Geminale Vinyldiazide, VII. Bis(oxazole) und Tetrazolylammonium‐Betaine aus Bis(vinylaziden)

Abstract

Bei der Umsetzung des geminalen Vinyldiazids 5 bei -30°C mit den 1,oDiaminen 6 entstehen primiir kristalline Bis(viny1azide) 8, die bei 110°C einem 3,5-RingschluB unterliegen. Dabei werden die Bis(azirine) 20 durchlaufea, die unter Ringoffnung iiber die Bignitrilylide) 21 die Bis(oxazo1e) 9 bdden. Nucleophile Spaltung der Bigvinylazide) 8 bei 20°C mit den korrespondierenden l , o Diaminen 6 liefert primiir die Vinyiazid-Zwischenstufen 10. Bei der thermischen Urnwandlung der Vinylazide 1 (X = R, NR:; Y = CR4Rs) konkurriert mit dem 1,5-RingschluD8) der 3,5-RingschluD8), der unter Eliminierung von Stickstoff zu 2H-Azirinen 3 (X = R, NR:; Y = CR4R5) fuhrt2".9). Dagegen unterliegen 3-Amino-3-azido-2-cyanacrylsaure-ester 1

Metal derivatives of tetrazoles

“…Depending on the nature of reactants and synthesis conditions, these tetrazoles react with alkali metal compounds to give (according to X-ray diffraction data) salts or complexes. 291,292 The reactions of these ligands or enol forms of compounds 156 with transition metal salts occur in different ways. By varying the nature of substituents and using metal ions with appropriate coordination properties, one can obtain mono-and binuclear complexes and also polymeric structures of different dimensionality.…”

Synthesis and Chemistry of Organic Geminal Di- and Triazides

“…While the photochemical decomposition was not examined in further detail, the thermal reaction of geminal vinyl diazides is well-studied (Scheme 17) [95,96,97,98,103,104,105,106,107,108]. The key intermediate is the very electrophilic [109] double acceptor-substituted N -cyanoimine 86 .…”

“…The existence of this intermediate 86 was also proven by cycloaddition with 2,3-dimethylbuta-1,3-diene leading to the Diels-Alder product 87 [95,96,97,108,109]. In the presence of alcohols [95,96,108,109] or amines [104,105,106,107,108], the N -cyanoimine 86 is immediately attacked at the electrophilic carbon and, after elimination of hydrogen cyanide, isolable structures 88 and 89 are obtained in good yields. Reaction of the N -cyanoimine 86 with hydrazines leads to 90 in an analogous fashion.…”

Synthesis, Structure and Properties of N-Acetylated Derivatives of Methyl 5-Amino-1H-[1,2,4]triazole-3-carboxylate

“…It seems that the readily accessible C-amino- [1,2,4]triazole-carboxylic acid 12) could also be applied to the above ends. However, its chemistry, including the structural and spectral properties of its derivatives, of which only the methyl ester 2 12) and its 1-acetyl congener 3 13) are mentioned in the literature, is little recognised.…”