Journal of the Chemical Society. Perkin transactions II p. 1363 - 1368 (1983)
Update date:2022-08-04
Topics:
Hudson, Harry R.
Kow, Aloysius
Roberts, John C.
The reactions of neopenthyl diphenylphosphinite with chloro-, bromo-, or iodo-methane and of dineopentyl phenylphosphphonite with bromo- or iodo-methane yield crystalline alkoxyphosphonium halides.In deuteriochloroform these intermediates decompose by a first-order process which involves rate-determining collapse of the phosphonium halide ion-pair with SN2-type fission of the alkyl-oxygen bond.Rates for chloride, bromide, and iodide are similar.In a more ionising medium (deuterioacetonitrile) dissociation leads to stabilisation of the intermediates and to deviation from first-order decomposition.Previously determined X-ray diffraction data for the bromides, together with relative rates of decomposition in deuteriochloroform for intermediates in the series Phn(RO)3-nP+MeX- (n = 0,1, or 2) suggest that the stability and reactivity of alkoxyphosphonium intermediates are determined largely by inductive rather than mesomeric effects of ligands.The presence of phenoxy-substituents on phosphorus may cause a tendency towards SN1-type fission of the alkyl-oxygen bond in certain circumstances.
View MoreSuzhou Tianma Specialty Chemicals Co.,Ltd
Contact:+86-512-68090577
Address:#199, Huayuan Rd, Mudu, Suzhou, Jiangsu, CHINA
Jinan Jianfeng Chemical Co., Ltd
Contact:0086-531-88110457
Address:sales01(-a-t-)pharmachemm{dot}c+o+m
Contact:+86+21-58956006 15800617331
Address:402 Room, 150# Cailun Road, Zhangjiang high tech park, Shanghai
Chengdu Aslee Biopharmaceuticals, Inc
Contact:18608018419
Address:Chengdu Aslee Biopharmaceuticals, Inc
Suzhou Time-chem Technologies Co., Ltd.
Contact:0512-63983931/68086856
Address:No. 1326 of Binhe Road, New District, Suzhou, Jiangsu, P. R. China
Doi:10.1021/jo00323a032
(1981)Doi:10.1002/jps.2600690916
(1980)Doi:10.1021/ic50220a003
(1981)Doi:10.1021/jo00057a029
(1993)Doi:10.1016/j.apcata.2016.10.007
(2016)Doi:10.1016/S0040-4039(00)81421-5
(1983)
