Prototropic isomerization of trans-4-benzamido-3-hydroxy-2-(4-carbomethoxybutylidene)thiophan to cis- and trans-4-benza mido-3-oxo-2-(4-carbomethoxybutyl) thiophan

trans-4-Benzamido-3-hydroxy-2-(4-carbomethoxybutylidene)thiophan (I) was prototropically isomerized in the presence of hydrogen chloride. It is shown that the two possible isomers cis- and trans-4-benzamido-3-oxo-2-(4-carbomethoxybutyl)thiophan — are formed in the process.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 2, pp. 175–177, February, 1973.     

Acylation of 1-hydroxyamino-2-hydroxyiminoethanes with α-halo acid chlorides and the preparation of 1-hydroxy-2-oxotetrahydropyrazine 4-oxides

The acylation of 1-hydroxyamino-2-hydroxyiminoethanes with -halo acid chlorides has given the products of N- and O-acylation at the hydroxyamino group. The action of bases on the products of N-acylation — N-(2-hydroxyiminoalkyl)-2-halohydroxamic acids — has given, depending on the conditions, 1-hydroxy-2-oxo-1,2,3,6- or -1,2,5,6-tetrahydropyrazine 4-oxides and 1,2-oxazetidin-3-ones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 115–120, January, 1984.     

New derivatives of coumarin: 2-(N-R-imino)-2H-1-benzopyrans

Methods of synthesizing previously unknown derivatives of coumarin — 2-(N-R-imino)-2H-1-benzopyrans, where R = Alk, Ar — are proposed. Possibilities of alternative synthetic schemes are discussed, and hypotheses concerning probable mechanisms of the reactions are formulated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 760–766, June, 1994. Original article submitted May 23, 1994.     

Synthesis of 5-(5-R-2-furyl)thiazole derivatives by the reaction of 2-(5-R-furfuryl)thiuronium salts with acetic anhydride

2-Acetamide-4-methyl-5-(5-R-2-furyl)thiazoles were obtained by the reaction of 2-(5-R-furfuryl)thiuronium salts with acetic anhydride. The reaction intermediates — 2-(5-R-furfuryl)-1,3-diacetylthioureas — were isolated and characterized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 557–562, April, 1990.     

Synthesis and lactonization of 1-(2-hydroxy-1,1-dimethylethyl)-aziridine-2-carboxylic acid esters

The reaction of 2,3-dibromopropanoates with 2-amino-2-methyl-1-propanol in the presence of triethylamine gave a number of 1-(2-hydroxy-1,1-dimethylethyl)aziridine-2-carboxylic acid esters, which, under the influence of basic catalysts, were converted to a bicyclic lactone — 2,2-dimethyl-4-oxa-1-azabicyclo[4.1.0]heptan-5-one. The effect of the structure of the substrate and the nature of the lactonizing agent on the rate of cyclization was studied. Two new catalysts for the cyclization of hydroxy esters to lactones, viz., CsF/Al₂O₃ and Cs₂CO₃/18-crown-6, are proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1340–1343, October, 1988.     

Keto-enol tautomerism of 4-hydroxy-3-phenyl-2-(2-chloroacetamidophenyl)-1-isoquinolone

Three crystalline modifications of the N-chloroacetyl derivative were obtained in the chloroacetylation of 2-(2-aminophenyl)-4-hydroxy-3-phenyl-1-isoquinolone. It was established by IR spectroscopy that they differ with respect to isomeric composition and the character of the intermolecular hydrogen bonds. For the first time, both keto-enol tautomeric forms were isolated in individual form in the 4-hydroxy-1-isoquinolone series.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 542–543, April, 1985.     

2-R-7-Hydroxy-8-methyl-3-(2-quinolyl)chromones

By condensation of 2-methyl resorcinol with 2-quinolyl acetonitrile, we have synthesized α-(2-quinolyl)-2,4-dihydroxy-3-methylacetophenone, which when reacted with carboxylic acid anhydrides followed by hydrolysis yields 2-R-7-hydroxy-8-methyl-3-(2-quinolyl)chromones.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 407–415, March, 2005.     

Photochemical synthesis of 2-amino-1-hydroxy-9,10-anthraquinone-9-alkyl(aryl)imines

Irradiation of a mixture of 1-aryloxy-2-amino-9,10-anthraquinone and amines in benzene results in formation of the derivatives of 2-amino-1-hydroxy-9,10-anthraquinone-9-alkyl(aryl)imines in a high yield. 2-Amino-1-hydroxy-9,10-anthraquinone-9-aikylimines were shown by¹³C and¹⁵N NMR to exist predominantly in the enaminoquinoid form whereas 2-amino-1-hydroxy-9,10-anthraquinone-9-arylimines exist in the oxyimine form. Sunlight irradiation of the derivatives of 2-benzoylamino-9,10-anthraqumone-9-alkylimines results in formation of the photocyclization products — 4-benzoylaminoanthra-[9,1-d,e]-1,3-oxasinones-7.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 940–944, May, 1993.     

Synthesis of the acetate of (±)-2,6-dimethylhepta-1,5-dien-3-ol — The racemic form of the sex pheromone of Pseudococcus comstocki

4-Methylpent-3-enal has been synthesized by the dehydration of trans-2-(1-hydroxy-1-methylethyl)-1-methoxycyclopropane, and this has been brought into reaction with propen-2-ylmagnesium bromide. Acetylation of the carbinol so formed gave the acetate of (±)-2,6-dimethylhepta-1,5-diene-3-ol — the racemic form of the sex pheromone of the Comstock mealybug.Scientific-Research Institute of Physicochemical Problems, V. I. Lenin Belorussian University, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 747–748, September–October, 1988.     

N-dealkylation of 2-(tert-butyl)-3-hydroxy-3-(4-chlorophenyl)isoindolinone and n-(tert-alkyl)-2-aroylbenzamides in concentrated sulfuric acid

It has been established that 2-(tert-butyl)-3-hydroxy-3-(4-chlorophenyl)isoindolinone and N-(tert-Alkyl)-2-aroylbenzamides are dealkylated in concentrated sulfuric acid to give 3-hydroxy-3-arylisoindolinones. The reaction is realizable. only when there is a tert-alkyl group attached to the nitrogen atom. The reaction mechanism is discussed on the basis of data on the change with time in the electronic spectra of the investigated compounds in concentrated sulfuric acid and a comparison with the spectra of model structures.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 763–765, June, 1977.     

Synthesis of 4-Hydroxy- and 4-Amino-2-Methyl-3-(2-Methylindol-3-Yl)methylquinolines and Their 6- and 8-Substituted Derivatives

A method has been developed for the synthesis of substituted 4-hydroxy- and 4-amino-2-methyl-3-(2-methylindol-3-yl)methylquinolines by treating the corresponding 4-hydroxy(chloro)-2-methyl-3-(3-oxobutyl)quinolines with phenylhydrazine hydrochloride. It was found that nucleophilic substitution occurred in the case of the 4-chloroquinolines together with subsequent rearrangement to give the 4-amino derivatives. The thiosemicarbazones of the corresponding 4-hydroxy-2-methyl-3-(3-oxobutyl)quinolines were also obtained.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 554–557, April, 2005.     

4-Hydroxy-2-quinolones 7. Synthesis and biological properties of 1-R-3-(2-benzimidazolyl)-4-hydroxy-2-quinolones

Condensation of 1-R-3-carbethoxy-4-hydroxy-2-quinolones with o-phenylene diamine gives the corresponding 1-R-3-(2-benzimidazolyl)-4-hydroxy-2-quinolones. Data on a study of the antithyroid activity of the synthesized compounds is presented.For Communication 6, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 105–108, January, 1993.We express our sincere thanks to A. A. Kirichenko and T. S. Bozhko for the study of the antithyroid activity.     

Synthesis of chiral α-substituted N-[((2S)-2-hydroxy-2-phenyl)-ethyl]-2-phenylglycine derivatives by diastereocontrolled alkylation of (6 R)-2,3,5,6-tetrahydro-3,6-diaryl-N-[(2′R)-(2′-methyl)phenyl-methyl]-4H-1,4-oxazin-2-ones

The synthesis of α-substituted N-[((2S)-2-hydroxy-2-phenyl)-ethyl]-2-phenylglycine derivatives is reported. The key step of the sequence is the highly diastereoselective alkylation of (6R)-2,3,5,6-tetrahydro-3,6-diaryl-N-[(2′R)-(2′-methyl)phenylmethyl]-4H-1,4-oxazin-2-ones after deprotonation with t-BuOK. Opening of the resulting oxazinone with ethanolic KOH, followed by hydrogenolysis of the corresponding N-[(2R)-(2-methyl)phenylmethyl] compound to furnish the expected 2-phenylglycine derivative, is also described.     

Spectrophotometric determination of magnesium with 1-azo-2-hydroxy-3-(2.4-dimethylcarboxanilido)-naphtha- lene-1-(2-hydroxybenzene)

1-Azo-2-hydroxy-3-(2.4-dimethylcarboxanilido)-naphthalene-1'-(2-hydroxybenzene) is recommended as a new reagent for the spectrophotometric determination of small quantities of magnesium. Optimum conditions for the determination have been outlined; data concerning the precision, sensitivity, range and effect of diverge ions are presented.     

Acid-Catalyzed Transformations of 2-(Phenylethynyl)isoborneol

2-(Phenylethynyl)isoborneol was synthesized by treatment of camphor with lithium phenylacetylide. Skeletal rearrangements of the title compound under the Ritter reaction conditions afforded a mixture of N-(4-phenylethynyl- and 4-benzoylmethyl-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)acetamides at a ratio of 8:3. The reaction of 2-(phenylethynyl)isoborneol with formic acid involved mainly Meyer-Schuster rearrangement instead of the expected Rupe rearrangement, and the major product was 2-(1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene)-1-phenylethanone. The minor product (∼6%) was 1-(2-hydroxy-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)-2-phenylethanone. The Ritter reaction of 2-(1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene)-1-phenylethanone selectively yielded N-(4-benzoylmethyl-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)acetamide.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 853–858.Original Russian Text Copyright © 2005 by Koval’skaya, Kozlov, Dikusar.     

Reaction of 3-[N-(2-naphthyl)formimidoyl]pyridine with substituted acetophenones

The reaction of 3-[N-(2-naphthyl)formimidoyl]pyridine with substituted acetophenones in the presence of a proton catalyst leads to 1-aryl-3-(3-pyridyl)benzo[f]quinolines. Noncyclic amino ketones — [1-aryl-3-(3-pyridyl)-3-(2-naphthylamino)]-1-propanones — precede the formation of the cyclic products. The IR, UV, PMR, and mass spectra of the synthesized compounds are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 351–354, March, 1989.     

Synthesis and Transformations of 4-(4-Ethoxycarbonylphenylamino)- and 4-(2-Carboxyphenylamino)quinolines

Synthesis was performed of 4-(4-ethoxycarbonylphenylamino)- and 4-(2-carboxyphenylamino)-2-methylquinolines by reaction of 2-methyl-4-chloroquinoline with anesthesin and anthranilic acid. In concentrated sulfuric acid 4-(2-carboxyphenylamino)-2-methylquinoline underwent cyclization into 6-hydroxy-7-methylquinolino[3,2-c]quinoline, and the alkaline hydrolysis of 4-(4-ethoxycarbonylphenyl-amino)quinoline afforded 2-methyl-4-(4-carboxyphenylamino)quinoline.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 786–787.Original Russian Text Copyright © 2005 by Avetisyan, Aleksanyan, Ambartsumyan.     

Mass-spectrometric study of 2- and 4-azafluorenones

A mass-spectrometric study of 2- and 4-azafluorenones and their mono- and polymethyl derivatives showed that the presence of a methyl group in the benzene ring leads to a sharp increase in the relative intensity of the [M — H]⁺ ion peak. In contrast to the fragmentation of 2- and 4-azafluorenes, the mass spectra of monomethyl-substituted compounds do not contain an [M — CH₃]⁺ fragment; this is probably associated with expansion of the pyridine or benzene ring to a seven-membered ring in the step involving the formation of the molecular ion due to inclusion of the methyl group. The intensity of the [M — CO]⁺ ion peak in the mass spectra of the 4-azafluorenones is higher by a factor of two with respect to the 2-azafluorenone isomers, and the [M — HCN]⁺ and [M — H, -HCN]⁺ ion peaks observed in the mass spectra of 2-azafluorenones are absent in them.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 89–95, January, 1979.     

Simultaneous Calorimetric and Potentiometric Investigations on Some Uncatalyzed Bromate Oscillators (UBOs)

Simultaneous calorimetric and potentiometric/thermometric measurements were performed on three uncatalyzed bromate oscillators (UBOs) showing distinct temporal structures. The following UBOs were chosen: a) the gallic acid (3,4,5-trihydroxy benzoic acid)—bromate; b) the 1-hydroxy-4-[(1-hydroxy-2-methylamino)ethyl] benzene (HME)—bromate; and c) the 1,4-cyclohexanedione (CHD)—bromate system. Their oscillating reactions were monitored by an isoperibolic batch calorimeter of the Calvet-type at 20°C and with a quasi-adiabatic Dewar setup at room temperature, and in addition by platinum/calomel potentiometry and thermometry. Shape of the calorimetric curves, number and duration of the oscillations and their frequencies varied considerably between these three UBOs. The underlying chemical reaction schemes are discussed in connection with the energetic background.This revised version was published online in November 2005 with corrections to the Cover Date.     

Acetylenic α-aziridinylcarbinols in reactions with hydrazine and methyl-substituted hydrazines

It is shown that hydrazones of phenylpropiolaldehyde are formed in the reaction of an acetylenic -aziridinylcarbinol — 1-hydroxy-1-aziridinyl-3-phenyl-2-propyne — with hydrazine and methyl — and 1, 1-dimethylhydrazine. The reaction of this carbinol with sym-dimethylhydrazine leads to the formation of phenylacetylene and 1-formyl-1, 2-dimethylhydrazine,1-aziridinyl-1-hydrazino-3-phenyl-2-propyne, or 3, 6-diphenylethynyl-1,2,4,5-tetramethyltetrazine, depending on the reaction conditions. It was established that the reaction of 1-hydroxy-1-aziridinyl-3-phenyl-2-propyne and 1-hydroxy-1-(2-methylaziridinyl)-2-propyne with hydrazine and methyl-substituted hydrazines is realized through an intermediate step involving the decomposition of the acetylenic aziridinylcarbinols to an -alkynyl aldehyde and ziridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 753–757, June, 1978.