First synthesis of 1,5-diazabicyclo[3.1.0]hexane complexes with cadmium salts

Abstract

Complexes of bicyclic diaziridines 6,6´ bi(1,5 diazabicyclo[3.1.0]hexane) (L 1 ) and 6 (4 methoxyphenyl) 1,5 diazabicyclo[3.1.0]hexane (L 2 ) with the salts Cd(NO 3 ) 2 •4H 2 O and Cd(ClO 4 ) 2 •6H 2 O have been synthesized. The fact of complexation has been established by cyclic voltammetry. The crystal structure of complex L 1 with Cd(NO 3 ) 2 (the coordination number of cadmium is 8) has been studied by X ray diffraction.

Reaction of 1-arylmethylidenepyrazolidin-1-azomethine imines with aryl ketenes

“…These reactions were success fully accomplished only in ionic liquids, that allowed us to develop simple methods for the preparation of a number of bicyclic structures 7-10 (Scheme 2). [16][17][18][19] The present work is devoted to the study of a possibility of condensation of azomethine imines 1, generated in situ from 6 aryl 1,5 diazabicyclo[3.1.0]hexanes 4 under con ditions found earlier, 15-19 with aryl ketenes 11 in order to obtain 3,4 diaryl(3,3,4 triaryl) 1,5 diazabicyclo[3.3.0] octan 2 ones 12, new γ lactam azaanalogs (Scheme 3).…”

“…[16][17][18][19] Azomethine imine 1a was generated upon the action of BF 3 •Et 2 O in catalyt ic amounts (0.1 mmol) on the starting compound 4a (0.3 mmol) in MeCN or ionic liquid (IL), then phenyl acetyl chloride and Et 3 N were added simultaneously drop wise at reduced temperature. However, in this case too the reaction took similar direction only at considerably higher rate, and 1,2 bis(phenylacetyl)pyrazolidine 19 was isolat ed in low yield as the reaction product independent on the structure of compound 4a-c involved into the reaction.…”

A new reaction of 1,2‐di‐ and 1,2,3‐trialkyldiaziridines: Ring expansion under the action of diethyl acetylenedicarboxylate in ionic liquids

“…These are based on the strained diaziridine ring transformation in readily available [1, 2] 1,2‐dialkyldiaziridines 1 and 1,5‐diazabicyclo[3.1.0]hexanes 2 under the action of electrophilic reagents, in particular, dipolarophiles. Herein, the diaziridine ring is capable of opening on the CN or NN bonds to generate dipolar intermediates prone to cycloaddition reactions (so‐called ring expansion reactions) resulting in other heterocyclic structures [3–10].…”

“…Arylketenes [3–6], aroyliso‐ and aroylisothiocyanates [7, 8], carbon disulfide [9, 10], and activated nitriles [10, 11] were investigated as dipolarophiles. Thus, the reaction of arylketenes with 1,2‐dialkyldiaziridines 1 resulted in 5‐aryl‐1,3‐dialkylimidazolidin‐4‐ones 3 and with 1,5‐diazabicyclo[3.1.0]hexanes 2— in heterocyclic compounds of two kinds—1‐(arylacetyl)pyrazolidines 4 and 1,5‐diazabicyclo[3.3.0]octan‐2‐ones 5 (Scheme ).…”

Diaziridine ring expansion in 6-aryl-1,5-diazabicyclo[3.1.0]hexanes upon reactions with activated olefins in ionic liquids

“…The reactions of 6 aryl 1,5 diaza bicyclo [ 6 ]) in the presence of a BF 3 •Et 2 O catalyst (Scheme 1) proceed through the formation of azomethine imine intermediates 7 with their subsequent cycloaddition to dipolarophiles, leading to 3 (aryl)dihydro 5H pyrazolo [1,2 c] [1,3,4]thiadiazole 1 thiones 5 and 1 aryl 6,7 di hydro 1H,5H pyrazolo[1,2 a] [1,2,4]triazoles 6. 7,8, 10 Earlier, 11 azomethine imines 7, generated similarly from 6 aryl 1,5 diazabicyclo[3.1.0]hexanes 2 in MeCN in the presence of Lewis acids (Et 2 O•BF 3 or In(OTf) 3 ) at 20 °C, were shown to undergo cycloaddition to N arylmaleimides, which are active dipolarophiles with the cis orientation of substituents at the double bond. Azomethine imines 7 can be generated thermally (110-140 °C) 12-15 and involved into reactions with other activated olefins.…”