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.     

1,2,3,6,7,11b-Hexahydro-4H-pyrimido[2,1-a]isoquinoline-2-ones

The reaction of 1-methyl-3,4-dihydroisoquinolinium salts with acrylamide forms 2-(2-carbamoylethyl)-1-methyl-3,4-dihydroisoquinolinium salts, which are cyclized by the action of bases to form 11b-methyl-1,2,3,6,7,11b-hexahydro-4H-pyrimido[2,1-a]isoquinolin-2-one. Treatment of this compound with iodomethane yields 5, 11b-dimethyl-2-oxo-1,2,3,6,7,11b-hexahydro-4H-pyrimido[2,1-a]isoquinolinium iodide. The 11b-methylpyrimido[2,1-a]isoquinolin-2-one enters into condensation with aromatic aldehydes, forming the corresponding styryl compounds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 499–502, April, 1993.     

Synthesis of 2-Methyl-4-quinolyl Isothiocyanate

A procedure has been developed for the synthesis of substituted 2-methylquinolin-4-ylthiuronium salts by reaction of 2-methyl-4-chloroquinoline with N-substituted thioureas. Alkaline hydrolysis of these salts yields 2-methyl-4-quinolyl isothiocyanate instead of the expected 2-methylquinoline-4-thiol.     

Synthesis and stereochemistry of 2,2,3-trimethyl-5-aryl-4-aroyloxazolidines

cis-2,2,3-Trimethyl-5-aryl-4-aroyloxazolidines were obtained by heating complex boron trifluoride salts of trans-1-methyl-2-aryl-3-aroylaziridines with acetone. The reaction of complex boron trifluoride salts of cis-1-methyl-2-aryl-3-aroyl-aziridines leads to substituted benzaldehydes and -N-methylaminoacetophenones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 38–42, January, 1981.     

Synthesis of Derivatives of (4-Methyl-2-Quinolylthio)acetic and (4-Methyl-2-Quinolylthio)propionic Acids

An efficient synthesis has been developed for derivatives of (4-methyl-2-quinolylthio)acetic and (4-methyl-2-quinolylthio)propionic acids by the reaction of 4-methyl-2-thioxoquinoline with methyl methacrylate, the amide of methacrylic acid, acrylonitrile, ethyl bromoacetate, and ethyl acrylate. The hydrolysis of the resultant intermediates by (quinolylthio)acetic and (quinolylthio)propionic acids gave the corresponding acid products, which are also formed in the reaction of 4-methyl-2-thioxoquinoline with chloroacetic and acrylic acids. The reaction of 4-methyl-2-thioxoquinoline with allyl bromide was studied. The potassium permanganate oxidation of the resultant 2-allylthio-4-methylquinoline led to (4-methyl-2-quinolylthio)acetic acid.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 403–406, April, 2005.     

Selective synthesis of 1,3-dialkyl-4-nitro-1,2,3-triazolium salts from 1-alkyl-4-nitro-1,2,3-triazoles and dialkyl sulfates

The process of alkylation of 1-alkyl-substituted 4-nitro-1,2,3-triazoles with dimethyl and diethyl sulfates has been studied. The structures of the N,N’-dialkyl-C-nitro-1,2,3-triazolium alkylsulfates and perchlorates has been confirmed by IR, ¹H and ¹³C NMR spectroscopy. Alkylation with an excess of dialkyl sulfate occurred regioselectively at N-3 with the formation of 1,3-dialkyl-4-nitro-1,2,3-triazolium salts, which is in agreement quantum-chemical calculations of the relative stability of the corresponding isomeric cations. The molecular and crystal structures of the first example of this type of salt – 1,3-diethyl-4-nitro-1,2,3-triazolium perchlorate – have been determined by X-ray crystallo-graphy. Nitrotriazolium salts with mixed alkyl substituents – 3-ethyl-1-methyl- and 1-ethyl-3-methyl-4-nitro-1,2,3-triazolium salts – have been synthesized an studied for the first time.     

Synthetic routes towards tetrazolium and triazolium dinitromethylides

Tetrazolium-5-dinitromethylide sodium salt has been prepared (91%) by cyclization of 1-amino-1-hydrazino-2,2-dinitroethene with nitrous acid in water. 5-Imino-1-(hydroxyiminonitromethyl) derivatives were obtained by nitration of 2-(5-amino-1,3-dimethyl-1H-1,2,4-triazol-4-ium-4-yl)- and 2-(5-amino-4-methyl-1H-tetrazolium-1-yl)acetate complex salts. Treatment of 4-methyl-1-(2-oxopropyl)-1-tetrazolium methylsulfate with nitric and sulfuric acid gave methyl (3-nitro-1,2,4-oxadiazol-5-yl)amine (27%) probably via dinitromethylide followed by cyclization and loss of nitrogen.__________Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 127–134, January, 2005.     

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.     

Nucleophilic substitution reactions in 4-halonitro-pyrazolecarboxylic acids

The reaction of 4-bromo-1-methyl-3-nitropyrazole-5- and 4-bromo-1-methyl-5-nitro-pyrazole-3-carboxylic acids with arylamines in aqueous solution in the presence of monovalent copper salts leads to the formation of 4-arylamino- and 4-hydroxy substituted nitropyrazolecarboxylic acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 328–330, March, 1986.     

New approach to the synthesis of substituted 5-arylcarbamoyl-3-cyano-6-methylpyridine-2(1h)-thiones. Molecular and crystal structure of 2-allylthio-3-cyano-5-(2-methoxyphenylcarbamoyl)-6-methyl-4-(5-methyl-2-furyl)-1,4-dihydropyridine

Morpholinium 5-arylcarbamoyl-3-cyano-6-methyl-4-(5-methyl-2-furyl)-1,4-dihydropyridine-2-thiolates have been obtained by the interaction of enamines of acetoacetanilides with 5-methyl-2-furfurylidenecyanothioacetamide. Alkylation of the salts gives thioethers and oxidation gives the corresponding substituted pyridine-2(1H)-thiones. The structure of 2-allylthio-3-cyano-5-(2-methoxyphenylcarbamoyl)-6-methyl-4-(5-methyl-2-furyl)-1,4-dihydropyridine was studied by X-ray crystallographic analysis. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 51–58, January, 2006.     

Synthesis,polarography and herbicidal activity of quaternary salts of 2-(4-pyridyl)-1,3,5-triazines, 5-(4-pyridyl)pyrimidine, 2-(4-pyridyl)pyrimidine and related compounds

2-(4-Pyridyl)-1,3,5-triazine, 2-(4-pyridyl)-4-methyl-1,3,5-triazine, 2-(4-pyridyl)-4,6-dimethyl-1,3,5-triazine and 2-(4-pyridyl)pyrimidine have been prepared by modification of established triazine and pyrimidine syntheses. These compounds and some of their relatives have been converted to quaternary pyridinium salts. The polarographic reduction potentials of the salts in aqueous solution are pH dependent. The activity of the salts as post-emergent herbicides is reported.     

Cyanoacetylene and Its Derivatives: XXXII. Addition of Ammonia and Methylamine to 4-Hydroxy-4,4-diphenyl-2-butynenitrile

Nucleophilic addition of ammonia (25% aqueous solution) and methylamine to 4-hydroxy-4,4-diphenyl-2-butynenitrile occurs under mild conditions to afford 4-amino(or methylamino)-2,5-dihydro-5,5-diphenyl-2-iminofurans. 4-Hydroxy-4,4-diphenyl-2-butynenitrile in anhydrous liquid ammonia gives rise to 3-amino-4-hydroxy-4,4-diphenyl-2- butenenitrile which is quantitatively converted into the corresponding iminodihydrofuran or iminodihydrofuran hydrochloride in the presence of 10 wt % of KOH or gaseous hydrogen chloride. 4-Amino- and 4-methylamino-2-iminofurans react with 4-hydroxy-4-methyl-2-pentynenitrile to give 3-(4-amino- and 4-methylamino-5,5-diphenyl-2,5-dihydrofuran-2-ylideneamino)-4-hydroxy-4-methyl-2-pentenenitriles.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 64–69.Original Russian Text Copyright © 2005 by Mal’kina, Sokolyanskaya, Kudyakova, Sinegovskaya, Albanov, Shemyakina, Trofimov.     

Acetylenic Hydroperoxides Derived from 2e-Methyldecahydroquinolin-4-one

2e-Methyldecahydroquinolin-4-one was reacted with lithium tert-alkylperoxy acetylides to prepare 4-hydroxy-2e-methyl-4-(2-methyl-2-tert-alkylperoxy-1-butyn-4-yl)decahydroquinolines. The latter readily react with carboxylic acids and methyl iodide, affording the corresponding salts.     

Cyanoacetylene and Its Derivatives: XXXIII. One-Pot Stereoselective Synthesis of Bis-iminodihydrofurans from 4-Hydroxy-4-methyl-2-pentynonitrile and Aromatic Amines

4-Hydroxy-4-methyl-2-pentynonitrile reacts with aniline, N-methylaniline, and 2-naphthylamine under mild conditions (20–80°C) to afford the corresponding 4-arylamino-2-(2-imino-5,5-dimethyl-2,5-dihydro-4-furylimino)-5,5-dimethyl-2,5-dihydrofurans in one preparative step. According to the X-ray diffraction data, both imino groups in the products have syn configuration with respect to the ring oxygen atom.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 903–909.Original Russian Text Copyright © 2005 by Trofimov, Mal’kina, Shemyakina, Kudyakova, Sokolyanskaya, Sinegovskaya, Albanov, Smirnov, Kazheva, Chekhlov, D’yachenko.     

Bisacylation of the anhydride and esters of 4-methyl-1,2,3,4-tetrahydrophthalic acid

The bisacylation of the anhydride and esters of 4-methyl-1,2,3,4-tetrahydrophthalic acid by anhydrides of carboxylic acids in the presence of perchloric acid results in the formation of derivatives of 1,3-dialkyl-6, 7-dicarboxy-5,6,7,8-tetrahydro-2-benzopyrylium salts. Some reactions of the salts obtained, including their recyclization under the action of nucleophiles, have been studied. A convenient preparative method for the synthesis of 6,7-dicarboalkoxy-5,6,7,8-tetrahydroixoquinolines has been developed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1318–1321, October, 1984.     

Synthesis of Ammonium 5-Arylcarbamoyl-4-heteryl-6-methyl-3-cyano-1,4-dihydropyridine-2-thiolates and 4-Heteryl-5-carbamoyl-6-methyl-3-cyano-1,4-dihydropyridine-2-selenolates

The condensation of enamines derived from acetoacetanilides, heterocyclic aldehydes, and cyanothioacetamide yielded ammonium 5-arylcarbamoyl-5-heteryl-6-methyl-3-cyano-1,4-dihydropyridine-2-thiolates, which were subsequently used for the synthesis of substituted 2-alkylthio-1,4-dihydropyridines, 2-alkylthiopyridines, and thieno[2,3-b]pyridines. The reaction of acetoacetamide with heteroaromatic aldehydes and cyanoselenoacetamide in the presence of N-ethylmorpholine yielded N-ethylmorpholinium 4-heteryl-5-carbamoyl-6-methyl-3-cyano-1,4-dihydrolyridine-2-selenolates, from which substituted 2-alkylseleno-1,4-dihydropyridines were prepared.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005, pp. 483–492.Original Russian Text Copyright © 2005 by Dyachenko.     

Tributylphosphine Catalyzed O -Vinylation of 3-Hydroxy-2-methyl-4 H -pyran-4-one

Protonation of the highly reactive 1:1 intermediates produced in the reaction between tributylphosphine and dimethyl acetylenedicarboxylate by 3-hydroxy-2-methyl-4 H -pyran-4-one leads to vinyltributylphosphonium salts, which undergo an addition-elimination reaction in CH 2 Cl 2 at room temperature to produce dimethyl 2-[(2-methyl-4-oxo-4 H -pyran-3-yl)oxy]-2-butenedioate (1:1 mixtures of E and Z isomers) in fairly good yields.     

N-oxides of 2- and 4-azafluorenones and nitro derivatives of 2- and 4-azafluorenes

It was demonstrated by PMR spectroscopy that mixtures of N-oxides of 6- and 7-nitro derivatives are formed in the nitration of the N-oxides of 3-methyl-2- and 4-azafluorenes. The products were deoxygenated to give nitro derivatives of 2- and 4-azafluorenes. The N-oxides of nitro-substituted azafluorenes were converted to salts of the aci forms by the action of alkali.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1396–1399, October, 1982.The authors thank K. F. Turchin for his assistance in recording the spectrum of nitration product VI at 200 MHz.     

Reaction of the Na salts of 2-amino-6-methyl-4-hydroxypyrimidine with bis(bromomethyl)phosphinic acid

The reaction of the Na salts of 2-amino-6-methyl-4-hydroxypyrimidine and bis(bromomethyl)phosphinic acid gave 3,5-dioxo-1,2,3,4,5,8-hexahydro-7-methyl-1,8-diaza-4a-azonia-3-phosphanaphthalene-3-olate, whose structure was determined by X-ray diffraction study. The molecule has a bipolar structure, in which a positive charge is delocalized on the guanidine fragment and a negative charge is on the phosphinic acid fragment.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1125–1128, June, 1995.     

Synthesis of 5-[2-(Phenoxy)ethyl] Derivatives of 6-Methyluracil, 6-Methyl-2-thioxo-2,3-dihydro-1H-pyrimidin-4-one,and 2-Imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one

A synthesis of novel derivatives of 6-methyluracil, 6-methyl-2-thioxo-, and 2-imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one containing a 2-(phenoxy)ethyl substituent at position 5 of the pyrimidine ring has been carried out. It was found that 5-[2-(phenoxy)ethyl] derivatives of 6-methyl-2-thioxo- and 2-imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one are obtained by the condensation of the corresponding ethyl 3-oxo-2-(2-phenoxyethyl)butanoates with thiourea or guanidine. 6-Methyl-5-[2-(phenoxy)ethyl]uracils can be prepared by treating 6-methyl-5-[2-(phenoxy)ethyl]-2-thioxo-2,3-dihydro-1H-pyrimidin-4-ones with an excess of aqueous monochloroacetic acid solution. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1213–1217, August, 2005.