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 Moreshanghai hekang chemical co.ltd
Contact:021-54173790
Address:328 WuHe Road, Building #A, 2nd Floor, Minhang, Shanghai 201109, China
Suzhou Lixin Pharmaceutical Co., Ltd.
Contact:86-512-88169812
Address:21 Tangxi Road, Suzhou New District, Suzhou 215151
KangZhiYuan Pharmaceutical Company Limited
Contact:(Sabrina)86-20-85273232
Address:4th floor, building B, Dadi industry zone, Tangxia, Tianhe, Guangzhou, China
Jiangxi Hessence Chemicals Co., Ltd.
Contact:+86 796 3511924
Address:Chengxi Industrial Park, Jishui County, Jiangxi Province 331600 China.
Zhejiang Sucon Silicone Co.,Ltd
Contact:+86-575-88046692
Address:Qisheng Rd., Paojiang Industrial Zone, Shaoxing, Zhejiang, China.
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)
