Condensation of o-aminophenol and α-dicarbonyl compounds. Part 2. Dibenzoxazolines

The study of 2′-aryl-2,2′-dibenzoxazolines (II), obtained together with 2-hydroxy-(2H)-1,4-benzoxazines (1) by condensation of o-aminophenol with a series of phenylglyoxal derivatives, emphasized that these compounds are an equilibrium mixture of dibenzoxazolines and related tautomeric ketimine forms. This behaviour was widely investigated by ir, uv and pmr spectroscopy. J. Heterocyclic Chem., 14, 957 (1977)     

Condensation of 2-aminophenols and α-dicarbonyl compounds. Part 3. Benzoxazines substituted with heterocycles

A series of 1,4-benzoxazines (I) and 2,2′-dibenzoxazolines (II) were obtained by condensation of 2-aminophenol and 2-amino-5-nitrophenol with glyoxal derivatives of the heterocyclic series. The structure of compounds (I) was investigated by uv, pmr and mass spectroscopy.     

Condensation of o-aminophenol and α-dicarbonyl compounds. Part 1. Benzoxazines

By condensation with o-aminophenol of a series of phenylglyoxal derivatives two species of products were obtained, namely 2-hydroxy-(2H)-1,4-benzoxazines (I) and 2′ -aryl-2,2′ -dibenzoxa-zolines (II). The structure of compounds I was investigated by ir, uv and pmr spectroscopy and a reaction mechanism was proposed. J. Chem. Soc., 14, 997 (1977)     

Studies on the synthesis of heterocyclic compounds. Part VI. The action of methyl salicylate on some 5-aminopyrazoles

Some 1-phenyl-3-R-5-aminopyrazoles reacted with methyl salicylate to give N-(1-phenyl-3-R-pyrazol-5-yl)-2-methoxybenzamides ( 3a,b,c ), 1-phenyl-2-methyl-3-R-salicyloilimino-3-pyrazolines ( 4a,b,c ) together with 1-phenyl-3-R-5-methylamino pyrazoles ( 5a,b,c ). The structures of the new compounds 3 and 4 were determined on the basis of analytical and spectroscopic data as well as on the acid hydrolysis products.     

Studies on the synthesis of heterocyclic compounds. Part II. Action of phosphorus oxychloride on N-Methyl-N-1-phenyl-3-methylpyrazol-5-yl)-2-acetamidobenzamide

During attempts to prepare the tricyclic ring system of type III by cyclization of N-methyl-N-(1-phenyl-3-methylpyrazol-5-yl)-2-acetamido benzamide (Ib) under Bischler-Napieralski reaction conditions, the formation of the macro-heterocycle IV was observed, whose structure was determined on the basis of analytical and spectroscopic data as well as on some transformation products.     

Reaction of ninhydrin with β-dicarbonyl compounds

The reactions of ninhydrin ( 1 ) with β-ketoesters and β-diketones were studied. Two kinds of products were observed, which were either simple adducts of the dicarbonyl compounds to the center carbonyl group of ninhydrin, or tricyclic indeno[1,2-b]furans. Treatment of methyl 3-aminocrotonate ( 2 ) with ninhydrin led in analogous fashion to an indeno[1,2-b]pyrrole ( 3 ) which was reduced to a complex tetracyclic dihydropyridine 12 . A mechanism for the production of 12 is presented. Structures for the novel heterocycles are supported by high resolution nmr studies and X-ray crystallography.     

Studies on the synthesis of heterocyclic compounds. Part IV. Further investigation of the pschorr reaction with some pyrazole derivatives

Thermal decomposition of the diazonium sulfate derived from N-methyl-(1-phenyl-3-methylpyrazol-5-yl)-2-aminobenzamide afforded products formulated as 1-phenyl-3-methyl[2]benzopyrano[4,3-c]pyrazol-5-one (yield 10%), 1,4-dimethyl-3-phenylpyrazolo[3,4-c]isoquinolin-5-one (yield 10%), N-methyl-(1-phenyl-3-methylpyrazol-5-yl)-2-hydroxybenzamide (yield 8%) and 4′-hydroxy-2,3′-dimethyl-1′-phenylspiro[isoindoline-1,5′-[2]-pyrazolin]-3-one (yield 20%). Decomposition of the diazonium sulfate derived from N-methyl-(1,3-diphenylpyrazol-5-yl)-2-aminobenzamide gave products formulated as 7,9-dimethyldibenzo[e,g]pyrazolo[1,5-a][1,3]-diazocin-10-(9H)one (yield 8%), 4-methyl-1,3-diphenylpyrazolo[3,4-c]isoquinolin-5-one (yield 7%) and 4′-hydroxy-2-methyl-1′,3′-diphenylspiro[isoindoline-1,5′-[2]pyrazolin]3-one (yield 10%). The spiro compounds 6a,b underwent thermal and acid-catalysed conversion into the hitherto unknown 2-benzopyrano[4,3-c]pyrazole ring system 7a,b in good yield. Analytical and spectral data are presented which supported the structures proposed.     

Condensation of 2-aminophenols and α-dicarbonyl compounds. Part 4. Dibenzoxazolines substituted with heterocycles

The tautomeric structure of 2,2′-dibenzoxazolines 2′-substituted with heterocycles was investigated by ir, pmr and uv spectroscopy.     

Studies on the synthesis of heterocyclic compounds. Part X. One-step route to 1,2-dimethyl-3-R-5-salicyloylimino-3-pyrazolines

This communication outlines the development of a direct synthetic route to 1,2-dimethyl-3-R-5-salicyloyl-imino-3-pyrazolines, starting from readily available 3(5)-aminopyrazoles 1a, b, c and methyl salicylate. The structures of the new compounds 3a, b, c were determined on the basis of analytical and spectroscopic data as well as on the acid hydrolysis products.     

Studies on the synthesis of heterocyclic compounds. Part I. The pschorr reaction in the pyrazole series

Preparation and structural evidence of N-methyl-(1,3-R,R'-pyrazol-5-yl)-o-nitrobenzamides (VIIIa, b) are discussed. Diazotisation of related o-aminobenzamides XIa,b followed by the Pschorr reaction afforded a very complex mixture from which pyrazolo[3,4-c]isoquinolin-5-ones XIIa.b in 7–10% yields together with N-methyl-(1,3-R,R'-pyrazol-5-yl)-o-hydroxybenzamides (XIIIa) in 15–20% yields were isolated.     

Studies on the synthesis of heterocyclic compounds. VII. Action of acyl halides on heterocyclic compounds containing the O-M-O (M  P,As, Sb) bond in the ring

The action of acyl halides on heterocyclic compounds of five-membered rings containing an O-M-O (M ? P, As, Sb) linkage is described. The reactions were either carried out in the presence of a solvent (benzene or toluene) or by direct heating of the reagent with the substrate. In the case of arsole, stibole and stannole derivatives, the cleavage of O-M bond and the formation of the respective mono- and diesters were always obtained, while with the phospholes, no cleavage of the compounds was observed. The products IIa-c (M = Sb) have been obtained in excellent yields starting from VIa-c and antimony trichloride. The structure of the compounds which were prepared was determined by analytical and spectroscopic methods and also by comparations with authentic samples where possible.     

NMR study of the influence of β-substituents on the intramolecular hydrogen bond in β-dicarbonyl compounds

The hydroxyl proton chemical shifts of β-dicarbonyl compounds involving various β-substituents have been studied. An additive influence of β-substituents on the δ_OH shift values has been found. The results obtained suggested the existence of only one potential proton energy minimum in the intramolecular hydrogen bond of the enol forms of the β-diketones. It has been shown that the enol forms of β-keto esters do not follow the additivity of the δ_OH values for the same substituents, which may be due to a change in the proton distribution potential function in the intramolecular hydrogen bond.     

Oxidation of bis-arylacetylhydrazones of α-dicarbonyl compounds

Oxidation of the title compounds (IV) with lead tetraacetate gives, instead of the expected 1-(α-arylacetyloxyarylethyleneamino)-1,2,3-triazoles, the amides (V), 1-(N-arylacetylamino)-1,2,3-triazoles, as the main products in moderate yields. The reaction mechanism is discussed.     

Studies on the synthesis of heterocyclic compounds. VIII. Action of acyl halides on 2,2-di-n-butyl-1,3,2-benzoxathiastannole, 2-chloro-1,3,2-benzoxathiaarsole and -stibole

The cleavage reaction of some 1,3,2-benzoxathiastannole, -arsole and -stibole derivatives with acetyl and benzoyl chloride is described. The reactions were carried out refluxing in benzene or at room temperature. In all cases, the reaction occurs through the initial cleavage of the S-M linkage with formation of the respective o-acylthio derivatives. The structure of the prepared compounds was assigned on the basis of their analytical, physical and spectral data.     

Studies on the syntheses of heterocyclic compounds. Part DCXII. A simple synthesis of benzopyran and dibenzopyran derivatives

trans-2-(3-Hydroxyphenyl)cyclohexanol (1b) was converted into 6-methyl-6-phenylbenzopyran (11a) and 6-spirocyclohexanobenzopyran (11b) by phenolic cyclization or under acidic condition. This type of reaction was also applied to the synthesis of 3,4-dihydro-6-methoxy-1-methoxycarbonyl-1-methyl-1H-2-benzopyran (IV).     

Studies on the syntheses of heterocyclic compounds. Part DXCVII. A synthesis of dienone analogs by electrolytic oxidation

Electrolytic coupling reaction of laudanosine (1) gave the O-methylflavinantine (II). N-Ethoxycarbonylated dihydrostilbene (IVa) gave a rearranged dienone (Va) and N-trifluoro-acetylated dihydrostilbene (IVb) contrastively gave an unrearranged dienone (Vb).