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WO2014029833A1 - Method for the preparation of tetraalkylammonium or tetraalkylphosphonium|tricyanidofluoroborates - Google Patents

Method for the preparation of tetraalkylammonium or tetraalkylphosphonium|tricyanidofluoroborates Download PDF

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WO2014029833A1
WO2014029833A1 PCT/EP2013/067435 EP2013067435W WO2014029833A1 WO 2014029833 A1 WO2014029833 A1 WO 2014029833A1 EP 2013067435 W EP2013067435 W EP 2013067435W WO 2014029833 A1 WO2014029833 A1 WO 2014029833A1
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Christiaan RIJKSEN
Lothar Ott
Katharina SIEVERT
Jörg HARLOFF
Axel Schulz
Stefan Ellinger
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Lonza Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5407—Acyclic saturated phosphonium compounds

Definitions

  • the invention discloses a method for the preparation of tetra alkylammonium and tetra alkylphosphonium tricyanidofluoroborate starting from tetraalkylammonium or tetra alkylphosphonium tetrafluoroborate and trimethylsilylcyanide.
  • ionic liquid 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, W. Keim, 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 vapour pressure. In addition, they have good solvent properties for numerous organic and inorganic substances. Owing to their ionic structure, ionic liquids also have interesting electrochemical properties, for example electrical conductivity which is often accompanied by a high electrochemical stability. Therefore, there is a fundamental need for ionic liquids having a variety of properties which open up additional opportunities for their use.
  • 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[BF 4 ] in methanol as disclosed by J. S. Wilkes et al., J. Chem. Soc. Chem. Commun. 1990, 965.
  • alkyl means linear, branched, cyclic or cyclo alkyl; cyclic alkyl or cyclo alkyl are intended to include cyclo and polycyclo, such as bicyclo or tricyclo, aliphatic residues;
  • 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;
  • A is N or P; Rl, R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of hydrogen and C 1-10 alkyl.
  • Rl is hydrogen or C 1-10 alkyl
  • R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of C 1-10 alkyl;
  • Rl, R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of C 1-10 alkyl;
  • Rl, R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of Ci_ 8 alkyl;
  • Rl , R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of methyl, ethyl, propyl, butyl or octyl;
  • Rl, R2, R3 and R4 are identical and are methyl, ethyl, n-butyl or n-octyl, or
  • Rl, R2 and R3 are ethyl and R4 is methyl
  • Rl, R2, R3 and R4 are n-butyl.
  • A is N, with Rl, R2, R3 and R4 being any of the mentioned embodiments.
  • reaction (reac-1) Preferably, from 3 to 10 mol equivalents, more preferably from 3.1 to 8 mol equivalents, even more preferably from 3.1 to 7 mol equivalents, especially from 3.1 to 5 mol equivalents, of trimethylsilylcyanide are used in reaction (reac-1), the mol equivalents being based on the mol of compound of formula (II).
  • reaction (reac-1) is done in the absence of a solvent, i.e. no solvent is used.
  • reaction temperatures of reaction (reac-1) is from 125 to 210°C or 130 to 210°C, more preferably from 125 to 200°C, especially from 125 to 190°C, more especially from 130 to 170°C, even more especially from 135 to 165°C; more especially from 140 to 160°C.
  • reaction time of reaction (reac-1) is from 30 min to 48 h, more preferably from 1 h to 48 h, even more preferably from 1 h to 24 h, especially from 1 h to 21 h, more especially from 2 h to 18 h; even more especially from 5 h to 18 h, in particular from 8 h to 18 h.
  • reaction (reac-1) is done in a closed system and at the pressure caused by the chosen temperature.
  • reaction (reac-1) is done under inert atmosphere.
  • 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.
  • reaction (reac-1) compound of formula (I) can be isolated by standard methods such as evaporation of volatile components, extraction, washing, drying, concentration,
  • 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).
  • the concentration of the hydrogen peroxide is from 10 to 40 wt% hydrogen peroxide, the wt% based on the total weight of the aqueous hydrogen peroxide.
  • the concentration of the hydrogen peroxide is from 10 to 40 wt% hydrogen peroxide, the wt% based on the total weight of the aqueous hydrogen peroxide.
  • from 1 to 10 mol equivalents, more preferably from 1 to 5 mol equivalents, even more preferably from 1 to 3 equivalents, of hydrogen peroxide are used, the mol equivalents being based on the mol of compound of formula (II).
  • mixture (M) is stirred for 5 min to 12 h, more preferably for 10 min to 6 h, even more preferably for 15 min to 2 h.
  • mixture (M) is stirred at a temperature (M), temperature (M) is preferably from ambient temperature to 100°C, more preferably from 40°C to 80°C.
  • temperature (M) is preferably filtrated.
  • the residue of the filtration is preferably washed with a solvent (WASH), solvent (WASH) is preferably water.
  • solvent is preferably CH 3 CN, CH 2 C1 2 , ethyl acetate, CHC1 3 , MeOH or EtOH.
  • the amount of solvent (DISSOLV) is preferably from 2 to 40 fold, more preferably from 3 to 20 fold, even more preferably from 5 to 15 fold, of the weight of compound of formula (II).
  • solution is treated with charcoal, preferably 1 to 10 times.
  • the amount of charcoal is preferably 0.1 to 1 fold of the weight of compound of formula (II).
  • mixture (M) is extracted with a solvent (EXTRACT).
  • Solvent is preferably selected from the group consisting of dichloromethane, diethyl ether and chloroform.
  • Any drying of an organic phase e.g. the organic phase obtained after extraction with solvent (EXTRACT), is preferably done with Na 2 S0 4 , K 2 C0 3 , CaCl 2 or MgS0 4 .
  • Any isolation from a solution e.g. from solution (SOLU), is preferably done by evaporation of the solvent.
  • Compounds of formula (II) are known compounds and can be prepared according to known methods, e.g. by metathesis reaction starting from HBF 4 , from KBF 4 or from LiBF 4 .
  • the method of the invention provides compound of formula (I) in high yield and high purity, the reaction time is significantly shorter and the molar amount of TMSCN with respect to
  • IR-spectra were recorded on a Nicolet 380 FT-IR spectrometer. Measurements were done at room temperature.
  • RAMAN-spectra were recorded on a Kaiser Optical Systems RXN 1-785. The intensity was normalized on 10 for the most intensive peak.
  • the teflon tube was closed using a teflon lid and place in an autoclave.
  • the autoclave was placed inside a muffle furnace which was heated to 150°C in 30 min. This temperature was held for 13 h.
  • RAMAN 500 mW, 400 scans cm “1 ): 2971 (5), 2941 (7), 2878 (6), 2219 (10), 1452 (3), 1324
  • Example 1 was repeated with the differences:
  • Example 1 was repeated with the differences:
  • Example 1 was repeated with the differences:
  • Example 1 was repeated with the differences:
  • Example 1 was repeated with the differences:
  • Example 1 was repeated with the differences:
  • Example 1 was repeated with the differences:
  • Example 1 was repeated with the differences:
  • the temperature was 140°C instead of 150°C, which was held for 20 h instead of 13 h.
  • Example 1 was repeated with the differences:
  • RAMAN (460 mW, 150 scans 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)
  • Example 12 was repeated with the differences:
  • Example 1 was repeated with the differences:

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  • Health & Medical Sciences (AREA)
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Abstract

The invention discloses a method for the preparation of tetra alkylammonium and tetra alkylphosphonium tricyanidofluoroborate starting from tetraalkylammonium or tetra alkylphosphonium tetrafluoroborate and trimethylsilylcyanide.

Description

METHOD FOR THE PREPARATION OF TETRAALKYLAMMONIUM OR TETRAALKYLPHOSPHONIUM|TRICYANIDOFLUOROBORATES
The invention discloses a method for the preparation of tetra alkylammonium and tetra alkylphosphonium tricyanidofluoroborate starting from tetraalkylammonium or tetra alkylphosphonium tetrafluoroborate and trimethylsilylcyanide.
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, W. Keim, 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 vapour pressure. In addition, they have good solvent properties for numerous organic and inorganic substances. Owing to their ionic structure, ionic liquids also have interesting electrochemical properties, for example electrical conductivity which is often accompanied by a high electrochemical stability. 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 tetra valent 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.
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.
In this text,
alkyl means linear, branched, cyclic or cyclo alkyl; cyclic alkyl or cyclo alkyl are intended to include cyclo and polycyclo, such as bicyclo or tricyclo, aliphatic residues;
EMIm 1 -ethyl-3 -methylimidazolium
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;
Oct octyl
RT room temperature, it is used synonymously with the expression ambient
temperature
TMSCN (CH3)3SiCN, trimethylsilylcyanide;
"wt%", "% by weight" and "weight-%" are used synonymously and mean percent by weight; if not otherwise stated.
There was a need for a process for the preparation of fluorotricyanidoborates, which provides economic access to this class of substances, which for example can be used as ionic liquids or as precursors for the preparation of ionic liquids. The process should have satisfactory yield and purity, and the reaction time should be short.
SUMMARY OF THE INVENTION
Subject of the invention is a method for the preparation of compound of formula (I)
Figure imgf000003_0001
R4 a reaction (reac-1) between compound of formula (II) and trimethylsilylcyanide;
Figure imgf000003_0002
R4
A is N or P; Rl, R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of hydrogen and C1-10 alkyl.
DETAILED DESCRIPTION OF THE INVENTION
In one embodiment,
preferably, Rl is hydrogen or C1-10 alkyl; and
R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of C1-10 alkyl;
more preferably, Rl, R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of C1-10 alkyl;
even more preferably, Rl, R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of Ci_8 alkyl;
especially, Rl , R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of methyl, ethyl, propyl, butyl or octyl;
more especially, Rl, R2, R3 and R4 are identical and are methyl, ethyl, n-butyl or n-octyl, or
Rl, R2 and R3 are ethyl and R4 is methyl;
even more especially, Rl, R2, R3 and R4 are n-butyl.
Preferably, A is N, with Rl, R2, R3 and R4 being any of the mentioned embodiments.
Preferably, from 3 to 10 mol equivalents, more preferably from 3.1 to 8 mol equivalents, even more preferably from 3.1 to 7 mol equivalents, especially from 3.1 to 5 mol equivalents, of trimethylsilylcyanide are used in reaction (reac-1), the mol equivalents being based on the mol of compound of formula (II).
Preferably, reaction (reac-1) is done in the absence of a solvent, i.e. no solvent is used.
Preferably, the reaction temperatures of reaction (reac-1) is from 125 to 210°C or 130 to 210°C, more preferably from 125 to 200°C, especially from 125 to 190°C, more especially from 130 to 170°C, even more especially from 135 to 165°C; more especially from 140 to 160°C.
Preferably, the reaction time of reaction (reac-1) is from 30 min to 48 h, more preferably from 1 h to 48 h, even more preferably from 1 h to 24 h, especially from 1 h to 21 h, more especially from 2 h to 18 h; even more especially from 5 h to 18 h, in particular from 8 h to 18 h.
Preferably, reaction (reac-1) is done in a closed system and at the pressure caused by the chosen temperature.
Preferably, reaction (reac-1) 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 reaction (reac-1) 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 reaction (reac-1) 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 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 10 mol equivalents, more preferably from 1 to 5 mol equivalents, even more preferably from 1 to 3 equivalents, of hydrogen peroxide are used, the mol equivalents being based on the mol of compound of formula (II).
Preferably mixture (M) is stirred for 5 min to 12 h, more preferably for 10 min to 6 h, even more preferably for 15 min to 2 h.
Preferably mixture (M) is stirred at a temperature (M), temperature (M) is preferably from ambient temperature to 100°C, more preferably from 40°C to 80°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.
The residue is preferably dissolved with a solvent (DISSOLV) to provide a solution (SOLU), solvent (DISSOLV) is preferably CH3CN, CH2C12, ethyl acetate, CHC13, MeOH or EtOH.
The amount of solvent (DISSOLV) is preferably from 2 to 40 fold, more preferably from 3 to 20 fold, even more preferably from 5 to 15 fold, of the weight of compound of formula (II).
Preferably, solution (SOLU) is treated with charcoal, preferably 1 to 10 times.
The amount of charcoal is preferably 0.1 to 1 fold of the weight of compound of formula (II).
In another preferred embodiment, mixture (M) is extracted with a solvent (EXTRACT). Solvent (EXTRACT) is preferably selected from the group consisting of dichloromethane, diethyl ether and chloroform.
Any drying of an organic phase, e.g. the organic phase obtained after extraction with solvent (EXTRACT), is preferably done with Na2S04, K2C03, CaCl2 or MgS04.
Any isolation from a solution, e.g. from solution (SOLU), is preferably done by evaporation of the solvent.
Compounds of formula (II) are known compounds and can be prepared according to known methods, e.g. by metathesis reaction starting from HBF4, from KBF4 or from LiBF4.
The method of the invention provides compound of formula (I) in high yield and high purity, the reaction time is significantly shorter and the molar amount of TMSCN with respect to
[BF4] compared to prior art. Examples Methods
1H and 13C NMR spectra were recorded on a Bruker AVANCE 300 (300 MHz) (300 MHz for 1H and 250 MHz for 13C) instruments in CD3CN. Chemical shifts are expressed in parts per million referred to TMS and coupling constants (J) in Hertz.
IR-spectra were recorded on a Nicolet 380 FT-IR spectrometer. Measurements were done at room temperature.
RAMAN-spectra were recorded on a Kaiser Optical Systems RXN 1-785. The intensity was normalized on 10 for the most intensive peak.
The C/H/N-analyses were measured on a C/H/N/S-Analysator (Thermoquest Flash EA 1112).
Melting points 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. Example 1 : Synthesis of [(n-Bu)4N] [BF(CN)3]
[(n-Bu)4N][BF4] (1.17 g, 3.55 mmol), prepared according to example 12, and (CH3)3SiCN (1.23 g, 12.44 mmol) were filled under argon atmosphere with a residual oxygen content of below 5 ppm and with a residual water content of below 1 ppm into a teflon tube.
The teflon tube was closed using a teflon lid and place in an autoclave. The autoclave was placed inside a muffle furnace which was heated to 150°C in 30 min. This temperature was held for 13 h.
After cooling to ambient temperature the reaction mixture was mixed with water and aqueous hydrogen peroxide (0.5 ml, 5 mmol, 30 wt%). After stirring at 60°C for an hour the solution was cooled to ambient temperature. The product was extracted with dichloromethane three times. The organic phase was separated and dried with MgS04 and filtered. The filtrate was evaporated on a rotary evaporator. The yield of the yellow crystalline product was 0.95 g (76%, 2.71 mmol). Only one boron and one fluorine species, the one of the desired product, is visible in nB NMR and in the 19F NMR respectively. Analytics
Mp: 60°C
C/H/N Analysis calc. % (found): C 65.14 (64.90), H 10.36 (10.15), N 15.99 (15.87)
1H NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 0.97 (t, 12H, CH3, 3J(1H-1H) = 7.2 Hz),
1.36 (m, 8H, CH3-CH2, 3J(1H-1H) = 7.6 Hz), 1.59 (m, 8H, CH2-CH2N), 3.08 (m, 8H,
NCH2)
13C NMR (25°C, CD3CN, 250.13 MHz, delta in ppm): 13.78 (s, 4C, CH3), 20.30 (m, 4C, CH3-CH2), 24.29 (m, 4C, CH2-CH2N), 59.33 (m, 4C, NCH2), 127.83 (3C, CN)
UB NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -17.87 (d, IB, BF(CN)3, ^("C^B = 44.02 Hz)
19F NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): -211.73 (q, IF, ^("B-^F) = 44.96 Hz,
2J(10B-19F) = 34.74 Hz)
IR (ATR, 32 scans, v in cm"1): 2964 (m), 2935 (m), 2876 (m), 2214 (w), 1474 (m), 1408(w),
1382 (w), 1361(w), 1350 (w), 1322 (w), 1311 (w), 1285(w), 1244 (w), 1171 (w), 1130
(w), 1110 (w), 1080 (w), 1040 (m), 991 (w), 959 (m), 938 (m), 926 (m), 903 (s), 821 (w),
803 (w), 736 (m), 668 (w), 592 (w), 532 (w)
RAMAN (500 mW, 400 scans cm"1): 2971 (5), 2941 (7), 2878 (6), 2219 (10), 1452 (3), 1324
(2), 1113 (2), 1062 (1), 910 (1), 883 (1), 594 (1), 264 (1), 224 (1), 130 (2) Example 2: Synthesis of [(n-Bu)4N] [BF(CN)3]
Example 1 was repeated with the differences:
1. [(n-Bu)4N][BF4] (0.340 g, 1.03 mmol) and (CH3)3SiCN (0.4 g, 4.0 mmol) were used.
2. The temperature was 140°C instead of 150°C, which was held for 20 h instead of 13 h. A light yellow crystalline product was obtained (0.276 g, 76%, 0.79 mmol).
Analytics
C/H/N Analysis calc. % (found): C 65.14 (65.27), H 10.36 (10.17), N 15.99 (15.97)
The NMR and IR data are the same as in example 1.
Example 3: Synthesis of [(n-Bu)4N] [BF(CN)3]
Example 1 was repeated with the differences:
1. [(n-Bu)4N][BF4] (1.07 g, 3.24 mmol) and (CH3)3SiCN (1.29 g, 13.00 mmol) were used.
2. The temperature was 170°C instead of 150°C, which was held for 10 h instead of 13 h. A yellow crystalline product was obtained (0.84 g, 74%, 2.40 mmol). Analytics
C/H/N Analysis calc. % (found): C 65.14 (65.24), H 10.36 (10.22), N 15.99 (16.28) The NMR and IR data are the same as in example 1.
Example 4: Synthesis of [(n-Bu)4N] [BF(CN)3]
Example 1 was repeated with the differences:
1. [(n-Bu)4N][BF4] (0.588 g, 1.79 mmol) and (CH3)3SiCN (0.71 g, 7.16 mmol) were used.
2. The temperature was 190°C instead of 150°C, which was held for 5 h instead of 13 h. A yellow crystalline product was obtained (0.39 g, 62%, 1.11 mmol).
Analytics
C/H/N Analysis calc. % (found): C 65.14 (65.29), H 10.36 (10.30), N 15.99 (15.96) The NMR and IR data are the same as in example 1.
Example 5: Synthesis of [(n-Bu)4N] [BF(CN)3]
Example 1 was repeated with the differences:
1. [(n-Bu)4N][BF4] (0.268 g, 0.81 mmol) and (CH3)3SiCN (0.29 g, 2.92 mmol) were used.
2. The temperature was 200°C instead of 150°C, which was held for 1 h instead of 13 h. A yellow crystalline product was obtained (0.172 g, 60%, 0.49 mmol).
Analytics
C/H/N Analysis calc. % (found): C 65.14 (64.55), H 10.36 (10.02), N 15.99 (15.73) The NMR and IR data are the same as in example 1.
Example 6: Synthesis of [Me4N] [BF(CN)3]
Example 1 was repeated with the differences:
1. [Me4N][BF ] (0.422 g, 2.62 mmol), prepared according to example 15, and (CH3)3SiCN (1.00 g, 10.08 mmol) were used.
2. After addition of water and aqueous hydrogen peroxide, stirring at 60°C for an hour and cooling to ambient temperature the solution was filtrated. The filtrate was evaporated on a rotary evaporator. The product was dried at 90°C and 0.001 mbar for 10 h. The yield of the white crystalline product was 0.39 g (82%>, 2.14 mmol). Analytics
Mp: 258°C with starting degradation
C/H/N Analysis calc. % (found): C 46.19 (45.90), H 6.65 (6.35) N 30.78 (30.33)
1H NMR (25°C, d6-DMSO, 300.13 MHz, delta in ppm): 3.09 (s, 12H, CH3)
13C NMR (25°C, d6-DMSO, 250.13 MHz, delta in ppm): 54.39 (t, 4C, CH3)
nB NMR (25°C, d6-DMSO, 96.29 MHz, delta in ppm): -17.90 (d, IB, BF(CN)3, ^("C^B = 44.82 Hz)
19F NMR (25°C, d6-DMSO, 300.13 MHz, delta in ppm): -210.81 (q, IF, ^("B-^F) = 44.79 Hz)
IR (ATR, 32 scans, v in cm"1): 2964 (m), 2935 (m), 2877 (m), 2214 (w), 1474 (m), 1382(w), 1361(w), 1322 (w), 1286(w), 1244 (w), 1171 (w), 1152 (w), 1130 (w), 1110 (w), 1083 (w), 1042 (m), 991 (w), 959 (m), 938 (m), 926 (m), 903 (s), 803 (w), 737 (m), 592 (w), 532 (w)
Example 7: Synthesis of [(n-Oct)4N] [BF(CN)3]
Example 1 was repeated with the differences:
1. [(n-Oct)4N][BF4] (0.117 g, 0.21 mmol), prepared according to example 14, and
(CH3)3SiCN (0.15 g, 1.51 mmol) were used.
2. After evaporation of the filtrate on a rotary evaporator the product was dried at 90°C and ca. 0.001 mbar for 10 h. The yield of the oily orange product was 0.092 g (76 %, 0.16 mmol).
Analytics
Mp: -3°C
C/H/N Analysis calc. % (found): C 73.14 (73.01), H 11.93 (11.23) N 9.75 (9.26)
1H NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 0.90 (t, 12H, CH3), 1.31 (m, 40H, CH3- (CH2)5), 1.58 (m, 8H, N-CH2-CH2), 3.06 (m, 8H, N-CH2)
13C NMR (25°C, CD3CN, 250.13 MHz, delta in ppm): 14.44 (s, 4C, CH3), 22.36 (s, 4C, CH3- CH2), 23.41 (s, 4C, N-(CH2)2-CH2), 26.89 (t, 4C, N-CH2-CH2), 29.64 (s, 4C, N-(CH2)3- CH2), 29.75 (s, 4C, CH3-(CH2)2-CH2), 32.49 (s, 4C, CH3-CH2-CH2), 59.48 (t, 4C, N- CH2)
UB NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -17.88 (d, IB, BF(CN)3, ^("C^B = 44.49 Hz)
19 F NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -211.77 (q, IF, ^("B-^F) = 43.98 Hz) IR (ATR, 32 scans, v in cm"1): 2954 (m), 2925 (s), 2857 (s), 2212 (w), 1483 (m), 1466 (m), 1378 (w), 1263 (w), 1183 (w), 1047 (m), 937 (m), 901 (s), 815 (w), 764 (w), 723 (w), 591 (w) Example 8: Synthesis of [Et3MeN[BF(CN)3]
Example 1 was repeated with the differences:
1. [Et3MeN][BF4] (0.657 g, 3.24 mmol), prepared according to example 13, and (CH3)3SiCN (1.29 g, 13.00 mmol) were used.
2. After addition of water and aqueous hydrogen peroxide, stirring at 60°C for an hour and cooling to ambient temperature the solution was filtrated. The filtrate was evaporated on a rotary evaporator. The product was recrystallized from CH3CN. The product was dried at 90°C and 0.001 mbar for 10 h. The yield of the white crystalline product was 0.385 g (53%, 1.72 mmol).
Analytics
Mp: 93°C
C/H/N Analysis calc. % (found): C 53.60 (53.11), H 8.10 (8.18), N 25.00 (24.66)
1H NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 1.24 (tt, 9H, CH3), 2.87 (s, 3H, CH3), 3.25 (q, 6H, CH2)
13C NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 8.11 (s, 3C, CH2-CH3), 47.52 (t, 1C,
CH3), 56.89 ( t, 3C, CH2)
nB NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -17.89(d, IB, BF(CN)3, ^("C^B = 44.27 Hz)
19 F NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -211.79 (q, IF, ^("B-^F) = 44.91 Hz) IR (ATR, 32 scans, v in cm"1): 2992 (w), 2955 (w), 2214 (w), 1487 (m), 1459(w), 1397 (m), 1360 (w), 1317 (w), 1207 (w), 1192 (w), 1125 (w), 1046 (s), 1008 (m), 958 (m), 937 (m), 901 (s), 810 (m), 788 (w), 682 (w), 592 (w)
Example 9: Synthesis of [(n-Bu)4N] [BF(CN)3]
Example 1 was repeated with the differences:
1. [(n-Bu)4N][BF4] (17.957 g, 54.5 mmol) and (CH3)3SiCN (21.1 g, 213 mmol) were used.
2. The temperature was 140°C instead of 150°C, which was held for 20 h instead of 13 h.
3. 5 ml of the aqueous hydrogen peroxide were used instead of 0.5 ml.
A light yellow crystalline product was obtained (15.847 g, 83%>, 45.2 mmol). Example 11: Synthesis of [(n-Bu4)P] [BF(CN)3]
Example 1 was repeated with the differences:
1. [(n-Bu)4P][BF4] (0.773 g, 2.23 mmol), prepared according to example 16, and (CH3)3SiCN (1.33 g, 13.4 mmol) were used.
2. The temperature was 160°C instead of 150°C, which was held for 20 h instead of 13 h. A light yellow crystalline product was obtained (0.649 g, 79%, 1.77 mmol).
C/H/N Analysis calc.% (found): C 62.13 (62.24), H 9.88 (9.92), N 11.44 (11.72 )
1H NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 0.95 (t, 12H, CH3), 3.83 (s, 16H, CH3), 1.48 (m, 8H, (CH2)2), 2.06 (m, 8H, PCH2)
13C NMR (25 °C, CD3CN, 250.13 MHz, delta in ppm): 13.54 (s, 4C, CH3), 18.91 (d, 4C,
PCH2, ^(^C-^P) = 48.1 Hz, 23.84 (d, 4C, CH2-CH3, 3J(13C-31P) = 4.5 Hz), 24.48 (d, 4C, CH2, 2J(13C-31P) = 15.6 Hz), 126.65 (q, 3C, CN, ^("B-^C) = 74.0 Hz, 2J(19F-13C) = 37.1 Hz)
UB NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -17.87 (d, IB, BF(CN)3, ^(^C^B) = 44.0 Hz)
19F NMR (25 °C, CD3CN, 300.13 MHz, delta in ppm): -211.76 (q, IF, ^("B-^F) = 43.8 Hz) 31P NMR (25 °C, CD3CN, 121.50 MHz, delta in ppm): 33.72 (s, IP)
Example 12: Synthesis of [(n-Bu4)N] [BF4]
K[BF4] (3.12 g, 24.78 mmol) was dissolved in 15 ml of H20. [(n-Bu)4N]Br (8.05 g, 24.98 mmol) was dissolved in 25 ml of CH2C12 and added to the aqueous solution of K[BF4]. After stirring for 24 hours 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). Analytics
Mp: 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, 3J(1H-1H) = 7.3 Hz), 1.35 (m, 8H, CH3-CH2, 1.61 (m, 8H, CH2-CH2N), 3.11 (m, 8H, NCH2) 13C 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)
UB NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -1.18 (s, IB, BF4)
19F NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): -151.61 (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 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)
Example 13: Synthesis of [Et3MeN] [BF4]
K[BF4] (2.02 g, 16.04 mmol) and [Et MeN]Br (3.14 g, 16.03 mmol) were dissolved in 25 ml of acetone died with molecular sieves. After stirring for 25 hours at ambient temperature the reaction mixture was 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
[Et3MeN][BF4] was 2.64 g (87 %, 13.9 mmol).
Analytics
C/H/N Analysis calc. % (found): C 41.41 (41.37), H 8.94 (9.07), N 6.90 (6.73)
1H NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 1.23 (m, 9H, CH3), 2.88 (s, 3H, CH3), 3.26 (m, 6H, CH2)
13C NMR (25 °C, CD3CN, 300.13 MHz, delta in ppm): 8.04 (s, 3C, CH3), 47.27 (t, 1C, CH3),
56.56 (t, 3C, CH2)
UB NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -1.19 (s, IB, BF4)
19F NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): -151.43 (q, 4F, BF4)
Example 14: Synthesis of [(n-Oct)4N] [BF4]
K[BF4] (0.136 g, 1.08 mmol) was dissolved in 5 ml of H20. [(n-Oct)4N]Br (0.334 g, 0.61 mmol) was dissolved in 5 ml of CH2C12 and added to the aqueous solution of K[BF4]. After stirring for 24 hours at ambient temperature the phases were separated. The organic phase was washed three times with 5 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-Oct)4N][BF4] as a white crystalline product was 0.321 g (95%, 0.58 mmol). Analytics
1H NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 0.89 (t, 12H, CH3), 1.30 (m, 40H,
CH3-(CH2)5), 1.78 (m, 8H, N-CH2-CH2), 3.05 (m, 8H, N-CH2)
13C NMR (25 °C, CD3CN, 250.13 MHz, delta in ppm): 14.34 (s, 4C, CH3), 22.26 (s, 4C, CH3-CH2), 23.32 (s, 4C, N-(CH2)2-CH2), 26.80 (t, 4C, N-CH2-CH2), 29.56 (s, 4C, N-
(CH2)3-CH2), 29.66 (s, 4C, CH3-(CH2)2-CH2), 32.40 (s, 4C, CH3-CH2-CH2), 59.38 (t, 4C,
N-CH2)
UB NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -1.19 (s, IB, BF4) Example 15 : Synthesis of [Me4N] [BF4]
[Me4N]OH (2.03 g, 22.27 mmol) was dissolved in 10 ml of water. Aqueous HBF4 (1.96 g, 22.53 mmol, 50 wt%) was added dropwise. Immediately a white precipitate occurred. The suspension was filtered. The obtained white solid was washed with 10 ml of water and dried at 90°C in vacuo for 15 hour. The yield of [Me4N][BF4] was 3.22 g (90%, 20.03 mmol).
C/H/N Analysis calc. % (found): C 29.85 (29.73), H 7.51 (7.48), N 8.70 (8.54)
1H NMR (25°C, d6-DMSO, 300.13 MHz, delta in ppm): 3.08 (s, 12H, CH3)
13C NMR (25 °C, d6-DMSO, 300.13 MHz, delta in ppm): 54.3 (t, 4C, CH3)
UB NMR (25°C, d6-DMSO, 96.29 MHz, delta in ppm): -1.24 (s, IB, BF4)
19F NMR (25°C, d6-DMSO, 300.13 MHz, delta in ppm): -151.53 (q, 4F, BF4)
Example 16: Synthesis of [(n-Bu)4P] [BF4]
Example 12 was repeated with the differences:
1. [(n-Bu)4P]Br (3.584 g, 10.56 mmol) and K[BF4] (1.323 g, 10.51 mmol) were used instead of K[BF4] (3.12 g, 24.78 mmol) and [(n-Bu)4N]Br (8.05 g, 24.98 mmol) of example 12. A white crystalline product was obtained (3.31 g, 91%, 9.57 mmol).
Analytics
C/H/N Analysis calc. % (found): C 29.85 (29.73), H 7.51 (7.48), N 8.70 (8.54)
1H NMR (25°C, CD3CN, 300.13 MHz, delta in ppm): 0.94 (t, 12H, CH3), 1.46 (m, 16H,
(CH2)2), 2.07 (m, 8H, P-CH2)
13C NMR (25 °C, CD3CN, 250.13 MHz, δ in ppm): 13.49 (s, 4C, CH3), 18.92 (d, 4C, PCH2),
23.83 (d, 4C, CH2-CH3), 24.48 (d, 4C, CH2)
UB NMR (25°C, CD3CN, 96.29 MHz, delta in ppm): -1.22 (d, IB, BF4) 'F NMR (25°C, CD3CN, 300.13 MHz, delta in pm): -151.40 (4F, BF4)
Example 17: Synthesis of [(n-Bu4)P] [BF(CN)3]
Example 1 was repeated with the differences:
1. [(n-Bu)4P][BF4] (0.774 g, 2.24 mmol) and (CH3)3SiCN (1.33 g, 13.4 mmol) were used.
2. The temperature was 200°C instead of 150°C, which was held for 20 h instead of 13 h. A light yellow crystalline product was obtained (0.525 g, 64%, 1.43 mmol).
Analytics
C/H/N Analysis calc.% (found): C 62.13 (62.04), H 9.88 (9.94), N 11.44 (11.25)
NMR data were found to be the same as in Example 11.

Claims

Claims
Method for the preparation of compound of formula (I)
Figure imgf000016_0001
R4 by a reaction (reac-1) between compound of formula (II) and trimethylsilylcyanide;
Figure imgf000016_0002
R4
A is N or P;
Rl , R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of hydrogen and Ci_io alkyl.
2. Method according to claim 1 , wherein
Rl is hydrogen or Ci_io alkyl; and
R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of Ci_io alkyl.
3. Method according to claim 1 or 2, wherein Rl , R2, R3 and R4 are identical or different and independently from each other selected from the group consisting of Ci_io alkyl.
4. Method according to one or more of claims 1 to 3, wherein A is N.
5. Method according to one or more of claims 1 to 4, wherein
from 3 to 10 mol equivalents of trimethylsilylcyanide are used in reaction (reac-1), the mol equivalents being based on the mol of compound of formula (II).
6. Method according to one or more of claims 1 to 5, wherein
from 3.1 to 5 mol equivalents of trimethylsilylcyanide are used in reaction (reac-1), the mol equivalents being based on the mol of compound of formula (II).
7. Method according to one or more of claims 1 to 6, wherein
reaction (reac-1) is done in the absence of a solvent.
8. Method according to one or more of claims 1 to 7, wherein
the reaction temperatures of reaction (reac-1) is from 125 to 210°C.
9. Method according to one or more of claims 1 to 8, wherein
the reaction time of reaction (reac-1) is from 30 min to 48 h.
10. Method according to one or more of claims 1 to 9, wherein
after reaction (reac-1) the reaction product is treated with hydrogen peroxide.
PCT/EP2013/067435 2012-08-24 2013-08-22 Method for the preparation of tetraalkylammonium or tetraalkylphosphonium|tricyanidofluoroborates WO2014029833A1 (en)

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JP2016521671A (en) * 2013-06-14 2016-07-25 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ Method for producing salt having monofluorotricyanoborate anion
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JP2016521671A (en) * 2013-06-14 2016-07-25 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ Method for producing salt having monofluorotricyanoborate anion
DE102014014967A1 (en) 2014-10-14 2016-04-14 Julius-Maximilians-Universität Würzburg Process for the preparation of compounds with monofluorotricyanoborate anions
WO2016058665A1 (en) * 2014-10-14 2016-04-21 Merck Patent Gmbh Method for producing compounds with monofluorotricyanoborate anions
WO2016162400A1 (en) 2015-04-09 2016-10-13 Lonza Ltd Method for preparation of cyano compounds of boron with a bronstedt acid
US11008244B2 (en) 2015-11-25 2021-05-18 Corning Incorporated Methods of separating a glass web

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