring to a solution of 1-ethyl-3-methylimidazolium chloride, [EMIM] Cl (5.0 g, 34.1 mmol) in deionized water (20 ml), and the mixture was stirred for 10 minutes. The aqueous phase is then separated from the ionic liquid using a pipette, washed with bidistilled water (4 × 5 ml) and dried at 50 ° C in high vacuum. The yield of liquid 1-ethyl-3-methylimidazolium cyanodifluorotrifluoromethyl borate is 5.7 g (22.4 mmol), 69% in terms of the potassium cyanodifluorotrifluoromethyl borate used. Melting point: 13 ° C. Water content (Karl Fischer titration): 40 ppm Dynamic viscosity (20 ° С): 16.5 MPa · s, (40 ° С): 10.3 MPa-s, (60 ° С) 6.9 MPa · s, (80 ° С) 5.0 MPa · s.

¹ H-NMR: δ, ppm = 1.5t (CH ₃ , 3H), ³ J _{H, .H} = 7 Hz; 4.0 s (CH ₃ , 3H); 4.3 q (CH ₂ , 2H), ³ J _{H, H} = 7 Hz; 7.6 m (CH, 1H); 7.7 m (CH, 1H); 8.9 br.s (CH, 1H).

¹³ C { ¹ H}-NMR (cation): δ, ppm = 136.8 s (1 C), 124.6 s (1 C), 122.9 s (1 C),

45.6 s (1 C), 36.5 s (1 C), 15.4 s (1 C).

¹¹ B-NMR: δ, ppm = - 3.8 tq (1B), ¹ J _{F, B} = 49.0 Hz, ² J _{F, B} = 34.5 Hz.

¹⁹ F-NMR: δ, ppm = - 77.4 q (CF ₃ , 3F), ² J _{F, B} = 34.5 Hz; -169.1 q (BF ₂ , 2F), ¹ J _{F, B} = 49.3 Hz

Example 12. 1-Ethyl-2,3-dimethylimidazolium cyanodifluorotrifluoromethylborate - [C ₇ H ₁₃ N ₂ ] [CF ₃ BF ₂ (CN)]

Potassium cyanodifluorotrifluoromethyl borate K [CF ₃ BF ₂ (CN)] (8.0 g, 43.7 mmol) was added to deionized water (5 ml) and a solution of 1-ethyl-2,3-dimethylimidazolium chloride [EDMIM] Cl (7.7 g, 47.9 mmol) in 10 ml of deionized water. The obtained ionic liquid was washed with deionized water (4 × 2 ml), separated and dried at 50 ° C in vacuo for 2 days. The yield of 1-ethyl-2,3-dimethyl imidazolium cyanodifluorotrifluoromethyl borate is 11.2 g (39.4 mmol), 90% based on the potassium cyanodifluorotrifluoromethyl borate K used [CF ₃ BF ₂ (CN)]. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; chloride: 28 ppm, fluoride: 236 ppm Water content (Karl Fischer titration): 57 ppm Dynamic viscosity (20 ° C): 51.6 MPa · s.

Raman spectroscopy:

¹ H-NMR: δ, ppm = 7.59 d (CH, 1H), ³ J _{H, .H} = 2.15 Hz; 7.53 d (CH, 1H), ³ J _H , _H = 2.15 Hz; 4.31 q (CH ₂ , 2H), ³ J _{H, H} = 7.30 Hz; 3.89 s (CH ₃ , 3H); 2.72 s (CH ₃ , 3H); 1.45t (CH ₃ , 3H), ³ J _{H, H} = 7.30 Hz.

¹³ C { ¹ H}-NMR (cation): δ, ppm = 145.37 s (C _t , 1C); 123.34 s (CH, 1C); 121.24 s (CH, 1C); 44.30 s (CH ₂ , 1C); 35.39 s (CH ₃ , 1C); 15.21 s (CH ₃ , 1C); 9.55 s (CH ₃ , 1C).

¹¹ B-NMR: δ, ppm = - 3.8 tq (1B), ¹ J _F , _B = 49.0 Hz, ² J _{F, B} = 34.5 Hz.

¹⁹ F-NMR: δ, ppm = - 77.4 q (CF ₃ , 3F), ² J _F , _B = 34.5 Hz; -169.1 q (BF ₂ , 2F), ¹ J _F , _B = 49.3 Hz

Elemental analysis: found,%, C 40.10, H 4.93, N 16.20; calculated for C ₇ H ₁₃ BF ₅ N ₃ ,%, C 40.18, H 4.87, N 15.62.

Example 13. Cyanodifluorotrifluoromethyl borate tetraphenylphosphonium -

Potassium trifluorotrifluoromethyl borate, K [CF ₃ BF ₃ ] (0.3 g, 1.7 mmol), is introduced into the cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and an armature of a magnetic stirrer. Trimethylsilyl cyanide (5.0 ml, 37.5 mmol) was added under argon atmosphere. The reaction mixture was stirred at room temperature for 24 hours. All volatile components are removed in vacuo, and most of the unreacted trimethylsilyl cyanide (4.3 ml, 32.3 mmol) is recovered by fractional distillation. The residue was dissolved in deionized water (10 ml) and precipitated using [Ph ₄ P] Br (1.2 g, 2.8 mmol) dissolved in deionized water (20 ml), filtered and dried in vacuo. Yield of tetraphenylphosphonium cyanodifluorotrifluoromethyl borate: 0.8 g (1.7 mmol), 97% based on the potassium trifluorotrifluoromethyl borate used, K [CF ₃ BF ₃ ].

Melting point: 219 ° C.

¹ H-NMR: δ, ppm = 7.80-7.92 m (4C ₆ H ₅ , 16 H); 7.97-8.05 m (4C ₆ H ₅ , 4 H).

¹³ C { ¹ H} -NMR (cation): δ, ppm = 136.3 s (4 C), 135.6 d (8 C), J _{C, P} = 10 Hz, 131.3 d (8 C), J _{C , P} = 13 Hz, 118.9 d (4 C), J _{C, P} = 91 Hz.

¹¹ B-NMR: δ, ppm = - 3.8 tq (1 V), ¹ J _F , _B = 49.0 Hz, ² J _{F, B} = 34.5 Hz.

¹⁹ F-NMR: δ, ppm = - 77.4 q (CF ₃ , 3F), ² J _{F, B} = 34.5 Hz; -169.1 q (BF ₂ , 2F), ¹ J _{F, B} = 49.3r4

Elemental analysis: found,%, C 64.22, H 4.65, N 2.91; calculated for C ₂ 6H ₂ oBF ₅ NP,%, C 64.62, H 4.17, N 2.90.

Example 14. N-butyl-N-methylpyrrolidinium cyanodifluorotrifluoromethylborate - [C ₉ H ₂₀ N] [CF ₃ BF ₂ (CN)]

.K [CF ₃ BF ₂ (CN)] (220 mg, 1.2 mmol) obtained as described in Example 2 was dissolved in deionized water (5 ml), and 1-butyl-1-methylpyrrolidinium chloride (250 mg, 1.4 mmol). The formed ionic liquid was extracted with CH2CI2 (2 × 10 ml). The dichloromethane solution was dried using MgSO ₄ , filtered, and CH ₂ Cl _{2 was} removed using a rotary evaporator. The yield of N-butyl-N-methylpyrrolidinium cyanodifluorotrifluoromethyl borate, which is a liquid at room temperature, is 293 mg (1.0 mmol), 85% based on the potassium cyanodifluorotrifluoromethyl borate used, K [CF ₃ BF ₂ (CN)]. Raman spectroscopy:

.

¹ H-NMR: δ, ppm = 3.68-3.75 m (2CH ₂ , 4H), 3.51-3.57 m (CH ₂ , 2H), 2.82 s (CH ₃ , 3H), 2.28-2.36 m (2CH ₂ , 4H), 1.86-1.95 m (CH ₂ , 2H), 1.44 m (CH ₂ , 2 N), ³ J _h .h = 7 Hz; 0.98 t (CH ₃ , 3H), ³ J _h .h = 7 Hz.

¹³ C { ¹ H} -NMR (cation): 6, ppm = 65.21 (2C); 65.01 (1C); 49.01 (1C); 26.2 s (1C); 22.3 s (2C); 20.3 s (1C); 13.7 s (1C).

¹¹ B-NMR: δ, ppm = - 3.8 tq (1B), ¹ J _F , _B = 49.0 Hz, ² J _F , _B = 34.5 Hz.

¹⁹ F-NMR: δ, ppm = - 77.4 q (CF ₃ , 3F), ² J _F , _B = 34.5 Hz; -169.1 q (BF _2, 2F), ¹ J _{F, a} = 49.3 Hz

Example 15. Tetraphenylphosphonium dicyanofluorotrifluoromethyl borate - [(C ₆ H ₅ ) ₄ P] [CF ₃ BF (CN) ₂ ]

The finely ground potassium cyanide (30.1 g, 462.2 mmol) and potassium iodide (6.1 g, 36.7 mmol) are dried at 115 ° C in vacuo for 5 hours in a 100 ml flask with a magnetic stirrer and reflux condenser. Then trimethylsilyl chloride (32.0 ml, 27.4 g, 252.2 mmol) was added and the reaction mixture was heated under reflux for 24 hours (60-80 ° C; bath temperature). Elemental iodine (1.0 g, 3.9 mmol) is then added in a counter flow of argon, and the mixture is heated at 110 ° C until reflux ceases. K [CF ₃ BF ₃ ] (1.6 g, 9.1 mmol) was added at room temperature, and the reaction mixture was heated under reflux for 48 hours. All volatile components are then removed at 100 ° C in vacuo, and K ₂ CO ₃ (2 g) is added to the resulting residue, and then extracted with THF (4 x 50 ml). An aqueous solution of potassium hydroxide (1.0 g, 17.8 mmol, 150 ml) was added to the combined THF phases. THF is separated at 70 ° C using a rotary evaporator. An aqueous solution of [Ph ₄ P] Br (4.5 g, 10.7 mmol, 100 ml) was slowly added to the reaction mixture. The colorless precipitate was filtered off, taken up in acetone (150 ml) and celite was added. The mixture was filtered and the solution was evaporated to a volume of 5 ml using a rotary evaporator. Slow addition of diethyl ether (100 ml) resulted in the precipitation of colorless [Ph ₄ P] [CF ₃ BF (CN) ₂ ]. The yield of tetraphenylphosphonium dicyanofluorotrifluoromethyl borate is 2.5 g (5.1 mmol), 56%, based on the potassium trifluorotrifluoromethyl borate used, K [CF ₃ BF ₃ ].

.Melting point: 150 ° C; decomposition from 290 ° C. Raman spectroscopy:

.

¹ H-NMR: δ, ppm = 7.8-7.92 m (4C ₆ H ₅ , 16 N); 7.97-8.05 m (4C ₆ H ₅ , 4 N).

¹³ C { ¹ H}-NMR (cation): δ, ppm = 136.3 s (4 C), 135.6 d (8 C), J _{C, P} = 10 Hz ,, 131.3 d (8 C), J _{C, P} = 13 Hz, 118.9 d (4 C), J _{C, p} = 91 Hz.

¹¹ B-NMR: δ, ppm = - 12.8 dq (1 V), ¹ J _{F, B} = 49.3 Hz, ² J _{F, B} = 35.7 Hz.

¹⁹ F-NMR: δ, ppm = - 74.0 qd (CF ₃ , 3F), ² J _F , _B = 35.7 Hz, ³ J _F , _F = 8.3 Hz; -219.7 qq (BF, 1F), ¹ J _F , _B = 49.2 Hz, ³ J _F , _F = 8.0 Hz.

Example 16. 1-Ethyl-3-methylimidazolium dicyanofluorotrifluoromethyl borate - [C ₆ H ₁₁ N ₂ ] [CF ₃ BF (CN) ₂ ]

Potassium dicyanofluorotrifluoromethyl borate, K [CF ₃ BF (CN) ₂ ] (5.0 g, 26.3 mmol), obtained as described in Example 3, was dissolved in deionized water (15 ml), and a solution of 1-ethyl-3 chloride was added with vigorous stirring -methylimidazolium, [EMIM] Cl (3.8 g; 26.3 mmol), in deionized water (15 ml). The mixture is stirred for 10 minutes. The aqueous phase is then removed using a pipette, and the resulting colorless ionic liquid is washed with bidistilled water (4 × 5 ml) and then dried at 50 ° C in vacuo. The yield of liquid 1-ethyl-3-methylimidazolium dicyanofluorotrifluoromethyl borate is 5.5 g (21.1 mmol, 80%). Melting point: -29 ° C. Water content (Karl Fischer titration): 20 ppm Dynamic viscosity (20 ° C): 14.0 MPa · s, (40 ° C): 8.6 MPa · s, (60 ° C) 5.8 MPa · s, (80 ° C) 4.2 MPa · s.

¹ H-NMR: δ, ppm = 1.51 (CH ₃ , 3H), ³ J _{H, H} = 7 Hz; 4.0 s (CH ₃ , 3H); 4.3 q (CH ₂ , 2H), ³ J _{H, H} = 7 Hz; 7.6 m (CH, 1H); 7.7 m (CH, 1H); 8.9 br.s (CH, 1H).

¹³ C { ¹ H}-NMR (cation): δ, ppm = 136.8 s (1 C), 124.6 s (1 C), 122.9 s (1 C), 45.6 s (1 C), 36.5 s ( 1 C), 15.4 s (1 C).

¹¹ B-NMR: δ, ppm = - 12.8 dq (1 V), ¹ J _F , _B = 49.3 Hz, ² J _{F, B} = 35.7 Hz.

¹⁹ F-NMR: δ, ppm = - 74.0 qd (CF ₃ , 3F), ² J _{F, B} = 35.7 Hz, ³ J _F , _F = 8.3 Hz; -219.7 qq (BF, 1F), ¹ J _F , _B = 49.2 Hz, ³ J _{F. F} = 8.0 Hz

Example 17. 1-Ethyl-3-methylimidazolium cyanodifluoropentafluoroethyl borate - [C ₆ H ₁₁ N ₂ ] [C ₂ F ₅ BF ₂ (CN)]

A.

Potassium cyanodifluoropentafluoroethyl borate, K [C2F ₅ BF ₂ (CN)] (6.9 g, 29.6 mmol), prepared as described in Example 5, and 1-ethyl-3-methylimidazolium chloride, [EMIM] Cl (4.5 g, 30.7 mmol) are added to a mixture of CH ₂ CI ₂ (100 ml) and deionized water (20 ml) and stirred for 1 hour. The aqueous phase is then separated, and the organic phase is washed with deionized water (5 × 50 ml) until the test for chloride ions using AgNO ₃ becomes negative. The dichloromethane phase is dried using MgSO ₄ , filtered and evaporated at 60 ° C using a rotary evaporator. The resulting virtually colorless liquid was dried at 50 ° C in vacuo. The yield of liquid 1-ethyl-3-methylimidazolium cyanodifluoropentafluoroethyl borate liquid is 6.5 g (21.3 mmol), 72% based on the potassium cyanodifluoropentafluoroethyl borate used, K [C ₂ F ₅ BF ₂ (CN)]. Melting point: <-55 ° C; decomposition from 225 ° C. Dynamic viscosity (20 ° C): 17.6 MPa · s, (40 ° C): 10.8 MPa · s, (60 ° C) 7.2 MPa · s, (80 ° C) 5.2 MPa · S.

Raman spectroscopy:

¹ H-NMR: δ, ppm = 1.51 (CH ₃ , 3H), ³ J _{H, H} = 7 Hz; 4.0 s (CH ₃ , 3H); 4.3 q (CH ₂ , 2H), ³ J _{H, H} = 7 Hz; 7.6 m (CH, 1H); 7.7 m (CH, 1H); 8.9 br.s (CH, 1H).

¹³ C { ¹ H}-NMR (cation): δ, ppm = 136.8 s (1 C), 124.6 s (1 C), 122.9 s (1 C), 45.6 s (1 C), 36.5 s ( 1 C), 15.4 s (1 C).

¹¹ B-NMR: δ, ppm = - 2.7 tt (1 V), ¹ J _{F, B} = 51.0 Hz, ² J _{F, B} = 25.3 Hz

¹⁹F-NMR: δ, ppm = - 83.3 t (CF₃, 3F),^fourJ_F,_F= 5.2 Hz; -136.3 q (CF₂, 2F)²J_{F, b}= 23.3 Hz; -167.2 qq (BF₂, 2F),^oneJ_F,_B= 51.1 Hz,^fourJ_F,_F= 5.1 Hz

Elemental analysis: found,%, C35.44, H 3.50, N 13.81; calculated for C ₉ H ₁₁ BF ₇ N ₃ ,%, C 35.44, H 3.64, N 13.78.

B.

Potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (1.0 g, 4.42 mmol) and 1-ethyl-3-methylimidazolium chloride, [EMIM] Cl (650 mg, 4.43 mmol) are weighed into a 10 ml reaction vessel with a glass faucet and PTFE rod (Young, London) and magnetic stir bar. Deionized water (1 ml) was added and the reaction mixture was stirred for 15 minutes. The aqueous phase was separated, and the remaining ionic liquid was washed with deionized water (1 ml) and dried at 50 ° C in vacuo for 4 hours. Then, NaCN (660 mg, 13.46 mmol) and trimethylsilyl chloride, (CH ₃ ) ₃ SiCl (1.7 ml, 13.45 mmol) were added, and the reaction mixture was stirred at 60 ° C (oil bath temperature) for 10 hours. Volatiles were removed in vacuo, the resulting suspension was washed with deionized water (3x2 ml), and the clear ionic liquid was dried at 50 ° C in vacuo. The yield of liquid 1-ethyl-3-methylimidazolium cyanodifluoropentafluoroethyl borate at room temperature is 1.2 g (3.93 mmol), 89% based on the potassium trifluoropentafluoroethyl borate used, K [C ₂ F ₅ BF ₃ ]. The purity of the product is £ 98% according to ¹¹ B- and ¹⁹ F-NMR spectroscopic studies.

Example 18. 1-Ethyl-2,3-dimethylimidazolium cyanodifluoropentafluoroethyl borate - [C ₇ H ₁₃ N ₂ ] [C ₂ F5BF ₂ (CN)]

Potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] (4.2 g, 18.0 mmol) was added to deionized water (2 ml) and a solution of 1-ethyl-2,3-dimethylimidazolium chloride [EDMIM] Cl (3.2 g) was added. , 19.9 mmol) in 3 ml of deionized water. The resulting ionic liquid was washed with deionized water (4 × 2 ml), separated and dried at 50 ° C in vacuo. The yield of 1-ethyl-2,3-dimethylimidazolium cyanodifluoropentafluoroethyl borate, which is liquid at room temperature, is 5.1 g (15.9 mmol), 88% based on the potassium cyanodifluoropentafluoroethylborate K used [C ₂ F ₅ BF ₂ (CN)]. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; chloride: 7 ppm, bromide: 16 ppm, fluoride: 14 ppm Water content (Karl Fischer titration): 161 ppm Dynamic viscosity (20 ° C): 47.2 MPa · s.

Raman spectroscopy: v (CN) = 2209 cm ^-1

¹ H-NMR: δ, ppm = 7.60 d (CH, 1H), ³ J _{H, H} = 2.15 Hz; 7.55 d (CH, 1H), ³ J _{H, H} = 2.15 Hz; 4.32 q (CH ₂ , 2H), ³ J _{H, H} = 7.30 Hz; 3.90 s (CH ₃ , 3H); 2.75 s (CH ₃ , 3H); 1.461 (CH ₃ , 3H), ³ J _{H, H} = 7.30 Hz.

¹³ C { ¹ H} -NMR (cation): δ, ppm = 145.32 s (C _tert , 1C); 123.30 s (CH, 1C); 121.19 s (CH, 1C); 44.20 s (CH ₂ , 1C); 35.35 s (CH ₃ , 1C); 15.07 s (CH ₃ , 1C); 9.46 s (CH ₃ , 1C).

¹¹ B-NMR: δ, ppm = - 2.7 tt (1 B), ¹ J _{F, B} = 51.0 Hz, ² J _F , _B = 25.3 Hz.

¹⁹ F-NMR: δ, ppm = - 83.31 (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _F , v = 23.3 Hz; -167.2 qq (BF ₂ , 2F), ¹ J _{F, B} = 51.1 Hz, ⁴ J _F , _F = 5.1 Hz

Elemental analysis: found,%, C 37.57, H 3.84, N 13.10; calculated for C ₁₀ H ₁₃ BF ₇ N ₃ ,%, C 37.65, H 4.11, N 13.17.

Example 19. 1-Butyl-3-methylimidazolium cyanodifluoropentafluoroethyl borate - [C ₈ H ₁₅ N ₂ ] [C ₂ F ₅ BF ₂ (CN)]

Potassium cyanodifluoropentafluoroethyl borate K [C2FsBF ₂ (CN)] (4.0 g, 17.1 mmol) obtained as described in Example 5 was dissolved in deionized water (2 ml) and a solution of 1-butyl-3-methylimidazolium chloride [BMIM] Cl was added (3.4 g, 19.4 mmol) in 3 ml of deionized water. The resulting ionic liquid was washed with deionized water (4 × 2 ml), separated and dried at 50 ° C in vacuo. The yield of 1-butyl-3-methylimidazolium cyanodifluoropentafluoroethyl borate,

which is liquid at room temperature, is 5.2 g (15.6 mmol), 91% based on the potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] used. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; chloride: <5 ppm, bromide: 5 ppm, fluoride: 22 ppm Water content (Karl Fischer titration): 25 ppm Dynamic viscosity (20 ° C): 27.4 MPa · s.

Raman spectroscopy:

¹ H-NMR: δ, ppm = 8.95 d, d (CH, 1H) ⁴ J _{H, H} ≈ 1.6 Hz; 7.69 d, d (CH, 1H), ³ J _{H, H} ≈ 4J _{H, H} ≈ 1.7 Hz; 7.65 d, d (CH, 1H) ³ J _{H, H} ≈ ⁴ J _{H, H} ≈ 1.7 Hz; 4.341 (CH ₂ , 2H), J _{H, H} = 7.33 Hz; 4.02 s (CH ₃ , 3H); 1.92 m (CH ₂ , 2 N); 1.39 m (CH ₂ , 2H); 0.92 t (CH ₃ , 3H), J _h , h = 7.37 Hz.

¹³ C { ¹ H} -NMR (cation): δ, ppm = 137.40 s (CH, 1C); 124.86 s (CH, 1C); 123.47 s (CH, 1C); 50.30 s (CH ₂ , 1C); 36.68 s (CH _3, 1C); 32.59 s (CH ₂ , 1C); 19.98 s (CH ₂ , 1C); 13.50 s (CH ₃ , 1C).

¹¹ B-NMR: δ, ppm = - 2.7 tt (1 B), ¹ J _F , _B = 51.0 Hz, ² J _F , _B = 25.3 Hz.

¹⁹ F-NMR: δ, ppm = - 83.31 (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _{F, B} = 23.3 Hz; -167.2 qq (BF ₂ , 2F), 'j _{F, B} = 51.1 Hz, ⁴ J _{F, F} = 5.1 Hz.

Elemental analysis: found,%, C 39.60, H 4.56, N 12.64; calculated for C ₁₁ H ₁₅ BF ₇ N ₃ ,%, C 39.67, H 4.54, N 12.62.

Example 20. 1- (2-Methoxyethyl) -3-methylimidazolium cyanodifluoropentafluoroethyl borate - [C ₇ H ₁₃ N ₂ O] [C ₂ F ₅ BF ₂ (CN)]

A solution of 1- (2-methoxyethyl) -3-methylimidazolium bromide [MOEMIM] Br (4.7 g, 21.2 mmol) in 3 ml of deionized water is added to a solution of potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] (4.5 g, 19.3 mmol) in 2 ml of deionized water. The resulting ionic liquid was washed with deionized water (4 × 2 ml), separated and dried at 60 ° C in vacuo. The yield of 1-methoxyethyl-3-methylimidazolium cyanodifluoropentafluoroethyl borate is 5.7 g (17.0 mmol), 88% based on the potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] used. The product is analyzed using ion. chromatography, it is characterized by low levels of halide contamination; bromide: <5 ppm, chloride: <5 ppm, fluoride: 23 ppm Water content (Karl Fischer titration): 215 ppm Dynamic viscosity (20 ° C): 27.1 MPa · s.

Raman spectroscopy: v (CN) = 2210 cm ^-1

¹ H-NMR: δ, ppm = 8.95 d, d (CH, 1H), ⁴ J _{H, H} ≈ 1.7 Hz; 7.68 d, d (CH, 1H), ³ J _H , _H ≈ ⁴ J _{H, H} ≈ 1.7 Hz; 7.67 d, d (CH, 1H), ³ J _{H, H} ≈ ⁴ J _{H, H} ≈ 1.7 Hz; 4.51 m (CH ₂ , 2H); 4.09 s (CH ₃ , 3H); 3.82 m (CH ₂ , 2H); 3.34 s (CH ₃ , 3H).

¹³ C { ¹ H} -NMR (cation): δ, ppm = 137.69 s (CH, 1C); 124.43 s (CH, 1C); 123.88 s (CH, 1C); 70.68 s (CH ₂ , 1C); 58.83 s (CH ₃ , 1C); 50.42 s (CH ₂ , 1C); 36.61 s (CH ₃ , 1C).

¹¹ B-NMR: δ, ppm = - 2.7 tt (1 V), ¹ J _{F, B} = 51.0 Hz, ² J _F , _B = 25.3 Hz.

¹⁹ F-NMR: δ, ppm = - 83.3 t (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _{F, B} = 23.3 Hz; -167.2 qq (BF ₂ , 2F), ¹ J _F , _B = 51.1 Hz, ⁴ J _{F, F} = 5.1 Hz.

Elemental analysis: found,%, C 35.13, H 4.03, N 12.58; calculated for C ₁₀ H ₁₃ BF ₇ N ₃₀ ,%, C 35.85, H 3.91, N 12.54.

Example 21. Cyanodifluoropentafluoroethyl borate tetra-n-butylammonium - [(n-C ₄ H ₉ ) ₄ N] [C ₂ F ₅ BF ₂ (CN)]

A.

Potassium trifluoropentafluoroethyl borate, K [C ₂ FsBF ₃ ] (1.0 g, 4.4 mmol), is weighed into a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London). The flask was evacuated and a mixture of trimethylsilyl cyanide (25.0 ml, 187.5 mmol) and acetonitrile (6 ml) was added in an argon counter stream. In a counter flow of argon, a reflux condenser was added and the reaction mixture was irradiated in a microwave oven (CEM Discover) (100 W, T _max = 75 ° C) for 10 minutes. All volatile components are removed in vacuo, and most of the unreacted trimethylsilyl cyanide (21.5 ml, 161.1 mmol) is recovered by fractional distillation. The residue was dissolved in deionized water (10 ml). The virtually colorless [n-Bu ₄ N] [C ₂ FsBF ₂ CN] is precipitated by adding an aqueous solution of [n-Bu ₄ N] Br (2.5 g; 7.8 mmol) in deionized water (20 ml). The yield of tetra-n-butylammonium cyanodifluoropentafluoroethyl borate is 1.8 g (4.1 mmol), 93% based on the potassium trifluoropentafluoroethyl borate used, K [C ₂ F ₅ BF ₃ ]. Melting point: 80 ° C; decomposition from 250 ° C.

¹ H-NMR: δ, ppm = 1.01 (4CH ₃ , 12 N), ³ J _{H, H} = 7 Hz; 1.4 m (4CH ₂ , 8 N), ³ J _{H, H} = 7 Hz, 1.7-1.8 m (4CH ₂ , 8 N); 3.3-3.5 m, (4CH ₂ , 8 N).

¹³ C { ¹ H} -NMR (cation): δ, ppm = 59.3 s (4 C), 24.3 s (4 C), 20.2 s (4 C), 13.7 s (4 C).

¹¹ B-NMR: δ, ppm = - 2.7 tt (1 V), ¹ J _{F, B} = 51.0 Hz, ² J _{F, B} = 25.3 Hz.

¹⁹ F-NMR: δ, ppm = - 83.3 t (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _{F, B} = 23.3 Hz; -167.2 qq (BF ₂ , 2F), ¹ J _F , _B = 51.1 Hz, ⁴ J _F , _F = 5.1 Hz.

B.

Potassium cyanodifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₂ CN] (0.5 g, 2.1 mmol), prepared as described in Example 5, was dissolved in deionized water (50 ml), and an aqueous solution of [n-Bu ₄ N was added with stirring. ] Br (1.4 g, 4.3 mmol, 100 ml). After 15 minutes, the colorless precipitate was filtered off and dried in vacuo. The yield of tetra-n-butylammonium cyanodifluoropentafluoroethyl borate is 0.84 g (1.9 mmol), 90% based on the potassium cyanodifluoropentafluoroethyl borate used, K [C ₂ F ₅ BF ₂ CN]. ¹ H and ¹³ C NMR spectra correspond to the values indicated in Example 21, A.

Example 22. Tributylmethylammonium cyanodifluoropentafluoroethyl borate - [(C ₄ H ₉ ) ₃ CH ₃ N] [C ₂ F ₅ BF ₂ (CN)]

Tributyl methyl ammonium chloride [(C ₄ H ₉ ) ₃ CH ₃ N] Cl (4.3 g, 18.2 mmol) dissolved in 4 ml of deionized water was added to an aqueous solution (4 ml) of potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN )] (3.8 g, 16.3 mmol). The formed ionic liquid is washed with deionized water (4 × 2 ml), separated and dried at 60 ° C in vacuo. The yield of tributylmethylammonium cyanodifluoropentafluoroethyl borate is 5.7 g (14.4 mmol), 88% based on the potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] used. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; chloride: 14 ppm, bromide: 9, fluoride: 19 ppm Water content (Karl Fischer titration): 142 ppm Dynamic viscosity (20 ° C): 216.7 MPa · s.

Raman spectroscopy:

¹ H-NMR: δ, ppm = 3.38 m (3CH ₂ , 6H); 3.10 s (CH ₃ , 3H); 1.78 m (3CH ₂ , 6H); 1.39 m (3CH ₂ , 6H); 0.951 (CH ₃ , 9H), ³ J _H , _H = 7.39 Hz.

¹³ C { ¹ H} -NMR (cation): δ, ppm = 62.31 s (CH ₂ , 3C); 48.69 s (CH ₃ , 1C); 24.63 s (CH ₂ , 3C); 20.15 s (CH ₂ , 3C); 13.65 s (CH ₃ , 3C).

¹¹ B-NMR: δ, ppm = - 2.7 tt (1), ¹ J _{F> B} = 51.0 Hz, ² J _FlB = 25.3 Hz..

¹⁹ F-NMR: δ, ppm = - 83.3 t (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _{F, B} = 23.3 Hz; -167.2 qq (BF ₂ , 2F), ¹ J _F , _B = 51.1 Hz, ⁴ J _F , _F = 5.1 Hz

Elemental analysis: found,%, C 48.79, H 7.81, N 7.21; calcd for C ₁₆ H ₃₀ BF ₇ N2,%, C 48.75, H 7.67, N 7.11.

Example 23. N-Butyl-M-methylpyrrolidinium cyanodifluoropentafluoroethyl borate - [C ₉ H ₂₀ N] [C ₂ F ₅ BF ₂ (CN)]

A. Each of potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF2 (CN)] (4.2 g, 18.0 mmol) and N-butyl-N-methylpyrrolidinium chloride [BMPL] Cl (3.5 g, 19.6 mmol) are dissolved in 2 ml of deionized water . The solutions were combined and the resulting ionic liquid was washed with deionized water (4 × 2 ml). The colorless liquid was dried at 60 ° C in vacuo. The yield of N-butyl-N-methylpyrrolidinium cyanodifluoropentafluoroethyl borate, which is liquid at room temperature, is 5.9 g (17.5 mmol), 97% based on the potassium cyanodifluoropentafluoroethyl borate K used [C ₂ F ₅ BF ₂ (CN)]. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; chloride: 8 ppm, bromide: 6 ppm, fluoride: 29 ppm Water content (Karl Fischer titration): 21 ppm Dynamic viscosity (20 ° C): 43.2 MPa · s.

Raman spectroscopy:

¹ H-NMR: δ = 3.59 m (2CH ₂ , 4H); 3.42 m (CH ₂ , 2H); 2.79 s (CH ₃ , 3H); 2.30 m (2CH ₂ , 4H); 1.85 m (CH ₂ , 2H); 1.40 m (CH ₂ , 2H); 0.97 ppm t (CH ₃ , 3H), ³ J _H , _{H =} 7.37 Hz.

¹³ C { ¹ H} (cation): δ = 65.10 s (CH ₂ , 2C); 64.89 s (CH ₂ , 1C); 48.92 s (CH ₃ , 1C); 26.11 s (CH ₂ , 1C); 22.20 s (CH ₂ , 2C); 20.21 s (CH ₂ , 1C); 13.51 s (CH ₃ , 1C)

¹¹ B-NMR: δ, ppm = - 2.7 tt (1B), ¹ J _{F, B} = 51.0 Hz, ² J _{F, B} = 25.3 Hz.

¹⁹ F-NMR: δ, ppm = - 83.31 (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _{F, B} = 23.3 Hz; -167.2 qq (BF ₂ , 2F), ¹ J _F , _B = 51.1 R4, ⁴ J _F , _F = 5.1 Hz.

Elemental analysis: found,%, C 42.90, H 5.99, N 8.32; calculated for C ₁₂ H ₂₀ BF ₇ N ₂ ,%, C 42.88, H 6.00, N 8.33.

B.

Potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (1.0 g, 4.4 mmol), and N-butyl-N-methylpyrrolidinium chloride [BMPL] Cl (865 mg, 4.9 mmol) are added together in deionized water (1 ml). The suspension is stirred for 15 minutes. The aqueous phase is then removed, and the remaining ionic liquid is washed with deionized water (1 ml). The ionic liquid is dried at 50 ° C in vacuo for 2 hours. Then, NaCN (660 mg, 13.5 mmol) was added and the suspension was dried at 50 ° C. in vacuo for 15 minutes. Then trimethylsilyl chloride (1.7 ml, 13.5 mmol) was added and the reaction mixture was stirred at 60 ° C. for 24 hours. Volatiles were removed in vacuo and the remaining suspension was taken up in acetone (10 ml), filtered (D4) and the acetone phase was evaporated in vacuo. Yield: 1.2 g (3.6 mmol, 81%).

¹ H, ¹⁹ F and ¹¹ B NMR spectra correspond to the values indicated in Example 23, A.

Example 24. Cyanodifluoropentafluoroethyl borate tetraphenylphosphonium - [(C ₅ H ₆ ) ₄ P] [C ₂ F ₅ BF ₂ (CN)]

Potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (495 mg, 2.2 mmol), is weighed into a cylindrical reaction vessel with a glass faucet and a PTFE rod (Young, London) and a magnetic stir bar anchor. Trimethylsilyl cyanide (7.0 ml; 52.5 mmol) is condensed in it in an argon atmosphere. The reaction mixture was stirred at 100 ° C for 5 hours. All volatile components are then removed in vacuo. Most of the unreacted trimethylsilyl cyanide (6.1 ml, 45.7 mmol) was recovered by fractional distillation. The residue was dissolved in deionized water (15 ml), and [Ph ₄ P] Br (1.3 g; 3.1 mmol) dissolved in deionized water (150 ml) was added. The precipitate was filtered off and dried in vacuo. The yield of solid colorless tetraphenylphosphonium cyanodifluoropentafluoroethyl borate is

.1.1 g (2.0 mmol), 93% based on the potassium trifluoropentafluoroethyl borate used, KJC2F5BF3]. Melting point: 130 ° C; decomposition from 310 ° C. Raman spectroscopy:

.

¹ H-NMR: δ, ppm = 7.8-7.92 m (4C ₆ H ₅ , 16 N); 7.97-8.05 m (4C ₆ H ₅ , 4 N).

¹³ C { ¹ H}-NMR (cation): δ, ppm = 136.3 s (4 C), 135.6 d (8 C), J _{C, P} = 10 Hz ,, 131.3 d (8 C), J _{C, P} = 13 Hz, 118.9 d (4 C), J _{C, P} = 91 Hz.

¹¹ B-NMR: δ, ppm = - 2.7 tt (1 V), ¹ J _{F, B} = 51.0 Hz, ² J _{F, B} = 25.3 Hz.

¹⁹ F-NMR: δ, ppm = - 83.31 (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _{F, B} = 23.3 Hz; -167.2 qq (BF ₂ , 2F), ¹ J _F , _B = 51.1 Hz, ⁴ J _{F, F} = 5.1 Hz.

Example 25. Tributylmethylphosphonium cyanodifluoropentafluoroethyl borate - [(C ₄ H9) ₃ CH ₃ P] [C ₂ P ₅ BF ₂ (CN)]

Potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] (2.6 g, 11.1 mmol) is dissolved in 2 ml of deionized water and tributyl methylphosphonium trifluoroacetate solution [(C ₄ H ₉ ) ₃ CH ₃ P ] [CP ₃ CO ₂ ] is added. (3.7 g, 11.1 mmol) in 3 ml of deionized water. The ionic liquid is washed with deionized water (4 × 2 ml), separated and dried at 50 ° C in vacuo. The yield of tributylmethylphosphonium cyanodifluoropentafluoroethyl borate is 4.0 g (9.7 mmol), 87% based on the potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] used. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; chloride: 8 ppm, fluoride: 8 ppm Water content (Karl Fischer titration): 129 lph

Raman spectroscopy:

¹ H-NMR: δ, ppm = 2.37 m (3CH ₂ , 6H); 2.00 d (CH ₃ , 3H), ² J _P , _H = 13.8 Hz; 1.67 m (3CH ₂ , 6H); 1.50 m (3CH ₂ , 6H); 0.94 t (3CH ₃ , 9H), ³ J _{H, H} = 7.37 Hz.

¹³ C { ¹ H} -NMR (cation): δ, ppm = 24.48 d (3CH ₂ , 3C), ³ J _{P, C} = 16.01 Hz; 23.90 d (3CH ₂ , 3C) ² J _{P, C} = 4.53 Hz; 20.53 d (3CH ₂ , 3C), ¹ J _{P, C} = 49.74 Hz; 13.55 d (3CH3, 3C), ⁴ J _{P, C} = 0.85 Hz; 4.08 d (CH ₃ , 1C), ¹ J _P , _C = 52.88 Hz.

¹¹ B-NMR: δ, ppm = - 2.7 tt (1 V), ¹ J _F , _B = 51.0 Hz, ² J _{F. B} = 25.3 Hz.

¹⁹ F-NMR: δ, ppm = - 83.31 (CF ₃ , 3F), ⁴ J _{F, F} = 5.2 Hz; -136.3 q (CF ₂₎ 2F), ² J _F , _B = 23.3 Hz; -167.2 qq (BF ₂ , 2F), ¹ J _{F, B} = 51.1 Hz, ⁴ J _F , _F = 5.1 Hz.

³¹ P { ¹ H}-NMR: δ, ppm = 32.2 s.

Elemental analysis: found,%, C 46.61, H 7.46, N 3.38; calculated for C ₁₆ H ₃₀ BF ₇ N _P ,%, C 46.74, H 7.35, N 3.41.

Example 26. Diethyl methylsulfonium cyanodifluoropentafluoroethyl borate - [(C ₂ H ₅ ) 2CH ₃ S] [C ₂ F ₅ BF ₂ (CN)]

Potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] (5.2 g, 22.3 mmol), prepared as described in Example 5, was dissolved in deionized water (2 ml), and an aqueous solution of diethyl methyl sulfonyl trifluoromethyl sulfonate (6.3 g, 24.8 mmol, 3 ml). The formed ionic liquid is washed with deionized water (6 × 2 ml) and then dried at room temperature in high vacuum for 12 hours and then at 60 ° C for 24 hours. The yield of diethylmethylsulfonium cyanodifluoropentafluoroethyl borate is 5.5 g (18.4 mmol), 82% based on the potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] used. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; bromide: <5 ppm, chloride: <5 ppm, fluoride: 31 ppm Water content (Karl Fischer titration): 94 ppm Dynamic viscosity (20 ° C): 22.2 MPa-s.

Raman spectroscopy:

¹ H-NMR: δ, ppm = 3.48 m (2CH ₂ , 4H); 3.02 s (CH ₃ , 3H); 1.52 t (2CH ₃ , 6H), ³ J _{H, H} = 7.44 Hz.

¹³ C { ¹ H} -NMR (cation): δ, ppm = 35.98 s (2CH ₂ , 2C); 21.42 s (CH ₃ , 1C); 8.75 s (2CH ₃ , 2C).

¹¹ B-NMR: δ, ppm = - 2.7 tt (1 V), ¹ J _F , _B = 51.0 Hz, ² J _F , _B = 25.3 Hz.

¹⁹ F-NMR: δ, ppm = - 83.3 t (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _{F, B} = 23.3 Hz; -167.2 qq (BF ₂ , 2F), ¹ J _F , _B = 51.1 Hz, ⁴ J _F , _F = 5.1 Hz.

Elemental analysis: found,%, C 32.14, H 4.30, N 4.87, S 10.71; calculated for C ₈ H ₁₃ BF ₇ NS,%, C 32.13, H 4.38, N 4.68, S 10.72.

Example 27. Cyano-difluoropentafluoroethyl borate S-3rnn-N, N, N ', N'-tetramethylisothiuronium - [{(CH ₃ ) ₂ N} ₂ CSC ₂ H ₅ ] [C ₂ F ₅ BF ₂ (CN)]

Potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] (6.0 g, 25.7 mmol) is dissolved in 10 ml of deionized water, and a solution of S-ethyl-N, N, N ', N'-tetramethylisothiuronium iodide is added with stirring [ {(CH ₃ ) ₂ N} ₂ CSC ₂ Hs] I (8.2 g, 28.4 mmol) in 10 ml of deionized water. The resulting black liquid was separated, washed with deionized water (4 × 2 ml) and then dried at room temperature in vacuo for 3 days. The crude product was dissolved in CH ₂ Cl ₂ (100 ml) and stirred slowly with activated carbon (5 g) for 12 hours. The mixture was filtered and dichloromethane was removed using a rotary evaporator. The amber-colored ionic liquid is dried at 50 ° C in high vacuum for 2 days. The yield of 5-ethyl-N, N, N ′, N′-tetramethylisothiuronium cyanodifluoropentafluoroethyl borate is 7.2 g (20.2 mmol), 78% based on the potassium cyanodifluoropentafluoroethyl borate K used [C ₂ F ₅ BF ₂ (CN)]. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; chloride: 12 ppm; fluoride: 121 ppm Water content (Karl Fischer titration): 20 ppm Dynamic viscosity (20 ° C): 40.2 MPa-s.

Raman spectroscopy:

¹ H-NMR: δ, ppm = 3.45 s (4CH ₃₎ 12H); 3.20 q (CH ₂ , 2H), ³ J _{H, .H} = 7.39 Hz; 1.38 t (CH ₃ , 3H), ³ J _{H, H} = 7.39 Hz.

¹³ C { ¹ H} -NMR (cation): δ, ppm = 176.58 s (C = S, 1C); 44.19 s (4CH ₃ , 4C); 29.62 s (CH ₂ , 1C); 14.98 s (CH ₃ , 1C).

¹¹ B-NMR: δ, ppm = - 2.7 tt (1 V), ¹ J _F , _B = 51.0 Hz, ² J _{F, B} = 25.3 Hz.

¹⁹ F-NMR: δ, ppm = - 83.31 (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _{F, B} = 23.3 Hz; -167.2 qq (BF ₂ , 2F), ¹ J _F , _B = 51.1 r4, ⁴ J _F , _F = 5.1 Hz.

Elemental analysis: found,%, C 33.91, H 4.82, N 12.35, S 9.73; calculated for C ₁₀ H ₁₇ BF ₇ N ₃ S,%, C 33.82, H 4.83, N 11.83, S 9.03.

Example 28. Tetraphenylphosphonium dicyanofluoropentafluoroethyl borate - [(C ₅ H ₆ ) ₄ P] [C ₂ F ₅ BF (CN) ₂ ]

A solution of potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (50 mg, 0.22 mmol) in trimethylsilyl cyanide (0.7 ml, 5.2 mmol) is heated sequentially at 70 ° C for 7 hours, at 100 ° C for 5 hours, at 125 ° C for 7.5 hours, at 140 ° C for 5 hours, and then at 150 ° C for 72 hours in an NMR tube with a glass tap and a PTFE rod (Young, London). The solution was evaporated in vacuo and the residue was taken up in an alkaline aqueous solution (0.1 g KOH, 10 ml), and [PruPJBr (0.5 g, 1.2 mmol) dissolved in deionized water (50 ml) was added dropwise. The colorless precipitate formed is filtered off and dried in vacuo. The yield of tetraphenylphosphonium dicyanofluoropentafluoroethyl borate is 85 mg (0.16 mmol), 73% based on the potassium trifluoropentafluoroethyl borate used, K [C ₂ F ₅ BF ₃ ]. Melting point: 103 ° C.

¹ H-NMR: δ, ppm = 7.8-7.92 m (4C ₆ H ₅ , 16 N); 7.97-8.05 m (4C ₆ H ₅ , 4 N).

¹³ C { ¹ H}-NMR (cation): δ, ppm = 136.3 s (4 C), 135.6 d (8 C), J _{C, P} = 10 Hz ,, 131.3 d (8 C), J _{C, P} = 13 Hz, 118.9 d (4 C), J _{C, P} = 91 Hz.

¹¹ B-NMR: δ, ppm = - 12.0 d, t (1 V), ¹ J _{F, B} = 51.6 Hz, ² J _F , _B = 25.2 Hz.

¹⁹ F-NMR: δ, ppm = - 82.6 d, t (CF ₃ , 3F), ³ J _F , _F = 1.0 Hz, ⁴ J _F , _F = 6.3 Hz; -132.0 q, d (CF ₂ , 2F), ³ J _F , _F = 5.0 Hz, ² J _F , _B = 25.3 Hz; -219.1 qqt (BF, 1F), ¹ J _F , _B = 52 Hz, ³ J _F , _F = 5-6 Hz, ⁴ J _F , _F = 5-6 Hz.

Example 29. 1-Ethyl-3-methylimidazolium dicyanofluoropentafluoroethyl borate - [C ₆ H ₁₁ N ₂ ] [C ₂ F ₅ BF (CN) ₂ ]

Potassium dicyanofluoropentafluoroethyl borate, K [C ₂ FsBF (CN) ₂ ] (7.0 g, 29.2 mmol), prepared as described in Example 6, and 1-ethyl-3-methylimidazolium chloride, [EMIM] Cl (5.0 g, 34.1 mmol) , add to bidistilled water (15 ml) and mix. The aqueous phase is then separated, the ionic liquid is washed with bidistilled water (4 × 5 ml), separated and then dried at 50 ° C in high vacuum. The yield of virtually colorless liquid 1-ethyl-3-methylimidazolium dicyanofluoropentafluoroethyl borate liquid is 6.4 g (20.5 mmol), 70% in terms of the potassium dicyanofluoropentafluoroethyl borate used, K [C ₂ F ₅ BF (CN) ₂ ]. Melting point: -48 ° C. Water content (Karl Fischer titration): 6 ppm Dynamic viscosity (20 ° C): 16.4 MPa · s, (40 ° C): 9.8 MPa · s, (60 ° C) 6.5 MPa · s, (80 ° C) 4.6 MPa · s.

¹ H-NMR: δ, ppm = 1.51 (CH ₃ , 3H), ³ J _{H, .H} = 7 Hz; 4.0 s (CH ₃ , 3H); 4.3 q (CH ₂ , 2H), ³ J _{H, H} = 7 Hz; 7.63 s (CH, 1H); 7.70 s (CH, 1H); 8.9 s (CH, 1H).

¹³ C { ¹ H}-NMR (cation): δ, ppm = 136.8 s (1 C), 124.6 s (1 C), 122.9 s (1 C), 45.6 s (1 C), 36.5 s ( 1 C), 15.4 s (1 C).

¹¹ B-NMR: δ, ppm = - 12.0 d, t (1 V), ¹ J _{F, B} = 51.6 Hz, ² J _{F, B} = 25.2 Hz.

¹⁹ P-NMR: δ, ppm = - 82.6 d, t (CF ₃ , 3F), ³ J _F , _F = 1.0 Hz, ⁴ J _{F, F} = 6.3 Hz; -132.0 qd (CF ₂ , 2F), ³ J _F , _F = 5.0 Hz, ² J _F , _B = 25.3 Hz; -219.1 qqt (BF, 1F), ¹ J _F , _B = 52 Hz, ³ J _F , _F = 5-6 Hz, ⁴ J _{F, F} = 5-6 Hz.

Example 30. 1-Butyl-3-methylimidazolium dicyanofluoropentafluoroethyl borate - [C ₈ H ₁₅ N ₂ ] [C ₂ F ₅ BF (CN) ₂ ]

Each of potassium dicyanofluoropentafluoroethyl borate K [C ₂ F ₅ BF (CN) ₂ ] (5.0 g, 20.8 mmol), prepared as described in Example 6, and 1-butyl-3-methylimidazolium chloride [BMIM] Cl (4.0 g, 22.9 mmol) is dissolved in 2 ml of deionized water. The two solutions are combined, and the formed ionic liquid is separated and then washed with deionized water (4 × 2 ml) and separated. The resulting practically colorless liquid is dried at 60 ° C. in vacuo. The yield of 1-butyl-3-methyl imidazolium dicyanofluoropentafluoroethyl borate is 6.5 g (19.1 mmol), 92% based on the potassium dicyanofluoropentafluoroethyl borate K [C ₂ F ₅ BF (CN) ₂ ] used. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; chloride: 10 ppm; fluoride: 6 ppm Water content (Karl Fischer titration): 154 ppm Dynamic viscosity (20 ° C): 25.1 mPa · s.

Raman spectroscopy:

¹ H-NMR: δ, ppm = 8.96 d, d (CH, 1H), ⁴ J _{H, H} ≈ 1.6 Hz; 7.70 dd (CH, 1H), ³ J _{H, H} ≈ ⁴ Jh.h * 1.7 Hz; 7.65 d, d (CH, 1H) ³ J _{H, .H} ≈ ⁴ J _{H, H} ≈1.7 Hz; 4.33 t (CH ₂ , 2H), J _{H, H} = 7.33 Hz; 4.03 s (CH ₃ , 3H); 1.92 m (CH ₂ , 2 N); 1.40 m (CH ₂ , 2H); 0.94 t (CH ₃ , 3H), J _{H, H} = 7.37 Hz.

¹³ C { ¹ H} -NMR (cation): δ, ppm = 137.40 s (CH, 1C); 124.86 s (CH, 1C); 123.47 s (CH, 1C); 50.30 s (CH ₂ , 1C); 36.68 s (CH ₃ , 1C); 32.59 s (CH ₂ , 1C); 19.98 s (CH ₂ , 1C); 13.50 s (CH ₃ , 1C).

¹¹ B-NMR: δ, ppm = - 12.0 d, t (1 V), ¹ J _F , _B = 51.6 Hz, ² J _F , _B = 25.2 Hz.

¹⁹ F-NMR: δ, ppm = - 82.6 dt (CF ₃ , 3F), ³ J _{F, F} = 1.0 Hz, ⁴ J _F , _F = 6.3 Hz; -132.0 q, d (CF ₂ , 2F), ³ J _F , _F = 5.0 Hz, ² J _F , _B = 25.3 Hz; -219.1 qqt (BF, 1F), ¹ J _F , _B = 52 Hz, ³ J _F , _F = 5-6 Hz, ⁴ J _F , _F = 5-6 Hz.

Elemental analysis: found,%, C 42.66, H 4.39, N 16.50; calculated for C ₁₂ H ₁₅ BF ₆ N ₄ ,%, C 42.38, H 4.45, N 16.47.

Example 31. 1-Methoxyethyl-3-methylimidazolium dicyanofluoropenta-fluoroethyl borate - [C7H ₁₃ N ₂ O] [C ₂ F ₅ BF (CN) ₂ ]

Each of potassium dicyanofluoropentafluoroethyl borate K [C ₂ F ₅ BF (CN) ₂ ] (5.1 g, 21.2 mmol) obtained as described in Example 6 and 1-methoxyethyl-3-methylimidazolium bromide [MOEMIM] Br (5.1 g, 23.0 mmol) is dissolved in 2 ml of deionized water. The two solutions are combined, and the resulting ionic liquid is separated and then washed with deionized water (4 × 2 ml). The resulting virtually colorless liquid was dried at 60 ° C in vacuo. The yield of 1-methoxyethyl-3-methylimidazolium dicyanofluoropentafluoroethyl borate is 6.9 g (20.1 mmol), 95% based on the potassium dicyanofluoropentafluoroethyl borate K [C ₂ F ₅ BF (CN) ₂ ] used. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; bromide: <5 ppm, chloride: <5 ppm, fluoride: <5 ppm Water content (Karl Fischer titration): 114 ppm Dynamic viscosity (20 ° C): 25.5 MPa · s.

Raman spectroscopy:

¹ H-NMR: δ, ppm = 8.94 d, d (CH, 1H), ⁴ J _{H, H} ≈1.7 Hz; 7.68 d, d (CH, 1H), ³ J _{H, H} ≈ 4J _{H, H} ≈ 1.7 Hz; 7.64 d, d (CH, 1H), ³ J _{H, H} ≈ ⁴ J _{H, H} ≈ 1.7 Hz; 4.49 m (CH ₂ , 2H); 4.04 s (CH ₃ , 3H); 3.79 m (CH ₂ , 2H); 3.33 s (CH ₃ , 3H).

¹³ C { ¹ H} -NMR (cation): δ, ppm = 137.67 d (CH, 1C); 124.42 s (CH, 1C); 123.86 s (CH, 1C); 70.65 s (CH ₂ , 1C); 58.79 s (CH ₃ , 1C); 50.38 s (CH ₂ , 1C); 36.58 s (CH ₃ , 1C)

¹¹ B-NMR: δ, ppm = - 12.0 d, t (1 V), ¹ J _{F, B} = 51.6 Hz, ² J _{F, B} = 25.2 Hz.

¹⁹ F-NMR: δ, ppm = - 82.6 d, t (CF ₃ , 3F), ³ J _{F, F} = 1.0 Hz, ⁴ J _F , _F = 6.3 Hz; -132.0 qd (CF ₂ , 2F), ³ J _F , _F = 5.0 Hz, ² J _{F, B} = 25.3 Hz; -219.1 qqt (BF, 1F), ¹ J _F , _B = 52 Hz, ³ J _{F, F} = 5-6 Hz, ⁴ J _{F, F} = 5-6 Hz.

Elemental analysis: found,%, C 38.86, H 3.82, N 16.43; calculated for C ₁₁ H ₁₃ BF ₆ ON ₄ ,%, C 38.63, H 3.83, N 16.38.

Example 32. Dicyanofluoropentafluoroethyl borate tetra-n-butylammonium - [(n-C ₄ H ₉ ) ₄ N] [C ₂ F ₅ BF (CN) ₂ ]

Potassium dicyanofluoropentafluoroethyl borate, K [C ₂ F ₅ BF (CN) ₂ ] (500 mg, 2.1 mmol), prepared as described in Example 6, was dissolved in deionized water (10 ml), and a solution of [H-Bu ₄ N] was added. Br (0.8 g; 2.5 mmol) in deionized water (20 ml). The fine precipitate formed is extracted with CH ₂ Cl ₂ (2 × 30 ml). The combined organic phases are dried using MgSO ₄ , filtered, and the solvent is removed using a rotary evaporator. The yield of tetra-n-butylammonium dicyanofluoropentafluoroethyl borate is 658 mg (1.5 mmol), 71% in terms of the potassium dicyanofluoropentafluoroethyl borate used, K [C ₂ F ₅ BF (CN) ₂ ]. Melting point: 52 ° C.

.Raman spectroscopy:

.

¹ H-NMR: δ, ppm = 1.0 t (4CH ₃ , 12 N), ³ J _H , _H = 7 Hz; 1.4 m (4CH ₂ , 8 N), ³ J _H , _H = 7 Hz, 1.7-1.8 m (4CH ₂ , 8 N); 3.3-3.5 m, (4CH ₂ , 8 N).

¹³ C { ¹ H} -NMR (cation): δ, ppm = 59.3 s (4 C), 24.3 s (4 C), 20.2 s (4 C), 13.7 s (4 C).

¹¹ B-NMR: δ, ppm = - 12.0 dt (1 V), ¹ J _{F, B} = 51.6 Hz, ² J _{F, B} = 25.2 Hz.

¹⁹ F-NMR: δ, ppm = - 82.6 dt (CF ₃ , 3F), ³ J _F , _F = 1.0 Hz, ⁴ J _{F, F} = 6.3 Hz; -132.0 qd (CF ₂ , 2F), ³ J _{F, F} = 5.0 Hz, ² J _{F, B} = 25.3 Hz; -219.1 q, q, t (BF, 1F), ¹ J _{F, B} = 52 Hz, ³ J _F , _F = 5-6 Hz, ⁴ J _F , _F = 5-6 Hz.

Example 33. N-6ymn-N-methylpyrrolidinium dicyanofluoropentafluoroethyl borate - [C ₉ H ₂₀ N] [C ₂ F ₅ BF (CN) ₂ ]

Each of potassium dicyanofluoropentafluoroethyl borate K [C ₂ F ₅ BF (CN) ₂ ] (5.0 g, 20.8 mmol) obtained as described in Example 6 and N-butyl-N-methylpyrrolidinium chloride [BMPL] Cl (4.1 g, 23.0 mmol) is dissolved in 2 ml of deionized water. The two solutions are combined, and the resulting ionic liquid is separated and then washed with deionized water (4 × 2 ml). The resulting colorless liquid was dried at 60 ° C in vacuo. The yield of N-butyl-N-methylpyrrolidinium dicyanofluoropentafluoroethyl borate is 6.6 g (19.2 mmol), 92% based on the potassium dicyanofluoropentafluoroethyl borate K [C ₂ F ₅ BF (CN) ₂ ] used. The product is analyzed by ion chromatography; it is characterized by low levels of halide contamination; bromide: <5 ppm, chloride: 10 ppm, fluoride: <5 ppm Water content (Karl Fischer titration): 191 ppm Dynamic viscosity (20 ° C): 38.5 MPa-s.

Raman spectroscopy:

¹ H-NMR: δ = 3.67 m (2CH ₂ , 4H); 3.50 m (CH ₂ , 2 N); 2.82 s (CH ₃ , 3 N), 2.30 m (2CH ₂ , 4 N); 1.88 m (CH ₂ , 2H); 1.44 m (CH ₂ , 2 N); 0.98 t (CH ₃ , 3H), ³ J _{H, H} = 7.37 Hz.

¹³ C { ¹ H}-NMR (cation): δ = 65.20 s (2CH ₂ , 2C); 65.00 s (CH ₂ , 1C); 48.98 s (CH ₃ , 1C); 26.17 s (CH ₂ , 1C); 22.23 s (2CH ₂ , 2C); 20.30 s (CH ₂ , 1C); 13.64 s (CH ₃ , 1C).

¹¹ B-NMR: δ, ppm = - 12.0 d, t (1 V), ¹ J _{F, B} = 51.6 Hz, ² J _{F, B} = 25.2 Hz.

¹⁹ F-NMR: δ, ppm = - 82.6 dt (CF _3l 3F), ³ J _{F, F} = 1.0 Hz, ⁴ J _F , _F = 6.3 Hz; -132.0 qd (CF ₂ , 2F), ³ J _{F, F} = 5.0 Hz, ² J _{F, B} = 25.3 Hz; -219.1 qqt (BF, 1F), ¹ J _{F, B} = 52 Hz, ³ J _{F, F} = 5-6 r4, ⁴ J _{F, F} = 5-6 Hz.

Elemental analysis: found,%, C 45.86, H 5.99, N 12.27; calculated for C ₁₃ H ₂₀ BF ₆ N3,%, C 45.51, H 5.88, N 12.25.

Example 34. Tetraphenylphosphonium dicyanofluoropentafluorophenyl borate - [(C ₆ H ₅ ) ₄ P] [C ₆ F ₅ BF (CN) ₂ ]

Dry sodium cyanide (12.5 g, 255.1 mmol) and sodium iodide (3.8 g, 25.1 mmol) were initially introduced into a 100 ml wide-necked flask with a magnetic stirrer and reflux condenser. Acetonitrile (5 ml) and trimethylsilyl chloride (30 ml, 25.8 g, 237.5 mmol) are added in a counter flow of argon. After the suspension was heated under reflux for 4 days, K [C ₆ F ₅ BF ₃ ] (1.0 g, 3.6 mmol) was added and the mixture was heated under reflux for an additional 20 hours. All volatile components are then condensed in vacuo and the formed trimethylsilyl cyanide (26.9 ml, 201.8 mmol) is purified by fractional distillation. The solid residue is dissolved in deionized water (10 ml) with the addition of K ₂ CO ₃ . The resulting aqueous phase was extracted with THF (4 × 20 ml). The combined organic phases are dried using K ₂ CO ₃ and evaporated to dryness on a rotary evaporator at 50 ° C. The residue is dissolved in deionized water (20 ml) and an aqueous solution of [Ph ₄ P] Br (1.8 g, 4.3 mmol, 120 ml). The resulting suspension was extracted with CH ₂ Cl ₂ (3 × 20 ml). Impurities are precipitated by addition of Et ₂ 0 (50 ml) to the combined dichloromethane phases and filtered. The filtrate was concentrated a little and stored at 8 ° C for 4 days. The crystals formed are filtered off and dried in vacuo. Yield: 0.6 g (1.1 mmol, 30%).

The composition of the product relative to borate anions was determined using ^{11 V-} NMR spectroscopy as [C ₆ F ₅ BF (CN) ₂ ] ^- (80%), [C ₆ F ₅ B (CN) ₃ ] ^- (16%) and unknown compounds (4%).

¹ H-NMR: δ ppm = 7.8-7.92 m (4C ₆ H ₅ , 16 N); 7.97-8.05 m (4C ₆ H ₅ , 4 N).

¹³ C { ¹ H}-NMR (cation): δ, ppm = 136.3 s (4 C), 135.6 d (8 C), J _{C, P} = 10 Hz ,, 131.3 d (8 C), J _{C, P} = 13 Hz, 118.9 d (4 C), J _{C, P} = 91 Hz.

Example 35. 1-Ethyl-3-methylimidazolium tricyanotrifluoromethyl borate - [C ₆ H ₁₁ N ₂ ] [CF ₃ B (CN) ₃ ]

Potassium tricyanotrifluoromethyl borate K [CF ₃ B (CN) ₃ ] (96 mg, 0.48 mmol) was dissolved in deionized water (1 ml), and a solution of 1-ethyl-3-methylimidazolium chloride [EMIM] Cl (100 mg, 0.68 mmol) was added. in 1 ml of deionized water. The aqueous phase is separated, and the resulting ionic liquid is washed with deionized water (2 × 2 ml), separated and dried at 50 ° C in vacuo. The yield of 1-ethyl-3-methylimidazolium tricyanotrifluoromethylborate is 98 mg (0.39 mmol). This corresponds to a yield of 75% based on the potassium tricyanotrifluoromethylborate K [CF ₃ B (CN) ₃ ] used. The product is characterized by NMR spectroscopy.

¹ H-NMR: δ, ppm = 8.85 d, d (CH, 1H), ⁴ J _H , _H ≈ 1.7 Hz; 7.79 d, d (CH, 1H), ³ J _H , _H ≈ ⁴ Jh, h * 1.8 Hz; 7.66 d, d (CH, 1H) ³ J _{H, H} ≈ ⁴ J _{H, H} ≈ 1.7 Hz; 4.42 t (CH ₂ , 2H), J _{H, H} = 7.36 Hz; 4.07 s (CH ₃ , 3H); 1.57 t (CH ₃ , 3H), J _{H, H} = 7.40 Hz.

¹³ C { ¹ H} -NMR (cation): δ, ppm = 136.98 s (CH, 1C); 125.21 s (CH, 1C); 122.54 s (CH, 1C); 45.69 s (CH ₂ , 1C); 36.57 s (CH ₃ , 1C); 15.42 s (CH ₃ , 1C).

¹¹ B-NMR: δ, ppm = - 32.0 q (1 V), ² J _{F, B} = 36.3 Hz.

¹⁹ F-NMR: δ, ppm = - 66.4 q (CF ₃ , 3F), ² J _F , _B = 36.3 Hz.

Example 36. 1-Ethyl-3-methylimidazolium tricyanopentafluoroethyl borate - [C ₆ H ₁₁ N ₂ ] [C ₂ F ₅ B (CN) ₃ ]

Potassium tricyanopentafluoroethyl borate K [C ₂ F ₅ B (CN) ₃ ] (160 mg, 0.64 mmol) was dissolved in deionized water (1 ml) and a solution of 1-ethyl-3-methylimidazolium chloride [EMIM] Cl (120 mg, 0.81) was added. mmol) in 1 ml of deionized water. The aqueous phase is separated, and the resulting ionic liquid is washed with deionized water (2 × 2 ml), separated and dried at 50 ° C in vacuo. The yield of 1-ethyl-3-methyl imidazolium tricyanopentafluoroethyl borate is 180 mg (0.56 mmol). This corresponds to a yield of 87% based on the potassium tricyanopentafluoroethyl borate K used [C2F ₅ B (CN) ₃ ]) ₃ ]. The product is characterized by NMR spectroscopy.

¹ H-NMR: δ, ppm = 8.77 d, d (CH, 1H), ⁴ J _{H, H} ≈1.7 Hz; 7.71 d, d (CH, 1H), ³ J _{H, H} ≈ ⁴ J _{H, H} ≈ 1.8 Hz; 7.62 d, d (CH, 1H) ³ J _{H, H} ≈ ⁴ J _{H, H} ≈ 1.7 Hz; 4.371 (CH ₂ , 2H), J _{H, H =} 7.31 Hz; 4.02 s (CH ₃ , 3H); 1.501 (CH ₃ , 3H), J _{H, H} = 7.40 Hz.

¹³ C { ¹ H} -NMR (cation): δ, ppm = 136.48 s (CH, 1C); 125.02 s (CH, 1C); 122.34 s (CH, 1C); 45.51 s (CH ₂ , 1C); 36.51 s (CH ₃ , 1C); 15.38 s (CH ₃ , 1C).

¹¹ B-NMR: δ, ppm = - 31.9 t (1B), ² J _F , _B = 25.2 Hz.

¹⁹ F-NMR: δ, ppm = - 82.3 s (CF ₃ , 3F); -124.2 q (CF ₂ , 2F), ² J _{F, B} = 25.2 Hz.

Example 37. Lithium cyanodifluoropentafluoroethyl borate-Li [C ₂ F ₅ BF ₂ (CN)]

A solution of lithium tetrafluoroborate in acetonitrile (0.95 M, 4.52 ml, 4.29 mmol LiBF ₄ ) is added at room temperature to a solution of potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] (1.0 g, 4.29 mmol) in acetonitrile (3 ml) . The resulting suspension was filtered at 0 ° C, and the precipitate (KBF ₄ ) was washed with acetonitrile (0 ° C, 3 ml) and dried in vacuo. The filtrate was evaporated in vacuo and the residue was dried at 50 ° C in vacuo for 20 hours.

The yield of potassium tetrafluoroborate KBF ₄ is 0.53 g (4.20 mmol, 98%).

The yield of lithium cyanodifluoropentafluoroethyl borate Li [C ₂ F ₅ BF ₂ (CN)] is quantitative. The product is characterized by NMR spectra.

¹¹ B-NMR: δ, ppm = - 2.7 tt (1B), ¹ J _F , _B = 51.0 Hz, ² J _{F, B} = 25.3 Hz.

¹⁹ F-NMR: δ, ppm = - 83.3 t (CF ₃ , 3F), ⁴ J _F , _F = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _{F, B} = 23.3r4; -167.2 qq (BF ₂ , 2F), ¹ J _F , _B = 51.1 Hz, ⁴ J _F , _F = 5.1 Hz.

Example 38. Potassium Dicyanofluorophenyl Borate - K [C ₆ H ₅ BF (CN) ₂ ]

K [C ₆ H ₅ BF ₃ ] (0.5 g, 2.7 mmol) was suspended in trimethylsilyl cyanide, (10.0 ml, 74.9 mmol) and stirred at room temperature for 2 days. The resulting slightly yellow solution was evaporated to dryness and dissolved in acetone (3 ml). K [C ₆ H ₅ BF (CN) ₂ ] is precipitated by the addition of CHCl ₃ (150 ml), filtered and dried in vacuo. Yield: 520 mg (2.62 mmol, 97%).

¹¹ B-NMR (acetone-d ₆ ): δ = -8.22 (d, ¹ J ( ¹⁹ F, ¹¹ B) = 53.6 Hz, 1B) ppm.

¹⁹ F-NMR (acetone-d ₆ ): δ = -206.06 (d, ¹ J ( ¹⁹ F, ¹¹ B) 54.6, 1F) ppm

1 H NMR (acetone-d ₆ ): δ = 7.51 (m, Ph, 2H), 7.18 (m, Ph, 2H), 7.11 (m, Ph, 1H) ppm.

¹³ C { ¹ H}-NMR (acetone-d ₆ ): δ = 147.3 (m, BC _Ph , 1C), 133.38 (m, CN, 2C), 132.00 (s, Ph, 2C), 127.65 (s, Ph , 2C), 126.77 (s, Ph, 1C) ppm.

IR (cm ^-1 ): 3075, 3022, 2959, 2215, 1593, 1486, 1432, 1317, 1255, 1171, 1057, 1005, 997, 968, 925, 984, 871, 850, 755, 704, 654.

Raman spectroscopy (cm ^-1 ): 3057, 2214, 1592, 1029, 996, 875, 655, 622.

Claims (14)

1. The method of obtaining salts of the formula I
M ^{a +} [B (R _f ) (CN) _x (F) _y ] _a ^- I,
Where
M ^{a +} means a cation of silver, copper (I), copper (II) or an organic cation,
R _f means a linear or branched perfluorinated alkyl group containing from 1 to 4 C, C ₆ F ₅ , C ₆ H ₅ atoms, partially fluorinated phenyl or phenyl, which is mono- or disubstituted with a perfluoroalkyl group containing from 1 to 4 C atoms, where the perfluoroalkyl group is independently selected,
and means 1 or 2,
x means 1, 2 or 3,
y means 0, 1 or 2, where 0 is excluded in the case of R _f = C ₆ H ₅ , and
x + y = 3,
by reaction of an alkali metal salt of formula II
Me ⁺ [B (R _f ) F ₃ ] ^- II,
Where
Me ⁺ means a cation of lithium, potassium, sodium, cesium or rubidium and R _f has the meaning indicated above,
with trialkylsilyl cyanide to give a salt of formula III
Me ⁺ [B (R _f ) (CN) _x (F) _y ] ^- III,
where Me ⁺ , R _f , x and y have the meanings indicated above, and the alkyl group of the trialkylsilyl cyanide is in each case, independently of each other, a linear or branched alkyl group containing from 1 to 4 C atoms,
and the subsequent salt-exchange reaction of salts of formula III with a salt of formula IV
MA IV,
Where
M has the meaning indicated for M ^{a +} and
And choose from the group of anions:
F ^- , Cl ^- , Br ^- , I ^- , OH ^- , [HF ₂ ] ^- , [CN] ^- , [SCN] ^- , [R ₁ COO] ^- , [R ₁ SO ₃ ] ^- , [R ₂ COO ] ^- , [R ₂ SO ₃ ] ^- , [R ₁ OSO ₃ ] ^- , [SiF ₆ ] ^2- , [BF ₄ ] ^- , [SO ₄ ] ^2- , [HSO ₄ ] ^1- , [NO ₃ ] ^- , [(R ₁ ) ₂ P (O) O] ^- , [R ₁ P (O) O ₂ ] ^2- , [(R ₁ O) ₂ P (O) O] ^- , [(R ₁ O) P (O) O ₂ ] ^2- , [(R ₂ ) ₂ P (O) O] ^- , [R ₂ P (O) O ₂ ] ^2- , tosylate, benzoate, oxalate, succinate, suerate, ascorbate, sorbate , tartrate, citrate, malate, malonate, malonates, which are optionally substituted with alkyl groups containing from 1 to 4 C atoms, or [CO ₃ ] ^2- ,
where R ₁ in each case, independently of one another, means H and / or a linear or branched alkyl group containing from 1 to 12 C atoms,
R ₂ in each case, independently of one another, means a partially fluorinated or perfluorinated linear or branched alkyl group containing from 1 to 12 C atoms, or pentafluorophenyl, and where electroneutrality must be ensured in the MA salt formula. 2. The method according to claim 1 for the preparation of salts of formula I, which have anions of formula Ia
[B (R _f ) (CN) (F) ₂ ] ^- Ia,
characterized in that the reaction of the compound of formula II with trialkylsilyl cyanide is carried out at temperatures between 10 ° C and 110 ° C or under microwave irradiation with a power of 100 watts. 3. The method according to claim 1 for the preparation of salts of formula I which have anions of formula Ib
[B (R _f ) (CN) ₂ (F)] ^- Ib,
characterized in that the reaction of the compound of formula II with trialkylsilyl cyanide is carried out at temperatures between 115 and 200 ° C or under microwave irradiation with a power of 200 watts. 4. The method according to claim 1 for the preparation of salts of formula I which have anions of formula Ic
[B (R _f ) (CN) ₃ ] ^- Ic,
characterized in that the reaction of the compound of formula II with trialkylsilyl cyanide is carried out under microwave irradiation with a power of more than 200 W, where C ₆ H ₅ for R _{f is} excluded. 5. The method according to one or more of claims 1 to 4, characterized in that the trialkylsilyl cyanide is prepared in situ from alkali metal cyanide and trialkylsilyl chloride in the presence of alkali metal iodide and optionally iodine before the reaction with the compound of formula II. 6. The method according to one or more of claims 1 to 4, characterized in that after the reaction of the compound of formula II with trialkylsilyl cyanide, the volatile by-products are separated off, and the compound of formula III is further reacted without further purification with the compound of formula IV. 7. The method according to one or more of claims 1 to 4, characterized in that the compounds of formula I are obtained in which the organic cation M ^{a + is} selected from the group of cations of the following formulas (1) to (8):
[N (R) ₄ ] ⁺ (1), [S (R) ₃ ] ⁺ (2) or [O (R) ₃ ] ⁺ (3),
Where
R in each case, independently of one another, means
- H, where all the substituents R cannot simultaneously mean H,
- straight or branched chain alkyl containing 1-20 C atoms,
- straight chain or branched alkenyl containing 2-20 C atoms and one or more double bonds,
- straight or branched chain alkynyl containing 2-20 C atoms and one or more triple bonds,
- saturated, partially or completely unsaturated cycloalkyl containing 3-7 C atoms, which may be substituted by alkyl groups containing 1-6 C atoms,
where one or two R can be fully substituted and / or one or more R can be partially substituted with halogens or partially with -OR ¹ , -NR ^{1 *} ₂ , -CN, -C (O) NR ¹ ₂ or -SO ₂ NR ¹ ₂ and where one or two non-adjacent carbon atoms that are not located in the α-position of the radical R can be replaced by atoms and / or groups of atoms selected from the group —O—, —S—, —S (O) -, -SO ₂ -,
-N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ - or -P (O) R ¹ -; or
[P (R ² ) ₄ ] ⁺ (4),
Where
R ² in each case independently of one another, means
- H, NR ^{1 *} ₂ ,
- straight or branched chain alkyl containing 1-20 C atoms,
- straight chain or branched alkenyl containing 2-20 C atoms and one or more double bonds,
- straight or branched chain alkynyl containing 2-20 C atoms and one or more triple bonds,
- saturated, partially or completely unsaturated cycloalkyl containing 3-7 C atoms, which may be substituted by alkyl groups containing 1-6 C atoms,
where one or two R ² can be fully substituted and / or one or more R ² can be partially substituted with halogens or partially with -OR ¹ , -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ¹ ₂
and where one or two non-adjacent carbon atoms that are not located at the α-position of R ² can be replaced by atoms and / or groups of atoms selected from the group —O—, —S—, —S (O) -, - SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ - or -P (O) R ¹ -; or
[C (NR ³ R ⁴ ) (OR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (5),
or
[C (NR ³ R ⁴ ) (SR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (6),
Where
R ³ -R ⁷ each, independently of one another, means
- H, NR ^{1 *} ₂ ,
- straight or branched chain alkyl containing 1-20 C atoms,
- straight chain or branched alkenyl containing 2-20 C atoms and one or more double bonds,
- straight or branched chain alkynyl containing 2-20 C atoms and one or more triple bonds,
- saturated, partially or completely unsaturated cycloalkyl containing 3-7 C atoms, which may be substituted by alkyl groups containing 1-6 C atoms,
where one or more substituents R ³ -R ⁷ can be partially or completely substituted with halogens or partially with -OH, -OR ¹ , -CN, -C (O) NR ¹ ₂ ,
-SO ₂ NR ¹ ₂
and where one or two non-adjacent carbon atoms that are not located at the α-position of R ³ -R ⁷ can be replaced by atoms and / or groups of atoms selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ - or -P (O) R ¹ -; or
[C (NR ⁸ R ⁹ ) (NR ¹⁰ R ¹¹ ) (NR ¹² R ¹³ )] ⁺ (7),
Where
R ⁸ -R ¹³ each, independently of one another, means
- H, NR ^{1 *} ₂ ,
- straight or branched chain alkyl containing 1-20 C atoms,
- straight chain or branched alkenyl containing 2-20 C atoms and one or more double bonds,
- straight or branched chain alkynyl containing 2-20 C atoms and one or more triple bonds,
- saturated, partially or completely unsaturated cycloalkyl containing 3-7 C atoms, which may be substituted by alkyl groups containing 1-6 C atoms,
where one or more substituents R ⁸ -R ¹³ can be partially or completely substituted with halogens or partially with -OR ¹ , -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ¹ ₂
and where one or two non-adjacent carbon atoms that are not located at the α-position of R ⁸ -R ¹³ can be replaced by atoms and / or groups of atoms selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ - or -P (O) R ¹ -; or
[HetN] ⁺ (8),
where [HetN] ⁺ means a heterocyclic cation selected from the group including

where the substituents R ^{1 ′} -R ^{4 ′} each, independently of one another, mean
- H, with the restriction that R ^{1 ′} and R ^{4 ′} cannot simultaneously mean H,
- straight or branched chain alkyl containing 1-20 C atoms, which may be fluorinated or perfluorinated,
- straight chain or branched alkenyl containing 2-20 C atoms and one or more double bonds, which may also be fluorinated or perfluorinated,
- straight or branched chain alkynyl containing 2-20 C atoms and one or more triple bonds, which may also be fluorinated or perfluorinated,
- saturated, partially or completely unsaturated cycloalkyl containing 3-7 C atoms, which may be substituted by alkyl groups containing 1-6 C atoms,
- saturated, partially or completely unsaturated heteroaryl, heteroaryl-C ₁ -C ₆ -alkyl or aryl-C ₁ -C ₆ -alkyl, where the substituents R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and / or R ^{4 ′} together can form a ring system
where one or more substituents R ^{1 ′} -R ^{4 ′} can be partially or completely substituted with halogens or partially with -OR ¹ , -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ¹ ₂ , but where R ^{1 ′} And R ^{4 ′} cannot simultaneously be completely replaced by halogens, and where one or two non-adjacent carbon atoms that are not attached to the heteroatom of the substituents R ^{1 ′} -R ^{4 ′} can be replaced by atoms and / or groups of atoms selected from groups -O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ - or -P (O) R ¹ -;
where R ¹ means H, non-, partially or perfluorinated C ₁ -C ₆ -alkyl, C ₃ -C ₇ -cycloalkyl, unsubstituted or substituted phenyl and R ^{1 *} means non-, partially or perfluorinated C ₁ -C ₆ -alkyl , C ₃ -C ₇ cycloalkyl, unsubstituted or substituted phenyl. 8. The method of obtaining compounds of formula III
Me ⁺ [B (R _f ) (CN) _x (F) _y ] ^- III,
where Me ⁺ means a cation of lithium, potassium, sodium, cesium or rubidium, R _f means a linear or branched perfluorinated alkyl group containing from 1 to 4 C atoms, C ₆ F ₅ , C ₆ H ₅ , partially fluorinated phenyl or phenyl, which mono- or disubstituted with a perfluoroalkyl group containing from 1 to 4 C atoms, where the perfluoroalkyl group is independently selected,
x means 1, 2 or 3,
y means 0, 1 or 2, where 0 is excluded in the case of R _f = C ₆ H ₅ , and
x + y means 3,
by reaction of an alkali metal salt of formula II
Me ⁺ [B (R _f ) F ₃ ] ^- II,
Where
Me ⁺ and R _f have the above meanings, with a trialkylsilyl cyanide, where the alkyl group of the trialkylsilyl cyanide is, in each case, independently, a linear or branched alkyl group containing from 1 to 4 C. 9. The method according to claim 8, characterized in that the reaction for obtaining compounds of formula III, where x = 1, y = 2, is carried out at temperatures between 10 ° C and 110 ° C or under microwave irradiation with a power of 100 W, in that the reaction to obtain compounds of formula III, where x = 2 and y = 1, is carried out at temperatures between 115 and 200 ° C or under microwave irradiation with a power of 200 W, or by the fact that the reaction to obtain compounds of formula III, where x = 3 and y = 0, where C ₆ H ₅ for R _{f is} excluded, carried out under microwave irradiation with a power of more than 200 watts. 10. Salts selected from
lithium pentafluoroethyl dicyanofluoroborate,
lithium trifluoromethylmonocyanodifluoroborate,
lithium pentafluoroethyl monocyanodifluoroborate. 11. The electrolyte for the electrochemical cell, including lithium salts in accordance with paragraph 10. 12. The electrolyte in accordance with claim 11, comprising at least one carbonate-containing solvent. 13. An electrochemical cell containing lithium salts in accordance with clause 10 or an electrolyte in accordance with clause 11. 14. An electrochemical cell according to claim 13, characterized in that it is a lithium ion battery, a lithium ion capacitor, or a lithium battery.