| 摘要 |
1,237,055. Ethylenically unsaturated compounds. ZOECON CORP. 17 Oct., 1969 [3 Feb., 1969; 11 April, 1969], No. 51168/69. Heading C2C.α,#-Ethylenically unsaturated compounds are prepared fromα,#-acetylenically unsaturated acid esters, amides, aldehydes, ketones or nitriles, having on the #-carbon atom a hydrogen atom or a saturated or unsaturated, substituted hydrocarbon group, by reacting with an organometallic compound. The metal atom of the organo-metallic compound is copper (I), manganese (II), iron (II), cobalt (II), chromium (II) and chromium (III) and the organo group is a saturated or unsaturated, substituted or unsubstituted hydrocarbon group, which is added to the #-carbon atom of the acetylenically unsaturated compound. The organometallic compound may be prepared by reacting (a) a metal salt with organo-lithium; (b) a metal salt with organo-magnesium halide; or metal salt with diorgano-magnesium in an inert anhydrous organic solvent at from - 150‹ C. to room temperature. Examples describe the preparation of methyl 3-methyl-pent-2-enoate from methyl 2-pentynoate using dimethyl copper lithium; methyl 3,7-dimethylocta-2,6-dienoate from methyl 2-butynoate using a 4-methylpent- 3-en-1-yl copper reagent; trans-pyrrolidyl-3,7,- 11 - trimethyldodeca - 2,6,10 - trienamide from pyrrolidylbut - 2 - ynamide; 1 - cyano - 3 - tbutylhex-1-ene from 1-cyano-1-hexyne; trans- and cis-ethyl 3-ethyloct-2-enoate from ethyl 2- octynoate; methyl 10,11-methylene-3,7,11-trimethyldodeca-2,6-dienoate from methyl 2- butynoate; methyl 4,4-dimethylpent-2-enoate from methyl propiolate; and methyl hept-2- enoate from methyl propiolate. |
