Journal of Organic Chemistry p. 7166 - 7169 (1995)
Update date:2022-08-17
Topics:
Hiscock, Stephen D.
Isaacs, Neil S.
King, Malcolm D.
Sue, Rodney E.
White, Rodney H.
Young, David J.
Allylic sulfinic acids have been prepared by cleavage of trialkyltin allylic sulfinates with trifluoroacetic acid (TFA).Allylsulfinic acid prepared in this way could be trapped as the sodium salt or observed by NMR and UV spectroscopy to undergo spontaneous decomposition to propene and sulfur dioxide at ambient temperatures.The corresponding reaction of 1- methylprop-2-enylsulfonic acid was regiospecific, yielding (E)- and (Z)-2-butene (E:Z = 82:18).Acidolysis of E/Z mixtures of trimethyltin 5-methylcyclohex-2-enylsulfinate with <2H>-TFA followed by desulfination indicated that the latter process proceeded with γ-syn deuterium migration, consistent with a concerted, retro-ene mechanism.A detailed kinetic investigation of allylsulfinic acid desulfination supported this conclusion.This reaction obeyed a first order rate law (k297K = (5.5 +/- 0.1)E-4 s-1 in toluene) with a large, negative activation entropy (ΔS(excit.) = -146 +/- 17 J K-1).The rate of desulfination was essentially independent of solvent.The volume profile (ΔV(excit.) = -5.5 +/- 1.0 cm3 mol-1, ΔV = 15 +/- 5 cm3 mol-1) is comparable to that of a retro Diels-Alder reaction and taken together with the above evidence and a relatively small deuterium kinetic isotope effect (kH/kD = 2.5 +/- 0.1) strongly supports a concerted desulfination, proceeding via a relatively compact, early transition state.
View MoreHenan Techway Chemical Co.,Ltd.
website:http://www.techwaychem.com
Contact:+86-371-66380080
Address:No.27 Shunhe Road,
Hubei Onward Bio-Development Co., Ltd.
Contact:+86-718-8417012
Address:No.517,Shizhou Avenue,Enshi City,Hubei Province,China,445002
Beijing Stable Chemcial Co.ltd
Contact:86-10-63785052
Address:A1301 Technological Edifice. No.4 FuFeng Road,FengTai District, Beijing. China
Hefei TNJ chemical industry co.,ltd
website:https://www.tnjchem.com
Contact:+86-551-65418695
Address:B911 Xincheng Business Center, Qianshan Road, Hefei Anhui China
Nanjing Samwon International Limited
Contact:+86-25-84873444
Address:1108, BLDG B, New Century Plaza, No 1, South Taiping Rd.,
Doi:10.1021/acs.orglett.1c00099
(2021)Doi:10.1002/zaac.19532720103
(1953)Doi:10.1039/c5ra15894j
(2015)Doi:10.1524/zpch.219.7.905.67088
(2005)Doi:10.1021/jo0347260
(2003)Doi:10.1016/j.apcata.2016.12.015
(2017)