76014-58-9Relevant academic research and scientific papers
Radical Reactions of Trimethylaluminium with a Sterically Hindered Chloro-nitroso-compound
Lub, Johan,Beekes, Marinus L.,Boer, Thymen J. de
, p. 721 - 725 (2007/10/02)
Trimethylaluminium does not methylate 1-chloro-1-nitroso-2,2,6,6-tetramethylcyclohexane (I), but functions as an electron donor and initiator of radical reactions that lead ultimately to products (II)-(V), oxime derivatives, and an imine as outlined in reaction (1).E.s.r. studies support the intermediacy of iminyl radical (VI) which can undergo ring opening to the cyano-substituted radical (VII).For a kinetic e.s.r. study of this isomerisation the iminyl radical (VI) was generated from the diphenylmethyl oxime ether (XI) by reaction with t-butoxyl radicals.Combination of radical (VII) with iminoxyl radicals gives rise to oxime ether (IV).The same product can be obtained by photolysis of the oxalate (XIII) and this supports the radical nature of the process.
C-NITROSO COMPOUNDS-XXXV REACTION OF ORGANOMETALLIC COMPOUNDS WITH 1-CHLORO-1-NITROSO-2,2,6,6-TETRAMETHYLCYCLOHEXANE
Schenk, C.,de Boer, Th. J.
, p. 1843 - 1846 (2007/10/02)
Reaction of Grignard reagents and organolithium compounds (RM) with the congested 1-chloro-1-nitroso-2,2,6,6-tetramethylcyclohexane 1 leads to the formation of significant amounts of the reduction product 2,2,6,6-tetramethylcyclohexanone oxime 3 (61-90percent) together with the corresponding oxime O-R ether 4 (0-11percent).Attack on nitrogen is unimportant as shown by very low yields of nitrone.Formation of the products is rationalised with a pathway involving transfer of an electron from RM to 1.This leads-after separation of MCl-to a radical pair consisting of R. and the relatively stable iminoxy radical 2 (Schemes 1 and 2).Combination of these radicals explains formation of oxime ether 4 and nitrone 5, while reaction of iminoxy radical 2 with excess of RM can give oxime 3.Reactive radicals R. (i.e.Me,Ph, and to a minor extent n-Bu) are furthermore capable of abstracting hydrogen from the solvent (diethyl ether, toluene, or cumene), and the solvent derived radicals can also combine with 2 on oxygen, under formation of oxime ether (26percent of 6a).The corresponding benzyl- and cumyl ethers 6b and 6c are only formed in trace amounts because dimerisation of benzyl radicals (7percent) and cumyl radicals (22percent) is favoured.
