oxide mixture (64.4% trans, 27.8% cis, and 7.8% 4,5dihydrooxepine) heated on a steam bath overnight resulted in the disappearance of cis-1,2-divinylethylene oxide. The composition after the heating period was 61.8% trans oxide and 38.2% 4,5-dihydrooxepine.The thermal requirements for ring expansion of 1,2divinylethylene oxide and 1,2-divinylcyclopropane3 are apparently analogous. In both cases, ring expansion of the cis isomer requires about 200°less than the corresponding trans isomer. Extension of valence tautomerism to other small ring heterocycles is currently under investigation in our laboratories. Experimental 3-Chloro-4-acetoxy-1,5-hexadiene.-The procedure used for the preparation of 3-chloro-4-acetoxy-l,5-hexadiene was an adaptation of Searles8 technique for preparation of chloro esters from 1,3-diols.Acetyl chloride, 190 g. (2.44 moles), was added to a stirred suspension of 41.6 g. (0.38 mole) of calcium chloride and 228 g.(2.0 moles) of 1,5-hexadiene-3,4-diol over a period of 45 min. During the addition, the temperature was maintained below 10°. The reaction mixture then was stirred for 40 hr. at room temperature and then 1 hr. at 50°. The dark brown viscous product was poured into ice, neutralized with cold aqueous sodium bicarbonate extracted with ether, and dried over anhydrous potassium carbonate. After filtration and removal of ether, thereChemistry Office, and was monitored by Army Ordnance under Contract No. DA-30-069-ORD-2487.cis-trans Isomerism of Exocyclic
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