Patent GB-795772-A (GB)
Title: Organosilanes
IPC: C07F7/12
Filed: 1956-01-20
Abstract: Organosilanes are prepared by reacting an organo-magnesium chloride complex of the formula RMgCl.nQ, where R is an aryl, vinylic or active-hydrogen-free heterocyclic group, Q is a heterocyclic ether (defined below) and n is an indeterminate integer of the order of 1 to 3, with a silicon compound of the formula AA1A11SiX, where A, A1 and A11 are a hydrogen atom, hydrocarbon group, halogen atom or an alkoxy or aroxy group and X is a halogen atom or alkoxy group.  The compound Q is a substituted or unsubstituted heterocyclic ether having 5 or 6 atoms in the ring, of which atoms only one is oxygen, the other ring atoms being carbon except that the one in the 4 position may be replaced by a substituted nitrogen atom when the ring has 6 atoms, the ring containing not more than one double bond and at least one carbon atom adjacent to the oxygen being free from substituents other than hydrogen.  The ether should be free from substituents which are reactive with organo magnesium chlorides or with the components or products of the reaction.  Suitable compounds are tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, 2-ethoxytetrahydropyran, tetrahydrofurfuryl ethyl ether, dihydropyran and N-methyl morpholine.  Permissible substituents include alkyl, aryl, alkoxy and aroxy groups.  Examples of silane starting materials are silicon halides, orthosilicates, alkyl-, aryl-, alkylaryl-, vinylic- and arylvinylic halosilanes, and alkoxy and aroxy silanes. The organo magnesium chloride complexes may be prepared as described in Specifications 776,993, 777,158 and 779,100, [all in Group IV (b)].  The reaction with the silicon compounds is preferably effected in a hydrocarbon solvent at temperatures of 40-80 DEG  C. and also preferably in an inert atmosphere, e.g. nitrogen.  In the examples: (1) a complex of phenyl magnesium chloride and tetrahydrofuran is added slowly to a solution of SiCl4 in a solvent, the mixture is refluxed and the solvents distilled off to give a mixture of Ph2SiCl2, PhSiCl3 and Ph3SiCl; (2) pentachlorophenyl magnesium chloride complex with tetrahydrofuran is reacted with SiCl4 to yield pentachloro phenyl trichlorosilane; (3) vinyl magnesium chloride complex with tetrahydrofuran is reacted with SiCl4, a small amount of hydroquinone dimethyl ether is added, and on distilling, a mixture of Vi2SiCl2, ViSiCl3 and Vi3SiCl is obtained; (5) vinyl silanes, including MeViSiCl2, are obtained from MeSiCl3 and vinyl magnesium chloride in tetrahydrofuran; (6) vinyl magnesium chloride is added to a solution containing MeSiCl3, petroleum ether, tetrahydrofuran and cadmium chloride to yield a mixture of silanes including MeViSiCl2; (7) to (10) vinyl magnesium chloride is added to solutions of varying amounts of SiCl4 and tetrahydrofuran in a solvent, to yield vinyl silanes including ViSiCl3 and Vi4Si; (11) p - chlorophenylmagnesium chloride in tetrahydrofuran is added to SiCl4 in a solvent to yield bis-p-chlorophenyldichlorosilane; (12) the reagent of the previous example is reacted with Me3SiCl, the mixture hydrolysed with HC1 and trimethyl-p-chlorophenylsilane is obtained; (13) and (14) PhViSiCl2 is obtained from ViSiCl3 and phenyl magnesium chloride in tetrahydrofuran; (15) to (20) PhSiCl3 is prepared from phenyl magnesium chloride in tetrahydrofuran and SiCl4.