METHOD FOR PREPARATION OF CYANO COMPOUNDS OF THE 13TH GROUP
WITH A LEWIS ACID
The invention discloses a method for preparation of cyano compounds of the 13th group of
the periodic table with 1, 2, 3 or 4 cyano residues, represented by formula (I),
[Catn + ] [(Z 1F4_m(CN)m) ]„ (I)
by a reaction of [(Z1F4) ] with trimethylsilylcyanide in the presence of a Lewis acid and in the
n+
presence of the cation Cat ;
n+ ,
Cat is a cation, Z is B, Al, Ga, In or Tl, 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 foremost 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][BF 4]) 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.
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.
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 + 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 3-1 1 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)3] salt.
There was a need for a simplified method with high yield and satisfactory purity for the
preparation of fluoro cyanide compounds of the 13th group of the periodic table with the
anion having the general formula [(Z1F4_m(CN)m) ] with Z1 is B, Al, Ga, In or Tl and 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 of 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 Lewis acid. No metal cyanide, 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 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_ alkyl encompasses inter alia methyl, ethyl, propyl, isopropyl, nbutyl,
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;
C -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 C -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_i 0 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_2oalkoxy 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 CI and C2 carbon atoms (a branched alkylene group),
or via its CI and C3 carbon atoms (linear alkylene group);
BMMIm n-Butyl-2-methyl-3 -methylimidazolium
n-Butylmethylpyridinium
BMPyrr n-Butylmethylpyrrolidinium
BMPip n-Butylmethylpiperidinium .
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;
HEIm 1-ethylimidazolium 2 5
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;
dec decomposition temperature;
THF tetrahydrofuran;
TMSCN (CH3)3SiCN, i.e. trimethylsilylcyanide;
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);
[Catn + ] [(Z 1F4_m(CN)m) ]„ (I)
the method comprises a step (Stl);
step (Stl) comprises a reaction (Real), wherein [(Z F4) ] is reacted with trimethylsilylcyanide
n+
in the presence of CATLEWISACID and in the presence of Cat ;
CATLEWISACID is a Lewis Acid selected from the group consisting of Lewis Acid from the
1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 14., 15. and 16. group of the periodic table,
zeolite, guanidinium and mixtures thereof;
Z1 is selected from the group consisting of B, Al, Ga, In and Tl;
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 , CatORGC+,
[(CH3)3SiFSi(CH3 )3] + , Ph3C+ , guanidinium and (H2(R18)N-R16-N(R19)H2) +;
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_20
perfluoroalkyl, C3-10 cycloalkyl and C -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_2operfluoroalkyl, C3-10
cycloalkyl and C -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_ alkenyl, Ci_2o
perfluoroalkyl, C3_i 0 cycloalkyl or C6-10 aryl;
CatORG-C+ is (YR9R10R1 1)+,
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, C3-10 cycloalkyl and C -io 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_2operfluoroalkyl,
C3-10 cycloalkyl and C -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, C3-10 cycloalkyl, C2 _ 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, 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 C i alkyl, C3-10 cycloalkyl,
C2 _8 alkenyl and Ci_s perfluoroalkyl;
R16 is selected from the group consisting of C2_ alkylen, C3_ cycloalkylen, phenylen,
C(H)(phenyl), R17(-0-R17)„i;
R17 is selected from the group consisting of CH2-CH2, CH2-CH2-CH2, CH2-C(H)(CH 3)-
CH2, CH2-CH2-C(H)(CH 3) 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 _ cycloalkyl, phenyl and benzyl;
n l is an integer from 1 to 20.
DETAILED DESCRIPTION OF THE INVENTION
Preferably, Z1 is B, also in connection with any of the embodiments disclosed in the
specification.
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, CATLEWISACID is selected from the group consisting of
[(CH3)3SiFSi(CH3)3]+ , Q1(R27) 3, guanidinium, (R26) 3C+ , adamantyl cation, [(R24)30 ]+ ,
[(R25) Si]+ , Q2(R36)(R28) , Q3(R29) , Q4(R30) 5, Q5(R32) , Q6(R33) 2, Q7(R31),
Q8(R34) 2, Q9(R35) 3, Q10(R37) 2, Q 11(R38), zeolite and mixtures thereof;
Ql is selected from the group consisting of B, Al and Ga;
R27 is selected from the group consisting of C1-10 alkoxy, halogen, C1-10 alkyl, CN, SCN and
R24 is CLIO alkyl;
R25 is Ci_io alkyl;
R26 is selected from the group consisting of CN, SCN, Ph and C1-10 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 C1-10 alkoxy, halogen, C1-10 alkyl, CN, SCN and C F ;
Q3 is selected from the group consisting of P, Sb and Bi;
R29 is selected from the group consisting of C1-10 alkoxy, halogen, CN, SCN, C1-10 alkyl and
Q4 is selected from the group consisting of P, Sb and Nb;
R30 is selected from the group consisting of C1-10 alkoxy, halogen, CN, SCN, C1-10 alkyl and
C F5;
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;
more preferably, CATLEWISACID is selected from the group consisting of
[(CH3)3SiFSi(CH 3 )3] + , Si(Cl)(C 6H5)3, B(R27) 3, A1(R27)3, GaF , GaCl 3, guanidinium,
(R26) 3C+ , [(R24) 30 ]+ , [(R25) 3Si]+ , Si(R28) 4, TiF4, TiCl 4, Q3(halogen) 3, Q3(CN) 3,
Q3(C 1-4 alkyl) , Q4(halogen) 5, Q4(d_ 10 alkyl) 5, Cr(Cl) , Fe(halogen) , 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, CuCl 2, CuF, CuBr, CuCN, CuF2, CuBr 2, Cu(CN) 2, ZnF2, ZnCl 2, ZnBr 2,
Zn(CN) 2, ScF , ScCl3, ScBr , LnF , LnCl 3, LnBr , CaCl 2, KF, zeolite and mixtures
thereof;
even more preferably, CATLEWISACID is selected from the group consisting of
[(CH3)3SiFSi(CH 3)3]+ , Si(Cl)(C 6H5)3, B(R27) 3, A1(R27)3, GaF3, GaCl 3, (R26) 3C+ ,
[(R24) 30 ]+ , [(R25) 3Si]+ , Si(halogen) 4, Si(Ci_i 0 alkyl) 4, TiF4, TiCl 4, P(halogen) 3, P(CN) 3,
Sb(halogen) , Bi(halogen) , Bi(CN) 3, P(halogen) , P(Ci_io alkyl) , Sb(halogen) ,
Nb(halogen) 5, CrCl 3, FeF 3, FeCl 3, FeBr 3, MnCl 2, FeF 2, FeCl 2, FeBr 2, PdF2, PdCl 2, PdBr 2,
PtF2, PtCl 2, PtBr 2, AgCN, CuCl, CuCl 2, CuF, CuBr, CuCN, CuF2, ZnF2, ZnCl 2, ZnBr 2,
Zn(CN) 2, ScF , ScCl3, LnF , LnCl 3, CaCl 2, KF, zeolite and mixtures thereof;
especially, CATLEWISACID is selected from the group consisting of [(CH3)3SiFSi(CH 3)3]+ ,
Si(Cl)(C 6H5) , BF , BC1 , BBr , B(Ci_4 alkyl) , B(C6F5) , A1F , A1C1 , Al(Ci_4 alkyl) ,
A1(C F5) , GaF , GaCl , (Ph) C+ , (CH ) C+ , [(C 1-3 alkyl) 0 ]+ , [(C 1-4 alkyl) Si]+ ,
Si(halogen) 4, Si(Ci_i 0 alkyl) 4, TiF4, TiCl 4, P(halogen) 3, P(CN) 3, SbF3, Sbl 3, BiF3, Bil 3,
Bi(CN) 3, P(halogen) 5, SbF5, NbF 5, NbCl 5, CrCl 3, FeCl 3, FeBr 3, MnCl 2, FeCl 2, FeBr 2,
PdCl 2, PdBr 2, PtCl 2, PtBr 2, AgCN, CuCl, CuCl 2, CuF, CuF2, ZnF2, ZnCl 2, ZnBr 2,
Zn(CN) 2, ScF , ScCl3, LnF , LnCl 3, CaCl 2, KF, zeolite and mixtures thereof;
more especially, CATLEWISACID is selected from the group consisting of
[(CH ) SiFSi(CH ) ]+ , Si(Cl)(C H5) , BF , BC1 , B(C 1-4 alkyl) , B(C F5) , A1C1 , GaF ,
GaCl 3, (Ph) 3C+ , (CH3)3C+ , [(Ci_4 alkyl) 3Si]+ , SiF4, SiCl4, Si(Ci_ alkyl) 4, TiF4, TiCl 4,
PC1 , PBr , PI , P(CN) , SbF , Sbl , Bi(CN) , PF5, PC15, PBr 5, PI5, SbF5, NbCl 5, CrCl ,
FeCl 3, FeBr 3, MnCl 2, FeCl 2, FeBr 2, PdCl 2, PdBr 2, PtCl 2, PtBr 2, AgCN, CuCl, CuCl 2,
CuF, CuF2, ZnF 2, Zn(CN) 2, ScF , ScCl3, LnF , LnCl 3, CaCl 2, KF, zeolite and mixtures
thereof;
even more especially, CATLEWISACID is selected from the group consisting of
[(CH3)3SiFSi(CH 3 )3] + , Si(Cl)(C H5)3, BF3, BC1 , B(C F5) , A1C13, GaF , GaCl , Ph C+ ,
[(Ci_4 alkyl) 3Si]+ , SiF4, SiCl4, Si(Ci_4 alkyl) 4, TiF4, TiCl 4,PCl 3, PBr 3, PI3, P(CN) 3, SbF3,
Sbl 3, Bi(CN) 3, PF5, PC15, PBr 5, PI5, SbF5, NbCl 5, CrCl 3, FeCl 3, FeBr 3, MnCl 2, FeCl 2,
FeBr 2, PdCl 2, PdBr 2, PtCl 2, PtBr 2, AgCN, CuCl, CuCl 2, CuF, CuF2, ZnF2, ScF3, ScCl 3,
LnF , LnCl , CaCl 2, KF, zeolite and mixtures thereof;
in particular, CATLEWISACID is selected from the group consisting of
[(CH ) SiFSi(CH ) ]+ , Si(Cl)(C H5) , BF , BC1 , B(C F5) , A1C13, GaF , GaCl , Ph C+ ,
[(ethyl) 3Si]+ , SiCl4, TiF4, TiCl 4, P(CN) 3, SbF3, Bi(CN) 3, PF5, PC15, SbF5, NbCl 5, CrCl 3,
FeCl 3, MnCl 2, AgCN, CuCl, CuCl 2, ZnF2, CaCl 2, KF, zeolite and mixtures thereof;
more in particular, CATLEWISACID is selected from the group consisting of
[(CH3)3SiFSi(CH 3)3]+ , Si(Cl)(C 6H5)3, BF , GaF , GaCl 3, [(ethyl) 3Si]+ , Ph3C+ , SiCl4,
TiF4, TiCl 4, P(CN) 3, PF5, PC15, SbF5, NbCl 5, CrCl 3, FeCl 3, MnCl 2, AgCN, CaCl 2, KF,
SiCl4, zeolite and mixtures thereof;
even more in particular, CATLEWISACID is selected from the group consisting of
[(CH3)3SiFSi(CH 3)3]+ , Si(Cl)(C 6H5)3, BF3, GaF3, GaCl 3, [(ethyl) 3Si]+ , Ph3C+ , SiCl4,
TiF4, TiCl 4, P(CN) 3, PF5, PC15, SbF5, NbCl 5, CrCl 3, FeCl 3, MnCl 2, SiCl4, zeolite and
mixtures thereof;
in a very preferred embodiment, CATLEWISACID is selected from the group consisting of
B(F) 3, GaF3, GaCl 3, [(ethyl) 3Si]+ , Ph3C+ , TiF4, TiCl 4, PF5, PC15, [(Ci_4 alkyl) 3Si]+ ,
[(CH3)3SiFSi(CH 3)3]+ , Sb(F) 5, zeolite and mixtures thereof;
in a more very preferred embodiment, CATLEWISACID is [(CH3)3SiFSi(CH 3)3]+ , GaF3,
GaCl 3, [(ethyl) 3Si]+ , Ph3C+ , TiF4, T1CI4, PF5, PC15, zeolite or mixtures thereof;
in an even more very preferred embodiment, CATLEWISACID is [(CH ) SiFSi(CH ) ]+ ,
GaF , GaCl 3, Ph C+ , TiF 4, TiCl 4, PF , PCI5, zeolite or mixtures thereof ;
in an especially very preferred embodiment, CATLEWISACID is GaF , GaCl 3, Ph C+ , TiF 4,
TiCl 4, PF , PCI5, zeolite or mixtures thereof .
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;
Pv27 is selected from the group consisting of Ci_7 alkoxy, CI, F, Br, Ci_7 alkyl and C F ;
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 C F ;
even more preferably,
Pv24 is methyl or ethyl;
R25 is Ci_4 alkyl;
Pv26 is Ph or methyl;
R27 is selected from the group consisting of Ci_3 alkoxy, CI, F, Ci_3 alkyl and C F .
In another preferred embodiment, CATLEWISACID is selected from the group consisting of
[(CH 3)3SiFSi(CH 3)3]+ , Ph3C+ , B(C 6F5)3, and mixtures thereof;
more preferably, CATLEWISACID is Ph3C+ .
Preferably, CATLEWISACID is used in the reaction (Real) in form of a catalyst CAT;
CAT is a Lewis Acid selected from the group consisting of Lewis Acid from the 1., 2., 3., 4.,
5., 6., 7., 8., 9., 10., 11., 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 [(CH 3)3SiFSi(CH 3)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, Q 11(R38), zeolite and mixtures thereof;
even more preferably, CAT is selected from the group consisting of
[(CH 3)3SiFSi(CH 3)3][ANIO], Si(Cl)(C 6H5)3, B(R27) 3, A1(R27) 3, GaF 3, GaCl 3,
guanidinium[ANIO], (R26) 3C[ANIO], [(R24) 30 ] [ANIO], [(R25) 3Si][ANIO], Si(R28) 4,
TiF 4, TiCl 4, Q3(halogen) 3, Q3(CN) 3, Q3(Ci_4 alkyl) 3, Q4(halogen) 5, Q4(Ci_i 0 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, CuCl 2, CuF, CuBr, CuCN, CuF2,
CuBr 2, Cu(CN) 2, ZnF 2, ZnCl 2, ZnBr 2, Zn(CN) 2, ScF3, ScCl 3, ScBr 3, LnF3, LnCl 3, LnBr 3,
CaCl 2, KF, zeolite and mixtures thereof;
especially, CAT is selected from the group consisting of [(CH3)3SiFSi(CH 3)3][ANIO],
Si(Cl)(C 6H5)3, B(R27) 3, A1(R27)3, GaF3, GaCl 3, (R26) 3C[ANIO], [(R24) 30][ANIO],
[(R25) 3Si][ANIO], Si(halogen) 4, Si(Ci_i 0 alkyl) 4, TiF4, TiCl 4, P(halogen) 3, P(CN) 3,
Sb(halogen) 3, Bi(halogen) 3, Bi(CN) 3, P(halogen) , P(Ci_i 0 alkyl) , Sb(halogen) ,
Nb(halogen) 5, CrCl 3, FeF 3, FeCl 3, FeBr 3, MnCl 2, FeF 2, FeCl 2, FeBr 2, PdF2, PdCl 2, PdBr 2,
PtF2, PtCl 2, PtBr 2, AgCN, CuCl, CuCl 2, CuF, CuBr, CuCN, CuF2, ZnF2, ZnCl 2, ZnBr 2,
Zn(CN) 2, ScF3, ScCl3, LnF3, LnCl 3, CaCl 2, KF, zeolite and mixtures thereof;
more especially, CAT is selected from the group consisting of [(CH3)3SiFSi(CH 3)3][ANIO],
Si(Cl)(C 6H5)3, BF3, BC13, BBr3, B(Ci_4 alkyl) 3, B(C6F5)3, A1F3, A1C13, Al(Ci_4 alkyl) 3,
A1(C6F5)3, GaF3, GaCl 3, (Ph) 3C[ANIO], (CH3)3C[ANIO], [(Ci_3 alkyl) 30][ANIO], [(Ci_4
alkyl) 3Si][ANIO], Si(halogen) 4, Si(Ci_i 0 alkyl) 4, TiF4, TiCl 4, P(halogen) 3, P(CN) 3, SbF3,
Sbl 3, BiF 3, Bil 3, Bi(CN) 3, P(halogen) 5, SbF5, NbF 5, NbCl 5, CrCl 3, FeCl 3, FeBr 3, MnCl 2,
FeCl 2, FeBr 2, PdCl 2, PdBr 2, PtCl 2, PtBr 2, AgCN, CuCl, CuCl 2, CuF, CuF2, ZnF 2, ZnCl 2,
ZnBr 2, Zn(CN) 2, ScF3, ScCl 3, LnF 3, LnCl 3, CaCl 2, KF, zeolite and mixtures thereof;
even more especially, CAT is selected from the group consisting of
[(CH3)3SiFSi(CH 3)3][ANIO], Si(Cl)(C H5)3, BF3, BC13, B(C 1-4 alkyl) 3, B(C F5)3, A1C13,
GaF3, GaCl 3, (Ph) 3C[ANIO], (CH3)3C[ANIO], [(Ci_4 alkyl) 3Si][ANIO], SiF4, SiCl4,
Si(Ci_ alkyl) 4, TiF4, TiCl 4, PC13, PBr3, PI3, P(CN) 3, SbF3, Sbl 3, Bi(CN) 3, PF5, PC15, PBr 5,
PI5, SbF5, NbCls, CrCl 3, FeCl 3, FeBr 3, MnCl 2, FeCl 2, FeBr 2, PdCl 2, PdBr 2, PtCl 2, PtBr 2,
AgCN, CuCl, CuCl 2, CuF, CuF2, ZnF2, Zn(CN) 2, ScF3, ScCl3, LnF3, LnCl 3, CaCl 2, KF,
zeolite and mixtures thereof;
in particular, CAT is selected from the group consisting of [(CH3)3SiFSi(CH 3)3][ANIO],
Si(Cl)(C H5)3, BF3, BC13, B(C F5)3, A1C13, GaF3, GaCl 3, Ph3C[ANIO], [(C1-4
alkyl) 3Si][ANIO], SiF4, SiCl4, Si(Ci_4 alkyl) 4, TiF4, TiCl 4, PCl 3, PBr 3, PI3, P(CN) 3, SbF3,
Sbl 3, Bi(CN) 3, PF5, PC15, PBr 5, PI5, SbF5, NbCl 5, CrCl 3, FeCl 3, FeBr 3, MnCl 2, FeCl 2,
FeBr 2, PdCl 2, PdBr 2, PtCl 2, PtBr 2, AgCN, CuCl, CuCl 2, CuF, CuF2, ZnF2, ScF3, ScCl 3,
LnF3, LnCl 3, CaCl 2, KF, zeolite and mixtures thereof;
more in particular, CAT is selected from the group consisting of [(CH3)3SiFSi(CH3)3][ANIO],
Si(Cl)(C 6H5)3, BF3, BC13, B(C6F5)3, A1C13, GaF3, GaCl 3, Ph3C[ANIO], SiCl4, TiF4, TiCl 4,
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, S1CI4, 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 BF3, B(CeF )3
GaF3, GaCl3, TiF4, TiCl4, PF5, PC15, [(CH3)3SiFSi(CH3)3] [ANIO], Ph3C[ANIO], Sb(F)5,
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, Ph3C[ANIO], zeolite or mixtures thereof;
in an even more very preferred embodiment, CAT is [(CH3)3SiFSi(CH 3)3][ANIO], B(C F )3
GaF3, GaCl3, TiF4, TiCl4, PF5, PC15, Ph3C[ANIO], zeolite or mixtures thereof;
in an especially very preferred embodiment, CAT is B(CeF )3 GaF3, GaCl3, TiF4, T1CI4, PF ,
PCI 5, Ph3C[ANIO], zeolite or mixtures thereof;
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 O, 1, 2, 3, 4 or 5;
R42 and R43 are identical of different in independently from each other selected from the
group consisting of C F5, 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) , B(R42)4 , F , CI , Br , I ,
CN and SCN ;
R40is selected from the group consisting of CN, SCN, F, CI, Br and I;
R42is selected from the group consisting of C F5, CN, SCN, F, CI, Br and I;
more preferably, ANIO is selected from the group consisting of P(R40) , B(R42)4 , F , CI ,
Br , CN and SCN ;
R40is selected from the group consisting of CN, SCN, F, CI and Br;
R42is selected from the group consisting of C F5, CN, SCN, F, CI and Br;
with Ql, R27, R24, R25, R26, Q2, R28, R36, Q3, R29, Q4, R30, Q5, R32, Q6, R33, Q7, R31,
Q8, R34, Q9, R35, Q10, R37, Ql 1 and R38 as defined herein, also with all their
embodiments.
Preferably, [ANIO] is [B(C6F5)4] or [BF4] .
Special embodiments of CAT are [(CH3)3SiFSi(CH 3) 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, 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(CH 3) 3][B(C F5)4], Si(ClXC H5)3, BF3, B(C F5)3, GaF3, GaCl3, Ph3C[BF4],
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
[(CH3)3SiFSi(CH 3) 3][B(C6F5)4], BF3, B(C6F5)3 GaF3, GaCl3, TiF4, TiCl4, PF5, PC15,
Sb(F) , zeolite and mixtures thereof;
in a more very preferred embodiment, CAT is [(CH 3)3SiFSi(CH 3) 3][B(C F )4], B(C F )3
GaF3, GaC , TiF4, TiCl4, PF , PC1 , Ph3C[BF4], zeolite or mixtures thereof;
in a even more very preferred embodiment, CAT is B(C F )3, GaF3, GaCi 3, TiF4, TiCl4, PF ,
PCI 5, Ph3C[BF4], zeolite or mixtures thereof.
In another preferred embodiment, CAT is selected from the group consisting of
(CH3)3SiFSi(CH 3)3[B(C6F5)4], [Ph3C][BF4], B(C6F5)3 and mixtures thereof;
more preferably, CAT is [Ph3C][BF4] .
CATLEWISACID and CAT respectively 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 Mn0 2, Fe20 3, Co30 4,
NiO, CuO, CuMn0 2, MgO, A 120 3, Si0 2, V20 5, Mo0 3,W0 3 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).
n+ n+
Preferably, Cat is, more preferably Cat and [(Z F4) ] are, used in the reaction (Real) in
form of a compound of formula (Al);
[Catn + ] [(Z l F4 ]„ (Al)
wherein
n+
Cat , Z and n are defined herein, also with all their embodiments.
In a preferred embodiment, compound of formula (Al) is reacted with trimethylsilylcyanide
in the presence of a catalyst CAT;
with compound of formula (Al) and catalyst CAT as defined herein, also with all their
embodiments;
preferably, catalyst CAT is (CH3)3SiFSi(CH3)3[B(C6F5)4] or [Ph3C][BF4],
more preferably, catalyst CAT is [Ph3C][BF4];
in one preferred embodiment, compound of formula (Al) is different from catalyst CAT;
in another preferred embodiment, compound of formula (Al) is identical with catalyst CAT.
Compound of formula (Al) and catalyst CAT can be one and the same compound, that
compound of formula (Al) can act simultaneously as catalyst CAT and vice versa.
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+, Ti +, Zr4+, Zr +, Hf4 , Hf +, V4+, V +, V2+,
Nb4+, Ta4+, Cr +,Mo4+,Mo +,Mo2+,W4+,W +,W2+,Mn4+,Mn +,Mn2+, Fe4+, Fe +, Fe2+,
Ru4+, Ru +, Ru2+, Os4+, Os +, Os2+, Co4+, Co +, Co2+, Rh4+, Rh +, Ir4+, Ir +,Ni4+,Ni +,
Ni2+, Pd4+, Pd +, Pd2+, Pt4+, Pt +, Pt2+, Cu4+, Cu +, Cu2+, Cu+, Ag4+, Ag +, Ag2+, Ag+, Au +,
Au +, Au+, Zn +, Zn+, Cd +, Cd+, Hg +, Hg+, B +, Al +, Ga +, Ga+, In +, In+, Tl +, Tl+,
Ge4+,Ge2+, Sn4+,Sn2+, Pb4+, Pb2+, As +, Sb +, Bi +, Bi1+, La +,Nb +, Sm +, Eu +, Gd +, and
NH4
+;
especially, CatINORGn+ is selected from the group consisting of Li+,Na+, K+,Mg +, Ca +,
Ti4+, Ti +, Zr4+, Zr +, V4+, V +, V2+, Cr +,Mo4+,Mo +,Mo2+,W4+,W +,W2+,Mn4+,Mn +,
Mn2+, Fe4+, Fe +, Fe2+, Ru4+, Ru +, Ru2+, Co4+, Co +, Co2+, Rh4+, Rh +, Ir4+, Ir +,Ni4+,
Ni +,Ni2+, Pd4+, Pd +, Pd2+, Pt4+, Pt +, Pt2+, Cu4+, Cu +, Cu2+, Cu+, Ag4+, Ag +, Ag2+, Ag+,
Zn +, Zn+, Al +, Ga +, Ga+, In +, In+, Sn4+,Sn +, Pb4+, Pb +, Sb +,Nb +, Sm +, Eu +, Gd +,
and NH4
+;
more especially, CatINORGn+ is selected from the group consisting of Li+,Na+, K+,Mg +,
Ca2+, Ti4+, V4+, V +, V2+, Cr +, Fe4+, Fe +, Fe2+, Co4+, Co +, Co2+, Cu4+, Cu +, Cu2+, Cu+,
Ag +, Ag+, Zn +, Zn+, Al +, Sn4+,Sn +, Pb4+, Pb +, Sb +, Eu +, Gd +, and NH4
+;
even more especially, CatINORGn+ is selected from the group consisting of Li+,Na+, K+,
2+ 4+ ·3+ 3+ Mg , Ca , Ti , V , V , Cr , Fe4+ , Fe3+ , Fe2+ , Co4+ , Co3+ , Co2+ , Cu4+ , Cu3+ , Cu2+ , Cu+ ,
Ag+, Zn +, Al +, Sn4+,Sn +, Pb4+, Pb +, Gd +, and NH4
+;
in particular, CatINORGn+ is selected from the group consisting of Li+,Na+, K+,NH4
+, Ag+,
Mg +, Ca +, Zn + and Cu +;
more in particular, CatINORGn is selected from the group consisting of Li+,Na+, K+,NH4
+,
Ag+,Mg +, Ca + and Zn +;
even more in particular, CatlNORG is Li+,Na+, K+, Ag+,Mg +, or Zn +;
especially in particular, CatINORGn is Li+, K+, Ag+,Mg +, or Zn +;
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, CatORGn contains a heteroatom selected from the group consisting of nitrogen,
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_ alkylen, C -6 cycloalkylen, phenylen,
C(H)(phenyl), R17(-0-R17) i;
R17 is selected from the group consisting of CH2-CH2, CH2-CH2-CH2 and
R18 and R19 are identical or different and independently from each other selected
from the group consisting of H, Ci_4 alkyl, C -6 cycloalkyl, phenyl and benzyl;
n l is an integer from 1 to 10;
more preferably,
R16 is selected from the group consisting of C2_4 alkylen, C 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,
C -6 cycloalkyl, phenyl and benzyl;
n l is an integer from 1 to 6;
even more preferably, for n being 2 CatORGn+ is (H2(R18)N-R16-N(R19)H2) +;
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,
C -6 cycloalkyl, phenyl and benzyl;
especially, when n is 2, then CatORGn+ is (H3N-CH2-CH2-NH3) +.
Preferably, n in CatORGn+ 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)R23f , [P(R20)(R21)(R22)R23f , [(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_2oalkyl, C3_i 0 cycloalkyl and allyl;
R22 is Ci_2oalkyl, C3_io cycloalkyl or allyl;
preferably,
R20, R21, R23 are identical or different and independently from each other
selected from the group consisting of H, C1-14 alkyl, C - cycloalkyl and allyl;
Pv22 is Ci_i 4 alkyl, C - 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_ alkyl, C5-7 cycloalkyl and allyl;
R22 is Ci_ alkyl, C _ cycloalkyl or allyl;
even more referably, CatORG is selected from the group consisting of
[N(C3H )4]+, [N(C4H )4]+, [P(C2H5)4]+, [P(C3H )4]+, [P(C4H )4]+, [P(C H13)3(C14H2 )]+,
[(CH3)3SiFSi(CH3)3]+ , Ph3C+ , and mixtures thereof;
especially, CatORG is selected from the group consisting of
[NH(C2H5)3]+, [NH(C4H )3]+, [N(C H5)4]
+
[N(C3H )4 , [N(C4H )4 , [P(C2H5)4]+, [P(C3H )4 , [P(C4H )4 , [(CH3)3SiFSi(CH3)3] ,
Ph3C , and mixtures thereof.
, [NH(C2H5)3]+, [NH(C4H )3]+, [N(C2H5)4]+, [N(C3H )4]+, [N(C4H )4]+,
[P(C2H5)4]+, [P(C3H7)4]+, [P(C4H )4]+, [(CH3)3SiFSi(CH3)3]+ , Ph C+ , and mixtures thereof.
In particular, Cat is a cation (Cat-Part 1);
cation (Cat-Part 1) is CatINORGn+ or CatORGn+ ,
with CatINORGn+ selected from the group consisting of Li+,Na+, K+,NH4
+, Ag+,Mg +, Ca
and Zn +;
and
with CatORG selected from the group consistin of
, [NH(C2H5)3]+, [NH(C4H )3 , [N(C H5)4 , [N(C3H )4]+, [N(C4H9)4]+,
[P(C2H5)4]+, [P(C3H )4]+, [P(C4H )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);
[Cat ] [(BF(CN)3) ]„ (la)
[Catn + ] [(B(CN)4) ]„ (lb)
Cat and n are as defined above, also with all their embodiments,
n+
preferably Cat is cation (Cat-Parti).
A special embodiment of compound of formula (I) is compound (GROUP-II), compound
(GROUP-II) is selected from the group consisting of K+ [(BF(CN)3)~ ],
Ag+ [(BF(CN)3) ], Li+ [(BF(CN)3) ], Mg + [(BF(CN)3) ] , Ca + [(BF(CN)3) ] ,
[N(n-Pr)4]+ [(BF(CN)3) ], [N(n-Bu)4]+ [(BF(CN)3) ], [P(n-Bu)4]+ [(BF(CN)3) ],
1,3-dimethylimidazolium [(BF(CN)3) ], l-ethyl-3-methylimidazolium [(BF(CN)3) ],
l-propyl-3-methylimidazolium [(BF(CN)3) ] and mixtures thereof.
Another special embodiment of compound of formula (I) is compound (GROUP-III),
+
compound (GROUP-III) is selected from the group consisting of K [((B(CN)4) ],
Ag+ [((B(CN)4) ], Li+ [((B(CN)4) ], Mg + [(B(CN)4) ]2, Ca + [(B(CN)4) ] ,
[N(n-Pr)4]+ [(B(CN)4) ], [N(n-Bu)4]+ [(B(CN)4) ], [P(n-Bu)4]+ [(B(CN)4) ],
1,3-dimethylimidazolium [(B(CN)4) ], l-ethyl-3-methylimidazolium [(B(CN)4) ],
l-propyl-3-methylimidazolium [(B(CN)4) ] and mixtures thereof.
Yet another special embodiment of compound of formula (I) is compound (GROUP-IV),
+
compound (GROUP-IV) is selected from the group consisting of K [((B(F)2(CN)2) ],
Ag+ [((B(F)2(CN)2) ], Li+ [((B(F) (CN) ) ], Mg + [(B(F) (CN) ) ] , Ca +
[(B(F) (CN) ) ] , [N(n-Pr)4]+ [(B(F) (CN) ) ], [N(n-Bu)4]+ [(B(F) (CN) ) ], [P(n-Bu)4]+
[(B(F)2(CN)2) ], 1,3-dimethylimidazolium [(B(F)2(CN)2) ],
l-ethyl-3-methylimidazolium [(B(F)2(CN)2) ], l-propyl-3-methylimidazolium
[(B(F)2(CN)2) ] and mixtures thereof.
Another special embodiment of compound of formula (I) is compound (GROUP-V),
+
compound (GROUP-V) is selected from the group consisting of K [((B(F)3(CN)) ],
Ag+ [((B(F)3(CN)) ], Li+ [((B(F)3(CN)) ], Mg + [(B(F)3(CN)) ] , Ca + [(B(F)3(CN))
] , [N(n-Pr)4]+ [(B(F)3(CN)) ], [N(n-Bu)4]+ [(B(F)3(CN)) ], [P(n-Bu)4]+ [(B(F)3(CN)) ],
1,3-dimethylimidazolium [(B(F)3(CN)) ], l-ethyl-3-methylimidazolium [(B(F)3(CN)) ],
l-propyl-3-methylimidazolium [(B(F)3(CN)) ] and mixtures thereof.
In particular, compound of formula (I) is compound (GROUP), compound (GROUP) is
selected from the group consisting of compound of formula (1), compound of formula (2),
compound of formula (3), compound of formula (4), compound of formula (5), compound of
formula (6), compound of formula (7), compound of formula (8), and mixtures thereof.
[(n-Bu)4N][BF(CN)3] (1)
[EMIm][BF(CN)3] (2)
[(n-Bu)4N][BF3(CN)] (3)
[(n-Bu)4N][BF2(CN)2] (4)
[(n-Bu)4N][B(CN)4] (5)
K[BF(CN)3] (6)
K[B(CN)4] (7)
[BMIm][B(CN)4] (8)
Li[BF(CN)3] (9)
Li[B(CN)4] (10)
Preferably, from 1 to 40 mol equivalents, more preferably 4 to 35 mol equivalents, even more
preferably from 6 to 25 mol equivalents, especially from 6 to 15 mol equivalents, of
trimethylsilylcyanide are used in reaction (Real), the mol equivalents being based on the
molar amount of the anion [(Z F4) ] .
Preferably, when CATLEWISACID is an uncharged compound, then the molar amount of
n+ -
Cat is equal to the molar amount of anion [(Z F4) ] .
Preferably, when CATLEWISACID is a cation, then the combined molar amount of
CATLEWISACID and Catn + is 1-fold to 40-fold, more preferably 1-fold to 35-fold, even
more preferably 1-fold to 25-foled, especially 1-fold to 15-fold, more especially 1-fold to 10-
fold, even more especially 1-fold to 5-fold, in particular 1-fold to 2-fold, of the molar amount
of the anion [( ) ] .
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 CATLEWISACID are used in reaction (Real), the mol
equivalents being based on the molar amount of the anion [( 1F4) ] .
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 CATLEWISACID are used in
reaction (Real), the mol% being based on the molar amount of the anion [( ) ] .
When reaction (Real) is done by reacting compound of formula (Al) with
trimethylsilylcyanide in the presence of a catalyst CAT, and
when compound of formula (Al) is different from catalyst CAT, then
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, more especially from 5 to 10 mol equivalents, of trimethylsilylcyanide
are used in reaction (Real), the mol equivalents being based on the molar amount of
compound of formula (Al); and
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 15 mol%, more especially from 0.5 to 10
mol%, even more especially from 0.5 to 5 mol%, of catalyst CAT are used in
reaction (Real), the mol% being based on the combined molar amount of compound
of formula (Al) and catalyst CAT;
whereas when compound of formula (Al) is identical with catalyst CAT, then
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, more especially from 5 to 10 mol equivalents, of trimethylsilylcyanide
are used in reaction (Real), the mol equivalents being based on the combined molar
amount of compound of formula (Al) and catalyst CAT.
The reaction temperatures of reaction (Real) 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 reaction (Real) 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.
Reaction (Real) can be done in a closed system and at the pressure caused by the chosen
temperature.
The reaction time of reaction (Real) is preferably from 15 min to 96 h, more preferably from
20 min to 85 h, even more preferably from 20 min to 48 h.
Another possible range of the reaction time of reaction (Real) is preferably from 30 min to 96
h, more preferably from 1 h to 85 h, even more preferably from 1 h to 48 h.
Preferably, reaction (Real) 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 _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 (M).
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 mixture (M) is stirred for 5 min to 12 h, more preferably for 10 min to 6 h.
Preferably mixture (M) is stirred at a temperature (M), temperature (M) is preferably from
ambient temperature to 100°C.
After treatment with hydrogen peroxide, mixture (M) is preferably filtrated. The residue of
the filtration is preferably washed with a solvent (WASH), solvent (WASH) is preferably
water or an ether such as diethylether, more preferably diethylether.
Preferably, the method comprises additionally to step (Stl) a step (St2), step (St2) is done
after step (Stl);
step (St2) comprises a reaction (Rea2), reaction (Rea2) is a metathesis reaction wherein cation
n+ n+
Cat in compound of formula (I) is exchanged for a cation different from Cat ;
compound of formula (I) having been prepared in step (Stl);
n+
Cat , n, compound of formula (I) and step (Stl) are as defined above, also with all their
embodiments.
Preferably, reaction (Rea2) provides for the preparation of a compound of formula (I-Cat-r);
[Cat- + ] [(Z 1F4_m(CN)m) ] (I-Cat-r)
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 (Stl), Z , m, CatlNORG and CatORG as defined above, also with all their
embodiments.
n+ r+
Preferably, in reaction (Rea2) Cat is exchanged for Cat-r from a compound of formula
(I-Cat-n);
(Cat-/ )t l (AnINORG )t2
q is 1 or 2;
t l is 1 or2;
t2 is 1, 2, 3 or 4;
when r is 1 and q is 1, then t l is 1 and t2 is 1;
when r is 2 and q is 1, then t l is 1 and t2 is 2;
when r is 3 and q is 1, then t l is 1 and t2 is 3;
when r is 4 and q is 1, then t l is 1 and t2 is 4;
when r is 1 and q is 2, then t l is 2 and t2 is 1;
when r is 2 and q is 2, then t l is 1 and t2 is 1;
when r is 3 and q is 2, then t l is 2 and t2 is 3;
when r is 4 and q is 2, then t l is 1 and t2 is 2;
AnINORG is an anion selected from the group consisting of halide, OH , CN , OCN ,
SCN ,N3 , sulfate, hydrogensulfate, nitrate, C0 3
2 , HC0 3 , BF4 , PF6 , SbF6 , CF3S0 3 ,
(CF3S0 2)2N , (FS0 2)2N , _ alkyl-S0 3 , _ alkyl
, anions of Ci_2omonocarboxylic aliphatic acids,
mono- and dianions of C2_6 dicarboxylic aliphatic acids, anions of benzoic acids, monoand
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;
Cat-r , r, CatlNORG and CatORG are as defined above, also with all their
embodiments.
Reaction (Rea2) is a metathesis reaction, also called a salt-exchange reaction. In a metathesis
reaction such as reaction (Rea2) a first cation in a first salt is exchanged for a second
cation, said second cation coming from a second salt.
Preferably, AnINORG is an anion selected from the group consisting of halide, OH , CN ,
sulfate, hydrogensulfate, nitrate, C0 3
~, HC0 3
~, BF4 , PF6 , CF3S0 3 , (CF3S0 2)2N ,
(FS0 2)2N , H3C-S0 3
~, H3C-CH2-S0 3
~, H3C-0-S0 3
~, H3C-CH2-0-S0 3
~, acetate, oleate,
fumarate, maleate, oxalate, benzoate, N(CN)2 , and mixtures thereof;
more preferably, AnINORG is an anion selected from the group consisting of Br , CI , OH ,
GST, sulfate, hydrogensulfate, C0 3
2 , HC0 3 , acetate, and mixtures thereof;
even more preferably, AnlNORG^ is an anion selected from the group consisting of CI , OH ,
GST, sulfate, hydrogensulfate, C0 3
2 , HC0 3 , acetate, and mixtures thereof.
In another preferred embodiment, AnlNORG^ is an anion selected from the group consisting
of halide, OH , CN , OCN , SCN ,N3 , sulfate, hydrogensulfate, nitrate, C0 3
2 , HC0 3 ,
BF4 , PF , SbF , CF3S0 3 , (CF3S0 2)2N , (FS0 2)2N , G _6 alkyl-S0 3 , Ci_6 alkyl-0-S0 3 ,
, anions of Ci_2o monocarboxylic aliphatic acids,
anions of C2_ 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.
r+
In case of reaction (Rea2), preferably a compound of formula (I-Cat-r) with Cat-r being
CatORGn is prepared by exchange of a Catn being a CatINORGn in compound of formula
(I) for a CatORGn+ .
,n+ Said CatORG is provided in reaction (Rea2) preferably in form of a compound of formula
(I-CatORG)
(CatORGn )q(AnINORG )n (I-CatORG)
wherein
Catn+ , n, CatORGn+ , CatINORGn+ , q and AnINORGq are as defined above, also with all
their embodiments.
Preferably, in reaction (Rea2) the cation different from Cat , that is preferably Cat-r , is
n+
present in 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 1to 1.2, required equivalents of Cat-r relative to
n+
the equivalents of Cat are present.
The reaction temperatures of reaction (Rea2) 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 reaction (Rea2) is preferably carried out in a solvent (Sol2), solvent (Sol2) is preferably
selected from the group consisting of water, DCM, ethyl acetate, C5-10 alkane, and mixtures
thereof.
C5_io alkane is preferably pentane, hexane or heptane.
In a more preferred embodiment, reaction (Rea2) is done in DCM or in a biphasic solvent
system of water and DCM.
As an alternative, the reaction 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).
Reaction (Rea2) can be done in a closed system and at the pressure caused by the chosen
temperature.
The reaction time of reaction (Rea2) 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, reaction (Rea2) 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 reaction (Rea2) there can be a further metathesis reaction or further metathesis
reactions.
After reaction (Rea2), 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 reaction (Rea2) 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 Na2S0 4, K2C0 3, CaCl2 or
MgS0 4, and finally evaporated.
Or as another example, when reaction (Rea2) 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 step (Stl) a
step (Stl-1), step (Stl-1) is done after step (Stl);
step (Stl-1) comprises a reaction (Real-1), wherein compound of formula (I), obtained in
step (1), is reacted with trimethylsilylcyanide;
preferably the reaction (Rea(l-l) is done in the presence of CATLEWISACID;
with CATLEWISACID as defined above, also in all its embodiments.
n+
Compounds of formula (Al) are commercially available depending on the cation Cat , e.g.
[(n-Bu4)N][BF ] and K[BF4] are commercially available, as well as catalyst CAT. Other
n+ compounds of formula (Al) with cations Cat different from K+ and (n-Bu + 4)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.
EXAMPLES
Methods
1H, 1 C, 1 F and 1P NMR spectra were recorded on a Bruker AVANCE 300 and Bruker
AVANCE 250 instruments in CD3CN, CDC13, D6-DMSO, D20 or CD2C 12. Chemical shifts
are expressed in parts per million referred to TMS in case of 1H and 1 C, C1 FC13 in case of
1 F, and H3
1P0 4 in case of 1P, 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 mixtures 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.
IPv-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 Tdec 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.
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 CH2C 12 was added to the
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 Mg2S0 4 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 OKmin 1)
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), 3.1 1 (m, 8H, NCH 2)
C NMR (25 °C, CD3CN, 250.13 MHz, delta in ppm): 14.42 (s, 4C, CH3), 20.94 (m, 4C,
CH3-CH2), 24.95 (m, 4C, CH2-CH2N), 59.93 (m, 4C, NCH2)
B NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -1.18 (s, IB, BF4)
F NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): -151.61 (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), 9 11 (2), 880 (1), 766 (1), 256 (2), 79 (1)
Preparation description B: Synthesis of EMIm[BF4]
K[BF4] (0.43 g, 3.4 mmol) and l-ethyl-3-methylimidazo um bromide (0.50 g, 3.4 mmol)
were suspended in 50 ml of acetone. After stirring for 24 hours under argon atmosphere at
ambient temperature the suspension was filtered. The solvent was removed in vacuo to obtain
a light yellow oil. The product was dried at 90°C in vacuo for 5 hours to yield 0.61 g (91%,
3.1 mmol) of EMIm[BF 4] .
DSC OKmin m.p. = 16°C
C/H/N Analysis calc. % (found): C 36.40 (36.32), H 5.60 (5.58), N 14.15 (12.90)
1H NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 1.42 (t, 3H, CH3), 3.82 (s, 3H, NCH 3),
4.16 (q, 2H, CH2), 7.37 (m, 1H, EtNCH), 7.43 (m, 1H, MeNCH), 8.57 (s, 1H, NCHN)
C NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 15.53 (s, 1C, NCH2-CH3), 36.73 (s,
1C, NCH3), 45.80 (s, 1C, NCH 2), 123.01 (s, 1C, EtNCH), 124.64 (s, 1C, MeNCH),
136.98 (s, 1 NCHN)
B NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -1.1 1 (s, IB, BF4)
F NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): -151.23 (s, 4F, BF4)
IR (ATR, 32 scans, v in cm 1) : 3163 (w), 3122 (w), 2989 (w), 2949 (w), 1574 (m), 1455 (w),
1432 (w), 1392 (w), 1336 (w), 1286 (w), 1170 (m), 1015 (s), 845 (m), 805 (w), 753 (m),
701 (w), 648 (m), 622 (m), 598 (w)
Example 1
[Ph3C][BF4] (207 mg, 0.63 mmol) and (CH3)3SiCN (625 mg, 6.3 mmol) were stirred at
ambient temperatures under argon atmosphere. After two hours of stirring an B NMR was
measured. In accordance to B NMR the product contained only [BF(CN)3] . After 20 hours
of stirring another B NMR was measured. In accordance to B NMR the product contained
only [B(CN)4] .
Example 2
[EMIm][BF4] (771 mg, 3.89 mmol), prepared according to Preparation Description B,
[Ph3C][BF4] (0.01 g, 0.8 mol%, the mol% being based on the combined molar amount of
[EMIm][BF4] and [Ph3C][BF4]) and (CH3)3SiCN (3.87 g, 39 mmol) were stirred under argon
atmosphere at ambient temperatures for Tx h. Then a B NMR of the reaction mixture was
measured and [Ph3C][BF4] was added, in order to have a desired mol% of [Ph3C][BF4] . Table
2 shows the details, Tx and the percentage of [BF3(CN)]~ [BF2(CN)2]~ and [BF(CN)3] in the
reaction mixture according to the NMR spectra.
Final B NMR of EMIm[BF(CN) 3] (25°C, CD3CN, 96.29 MHz, delta in ppm): -3.70 (q, IB,
BF3(CN)), -7.61 (t, IB, BF2(CN)2), -17.88 (d, IB, BF(CN)3)
Example 3
[(n-Bu)4N][BF4] (1.189 g, 3.6 mmol), prepared according to Preparation Description A,
[Ph3C][BF4] (3.6 mol%, the mol% being based on the combined molar amount of
[(n-Bu)4N][BF4] and [Ph3C][BF4], 44 mg) and (CH3)3SiCN (3.55 g, 36 mmol) were stirred
under argon atmosphere at ambient temperatures for 19 h. The excess (CH3)3SiCN and any
(CH3)3SiF were removed in vacuo resulting in a light brown crystalline residue, which was
suspended in aqueous H20 2 (4 ml, 40 mmol, 30 w%), the suspension was stirred at 70°C for 1
h. After cooling to ambient temperature the suspension was filtered. The remaining solid was
washed two times with water and extracted with 15 ml of CH2C 12. The organic layer was
dried over MgS0 4 and filtered.
After removing the solvent in vacuo a white solid substance was obtained which was washed
three times with 5 ml of diethyl ether. The product was dried at 50°C in vacuum to yield
1.063 g (84%, 3.03 mmol) of compound of formula (1).
C/H/N-Analysis calc. % (found): C 65.14 (65.49), H 10.36 (10.51), N 15.99 (16.29)
1H NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 0.97 (t, 12H, CH3), 1.35 (m, 8H, CH3-
CH2), 1.61 (m, 8H, CH2-CH2N), 3.09 (m, 8H, NCH2)
C NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 13.87 (s, 4C, CH3), 20.36 (t, 4C, CH2-
CH3), 24.35 (s, 4C, N-CH 2-CH2), 59.40 (t, 4C, NCH2), 127.92 (dq, 3C, BF(CN) 3, J(1 CB)
= 75 Hz, 2J(1 C-1 F) = 37 Hz)
B NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -17.86 (d, IB, BF(CN) 3)
F NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): -21 1.68 (q, F, BF(CN) 3)
Example 4
EMIm[BF 4] (0.739 g, 3.73 mmol), prepared according to Preparation Description B,
[Ph C][BF4] (3.4 mol%, the mol% being based on the combined molar amount of
[EMIm][BF 4] and [Ph3C][BF4], 43 mg) and (CH3)3SiCN (3.67 g, 37 mmol) were stirred under
argon atmosphere at ambient temperatures for 20 h. The excess (CH3)3SiCN and any
(CH ) SiF were removed in vacuo resulting in a light brown oily residue, which was
suspended in aqueous H20 2 (4 ml, 40 mmol, 30 w%), the suspension was stirred at 70°C for 1
h. After cooling to ambient temperature 20 ml butyl acetate was added to the H20 2 solution.
The resulting mixing was transferred into centrifuge tubes. After centrifugation (2000 rpm, 2
minutes) the supernatant layer was separated. The butyl acetate was removed on a rotary
evaporator.
The obtained light yellow oil was washed three times with 5 ml of diethyl ether. After drying
at 70°C in vacuo 0.694 g (85%, 3.17 mmol) of compound of formula (2) were obtained.
1H NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 1.46 (t, 3H, CH3), 3.82 (s, 3H, NCH3),
4.16 (q, 2H, CH2), 7.32 (m, 1H, EtNCH), 7.38 (m, 1H, MeNCH), 8.40 (s, 1H, NCHN)
B NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -17.88 (d, IB, BF(CN) 3)
F NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): -21 1.64 (q, 4F, BF(CN)3)
Example 5
[(n-Bu)4N][BF(CN) 3] (0.734 g, 2.10 mmol), prepared according to example 3, and
[Ph3C][BF4] (86 mg, 11 mol%, the mol% being based on the combined molar amount of
[(n-Bu)4N][BF4] and [Ph3C][BF4]) were dissolved in TMSCN (3.12 g, 31.4 mmol). After Tx
hours of stirring at ambient temperature a B NMR and spectrum of the reaction mixture was
measured and [Ph3C][BF4] was added, in order to have a desired mol% of [Ph3C][BF4] . Table
1 shows the details, Tx and the percentage of [BF(CN) ]~and [B(CN)4] in the reaction
mixture according to the NMR spectra.
NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -17.88 (d, IB, BF(CN)3), -38.59 (s, IB,
B(CN)4)
Example 8
[(n-Bu)4N][BF4] (0.491 g, 1.49 mmol), prepared according to Preparation Description A,
FeCl (20 mg, 7 mol%, the mol% being based on the combined molar amount of [(n-
Bu)4N][BF4] and FeCl3) and (CH3)3SiCN (1.58 g, 1.59 mmol) were stirred under argon
atmosphere at ambient temperature for 3 h.
After the stirring at ambient temperature for 3 h an B and 1 F NMR spectra were measured.
In accordance to 1 F NMR and B NMR the product contained 100% of compound of
formula (4).
After removing the solvent the obtained light yellow solid substance was dried at 50°C in
vacuo to yield 0.400 g (69%, 1.17 mmol) of compound of formula (4).
C/H/N Analysis calc. % (found): C 62.97 (62.58), H 10.57 (10.65), N 12.24 (12.35)
1H NMR (25°C, CDCls, 300.13 MHz, delta in pm) : 0.99 (t, 12H, CH3), 1.41 (m, 8H,
CH3-CH 2) , 1.61 (m, 8H, CH2-CH 2N), 3.13 (m, 8H, NCH2)
B NMR (25°C, CDCI 3, 300.13 MHz, delta in ppm): -7.2 (q, IB, BF2(CN)2, ^("B-^F) = 42
Hz)
C NMR (25°C, CDCI 3, 300.13 MHz, delta in ppm): 13.3 (s, 4C, CH3), 19.4 (t, 4C,
CH2-CH3), 23.6 (s, 4C, N-CH 2-CH2), 58.6 (t, 4C, NCH2)
F NMR (25°C, CDCI 3, 300.13 MHz, delta in ppm): -153.1 (q, 2F, BF2(CN)2, ^("B-^F) =
42 Hz)
IR (ATR, 32 scans, v in cm 1) : 2966 (m), 2939 (m), 2878 (m), 2210 (m), 1474 (m), 1383 (m),
1242 (w), 1170 (w), 1006 (m), 1050 (s), 1007 (s), 939 (m), 880 (s), 797 (m), 737 (m),
632 (w), 550 (w)
Example 9
Example 8 was repeated with the differences:
1. MnCl2 (9 mg, 5 mol%, the mol% being based on the combined molar amount of [(n-
Bu)4N][BF ] and MnCl2) were used instead of FeCl 3.
2. The reaction mixture was stirred for 20 h at ambient temperature instead of 3 h.
After the stirring for 20 h an B and 1 F NMR spectra were measured. In accordance to 1 F
NMR and B NMR the product contained 100% of compound of formula (4).
NMR data was the same as in example 8.
Example 10
Example 8 was repeated with the difference:
1. PCI 5 (30 mg, 6 mol%, the mol% being based on the combined molar amount of [(n-
Bu)4N][BF ] and PCI 5) were used instead of FeCl 3.
After the stirring for 3 h an B and 1 F NMR spectra were measured. In accordance to 1 F
NMR and B NMR the product contained 100% of compound of formula (1).
After removing the solvent the obtained white solid substance was dried at 50°C in vacuo to
yield 0.680 g (90%>, 1.66 mmol) of compound of formula (1).
C/H/N Analysis calc. % (found): C 65.14 (64.44), H 10.36 (10.41), N 15.99 (16.20)
1H NMR (25°C, CDCI3, 300.13 MHz, delta in pm) : 1.00 (t, 12H, CH3), 1.41 (m, 8H,
CH3-CH2), 1.60 (m, 8H, CH2-CH2N), 3.12 (m, 8H, NCH2)
B NMR (25°C, CDCI3, 300.13 MHz, delta in ppm): -17.6 (d, IB, BF(CN)3, ^(" B-^F ) = 45
Hz)
C NMR (25°C, CDC13, 300.13 MHz, delta in ppm): 13.3 (s, 4C, CH3), 19.4 (t, 4C,
CH2-CH3), 23.6 (s, 4C, N-CH 2-CH2), 58.7 (t, 4C, NCH2), 127.2 (dq, 3C, BF(CN)3,
j c F = 3 8 j ( c i iB ) = 5 Hz)
F NMR (25°C, CDC13, 300.13 MHz, delta in ppm): -210.9 (q, IF, BF(CN)3, ^("B-^F) =
45 Hz)
IR (ATR, 32 scans, v in cm 1) : 2964 (m), 2935 (m), 2876 (m), 2214 (w), 1474 (m), 1381 (m),
1171 (w), 1040 (m), 960 (w), 938 (,), 903 (s), 803 (w), 736 (m), 536 (w)
Example 11
Example 8 was repeated with the difference:
1. GaCl3 (30 mg, 5 mol%, the mol% being based on the combined molar amount of [(n-
Bu)4N][BF 4] and GaCl3) were used instead of FeCl3.
2. The reaction mixture was stirred longer then 3 h.
After stirring for 3 h an B and 1 F NMR spectra were measured. In accordance to 1 F NMR
and B NMR the product contained 99.9% of compound of formula (1).
NMR data was the same as in example 10.
After further stirring for additional 4 1 h another B NMR spectra was measured. In
accordance to B NMR the reaction mixture contained 93.1% of compound of formula (1)
and 6 .9% of compound of formula (5).
NMR data was the same as in example 5.
Example 12
Example 8 was repeated with the difference:
1. TiCl4 (0.01 ml, 5 mol%, the mol% being based on the combined molar amount of [(n-
Bu)4N][BF ] and TiCl4) were used instead of FeCl 3.
After the stirring for 3 h an B and 1 F NMR spectra were measured. In accordance to 1 F
NMR and B NMR the product contained 100% of compound of formula (1).
NMR data was the same as in example 10.
Example 13
Example 8 was repeated with the differences:
1. CrCl3 (14 mg, 5 mol%, the mol% being based on the combined molar amount of [(n-
Bu)4N][BF ] and CrCl3) were used instead of FeCl3.
2. The reaction mixture was stirred for 25 h at ambient temperature instead of 3 h.
After the stirring for 25 h an B and 1 F NMR spectra were measured. In accordance to 1 F
NMR and B NMR the product contained 100% of compound of formula (4).
NMR data was the same as in example 8.
Example 15
Example 8 was repeated with the difference:
1. NbCl (20 mg, 5 mol%, the mol% being based on the combined molar amount of [(n-
Bu)4N][BF4] and NbCl5) were used instead of FeCl3.
After the stirring for 3 h an B and 1 F NMR spectra were measured. In accordance to B
and 1 F NMR the reaction mixture contained 100% of compound of formula (4).
After further stirring at ambient temperature in addition for 142 h again an B and 1 F NMR
were measured. In accordance to B and 1 F NMR the reaction mixture contained 56% of
compound of formula (4) and 44% of compound of formula (1).
NMR data was the same as in example 8 and 3.
Example 16
Example 8 was repeated with the difference:
1. SiCl4 (0.01 ml, 5 mol%, the mol% being based on the combined molar amount of [(n-
Bu)4N][BF ] and SiCl4) were used instead of FeCl3.
After the stirring for 3 h an B and 1 F NMR spectra were measured. In accordance to B
and 1 F NMR the reaction mixture contained 100% of compound of formula (4).
NMR data was the same as in example 8.
Example 17
Example 8 was repeated with the difference:
1. GaCl3 (30 mg, 5 mol%, the mol% being based on the combined molar amount of [(n-
Bu)4N][BF ] and GaCl3) were used instead of FeCl3.
2. The reaction mixture was refluxed instead of stirring at ambient temperature.
After the stirring for 3 h an B and 1 F NMR spectra were measured. In accordance to B the
reaction mixture contained 100% of compound of formula (5).
After removing the solvent the obtained light yellow solid substance was dried at 50°C in
vacuo to yield 0.425 g (79%, 1.19 mmol) of compound of formula (5).
C/H/N Analysis calc. % (found): C 67.22 (66.43), H 10.15 (9.96), N 19.60 (19.00)
1H NMR (25°C, CDCls, 300.13 MHz, delta in ppm): 1.03 (t, 12H, CH3), 1.44 (m, 8H,
CH3-CH2), 1.62 (m, 8H, CH2-CH2N), 3.12 (m, 8H, NCH2)
B NMR (25°C, CDCI3, 300.13 MHz, delta in ppm): -38.2 (s, IB, B(CN)4, ^("B-^F) = 7 1
Hz)
C NMR (25°C, CDCI3, 300.13 MHz, delta in ppm): 13.5 (s, 4C, CH3), 19.5 (t, 4C,
CH2-CH3), 23.6 (s, 4C, N-CH 2-CH2), 58.7 (t, 4C, NCH2), 122.5 (q / sept, 4C, B(CN)4,
^("B-^C) = 7 1 Hz, ( B- C) = 23 Hz)
IR (ATR, 32 scans, v in cm 1) : 2964 (m), 2935 (m), 2877 (m), 2214 (w), 1474 (m), 1381 (m),
1168 (w), 1110 (w), 1061 (w), 1035 (w), 991 (m), 967 (m), 931 (s), 886 (m), 802 (w),
735 (m), 535 (w)
Example 18
K[BF4] (0.67 g, 5.32 mmol), GaCl3 6 mol%, the mol% being based on the combined molar
amount of [(n-Bu)4N][BF 4] and GaCl3, 63 mg) and (CH3)3SiCN (5.8 g, 58.9 mmol) were
stirred at ambient temperature for 15 h. Then a B NMR spectrum of the reaction mixture
was measured. In accordance to B NMR the reaction mixture contained 93% of compound
of formula (6) and 7% of K[BF4] .
Then the reaction mixture was refluxed for 9 h and a B NMR spectrum was measured. In
accordance to B NMR the reaction mixture contained 95% of compound of formula (6) and
5% of compound of formula (7).
Example 20
Example 8 was repeated with the differences:
1. P(CN)3 (17 mg, 5 mol%, the mol% being based on the combined molar amount of [(n-
Bu)4N][BF 4] and P(CN)3) were used instead of FeCl3.
2. The reaction mixture was stirred for 100 h at ambient temperature instead of 3 h.
After stirring at ambient temperature for 100 h an B and 1 F NMR spectra were measured.
In accordance to 1 F and B NMR the product contained about 95.5% of compound of
formula (4) and 4.5% of compound of formula (1).
NMR data was the same as in example 8.
Example 21
Example 1 was repeated with the differences:
1. l-Butyl-3-methylimidazolium tetrafluoroborate ( 1.05 g, 4.65 mmol) were used instead of
[(n-Bu)4][BF4] .
2. The reaction mixture was stirred for 2 h at reflux temperature instead of 3 h.
After the stirring for 2 h an B and 1 F NMR spectra were measured. In accordance to 1 F and
B NMR the product contained 100% of compound of formula (8).
The excess (CH3)3SiCN and any (CH3)3SiF were removed in vacuo resulting in a dark brown
oily residue, which was suspended in aqueous H20 2 (7 ml, 70 mmol, 30 w%), the solution
was stirred at 90°C for 1 h. After cooling to ambient temperature 50 ml butyl acetate was
added to the H20 2 solution. The resulting mixing was transferred into centrifuge tubes. After
centrifugation (2000 rpm, 2 minutes) the supernatant layer was separated. The butyl acetate
was removed on a rotary evaporator.
After drying at 100°C in vacuo 1.00 g (85%, 3.95 mmol) of compound of formula (8) were
obtained.
1H NMR (25°C, CD3CN, 250.13 MHz, delta in ppm): 0.97 (t, 3H, CH2-CH3), 1.37 (m, 2H,
CH2-CH3), 1.87 (m, 2H, CH2-CH2), 3.94 (s, 3H, NCH3), 4.17 (t, 2H, NCH2), 7.33 (s, 1H,
BuNCH), 7.34 (s, 1H, MeNCH), 8.44 (s, 1H, NCFJN)
B NMR (25°C, CDC13, 80.25 MHz, delta in ppm): -38.4 (s, IB, B(CN)4, ^("B-^F) = 7 1
Hz)
C NMR (25°C, CD3CN, 250.13 MHz, delta in ppm): 13.07 (s, 1C, CH3), 19.15 (s, 1C, CH2-
CH3), 31.56 (s, 1C, CH2-CH2), 36.39 (s, 1C, NCH3), 49.94 (s, 1C, NCH2), 122.3 (q+sep,
4C, B(CN) 4, ^("B-^C) = 7 1 Hz, ( B- C) = 24 Hz), 122.5 (s, 1C, BuNCH), 123.7 (s,
1C, MeNCH), 135.0 (s, 1C, NCHN)
Table 3
Tabel 3 gives an overview of some of the examples and their results, where the reaction has
been done at ambient temperature.
Ex example
m m as in formula (I)
t l reaction time of reaction (Real)
[%] is the crude yield according to 1 F NMR, except for those examples marked with (*),
in the reaction mixture before any isolation or purification
(*) in case of the examples marked with (*) the crude yield is according to B NMR
instead of 1 F NMR
Table 4
Tabel 4 gives an overview of some of the examples and their results, where the reaction has
been done at reflux temperature, which was ca. 125°C.
Ex example
m m as in formula (I)
t l reaction time of reaction (Real)
[%] is the crude yield according to 1 F NMR, except for those examples marked with (*),
in the reaction mixture before any isolation or purification
(*) in case of the examples marked with (*) the crude yield is according to B NMR
instead of 1 F NMR
Comparative Example 1: No CATLEWISACID
Example 8 was repeated with the differences:
1. That no FeCl3 was added to the reaction mixture.
2. The reaction mixture was stirred for 100 h instead of 3 h.
After stirring at ambient temperature for 100 h an B and 1 F NMR spectra were measured.
In accordance to 1 F and B NMR the product contained about 82% of compound of formula
(3) and 18% of compound of formula (4).
NMR data are the same as stated here:
1H NMR (25°C, CDCI 3, 300.13 MHz, delta in ppm): 0.98 (t, 12H, CH3), 1.41 (m, 8H,
CH3-CH 2) , 1.61 (m, 8H, CH2-CH 2N), 3.16 (m, 8H, NCH 2)
B NMR (25°C, CDCI 3, 300.13 MHz, delta in ppm): -3.6 (q, IB, BF3(CN), ^("B-^F) = 28
Hz)
C NMR (25°C, CDC13, 300.13 MHz, delta in ppm): 13.4 (s, 4C, CH3), 19.5 (t, 4C,
CH2-CH 3) , 23.7 (s, 4C, N-CH 2-CH 2) , 58.5 (t, 4C, NCH2)
F NMR (25°C, CDCI 3, 300.13 MHz, delta in ppm): -137.0 (q, 3F, BF3(CN), ^("B-^F) =
28 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)
and as in example 8.
Example 22
Example 8 was repeated with the differences:
1. Montmorillonit K10 (available at Sigma Aldrich, CAS Number 1318-93-0) (16 mg) was
used instead of FeCl3.
2. The reaction mixture was stirred for 146 h at ambient temperature instead of 3 h.
After the stirring for 146 h an B and 1 F NMR spectra were measured. In accordance to 1 F
NMR and B NMR the product contained 100% of compound of formula (4).
NMR data was the same as in example 8.
Example 23
MCM-41 (mesostructured silica, available at Sigma Aldrich, CAS Number 7631-86-9) (0.93
g) and GaCl3 (0.38 g) were stirred in benzene (10 ml) for 3 h at ambient temperature, then the
reaction suspension was filtered, the residue was washed with benzene (10 ml), then the
residue was dried in vacuo at 80°C to provide a GaCl3 catalyst supported on MCM-41 .
Example 24
[(n-Bu)4N][BF4] (0.351 g, 1.07 mmol), prepared according to Preparation Description A, the
GaCl3 catalyst supported on MCM-41, prepared according to example 23, (7 mg) and
(CH3)3SiCN ( 1.01 g, 10.4 mmol) were stirred under argon atmosphere at ambient temperature
for 26 h.
After the stirring for 26 h an B and 1 F NMR spectra were measured. In accordance to 1 F
NMR and B NMR the product contained 100% of compound of formula (1).
NMR data was the same as in example 10.
Example 25
SBA-15 (mesostructured silica, available at Sigma Aldrich, CAS Number 7631-86-9) (0.76 g)
and GaCl3 (0.44 g) were stirred in benzene (10 ml) for 3 h at ambient temperature, then the
reaction suspension was filtered, the residue was washed with benzene (10 ml), then the
residue was dried in vacuo at 80°C to provide a GaCl3 catalyst supported on SBA-15.
Example 26
[(n-Bu)4N][BF4] (0.366 g, 1.1 1 mmol), prepared according to Preparation Description A, the
GaCl3 catalyst supported on SBA-15, prepared according to example 25, (7 mg) and
(CH3)3SiCN ( 1.09 g, 11.1 mmol) were stirred under argon atmosphere at ambient temperature
for 26 h.
After the stirring for 26 h an B and 1 F NMR spectra were measured. In accordance to 1 F
NMR and B NMR the product contained 100% of compound of formula (1).
NMR data was the same as in example 10.
Example 27
Li[BF 4] (0.474 g, 5.06 mmol), GaCl 3 (61 mg, 0.35 mmol, 6 mol%, the mol% being based on
the combined molar amount of Li[BF 4] and GaCl 3) and (CH 3)3SiCN (4.98 g, 50 mmol) were
refluxed for 10 hours. Then a B NMR spectrum of the reaction mixture was measured. In
accordance to B NMR the reaction mixture contained 22% of compound of formula (9) and
78%o of compound of formula (10).
B NMR (25°C, D20 , 80.25 MHz, delta in ppm): -17.8 (d, IB, BF(CN) 3, ^("B-^F) = 43
Hz), -38. 3 (s, IB, B(CN) 4)

CLAIMS
Method for the preparation of compound of formula (I);
[Catn + ] [(Z 1F4_m(CN)m) ]„
the method comprises a step (Stl);
step (Stl) comprises a reaction (Real), wherein [(Z F4) ] is reacted with trimethylsilylcyanide
n+
in the presence of CATLEWISACID and in the presence of Cat ;
CATLEWISACID is a Lewis Acid selected from the group consisting of Lewis Acid from the
1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 14., 15. and 16. group of the periodic table,
zeolite, guanidinium and mixtures thereof;
Z1 is selected from the group consisting of B, Al, Ga, In and Tl;
m is 1, 2, 3 or 4;
n is 1, 2, 3 or 4;
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
+;
CatORGn+ is selected from the group consisting of CatORG-A+, CatORG-B+, CatORGC+,
[(CH3)3SiFSi(CH3 )3] + , Ph3C+ , guanidinium and (H2(R18)N-R16-N(R19)H2) +;
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, C3-10 cycloalkyl and C -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_20 alkyl, Ci_20 perfluoroalkyl, C3_i 0
cycloalkyl and C -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_ alkenyl, Ci_2o
perfluoroalkyl, C3-10 cycloalkyl or C -io aryl;
CatORG-C+ is (YR9R10R1 1)+,
wherein
Y is sulphur;
(i) R9, R10 and Rl 1 are identical or different and independently from each other
selected from the group consisting of H, Ci_20 alkyl, Ci_20
perfluoroalkyl, C3_io cycloalkyl and C -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_20 alkyl, Ci_20 perfluoroalkyl,
C3_io cycloalkyl and C _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, C3-10 cycloalkyl, C2_ 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, 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 C i alkyl, C3-10 cycloalkyl,
C2_8 alkenyl and Ci_s perfluoroalkyl;
R16 is selected from the group consisting of C2_ alkylen, C3-8 cycloalkylen, phenylen,
C(H)(phenyl), R17(-0-R17)„i;
Rl 7 is selected from the group consisting of CH2-CH2, CH2-CH2-CH2, CH2-C(H)(CH 3)-
CH2, CH2-CH2-C(H)(CH 3) 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, C3-8 cycloalkyl, phenyl and benzyl;
n l is an integer from 1 to 20.
2. Method according to claim 1, wherein
Z1 is B.
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
CATLEWISACID is selected from the group consisting of [(CH3)3SiFSi(CH 3)3]+ ,
Q1(R27) 3, guanidinium, (R26) 3C+ , adamantyl cation, [(R24) 30 ]+ , [(R25) 3Si]+ ,
Q2(R36)(R28) 3, Q3(R29) 3, Q4(R30) 5, Q5(R32) 3, Q6(R33) 2, Q7(R3 1), 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;
R27 is selected from the group consisting of C1-10 alkoxy, halogen, C1-10 alkyl, CN, SCN and
R24 is C IOalkyl;
R25 is Ci_io alkyl;
R26 is selected from the group consisting of CN, SCN, Ph and C1-10 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 C1-10 alkoxy, halogen, C1-10 alkyl, CN, SCN and C F ;
Q3 is selected from the group consisting of P, Sb and Bi;
R29 is selected from the group consisting of C1-10 alkoxy, halogen, CN, SCN, C1-10 alkyl and
Q4 is selected from the group consisting of P, Sb and Nb;
R30 is selected from the group consisting of C1-10 alkoxy, halogen, CN, SCN, C1-10 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;
R3 1 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.
5. Method according to one or more of claims 1 to 4, wherein
CATLEWISACID is selected from the group consisting of [(CH3)3SiFSi(CH3)3]+ ,
Si(Cl)(C 6H5)3, B(R27) 3, A1(R27)3, GaF , GaCl3, guanidinium, (R26) 3C+ , [(R24) 30 ]+ ,
[(R25) 3Si]+ , Si(R28) 4, TiF4, TiCl 4, Q3(halogen) 3, Q3(CN) 3, Q3(Ci_4 alkyl) 3,
Q4(halogen) 5, Q4(Ci_i0 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;
with R27, R24, R25, R26, R28, Q3, R29 and Q4 as defined in claim 4.
6. Method according to one or more of claims 1 to 5, wherein
Preferably, CATLEWISACID is used in the reaction (Real) in form of a catalyst CAT;
CAT is a Lewis Acid selected from the group consisting of Lewis Acid from the 1., 2., 3., 4.,
5., 6., 7., 8., 9., 10., 11., 12., 13., 14., 15. and 16. group of the periodic table, zeolite,
guanidinium[ANIO] and mixtures thereof;
ANIO is selected from the group consisting of [P(R40)6_mi(R41)mi] , [B(R42)4_m2(R43)m2 ] ,
F , C , 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 C F5, CN, SCN, F, CI, Br and I;
m2 is O, 1, 2 or 3.
7. Method according to one or more of claims 1 to 6, 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(R3 1),
Q8(R34)2, Q9(R35)3, Q10(R37)2, Q 11(R38), zeolite and mixtures thereof;
with Ql, R27, R24, R25, R26, Q2, R28, R36, Q3, R29, Q4, R30, Q5, R32, Q6, R33, Q7, R31,
Q8, R34, Q9, R35, Q10, R37, Ql 1 and R38 as defined in claim 4; and with
ANIO as defined in claim 6.
8. Method according to one or more of claims 1 to 7, wherein
n+
Cat is used in the reaction (Real) in form of a compound of formula (Al);
n+
[Cat ] [(Z'F 4) ]„ (Al)
wherein
n+ ,
Cat , Z and n are defined as in claim 1.
9. Method according to one or more of claims 1 to 8, wherein
m is 2, 3 or 4.
10. Method according to one or more of claims 1 to 9, wherein
m is 3 or 4.
11. Method according to one or more of claims 1 to 10, 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
+.
12. Method according to one or more of claims 1 to 11, 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, [(CH 3)3SiFSi(CH3 )3] + ,
Ph3C , and mixtures thereof.
13. Method according to one or more of claims 1 to 12, wherein
CatORG is selected from the group consisting of
[N(R20)(R21)(R22)R23]'
[P(R20)(R21)(R22)R23f, [(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_2oalkyl, C3_io cycloalkyl and allyl;
R22 is Ci_20 alkyl, C3_i 0 cycloalkyl or allyl.
14. Method according to one or more of claims 1 to 13, 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);
[Catn + ] [(BF(CN)3) ]„ (la)
[Catn + ] [(B(CN)4) ] (lb)
n+
Cat and n are as defined in claim 1 or 3.
15. Method according to one or more of claims 1 to 14, wherein
compound of formula (I) is compound (GROUP-II), compound (GROUP-II) is selected from
the group consisting of K+ [(BF(CN)3) ], Ag+ [(BF(CN)3) ], Li+ [(BF(CN)3) ], Mg +
[(BF(CN)3) ]2, Ca + [(BF(CN)3) ]2, [N(n-Pr)4]+ [(BF(CN)3) ], [N(n-Bu)4]+
[(BF(CN)3) ], [P(n-Bu)4]+ [(BF(CN)3) ], 1,3-dimethylimidazolium [(BF(CN)3) ],
l-ethyl-3-methylimidazolium [(BF(CN)3) ], l-propyl-3-methylimidazolium
[(BF(CN)3) ] and mixtures thereof.
16. Method according to one or more of claims 1 to 14, wherein
compound of formula (I) is compound (GROUP-III), compound (GROUP-III) is selected
from the group consisting of K+ [((B(CN)4)~ ], Ag+ [((B(CN)4) ], Li+ [((B(CN)4) ],
Mg + [(B(CN)4) ]2, Ca + [(B(CN)4) ]2, [N(n-Pr)4]+ [(B(CN)4) ], [N(n-Bu)4]+
[(B(CN)4) ], [P(n-Bu)4]+ [(B(CN)4) ], 1,3-dimethylimidazolium [(B(CN)4) ],
l-ethyl-3-methylimidazolium [(B(CN)4) ], l-propyl-3-methylimidazolium [(B(CN)4) ]
and mixtures thereof.
17. Method according to one or more of claims 1 to 13, wherein
compound of formula (I) is compound (GROUP-IV), compound (GROUP-IV) is selected
from the group consisting of K+ [((B(F)2(CN)2) ], Ag+ [((B(F)2(CN)2) ], Li+
[((B(F) (CN) ) ], Mg + [(B(F) (CN) ) ] , Ca + [(B(F) (CN) ) ] , [N(n-Pr)4]+
[(B(F) (CN) ) ], [N(n-Bu)4]+ [(B(F) (CN) ) ], [P(n-Bu)4]+ [(B(F) (CN) ) ],
1,3-dimethylimidazolium [(B(F)2(CN)2) ], l-ethyl-3-methylimidazolium
[(B(F)2(CN)2) ], l-propyl-3-methylimidazolium [(B(F)2(CN)2) ] and mixtures thereof.
18. Method according to one or more of claims 1 to 13, wherein
compound of formula (I) is compound (GROUP-V), compound (GROUP-V) is selected from
the group consisting of K+ [((B(F)3(CN)) ], Ag+ [((B(F)3(CN)) ], Li+ [((B(F)3(CN)) ],
Mg + [(B(F)3(CN)) ] , Ca + [(B(F)3(CN)) ] , [N(n-Pr)4]+ [(B(F)3(CN)) ], [N(n-Bu)4]+
[(B(F)3(CN)) ], [P(n-Bu)4]+ [(B(F)3(CN)) ], 1,3-dimethylimidazolium [(B(F)3(CN)) ],
l-ethyl-3-methylimidazolium [(B(F)3(CN)) ], l-propyl-3-methylimidazolium
[(B(F)3(CN))~ ] and mixtures thereof.
19. Method according to one or more of claims 1 to 18, wherein
compound of formula (I) is compound (GROUP), compound (GROUP) is selected from the
group consisting of compound of formula (1), compound of formula (2), compound of
formula (3), compound of formula (4), compound of formula (5), compound of formula (6),
compound of formula (7), compound of formula (8), and mixtures thereof.
[(n-Bu)4N][BF(CN)3] (1)
[EMIm][BF(CN)3] (2)
[(n-Bu)4N][BF3(CN)] (3)
[(n-Bu)4N][BF2(CN)2] (4)
[(n-Bu)4N][B(CN)4] (5)
K[BF(CN)3] (6)
K[B(CN)4] (?)
[BMIm][B(CN)4] (8)
Li[BF(CN)3] (9)
Li[B(CN)4] (10)
20. Method according to one or more of claims 1 to 19, wherein
the method comprises additionally to step (Stl) a step (St2), step (St2) is done after step (Stl);
step (St2) comprises a reaction (Rea2), reaction (Rea2) is a metathesis reaction wherein cation
n+ n+
Cat in compound of formula (I) is exchanged for a cation different from Cat ;
compound of formula (I) having been prepared in step (Stl);
n+
Cat , n, compound of formula (I) and step (Stl) are as defined in claim 1.
2 1. Method according to one or more of claims 1 to 20, wherein
the method comprises additionally to step (Stl) a step (Stl-1), step (Stl-1) is done after step
(Stl);
step (Stl-1) comprises a reaction (Real-1), wherein compound of formula (I), obtained in
step (1), is reacted with trimethylsilylcyanide.
22. Method according to claim 21, wherein
the reaction (Rea(l-l) is done in the presence of CATLEWISACID;
with CATLEWISACID as defined in claim 1.