Journal of the Chemical Society. Perkin transactions II p. 411 - 418 (1984)
Update date:2022-08-03
Topics:
Alder, Roger W.
Sessions, Richard B.
Gmuender, John O.
Grob, Cyril A.
The reactions of hexa-alkylhydrazinium dications with bases and nucleophiles are described. 1,5-Diazonia-tricyclo<3.3.2.0>decane (1) is hydrolysed rapidly by SN2 attack on the four-membered ring with ring opening (C-N+ cleavage).In all other cases deprotonation at α-C with concomitant N+-N+ cleavage (E2 reaction) is the only primary process.The cis-1,6-dimethyl-1,6-diazoniabicyclo<4.4.0>decane ion (6), is exclusively deprotonated at a methyl group (Hofmann orientation). 1,5-Diazoniatricyclo<3.3.3.0>undecane (2), 1,6-diazoniatricyclo<4.3.3.0>dodecane (3), 1,6-diazoniatricyclo<4.4.3.0>tridecane (4), and 1,6-diazoniatricyclo<4.4.4.0>tetradecane (5) ions generate bridgehead iminium ions, which may be trapped intramolecularly by the transannular amino group or externally by added nucleophiles.Reaction with cyanide ion gives detailed information on the regio- and stereo-chemistry of the trapping sequence.Although intramolecular/external trapping is truly competitive, the products of these reactions (α-amino-ammonium ions and α-aminonitriles) may be interconverted under different reaction conditions.The solvolysis of 1-(3-phenoxypropyl)-1,5-diazabicyclo<3.3.0>octanium bromide in aqueous 48percent HBr is 103 faster than that of 3-phenoxypropyltrimethylammonium bromide, and the products are consistent with the intermediacy of the dication (2).These observations provide an explanation for the formation of 1,5-diazacyclo-octane in the reaction of 1,3-dibromopropane with hydrazine.
View MoreYingkou Sanzheng Organic Chemical Co. Ltd.
Contact:+86-417-3638818
Address:25 Gengxinli Village, Daqing Road, Yingkou, Liaoning, China
Suzhou Health Chemicals Co., Ltd.
website:http://www.healthchems.com
Contact:13776257979
Address:No. 338, Jingang Avenue,
Jurong Huaheng Natural Biological Products Factory
website:http://www.risebiochem.com
Contact:+86-13921007726
Address:Chuncheng town,Jurong city,Jiangsu province,China
Contact:+86-574-87065746
Address:10th Floor, No.787 Baizhang East Road,
BAODING SINO-CHEM INDUSTRY CO.,LTD
Contact:0312-5956088
Address:NO.8 FUXING ROAD,CHINA
Doi:10.1021/acs.orglett.6b02113
(2016)Doi:10.1021/jo01315a015
(1979)Doi:10.1055/s-2004-815947
(2004)Doi:10.1246/bcsj.51.1805
(1978)Doi:10.1007/BF01940792
(1976)Doi:10.1016/S0008-6215(00)83664-2
(1980)
