公开(公告)号：US3347891A

公开(公告)日：1967-10-17

申请号：US31643563

申请日：1963-10-15

Applicant: STUDIENGESELLSCHAFT KOHLE MBH

Inventor： PAUL NEUMANN WILHELM ,  HORST NIERMANN

IPC: C07F7/22

CPC classification number: C07F7/222

Abstract: Organo-tin hydrides of the formula RmSnH4- m where R represents an alkyl and/or aryl group and m = 1, 2 or 3 are stabilized by hydrolysis and/or alcoholysis which removes impurities. The hydrolysis and/or alcoholysis may be carried out in the presence of an acid binding agent, e.g. ammonia, alkali metal or alkaline earth metal hydroxides or carbonates, or organic amines. The alcoholysis may be carried out using methanol, butyl alcohol or 2 ethyl hexanol. The subject-matter of Specification 951,150 is disclaimed.

Abstract translation: 其中R表示烷基和/或芳基并且m = 1,2或3的式RmSnH4-m的有机锡氢化物通过除去杂质的水解和/或醇解来稳定。 水解和/或醇解可以在酸结合剂的存在下进行，例如 氨，碱金属或碱土金属氢氧化物或碳酸盐或有机胺。 醇解可以使用甲醇，丁醇或2-乙基己醇进行。 规格951,150的标的物被放弃。

公开(公告)号：US3256253A

公开(公告)日：1966-06-14

申请号：US26605463

申请日：1963-03-18

Applicant: STUDIENGESELLSCHAFT KOHLE MBH

Inventor： PAUL NEUMANN WILHELM ,  HORST NIERMANN

IPC: C07F7/22 ,  C08G79/12

CPC classification number: C08G79/12 ,  C07F7/2212 ,  Y10S585/931

Abstract: Organotin compounds are prepared by reacting organotin hydrides with olefinically unsaturated hydrocarbons in the presence of a catalyst consisting of AlH3, a complex Al hydride e.g. LiAlH4 or Mg(AlH4)2, or an alkyl Al hydride, e.g. diisobutyl or diethyl Al hydride. The latter may be formed in situ from a trialkyl Al compound, e.g. triisobutyl or trioctyl Al. The starting materials may contain aliphatic, cycloaliphatic, or aromatic radicals, and organotin mono-, di-, or tri-hydrides may be used. 1-15 % mole of the catalyst is used, based on the tin. Reaction may be effected, e.g. in an inert solvent such as toluene, octane, cyclohexane and hydrocarbon mixtures, by mixing the reactants and catalyst and heating to 180 DEG C., or by heating the catalyst with the olefin and adding the tin hydride dropwise at the rate of its consumption. After reaction, the catalyst may be hydrolysed or oxidized and removed by shaking with water, acid, or alkali, or by fractional distillation, or the product may be distilled off and the catalyst recovered.ALSO:Organo-tin polymers are prepared by reacting a diene or triene with an organo-tin di- or tri hydride in the presence of a catalyst consisting of AlH3, a complex Al hydride, e.g. LiAlH4 or Mg(AlH4)2, or an alkyl Al hydride. The latter may be formed in situ from a trialkyl Al compound. The reactants may contain aliphatic, cycloaliphatic or aromatic radicals. Stoichiometric amounts of reactants are used, or an excess of olefin may provide the polymer with unsaturated groups. 1-15 mole per cent of the catalyst is used, based on the tin. Reaction may be effected, e.g., in an inert solvent such as toluene, octane, cyclohexane, and hydrocarbon mixtures, by mixing the reactants and catalyst and heating to 180 DEG C., or by heating the catalyst with the olefin and adding the tin hydride dropwise at the rate of its consumption. After reaction, the catalyst may be hydrolysed or oxidised and removed by shaking with water, acid or alkali, or by fractional distillation, or the product may be distilled off and the catalyst recovered. Examples describe the reaction of di-n-butyl tin dihydride with 1,2,4-trivinyl cyclohexane (Example 8), 1, 7-octadiene (9, 10 and 11), and 1, 5-cyclooctadiene (12); diethyl tin dihydride with divinyl pentene (7); isobutyl tin trihydride with 1, 7-octadiene (14); and a mixture of di-n-butyl tin dihydride and iso-butyl tin trihydride with 1, 7-octadiene.

公开(公告)号：US3398169A

公开(公告)日：1968-08-20

申请号：US47055465

申请日：1965-07-08

Applicant: STUDIENGESELLSCHAFT KOHLE MBH

Inventor： PAUL NEUMANN WILHELM ,  ALFRED PEDAIN JOSEF

IPC: C07F7/22

CPC classification number: C07F7/2232 ,  C07F7/2216

Abstract: Halogen-containing organo-tin compounds are prepared by reacting organo-tin-halohydrides with compounds having unsaturated groups (e.g. olefins, alkynes, aldehydes, ketones, unsaturated nitriles, Schiff's bases, and azo compounds) preferably in the presence of a radical producing catalyst (e.g. benzyl hyponitrile, azoisobutyric dinitrile or an azoisobutyric dialkyl ester) at less than 50 DEG C. with or without a solvent in an inert atmosphere (N2). Alkyl, aryl or aralkyl tin halohydrides of the formulae R2Sn(X)H,RSn(X)H2 or RSn(X2)H (preferably where R=C1-C8 alkyl or simple aryl, e.g. Ph) are prepared in situ from the corresponding organo-tin hydrides and organotin halides and may be reacted with the unsaturated compound to give organo-tin halohydrides with dissimilar organo-radicals and/or containing functional groups. The Sn-H group adds across the multiple bond. The following compounds are among those prepared in the examples: Ex. 2: (isoBu)2Sn(Br)-CH2-CH2CN; Ex. 3: Ph2Sn(Cl)-CH2-CHMePh; Ex. 5: Ph2Sn(Cl)(CH2)6-Sn(Cl)Ph2; Ex. 6: (nBu)2Sn(Cl)(CH2)3O(CH2)2OH; Ex. 11: EtSn(Br)2CH=CHPh; Ex. 14: (isoBu)2Sn(F)(CH2)3OH; Ex. 16: (nBu)2Sn(Cl)-N(nBu)CH2Ph.

Abstract translation: 含有卤素的有机锡化合物是通过有机锡卤化物与具有不饱和基团的化合物（例如烯烃，炔烃，醛，酮，不饱和腈，希夫碱和偶氮化合物）反应而制备的，优选在自由基产生催化剂存在下 （例如苄基低腈，偶氮异丁腈或偶氮异丁基二烷基酯）在惰性气氛（N 2）中，在或不用溶剂下在小于50℃下进行。 式R2Sn（X）H，RSn（X）H2或RSn（X2）H（优选其中R = C1-C8烷基或简单芳基，例如Ph）的烷基，芳基或芳烷基锡卤素原位从相应的 有机锡氢化物和有机锡卤化物，并且可以与不饱和化合物反应，得到具有不同有机基团和/或含有官能团的有机锡卤化物。 Sn-H组增加了多重键。 以下化合物是实施例中制备的化合物： 2：（异丁基）2Sn（Br）-CH 2 -CH 2 CN; 例如 3：Ph 2 Sn（Cl）-CH 2 -CHMePh; 例如 5：Ph2Sn（Cl）（CH2）6-Sn（Cl）Ph2; 例如 6：（nBu）2Sn（Cl）（CH 2）3 O（CH 2）2 OH; 例如 11：EtSn（Br）2CH = CHPh; 例如 14：（异丁基）2Sn（F）（CH 2）3 OH; 例如 16：（nBu）2Sn（Cl）-N（nBu）CH 2 Ph。

公开(公告)号：US3248411A

公开(公告)日：1966-04-26

申请号：US18209562

申请日：1962-03-23

Applicant: STUDIENGESELLSCHAFT KOHLE MBH

Inventor： PAUL NEUMANN WILHELM ,  GOTTFRIED BURKHARDT

IPC: C07F7/22

CPC classification number: C07F7/22 ,  C07F7/2208 ,  C07F7/2216

Abstract: Alkyl tin trihalides may be made by reacting a tetra-alkyl tin with tin tetra-chloride, -bromide or -iodide in the molar ratio 1:2. The reaction takes place in two stages which may be carried out independently: SnR4=SnX4--->RSnX3+R3SnX R3SnX=SnX4--->RSnX3+R2SnX2 Using short, unbranched chain alkyl groups the reaction may be initiated at between 0 DEG and 20 DEG C. and is faster than when using longer or branched chain alkyl groups, which require initiation at elevated temperatures. The process is preferably carried out by adding the tetraalkyl tin dropwise to the tin tetrahalide, thus ensuring an excess of the latter throughout the reaction. If desired, the tin tetrahalide may be used as a complex, e.g. with an ether. The product, which contains RSnX3 and R2SnX2 may be separated into its constituents by distillation. The process may be modified using a trialkyltin halide in place of the tetraalkyl tin.