Investigation of nitrogen- and sulfur-containing heterocycles

The chlorine atom in 4-chloro-6,7-dihydro-8H-pyrimido[5,4-b][1,4-oxazin-7-ones is replaced by amine residues and mercapto and methoxy groups and can also be removed in the presence of Pd/C. Pyrimidooxazin-7-ones are alkylated in the 8 position, while, depending on the conditions, the 4-mercapto derivatives are alkylated either at the mercapto group or simultaneously at the mercapto group and in the 8 position.     

Investigation of nitrogen- and sulfur-containing heterocycles

The reaction of 5-amino-4-chloro- and -4-methoxy-6~mercaptopyrimidines with 4-methoxy-, 4-amino-, and 2,4-diethoxyphenacyl chlorides has yielded 5-amino-4-chloro- and -4-methoxy-6-phenacylthiopyrimidines. The reaction of 2, 5-diamino-4-methyl-6-mercaptopyrimidine with 4-methoxyphenacyl chloride has yielded 2-amino-6-hydroxy-6-(4-methoxyphenyl)-4-methyl-5, 6-dihydropyrimido[4, 5-b]-1,4-thiazine, and that with 4-aminophenacyl chloride has yielded the corresponding 7H-pyrimido[4, 5-b]-1,4-thiazine.For part IV, see [1].     

Investigation of nitrogen- and sulfur-containing heterocycles

The reaction of (3-amino-6-chloro-2-pyridylmercapto)oxalacetic ester with ammonia, benzylamine, morpholine, and piperidine yielded amides, while the reaction of the ester with hydrazine hydrate gave [2-(ethoxycarbonylmethylthio)-3-pyridyl]oxamic acid hydrazide. The benzylamide and morpholide of this acid were obtained by treatment of 2-chloro-6-hydroxy-6,7-di(ethoxycarbonyl)dihydropyridothiazine with the appropriate amines. The reaction of 2-mercapto-3-amino-6-chloropyridine with chlorooxalacetic ester in the presence of alkali yielded potassium [2-(ethoxycarbonylmethylthio)-3-pyridyl]oxamate.See [1] for communication XXI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1502–1505, November, 1971.     

Investigation of nitrogen- and sulfur-containing heterocycles

A number of derivatives of a new heterocyclic system — pyrimido[5,4-b][1,4]-7-oxazinone- were obtained by the reaction of substituted 5-hydroxy-6-aminopyrimidines with ethyl esters of-halocarboxylic acids.See [1] for communication XXIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1285–1288, September, 1972.     

Investigation of nitrogen- and sulfur-containing heterocycles

Catalytic hydrogenation of cyanoacetyl-, -cyanopropionyl-, and cyanobutyrylurethanes in aqueous media in the presence of Raney nickel and the hydrochlorides of o- and p-toluidines, o- and p-alkoxyphenylamines, p-aminoacetophenone, ethyl p-aminobenzoate, and ethyl p-aminophenylacetate, and in the presence of sodium p-aminosalicylate and acetic acid gave the corresponding -arylaminoacryloyl(or -alkylacryloyl)urethanes, which were converted, without isolation in the pure state, to 1-aryl- and 1-aryl-5-alkyluracils by heating in dilute alkali solutions.See [1] for communication XXV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1280–1282, September, 1974.     

Investigation of nitrogen- and sulfur-containing heterocycles

2-Mercapto-3-ureido-6-chloropyridine reacts with the ortho, meta, and para derivatives of phenacyl halides to give 2-phenacylthio-3-ureido-6-chloropyridines, which are readily cyclized to 6-arylpyrido[2,3-b][1,4]thiazines regardless of the presence or absence of a substituent in the meta and para positions of the benzene ring.See [1] for communication XXIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 798–800, June, 1974.     

Investigation of nitrogen- and sulfur-containing heterocycles

The reaction of o-aminomercapto derivatives of pyrimidine, pyrazine, and pyridine, with -halo acid nitriles was investigated. The corresponding cyanoalkylthio heterocycles, which were converted to 6-amino derivatives of pyrimido[4,5-b]-, pyrazino[2,3-b]-, and pyrido-[2,3-b]-1,4-thiazines, were obtained. The structures of the substances obtained were confirmed by IR, UV, and PMR spectroscopy.See [10] for communication XXII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 944–948, July, 1972.     

Investigation of nitrogen- and sulfur-containing heterocycles

5-Acylamino-6-acylmethylmercaptopyrimidines are formed by reaction of 5-amino-6-mercaptopyrimidines with halo--diketones in alkaline media, while 7-acylpyrimido[4,5-b]-[1, 4]thiazines are formed in close-to-neutral media.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 120–123, January, 1973.     

Investigation of nitrogen- and sulfur-containing heterocycles

The synthesis of two-ring 1,4-thiazine systems was previously accomplished on the basis of the reaction of o-amino mercapto derivatives of pyridine and pyrimidine with dicarbonyl compounds — halo -keto esters and halo -diketones. In the present paper it is shown that the primary products of this reaction are S--keto-alkylmercapto derivatives, which are subsequently cyclized to the corresponding hydroxy amino compounds. The latter are converted to N-acylamino-S--carbethoxy (keto)alkylmercapto derivatives under the influence of an alkaline agent. The indicated compounds were isolated and characterized [2, 3].See [1] for communication 36.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 250–253, February, 1979.     

A study of nitrogen- and sulfur-containing heterocycles

The reduction of -cyanoacylurethanes in an aqueous medium in the presence of hydrochlorides of aromatic amines and Raney nickel has given -arylaminoacryloyl-and -alkyl--arylaminoacryloylurethanes which have been converted by heating with 10 % aqueous caustic alkalis into 1-aryl-and 5-alkyl-1-aryluracils.For Communication X, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1088–1091, August, 1970.     

An investigation of nitrogen- and sulfur-containing heterocycles

The reaction of 3-amino-6-chloro-2-mercaptopyridine with ortho-substituted phenacyl halides has been investigated. Two types of intermediate compounds have been isolated: 3-amino-6-chloro-2-(phenacylthio)pyridines and 2-aryl-2-hydroxy-1,2-dihydro-3H-pyrido[2,3-b][1,4]thiazines. Boiling 3-amino-6-chloro-2-mercaptopyridine with ortho-substituted phenacyl halides in ethanol has given 2-aryl-3H-pyrido[2,3-b][1,4]thiazines.For Communication XXVII, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1262–1265, September, 1973. Original article submitted March 15, 1972,     

A study of nitrogen- and sulfur-containing heterocycles

The catalytic hydrogenation of N--cyanoacylureas and 1-alkyl-3--cyanoacylureas in the presence of hydrochlorides of aromatic amines has given N--arylaminoacryloyl-, 1-alkyl-3--arylaminoacryloyl-, N--alkyl--arylaminoacryloyl-, and 1-alkyl-3--alkyl--arylaminoacryloylureas. The action of N- -phenylaminoacryloyl- and 1-methyl -3- -phenylaminoacryloylureas of ethanolic hydrogen chloride has given uracil and 1-methyluracil.For Communication IX, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 847–850, June, 1970.     

Investigation of nitrogen- and sulfurcontaining heterocycles

It is shown that 5-acetamido-6-carbethoxymethylmercaptopyrimidines (IV-VII) a r e formed by reaction of 5-amino-6-mercaptopyrimidines (I-IlI) with -chloro- and -chloro--methylacetoacetic esters in the presence of excess alkali, while 6-methyl-7-carbethoxy-pyrimidothiazines (XI-XIII) are formed in the absence of alkali; under similar conditions, hydroxyamino compounds VIII-X and 6-carbethoxymethylpyrimidothiazines XIV-XVI are obtained from I-III and -chloroacetoacetic ester. 6-Carbethoxy- and 7-carbethoxypyrimidothiazines XVII-XXI were synthesized from I-III and ethyl bromopyruvate, II, and chloroformylacetic ester, respectively.For Communication XV, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1423–1427, October, 1970.     

Investigation of nitrogen- and sulfur-containing heterocyclic compounds

The halogenation of 2,3-dimethylpyrazino[2,3-b][1,4]thiazin-6-one with bromine or 1 mole of sulfuryl chloride gives 7-bromo-and 7-chloropyrazino[2,3-b][1,4]thiazin-6-ones, while 2 moles of sulfuryl chloride give 7,7-dichloropyrazino[2,3-b][1,4]thiazin-6-one. A number of 7-amino-and 7,7-diaminopyrazino[2,3-b][1,4]thiazin-6-ones were obtained by the reaction of the appropriate halo derivatives with amines. Some of the pyrazino[2,3-b][1,4]thiazin-6-one derivatives inhibit the growth of interweavable tumors in animals.See [3] for communication XX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1498–1501, November, 1971.     

Investigation of nitrogen-and sulfur-containing heterocycles

Reaction of 4-chloro-5-hydroxy-6-aminopyrimidine and its 2-methyl derivatives with -chloroacetoacetic ester gave the corresponding 4-chloro-6-carbethoxy-8H-pyrimido-[5,4-b][1,4]oxazines, which were converted to 4-aminopyrimidooxazines by reaction with amines.See [1] for communication XXVIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1694–1696, December, 1973. Original article submitted.     

Investigation of nitrogen- and sulfur-containing heterocycles. 38. Reactions of 2-mercapto-3-ureidopyridines with halo β-diketones

The reaction of 2-mercapto-3-ureido-6-chloropyridine with chlorodibenzoylmethane in the presence of alkali leads to 2-(benzoylmethylthio)-3-benzamido-6-chloropyridine, whereas the reaction in the absence of alkali leads to 2-chloro-6-phenyl-7-benzoylpyrido[2,3-b] [1,4]thiazine. Under similar conditions 2-(diacetylmethylthio)-3-ureido-6-chloropyridine, 2-(acetylmethylthio)-3-ureido-6-chloropyridine, and 2-chloro-6-methyl-7-acetylpyrido[2,3-b][1,4]thiazine were obtained from 2-mercapto-3-ureido-6-chloropyridine and chloroacetylacetone. Treatment of 2-(diacetylmethylthio)-3-ureido-6-chloropyridine with alcoholic alkali leads to 2-(acetylmethylthio)-3-ureido-6-chloropyridine. 2-Chloro-6-phenyl-7-acetylpyrido-[2,3-b] [1,4]thiazine and 2-(benzoylmethylthio)-3-ureido-6-chloropyridine are formed in the reaction of 2-mercapto-3-ureido-6-chloropyridine with chlorobenzoylacetone in the presence of an equimolar amount of alkali, while 2-(benzoylmethylthio)-3-acetamido-6-chloropyridine is formed when excess alkali is used. See [1] for communication 37. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 787–790, June, 1980.     

Nitrogen- and sulfur-containing heterocycles

4-Chloro-5-amino- and 4-chloro-5-methylamino-6-phenacylmercaptopyrimidines (II–V and XVI–XX) were obtained by the reaction of 4-chloro-5-amino- and 4-chloro-5-methylamino-6-mercaptopyrimidines (I and XV) with phenacyl halides. It is shown that II–V are cyclized by alkalis to 4-chloro-6-aryl-6-hydroxy-5,6-dihydropyrimido[4,5-b][1,4]thiazines (VI–IXa), while both II–IXa and XVI–XIX, respectively, are converted to 7H-4-chloro-6-aryl- (X–XIII) and 5H-4-chloro-5-methyl-6-arylpyrimido[4,5-b][1,4]thiazines (XX–XXIII) under the influence of acidic reagents.See [5] for communication XVIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 73–77, January, 1971.     

Cyclothiomethylation of primary amines with formaldehyde and hydrogen sulfide to nitrogen- and sulfur-containing heterocycles (review)

Published data and the authors' own experimental results on the synthesis of nitrogen- and sulfur-containing heterocycles based on the cyclothiomethylation of amines with formaldehyde and H₂S are reviewed. Features of the three-component condensation are discussed in relation to the nature and structure of the initial amines and also the reaction conditions.     

New nitrogen- and sulfur-containing derivatives of chlorocyclopentenones

Reactions of 2,3,5-trichloro-4,4-ethylenedioxy- and 2,3,5-trichloro-5-(1,1-dimethylprop-2-en-1-yl)-4,4-dimethoxycyclopent-2-en-1-ones with amino acids gave products of AdNE substitution at the C³ atom, the corresponding vinylogous amides. Sodium carbamodithioates generated in situ from amines, carbon disulfide, and sodium hydride in tetrahydrofuran reacted with di- and trichlorocyclopentenones in a similar way. Cyanosilylation of 2,3,5-trichloro-4,4-ethylenedioxycyclopent-2-en-1-one with trimethylsilyl cyanide smoothly occurred in toluene at 25°C in the presence of glycine as catalyst.