WO2016058665A1

WO2016058665A1 - Method for producing compounds with monofluorotricyanoborate anions

Info

Publication number: WO2016058665A1
Application number: PCT/EP2015/001865
Authority: WO
Inventors: Jan Arke Peter Sprenger; Lisa Alexandra Bischoff; Michael DRISCH; Lorena HERKERT; Maik Finze; Helge Willner; Eduard Bernhardt; Nikolai Ignatyev; Michael Schulte
Original assignee: Merck Patent Gmbh
Priority date: 2014-10-14
Filing date: 2015-09-18
Publication date: 2016-04-21
Also published as: DE102014014967A1

Abstract

The invention relates to a method for producing compounds with monofluorotricyanoborate anions selected from compounds of formulas [Cat]⁺[BF(CN)₃]^- ([Cat]+ = an alkali metal cation, a trialkyl ammonium, a tetraalkyl ammonium, a tetraalkyl phosphonium, or a tetraphenyl phosphonium),[Kt]^z+ z[BF(CN)₃]^- ([Kt]^z+ ([Kt]z+ is an inorganic or organic cation), and [H₃O]⁺[BF(CN)₃]^- ([Cat]⁺ = an alkali metal cation, a trialkyl ammonium, a tetraalkyl ammonium, a tetraalkyl phosphonium, or a tetraphenyl phosphonium). A compound of the formula [Me¹]⁺[BH(CN)₃]^- ([Me¹]⁺ is an alkali metal cation) is used as the starting material for the method.

Description

Process for the preparation of compounds with

Monofluorotricyanoborat anions

The invention relates to a process for the preparation of compounds with monofluorotricyanoborate anions

Alkalimetallmonohydridotricyanoboraten.

Alkali metal, ammonium and phosphonium salts with

Monofluorotricyanoborate anions are suitable starting materials for the preparation of ionic liquids with monofluorotricyanoborate

Anions. The use of such ionic liquids is varied, as described, for example, in WO 2004/072089 or in WO 2012/041437. They are suitable, for example, as an electrolyte component for electrochemical cells, in particular for dye-sensitized solar cells.

The preparation of alkali metal monofluorotricyanoborates can

for example, by reacting an alkali metal cyanide with boron trifluoride etherate, as described in WO 2004/072089. Alternatively, alkali metal monofluorotricyanoborates can be prepared by reacting an alkali metal tetrafluoroborate with a trialkylsilyl cyanide.

The reaction of a tetrafluoroborate with trimethylsilyl cyanide is described, for example, in B.H. Hamilton et al., Chem. Commun., 2002, 842-843 or in E. Bernhardt et al., Z. Anorg. Gen. Chem. 2003, 629, 677-685.

The trialkylsilyl cyanide can also be prepared in situ to prepare the alkali metal monofluorotricyanoborates. Many preparation methods for the synthesis of trialkylsilyl cyanide are described. Trialkylsilyl cyanide can be prepared, for example, from an alkali metal cyanide and a trialkylsilyl chloride. EP 76413 describes that this reaction is carried out in the presence of an alkali metal iodide and in

Presence of N-methylpyrrolidone was carried out.

EP 40356 describes that this reaction was carried out in the presence of a heavy metal cyanide.

In WO 2008/102661 it is described that this reaction in

Presence of iodine and zinc iodide was carried out. WO 2011/085966 describes that this reaction in

Presence of an alkali metal iodide or fluoride and optionally iodine can take place. In this case, sodium cyanide and sodium iodide or potassium cyanide and potassium iodide are preferably used, the alkali metal iodide preferably being in a molar amount of 0.1 mol, based on 1 mol

Alkali metal cyanide and trialkylsilyl chloride is added. Generally, this method of preparation is based on the description of M.T. Reetz, I. Chatziiosifidis, Synthesis, 1982, p. 330; J.K. Rasmussen, S.M. Heilmann and L.R. Krepski, The Chemistry of Cyanotrimethylsilanes in G.L. Larson (Ed.), Advances in Silicon Chemistry, Vol. 1, p. 65-187, JAI Press Inc., 1991 or WO 2008/102661.

The production of ammonium or

Phosphoniummonofluorotricyanoboraten can, for example, by

Metathesis of the alkali metal monofluorotricyanoborates done.

The production of ammonium or

Phosphonium monofluorotricyanoborates can also by reaction of an ammonium or phosphonium tetrafluoroborate with

Trimethylsilylcyanid carried out, as described in WO 2014/029833. However, there remains a need for economical alternative synthetic methods to produce salts with monofluorotricyanoborate anions. The object of the present invention is therefore an alternative

Develop manufacturing process.

Surprisingly, it has been found that alkali metal monohydrido tricyanoborates, which are readily available, are excellent starting materials for the synthesis of the desired monofluorotricyanoborates.

This finding is surprising because the B-H bond can be selectively fluorinated, chlorinated and / or brominated without destroying the cyano groups.

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

[Cat] ⁺ [BF (CN) ₃ ] - I,

in which

[Cat] ⁺ an alkali metal cation, a trialkylammonium

Tetraalkylammonium, a tetraalkylphosphonium or a

Tetraphenylphosphonium means and

the alkyl group in the cations is, independently of one another, a linear or branched alkyl group having 1 to 4 C atoms, by reaction of a compound of the formula II

[Me ¹ ] ⁺ [BH (CN) ₃ ] - II,

where [Me ¹ ] ⁺ denotes an alkali metal cation,

a) with a fluorinating agent to give a compound of the formula I in which [Cat] ⁺ denotes an alkali metal cation,

optionally followed by a metathesis reaction with a

Compound of formula IV

[Cat] XIV, wherein [Cat] is a trialkylammonium, a tetraalkylammonium, a

Represents tetraalkylphosphonium or a tetraphenylphosphonium and the alkyl group in the cations in each case independently of one another is a linear or branched alkyl group having 1 to 4 C atoms and X is Cl-Br-I-HO "[HF ₂ ] - [CN] - [SCN] - [RiCOO] - [RiOC (0) 0] -

[R1SO3] -, [R2COO] -, [R2SO3] - [R1OSO3] - [PFe] -, [BF4] - [HSO4] ^{1 "[NO3]} - [(R2) ₂ P (O) O] -, [ R ₂ P (O) O ₂ ] ² -, [(R ₁ O) ₂ P (O) O] -, [(R 10 O) P (O) O ₂ ] ^{2 "} , [(R ₁ O) R i P (O) O] , Tosylate, malonate, which may be substituted by straight-chain or branched alkyl groups having 1 to 4 carbon atoms, [HOCO ₂ ] ^" or [CO ₃ ] ^2" ,

wherein each R1 independently represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms, and

Each R ₂ independently represents a straight-chain or branched perfluorinated alkyl group having 1 to 12 C atoms and wherein in the compound of formula IV, the electroneutrality is taken into account.

or

with a chlorinating agent or a brominating agent to a compound of formula III

[Me ¹ ] ⁺ [BY (CN) ₃ ] - III, where Y is Cl or Br and [Me] ⁺ has the meaning given in formula II,

followed by a reaction of this compound of the formula III with a metal fluoride, tetraalkylammonium fluoride, metal bifluoride or ammonium bifluoride, trialkylammonium polyhydrogen fluoride or

Pyridinium polyhydrogen fluoride and optionally followed by a Metathesereaktion with a compound of formula IV

[Cat] XIV,

wherein [Cat] is an alkali metal cation, trialkylammonium

Tetraalkylammonium, a tetraalkylphosphonium or a

Tetraphenylphosphonium means and the alkyl group in the cations each independently a linear or branched

Alkyl group having 1 to 4 carbon atoms and

X Ol ^" Br- I - HO ^" CHsO ^" [HF2] ^- , [CN] ^" [SCN] ^" , [RiCOO] ^"

[RiOC (0) 0] -, [R1SO3] -, [R2COO] -, [R2SO3] - [R1OSO3] - [PFe] -, [BF4] ^- [HSO4] ^{1 "} [NOs] - [(R ₂ ) ₂ P (0) 0] -, [R ₂ P (0) 0 _2] ² -, [(RiO) ₂ P (0) 0] ^",

[(RiO) P (0) 0 ₂ ] ^{2 "} , [(RiO) RiP (0) 0] -, tosylate, malonate, which may be substituted by straight-chain or branched alkyl groups having 1 to 4 carbon atoms, [HOCO ₂ ] - or [CO3] ² - means

Alkali metals are the metals lithium, sodium, potassium, cesium or rubidium. Preferred alkaline earth metals are calcium or barium.

A straight-chain or branched alkyl group having 1 to 4 C atoms is selected from methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl. If no other name is used in the alkyl group, then it is a linear alkyl group.

In compounds of the formula I, the alkali metal cation is preferably the potassium cation.

Accordingly, the process according to the invention is preferably suitable for the synthesis of potassium monofluorotricyanoborate. In compounds of the formula I, the tetraalkylammonium cation is preferably tetramethylammonium, tetraethylammonium, tetraisopropylammonium, tetrapropylammonium, tetrabutylammonium, trimethyl (ethyl) ammonium, Triethyl (methyl) ammonium, tripropyl (methyl) ammonium,

Tributyl (methyl) ammonium, propyl (dimethyl) ethylammonium. The tetraalkylammonium cation is particularly preferably tetrabutylammonium. Accordingly, the process according to the invention is particularly preferably suitable for the synthesis of tetra-n-butylammonium monofluorotricyanoborate.

In compounds of the formula I, the trialkylammonium cation is preferably trimethylammonium, triethylammonium, tri (isopropyl) ammonium, tripropylammonium, tributylammonium, dimethyl (ethyl) ammonium, diethyl (methyl) ammonium, dipropyl (methyl) ammonium,

Dibutyl (methyl) ammonium or propyl (methyl) ethylammonium. Particularly preferred is the trialkylammonium cation triethylammonium. In compounds of the formula I, the tetraalkylphosphonium cation is preferably tetramethylphosphonium, tetraethylphosphonium, tetra-n-propylphosphonium, tetra - / - butylphosphonium,

Trimethyl (ethyl) phosphonium, triethyl (methyl) phosphonium,

Tripropyl (methyl) phosphonium, tributyl (methyl) phosphonium,

Propyl (dimethyl) ethylphosphonium or butyl (dimethyl) ethylphosphonium.

The process according to the invention is likewise preferably suitable for the synthesis of tetraphenylphosphonium monofluorotricyanoborate. The compounds of formula II are accessible by known synthetic methods. In the compounds of formula II Me ¹ may be an alkali metal selected from the group consisting of lithium, sodium, potassium, cesium or rubidium. The alkali metal cation of the end product of the formula I preferably corresponds to the alkali metal cation [Me ¹ ] ⁺ in formula II. In compounds of formula II, [Me ¹ ] ^{+ is} preferably a cation of sodium or potassium. In compounds of formula II, [Me ¹ ] ^{+ is} especially

preferably a potassium cation. Alkali metal salts with Monohydridotricyanoborat anions are from the

Publication WO 2012/163489 known and used for example as starting materials for the synthesis of monohydridotricyanoborate salts with preferably organic cations. WO 2012/163489 also describes the synthesis of these alkali metal salts, for example by the processes of claims 4 to 6.

In these processes are used as starting materials either

Alkalimetalltetracyanoborate or Alkalimetalltetrahydridoborate used.

B. Gyori et al., Journal of Organometallic Chemistry, 255, 1983, 17-28 describes, for example, the isomerization of sodium triisocyanurohydridoborate (adduct with 0.5 mol of dioxane) to sodium monohydridotricyanoborate in boiling n-dibutyl ether.

The compounds of formula IV

[Cat] XIV,

wherein [Cat] is an alkali metal cation, trialkylammonium

Tetraalkylammonium, a tetraalkylphosphonium or a

Tetraphenylphosphonium means, as described above and preferably described, and the alkyl group in the cations each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, and

X is Cl-, Br-, I-, HO ^" , CHaO ^" , [HF2] -, [CN] - [SCN] ^" , [RiCOO] ^" ,

[RiOC (O) O] - [R1SO3] - [R2COOJ- [R2SO3] - [R1OSO3] -, [PFe] -, [BF4] -, [HSO4] ¹ -, [NO3] - [(R2) ₂ P (O) O] -, [R ₂ P (O) O ² ] ² -, [(R ₁ O) ₂ P (O) O] -,

[(R ₁ O) P (O) O ₂ ] ² [(R 1 O) RiP (O) O] -, tosylate, malonate, which may be substituted by straight-chain or branched alkyl groups having 1 to 4 C atoms, [HOCO 2] - or [CO ₃ ] ^{2 "} , wherein each Ri is independently a straight or branched alkyl group having 1 to 12 carbon atoms, and

R 2 each, independently of one another, denotes a straight-chain or branched perfluorinated alkyl group having 1 to 12 C atoms, are commercially available or obtainable by known synthesis processes.

A perfluorinated linear or branched alkyl group having 1 to 4 C atoms is, for example, trifluoromethyl, pentafluoroethyl, / 7-heptafluoropropyl, iso-heptafluoropropyl, n-nonafluorobutyl, sec-nonafluorobutyl or tert-nonafluorobutyl. R2 analogously defines a linear or branched perfluorinated alkyl group having 1 to 12 C atoms, comprising the aforementioned 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.

R2 is particularly preferably trifluoromethyl, pentafluoroethyl or

Nonafluorobutyl, most preferably trifluoromethyl or

Pentafluoroethyl.

R1 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.

Preferably, the anion X of the salt of formula IV HO ^", Cl ^~, Br ^~ l ^~ [CH3SO3] - [CH3OSO3] -, [CF 3 COO] -, [CF3SO3] -, [(C ₂ F ₅₎ 2 P (O) O] -, [PFe] -,

[BF ₄ ] ^" or [CO ₃ ] ² \

Particularly preferred is the anion X of the salt of formula IV HO

Br- [CHsOSOs] -, [CF3SO3] - [CH3SO3] - or [(C ₂ F ₅₎ 2 P (O) O] -. Very particular preference is the anion X of the salt of formula IV HO ^~ , Cl - or Br ^~ Suitable fluorinating agent for process variant a)

For example, elemental fluorine, fluorine in anhydrous hydrogen fluoride, xenon difluoride, 1-chloromethyl-4-fluoro-1, 4-diazoniabicyclo [2.2.2] octane bis (tetrafluoroborate), potassium hexafluoronickelate (IV) or

Diethylaminosulfur.

Another object of the invention is therefore the method as described above, wherein the fluorinating agent in process variant a) is selected from the group of elemental fluorine, fluorine in anhydrous hydrogen fluoride, xenon difluoride, 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2.2.2] octane bis (tetrafluoroborate),

Potassium hexafluoronickelate (IV) or diethylaminosulfur trifluoride.

Alternatively, electrochemical fluorination is also possible for this process variant a). Principles of electrochemical fluorination are described, for example, in P. Sartori et al., Journal of Fluorine Chemistry, 87, (1998), 157-162.

Another object of the invention is therefore the method as described above, characterized in that in the process variant a) an electrochemical fluorination is carried out in anhydrous hydrogen fluoride.

Depending on the choice of the fluorinating agent, the

Reaction conditions for the process variant a) selected.

The reaction with xenon difluoride is preferably carried out in the presence of an organic solvent. Suitable solvents are tetrahydrofuran, Acetone, nitriles such as acetonitrile, alcohols such as methanol, ethanol or butanol, dialkyl ethers such as

Diethyl ether, monoglyme or diglyme. A preferred solvent is acetonitrile. Preferably, it is reacted with dried solvents as described above. ^'

The reaction with xenon difluoride is preferably carried out at temperatures of 20 to 70 ° C, more preferably at 50 ° C. The reaction time is several hours to days. Detailed reaction conditions are described in Example 4 of the embodiment.

The reaction with xenon difluoride is preferably suitable for the preparation of alkali metal salts of the formula I as described above or described as being preferred.

The reaction with fluorine in anhydrous hydrogen fluoride is preferably carried out under inert gas conditions. This reaction is preferably carried out without the presence of an organic solvent. In this embodiment of the process, the compound of formula II is dissolved in anhydrous hydrogen fluoride as described above and the solution is cooled to -78 ° C. Then, fluorine is slowly added and the mixture is slowly heated in the cooling bath to a temperature of 15 ° C to 30 ° C. Preference is given to heating to room temperature.

In this embodiment of the invention, the final process product of this reaction may be a salt mixture of a

Alkali metal monofluorotricyanoborate and an alkali metal carbamoyl monofluorodicyanoborate. To convert the unwanted

By-product in the final product, various methods are possible.

Preferably, the salt mixture is first isolated from the reaction mixture and then in a suitable solvent with

Dehydrating reagents such as oxalyl chloride, phosgene or phosphorus or sulfur chlorides and a base added. Suitable examples are organic bases. Preferably, a base is used Alkylamine, for example triethylamine, used. Preferably, in the

Working up of the alkali metal salt mixture oxalyl chloride used.

Preferably, the resulting from this reaction

Alkalimetallmonofluorotricyanoborat directly in a Metathesereaktion on to a tetraalkylammonium, trialkylammonium,

Tetraalkylphosphonium or

Tetraphenylphosphonium monofluorotricyanoborate of the formula I

transformed.

Preferably, the resulting from this reaction

Alkali metal monofluorotricyanoborate converted directly in a Metathesereaktion to a compound of formula V or to an acid of formula VI, as described below.

The reaction conditions of classical metathesis are described in detail below and apply accordingly here.

For the reaction with oxalyl chloride suitable solvents

for example, tetrahydrofuran, nitriles such as acetonitrile, dialkyl ethers such as diethyl ether, monoglyme or diglyme. Preferred solvents for this reaction are tetrahydrofuran or acetonitrile. Detailed reaction conditions are given in Example 3 of the

Execution part described.

An alternative embodiment using the fluorinating agent fluorine in anhydrous hydrogen fluoride is the reaction of the compound of formula II as described above, but prior to reaction with a base and the oxalyl chloride or phosgene, metathesis to a compound of formula I with a tetraalkylammonium,

Trialkylammonium, tetraalkylphosphonium or

Tetraphenylphosphonium cation is performed. The resulting organic salt mixture containing the monofluorotricyanoborate anion and the carbamoylmonofluorodicyanoborate anion is then reacted with the base and the dehydrating agent as described previously, as described above previously described. Detailed reaction conditions are described in Example 2 of the embodiment.

The reaction with the fluorinating agent 1-chloromethyl-4-fluoro-1, 4-diazoniabicyclo [2.2.2] octane bis (tetrafluoroborate), commercially available as Selectfluor® or also referred to as F-TEDA (Aldrich Art. No. 439479, CAS No. [140681-55-6]), is preferably carried out at temperatures of 20 to 70 ° C, more preferably at 50 ° C. The reaction time is several hours to days. The reaction is preferably carried out under

Inert gas conditions.

Inert gas conditions in the sense of the invention mean that under

Presence of an inert gas, for example nitrogen, dried nitrogen, dried argon or argon, is worked.

The reaction with F-TEDA is preferably carried out in the presence of an organic solvent. Suitable solvents are tetrahydrofuran, acetone, nitriles such as acetonitrile, nitromethane,

Dimethylformamide (DMF), alcohols such as methanol, ethanol or butanol, dialkyl ethers such as diethyl ether, monoglyme or diglyme. A preferred solvent is acetonitrile.

Preferably, immediately followed by a metathesis reaction with a compound of formula IV, as described below.

Detailed reaction conditions are described in Example 5 of the embodiment.

The reaction with F-TEDA and subsequent metathesis reaction is preferably suitable for the preparation of organic salts of the formula I as described above or described as being preferred.

The reaction conditions when using the alternative

Fluorinating agents, as described above, the skilled person can be deduced in an obvious manner from the reaction conditions described above. The electrochemical fluorination takes place in a corresponding electrochemical cell having a nickel anode. The compound of formula II, as described above, is reacted with anhydrous hydrogen fluoride. The reactive species (NiF3 / NiF4) of the fluorination arise at the nickel anode. The construction of a corresponding electrochemical cell is known to the person skilled in the art and is described, for example, in P. Sartori et al., Journal of Fluorine Chemistry, 87, (1998), 157-162.

Preferably, work is carried out at a voltage of 5 to 5.5 volts and a current density of 0.2 A * dnr ² . If

Sodium monohydridotricyanoborate is used as the compound of formula II and the end product potassium monofluorotricyanoborate is desired, followed by electrolysis, a workup, wherein after removal of the hydrogen fluoride, the residue is taken up in a suitable solvent and stirred with potassium carbonate. Depending on the reaction conditions, it is also possible with electrochemical fluorination that the final process product of this electrolysis a

Salt mixture of an alkali metal monofluorotricyanoborate and an alkali metal carbamoyl monofluorodicyanoborate. The corresponding statements on the conversion to the end product, as described above, also apply here accordingly.

Suitable chlorinating agents for process variant b) are

for example, chlorine or hypochlorites, e.g. tert-butyl hypochlorite.

Suitable brominating agents for process variant b) are bromine or hypobromites, e.g. fe / f-butyl hypobromite. A preferred one

Bromination agent is bromine.

Another object of the invention is therefore the method as described above, wherein the chlorinating agent in process variant b) from the group chlorine or te / t-butyl hypochlorite is selected. Another object of the invention is therefore the method as described above, wherein the brominating agent in the process variant b) is bromine. Depending on the choice of chlorinating agent, the

Reaction conditions for the process variant b) selected.

The reaction with ferf-butyl hypochlorite is preferably carried out in the presence of an organic solvent. Suitable solvents are tetrahydrofuran, nitriles such as acetonitrile, butanol, dialkyl ethers such as

For example, methyl-ferf-butyl ether, monoglyme or diglyme. A preferred solvent is acetonitrile. Preferably, dried solvents are used.

Preferably, the compound of formula II is dissolved in the appropriate organic solvent and cooled to 0 ° C. Then ferf-butyl hypochlorite is added, first stirred at 0 ° C and then the

Reaction temperature set to 15 ° C to 30 ° C, more preferably adjusted to room temperature. The reaction time is several hours. Preference is given to reacting under dry air.

Detailed reaction conditions are described in Example 1 of the embodiment.

The resulting compound of formula III is first separated from unreacted starting material and solvent. The

Monochloro-tricyanoborate can then be reacted with the further fluorinating agent for halogen exchange to give a compound of the formula I, as described below.

The reaction with chlorine is likewise preferably carried out in the presence of an organic solvent or in hydrofluoric acid (aqueous HF). Suitable solvents are tetrahydrofuran, nitriles such as acetonitrile,

Alcohols such as ferf-butanol, dialkyl ethers such as methyl-ferf-butyl ether, monoglyme or diglyme. A preferred one Solvent is acetonitrile. Preferably, it is reacted in dried solvents.

Preferably, the compound of formula II is dissolved in the appropriate organic solvent and cooled to -78 ° C. Then chlorine is condensed in and then stirred at 0 ° C. The reaction time is several hours. Preference is given to reacting under dry air. Detailed reaction conditions are described in Example 6 of the embodiment.

Monochlorotricyanoborate can then be reacted with the further fluorinating agent with halogen exchange to give a compound of the formula I, as described below.

The reaction with bromine is preferably carried out in the presence of an organic solvent or in hydrofluoric acid (aqueous HF). Suitable solvents are tetrahydrofuran, nitriles such as acetonitrile, alcohols such as methanol, ethanol or butanol, dialkyl ethers such as methyl-ferf-butyl ether, monoglyme or diglyme. A preferred solvent is acetonitrile. Preferably, a dried solvent is used.

Preferably, the compound of formula II is dissolved in the appropriate organic solvent and cooled to 0 ° C. Then bromine is added, first stirred at 0 ° C and then the reaction temperature adjusted to 15 ° C to 30 ° C, more preferably adjusted to room temperature. The reaction time is several hours. Preference is given to reacting under dry air. Detailed reaction conditions are described in Example 8 of the embodiment.

The resulting compound of formula III is first separated from unreacted starting material and solvent. The Monobromotricyanoborate can then be reacted with the further fluorinating agent with halogen exchange to give a compound of the formula I, as described below. The halogen exchange of the compound of the formula III to give a compound of the formula I can be carried out with a metal fluoride, tetraalkylammonium fluoride, a metal bifluoride, an ammonium bifluoride,

Trialkylammonium polyhydrogen fluoride, for example

Triethylamine trihydrogen fluoride, or Pyridiniumpolyhydrogenfluoriderfolgen, wherein the reaction conditions of the fluorinating agent used is dependent.

The halogen exchange with a metal fluoride, a

Tetraalkylammonium fluoride, a bifluoride is preferably carried out in

Presence of an organic solvent. Suitable organic

Solvents are tetrahydrofuran, acetone, nitriles such as

Acetonitrile, alcohols such as methanol, ethanol or butanol, dialkyl ethers such as diethyl ether, monoglyme or diglyme. A preferred solvent is acetonitrile. Preferably, the reaction takes place under inert gas conditions. The reaction with the fluorides mentioned is preferably carried out at temperatures of 15 to 30 ° C, more preferably at room temperature. The reaction time is several hours to days. Preferably closes immediately

Metathesis reaction with a compound of formula IV, as described below.

Detailed reaction conditions are described in Example 7 of the embodiment.

The halogen exchange with triethylamine trihydrogen fluoride takes place

preferably without the presence of an organic solvent. Alternatively, it may be reacted in the presence of an organic solvent.

Suitable organic solvents are nitriles such as acetonitrile, Alcohols such as methanol, ethanol or butanol, dialkyl ethers such as diethyl ether, monoglyme or diglyme. A preferred solvent is acetonitrile. Preferably, the reaction takes place

Inert gas conditions instead.

The reaction with triethylamine trihydrogen fluoride is preferably carried out at temperatures of 20 to 70 ° C, more preferably at 50 ° C. The

Reaction time is several hours. Preferably, immediately followed by a metathesis reaction with a compound of formula IV, as described below.

Detailed reaction conditions are described in Example 6 or Example 8 of the embodiment.

Regardless of which embodiment of process variant a) or b) of the process according to the invention is selected, it is preferred if the reaction of the reactants in each case followed by a purification step to separate intermediates or the end product of formula I, as described above, from by-products or reaction products ,

Suitable purification steps include the separation of volatile components by distillation or condensation, a

Extraction with an organic solvent or a combination of these methods. Any known separation method can be used or combined for this purpose. Another object of the invention is therefore the inventive method, as described above, characterized in that both after variant a) and after variant b) after the reaction of the reactants in each case followed by a purification step. After the reaction of the compound of formula II as described above with a fluorinating agent as described above, it is preferred that the reaction be a purification step in the form of an extraction followed. Preference is given to the compounds of the formula I or the salt mixture of the compound of the formula I with a

Likewise, carbamoylmonofluorodicyanoborate is precipitated with dichloromethane, separated and then reacted further as described above. For the purification of the alkali metal salts of the compounds of the formula I, it is further preferred to dry the compounds over the corresponding alkali metal carbonate. Preferably, for the production of

Kaliummonofluorotricyanoborat dried with potassium carbonate. After the reaction of the compounds of formula II, as before

described with a chlorinating agent or a brominating agent, all volatiles are preferably removed in vacuo and the residue is then reacted further accordingly. Should a metathesis reaction be necessary after the reaction of the compound of the formula II with the indicated reactants, as described above and below, because a compound of the formula I having an organic cation is the target product of the formula I, then it is preferred in one embodiment of the invention when the

Metathesis reaction connects directly. The

Alkalimetallmonofluorotricyanoborate from the reactions, as described above, are preferably not purified here.

Should a metathesis reaction occur after the reaction of the compound of formula II with the indicated reactants to give a compound of formula I wherein [Cat] ^{+ is} an alkali metal cation or a

Trialkylammonium cation is desired to produce a compound of formula V, as described below, it is preferred in one embodiment of the invention, when the

Metathesis reaction connects directly. The

Alkalimetallmonofluorotricyanoborate or Trialkylammonium monofluorotricyanoborates from the reactions as described above are preferably not purified here.

The metathesis reaction, or in other words the salting reaction of the salt of the formula I with a compound of the formula IV as described above, is advantageously carried out in water, temperatures of 0 ° -100 ° C., preferably 15 ° -60 ° C. being suitable. Particularly preferred is reacted at room temperature (25 ° C). Alternatively, however, the aforementioned salification reaction may take place in organic solvents at temperatures between -50 ° and 100 ° C. Suitable solvents are acetonitrile, propionitrile, dioxane, dichloromethane, dimethoxyethane, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, acetone or alcohols, for example methanol, ethanol or isopropanol, diethyl ether or mixtures of the solvents mentioned.

In a further embodiment of the method according to the invention, the compound of formula II is previously in situ from a

Alkali metal tetracyanoborate or alkali metal tetrahydridoborate, as for example in the methods of claims 4 to 6 of WO

2012/163489 described. However, any other process for the preparation of the compounds of the formula II can also be preceded by the process according to the invention. Another object of the invention is therefore a method for

Preparation of compounds of the formula I as described above or described as being preferred, wherein the compound of the formula II is prepared in situ. The process according to the invention for the preparation of compounds of the formula I.

[Cat] ⁺ [BF (CN) ₃ ] - I, in which

[Cat] ⁺ denotes an alkali metal cation or a trialkylammonium and the alkyl group in the cations in each case independently of one another represents a linear or branched alkyl group having 1 to 4 C atoms, another classical metathesis reaction can now follow, a compound of the formula V

[Kt] ^{z +} z [BF (CN) ₃ ] - V, arises,

in the

[Kt] ^{z + is} an inorganic or organic cation, z corresponds to the charge of the cation.

Another object of the invention is therefore a process for the preparation of compounds of formula V

[Kt] ^{z +} z [BF (CN) ₃ ] - V,

in which

[Kt] ^{z + is} an inorganic or organic cation,

z corresponds to the charge of the cation,

by anion exchange, wherein a salt containing the cation [Kt] ^{z +} with a compound of formula I.

[Cat] ⁺ [BF (CN) ₃ ] - I,

prepared by the process according to the invention as described above, where [Cat] ⁺ denotes an alkali metal cation or a trialkylammonium cation.

Preferably, [Kt] ^{z + has} the meaning of an organic cation or an inorganic cation, wherein the cation [Kt] ^{z +} does not have the

cation of the compound of the formula I used and the anion A of the salt containing [Kt] ^{z +}

F-Cl-, Br-I-HO - CHsO ^' , [HF2] ^~ [CN] ^" [SCN] ^" [R1COO] -,

[RiOC (O) O] -, [RiSO ₃ ] -, [R2COO] -, [R ₂ SO ₃ ] -, [RiOSOs] ^" [PFe] ^" [BF ₄ ] [HSO 4] ^{1 "} [NO ₃ ] - , [(R ₂ ) ₂ P (O) O] -, [R ₂ P (O) O ₂ ] ² -, [(R ₁ O) ₂ P (O) O] ^" ,

[(RiO) P (O) O _2] ² -, [(RiO) RiP (O) O] -, tosylate, malonate, that with straight-chain or branched alkyl groups having 1 to 4 carbon atoms, [HOCO 2] - or [C0 ₃ ] ^{2 "} ,

R 2 each independently represents a straight-chain or branched perfluorinated alkyl group having 1 to 12 C atoms and wherein in the formula of the salt [KtA] the electroneutrality is taken into account.

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 way of example, 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 / 7-nonyl, perfluorinated n-decyl, perfluorinated n-undecyl or perfluorinated n-dodecyl.

R2 is particularly preferably trifluoromethyl, pentafluoroethyl or

Nonafluorobutyl, most preferably trifluoromethyl or

Pentafluoroethyl.

Preferably, the anion A of the salt comprising [Kt] ^{z +} HO-, Cl ^~, Br ^~, I -, [CH3SO3] - [CH3OSO3] -, [CF 3 COO] -, [CF3SO3] -, [PFe] -, [BF4 ] ~

[(C2F ₅ ) 2P (O) O] - or [CO ₃ ] ² -, more preferably HO ^" , CI ^" Br ^- ,

[CH3OSO3] -, [CF3SO3] - [CH ₃ SO _3] - or [(C ₂ F ₅₎ 2 P (O) O] -. The organic cation for [Kt] ^{z +} is selected, for example, from iodonium cations, ammonium cations, sulfonium cations,

Oxonium cations, phosphonium cations, uronium cations,

Thiouronium cations, guanidinium cations, tritylium cations or heterocyclic cations.

Preferred heterocyclic cations are

wherein the substituents R ^{1 '} to R ^4' each independently have a meaning described below.

Preferred substituents R ^{1 '} and R ^4' are: straight-chain or branched C 1 - to C 20, in particular straight-chain or branched C 1 - to C 12 -alkyl groups, saturated C 3 - to C -cycloalkyl groups which contain straight-chain or branched C 1 - to C 6 Alkyl groups may be substituted or phenyl which may be substituted with straight-chain or branched Ci- to C6-alkyl groups.

Suitable substituents R ^{2 '} and R ^3' according to the invention in this case in addition to H are preferably: straight-chain or branched Ci- to C20, in particular straight-chain or branched Ci- to Ci2-alkyl groups. The substituents R ^'and R ^4' are each independently of one another particularly preferably methyl, ethyl, / ^'so-propyl, isopropyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl or benzyl. They are very particularly preferably methyl, ethyl, n-butyl or n-hexyl. In pyrrolidinium, piperidinium or indolinium compounds, the two substituents R ^{1 '} and R ^{4' are} preferably different.

Preferred 1,1-dialkylpyrrolidinium cations are, for example, 1,1-dimethylpyrrolidinium, 1-methyl-1-ethylpyrrolidinium, 1-methyl-1-propylpyrrolidinium, 1-methyl-1-butyl-pyrrolidinium, 1 Methyl 1-pentyl-pyrrolidinium, 1-methyl-1-hexyl-pyrrolidinium, 1-methyl-1-heptyl-pyrrolidinium, 1-methyl-1-octyl-pyrrolidinium, 1-methyl-1-nonyl-pyrrolidinium, 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-heptylpyrrolidinium, 1-ethyl-1-octylpyrrolidinium, 1-ethyl-1-nonylpyrrolidinium, 1-ethyl-1-decylpyrrolidinium, 1, 1- Dipropylpyrrolidinium, 1-propyl-1-methylpyrrolidinium, 1-propyl-1-butylpyrrolidinium, 1-propyl-1-pentylpyrrolidinium, 1-propyl-1-hexylpyrrolidinium, 1-propyl-1 - heptylpyrrolidinium, 1-propyl-1-octylpyrrolidinium, 1-propyl-1-nonylpyrrolidinium, 1-propyl-1-decylpyrrolidinium, 1,1-di butyl-pyrrolidinium, 1-butyl-1-methyl-pyrrolidinium, 1-butyl-1-pentyl-pyrrolidinium, 1-butyl-1-hexyl-pyrrolidinium, 1-butyl-1-heptyl-pyrrolidinium, 1-butyl-1 - octyl pyrrolidinium, 1-butyl-1-nonylpyrrolidinium, 1-butyl-1-decylpyrrolidinium, 1, 1-dipentylpyrrolidinium, 1-pentyl-1-hexylpyrrolidinium, 1-pentyl-1-heptyl -pyrrolidinium, 1-pentyl-octylpyrrolidinium, 1-pentyl-1-nonylpyrrolidinium, 1-pentyl-1-decylpyrrolidinium, 1,1-dihexylpyrrolidinium, 1-hexyl-1-heptyl-pyrrolidinium, 1-hexyl-1-octylpyrrolidinium, 1-hexyl-1-nonylpyrrolidinium, 1-hexyl-1-decylpyrrolidinium, 1,1-dihexylpyrrolidinium, -hexyl-1-heptylpyrrolidinium, 1-hexyl 1-octylpyrrolidinium, 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 given to 1-butyl-1-methylpyrrolidinium or 1-propyl-1-methylpyrrolidinium.

Preferred 1-alkyl-1-alkoxyalkylpyrrolidinium cations are, for example, 1-methoxyethyl-1-methylpyrrolidinium, 1-methoxyethyl-1-ethylpyrrolidinium, 1-methoxyethyl-1-propyl-pyrrolidinium, 1-methoxyethyl-1-butyl- pyrrolidinium, 1-ethoxyethyl-1-methylpyrrolidinium, 1-ethoxymethyl-1-methyl-pyrrolidinium. Very particular preference is 1-methoxyethyl-1 - methyl-pyrrolidinium.

Preferred 1, 3-dialkylimidazolium cations are, for example, 1-ethyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1-methyl-3-pentylimidazolium, Ethyl 3-propylimidazolium, 1-butyl-3-ethylimidazolium, 1-ethyl-3-pentylimidazolium, 1-butyl-3-propylimidazolium, 1, 3-dimethylimidazolium, 1.3- Diethylimidazolium, 1,3-dipropylimidazolium, 1,3-dibutylimidazolium, 1,3-dipentylimidazolium, 1,3-dihexylimidazolium, 1,3-diheptylimidazolium, 1,3-dioctylimidazolium, 1,3-dinonylimidazolium, 1, 3 Didecylimidazolium, 1-hexyl-3-methylimidazolium, 1-heptyl-3-methylimidazolium, 1-methyl-3-octylimidazolium, 1-methyl-3-nonylimidazolium, 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.

Preferred inorganic cations are alkali metal cations,

Metal cations of the metals of the group 2 to 12 or also NO ⁺ or H30 ⁺ . Preferred inorganic cations are Ag ⁺ , Mg ²⁺ , Cu ⁺ , Cu ²⁺ , Zn ²⁺ , Ca ²⁺ , Y ^{+ 3} , Yb ^{+ 3} , La ^{+ 3} , Sc ^{+ 3} , Ce ^{+ 3} , Nd ^{+ 3} , Tb ⁺³ , Sm ⁺³ or complex (ligand-containing) metal cations, the rare earth, transition or noble metals such as rhodium, ruthenium, iridium, palladium, platinum, osmium, cobalt, nickel, iron, chromium, molybdenum, tungsten, vanadium, Titanium, zirconium, hafnium, thorium, uranium, gold included.

The process according to the invention for the preparation of compounds of the formula I.

[Cat] ⁺ [BF (CN) ₃ ] - I,

in which

[Cat] ⁺ an alkali metal cation, a trialkylammonium

Tetraalkylammonium, a tetraalkylphosphonium or a

Tetraphenylphosphonium means and

The alkyl group in the cations each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, as described above, can also be followed by an anion exchange by the compound of formula I with an acid to the compound of formula VI

[H ₃ O] ⁺ [BF (CN) ₃ ] - VI,

is implemented.

In the compound of formula VI, the cation [H ₃ O] ⁺ includes any type of water-stabilized proton. Accordingly, the cation [H ₃ O] ⁺ also includes the notation H ⁺ * nH2O, where n is 1. The compound of formula VI is a strong acid and is particularly suitable for

Produce metal salts with Monofluorortricyanoborat anions.

In principle, any inorganic or organic acid is for this

Anion exchange usable. Suitable acids for anion exchange are, for example

Hydrochloric acid, hydrobromic acid, hydroiodic acid, RiCOOH,

R1SO3H, R 2 COOH, R2SO3H, RiOSOaH, {[H ₃ 0] ⁺ [PFe] -}, {[H ₃ O] ⁺ [BF4] ^"}, H2SO4, HNO3, (R ₂₎ ₂ P (0) OH, [ R ₂ P (O) (OH) ₂ , (RiO) RiP (0) OH, wherein R _{1 and} R ₂ have one of the meanings given above.

Particularly suitable acids for the anion exchange are hydrochloric acid, hydrobromic acid, ChbSOsH, CH3OSO3H, CF3COOH, CF3SO3H, {[H ₃ 0] ⁺ [PF _6] -}, {[H ₃ 0] ⁺ [BF _4] -}, (C ₂ F ₅ ) 2P (O) OH or sulfuric acid.

In the aforementioned anion exchange, aqueous hydrochloric acid is particularly preferably used.

The anion exchange can, as described above, advantageously be carried out in aqueous acid, temperatures of 0 ° -100 ° C., preferably 15 ° -60 ° C., being suitable. Particularly preferred is at

Room temperature (25 ° C) reacted.

However, the aforesaid salting reaction with said acids as described above may alternatively take place in organic solvents at temperatures between -50 ° and 100 ° C. suitable

Solvents are here acetonitrile, propionitrile, dioxane, dichloromethane, dimethoxyethane, dimethyl sulfoxide, dimethylformamide, alcohols, for example methanol, ethanol or isopropanol, dialkyl ethers, for example diethyl ether, or mixtures of the solvents mentioned.

Detailed reaction conditions are described in Example 13 or Example 14 of the embodiment. Another object of the invention is therefore a method for

Preparation of the compound of the formula VI

[H ₃ O] ⁺ [BF (CN) ₃ f VI, by anion exchange, whereby a compound of formula I

[Cat] ⁺ [BF (CN) ₃ ] - I,

wherein [Cat] ^{+ is an} alkali metal cation, a trialkylammonium

Tetraalkylammonium, a tetraalkylphosphonium or a

Tetraphenylphosphonium means and

the alkyl group in the cations each independently of one another is a linear or branched alkyl group having 1 to 4 carbon atoms and is reacted with an acid.

The obtained substances are characterized by NMR spectra. The NMR spectra are applied to solutions in deuterated acetone-D6 or in

CD3CN measured on a Bruker Avance 500 spectrometer with deuterium lock. The measurement frequencies of the different cores are: ¹ H: 500.1 MHz, ¹ B: 160.5 MHz and ¹³ C: 125.8 MHz. Alternatively, the spectra were detected on a Bruker Avance 200 spectrometer. The corresponding frequencies are listed together with the NMR spectroscopic data in the following examples.

Referencing is done with external reference: TMS for ¹ H and ¹³ C spectra and BF3-Et20 - for ¹¹ B spectra.

Example 1.

1) K [HB (CN) ₃ ] ⁺ f-BuOCl K [CIB (CN) ₃ ]

1) 4d, RT

2) K [CIB (CN) ₃ ] * Et ₃ N - 3 HF _{2) [BÜ4N] 0H,} H ₂ _O »[Bu ₄ N] [FB (CN) ₃ ]

Potassium hydridotricyanoborate (2.00 g, 15.5 mmol) is dissolved in 10 mL acetonitrile, cooled to 0 ° C. in an ice bath, and then tert-BuOCl (3.37 g, 31.0 mmol) is added. The reaction mixture is stirred for an additional 1.5 hours in an ice bath and then for 4 hours at room temperature. All volatiles are removed in vacuo and the residue taken up in 3 mL acetonitrile. Unresolved was filtered off (Pore 4) and the filtrate is concentrated to dryness in vacuo and the resulting

Solid in a fine vacuum (1 -10 ^-3 mbar) dried. The solid is placed in a PFA flask and dissolved in 12 mL triethylamine trihydrogen fluoride. The reaction mixture is stirred at room temperature for 4 days. The solution is mixed with 40 mL dichloromethane and the precipitated solid is filtered off (Pore 4). The filtrate is concentrated to dryness and the residue taken up in water. Subsequently, the solution is added with stirring to 15 ml of 20% strength aqueous tetrabutylammonium hydroxide solution. The resulting white solid [Bu4N] [BF (CN) 3] is filtered off and dried in vacuo to a pressure of 1 × 10 ^-3 mbar.

Yield of tetrabutylammonium tricyanofluoroborate: 4.91 g (13.9 mmol, corresponding to 90% based on the K [HB (CN) 3] used).

NMR (200 MHz), acetone-d6, δ in ppm:

¹⁹ F-NMR (188.09 MHz, acetone-d6) δ: -212.08 (q, Vf ¹ B, ¹⁹ F) = 44.4 Hz). ¹¹ B NMR (64.14 MHz, acetone-d6) δ -17.88 (d, Vf B, ⁹ F) = 44.4 Hz).

Example 2.

1) F ₂ aHF

1) K [HB (CN) ₃ ] _{2) [ph4p] Br} »[Ph ₄ P] [FB (CN) ₃ ] + [Ph ₄ P] [H ₂ NC (0) BF (CN) ₂ ]

OCCI ₂ NEt ₃

2) [Ph ₄ P] [FB (CN) ₃ ] + [Ph ₄ P] [H ₂ NC (0) BF (CN) ₂ ] _CH ₃ CN »[Ph ₄ P] [FB (CN) ₃ ]

280 mg (2.17 mmol) K [BH (CN) 3] are weighed into a 100 mL PFA flask and dissolved in 10 mL anhydrous hydrogen fluoride. The

Cool the solution to -78 ° C and slowly add 90.82 mg (2.39 mmol) F2. The mixture is slowly brought to room temperature in a cold bath and stirred overnight. Afterwards, all volatiles are removed in vacuo. The residue is dissolved in 10 mL water and treated with a solution of 907 mg (2.17 mmol) [PPr] Br in 10 mL water. The aqueous phase is washed three times with 10 ml each

Dichloromethane extracted and the combined organic phases in Vacuum to dryness. The resulting white solid mixture ([Ph ₄ P] [FB (CN) ₃ ] + [Ph ₄ P] [H ₂ NC (O) BF (CN) 2]) is dried to a pressure of 1 × 10 ^-3 mbar Subsequently, the solid mixture is dissolved in 7 mL acetonitrile, then 0.8 mL (5.79 mmol) triethylamine are added and the mixture is cooled to -78 ° C. At -78 ° C., 103 mg (4 mmol) phosgene are condensed in and the reaction mixture is again brought to room temperature and stirred overnight

Following all volatiles are removed in vacuo. The product is isolated as solid [Ph ₄ P] [FB (CN) 3].

0 Yield of tetraphenylphosphonium tricyanofluoroborate: 850 mg (1.91 mmol, 88% based on the borate used).

¹⁹ F-NMR (188.09 MHz, acetone-d6) δ: -212.08 (q, ¹ J ( ¹ B, ⁹ F) = 44.4 Hz). 1 ¹ B { ¹ H} NMR (64.14 MHz, acetone-d6) δ: -17.88 (d, ¹ J ( ¹¹ B, ⁹ F) = 44.4 Hz).

5

Example 3.

K [HB (CN) ₃ ] - → K [FB (CN) ₃ ] ⁺ K [H ₂ NC (0) BF (CN) ₂ ]

3HF

Q Into a 250 mL PFA flask is added 1.00 g (7.75 mmol) K [BH (CN) ₃ ]

weighed and dissolved in 30 mL of anhydrous hydrogen fluoride. The solution is cooled to -78 ° C and then 90 mg (8.14 mmol) of F2 slowly added. The mixture is warmed to room temperature, stirred for two hours at room temperature and then in vacuo

5 concentrated to dryness. The residue is taken up in 3 ml of THF.

By adding 25 mL of dichloromethane, (K [BF (CN) 3] +

K [H2NC (0) BF (CN) 2]) precipitated. This mixture of solids is separated, washed with 10 mL dichloromethane and concentrated in vacuo to a pressure of 0 ^"3 mbar. The yield of this mixture, 1.03 g.

Q The crude product can be purified as follows:

a) 1) (OCCI) ₂ NEt ₃ THF

K [FB (CN) ₃ ] ⁺ K [H ₂ NC (0) BF (CN) ₂ ] ^:: [Bu ₄ N] [FB (CN) ₃ ]

2) [Bu ₄ N] OH, H ₂ O

500 mg (about 3.41 mmol) product mixture (K [FB (CN) 3] +

K [H ₂ NC (O) BF (CN) ₂ ]) are dissolved in 10 mL THF. Thereafter, 1 mL

(7.22 mmol) of triethylamine was added and 1 mL (11.6 mmol) of oxalyl chloride is slowly added dropwise. The reaction mixture turns slowly

black and is stirred for 2 hours. The resulting solid is filtered off and washed with 5 mL THF. The combined THF phases are concentrated to dryness in vacuo and the residue is dissolved in 7 ml of water. Undissolved solid is filtered off (Pore 4) and the aqueous solution is mixed with 5 mL of 20% tetrabutylammonium hydroxide solution. The precipitated white solid ([Bu4N] [FB (CN) 3]) is filtered off (Pore 4), washed with 5 mL of water and dried in vacuo to a pressure of 1-10 ^"3 mbar.

Yield of tetrabutylammonium tricyanofluoroborate: 850 mg (2.42 mmol, 62% with respect to the borate used). ^

1) OCCI? NEt ₃ CH3CN

K [FB (CN) _3] ₊ K [H ₂ NC (0) BF (CN) _2] _{2) [Bll4N] 0Hi Hz0} * ~ [Bu ₄ N] [FB (CN) _3]

500 mg (about 3.41 mmol) product mixture (K [FB (CN) 3] +

K [H2NC (0) BF (CN) 2]) are dissolved in 10 mL acetonitrile. Thereafter, 1 mL (7.22 mmol) of triethylamine is added and the mixture is cooled to -78 ° C

cooled. At -78 ° C., 103 mg (4 mmol) of phosgene are condensed in and the reaction mixture is warmed to room temperature and stirred for 2 hours. Afterwards, all volatiles are removed in vacuo. The residue is dissolved in 5 ml of water and the solution is combined with 4 ml of aqueous tetrabutylammonium hydroxide solution (20% by weight) with stirring. The solid ([Bu4N] [FB (CN) 3]) is filtered off (Pore 4), washed with 10 mL of water and in vacuo to a pressure of

1 ^■ 10 ^-3 mbar dried.

Yield of tetrabutylammonium tricyanofluoroborate: 820 mg (2.34 mmol, 60% with respect to the borate mixture used).

The spectra of tetrabutylammonium tricyanofluoroborate are identical to those given in Example 1.

Example 4.

K [HB (CN) ₃ ] * XeF _{2 CH} ₃ CN K [FB (CN) ₃ ]

K [HB (CN) 3] (110 mg, 0.85 mmol) and XeF2 (200 mg, 1.18 mmol) are taken up in 4 mL of dried acetonitrile. The solution is stirred for 2 days at 50 ° C and then concentrated in vacuo to dryness. The residue is dissolved in 3 mL THF and added by adding 15 mL

Dichloromethane is precipitated K [BF (CN) 3]. This is filtered off and with

Washed 2 mL dichloromethane. The colorless solid is dried in vacuo to a pressure of 1 0 ³ mbar.

Yield of K [BF (CN) 3]: 93.0 mg (0.63 mmol, 74% based on the borate used). 9F NMR (188.09 MHz, acetone-d6) δ: -212.08 (q, V ( ¹ B, ¹⁹ F) = 44.4 Hz). 1B NMR (64.14 MHz, acetone-d6) δ: -17.88 (d, V ( ¹¹ B, ⁹ F) = 44.4 Hz).

Example 5.

1) CH ₃ CN

K [HB (CN) ₃ ] * F-TEDA ₂₎ ^ ^ '[Bu ₄ N] [FB (CN) ₃ ]

K [HB (CN) ₃ ] (200 mg, 1.54 mmol) and F-TEDA (Selectfluor®) (1.10 g, 3.11 mmol) are weighed into a flask with glass valve and Teflon stopper (Young, London) and placed under argon. Atmosphere 10

mL acetonitrile added. The solution is kept at 50 ° C for three days touched. Afterwards, all volatiles are removed in vacuo. The residue is dissolved in 5 ml of water and combined with 3 g of KOH. The solution is stirred for 10 min and then with

Extracted dichloromethane. The aqueous phase is concentrated and then added while stirring with 6 mL of 20% aqueous tetrabutyl ammonium hydroxide solution. The resulting solid

([Bu4N] [FB (CN) 3]) is filtered off and dried in vacuo to a pressure of 1 × 10 ³ mbar.

Yield of tetrabutylammonium tricyanofluoroborate: 197 mg (1.34 mmol, 87% based on K [HB (CN) ₃ ]).

Example 6.

1) CI ₂ / CH ₃ CN

2) Et ₃ N-3HF

K [HB (CN) ₃ ] ³⁾ _e ^ ^U ₂ ^N ^ ^H »[Bu ₄ N] [FB (CN) ₃ ] + Bu ₄ NCI + KCl + 2H ₂ 0

Potassium hydridotricyanoborate (220 mg, 1.67 mmol) is dissolved in 10 mL acetonitrile, cooled to -78 ° C. in a dry ice bath, and then CI 2 (3.2 g, 4.51 mmol) is condensed in. The reaction mixture is stirred for one hour at -78 ° C and then stored at 0 ° C overnight. All volatiles are removed in vacuo and the residue is dissolved in 5 mL of THF and transferred to a PFA flask. The solution is concentrated using a rotary evaporator and the residue obtained in a fine vacuum (1-10 ³ mbar) dried.

The residue is mixed with 3 ml of triethylamine trihydrogen fluoride. The reaction mixture is heated to 50 ° C and stirred for 24 hours. The solution is mixed with 10 mL dichloromethane and the precipitating

Solid is filtered off (Pore 4). The filtrate is concentrated and the

Residue taken up in water. Subsequently, the solution is under Stir with 3 mL of 20% aqueous tetrabutylammonium hydroxide solution. The resulting solid ([Bu4N] [BF (CN) 3]) is filtered off and dried in vacuo to a pressure of 1-10 ³ mbar.

Yield of tetrabutylammonium tricyanofluoroborate: 110 mg (0.49 mmol, corresponding to 29% based on the K [HB (CN) 3] used).

The spectra of tetrabutylammonium tricyanofluoroborate are identical to those given in Example 1. Example 7.

1) CI ₂ / CH ₃ CN

2) Me ₄ NF

K [HB (CN) ₃ ] ^{/ L} ► [Bu ₄ N] [FB (CN) ₃ ] + Me ₄ NCI + KCl + H ₂ O

Potassium hydridotricyanoborate (1 g, 7.75 mmol) is dissolved in 10 mL acetonitrile, cooled to -78 ° C. in a dry ice bath, and then CI 2 (6.4 g, 9.02 mmol) is condensed in. The reaction mixture is in the 1 hour

Dry ice bath and then stored overnight at 0 ° C without stirring. All volatiles are removed in vacuo and the residue dissolved in 20 mL acetonitrile. Subsequently, tetramethylammonium fluoride (500 mg, 5.37 mmol) is added with stirring in an argon countercurrent. After two hours at room temperature is further

Tetramethylammonium fluoride (600 mg, 6.44 mmol) was added and stirring was continued overnight. The solution is filtered and the filtrate is concentrated to dryness using a rotary evaporator. The residue is dissolved in 30 ml of water, the insoluble constituents are filtered off, and precipitated from the filtrate by addition of 6 ml of 20% aqueous tetrabutylammonium hydroxide solution ([Bu4N] [FB (CN) 3]). This is filtered off (Pore 4) and washed with water. The colorless solid is dried in vacuo to a pressure of 1 ^× 10 ^-3 mbar.

Yield of tetrabutylammonium tricyanofluoroborate: 2.16 g (6.18 mmol, 79% with respect to the K [HB (CN) 3] used). The spectra of tetrabutylammonium tricyanofluoroborate are identical to those given in Example 1.

Example 8.

1) Br ₂ / CH ₃ CN

2) Et ₃ N - 3HF

K [HB (CN) ₃ ] [Bu ₄ N] [FB (CN) ₃ ] + Bu ₄ NBr + KBr + 2H ₂ 0

Potassium hydridotricyanoborate (500 mg, 3.88 mmol) is dissolved in 10 ml acetonitrile, cooled to 0 ° C. in an ice bath and then combined with Br 2 (1.24 g, 7.75 mmol). The reaction mixture is stirred for 1.5 hours in an ice bath and for 12 hours at room temperature. All volatiles are removed in vacuo and the residue taken up in 3 ml of acetonitrile. Undissolved material is filtered off (Pore 4) and the filtrate is concentrated to dryness in vacuo and the resulting solid is then dried in vacuo to a pressure of 1-10 ³ mbar. The dry solid is placed in a PFA flask and dissolved in 5 ml of triethylamine trihydrogen fluoride. The reaction mixture is warmed to 50 ° C and stirred for 6 hours. The solution is mixed with 10 mL dichloromethane and the precipitated solid is filtered off (Pore 4). The filtrate is concentrated and the residue taken up in water. Subsequently, the solution is mixed with stirring with 6 mL of 20% aqueous tetrabutylammonium hydroxide solution. The resulting solid ([Bu4N] [BF (CN) 3]) is filtered off and dried in vacuo to a pressure of 1-10 ³ mbar.

Yield of tetrabutylammonium tricyanofluoroborate: 855 mg (2.44 mmol, 63% with respect to the K [HB (CN) 3] used).

Example 9. 1) Br ₂ / CH ₃ CN

2) Et ₃ N 3HF

3) K ₂ CQ ₃

K [HB (CN) ₃ ] K [FB (CN) ₃ ] + 2KBr + H ₂ O + C0 ₂

Et ₃ N 2HF

Potassium hydridotricyanoborate (9.00 g, 69.8 mmol) is dissolved in 50 ml of acetonitrile in a 250 ml PFA flask, cooled to 0 ° C. in an ice bath and then admixed with Br 2 (22.3 g, 139.55 mmol) under an argon atmosphere. The reaction mixture is stirred for 1.5 hours in an ice bath and for 12 hours at room temperature. All volatiles are removed in vacuo. The dry residue is mixed with 22 ml (22.5 g, 139.55 mmol) of triethylamine trihydrogen fluoride, warmed to 50 ° C. and stirred for 16 hours. The mixture is mixed with 30 ml of water and 15 g of potassium carbonate (until the solution is basic). All volatiles are removed in vacuo and the residue extracted five times with 10 ml of THF. The combined organic phases are dried with 5 g of potassium carbonate and filtered. The THF phase is on

Concentrated rotary evaporator to a volume of about 10 mL and slowly added with CH 2 Cl 2. First, a black solid (450 mg) precipitates, which is separated. Further addition of CH 2 Cl 2 gives K [FB (CN) 3]. This is filtered off and dried in vacuo to a pressure of 1 -10 ^{~ 3} mbar. Yield

Potassium tricyanofluoroborate, K [FB (CN) 3] (purity with respect to ¹¹ B NMR spectrum: 99%): 6.31 g (42.9 mmol, 61% with respect to the K [HB (CN) ₃ ] used).

The spectra of potassium tricyanofluoroborate are identical to those given in Example 4.

Example 10.

1) CI ₂ / CH ₃ CN

2) Et ₃ N - 3HF

3) K2CO3

K [HB (CN) ₃ ] K [FB (CN) ₃ ] + 2KCl + H ₂ O + C0 ₂

- Et ₃ N 2HF Potassium hydridotricyanoborate (3 g, 23.3 mmol) is dissolved in 15 mL acetonitrile in a 100 mL PFA flask, cooled to -78 ° C. in a dry ice bath, and then CI 2 (3.3 g, 46.6 mmol) is condensed in. The reaction mixture is stirred for one hour at -78 ° C and then allowed to warm to rt. All volatiles are removed in vacuo and the residue is washed with 1 mL (11.3 g, 69.8 mmol).

Triethylamine trihydrogen fluoride added. The reaction mixture is heated to 50 ° C and stirred for 24 hours. The mixture is treated with 10 ml of water and 10 g of potassium carbonate (until the solution is basic). All volatiles are removed in vacuo and the residue extracted 7 times with 15 mL THF. The combined organic phases are dried with 5 g of potassium carbonate and filtered. The THF phase is concentrated on a rotary evaporator to about 5 ml. Addition of CH 2 Cl 2 gives K [FB (CN) 3]. The precipitated solid is filtered off and dried in vacuo up to a pressure of ³ mbar. Yield of potassium tricyanofluoroborate, K [FB (CN) 3] (purity with respect to ¹¹ B NMR spectrum: 96%): 2.31 g (15.7 mmol , 67% with respect to the employed K [HB (CN) ₃ ]).

Example 11.

1) aHF

K ' ^HB < ^CN M ^{* K} ^ ^ Ν, ΟΗ, Η, θ' 1 ^Bu 4N] [FB (CN _{) 3} ]

Potassium hydridotricyanoborate (50.0 mg, 0.39 mmol) and

Potassium hexafluoronickelate (IV) (30 mg, 0.52 mmol) are added

Weigh the argon atmosphere into a PFA flask and aHF (approx. 15 mL) is condensed. The reaction solution is stirred overnight and then all volatiles removed in vacuo. The residue is dissolved in water and the undissolved solid is filtered off. The solution will be with 5 mL of 20% aqueous tetrabutylammonium hydroxide solution. The resulting light green solid ([Bii4N] [FB (CN) 3]) is filtered off and dried in vacuo to a pressure of 1 × 10 ³ mbar.

Yield of tetrabutylammonium tricyanofluoroborate: 20 mg (0.06 mmol, 15% with respect to the K [HB (CN) 3] used).

Example 12. Preparation of [Et4N] [BF (CN) ₃ ] starting from K [BF (CN) ₃ ].

K [FB (CN) ₃ ] + Et ₄ NCI _Q »[Et ₄ N] [FB (CN) ₃ ] + KCl

To a solution of 2.00 g (13.6 mmol) of K [BF (CN) 3] in 30 mL of water, a solution of 9.02 g (54.4 mmol) of Et4NCI in 20 mL of water is slowly added dropwise. 40 mL of dichloromethane are added and the mixture is stirred for 30 minutes at room temperature. The phases are separated and the aqueous phase is extracted with dichloromethane (3 ^× 30 ml). The combined organic phases are dried over anhydrous magnesium sulfate, the solvent is removed under reduced pressure and the residue is dried in vacuo. Yield: 3.13 g (13.1 mmol, 97%) of a colorless solid.

NMR spectra:

¹ H-NMR (500.13 MHz, CDsCN, δ ppm): 3.17 q (8H, ³ JHH = 7.3 Hz, CH ₂ ), 1.21 t (12H, ³ JHH = 7.3 Hz, ³ J _NH = 1.9 Hz, CH ₃ ) ,

¹³ C { ¹ H} NMR (125.77 MHz, CDsCN, δ ppm): 127.8 (qd, 3C, ¹ JCB = 74.6 Hz, ² JCF = 37.3 Hz), 53.0 (t, 4C, VCN = 3.1 Hz, CH ₂ ), 7.6 (s, 4C, CH ₃ ).

1 ¹ B NMR (160.46 MHz, CDsCN, δ ppm): -18.3 (d, 1 B, VBF = 44.3 Hz).

1 ⁹ F-NMR (470.54 MHz, CDaCN, δ ppm): -211.8 (q, 1 F, VBF = 44.3 Hz).

Example 13. Preparation of [H30] [BF (CN) 3] starting from K [BF (CN) s]. K [FB (CN) ₃ ] + HCl (10%) _{Et 0 / HQ} »[H ₃ O] [FB (CN) ₃ ] + KCl

100 mL of diethyl ether are added to a solution of 10.6 g (72.1 mmol) of K [BF (CN) 3] in 150 mL of 10% hydrochloric acid. The mixture is stirred for 30 minutes at room temperature. The phases are then separated and the aqueous phase is extracted with diethyl ether (3 ^× 50 ml). The combined organic phases are anhydrous

Dried magnesium sulfate and the solvent removed under reduced pressure, leaving a crystalline solid remains. The solid is then dried at 50 ° C in a vacuum. Yield: 8.69 g (70.6 mmol, 98%) of a colorless solid. Storage takes place under

Inert gas atmosphere. By titration of 322 mg of product in 50 mL of water with 25.25 mL of a 0.1 M NaOH solution, the molecular formula

[H30] [BF (CN) 3]. Calculated: M = 126.89 g / mol; found: M = 127.52 g / mol.

Elemental analysis (%) calculated for C3H3BFN3O: C, 28.40, H, 2.38, N, 33.12; found: C 28.11, H 2.44, N 32.36.

NMR spectra:

H-NMR (500.13 MHz, CD3CN, δ ppm): 8.60 s.

¹³ C {H} NMR (125.77 MHz, CD3CN, δ ppm): 126.7 qd (3C, ¹ JCB = 74.7 Hz, ² JCF = 37.3 Hz).

¹ B NMR (160.46 MHz, CD3CN, δ ppm): -18.8 d (1B, ¹ JBF = 44.2 Hz).

1 ⁹ F-NMR (470.54 MHz, CD3CN, δ ppm): -212.0 q (1F, ¹ JBF = 44.2 Hz).

IR Spertrum, v, cm ^-1 : 2259 w, (CEN).

Raman Spertrum, v, cm ^-1 : 2256 s, V (CN).

Example 14. Preparation of [H30] [BF (CN) 3], starting from

[Et ₄ N] [BF (CN) ₃ ]. [Et ₄ N] [FB (CN) ₃ ] + HCl (10%) Et ₂ O / H ₂ O * 1 ^H 30] [FB (CN) ₃ ] + [Et ₂ Cl

1.58 g (6.64 mmol) of [Et4N] [BF (CN) ₃ ] are added to 20 ml of 10% strength hydrochloric acid, and 15 ml of diethyl ether are added. The mixture is stirred for 30 minutes at room temperature. The phases are then separated and the aqueous phase is extracted with diethyl ether (3 × 15 ml). The combined organic phases are dried over anhydrous magnesium sulfate, the solvent is removed under reduced pressure and the residue is dried at 50 ° C. in vacuo. Yield: 810 mg (6.38 mmol, 96%) of a colorless solid.

The abbreviation Et corresponds to ethyl.

The spectra of [H30] [BF (CN) 3] are identical to the data given in Example 13.

Example 15: Preparation of K [BF (CN) 3].

Na [HB (CN) ₃ ] ^ - K [FB (CN) ₃ ]

aHF

250 mL aHF (anhydrous hydrogen fluoride) are added to the

electrochemical fluorination cell (ECF cell) and dried at a voltage of 5.2 V until the current has dropped to 0.6 A. Subsequently, Na [HB (CN) 3] (5.00 g, 0.044 mol) is dissolved in 10 mL aHF and added to the ECF cell via a PFA cannula (PFA stands for perfluoroalkoxy polymers). The temperature of the cell is set to 0 ° C and the condenser to -35 ° C. The electrolysis takes place at a voltage of 5.1-5.4 V and a current density of 0.2 A * dm ^-2 in 19 hours. The progress of the reaction is monitored by NMR spectroscopy. The electrolysis is completed after 291 ADmin (current efficiency: 204%) and the entire HF solution is removed from the cell. The excess HF is distilled off from the solution and the residue is dried in vacuo. Of the

The residue is then dissolved in 15 mL THF and filtered. Of the

The residue is washed with THF (3 × 5 ml). The THF phase will be a Drops of water and 5 g of K2CO3 are added. The mixture is stirred for 10 minutes and then filtered off. The K2CO3 is extracted with THF (2 x 5 mL). The combined THF phases are concentrated and the product is precipitated by adding CH 2 Cl 2.

Yield: 3.33 g of a product mixture of 86% K [FB (CN) 3], 12% KFB (CN) ₂ (C (O) NH ₂ )] and 2% K [HB (CN) ₃ ].

By further working up of the product mixture, the yield of K [FB (CN) 3] can be increased since the by-product

KFB (CN) ₂ (C (O) NH ₂ )] can be reacted to K [FB (CN) ₃ ]:

3.33 g (about 22.6 mmol) of product mixture are dissolved in 10 ml of THF.

Thereafter, 4 mL (28.88 mmol) of triethylamine are added and 3 mL (34.8 mmol) of oxalyl chloride are slowly added dropwise. The

Reaction mixture slowly turns black and is stirred for 2 hours. The resulting solid is filtered off (Pore 4) and washed with 20 mL THF. The combined THF phases are concentrated to dryness in vacuo and the residue is dissolved in 7 ml of water. Undissolved solid is filtered off (Pore 4) and the aqueous solution is concentrated to dryness. The residue is dissolved in 3 ml of THF and the product is precipitated by addition of CH ₂ Cl ₂ . The precipitated solid (K [FB (CN) 3]) is filtered off (Pore 4), washed with 10 mL CH ₂ Cl ₂ and dried in vacuo to a pressure of 1 □ 10 ^-3 mbar.

Yield: 2.93 g (19.7 mmol, 45%; NMR spectroscopically the [BF (CN) 3] "anion was detected).

1 ⁹ F-NMR (188 MHz, acetone-d6) δ: -212.08 (q, ¹ J ( ¹¹ B, ¹⁹ F) = 44.4 Hz).

1B { ¹ H} NMR (64 MHz, acetone-d6) δ: -17.88 (d, ¹ J ( ¹ B, ⁹ F) = 44.4 Hz).

Claims

claims

Process for the preparation of compounds of the formula I

[Cat] ⁺ [BF (CN) ₃ ] - I,

in which

[Cat] ⁺ an alkali metal cation, a trialkylammonium

Tetraalkylammonium, a tetraalkylphosphonium or a

Tetraphenylphosphonium means and

[Me] ⁺ [BH (CN) ₃ ] - II,

where [Me ¹ ] ⁺ denotes an alkali metal cation,

optionally followed by a metathesis reaction with a compound of formula IV

[CatJX IV,

where [Cat] is a trialkylammonium, a tetraalkylammonium, a tetraalkylphosphonium or a tetraphenylphosphonium and the alkyl group in each of the cations is independently

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

X CI, Br, I, HO - [HF 2] ^{^"[CN]"} [SCN] ^{^"[RiCOO]"}

[RiOC (O) O] -, [R1SO3] - [R2COO] -, [R2SO3] -, [R1OSO3] - [PFe] -, [BF ₄ ] - [HSO4] ¹ - [NO3] - [(R ₂ ) ₂ P (O) O] -, [R ₂ P (O) O _2] ² -,

[(RiO) ₂ P (O) O] ^", [(RiO) P (O) O _2] ² -, [(RiO) RiP (O) ^O]", tosylate,

Malonate which may be substituted by straight-chain or branched alkyl groups having 1 to 4 carbon atoms, [HOCO ₂ ] ^_ or [CO ₃ ] ^2_ ,

wherein each R1 independently represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms, and Each R2 is independently a straight-chain or branched perfluorinated alkyl group having 1 to 12 carbon atoms and wherein in the compound of formula IV the

Electroneutrality is to be considered.

or

b) with a chlorinating agent or a brominating agent

a compound of formula III

[Me ¹ ] ⁺ [BY (CN) ₃ ] - III,

wherein Y is Cl or Br and [Me ¹ ] ^{+ has} a meaning as given in formula II,

followed by reaction of this compound of formula III with a metal fluoride, tetraalkylammonium fluoride, metal bifluoride or ammonium bifluoride, trialkylammonium polyhydrogen fluoride or pyridinium polyhydrogen fluoride and optionally followed by a metathesis reaction with a compound of formula IV

[Cat] XIV,

wherein [Cat] is an alkali metal cation, trialkylammonium

Tetraalkylammonium, a tetraalkylphosphonium or a

Tetraphenylphosphonium means and the alkyl group in the cations are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and

X Cl ^" , Br-, I-HO ^" CH3O- [HF2] ^" [CN] ^" [SCN] ^" [RiCOO] ^" [RiOC (O) O] ^" , [R1SO3] - [R2COO] -, [R2SO3] - [R1OSO3] -, [PFe] -, [BF4] -, [HSO4] ¹ -, [NO3] - [(R ₂₎ ₂ P (O) O] -, [R ₂ P (O) O _2] ² -,

[(RiO) ₂ P (O) O] -, [(RiO) P (O) O _2] ² -, [(RiO) RiP (O) O] ^", tosylate, malonate, which with having straight-chain or branched alkyl groups 1 to 4 carbon atoms may be substituted, [HOCO2] - or [CO3] ^2_ , wherein each R1 independently of one another is a straight-chain or branched alkyl group having 1 to 12 carbon atoms, and

R 2 each independently represents a straight-chain or branched perfluorinated alkyl group having 1 to 12 C atoms and wherein in the compound of formula IV, the electroneutrality is taken into account.

Process according to Claim 1, characterized in that X in the compound of the formula IV denotes HO ^- Cl ^- or Br ^- .

A method according to claim 1 or 2, characterized in that the fluorinating agent in the process variant a) is selected from the group of elemental fluorine, fluorine in anhydrous hydrogen fluoride, xenon difluoride, 1-chloromethyl-4-fluoro-1, 4-diazoniabicyclo [2.2.2 ] octane bis (tetrafluoroborate), potassium hexafluoronickelate (IV) or

Diethylaminosulfur.

A method according to claim 1 or 2, characterized in that in the process variant a) an electrochemical fluorination is carried out in anhydrous hydrogen fluoride.

A method according to claim 1 or 2, characterized in that the chlorinating agent in the process variant b) is chlorine or tert-butyl hypochlorite.

A method according to claim 1 or 2, characterized in that the brominating agent in the process variant b) is bromine.

Method according to one or more of claims 1 to 6, characterized in that both after variant a) and after variant b) in each case after the reaction of the reactants

Purification step connects.

Method according to one or more of claims 1 to 3 or 5, characterized in that the compound of formula II is prepared in situ.

9. Process for the preparation of compounds of the formula V

[Kt] ^{z +} z [BF (CN) ₃ ] - V,

in which

[Kt] ^{z + is} an inorganic or organic cation,

z corresponds to the charge of the cation,

[Cat] ⁺ [BF (CN) ₃ ] - I,

prepared according to one or more of claims 1 to 8, wherein [Cat] ⁺ an alkali metal cation or a

Trialkylammonium means and

the alkyl group in each of the cations independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.

10. Process for the preparation of the compound of the formula VI

[H ₃ O] ⁺ [BF (CN) ₃ ] - VI,

by anion exchange, whereby a compound of formula I

[Cat] ⁺ [BF (CN) ₃ ] ^" I,

prepared according to one or more of claims 1 to 8, wherein [Cat] ⁺ an alkali metal cation, a trialkylammonium, a

Tetraalkylammonium, a tetraalkylphosphonium or a

Tetraphenylphosphonium means and

the alkyl group in the cations each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, is reacted with an acid.