WO2016162400A1

WO2016162400A1 - Method for preparation of cyano compounds of boron with a bronstedt acid

Info

Publication number: WO2016162400A1
Application number: PCT/EP2016/057584
Authority: WO
Inventors: Stefan Ellinger; Christoph Taeschler; Cornelia Zur Taeschler; Katharina SIEVERT; Axel Schulz; Jörg HARLOFF
Original assignee: Lonza AG
Current assignee: Lonza AG
Priority date: 2015-04-09
Filing date: 2016-04-07
Publication date: 2016-10-13
Anticipated expiration: 2017-10-09
Also published as: TW201636322A

Abstract

The invention discloses a method for preparation of cyano compounds of boron with 1, 2, 3 or 4 cyano residues, represented by formula (I): [Catⁿ⁺] [(BF_4-m(CN)m)^- ]_n by a reaction of compound of formula (A1) with trimethylsilylcyanide in the presence of a Bronstedt acid; [Catⁿ⁺] [(BF₄)^- ]_n (A1); n+ Cat is a cation, m is 1, 2, 3 or 4 and n is 1, 2, 3 or 4. In a specific embodiment, the method is for prepration of the following three compounds: [(n-Bu)₄N][BF(CN)₃] (1), [(n-Pr)₃NH][BF(CN)₃] (2), [(n-Pr)₃NH][B(CN)₄] (3).

Description

METHOD FOR PREPARATION OF CYANO COMPOUNDS OF BORON WITH A

BRONSTEDT ACID

The invention discloses a method for preparation of cyano compounds of boron with 1, 2, 3 or 4 cyano residues, represented by formula (I),

[Catⁿ⁺] [(BF₄__m(CN)_m)^" ]_n (I) by a reaction of compound of formula (Al) with trimethylsilylcyanide in the presence of a Bronstedt acid; [Catⁿ⁺] [(BF₄)^" ]_n (Al) n+

Cat is a cation, m is 1 , 2, 3 or 4 and n is 1 , 2, 3 or 4.

BACKGROUND OF THE INVENTION

The term "ionic liquid" (IL) is usually used to refer to a salt which is liquid at temperatures below 100°C, in particular at room temperature. Such liquid salts typically comprise organic cations and organic or inorganic anions, and are described inter alia in P. Wasserscheid et al., Angew. Chem., 2000, 112, 3926-3945. Ionic liquids have a series of interesting properties: Usually, they are thermally stable, relatively non-flammable and have a low vapor pressure. They show good solvability for numerous organic and inorganic substances. In addition, ionic liquids have interesting electrochemical properties, for example electrical conductivity which is often accompanied by a high electrochemical stability.

These attributes give rise to many applications of ionic liquids: They can be used for example as solvent in synthesis, as electrolyte, as lubricant and as hydraulic fluid. Moreover they serve as phase-transfer catalyst, as extraction medium, as heat-transfer medium, as surface-active substance, as plasticizer, as conductive salt, organic salt or additive in electrochemical cells, as electrolyte, as component in electrolyte formulations, wherein such electrolyte formulation comprising an ionic liquid is preferably used in electrochemical and/or optoelectronic device such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, particularly preferred in a dye sensitized solar cell. Therefore, there is a fundamental need for ionic liquids having a variety of properties which open up additional opportunities for their use.

An interesting family of ionic liquids contains tetravalent boron anions. Tetrafluoroborate containing ionic liquids were among the first of this new generation of compounds and 1- ethyl-3-methylimidazolium tetrafluoroborate ([EMIm][BF₄]) was prepared via metathesis of [EMIm]I with Ag[BF₄] in methanol as disclosed by J. S. Wilkes et al., J. Chem. Soc. Chem. Commun. 1990, 965. WO 2014/029833 Al a method for the preparation of tetra alkylammonium and tetra alkylphosphonium tricyanidofluoroborate starting from tetraalkylammonium or tetra alkylphosphonium tetrafluoroborate and trimethylsilylcyanide. Exemplified are inter alia [(nBu)₄N], [Me₄N] and [(nOct)₄N] as ammonium ions. Bronstedt acid is not disclosed. EP 2772495 Al discloses a method for the preparation of tricyanidofluoroborate in two steps via tetra alkylammonium and tetra alkylphosphonium tricyanidofluoroborate, starting from tetraalkylammonium or tetra alkylphosphonium tetrafluoroborate and trimethylsilylcyanide in the first step and exchanging the cation in the second step. Exemplified are inter alia

[(nBu)4N], [Me4N] and [(nOct)4N] as ammonium ions. Bronstedt acid is not disclosed.

WO 2014/029834 Al discloses a method for the preparation of tetra alkylammonium tetracyanidoborate starting from tetraalkylammonium tetrafluoroborate and

trimethylsilylcyanide. Exemplified are inter alia [(nBu)4N] and [(nOct)4N] as ammonium ions. Bronstedt acid is not disclosed.

Jan A. P. Sprenger et al, Inorg. Chem. 2015, 54, 3403-3412, discloses a method for producing K[BF(CN)₃] from Na[BF₄] and TMS-CN using TMS-C1 as catalyst, see scheme 2. It discloses that TMS-C1 plays the role of a catalysts that enables a cleaner reaction, page 3406, right column. Bronstedt acid is not disclosed.

E. Bernhardt, Z. Anorg. AUg. Chem. 2003, 629, 677-685, discloses the reaction of M[BF₄] (M = Li, K) with (CH₃)₃SiCN (TMSCN). The preparation of Li[BF(CN)₃] is disclosed to take 7 days, that of K[BF(CN)₃] takes one month. The yield of K[BF(CN)₃] was 60%, the product contained 5% K[BF₂(CN)₂]. The molar ratio of [BF₄] : TMSCN was 1 : 7.8. Bronstedt acid is not disclosed.

Darrick Williams et al, J. Am. Chem. Soc. 2000, 122, 7735-7741, discloses a method for producing Li[B(CN)₄] from Li[BF₄] and TMS-CN, see page 7740, compound 1. Bronstedt acid is not disclosed.

E. Bernhardt et al, Z. Anorg. Allg. Chem. 2003, 629, 1229-1234, discloses a sintering process for the preparation of LiB(CN)₄ and KB(CN)₄ at temperatures of 280 to 340°C; other cations can be introduced starting from e.g. KB(CN)₄ by metathesis. Bronstedt acid is not disclosed.

T. Kueppers et al, Inorg. Chem. 2005, 44, 1015-1022, discloses also teh use of teh sintering process, which is disclosed in E. Bernhardt et al, Z. Anorg. Allg. Chem. 2003, 629, 1229- 1234, for teh preparation of KB(CN)₄. Bronstedt acid is not disclosed.

EP 2 327 707 A claims in claim 7 a method for producing an ionic compound represented by the general formula (I), comprising a step of reacting starting materials containing a cyanide and a boron compound. General formula (I) is a salt of a cation Kt^m+ with [B(CN)₄] .

The examples disclose various methods for preparing tetrabutylammonium tetracyanoborate, for example:

1) Example 1-1 of EP 2 327 707 A discloses a reaction of tetrabutylammonium bromide, zinc (II) cyanide and boron tribromide in toluene at 130°C for 2 days, with a yield of 35%. The molar ratio of boron compound : TMSCN was 1 : 5.5.

2) Example 2-1 of EP 2 327 707 A discloses a reaction of tetrabutylammonium bromide, tetrabutylammonium cyanide and boron tribromide in toluene at 130°C for 2 days, with a yield of 77%. The molar ratio of boron compound : tetrabutylammonium cyanide was 1 : 7.1.

3) Example 3-3 of EP 2 327 707 A discloses a reaction of tetrabutylammonium bromide, trimethylsilyl cyanide and boron trichloride in p-xylene at 150°C for 30 hours, with a yield of 98%. The molar ratio of boron compound : TMSCN was 1 : 5.5.

4) Example 3-11 of EP 2 327 707 A discloses a reaction of boron trifluoride diethyl ether, tetrabutylammonium bromide and trimethylsilylcyanide at 170°C for 30 hours, with a yield of 75%.

But not all embodiments which fall under claim 7 actually work well: Example 3 of the instant invention shows one embodiment also starting with boron trifluoride diethyl ether, which falls under claim 7, but produces the desired [B(CN)₄] salt only as a by-product in negligible amounts, the main product is a [BF(CN)B] salt.

There was a need for a simplified method with high yield and satisfactory purity for the preparation of fluoro cyanide compounds of boron with the anion having the general formula

[(BF₄__m(CN)_m) ] with m being 1 , 2, 3 or 4. The boron source should be a readily available compound with low costs. The cyanide source should not be a metal cyanide to avoid its negative impact on the environment. The number of reactants should be small and the method should allow the conversion without the presence of a solvent. The content of CI and Br in the final product should be low. Also the content of Si and cyanide in the final product should be low. The method should require as few steps as possible. The method should allow also the preparation of compounds with m being 1 , 2, 3 or 4 and not only of either a compound with m being 3 or a compound with m being 4. The method should avoid the use of Cl₂, AgCN or AgBF₄. The method should provide stable compounds of said formula which can be used as ionic liquids or as precursors of ionic liquids and can be used e.g. in electrolyte formulations and in electrochemical or optoelectronic devices. These compounds should be able to be disposed of in an environmentally friendly manner after use.

The method should allow the preparation of the desired compounds in high yields and under mild conditions with respect to methods disclosed in the prior art.

This object is achieved by a method using trimethylsilylcyanide as CN source and by doing the reaction in the presence of a Bronstedt acid. No Cl₂, AgCN or AgBF₄ is required. The content of CI, Br, Si and cyanide in the final product is low. Another advantage is that the reaction does not require mandatorily an extra solvent. The method has a reduced number of steps compared to the methods known from the prior art. The method allows for the preparation not only of compounds with m being only 3 or only 4, but for compounds with n being 1 , 2, 3 or 4. These compounds can be prepared specifically and individually, and not only as mixtures. The reaction can be done under milder conditions than those used in the methods of the prior art, the reaction can be done at lower temperature or in shorter time.

In this text, the following meanings are used, if not otherwise stated:

alkyl linear or branched alkyl;

Ci__q alkyl refers to any alkyl residue which contains from 1 to q carbon atoms; for

example Ci_₆ alkyl encompasses inter alia methyl, ethyl, propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), n-hexyl and isohexyl (4-methylpentyl); C₂-_q alkenyl refers to an alkenyl residue which contains from 2 to q carbon atoms and contains at least one double bond, the carbon chain can be linear or branched; for example C₂_₄ alkenyl encompasses inter alia ethenyl, 1-methylethenyl, prop-l-enyl, prop-2-enyl, 2-methylprop-2-enyl and buta-l ,3-dienyl;

C₂__q alkynyl refers to an alkynyl residue which contains from 2 to q carbon atoms and contains at least one triple bond, the carbon chain can be linear or branched; for example C₂_₄ alkynyl encompasses inter alia ethynyl, prop-l-ynyl and prop-2-ynyl;

C₆-io aryl refers to an aryl residue which has from 6 to 10 carbon atoms and is

unsubstituted or substituted by 1 , 2, 3 or 4 identical or different substituents independently from each other selected from the group consisting of Ci_₄ alkyl and Ci_₄ alkoxy; for example C₆-io aryl encompasses inter alia phenyl, methylphenyl, methoxyphenyl, dimethylphenyl, ethylmethylphenyl, diethylphenyl and naphthyl;

cyclic alkyl or cycloalkyl include cyclo and polycyclo, such as bicyclo or tricyclo,

aliphatic residues;

C3__q cycloalkyl refers to a cycloalkyl group having from 3 to q carbon atoms; for

example C3-10 cycloalkyl encompasses inter alia cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl;

Ci__q alkoxy refers to an linear or branched alkoxy group having from 1 to q carbon atoms; for example Ci_₂o alkoxy encompasses inter alia methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, 1 ,4- dimethylpentyloxy, hexyloxy, heptyloxy, octyloxy, 1 ,5-dimethylhexyloxy, nonyloxy, decyloxy, 4-ethyl- 1 ,5-dimethylhexyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy and eicosyloxy;

alkylene means a linear or branched alkylene group; e.g. propylene, and e.g. propylene can be connected via its C I and C2 carbon atoms (a branched alkylene group), or via its C I and C3 carbon atoms (linear alkylene group);

DCM dichloromethane;

EMIm l-ethyl-3-methylimidazolium

eq. molar equivalent;

halide F , CI , Br or I , preferably F , CI or Br , more preferably CI ;

halogen F, CI, Br or I; preferably F, CI or Br;

IL ionic liquid;

"linear" and "n-" are used synonymously with respect to the respective isomers of alkanes; RT room temperature, it is used synonymously with the expression ambient

temperature;

Tdec decomposition temperature;

THF tetrahydrofuran;

TMSCN (CH₃)₃SiCN, i.e. trimethylsilylcyanide;

triflic acid trifluoromethanesulfonic acid, CF₃S0₃H;

Trityl means the trityl cation, i.e. [Ph₃C] ;

"wt%", "% by weight" and "weight-%" are used synonymously and mean percent by weight. The expressions dye sensitized solar cell and photosensitized solar cell are used

synonymously.

SUMMARY OF THE INVENTION

Subject of the invention is a method for the preparation of compound of formula (I);

[Cat ] [(BF₄__m(CN) the method comprises a step STEP1;

STEP1 comprises a reaction REAC1, wherein compound of formula (Al)

[Catⁿ⁺] [(BF₄)^~ ]_n (Al) is reacted with trimethylsilylcyanide in the presence of a compound CATACID;

CAT ACID is selected from the group consisting of HF, HCl, HBr, HI, HN0₃, H₂S0₃, H₂S0₄, NaHS0₄, Oleum, KHS0₄, NaHC0₃, KHC0₃, H₃P0₄, H₃P0₃, HS0₃F, HS0₃C1,

CH₃COOH, CF₃COOH, C(Cl₃)COOH, methansulfonic acid, HCOOH, AR-COOH, AR- S0₃H, C(OH)(COOH)₃, CF₃S0₃H HCN, HOCN, HSCN, HSeCN, HNCO, HNCS, HN₃, HQ20(X1)4, polymolybdate, polytungstate, HQ21(X1)₆, and mixtures thereof; AR is Phe or Phe substituted with 1 , 2 or 3 identical or different residues selected from the group consisting of halogen and CH₃;

Q20 is B, Al, Ga, In or Th;

Q21 is P, As, Sb or Bi;

XI is halogen; m is 1, 2, 3 or 4;

n is 1, 2, 3 or 4; n+ n+

Cat is selected from the group consisting of inorganic cation CatlNORG and organic n+

cation CatORG ;

CatINORGⁿ⁺ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 14.,

15. or 16. group of the periodic table, or is a cation from the lanthanides or is a cation from the actinides or is NH₄ ⁺;

CatORG is selected from the group consisting of CatORG- A , CatORG-B , CatORG- C⁺, [(CH₃)₃SiFSi(CH₃)₃]⁺, Ph₃C⁺, guanidinium and (H₂(R18)N-R16-N(R19)H₂)²⁺;

CatORG-A is (WR2R3R4R5) ,

wherein

W is a nitrogen or phosphorus; and

(i) R2, R3, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_₂o alkyl, Ci_₂o

perfluoroalkyl, C₃_io cycloalkyl and C₆-io aryl, with the proviso, that at least one of the residues R2, R3, R4 and R5 is not H; or

(ii) R2 and R3 together are a hydrocarbon chain and form together with W a 5- to

7-membered saturated or unsaturated heterocyclic ring,

R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_₂o alkyl, Ci_₂o perfluoroalkyl, C₃_io cycloalkyl and C₆-io aryl; or (iii) R2 and R3 together are a hydrocarbon chain and form together with W, and R4 and R5 together are a hydrocarbon chain and form together with W, independently from each other, 5- to 7-membered saturated or unsaturated heterocyclic rings;

CatORG-B⁺ is (XR6R7R8)⁺,

wherein

X is nitrogen,

R6 and R7 together are a hydrocarbon chain and form together with X a 5- to 7-membered unsaturated heterocyclic ring in which X is connected by a single bond and a double bond to R6 and R7 respectively,

R8 is selected from the group consisting of H, Ci_₂o alkyl, C₂_s alkenyl, Ci_₂o

perfluoroalkyl, C_3-10 cycloalkyl or C₆-io aryl; CatORG-C⁺ is (YR9R10R11)⁺,

wherein

Y is sulphur;

(i) R9, RIO and Rl 1 are identical or different and independently from each other selected from the group consisting of H, Ci_₂o alkyl, Ci_₂o

perfluoroalkyl, C_3-10 cycloalkyl and C₆-io aryl; or

(ii) R9 and R10 together are a hydrocarbon chain and form together with Y a 5- to

7-membered saturated or unsaturated ring,

Rl 1 is selected from the group consisting of H, Ci_₂o alkyl, Ci_₂o perfluoroalkyl, C3-10 cycloalkyl and C₆-io aryl; the residues R2, R3, R4, R5, R6, R7, R8, R9, R10 and Rl 1 are, independently from each other, unsubstituted or, where applicable, substituted by 1, 2, 3, 4, 5 or 6 substituents selected from the group consisting of Ci_₄ alkyl, C_3-10 cycloalkyl, C₂_s alkenyl, phenyl, benzyl, halogen, cyano and Ci_₄ alkoxy; in any of said hydrocarbon chains formed by R2 and R3, by R4 and R5, by R6 and R7, and by R9 and R10, 1 or 2 carbon atoms of said hydrocarbon chains can be exchanged for 1 or 2 heteroatoms respectively, said one or two heteroatoms being selected from the group consisting of O, N and S; in case of an exchange for N, this N is unsubstituted or substituted by a residue selected from the group consisting of Ci_₈ alkyl, C₃_i₀ cycloalkyl, C2-8 alkenyl and Ci_s perfluoroalkyl;

R16 is selected from the group consisting of C₂_s alkylen, C₃_s cycloalkylen, phenylen,

C(H)(phenyl), R17(-0-R17)_ni;

R17 is selected from the group consisting of CH₂-CH₂, CH₂-CH₂-CH₂, CH₂-C(H)(CH₃)-

CH₂, CH₂-CH₂-C(H)(CH₃) and CH₂-CH₂-CH₂-CH₂;

R18 and R19 are identical or different and independently from each other selected from the group consisting of H, Ci_s alkyl, C₃_s cycloalkyl, phenyl and benzyl;

nl is an integer from 1 to 20.

DETAILED DESCRIPTION OF THE INVENTION

Preferably, m is 2, 3 or 4;

more preferably, m is 3 or 4;

also in connection with any of the embodiments disclosed in the specification.

Preferably, n is 1 or 2, also in connection with any of the embodiments disclosed in the specification. Preferably, CAT ACID is selected from the group consisting of HF, HCl, HBr, H₂S0₄,

NaHS0₄, Oleum, KHS0₄, H₃P0₄, HS0₃F, HS0₃C1, CH₃COOH, CF₃COOH,

C(Cl₃)COOH, methansulfonic acid, HCOOH, AR-S0₃H, C(OH)(COOH)₃, CF₃S0₃H HCN, HQ20(X1)4, polymolybdate, polytungstate, HQ21(X1)₆, and mixtures thereof; AR is Phe or Phe substituted with 1 , 2 or 3 identical or different residues selected from the group consisting of halogen and CH₃;

Q20 is B, Al or Ga;

Q21 is P, Sb or Bi;

XI is F, CI or Br. More preferably, CAT ACID is selected from the group consisting of HF, HCl, HBr, H₂S0₄, Oleum, H₃P0₄, HS0₃F, HS0₃C1, CH₃COOH, CF₃COOH, methansulfonic acid, AR- S0₃H, CF₃S0₃H HCN, HQ20(X1)4, polymolybdate, polytungstate, and mixtures thereof;

AR is Phe substituted with 1 residue selected from the group consisting of F, CI and CH₃; Q20 is B, Al or Ga;

XI is F, CI or Br.

Even more preferably, CAT ACID is selected from the group consisting of HF, HCl, H₂SO₄, Oleum, H₃PO₄, HSO₃F, HSO₃CI, CH₃COOH, CF₃COOH, methansulfonic acid, AR- SO₃H, CF₃SO₃H HCN, HQ20(X1)4, and mixtures thereof;

AR is Phe substituted with 1 residue selected from the group consisting of F, CI and CH₃;

Q20 is B, Al or Ga;

XI is F or CI.

Especially, CAT ACID is selected from the group consisting of HF, HCl, H₂S0₄, Oleum,

HSO₃F, HSO₃CI, CF₃COOH, methansulfonic acid, AR-SO₃H, CF₃SO₃H and mixtures thereof;

AR is Phe substituted with CH₃. More especially, CATACID is CF₃SO₃H.

Preferably, CatINORGⁿ⁺ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11.,

12., 13., 14. or 15. group of the periodic table or is a cation from the lanthanides or is

NH₄ ⁺;

more preferably, CatINORGⁿ⁺ is a cation selected from the 1., 2., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 14. or 15. group of the periodic table or is a cation from the lanthanides or NH₄ ⁺; even more preferably, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ti⁴⁺, Ti³⁺, Zr⁴⁺, Zr³⁺, Hf⁴*, Hf³⁺, V⁴⁺, V³⁺, V²⁺, Nb⁴⁺, Ta⁴⁺, Cr³⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, W⁴⁺, W³⁺, W²⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁴⁺, Os³⁺, Os²⁺, Co⁴⁺, Co³⁺, Co²⁺, Rh⁴⁺, Rh³⁺, Ir⁴⁺, Ir³⁺, Ni⁴⁺, Ni³⁺, Ni²⁺, Pd⁴⁺, Pd³⁺, Pd²⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag⁴⁺, Ag³⁺, Ag²⁺, Ag⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Cd²⁺, Cd⁺, Hg²⁺, Hg⁺, B³⁺, Al³⁺, Ga³⁺, Ga⁺, In³⁺, In⁺, Tl³⁺, Tl⁺, Ge⁴⁺,Ge²⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, As³⁺, Sb³⁺, Bi³⁺, Bi¹⁺, La³⁺, Nb³⁺, Sm³⁺, Eu³⁺, Gd³⁺, and NH₄ ⁺;

especially, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺,

Ti⁴⁺, Ti³⁺, Zr⁴⁺, Zr³⁺, V⁴⁺, V³⁺, V²⁺, Cr³⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, W⁴⁺, W³⁺, W²⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Co⁴⁺, Co³⁺, Co²⁺, Rh⁴⁺, Rh³⁺, Ir⁴⁺, Ir³⁺, Ni⁴⁺, Ni³⁺, Ni²⁺, Pd⁴⁺, Pd³⁺, Pd²⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag⁴⁺, Ag³⁺, Ag²⁺, Ag⁺, Zn²⁺, Zn⁺, Al³⁺, Ga³⁺, Ga⁺, In³⁺, In⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, Sb³⁺, Nb³⁺, Sm³⁺, Eu³⁺, Gd³⁺, and NH₄ ⁺;

more especially, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Ti⁴⁺, V⁴⁺, V³⁺, V²⁺, Cr³⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Co⁴⁺, Co³⁺, Co²⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺,

Ag²⁺, Ag⁺, Zn²⁺, Zn⁺, Al³⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, Sb³⁺, Eu³⁺, Gd³⁺, and NH₄ ⁺;

even more especially, CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, 2+ _Λ τ4+ 3+ 4+ 3+ 2+ 4+ 3+ 2+ 4+ 3+ 2+ ^ +

Mg , Ca , Ti , V , V , Cr , Fe , Fe , Fe , Co , Co , Co , Cu , Cu , Cu , Cu ,

Ag⁺, Zn²⁺, Al³⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, Gd³⁺, and NH₄ ⁺;

in particular, CatINORGⁿ is selected from the group consisting of Li⁺, Na⁺, K⁺, NH₄ ⁺, Ag⁺,

Mg²⁺, Ca²⁺, Zn²⁺ and Cu²⁺;

more in particular, CatINORGⁿ is selected from the group consisting of Li⁺, Na⁺, K⁺, NH₄ ⁺,

Ag⁺, Mg²⁺, Ca²⁺ and Zn²⁺;

even more m particular, CatlNORG is Li⁺, Na⁺, K⁺, Ag⁺, Mg²⁺, or Zn²⁺; especially in particular, CatINORGⁿ⁺ is Li⁺, K⁺, Ag⁺, Mg²⁺, or Zn²⁺; more especially in particular, CatINORGⁿ is Li⁺, K⁺ or Ag⁺.

Preferably, n in CatlnORG is 1 or 2.

The term "where applicable" in the definition of CatORG means, that any of the optional substituents of the residues R2 to Rl 1 requires a respective site, and e.g. in case of R2 being a perfluorinated side chain no respective site is available any more for a substituent.

Preferably, CatORG contains a heteroatom selected from the group consisting of nitrogi phosphorus, sulfur and oxygen;

more preferably, CatORGⁿ contains a heteroatom selected from the group consisting of

nitrogen and phosphorus.

Preferably,

R16 is selected from the group consisting of C₂_₆ alkylen, C5-6 cycloalkylen, phenylen,

C(H)(phenyl), R17(-0-R17)„i; R17 is selected from the group consisting of CH₂-CH₂, CH₂-CH₂-CH₂ and CH₂-CH₂-CH₂-CH₂;

R18 and R19 are identical or different and independently from each other selected from the group consisting of H, Ci_₄ alkyl, C₅-6 cycloalkyl, phenyl and benzyl; nl is an integer from 1 to 10;

more preferably,

R16 is selected from the group consisting of C₂_₄ alkylen, C₆ cycloalkylen, phenylen,

C(H)(phenyl), R17(-0-R17)„i;

R17 is selected from the group consisting of CH₂-CH₂ and CH₂-CH₂-CH₂;

R18 and R19 are identical and selected from the group consisting of H, Ci_₄ alkyl,

C₅_6 cycloalkyl, phenyl and benzyl;

nl is an integer from 1 to 6;

even more preferably, for n being 2 CatORGⁿ⁺ is (H₂(R18)N-R16-N(R19)H₂)²⁺;

R16 is selected from the group consisting of C₂_₄ alkylen, phenylen and C(H)(phenyl); R18 and R19 are identical and selected from the group consisting of H, Ci_₄ alkyl, C₅-6 cycloalkyl, phenyl and benzyl;

especially, when n is 2, then CatORGⁿ⁺ is (H₃N-CH₂-CH₂-NH₃)²⁺.

Preferably, n in CatORG is 1. Preferably, CatORGⁿ⁺ is selected from the group consisting of ammonium, phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, pyrazolinium, imidazolium, imidazolinium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1 ,3- dioxolium, pyrylium, thiopyrylium, quinoxalinium, indolinium, indolium,

[(CH₃)₃SiFSi(CH₃)₃]⁺, Ph₃C⁺, and mixtures thereof;

more preferably from the group consisting of ammonium, phosphonium, sulfonium,

pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, imidazolium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1 ,3-dioxolium, pyrylium, thiopyrylium,

[(CH₃)₃SiFSi(CH₃)₃]⁺, Ph₃C⁺, and mixtures thereof. More preferably, CatORG is selected from the group consisting of

[N(R20)(R21)(R22)R23]⁺, [P(R20)(R21)(R22)R23]⁺, [(CH₃)₃SiFSi(CH₃)3] ^' , Ph₃C ^' , and mixtures thereof; wherein

R20, R21 , R23 are identical or different and independently from each other

selected from the group consisting of H, Ci_₂o alkyl, C3-10 cycloalkyl and allyl;

R22 is Ci_₂o alkyl, C3-10 cycloalkyl or allyl; preferably,

R20, R21 , R23 are identical or different and independently from each other

selected from the group consisting of H, Ci_i4 alkyl, C5-8 cycloalkyl and allyl;

R22 is Ci_i4 alkyl, C₅_s cycloalkyl or allyl; more preferably,

R20, R21 , R23 are identical or different and independently from each other

selected from the group consisting of H, Ci_s alkyl, C5-7 cycloalkyl and allyl;

R22 is Ci_8 alkyl, C₅_₇ cycloalkyl or allyl; even more referably, CatORGⁿ⁺ is selected from the group consisting of

, , [NH(C₂H₅)₃]⁺, [NH(C₃H₇)₃]⁺, [NH(C₄H₉)₃]⁺, [N(C₂H₅)₄]⁺

[N(C₃H₇)₄]⁺, [N(C₄H₉)₄]⁺, [P(C₂H₅)₄]⁺, [P(C₃H₇)₄]⁺, [P(C₄H₉)₄]⁺, [P(C₆H₁₃)₃(C₁₄H₂₉)]⁺,

[(CH₃)₃SiFSi(CH₃)₃]⁺, Ph₃C⁺, and mixtures thereof;

es ecially, CatORG is selected from the group consisting of

, , , [NH(C₂H₅)₃]⁺, [NH(C₃H₇)₃]⁺,

[NH(C₄H₉)₃]⁺, [N(C₂H₅)₄]⁺, [N(C₃H₇)₄]⁺, [N(C₄H₉)₄]⁺, [P(C₂H₅)₄]⁺, [P(C₃H₇)₄]⁺, [P(C₄H₉)₄]⁺,

[(CH₃)₃SiFSi(CH₃)₃]⁺, Ph₃C⁺, and mixtures thereof.

, [NH(C₂H₅)₃]⁺, [NH(C₃H₇)₃]⁺, [NH(C₄H₉)₃]⁺, [N(C₂H₅)₄]⁺, [N(C₃H₇)₄]⁺,

[N(C₄H₉)₄]⁺, [P(C₂H₅)₄]⁺, [P(C₃H₇)₄]⁺, [P(C₄H₉)₄]⁺, [(CH₃)₃SiFSi(CH₃)₃]⁺, Ph₃C⁺, and mixtures thereof. n+ .

In particular, Cat is a cation (Cat-Partl); cation (Cat-Partl) is CatINORGⁿ⁺ or CatORGⁿ⁺, with CatlNORG selected from the group consisting of Li⁺, Na⁺, K⁺, NH₄ ⁺, Ag⁺, Mg²⁺, Ca² and Zn²⁺;

and

[N(C₄H₉)₄]⁺, [P(C₂H₅)₄]⁺, [P(C₃H₇)₄]⁺, [P(C₄H₉)₄]⁺, [(CH₃)₃SiFSi(CH₃)₃]⁺, Ph₃C⁺, and mixtures thereof.

Even more preferably, compound of formula (I) is compound (Group-I),

compound (Group-I) is selected from the group consisting of compound of formula (la) and compound of formula (lb);

] [(BF(CN)₃)^" ]_n

[Cat ] [(B(CN)₄)^" ]„ (lb) n+

Cat and n are as defined above, also with all their embodiments,

n+

preferably Cat is cation (Cat-Part 1).

In particular, compound of formula (I) is selected from the group consisting of compound of formula (1), compound of formula (2), compound of formula (3), and mixtures thereof.

[(n-Bu)₄N][BF(CN)₃] (1)

[(n-Pr)₃NH][BF(CN)₃] (2)

[(n-Pr)₃NH][B(CN)₄] (3)

Preferably, from 1 to 40 mol equivalents, more preferably 4 to 35 mol equivalents, even more preferably from 5 to 25 mol equivalents, especially from 5 to 15 mol equivalents, of trimethylsilylcyanide are used in REACl, the mol equivalents being based on the molar amount of the anion [(BF₄) ] of compound of formula (Al).

The reaction temperatures of REACl is preferably from -75 to 150°C, more preferably from - 50 to 120°C, more preferably from -50 to 100°C, even more preferably -50 to 80°C.

Another possible range of the reaction temperatures of REACl is preferably from -10 to 150°C, more preferably from -10 to 120°C, more preferably from 0 to 100°C, even more preferably 10 to 80°C. REACl can be done in a closed system and at the pressure caused by the chosen temperature.

The reaction time of REACl is preferably from 15 min to 96 h, more preferably from 20 min to 84 h, even more preferably from 20 min to 48 h, especially from 20 min to 24 h, more especially from 20 min to 12 h, even more especially from 20 min to 6 h.

Preferably, REACl is done under inert atmosphere. Preferably, the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof. The lower boiling alkane is preferably a Ci_₃ alkane, i.e. methane, ethane or propane.

After the reaction, compound of formula (I) can be isolated by standard methods such as evaporation of volatile components, extraction, washing, drying, concentration,

crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.

Preferably, after the reaction the reaction product is treated with hydrogen peroxide, preferably with aqueous hydrogen peroxide.

More preferably for isolation, the reaction product is mixed with aqueous hydrogen peroxide to provide a mixture MIXT.

Preferably, the concentration of the aqueous hydrogen peroxide is from 10 to 40 wt% hydrogen peroxide, the wt% based on the total weight of the aqueous hydrogen peroxide.

Preferably, from 1 to 30 mol equivalents, more preferably from 1 to 20 mol equivalents, of hydrogen peroxide are used, the mol equivalents being based on the molar amount of compound of formula (Al). Preferably MIXT is stirred for 5 min to 24 h, more preferably for 10 min to 20 h.

Preferably MIXT is stirred at a temperature TEMPMIXT, TEMPMIXT is preferably from ambient temperature to 100°C. After treatment with hydrogen peroxide, MIXT is preferably filtrated. The residue of the filtration is preferably washed with a solvent WASHMIXT, WASHMIXT is preferably water or an ether such as diethylether or dichloromethane.

REAC1 can be done in the presence of a compound CAT;

CAT is a Lewis Acid selected from the group consisting of Lewis Acids derived , that is based on, the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 1 1., 12., 13., 14., 15. and 16. group of the periodic table, zeolite, guanidinium[ANIO] and mixtures thereof;

more preferably, CAT is selected from the group consisting of [(CH₃)₃SiFSi(CH₃)₃][ANIO], Q1(R27)₃, guanidinium[ANIO], (R26)₃C[ANIO], adamantyl[ANIO], [(R24)₃0][ANIO], [(R25)₃Si][ANIO], Q2(R36)(R28)₃, Q3(R29)₃, Q4(R30)₅, Q5(R32)₃, Q6(R33)₂, Q7(R31), Q8(R34)₂, Q9(R35)₃, Q10(R37)₂, Q1 1(R38), zeolite and mixtures thereof;

even more preferably, CAT is selected from the group consisting of

[(CH₃)₃SiFSi(CH₃)₃][ANIO], Si(Cl)(C₆H₅)₃, B(R27)₃, A1(R27)₃, GaF₃, GaCl₃, guanidinium[ANIO], (R26)₃C[ANIO], [(R24)₃0][ANIO], [(R25)₃Si][ANIO], Si(R28)₄,

TiF₄, TiCl₄, Q3(halogen)₃, Q3(CN)₃, Q3(C_1-4 alkyl)₃, Q4(halogen)₅, Q4(d_₁₀ alkyl)₅, Cr(Cl)₃, Fe(halogen)₃, Mn(Cl)₂, Fe(halogen)₂, Pd(halogen)₂, Pt(halogen)₂, Pd(CN)₂, Pt(CN)₂, Pd(SCN)₂, Pt(SCN)₂, AgCl, AgCN, CuCl, CuCl₂, CuF, CuBr, CuCN, CuF₂, CuBr₂, Cu(CN)₂, ZnF₂, ZnCl₂, ZnBr₂, Zn(CN)₂, ScF₃, ScCl₃, ScBr₃, LnF₃, LnCl₃, LnBr₃, CaCl₂, KF, zeolite and mixtures thereof;

especially, CAT is selected from the group consisting of [(CH₃)₃SiFSi(CH₃)₃][ANIO],

Si(Cl)(C₆H₅)₃, B(R27)₃, A1(R27)₃, GaF₃, GaCl₃, (R26)₃C[ANIO], [(R24)₃0][ANIO], [(R25)₃Si][ANIO], Si(halogen)₄, Si(Ci_i₀ alkyl)₄, TiF₄, TiCl₄, P(halogen)₃, P(CN)₃, Sb(halogen)₃, Bi(halogen)₃, Bi(CN)₃, P(halogen)₅, P(Ci_io alkyl)₅, Sb(halogen)₅,

Nb(halogen)₅, CrCl₃, FeF₃, FeCl₃, FeBr₃, MnCl₂, FeF₂, FeCl₂, FeBr₂, PdF₂, PdCl₂, PdBr₂,

PtF₂, PtCl₂, PtBr₂, AgCN, CuCl, CuCl₂, CuF, CuBr, CuCN, CuF₂, ZnF₂, ZnCl₂, ZnBr₂, Zn(CN)₂, ScF₃, ScCl₃, LnF₃, LnCl₃, CaCl₂, KF, zeolite and mixtures thereof;

more especially, CAT is selected from the group consisting of [(CH₃)₃SiFSi(CH₃)₃][ANIO], Si(Cl)(C₆H₅)₃, BF₃, BC1₃, BBr₃, B(Ci_₄ alkyl)₃, B(C₆F₅)₃, A1F₃, A1C1₃, Al(Ci_₄ alkyl)₃, A1(C₆F₅)₃, GaF₃, GaCl₃, (Ph)₃C[ANIO], (CH₃)₃C[ANIO], [(Ci_₃ alkyl)₃0][ANIO], [(Ci_₄ alkyl)₃Si][ANIO], Si(halogen)₄, Si(Ci_i₀ alkyl)₄, TiF₄, TiCl₄, P(halogen)₃, P(CN)₃, SbF₃, Sbl₃, BiF₃, Bil₃, Bi(CN)₃, P(halogen)₅, SbF₅, NbF₅, NbCl₅, CrCl₃, FeCl₃, FeBr₃, MnCl₂, FeCl₂, FeBr₂, PdCl₂, PdBr₂, PtCl₂, PtBr₂, AgCN, CuCl, CuCl₂, CuF, CuF₂, ZnF₂, ZnCl₂, ZnBr₂, Zn(CN)₂, ScF₃, ScCl₃, LnF₃, LnCl₃, CaCl₂, KF, zeolite and mixtures thereof; even more especially, CAT is selected from the group consisting of

[(CH₃)₃SiFSi(CH₃)₃][ANIO], Si(Cl)(C₆H₅)₃, BF₃, BC1₃, B(C_1-4 alkyl)₃, B(C₆F₅)₃, A1C1₃, GaF₃, GaCl₃, (Ph)₃C[ANIO], (CH₃)₃C[ANIO], [(Ci_₄ alkyl)₃Si][ANIO], SiF₄, SiCl₄, Si(Ci_₈ alkyl)₄, TiF₄, TiCl₄, PC1₃, PBr₃, PI₃, P(CN)₃, SbF₃, Sbl₃, Bi(CN)₃, PF₅, PC1₅, PBr₅, PI₅, SbF₅, NbCls, CrCl₃, FeCl₃, FeBr₃, MnCl₂, FeCl₂, FeBr₂, PdCl₂, PdBr₂, PtCl₂, PtBr₂, AgCN, CuCl, CuCl₂, CuF, CuF₂, ZnF₂, Zn(CN)₂, ScF₃, ScCl₃, LnF₃, LnCl₃, CaCl₂, KF, zeolite and mixtures thereof;

in particular, CAT is selected from the group consisting of [(CH₃)₃SiFSi(CH₃)₃][ANIO], Si(Cl)(C₆H₅)₃, BF₃, BC1₃, B(C₆F₅)₃, A1C1₃, GaF₃, GaCl₃, Ph₃C[ANIO], [(C_1-4

alkyl)₃Si][ANIO], SiF₄, SiCl₄, Si(Ci_₄ alkyl)₄, TiF₄, TiCl₄, PCl₃, PBr₃, PI₃, P(CN)₃, SbF₃, Sbl₃, Bi(CN)₃, PF₅, PC1₅, PBr₅, PI₅, SbF₅, NbCl₅, CrCl₃, FeCl₃, FeBr₃, MnCl₂, FeCl₂,

FeBr₂, PdCl₂, PdBr₂, PtCl₂, PtBr₂, AgCN, CuCl, CuCl₂, CuF, CuF₂, ZnF₂, ScF₃, ScCl₃,

LnF₃, LnCl₃, CaCl₂, KF, zeolite and mixtures thereof;

more in particular, CAT is selected from the group consisting of [(CH₃)₃SiFSi(CH₃)₃][ANIO], Si(Cl)(C₆H₅)₃, BF₃, BC1₃, B(C₆F₅)₃, A1C1₃, GaF₃, GaCl₃, Ph₃C[ANIO], SiCl₄, TiF₄, TiCl₄,

P(CN)₃, SbF₃, Bi(CN)₃, PF₅, PC1₅, SbF₅, NbCl₅, CrCl₃, FeCl₃, MnCl₂, AgCN, CuCl,

CuCl₂, ZnF₂, CaCl₂, KF, zeolite and mixtures thereof;

even more in particular, CAT is selected from the group consisting of

[(CH₃)₃SiFSi(CH₃)₃][ANIO], Si(Cl)(C₆H₅)₃, BF₃, B(C₆F₅)₃ GaF₃, GaCl₃, Ph₃C[ANIO], SiCl₄, TiF₄, TiCl₄, P(CN)₃, PF₅, PC1₅, SbF₅, NbCl₅, CrCl₃, FeCl₃, MnCl₂, AgCN, CaCl₂,

KF, SiCl₄, zeolite and mixtures thereof;

very even more in particular, CAT is selected from the group consisting of

[(CH₃)₃SiFSi(CH₃)₃][ANIO], Si(Cl)(C₆H₅)₃, BF₃, B(C₆F₅)₃ GaF₃, GaCl₃, Ph₃C[ANIO],

SiCl₄, TiF₄, TiCl₄, P(CN)₃, PF₅, PC1₅, SbF₅, NbCl₅, CrCl₃, FeCl₃, MnCl₂, SiCl₄, zeolite and mixtures thereof;

in a very preferred embodiment, CAT is selected from the group consisting of BF , B(C₆F₅)

GaF₃, GaCl₃, TiF₄, TiCl₄, PF₅, PC1₅, SbF₅, [(CH₃)₃SiFSi(CH₃)₃] [ANIO], Ph₃C[ANIO],

SbF₅, zeolite and mixtures thereof;

in a more very preferred embodiment, CAT is [(CH₃)₃SiFSi(CH₃)₃][ANIO], B(C₆F₅)₃ GaF₃, GaCl₃, TiF₄, TiCl₄, PF₅, PC1₅, SbF₅, Ph₃C[ANIO], zeolite or mixtures thereof;

in an even more very preferred embodiment, CAT is [(CH ) SiFSi(CH ) ][ANIO], B(C₆F₅)

GaF₃, GaCl₃, TiF₄, TiCl₄, PF₅, PC1₅, SbF₅, Ph₃C[ANIO], zeolite or mixtures thereof; in an especially very preferred embodiment, CAT is B(CeF₅)₃ GaF₃, GaCl₃, TiF₄, TiCl₄, PF₅,

PC1₅, SbF₅, Ph₃C[ANIO], zeolite or mixtures thereof;

Ql is selected from the group consisting of B, Al and Ga;

R27 is selected from the group consisting of Ci_io alkoxy, halogen, Ci_io alkyl, CN, SCN and R24 is CLIO alkyl;

R25 is Ci_io alkyl;

Pv26 is selected from the group consisting of CN, SCN, Ph and C_1-10 alkyl;

Q2 is selected from the group consisting of Si and Ti;

Pv28 and R36 are identical or different and independently from each other selected from the group consisting of C_1-10 alkoxy, halogen, C_1-10 alkyl, CN, SCN and C₆F₅; Q3 is selected from the group consisting of P, Sb and Bi;

R29 is selected from the group consisting of C_1-10 alkoxy, halogen, CN, SCN, C_1-10 alkyl and C₆F₅;

Q4 is selected from the group consisting of P, Sb and Nb;

R30 is selected from the group consisting of C_1-10 alkoxy, halogen, CN, SCN, C_1-10 alkyl and C₆F₅;

Q5 is selected from the group consisting of Cr and Fe;

R32 is selected from the group consisting of halogen, CN and SCN;

Q6 is selected from the group consisting of Mn, Fe, Pd and Pt;

R33 is selected from the group consisting of halogen, CN and SCN;

Q7 is Cu or Ag;

R31 is selected from the group consisting of halogen, CN and SCN;

Q8 is selected from the group consisting of Cu, Zn, Cd and Hg;

R34 is selected from the group consisting of halogen, CN, and SCN;

Q9 Sc or Ln;

R35 is selected from the group consisting of halogen, CN, and SCN;

Q10 Ca;

R37 is halogen;

Ql l K;

R38 is halogen;

ANIO is selected from the group consisting of [P(R40)₆-_mi(R41)_mi]^", [B(R42)₄__m2(R43)_m2]^",

F^", Cl^", Br^", I^", CN^" and SCN^";

R40 and R41 are identical of different in independently from each other selected from the group consisting of CN, SCN, F, CI, Br and I;

ml is 0, 1, 2, 3, 4 or 5;

R42 and R43 are identical of different in independently from each other selected from the group consisting of C₆F₅, CN, SCN, F, CI, Br and I;

m2 is 0, 1, 2 or 3;

preferably, ANIO is selected from the group consisting of P(R40)₆ , B(R42)₄ , F , CI , Br , I , CN^" and SCN^";

R40 is selected from the group consisting of CN, SCN, F, CI, Br and I;

R42 is selected from the group consisting of C₆F5, CN, SCN, F, CI, Br and I; more preferably, ANIO is selected from the group consisting of P(R40)₆ , B(R42)₄ , F , CI ,

Br^", CN^" and SCN^~;

R40 is selected from the group consisting of CN, SCN, F, CI and Br;

R42 is selected from the group consisting of C₆F₅, CN, SCN, F, CI and Br.

Preferably,

Ql is B.

Preferably,

R24 is Ci_₄ alkyl;

R25 is Ci_₇ alkyl;

R26 is selected from the group consisting of Ph and Ci_₄ alkyl;

R27 is selected from the group consisting of Ci_₇ alkoxy, CI, F, Br, Ci_₇ alkyl and CeF₅; more preferably,

R24 is Ci_3 alkyl;

R25 is Ci_5 alkyl;

R26 is selected from the group consisting of Ph and Ci_₂ alkyl;

R27 is selected from the group consisting of Ci_₄ alkoxy, CI, F, Ci_₄ alkyl and C₆F₅; even more preferably,

R24 is methyl or ethyl;

R25 is Ci_4 alkyl;

R26 is Ph or methyl;

R27 is selected from the group consisting of Ci_₃ alkoxy, CI, F, Ci_₃ alkyl and C₆F₅. Preferably, [ANIO] is [B(C₆F₅)₄] or [BF₄].

In a special embodiments, CAT is selected from the group consisting of

[(CH₃)₃SiFSi(CH₃)₃][B(C₆F₅)₄], Si(Cl)(C₆H₅)₃, BF₃, BC1₃, B(C₆F₅)₃, A1C1₃, GaF₃, GaCl₃, Ph₃C[BF₄], SiCl₄, TiF₄, TiCl₄, P(CN)₃, SbF₃, Bi(CN)₃, PF₅, PC1₅, SbF₅, NbCl₅, CrCl₃, FeCl₃, MnCl₂, AgCN, CuCl, CuCl₂, ZnF₂, CaCl₂, KF, zeolite, and mixtures thereof; preferably, CAT is selected from the group consisting of [(CH₃)₃SiFSi(CH₃)₃][B(C₆F₅)₄], Si(Cl)(C₆H₅)₃, BF₃, B(C₆F₅)₃, GaF₃, GaCl₃, Ph₃C[BF₄], SiCl₄, TiF₄, TiCl₄, P(CN)₃, PF₅, PC1₅, SbF₅, NbCls, CrCl₃, FeCl₃, MnCl₂, S1CI₄, zeolite, and mixtures thereof; more preferably, CAT is selected from the group consisting of

[(CH₃)3SiFSi(CH3)3][B(C6F₅)₄], BF₃, B(C₆F₅)₃ GaF₃, GaCl₃, Ph₃C[BF₄], TiF₄, TiCl₄, PF₅,

PCI₅, SbF₅, zeolite, and mixtures thereof;

even more preferably, CAT is [(CH₃)₃SiFSi(CH₃)3][B(C₆F₅)₄], B(C₆F₅)₃ GaF₃, GaCl₃, TiF₄, TiCl₄, PF₅, PCI₅, SbF₅, Ph₃C[BF₄], zeolite or mixtures thereof;

especially, CAT is B(C₆F₅)₃, GaF₃, GaCl₃, TiF₄, TiCl₄, PF₅, PC1₅, SbF₅, Ph₃C[BF₄], zeolite or mixtures thereof.

In another preferred embodiment, CAT is selected from the group consisting of

(CH₃)₃SiFSi(CH₃)3[B(C₆F₅)₄], [Ph₃C][BF₄], B(C₆F₅)₃ and mixtures thereof;

more preferably, CAT is [Ph₃C][BF₄].

CAT can be used in immobilized form on a carrier CARR;

CARR is a carrier conventionally used for immobilizing catalysts in heterogeneously

catalyzed reactions;

preferably, CARR is seleceted from the group consisting of epoxide, polystyrene, zeolite, activated carbon and metal oxide;

said metal oxide is preferably selected from the group consisting of Mn0₂, Fe₂C>3, C0₃O₄,

NiO, CuO, CuMn0₂, MgO, A1₂0₃, Si0₂, V₂0₅, M0O3, W0₃ and mixed oxides thereof.

Zeolite can be any zeolite, preferably montmorrilonte or bentonite, more preferably

Montmorillonite K10®, BASF, Germany (also available at Sigma Aldrich, CAS Number 1318-93-0). Compound of formula (Al) and CAT can be one and the same compound, therefore in one preferred embodiment, compound of formula (Al) is different from CAT;

in another preferred embodiment, compound of formula (Al) is identical with CAT.

Preferably, from 0.0001 to 40 mol equivalents, more preferably 0.001 to 35 mol equivalents, even more preferably from 0.005 to 25 mol equivalents, especially from 0.005 to 25 mol equivalents, more especially from 0.005 to 15 mol equivalents, even more especially from 0.005 to 5 mol equivalents, of CAT are used in REAC1, the mol equivalents being based on the combined molar amount of the anion [(BF₄) ] of compound of formula (Al), CATACID and CAT. In another preferable embodiment, from 0.01 to 40 mol%, more preferably 0.1 to 35 mol%, even more preferably 0.1 to 25 mol%, especially from 0.5 to 15 mol%, more especially from 0.5 to 10 mol%, even more especially from 0.5 to 5 mol%, of CAT are used in REAC1, the mol% being based on the combined molar amount of the anion [(BF₄) ] of compound of formula (Al), CATACID and CAT.

Preferably, from 0.01 to 40 mol%, more preferably 0.1 to 35 mol%, even more preferably 0.1 to 25 mol%, especially from 0.5 to 17.5 mol%, more especially from 0.5 to 12.5 mol%, even more especially from 0.5 to 10 mol%, of CATACID are used in REAC1, the mol% being based on the combined molar amount of of the anion [(BF₄) ] compound of formula (Al),

CATACID and, if present, CAT.

Preferably, the method comprises additionally to STEP1 a step STEP2, STEP2 is done after STEP1;

n+

STEP2 comprises a reaction REAC2, REAC2 is a metathesis reaction wherein cation Cat in n+

compound of formula (I) is exchanged for a cation different from Cat ;

compound of formula (I) having been prepared in STEP1;

n+

Cat , n, compound of formula (I) and STEP1 are as defined above, also with all their

embodiments.

REAC2 is a metathesis reaction, also called a salt-exchange reaction. In a metathesis reaction such as REAC2 a first cation in a first salt is exchanged for a second cation, said second cation coming from a second salt.

Preferably, REAC2 provides for the preparation of a compound of formula (I-Cat-r);

[Cat-r ] [(BF₄__m(CN) r+ n+ n+

Cat-r is selected from the group consisting of CatlNORG and CatORG and is

n+

different from Cat ; r is 1, 2, 3 or 4;

n+ n+

with STEP 1 , m, CatlNORG and CatORG as defined above, also with all their embodiments. Preferably, in REAC2 Cat is exchanged for Cat-r from a compound of formula (I-Cat-n);

(Cat-/ )_tl (AnINORG^q")t2 is 1 or 2;

is 1 or2;

is 1, 2, 3 or 4;

when r is 1 and q is 1 , then tl is 1 and t2 is 1

when r is 2 and q is 1 , then tl is 1 and t2 is 2

when r is 3 and q is 1 , then tl is 1 and t2 is 3

when r is 4 and q is 1 , then tl is 1 and t2 is 4

when r is 1 and q is 2, then tl is 2 and t2 is 1

when r is 2 and q is 2, then tl is 1 and t2 is 1

when r is 3 and q is 2, then tl is 2 and t2 is 3

when r is 4 and q is 2, then tl is 1 and t2 is 2

AnINORG^q is an anion selected from the group consisting of halide, OH^", CN , OCN , SCN^~, N₃ ^~, sulfate, hydrogensulfate, nitrate, C0₃ ^2", HC0₃ ^", BF₄ ^", PF₆ ^", SbF₆ ^", CF₃S0₃ ^" (CF₃S0₂)₂N^~, (FS0₂)₂N , C_1-6 alkyl-S0₃ ^", C_1-6 alkyl-0-S0₃ ^",

, anions of Ci_₂o monocarboxylic aliphatic acids, mono- and dianions of C₂_₆ dicarboxylic aliphatic acids, anions of benzoic acids, mono- and dianions of phthalic acids, of isophthalic acids and of terephthalic acids, N(CN)₂ , C(CN)₃ ^", B(CN)₄ ^", P(CN)₆ ^", Sb(CN)₆ ^", and mixtures thereof; r+ n+ n+

Cat-r , r, CatlNORG and CatORG are as defined above, also with all their

embodiments.

Preferably, AnINORG is an anion selected from the group consisting of halide, OH^", CN , sulfate, hydrogensulfate, nitrate, C0₃ ^2", HC0₃ ^", BF₄ ^", PF₆ ^", CF₃S0₃ ^", (CF₃S0₂)₂N^~,

(FS0₂)₂N^~, H₃C-S0₃ ^", H₃C-CH₂-S0₃ ^", H₃C-0-S0₃ ^", H₃C-CH₂-0-S0₃ ^", acetate, oleate, fumarate, maleate, oxalate, benzoate, N(CN)₂ , and mixtures thereof;

more preferably, AnINORG*^"1 is an anion selected from the group consisting of Br , CI , OH^", GST, sulfate, hydrogensulfate, C0₃ ² , HC0₃ , acetate, and mixtures thereof;

even more preferably, AnINORG*^"1 is an anion selected from the group consisting of CI , OH^" GST, sulfate, hydrogensulfate, C0₃ ² , HC0₃ , acetate, and mixtures thereof.

In another preferred embodiment, AnINORG is an anion selected from the group consisting of halide, OH^", CN^~, OCN , SCN^~, N₃ ^~, sulfate, hydrogensulfate, nitrate, C0₃ ^2", HC0₃ ^", BF₄ ^", PF₆ ^", SbF₆ ^", CF₃S0₃ ^", (CF₃S0₂)₂N^~, (FS0₂)₂N^~, C_I_₆ alkyl-S0₃ ^", Ci_₆ alkyl-0-S0₃ ^",

anions of C₂_₆ dicarboxylic aliphatic acids, benzoate, phthalates, N(CN)₂ , C(CN)₃ B(CN)₄ ^", P(CN)₆ ^", Sb(CN)₆ ^", and mixtures thereof. Preferably, r is 1 or 2.

In case of REAC2, preferably a compound of formula (I-Cat-r) with Cat-r being CatORG is prepared by exchange of a Catⁿ being a CatINORGⁿ in compound of formula (I) for a CatORGⁿ⁺.

Said CatORGⁿ is provided in REAC2 preferably in form of a compound of formula (I-

CatORG) (CatORGⁿ )q(AnINORG^q")_n (I-CatORG) wherein

Catⁿ⁺, n, CatORGⁿ⁺, CatINORGⁿ⁺, q and AnINORG^q are as defined above, also with all their embodiments.

Preferably, in REAC2 the cation different from Cat , that is preferably Cat-r , is present in n+

at least such a molar amount relative to the molar amount of Cat as required for a stoichiometric exchange of said two cations;

more preferably, compound of formula (I) and compound of formula (I-Cat-n) are present in n+

at least such a molar amount relative to each other, that Cat is stoichiometrically

r+

exchanged for Cat-r ;

even more preferably, the molar amount of compound of formula (I-Cat-n) is such, that from r+

1 to 1.5, even more preferably from 1 to 1.2, required equivalents of Cat-r relative to n+

the equivalents of Cat are present.

The reaction temperatures of REAC2 is preferably from 0 to 250 °C, more preferably from 10 to 200 °C, even more preferably from 10 to 150 °C, especially from 10 to 100°C, more especially from 10 to 50°C.

The REAC2 is preferably carried out in a solvent SOLV2, SOLV2 is preferably selected from the group consisting of water, DCM, ethyl acetate, C5-10 alkane, and mixtures thereof. C5-10 alkane is preferably pentane, hexane or heptane.

In a more preferred embodiment, REAC2 is done in DCM or in a biphasic solvent system of water and DCM.

As an alternative, REAC2 can also be carried out in the absence of a solvent or in a solvent in which the inorganic salt formed as side product is sparingly soluble or insoluble. As a further alternative, it is also possible to carry out the reaction in an aqueous solution using an ion exchanger loaded with the desired cation Catⁿ . The amount of solvent is preferably from 2 to 40 fold, more preferably from 3 to 20 fold, of the weight of compound of formula (I). REAC2 can be done in a closed system and at the pressure caused by the chosen temperature.

The reaction time of REAC2 is preferably from 15 min to 96 h, more preferably from 15 min to 48 h, even more preferably from 15 min to 24 h. Preferably, REAC2 is done under inert atmosphere. Preferably, the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.

The lower boiling alkane is preferably a Ci_₃ alkane, i.e. methane, ethane or propane. Subsequent to REAC2 there can be a further metathesis reaction or further metathesis reactions.

After REAC2, compound of formula (I) can be isolated from the reaction mixture by standard methods such as filtration, evaporation of volatile components, extraction, washing, drying, concentration, crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.

For example, when REAC2 was done in a biphasic solvent system of water and DCM, the aqueous and organic phases are separated, the organic phase is preferably washed, preferably with water, then preferably dried, preferably with Na₂S0₄, K₂C0₃, CaCl₂ or MgS0₄, and finally evaporated.

Or as another example, when REAC2 was done in DCM and a suspension was formed, filtration and evaporation of the solvent will isolate the product.

It is possible use compound of formula (I), which was obtained by the method of instant invention, as substrate in a similar reaction with trimethylsilylcyanide.

Therefore the method of instant invention can comprise additionally to STEP1 a

step STEP 1-1 , STEPl-1 is done after STEP1 ; STEP 1-1 comprises a reaction REACl-1, wherein compound of formula (I), obtained in

STEP1, is reacted with trimethylsilylcyanide;

preferably, REACl-1 is done in the presence of CAT ACID, in the presence of CAT, or in the presence of both CAT ACID and CAT;

with CAT and CAT ACID as defined above, also in all their embodiments.

CAT ACID is commercially available compounds or can be prepared according to known methods. Compounds of formula (Al) are commercially available depending on the cation n+

Cat , e.g. [(n-Bu₄)N][BF₄] and K[BF₄], as well as CAT are commercially available. Other n+ _{+ +}

compounds of formula (Al) with cations Cat different from K and (n-Bu₄)N , and which are not commercially available, can be prepared by conventional metathesis reaction, i.e. substitution of the respective cation K⁺ or (n-Bu₄)N⁺ against another cation, or by reaction of tetrafluoroboric acid with a respective compound, such as exemplified herein.

EXAMPLES

Methods

1H, ¹³C, ¹⁹F and ³¹P NMR spectra were recorded on a Bruker AVANCE 300 and Bruker AVANCE 250 instruments in CD₃CN, CDC1₃, D₆-DMSO, D₂0 or CD₂C1₂. Chemical shifts are expressed in parts per million referred to TMS in case of 1H and ¹³C, C¹⁹FC1₃ in case of ¹⁹F, and H₃ ³¹P0₄ in case of ³¹P, and coupling constants (J) in Hertz. When a % value for the amount of compounds is stated based on NMR measurement, the % value represents an area- %, the area-% being based on the total area of peaks in the spectrum. In case of the individual amount of a component in a mixture the stated % value for the amount of the component in the mixture represents an area-%, this area-% being based on the combined area of peaks of all components of the mixture; if not stated otherwise.

IR-spectra were recorded on a Nicolet 380 FT-IR spectrometer. Measurements were done at room temperature .

RAMAN-spectra were recorded on a LabRAM HR 800 Horiba Jobin YVON. Measurements were done at room temperature. The C/H/N-analyses were measured on a C/H/N/S-Analysator (Thermoquest Flash EA 1112).

Melting points and temperature of decomposition Td_ec were measured on a DSC 823e from Mettler-Toledo. The calibration was carried out with the melting points of In (156.6 ± 0.3°C) and Zn (419.6 ± 0.7°C) with an heating rate of 5 K per min.

TGA/DSC measurements were conducted on a Setaram Labsys TGA / DSC 1600. The measurements were carried out under argon atmosphere with a heating rate of 5 K per min, corrected via a blank measurement. Preparation description A: Synthesis of [(n-Bu)₄N] [BF₄]

A solution of [(n-Bu₄)N]Br (8.05 g, 24.98 mmol) in 50 ml of CH₂C1₂ was added to a solution of K[BF₄] (3.12 g, 24.78 mmol) in 30 ml of H₂0. After stirring for 24 h at ambient temperature the phases were separated. The organic phase was washed three times with 10 ml of water, dried over anhydrous Mg₂S0₄ and filtered. The filtrate was concentrated on a rotary evaporator to obtain a white solid. The obtained solid was dried at 90°C in vacuo for 15 hours. The yield of [(n-Bu₄)N][BF₄] was 7.83 g (96%, 23.8 mmol).

DSC (10 Kmin^{" !}): m.p. = 153°C

C/H/N Analysis calc. % (found): C 58.36 (58.48), H 11.02 (10.84), N 4.25 (4.13)

1H NMR (25°C, CD₃CN, 300.13 MHz, delta in ppm): 0.96 (t, 12H, CH₃), 1.35 (m, 8H, CH₃-

CH₂, 1.61 (m, 8H, CH₂-CH₂N), 3.11 (m, 8H, NCH₂)

1³C NMR (25 °C, CD₃CN, 75.47 MHz, delta in ppm): 14.4 (s, 4C, CH₃), 20.9 (m, 4C, CH₃- CH₂), 25.0 (m, 4C, CH₂-CH₂N), 59.9 (m, 4C, NCH₂)

UB NMR (25°C, CD₃CN, 96.29 MHz, delta in ppm): -1.2 (s, IB, BF )

¹⁹F NMR (25°C, CD₃CN, 282.40 MHz, delta in ppm): -151.6 (s, 4F, BF₄)

IR (ATR, 32 scans, v in cm^"1): 2960 (m), 2935 (w), 2875 (w), 1486 (m), 1468 (w), 1382 (w),

1285 (w), 1152 (w), 1093 (m), 1047 (s), 1034 (s), 881 (w), 800 (w), 739 (w)

RAMAN (460 mW, 150 scans, v in cm^"1): 2964 (7), 2933 (10), 2876 (10), 2746 (1), 1453 (4), 1327(2), 1153(1), 1137 (2), 911 (2), 880 (1), 766 (1), 256 (2), 79 (1)

Preparation description B: Synthesis of [(n-Pr)₃NH] [BF₄]

Tetrafluoroboric acid (18 mL, 35 wt% aqueous solution, 88 mmol) was cooled to ca. 0 °C. n-Pr₃N (17 ml, 89 mmol) was added dropwise to the aqueous solution. After 30 min of stirring the product was extracted with CH₂C1₂ (three times a 50 ml). The combined organic phases were dried over anhydrous Na₂S0 and filtered After evaporating the solvent and drying the white solid in vacuo 18.9 g (93 %, 82 mmol) of [(n-Pr)₃NH][BF ] were obtained.

C/H/N Analysis % calc. (found): C 46.78 (47.05) H 9.60 (10.01) N 6.06 (6.36)

1H NMR (300 K, CD₂C1₂, 300.13 MHz, delta in ppm): 1.00 (t, 9H, CH₃), 1.77 (m, 6H., CH₂- CH₃), 3.05 (m, 6H, NCH₂), 7.25 (br, 1H, NH)

UB NMR (25°C, CD₂C1₂, 96.29 MHz, delta in ppm): -1.2 (s, IB, BF )

IR (25 °C, ATR, 32 scans, cm^"1): 756 (m), 764 (m), 993 (s), 1036 (s), 1051 (s), 1246 (w),

1284 (w), 1387 (w), 1425 (m), 1462 (m), 1477 (m), 2885 (w), 2945 (w), 2978 (w), 3161 (w)

Example 1: Synthesis of compound of formula 1

[(n-Bu)₄N][BF ] (764 mg, 2.32 mmol), prepared according to Preparation Description A, triflic acid (34 mol%, the mol% being based on the combined molar amount of [(n-Bu)₄N][BF₄] and triflic acid, 177 mg, 1.18 mmol) and (CH₃)₃SiCN (2.30 g, 23 mmol) were stirred under argon atmosphere at ambient temperature. After 2 hours of stirring an ⁿB NMR spectrum was measured. According to the ⁿB NMR spectrum the reaction mixture contained only compound of formula (1).

nB NMR (300 K, CD₃CN, 96.29 MHz, delta in ppm): -17.9 (d, IB, BF(CN)₃, ^("B- 'F) = 44 Hz, ¹J(¹¹B-¹³C) = 75 Hz)

Example 2: Synthesis of compound of formula 2

[(n-Pr)₃NH][BF ] (681 mg, 2.95 mmol), prepared according to Preparation Description B, triflic acid (21 mol%, the mol% being based on the combined molar amount of

[(n-Pr)₃NH][BF₄] and triflic acid, 122 mg, 0.81 mmol) and (CH₃)₃SiCN (2.9 g, 29 mmol) were stirred under argon atmosphere at ambient temperature. After 2 hours of stirring an ⁿB NMR spectrum was measured. According to ⁿB NMR the reaction mixture contained only compound of formula (2). ⁿB NMR (300 K, CD₃CN, 96.29 MHz, delta in ppm): -17.9 (d, IB, BF(CN)₃, ^("B- 'F) = 44 Hz, ¹J(¹¹B-¹³C) = 75 Hz)

Example 3:

[(n-Pr)₃NH][BF₄] (922 mg, 3.99 mmol), prepared according to Preparation Description B, triflic acid (15 mol%, the mol% being based on the combined molar amount of

[(n-Pr)₃NH][BF₄] and triflic acid, 108 mg, 0.72 mmol) and (CH₃)₃SiCN (4.0 g, 40 mmol) were refluxed under argon atmosphere. After 3 hours of refluxing an ⁿB NMR spectrum was measured. According to the ⁿB NMR spectrum the reaction mixture contained 76 % of compound of formula (2) and 24 % compound of formula (3). After a total of 31.5 hours of refluxing again an ⁿB NMR spectrum was measured. According to the ⁿB NMR spectrum the reaction mixture contained 29 % of compound of formula (2) and 71 % compound of formula (3). ⁿB NMR (300 K, CD₃CN, 96.29 MHz, delta in ppm): -17.9 (d, IB, BF(CN)₃, ^("B- 'F) = 44 Hz, ^("B-^C) = 75 Hz), -38.6 (s, IB, B(CN)₄, ^("B-^C) = 70 Hz)

Example 4: [(n-Bu)₄][BF₄] (618 mg, 1.88 mmol), prepared according to Preparation Description A, triflic acid, TiCl₄ (7 mol%, 25 mg, 0,17 mol triflic acid and 9 mol%, 40 mg, 0.21 mol TiCl₄, the mol% being based on the combined molar amount of [(n-Bu)₄N][BF₄], triflic acid and TiCl₄) and (CH₃)₃SiCN (1.9 g, 19 mmol) were stirred under argon atmosphere and ambient temperature. After 3 hours of stirring an ⁿB NMR spectrum was measured. According to ⁿB NMR the reaction mixture contained only compound of formula (1).

NMR data was the same as in example 1.

Example 5:

Example 4 was repeated with the differences:

GaCl₃ was used instead of TiCl (7 mol% GaCl₃, the mol% being based on the combined molar amount of [(n-Bu)₄N][BF₄], GaCl₃, and triflic acid (15 mol% instead of 9 mol%)).

After the stirring for 3 h an ⁿB NMR spectrum were measured. In accordance to ⁿB NMR the product contained 100% of compound of formula (1).

NMR data was the same as in example 1.

Example 6:

Example 4 was repeated with the difference:

SbF₅ was used instead of TiCl₄ (7 mol% SbF₅, the mol% being based on the combined molar amount of [(n-Bu)₄N] [BF ] , SbF₅, and triflic acid ( 10 mol% instead of 9 mol%).

NMR data was the same as in example 1. Comparative Example 1: No CAT ACID

[(n-Bu)₄N][BF ] (0.491 g, 1.49 mmol), prepared according to Preparation Description A, and (CH₃)₃SiCN (1.58 g, 1.59 mmol) were stirred under argon atmosphere at ambient temperature for 100 h.

After the stirring at ambient temperature for 100 h an ⁿB and ¹⁹F NMR spectra were measured. In accordance to ¹⁹F and ⁿB NMR the product contained about 82% of compound of formula (4) and 18% of compound of formula (5).

[(n-Bu)₄N][BF₃(CN)] [(n-Bu)₄N][BF₂(CN)₂] (5)

1H NMR (25°C, CDCls, 300.13 MHz, delta in ppm): 0.98 (t, 12H, CH₃), 1.41 (m, 8H,

CH₃-CH₂), 1.61 (m, 8H, CH₂-CH₂N), 3.16 (m, 8H, NCH₂)

nB NMR (25°C, CDCI₃, 300.13 MHz, delta in ppm): -3.6 (q, IB, BF₃(CN), ^("B-^F) = 28

Hz), -7.2 (q, IB, BF₂(CN)₂, ^("B-^F) = 42 Hz)

1³C NMR (25°C, CDCI₃, 300.13 MHz, delta in ppm): 13.4 (s, 4C, CH₃), 19.5 (t, 4C,

CH₂-CH₃), 23.7 (s, 4C, N-CH₂-CH₂), 58.5 (t, 4C, NCH₂)

1⁹F NMR (25°C, CDC1₃, 300.13 MHz, delta in ppm): -137.0 (q, 3F, BF₃(CN), ^("B-^F) =

28 Hz), -153.1 (q, 2F, BF₂(CN)₂, ^("B-^F) = 42 Hz)

IR (ATR, 32 scans, v in cm^"1): 2964 (m), 2937 (m), 2877 (m), 2206 (w), 1474 (m), 1383 (m),

1261 (w), 1106 (s), 1058 (s), 990 (m), 952 (s), 881 (m), 799 (m), 738 (m), 681 (m), 532

(w)

Comparative Example 2:

[(n-Bu)₄N][BF₄] (0.498 g, 1.41 mmol), prepared according to Preparation Description A, and (CH₃)₃SiCN (1.58 g, 1.59 mmol) were stirred under argon atmosphere at ambient temperature for 3 h. An ⁿB NMR was then measured and revealed 1 % of [(n-Bu)₄N][BF₄], 79 % of compound of formula (4) ([(n-Bu)₄N][BF₃(CN)]), and 20 % of compound of formula (5) ([(n-Bu)₄N][BF₂(CN)₂]).

Claims

1. Method for the preparation of compound of formula (I);

[Cat ] [(BF₄__m(CN) the method comprises a step STEP1;

STEP1 comprises a reaction REAC1, wherein compound of formula (Al)

[Catⁿ⁺] [(BF₄)^" ]_n (Al) is reacted with trimethylsilylcyanide in the presence of a compound CATACID;

CAT ACID is selected from the group consisting of HF, HCl, HBr, HI, HN0₃, H₂S0₃, H₂S0₄, NaHS0₄, Oleum, KHS0₄, NaHC0₃, KHC0₃, H₃P0₄, H₃P0₃, HS0₃F, HS0₃C1, CH₃COOH, CF₃COOH, C(Cl₃)COOH, methansulfonic acid, HCOOH, AR-COOH, AR- S0₃H, C(OH)(COOH)₃, CF₃SO₃H, HCN, HOCN, HSCN, HSeCN, HNCO, HNCS, HN₃, HQ20(X1)4, polymolybdate, polytungstate, HQ21(X1)₆, and mixtures thereof;

AR is Phe or Phe substituted with 1 , 2 or 3 identical or different residues selected from the group consisting of halogen and CH₃;

Q20 is B, Al, Ga, In or Th;

Q21 is P, As, Sb or Bi;

XI is halogen; m is 1, 2, 3 or 4;

n is 1, 2, 3 or 4; n+ n+

cation CatORG ; CatINORGⁿ⁺ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 1 1., 12., 13., 14.,

15. or 16. group of the periodic table, or is a cation from the lanthanides or is a cation from the actinides or is NH₄ ⁺; CatORGⁿ⁺ is selected from the group consisting of CatORG- A⁺, CatORG-B⁺, CatORG- C⁺, [(CH₃)3SiFSi(CH₃)3]⁺, Ph₃C⁺, guanidinium and (H₂(R18)N-R16-N(R19)H₂)²⁺;

CatORG-A is (WR2R3R4R5) ,

wherein

W is a nitrogen or phosphorus; and

perfluoroalkyl, C₃_io cycloalkyl and C_6-1o aryl, with the proviso, that at least one of the residues R2, R3, R4 and R5 is not H; or

7-membered saturated or unsaturated heterocyclic ring,

R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_₂o alkyl, Ci_₂o perfluoroalkyl, C₃_io cycloalkyl and C₆-io aryl; or

(iii) R2 and R3 together are a hydrocarbon chain and form together with W, and R4 and R5 together are a hydrocarbon chain and form together with W, independently from each other, 5- to 7-membered saturated or unsaturated heterocyclic rings;

CatORG-B⁺ is (XR6R7R8)⁺,

wherein

X is nitrogen,

perfluoroalkyl, C₃_io cycloalkyl or C₆-io aryl; CatORG-C⁺ is (YR9R10R1 1)⁺,

wherein

Y is sulphur;

perfluoroalkyl, C₃_i₀ cycloalkyl and C_6-10 aryl; or

(ii) R9 and RIO together are a hydrocarbon chain and form together with Y a 5- to

7-membered saturated or unsaturated ring,

Rl 1 is selected from the group consisting of H, Ci_₂o alkyl, Ci_₂o perfluoroalkyl, C₃_io cycloalkyl and C₆-io aryl; the residues R2, R3, R4, R5, R6, R7, R8, R9, RIO and Rl 1 are, independently from each other, unsubstituted or, where applicable, substituted by 1 , 2, 3, 4, 5 or 6 substituents selected from the group consisting of Ci_₄ alkyl, C₃_io cycloalkyl, C₂_s alkenyl, phenyl, benzyl, halogen, cyano and Ci_₄ alkoxy; in any of said hydrocarbon chains formed by R2 and R3, by R4 and R5, by R6 and R7, and by R9 and RIO, 1 or 2 carbon atoms of said hydrocarbon chains can be exchanged for 1 or 2 heteroatoms respectively, said one or two heteroatoms being selected from the group consisting of O, N and S; in case of an exchange for N, this N is unsubstituted or substituted by a residue selected from the group consisting of Ci_₈ alkyl, C₃_i₀ cycloalkyl, C₂_8 alkenyl and Ci_s perfluoroalkyl;

C(H)(phenyl), R17(-0-R17)„i;

CH₂, CH₂-CH₂-C(H)(CH₃) and CH₂-CH₂-CH₂-CH₂;

nl is an integer from 1 to 20.

2. Method according to claim 1 , wherein

m is 2, 3 or 4.

3. Method according to claim 1 or 2, wherein

n is 1 or 2.

4. Method according to one or more of claims 1 to 3, wherein

CAT ACID is selected from the group consisting of HF, HCl, HBr, H₂S0₄, NaHS0₄, Oleum, KHS0₄, H₃P0₄, HS0₃F, HS0₃C1, CH₃COOH, CF₃COOH, C(Cl₃)COOH,

methansulfonic acid, HCOOH, AR-S0₃H, C(OH)(COOH)₃, CF₃S0₃H HCN,

HQ20(X1)4, polymolybdate, polytungstate, HQ21(X1)₆, and mixtures thereof;

Q20 is B, Al or Ga;

Q21 is P, Sb or Bi;

XI is F, CI or Br. 5. Method according to one or more of claims 1 to 4, wherein

CatINORGⁿ⁺ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 14. or 15. group of the periodic table or is a cation from the lanthanides or is NH₄ ⁺.

6. Method according to one or more of claims 1 to 5, wherein

CatINORGⁿ⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Mg²⁺,

Ca²⁺, Sr²⁺, Ba²⁺, Ti⁴⁺, Ti³⁺, Zr⁴⁺, Zr³⁺, Hf⁴*, n ⁺, V⁴⁺, V³⁺, V²⁺, Nb⁴⁺, Ta⁴⁺, Cr³⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, W⁴⁺, W³⁺, W²⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁴⁺, Os³⁺, Os²⁺, Co⁴⁺, Co³⁺, Co²⁺, Rh⁴⁺, Rh³⁺, Ir⁴⁺, Ir³⁺, Ni⁴⁺, Ni³⁺, Ni²⁺, Pd⁴⁺, Pd³⁺, Pd²⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag⁴⁺, Ag³⁺, Ag²⁺, Ag⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Cd²⁺, Cd⁺, Hg²⁺, Hg⁺, B³⁺, Al³⁺, Ga³⁺, Ga⁺, In³⁺, In⁺, Tl³⁺, Tl⁺, Ge⁴⁺,Ge²⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺,

Pb²⁺, As³⁺, Sb³⁺, Bi³⁺, Bi¹⁺, La³⁺, Nb³⁺, Sm³⁺, Eu³⁺, Gd³⁺, and NH₄ ⁺.

7. Method according to one or more of claims 1 to 6, wherein

CatORGⁿ is selected from the group consisting of ammonium, phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, pyrazolinium, imidazolium, imidazolinium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1,3-dioxolium,

.+ pyrylium, thiopyrylium, quinoxalinium, indolinium, indolium, [(CH₃)₃SiFSi(CH₃)3] PI13C , and mixtures thereof.

Method according to one or more of claims 1 to 7, wherein

CatORG is selected from the group consisting of _?

_f , , [N(R20)(R21)(R22)R23]

[P(R20)(R21)(R22)R23]⁺, [(CH₃)3SiFSi(CH₃)3]⁺, Ph₃C⁺, and mixtures thereof; wherein

R20, R21, R23 are identical or different and independently from each other selected from the group consisting of H, Ci_₂o alkyl, C3-10 cycloalkyl and allyl;

R22 is Ci_₂o alkyl, C3-10 cycloalkyl or allyl.

9. Method according to one or more of claims 1 to 8, wherein

compound of formula (I) is compound (Group-I),

compound (Group-I) is selected from the group consisting of compound of formula (la) and compound of formula (lb).

[Cat ] [(BF(CN)₃)^" ]n [Catⁿ⁺] [(B(CN)₄)^" ]_n

10. Method according to one or more of claims 1 to 9, wherein

compound of formula (I) is selected from the group consisting of compound of formula (1), compound of formula (2), compound of formula (3), and mixtures thereof.

[(n-Bu)₄N][BF(CN)₃] (1) [(n-Pr)₃NH][BF(CN)₃] (2)

[(n-Pr)₃NH][B(CN)₄] (3)

1 1. Method according to one or more of claims 1 to 10, wherein

REAC1 is done in the presence of a compound CAT;

CAT is a Lewis Acid selected from the group consisting of Lewis Acids derived , that is

based on, the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 1 1., 12., 13., 14., 15. and 16. group of the periodic table, zeolite, guanidinium[ANIO] and mixtures thereof.

12. Method according to claims 1 1 , wherein

CAT is selected from the group consisting of [(CH₃)₃SiFSi(CH₃)₃][ANIO], Q1(R27)₃,

guanidinium[ANIO], (R26)₃C[ANIO], adamantyl[ANIO], [(R24)₃0][ANIO],

[(R25)₃Si][ANIO], Q2(R36)(R28)₃, Q3(R29)₃, Q4(R30)₅, Q5(R32)₃, Q6(R33)₂, Q7(R31), Q8(R34)₂, Q9(R35)₃, Q10(R37)₂, Ql 1(R38), zeolite and mixtures thereof;

Ql is selected from the group consisting of B, Al and Ga;

R25 is Ci_io alkyl;

R26 is selected from the group consisting of CN, SCN, Ph and C_1-10 alkyl;

Q2 is selected from the group consisting of Si and Ti;

R28 and R36 are identical or different and independently from each other selected from the group consisting of C_1-10 alkoxy, halogen, C_1-10 alkyl, CN, SCN and C₆F₅;

Q3 is selected from the group consisting of P, Sb and Bi;

R29 is selected from the group consisting of C_1-10 alkoxy, halogen, CN, SCN, C_1-10 alkyl and

Q4 is selected from the group consisting of P, Sb and Nb;

R30 is selected from the group consisting of C_1-10 alkoxy, halogen, CN, SCN, C_1-10 alkyl and

Q5 is selected from the group consisting of Cr and Fe;

R32 is selected from the group consisting of halogen, CN and SCN;

Q6 is selected from the group consisting of Mn, Fe, Pd and Pt; R33 is selected from the group consisting of halogen, CN and SCN;

Q7 is Cu or Ag;

R31 is selected from the group consisting of halogen, CN and SCN;

Q8 is selected from the group consisting of Cu, Zn, Cd and Hg;

R34 is selected from the group consisting of halogen, CN, and SCN;

Q9 Sc or Ln;

R35 is selected from the group consisting of halogen, CN, and SCN;

Q10 Ca;

R37 is halogen;

Ql l K;

R38 is halogen;

F^", Cl^", Br^", I^", CN^" and SCN^";

ml is 0, 1, 2, 3, 4 or 5;

R42 and R43 are identical of different in independently from each other selected from the group consisting of C₆F5, CN, SCN, F, CI, Br and I;

m2 is 0, 1, 2 or 3.

13. Method according to one or more of claims 1 to 12, wherein

the method comprises additionally to STEP1 a step STEP2, STEP2 is done after STEP1;

STEP2 comprises a reaction REAC2, REAC2 is a metathesis reaction wherein cation Cat n+

compound of formula (I) is exchanged for a cation different from Cat ;

compound of formula (I) having been prepared in STEP1.