4,5-SUBSTITUTED 1-NITRONYL-3-NITROXIDE-IMIDAZOLES

摘要

1,269,731. Imidazole derivatives. SYNTEX ENERGY RESEARCH Inc., and VARIAN ENERGY. 28 May, 1969 [3 June, 1968], No. 27042/69. Headings C2C and C2U. 4,5 - Substituted 1 - nitronyl - 3 - nitroxide- 4,5-dihydro-imidazole derivatives of the general formula (wherein each of RSP1/SP to RSP4/SP represents an alkyl, alkenyl, alkynyl, or aryl group containing up to 12 carbon atoms, or RSP1/SP-RSP2/SP or RSP3/SP-RSP4/SP may form an alkylene or alkenylene group having from 3 to 10 carbon atoms; Y denotes O or NH and RSP5/SP or -ORSP6/SP or -NRSP6/SPRSP6/SP with the proviso that each RSP6/SP is independently a hydrogen atom or an organic group) maybe prepared by reacting an imidazole of general formula (wherein R denotes -C#N or -COORSP7/SP and RSP7/SP is an alkyl or aryl group) with an alcohol RSP6/SPOH or NH 3 or an amine HNRSP6/SPRSP6/SP, preferably in an inert solvent and in the presence of a basic catalyst. Specified alcohols RSP6/SPOH include saturated and unsaturated alkanols, benzyl alcohols, sucrose, cellulose, cholesterol, halo-; amino-, amido- and alkoxy-substituted alcohols, cycloalkanols, polyvinyl alcohol, and thienyl alcohol; specified amines HNRSP6/SPRSP6/SP include aniline, p-nitro-aniline, ethylamine, cyclohexylamine, methylaniline, dicyclohexylamine, butylamine, dimethylamine, #-naphthylamine and amino-ethyl cellulose. Examples detail the preparation of 1-nitronyl-3-nitroxide-4,4,5,5- tetramethyl - 4,5 - dihydro - 2 - imidazolyl derivatives where the 2-substituent is The novel imidazoles are useful as antioxidants, and because of their free radical structure, can be used for " spin labelling " other molecules, e.g. biologically active molecules. 2 - Cyano - N - nitronyl - 3 - nitroxide - 4,4,5,5- tetramethyl - 4,5 - dihydroimidazole is prepared by reacting the 2-bromo analogue with NaCN in dimethyl formamide.