Methyl (E)‐2‐(1‐Aryl‐4,5‐dihydro‐1H‐tetrazol‐5‐ylidene)‐2‐cyanoacetate from Methyl 3,3‐Diazido‐2‐cyanoacrylate and Primary Aromatic Amines

Abstract

8] The C r -0 bond in 3 (2.!82(2) A [7]) is significantly longer than that in [(CO),Cr(thf)] (2.123(3) A [9]), which usually serves as a source of coordinatively unsaturated chromium carbonyl fragments. (1981)811. 1121 A. V. Rama Rao, V. H. Deshpande, N. L. Reddy, Tetrahedron Lett. 23 (1982) 775. [I31 The alkynes 4a and 46 were synthesized from 1,4-cyclohexanedione monoethylene acetal via 4-pyrrolidino-3-cyclohexen-1-one ethylene acetal [I41 and propargyl bromide.

Synthesis and Chemistry of Organic Geminal Di- and Triazides

“…Formally, this must be seen as a 1,4-addition followed by elimination of hydrazoic acid. The resulting vinyl azides 92 can, in most cases, be isolated in good yields as crystalline solids [98,102,104,105,106,107,108,110,111]. Because of the thermal instability of geminal vinyl azides 83 , this reaction has to be performed at temperatures below −20 °C.…”

“…Otherwise, the N -cyanoimine 86 (Scheme 17) would be generated before an intermolecular reaction can take place. As nucleophiles, primary [98,102,104,105,107,108,110,111] and secondary [102,107,111] amines, diamines [106,108,111] and hydrazines [98] were tested. With diamines, the substitution occurs either on two different molecules of the diazide 73 generating vinyl azides 93 [106,108,111] or on the same molecule delivering cyclic products 94 [106].…”

Synthesis and Characterization of 5-Dinitromethyltetrazole

“…When -OH and -SH were substituted at C-5, tetrazoline forms were predominant. 8 While 1-phenyl tetrazolylcyanoacetate was confirmed as in the form of tetrazoline, 9 5-dinitromethyltetrazole (1) was depicted as in tetrazole form. 5,6 In this paper, we report an useful synthetic method of 5-dinitromethyltetrazole, and discuss its tautomerism.…”

“…11 Although treatment of 3,3-diazido-2-cyanoacrylates with substituted amines afforded dihydrotetrazolidene moieties, 9 diazodinitro compounds might not be useful for the large scale synthesis of 5-dinitromethyltetrazole.…”

“…X-ray analysis revealed that 1-phenyltetrazolidene cyanoacetate exists in the form of tetrazoline. 9 But dinitromethyltetrazole was depicted as in tetrazole form without proper experimental data in the previous papers. 5,6 In IR spectra, a NO 2 group generally shows higher asymmetric mode and lower symmetric one.…”