Patent GB-966813-A (GB)
Title: Manufacture of organo tin compounds
IPC: C07F7/22
Filed: 1962-08-01
Abstract: Organotin compounds are prepared by adding alkyl or aryl tin hydrides of formula RnSnH4-n wherein R is an alkyl or aryl radical and n is a number up to 3, to olefines, olefinic compounds or compounds of general formulae O=CR1R11 or R1N=CR11R111 wherein R1, R11-R111 are any aliphatic, aromatic or heterocyclic hydrocarbon radical, said addition being effected with exclusion of air and at a temperature below 120 DEG C. in the presence as catalyst of a compound which decomposes to form free-radicals at the temperature employed. Catalysts specified include azo-compounds, peroxides, hydrazine compounds and hydrocarbon substituted ethanes such as hexaphenyl ethane, and analogous compounds capable of forming free radicals at temperatures up to 120 DEG C. Free-radical forming compounds containing free carboxyl groups or other protondonating functional groups such as sulphinic acid groups are not suitable as catalysts. The reaction is carried out at temperatures as low as possible, with a maximum of 90 DEG -120 DEG C. The products may be monomeric or polymeric depending on the components. The examples are summarised as follows:  Example 1. Triethyl tin hydride is reacted with methyl methacrylate in presence of azoisobutyronitrile (I); Example 2, as 1 using di-tert. butyl peroxide; Example 3, triethyl tin hydride, ethyl ester of undecylenoic acid and catalyst I; Example 4, triethyl tin hydride, alpha octene and catalyst I; Example 5, as 4 using phenyl azoisobutyronitrile; Example 6, as 5 using tri-n-butyl hydride giving tributyl octyl tin; Example 7, (C2H5)3Sn-(CH2)3-O-COCH3, from triethyl tin hydride, allyl acetate and phenyl azotriphenyl methane. Example 8, as 7 using hexaphenyl ethane, tetraphenyl -dibiphenyl ethane, diethyl-bis-fluorenyl or tetraphenyl-diethyl ethane; Example 9, as 8 using tetraphenyl hydrazine as catalyst; Example 10, (C2H5)3Sn(CH2)3-OH from triethyl tin hydride, allyl alcohol and catalyst I; Example 12, (C4H9)2Sn(CH2-CH2-CH2 -OCOCH3)2 from dibutyl tin dihydride, allyl-acetate and catalyst I; Example 13, (C8H17)3 Sn-(CH2)3-O-(CH2)2-OH from tri-n-octyl tin hydride, ethylene glycol mono-allyl ether and catalyst I; Example 14, (C2H5)3Sn-CH2-CH2-C12H8N from triethyl tin hydride, N-vinyl-carbazole and catalyst I; Example 15, (C2H5)3 Sn-(CH2)2-O-(CH2)3-CH3 from triethyl tin hydride, vinyl butyl ether and catalyst I; Example 16, (C2H5)3Sn-(CH2)2-CONH2 from triethyl tin hydride, acrylic amide and catalyst I; Example 17, as 16 using tri-n-butyl tin hydride giving (C4H9)3Sn-(CH2)2-CONH2; Example 18, (C2H5)3Sn-(CH2)2-CN from triethyl tin hydride, acrylonitrile and catalyst I; Example 19, (C6H5)3\t Sn-CH2-CHCH3-COOCH3 from triphenyl tin hydride, methyl methacrylate and catalyst I; Example 20, as 19 using triethyl tin hydride giving (C2H5)3Sn-CH2-CHCH3 -COOCH3; Example 21, triethyl tin hydride, styrene and catalyst I; Example 22, triethyl tin hydride, vinyl acetate and catalyst I; Example 23, (C2H5)3Sn \N(C6H5)-CH2-C6H5 from triethyl tin hydride, benzalaniline and catalyst I; Example 24, as Example 1, using methyl or ethyl azoisobutyrate as catalyst; Example 25, C4H9Sn(CH2-CH (CH3)COOCH3) from n-butyl tin trihydride, methyl methacrylate and catalyst I; Example 26, a glass-like polymer from diethyl tin dihydride p-divinyl benzene and catalyst I; Example 27, (C2H5)3Sn-(CH2)4-CH=CH2 from triethyl tin hydride, diallyl and catalyst I, and (C2H5)3Sn -CH2-CH2-C6H4-CH=CH2 from triethyl tin hydride and p-divinyl benzene-this product may be polymerised by benzoyl peroxide; Example 28, (C2H5)2Sn(CH2-CH2-CH2 -O-CH2-CH2-OH)2 from diethyl tin dihydride, ethylene glycol mono-allyl ether and catalyst I; Example 29, di-n-butyl tin dihydride, diallyl phthalate and catalyst I; Example 30, a solid cross-linked polymer from isobutyl tin trihydride, ethylene glycol dimethacrylate and azoisobutyrodinitrile; and Example 31, (C6H5)2Sn(CH2-CHCH3 -COOCH3)2 from diphenyl tin dihydride, methyl methacrylate and catalyst I.ALSO:Polymeric products containing tin are prepared by adding alkyl or aryl tin hydrides of formula RnSnH4-n wherein R is an alkyl or aryl radical and n is a number up to 3 to compounds containing more than one unsaturated group, e.g. diolefins with exclusion of air and at a temperature below 120 DEG C. in the presence as catalyst of a compound which decomposes to form free radicals at the temperature employed.  Catalysts specified include azo-compounds, peroxides, hydrazine compounds and hydrocarbon substituted ethanes such as hexaphenyl ethane. The products are produced according to the reaction: nR2SnH2+nH2C=CH.R1.CH=CH2---> (-R2Sn-CH2.CH2.R1.CH2.CH2-) In the examples the following are reacted: Example 26, p-divinylbenzene, diethyl tin dihydride and azo-iso-butyronitrile; Example 27, p-divinyl benzene, triethyl tin hydride and azo-isobutyronitrile give (C2H5)3Sn-CH2-CH2-C6H4\t -CH=CH2 which may be polymerized by benzoylperoxide; Example 29, diallylphthalate, di-n-butyl tin dihydride and azo-isobutyronitrile; Example 30, ethylene glycol dimethacrylate, isobutyl tin trihydride and azo-isobutyronitrile.