Journal of the Chemical Society. Perkin transactions I p. 3265 - 3271 (1981)
Update date:2022-09-26
Topics:
Bloodworth, A. J.
Lapham, David J.
Hex-1-ene reacts with thallium(III) acetate in methanol to afford 2-methoxyhexylthallium diacetate which undergoes no appreciable decomposition when kept in methanol at room temperature for one week, but which, upon treatment with solid potassium bromide and a catalytic amount of 2,6-dimethyl-18-crown-6, cleanly affords a high yield of 1-bromo-2-methoxyhexane (1).By contrast, the methoxythalliation adduct obtained with thallium(III) trifluoroacetate undergoes oxidative dethalliation fairly rapidly (ca. 85percent dethalliation after 2 h) to give 1,2-dimethoxyethane (2) and 2-methoxyhexanol (3) as major products.It is suggested that compounds (2) and (3) arise by facile ligand exchange followed by transfer of methoxy- or hydroxy-groups from thallium to C-1 in an SNi process.If the methoxythalliation is carried out with thallium(III) trifluoroacetate in dichloromethane with methanol (2 equiv.) the oxidative dethalliation is complete after only 1 h, but 1-methoxyhexan-2-ol (4) and 2-methoxy-1-trifluoroacetoxyhexane (5) are obtained as additional products.It is suggested that ligand exchange is not effective under these conditions and that dethalliation via an oxonium ion, which leads to compounds (2) - (4), competes with the SNi process which affords compounds (5).Only small amounts (<10percent) of hexan-2-one are obtained in the oxidations.
View MoreContact:852-27701081
Address:Room 2509, New Tech Plaza, 34 Tai Yau St., San Po Kong, HK
Shandong Yubin Chemical CO.,LTD
website:http://www.yukaichem.com/en.html
Contact:+86-536-8865336
Address:binhai economic development zone，262737 shangdong，china
Contact:0086-21-80264647
Address:RM 202, NO 1602 West Zhongshan Rd, Shanghai, China
Jinhua City Mingzhu Pharmaceutical Co.,Ltd.
Contact:15857995878 0579-82207761
Address:No.169 Shenze Road, New Area,Jinpan Development Zone, Jinhua
Hangzhou LINGEBA Technology Co., Ltd.
Contact:+0086-571-87389059
Address:Office 1-913,NewYouth Plaza, GongShu Area, HangZhou,ZheJiang,P.R.China
Doi:10.1002/anie.199711811
(1997)Doi:10.1007/s11243-009-9323-8
(2010)Doi:10.1007/BF03192339
(1932)Doi:10.1055/s-2006-926374
(2006)Doi:10.1016/0040-4039(94)85202-2
(1994)Doi:10.1016/j.bmc.2005.05.015
(2005)
