Diols and epoxides Communication 8. Reactions of isomeric γ-chloro butanol acetates with potassium hydroxide
- 54 Downloads
The reactions of 4-chloro-2-butanol acetate (I) and 3-chloro-1-butanol acetate (II) with potassium hydroxide were investigated. From (I) 1,3-epoxybutane is formed in 80–85% yield, but from (II) the yield of 1,3-epoxybutane is low (about 7%), and propene (about 55%), trans-2-buten-1-ol (about 6%), and 3-buten-1-ol (about 17%) are formed.
The course of the transformations of a γ-chloro alkanol acetate under the action of caustic alkali is essentially determined by the structure of the compound. For a system with the chlorine atom in a primary position, the main course is the formation of the β-epoxide by the mechanism of intramolecular nucleophilic exchange. In the case of a compound with the chlorine atom in a secondary position the main course is the formation of an olefin and an oxo compound. These two main processes pass through the intermediate stage of a chloroalkoxide.
The two main reactions may be accompanied by bimolecular nucleophilic exchange processes—the formation of a 1,3-diol and unsaturated alcohols. In the case of γ-chloro alkanol acetates, with increase in the order of the carbon atom carrying the chlorine atom the intramolecular nucleophilic exchange reaction is displaced toward 1,4- and 1,2-elimination.
KeywordsPropene Carbon Atom Exchange Reaction Butanol Epoxide
Unable to display preview. Download preview PDF.
- 1.F. Sondheimer and R. B. Woodward, J. Amer. Chem. Soc.75, 5439 (1953).Google Scholar
- 2.N. G. Gaylord, J. H. Crowdle, W. A. Himmler, and H. J. Pepe, J. Amer. Chem. Soc.76, 59 (1954).Google Scholar
- 3.S. Searles, K. A. Pollart, and E. F. Lutz, J. Amer. Chem. Soc.79, 948 (1957).Google Scholar
- 4.M. Bartok and A. S. Gilde, Acta Phys. et Chem. (Szeged)9, 25 (1963).Google Scholar
- 5.J. B. Rose, J. Chem. Soc.1956, 542.Google Scholar
- 6.S. Searles, K. A. Pollart, and F. Block, J. Amer. Chem. Soc.79, 952 (1957).Google Scholar
- 7.A. Rosowsky and D. S. Tarbell, J. Organ. Chem.26, 2255 (1961).Google Scholar
- 8.G. Forsberg, Acta Chem. Scand.8, 135 (1954).Google Scholar
- 9.G. Forsberg, Nagra alifatiska klorhydriner och deras alkaliska hydrolys. Lund,1954, 84.Google Scholar
- 10.D. C. Dittmer, W. R. Hertler, and H. Winicov, J. Amer. Chem. Soc.79, 4431 (1957).Google Scholar
- 11.R. B. Clayton, H. B. Henbest, and M. Smith, J. Chem. Soc.1957, 1982.Google Scholar
- 12.S. Searles, R. G. Nickerson, and W. K. Witsiepe, J. Organ. Chem.24, 1839 (1959).Google Scholar
- 13.D. Kram., Steric Effects in Organic Chemistry. Ed. M. S. Newman, N.Y., 1956, p. 297.Google Scholar
- 14.S. Searles and M. J. Gortatowski, J. Amer. Chem. Soc.75, 3030 (1953).Google Scholar
- 15.H. B. Henbest and B. B. Millward, J. Chem. Soc.1960, 3575.Google Scholar
- 16.E. Kovacs, N. I. Shuikin, M. Bartok, and I. F. Bek'skii, Izv. AN SSSR. Otd. khim. n.1962, 124.Google Scholar
- 17.M. Bartok, B. Kozma, and J. Apjok, Izv. AN SSSR. Ser. khim.1964, 2192.Google Scholar