130149-20-1Relevant articles and documents
Geminal Vinyl Diazides, X. - Methyl 3,3-Diazido-2-cyanoacrylate: Synthesis of Vinyl Azides, 4,5-Dihydro-1H-tetrazol-5-ylidenes, Oxazoles, and N-Cyanimines
Saalfrank, Rolf W.,Lurz, Claus-Juergen,Hassa, Juergen,Danion, Daniel,Toupet, Loic
, p. 595 - 608 (2007/10/02)
Reaction of methyl 3,3-diazido-2-cyanoacrylate (1) with amines 2 at -30 deg C yields aminovinyl azides 4.In the presence of equivalent amounts of triethylamine the vinyl azide 4 undergo 1,5'-ring closure to afford the triethylammonium salts 5.Treatment of 5 with hydrochloric acid gives the corresponding 4,5-dihydro-1H-tetrazol-5-ylidene derivatives 6.In contrast thermolysis of 4 leads via azirines 7 to oxazoles 8.Reaction of vinyl diazide 1 with lysine and cystine, respectively, yields bis(vinyl azides) 9.Triethylamine-induced 1,5'-ring closure of 9 produces the bis(triethylammonium) salts 10, which can be transformed under acidic conditions into the corresponding bis(4,5-dihydro-1H-tetrazol-5-ylidene) derivatives 11.With methyl acrylate (17) oxazole 15 reacts via carbonyl ylide 16 in a 1,3-dipolar cycloaddition to give pyrroline 18 (X-ray structure analysis).Thermolysis of the geminal vinyl diazide 1 in the presence of alcohols 19 or primary amines 21 forms the cyanimines 20 and 22, respectively, via methyl 3-aza-2,3-dicyanoacrylate 25. 25 exists as syn/anti isomers which fully agree with AM1 calculations carried out on cyanimine model systems.
