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Unconventional reactivity of epichlorohydrin in the presence of triphenylphosphine: isolation of ((1,4-dioxane-2,5-diyl)-bis-(methylene))-bis-(triphenylphosphonium) chloride

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Abstract

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 Brønsted 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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Authors and Affiliations

  1. Department of Chemistry, Materials and Chemical Engineering “G. Natta”, Politecnico di Milano, Piazza L. da Vinci 32, 20133, Milan, Italy

    Alberto Mannu, Maria Enrica Di Pietro, Alessandro Sacchetti & Andrea Mele

  2. Dipartimento di Chimica, Università di Torino, Via Pietro Giuria, 7, 10125, Turin, Italy

    Alberto Mannu, Emanuele Priola & Salvatore Baldino

  3. CNR-ICRM Istituto di Chimica del Riconoscimento Molecolare, “U.O.S. Milano Politecnico”, Via L. Mancinelli, 7, 20131, Milan, Italy

    Andrea Mele

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  1. Alberto Mannu
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Mannu, A., Di Pietro, M.E., Priola, E. et al. Unconventional reactivity of epichlorohydrin in the presence of triphenylphosphine: isolation of ((1,4-dioxane-2,5-diyl)-bis-(methylene))-bis-(triphenylphosphonium) chloride. Res Chem Intermed 47, 1663–1674 (2021). https://doi.org/10.1007/s11164-020-04364-9

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