Ein Diaziridinimin

Abstract

und (7)

Heterocyclic Analogues of Methylenecyclopropanes

“…(u)]["~. Here, dimethyl carbodiimide is obtained alongside (83). When the irradiation was carried out at low temperature ( -195 No formation of diaziridinimines by thermal decomposition of trisubstituted tetrazolin-5-imines has been reported, In a Japanese patent the synthesis of l-alkoxycarbonylsubstituted diaziridinimines (87) was claimed by dehydrohalogenation of N-chloroguanidines (86)[s71. No spectral data were given to substantiate the structure and a reinvestigation of the reaction products by spectral and X-ray analyses established that 1,3,4-0xadiazoles (88) Diaziridinimines undergo cycloaddition reactions initiated by nucleophilic attack of the imino function on the electrophilic center of the reaction partner.…”

“…(u)]["~. Here, dimethyl carbodiimide is obtained alongside (83). When the irradiation was carried out at low temperature ( -195 "C), tris(imino)methane (84) was identified by ESRfa4].…”

Syntheses and15N NMR Spectra of Iminodiaziridines – Ring‐Expansions of 1‐Aryl‐3‐iminodiaziridines to 1H‐ and 3aH‐Benzimidazoles, 2H‐Indazoles, and 5H‐Dibenzo[d,f][1,3]diazepines

“…These were immediately dehydrochlorinated with potassium tert ‐butoxide to afford iminodiaziridines 6 in good yields (Scheme ). In contrast with the synthesis of 2b ,7b,7c use of an excess of base had to be avoided because it led to substantial amounts of isocyanides. The isolation of multi‐gram quantities of pure compounds 6 shows that shielding of the iminodiaziridine system by tertiary alkyl groups is not necessary for convenient preparation and handling.…”

“…( tert ‐Butyl)(1,2‐di‐ tert ‐butyldiaziridin‐3‐ylidene)amine (2b): 7b,7c 1 H NMR (400 MHz, C 6 D 6 ): δ = 1.08 (s, 9 H, t Bu A ), 1.10 (s, 9 H, t Bu B ), 1.24 (s, 9 H, =N t Bu) ppm. 13 C NMR (100 MHz, HC‐gHMBC, C 6 D 6 ): δ = 26.36 [(CH 3 ) 3 , t Bu A ], 27.96 [(CH 3 ) 3 , t Bu B ], 31.58 [(CH 3 ) 3 , =N t Bu], 53.59 (quat.…”

“…However, only a few of these promising systems are readily accessible with variable substitution patterns; examples include methylenaziridines,3a alkylideneoxiranes, [1c–1f,3b,3c] alkylidenethiiranes,4 aziridinones,1g and iminoaziridines 5. So far, iminodiaziridines do not belong to this group – although some of them have been employed in syntheses6 – because only iminodiaziridines containing at least two tert ‐butyl groups, such as 2a ,7a,7c 2b ,7b–7d and 2d ,7e have been obtained in useful quantities. The parent iminodiaziridine ( 1a ) and monoalkyl derivatives 1b and 1c are elusive intermediates,8 whereas the methyl compounds 3 have been generated in small‐scale experiments by photodenitrogenation of 5‐iminodihydrotetrazoles 9…”