WO2023222245A1 - Procédé de production de composes organosiliciés - Google Patents

Procédé de production de composes organosiliciés Download PDF

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WO2023222245A1
WO2023222245A1 PCT/EP2022/063822 EP2022063822W WO2023222245A1 WO 2023222245 A1 WO2023222245 A1 WO 2023222245A1 EP 2022063822 W EP2022063822 W EP 2022063822W WO 2023222245 A1 WO2023222245 A1 WO 2023222245A1
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alkyl
alkenyl
alkoxy
heteroaryl
aryl
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PCT/EP2022/063822
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German (de)
English (en)
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Alexander David BECK
Stefan Haufe
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Wacker Chemie Ag
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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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/0827—Syntheses with formation of a Si-C bond
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0896—Compounds with a Si-H linkage
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/046—Alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon

Definitions

  • Co12204 / Be Process for the production of organosilicon compounds The invention relates to a process for the production of organosilicon compounds, in which at least one hydridosilane and at least one organic halide are electrochemically formed in the presence of at least one borane-containing catalyst and at least one conductive salt to form at least one Si- C bond can be implemented.
  • Methods for synthesizing organosilicon compounds are known. For example, US 2019/0337967 A1 and US 5,929,269 A describe processes for producing organosilicon compounds starting from hydridosilane. What these processes have in common is that the reaction takes place in the presence of a metal catalyst.
  • the Si-C bond is not formed by splitting off a halide, but rather by reacting a carbon double or triple bond with the substrate.
  • US 3,772,347 A describes a process in which organosilicon compounds are produced by reacting disilanes with organic halides in the presence of a noble metal catalyst. Processes for producing organosilicon compounds based on the conversion of organic halides with hydridosilane in the presence of an auxiliary base are described in WO 2014/009156 A1 and US 3,478,074. According to US 2011/0130585 A1, an auxiliary base can be dispensed with by increasing the temperature and reacting in the gas phase. Organosilicon compounds can also be produced by reacting halosilanes with organic halides.
  • Co12204 / Be 3 uses an inert anode, an undefined anode reaction can produce elemental halogen, which can trigger undesirable subsequent reactions, such as halogenation of the solvent. If an anode that is not completely inert is used, stoichiometric amounts of metal halides can form, which usually have to be laboriously processed and disposed of. The anode is also consumed in the reaction and must be replaced regularly. If, as disclosed in WO 2005/123811 A1 and US 5,538,618 A, a hydrogen anode is used, undefined anode reactions can be prevented by the targeted release of gaseous HCl. Furthermore, no stoichiometric amounts of metal halides are produced.
  • the electrode structure is complex and precious metals such as Pd or Pt cannot be dispensed with as a coating on the electrode surface. Furthermore, a continuous supply of the electrode by a gaseous halogen trap must be guaranteed.
  • Borane-containing compounds such as B(C 6 F 5 ) 3 , are generally known as catalysts for chemical transformations. Their use in electrochemical transformations for Si-C bond formation, especially starting from hydridosilanes, has not yet been described. So far their use has been mainly limited to electroanalytical studies and is described, for example, by EJ Lawrence et al. (J. Am. Chem. Soc. 2014, 136, 6031-6036) for the activation of hydrogen. AD Beck et al.
  • the object of the invention was to provide a safe and industrially applicable process for producing organosilicon compounds.
  • the use of precious metals should be avoided and the problems known from the prior art should be avoided.
  • This object is achieved by a process for producing organosilicon compounds, in which at least one hydridosilane and at least one organic halide are reacted electrochemically in the presence of at least one borane-containing catalyst and at least one conductive salt to form at least one Si-C bond.
  • borane-containing catalysts are suitable for forming Si-C bonds in an electrochemical reaction.
  • the electrochemical reaction can be stopped at any time by interrupting the current flow, i.e. converted into a safe state, especially from an industrial perspective.
  • the use of the catalyst not only enables a significant increase in product yield, but also allows certain organic halides to be converted in the first place.
  • the radical R 1 is independently selected from the group containing halogen, substituted or unsubstituted C 6 -C 18 aryl, C 3 -C 18 heteroaryl, C 1 -C 30 alkyl, C 2 -C 30 -Alkenyl-, C 3 -C 30 -alkynyl-, C 1 -C 30 -alkoxy-, C 2 -C 30 -alkenyloxy-, C 3 -C 30 -alkynyloxy-, C 6 -C 18 -aryl-C 1 -C 30 -alkyl-, C 3 -C 18 -heteroaryl-C 1 -C 30 -alkyl-, C 6 -C 18 -aryl-C 2 -C 30 -alkenyl-, C 3 -C 18 -heteroaryl-C 2 -C 30 -alkenyl-, C 1 -C 18 -alkoxy-C 1 -C 30 -al
  • the radical R 2 is independently selected from the group containing substituted or unsubstituted C 6 -C 18 aryl, C 3 -C 18 heteroaryl, C 1 -C 30 alkyl, C 2 -C 30 alkenyl -, C 3 -C 30 -alkynyl-, C 6 -C 18 -aryl-C 1 -C 30 -alkyl-, C 3 -C 18 -heteroaryl-C 1 -C 30 -alkyl-, C 6 -C 18 -Aryl-C 2 -C 30 -alkenyl-, C 3 -C 18 -heteroaryl-C 2 -C 30 -alkenyl-, C 1 -C 18 -alkoxy-C 1 -C 30 -alkyl-, C 1 -C 18 -alkoxycarbonyl-, C 1 -C 18 -alkoxy-C 2 -C 30 -alkenyl-, C 6 -
  • the oligomer and polymer residue can be, for example, polyvinyl chloride, polyethylene, polypropylene, polyvinyl acetate, polycarbonate, polyacrylate, polymethacrylate, polymethyl methacrylate, polystyrene, polyacrylonitrile, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene cyanide, polybutadiene, Polyisoprene, polyether, polyester, polyamide, polyimide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and polyethylene glycol.
  • copolymers such as styrene-acrylate copolymers, vinyl acetate-acrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-propylene terpolymers, ethylene-propylene rubber, polybutadiene, polyisobutene isoprene, polyisoprene and styrene-butadiene rubber.
  • oligomer and polymer residues are cellulose, starch, casein, natural rubber, semi-synthetic Co12204 / Be 7 Oligomers and polymers, cellulose derivatives, methylcellulose, hydroxymethylcellulose, carboxymethylcellulose, silicone polymers and organosilyl-functionalized organopolysiloxane resins.
  • the radical R 3 is independently selected from the group containing halogen, substituted or unsubstituted C 6 -C 18 aryl, C 3 -C 18 heteroaryl, C 1 -C 30 alkyl, C 2 -C 30 -Alkenyl-, C 3 -C 30 - Alkynyl-, C 6 -C 18 -Aryl-C 1 -C 30 -Alkyl-, C 3 -C 18 -Heteroaryl-C 1 -C 30 - Alkyl-, C 6 - C 18 -aryl-C 2 -C 30 -alkenyl-, C 3 -C 18 -heteroaryl-C 2 -C 30 -alkenyl-, C 1 -C 18 -alkoxy-C 1 -C 30 -alkyl-, C 1 -C 18 -alkoxycarbonyl-, C 1 -C 18 -alkoxy-C 2 -C 30 -alkeny
  • any mixtures of hydridosilanes of the general formula (I) and any mixtures of the organic halide of the general formula (II) can be used.
  • the electrochemical reaction of the individual components can take place simultaneously or one after the other.
  • the conductive salt, the catalyst and, if appropriate, a solvent are preferably introduced.
  • the halide and the hydridosilane can be added one after the other or together.
  • the substituent is preferably selected from the group containing substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, hydroxy, alkoxy, acyloxy -, silyloxy, carboxylate, alkoxycarbonyl, amino, nitro and halogen residue.
  • R 1 is selected from the group containing halogen, substituted or unsubstituted C 6 -C 12 aryl, C 3 -C 12 heteroaryl, C 1 -C 18 alkyl, C 2 -C 18 -Alkenyl-, C 3 -C 18 -alkynyl-, C 1 -C 18 -alkoxy-, C 2 -C 18 -alkenyloxy-, C 3 -C 18 -alkynyloxy-, C 6 -C 12 -aryl-C 1 -C 18 -alkyl-, C 3 -C 12 -heteroaryl-C 1 -C 18 -alkyl-, C 6 -C 12 -aryl- C 2 -C 18 -alkenyl-, C 3 -C 12 -heteroaryl-C 2 -C 18 -alkenyl-, C 1 -C 12 -alkoxy- C 1
  • the silyl radical can be, for example, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, allyldimethylsilyl, benzyldimethylsilyl, vinyldimethylsilyl or tris-(trimethylsilyl). silyl residue act.
  • the silyloxy radical can be, for example, a trimethylsilyloxy, triethylsilyloxy, tri-isopropylsilyloxy, tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy, allyldimethylsilyloxy, benzyldimethylsilyloxy or vinyldimethylsilyloxy radical.
  • R 1 is particularly preferably selected from the group containing chloride, bromide, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-decyl, n-dodecyl, n-octadecyl, Vinyl, allyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, phenyl, naphthyl, anthryl, phenanthryl, o-tolyl, m-tolyl, p-tolyl, xylyl and Ethylphen
  • R 1 is selected from the group containing methyl, ethyl, phenyl, vinyl, benzyl and allyl radicals.
  • the radical R 2 is preferably selected from the group containing substituted or unsubstituted C 6 -C 12 aryl, C 3 -C 12 heteroaryl, C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 3 -C 18 -alkynyl-, C 1 -C 18 -alkoxy-, C 2 -C 18 -alkenyloxy-, C 3 -C 18 -alkynyloxy-, C 6 -C 12 - aryl-C 1 -C 18 - Alkyl-, C 3 -C 12 -heteroaryl-C 1 -C 18 -alkyl-, C 6 -C 12 -aryl- C 2 -C 18 -alkenyl-, C 3 -C 12 -heteroaryl-C 2
  • R 2 is particularly preferably selected from the group containing methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl. , n-hexyl, n-heptyl, n-octyl, n-decyl, vinyl, allyl, benzyl, cyclopentyl, cyclohexyl, unsubstituted and substituted phenyl, naphthyl, anthryl, phenanthryl , substituted silyl alkyl radical and polyvinyl radical.
  • R 2 is selected from the group containing allyl, vinyl, benzyl, methyl, ethyl, substituted and unsubstituted phenyl and methoxymethyl-substituted silylalkyl radicals.
  • R 3 is preferably selected from the group containing fluoride, chloride, bromide, substituted or unsubstituted C 6 -C 12 aryl, C 3 -C 12 heteroaryl, C 1 -C 18 alkyl, C 2 -C 18 -alkenyl-, C 3 -C 18 -alkynyl-, C 1 -C 18 -alkoxy-, C 2 -C 18 -alkenyloxy-, C 3 -C 18 -alkynyloxy-, C 6 -C 12 -aryl -C 1 -C 18 -alkyl-, C 3 -C 12 -heteroaryl-C 1 -C 18 -alkyl-, C 6 -C 12 - aryl-C 2 -C 18 -alkenyl-, C 3 -C 12 - Heteroaryl-C 2 -C 18 -alkenyl-, C 1 -C 12 - alkoxy-C 1
  • R 3 is particularly preferably selected from the group containing fluoride, chloride, bromide, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, vinyl, allyl, benzyl, cyclopentyl, cyclohexyl, methoxymethyl, unsubstituted and substituted phenyl, naphthyl, anthryl and phenanthryl residue.
  • R 3 is selected from the group containing fluoride, chloride, ethyl, substituted and unsubstituted phenyl radicals.
  • Typical examples of the borane-containing catalyst of the general formula (III) are B(C 6 F 5 ) 3 , BEt 3 and BCl 3 .
  • the catalyst is in a concentration of 0.01 to 50 mol%, preferably 0.02 to 30 mol%, particularly preferably 0.05 to 15 mol%, Co12204 / Be 11 in particular from 0.1 to 5 mol%, the information referring to the amount of hydridosilane.
  • Inert salts or mixtures thereof which do not react with the reaction components are generally used as conductive salts.
  • the conductive salt is preferably a compound from the group consisting of tetrabutylammonium tetrafluoroborate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium perchlorate, lithium perchlorate and mixtures thereof.
  • the conductive salt is preferably added in a concentration of 0.01 to 5 mol/L, preferably 0.02 to 2 mol/L, particularly preferably 0.05 to 0.5 mol/L.
  • the process is preferably carried out in a solvent. All aprotic solvents can be used as solvents. Polar solvents which do not react with the starting materials and which are inert under the given electrochemical conditions are preferred.
  • the organic halide of the general formula (II) and/or the hydridosilane of the general formula (I) can themselves function as solvents.
  • solvents are ethers such as tetrahydrofuran, 1,2-dimethoxyethane, 1,3-dioxolane or bis (2-methoxy-ethyl) ether.
  • Further examples are dioxane, acetonitrile, ⁇ -butyrolactone, ⁇ -valerolactone, nitromethane, liquid sulfur dioxide, tris(dioxa-3,6-heptyl)amine, trimethylurea, dimethylformamide, dimethyl sulfoxide and mixtures of the above Co12204 / Be 12 examples.
  • Mixtures can contain more than two components, with the solvent with the highest volume content preferably being added in 5 to 95 vol.% and the second highest volume content in 5-50 vol.%.
  • Supercritical media such as supercritical CO 2 or ionic liquids, can also be used as solvents. When using ionic liquids as solvents, they can take on the function of the conductive salt.
  • the solvent or solvents used are preferably dry (water content preferably ⁇ 10,000 ppm, particularly preferably ⁇ 1000 ppm, in particular ⁇ 100 ppm; can be determined using the Karl Fischer method).
  • a particularly preferred solvent is 1,2-dimethoxyethane. If necessary, the reaction can take place in the presence of a halogen scavenger.
  • the halogen scavenger is selected from the group consisting of carbonates, silver and potassium salts, nucleophilic and non-nucleophilic bases, supported and unsupported bases, epoxides and mixtures thereof.
  • Typical examples of the halogen scavenger are pyridine, 2,6-di-tert-butylpyridine, 1,4-diazabicyclo[2.2.2]octane, polyethyleneimine on silica gel, potassium carbonate and silver nitrate.
  • the anode and cathode used for the process can generally consist of any material that has sufficient electrical conductivity and behaves in a chemically stable manner under the selected reaction conditions.
  • Co12204 / Be 13 The reaction is preferably carried out with an anode and a cathode, the material for the anode and for the cathode being independently selected from the group of graphite, glassy carbon, boron-doped diamond, gold, silver, platinum, rhenium , ruthenium, rhodium, osmium, iridium, palladium, copper, lead, tin and alloys made from the metals mentioned such as lead bronze.
  • a preferred material for the anode is glassy carbon.
  • Typical examples of this are CuSn7Pb15, CuSn10Pb10 and CuSn5Pb20.
  • CuSn7Pb15 is particularly preferred.
  • the use of the borane-containing catalyst for the formation of the Si-C bond, starting from the organic halide (formula (II)) and the hydridosilane (formula (I)), is in contrast to a variant using a hydrogen anode (cf. WO 2005/123811 A1) a particularly simple and easily scalable method in which inexpensive and long-term stable electrode materials can be used.
  • Precious metal-coated anodes which generally have to be fed by a continuous gas stream from a halogen catcher, can be dispensed with.
  • the cell design is not very complex because no gas introduction is necessary.
  • hydridosilanes in conjunction with organic halides, halogenation of the solvent due to released hydrogen chloride can be prevented even without using a hydrogen anode.
  • Co12204 / Be 14 The use of the borane-containing catalyst enables an electrochemical reaction with significantly higher conversion and significantly higher yield. Furthermore, the process can be operated much more economically. Surprisingly, it has also been found that the use of a conductive salt does not cause complexation of the borane-containing catalyst. As would be expected, the catalyst is not removed from the reaction through complexation.
  • the conductive salt can prevent a catalytic and unwanted reaction of the hydridosilane with the solvent, which can otherwise be made possible by activating the hydridosilane with the borane-containing catalyst. Furthermore, it has been shown that by using inexpensive and generally easy-to-handle halogen scavengers, the amount of chlorosilanes that can be released as by-products can be significantly reduced.
  • the process can be carried out in a known manner using an electrolytic cell with a cathode and an anode.
  • the electrolysis cell can be a flow cell or pot cell. It can be a divided or undivided electrolytic cell, with the undivided electrolytic cell being preferred since it usually has an uncomplicated structure.
  • the electrolysis cell is preferably made of a material that is inert to the components used. Particularly preferred is an electrolysis cell made of an inert plastic (eg polytetrafluoroethylene (PTFE)), glass or a material provided with an inert coating.
  • the electrodes are preferably in a vertical design Co12204 / Be 15 reaction solution was introduced. A horizontal arrangement is also possible.
  • the process preferably takes place under an inert gas atmosphere, with nitrogen, argon or helium being preferred as inert gases.
  • the electrolysis cell is preferably provided with a potentiostat or a galvanostat to regulate the potential or the intensity of the current. The procedure can be carried out with or without control of the potential.
  • electrolysis setup In order to prevent contamination of the reaction process by water or oxygen, the electrolysis setup is carried out under inert gas (water content ⁇ 0.1 ppm, oxygen content ⁇ 0.1 ppm). Undivided cells made of PTFE are used, which have a volume of 5 mL. Special dryness requirements are placed on the electrolyte.
  • the electrolyte is generally a mixture of solvent and conductive salt, whereby, as described above, the hydridosilane and/or the halide can also function as a solvent.
  • the solvent used is anhydrous 1,2-dimethoxyethane stored over a molecular sieve (preferably 3 ⁇ ).
  • Bu 4 NClO 4 as the conductive salt is dried for 24 h at 60°C under vacuum (1.0 ⁇ 10 -3 mbar) before use.
  • the borane-containing catalyst, the electrolyte, the hydridosilane and the organic halide are transferred into the cell one after the other.
  • the cell is closed with a PTFE cover, which also serves as a holder for the electrodes.
  • the electrode distance is 0.5 cm.
  • the Co12204 / Be 16 cuboid electrodes measure 0.3 x 1.0 x 7.0 cm. During the reaction, 0.3 x 1.0 x 1.3 cm of the electrodes are immersed in the reaction solution.
  • Example 1a Preparation of allyldimethylphenylsilane First, the catalyst (tris(pentafluorophenyl)borane B(C 6 F 5 ) 3 , 12.8 mg, 2.5*10 -2 mmol) is placed in the cell. The electrolyte (solution of tetrabutylammonium perchlorate Bu 4 NClO 4 , 0.12 mol*L -1 in 5.0 mL dimethoxyethane) is introduced and dimethylphenylsilane (Me 2 PhSiH, 383.2 ⁇ L, 2.5 mmol) and allyl chloride (135 .7 ⁇ L, 1.7 mmol) added.
  • the catalyst tris(pentafluorophenyl)borane B(C 6 F 5 ) 3 , 12.8 mg, 2.5*10 -2 mmol
  • the electrolyte solution of tetrabutylammonium perchlorate Bu 4 NClO 4 , 0.12 mol
  • the cell is closed with the PFTE cover, lead bronze (CuSn7Pb15) is used as the cathode material and glassy carbon is used as the anode material.
  • the electrolysis is carried out with a constant current of 10 mA/cm 2 and a charge amount of 1.0 F while stirring at 500 rpm at room temperature (RT). After the electrolysis has ended, volatile products are removed at 40 ° C and 10 mbar. The organic residue is washed with distilled water and n-pentane (3 x 25 mL each). The organic fractions are separated off, combined and dried over Na 2 SO 4 and again separated from volatile compounds at 40 ° C and 10 mbar.
  • Example 1b Preparation of Allyldimethylphenylsilane The experimental procedure corresponds to that of Example 1a, but the reaction is carried out in the currentless state. After a reaction time of 24 hours, the desired product is not detectable.
  • Example 4b Preparation of Benzyldimethylphenylsilane Experiment carried out analogously to Example 4a, but the reaction is carried out in the currentless state. After a reaction time of 24 hours, the desired product is not detectable.
  • Example 4d Preparation of benzyldimethylphenylsilane Experiment carried out analogously to Example 4a, but a copper cathode is used instead of lead bronze. After 3.0 F the product benzyldimethylphenylsilane is obtained in 60% yield.
  • Table 1 Co12204 / Be 21
  • Table 2 The undesirable by-product (chlorodimethylphenylsilane) formed during the Si-C bond formation (to form allyldimethylphenylsilane) can be reduced by 8% from 54% to 46% by adding the halogen scavenger (Table 2, Example 1a and Comparative Example 1a) .

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Abstract

L'invention concerne un procédé de production de composés organosiliciés, consistant à faire réagir électrochimiquement au moins un hydridosilane et au moins un halogénure organique en présence d'au moins un catalyseur contenant du borane et d'au moins un sel conducteur pour former au moins une liaison Si-C.
PCT/EP2022/063822 2022-05-20 2022-05-20 Procédé de production de composes organosiliciés WO2023222245A1 (fr)

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Citations (14)

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