| 摘要 |
Chemical reactions involving the formation of a carbanion intermediate and catalysed by an alkali metal or hydroxide, alkoxide, hydride, amide or alkyl thereof are effected in an aprotic (neither donating nor readily accepting a proton) organic liquid, free of hydroxyl groups, having a dielectric constant above 15 at 25 DEG C. containing a dipolar radical with the proviso that when an alkali metal is used the organic liquid is free of hydrogen atoms on the dipolar radical and adjacent atoms. Specified liquids containing PO, CO, SO, SO2 or CS radicals are dimethyl sulphoxide, diisopropylsulphoxide, tetramethyl sulphonamide, bis-dialkylamino sulphoxide, tetramethylene sulphone, tetramethyl urea, dimethy acetamide, N,N-dimethyl formamide, t-butyl, N,N-dimethyl formamide, trimethyl phosphoramide, hexamethyl phosphoramide, tri-(ethyleneimine) phosphoramide, trimethyl phosphate, tris-(methylmercapto) phosphine oxide, N,N1-dimethyl thiourea and tetramethyl thiourea. The reaction mixture may be homogeneous or heterogeneous. Conditions used vary according to the reaction but generally the alkali metal or compound thereof forms 10-40% by weight of the catalyst-diluent composition. The reaction preferably runs at a rate of at least 0.1 wt. of feed/hour/wt. of catalyst. The temperature is in the range 15-400 DEG C. Specified reactions are: (1) Polymerization of mono- and di-olefins and vinyl compounds. In examples: (14) butadiene is polymerized to a viscous product in the presence of butyl lithium and hexamethylphosphoramide; (15) ethylene is polymerized to a viscous liquid in the presence of benzyl potassium and hexamethyl phosphoramide; (20) ethylene is converted to butane in the presence of sodium and hexamethyl phosphoramide followed by the addition of water or methy alcohol; (21) butadiene is polymerized to a viscous product in the presence of lithium or sodium and hexamethyl phophoramide and optionally added pentane. (2) Alkylation of alkyl aromatic side chains with olefins. An Example (19) describes the conversion of ethylene and toluene to propyl benzene and amyl benzene. (3) Isomerization of olefins. Examples describe the converion of 2-methylpentene-1 to 2-methylpentene-2 (Examples 1, 2, 6,8, 17, 18 and 23) butene-1 to cis-butene-2 (3) and other olefins (4 and 7) including 3-phenylpropane to 1-phenylpropane. (4) Generation of the carbene radical from halides, ethers, sulphides, or ammonia salts and the addition of the carbene to olefins, diolefins and aromatics. Norcarane is produced from cyclohexene and methyl chloride, or (Examples 11 and 12). (5) Homogeneous hydrogenation of olefins, diolefins and aromatics. (6) Formation of benzyne from any known benzyne precursors and reactions thereof. (7) Production of metal alkyls from metal and organic halides or of Grignard reagents from magnesium and organic halides. In an Example (22), benzyl chloride is added to a solution of potassium in hexamethylphosphoramide; on addition of water, toluene is formed.ALSO:Chemical reactions involving the formation of a carbanion intermediate and catalysed by an alkali metal or hydroxide, alkoxide, hydride, amide or alkyl thereof are effected in an aprotic (neither donating nor readily accepting a proton) organic liquid, free of hydroxyl groups, having a dielectric constant above 15 to 25 DEG C. containing a dipolar radical with the proviso that when an alkali metal is used the organic liquid is free of hydrogen atoms on the dipolar radical and adjacent atoms. Specified liquids containing PO, CO, SO, SO2 or CS radicals are dimethyl sulphoxide, diisopropylsulphoxide, tetramethyl sulphonamide, bis-dialkylamino sulphoxide, tetramethylene sulphone, tetramethyl urea, dimethyl acetamide, N,N-dimethyl formamide, t-butyl, N,N-dimethyl formamide, trimethyl phosphoramide, hexamethyl phosphoramide, tri-(ethyleneimine) phosphoramide, trimethyl phosphate, tris-(methyl mercapto) phosphine oxide, N,N1-dimethyl thiourea and tetramethyl thiourea. The reaction mixture may be homogeneous or heterogeneous. Conditions used vary according to the reaction but generally the alkali metal or compound thereof forms 10-40% by weight of the catalyst-diluent composition. The reaction preferably runs at a rate of at least 0.1 wt. of feed/hour/wt. of catalyst. The temperature is in the range 15-400 DEG C. Specified reactions are: (1) Polymerization of mono- and di-olefins and vinyl compounds. In examples: (14) butadiene is polymerized to a viscous product in the presence of butyl lithium and hexamethyl-phosphoramide; (15) ethylene is polymerized to a viscous liquid in the presence of benzyl potassium and hexamethyl phosphoramide; (21) butadiene is polymerized to a viscous product in the presence of lithium or sodium and hexamethyl phosphoramide and optionally added pentane.ALSO:Chemical reactions involving the formation of a carbanion intermediate and catalysed by an alkali metal or hydroxide, alkoxide, hydride, amide or alkyl thereof are effected in an aprotic (neither donating nor readily accepting a proton) organic liquid, free of hydroxyl groups, having a dielectric constant above 15 at 25 DEG C. containing a dipolar radical with the proviso that when an alkali metal is used the organic liquid is free of hydrogen atoms on the dipolar radical and adjacent atoms. Specified liquids containing PO, CO, SO, SO2 or CS radicals are dimethyl sulphoxide, diisopropylsulphoxide, tetramethyl sulphonamide, bis-dialkylamino sulphoxide, tetramethylene sulphone, tetramethyl urea, dimethyl acetamide, N,N-dimethyl formamide, t.-butyl, N,N-dimethyl formamide, trimethyl phosphoramide, hexamethylphosphoramide, tri-(ethyleneimine) phosphoramide, trimethyl phosphate, tris-(methylmercapto) phosphine oxide, N,N1-dimethyl thiourea and tetramethyl thiourea. The reaction mixture may be homogeneous or hterogeneous. Conditions used vary according to the reaction but generally the alkali metal or compound thereof forms 10-40% by weight of the catalyst-diluent composition. The reaction preferably runs at a rate of at least 0.1 wt. of feed/hour/wt. of catalyst. The temperature is in the range 15-400 DEG C. Specified reactions are:-(1) alcohol and cannizzaro condensations, malonic ester condensations and Michael additions; (2) alkylation of ketones with organic halides and metal alkyls with olefins; (3) carboxylation of alkyl aromatics or olefins to carboxylic acids, e.g. toluene yields phenylacetic acid and propylene yields acrylic acid; (4) carbonylation of alkyl aromatics or olefins to yield aldehydes; (5) generation of the carbene radical from halides, ethers, sulphides, or ammonia salts and the addition of the carbene to olefins, diolefins and aromatics; (6) hydroboration of olefine and diolefins; (7) reacting alkynes and alcohols to form vinyl ethers; (8) oxidation of alkyl aromatics or heterocyclics or of olefins to carboxylic acids or, in the presence of ammonia to the corresponding ammonium salt, or the oxidation of these starting materials to alcohols; the oxidation of benzene to phenol; the oxidation of alkyl aromatics to ketones and the oxidation of mercaptans to disulphides or sulphonic acids. In Examples (5) a butyl mercaptan is oxidized to the disulphide, (6) toluene is oxidized to benzoic acid and xylene to phthalic acid and (13) n-butyl mercaptan is oxidized to n-butyl sulphonc acid; (9) production of metal alkyls from metal and organic halides or of Grignard reagents from magnesium and organic halides. In an Example (22), benzyl chloride is added to a solution of potassium in hexamethylphosphoramide; on addition of water, toluene is formed. |
