Journal of Organic Chemistry p. 1804 - 1811 (1993)
Update date:2022-08-17
Topics:
Brace, Neal O.
Heating of formamide with an alkyl halide (with or without water) affords a mild, nonhydrolytic, high-yield synthesis of alcohols and formate esters.Yet the way in which substitution on the alkyl halide actually occurs remains obscure.To explore this question, thermal reaction of 1-bromooctane (1a) with formamides (HC(O)NHR, R=H, Me; 2a, 2b) was studied quantitatively.Major products are 1-octanol (3) and n-octyl formate (5); minor products are 1-octene (4), di-n-octyl ether (6), and N-octylformamide (7, from 2a, only).Solid coproduct is HC(=NR)NHR + Br(1-) (e.g., 8a, R=H, methanimidamide hydrobromide).Analogously, 1a and N-methylformamide (2b) give alkylated products 3,5, and 6 along with 8b (R=Me). 1-Iodooctane (1b) reacts similarly.Probe samples show that 1-octanol (3) is first formed, followed by 5 and 6.Occurence of 8a-c is key to a mechanistic interpretation of the reaction.An imidate ("salt I"), e.g.,
Yancheng Creator Chemical Co., Ltd
Contact:0086-515-88710008 88710068 88710858 88710868
Address:No.21 Renming Road, Longgang Town, Yandu County,Yancheng City
LIAONING DMSO CHEMICALS CO.,LTD.
website:http://www.chinadmso.com
Contact:+86-427-6503033
Address:FLOOR 16, BLOCK A, FINANCIAL SQUARE, XINGLONGTAI DISTRICT, PANJIN CITY, LIAONING P.R. CHINA
Suzhou Tianma Specialty Chemicals Co.,Ltd
Contact:+86-512-68090577
Address:#199, Huayuan Rd, Mudu, Suzhou, Jiangsu, CHINA
Shifang Taifeng New Flame Retardant Co., Ltd
Contact:02884721008
Address:tingjiang industrial park, hefeng town
Guangxi Nanning Guangtai Agriculture Chemical Co.,Ltd
Contact:+86-771-2311266
Address:Room703,Building12, Software Park Phase II,NO.68,Keyuan Road,Nanning City,Guangxi,China
Doi:10.1016/j.bioorg.2018.10.055
(2019)Doi:10.1021/bm3009445
(2012)Doi:10.1002/hlca.193702001205
(1937)Doi:10.1016/j.cclet.2010.01.030
(2010)Doi:10.1016/j.ejmech.2020.112443
(2020)Doi:10.1002/jps.2600580726
(1969)