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 MoreZHIJIANG ZENVA SINO COMMERCE AND TRADE CO., LTD.
website:http://www.zenvasino.com
Contact:+86-138-72658998
Address:Shibeishan Road,Zhijiang, Hubei, China
QINGDAO HONG JIN CHEMICAL CO.,LTD.
website:http://www.hongjinchem.com
Contact:+86-532-83657313
Address:2ND Building, 8 Shangqing Road, Qingdao, Shandong Province, China.
Xiamen XM-Innovation Chemical Co., Ltd
Contact:+86-592-3216205
Address:Unit Q, 11/F, No.1 Office Building, Wuyuan Bay Business Center, Huli District, Xiamen City, Fujian Province, P.R.C
Jurong Huaheng Natural Biological Products Factory
website:http://www.risebiochem.com
Contact:+86-13921007726
Address:Chuncheng town,Jurong city,Jiangsu province,China
Shanghai Hanshare Industry Co.,Ltd.
Contact:86 21 20960688
Address:RM902-903,Building E, Wanda Plaza,No.26,Zhoukang Road, Pudong District, Shanghai, 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)
