Rate and Product Studies in the Solvolyses of Two Cyclic Phosphorochloridate Esters |
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| Authors: | Han Joong Koh Suk Jin Kang Dennis N. Kevill |
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| Affiliation: | 1. Department of Science Education , Chonju National University of Education , Chonju, Korea;2. Department of Chemistry and Biochemistry , Northern Illinois University , DeKalb, Illinois, USA |
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| Abstract: | Kinetic and product studies of the solvolyses of acyclic phosphorochloridates are extended to two cyclic diesters, 2-chloro-1,3,2-dioxaphospholane-2-oxide (1) and 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane-2-oxide (2). Slightly faster solvolyses are observed for 1 than for the acyclic dimethyl phosphorochloridate (3), and 2 solvolyzes somewhat slower than 3. An extended Grunwald–Winstein equation treatment shows similar sensitivities to changes in solvent nucleophilicity and solvent ionizing power for 1, 2, and 3, and a concerted SN2 attack is proposed in each case. Product studies for the solvolyses of 2 in aqueous alcohols are presented.  | |
| Keywords: | Cyclic phosphorochloridates extended Grunwald–Winstein equation solvolysis |
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