Diaziridine ring

The diaziridine ring exhibits a surprising stability towards strong oxidizing agents. Diaziridines unsubstituted at both N atoms can be transformed into diazirines by dichromate in acidic solution or by chlorine (Section 5.08.4.3). Radical attack by decomposing peroxide converts (136) to the diaziridinyl radical (137), as evidenced by ESR spectroscopy (76TL4205). 

Several reactions lead to opening of the diaziridine ring leaving the N—N bond intact. Besides the generally possible hydrolysis to hydrazines there are some thermal reactions of acylated diaziridines proceeding especially cleanly. 

These reductions are not important for preparative purposes. The same can be said for reductions with LiAlH4, and with hydrogen over a catalyst, converting diaziridines to a mixture of amines including products of reductive amination of the former carbon atom of the diaziridine ring. 

A few- reagents react with the N—-H groups of the diaziridines. It is easy to decide w hether the resulting compounds still contain a true diaziridine ring by testing for the characteristic property of such rings to liberate from iodide solution two equivalents of iodine. 

Thermolysis of 6-substituted l,5-diazabicyclo[3.1.0]hexanes 326, easily available from 325, leads to a diaziridine ring opening and to the intermediate formation of labile azomethine imines 327. These compounds can be stabilized by a proton shift to form 1-substituted 2-pyrazolines 328. However, when the thermolysis is carried out in the presence of a 1,3-dipolarophile, the corresponding products of dipolar cycloaddition can be obtained. For example, iV-arylmaleimides provide mixtures of the major trans- and minor air-products 329 and 330, respectively (Scheme 47) C1999RJO110, 2001RJ0841, 2003RJ01338, 2004RJ067>. 

The addition of 3,3-dialkyl-, 1,3-dialkyl-, and 1,3,3-trialkyldiaziridines to DEAD and EPP gives, generally, adducts in which the diaziridine ring is no longer intact.61... 

Diaziridines differ from simple amines and hydrazines radically in many properties. First of all, the nitrogen atoms of diaziridines feature high pyramidal stability. The inversion of nitrogen atoms in diaziridine rings has been studied actively since 1967 <67CB1778>. Optically active diaziridines with an asymmetric nitrogen atom have been studied since 1974 <74izvi67i>. In the molecules of... 

The Anamination is particularly smooth when formation of a diaziridine ring occurs simultaneously with that of the N-N bond.283 284 The diaziridine ring is formed when chloramine, an Af-chloroalkylamine, or hydroxylamine-O-sulfonic acid reacts with a Schiff base or when hydroxylamine-O-sulfonic acid reacts with an aqueous solution of a ketone and an amine warming the diaziridines with aqueous acid then cleaves them to the carbonyl compounds and the substituted hydrazine ... 

Pyridine s. under N-Bromosuccinimide Silver nitrate sodium hydroxide Diazirine ring from diaziridine ring... 

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