Journal of the Chemical Society. Perkin transactions II p. 121 - 126 (1980)
Update date:2022-07-29
Topics:
Brady, Kieran
Hegarty, Anthony F.
When imidoyl chlorides (8) are solvolysed in the pH range 3-13 in aqueous dioxan in the presence of acetate or benzoate ions, the isoimides (10) are formed in situ.These isoimides undergo acid (pH <4.5) and base (pH >11.5) catalysed acyl transfer to the solvent, giving the amides (12).But at intermediate pH (6-11) rearrangement to the N-acyl form (11) ( the Mumm rearrangement) alone occurs.The specific rate of this O <*> N acyl group migration is pH independent and shows a low solvent effect (m 0.175).Substituents attached to carbon or nitrogen have the same effect (ρ -0.84).When the migrating group R is varied a non-linear Hammet plot is observed, with ρ +0.60 for electron-withdrawing and +1.65 for electron-donating substituents.The changeover point is a function of the migrating terminus varying from R=Ph (when Y=H) to R=p-tolyl (when Y=p-NO2).Rate-determining O <*> N acyl transfer is suggested in all cases, but this is preceded by an equilibrium which favours the Z form (10a) when R is electron donating.
View MoreBeijing Green Guardee Technology CO,.LTD
Contact:+86-10-69706062
Address:F2 BLdj,5 No.37 Chaoqian Road
Yancheng Smiling Imp & Exp Co., Ltd.
Contact:+86-515-83173586
Address:Rm1207, BLD#03, Phoenix Plaza, Juheng Road, Yancheng, Jiangsu, P.R. China
Contact:+86-15850770348
Address:51 OF XIANGFANGCUN ROAD, Nanjing 210002, China
Jinan Decheng Hemu Medical Technology Co.，Ltd.
Contact:+86-531-68650525
Address:NO.554 Zhengfeng Road High-new Technology Development Zone
HK Vast Medicinal Chemistry Int'l Group Limited(expird)
website:http://www.hkvast.com/
Contact:+86-15000309979
Address:NO.6,Lane 108,Qinzhou Road,Xuhui District,Shanghai
Doi:10.1002/hlca.19890720105
(1989)Doi:10.1016/S0022-328X(00)83476-2
(1981)Doi:10.1016/j.bmcl.2011.12.015
(2012)Doi:10.1016/S0040-4020(01)97660-4
(1981)Doi:10.1021/jo00332a043
(1981)Doi:10.1021/ja00977a023
(1967)
