WO2015185183A1 - Procédé de préparation de sels incluant des anions monohydridocyanoborate - Google Patents

Procédé de préparation de sels incluant des anions monohydridocyanoborate Download PDF

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Publication number
WO2015185183A1
WO2015185183A1 PCT/EP2015/001009 EP2015001009W WO2015185183A1 WO 2015185183 A1 WO2015185183 A1 WO 2015185183A1 EP 2015001009 W EP2015001009 W EP 2015001009W WO 2015185183 A1 WO2015185183 A1 WO 2015185183A1
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Prior art keywords
formula
compound
trialkylsilyl
reaction
alkali metal
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PCT/EP2015/001009
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German (de)
English (en)
Inventor
Jan Arke Peter SPRENGER
Maik Finze
Lisa Alexandra BISCHOFF
Johannes LANDMANN
Nikolai IGNATYEV, (Mykola)
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Merck Patent Gmbh
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Publication of WO2015185183A1 publication Critical patent/WO2015185183A1/fr

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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

Definitions

  • the invention relates to a process for the preparation of alkali metal salts with monohydridotricyanoborate anions of Alkalimetalltetrahydridoborat, Alkalimetallmonocyanotrihydridoborat or
  • Alkali metal salts with monohydridotricyanoborate anions are known from published patent application WO 2012/163489 and serve, for example, as starting materials for the synthesis of monohydridotricyanoborate salts with preferably organic cations.
  • Such ionic liquids with monohydridotricyanoborate anions are for example as
  • Electrolyte component for electrochemical cells in particular for dye solar cells suitable.
  • WO 2012/163489 also describes the synthesis of these alkali metal salts, for example by the processes of claims 4 to 6.
  • Alkali metal salts with Dihydridodicyanoborat anions are from the
  • the trialkylsilyl cyanide is added in a threefold amount, based on the borate.
  • Alkali metal monohydridotricyanoborates to develop which emanate from readily available and relatively cheap starting materials.
  • the alternative process has short reaction times with good yield and good product purity.
  • alkali metal monohydridotricyanoborates from an alkali metal tetrahydridoborate, a
  • the alkali metal monohydridotricyanoborate is prepared by reacting an alkali metal tetrahydridoborate with trimethylsilyl cyanide.
  • the subject of the invention is therefore a process for the preparation of compounds of the formula I. [Me] + [BH (CN) 3 ] - I,
  • Me means an alkali metal
  • Me 1 represents an alkali metal which may be the same or different than Me
  • n 2, 3 or 4
  • Trialkylsilylhalogenids each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms
  • Alkali metals are the metals lithium, sodium, potassium, cesium or rubidium.
  • Me is preferably sodium or potassium, particularly preferably potassium.
  • the inventive method is preferred for the synthesis of sodium monohydridotricyanoborate or
  • Potassium monohydridotricyanoborate suitable The compounds of formula II are commercially available or accessible by known synthetic methods.
  • Me 1 may be an alkali metal selected from the group lithium, sodium, potassium, cesium or
  • Me 1 in formula II may be the same or different than Me in formula I.
  • Me 1 is preferably sodium or potassium. In compounds of the formula II, Me 1 is particularly preferably sodium.
  • a linear or branched alkyl group having 1 to 10 carbon atoms is, for example, methyl, ethyl, n-propyl, / 'so-propyl, n-butyl, sec-butyl, tert-butyl, r? Pentyl, n-hexyl, n Heptyl, n-octyl, ethyl-hexyl, n-nonyl or n-decyl.
  • Trialkylsilyl cyanides are commercially available or are accessible by known synthetic methods.
  • the alkyl groups of the trialkylsilyl cyanide may be the same or different.
  • the alkyl groups of the trialkylsilyl cyanide have 1 to 10 C atoms, preferably 1 to 8 C atoms, particularly preferably 1 to 4 C atoms.
  • the alkyl groups of the trialkylsilyl cyanide are preferably the same if they are alkyl groups having 1 to 4 C atoms.
  • An alkyl group of the trialkylsilyl cyanide is preferably different when it is an alkyl group of 5 to 10 C atoms or 5 to 8 C atoms.
  • Suitable examples of trialkylsilyl cyanides are trimethylsilyl cyanide, triethylsilyl cyanide, triisopropylsilyl cyanide, tripropylsilyl cyanide,
  • Octyldimethylsilylcyanide butyldimethylsilylcyanide, f-butyldimethylsilylcyanide or tributylsilylcyanide.
  • Particularly preferred trimethylsilyl cyanide is used, which is commercially available or can be prepared in situ.
  • the trialkylsilyl cyanide as described or preferred as described or selected from the group consisting of trimethylsilyl cyanide, triethylsilylcyanide, triisopropylsilylcyanide, tripropylsilylcyanide, octyldimethylsilylcyanide, butyldimethylsilylcyanide, t-butyldimethylsilylcyanide or tributylsilylcyanide is not prepared in situ.
  • the trialkylchlorosilane, trialkylbromosilane or trialkyliodosilane is commercially available or can be prepared by standard methods.
  • Trialkylbromosilane or trialkyliodosilane can be prepared in situ from
  • Trialkylchlorosilane and an alkali metal bromide or alkali metal iodide are provided.
  • trialkylsilyl chlorides for the process according to the invention (or synonymously trialkylchlorosilanes), trialkylsilyl bromides (synonymous with trialkylbromosilanes) and / or trialkylsilyl iodides (synonymous thereto
  • Trialkyliodosilanes have alkyl groups which are each independently linear or branched and have 1 to 10 carbon atoms.
  • alkyl groups of the trialkylsilyl halide may be the same or
  • the alkyl groups of the trialkylsilyl halide preferably have 1 to 8 C atoms, particularly preferably 1 to 4 C atoms.
  • the alkyl groups of the trialkylsilyl halide are preferably the same if they are alkyl groups having 1 to 4 carbon atoms.
  • An alkyl group of the trialkylsilyl halide is preferably different when it is an alkyl group of 5 to 10 C atoms or 5 to 8 C atoms.
  • the trialkylsilyl halide is a trialkylsilyl chloride.
  • Suitable trialkylsilyl chlorides are trimethylsilyl chloride (or synonymously trimethylchlorosilane), triethylsilyl chloride, triisopropylsilyl chloride,
  • Tripropylsilyl chloride octyldimethylsilyl chloride, butyldimethylsilyl chloride, t-butyldimethylsilyl chloride or tributylsilyl chloride. Particular preference is given to using trimethylsilyl chloride. Very particularly preferred
  • Suitable trialkylbromosilanes are trimethylbromosilane (or synonymously trimethylsilylbromide), triethylsilylbromide, triisopropylsilylbromide,
  • Particularly preferred trimethylsilyl bromide is used in admixture with trimethylsilyl chloride.
  • Suitable trialkyliodosilanes are trimethyliodosilane (or synonymously trimethylsilyl iodide), triethylsilyl iodide, triisopropylsilyl iodide,
  • Particularly preferred trimethylsilyl iodide is used in admixture with trimethylsilyl chloride.
  • trialkylsilyl halide or a mixture of trialkylsilyl halides as described above or described as being preferred, in a total amount of from 1 to 20 mol%, based on the amount of the trialkylsilyl cyanide used.
  • Trialkylsilylcyanids It is preferable to mix the starting materials in an inert gas atmosphere whose oxygen content is at most 1000 ppm. It is particularly preferred if the oxygen content is less than 500 ppm, very particularly preferably not more than 100 ppm.
  • the water content of the reagents and the inert gas atmosphere is at most 1000 ppm. It is particularly preferred if the water content of the reagents and the atmosphere is less than 500 ppm, quite
  • Another object of the invention is therefore a method as described above or described as preferred, wherein the reaction of the compound of formula II with trialkylsilyl cyanide takes place in the presence of 1 to 20 mol% trialkylsilyl halide, based on the amount of Trialklylsilylcyanids used.
  • reaction according to the invention at a reaction temperature of 200 to 275 ° C instead.
  • reaction according to the invention at a pressure between 5 and 25 bar instead.
  • the reaction according to the invention takes place at a reaction temperature of 200 ° C. to 275 ° C. and a pressure of between 5 and 25 bar.
  • the reaction according to the invention takes place with a compound of the formula II in which n is 4, ie with an alkali metal tetrahydridoborate.
  • Trialkylsilylcyanid as described above, is added with a 6-fold to 15-fold amount, based on the amount of
  • Another object of the invention is therefore the method as described above or described as preferred, characterized in that the reaction of the compound of formula II wherein n is 4, is carried out with a 6-fold to 15-fold amount of trialkylsilyl cyanide, based on the amount the compound of formula II.
  • n is 2 or 3 or in which n is very particularly preferably 2.
  • Trialkylsilylcyanid as described above, is added with a 4-fold to 13-fold amount, based on the amount of the compound of formula II.
  • Another object of the invention is therefore the method as described above or described as preferred, characterized in that the reaction of the compound of formula II, wherein n is 2 or 3, is carried out with a 4-fold to 13-fold amount of trialkylsilyl cyanide, based on the amount of the compound of formula II.
  • Another object of the invention is therefore the inventive method, as described above, characterized in that the reaction is followed by a purification step.
  • the metal cation exchange is a
  • a preferred method for the metal cation exchange or preferably the alkali metal cation exchange for example, the reaction of the resulting reaction mixture with a corresponding carbonate (Me) 2C03 and / or a corresponding hydrogen carbonate MeHC03, wherein Me corresponds to the alkali metal Me of the desired end product of the formula I.
  • reaction mixture obtained from the reaction is cooled to room temperature and all volatile components are removed in vacuo.
  • the resulting solid is then taken up in an organic solvent and water and mixed with the
  • Me corresponds to the alkali metal Me of the desired end product of the formula I.
  • the phases are separated and the organic solvent is separated off.
  • the product obtained can be dried as usual or further purified. Preferably, this purification is followed by recrystallization.
  • Another object of the invention is therefore the inventive method, as described above, wherein the metal cation exchange, preferably the alkali metal cation exchange, during the
  • Another object of the invention is therefore the inventive method, as described above, wherein the metal cation exchange by reaction with the compound (Me2) C03 and / or the compound MeHCÜ3 takes place, wherein Me the alkali metal Me of the desired
  • reaction of the compound of the formula II as described above or described as preferred takes place without an organic solvent.
  • the reaction mixture in this embodiment of the process according to the invention form the compound of the formula II, the trialkylsilyl cyanide and the trialkylsilyl halide.
  • Another object of the invention is therefore the inventive method, as described above, wherein the reaction of the compound of formula II, as described above or described below as preferred, takes place without an organic solvent.
  • Suitable solvents are acetonitrile, propionitrile or benzonitrile.
  • the inventive method may now be a classic
  • [Kt] z + is an inorganic or organic cation and z corresponds to the charge of the cation.
  • Another object of the invention is therefore a process for the preparation of compounds of formula III
  • [Kt] z + is an inorganic or organic cation
  • Me means an alkali metal
  • [Kt] z + has the meaning of an organic cation or an inorganic cation, wherein the cation [Kt] z + does not have the
  • Me + corresponds to the compound of formula I and the anion A of the salt containing [Kt] z +
  • R 1 each independently represents a straight-chain or branched alkyl group having 1 to 12 C atoms
  • R 2 each independently represents a straight-chain or branched perfluorinated alkyl group having 1 to 12 C atoms and wherein in the formula of the salt [KtA] the electroneutrality is taken into account.
  • a perfluorinated linear or branched alkyl group having 1 to 4 C atoms is, for example, trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl, iso-heptafluoropropyl, / 7-nonafluorobutyl, sec-nonafluorobutyl or tert-nonafluorobutyl.
  • R2 similarly defines a linear or branched perfluorinated alkyl group having 1 to 12 C atoms, comprising the aforementioned perfluoroalkyl groups and, for example, perfluorinated n-hexyl, perfluorinated n-heptyl, perfluorinated n-octyl, perfluorinated ethylhexyl, perfluorinated A7-nonyl, perfluorinated n -Decyl, perfluorinated n-undecyl or perfluorinated n-dodecyl.
  • R2 is particularly preferably trifluoromethyl, pentafluoroethyl or
  • Nonafluorobutyl most preferably trifluoromethyl or
  • R1 is particularly preferably methyl, ethyl, n-butyl, n-hexyl or n-octyl, very particularly preferably methyl or ethyl.
  • Substituted malonates are, for example, the compounds methyl or ethyl malonate.
  • the organic cation for [Kt] z + is selected, for example, from iodonium cations, ammonium cations, sulfonium cations,
  • Thiouronium cations are guanidinium cations, tritylium cations or heterocyclic cations.
  • Preferred inorganic cations are metal cations of the metals of group 2 to 12 or also NO + or KbO + .
  • Preferred inorganic cations are Ag + , Mg 2+ , Cu + , Cu 2+ , Zn 2+ , Ca 2+ , ⁇ 3 + Yb 3 + La 3 + Sc 3 + j Ce 3 + Nd 3 + Tb 3 + Sm 3 + or complex (ligand-containing) metal cations, the rare earth, transition or noble metals such as rhodium, ruthenium, iridium, palladium, platinum, osmium, cobalt, nickel, iron, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, hafnium, thorium, Uranium, gold included.
  • the rare earth, transition or noble metals such as rhodium, ruthenium, iridium, palladium, platinum, osmium, cobalt, nickel, iron, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, hafnium,
  • the salting reaction of the salt of the formula I with a salt containing [Kt] z + , as described above, is advantageously carried out in water, temperatures of 0 ° -100 ° C., preferably 15 ° -60 ° C. being suitable. Particularly preferred is reacted at room temperature (25 ° C). However, the aforementioned salting reaction may alternatively take place in organic solvents at temperatures between -30 ° and 100 ° C. Suitable solvents here are acetonitrile, propionitrile, dioxane, dichloromethane, dimethoxyethane, dimethyl sulfoxide, tetrahydrofuran,
  • Dimethylformamide, acetone or alcohol for example methanol, ethanol or isopropanol, diethyl ether or mixtures of the above
  • the substances obtained are characterized by means of NMR spectra.
  • the NMR spectra are measured on solutions in deuterated acetone-De or in CD3CN on a Bruker Avance 500 spectrometer with deuterium lock.
  • the measurement frequencies of the different cores are: 1 H: 500.1 MHz, 11 B: 160.5 MHz and 13 C: 125.8 MHz.
  • Referencing is done with external reference: TMS for 1 H and 13 C spectra and BFs EtaO - for 11 B spectra.
  • Model (I) 100 mL working volume, empty space 140 mL with heating hood 10S; Model (II): approx. 200 mL
  • Trimethylsilyl cyanide 120 mL, 0.90 mol
  • trimethylchlorosilane, (CH 3 ) 3 SiCl (10.0 mL, 79.2 mmol) for 10 hours at 250 ° C (temperature is equivalent to the specifications of the temperature control of the heating hoods) heated.
  • the cooled reaction mixture is concentrated to dryness under reduced pressure and the solid obtained in a fine vacuum (1 x 10 3 mbar) dried.
  • the black solid is taken up in tetrahydrofuran (100 mL) and water (30 mL) and treated with K 2 CO 3 (20 g) and KHCO 3 (20 g).
  • the organic phase is separated, the aqueous phase extracted once more with THF (50 mL) and the combined organic phases are dried with K2CO3 (20 g).
  • the suspension is filtered, the solvent removed with a rotary evaporator and the black
  • the yield of K [BH (CN) 3] is 7.7 g (59.9 mmol), corresponding to 75% based on the borate used.
  • Trimethylsilyl cyanide 180 mL, 1.35 mol
  • trimethylchlorosilane, (CH3) 3SiCl 15.0 mL, 118.7 mmol
  • Heating hoods heated.
  • the maximum pressure in the autoclave is 20 bar.
  • the cooled reaction mixture is brought to reduced pressure under reduced pressure
  • a final purification of the crude product is carried out by crystallization from acetone by addition of dichloromethane.
  • the NMR data are in accordance with those described in WO2012 / 163489 and
  • Trimethylsilyl cyanide 220.0 mL, 1.65 mol was added.
  • the suspension is treated with trimethylchlorosilane (10.0 mL, 79.16 mmol) and the
  • K2CO3 (15 g) added.
  • the aqueous phase is extracted with THF (2 ⁇ 70 ml) and then treated with further K 2 CO 3 (15 g) and extracted again with THF (2 ⁇ 50 ml).
  • the combined organic phases are dried with K 2 CO 3 (80 g) and then concentrated to a residual volume of about 20 ml.
  • CH2Cl2 150 mL
  • colorless K [BH (CN) 3] is precipitated. This is dried in a fine vacuum to a final pressure of 3 ⁇ 10 -3 mbar.
  • the yield of K [BH (CN) 3] is 4.2 g (32.56 mmol), corresponding to 25% based on the borate used.

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  • Organic Chemistry (AREA)

Abstract

L'invention concerne un procédé de préparation de sels de métal alcalin incluant des anions monohydridotricyanoborate dérivés de tétrahydridoborate, de monocyanotrihydridoborate ou de dihydridodicyanoborate de métal alcalin: [Me]+ [BH(CN)3]- (I), [Me1]+ [BHn(CN)4-n]- (II), [Kt]z+ z[BH(CN)3]- (III).
PCT/EP2015/001009 2014-06-06 2015-05-15 Procédé de préparation de sels incluant des anions monohydridocyanoborate WO2015185183A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014008131.1A DE102014008131A1 (de) 2014-06-06 2014-06-06 Verfahren zur Herstellung von Salzen mit Monoydridocyanoborat-Anionen
DE102014008131.1 2014-06-06

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WO2015185183A1 true WO2015185183A1 (fr) 2015-12-10

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012163489A1 (fr) * 2011-05-31 2012-12-06 Merck Patent Gmbh Composés contenant des anions hydrido-tricyano-borate
WO2012163488A1 (fr) * 2011-05-31 2012-12-06 Merck Patent Gmbh Procédé de préparation de sels de dihydrurodicyanoborate
WO2012163490A1 (fr) * 2011-05-31 2012-12-06 Merck Patent Gmbh Formulations d'électrolyte
WO2015022048A1 (fr) * 2013-08-16 2015-02-19 Merck Patent Gmbh Hexacyanodiborates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012163489A1 (fr) * 2011-05-31 2012-12-06 Merck Patent Gmbh Composés contenant des anions hydrido-tricyano-borate
WO2012163488A1 (fr) * 2011-05-31 2012-12-06 Merck Patent Gmbh Procédé de préparation de sels de dihydrurodicyanoborate
WO2012163490A1 (fr) * 2011-05-31 2012-12-06 Merck Patent Gmbh Formulations d'électrolyte
WO2015022048A1 (fr) * 2013-08-16 2015-02-19 Merck Patent Gmbh Hexacyanodiborates

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GYÖRI B ET AL: "Preparation and properties of novel cyano and isocyano derivatives of borane and the tetrahydroborate anion", JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 255, 1 January 1983 (1983-01-01), pages 17 - 28, XP002679584, ISSN: 0022-328X *
YAO HAIJUN ET AL: "Organo-tricyanoborates as tectons: illustrative coordination polymers based on copper(I) derivatives", INORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, EASTON, US, vol. 44, no. 18, 5 September 2005 (2005-09-05), pages 6256 - 6264, XP002524309, ISSN: 0020-1669, [retrieved on 20050811], DOI: 10.1021/IC0506153 *

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