Patent GB-766875-A (GB)
Title: A method of preparing organo-substituted stannane derivatives
Inventor: MACK GERRY P
IPC: C07F7/22
Filed: 1953-03-13
Abstract: Monomeric organo-substituted stannane derivatives are prepared by reacting an organotin alkoxide of the general formula R1mR11nSn(OR)4-(m+n) where R1 and R11 are the same or different monovalent hydrocarbon radicals, R is an alkyl group containing not more than 3 carbon atoms, m+n is 2 or 3 and m and n are 0, 1, 2 or 3, either under anhydrous conditions with an organic compound containing active hydrogen, i.e. alcohols containing more than 3 carbon atoms, compounds other than alcohols containing a free hydroxyl group, carboxylic acids, amides, imides, aldoximes, ketoximes, compounds containing an activated methylene group and hydrocarbons containing a conjugated double bond system, at an elevated temperature sufficient to distil off the formed alcohol, or with the anhydride of a dicarboxylic acid in the presence of small amounts of a compound containing a free hydroxyl group, thereby replacing at least one of the alkoxy groups by the radical derived from the organic compound containing active hydrogen or by the radical of the dicarboxylic acid monoester formed by the reaction of the dicarboxylic acid with said alkoxy groups.  According to the ratio of the reactants, one or both alkoxy groups of a organo-tin dialkoxide reactant may be replaced by the residue derived from the organic compound containing the active hydrogen or from two different residues derived from organic compounds containing active hydrogen.  In certain cases, however, only one alkoxy group may be replaced of the organo-tin dialkoxide reactant particularly when the atom bearing the active hydrogen is linked to bulky aromatic nuclei or to unsaturated aliphatic carbon to carbon linkages.  Suitable compounds having active hydrogen mentioned are compounds in which active hydrogen is bound to an oxygen atom including aliphatic saturated and unsaturated alcohols, cyclic alcohols and aromatic alcohols, e.g. allyl, butyl, hexyl, 2-ethylhexyl, nonyl, lauryl, oleyl, stearyl, furfuryl, tetrahydrofurfuryl, dicyclopentenyl, cinnamyl, phenylethyl and benzyl alcohol, ether-alcohols, e.g. alkoxy and aryloxy glycols and polyglycols, acetals and ketals of trihydric alcohols having one free hydroxyl group, e.g. glycerol acetal, esters of hydroxyacetic acids, e.g. ethyl hydroxy-isobutyrate, butyl lactate, tributyl citrate and ethyl ricinoleate, aldehyde and keto alcohols, e.g. glycolic aldehyde, aldol, hydroxyacetone, acetoin and diacetone alcohol, phenols and derivatives thereof containing at least one free hydroxy group, saturated and unsaturated aliphatic, cyclic and aromatic monocarboxylic acids, e.g. acrylic, crotonic, sorbic, furoic, furylacrylic, fenholic, benzoic and cinnamic acids, substituted acids such as aldehydeacids and amino-acids, e.g. glycine, alanine, leucine, glyoxylic and pyromucic acids, esters of di- and polycarboxylic acids having one free carboxylic group, aliphatic and aromatic dicarboxylic acids, e.g. oxalic, malonic, succinic, adipic, sebacic, maleic, fumaric, itaconic, phthalic and terephthalic acids; compounds in which the active hydrogen is bound to nitrogen, including amides and imides, e.g. phthalimide and succinimide, ureides, e.g. barbituric acid, sulphonamides, sulphonimides, and aldoximes and ketoximes, e.g. butyraldoxime and cyclohexanone oxime, compounds containing an activated methylene group, e.g. malonic esters, amides and nitriles, 1,3-diketones, disulphones, sulphone ketones, compounds containing three negative groups and a hydrogen atom attached to carbon and compounds having a methylene group between a conjugated double-bond system and a negative group such as esters of phenyl-acetic acid, phenyl-acetonitrile and phenyl-acetone; and hydrocarbons having a conjugated double-bond system, e.g. indene and cyclopentadiene. In the reactions using dicarboxylic acid anhydrides, the trace of compound containing a free hydroxyl group may be water or the alcohol corresponding to the alkoxy groups in the organo-tin alkoxide reactant.  The reaction product obtained using a dicarboxylic acid as the reactant may be of the formula <FORM:0766875/IV(b)/1> or <FORM:0766875/IV(b)/2> wherein R represents the hydrocarbon group, R1 is the alkyl group containing not more than 3 carbon atoms and R11 is the residue of the dicarboxylic acid.  In the examples, dibutyltin dimethoxide is reacted with each of the following compounds: lauryl alcohol, butoxytriethylene glycol, glycerine acetal, methyl salicylate, butyraldoxme, succinimide, N-butyl benzene sulphonamide, bibutyl malonate, ethyl benzoylacetate, methyl cyanoacetate, 2,4-pentanedione, diacetyl benzoyl methane, indene, 2-ethylhexyl ester of phenylacetic acid, sorbic acid and maleic anhydride; diethyl-tin dimethoxide is reacted with butyl lactate and with benzyl alcohol; diphenyl-tin dimethoxide is reacted with furfuryl alcohol; tributyl-tin monomethoxide is reacted with diacetone alcohol and with 2,4-pentanedione.  Specifications 711,145 and 735,030 are referred to.