Patent GB-574653-A (GB)
Title: Improved organo silicon compounds and method of making them
IPC: C07F7/18
Filed: 1943-08-20
Abstract: Organo-silicon compounds are prepared by reacting a compound of the general formula X4-nSiYn with a lithium compound of the formula RLi where X and R are hydrocarbon radicals or hydroxy-, halogen-, alkoxy-, or amino-substituted hydrocarbon radicals, n represents an integer from 1-4, and Y represents a halogen or alkoxy radical.  The reaction is preferably carried out in an inert solvent such as diethyl ether benzene, low-boiling petroleum ether or mixtures of these.  An alternative procedure is to use instead of the preformed RLi compound the ingredients p  thereof by slowly adding an organic halide to a mixture of lithium and the silicon compound in an inert solvent.  In examples: (1) methyl lithium is prepared by reacting methyl chloride and lithium in ether solution, and adding the compound so formed to an ether solution of silicon tetrachloride. The product is treated with ethyl alcohol to form the silicon esters, and then hydrolysed; (2) phenyl lithium prepared from phenyl bromide and lithium is added to silicon tetrachloride and the product distilled to give a mixture of diphenyl silicon dichloride and triphenyl silicon chloride; (3) ethyl lithium is reacted with phenyl silicon trichloride in ether and the product fractionated to give phenyl ethyl silicon dichloride; (4), (5) and (6) phenyl lithium is made from phenyl chloride and lithium and reacted with silicon tetrachloride to give phenyl silicon trichloride; (7) ethyl lithium is made from ethyl chloride and lithium and added to phenyl silicon trichloride to form a mixture of phenyl ethyl silicon dichloride and phenyl silicon trichloride; (8) ethyl lithium is added to silicon tetrachloride to give diethyl silicon dichloride; (9) benzyl chloride is added to an ether solution of lithium and silicon tetrachloride and the mixture refluxed and then fractionated to form benzyl lithium trichloride; (10) an ether solution of p-bromanisole is added to an ether suspension of lithium and this solution added to silicon tetrachloride to form anisyl silicon trichloride; (11) chlorbenzene is added to a mixture of lithium and ethyl orthosilicate to form phenyl triethoxy silicon; (12) lithium is added to an ether solution of methyl triethoxy silicon and the product fractionated to give phenyl methyl diethoxy silicon; (13) p-bromodimethylaniline is added to an ether solution of lithium and ethyl orthosilicate to form dimethylanilino triethoxy silicon; (14) p-bromotoluene is added to an ether solution of lithium and ethyl orthosilicate to form p-tolyl triethoxy silicon; (15) 2-bromo-1 : 4-dimethylbenzene is added to an ether solution of lithium and ethyl orthosilicate to form xylyl triethoxy silicon; (16) p-bromo-diphenyl is added to an ether solution of lithium and ethyl orthosilicate to give diphenyl triethoxy silicon; (17) an ether solution of p-bromaniline is added to a mixture of lithium and ethyl orthosilicate to form p-aminophenyl triethoxy silicon; (18) p-bromodimethylaniline is reacted with lithium to form p-dimethyl-aminophenyl-lithium which is then added to an ether solution of ethyl orthosilicate to form tri-(dimethylaminophenyl) silicon hydroxide; (19) amyl chloride is treated with lithium in ether to form amyl lithium which is then reacted with benzyl alcohol to form di(hydroxymethylphenyl) diethoxy silicon.  The compounds of the present invention are useful as intermediates in the production of organosilicones.