Diaziridines 2- acyl

Diaziridine, 3-benzyl-1,3-dimethyl-inversion, 7, 7 Diaziridine, 1,2-dialkyl-reaction with iodides, 7, 217 thermal decomposition, 7, 217 Diaziridine, dibenzoyl-rearrangement, 7, 214 Diaziridine, 3,3-dimethyl-Raman spectra, 7, 202 Diaziridine, fluoro-synthesis, 7, 232 Diaziridines acylation, 7, 213 from azomethines, 7, 231 calculations, 7, 198 from chloramine, 7, 230 cycloaddition reactions, 7, 28 electron diffraction, 7, 19 199 c/s-fused NMR, 7, 201 hydrolysis, 7, 216 inversion stability, 7, 200... 

In the diaziridine field many compounds are known bearing N-YL, A/-alkyl and A-acyl groups, but here no dramatic changes in reactivity are caused by A-substituents. N-Aryldiaziridines are underrepresented. The ring carbon is in the oxidation state of a carbonyl compound or, in the diaziridinones (5) and the diaziridinimines (6) that of carbonic acid. In single cases, diaziridine carbon bears chlorine or fluorine. 

Acylations were often carried out with diaziridines. Twofold acylation is normally observed when two NH groups are present. Most acylations were performed with benzoyl chloride, acetyl chloride or phenyl isocyanate (B-67MI50800). Ring opening reactions during acylation, foreseeable for intermediates of electrophilic attack on nitrogen, were observed only seldom, provided mild conditions were used. 

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. 

Ring enlargement of A-acyl compounds, generally observed with oxaziridines, is observed only occasionally with diaziridines. Under more forced conditions of acylation with acetic anhydride, oxadiazolines like (139) were obtained (76MIP50800). A 4-nitrobenzoyl derivative rearranged at room temperature (76JOC3229). 

Acylation yields products retaining the three-membered ring only if the diaziridine is derived from an aldel yde. 3,3-DiaIkyl-diaziridines... 

The amines which are formed by the iodide reduction [Eq. (41)] can be isolated and used in the proof of structure of the diaziridines. For example, ammonia and cyclohexylamine were obtained from 1-cyclohexyldiaziridine [Eq. (42)] cyclohexylamine and phenylurea were obtained from the acylated diaziridine 58 [Eq. (43)]. ... 

The hydrolysis of l-alkyl-2-acyldiaziridines to A -alkyl-A -acyl-hydrazines possesses preparative interest. For example, A -cyclohexyl-A" -toluenesulfonylhydrazine [Eq. (51), yield 67% ] and 1-cyclohexyl-4-phenylsemicarbazide [Eq, (52) yield 73%] can be prepared by hydrolysis of the substituted diaziridines 46 and 62. ... 

Reactions without ring cleavage would include A-alkylation (most of the A-alkylated diaziridines are easily synthesized as and when the ring is synthesized), A-arylation, A-acylation. A-phos-phorylation, A-tosylation, A-silylation, and smooth A-deacylation <84CHEC-I(7)195>. 

---