Showing papers in "Chemistry of Heterocyclic Compounds in 1982"
TL;DR: Condensation of p-nitrobenzaldehyde with pyrrole in propionic acid with added acetic anhydride gave tetrakis(4-nitrophenyl)porphin (24%).
Abstract: Condensation of p-nitrobenzaldehyde with pyrrole in propionic acid with added acetic anhydride gave tetrakis(4-nitrophenyl)porphin (24%), by the reduction of which tetrakis(4-aminophenyl)porphin, which was also obtained by hydrolysis of tetrakis(4-acetamidophenyl)porphin, was synthesized.
30 citations
TL;DR: In this paper, the reaction of 3-methyl-1-phenyl-5-pyrazolene with arylideneamino nitriles in alcohol leads to the formation of 3methyl-4(1-aryl-2,2-dicyanoethyl)-5-pyrans.
Abstract: The reaction of 3-methyl-1-phenyl-5-pyrazolene with arylideneamino nitriles in alcohol leads to the formation of 3-methyl-4(1-aryl-2,2-dicyanoethyl)-5-pyrazolones, which are readily cyclized in the presence of bases to the corresponding 6-amino-5-cyano-3-methyl-4-aryl- 1H,4H-pyrazolo[3,4-b]pyrans. The structures of the intermediate and final products were confirmed by the IR, UV, PMR, and mass spectra.
15 citations
TL;DR: By means of catalytic dehydrocyclization of dimethyl-substituted 2-phenylpyridines in a pyridine ring to 1(2,3)methyl-4-azafluorenes with subsequent oxidation, synthesis of alkaloid onychine and several of its isomers were achieved as discussed by the authors.
Abstract: By means of catalytic dehydrocyclization of dimethyl-substituted 2-phenylpyridines in a pyridine ring to 1(2,3)methyl-4-azafluorenes with subsequent oxidation, synthesis of alkaloid onychine — 1-methyl-4-azafluorene — several of its isomers were achieved. Using 1-methyl-4-azafluorene, we obtained a C9 furfurylidene product, substituted tetrahydroindine[1,2-b]pyridine and NH-indine[1,2-b]-pyridine. We obtained 7-nitro-1-methyl-4azafluorene by nitration of onychine and oxidation of nitro-substituted azafluorene; this indicates an identical orientation of 4-azafluoren(one) and fluoren(one) during nitration.
11 citations
TL;DR: The most promising method for the preparation of 2,3-dihydrofuran is the conversion of 1,4-butanediol on cobalt catalysts as discussed by the authors.
Abstract: Various methods for the preparation of 2,3-dihydrofuran, 2,5-dihydrofuran, 2-methylenetetrahydrofuran, and their alkyl and aryl derivatives are examined. The most promising method for the preparation of 2,3-dihydrofuran is the conversion of 1,4-butanediol on cobalt catalysts. 2,5-Dihydrofuran is obtained by dehydration of 2-butene-1,4-diol on Al2O3, cobalt-containing and other catalysts, while 2-methylenetetrahydrofuran is obtained by dehydrohalogenation of tetrahydrofurfuryl halides. The various methods for the isomerization of 2,5-dihydrofuran to 2,3-dihydrofuran are discussed. Examples of the application of dihydrofurans in organic synthesis are presented.
9 citations
TL;DR: In this paper, 2-amino-1-benzylideneaminoimidazole and 1-bromopropiophenone with benzaldehyde guanylhydrazone were obtained in the reaction of α-bronoprophenone and guanyl hydrazone with 4-alkyl- and 4-aryl-Ω-haloacetophenones.
Abstract: 2-Amino-1-benzylideneamino-4-arylimidazoles were obtained by the reaction of benzaldehyde guanylhydrazone with 4-alkyl- and 4-aryl-Ω-haloacetophenones. Side products of this reaction were cis- and trans-1,1′-bis(benzylideneamino)-4,4′-diaryl-2,2′-azoimidazoles. The corresponding 2-amino-1-benzylideneaminoimidazole and 1-benzyl-ideneaminoimidazo[l,2-a]imidazole were obtained in the reaction of α-bromopropiophenone with benzaldehyde guanylhydrazone. The 2-amino-1-benzylideneamino-4-arylimidazoles were converted by successive reactions to 1,2-diatnino-4-arylimidazoles and then to imidazo[1,2-b]-1,2,4-triazine derivatives —dyes for liquid crystals with positive dichroism.
8 citations
TL;DR: The Wittig reaction with formylporphyrin and its copper and cobalt complexes with methoxycarbonylmethinyltriphenylphosphorane and diethylamidocarbonyl methinylmethinitrioptrichexamethyltriamethylltriamide-POC13 was studied in this article, and conditions that affect the ratios of the Z and E isomers of the acrylic derivatives obtained were studied.
Abstract: The Vilsmeier formylatlon of the cobalt complex of 5,10,15,20-tetraphenylporphyrin was realized, and its intermediate salt with the dimethylformamide-POC13 complex was isolated; demetallation of the latter gave 1-formyl-5,10,15,20-tetraphenylporphyrin. Formyltetraphenylporphyrin oxime and its 0-acetyl derivative and 1-cyano-5,10,15, 20-tetraphenylporphyrin were synthesized. The Wittig reaction with formylporphyrin and its copper and cobalt complexes with methoxycarbonylmethinyltriphenylphosphorane and diethylamidocarbonylmethinylhexamethyltriamidophosphorane was realized, and conditions that affect the ratios of the Z and E isomers of the acrylic derivatives obtained were studied.
8 citations
TL;DR: In this article, the meso positions of azaanthracene fragment were used for the hydrogenation of 6-phenyl-5-azabenzo[f]fluoranthene in the presence of rhenium heptasulfide.
Abstract: The hydrogenation of 6-phenyl-5-azabenzo[f]fluoranthene in the presence of rhenium heptasulfide takes place in the meso positions of its azaanthracene fragment. The reaction of 5-azabenzo[f]fluoranthene with acid chlorides and aluminum chloride in nitrobenzene gives its 8-chloro derivative. The reduction of the adducts of the diene synthesis of 6-phenyl-5-azabenzo[f]fluoranthene with acrylonitrile by means of sodium in butyl alcohol leads to the corresponding aminomethyl derivatives and a product of retrodiene synthesis, viz., the starting azabenzofluoranthene. The reduction of the adduct of the diene synthesis of 1,3-diphenyl-2-azaanthracene with acrylonitrile proceeds similarly.
8 citations
TL;DR: The corresponding l-alkyl-6-acetylindolo [3,2-b] indoles were formed in the reaction of Nacetyl-indoxyl with N-methyl- and N-benzyl-N-phenylhydrazines in acetic acid.
Abstract: The corresponding l-alkyl-6-acetylindolo [3,2-b] indoles are formed in the reaction of N-acetylindoxyl with N-methyl- and N-benzyl-N-phenylhydrazines in acetic acid. The structures of the compounds were confirmed by alternative synthesis and by the UV, PMR, and mass spectra.
7 citations
TL;DR: In this article, the nitration of 3-phenyl-4-substituted furazans with various nitrating agents was investigated, and it was shown that the orientation of the nitro group that is incorporated in the phenyl ring is determined by the substituent in the 4 position of the furazan ring.
Abstract: The nitration of 3-phenyl-4-substituted furazans with various nitrating agents was investigated. It is shown that the orientation of the nitro group that is incorporated in the phenyl ring is determined by the substituent in the 4 position of the furazan ring, whereas the introduction of a furazan substituent in the phenyl ring lowers the reactivity of the latter. The corresponding dinitro derivatives can be obtained by means of acid mixtures.
7 citations
TL;DR: In this paper, the reaction of methallylcarbinols with aldehydes and ketones in the presence of acidic catalysts, which leads to mixtures of dihydropyrans and tetrahydropyranols, was studied.
Abstract: The reaction of methallylcarbinols with aldehydes and ketones in the presence of acidic catalysts, which leads to mixtures of dihydropyrans and tetrahydropyranols, was studied. It is shown that the formation of tetrahydropyranols occurs as a result of intramolecular bonding of the hydroxy group in the intermediate hemiacetal formed under the influence of the catalyst.
6 citations
TL;DR: In this paper, anhydro bases of the pyridine series were used as intermediates in many reactions intended for the preparation of new heterocyclic systems, and the results of these reactions were demonstrated.
Abstract: Methods for the preparation of anhydro bases of the pyridine series by deprotonation of the corresponding quaternary salts under the influence of bases, as well as by the direct reaction of quaternary pyridinium or halopyridinium salts with CH acids in the presence of bases, are examined. The reactions of anhydro bases with various reagents (alkyl cations, acylium cations, the proton, aldehydes, isothiocyanates, carbon disulfide, the hydroxide ion, etc.), which constitute evidence for their high reactivities, are examined. The participation of anhydro bases as intermediates in many reactions intended for the preparation of new heterocyclic systems is demonstrated.
TL;DR: In this paper, it was shown that 2-Acetyloxiranes react with acetonitrile in the presence of equimolar amounts of Lewis acids, and that the resulting substituted 2-methyl-5-acetyl-2-oxazolines have a cis configuration.
Abstract: 2-Acetyloxiranes react with acetonitrile in the presence of equimolar amounts of Lewis acids. It was established that the use of boron trifluoride etherate or sulfuric acid as the catalyst leads to 2,7- and 3,6-diepoxy-1,5-dioxocanes, the use of aluminum trichloride, as well as stannic chloride, leads to the corresponding chlorohydrins, while the use of gaseous boron trifluoride leads to 2-oxazolines in satisfactory yields. It is shown that the reaction is regio- and stereospecific and that the resulting substituted 2-methyl-5-acetyl-2-oxazolines have a cis configuration.
TL;DR: The corresponding monobromides were obtained in the bromination of 1-alkyl-2-pyridones with bonded bromine (with N-bromosuccinimide and dioxane dibromide).
Abstract: The corresponding monobromides were obtained in the bromination of 1-alkyl-2-pyridones with bonded bromine (with N-bromosuccinimide and dioxane dibromide). The conditions under which the yields of the mixtures of isomers were 60–80%, and almost no dibromides were obtained, were found. It was established that the ratios of the 3- and 5-bromo isomers depend on the character of the brominating agent.
TL;DR: In this article, 3-oxoisothiazolo[5,4-b]pyridines were synthesized for the first time by the reaction of 3-cyanopyridine-2-thiones or bis(3-cyanopyridyl) disulfides with concentrated sulfuric acid.
Abstract: 3-Oxoisothiazolo[5,4-b]pyridines were synthesized for the first time by the reaction of 3-cyanopyridine-2-thiones or bis(3-cyanopyridyl) disulfides with concentrated sulfuric acid. It is demonstrated that 3-carbamoylpyridine-2-thiones are formed as intermediates. The 3-oxoisothiazolopyridines were converted to 3-bromoisothiazolopyridines and pyridine-2-thiones. The bromination of pyridine-2-thione was studied.
TL;DR: In this article, the reaction of chloroglyoximes with substituted aziridines was investigated and it was shown that the barrier to inversion of the nitrogen atom in the aziridine is 12.0 kcal/mole.
Abstract: The reactions of chloroglyoximes with substituted aziridines were investigated. In the case of donor substituents in the aziridine the reaction takes place with the formation of anti-aziridino dioximes, while the formation of furoxanoglyoximes is also observed when electron-acceptor substituents are present. Aziridinofuroxans were obtained by oxidation of the aziridino dioximes. The barrier to inversion of the nitrogen atom in the aziridinofuroxans is 12.0 kcal/mole. The expansion of the aziridine ring of the aziridino dioximes, which leads to the formation of 1,2,4-oxadiazines, was investigated.
TL;DR: In this paper, the effect of substituted (OCH3, Cl) on the ratio of the isomeric N-aryloxindoles formed in the Stolle reaction from mono (m-substituted) chloroacetyldiarylamines was studied.
Abstract: The effect of substituted (OCH3, Cl) on the ratio of the isomeric N-aryloxindoles formed in the Stolle reaction from mono (m-substituted) chloroacetyldiarylamines was studied. It was shown by means of gas—liquid chromatography (GLC) and PMR spectroscopy that in the case of the methoxy group electrophilic substitution occurs only in the ring activated by the substituent. The presence of a halogen atom leads only to 1-(m-chlorophenyl)oxindole. The results show that high selectivity of the attack by the carbonium ion on the phenyl rings with electrondonor and electron-acceptor substituents is also retained in the case of intramolecular electrophilic substitution under conditions of kinetic control.
TL;DR: In this article, the rate constants of the cyclopropane reaction were determined and the reaction was shown to retain the threemembered ring of the ring of a cycloprocessor.
Abstract: Olefins of the cyclopropane series add to N-(phenylaminooxoethylidene) aniline N-oxide to give the corresponding isoxazolidines with retention of the threemembered ring. The rate constants of the reaction were determined.
TL;DR: The reactivity of the ester group of 3,5-dialkoxycarbonyl-1,4-dihydropyridines upon reaction with nucleophilic reagents increases when substituents are absent in the ortho positions relative to the esters group and also in the case of steric disruption of the coplanarity of the β-aminovinyl carbonyl system.
Abstract: The reactivity of the ester group of 3,5-dialkoxycarbonyl-1,4-dihydropyridines upon reaction with nucleophilic reagents increases when substituents are absent in the ortho positions relative to the ester group and also in the case of steric disruption of the coplanarity of the β-aminovinylcarbonyl system when substituents are introduced at the nitrogen atom in 2,6-dimethyl derivatives. Mono- and dicarboxylic acids were obtained by hydrolysis of such esters. Thus use of esters of propiolic acid esters and arylamines in the Hantzsch synthesis made it possible to obtain 1-aryl-2,6-unsubstituted derivatives of 1,4-dihydropyridine.
TL;DR: In this article, 3-bromo and 1,4-diaminomethyl derivatives of 4-aminopyrazolo[3,4d]pyrimidine were obtained by bromination and aminomethemylation, respectively.
Abstract: New 3-bromo and 1,4-diaminomethyl derivatives of 4-aminopyrazolo[3,4-d]pyrimidine were obtained by bromination and aminomethylation, respectively. 4-Bromopyrazolo[3,4-d]pyrimidines were synthesized for the first time by diazotization of 4-aminopyrazolo[3,4-d]pyrimidines.
TL;DR: A number of derivatives of mercaptomono- and dinitroimidazoles were synthesized by the action of potassium sulfide on the corresponding halonitroimidsoles as mentioned in this paper.
Abstract: A number of derivatives of mercaptomono- and dinitroimidazoles were synthesized by the action of potassium sulfide on the corresponding halonitroimidazoles. Mono- and dipotassium salts of mercaptonitroimidazoles were obtained. It was established that the monopotassium salts of mercaptomono- and dinitroimidazoles react with 2,4,6-trinitrochlorobenzene to give picrylmercapto derivatives, dipotassium salts of mononitromercaptoimidazoles give, depending on the ratio of the components, picrylmercaptonitroimidazoles or S.N-dipicrylmercaptonitroimidazoles, and dipotassium salts of mercaptodinitroimidazole give only picrylmercaptonitroimidazoles.
TL;DR: The aminomethylation of 4-hydroxycoumarin gave 3-pyrrolidinmethyl- and 3-iperidinomethodinomethlyl-4-hydroxymethyl 4-chloro derivatives by the action of phosphorus oxychloride.
Abstract: The aminomethylation of 4-hydroxycoumarin gave 3-pyrrolidinomethyl- and 3-piperidinomethyl-4-hydroxycoumarins, which were converted to 4-chloro derivatives by the action of phosphorus oxychloride. A number of 3-pyrrolidinomethyl- and 3-piperidinomethyl-4-aminocoumarins were synthesized by reaction of the 4-chloro derivatives with various amines, and some of their properties were studied.
TL;DR: In this article, a number of new organic luminophores were synthesized by PO olefination from 2- (4′-bromomethylphenyl)-5-phenyloxazole and -1,3,4-oxadiazole and various heterocyclic aldehydes that contain a furan ring.
Abstract: A number of new organic luminophores was synthesized by PO olefination from 2- (4′-bromomethylphenyl)-5-phenyloxazole and -1,3,4-oxadiazole and various heterocyclic aldehydes that contain a furan ring. The absorption and fluorescence spectra of the products in toluene, as well as their scintillation characteristics, were measured. The effect of the electronic nature of the substituents on the spectral-luminescence properties of the luminophores is discussed.
TL;DR: In this paper, the PMR spectra and biological activity of isoflavones and their derivatives are discussed and data from PMR and on biological activity are presented and discussed.
Abstract: Thiazole analogs of isoflavones and their 4-thioxo derivatives undergo recyclization to pyrazole derivatives and isomeric isoxazoles under the influence of hydrazine, methylhydrazine, phenylhydrazine, and hydroxylamine. A new group enters the 8 position or two groups simultaneously enter the 6 and 8 positions of the chromone ring in electrophilic substitution reactions. Data from the PMR spectra and on the biological activity are presented and discussed.
TL;DR: In this paper, the regiochemistry of the reaction of an acetoacetic ester with vinylacetylene, isopropenylacetylene and vinylisopropensylacetyl-acetylene in the presence of the manganese acetate/copper acetate oxidative system was studied.
Abstract: The regiochemistry of the reaction of acetoacetic ester with vinylacetylene, isopropenylacetylene, and vinylisopropenylacetylene in the presence of the manganese acetate/copper acetate oxidative system was studied. Derivatives of furan and 4,5-dihydrofuran were obtained as a result of oxidative cyclization of intermediate radicals that contain unsaturated groups in the α position. Data from the IR, UV, PMR, 13C NMR, and mass spectra of the synthesized compounds are presented.
TL;DR: In this article, the products of condensation of 2-acetylbenzothiazole with 2-formylbenzo-ldiazole and other aldehydes of the heterocyclic series were obtained, and their structures and properties were investigated.
Abstract: Products of condensation of 2-acetylbenzothiazole with 2-formylbenzothiazole and other aldehydes of the heterocyclic series were obtained, and their structures and properties were investigated. It is shown that some of them react with acids or alkalis to give dyes.
TL;DR: The action of reduced iron on solutions of nitro ketones of the thiophene series in a mixture of acetic acid and acetic anhydride gave the corresponding acetamido ketones, which can be used, for example, for the synthesis of diacetamidothiophenes (through the oximes).
Abstract: The action of reduced iron on solutions of nitro ketones of the thiophene series in a mixture of acetic acid and acetic anhydride gave the corresponding acetamido ketones, which can be used, for example, for the synthesis of diacetamidothiophenes (through the oximes).
TL;DR: In this article, it was shown by means of the 13C NMR spectra that the product of the condensation of phthalic monoaldehyde with the Fischer base is not a seven-membered spirolactone, as previously assumed, but rather a phthalide derivative.
Abstract: The product of the condensation of the Fischer base with unsubstituted 8-hydroxy-1-naphthaldehyde is a bisindolinespirooxepine. 5,7-Dinitro-8-hydroxy-1-naphthaldehyde reacts with the Fischer base to give a merocyanine that does not display a tendency to undergo conversion to the cyclic form. 2H-Naphtho[1,8-bc]furan derivatives are formed in the reaction of the Fischer base with 5-nitro-, 5-bromo-, and 5,7-dibromo-8-hydroxy-1-naphthaldehydes. The structures of the compounds obtained were established on the basis of data from the PMR and 13C NMR spectra. It was shown by means of the 13C NMR spectra that the product of the condensation of phthalic monoaldehyde with the Fischer base is not a seven-membered spirolactone, as previously assumed, but rather a phthalide derivative.
TL;DR: In this paper, it was shown that the methyl esters of adamantane-2,6-dione-1,5-dicarboxylic and -1,3,5,7-tetracarboxylates cannot be converted to -1.3, 5, 7, 7-tetrachloromethane under the conditions of the Huang-Minlon and Locke reactions.
Abstract: The dihydrazones, bis(diphenylhydrazones), and bis (2,4-dinitrophenylhydrazones) of adamantanone-2-carboxylic acid, dimethyl adamantane-2,6-dione-1,5-dicarboxylate, and tetramethyl adamantane-2,6-dione-1,3,5,7-tetracarboxylate and the pyrazolones of the corresponding acids were synthesized. It is shown that the methyl esters of adamantane-2,6-dione-1,5-dicarboxylic and -1,3,5,7-tetracarboxylic acids and their hydrazones cannot be converted to adamantane-1,5-dicarboxylic and -1,3,5,7-tetracarboxylic acids under the conditions of the Huang-Minlon and Locke reactions.
TL;DR: In this article, the effect of the conformational structures of the reacting molecules and dipolar aprotic solvents on the reaction and yields of cyclization products is demonstrated, as well as the yield of the resulting cyclization product.
Abstract: Literature data on reactions involving intramolecular nucleophilic substitution of nitro groups that lead to new five-, six-, and seven-membered heterorings in various di-, tri-, and polycyclic systems are systematized and correlated. The effect of the conformational structures of the reacting molecules and dipolar aprotic solvents on the reaction and the yields of cyclization products is demonstrated.
TL;DR: The mechanisms of the electrocyclic reactions of oxetene (I), 2H-pyran (II), 2-amino-2-hexagonal-2H-polycyclic 2-thiopyran(III), 2h-thypyran and chromene (V) in the ground, first singlet, and tripletexcited states were studied by means of the MINDO/3 method.
Abstract: The mechanisms of the electrocyclic reactions of oxetene (I), 2H-pyran (II), 2-amino-2H-pyran (III), 2H-thiopyran (IV), and chromene (V) in the ground, first singlet, and tripletexcited stateswere studiedby means of the MINDO/3 method. The enthalpies of excitation are 125 (I, So), 32 (I, S1), 113 (I, T1), 188 (II, So), 109 (III, So), 150 (IV, So), and 239 kJ/mole (V, So). The number of isomers of the open form in So is determined by the nature of the substituent attached to the final carbon atom. It was observed that π donors stabilize both the transoid isomer and the cisoid isomer, which is twisted 20 ° with respect to the formally single β-γ carbon-carbon bond. Bulky substituents cause ∼105 ° rotation about the same bond.