Journal of Organic Chemistry p. 2025 - 2029 (1983)
Update date:2022-07-30
Topics:
Lewis, Edward S.
Hamp, Donald
The kinetics of the Arbuzov reactions of trivalent phosphorus esters of the type ABPOCH3 catalyzed by CH3X have been studied.The alkoxyphosphonium ion ABCH3POCH3+ is always intermediate but often undetected.In all cases studied using methyl iodide, the rate-determining step is the alkylation of the trivalent phosphorus and the intermediate alkoxyphosphonium ion does not accumulate detectibly by NMR.In all cases with methyl triflate, the alkylation is fast and complete, and the resulting alkoxyphosphonium salt then has a constant concentration.It methylates the triv alent compound (if any remains) in a measurably slow reaction, the only observed process.This reaction represents the pure "autocatalytic" mechanism.With dimethyl sulfate the intermediate accumulates but does not ordinarily persist, and the reaction course is best fit by a combination of the "autocatalytic" mechanism with attack on the intermediate phosphonium ion by ABPOCH3 and the "textbook" mechanism in which the intermediate alkoxyphosphonium ion is dealkylated by attack of the methyl sulfate anion.
View MoreHangzhou Haiqiang Chemical Co.,Ltd.
Contact:+86-571-86960370
Address:Add: 5/F, Around Town North Road,No. 10, Hangzhou, Zhejiang,China
Shanghai Dano Pharmaceutical Co.,Ld.(expird)
Contact:+86-592-6266840
Address:Building 1 Room 512, 720 Cailun Rd, Zhangjiang High-Tech Park, Shanghai 201203, China
SHANGHAI T&W PHARMACEUTICAL CO., LTD.
website:http://www.trustwe.com
Contact:+86-21-61551611
Address:601, No. 1, 2277 Nong, Zu Chongzhi Road, Zhangjiang Hightech. Park, Pudong
Contact:86-21-58226973
Address:No 351,Guoshoujing Road, Zhangjiang Hi-tech Park, Pudong, Shanghai, China
Shantou Baokang Pharmaceutical Co., Ltd.
Contact:+86-754-88873487
Address:5/F B Block Huangshan Bldg Huangshan Rd Shantou
Doi:10.1002/jccs.200700154
(2007)Doi:10.1021/acs.orglett.7b01778
(2017)Doi:10.1016/j.tet.2008.05.068
(2008)Doi:10.1002/anie.200801359
(2008)Doi:10.1007/s00044-013-0855-2
(2014)Doi:10.1016/S0040-4039(00)84389-0
(1986)