EP2526107A1

EP2526107A1 - Method for producing perfluoroalkyl cyanoborates or perfluoroalkyl cyanofluoroborates

Info

Publication number: EP2526107A1
Application number: EP11700796A
Authority: EP
Inventors: Nikolai Ignatyev (Mykola); Michael Schulte; Jan Sprenger; Maik Finze; Walter Frank
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2010-01-18
Filing date: 2011-01-12
Publication date: 2012-11-28
Also published as: CN102712661A; JP2013517231A; US20150166588A1; WO2011085966A1; US8927757B2; US9175021B2; RU2012135091A; CN102712661B; JP5810097B2; KR20120131160A; US20120309981A1

Abstract

The invention relates to a method for producing salts having perfluoroalkyl tricyanoborate or perfluoroalkyl cyanofluoroborate anions, ((per)fluoro)phenyl tricyanoborate or ((per)fluoro)phenyl cyanofluoroborate anions, phenyl tricyanoborate anions monosubstituted or disubstituted by perfluoroalkyl groups having 1 to 4 C atoms or phenyl cyanofluoroborate anions monosubstituted or disubstituted by perfluoroalkyl groups having 1 to 4 C atoms by reacting alkali metal trifluoroperfluoraklyl borate and trialkylsilyl cyanide and a subsequent salt conversion reaction or by directly reacting an organic trifluoroperfluoroalkyl borate and trialkylsilyl cyanide.

Description

Process for the preparation of Perfluoralkylcyano- or Perfluoralkylcyanofluorboraten

The invention relates to a process for the preparation of salts with

Perfluoroalkyltricyano or perfluoroalkylcyanofluoroborate anions,

((Per) fluoro) phenyltricyano- or ((per) fluoro) phenylcyanofluoroborate anions, mono- or by perfluoroalkyl groups having 1 to 4 carbon atoms

disubstituted phenyltricyanoborate anions or mono- or disubstituted by Perfluoralkylgrupen with 1 to 4 carbon atoms

Phenylcyanofluorboratanionen by reaction of

Alkalimetalltrifluorperfluoralkylborat with trialkylsilyl cyanide and a subsequent Umsalzungsreaktion or by direct reaction of an organic Trifluorperfluoralkylborat.es with trialkylsilyl cyanide. Salts of the formula M ^{a +} [B (R _f ) 4. _x .y (CN) _x (F) _y ] _a , where M ^{a + can 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, but only the salts potassium tris (trifluoromethyl) cyanoborate,

Guanidinium tris (trifluoromethyl) cyanoborate and tritylium

Tris (trifluoromethyl) cyanoborate are disclosed. WO 2006/045405 describes that salts with organic cations and Anioneh the formula given are ionic liquids.

An ionic liquid is understood as meaning salts which as a rule consist of an organic cation and an inorganic anion. They contain no neutral molecules and usually have melting points of less than 373 K [Wasserscheid P, Keim W, 2000, Angew. Chem. 1 12: 3926]. Due to their salt character, ionic liquids have unique material properties, such as a low one

Vapor pressure, a liquid state over a wide

Temperature range, are not flammable, show high electrical conductivity and high electrochemical and thermal stability.

CONFIRMATION COPY Surprisingly, ionic liquids having a borate anion containing both perfluoroalkyl and cyano groups have a lower viscosity than ionic liquids containing borate anions containing perfluoroalkyl groups and fluoro groups, such as perfluoroalkyl trifluoroborate or lower viscosity than ionic ones

Liquids with Tetracyanoboratanionen. Viscosity is an important material property when applied to applications of salts

Perfluoralkylcyanofluorboratanionen is thought, especially in electrochemistry.

In particular, salts with the anions perfluoroalkyltricyanoborate, perfluoroalkylcyanodifluoroborate or perfluoroalkyldicyanofluoroborate exhibit dynamic viscosities, for example of the order of 13 to 17 cP at 25 ° C. Such salts with these selected anions are novel, and in particular a selection invention to WO 2006/045405.

The synthesis of the borate anions [B (R _f ) _4-xy (CN) x (F) y] with x = 1, 2 or 3, y = 0 or 1 and x + y <4 succeeds according to the description of

Publication WO 2006/045405 by isomerization of

corresponding isocyanoborate salts at temperatures between 150 ° and 300 ° C. The isocyanate borate salts are formed by reaction of the

Isocyanoboric acid with a strong base and are characterized in that the nitrogen atom is bonded to the boron atom. In comparison, in the case of the salts of WO 2006/045405, the cyanide is bonded to the boron atom via the C atom.

E. Bernhard et al, Chemistry A European J. 2001, 7, No. 21, 4696-4705) describes NMR data of the anions [(CF ₃ ) BF ₂ (CN)] ^" and [(CF ₃ ) BF (CN ) _2] ^', the cyanoborate (NH ₄ [B (CN) during the fluorination of lithium, silver or Ammoniumtetra- _4]) with CIF ₃ observed, but were not isolated. the final product of this fluorination are salts with a Tetratrifluor- methylborate anion ([B (CF ₃ ) ₄ ]). The synthesis of alkali metal tetracyanoborates by a solid state reaction of an alkali metal tetrafluoroborate in the presence of

Potassium cyanide / lithium chloride is described, for example, in WO 2004/072089.

The synthesis of borate anions without perfluoroalkyl group [B (CN) _x (F) _y ] with x = 2 or 3, y = 1 or 2 and x + y = 4 succeeds as described by E. Bernhard et al, Z. for Anorg , Gen. Chem. 2003, 629, 677-685

Reaction of lithium or potassium tetrafluoroborate with trimethylsilyl cyanide. It is further described in this reference that the reaction rate is very slow, the reaction time is several hours to several weeks and that usually mixtures of

Dicyanodifluoroborate anions and tricyanofluoroborate anions are formed. The synthesis and isolation of trifluoromonocyanoborate anions was not possible by this method.

However, there is still a need for economical alternative synthetic methods to using this interesting class of salts

Perfluoroalkyl cyanofluoroborate anions or

Perfluoroalkyl tricyanoborate anions, perfluorophenyl cyanofluoroborate anions or perfluorophenyl tricyanoborate anions,

Fluorophenylcyanofluorboratanionen or Fluorophenyltricyanoboratanionen, Phenylcyanofluorboratanionen or Phenyltricyanoboratanionen, which may be mono- or disubstituted by perfluoroalkyl groups having 1 to 4 carbon atoms, if necessary, to produce.

The object of the present invention is therefore an alternative

To develop a manufacturing process which leads in good yield to the desired salts and thereby easily accessible

Starting materials go out. Surprisingly, it has been found that alkali metal trifluoroperfluoroalkylborates represent excellent starting materials for the synthesis of the desired mixed borates, which are readily available.

The subject of the invention is therefore a process for the preparation of salts of the formula I.

M ^{a +} [B (R _f ) (CN) _x (F) y] _a - I,

in which

M ^{a + is} a silver, magnesium, copper (I), copper (II), zinc (II), calcium cation, NH ₄ ⁺ or an organic cation,

R _f denotes a linear or branched perfluorinated alkyl group having 1 to 4 C atoms, C 6 F ₅ , C 6 H ₅ , partially fluorinated phenyl or phenyl monosubstituted or disubstituted by a perfluoroalkyl group having 1 to 4 C atoms, the perfluoroalkyl group being selected independently of one another,

a is 1 or 2,

x is 1, 2 or 3,

y is 0, 1 or 2 and

x + y = 3, by reaction of an alkali metal salt of formula II

Me ⁺ [B (R _f) R _3] - II,

in which

Me ^{+ is} a lithium, potassium, sodium, cesium or rubidium salt and Rf has a meaning given above

with trialkylsilyl cyanide to a salt of formula III

Me ⁺ [B (R _f) (CN) _x (F) _y r III,

where Me ⁺ , R _f , x and y have the abovementioned meaning and the alkyl group of the trialkylsilyicyanide is, independently of one another, a linear or branched alkyl group having 1 to 4 C atoms, and by the subsequent salting reaction of the salts of the formula III with a salt of the formula IV,

MA IV,

in which

M has a meaning given for M ^{a +} and

A is selected from the group of anions

F - Cr, Br ^"Γ, ^OH", [HF _2] ^~ [CN] ^', [SCN] ^{^"[RiCOO]"} [R1SO3] -,

[RzCOO] - [R ₂ S0 ₃ ] - [R1OSO3] - [SiF ₆ ] ² -, [BF ₄ ] -, [SO ₄ ] ² - [HSO 4] ¹ - [NO ³ ] - [(Ri) ₂ P (0 ) Or, [RiP (0) 0 ₂ ] ^{2 '} , [(^ Ο) ₂ Ρ (Ο) Ο] \ [(RiO) P (0) 0 ₂ ] ² -,

[(R ₂₎ 2 P (0) 0] ^", [R ₂ P (O) O _2] ^2", tosylate, benzoate, oxalate, succinate, suberate, ascorbate, sorbate, tartrate, citrate, malate, malonate, optionally with Malonates or [CO ₃ ] ^2_ substituted by alkyl groups having 1 to 4 carbon atoms, where each R independently of one another is H and / or a linear or branched alkyl group having 1 to 12 C atoms,

R ₂ each independently represents a partially fluorinated or perfluorinated linear or branched alkyl group having 1 to 12 C atoms or pentafluorophenyl and wherein in the formula of the salt MA the

Electroneutrality is observed. A perfluorinated linear or branched alkyl group having 1 to 4 C atoms is, for example, trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl, iso-heptafluoropropyl, n-nonafluorobutyl, sec-nonafluorobutyl or tert-nonafluorobutyl. By analogy, R ₂ defines a linear or branched perfluorinated alkyl group having 1 to 12 C atoms, comprising the abovementioned perfluoroalkyl groups and, for example, perfluorinated n-hexyl, perfluorinated n-heptyl, perfluorinated n-octyl, perfluorinated ethylhexyl, perfluorinated n-nonyl, perfluorinated n-decyl, perfluorinated n-undecyl or perfluorinated n-dodecyl. R _f is preferably trifluoromethyl, pentafluoroethyl, heptafluoropropyl,

Nonafluorobutyl, perfluorohexyl, C ₆ F ₅ , p-FC ₆ H ₄ , 3,5- (CF ₃ ) ₂ C ₆ H ₃ or C ₆ H ₅ ; particularly preferably a linear or branched perfluorinated alkyl group with 1 to 4 C atoms or C ₆ F ₅ , very particularly preferably trifluoromethyl or pentafluoroethyl, very preferably pentafluoroethyl.

Accordingly, preferred salts of the formula I in which the borate anions are selected from the group Trifluormethyltricyanoborat,

Pentafluoroethyl tricyanoborate, heptafluoropropylcyanoborate,

Trifluoromethyldicyanofluoroborate, pentafluoroethyldicyanofluoroborate,

Heptafluoropropyldicyanofluoroborate, trifluoromethylmonocyanodifluoroborate, pentafluoromethylmonocyanodifluoroborate, heptafluoropropylmonocyanodifluoroborate, nonafluorobutylmonocyanodifluoroborate,

Pentafluorophenyl tricyanoborate, pentafluorophenyl dicyanofluoroborate,

Pentafluorophenylmonocyanodifluoroborate, phenyltricyanoborate,

Phenyldicyanofluoroborate, phenylmonocyanodifluoroborate, p-fluorophenyltricyanoborate, p-fluorophenyldicyanofluoroborate, p-fluorophenylmonocyanodifluoroborate, 3,5-

Bis (trifluoromethyl) phenyl tricyanoborate, 3,5-bis (trifluoromethyl) phenyl dicyanofluoroborate or 3,5-bis (trifluoromethyl) phenyl monocyanodifluoroborate. R ₂ is particularly preferably trifluoromethyl, pentafluoroethyl or

Nonafluorobutyl, most preferably trifluoromethyl or

Pentafluoroethyl.

A linear or branched alkyl group having 1 to 4 C atoms is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl. By analogy, R 1 defines a linear or branched alkyl group having 1 to 12 C atoms, comprising the abovementioned alkyl groups and, for example, n-hexyl, n-heptyl, n-octyl, ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Ri is particularly preferably methyl, ethyl, n-butyl, n-hexyl or n-octyl, very particularly preferably methyl or ethyl. Substituted malonates are, for example, the compounds - methyl or ethyl malonate. M ^{a +} is preferably an organic cation selected from

Ammonium cations, sulfonium cations, oxonium cations,

Phosphonium cations, uronium cations, thiouronium cations,

Guanidinium cations or heterocyclic cations, as described below in particular by the formulas (1) to (8) and their preferred meanings.

The alkyl groups of the trialkylsilyl cyanide may be the same or different. Preferably, the alkyl groups are the same. Examples of

Trialkylsilyl cyanides are therefore trimethylsilyl cyanide, triethylsilyl cyanide, triisopropylsilyl cyanide, tripropylsilyl cyanide or tributylsilyl cyanide.

Particularly preferred trimethylsilyl cyanide is used, which is commercially available or can be prepared in situ.

Preference is given to using compounds of the formula II in which the alkali metal is lithium, sodium or potassium, particularly preferably potassium. Very particularly preferred compounds of the formula II for the synthesis of the compounds of the formula I, as described above, are therefore

select from potassium trifluoromethyl trifluoroborate, potassium pentafluoroethyl trifluoroborate, potassium heptafluoropropyl trifluoroborate or potassium pentafluorophenyl trifluoroborate.

It is now possible to choose the reaction conditions of this reaction in such a way that in particular in the conversion of the compounds of formula II to compounds of formula III, as described above, specifically a specific borate anion is obtained in high yield. Without targeted temperature control usually results in a mixture of salts with different borate anions, as defined above or as preferred described. The temperature control is advantageous by

Microwave irradiation.

The preparation of compounds of the formula II can be carried out by customary methods known to the person skilled in the art, for example based on the description in US Pat. No. 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), p. 5296-5301; H.-J-Frohn and V.V. Bardin, Z. for Inorganic and General Chemistry, 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].

Finds the reaction of the compound of formula II

Me ⁺ [B (R _f) F _3] ^"II,

in which

Me ^{+ is} a lithium, potassium, sodium, cesium or rubidium salt and R _{f has} a meaning given above

with trialkylsilyl cyanide, as described above, at temperatures between 10 ° C and 110 ° C instead of or with microwave irradiation with 100W, so in particular compounds of formula III

Me ⁺ [B ( _Rf ) (CN) _x (F) _y ] - III,

wherein Me ⁺ , R _f , have the meaning as for the compound of formula II and x = 1 and y = 2, that is, a fluorine atom by a

Replaced cyano group. It thus arise in high yield

Compounds of the formula III with an anion of the formula Ia

[B ( _Rf ) (CN) (F) ₂ ] - la.

If the group R _{f is} trifluoromethyl, the corresponding salt is formed with the trifluoromethyl monocyanodifluoroborate anion, preferably at room temperature or under microwave irradiation with 100W. A

Reaction time of several hours can be observed. The details in this regard are described in the examples. If the group R _f Pentafluoroethyl means, the corresponding salt is formed preferably at temperatures of 100 ° C at a reaction time of the order of one hour or microwave irradiation with 100W. If the group Rf phenyl, partially fluorinated phenyl, mono- or di-substituted by perfluoroalkyl groups having 1 to 4 carbon atoms, or

Perfluorophenyl means, the corresponding arises

Monocyanodifluoroborate salt preferably at room temperature at a reaction time of several days. A preferred embodiment for preparing salts of the formula I with anions of the formula Ia is therefore characterized in that the reaction of the formula II with the trialkylsilyl cyanide, as described above, at temperatures between 10 ° C and 110 ° C, preferably between room temperature (25 ° C) and 100 ° C takes place or takes place with microwave irradiation with 100W. Finds the reaction of the compound of formula II

in which

with trialkylsilyl cyanide as described above at temperatures between

115 ° C and 200 ° C instead of or microwave irradiation with 200W, so in particular compounds of formula III

Me ⁺ [B (R _f) (CN) _x (F) _y r III,

wherein Me ⁺ , R _f , have the meaning as for the compound of formula II and x = 2 and y = 1, that is, two fluorine atoms by

Exchanged cyano groups. It thus arise in high yield

Compounds of the formula III with an anion of the formula Ib

If the group R _{f is,} for example, trifluoromethyl, then the corresponding salt is formed with the trifluoromethyldicyanofluoroborate anion, preferably at 130 ° C. or under microwave irradiation with 200W. The Reaction time is on the order of 5 hours. The details in this regard are described in the examples. Does that mean

Group R _f, for example, pentafluoroethyl, the result is the corresponding salt of the formula Ib preferably at temperatures of 180 ° C at a reaction time in the order of 6 hours or less

Microwave irradiation with 200W at a reaction time in the

Order of magnitude of several minutes. A preferred embodiment for the preparation of salts of the formula I with anions of the formula Ib is therefore characterized in that the reaction of the formula II with the

Trialkylsilylcyanid, as described above, at temperatures between 115 ° C and 200 ° C, preferably between 130 ° C and 180 ° C or at

Microwave irradiation with 200W takes place.

Finds the reaction of the compound of formula II

Me ⁺ [B (R _f) F _3] ^"II,

in which

with trialkylsilyl cyanide, as described above under microwave irradiation greater than 200W instead of, in particular with 300W, the result in particular

Compounds of the formula III

Me ⁺ [B (Rf) (CN) _x (F) _y ] - III,

where Me ⁺ and R _{f have} the meaning as for the compound of formula II and x = 3 and y = 0, ie all three fluorine atoms are replaced by cyano groups. It thus arise in high yield

Compounds of the formula III with an anion of the formula Ic

A preferred embodiment for preparing salts of the formula I with anions of the formula Ic is therefore characterized in that the reaction of the formula II with the trialkylsilyl cyanide, as before described under microwave irradiation greater than 200W takes place, preferably under microwave irradiation with 300W.

If the group R _{f is,} for example, trifluoromethyl, the corresponding salt is formed with the trifluoromethyltricyanofluoroborate anion, preferably at a microwave irradiation of 300W. The reaction time is on the order of one to two hours. The details in this regard are described in the examples. If the group R _{f is,} for example, pentafluoroethyl, then the corresponding salt is preferably formed under microwave irradiation with 300 W at one

Reaction time of the order of one hour.

It was not foreseeable that the compounds of the formula II, as described above, as starting materials for the preparation of

Compounds of formula III and after Umsalzungsreaktion for the preparation of compounds of formula I are suitable. In contrast to the reaction described in Bernhard et al. (Z. for Anorg. Allg. Chem. 2003, 629, 677-685) of an alkali metal tetrafluoroborate with trimethylsilyl cyanide, it is not to be expected that the reactivity in the presence of the steric

demanding group RF, for example in the presence of a

Perfluoroalkylgruppe, sufficient to allow an exchange of fluorine atoms by cyano groups. Furthermore, it is surprising that the reaction rate even increases in proportion. The exchange of three fluorine atoms did not succeed in the aforementioned reference, whereas in the presence of 300W microwave radiation, precisely such exchange takes place in the process of the invention. Microwave irradiation as a heating source is not described in the literature. Unexpectedly and unexpectedly, trimethylsilyl cyanide selectively attacks only the fluorine atoms bound to boron, but not the

Fluorine atoms in the perfluoroalkyl chain.

The reaction of the compounds of the formula II with the trialkylsilyl cyanide can be carried out without a protective gas atmosphere. Preferably However, the reaction takes place under dried air or in a

Inertgasatmosphäre instead.

The reaction of the compounds of the formula II with the trialkylsilyl cyanide is preferably carried out without a solvent. The implementation in

Presence of an organic solvent, for example

Tetrahydrofuran or acetonitrile, however, is possible.

In a further embodiment, the trialkylsilyl cyanide used before being reacted with a compound of formula II as described above in situ from an alkali metal cyanide and a

Trialkylsilyl chloride prepared in the presence of one

Alkali metal iodide or fluoride and optionally iodine. Sodium cyanide and sodium iodide are preferably used here or potassium cyanide and potassium iodide are used, the alkali metal iodide preferably being in a molar amount of 0.1 mol / l based on 1 mol / l alkali metal cyanide and

Trialkylsilyl chloride is added. Details of this preparation can be taken from the examples. Generally, this method is based on

Preparation 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 Cyanotrimethylsilanes in G.L. Larson

(Ed.), Advances in Silicon Chemistry, Vol. 1, pp. 65-187, JAI Press Inc., 1991 or WO 2008/102661 A1.

An article of the invention is therefore also a process for the preparation of compounds of the formula I, as described above, characterized

in that the trialkylsilyl cyanide, prior to reaction with a compound of the formula II, is prepared in situ from an alkali metal cyanide and a trialkylsilyl chloride in the presence or catalysis of a

Alkali metal iodide and optionally iodine is produced.

When carrying out the preparation according to the invention of compounds of the formula I as described above, it is possible to obtain the compounds obtained. fertilize the formula III from the first stage of the reaction to purify and use as an isolated, pure compound in the second stage of the salting reaction or metathesis reaction. However, it is advantageous in a further embodiment, if the

Intermediate compound of formula III is not worked up to the pure substance, but only the insoluble in organic solvents or volatile by-products, such as trialkylsilyl fluoride or an excess of trimethylsilyl cyanide, are separated and the

Compound of formula III without further purification to pure substance with a compound of formula IV, as described above, is reacted.

Alternatively, the synthesis of the compounds of the formula I as described above can also be carried out by reacting a compound of the formula II as described above with an alkali metal cyanide in the presence of an alkali metal chloride, as for example in Example 5C

described. A separation of the compounds obtained by

Crystallization is possible. If the mixture for the production of

Compounds with corresponding organic cations in one

Used salting reaction, it is possible to separate the salts with organic cations, for example via extraction methods. This alternative method is preferably suitable for the production of

Alkali metal (pentafluoroethyl) difluoromonocyanoborates and the

corresponding organic salts or alternative metal salts after resalendering. A preferred alkali metal chloride is lithium chloride. This is a sintering reaction, especially at

Temperatures between 160 ° C and 200X.

Examples of organic cations of the 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) [N (R) ₄ ] ⁺ (1), [S (R) ₃ ] ⁺ (2) or [O (R) ₃ ] ⁺ (3) where

R each independently

- H, where not all substituents R may be H at the same time, - straight-chain or branched alkyl having 1-20 C atoms,

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

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

- saturated, partially or fully unsaturated cycloalkyl with

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

means

where one or two R is complete and / or one or more R is partially halogen or partially -OR ¹ , -NR ₂ , -CN,

-C (O) NR ¹ 2 or -SO ₂ NR ₂ may be substituted,

and wherein one or two non-adjacent and non-stationary carbon atoms of the radical R are substituted 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 - may be replaced; or

Phosphonium cations of the formula (4)

[P (R ² ) ₄ f (4)

in which

R ² each independently

- H, NR ₂ ,

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

- saturated, partially or fully unsaturated cycloalkyl with

3-7 C atoms, that with alkyl groups with 1-6 C atoms may be substituted

means

where one or two R ² may be substituted completely and / or one or more R ^{2 may be} partially substituted by halogens or partially by -OR, -CN, -C (O) NR ₂ , -SO ₂ NR ₂ ,

and one or two non-contiguous and non-permanent ones

Carbon atoms of R ² , by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR - , -SO ₂ NR ¹ -, or -P (O) R ¹ - may be replaced; or

Uronium cations of the formula (5) or thiouronium cations of the formula

(6)

[C (NR ³ R) (OR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (5)

or [C (NR ³ R ⁴ ) (SR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (6), where

R ³ to R ^{7 are} each independently

- H, NR ^* ₂ ,

straight-chain or branched alkyl having 1 to 20 C atoms,

- saturated, partially or fully unsaturated cycloalkyl with

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

mean,

wherein one or more of substituents R ³ to R ^{7 may be} partially or completely substituted with halogens, or partially substituted with -OH, -OR ¹ , -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ¹ ₂ ,

and one or two non-contiguous and non-permanent ones

Carbon atoms of R ³ to R ⁷ by atoms and / or

Atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR -, -SO ₂ NR -, or -P (O) R ¹ - may be replaced; or guanidinium cations of the formula (7)

[C (NR ⁸ R ⁹ ) (NR ¹⁰ R ¹¹ ) (NR ² R ³ )] ⁺

in which

R> 8 u b; is_ D R13 j:, in each case independent of each other

- H, NR ₂ ,

straight-chain or branched alkyl having 1 to 20 C atoms,

- saturated, partially or fully unsaturated cycloalkyl with

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

mean,

wherein one or more of the substituents R ⁸ to R ^{13 may be} partially or completely substituted by halogens or partially substituted by -OR ¹ , -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ¹ 2,

and one or two non-contiguous and non-permanent ones

Carbon atoms of R ⁸ to R ¹³ by atoms and / or

Atomic moieties selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ 2-, -C (O) NR ¹ -, -SO ₂ NR -, or - P (0) R - can be replaced; or heterocyclic cations of the formula (8)

[HetN] ⁺ (8),

wherein [HetN] ^{+ is} a heterocyclic cation selected from the group comprising

Imidazolium 1 H-pyrazolium 3H-pyrazolium 4H-pyrazolium 1-pyrazolinium

2-pyrazolinium 3-pyrazolinium 2,3-dihydroimidazolinium 4,5-dihydroimidazolinium

-Dihydro-imidazolinium pyrrolidmium _{2 4} -triazolium 1, 2,4-triazolium

Isoquinolinium quinoxaline

and

wherein the substituents R to R ^{4 are} each independently

H, with the restriction that R ¹ and R ^{4 may} not be H at the same time,

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

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

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

- saturated, partially or fully unsaturated cycloalkyl with

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

saturated, partially or completely unsaturated heteroaryl,

Heteroaryl-C ₁ -C ₆ -alkyl or aryl-C ₁ -C ₆ -alkyl,

mean,

wherein the substituents R ¹ , R ² , R ³ and / or R ⁴ together

Can form ring system,

wherein one or more substituents R ¹ to R ^{4 may be} partially or completely substituted by halogens or partially substituted by -OR ¹ , -CN, -C (O) NR ¹ _2> -SO ₂ NR ¹ 2, but not simultaneously R ¹ and R ⁴ may be completely substituted by halogens, and wherein one or two nonadjacent and not heteroatom-bonded carbon atoms of the substituents R ¹ to R ⁴ , by atoms and / or atomic groups selected from the group -O-, -S-, - S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR -, -SO ₂ NR ¹ -, or -P (O) R ¹ - may be replaced; wherein R ^{1 is} H, not, partially or perfluorinated C ¹ to C ₆ alkyl, C ₃ to C ₇ cycloalkyl, unsubstituted or substituted phenyl and R is not, partially or perfluorinated C to C ₆ alkyl, C 3 to C ₇ - cycloalkyl, unsubstituted or substituted phenyl.

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

Tetrakis (nonafluorobutyl) ammonium cation.

In the context of the present invention, completely unsaturated substituents are also understood as meaning aromatic substituents.

Suitable substituents R and R ² to R ^{3 of} the compounds of the formulas (1) to (7) according to the invention are preferably: C to C2o, in particular C 1 to C ₁₄ alkyl groups, and saturated or unsaturated, ie also aromatic , C ₃ - to C -cycloalkyl groups which may be substituted by C ₁ - to C ₆ -alkyl groups, in particular phenyl.

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

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 ⁰ R ¹¹ ) (NR ¹² R ¹³ )] ⁺ may also be linked in pairs in such a way that mono-, bi- or polycyclic molecules are formed.

Without limitation of generality are examples of such

Guanidinium cations are:

or N = N where the substituents R ⁸ to R ¹⁰ and R ^{13 may have} a previously stated or particularly preferred meaning.

Optionally, the carbocycles or heterocycles of the above-mentioned guanidinium cations can still by d- to C ₆ alkyl, C to Ce alkenyl, CN, NR ¹ ₂ , F, Cl, Br, I, C _r C ₆ alkoxy, SCF ₃ , SO ₂ CF ₃ or SO ₂ NR 2, where R ¹ has the meaning given above, substituted or unsubstituted phenyl or unsubstituted or substituted heterocycle. Up to four substituents of the thiouronium cation [C (NR ³ R) (SR ⁵ ) (NR ⁶ R ⁷ )] ⁺ may also be linked in pairs to form mono-, bi-, or polycyclic molecules. Without restriction of generality, examples of such thiouronium cations are given below:

where Y = S

and wherein the substituents R ³ , R ⁵ and R ^{6 may have} a previously given or particularly preferred meaning.

Optionally, the carbocycles or heterocycles of the abovementioned molecules can also be replaced by C ₁ - to C ₆ -alkyl, C ₁ -C ₆ -alkenyl, CN, NR ¹ _2> F, Cl, Br, I, CC ₆ -alkoxy, SCF ₃₎ SO ₂ CF ₃ or SO ₂ NR ¹ ₂ or substituted or unsubstituted phenyl or unsubstituted or substituted heterocycle, wherein R ^{1 is} a previously

has meaning given. The substituents R ³ to R ³ are each, independently of one another, preferably a straight-chain or branched alkyl group having 1 to 10 C atoms. The substituents R ³ and R ⁴ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ⁰ and R ¹ and R ² and R ¹³ in compounds of the formulas (5) to (7) may be identical or different. R ³ to R ^{13 are} each particularly preferably, independently of one another, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, phenyl or cyclohexyl, very particularly preferably methyl, ethyl, n-propyl, Isopropyl or n-butyl.

As the substituents R ¹ to R ⁴ of compounds of the formula (8) are according to the invention In addition to H, are preferably: C to C ₂ o, in particular d- to C ₂ alkyl groups, and saturated or unsaturated, ie also aromatic, C ₃ - to C ₇ -cycloalkyl groups which may be substituted by Ci to C ₆ - alkyl groups, in particular phenyl.

The substituents R ¹ and R ⁴ are each, independently of one another, particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl or benzyl. They are very particularly 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 is 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. Most preferably, R ² and R ^{3 are} H.

The C 1 -C 2 -alkyl group is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, and 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. Possibly

Difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl or

Nonafluorobutyl. A straight-chain or branched alkenyl having 2 to 20 C atoms, wherein several double bonds may also be present, is, for example, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, -C ₉ Hi _7l -C10H19 to -C20H39;

preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore preferred is 4-pentenyl, iso-pentenyl or hexenyl. Are the

Partially fluorinated compounds, so 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 exchanged for F atoms. A straight-chain or branched alkynyl having 2 to 20 carbon atoms, wherein a plurality of triple bonds may also be present, is

For example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, further 4- pentynyl, 3-pentynyl, hexynyl, heptynyl, octynyl, -C9H15, -Ci ₀ H ₇ to -C20H37, preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3-pentynyl or hexynyl. If the compounds are partially fluorinated, then

at least one H atom replaced by an F atom. Are the

Perfluorinated compounds, all H atoms of the corresponding alkyl group are exchanged for F atoms. ArylCrCe-alkyl is, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, where both the phenyl ring and the alkylene chain, as described above, partially or completely with halogens, in particular -F and / or -Cl, or partially with - OR ¹ , - NR ¹ ₂ , -CN, -C (O) NR ¹ 2, -SO ₂ NR ¹ ₂ may be substituted.

Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, phenyl, cycloheptenyl, which may be substituted by C ₁ to C ₆ alkyl groups, again wherein the cycloalkyl group or the C ₁ to C ₆ alkyl substituted cycloalkyl group may be substituted by halogen atoms such as F, Cl, Br or I, in particular F or Cl or with -OR, -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ¹ ₂ may be substituted.

In the substituents R, R ² to R ¹³ or R ¹ to R ⁴ , one or two non-adjacent and not α-bonded to the heteroatom carbon atoms, 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 - be replaced, with R ¹ = not, partially or perfluorinated C ¹ to C ₆ alkyl, C ₃ to C ₇ cycloalkyl, unsubstituted or substituted phenyl.

Without restriction of generality, examples of such modified substituents R, R ² to R ¹³ and R ^{1 '} to R 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, -S0 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 ^r , C ₃ - to C -cycloalkyl is, for example, cyclopropyl,

Cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

In R ¹ or R ^{1 *} , substituted phenyl, by C ¹ to C ₆ alkyl, C to Ce alkenyl, CN, NR ¹ ₂ , F, Cl, Br, I, C ₁ -C ₆ alkoxy, SCF ₃ , SO ₂ CF ₃ or SO ₂ NR ^* ₂ substituted phenyl, wherein R ^{* is} a non, partial or

perfluorinated C to C ₆ -alkyl or C ₃ to 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.

In R ¹ to R ⁴ as heteroaryl is a saturated or unsaturated mono- or bicyclic heterocyclic radical having 5 to 13 ring members

understood, where 1, 2 or 3 N and / or 1 or 2 S or O atoms may be present and the heterocyclic radical may be mono- or polysubstituted by C to C ₆ alkyl, d- to C ₆ alkenyl, CN, NR ¹ ₂ , F, Cl, Br, I, C ₁ -C ₆ -alkoxy, SCF ₃ , SO ₂ CF ₃ or SO ₂ NR ¹ ₂ may be substituted, wherein R ^{1 has} a meaning given above.

The heterocyclic radical is 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-pyrimidinyl, more preferably 1, 2,3-triazole-1, -4- or -5-yl, 1, 2,4-triazole-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-thiadiazole-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- 4H-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 7-1H-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-benzthiazolyl, 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.

By heteroaryl-C 1 -C ₆ -alkyl, by analogy with aryl-C 1 -C ₆ -alkyl, pyridinyl-methyl, pyridinyl-ethyl, pyridinyl-propyl, pyridinyl-butyl, pyridinyl-pentyl, pyridinyl-hexyl are now understood, furthermore those previously described Heterocycles can be linked in this way with the alkylene chain.

HetN ⁺ is preferred

Pyridinium Pyrimidinium

Imidazolium P razolium Pyrrolidinium

wherein the substituents R to R ⁴ each independently have the meaning previously described.

More preferably, the organic cation [Kt is selected from the group comprising imidazolium, pyridinium, pyrrolidinium, ammonium or phosphonium cations as defined above. Particularly suitable cations are selected from the group

Tetraalkylammonium, 1, 1-dialkylpyrrolidinium, 1-alkyl-1-alkoxyalkylpyrrolidnium or 1, 3-dialkylimidazolium, wherein the

Alkyl groups or the alkoxy group in the alkoxyalkyl group may each independently have 1 to 10 carbon atoms. The alkyl groups very particularly preferably have 1 to 6 C atoms and the alkoxy group 1 to 3 C atoms.

The alkyl groups in the tetraalkylammonium may therefore be the same or different. Preferably, three alkyl groups are the same and one

Alkyl group different or two alkyl groups are the same and the other two 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) ethylammonium. 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, Methyl 1-pentylpyrrolidinium, 1-methyl-1-hexylpyrrolidinium, 1-methyl-1-heptylpyrrolidinium, 1-methyl-octylpyrrolidinium, 1-methyl-1-nonylpyrrolidinium, 1-methyl 1-decyl-pyrrolidinium, 1, 1-diethyl-pyrrolidinium, 1-ethyl-1-propyl-pyrrolidinium, 1-ethyl-1-butyl-pyrrolidinium, 1-ethyl-1-pentyl pyrrolidinium, 1-ethyl-1-hexyl-pyrrolidinium, 1-ethyl-1-heptyl-pyrrolidinium, 1-ethyl-1-octyl-pyrrolidinium, 1-ethyl-1-nonyl-pyrrolidinium, 1-ethyl-1-decyl pyrrolidinium, 1, 1-dipropylpyrrolidinium, 1-propyl-1-methylpyrrolidinium, 1-propyl-1-butyl-pyrrolidinium, 1-propyl-1-pentyl-pyrrolidinium, 1-propyl-1-hexyl-pyrrolidinium, 1-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-octyl-pyrrolidinium, 1 - Butyl-1-nyl-pyrrolidinium, 1-butyl-1-decylpyrrolidinium, 1, 1-dipentyl-pyrrolidinium, 1-pentyl-1-hexyl-pyrrolidinium, 1-pentyl-1-heptyl-pyrrolidinium, 1-pentyl 1-octylpyrrolidinium, 1-pentyl-1-nonylpyrrolidinium, 1-pentyl-1-decylpyrrolidinium, 1, 1-dihexylpyrrolidinium, 1-hexyl-1-heptylpyrrolidinium, 1-hexyl-1 octyl-pyrrolidinium, 1-hexyl-1-nonylpyrrolidinium, 1-hexyl-1-decylpyrrolidinium, 1,1-dihexylpyrrolidinium, 1-hexyl-1-heptyl-pyrrolidinium, 1-hexyl-1-octyl -pyrrolidinium, 1-hexyl-1-nonylpyrrolidinium, 1-hexyl-1-decylpyrrolidinium, 1, 1-diheptylpyrrolidinium, 1-heptyl-1-octylpyrrolidinium, 1-heptyl-1-nonylpyrrolidinium , 1-Heptyl-1-decylpyrrolidinium, 1,1-dioctylpyrrolidinium, 1-octyl-1-nonylpyrrolidinium, 1-octyl-1-decylpyrrolidinium, 1-1-dinonyl-pyrrolidinium, 1-nony 1-decylpyrrolidinium or 1, 1-didecylpyrrolidinium. Very particular preference is 1-butyl-1-methyl-pyrrolidinium or 1-propyl-1-methyl-pyrrolidinium.

Preferred 1-alkyl-1-alkoxyalkylpyrrolidinium cations are, for example, 1- (2-methoxyethyl) -1-methylpyrrolidinium, 1- (2-methoxyethyl) -1-ethylpyrrolidinium, 1- (2-methoxyethyl) -1- propylpyrrolidinium, 1- (2-methoxyethyl) -1-butylpyrrolidinium, 1- (2-ethoxyethyl) -1-methylpyrrolidinium, 1-ethoxymethyl-1-methylpyrrolidinium. Very particular preference is given to 1- (2-methoxyethyl) -1-methyl-pyrrolidinium.

Preferred 1,3-dialkylimidazolium cations are, for example, 1-ethyl-3-methyl-imidazolium, 1-methyl-3-propyl-imidazolium, 1-butyl-3-methyl- imidazolium, 1-methyl-3-pentylimidazolium, ethyl-3-propyl-imidazolium, 1-butyl-3-ethyl-imidazolium, 1-ethyl-3-pentyl-imidazolium, 1-butyl-3-propyl-imidazolium, 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, 1-methyl-3-octylimidazolium, 1-methyl-3-nonyl -imidazolium, 1-decyl-3-methyl-imidazolium, 1-ethyl-3-hexyl-imidazolium, 1-ethyl-3-heptyl-imidazolium, 1-ethyl-3-octyl-imidazolium, 1-ethyl-3-nonyl imidazolium or 1-decyl-3-ethyl-imidazolium. Particularly preferred cations are 1-ethyl-3-methyl-imidazolium, 1-butyl-3-methyl-imidazolium or 1-methyl-3-propyl-imidazolium.

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 the formula I are preferably heterocyclic cations of the formula (8) in which HetN ^{z +} imidazolium, pyrrolidinium or pyridinium, having substituents R to R, each independently of one another have the stated or preferred meaning. The organic cation of the compounds of the formula I are particularly preferably imidazolium, where the substituents R ¹ to R have the abovementioned meaning or preferred

Meaning or you have the meaning of preferred

given meanings for 1, 1-dialkylpyrrolidinium, 1-alkyl-1-alkoxyalkylalkylpyrrolidinium, 1, 3-dialkylimidazolium, 1-alkenyl-3-alkylimidazolium or 1-alkoxyalkyl-3-alkylimidazolium, as described above. Accordingly, particularly preferred organic cations of the formula I 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, tetra-phenylphosphonium, diethylmethylsulfonium, S-ethyl-N, N, N ', N'-tetramethylisothiouronium, 1-allyl-3-methylimidazolium, 1 - Allyl-2,3-dimethylimidazolium, 1-cyanomethyl-3-methylimidazolium, 1-methyl-3-propynylimidazlium, 1, 1-dimethylpyrrolidinium or trimethylsulfonium.

The synthesis of the compounds of formula I is carried out from the compounds of formula III in one embodiment by the following

Saline reaction with compounds of formula IV, as before

described.

Preferably, the anion of formula (IV) is OFT, CI ^" , Br ^- , Γ, [CH ₃ SO ₃ ] ^" [CH ₃ OSO ₃ ] ^" , [CF ₃ COO] -, [CF ₃ SO 3] ^" , [(C ₂ F ₅₎ ₂ P (0) oR or [C0 _3] ^{2 ",} more preferably ^OH", Cr, Br, [CH ₃ OSO _3] ^", ^[CF3SO3]", [CH3SO3] ^"or

The reaction is advantageously carried out in water, temperatures of 0 ° -100 ° C, preferably 15 ° -60 ° C are suitable. Particularly preferred is reacted at room temperature (25 ° C).

However, the reaction may alternatively take place in organic solvents at temperatures between -30 ° and 100 ° C. Suitable solvents are acetonitrile, dioxane, dichloromethane, dimethoxyethane,

Dimethylsulfoxide, tetrahydrofuran, dimethylformamide or alcohol, for example, methanol, ethanol or isopropanol.

In an alternative embodiment, depending on the respective desired organic cation of the compounds of formula I, a

Compound of formula II with an organic cation, as desired for the compound of formula I, with trialkylsilyl cyanide, as described above, are reacted. This synthesis is particularly suitable for ammonium or phosphonium cations. The subject of the main claim, ie the process for the preparation of compounds of formula I, as described above, is essentially novel and inventive, because the compounds of formula III can be produced economically for the first time.

Therefore, an object of the invention is also a method for

Preparation of compounds of the formula III

Me ⁺ [B (R,) (CN) _x (F) _y r III.

where Me ^{+ is} a lithium, potassium, sodium, cesium or rubidium salt,

R _{f is} a linear or branched perfluorinated alkyl group having 1 to 4 C

Atoms, C ₆ F _5l C ₆ H ₅ , partially fluorinated phenyl or mono- or disubstituted by a perfluoroalkyl group having 1 to 4 carbon atoms substituted phenyl, wherein the perfluoroalkyl group is selected independently of one another,

a is 1 or 2,

x is 1, 2 or 3,

y is 0, 1 or 2 and

x + y = 3,

by reaction of an alkali metal salt of the formula II

Me ⁺ [B (R _f) F _3] ^"II,

in which

Me ⁺ and R _{f have} a previously given meaning with a

Trialkylsilyl cyanide, wherein the alkyl group of Trialkylsilylcyanids each independently a linear or branched alkyl group having 1 to 4 carbon atoms.

As also described above, this process according to the invention, characterized in that the reaction for the preparation of

Compounds of formula III with x = 1, y = 2 takes place at temperatures between 10 ° C and 110 ° C or under microwave irradiation with 100W or that the reaction for the preparation of compounds of formula III with x = 2 and y = 1 takes place at temperatures between 115 ° C and 200 ° C or under microwave irradiation with 200W or that the reaction for the preparation of compounds of formula III with x = 3 and y = 0 under microwave irradiation with greater than 200W, preferably at 300W, takes place. The same detailed descriptions also apply to this method, which comprises a substep from the method according to the invention in accordance with the main claim.

Another object of the invention are the salts of the formula III, Me ⁺ [B (R f) (CN) _x (F) _y r IM,

wherein Me ^{+ is} a lithium, potassium, sodium, cesium or rubidium, R _{f is} a linear or branched perfluorinated alkyl group having 1 to 4 carbon atoms, C ₆ F ₅ , C6H ₅ , partially fluorinated phenyl or a single or double a perfluoroalkyl group having 1 to 4 carbon atoms substituted phenyl, wherein the perfluoroalkyl group is selected independently of one another,

a is 1 or 2,

x is 1, 2 or 3,

y is 0, 1 or 2, where 0 is excluded for R _f = CeH ₅ and

x + y = 3.

The invention also provides the salts of the formula III, Me ⁺ [B ( _Rf ) (CN) x (F) _y ] - III,

wherein Me ^{+ is} a lithium, potassium, sodium, cesium or rubidium salt, R _{f is} a linear or branched perfluorinated alkyl group having 1 to 4 carbon atoms, C ₆ F ₅ , C ₆ H ₅ , partially fluorinated phenyl or mono- or phenyl which is monosubstituted by a perfluoroalkyl group having 1 to 4 carbon atoms, the perfluoroalkyl group being selected independently of one another,

a is 1 or 2,

x is 1, 2 or 3,

y is 0, 1 or 2, where 0 is excluded for R _f = C ₆ H ₅ and x + y = 3,

wherein lithium trifluoromethyl difluoromonocyanoborate, lithium

Trifluoromethylfluorodicyanoborate, potassium

Trifluoromethyl difluoromonocyanoborate and potassium

Trifluoromethylfluordicyanoborat are excluded.

According to the invention, the potassium and sodium salts are particularly suitable for the preparation of the compounds of the formula I as described above.

The lithium salts of the compounds of the formula III are particularly suitable for the preparation of electrolyte preparations, in particular for

electrochemical or optoelectronic devices. The lithium salts of the formula III are particularly suitable as conductive salt for electrochemical batteries, in particular lithium-ion batteries,

Lithium ion conditioners or lithium batteries. The ability of the lithium salts of the formula III to dissolve in high concentrations in carbonate-containing solvents, you stand out against known

Lithium salts with borate anions, such as lithium tetrafluoroborate or lithium tetracyanoborate, from. For example, it has been found that the lithium salt of Example 37 dissolves 2 molar in diethyl carbonate 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 particularly advantageous.

Another object of the invention is therefore particularly preferably a lithium salt of the formula III.

The following salts are preferred, with the lithium salts being particularly preferred:

Potassium trifluoromethyl tricyanoborate, potassium pentafluoroethyl tricyanoborate, potassium heptafluoropropyl tricyanoborate, potassium Trifluoromethyldicyanofluoroborate, potassium pentafluoroethyldicyanofluoroborate, potassium heptafluoropropyldicyanofluoroborate, potassium

Trifluoromethyl monocyanodifluoroborate, potassium

Pentafluoromethyl monocyanodifluoroborate, potassium

Heptafluoropropyl monocyanodifluoroborate, potassium nonafluorobutyl monocyano difluoroborate, potassium pentafluorophenyl tricyanoborate, potassium

Pentafluorophenyl dicyanofluoroborate, potassium

Pentafluorophenyl monocyanodifluoroborate, potassium phenyldicyanofluoroborate,

Potassium phenyimonocyanodifluoroborate, potassium p-fluorophenyl tricyanoborate, potassium p-fluorophenyl dicyanofluoroborate, potassium p-

Fluorophenyl monocyanodifluoroborate, potassium 3,5-

Bis (trifluoromethyl) phenyl tricyanoborate, potassium 3,5-

Bis (trifluoromethyl) phenyldicyanofluoroborate or potassium 3,5-

Bis (trifluoromethyl) phenylmonocyanodifluorborat,

Lithium trifluoromethyl tricyanoborate, lithium pentafluoroethyl tricyanoborate,

Lithium heptafluoropropyl tricyanoborate, lithium

Trifluoromethyldicyanofluoroborate, lithium pentafluoroethyldicyanofluoroborate, lithium heptafluoropropyldicyanofluoroborate, lithium

Trifluoromethyl monocyanodifluoroborate, lithium

Pentafluoromethyl monocyanodifluoroborate, lithium

Heptafluoropropyl monocyanodifluoroborate, lithium nonafluorobutyl monocyano difluoroborate, lithium pentafluorophenyl tricyanoborate, lithium

Pentafluorophenyl dicyanofluoroborate, lithium

Pentafluorophenylmonocyanodifluoroborate, lithium phenyldicyanofluoroborate, lithium phenyimonocyanodifluoroborate, lithium p-fluorophenyltricyanoborate,

Lithium p-fluorophenyl dicyanofluoroborate, lithium p-

Fluorophenyl monocyanodifluoroborate, lithium 3,5-

Bis (trifluoromethyl) phenyl tricyanoborate, lithium 3,5-

Bis (trifluoromethyl) phenyldicyanofluoroborate or lithium 3,5-bis (trifluoromethyl) phenylmonocyanodifluoroborate,

Sodium trifluoromethyl tricyanoborate, sodium pentafluoroethyl tricyanoborate,

Sodium heptafluoropropyltricyanoborate, sodium Trifluoromethyldicyanofluoroborate, sodium pentafluoroethyldicyanofluoroborate, sodium heptafluoropropyldicyanofluoroborate, sodium

Trifluoromethyl monocyanodifluoroborate, sodium

Pentafluoromethyl monocyanodifluoroborate, sodium

Heptafluoropropyl monocyanodifluoroborate, sodium

Nonafluorobutyl monocyanodifluoroborate, sodium

Pentafluorophenyl tricyanoborate, sodium pentafluorophenyl dicyanofluoroborate sodium pentafluorophenyl monocyanodifluoroborate, sodium

Phenyldicyanofluoroborate, sodium phenylmonocyanodifluoroborate, sodium p-fluorophenyltricyanoborate, sodium p-fluorophenyldicyanofluoroborate, sodium p-fluorophenylmonocyanodifluoroborate, sodium 3,5-bis (trifluoromethyl) phenyltricyanoborate, sodium 3,5-bis (trifluoromethyl) phenyldicyanofluoroborate or sodium 3,5-bis (trifluoromethyl ) phenylmonocyanodifluorborat,

Cesium trifluoromethyl tricyanoborate, cesium pentafluoroethyl tricyanoborate, cesium heptafluoropropyltricyanoborate, cesium

Trifluoromethyldicyanofluoroborate, cesium pentafluoroethyldicyanofluoroborate, cesium heptafluoropropyldicyanofluoroborate, cesium

Trifluoromethyl monocyanodifluoroborate, cesium

Pentafluoromethyl monocyanodifluoroborate, cesium

Heptafluoropropyl monocyanodifluoroborate, cesium

Nonafluorobutyl monocyanodifluoroborate, cesium

Pentafluorophenyl tricyanoborate, cesium pentafluorophenyl dicyanofluoroborate, cesium pentafluorophenyl monocyanodifluoroborate, cesium

Phenyldicyanofluoroborate, cesium phenylmonocyanodifluoroborate, cesium p-fluorophenyltricyanoborate, cesium p-fluorophenyldicyanofluoroborate, cesium p-fluorophenylmonocyanodifluoroborate, cesium 3,5-bis (trifluoromethyl) phenyltricyanoborate, cesium 3,5-bis (trifluoromethyl) phenyldicyanofluoroborate or cesium 3,5-bis (trifluoromethyl ) phenylmonocyanodifluorborat,

Rubidium trifluoromethyl tricyanoborate, rubidium

Pentafluoroethyl tricyanoborate, rubidium heptafluoropropyltricyanoborate, Rubidium trifluoromethyldicyanofluoroborate, rubidium

Pentafluoroethyldicyanofluoroborate, rubidium

Heptafluoropropyldicyanofluoroborate, rubidium

Trifluoromethyl monocyanodifluoroborate, rubidium

Pentafluoromethyl monocyanodifluoroborate, rubidium

Heptafluoropropyl monocyanodifluoroborate, rubidium

Nonafluorobutyl monocyanodifluoroborate, rubidium

Pentafluorophenyl tricyanoborate, rubidium pentafluorophenyl dicyanofluoroborate, rubidium pentafluorophenyl monocyanodifluoroborate, rubidium

Phenyldicyanofluoroborate, rubidium phenylmonocyanodifluoroborate,

Rubidium p-fluorophenyl tricyanoborate, rubidium p-

Fluorophenyl dicyanofluoroborate, rubidium p-

Fluorophenyl monocyanodifluoroborate, Rubidium 3,5-

Bis (trifluoromethyl) phenyl tricyanoborate, rubidium 3,5-bis (trifluoromethyl) phenyldicyanofluoroborate or rubidium 3,5-

phenylmonocyanodifluorborat bis (trifluoromethyl).

Another object of the invention is therefore also an electrolyte containing a compound of formula III,

Me ⁺ [B ( _Rf ) (CN) _x (F) _y ] - III,

where Me ^{+ is} a lithium, potassium, sodium, cesium or rubidium salt,

R _{f is} a linear or branched perfluorinated alkyl group having 1 to 4 C

Atoms, C ₆ F ₅ , C ₆ H ₅ , partially fluorinated phenyl or mono- or disubstituted by a perfluoroalkyl group having 1 to 4 carbon atoms substituted phenyl, wherein the perfluoroalkyl group is selected independently of one another,

a is 1 or 2,

x is 1, 2 or 3,

y is 0, 1 or 2 and

χ + y = 3,

or described as preferred. Another object of the invention is therefore also a

electrochemical cell containing a compound of the formula III, as described above as a constituent for the electrolyte or described as preferred or an electrolyte containing these compounds.

In particular, as the electrochemical cell, a lithium-ion battery, a lithium-ion capacitor or a lithium battery is particularly

prefers. The following embodiments are intended to illustrate the invention without limiting it. The invention is correspondingly executable throughout the claimed area. Based on the examples, possible variants can also be derived. In particular, the features and

Conditions of the reactions described in the examples also applicable to other, not detailed, but falling within the scope of the claims reactions.

Examples: The materials obtained are characterized by Raman spectroscopy, elemental analysis and NMR spectroscopy. The NMR spectra are measured on solutions in deuterated acetone-D ₆ on a Bruker Avance III spectrometer with deuterium lock. The measurement frequencies of the different cores are: ¹ H: 400.17 MHz, ⁹ F: 376.54 MHz, ¹ B: 128.39 MHz, ³¹ P: 161, 99 MHz and ³ C: 100.61 MHz. Referencing is done with external reference: TMS for ¹ H and ¹³ C spectra; CCI ₃ F - for ⁹ F and BF ₃ Et ₂ 0 - for ¹¹ B spectra.

For the anions in the compounds described below, the following values are measured in ¹³ C-NMR spectra (solvent: acetone-D ₆ 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 ₂ , 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 trifluoropentafluoroethylborate - K [C ₂ F ₅ BF ₃ ]

In a 100 mL reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirrer is

Pentafluorethyliodid C ₂ F ₅ I (1.5 g, 6.1 mmol) and condensed

subsequently dissolved in 50 ml of diethyl ether and reacted at -78 ° C. with a solution of ethylmagnesium bromide in diethyl ether (2.0 ml, 6.1 mmol, 3 mol of L ^"1 ) and stirred at -78 ° C. for 1 hour

Reaction mixture at -78 ° C to trimethoxyborane (1.2 mL, 10.8 mmol). The mixture is slowly warmed to room temperature. To the suspension we added spray-dried KF (1.3 g, 22.4 mmol) and this is stirred for a further hour at room temperature. Subsequently, the reaction mixture with 50 mL THF in a PFA flask

washed and all volatile constituents are distilled off. To the solid is added 10 mL of anhydrous HF and the mixture is stirred for several hours at room temperature. The HF is removed in vacuo and the solid is taken up in 15 mL acetonitrile and filtered. The obtained solution of K [C ₂ F ₅ BF ₃ ] in acetonitrile (about 0.29 mol L ^"1 ) can be used directly for the preparation of compounds of formula III or after solvent removal to K [C ₂ F ₅ BF ₂ (CN)], K [C ₂ F ₅ BF (CN) ₂ ] or K [C ₂ F ₅ B ( CN) ₃ ] are reacted according to Example 5, 6 or 7.

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

K [CF ₃ BF ₃ ] + (CH ₃ ) ₃ SiCN -> - K [CF ₃ BF ₂ (CN)]

- (CH ₃ ) ₃ SiF

Potassium trifluorotrifluoromethyl borate, K [CF ₃ BF ₃ ] (3.0 g, 17.0 mmol) is weighed into a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stir bar. Trimethylsilyl cyanide (6.0 mL, 45.0 mmol) is added in an argon atmosphere. The reaction mixture is stirred for 20 hours at room temperature. All volatiles are removed in vacuo and most of the unreacted trimethylsilyl cyanide (3.0 mL, 22.5 mmol) is recovered by fractional distillation. The solid residue is taken up in THF (3 mL) and by addition of CH ₂ Cl ₂ (150 mL) K [CF ₃ BF ₂ CN] is precipitated and then filtered off. The colorless solid is dried in vacuo. Yield based on the potassium trifluorotrifluoromethylborate used: 3.0 g (16.4 mmol, 96%).

Decomposition from 200 ° C.

Raman spectroscopy: v (CN) = 2226 cm ^-1 .

¹ B-NMR: ö ^~, ppm = -3.8 tq (1 B), 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 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 ] K [CF ₃ BF ₃ ] + 2 (CH ₃ ) ₃ SiCN - K [CF ₃ BF (CN) ₂ ]

- 2 (CH ₃ ) ₃ SiF

Microwave irradiation 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 valve and a PTFE spindle (Young, London) and a magnetic stirrer.

Under argon, trimethylsilyl cyanide (17.1 mL, 127.5 mmol) is added. The reaction mixture is stirred for 12 days at room temperature. Most of the trimethylsilyl fluoride formed is removed in vacuo. The reaction mixture is then irradiated in a microwave (CEM Discover) (200 W, T _ma x = 90 ° C., 20 minutes). All volatiles are removed in vacuo and most unreacted trimethylsilyl cyanide (6.3 mL, 47.2 mmol) is recovered by fractional distillation. The residue is taken up in aqueous H ₂ O ₂ (30% strength, 50 ml) and stirred for one hour. The pH of the solution is adjusted to 1 with 37% hydrochloric acid. The reaction mixture is admixed with N (C ₃ H ₇ ) ₃ (7.0 mL, 36.8 mmol) and the tripropylammonium salt is extracted with CH ₂ Cl ₂ (3 × 50 mL). The combined organic phases are dried with MgSO ₄ , filtered and treated with an aqueous potassium

20 hydroxide solution (6 g, 30 mL). The organic phase becomes

decanted, a second time with an aqueous KOH solution (6 g, 30 mL) and decanted again. The aqueous phases are extracted with THF (3 × 50 ml). The collected tetrahydrofuran fractions are dried with K ₂ CO ₃ , filtered and concentrated. By adding

25 CH ₂ Cl ₂ (150 mL) is precipitated K [CF ₃ BF (CN) ₂ ], which is dried in vacuo. Yield based on the potassium trifluorotrifluoromethyl borate used: 5.0 g (26.3 mmol, 77%). Decomposition from 260 ° C;

Raman spectroscopy: v (CN) = 2215 cm ^-1 .

30 B NMR: δ, ppm = -12.8 dq (1 B), 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, 1 F), ¹ J _F , _B = 49.2 Hz, ³ J _F , _F = 8.0 Hz

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

K [CF ₃ BF ₃ ] + 3 (CH ₃ ) ₃ SiCN * - K [CF ₃ B (CN) ₃ ]

- 3 (CH ₃ ) ₃ SiF

Microwave irradiation 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 valve and a PTFE spindle (Young, London) and a magnetic stir bar.

Trimethylsilyl cyanide (10.0 mL, 74.9 mmol) is added in an argon atmosphere. The reaction mixture is stirred for 2 hours at 100.degree.

Subsequently, most of the trimethylsilyl fluoride formed is removed in vacuo and the reaction mixture in a microwave (CEM Discover) irradiated (300 W, T _max = 120 ° C, 95 minutes). Subsequently, all volatiles are removed under reduced pressure and most unreacted trimethylsilyl cyanide (8.0 mL, 59.9 mmol) is recovered by fractional distillation. The residue is dissolved in 30% aqueous H ₂ O ₂ (5 mL). The solution is treated with K ₂ CO ₃ and stirred for one h. The mixture is concentrated to dryness using a rotary evaporator and the residue is extracted with diethyl ether (3 × 50 ml). The volume of the combined ethereal phases is reduced to 5 mL and the addition of CH ₂ Cl ₂ (100 mL) yields colorless

K [CF ₃ B (CN) ₃ ]. The potassium salt is filtered off and dried in vacuo. Yield based on the potassium trifluorotrifluoromethylborate used: 0.53 g (2.74 mmol, 95%).

Decomposition from 320 ° C; Raman spectroscopy: μ (CN) = 2237, 2231 cm ^-1 . 1B NMR: δ, ppm = -32.0 q (1 B), 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 cyanodifluoropentafluoroethylborate - K [C ₂ F ₅ BF ₂ (CN)] A. K [C ₂ F ₅ BF ₃ ] + (CH ₃ ) ₃ SiCN K [C ₂ F ₅ BF ₂ (CN)]

- (CH ₃ ) ₃ SiF

In a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirrer is

Potassium trifluoropentafluoro-ethyl borate, K [C ₂ F ₅ BF ₃ ] (10.4 g, 46.0 mmol). The flask is seked and in an argon atmosphere trimethylsilyl cyanide (70.0 mL, 524.9 mmol) is added. The reaction mixture is stirred for 45 min at 100 ° C and the resulting

Trimethylsilylfluorid is distilled off continuously. Subsequently, all volatiles are removed in vacuo. Most unreacted trimethylsilyl cyanide (58.1 mL, 159.9 mmol) is recovered by fractional distillation. The residue is washed with CH ₂ Cl ₂ (200 ml), filtered and dried in vacuo. Potassium cyanodifluoropentafluoroethylborate, K [C ₂ F ₅ BF ₂ (CN)], is obtained as a colorless solid. Yield based on the used

Potassium trifluoropentafluoroethyl borate: 9.8 g (42.1 mmol, 92%).

Decomposition from 260 ° C; Raman spectroscopy: v (CN) = 2235 cm ^-1 .

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

¹⁹ F-NMR: <5, ppm = -83.3 t (CF ₃ , 3F), ⁴ J _FF = 5.2 Hz; -136.3 q (CF ₂ , 2F), 2J _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.

K [C ₂ F ₅ BF ₃ ] + (CH ₃ ) ₃ SiCN K [C ₂ F ₅ BF ₂ (CN)]

- (CH ₃ ) ₃ SiF

A cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirrer is with

Potassium trifluoro-pentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (15.8 g, 69.9 mmol). Trimethylsilyl cyanide (35.0 mL, 262.5 mmol) is added in a protective gas atmosphere. The reaction mixture is stirred for 1 hour at 100 ° C and the formed trimethylsilyl fluoride is distilled off continuously. Subsequently, all volatiles are removed in vacuo. Most unreacted trimethylsilyl cyanide (21.3 mL, 159.9 mmol) is recovered by fractional distillation. The residue is dissolved in THF (5 mL) and precipitated by addition of CH ₂ Cl ₂ (200 mL) colorless potassium cyanodifluoropentafluoroethylborate, K [C ₂ F ₅ BF ₂ (CN)], then filtered off and dried in vacuo. Yield based on the potassium trifluoropentafluoroethylborate used: 15.8 g (67.8 mmol, 97%). ¹ B and ¹⁹ F NMR spectra correspond to those in Example 5, A

specified values.

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

C.

In a dry box, K [C ₂ F ₅ BF ₃ ] (100 mg, 0.44 mmol), LiCl (180 mg, 4.2 mmol) and KCN (260 mg, 3.99 mmol) are finely ground together and placed in a cylindrical reaction vessel filled with a glass valve and a PTFE spindle (Young, London). The reaction mixture is heated to 180 ° C under vacuum for 20 hours.

The ¹¹ B NMR spectroscopic analysis shows that the reaction mixture contains the following borate anions:

Anion <5 ( ¹¹ B) [ppm] Share in%

unknown -20.5 1

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

K [C ₂ F ₅ BF ₃ ] + 2 (CH ₃ ) ₃ SiCN --- K [C ₂ F ₅ BF (CN) ₂ ]

- 2 (CH ₃ ) ₃ SiF

Potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (1.0 g, 4.4 mmol) is dissolved in a cylindrical reaction vessel with a glass valve and a PTFE Spindel (Young, London) and a magnetic stirrer in one

Argon atmosphere dissolved in trimethylsilyl cyanide (10.0 mL, 74.9 mmol). The reaction mixture is stirred for 1 hour at 1 10 ° C and the forming trimethylsilyl fluoride is distilled off continuously. Subsequently, the reaction mixture is stirred at 10 intervals in each case for about 30 minutes at 180 ° C, cooled and most of the trimethylsilyl formed is removed. Subsequently, all volatiles are removed in vacuo. Most unreacted trimethylsilyl cyanide (7.1 mL, 53.0 mmol) is purified by fractional distillation. The residue is dissolved in THF (3 mL) and by addition of CH ₂ Cl ₂ (100 mL) is precipitated colorless K [C ₂ F ₅ BF (CN) ₂ ]. The salt is filtered off and dried in vacuo. Yield based on the potassium trifluoropentafluoroethyl borate used: 0.97 g (4.0 mmol, 92%).

Decomposition from 260 ° C; Raman spectroscopy: v (CN) = 2224 cm ^-1 . ¹¹ B-NMR: δ, ppm = -12.0 dt (1 B), J _F, B = 51.6 Hz, ² J _F , _B = 25.2 Hz. 9F-NMR: δ, ppm = -82.6 dt (CF ₃ , 3F ), ³ J _FF = 1.0 Hz, ⁴ J _FF = 6.3 Hz;

-132.0 qd (CF ₂ , 2F), ³ J _FF = 5.0 Hz, ² J _FB = 25.3 Hz; -219.1 qqt (BF, 1F), J _F, B = 52 Hz, ³ J _F, F = 5-6 Hz, ⁴ J _{F, F} = 5-6 Hz.

B.

K [C ₂ F ₅ BF ₃ ] + 2 (CH ₃ ) ₃ SiCN K [C ₂ F ₅ BF (CN) ₂ ]

- 2 (CH ₃ ) ₃ SiF

In an argon atmosphere, potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (1.0 g, 4.4 mmol) trimethylsilyl cyanide (10.0 mL, 74.9 mmol.) In a cylindrical reaction vessel with a glass valve and PTFE spindle (Young, London) and magnetic stirrer ). The

Reaction mixture is stirred for 52 hours at 150 ° C with regular degassing. Subsequently, all volatiles are removed in vacuo. Most unreacted trimethylsilyl cyanide (7.1 mL, 53.0 mmol) is recovered by fractional distillation. Colorless K [C ₂ F ₅ BF (CN) ₂ ] is precipitated from THF (3 mL) with CH ₂ Cl ₂ (100 mL), filtered and dried in vacuo. Yield based on the used

Potassium trifluoropentafluoroethyl borate: 0.95 g (3.9 mmol, 90%). ¹¹ B and ¹⁹ F NMR spectra correspond to the values given in Example 6, A.

C.

K [C ₂ F ₅ BF ₃ ] + 2 (CH ₃ ) ₃ SiCN - K [C ₂ F ₅ BF (CN) ₂ ]

- 2 (CH ₃ ) ₃ SiF

Microwave irradiation 200 W, 15 min

Potassium trifluoropentafluoro-ethyl borate, K [C ₂ F ₅ BF ₃ ] (5.0 g, 22.1 mmol) is weighed into a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirring bar. The flask is evacuated and trimethylsilyl cyanide (10.0 mL, 74.9 mmol) is condensed. The reaction mixture is irradiated for 15 min in a microwave (CEM Discover) (200 W, T _max = 70 ° C.). All fleeting

Ingredients are removed in vacuo and most unreacted trimethylsilyl cyanide (3.1 mL, 23.1 mmol) is recovered by fractional distillation. The residue is dissolved in 30% aqueous H ₂ 0 ₂ (200 mL) and the solution is adjusted to pH = 1 with stirring by addition of 37% hydrochloric acid. Subsequently, N (C ₃ H ₇ ) ₃ (7.0 mL, 36.8 mmol) is added. The mixture is extracted with CH ₂ Cl ₂ (2 × 100 and 1 × 50 ml). The combined organic phases are dried with MgS0 ₄ , filtered and treated with an aqueous KOH solution (6 g, 30 mL). The organic phase is decanted off and treated a second time with an aqueous KOH solution (10 g, 40 mL) and stirred for one hour. Then the organic phase is separated and the aqueous phase is extracted with Et ₂ O (3 x 100 mL). In each of the three extraction steps, more K ₂ CO _{3 is} added to the aqueous phase. The collected ethereal phases are dried with K ₂ CO ₃ , filtered and concentrated to dryness. The residue obtained is suspended in CH ₂ Cl ₂ (50 ml), filtered and dried in vacuo. Yield of potassium dicyanofluoropentafluoroethylborate, K [C2F ₅ BF (CN) 2], is 3.4 g (14.3 mmol, 65%) based on the potassium trifluoropentafluoroethylborate used. ¹¹ B and ⁹ F NMR spectra correspond to the values given in Example 6, A.

D.

K [C ₂ F ₅ BF ₃ ] + 2 (CH ₃ ) ₃ SiCN K [C ₂ F ₅ BF (CN) ₂ ]

- 2 (CH ₃ ) ₃ SiF

Microwave irradiation 200 W, 15 min

To potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ] (8.0 g, 35.4 mmol) in a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirrer is in an argon atmosphere trimethylsilyl cyanide (25.0 mL, 187.5 mmol ). The reaction mixture is stirred at room temperature for 3 days. The mixture is degassed and then irradiated for 15 minutes in a microwave (CEM Discover) (200 W, T _max = 78 ° C). All volatiles are removed in vacuo and most unreacted

Trimethylsilyl cyanide (13.5 mL, 101.5 mmol) is fractionated through

Recovered distillation. The residue is dissolved in 30% H ₂ O ₂ (20 mL) and treated with K 2 CO 3 (5 g). The mixture is stirred for 1 hour at room temperature. The solution is concentrated at 70 ° C on a rotary evaporator to dryness and the resulting solid is extracted with Et ₂ 0 (7 * 50 mL). The combined organic phases are dried over K ₂ C0 ₃ , filtered and concentrated to dryness. The residue is dissolved in acetone (5 mL). Addition of CH ₂ Cl ₂ (50 mL) gives colorless potassium dicyanofluoropentafluoroethylborate,

K [C ₂ F ₅ BF (CN) ₂ ], which is filtered and dried in vacuo. Yield based on the potassium trifluoropentafluoroethyl borate used: 7.8 g (32.5 mmol, 92%).

¹ B and ¹⁹ F NMR spectra correspond to the values given in Example 6, A.

Example 7 Potassium Tricyanopentafluoroethyl Borate - K [C ₂ F ₅ B (CN) ₃ ] K [C ₂ F ₅ BF ₃ ] + 3 (CH ₃ ) ₃ SiCN - K [C ₂ F ₅ B (CN) ₃ ]

- 3 (CH ₃ ) ₃ SiF

Microwave irradiation 300 W, 60 min

Potassium trifluoropentafluoro-ethyl borate, K [C ₂ F ₅ BF ₃ ] (0.5 g, 2.2 mmol) is weighed into a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirring bar. The flask is seked and in an argon atmosphere trimethylsilyl cyanide (10.0 mL, 74.9 mmol) is added. The reaction mixture is stirred at room temperature for 2 days and then irradiated in a microwave (CEM Discover) (300 W, T _max = 120 ° C., 60 min). All volatiles are removed in vacuo and most of the unreacted trimethylsilyl cyanide (6.9 mL, 52.0 mmol) is recovered by fractional distillation. The residue is dissolved in 30% aqueous H ₂ O ₂ (10 mL) and treated with K 2 CO 3 (2 g). The mixture is stirred for 1 hour at room temperature. The solution is concentrated at 80 ° C with a rotary evaporator to dryness. The residual solid is extracted with Et ₂ O (4 x 50 mL). The combined organic phases are dried with K 2 CO 3, filtered and concentrated to a residual volume of 5 ml. By slow addition of CH ₂ Cl ₂ (150 mL) becomes a colorless

Obtained precipitation. The colorless K [C ₂ F ₅ B (CN) ₃ ] is filtered off and dried in vacuo. Yield based on the used

Potassium trifluoropentafluoroethyl borate: 480 mg (1.9 mmol, 88%).

Decomposition from 350 ° C; Raman spectroscopy: v (CN) = 2236, 2232 cm ^-1 .

¹ B NMR: δ, ppm = -31.9 t (1 B), 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; calculates C ₅ BF ₅ KN _3> %, C 24.32, N 17.01.

Example 8. Potassium cyanodifluoropentafluorophenyl borate - K [C ₆ F ₅ BF ₂ (CN)]

K [C ₆ F ₅ BF ₃ ] + (CH ₃ ) ₃ SiCN K [C ₆ F ₅ BF ₂ (CN)]

- (CH ₃ ) ₃ SIF 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 valve and a PTFE spindle (Young, London) and a magnetic stir bar. In a protective gas atmosphere, trimethylsilyl cyanide (10.0 mL, 74.9 mmol) is added. The reaction mixture is stirred for 7 days at room temperature. All volatiles are removed in vacuo and most of the unreacted trimethylsilyl cyanide (7.7 mL, 57.9 mmol) is recovered by fractional distillation. The residue is dissolved in acetone (5 mL). Addition of CHCl ₃ (25 mL) precipitates colorless K [C ₆ F ₅ BF 2 CN]. Yield based on the used

Potassium trifluoropentafluorophenyl borate: 2.1 g (7.5 mmol, 82%).

Decomposition from 190 ° C; Raman spectroscopy: v (C) = 2224 cm ^-1 .

¹¹ B NMR: δ, ppm = -1.3 t, J _F , _B = 52 Hz.

¹⁹ F-NMR: δ, ppm = -136.4 m (2F), -151, 1 tq (2F, BF2), J _BF = 52 Hz, ⁴ J _FF = 14 Hz; -161.9 t (1 F), ³ J _{F, F} = 19 Hz; -167.2 m (2 F).

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

K [C ₆ F ₅ BF ₃ ] + 3 (CH ₃ ) ₃ SiCN - C K [C ₆ F ₅ B (CN) ₃ ]

In a 50mL two-necked flask with a stirrer and a

Reflux is a suspension of potassium trifluoropentafluorophenylborate, K [C ₆ F ₅ BF ₃ ] (2.0 g, 7.3 mmol) in trimethylsilyl cyanide (15.0 mL, 112.5 mmol) filled in an argon countercurrent. The

Reaction mixture is heated to reflux for 3 days and all volatiles are distilled off and most unreacted

Trimethylsilyl cyanide (10.8 mL, 81.1 mmol) is fractionated through

Recovered distillation. The residue is taken up in THF (80 ml) with addition of K ₂ CO ₃ and filtered. The filtrate is concentrated to a volume of 10 mL and by slowly adding CHCl ₃ (100 mL) almost colorless K [C ₆ F ₅ B (CN) ₃ ] is precipitated. The precipitate is filtered and dried in vacuo. Yield of potassium tricyanopentafluoro- phenylborate, K [C ₆ F ₅ B (CN) ₃ ], is 1.7 g (5.9 mmol), 81% based on the potassium trifluoropentafluorophenylborate used. Decomposition from 280 ° C.

¹ B NMR: δ, ppm = -33.8 t, ³ J _F , _B = 7 Hz. 9F NMR: δ, ppm = -132.0 m (1 F), -158.7 t (2F), ³ J _FF = 19 Hz; -165.4 m (2F).

Example 10. Tetra- / J-butylammonium cyanodifluorotrifluoromethylborate -

[(/ 7-C ₄ H 9) ₄ N] [CF ₃ BF 2 (CN)]

A.

H ₂ 0

K [BF ₃ CF ₂ (CN)] + [(C ₄ H ₉₎ ₄ N] Br> - _[(C4 H9) ₄ N] [CF ₃ BF2 (CN)] + j KBr

Potassium cyanodifluorotrifluoromethylborate, K [CF ₃ BF ₂ CN] (0.5 g, 2.7 mmol), prepared as described in Example 2, is dissolved in deionized water (20 mL) and slowly added with an aqueous solution of f / BuBu ₄ N with stirring. Br (1.7 g, 5.4 mmol, 20 mL). The educated colorless

Precipitate is filtered off and dried in vacuo. Yield of tetra-n-butylammonium cyano-difluorotrifluoromethylborate is 0.7 g (1.9 mmol), 67% based on the potassium cyanodifluorotrifluoromethylborate used. Melting point: 73 ° C; Raman spectroscopy: y (CN) = 2208 cm ^-1 . H-NMR: δ, ppm = 1.0 1 (4CH ₃ , 12 H), ³ J _HH = 7 Hz; 1 .4 m (4CH ₂ , 8 H), ³ J _HH = 7 Hz, 1 .7-1.8 m (4CH ₂₎ 8 H); 3.3-3.5 m, (4CH ₂ , 8 H).

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 (1 B), ¹ J _{F, B} = 49.0 Hz, ² J _{F, B} = 34.5 Hz.

¹⁹ F-NMR: <5, ppm = -77.4 q (CF ₃ , 3F), ² J _{F, B} = 34.5 Hz; -169.1 q (BF ₂ , 2F), J _{Fi B} = 49.3 Hz

Elemental analysis: Found,%, C 57.19, H 9.36, N 7.44; calculated for Ci ₈ H ₃₆ BF ₅ N ₂ ,%, C 55.97, H 9.39, N 7.25.

B. K [CF ₃ BF ₃ ] + (CH ₃ ) ₃ SiCl + NaCN + [(C ₄ H ₉ ) ₄ N] Br »

- (CH ₃ ) ₃ SiF

** [(C ₄ H 9) ₄ N] [CF ₃ BF 2 (CN)] + NaCl + KBr

In a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirrer

Sodium cyanide (13.1 g, 267.3 mmol) and sodium iodide (3.8 g, 25.4 mmol) dried in vacuo at 130 ° C in 4 hours. Then be

Acetonitrile (15 mL) and trimethylsilyl chloride (30.0 mL, 25.8 g, 237.5 mmol) were added. The suspension is stirred for 24 hours at 50 ° C and 3 days at room temperature. Then K [CF ₃ BF ₃ ] (0.5 g, 2.8 mmol) is added in an argon countercurrent and the reaction mixture is stirred at 50 ° C. for 24 hours and then at 80 ° C. for 4 days. At room temperature, all volatiles are removed in vacuo. From the

condensed phase is isolated by fractional distillation trimethyl silyl cyanides (28.2 mL, 211.2 mmol) as a by-product, which is used in further reactions. The resulting solid residue is taken up in deionized water (15 mL). The resulting solution is mixed with stirring 30% aqueous H ₂ 0 ₂ (25 mL) and K ₂ CO ₃ and stirred for one hour. The solution is concentrated to dryness in vacuo and the residue is extracted with acetone (3 ^× 50 ml). The combined organic phases are mixed with deionized water (30 mL) and the acetone is removed in vacuo. By adding a solution of [nBu ₄ N] Br (1.0 g, 3.1 mmol) in deionized water (20 mL), pure [nBu ₄ N] [CF ₃ BF ₂ (CN)] is obtained. Yield of tetra-n-butylammonium cyanodifluorotrifluoromethylborate is 0.9 g (2.4 mmol), 86% based on the potassium cyanodifluorotrifluoromethylborate used.

1 H and ¹³ C NMR spectra are consistent with the surrounded in Example 10, A values. Example 11. 1-Ethyl-3-methylimidazolium cyanodifluorotrifluoromethylborate - [C ₆ H ₁₁ N ₂ ] [CF ₃ BF 2 (CN)] C ₂ H ₅ - + KCl

To a solution of 1-ethyl-3-methylimidazolium chloride, [EMIM] Cl (5.0 g, 34.1 mmol) in deionized water (20 mL) with vigorous stirring K [CF ₃ BF ₂ (CN)] (5.9 g, 32.5 mmol ), prepared as in Example 2

described, and stirred for 10 min. 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. under a high vacuum. Yield of liquid 1-ethyl-3-methylimidazolium cyano difluorotrifluoromethylborate is 5.7 g (22.4 mmol), 69% based on the potassium cyanodifluorotrifluoromethylborate used.

Melting point: 13 ° C. Water content (Karl Fischer titration): 40 ppm.

Dynamic viscosity (20 ° C): 16.5 mPa-s, (40 ° C): 10.3 mPa-s, (60 ° C) 6.9 mPa-s, (80 ° C) 5.0 mPa-s.

¹ H NMR: δ, ppm = 1.51 (CH ₃ , 3H), ³ J _H H = 7 Hz; 4.0s (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 {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).

1B NMR: δ, ppm = -3.8 tq (1 B), 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 cyanodifluorotrifluoromethyl borate - [C ₇ H ₁₃ 2] [CF 3 BF 2 (C)]

Potassium cyanodifluorotrifluoromethylborate K [CF ₃ BF ₂ (CN)] (8.0 g, 43.7 mmol) is taken up in deionized water (5 mL) and washed with a solution of 1-ethyl-2,3-dimethylimidazolium chloride [EDMIM] CI (7.7 g, 47.9 mmol) in 10 mL of deionized water. The resulting ionic liquid is washed with deionized water (4 × 2 ml), separated off and dried at 50 ° C. under reduced pressure for 2 days. The yield of 1-ethyl-2,3-dimethyl-imidazolium cyanodifluorotrifluoromethylborate is 1.2 g (39.4 mmol), 90%, based on the potassium cyanodifluoro-trifluoromethyl borate K [CF3BF ₂ (CN)] used. The product is analyzed by ion chromatography and has low levels of halide impurities; Chloride: 28 ppm, fluoride: 236 ppm. Water content (Karl Fischer titration): 57 ppm. Dynamic viscosity (20 ° C): 51.6 mPa-s.

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

¹ H-NMR: δ, ppm = 7.59 d (CH, 1 H), ³ J _HH = 2.15 Hz; 7.53 d (CH, 1H), ³ J _HH = 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); 1.45 t (CH ₃ , 3H), ³ J _HH = 7.30 Hz.

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

¹¹ B NMR: <5, ppm = -3.8 tq (1 B), 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 JF _, B = 49.3 HZ

Elemental analysis: found,%, C 40.10, H 4.93, N 16.20; calculated for C ₇ Hi ₃ BF ₅ N _3> %, C 40.18, H 4.87, N 15.62.

Example 13. Tetraphenylphosphonium cyanodifluorotrifluoromethylborate - [(C ₆ H ₅ ) ₄ P] [CF ₃ BF ₂ (CN)]

K [CF ₃ BF ₃ ] + (CH ₃ ) ₃ SiCN + [(C ₆ H ₅ ) ₄ P] Br> [(C ₆ H ₅ ) ₄ P] [CF ₃ BF ₂ (CN)] + KBr

Potassium trifluorotrifluoromethyl borate, K [CF ₃ BF ₃ ] (0.3 g, 1.7 mmol), is placed in a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stir bar.

Trimethylsilyl cyanide (5.0 mL, 37.5 mmol) is added under argon atmosphere. The reaction mixture is left at room temperature for 24 hours touched. All volatiles are removed in vacuo and most unreacted trimethylsilyl cyanide (4.3 mL, 32.3 mmol) is recovered by fractional distillation. The residue is dissolved in deionized water (10 mL) and precipitated with [Ph ₄ P] Br (1.2 g, 2.8 mmol) dissolved in deionized water (20 mL), filtered off and dried in vacuo. Yield of Tetraphenylphosphoniumcyanodifluortrifluoromethylborat: 0.8 g (1.7 mmol), 97% based on the used

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

¹¹ B-NMR: δ, ppm = -3.8 tq (1 B), J _F , B = 49.0 Hz, ² J _F , _B = 34.5 Hz. ¹⁹ F-NMR: <5, ppm = -77.4 q (CF _{3 >} 3F), ² J _FB = 34.5 Hz; -169.1 q (BF ₂ , 2F), ¹ J _{F, B} = 49.3 Hz

Elemental analysis: found,%, C 64.22, H 4.65, N 2.91; calculated for C26H20BF5NP,%, C 64.62, H 4.17, N 2.90. Example 14. N-Butyl-N-methylpyrrolidinium cyanodifluoro trifluoro-

In deionized water (5 mL), K [CF ₃ BF ₂ (CN)] (220 mg, 1.2 mmol), prepared as described in Example 2, is dissolved and treated with 1-butyl-1-methylpyrrolidinium chloride (250 mg, 1.4 mmol). added. The resulting ionic liquid is extracted with CH ₂ Cl ₂ (2 x 10 mL). The

Dichloromethane solution is dried with MgS0 ₄ , filtered and the CH ₂ Cl ₂ is removed with a rotary evaporator. Yield of liquid at room temperature N-butyl-N-methyl-pyrrolidiniumcyanodifluortriflu- ormethylborat is 293 mg (1, 0 mmol), 85% based on potassium cyanodifluoro-trifluoromethyl borate, K [CF ₃ BF ₂ (CN)].

Raman spectroscopy: v (CN) = 2208 cm ^-1 _.

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 H), ³ J _H , H = Hz; 0.98 1 (CH ₃₎ 3H), ³ J _H , H = 7 Hz.

3C {H} -NMR (cation): δ, ppm = 65.2 t (2C); 65.0 t (1 C); 49.0 t (1 C); 26.2 s (1 C); 22.3 s (2C); 20.3s (1C); 13.7 s (1C).

¹¹ B-NMR: <5, ppm = -3.8 tq (1 B), 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 _{Fi B} = 49.3 Hz

Example 15. Tetraphenylphosphoniumdicyanofluortrifluormethylborat - [(C6H ₅₎ 4P] [CF ₃ BF (CN) 2]

K [CF ₃ BF ₃ ] + 2 (CH ₃ ) ₃ SiCl + 2 KCN + [(C ₆ H ₅ ) ₄ P] Br _ ₂ *

[(C ₆ H ₅ ) ₄ P] [CF ₃ BF (CN) ₂ ] + 2 KCl + KBr

In a 100 mL flask with a magnetic stirrer and a

Reflux cooler is finely ground potassium cyanide (30.1 g, 462.2 mmol) and potassium iodide (6.1 g, 36.7 mmol) at 1 15 ° C in vacuo in 5

Hours dried. Subsequently, trimethylsilyl chloride (32.0 mL, 27.4 g, 252.2 mmol) is added and the reaction mixture is refluxed for 24 hours (60-80 ° C, bath temperature). Elementary iodine (1.0 g, 3.9 mmol) is then added in an argon countercurrent and the mixture is heated to 110.degree. C. until no reflux is observed. At room temperature, K [CF ₃ BF ₃ ] (1.6 g, 9.1 mmol) is added and the reaction is heated to reflux for 48 hours. Subsequently, at 100 ° C, all volatiles are removed in vacuo and the residue obtained is treated with K ₂ C0 ₃ (2 g) and then extracted with THF (4 * 50 mL). To the combined THF phases is added an aqueous potassium hydroxide solution (1.0 g, 17.8 mmol, 150 mL). With a rotary evaporator, the THF is separated at 70 ° C. To the Reaction mixture is slowly added an aqueous [Ph ₄ P] Br solution (4.5 g, 10.7 mmol, 100 ml). The colorless precipitate is filtered off, taken up in acetone (150 ml) and mixed with Celite. The mixture is filtered and the solution is concentrated with a rotary evaporator to a volume of 5 mL. Slow addition of diethyl ether (100 mL) leads to the precipitation of colorless [Ph ₄ P] [CF ₃ BF (CN) ₂ ]. Yield of Tetraphenylphosphoniumdicyanofluor-trifluoromethylborate is 2.5 g (5.1 mmol), 56% based on the potassium trifluorotrifluoromethyl borate, K [CF ₃ BF ₃ ].

Melting point: 150 ° C; Decomposition from 290 ° C. Raman spectroscopy: v (CN) = 2215 cm ^-1 .

¹ H-NMR: δ, ppm = 7.8-7.92 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 _CP = 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 B), 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 _FF = 8.3 Hz;

-219.7 qq (BF, 1 F), ¹ J _F , _B = 49.2 Hz, ³ J _F , _F = 8.0 Hz.

Example 16. 1-Ethyl-3-methylimidazolium dicyanofluorotrifluoromethylborate - CeHnNzltCFaBFiCNJz]

Potassium dicyanofluorotrifluoromethyl borate, K [CF ₃ BF (CN) ₂ ] (5.0 g, 26.3 mmol), prepared as described in Example 3, is dissolved in deionized water (15 mL) and treated with a solution of 1-ethyl-3-methylimidazolium chloride, EMIM] CI (3.8 g, 26.3 mmol) in deionized water (15 mL) with vigorous stirring. The mixture is stirred for 10 minutes. The aqueous phase is then taken off with a pipette and the resulting colorless ionic liquid is washed with bidistilled water (4 <5 ml_) and then dried in vacuo at 50 ° C. Yield of liquid 1-ethyl-3-methylimidazolium dicyanofluorotrifluoromethylborate 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. H-NMR: δ, ppm = 1.51 (CH ₃₎ 3H), ³ J _HH = 7 Hz; 4.0s (CH3 ₎ 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) , 15.4s (1C).

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

¹⁹ F-NMR: δ, ppm = -74.0 qd (CF ₃₎ ³ _F ), ² J _FB = 35.7 Hz, ³ J _F , F = 8.3 Hz;

-219.7 qq (BF, 1 F), ¹ J _F , _B = 49.2 Hz, ³ J _F , _F = 8.0 Hz

Example 17. 1-Ethyl-3-methylimidazolium cyanodifluoropentafluoroethylborate - [CeHnNzHCzFgBFziCN)]

C ₂ H + KCl

A.

Potassium cyanodifluoropentafluoroethylborate, K [C ₂ F ₅ BF ₂ (CN)] (6.9 g, 29.6 mmol), prepared as described in Example 5, and 1-ethyl-3-methylimidazolium chloride, [EMIM] CI (4.5 g, 30.7 mmol) taken up in a mixture of CH ₂ Cl ₂ (100 ml) and deionized water (20 ml) and stirred for 1 hour. Subsequently, the aqueous phase is separated and the organic phase washed with deionized water (5 ^χ 50 mL) until the test for chloride ion with AgN0 ₃ is negative. The dichloromethane phase is dried with MgSO ₄ , filtered and concentrated by rotary evaporation at 60 ° C. The resulting nearly colorless liquid is dried in vacuo at 50 ° C. The yield of liquid 1-ethyl-3-methylimidazolium cyanodifluoropentafluoroethylborate is 6.5 g (21.3 mmol), 72% based on the potassium cyanodifluoropentafluoroethylborate, 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: v (CN) = 2208 cm ^-1

¹ H-NMR: δ, ppm = 1.5 t (CH ₃ , 3H), ³ J _H , _H = 7 Hz; 4.0s (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). 3C { 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). B-NMR: δ, ppm = -2.7 t (1 B), ¹ J _F , B ⁼ 51.0 Hz, ² J _F , _B = 25.3 Hz 9F-NMR: δ, ppm = -83.3 t (CF ₃ , 3F) , ⁴ J _FF = 5.2 Hz; -136.3 q (CF ₂ , 2F), 2J _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, 35.44, H, 3.50, N, 13.81; calculated for CgHuBFyNa,%, 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- are placed in a 10 mL reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirrer. methylimidazolium chloride, [EMIM] CI (650 mg, 4.43 mmol). Deionized water (1 mL) is added and the reaction mixture is stirred for 15 minutes. The aqueous phase is separated off and

remaining ionic liquid is washed with deionized water (1 mL) and dried at 50 ° C for 4 hours in vacuo. Thereafter, NaCN (660 mg, 13.46 mmol) and trimethylsilyl chloride, (CH ₃ ) ₃ SiCl (1.7 mL, 13.45 mmol) are added and the reaction mixture is stirred for 10 hours at 60 ° C (the temperature of the oil bath). The volatiles are removed in vacuo, the resulting suspension is washed with deionized water (3 x 2 mL) and the clear ionic liquid is dried at 50 ° C in vacuo. The yield of liquid 1-ethyl-3-methylimidazolium cyanodifluoropentafluoroethylborate at Room temperature is 1.2 g (3.93 mmol), 89% based on the potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ]. The purity of the product is> 98% according to the ¹ B and ¹⁹ F NMR spectroscopic investigations.

Example 18. 1-Ethyl-2,3-dimethyl-limidazolium cyanodifluoropentafluoroethyl borate - [C ₇ Hi ₃ 2] [C ₂ F 5 BF ₂ (C)]

Potassium cyanodifluoropentafluoroethylborate K [C ₂ F ₅ BF ₂ (CN)] (4.2 g, 18.0 mmol) is taken up in deionized water (2 mL) and treated with a solution of 1-ethyl-2,3-dimethylimidazolium chloride [EDMIM] CI (3.2 g , 19.9 mmol) in 3 mL of deionized water. The resulting ionic liquid is washed with deionized water (4 x 2 mL), separated and dried in vacuo at 50 ° C. The yield of liquid at room temperature 1-ethyl-2,3-dimethylimidazoliumcyanodifluorpenta- fluoroethylborate is 5.1 g (15.9 mmol), 88% based on the potassium cyanodifluoropenta-fluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)]. The product is analyzed by ion chromatography and has low levels of halide impurities; 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, 1 H), ³ J _HH = 2.15 Hz, 7.55 d (CH, 1 H), ³ J _HH = 2.15 Hz, 4.32 q (CH ₂ , 2H), ³ J _HH = 7.30 Hz, 3.90 s (CH ₃ , 3H), 2.75 s (CH ₃ , 3H), 1.46 t (CH ₃ , 3H), ³ J _H , H = 7.30 Hz.

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

¹¹ B-NMR: δ, ppm = -2.7 t (1 B), ¹ J _F , _B = 51.0 Hz, ² J _F, B = 25.3 Hz. ⁹ F-NMR: δ, ppm = -83.31 (CF ₃ , 3F), ⁴ J _FF = 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 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 cyanodifluoropentafluoroethylborate - [CeHisNzHCzFgBFziCN)]

Potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] (4.0 g, 17.1 mmol), prepared as described in Example 5, is dissolved in deionized water (2 ml) and treated with a solution of 1-butyl-3-methylimidazolium chloride. BMIM] CI (3.4 g, 19.4 mmol) in 3 ml deionized water. The resulting ionic liquid is washed with deionized water (4 2 mL), separated and dried in vacuo at 50 ° C. The yield of liquid at room temperature 1-butyl-3-methylimidazolium cyanodifluorpentafluorethylborat is 5.2 g (15.6 mmol), 91% based on the potassium cyanodifluoro-pentafluoroethylborate K [C ₂ F ₅ BF ₂ (CN)]. The product is analyzed by ion chromatography and has low levels of halide impurities; 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: v (CN) = 2209 cm ^-1 ¹ H-NMR: δ, ppm = 8.95 d, d (CH, 1 H) ⁴ J _HH ^s 1 -6 Hz; 7.69 d, d (CH, 1 H), ³ J _HH « ⁴ J _H H = 1 -7 Hz; 7.65 d, d (CH, 1 H) ³ J _H H * ⁴ JH H = 1 -7 Hz; 4.34 t (CH ₂ , 2H), J _HH = 7.33 Hz; 4.02 s (CH ₃ , 3H); 1.92m (CH ₂ , 2H); 1.39 m (CH ₂ , 2H); 0.92 t (CH ₃ , 3H), J _H , H = 7.37 Hz.

3C {H} -NMR (cation): <5, 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). ¹ B NMR: δ, ppm = -2.7 t (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} = 23.3 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 39.60, H 4.56, N 12.64; calculated for CiiH ₁₅ BF ₇ N ₃ ,%, C 39.67, H 4.54, N 12.62.

Example 20. 1 - (2-Methoxyethyl) -3-methylimidazolium cyanodifluoropentafluoroethylborate - [C _/ HisNzOliCzFsBFziC)] + KBr

A solution of potassium cyanodifluoropentafluoroethylborate K [C ₂ F ₅ BF ₂ (CN)] (4.5 g, 19.3 mmol) in 2 mL of deionized water is added a solution of 1- (2-methoxyethyl) -3-methylimidazolium bromide [MOEMIM] Br (4.7 g, 21.2 mmol) in 3 mL of deionized water. The resulting ionic liquid is washed with deionized water (4 x 2 mL), separated and dried in vacuo at 60 ° C. The yield of 1-methoxyethyl-3-methylimidazolium cyanodifluoropentafluoroethylborate is 5.7 g (17.0 mmol), 88% based on the potassium cyanodifluoropentafluoroethylborate K [C ₂ F ₅ BF ₂ (CN)] used. The product is analyzed by ion chromatography and has low levels of halide impurities; 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, 1 H), ⁴ J _HH ^λ 1 7 Hz; 7.68 d, d (CH, 1H), 3HH H * ⁴ JH, H = 1-7 Hz; 7.67 d, d (CH, 1 H), ³ J _H , _H * ⁴ JH, H ^ä 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 {1H} -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).

B-NMR: δ, ppm = -2.7 t (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), 2J _{F, B} = 23.3 Hz; -167.2 qq (BF ₂ , 2F), J _F , _B = 51.1 Hz, ⁴ J _F. _F = 5.1 Hz.

Elementary analysis: found,%, C 35.13, H 4.03, N 12.58; calculated for ₅ CioHisBFyNsO,%, C 35.85, H 3.91, N 12.54.

Example 21. Tetra-n-butylammonium cyanodifluoropentafluoroethyl borate

- [(nC ₄ H 9) ₄ N] [C ₂ F ₅ BF ₂ (CN)]

A.

K [C ₂ F ₅ BF ₃ ] + (CH ₃ ) ₃ SiCN + [(C ₄ H ₉ ) ₄ N] Br --- [(C ₄ H ₉ ) ₄ N] [C ₂ F ₅ BF ₂ (CN )] + KBr

- | Q - (<- H ₃ ) ₃ blt- In a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) is potassium trifluoropentafluoroethylborate,

Weighed K [C ₂ F ₅ BF ₃ ] (1.0 g, 4.4 mmol). The flask is evacuated and a mixture of trimethylsilyl cyanide (25.0

15 ml, 187.5 mmol) and acetonitrile (6 ml) were added. A reflux condenser is placed in the argon countercurrent and the reaction mixture is irradiated for 10 min in a microwave (CEM Discover) (100 W, T _max = 75 ° C.). All volatiles are removed in vacuo and most unreacted trimethylsilyl cyanide (21.5 mL, 161.1 mmol) is passed through

20 fractional distillation recovered. The residue we in

deionized water (10 mL). Addition of an aqueous solution of [n-Bu ₄ N] Br (2.5 g, 7.8 mmol) in deionized water (20 mL) precipitates almost colorless [n-Bu ₄ N] [C ₂ F ₅ BF ₂ CN]. The yield of tetra-n-butylammonium cyanodifluoropentafluoroethylborate is 1.8 g (4.1 mmol), 93%

25 based on the potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ].

Melting point: 80 ° C; Decomposition from 250 ° C.

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

30 ³ 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 t (1 B), J _{F, B} = 51.0 Hz, ² J _{F, B} = 25.3 Hz. ¹⁹ F-NMR: δ, ppm = -83.3 t (CF ₃ , 3F), J _FF = 5.2 Hz; -136.3 q (CF ₂ , 2F), ² J _{Fi 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.

K [C ₂ F ₅ BF ₂ (CN)] + °> [(C ₄ H9) 4 N] [(C ₄ H ₉₎ ₄ N] Br ^Ηζ [C ₂ F ₅ BF ₂ (C)] | + KBr

In deionized water (50 mL), potassium cyanodifluoropentafluoroethylborate, K [C ₂ F ₅ BF ₂ CN] (0.5 g, 2.1 mmol), prepared as described in Example 5, is dissolved and stirred with an aqueous solution of

[n -Bu ₄ N] Br (1.4 g, 4.3 mmol, 100 mL). After 15 minutes, the colorless precipitate is filtered off and dried in vacuo. The yield of tetra-n-butylammonium cyanodifluoropentafluoroethylborate is 0.84 g (1.9 mmol), 90% based on the potassium cyanodifluoropentafluoroethylborate used, K [C ₂ F ₅ BF ₂ CN].

¹ H and ¹³ C NMR spectra correspond to the values given in Example 21, A.

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

Η, Ο

[(C ₄ H ₉ ) ₃ CH ₃ N] Cl + K [C ₂ F ₅ BF ₂ (CN)] [(C ₄ H ₉ ) ₃ CH ₃ N] [C ₂ F ₅ BF ₂ (CN)] + KCl

Aqueous solution (4 mL) of potassium cyanodifluoropentafluoroethylborate K [C ₂ F ₅ BF ₂ (CN)] (3.8 g, 16.3 mmol) is treated with tributylmethylammonium chloride [(0 ₄ Η ₉ ) ₃ ΟΗ ₃ Ν] ΟΙ (4.3 g, 18.2 mmol) dissolved in 4 mL of deionized water. The ionic liquid formed is washed with deionized water (4 × 2 ml), separated off and dried in vacuo at 60 ° C. The yield of tributylmethylammonium cyanodifluoropentafluoroethylborate is 5.7 g (14.4 mmol), 88% based on the potassium cyanodifluoropentafluoroethylborate K [C ₂ F ₅ BF ₂ (CN)] used. The product is analyzed by ion chromatography and has low levels of halide impurities; 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: v (CN) = 2208 cm H-NMR: <5, 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); 0.95 1 (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); 24.63s (CH _2> 3C); 20.15 s (CH ₂ , 3C); 13.65 s (CH ₃₎ 3C). 1B NMR: <5, ppm = -2.7 t (1 B), 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 48.79, H 7.81, N 7.21; calculated for C ₁₆ H ₃ oBF ₇ N ₂ ,%, C 48.75, H 7.67, N 7.1 1.

Example 23. N-Butyl-N-methylpyrrolidinium cyanodifluoropentafluoroethylborate - [C ₉ H 2 O N] [C 2 F ₅ BF 2 (CN)]

A. Potassium cyanodifluoropentafluoroethylborate K [C ₂ F ₅ BF ₂ (CN)] (4.2g, 18.0mmol) and A / Butyl / V-methylpyrrolidinium chloride [BMPL] CI (3.5g, 19.6mmol) are each added in 2mL deionized water solved. The solutions are combined and the resulting ionic liquid washed with deionized water (4 x 2 mL). The colorless liquid is dried in vacuo at 60 ° C. The yield of liquid at room temperature Λ / - butyl - / \ / - methylpyrrolidiniumcyano-difluoropentafluorethylborat is 5.9 g (17.5 mmol), 97% based on the potassium cyanodifluoro-pentafluorethylborat K [C ₂ F ₅ BF ₂ (CN)]. The product is analyzed by ion chromatography and has low levels of halide impurities; 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: v (CN) = 2208 cm ^-1 ¹ H-NMR: δ = 3.59 m (2CH _2> 4H); 3.42 m (CH _{2 1} 2H); 2.79 s (CH ₃ , 3H); 2.30 m (2CH ₂₎ 4H); 1.85 m (CH _{2 1} 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 , 1 C); 48.92 s (CH _{3 I} 1 C); 26.1 1 s (CH ₂ , 1 C); 22.20 s (CH _{2 I 2 C} ); 20.21 s (CH ₂ , 1 C); 13.51s (CH _3l 1C)

^{0 11} B-NMR: δ, ppm = -2.7 t (1 B), 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), J _F , F = 5.2 Hz; -136.3 q (CF ₂ , 2F), 2J _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 42.90, H 5.99, N 8.32; calculated for Ci ₂ H ₂₀ BF ₇ N _2l %, C 42.88, H 6.00, N 8.33.

5

B.

Potassium trifluoropentafluoroethylborate, K [C ₂ F ₅ BF ₃ ] (1.0 g, 4.4 mmol) and N-butyl / S / -methylpyrrolidinium chloride [BMPL] Cl (865 mg, 4.9 mmol) are taken up together in deionized water (1 mL). The

Q 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 for 2 hours in vacuo at 50 ° C. Then NaCN (660 mg, 13.5 mmol) is added and the suspension is kept at 50 ° C. for 15 minutes in vacuo

, ₅ dried. Subsequently, trimethylsilyl chloride (1.7 mL, 13.5 mmol) is added and the reaction mixture is stirred at 60 ° C. for 24 hours. The volatiles are removed in vacuo and the remaining suspension in acetone (10 mL), filtered (D4) and the acetone phase concentrated in vacuo.

₅₀ Yield: 1.2 g (3.6 mmol, 81%).

¹ H, ¹⁹ F and ¹¹ B NMR spectra correspond to those in Example 23, A

specified values. Example 24. Tetraphenylphosphonium cyanodifluoropentafluoroethyl borate - [(C ₅ H ₆ ) ₄ P] [C ₂ F ₅ BF 2 (CN)]

K [C ₂ F ₅ BF ₃ ] + (CH ₃ ) ₃ SiCN + [(C ₆ H ₅ ) ₄ P] Br> [(C ₆ H ₅ ) ₄ P] [C ₂ F ₅ BF ₂ (CN)] + KBr

- (CH ₃ ) ₃ SiF

Potassium trifluoropentafluoro-ethyl borate, K [C ₂ F ₅ BF ₃ ] (495 mg, 2.2 mmol) is weighed into a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirring bar. Trimethylsilyl cyanide (7.0 mL, 52.5 mmol) is condensed in an argon atmosphere. The reaction mixture is stirred for 5 hours at 100.degree.

Subsequently, all volatiles are removed in vacuo. Most unreacted trimethylsilyl cyanide (6.1 mL, 45.7 mmol) is recovered by fractional distillation. Dissolve the residue in deionized water (5 mL) and add [Ph P] Br (1.3 g, 3.1 mmol) dissolved in deionized water (150 mL). The precipitate is 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, K [C ₂ F ₅ BF ₃ ]. Melting point: 130 ° C; Decomposition from 310 ° C.

Raman spectroscopy: v (CN) = 2211 cm ^-1 .

¹³ C { ¹ H} -NMR (cation): δ, ppm = 136.3 s (4 C), 135.6 d (8 C), J _CP = 10 Hz,, 131.3 d (8 C), J _C , P = 3 Hz, 118.9 d (4 C), J _C , _P = 91 Hz.

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

9F-NMR: δ, ppm = -83.3 t (CF ₃ , 3F), ⁴ J _FF = 5.2 Hz; -136.3 q (CF ₂ , 2F),

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

Example 25. Tributylmethylphosphonium cyanodifluoropentafluoroethyl borate - [(C ₄ H 9) 3 CH 3 P] [C ₂ F ₅ BF 2 (CN)]

[(C ₄ H ₉ ) ₃ CH ₃ P] [CF ₃ COO] + K [C ₂ F ₅ BF ₂ (CN)] [(C ₄ H ₉ ) ₃ CH ₃ P] [C ₂ F ₅ BF ₂ (CN)] + K [CF ₃ COO] Potassium cyanodifluoropentafluoroethylborate K [C ₂ F ₅ BF ₂ (CN)] (2.6 g, 11.1 mmol) is dissolved in 2 mL of deionized water with a solution of tributylmethylphosphonium trifluoroacetate [(C ₄ H ₉ ) 3CH ₃ P] [CF ₃ CO 2] (3.7 g, 11.1 mmol) in 3 mL of deionized water. The ionic liquid is washed with deionized water (4 × 2 ml), separated by agitation and dried in vacuo at 50 ° C. The yield of tributylmethylphosphonium cyanodifluoropentafluoroethylborate is 4.0 g (9.7 mmol), 87% based on the potassium cyanodifluoropentafluoro-ethyl borate K [C ₂ F ₅ BF ₂ (CN)] used. The product is analyzed by ion chromatography and has low levels of halide impurities; Chloride: 8 ppm, fluoride: 8 ppm. Water content (Karl Fischer titration): 129 ppm.

Raman spectroscopy: v (CN) = 2208 cm ^-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 _PC = 4.53 Hz; 20.53 d (3CH ₂ , 3C), J _PC = 49.74 Hz; 13.55 d (3CH ₃ , 3C), ⁴ J _P , _C = 0.85 Hz; 4.08 d (CH ₃ , 1C), J _P , _C = 52.88 Hz.

¹ B NMR: δ, ppm = -2.7 t (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 _FF = 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, J _F , _F = 5.1 Hz.

³¹ P {H} -NMR: <5, 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. Diethylmethylsulfonium cyanodifluoropentafluoroethylborate - [(C ₂ H ₅ ) ₂ CH ₃ S] [C ₂ F ₅ BF ₂ (CN)]

[(C ₂ H5) ₂ CH3S] [CF ₃ S0 _3] + K [C ₂ F ₅ BF ₂ (CN)] - ^ [(C ₂ H ₅₎ ₂ CH ₃ S] [C ₂ F ₅ BF ₂ ( CN)] j + K [CF ₃ S0 ₃ ]

Potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] (5.2 g, 22.3 mmol), prepared as described in Example 5, is dissolved in deionized water (2 mL) and treated with an aqueous diethylmethylsulfonium trifluoromethylsulfonate solution (6.3 g, 24.8 mmol, 3 mL). The ionic liquid formed is washed with deionized water (6 × 2 ml) and then dried under high vacuum for 12 hours at room temperature and then at 60 ° C. for 24 hours. The yield of diethylmethylsulfonium cyanodifluoropentafluoroethylborate is 5.5 g (18.4 mmol), 82% based on the potassium cyano difluoropentafluoroethylborate K [C ₂ F ₅ BF ₂ (CN)] used. The product is analyzed by ion chromatography and has low levels of halide impurities; 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: v (CN) = 2209 cm ^-1

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 {H} -NMR (cation): δ, ppm = 35.98 s (2CH ₂ , 2C); 21.42 s (CH ₃ , 1 C); 8.75 s (2CH3 _> 2C).

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

¹⁹ F-NMR: δ, ppm = -83.3 1 (CF ₃ , 3F), ⁴ J _FF = 5.2 Hz; -136.3 q (CF ₂₎ ² _F ), 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. S-Ethyl-W, W, W, / V ^' -tetramethylisothiouronium cyano difluoropentafluoroethylborate -

H ₂ 0

[{(CH ₃ ) ₂ N} ₂ CSC ₂ H ₅ ] I + K [C ₂ F ₅ BF ₂ (CN)] [{(CH ₃ ) ₂ N} ₂ CSC ₂ H ₅ ] [C ₂ F ₅ BF ₂ (CN)] + KI

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 stirred with a solution of S-ethyl - / \ /, / \ /, / \ / ^' , / V ^' tetramethylisothiouronium iodide

[{(CH ₃ ) ₂ N} ₂ CSC ₂ H ₅ ] I (8.2 g, 28.4 mmol) in 10 mL of deionized water added. The resulting black liquid is separated, washed with deionized water (4 x 2 mL) and then dried in vacuo at room temperature for 3 days. The crude product is dissolved in CH ₂ Cl ₂ (100 mL) and stirred slowly with activated charcoal (5 g) for 12 hours. The mixture is filtered and the dichloromethane is removed on a rotary evaporator. The amber-colored ionic liquid is dried for 2 days under high vacuum at 50.degree. The yield of S-ethyl-Λ /, Λ /, Λ, Λ - tetramethylisothiouroniumcyanodifluorpentafluorethylborat is 7.2 g (20.2 mmol), 78% based on the potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)]. The product is analyzed by ion chromatography and has low levels of halide impurities; Chloride: 12 ppm, fluoride: 121 ppm. Water content (Karl Fischer titration): 20 ppm. Dynamic viscosity (20 ° C): 40.2 mPa-s.

Raman spectroscopy: v (CN) = 2208 cm ^-1

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).

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

9F-NMR: δ, ppm = -83.3 t (CF ₃₎ 3F), ⁴ J _FF = 5.2 Hz; -136.3 q (CF ₂ , 2F), 2J _{Fi 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 33.91, H 4.82, N 12.35, S 9.73; calculated for Ci ₀ Hi ₇ 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]

K [C ₂ F ₅ BF ₃ ] + 2 (CH ₃ ) ₃ SiCN + [(C ₆ H ₅ ) ₄ P] Br [(C ₆ H ₅ ) ₄ P] [C ₂ F ₅ BF (CN) ₂ ] + KBr

- 2 (CH ₃ ) ₃ SIF

In a NMR tube with a glass valve and a PTFE spindle (Young, London), 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 added sequentially to 7 hours at 70 ° C, 5 hours at 100 ° C, 7.5 hours at 125 ° C, 5 hours at 140 ° C and then heated at 150 ° C for 72 hours. The solution is concentrated in vacuo and the residue is taken up in alkaline aqueous solution (0.1 g KOH, 10 mL) and treated dropwise with [Ph ₄ P] Br (0.5 g, 1.2 mmol), dissolved in deionized water (50 mL), added. The resulting colorless precipitate is filtered off and dried in vacuo. The yield of tetraphenylphosphonium dicyanofluoropentafluoroethylborate is 85 mg (0.16 mmol), 73% based on the

potassium trifluoropentafluoroethyl borate, K [C ₂ F ₅ BF ₃ ]. Melting point:

103 ° C.

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

1 ¹ B NMR: <5, ppm = -12.0 d, t (1 B), 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 _FF = 1.0 Hz, ⁴ J _FF = 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, 1 F), ¹ J _FB = 52 Hz, ³ J _F F = 5-6 Hz, ⁴ J _FF = 5-6 Hz.

Example 29. 1-Ethyl-3-methylimidazolium dicyanofluoropentafluoroethylborate - [C ₆ HiiN 2] [C ₂ F ₅ BF (CN) 2]

Potassium dicyanofluoropentafluoroethyl borate, K [C ₂ F ₅ BF (CN) ₂ ] (7.0 g, 29.2 mmol), prepared as described in Example 6, and 1-ethyl-3-methylimidazolium chloride, [EMIM] CI (5.0 g, 34.1 mmol ) are taken up in bidistilled water (15 ml) and stirred. Subsequently, the aqueous phase is separated, the ionic liquid is washed with bidistilled water (4 x 5 mL), separated and then dried under high vacuum at 50 ° C. Yield of almost colorless liquid ethyl-3-methylimidazoliumdicyanofluoropentafluoroethylborate is 6.4 g (20.5 mmol), 70% based on the potassium dicyanofluoropentafluoroethylborate 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; 4.0s ( _CH313H ); 4.3 q (CH ₂ , 2H), ³ J _H , H = 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 B), 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 _FF = 1.0 Hz, ⁴ J _FF = 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 q, q, t (BF, 1 F), 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]

C ₄ H ₉ N 1 N-CH ₃ + K [C ₂ F ₅ BF (CN) 2] - ^ - ^ C ₄ H ₉ -N ^ N-CH ₃ + KCl

Ol ^" [C ₂ F ₅ BF (CN) 2] - |

Potassium dicyanofluoropentafluoroethylborate 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) dissolved in 2 mL of deionized water. Both solutions are combined and the ionic liquid formed is separated and then washed with deionized water (4 x 2 mL) and separated. The resulting, almost colorless liquid is added in vacuo

Dried 60 ° C. The yield of 1-butyl-3-methylimidazoliumdicyano fluorpentafluorethylborat is 6.5 g (19.1 mmol), 92% based on the potassium dicyanofluoropentafluoroethyl borate K [C ₂ F ₅ BF (CN) ₂ ]. The product is analyzed by ion chromatography and has low levels of halide impurities; Chloride: 10 ppm, fluoride: 6 ppm. Water content (Karl Fischer titration): 154 ppm. Dynamic viscosity (20 ° C): 25.1 mPa-s.

Raman spectroscopy: v (CN) = 2215 cm H-NMR: δ, ppm = 8.96 d, d (CH, 1 H), ⁴ J _HH * 1.6 Hz; 7.70 d, d (CH, 1 H), ³ JH, H * ⁴ JH, H = 1 -7 Hz; 7.65 d, d (CH, 1 H) ³ J _H, _H ^Ä JH, H ^ä 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 H); 1.40 m (CH ₂ , 2H); 0.94 t (CH ₃ , 3H), J _H , H = 7.37 Hz. 3C { ¹ H} -NMR (cation): <5, ppm = 137.40 s (CH, 1 C); 124.86 s (CH, 1 C); 123.47 s (CH, 1 C); 50.30 s (CH ₂ , 1 C); 36.68 s (CH ₃ , 1 C); 32.59 s (CH ₂ , 1C); 19.98 s (CH ₂ , 1 C); 13.50 s (CH ₃ , 1 C). 1 B NMR: δ, ppm = -12.0 d, t (1 B), 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 _FF = 1.0 Hz, ⁴ J _FF = 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 q, q, t (BF, 1 F), 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 Hi ₅ BF ₆ N 4,%, C 42.38, H 4.45, N 16.47.

Example 31 1-methoxyethyl-3-methylimidazoliumdicyanofluorpenta- fluorethylborat - [C ₇ H ₁₃ N20] [C ₂ F ₅ BF (CN) 2]

Potassium dicyanofluoropentafluoroethylborate K [C ₂ F ₅ BF (CN) ₂ ] (5.1 g, 21.2 mmol), prepared as described in Example 6, and 1-methoxyethyl-3-methylimidazolium bromide [MOEMIM] Br (5.1 g, 23.0 mmol) are each Dissolved 2 mL of deionized water. Both solutions are combined and the resulting ionic liquid separated and then washed with deionized water (4 x 2 mL). The resulting, almost colorless liquid is dried in vacuo at 60 ° C. The yield of 1-methoxyethyl-3-methylimidazolium dicyanofluoropentafluoroethylborate 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 will analyzed by ion chromatography and has low impurities of halide; 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: v (CN) = 2215 cm ^-1

¹ H-NMR: δ, ppm = 8.94 d, d (CH, 1H), J _HH * 1.7 Hz; 7.68 dd (CH, 1H), ³ JHH * ⁴ JHH * 1.7 Hz; 7.64 d, d (CH, 1H), ³ J _H , _H * ⁴ JH, 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).

3C { 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 (1B), 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 _FF = 1.0 Hz, J _FF = 6.3 Hz; -132.0 qd (CF ₂ , 2F), ³ J _FF = 5.0 Hz, ² J _F , _B = 25.3 Hz; -219.1 qqt (BF, 1F), J _F , _B = 52 Hz, ³ J _FiF = 5-6Hz, ⁴ J _{F, F} = 5-6Hz.

Elemental analysis: found,%, C, 38.86, H, 3.82, N, 16.43; calculated for CnHi ₃ BF ₆ ON ₄ ,%, C 38.63, H 3.83, N 16.38.

Example 32. Tetra-n-butylammonium dicyanofluoropentafluoroethylborate

- [(nC ₄ H ₉ ) ₄ N] [C ₂ F ₅ BF (CN) 2]

H O

K [C ₂ F ₅ BF (CN) ₂ ] + [(C ₄ H ₉ ) ₄ N] Br ² > [(C ₄ H ₉ ) ₄ N] [C ₂ F ₅ BF (CN) ₂ ] | + KBr

Potassium dicyanofluoropentafluoroethylborate, K [C ₂ F ₅ BF (CN) ₂ ] (500 mg, 2.1 mmol), prepared as described in Example 6, is dissolved in deionized water (10 mL) and treated with a solution of [n -Bu N] Br (0.8 g, 2.5 mmol) in deionized water (20 ml). The resulting fine precipitate is extracted with CH ₂ Cl ₂ (2 x 30 ml). The combined organic phases are dried with MgSO ₄ , filtered and the solvent is removed using a rotary evaporator. The yield of tetra-n-butylammonium dicyanofluoropentafluoroethylborate is 658 mg (1.5 mmol), 71% based on the potassium dicyanofluoropentafluoro-ethyl borate used, K [C ₂ F ₅ BF (CN) ₂ ]. Melting point: 52 ° C. Raman spectroscopy: v (CN) = 2212 cm

¹ H-NMR: δ, ppm = 1.0 1 (4CH ₃ l 12 H), ³ J _HH = 7 Hz; 1.4 m (4CH _2l 8 H), ³ J _HH = 7 Hz, 1.7-1.8 m (4CH ₂ , 8 H); 3.3-3.5 m, (4CH ₂ , 8 H).

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). 1B NMR: <5, ppm = -12.0 d, t (1 B), J _F , _B = 51.6 Hz, ² J _F , _B = 25.2 Hz. 9F NMR: δ, ppm = -82.6 d, t ( CF ₃ , 3F), ³ J _FF = 1.0 Hz, J _FF = 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, 1 F), ¹ J _F , _B = 52 Hz, ³ J _F, F = 5-6 Hz, ⁴ J _F , F = 5-6 Hz.

Example 33. N-Butyl-N-methylpyrrolidinium dicyanofluoropentafluoroethyl borate - [C H2oN] [C ₂ F ₅ BF (C

Potassium dicyanofluoropentafluoroethylborate K [C ₂ F ₅ BF (CN) ₂ ] (5.0 g, 20.8 mmol), prepared as described in Example 6, and A / -butyl-A / -methylpyrrolidinium chloride [BMPLJCl (4.1 g, 23.0 mmol) dissolved in 2 ml_ deionized water. Both solutions are combined and the resulting ionic liquid is separated and then washed with deionized water (4 x 2 mL). The resulting colorless liquid is dried in vacuo at 60 ° C. The yield of A / butyl / V-methylpyrrolidiniumdicyanofluoropentafluoroethylborate 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 and has low levels of halide impurities; 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: v (CN) = 2214 cm ^-1 ¹ H NMR: δ = 3.67 m (2CH ₂₎ 4H); 3.50 m (CH ₂ , 2 H); 2.82 s (CH _3, 3H), 2.30 m, (2CH _2, 4H); 1.88 m (CH ₂ , 2H); 1.44 m (CH ₂ , 2H); 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); 22.23s (2CH ₂ , 2C); 20.30 s (CH _{2 I 1 C} ); 13.64 s (CH3 _> 1C).

B-NMR: δ, ppm = -12.0 d, t (1 B), 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 _FF = 1.0 Hz, ⁴ J _FF = 6.3 Hz; -132.0 qd (CF ₂ , 2F), ³ J _FF = 5.0 Hz, ² J _F , _B = 25.3 Hz; -219: 1 q, q, t (BF, 1 F), ¹ J _F , _B = 52 Hz, ³ J _{F, F} = 5-6 Hz, 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 N ₃ ,%, C 45.51, H 5.88, N 12.25.

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

K [C ₆ F ₅ BF ₃ ] + 2 (CH ₃ ) ₃ SiCl + 2 NaCN + [(C ₆ H ₅ ) ₄ P] Br »

- I (UM3) ₃ bll-

[(C ₆ H ₅ ) ₄ P] [C ₆ F ₅ BF (CN) ₂ ] + 2 KCl + KBr

In a 100 mL wide-mouth flask with a stirrer and a

Reflux condenser are charged with dry sodium cyanide (12.5 g, 255.1 mmol) and sodium iodide (3.8 g, 25.1 mmol). In the argon countercurrent, acetonitrile (5 mL) and trimethylsilyl chloride (30 mL, 25.8 g, 237.5 mmol) are added. After heating to reflux for 4 days, K [CeF ₅ BF ₃ ] (1.0 g, 3.6 mmol) is added to the suspension and the mixture is refluxed for a further 20 hours

Reflux heated. Subsequently, all volatiles are condensed off in vacuo and the formed trimethylsilyl cyanide (26.9 mL, 201.8 mmol) is purified by fractional distillation. The solid

The residue is dissolved in deionized water (10 ml) with addition of K ₂ CO ₃ . The resulting aqueous phase is extracted with THF (4 χ 20mL). The combined organic phases are dried with K ₂ C0 ₃ and concentrated at 50 ° C on a rotary evaporator to dryness. The residue is dissolved in deionized water (20 ml) and treated dropwise with an aqueous [Ph ₄ P] Br solution (1.8 g, 4.3 mmol, 120 mL). The resulting suspension is extracted with CH ₂ Cl ₂ (3 * 20mL). By adding of Et ₂ O (50 mL) to the combined dichloromethane phases

Impurities precipitated and filtered off. The filtrate is slightly concentrated and stored at 8 ° C for 4 days. The crystals formed are filtered and dried in vacuo. Yield: 0.6 g (1.1 mmol, 30%).

1 ¹ B NMR spectroscopy revealed that the product composition for the borate anions was [C ₆ F ₅ BF (CN) ₂ (80%), [C ₆ F ₅ B (CN) ₃ r (16%), and an unknown species (4 %) certainly.

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 - [CeHn zHCFaBfC h]

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

¹ H-NMR: δ, ppm = 8.85 d, d (CH, 1 H), ⁴ J _HH * 1.7 Hz; 7.79 d, d (CH, 1H), 3JH H * ⁴ JH _, H = 1.8 Hz; 7.66 d, d (CH, 1 H) ³ J _H , _H *, H * 1.7 Hz; 4.42 t (CH ₂ , 2H), J _H H = 7.36 Hz; 4.07s (CH ₃ , 3H); 1.57 t (CH ₃ , 3H), J _H, H = 7.40 Hz. ³ 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 B), ² J _FB = 36.3 Hz.

9F-NMR: δ, ppm = -66.4 q (CF ₃ , 3F), ² J _FB = 36.3 Hz.

Example 36. 1-Ethyl-3-methylimidazolium tricyanopentafluoroethyl borate - [CeHnNJICzFsBiCNJs]

Potassium tricyanopentafluoroethylborate K [C ₂ F ₅ B (CN) ₃ ] (160 mg, 0.64 mmol) is dissolved in deionized water (1 mL) and treated with a solution of 1-ethyl-3-methylimidazolium chloride [EMIM] CI (120 mg, 0.81 mmol) 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 in vacuo at 50 ° C. The yield of 1-ethyl-3-methylimidazolium tricyanopentafluoroethylborate is 180 mg (0.56 mmol). This corresponds to the yield 87% based on the potassium tricyanopentafluoroethylborate K [C ₂ F ₅ B (CN) ₃ ] used. The product is characterized by NMR spectroscopy.

¹ H NMR: δ, ppm = 8.77 d, d (CH, 1 H), ⁴ J _HH = 1.7 Hz; 7.71 d, d (CH, 1 H), ³ J _H .H * ⁴ JH, H * 1.8 Hz; 7.62 d, d (CH, 1 H) ³ J _H, _H = JH, H = 1.7 Hz; 4.37 t (CH ₂ , 2H), J _{H, H} = 7.31 Hz; 4.02 s (CH3 _> 3H); 1.50 t (CH ₃ , 3H), J _H , H = 7.40 Hz.

3C { 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 I 1 C} ); 36.51 s (CH ₃ , 1C); 15.38 s (CH _3>

1C).

¹¹ B-NMR: δ, ppm = -31.9 t (1 B), 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 potassium cyanodifluoropentafluoroethyl borate K [C ₂ F ₅ BF ₂ (CN)] (1.0 g, 4.29 mmol) in acetonitrile (3 mL) is added at room temperature with a Solution of lithium tetrafluoroborate in acetonitrile (0.95 M, 4.52 mL, 4.29 mmol LiBF ₄ ). The resulting suspension is filtered at 0 ° C and the precipitate (KBF ₄ ) is washed with acetonitrile (0 ° C, 3 mL) and dried in vacuo. The filtrate is concentrated in vacuo and the residue dried at 50 ° C for 20 hours in vacuo.

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

The yield of lithium cyanodifluoropentafluoroethylborate Li [C ₂ F ₅ BF ₂ (CN)] is quantitative. The product is characterized by NMR spectra. 1B NMR: δ, ppm = -2.7 t (1B), ¹ J _F , _B = 51.0 Hz, ² J _{F, B} = 25.3 Hz.

1 ⁹ 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), J _{F, B} = 51.1 Hz, ⁴ J _{F, F} = 5.1 Hz. Example 38. Potassium Dicyanofluorophenylborate - K [C ₆ H ₅ BF (CN) 2]

K [C ₆ H ₅ BF ₃ ] (0.5 g, 2.7 mmol) is suspended in trimethylsilyl cyanide (10.0 mL, 74.9 mmol) and stirred for 2 days at room temperature. The resulting, slightly yellow solution is concentrated to dryness and dissolved in acetone (3 mL). By addition of CHCl ₃ (150 mL), K [C ₆ H ₅ BF (CN) ₂ ] is precipitated, filtered off 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, ¹ B) = 53.6 Hz, 1 B) ppm.

1 ⁹ F-NMR (acetone-de): δ = -206.06 (d, ¹ J ( ¹⁹ F, ¹ B) 54.6, 1 F) ppm.

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

¹³ C {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 (cm- ¹ ): 3057, 2214, 1592, 1029, 996, 875, 655, 622.

Claims

claims

Process for the preparation of salts of the formula I.

M ^{a +} [B (R _f ) (CN) _x (F) _y ] _a - I,

in which

R _{f is} a linear or branched perfluorinated alkyl group having 1 to 4 C atoms, C6F5, C ₆ H ₅ , partially fluorinated phenyl or mono- or disubstituted by a perfluoroalkyl group having 1 to 4 carbon atoms substituted phenyi, wherein the perfluoroalkyl independently

is selected from each other,

a is 1 or 2,

x is 1, 2 or 3,

y is 0, 1 or 2 and

x + y = 3, by reaction of an alkali metal salt of formula II

Me ⁺ [B (R _f) F _3] ^"II,

in which

with trialkylsilyl cyanide to a salt of formula III

Me ⁺ [B (R _f) (CN) _x (F) _y r IM,

wherein Me ⁺ , R _f , x and y have the meaning given above and the alkyl group of Trialkylsilylcyanids each independently

each other is a linear or branched alkyl group having 1 to 4 carbon atoms,

and by the subsequent salting reaction of the salts of the formula III with a salt of the formula IV,

MA IV, in which

M has a meaning given for M ^{a +} and

A is selected from the group of anions

F - Cr, Br ^" Γ, OH ^" , [HF ₂ ] - [CN] ^" [SCN] ^" [R ₁ COO] ^" , [R ₁ SO 3] -, [R ₂ COO] -, [R ₂ SO 3] - [ R ₁ OSO3] - [SiF ₆ ] ² - [BF ₄ ] [SO ₄ ] ² - [HSO ₄ ] ¹ - [NO ₃ ] - [(i) ₂ P (0) 0] -, [RiP (0) 0 _2] ² -, [(RiO) ₂ P (0) 0] -, [(RiO) P (O) O _2] ^{2 ",} [(R ₂₎ ₂ P (O) O] \ [R ₂ P (O) O ₂ ] ^{2 ~} , tosylate, benzoate, oxalate, succinate, suberate, ascorbate, sorbate, tartrate, citrate, malate, malonate,

optionally malonates substituted with alkyl groups having 1 to 4 carbon atoms or [CO ₃ ] ^{2 ~} where R ₁ is, independently of one another, H and / or a linear or branched alkyl group having 1 to 12 C atoms,

R ₂ each independently represents a partially fluorinated or perfluorinated linear or branched alkyl group having 1 to 12 C atoms or pentafluorophenyl and wherein in the formula of the salt MA, the electroneutrality is observed.

A process as claimed in claim 1 for the preparation of salts of the formula I

Anions of the formula Ia

[B ( _Rf ) (CN) (F) ₂ ] - la,

characterized in that the reaction of the compound of formula II with the trialkylsilyl cyanide takes place at temperatures between 10 ° C and 110 ° C or under microwave irradiation with 100W.

A process as claimed in claim 1 for the preparation of salts of the formula I

Anions of the formula Ib

[B ( _Rf ) (CN) ₂ (F)] - Ib,

characterized in that the reaction of the compound of formula II with the trialkylsilyl cyanide takes place at temperatures between 115 and 200 ° C or under microwave irradiation with 200W. Process according to Claim 1 for the preparation of salts of the formula I with anions of the formula Ic,

[B ( _Rf ) (CN) ₃ ] - Ic,

characterized in that the reaction of the compound of formula II with the trialkylsilyl cyanide takes place under microwave irradiation greater than 200W.

Method according to one or more of claims 1 to 4, characterized in that the trialkylsilyl cyanide is prepared before the reaction with a compound of formula II in situ from an alkali metal cyanide and a trialkylsilyl chloride in the presence of an alkali metal iodide and optionally iodine.

Method according to one or more of claims 1 to 5, characterized in that after the reaction of the compound of formula II with the trialkylsilyl cyanide readily volatile by-products are separated, but the compound of formula III is reacted further without further purification with a compound of formula IV.

Method according to one or more of claims 1 to 6, characterized in that compounds of formula I are prepared 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)

in which

R each independently

- H, where not all substituents R may be H at the same time,

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

straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, - saturated, partially or fully unsaturated cycloalkyl with

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

means

where one or two R is complete and / or one or more R is partially halogen or partially -OR, -NR ^{1 *} ₂₎ -CN,

-C (O) NR ¹ 2 or -SO ₂ NR ¹ ₂ may be substituted,

and one or two non-contiguous and non-permanent ones

Carbon atoms of the radical R 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 - may be replaced; or

[P (R ² ) ₄ ] ⁺ (4),

in which

R ² each independently

- H, NR ^{1 *} ₂ ,

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

- saturated, partially or fully unsaturated cycloalkyl with

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

means

where one or two R ² completely and / or one or more R ^{2 is} partially substituted by halogens or partially by -OR, -CN, -C (O) NR _2, -SO ₂ NR ¹ ₂ can be substituted,

and one or two non-contiguous and non-permanent ones

Carbon atoms of R ² , by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -S0 ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -S0 ₂ NR ¹ -, or -P (0) R ¹ - may be replaced; 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 to R ^{7 are} each independently

- H, NR ₂ ,

straight-chain or branched alkyl having 1 to 20 C atoms,

- saturated, partially or fully unsaturated cycloalkyl with

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

mean,

wherein one or more of the substituents R ³ to R ^{7 may} be partially or fully substituted by halogens or partially by -OH, -OR, -CN, - C (O) NR 2, -SO ₂ NR ¹ ₂ can be substituted,

and one or two non-contiguous and non-permanent ones

Carbon atoms of R ³ to R ⁷ by atoms and / or

Atomic moieties 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 - may be replaced; or

[C (NR ⁸ R ⁹ ) (NR ¹⁰ R ¹¹ ) (NR ¹² R ³ )] ⁺ (7) where

R ⁸ to R ^{13 are} each independently

- H, NR ^{1 *} ₂ ,

straight-chain or branched alkyl having 1 to 20 C atoms,

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

mean,

wherein one or more of the substituents R ⁸ to R ¹³ partially or completely with halogens or partially with -OR ¹ , -CN, -C (O) NR ¹ ₂ ,. -SÜ ₂ R ¹ ₂ may be substituted,

and one or two non-contiguous and non-permanent ones

Carbon atoms of R ⁸ to R ¹³ by atoms and / or

Atomic moieties selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -N ⁺ R ¹ ₂ -, -C (O) NR ¹ -, -SO ₂ NR ¹ -, or -P (0) R ¹ - may be replaced; or

[HetNf (8),

wherein [HetN] ^{+ is} a heterocyclic cation selected from the group comprising

Imidazolium 1 H-pyrazolium 3H-pyrazolium 4H-pyrazolium 1-pyrazolinium

2-pyrazolinium 3-pyrazolinium 2,3-dihydroimidazolinium 4,5-dihydroimidazolinium

2,5-dihydro-imidazolinium pyrrolidinium 4-ri Pyridinium pyridazine

1, 2,3-Triazolium 1, 2,3-triazolium

where the substituents R to R ^{4 are} each independently of one another - H, with the proviso that R and R ^{4 may} not be H at the same time,

straight-chain or branched alkyl having 1-20 C atoms, which may be fluorinated or perfluorinated, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, which may also be fluorinated or perfluorinated,

- saturated, partially or fully unsaturated cycloalkyl with

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

saturated, partially or completely unsaturated heteroaryl,

Heteroaryl-C ₁ -C ₆ -alkyl or aryl-C 1 -C ₆ -alkyl,

mean,

wherein the substituents R ¹ , R ² , R ³ and / or R ⁴ together

Can form ring system,

wherein one or more substituents R to R ^{4 may be} partially or completely substituted by halogens or partially substituted by -OR ¹ , -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ₂ , but not simultaneously R ¹ and R ³ ⁴ may be completely substituted by halogens, and wherein one or two non-adjacent and not bonded to the heteroatom carbon atoms of the substituents R ¹ to R ⁴ , 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 - may be replaced; wherein R ^{1 is} H, not, partially or perfluorinated C to C6 alkyl, C ₃ - to cy-cycloalkyl, unsubstituted or substituted phenyl and R ^{* is} not, partially or perfluorinated C to C ₅ alkyl, C3 to C ₇ - Cycloalkyl, unsubstituted or substituted phenyl.

Process for the preparation of compounds of formula III

Me ⁺ [B ( _Rf ) (CN) _x (F) _y ] - III,

where Me ^{+ is} a lithium, potassium, sodium, cesium or rubidium salt, R _{f is} a linear or branched perfluorinated alkyl group having 1 to 4 C atoms, C ₆ F ₅ , C6H ₅ , partially fluorinated phenyl or mono- or di-substituted by a perfluoroalkyl group having 1 to 4 carbon atoms substituted phenyl, wherein the perfluoroalkyl independently

is selected from each other,

x is 1, 2 or 3,

y is 0, 1 or 2 and

x + y is 3,

by reaction of an alkali metal salt of the formula II

in which

Me ⁺ and R _{f have} a previously given meaning with a

Trialkylsilyl cyanide, wherein the alkyl group of Trialkylsiiylcyanids each independently a linear or branched alkyl group having 1 to 4 carbon atoms.

9. The method according to claim 8, characterized in that the

Reaction for the preparation of compounds of formula III with x = 1, y = 2 takes place at temperatures between 10 ° C and 110 ° C or at microwave irradiation of 100W that the reaction for the preparation of compounds of formula III with x = 2 and y = 1 takes place at temperatures between 115 and 200 ° C or at microwave irradiation of 200W or that the reaction for the preparation of compounds of formula III with x = 3 and y = 0 takes place under microwave irradiation of greater than 200W.

10. Salts of the formula III

M ^{a +} [B (R _f ) (CN) _x (F) _y ] _a - I,

in which

M ^{a + is} a lithium, potassium, sodium, cesium or rubidium salt, R _{f is} a linear or branched perfluorinated alkyl group having 1 to 4 carbon atoms, C ₆ F ₅ , C ₆ H ₅ , partially fluorinated phenyl or mono- or di-lower phenyl which is substituted by a perfluoroalkyl group having 1 to 4 carbon atoms, the perfluoroalkyl group being independent

is selected from each other,

a is 1,

x is 1, 2 or 3,

y is 0, 1 or 2, where 0 is excluded for R _f = C ₆ H ₅ and x + y is 3. ally according to claim 10, selected from

Potassium trifluoromethyl tricyanoborate, potassium

Pentafluoroethyl tricyanoborate, potassium heptafluoropropyl tricyanoborate, potassium trifluoromethyl dicyanofluoroborate, potassium

Pentafluoroethyldicyanofluoroborate, potassium

Heptafluoropropyldicyanofluoroborate, potassium

Trifluoromethyl monocyanodifluoroborate, potassium

Pentafluoromethyl monocyanodifluoroborate, potassium

Heptafluoropropyl monocyanodifluoroborate, potassium

Nonafluorobutyl monocyanodifluoroborate, potassium

Pentafluorophenyl tricyanoborate, potassium pentafluorophenyl dicyanofluoroborate, potassium pentafluorophenyl monocyanodifluoroborate, potassium

Phenyldicyanofluoroborate, potassium phenylmonocyanodifluoroborate, potassium p-fluorophenyltricyanoborate, potassium p-fluorophenyldicyanofluoroborate, potassium p-fluorophenylmonocyanodifluoroborate, potassium 3,5-bis (trifluoromethyl) phenyltricyanoborate, potassium 3,5-bis (trifluoromethyl) phenyldicyanofluoroborate or potassium 3,5-bis (trifluoromethyl ) phenylmonocyanodifluorborat,

Lithium trifluoromethyl tricyanoborate, lithium

Pentafluoroethyl tricyanoborate, lithium heptafluoropropyltricyanoborate, lithium trifluoromethyldicyanofluoroborate, lithium

Pentafluoroethyldicyanofluoroborate, lithium

Heptafluoropropyldicyanofluoroborate, lithium

Trifluoromethyl monocyanodifluoroborate, lithium Pentafluoromethyl monocyanodifluoroborate, lithium

Heptafluoropropyl monocyanodifluoroborate, lithium

Nonafluorobutyl monocyanodifluoroborate, lithium

Pentafluorophenyl tricyanoborate, lithium pentafluorophenyl dicyanofluoroborate, lithium pentafluorophenyl monocyanodifluoroborate, lithium phenyldicyanofluoroborate, lithium phenylmonocyanodifluoroborate, lithium p-fluorophenyl tricyanoborate, lithium p-fluorophenyl dicyanofluoroborate, lithium p-fluorophenyl monocyanodifluoroborate, lithium 3,5-bis (trifluoromethyl) phenyl tricyanoborate, lithium 3,5-bis (trifluoromethyl ) phenyldicyanofluoroborate or lithium 3,5-bis (trifluoromethyl) phenylmonocyanodifluoroborate,

Sodium trifluoromethyl tricyanoborate, sodium

Pentafluoroethyl tricyanoborate, sodium heptafluoropropyl tricyanoborate, sodium trifluoromethyl dicyanofluoroborate, sodium

Pentafluoroethyldicyanofluoroborate, sodium

Heptafluoropropyldicyanofluoroborate, sodium

Trifluoromethyl monocyanodifluoroborate, sodium

Pentafluoromethyl monocyanodifluoroborate, sodium

Heptafluoropropyl monocyanodifluoroborate, sodium

Nonafluorobutyl monocyanodifluoroborate, sodium

Pentafluorophenyl tricyanoborate, sodium pentafluorophenyl dicyanofluoroborate sodium pentafluorophenyl monocyanodifluoroborate, sodium phenyldicyanofluoroborate, sodium phenyl monocyanodifluoroborate, sodium p-fluorophenyl tricyanoborate, sodium p-fluorophenyl dicyanofluoroborate, sodium p-fluorophenyl monocyanodifluoroborate, sodium 3,5-bis (trifluoromethyl) phenyl tricyanoborate, sodium 3,5-bis (trifluoromethyl ) phenyldicyanofluoroborate or sodium 3,5-bis (trifluoromethyl) phenylmonocyanodifluoroborate,

Cesium trifluoromethyl tricyanoborate, cesium

Pentafluoroethyl tricyanoborate, cesium heptafluoropropyltricyanoborate, Cesium trifluoromethyldicyanofluoroborate, cesium

Pentafluoroethyldicyanofluoroborate, cesium

Heptafluoropropyldicyanofluoroborate, cesium

Trifluoromethyl monocyanodifluoroborate, cesium

Pentafluoromethyl monocyanodifluoroborate, cesium

Heptafluoropropyl monocyanodifluoroborate, cesium

Nonafluorobutyl monocyanodifluoroborate, cesium

Rubidium trifluoromethyl tricyanoborate, rubidium

Pentafluoroethyl tricyanoborate, rubidium heptafluoropropyl tricyanoborate, rubidium trifluoromethyl dicyanofluoroborate, rubidium

Pentafluoroethyldicyanofluoroborate, rubidium

Heptafluoropropyldicyanofluoroborate, rubidium

Trifluoromethyl monocyanodifluoroborate, rubidium

Pentafluoromethyl monocyanodifluoroborate, rubidium

Heptafluoropropyl monocyanodifluoroborate, rubidium

Nonafluorobutyl monocyanodifluoroborate, rubidium

Pentafluorophenyl tricyanoborate, rubidium pentafluorophenyl dicyanofluoroborate, rubidium pentafluorophenyl monocyanodifluoroborate, rubidium phenyldicyanofluoroborate, rubidium phenylmonocyanodifluoroborate, rubidium p-fluorophenyl tricyanoborate, rubidium p-fluorophenyl dicyanofluoroborate, rubidium p-fluorophenyl monocyanodifluoroborate, rubidium 3,5-bis (trifluoromethyl) phenyl tricyanoborate, rubidium 3,5- Bis (trifluoromethyl) phenyldicyanofluoroborate or rubidium 3,5-bis (trifluoromethyl) phenylmonocyanodifluoroborate.

12. electrolyte containing a compound of formula III

M ^{a +} [B (R _f ) (CN) _x (F) _y ] _a - I,

in which

M ^{a + is} a lithium, potassium, sodium, cesium or rubidium salt, R _{f is} a linear or branched perfluorinated alkyl group having 1 to 4 C atoms, CeF ₅ , C ₆ H ₅ , partially fluorinated phenyl or mono- or disubstituted by a perfluoroalkyl group phenyl substituted with 1 to 4 carbon atoms, the perfluoroalkyl group being selected independently of one another,

a is 1, x is 1, 2 or 3, y is 0, 1 or 2 and

x + y is 3 or a compound according to claim 11.

13. Electrochemical cell containing a compound of formula III

M ^{a +} [B (R _f ) (CN) _x (F) _y ] _a - I,

in which

M ^{a + is} a lithium, potassium, sodium, cesium or rubidium salt,

R _{f is} a linear or branched perfluorinated alkyl group having 1 to 4 C

Atoms, C ₆ F ₅ , C ₆ H ₅ , partially fluorinated phenyl or mono- or di-substituted by a perfluoroalkyl group having 1 to 4 carbon atoms

Phenyl, wherein the perfluoroalkyl group is selected independently of one another,

a is 1, x is 1, 2 or 3, y is 0, 1 or 2 and

x + y is 3 or a compound according to claim 11 or a

Electrolytes according to claim 12.

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.