Diazabicyclohexane

Catalytic opening of diazabicyclohexane 331 in the presence of boron trifluoride-diethyl ether complex or concentrated hydrochloric acid leads to formation of a dimer 493 <1999RJO 44>, in contrast to the thermal process... 

Treatment of 2-aminomethylaziridine (59) with a variety of aromatic or aliphatic aldehydes or ketones in refluxing ethanol gives rise to several examples of 2-substituted l,3-diazabicyclo[3.1.0]hexanes 60. The NMR spectra of these diazabicyclohexanes have been reported and the crystal structure of 2-p-bromophenyl-l,3-diazabicyclo[3.1.0]hexane has been determined. ... 

Matsumoto and Maruyama have prepared more highly substituted examples of this system by the reaction of several aziridines 61 with a large excess of 2-phenylazirine 62a in benzene or toluene, to give, in most cases, the isomeric diazabicyclohexanes 63 and 64 as crystalline solids (77-81%). Tills condensation is not restricted to A -cyclohexyl- or benzoyl-substituted aziridines. ... 

Reaction of the diazabicyclohexane 97b with methanolic sodium meth-oxide results in nucleopliilic attack at the amide function, to cause ring opening to the aziridine ester 98. Potassium hydroxide also attacks the diazabicyclohexane 97a at the amide, but to cleave both rings to the hy-drazone 99. The less nucleophilic potassium tert-butoxide converts 97b into the pyrimidine 100 (26%). ... 

NMR spectra of these diazabicyclohexanes have been reported and the crystal structure of 2-p-bromophenyl-l,3-diazabicyclo[3.1.0]hexane has been determined. ... 

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