Journal of the American Chemical Society p. 3735 - 3739 (1987)
Update date:2022-09-26
Topics:
Saunders, Martin
Jarret, Ronald M.
Pramanik, Pradip
The stable carbocation which is formed from either 3-nortricyclyl or norbornenyl precursors was studied with the deuterium isotopic perturbation method. 13C NMR signals from the two carbons, expected to be videly split by isotopic perturbation if an equilibrium exist between rapidly interconverting norbornenyl structures, showed only a small, temperature-independentsplitting.It was concluded that a maximum of ca. 1percent of the equilibrating norbornenyl ions might be present.A single structure (nortricyclyl with extensive charge delocalization) adequately represents the cation.This is verified by di-13C-labeled cation precursor, which also provides the complete set of J12 13C-13C coupling constants.NMR spectra of the deuteriated ion and of 1,7-di-13C-labeled ion revealed that the cation is undergoing at least three different scrambling processes below 0 deg C.The spectra show that the fastest process involves reversible skeletal rearrangement to the bicyclo<3.1.1>heptenyl cation.A still slower process including a hydride shift also occurs.The observed rearrangements ultimately result in complete scrambling of all carbons and hydrogens in the cation.
View MoreNanjing Spring & Autumn Biological Engineering Co., Ltd.
Contact:86-180510-83338
Address:Suite# 210, No. 1 BuildingNanjing Agricultural Biotechnology High-tech Entrepreneurship Center, No. 4 Tongwei Road, Xuanwu District, Nanjing,China
XI'AN CHUKANG BIOTECHNOLOGY CO.,LTD
Contact:29-63685658 63685359
Address:Room 3-1202,Building 1,Oriental oasis,East of Xianning Road,Xi'an,Shaanxi 710043 P.R.China
Shanghai Micro-mega Industry Co., Ltd.
Contact:0086-21-34628682;57153848
Address:Rm413,No.413,West Meilong Road, Minhang District,Shanghai P R China
Suzhou BEC Fine Chemicals Co., Ltd.
website:http://www.bek.com.cn
Contact:0512-68095917 18913193865
Address:6, Jin Shan Road, Suzhou New District, 215011 China Suzhou Nations Pharmaceutical Innovation Center Inside
Luojiang Chenming Biological Products Co
Contact:+86 15000297032
Address:GROUP NO.4, HE SHENG VILLAGE, PANLONG TOWN,
Doi:10.1021/jo00236a008
(1988)Doi:10.1002/jhet.5570240121
(1987)Doi:10.1038/sj.tpj.6500013
(1959)Doi:10.1016/S0040-4039(00)96300-7
(1987)Doi:10.1021/jo8023363
(2009)Doi:10.1002/ejoc.201700353
(2017)