Journal of Organic Chemistry p. 761 - 764 (1989)
Update date:2022-07-30
Topics:
Rosnati, Vittorio
Vona, M.Luisa Di
Traldi, Pietro
The acetolysis and the thioacetolysis of the title compound, selectively deuteriated at one of the two methylenes, was studied.The excess of the unrearranged acetate in the acetolysis at 40 deg C has been explained in terms of coordination of the acid to the sulfur, followed by a "quasi-SNi" displacement of the leaving group.This pathway is concurrent with the equilibration of the two isomeric tosylates (through the agency of the episulfonium ion 2) and with the acetolysis of 2, resulting in a 1:1 mixture of 4 and 5.The thioacetolysis of 1 and 3 at 40 deg C gave in turn a 1:1 mixture of the thiolacetates 8 and 9, along with the thionoacetate 6 in the reaction of 1 and the thionoacetate 7 in that of 3.When the acetolysis and the thioacetolysis of 1 were run at the boiling temperature of the solvent, the reactions afforded only a 1:1 mixture of 4 and 5 and 8 and 9, respectively, showing that at higher temperature coordination of the acid is not at work.In the dichloroacetolysis of 1, a 1:1 mixture of the isomeric dichloroacetates 10 and 11 was always obtained.The results show that in the case of 2-(arylthio)ethyl tosylates there are several competing solvolytic pathways, whose relative importance depends upon the acidity and nucleophilicity of the solvent.
View MoreJiangxi Province Bethel Pharmaceutical Co., Ltd.
Contact:+86-795-259 3456 ,+86-15957688008 13566650571
Address:Huangjindui Chemical Park, Shanggao County ,Yichun city,Jiangxi Province
Contact:18698110882
Address:1303 No2 building,LuoMa Garden,YongAn Road,Hexi District,Tianjin city
ZHIJIANG ZENVA SINO COMMERCE AND TRADE CO., LTD.
website:http://www.zenvasino.com
Contact:+86-138-72658998
Address:Shibeishan Road,Zhijiang, Hubei, China
Changzhou LanXu Chemical Co.,ltd.(expird)
Contact:86-0519-86330911,13656129734,15261186386
Address:Room 524, Depart.Chemical, Changzhou Science and Eductaion town, Jiangsu, China;Factory: Haian Fine Chemical Industry Park,Nantong,Jiangsu,China
Chengdu Boon Stream Chemical Industry Co.,Ltd.
Contact:+86-28-83156758
Address:No.859,Dongzikou Road,Jinniu District,Chengdu,Sichuan,P.R.China
Doi:10.1002/mrc.2305
(2008)Doi:10.1016/j.ejmech.2007.10.001
(2008)Doi:10.1080/00397911.2011.605242
(2013)Doi:10.1055/s-0028-1083518
(2008)Doi:10.1016/0022-328X(87)87126-7
(1987)Doi:10.1016/S0040-4039(00)85371-X
(1986)