Journal of the Chemical Society. Perkin transactions II p. 2029 - 2034 (1988)
Update date:2022-08-10
Topics:
Breuer, Eli
Karaman, Rafik
Goldblum, Amiram
Leader, Haim
Heating of dialkyl acylphosphonates with sulphonic acids under anhydrous conditions leads to the formation of alkyl sulphonates and alkyl carboxylates. 31P N.m.r. spectroscopy revealed that the reaction of equimolar amounts of dimethyl benzoylphosphonate (1) and toluene-p-sulphonic acid at room temperature gives dimethyl phosphonate (6) in 50percent yield.It is proposed that the by-product of this reaction, benzoic toluene-p-sulphonic anhydride (8), reacts with the excess of toluene-p-sulphonic acid, to yield toluene-p-sulphonic anhydride (9) and benzoic acid.Heating of these two compounds with dimethyl phosphonate was shown to yield methyl toluene-p-sulphonate and methyl benzoate, respectively.A postulated by-product of these reactions is phosphenous acid (HPO2).Quantum mechanical calculations by the MNDO/H method carried out on dimethyl benzoylphosphonate and its protonation products show that the preferred site of protonation of dimethyl benzoylphosphonate is the P=O oxygen, and that protonation at this site is followed by C-P bond breaking, with zero energy of activation, leading to dimethyl phosphite and benzoylium cation.
View MorePenglai Qianwei Chemical Co., Ltd.
Contact:86-535-3357802
Address:Shahelu (north), Penglai, Shandong, China
Tianjin Te-An Chemtech Co., Ltd.(expird)
Contact:+86-22-65378638
Address:A5-8, No.80 Haiyun Street, TEDA
Taizhou Sunny Chemical Co.,Ltd
Contact:+86-523-86920899 +86-13951172783
Address:No.11 Xingyuang road, Gaoyong Chemical Industry Park, Gaogang Jiangsu China
Contact:86-510-82853889
Address:Rm.3732, No.18-2,Yonghe Rd.,Wuxi,Jiangsu,214023,China
Beijing Mesochem Technology Co.,LTD
website:http://www.mesochem.com
Contact:0086-10-57862036
Address:2301, Floor 23, Building 9 Lippo Plaza, Yard 8 Ronghua Middle Road, ETDZ, Beijing, China
Doi:10.1007/s00706-018-2212-0
(2018)Doi:10.1039/c5ob01081k
(2015)Doi:10.1016/S0040-4039(00)93149-6
(1976)Doi:10.1021/acscatal.9b01646
(2019)Doi:10.1023/A:1012315513204
(2001)Doi:10.1002/poc.610060802
(1993)
