Journal of the Chemical Society. Perkin transactions II p. 177 - 182 (1988)
Update date:2022-08-04
Topics:
Al-Awadi, Nouria
Taylor, Roger
We have measured rates of thermal decomposition and Arrhenius parameters for S-alkyl O-phenyl thiocarbonates, O-alkyl O'-phenyl thiocarbonates, S-alkyl O-phenyl and O-alkyl S-phenyl dithiocarbonates (xanthates), and alkyl phenyl trithiocarbonates between 671.4 and 819.2 deg K.The reactivity order is: PhOCSOR>PhOCO2R>PhSCSOR>PhSCO2R>PhOCSSR>PhSCSSR>PhOCOSR>(PhSCOSR).Compared with the pyrolysis of acetates the rate decrease accompanying change of carbonyl to thiocarbonyl is smaller, whilst that accompanying change of OR to SR is greater, because the transition state for carbonate pyrolysis is more E1-like within the overall semi-concerted process.The accelerating effect of thion sulphur is greatest for ethyl derivatives which have the least E1-like transition state.The iPr/Et rate ratios at 700 deg K are: 30.7 (PhOCO2R), α-X bond breaking may be the most important rate determining step.Compounds containing thione sulphur and O-alkyl groups (but not O-phenyl groups) undergo sulphur-oxygen exchange.A mechanism for this exchange is given which accounts both for these structural aspects and the much slower exchange in thionacetates.For carbonates, exchange is more severe for compounds which have the slowest competing elimination.Compounds PSCSSiPr, PhSCSSEt, PhOCSSEt, and PhOCOSEt each gave abnormally low activation energies (and low stoicheiometry) due to competing nucleophilic substitution which gives ethers.This reaction is predicted to be important also for compounds PhSCOSR.
View MoreHUNAN CHEMAPI BIOLOGICAL TECHNOLOGY CO.,LTD.
Contact:+86-186-02659358
Address:1004, building 3, Wanke Jinsemaitianyuan, 498 Guitang Road, Yuhua District, Changsha City, Hunan Province, China
website:http://www.afinechem.com
Contact:+86-571-85134551
Address:No. 206 Zhen Hua Road, Hangzhou 310030, Zhejiang, China
Contact:86-931-8272767
Address:Room 602, No.461, Nanchang Road, Chengguan District, Lanzhou City, China PRC
ShanDong XinDa Chemical CO.,LTD(expird)
Contact:086-0311-87580543
Address:No.168, High Technology Development Zone Jinan Shandong China
jintan yufan Medicine Raw materials Co.,Ltd.(expird)
Contact:86-519-82808282
Address:6th,Jincheng Huangzhuang
Doi:10.1016/j.tetlet.2009.05.042
(2009)Doi:10.1021/jm900488k
(2009)Doi:10.1021/je00055a037
(1989)Doi:10.1016/j.tetasy.2009.03.002
(2009)Doi:10.1002/anie.201503941
(2015)Doi:10.1039/b903374m
(2009)
