5834-97-9Relevant academic research and scientific papers
Pd-catalyzed regioselective allylation of Mono- and disubstituted hydrazines
Tsupova, Svetlana,Maeeorg, Uno
supporting information, p. 3381 - 3383 (2013/07/26)
Palladium-catalyzed allylation of hydrazines using allyl alcohols is reported. This highly efficient protocol furnishes monoallylated hydrazines selectively, in 27-99% yields. Following an optimization of the reaction conditions and of the Pd-ligands, the allylations of both mono- and disubstituted hydrazines were investigated, as well as the effects of C2-substitution on the allylating agent. Of particular interest, a novel method for the selective monoallylation of monosubstituted hydrazines is demonstrated.
Photochemistry of 5-allyloxy-tetrazoles: Steady-state and laser flash photolysis study
Frija,Khmelinskii,Serpa,Reva,Fausto,Cristiano
scheme or table, p. 1046 - 1055 (2009/02/05)
The photochemistry of three 5-allyloxy-tetrazoles, in methanol, acetonitrile and cyclohexane was studied by product analysis and laser flash photolysis. The exclusive primary photochemical process identified was molecular nitrogen elimination, with formation of 1,3-oxazines. These compounds were isolated in reasonable yields by column chromatography on silica gel and were fully characterized. DFT(B3LYP)/6-31G(d,p) calculations predict that these 1,3-oxazines can adopt two tautomeric forms (i) with the NH group acting as a bridge connecting the oxazine and phenyl rings and (ii) with the -N bridge and the proton shifted to the oxazine ring. Both tautomeric forms are relevant in the photolysis of oxazines in solution. Secondary reactions were observed, leading to the production of phenyl vinyl-hydrazines, enamines, aniline and phenyl-isocyanate. Transient absorption, detected by laser flash photolysis, is attributed to the formation of triplet 1,3-biradicals generated from the excited 5-allyloxy-tetrazoles. The 1,3-biradicals are converted to 1,6-biradicals by proton transfer, which, after intersystem crossing, decay to generate the products. Solvent effects on the photoproduct distribution and rate of decomposition are negligible.
1-PHENYLAZO-1-ALKENES
Schantl, Joachim G.,Hebeisen, Paul
, p. 395 - 406 (2007/10/02)
Aliphatic aldehyde phenylhydrazones 1 were converted into 1-phenylazo-1-alkenes 3 either by the reaction with I2 and pyridine followed by base induced 1,4-elimination of pyridine.HI (Method A), or via N-(4-methylbenzenesulfonyl)-N-phenylhydrazones 7 which undergo 1,4-elimination of p-toluenesulfinic acid upon treatment with KOt-Bu (Method B).Both procedures yield mixtures of configurational isomers of the phenylazo-alkenes EE- and EZ- 3b-3e; Method B is giving rise to the kinetically controlled isomer mixture (EZ-3 predominant), which equilibrates to the thremodynamicratio (EE-3 predominant) as afforded by Method A.
