Darstellung verschieden substituierter 1‐Benzolazo‐alkene und Additionsprodukte

Abstract

Die I-Benzolazo-LyLlohexene-~l) 4a 4e (analog I-Benzolazo-cyclopenten-(I)) lassen sic11 uber die 2-Pyrrdinio-cyclohexanon-( 1)-phenylhydrazon-haloge~ude 3 in befriedigenden Ausbeuten leicht gewinneii orlho-Standige Nitrogruppen in 3 fuhren zu den En-phenylhydrazonen 6. Addition von Piperidin bzw. Methanol an 1-Benzo1azo-cyclohexen-( 1) (4a) bzw. 1 -[p-Nitro-bcnzoldzo]-cycJohcxeii-(I ) (4 b) ergibt JC zwei Stercoisomerc Im Rahmen unserer lintersuehungen uber ZuLkerphenylhydrazonel' und O\azone2-4' bzw. der zugehorigen hlodellstudien5' interessierten wir iins fur das Verhalten \on am BenLolkern verschieden siibstituiertcn BCnZoldzo-dlkCnen Cugholr und Mitdrbb 4 ) beobxhteten I -Benzolazo-cyclohexen-(I) (4a) bei der Osazonbildung aus x-Acctoxy-cyclohexanon. In satirem Medium enktehen Benzolazo-alkene sowohl dus a-Hydi oxy-phenylhydrazonen 2 , % 5 ) wie a-Hydroxy-phenyloaazonen4). In Pyridin/Acetanhydrid crhiclten U'olJrom und Mitarbb 7,s) aus Aldosephenylhydrdzoiien 1 -Benroldzo-3 4.5 6-tetradcetoxy-lrans-hexci~e-( 1 ). Caglioii und Mitarbb. zeigten die Addition von Phciiylhydrdzin 61, Thiophenol uiid p-ToluolsulfmsdLtre 91 an 4a und Derivdte ~o w i e die Isomcriwxuny von I-Tosylazo-cyclohexen-( 1) zu 3-Tosylhydrdzono-Lyclohexen-( I ) 10) Wir dddicrten Methanol und Piperidin an 4 a und beobxhteten dessen Isomerisierung zu 3-Phenylhydra7ono-cyclohexen-(l) 5 ) . Die Bildung \on 3.6-Anhydroosazonen au? Hexoseoiaionen bzm 3-Alkoxy-phenyloaazonen aus Peiitose-oder Tetroseosazonen in alkoholisch-saurem Medium verlauft ubcr 2-Benzoldzo-2-en-1 -phenylhq drdzone4).Die Ddrstellung von Benzolazo-alkenen errolgte bisher meist aus a-Halogen-ketonen mit Hydrdzinen 5510 131, cc-Acetoxy-phenylhydrazonen 6.71 b7w Tosylphenylhydrazonen 6,141 oder aus 5c p-Epoxy-ketonen 15, I 5 d ~ * ) Postanschrift . D 80s Frcising-Weihenstephan.

Unusual Reactions Between Aromatic Carbon Supernucleophiles and 1,2‐Diazabuta‐1,3‐dienes: Useful Routes to New Pyrazolone and Cinnoline Derivatives

“…General Remarks: NMR spectra were recorded with Varian Gemini 300 or Mercury 400 spectrometers operating at 300 or 400 MHz (for 1 [2a] and DBDs 3, [19] 4, [20] 5, 6, [21] 7, 18 [22] and 19 were synthesized according to previously reported procedures [23] as (E)/(Z) mixtures in variable relative ratios, depending on the structures. Their characterization data, if not already reported, are described in the Supporting Information.…”

Thermolysis of polyazapentadienes. Part 10. Flash vacuum pyrolysis of azoalkenes and some azocarbonyl compounds

“…30 "C); v, , , . 1 710 cm-' ((20); m/z 212 [ ( M + 2)+, 4x1, 182 (6), 105 (loo), and 77 (97); (17), 91 (29), and 77 (100).…”

“…We had difficulties in separating analogous catalysts from the final product, and found that the oxidation proceeded satisfactorily in up to 86% yield, in complete absence of catalyst, to give the ketones (15)-( 18) as red oils. In their mass spectra (17) R =o-MeOCsHb (18) R = M e the molecular ion was not normally observable, though significant ( M + 2) peaks were always obtained.…”

Cycloaddition reactions of sulphines and thiones with azoalkenes

“…Phenylazoalkenes were prepared by published general procedures. [21][22][23] PhenyZazostiZbePie (3) .-Phenylhydraxine (8.64 g, 8 mmol)…”