Synthesis and some chemical transformations of N-cyclohexyl-2-imino-4-methyl-5,5-pentamethylene-2,5-dihydrofuran-3-carboxamide

Russian Journal of Organic Chemistry -     

Synthesis and some transformations based on 8-chloro-3-methylxanthine

The reactions of 8-chloro-7-(β-chloro-γ-hydroxypropyl)-3-methylxanthine with primary and secondary amines have been studied. A method has been developed for obtaining derivatives of 7-hydroxy-1-methyl-6,7,8,9-tetrahydro-3H-pyrimido[2,1-f]-xanthine. The structures of the compounds synthesized have been confirmed by IR and PMR spectroscopy. Zaporozh'e Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 626–629, September–October, 1980.     

Synthesis and some transformations of 3-(2,2-dimethyloxan-4-yl)-4-methylpentanenitrile

2,2-Dimethyloxane-4-carbaldehyde reacted with ethyl cyanoacetate to give ethyl 2-cyano-3-(2,2-dimethyloxan-4-yl)prop-2-enoate whose reaction with isopropylmagnesium bromide afforded ethyl 2-cyano-3-(2,2-dimethyloxan-4-yl)-4-methylpentanoate. Elimination of the ester group from the latter led to the formation of 3-(2,2-dimethyloxan-4-yl)-4-methylpentanenitrile.     

Synthesis and some transformations of 6(8)-substituted 4-hydrazino-2-methylquinolines

6(8)-Substituted 4-hydrazino-2-methylquinolines were synthesized by reaction of the corresponding 4-chloro-2-methylquinolines with hydrazine hydrate. Reactions of the title compounds with ethyl acetoacetate and acetone gave 2,4-dimethyl-1H-pyrrolo[3,2-c]quinolines and 4-(5-ethoxy-3-methyl-1H-pyrazol-1-yl)-2-methylquinolines.     

Synthesis and some reactions of 3-chloro-2-(cyanomethylene)-1,2-dihydroquinoxalines

2,3-Dichloroquinoxaline and some of its derivatives have been reacted with malononitrile and ethyl cyanoacetate to yield a variety of 3-chloro-2-(cyanomethylene)- 1,2-dihydroquinoxaline derivatives. The reaction of 3-chloro-2-(dicyanomethylene)-1,2- dihydroquinoxaline (2e) with pyridine and its methyl derivatives led to the zwitterionic structures 6a-6c. The structures of the newly synthesized compounds were assigned by spectroscopic data and elemental analyses.     

Synthesis and some transformations of 2-[2-isopropyl-4-(3-methylbutyl)tetrahydropyran-4-yl]-ethylamine

The condensation of 2-[2-isopropyl-4-(3-methylbutyl)tetrahydropyran-4-yl]ethylamine with aromatic aldehydes followed by reduction gave rise to secondary amines of tetrahydropyrane series. Reactions of the obtained amines with acetyl chloride, succinic and phthalic anhydrides resulted in the corresponding acetamides, succinimide, and phthalimide.     

Synthesis and some transformations of methyl [4-(oxoacetyl)phenyl]carbamate

The oxidation of methyl (4-acetylphenyl)carbamate with selenium dioxide in dioxane–water (30: 1) gave methyl [4-(oxoacetyl)phenyl]carbamate whose condensation with ethyl acetoacetate or diethyl malonate and hydrazine hydrate afforded ethyl 3-methyl-6-[4-(methoxycarbonylamino)phenyl]pyridazine-4-carboxylate and methyl {4-[5-(hydrazinecarbonyl)-6-oxo-1,6-dihydropyridazin-3-yl]phenyl}carbamate, respectively. The reaction of methyl [4-(oxoacetyl)phenyl]carbamate with o-phenylenediamine in dimethylformamide–ethanol on heating led to the formation of methyl [4-(quinoxalin-2-yl)phenyl]carbamate. Methyl {4-(5,7-dioxo- 4,4a,5,6,7,8-hexahydropyrimido[4,5-c]pyridazin-3-yl)phenyl}carbamate and methyl {4-(5-oxo-7-sulfanylidene- 4,4a,5,6,7,8-hexahydropyrimido[4,5-c]pyridazin-3-yl)phenyl}carbamate were synthesized by reactions of methyl [4-(oxoacetyl)phenyl]carbamate with barbituric and thiobarbituric acids, respectively, and hydrazine hydrate in the presence of zirconyl chloride octahydrate at room temperature.     

New 4-quinaldinol derivatives XVII. 2-Methyl-3-(3-chloro-2-buten-1-yl)-4-hydroxyquinoline-6-carboxylic acid and some of its transformations

1-(2-Methyl-4-hydroxy-6-carboxy-3-quinolinyl)-3-butanone and 1-(2-methyl-4-chloro-6-carboxy-3-quinolinyl)-3-butanone were obtained by the acid hydrolysis of 2-methyl-3-(3-chloro-2-buten-1-yl)-4-hydroxy(chloro)quinoline-6-carboxylic acids and their esters.See [6] for communication XVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1681–1682, December, 1971.     

Synthesis and some transformations of benzo-substituted 2-bromomethyl-4-methyl-2-chloro-2,3-dihydrofuro[3.2-c]-quinolines

A convenient synthetic procedure for substituted 2-bromomethyl-4-methyl-2-chloro-2,3-dihydrofuro[3.2-c]quinolines hydrobromides was developed, synthons for preparation of new substituted furoquinolines. Reactions with various nucleophiles were performed, and 2-(R’-methyl)-4-methyl-furo[3.2-c]quinolines substituted in the benzene ring were obtained.     

Synthesis and some transformations of 2-alkenyl-4-alkoxymethylbutanolides

The alkylation of 4-alkoxymethyl-2-ethoxycarbonylbutanolides led to the formation of 2-alkenyl-4-alkoxymethyl-2-ethoxycarbonylbutanolides which at alkaline hydrolysis provided new 2-alkenyl-4-alkoxymethylbutanolides. By oxidation of the latter with a mixture of hydrogen peroxide and formic acid 4-alkoxymethyl-2-(2-R-2,3-dihydroxy)propylbutanolides were obtained. The diololactones were shown to suffer under the conditions of the pinacol-pinacolone rearrangement a conversion into previously unknown formyl-and epoxylactones.     

Synthesis and some transformations of 2,6-diphenyl-4-hydroxybenzofuran

A 4-oxotetrahydrobenzofuran derivative was obtained from 5-phenylcyclohexane-1,3-dione and phenacyl bromide, and dehydrogenation of the latter gave 2,6-diphenyl-4-hydroxybenzofuran. Some reactions of 2,6-diphenyl-4-hydroxybenzofuran and its derivatives were studied.     

Synthesis of 5-alkyl(aryl)sulfanyl-4-chloro-3-trichloromethyl-1,2-thiazoles and 5-Alkyl(aryl)sulfanyl-4-chloro-1,2-thiazole-3-carboxylic acids

Butane-, phenylmethane-, and benzenethiols reacted with 4,5-dichloro-3-trichloromethyl-1,2-thiazole in the presence of sodium ethoxide to give the corresponding 5-alkyl(aryl)sulfanyl-4-chloro-3-trichloromethyl-1,2-thiazoles. The reaction of 4,5-dichloro-1,2-thiazole-3-carboxylic acid with the same thiols under similar conditions resulted in the formation of sodium 4,5-dichloro-1,2-thiazole-3-carboxylate, while in the presence of pyridine 5-alkyl(aryl)sulfanyl-4-chloro-1,2-thiazole-3-carboxylic acids were obtained.     

Synthesis and some chemical transformations of 3-ferrocenyl-3-phenylcyclopropene

Crystalline 3-ferrocenyl-3-phenylcyclopropene was obtained by dehydrobromination of 2-bromo-l-ferrocenyl-l-phenylcyclopropane with potassiumtert-butoxide in dimethyl sulfoxide. The compound synthesized undergoes catalytic hydrogenation to l-ferrocenyl-I-phenylcyclopropane, reacts with 1,3-diphenylisobenzofuran to give the expected product of stereospecific [4+2[-cycloaddition and 3-ferrocenylindene, and also undegoes opening of the small ring on treatment with superacids to give 3-ferrocenylindene as the major product. The data of single crystal X-ray diffraction analysis of 1-ferrocenyl-l-phenylcyclopropane and the diene adduct of 3-ferrocenyl-3-phenylcyclopropene with 1,3-diphenylisobenzofuran are given.     

Synthesis of 4-tosyl-5-chloro-1,3-thiazole-2-carbonitrile and its transformations

Reaction of the available 1-tosyl-2,2-dichloroethenyl isothiocyanate with sodium cyanide yields new clearly electrophilic substrate of thiazole nature containing the nitrile group, the tosyl residue, and the chlorine atom at C², C⁴, and C⁵ respectively. The direction of the reaction of this substrate with nucleophile depends significantly on the nature of the latter. It was used in regioselective syntheses of a series of the unknown previously trifunctional thiazoles.     

Synthesis of 1-(4-bromo-1-naphthyl)-dihydrouracil and some of its transformations

1-(4-Bromo-1-naphthyl)dihydrouracil, which is also obtained from 1-(4-bromo-1-naphthyl)--alanine, is formed by the bromination of 1-(1-naphthyl)dihydrouracil. Hydrogenation of 1-(4-bromo-1-naphthyl)dihydrouracil with lithium aluminum hydride yields either 1-(1-naphthyl)-2-oxohexahydropyrimidine or 1-(4-bromo-1-naphthyl)-2-oxohexahydropyrimidine, depending on the solvent used. 1-(4-Bromo-1-naphthyl)-2-oxohexahydropyrimidine is formed by the bromination of 1-(1-naphthyl)-2-oxohexahydropyrimidine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 524–526, April, 1971.     

Synthesis,structure, and chemical properties of some N-(3-chloro-2-quinoxalyl)arylsulfonamides

We have developed a method for synthesis of N-(3-clzloro-2-quinoxalyl)sulfonamides by reaction of 2,3-dichloroquinoxaline with substituted arylsufonamides. Based on the IR spectra, we have established that in the solid state, the synthesized compounds exist in the form of amide tautomers. Alkylation of these compounds leads to N-metliyl-N-(3-chloro-2-quinoxalyl)arylsulfonamides. We demonstrate the possibility of nucleophilic substitution of the halogen upon treatment with O- and N-nucleophiles. The use of bifunctional nucleophiles leads to condensed quinoxalines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 30, No. 3, pp. 387–392, March, 1994.     

Synthesis of some new 3-pyrazolyl-substituted-4(3H)quinazolinones

N-(1-Phenyl-3-methylpyrazol-5-yl)-o-aminobenzamide reacted with orthoesters to yield some new 3-pyrazolyl-substituted-4(3H)quinazolinones (VIIa,b,c,d). An alternative synthesis of Vllb was accomplished by reaction of acetylanthranyl with l-phenyl-3-methyl-5-aminopyrazole.     

Synthesis and some transformations of 1, 2, 3, 4-tetrahydrophenothiazine derivatives

1,2,3,4-Tetrahydrophenothiazine derivatives were obtained from cyclic monoketones and 1,3-diketones and o-nitroarenesulfenyl chlorides. The alkylation, aminomethylation, and oxidation of the compounds obtained were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1509–1513, November, 1972.     

Synthesis and acid-base transformations of (4-styrylpyridinio)-alkanesulfonates

(4-Styrylpyridinio)alkanesulfonates were synthesized by condensation of 2-(4-methylpyridinio)- and 2-(4-ethylpyridinio)-1-ethanesulfonates with aromatic aldehydes, and also by quaternization of 4-styrylpyridine by sulfoalkylating agents. For the p- and o-hydroxystyrylpyridinium compounds in aqueous solutions, the pK _a values were determined spectrophotometrically. It is believed that the planarity of the o-hydroxypyridinium compounds is disturbed because of the reaction of the hydroxy and the -sulfonatomethyl groups.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1357–1362, October, 1986.