873-99-4Relevant articles and documents
Rate and product studies in the solvolyses of two cyclic phosphorochloridate esters
Koh, Han Joong,Kang, Suk Jin,Kevill, Dennis N.
scheme or table, p. 1404 - 1415 (2010/08/21)
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. [image presented]. Copyright Taylor & Francis Group, LLC.
Reaction mechanism studies of solvolytic displacement of chloride from phosphorus
Koh, Han Joong,Kang, Suk Jin,Kevill, Dennis N.
body text, p. 364 - 368 (2009/04/04)
The extended Grunwald-Winstein equation is applied to solvolytic displacement at phosphorus. Previous studies of the solvolyses of phosphorochloridates (RO)2POCl, Ph2POCl and [(CH3)2N]2POCl are extended to cyclic phosphorochloridates, with five and six me
Phosphorochloridates from phosphorohydrazides with ButOCl: Stereospecificity, selectivity and phosphorylium ion intermediates
Harger, Martin J.P
, p. 6749 - 6752 (2007/10/03)
The efficiency with which a six-membered cyclic phosphorochloridate can be obtained from the corresponding hydrazide with retention of configuration at phosphorus, using tert-butyl hypochlorite in tert-butyl alcohol, depends on how stereoelectronic factors influence the fate of an intermediate chloride-phosphorylium ion pair.