Acetophenone azine

In the hydrogenation, 200 g of acetophenone azine, 1000 ml of EtOAc and 5 g of 10% Pd-on-C was shaken at 30-50 psig for 10 h. Hydrogen absorption had ceased. About 7.6 g of phenylethylamine, formed by cleavage of the N—N bond, was obtained as a by-product. Oxidation of hydrazines can be done catalytically. Ethyl 2-arylhydrazine carboxylates were oxidized easily by bubbling air at 25 "C through a toluene or dioxane solution in the presence of Pd or Pt (5d). 

The formation of acetophenone hydrazone has been accomplished by heating acetophenone with hydrazine or hydrazine hydrate,7 10 by heating acetophenone azine with anhydrous hydrazine, 11 by the reaction of a-dimethylaminoacetophenone vvilh hydrazine,5 and by the present method.4... 

The fate of diazirines on decomposition can be influenced by the addition of y -cyclodextrin (j6-CD). When 3-methyl-3-phenyl-3jf/-diazirine (3) was thermolyzed under argon, 1 -methyl-1,2-diphenylcyclopropane (4) was obtained as an isomeric mixture in close to 20% yield the main product (43% yield) was acetophenone azine (5). Cyclodextrin complexation prior to pyrolysis, however, increased the yield of 4 tremendously. The carbohydrate, therefore, facilitates both styrene (6) and cyclopropane formation.It is also interesting to note that the trans-41 cis-4 ratio increased concomitantly and that styrene appears as an isolable product after photochemical, but not after thermal degradation of the 3 /(-CD complex. 

Examples of pyridazine synthesis from azines involve reaction between tetrafluoroformaldazine and perfluorosuccinyl fluoride in the presence of cesium fluoride to give a perfluoropyridazine, or via ketazine anions, as for acetophenone azine [Eq. (3)]. The azine from benzyl monohydrazone and ethyl acetoacetate or benzoylacetate is cyclized under basic conditions into the pyridazine 17. ... 

Die Vilsmeier-Haack-Reaktion mit Acetophenon-azin und 2 mol Dimethylformamid-Phos-phoroxychlorid-Komplex fuhrt praktisch quantitativ zu 4-Formyl-3-phenyl-l-( 1-phenyl-ethe-nyl)-lH-pyrazol (Schmp. 62°)738. 

Bromination of the corresponding dicyano derivative (132) (readily prepared from 2-bromo-acetophenone azine) gives mixtures of 3,6-diphenylpyridazine and 4-dicyanomethylene-l,4-dihydro-... 

Azin des l-Oxy S thyl-benzaldehyds 8, 111. 2-0 -3-methyl acetophenon-azin 8 1549. B 0 -3 metl l acetophenon azm 8 1549. 2.0 4 methyl acetophenon azin 81560. Azin des 4 03 -2.3 diinethyl-benza)dehyd8... 

The syntheses of 1-amino-1-azocyclopropanes from enaminosulphonium salts and tosylhydrazides and of 1,1-azohydroperoxides from hydrazones, and an improved synthesis of mejo-azobis(a-phenylethane) from acetophenone azine have also been reported. 

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