A. N. Antonov

Oxidative transformations of peridazines

Reactions of peridazines (1H-1,2-diazaphenalenes) with electron-donor reagents (quinones, potassium ferrocyanide) involve multistage oxidative transformations resulting in products of dimarization and (or) dehydration.

peri-Amino ketones of the acenaphthene and acenaphthylene series

Abstractperi-Amino-substituted methyl and aryl ketones of the acenaphthene and acenaphthylene series were subjected to protonation and acylation at the nitrogen atom, dehydrogenation, and reactions with aldehydes. Conformations of substituents in the peri positions and probability for their participation in intra- and intermolecular transformations were determined on the basis of spectral data and quantum-chemical calculations.

Polynuclear heterocyclic systems based on naphthalene-1,5-diol: I. Reaction of naphthalene-1,5-diol and its derivatives with β-dicarbonyl and α, β-unsaturated carbonyl compounds

Reactions of naphthalene-1,5-diol and its derivatives (5-methoxynaphthalen-1-ol, 2-bromo-5-methoxynaphthalen-1-ol, and 2,6-di-tert-butylnaphthalene-1,5-diol) with ethyl acetoacetate, acetylacetone, and p-methoxycinnamic acid under acidic conditions (HCl, HClO4, CF3CO2H) gave substituted benzo[h]-chromenes, naphtho[1,2-b]pyrylium salts, and 3,4-dihydrobenzo[h]chromenes, respectively. Possible mechanisms were proposed for the observed acid-catalyzed heterocyclizations.

Building up of a peri-Hydroxynaphthoyl Fragment on the Core of 2H-Naphtho[1,8-bc] furan

The reaction of 2-aryl-5-acetoxy-4,8-di-tert-butyl-2H-naphtho[1,8-bc]furan with dichloromethyl ethyl ether in the presence of aluminum chloride gave rise to 6-formyl derivatives of the title heterocyclic system, and at the use of aliphatic acids anhydrides in the presence of perchloric acid 6-acyl derivatives were obtained. The target products with a peri-hydroxycarbonyl group were obtained by the ester group elimination.

Oxidative transformatons of 2-aryl-1,2,3,4,7,8-hexahydroacenaphtho[5,6-bc]azepin-4-ones

Reactions of partial (elimination of H2 from the bimethylene unit) and exhaustive (elimination of 2H2 from the bimethylene unit and the seven-membered heterocycle) dehydrogenation of 2-aryl-1,2,3,4,7,8-hexahydroacenaphtho[5,6-bc]azepin-4-ones were performed. The effect of the electronic structure of initial and dehydrogenated compounds on their spectral characteristics was discussed. New peri-fused heterocyclic systems were obtained.

Specific example of the mannich reaction in the series of 5-acetyl-6-aminoacenaphthene and its derivatives

Reactions of 5-acetyl-6-aminoacenaphthene and 5-acetyl-6-acetylaminoacenaphthene with aromatic aldehydes under conditions of base and acid catalysis gave derivatives of a new peri-fused heterocyclic system, 2,3,7,8-tetrahydroacenaphtho[5,6-bc]azepin-4(1H)-ones.

Synthesis and structure of 2-aryl-4H-acenaphth[5,6-bc]oxepin-4-ones

Oxidation of 2-aryl-7,8-dihydro-4H-acenaphth[5,6-bc]oxepin-4-ones with chloranil led to the formation of 2-aryl-4H-acenaphth[5,6-bc]oxepin-4-ones. Their spectral characteristics were analyzed, and a calculation of the molecular structure of model and real compounds was carried out.

1-azaacepleiadylene—A novel peri-fused heterocyclic system

Treatment of 2-aryl-1H,4H-2,3,7,8-tetrahydroacenaphtho[5,6-bc]azepin-4-one with hydrazine hydrate on heating in ethylene glycol in the presence of alkali resulted in the reduction of the oxo group to CH2. Dehydrogenation of the reduction product with 2,3,5,6-tetrachloro-1,4-benzoquinone gave 2-aryl-1-azaacepleiadylene which is the first representative of a novel peri-fused heterocyclic system.

New functionalization opportunities for peri-hydroxynaphthoyl and peri-fused heterocyclic compounds

A capability was studied of hydrogenated α-pyrone heterocycle in 7-methoxy-4-(4-methoxy-phenyl)-3,4-dihydro-2H-benzo[h]chromen-2-one to undergo aminolysis under the treatment with hydrazine hydrate, primary and secondary aliphatic and aromatic amines. A new approach was developed to the preparation of perihydroxyketone of naphthalene series containing a specific functional substituent in the ortho-position with respect to hydroxy group. The effect was revealed of an acetyl group in the position 9 of 7-methoxy-4-(4-methoxyphenyl)-3,4-dihydro-2H-benzo[h]chromen-2-one on the reaction of this compound with aliphatic amines and hydrazine hydrate. 9-Methoxy-1-(4-methoxyphenyl)-6-methyl-3H-benzo[de]pyrido[3,2,1-if]cinnolin-3-one [9-methyl-6-methoxy-3-(4-methoxyphenyl)-10,10a-diazapyren-1-one] was obtained, a new bis-peri-fused heteroaromatic system.