Conclusions
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1.
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.
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2.
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.
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3.
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.
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For Communication 7 see Acta Phys. et Chem. Szeged,9, 124 (1963).
Translated from Izvestiya Akademii Nauk USSR, Seriya Khimicheskaya, No. 5, pp. 878–882, May, 1966.
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Shuikin, N.I., Bartok, M. & Kozma, B. Diols and epoxides Communication 8. Reactions of isomeric γ-chloro butanol acetates with potassium hydroxide. Russ Chem Bull 15, 840–843 (1966). https://doi.org/10.1007/BF00849383
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DOI: https://doi.org/10.1007/BF00849383