Patent GB-789983-A (GB)
Title: Manufacture of organic metal compounds
IPC: C07F5/06
Filed: 1954-10-04
Abstract: Organic metal compounds are manufactured by reacting an alcoholate of a tri- or tetra-valent metal with an aliphatic or cycloaliphatic diketene, if necessary at a raised temperature, and, if desired, reacting the product, if it still contains part of the original alcohol residues in the alcoholate form, with a compound containing a metal reactive hydroxy group (e.g. water, an alcohol or an organic acid, or also a mono- or dicarboxylic acid anhydride, these respectively reacting, in the presence of traces of alcohol present in the alcoholate, as a mixture of acid and ester or as a semi-ester).  The process may be carried out in the presence of an inert solvent or diluent and of a basic catalyst, and the first part thereof, if desired, in stages by first reacting one reaction component with part of the other and reacting the remainder of the latter at a subsequent reaction stage and/or when the reaction product is heated.  Suitable alcoholates are: compounds in which about 0.2-1.0 equivalent of a hydrocarbon radical is bound through oxygen to one equivalent of the metal atom (obtainable by reacting the metal with the anhydrous or weakly hydrous alcohol, or a halide of the metal with the alcohol in the presence of an alkaline agent or with ethylene oxide); alcoholates of alcohols containing substituents inert under the conditions of the reaction (such as chlorine) or having their carbon chain interrupted by hetero-atoms (e.g. oxygen); "polymeric" metal alcoholates (obtained from the monomers by thermal and/or hydrolytic treatment with splitting off of alkoxy radicals and linking of the metal atoms by oxygen); acylated metal alcoholates (in which part of the alkoxy radicals has been replaced by reaction with an acid); and reaction products of a polyvalent metal alcoholate with less than the theoretical molecular proportion of an aliphatic substance which contains hydroxy groups or groups capable of desmotropic transformation into the aci form capable of forming complex compounds (such as a ketoenol compound or a known CO2 or SO2 addition product of a metal alcoholate).  Examples describe the interaction of: (1) 0.5 mol. of diketene with 1 mol. of aluminium ethoxide in ethyl acetate; (2) 3 mols. of diketene with 1 mol. of aluminium ethoxide (or aluminium ethoxide stabilized with 1 mol. of CO2) in xylene; (3) 2 mols. of diketene with 1 mol. of zirconium tetra-isopropoxide in xylene; (4) 3 mols. of diketene with 1 mol. of titanium tetraisopropoxide (or titanium tetra-isopropoxide stabilized with 0.5 mol. of acetoacetic acid ethyl ester) in xylene; (5) the product of (1) with 0.8 mol. of stearic acid in ethyl acetate and carbon tetrachloride; (6) 2 mols. of dibutyl-(or didecyl) diketene with 2 mols. of titanium tetra-isopropoxide in xylene; alternatively 1 mol. of didecyldiketene with 1 mol. of aluminium isopropoxide, preferably in the presence of triethylamine; (7) 1 mol. of aluminium sec.-butoxide (or the equivalent of a basic aluminium sec.-butoxide containing 2.2 equivalents of butoxyl per aluminium atom) with 0.5 mol. of lauric (or myristic or oleic) acid and the product with 0.5 mol. of diketene in xylene; (8) 1 mol. of aluminium sec.-butoxide with 1 mol. of benzoic (or o-toluic or a -naphthoic) acid and the product with 1 mol. of diketene in toluene; (9) 1 mol. of aluminium sec.-butoxide with 1 mol. of acetic (or propionic) acid and the product with 1 mol. of diketene, both steps in xylene; (10) 1 mol. of aluminium sec.-butoxide with 0.5 mol. of diketene and the product with 1 mol. of 12-hydroxystearic (or linolenic) acid, both steps in benzene, and the product further, if desired, with 1 mol. of 2-ethylhexanol-1; (11) 1 mol. of the product of the first step of (10) with 0.5 mol. of acetic acid and the product with 0.5 mol. of lauric acid (or resin acid or benzoic acid), both steps in benzene; (12) 1 mol. of "dimeric" titanium isopropoxide (or butoxide) with 2 mols. of diketene in benzene, and, if desired, the product with a further 2 mols. of diketene in the presence of pyridine; (13) "polymeric" zirconium isopropoxide (or butoxide) (from 2 mols. of monomer) with 1 mol. of diketene in benzene, and, if desired, the product with a further mol. of diketene in the presence of pyridine; (14) the initial product of (13) with 1 mol. of stearic (or benzoic, lauric or propionic) acid in benzene; (15) 1 mol. of aluminium sec.-butoxide (or 2-chlorethoxide) with 0.5 mol. of acetoacetic ester and 0.5 mol. of phthalic anhydride, and the product with 1 mol. of diketene, all steps in xylene. Additional reactants specified are: dihexadecyldiketene, and dimeric ketenes from naphthenic acids and resin acids; alcoholates of iron and chromium, and from cyclohexanol, 2 : 5-hexanediol, diglycol, benzyl alcohol and furfuryl alcohol; butyric and capric acids.ALSO:Organic metal compounds, some of which are resinous, are manufactured by reacting an alcoholate of a tri- or tetra-valent metal with an aliphatic or cycloaliphatic diketene, if necessary at a raised temperature, and, if desired, reacting the product, if it still contains part of the original alcohol residues in the alcoholate form, with a compound containing a metal reactive hydroxy group (including, inter alia, resin acids).  (In certain of the examples, resinous products are formed by the interaction of: (2) 3 mols. of diketene with 1 mol. of aluminium ethoxide (or aluminium ethoxide stabilized with 1 mol. of CO2) in xylene at 80-120 DEG  C.; (10) 1 mol. of aluminium sec.-butoxide with 0.5 mol. of diketene and the product with 1 mol. of 12-hydroxystearic (or linolenic) acid, both steps in benzene, and the product further, if desired (to improve its compatability with organic plastics), with 1 mol. of 2-ethylhexanol-1; (11) 1 mol. of the product of the first step of (10) with 0.5 mol. of acetic acid and the product with 0.5 mol. of lauric acid (or colophony or benzoic acid), both steps in benzene.