Patent GB-476329-A (GB)
Title: A process for the manufacture of organic addition compounds containing heavy metals
IPC: C07F1/08
Filed: 1936-03-30
Abstract: Complex double compounds containing metals are prepared by combining non-noble heavy metal compounds derived from alcohols, esters, ketones or mercaptans, which in aqueous or alcoholic solution do not have an acid reaction to phenol phthalein and do not contain nitrogen, with completely alkylated and/or arylated compounds of nitrogen, phosphorus or sulphur not substituted in the alkyl or aryl groups, or with alkyl and/or aryl phosphites. The metal compounds may be prepared in situ, e.g. by reacting the oxides or hydroxides of the metals with the organic compounds. The products are useful as additions to hydrocarbon mixtures, including gasoline and lubricating oils.  Added to gasoline, they improve the anti-knock properties, whilst their addition to lubricants render them suitable as extreme-pressure lubricants or act as anti-oxidants.  Examples of organic metallic compounds are cupro-n-propylmercaptide, cupro-methylethylketone, cupro-methylpropylketone and cupric alcoholate; second components specified are pyridine, quinoline, triethylamine, triethylphosphine, tripropylphosphine, triphenylphosphine, triethylphosphite, triheptylphosphite, thioethylether and ethylene-diethylsulphide.  Examples are given of the preparation of: (1) cupric alcoholate-tripropylphosphine from 1 molecular proportion of the first and 2 of the second in benzene, and (2) cupro-methylpropylketone-pyridine from sodium methylpropylketone, obtained by interaction of methylpropylketone and sodamide, cuprous bromide and pyridine in ethereal solution. The double compounds cupro-n-propylmercaptide-triheptylphosphite, cupro-methylethylketone-pyridine and cupro-methylpropylketonequinoline are referred to.  The samples furnished under Sect. 2 (5) comprise: (1) silver tert-butylmercaptide-triethylphosphite prepared by heating the components together; (2) nickel malonic acid diethylester - triethylphosphine obtained by treating nickel chloride with malonic acid diethylester in methyl alcoholic sodium methylate solution, distilling off the alcohol and heating the residue with triethylphosphine; (3) cupro - n - propylmercaptide - trimethylphosphite prepared by adding cuprous oxide to a mixture of trimethylphosphite and n-propylmercaptan; (4) cupro-pentanone-2-triethylphosphite formed from cuprous oxide, triethylphosphite and pentanone-2.  The Specification as open to inspection under Sect. 91 describes the combination of organic metal compounds, except those derived from acids or phenols, with substituted or non-substituted alkyl or aryl compounds of nitrogen, phosphorus, arsenic, antimony, sulphur, selenium or tellurium, or esters of the acids of these elements.  The metal compounds may be derived from the following additional classes of compounds, viz.: oximes, acid amides, amines, nitriles, amino-alcohols, phosphines, triazenes, benzene azo compounds and such hydrocarbons as cyclopentadiene, butadiene, acetylene and homologues.  Other second components specified are ethylamine, ethanolamine, amino-acetic acid, ethylenediamine, ethylcarbylamine, phenylcarbylamine, acetonitrile, triethylstibine, ethyl thioglycollic acid ethyl ester, dimethylselenium and dimethyltellurium.  It also describes the preparation of (1) silver acetamide-triethylphosphine by interaction of sodium acetamide, triethylphosphine and silver chloride in benzene; (2) cupro-g -chloracetylacetic acid ethyl ester-di-n-butyl sulphide from g -chloracetylacetic acid ethyl ester, sodium ethylate, cuprous chloride and di-n-butyl sulphide in alcohol solution; (3) cupric urea-tri-n-propylphosphite by heating the phosphite with cupric oxide and urea in a nitrogen atmosphere; (4) silver acetamide-tri-n-propylphosphine by boiling the phosphine in a nitrogen atmosphere with silver oxide, acetamide and benzol; (5) nickel formanilide-tri-n-propylphosphite by heating the phosphite with nickel hydroxide and formanilide in a nitrogen atmosphere; (6) cupro - cyclopentadiene - tri - n - propylphosphine by boiling the phosphine with cuprous oxide, cyclopendadiene and benzol in a nitrogen atmosphere.  The following double compounds are also referred to: cupro-urea-triethylphosphine, silver acetamide-triethylphosphite, cupro - aniline - triethylphosphite, nickel formamide - triethylphosphite, cobalti-formanilide - tripropylphosphite, cupro - acetamide - trimethylamine, cupro - benzol - azoacetylacetic acid ethyl ester-triethylphosphine and cupric isovaleramide - dibutyl sulphide.  This subject-matter does not appear in the Specification as accepted.ALSO:Complex double compounds containing metals, which are useful as additions to gasoline and lubricants, are prepared by combining, on the one hand, non-noble heavy metal compounds derived from alcohols, esters, ketones or mercaptans which in aqueous or alcoholic solution do not have an acid reaction to phenol phthalein and do not contain nitrogen, and on the other hand, completely alkylated and/or arylated compounds of nitrogen, phosphorus or sulphur not substituted in the alkyl or aryl groups, or alkyl and/or aryl phosphites.  Added to gasoline, the compounds improve their anti-knock properties, whilst their addition to lubricants render them suitable as extremepressure lubricants or act as anti-oxidants.  Examples of organic metallic compounds are cupro-n-propylmercaptide, cupro-methylethylketone, cupro-methylpropylketone and cupric alcoholate; second components specified are pyridine, quinoline, triethylamine, triethylphosphine, tripropylphosphine, triphenylphosphine, triethylphosphite, triheptylphosphite, thioethylether and ethylene-diethylsulphide. Examples are given of the preparation of cupric alcoholate - tripropylphosphine and cupromethylpropylketone-pyridine.  The double compounds cupro - n - propylmercaptide - triheptylphosphite, cupro - methylethylketone - pyridine and cupro-methylpropylketone-quinoline are referred to.  The samples furnished under Sect. 2 (5) comprise (1) silver tert-butylmercaptide-triethylphosphite, (2) nickel malonic acid diethylester-triethylphosphine, (3) cupro - n - propylmercaptide - trimethylphosphite, and (4) cupro-pentanone-2-triethylphosphite. The Specification as open to inspection under Sect. 91 describes the combination of organic metal compounds, except those derived from acids or phenols, with substituted or non-substituted alkyl or aryl compounds of nitrogen, phosphorus, arsenic, antimony, sulphur, selenium or tellurium, or esters of the acids of these elements.  The metal compounds may be derived from the following additional classes of compounds, viz: oximes, acid amides, amines, nitriles, amino-alcohols, phosphines, triazenes, benzene azo compounds and such hydrocarbons as cyclopentadiene, butadiene, acetylene and homologues. Other second components specified are ethylamine, ethanolamine, amino-acetic acid, ethylenediamine, ethylcarbylamine, phenylcarbylamine, acetonitrile, triethylstibine, ethyl thioglycollic acid ethyl ester, dimethylselenium and dimethyltellurium.  It also describes the preparation of (1) silver acetamide-triethylphosphine, (2) cupro - g  - chloracetylacetic acid ethyl ester-di-n-butyl sulphide, (3) cupric urea - tri - n - propylphosphite, (4) silver acetamide - tri - n - propylphosphine, (5) nickel formanilide - tri - n - propylphosphite, and (6) cupro-cyclopentadiene-tri-n-propylphosphine.  The following double compounds are also referred to:--cupro-urea-triethylphosphine, silver acetamide-triethylphosphite, cupro-aniline-triethylphosphite, nickel formamidetriethylphosphite, cobalti-formanilide-tripropylphosphite, cupro-acetamide-trimethylamine, cupro-benzol-azo-acetylacetic acid ethyl ester-triethylphosphine and cupric isovaleramidedibutyl-sulphide.  This subject-matter does not appear in the Specification as accepted.