Hydrochloric Acid → 5-Hexenoic acid, 4,6,6-trichloro-3,3-dimethyl-, methyl ester

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Reaction Steps

In 80 parts of methanol was dissolved 12.0 parts of sodium hydroxide and, at the reflux temperature of methanol, 51.9 parts of methyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate was added dropwise to the above solution over a period of 30 minutes, followed by stirring the mixture at that temperature for 30 minutes. Then, about 50 parts of water was added and, after refluxing for about 30 minutes, the reaction mixture was allowed to cool and neutralized with concentrated hydrochloric acid. The methanol was distilled off under reduced pressure and the residue was extracted with diethyl ether. The ether layer was dried and the ether was distilled off, whereupon 42.2 parts of a mixture of 2,2-dimethyl-3-(2',2'-dichlorovinyl) cyclopropanecarboxylic acid and 3,3-dimethyl-4-(2',2'-dichloroviyl)-4-butanolide. This mixture was further distilled under reduced pressure to separate 10.4 parts of 3,3-dimethyl-4-(2',2'-dichlorovinyl)-4-butanolide (yield 25%; bp: 86°-91° C./0.2 mmHg) and 22.3 parts of 2,2-dimethyl-3-(2',2'-dichlorovinyl) cyclopropanecarboxylic acid (yield 53%; bp: 105°-108° C./0.2 mmHg). Then, 10.4 parts of the former product 3,3-dimethyl-4-(2',2'-dichlorovinyl)-4-butanolide was dissolved in 70 parts of methanol and, under cooling with ice, hydrogen chloride gas was bubbled into the solution for about 1.5 hours. Thereafter, the excess hydrogen chloride and methanol were distilled off under reduced pressure and the residue was further subjected to distillation under reduced pressure. By this procedure was obtained 12.1 parts of methyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate (yield 23% based on starting material).

Provenance & Evidence