Die Umlagerung von Oxalodinitril‐bis‐aryliminen

Abstract

Oxalodinitril-bis-arylimine 2 konnen aus den entsprechenden Hydrazidchloriden durch Dehydrohalogenierung in situ dargestellt und mit Dipolarophilen abgefangen werden. In Abwesenheit der letzteren dimerisieren 2 (Aryl = Phenyl oder o-Tolyl) zu meso-ionischen 1.2.4.5-Tetraaza-pentalenen 17, einem bisher unbekannten heteroaromatischen System. Das sterisch stark gehinderte 2c (Aryl = 2.6-Dimethyl-phenyl) lagert sich intramolekular in 2-[2.6-Dimethyl-phenylimino]-2-[7-methyl-indazolyl-(2)]-acetonitril (25) um. Der Mechanismus dieser Reaktionen wird diskutiert. Rearrangement of Oxalodinitrile-bis-aryliminesThe title compounds 2 are obtained in situ from the corresponding hydrazidehalides by dehydrohalogenation and may be trapped by suitable dipolarophiles. In the absence of the latter, they dimerize (if aryl = phenyl or o-tolyl) to mesoionic 1,2,4,5-tetraazapentalenes 17, a so far unknown heteroaromatic system. The strongly sterically hindered 2c (aryl = 2,6dimethylphenyl) undergoes intramolecular rearrangement to [7-methylindazolyl-2]-[2,6dimethylphenylimino]-acetonitrile (25). The mechanisms of these reactions are discussed.

Regioselectivity in Reactions of Bis‐Hydrazonoyl Halides with Some Bifunctional Heterocycles

“…The re quired bis-hydrazonoyl chlo ride 1, 10 the thiones 2a-c [11][12][13] and their methylthio de riv a tives 3a-c 11,14,15 were prepared by known meth ods. Also, 6-methyl-2-phenylamino-4(3H)-pyrimidinone 4a was pre pared by a method from the lit er a ture.…”

Potassium 1,1′‐Dinitramino‐5,5′‐bistetrazolate: A Primary Explosive with Fast Detonation and High Initiation Power

“…Looking for better starting materials, the bisnitrileimine seems to be a suitable precursor for this molecule. Unfortunately unprotected bisnitrilimine is only known as its diphenyl derivative,13 so another more easily removable protecting group than a phenyl moiety was chosen. The following synthetic process describes the synthesis of K 2 DNABT starting from commercially available dimethyl carbonate.…”

Regioselectivity of nitrilimines 1,3‐dipolar cycloaddition: Novel synthesis of spiro[4,4]nona‐2,8‐dien‐6‐one derivatives

“…It is worthy to mention that all attempts to isolate products from the reaction of N ‐phenyl‐2‐oxopropanehydrazonoyl chloride 9 32, ethyl N ‐(phenylhy‐drazono)chloroacetate 10 33, N ‐phenyl‐C‐phenyl‐aminocarbonylmethanohydrazonoyl chloride 11 34, and N , N ′‐diphenylethane(bis‐hydrazonoyl chloride) 12 35 (Fig. 3) with 3 failed.…”