- Reaction mechanism studies of solvolytic displacement of chloride from phosphorus
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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
- Koh, Han Joong,Kang, Suk Jin,Kevill, Dennis N.
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- Rate and product studies in the solvolyses of two cyclic phosphorochloridate esters
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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.
- Koh, Han Joong,Kang, Suk Jin,Kevill, Dennis N.
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- FACTORS DETERMINING THE REACTIVITY OF PHOSPHOROUS TRIESTERS IN REACTIONS WITH CUMENE HYDROPEROXIDE
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The kinetics of reduction of cumene hydroperoxide with a wide range of aliphatic and aromatic phosphorous triesters in benzene were studied by the polarographic method.Factors determining the reactivity of the phosphites in this reaction were investigated by the method of correlation analysis.
- Cherkasova, O. A.,Galkin, V. I.,Sayakhov, R. D.,Mukmeneva, N. A.,Cherkasov, R. A.
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p. 862 - 865
(2007/10/02)
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- 2-Alkyl-5,5-dimethyl-1,3,2-dioxaphosphorinan-2-ones α-Lithiated Carbanions. Synthesis, Stability, and Conformation
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The preparation and a conformational study of lithiated 2-alkyl-5,5-dimethyl-1,3,2-dioxaphosphorinan-2-ones (2) in THF-hexane are described.These anions are present as two rapidly interconverting species with the P=O bond either axial (2a) or equatorial (2e).They are thermally unstable, but can be stabilised by the presence of one equivalent of LiBr or of lithium di-isopropylamide.A 31P NMR study of the self condensation of the carbanions (2) showed that the phosphorus atom in the axial conformation (2a) is more electrophilic than in the equatorial one (2e).An X-ray structural study of 2,5,5-trimethyl-1,3,2-dioxaphosphorinan-2-one is described.
- Patois, Carl,Ricard, Louis,Savignac, Philippe
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p. 1577 - 1581
(2007/10/02)
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