WO2016162400A1 - Procédé de préparation de composés cyano de bore avec un acide de bronstedt - Google Patents

Procédé de préparation de composés cyano de bore avec un acide de bronstedt Download PDF

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WO2016162400A1
WO2016162400A1 PCT/EP2016/057584 EP2016057584W WO2016162400A1 WO 2016162400 A1 WO2016162400 A1 WO 2016162400A1 EP 2016057584 W EP2016057584 W EP 2016057584W WO 2016162400 A1 WO2016162400 A1 WO 2016162400A1
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group
alkyl
cat
compound
halogen
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PCT/EP2016/057584
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Stefan Ellinger
Christoph Taeschler
Cornelia Zur Taeschler
Katharina SIEVERT
Axel Schulz
Jörg HARLOFF
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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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/06—Boron halogen compounds
    • C01B35/063—Tetrafluoboric acid; Salts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention discloses a method for preparation of cyano compounds of boron with 1, 2, 3 or 4 cyano residues, represented by formula (I),
  • Cat is a cation, m is 1 , 2, 3 or 4 and n is 1 , 2, 3 or 4.
  • 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 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.
  • ionic liquids have interesting electrochemical properties, for example electrical conductivity which is often accompanied by a high electrochemical stability.
  • ionic liquids can be used for example as solvent in synthesis, as electrolyte, as lubricant and as hydraulic fluid. Moreover they serve as phase-transfer catalyst, as extraction medium, as heat-transfer medium, as surface-active substance, as plasticizer, as conductive salt, organic salt or additive in electrochemical cells, as electrolyte, as component in electrolyte formulations, wherein such electrolyte formulation comprising an ionic liquid is preferably used in electrochemical and/or optoelectronic device such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, particularly preferred in a dye sensitized solar cell. Therefore, there is a fundamental need for ionic liquids having a variety of properties which open up additional opportunities for their use.
  • 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.
  • WO 2014/029833 Al a method for the preparation of tetra alkylammonium and tetra alkylphosphonium tricyanidofluoroborate starting from tetraalkylammonium or tetra alkylphosphonium tetrafluoroborate and trimethylsilylcyanide. Exemplified are inter alia [(nBu) 4 N], [Me 4 N] and [(nOct) 4 N] as ammonium ions. Bronstedt acid is not disclosed.
  • EP 2772495 Al discloses a method for the preparation of tricyanidofluoroborate in two steps via tetra alkylammonium and tetra alkylphosphonium tricyanidofluoroborate, starting from tetraalkylammonium or tetra alkylphosphonium tetrafluoroborate and trimethylsilylcyanide in the first step and exchanging the cation in the second step.
  • Exemplified are inter alia
  • WO 2014/029834 Al discloses a method for the preparation of tetra alkylammonium tetracyanidoborate starting from tetraalkylammonium tetrafluoroborate and
  • trimethylsilylcyanide Exemplified are inter alia [(nBu)4N] and [(nOct)4N] as ammonium ions. Bronstedt acid is not disclosed.
  • General formula (I) is a salt of a cation Kt m+ with [B(CN) 4 ] .
  • 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.
  • 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.
  • 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.
  • Example 3-11 of EP 2 327 707 A discloses a reaction of boron trifluoride diethyl ether, tetrabutylammonium bromide and trimethylsilylcyanide at 170°C for 30 hours, with a yield of 75%.
  • Example 3 of the instant invention shows one embodiment also starting with boron trifluoride diethyl ether, which falls under claim 7, but produces the desired [B(CN) 4 ] salt only as a by-product in negligible amounts, the main product is a [BF(CN)B] salt.
  • 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.
  • 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 Cl 2 , AgCN or AgBF 4 .
  • the method should provide stable compounds of said formula which can be used as ionic liquids or as precursors of ionic liquids and can be used e.g. in electrolyte formulations and in electrochemical or optoelectronic devices. These compounds should be able to be disposed of in an environmentally friendly manner after use.
  • the method should allow the preparation of the desired compounds in high yields and under mild conditions with respect to methods disclosed in the prior art.
  • This object is achieved by a method using trimethylsilylcyanide as CN source and by doing the reaction in the presence of a Bronstedt acid. No Cl 2 , AgCN or AgBF 4 is required. The content of CI, Br, Si and cyanide in the final product is low. Another advantage is that the reaction does not require mandatorily an extra solvent.
  • the method has a reduced number of steps compared to the methods known from the prior art. The method allows for the preparation not only of compounds with m being only 3 or only 4, but for compounds with n being 1 , 2, 3 or 4. These compounds can be prepared specifically and individually, and not only as mixtures. The reaction can be done under milder conditions than those used in the methods of the prior art, the reaction can be done at lower temperature or in shorter time.
  • alkyl linear or branched alkyl
  • Ci_ q alkyl refers to any alkyl residue which contains from 1 to q carbon atoms
  • Ci_ 6 alkyl encompasses inter alia methyl, ethyl, propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), n-hexyl and isohexyl (4-methylpentyl);
  • C 2 - 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 C 2 _ 4 alkenyl encompasses inter alia ethenyl, 1-methylethenyl, prop-l-enyl, prop-2-enyl, 2-methylprop-2-enyl and buta-l ,3-dienyl;
  • C 2 _ 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 C 2 _ 4 alkynyl encompasses inter alia ethynyl, prop-l-ynyl and prop-2-ynyl;
  • C 6 -io aryl refers to an aryl residue which has from 6 to 10 carbon atoms and is
  • Ci_ 4 alkyl and Ci_ 4 alkoxy for example C 6 -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,
  • C3_ q cycloalkyl refers to a cycloalkyl group having from 3 to q carbon atoms
  • C3-10 cycloalkyl encompasses inter alia cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl;
  • Ci_ q alkoxy refers to an linear or branched alkoxy group having from 1 to q carbon atoms; for example Ci_ 2 o alkoxy encompasses inter alia methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, 1 ,4- dimethylpentyloxy, hexyloxy, heptyloxy, octyloxy, 1 ,5-dimethylhexyloxy, nonyloxy, decyloxy, 4-ethyl- 1 ,5-dimethylhexyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy and eicosyloxy;
  • alkylene means a linear or branched alkylene group; e.g. propylene, and e.g. propylene can be connected via its C I and C2 carbon atoms (a branched alkylene group), or via its C I and C3 carbon atoms (linear alkylene group);
  • 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;
  • TMSCN (CH 3 ) 3 SiCN i.e. trimethylsilylcyanide
  • Trityl means the trityl cation, i.e. [Ph 3 C] ;
  • STEP1 comprises a reaction REAC1, wherein compound of formula (Al)
  • CAT ACID is selected from the group consisting of HF, HCl, HBr, HI, HN0 3 , H 2 S0 3 , H 2 S0 4 , NaHS0 4 , Oleum, KHS0 4 , NaHC0 3 , KHC0 3 , H 3 P0 4 , H 3 P0 3 , HS0 3 F, HS0 3 C1,
  • AR is Phe or Phe substituted with 1 , 2 or 3 identical or different residues selected from the group consisting of halogen and CH 3 ;
  • Q20 is B, Al, Ga, In or Th;
  • Q21 is P, As, Sb or Bi
  • n 1, 2, 3 or 4; n+ n+
  • Cat is selected from the group consisting of inorganic cation CatlNORG and organic n+
  • CatINORG n+ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 14.,
  • CatORG is selected from the group consisting of CatORG- A , CatORG-B , CatORG- C + , [(CH 3 ) 3 SiFSi(CH 3 ) 3 ] + , Ph 3 C + , guanidinium and (H 2 (R18)N-R16-N(R19)H 2 ) 2+ ;
  • CatORG-A is (WR2R3R4R5) ,
  • W is a nitrogen or phosphorus
  • R2, R3, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_ 2 o alkyl, Ci_ 2 o
  • R2 and R3 together are a hydrocarbon chain and form together with W a 5- to
  • R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_ 2 o alkyl, Ci_ 2 o perfluoroalkyl, C 3 _io cycloalkyl and C 6 -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) + ,
  • 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_ 2 o alkyl, C 2 _s alkenyl, Ci_ 2 o
  • CatORG-C + is (YR9R10R11) + ,
  • Y is sulphur
  • R9, RIO and Rl 1 are identical or different and independently from each other selected from the group consisting of H, Ci_ 2 o alkyl, Ci_ 2 o
  • R9 and R10 together are a hydrocarbon chain and form together with Y a 5- to
  • Rl 1 is selected from the group consisting of H, Ci_ 2 o alkyl, Ci_ 2 o perfluoroalkyl, C3-10 cycloalkyl and C 6 -io aryl; the residues R2, R3, R4, R5, R6, R7, R8, R9, R10 and Rl 1 are, independently from each other, unsubstituted or, where applicable, substituted by 1, 2, 3, 4, 5 or 6 substituents selected from the group consisting of Ci_ 4 alkyl, C 3-10 cycloalkyl, C 2 _s alkenyl, phenyl, benzyl, halogen, cyano and Ci_ 4 alkoxy; in any of said hydrocarbon chains formed by R2 and R3, by R4 and R5, by R6 and R7, and by R9 and R10, 1 or 2 carbon atoms of said hydrocarbon chains can be exchanged for 1 or 2 heteroatoms respectively, said one or two heteroatoms being selected from the group consisting of O, N and S; in
  • R16 is selected from the group consisting of C 2 _s alkylen, C 3 _s cycloalkylen, phenylen,
  • R17 is selected from the group consisting of CH 2 -CH 2 , CH 2 -CH 2 -CH 2 , CH 2 -C(H)(CH 3 )-
  • R18 and R19 are identical or different and independently from each other selected from the group consisting of H, Ci_s alkyl, C 3 _s cycloalkyl, phenyl and benzyl;
  • nl is an integer from 1 to 20.
  • n 2, 3 or 4;
  • m is 3 or 4;
  • n is 1 or 2, also in connection with any of the embodiments disclosed in the specification.
  • CAT ACID is selected from the group consisting of HF, HCl, HBr, H 2 S0 4 ,
  • Q20 is B, Al or Ga
  • Q21 is P, Sb or Bi
  • XI is F, CI or Br. More preferably, CAT ACID is selected from the group consisting of HF, HCl, HBr, H 2 S0 4 , Oleum, H 3 P0 4 , HS0 3 F, HS0 3 C1, CH 3 COOH, CF 3 COOH, methansulfonic acid, AR- S0 3 H, CF 3 S0 3 H HCN, HQ20(X1)4, polymolybdate, polytungstate, and mixtures thereof;
  • AR is Phe substituted with 1 residue selected from the group consisting of F, CI and CH 3 ;
  • Q20 is B, Al or Ga;
  • XI is F, CI or Br.
  • CAT ACID is selected from the group consisting of HF, HCl, H 2 SO 4 , Oleum, H 3 PO 4 , HSO 3 F, HSO 3 CI, CH 3 COOH, CF 3 COOH, methansulfonic acid, AR- SO 3 H, CF 3 SO 3 H HCN, HQ20(X1)4, and mixtures thereof;
  • AR is Phe substituted with 1 residue selected from the group consisting of F, CI and CH 3 ;
  • Q20 is B, Al or Ga
  • XI is F or CI.
  • CAT ACID is selected from the group consisting of HF, HCl, H 2 S0 4 , Oleum,
  • HSO 3 F HSO 3 CI, CF 3 COOH, methansulfonic acid, AR-SO 3 H, CF 3 SO 3 H and mixtures thereof;
  • AR is Phe substituted with CH 3 . More especially, CATACID is CF 3 SO 3 H.
  • CatINORG n+ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11.,
  • CatINORG n+ 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 NH 4 + ; even more preferably, CatINORG n+ is selected from the group consisting of Li + , Na + , K + , Rb + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ti 4+ , Ti 3+ , Zr 4+ , Zr 3+ , Hf 4 *, Hf 3+ , V 4+ , V 3+ , V 2+ , Nb 4+ , Ta 4+ , Cr 3+ , Mo 4+ , Mo 3+ , Mo 2+ , W 4+ , W 3+ , W 2+ , Mn 4+ , Mn 3+ , Mn 2+ , Fe 4
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , Mg 2+ , Ca 2+ ,
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , Mg 2+ , Ca 2+ , Ti 4+ , V 4+ , V 3+ , V 2+ , Cr 3+ , Fe 4+ , Fe 3+ , Fe 2+ , Co 4+ , Co 3+ , Co 2+ , Cu 4+ , Cu 3+ , Cu 2+ , Cu + ,
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , 2+ ⁇ ⁇ 4+ 3+ 4+ 3+ 2+ 4+ 3+ 2+ 4+ 3+ 2+ ⁇ +
  • CatINORG n is selected from the group consisting of Li + , Na + , K + , NH 4 + , Ag + ,
  • CatINORG n is selected from the group consisting of Li + , Na + , K + , NH 4 + ,
  • CatlNORG is Li + , Na + , K + , Ag + , Mg 2+ , or Zn 2+ ; especially in particular, CatINORG n+ is Li + , K + , Ag + , Mg 2+ , or Zn 2+ ; more especially in particular, CatINORG n is Li + , K + or Ag + .
  • n in CatlnORG is 1 or 2.
  • CatORG contains a heteroatom selected from the group consisting of nitrogi phosphorus, sulfur and oxygen;
  • CatORG n contains a heteroatom selected from the group consisting of
  • R16 is selected from the group consisting of C 2 _ 6 alkylen, C5-6 cycloalkylen, phenylen,
  • R17 is selected from the group consisting of CH 2 -CH 2 , CH 2 -CH 2 -CH 2 and CH 2 -CH 2 -CH 2 -CH 2 ;
  • R18 and R19 are identical or different and independently from each other selected from the group consisting of H, Ci_ 4 alkyl, C 5 -6 cycloalkyl, phenyl and benzyl; nl is an integer from 1 to 10;
  • R16 is selected from the group consisting of C 2 _ 4 alkylen, C 6 cycloalkylen, phenylen,
  • R17 is selected from the group consisting of CH 2 -CH 2 and CH 2 -CH 2 -CH 2 ;
  • R18 and R19 are identical and selected from the group consisting of H, Ci_ 4 alkyl,
  • nl is an integer from 1 to 6;
  • n is (H 2 (R18)N-R16-N(R19)H 2 ) 2+ ;
  • R16 is selected from the group consisting of C 2 _ 4 alkylen, phenylen and C(H)(phenyl); R18 and R19 are identical and selected from the group consisting of H, Ci_ 4 alkyl, C 5 -6 cycloalkyl, phenyl and benzyl;
  • CatORG n+ is (H 3 N-CH 2 -CH 2 -NH 3 ) 2+ .
  • n in CatORG is 1.
  • CatORG n+ 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,
  • pyrrolidinium pyrrolinium, pyrrolium, pyrazolium, imidazolium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1 ,3-dioxolium, pyrylium, thiopyrylium,
  • CatORG is selected from the group consisting of
  • R20, R21 , R23 are identical or different and independently from each other
  • R22 is Ci_ 2 o alkyl, C3-10 cycloalkyl or allyl; preferably,
  • R20, R21 , R23 are identical or different and independently from each other
  • R22 is Ci_i4 alkyl, C 5 _s cycloalkyl or allyl; more preferably,
  • R20, R21 , R23 are identical or different and independently from each other
  • R22 is Ci_8 alkyl, C 5 _ 7 cycloalkyl or allyl; even more referably, CatORG n+ is selected from the group consisting of
  • CatORG is selected from the group consisting of
  • Cat is a cation (Cat-Partl); cation (Cat-Partl) is CatINORG n+ or CatORG n+ , with CatlNORG selected from the group consisting of Li + , Na + , K + , NH 4 + , Ag + , Mg 2+ , Ca 2 and Zn 2+ ;
  • 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 and n are as defined above, also with all their embodiments,
  • Cat-Part 1 preferably Cat is cation (Cat-Part 1).
  • compound of formula (I) is selected from the group consisting of compound of formula (1), compound of formula (2), compound of formula (3), and mixtures thereof.
  • mol equivalents from 1 to 40 mol equivalents, more preferably 4 to 35 mol equivalents, even more preferably from 5 to 25 mol equivalents, especially from 5 to 15 mol equivalents, of trimethylsilylcyanide are used in REACl, the mol equivalents being based on the molar amount of the anion [(BF 4 ) ] of compound of formula (Al).
  • the reaction temperatures of REACl is preferably from -75 to 150°C, more preferably from - 50 to 120°C, more preferably from -50 to 100°C, even more preferably -50 to 80°C.
  • reaction temperatures of REACl is preferably from -10 to 150°C, more preferably from -10 to 120°C, more preferably from 0 to 100°C, even more preferably 10 to 80°C.
  • REACl can be done in a closed system and at the pressure caused by the chosen temperature.
  • the reaction time of REACl is preferably from 15 min to 96 h, more preferably from 20 min to 84 h, even more preferably from 20 min to 48 h, especially from 20 min to 24 h, more especially from 20 min to 12 h, even more especially from 20 min to 6 h.
  • REACl 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.
  • compound of formula (I) can be isolated by standard methods such as evaporation of volatile components, extraction, washing, drying, concentration,
  • the reaction product is treated with hydrogen peroxide, preferably with aqueous hydrogen peroxide.
  • reaction product is mixed with aqueous hydrogen peroxide to provide a mixture MIXT.
  • 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.
  • mol equivalents 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).
  • MIXT is stirred for 5 min to 24 h, more preferably for 10 min to 20 h.
  • MIXT is stirred at a temperature TEMPMIXT, TEMPMIXT is preferably from ambient temperature to 100°C. After treatment with hydrogen peroxide, MIXT is preferably filtrated. The residue of the filtration is preferably washed with a solvent WASHMIXT, WASHMIXT is preferably water or an ether such as diethylether or dichloromethane.
  • REAC1 can be done in the presence of a compound CAT
  • CAT is a Lewis Acid selected from the group consisting of Lewis Acids derived , that is based on, the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 1 1., 12., 13., 14., 15. and 16. group of the periodic table, zeolite, guanidinium[ANIO] and mixtures thereof;
  • CAT is selected from the group consisting of [(CH 3 ) 3 SiFSi(CH 3 ) 3 ][ANIO], Q1(R27) 3 , guanidinium[ANIO], (R26) 3 C[ANIO], adamantyl[ANIO], [(R24) 3 0][ANIO], [(R25) 3 Si][ANIO], Q2(R36)(R28) 3 , Q3(R29) 3 , Q4(R30) 5 , Q5(R32) 3 , Q6(R33) 2 , Q7(R31), Q8(R34) 2 , Q9(R35) 3 , Q10(R37) 2 , Q1 1(R38), zeolite and mixtures thereof;
  • CAT is selected from the group consisting of
  • CAT is selected from the group consisting of [(CH 3 ) 3 SiFSi(CH 3 ) 3 ][ANIO],
  • CAT is selected from the group consisting of [(CH 3 ) 3 SiFSi(CH 3 ) 3 ][ANIO], Si(Cl)(C 6 H 5 ) 3 , BF 3 , BC1 3 , BBr 3 , B(Ci_ 4 alkyl) 3 , B(C 6 F 5 ) 3 , A1F 3 , A1C1 3 , Al(Ci_ 4 alkyl) 3 , A1(C 6 F 5 ) 3 , GaF 3 , GaCl 3 , (Ph) 3 C[ANIO], (CH 3 ) 3 C[ANIO], [(Ci_ 3 alkyl) 3 0][ANIO], [(Ci_ 4 alkyl) 3 Si][ANIO], Si(halogen) 4 , Si(Ci_i 0 alkyl) 4 , TiF 4 , TiCl 4 , P(halogen) 3 , P(CN) 3 , SbF 3 , Sbl 3 , S
  • CAT is selected from the group consisting of [(CH 3 ) 3 SiFSi(CH 3 ) 3 ][ANIO], Si(Cl)(C 6 H 5 ) 3 , BF 3 , BC1 3 , B(C 6 F 5 ) 3 , A1C1 3 , GaF 3 , GaCl 3 , Ph 3 C[ANIO], [(C 1-4
  • CAT is selected from the group consisting of [(CH 3 ) 3 SiFSi(CH 3 ) 3 ][ANIO], Si(Cl)(C 6 H 5 ) 3 , BF 3 , BC1 3 , B(C 6 F 5 ) 3 , A1C1 3 , GaF 3 , GaCl 3 , Ph 3 C[ANIO], SiCl 4 , TiF 4 , TiCl 4 ,
  • CAT is selected from the group consisting of
  • CAT is selected from the group consisting of
  • SiCl 4 TiF 4 , TiCl 4 , P(CN) 3 , PF 5 , PC1 5 , SbF 5 , NbCl 5 , CrCl 3 , FeCl 3 , MnCl 2 , SiCl 4 , zeolite and mixtures thereof;
  • CAT is selected from the group consisting of BF , B(C 6 F 5 )
  • CAT is [(CH 3 ) 3 SiFSi(CH 3 ) 3 ][ANIO], B(C 6 F 5 ) 3 GaF 3 , GaCl 3 , TiF 4 , TiCl 4 , PF 5 , PC1 5 , SbF 5 , Ph 3 C[ANIO], zeolite or mixtures thereof;
  • CAT is [(CH ) SiFSi(CH ) ][ANIO], B(C 6 F 5 )
  • CAT is B(CeF 5 ) 3 GaF 3 , GaCl 3 , TiF 4 , TiCl 4 , PF 5 , PC1 5 , SbF 5 , Ph 3 C[ANIO], zeolite or mixtures thereof; in an especially very preferred embodiment, CAT is B(CeF 5 ) 3 GaF 3 , GaCl 3 , TiF 4 , TiCl 4 , PF 5 ,
  • Ql is selected from the group consisting of B, Al and Ga;
  • R27 is selected from the group consisting of Ci_io alkoxy, halogen, Ci_io alkyl, CN, SCN and R24 is CLIO alkyl;
  • R25 is Ci_io alkyl
  • Pv26 is selected from the group consisting of CN, SCN, Ph and C 1-10 alkyl;
  • Q2 is selected from the group consisting of Si and Ti;
  • Pv28 and R36 are identical or different and independently from each other selected from the group consisting of C 1-10 alkoxy, halogen, C 1-10 alkyl, CN, SCN and C 6 F 5 ;
  • Q3 is selected from the group consisting of P, Sb and Bi;
  • R29 is selected from the group consisting of C 1-10 alkoxy, halogen, CN, SCN, C 1-10 alkyl and C 6 F 5 ;
  • Q4 is selected from the group consisting of P, Sb and Nb;
  • R30 is selected from the group consisting of C 1-10 alkoxy, halogen, CN, SCN, C 1-10 alkyl and C 6 F 5 ;
  • 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;
  • R35 is selected from the group consisting of halogen, CN, and SCN;
  • R37 is halogen
  • R38 is halogen
  • ANIO is selected from the group consisting of [P(R40) 6 - m i(R41) m i] " , [B(R42) 4 _ m 2(R43) m2 ] " ,
  • 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;
  • ntl 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 6 F 5 , CN, SCN, F, CI, Br and I;
  • n2 0, 1, 2 or 3;
  • ANIO is selected from the group consisting of P(R40) 6 , B(R42) 4 , F , CI , Br , I , CN “ and SCN “ ;
  • R40 is selected from the group consisting of CN, SCN, F, CI, Br and I;
  • R42 is selected from the group consisting of C 6 F5, CN, SCN, F, CI, Br and I; more preferably, ANIO is selected from the group consisting of P(R40) 6 , B(R42) 4 , F , CI ,
  • R40 is selected from the group consisting of CN, SCN, F, CI and Br;
  • R42 is selected from the group consisting of C 6 F 5 , CN, SCN, F, CI and Br.
  • R24 is Ci_ 4 alkyl
  • R25 is Ci_ 7 alkyl
  • R26 is selected from the group consisting of Ph and Ci_ 4 alkyl
  • R27 is selected from the group consisting of Ci_ 7 alkoxy, CI, F, Br, Ci_ 7 alkyl and CeF 5 ; 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 6 F 5 ; even more preferably,
  • R24 is methyl or ethyl
  • R25 is Ci_4 alkyl
  • R26 is Ph or methyl
  • R27 is selected from the group consisting of Ci_ 3 alkoxy, CI, F, Ci_ 3 alkyl and C 6 F 5 .
  • [ANIO] is [B(C 6 F 5 ) 4 ] or [BF 4 ].
  • CAT is selected from the group consisting of
  • CAT is selected from the group consisting of [(CH 3 ) 3 SiFSi(CH 3 ) 3 ][B(C 6 F 5 ) 4 ], Si(Cl)(C 6 H 5 ) 3 , BF 3 , BC1 3 , B(C 6 F 5 ) 3 , A1C1 3 , GaF 3 , GaCl 3 , Ph 3 C[BF 4 ], SiCl 4 , TiF 4 , TiCl 4 , P(CN) 3 , SbF 3 , Bi(CN) 3 , PF 5 , PC1 5 , SbF 5 , NbCl 5 , CrCl 3 , FeCl 3 , MnCl 2 , AgCN, CuCl, CuCl 2 , ZnF 2 , CaCl 2 , KF, zeolite, and mixtures thereof; preferably, CAT is selected from the group consisting of [(CH 3 ) 3 SiFSi(CH 3 ) 3 ][B(C
  • PCI 5 PCI 5 , SbF 5 , zeolite, and mixtures thereof;
  • CAT is [(CH 3 ) 3 SiFSi(CH 3 )3][B(C 6 F 5 ) 4 ], B(C 6 F 5 ) 3 GaF 3 , GaCl 3 , TiF 4 , TiCl 4 , PF 5 , PCI 5 , SbF 5 , Ph 3 C[BF 4 ], zeolite or mixtures thereof;
  • CAT is B(C 6 F 5 ) 3 , GaF 3 , GaCl 3 , TiF 4 , TiCl 4 , PF 5 , PC1 5 , SbF 5 , Ph 3 C[BF 4 ], zeolite or mixtures thereof.
  • CAT is selected from the group consisting of
  • CAT is [Ph 3 C][BF 4 ].
  • CAT can be used in immobilized form on a carrier CARR;
  • CARR is a carrier conventionally used for immobilizing catalysts in heterogeneously
  • 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 , Fe 2 C>3, C0 3 O 4 ,
  • Zeolite can be any zeolite, preferably montmorrilonte or bentonite, more preferably
  • Compound of formula (Al) and CAT can be one and the same compound, therefore in one preferred embodiment, compound of formula (Al) is different from CAT;
  • compound of formula (Al) is identical with CAT.
  • mol equivalents Preferably, from 0.0001 to 40 mol equivalents, more preferably 0.001 to 35 mol equivalents, even more preferably from 0.005 to 25 mol equivalents, especially from 0.005 to 25 mol equivalents, more especially from 0.005 to 15 mol equivalents, even more especially from 0.005 to 5 mol equivalents, of CAT are used in REAC1, the mol equivalents being based on the combined molar amount of the anion [(BF 4 ) ] of compound of formula (Al), CATACID and CAT.
  • from 0.01 to 40 mol%, more preferably 0.1 to 35 mol%, even more preferably 0.1 to 25 mol%, especially from 0.5 to 15 mol%, more especially from 0.5 to 10 mol%, even more especially from 0.5 to 5 mol%, of CAT are used in REAC1, the mol% being based on the combined molar amount of the anion [(BF 4 ) ] of compound of formula (Al), CATACID and CAT.
  • CATACID a compound of formula (Al)
  • mol% being based on the combined molar amount of of the anion [(BF 4 ) ] compound of formula (Al)
  • CATACID and, if present, CAT.
  • the method comprises additionally to STEP1 a step STEP2, STEP2 is done after STEP1;
  • STEP2 comprises a reaction REAC2, REAC2 is a metathesis reaction wherein cation Cat in n+
  • REAC2 is a metathesis reaction, also called a salt-exchange reaction.
  • a metathesis reaction such as REAC2 a first cation in a first salt is exchanged for a second cation, said second cation coming from a second salt.
  • REAC2 provides for the preparation of a compound of formula (I-Cat-r);
  • Cat-r is selected from the group consisting of CatlNORG and CatORG and is
  • r is 1, 2, 3 or 4;
  • AnINORG q is an anion selected from the group consisting of halide, OH “ , CN , OCN , SCN ⁇ , N 3 ⁇ , sulfate, hydrogensulfate, nitrate, C0 3 2" , HC0 3 “ , BF 4 " , PF 6 “ , SbF 6 " , CF 3 S0 3 “ (CF 3 S0 2 ) 2 N ⁇ , (FS0 2 ) 2 N , C 1-6 alkyl-S0 3 " , C 1-6 alkyl-0-S0 3 " ,
  • Ci_ 2 o monocarboxylic aliphatic acids anions of Ci_ 2 o monocarboxylic aliphatic acids, mono- and dianions of C 2 _ 6 dicarboxylic aliphatic acids, anions of benzoic acids, mono- and dianions of phthalic acids, of isophthalic acids and of terephthalic acids, N(CN) 2 , C(CN) 3 " , B(CN) 4 " , P(CN) 6 “ , Sb(CN) 6 “ , and mixtures thereof; r+ n+ n+
  • Cat-r , r, CatlNORG and CatORG are as defined above, also with all their
  • AnINORG is an anion selected from the group consisting of halide, OH “ , CN , sulfate, hydrogensulfate, nitrate, C0 3 2" , HC0 3 “ , BF 4 " , PF 6 “ , CF 3 S0 3 “ , (CF 3 S0 2 ) 2 N ⁇ ,
  • AnINORG* “1 is an anion selected from the group consisting of Br , CI , OH " , GST, sulfate, hydrogensulfate, C0 3 2 , HC0 3 , acetate, and mixtures thereof;
  • AnINORG* “1 is an anion selected from the group consisting of CI , OH " GST, sulfate, hydrogensulfate, C0 3 2 , HC0 3 , acetate, and mixtures thereof.
  • AnINORG is an anion selected from the group consisting of halide, OH “ , CN ⁇ , OCN , SCN ⁇ , N 3 ⁇ , sulfate, hydrogensulfate, nitrate, C0 3 2" , HC0 3 “ , BF 4 " , PF 6 “ , SbF 6 " , CF 3 S0 3 “ , (CF 3 S0 2 ) 2 N ⁇ , (FS0 2 ) 2 N ⁇ , C I _ 6 alkyl-S0 3 " , Ci_ 6 alkyl-0-S0 3 " ,
  • r is 1 or 2.
  • a compound of formula (I-Cat-r) with Cat-r being CatORG is prepared by exchange of a Cat n being a CatINORG n in compound of formula (I) for a CatORG n+ .
  • Said CatORG n is provided in REAC2 preferably in form of a compound of formula (I-
  • CatORG (CatORG n )q(AnINORG q" ) n (I-CatORG) wherein
  • Cat n+ , n, CatORG n+ , CatINORG n+ , q and AnINORG q are as defined above, also with all their embodiments.
  • the cation different from Cat that is preferably Cat-r , is present in n+
  • compound of formula (I) and compound of formula (I-Cat-n) are present in n+
  • the molar amount of compound of formula (I-Cat-n) is such, that from r+
  • the reaction temperatures of REAC2 is preferably from 0 to 250 °C, more preferably from 10 to 200 °C, even more preferably from 10 to 150 °C, especially from 10 to 100°C, more especially from 10 to 50°C.
  • the REAC2 is preferably carried out in a solvent SOLV2, SOLV2 is preferably selected from the group consisting of water, DCM, ethyl acetate, C5-10 alkane, and mixtures thereof.
  • C5-10 alkane is preferably pentane, hexane or heptane.
  • REAC2 is done in DCM or in a biphasic solvent system of water and DCM.
  • REAC2 can also be carried out in the absence of a solvent or in a solvent in which the inorganic salt formed as side product is sparingly soluble or insoluble.
  • the amount of solvent is preferably from 2 to 40 fold, more preferably from 3 to 20 fold, of the weight of compound of formula (I).
  • REAC2 can be done in a closed system and at the pressure caused by the chosen temperature.
  • the reaction time of REAC2 is preferably from 15 min to 96 h, more preferably from 15 min to 48 h, even more preferably from 15 min to 24 h.
  • REAC2 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. Subsequent to REAC2 there can be a further metathesis reaction or further metathesis reactions.
  • 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.
  • the organic phase is preferably washed, preferably with water, then preferably dried, preferably with Na 2 S0 4 , K 2 C0 3 , CaCl 2 or MgS0 4 , and finally evaporated.
  • the method of instant invention can comprise additionally to STEP1 a
  • step STEP 1-1 STEPl-1 is done after STEP1 ;
  • STEP 1-1 comprises a reaction REACl-1, wherein compound of formula (I), obtained in
  • REACl-1 is done in the presence of CAT ACID, in the presence of CAT, or in the presence of both CAT ACID and CAT;
  • CAT ACID is commercially available compounds or can be prepared according to known methods.
  • Compounds of formula (Al) are commercially available depending on the cation n+
  • IR-spectra were recorded on a Nicolet 380 FT-IR spectrometer. Measurements were done at room temperature .
  • Melting points and temperature of decomposition Td ec were measured on a DSC 823e from Mettler-Toledo. The calibration was carried out with the melting points of In (156.6 ⁇ 0.3°C) and Zn (419.6 ⁇ 0.7°C) with an heating rate of 5 K per min.
  • RAMAN (460 mW, 150 scans, v in cm “1 ): 2964 (7), 2933 (10), 2876 (10), 2746 (1), 1453 (4), 1327(2), 1153(1), 1137 (2), 911 (2), 880 (1), 766 (1), 256 (2), 79 (1)
  • Tetrafluoroboric acid (18 mL, 35 wt% aqueous solution, 88 mmol) was cooled to ca. 0 °C.
  • n-Pr 3 N (17 ml, 89 mmol) was added dropwise to the aqueous solution.
  • CH 2 C1 2 three times a 50 ml.
  • the combined organic phases were dried over anhydrous Na 2 S0 and filtered After evaporating the solvent and drying the white solid in vacuo 18.9 g (93 %, 82 mmol) of [(n-Pr) 3 NH][BF ] were obtained.
  • Example 4 [(n-Bu) 4 ][BF 4 ] (618 mg, 1.88 mmol), prepared according to Preparation Description A, triflic acid, TiCl 4 (7 mol%, 25 mg, 0,17 mol triflic acid and 9 mol%, 40 mg, 0.21 mol TiCl 4 , the mol% being based on the combined molar amount of [(n-Bu) 4 N][BF 4 ], triflic acid and TiCl 4 ) and (CH 3 ) 3 SiCN (1.9 g, 19 mmol) were stirred under argon atmosphere and ambient temperature. After 3 hours of stirring an n B NMR spectrum was measured. According to n B NMR the reaction mixture contained only compound of formula (1).
  • GaCl 3 was used instead of TiCl (7 mol% GaCl 3 , the mol% being based on the combined molar amount of [(n-Bu) 4 N][BF 4 ], GaCl 3 , and triflic acid (15 mol% instead of 9 mol%)).
  • SbF 5 was used instead of TiCl 4 (7 mol% SbF 5 , the mol% being based on the combined molar amount of [(n-Bu) 4 N] [BF ] , SbF 5 , and triflic acid ( 10 mol% instead of 9 mol%).

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Abstract

L'invention concerne un procédé de préparation de composés cyano de bore comportant 1, 2, 3 ou 4 résidu(s) cyano et qui sont représentés par la formule (I): [Catn+] [(BF4-m(CN)m)- ]n, ledit procédé consistant à faire réagir le composé représenté par la formule (A1) avec du triméthylsilylcyanure en présence d'un acide de Bronstedt; [Catn+] [(BF4)- ]n (A1); n+Cat représente un cation, m représente 1, 2, 3 ou 4 et n représente 1, 2, 3 ou 4. Dans un mode de réalisation spécifique, le procédé sert à préparer les trois composés suivants : [(n-Bu)4N][BF(CN)3] (1), [(n-Pr)3NH][BF(CN)3] (2), [(n-Pr)3NH][B(CN)4] (3).
PCT/EP2016/057584 2015-04-09 2016-04-07 Procédé de préparation de composés cyano de bore avec un acide de bronstedt WO2016162400A1 (fr)

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