Journal
RESEARCH ON CHEMICAL INTERMEDIATES
Volume 47, Issue 4, Pages 1663-1674Publisher
SPRINGER
DOI: 10.1007/s11164-020-04364-9
Keywords
Epichlorohydrin; Triphenylphosphine; Zwitterion; Phosphonium; Dioxane
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The selective formation of the heterocyclic salt was observed when epichlorohydrin and triphenylphosphine were reacted in CH2Cl2 at room temperature. Mechanistic investigations showed the formation of a zwitterionic intermediate and the generation of the 1,4-dioxane derivative through dimerization.
The selective formation of the heterocyclic salt ((1,4-dioxane-2,5-diyl)-bis-(methylene))-bis-(triphenylphosphonium) chloride was observed when epichlorohydrin and triphenylphosphine were reacted in CH2Cl2 at room temperature. Slow evaporation from a mixture of ethanol and ethyl acetate allows to isolate monocrystals of the heterocyclic phosphonium salt. Mechanistic investigations point to the formation of the zwitterionic intermediate 1-chloro-3-(triphenylphosphonio)-propan-2-olate, which can dimerize and generate the 1,4-dioxane derivative. In the exclusive presence of a Bronsted acid as HCl, which usually facilitates epoxide ring opening, the exclusive formation of 1,3-dichloro-2-propanol was although observed. Also, when epichlorohydrin, PPh3, and a stoichiometric amount of HCl were mixed, (2-chloro-3-hydroxypropyl)-triphenylphosphonium chloride was formed and its isolation in pure form provides monocrystals subjectable to X-ray analysis.
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