Abstract:
Organometallic complexes of transition metals, free of carbon monoxid are produced electrochemically by electrolysis in a cell having two metal electrodes and electrolyte solution comprising an organic solvent, a suitable complexing agent and, optionally, a conducting salt. The transition metal compounds involved comprise those of Groups IVb to VIIb and VIII and they may be used in metallic form as the anode. The cathode is advantageously a metal toward which the electrolyte is inert, e.g. aluminum. The complexing agent preferably comprises a compound of a transition metal of Group IVb, VIb or VIII, e.g. an acetylacetonate, organic acid salt or alkanolate of titanium, chromium, iron, cobalt or nickel. Quaternary ammonium or alkali metal salts may be used as conductors. The products are suited for catalysis of hydrogenation, oligomerization and isomerization.
Abstract:
PROCESS OF CYCLOCO-OLIGOMERIZATION OF A CONJUGATED DIOLEFIN, SUCH AS BUTADIENE OR A SUBSTITUTED BUTADIENE, WITH A DIFFERENT CYCLIC UNSATURATED HYDROCARBON, WHICH IS AN ACETYLENE AND/OR A NON-CONJUGATED OLEFIN, PREFERABLY A MONOOLEFIN, TO PRODUCE MULTICYCLIC PRODUCTS HAVING OLEFINIC UNSATURATION IN AT LEAST ONE OF THE RINGS. THESE PRODUCTS ARE MADE BY REACTING THE ABOVE-MENTIONED REACTANTS TOGETHER IN CONTACT WITH A CARBONYL-FREE, O-VALENT NICKEL COMPOUND CATALYST. MANY OF THE NEW PRODUCTS FORMED BY THIS PROCESS ARE DESCRIBED, CHARACTERIZED AND CLAIMED.
Abstract:
Alkyl tin trihalides are prepared by the reaction between dialkyl tin dihalides or tetra-alkyl tin and tin tetrahalides in the presence of phosphorus-halogen compounds, alone or in admixture with phosphorus oxides, or a hydrogen halide. Specific catalysts are phosphorus oxychloride, alone or in admixture with phosphorus pentoxide, and hydrochloric acid. The reaction is carried out at the boiling point of the mixture, advantageously under pressure and optionally in the presence of an inert diluent. The process of the invention may be modified in that tin tetrahalide and tetra-alkyl tin are reacted in known manner to form alkyl tin trihalides, which may be separated, and other alkyl tin halides, and the reaction completed by adding further tin tetrahalide and the catalyst of the invention.
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:
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.