Synthesis,isomerism, and spectral luminescence properties of methyl hexahydrobenzo[<Emphasis Type="Italic">a</Emphasis>]acridine-9- and -[<Emphasis Type="Italic">c</Emphasis>]acridine-10-carboxylates

The three-component condensation of 1- or 2-naphthylamines, aromatic aldehydes, and methyl 2-(benzo[1,3]dioxol-5-yl)-4,6-dioxocyclohexane-1-carboxylate led to the formation of methyl 9-(cis,trans)-10-(1,3-benzodioxol-5-yl)-7-aryl-8-oxo-7,8,9,10,11,12-hexahydrobenzo[c]acridine-9-carboxylates or methyl 10-(cis,trans)-9-(1,3-benzodioxol-5-yl)-12-aryl-11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridine-10-carboxylates. The spectral luminescence properties of compounds obtained were investigated in ethanol at 293 and 77 K.     

Synthesis of methyl 9-(benzo[<Emphasis Type="Italic">d</Emphasis>][1,3]dioxol-5-yl)-12-aryl(heteryl,cyclohexenyl)-11-oxo-7,8,9,10,11,12-hexahydrobenzo[<Emphasis Type="Italic">b</Emphasis>][4,7]phenanthroline-10-carboxylates

By condensation of 6-aminoquinoline with methyl 2-(benzo[d][1,3]dioxol-5-yl)-4,6-dioxocyclohexanecarboxylate and aldehydes of aromatic, heteroaromatic, and cyclohexene series new 4,7-phenanthroline derivatives were synthesized. The reaction performed in 1-butanol proceeded regiospecifically and with a moderate degree of stereoselectivity resulting in a mixture of cis- and trans-methyl 9-(benzo-[d][1,3] dioxol-5-yl)-12-aryl(heteryl, cyclohexenyl)-11-oxo-7,8,9,10,11,12-hexahydrobenzo-[b][4,7]-phenanthroline-10-carboxylates (∼30: 70).     

Synthesis and characterization of some chalcones and their cyclohexenone derivatives

A series of chalcones and their derivatives have been synthesized. Chalcones, 1-(1,3-benzodioxol-5-yl)-3-(aryl)-prop-2-en-1-ones were prepared by the aldol condensation of 1-(1,3-benzodioxol-5-yl)ethanones and aryl aldehydes. Based-catalyzed condensation of 1-(1,3-benzodioxol-5-yl)-3-(aryl)prop-2-en-1-ones with ethyl acetoacetate yields corresponding ethyl 4-(1,3-benzodioxol-5-yl)-6-(aryl)-2-oxocyclohex-3-ene-1-carboxylates. Some of the synthesized chalcones were reported in the literature; the newly synthesized compounds were characterized by single crystal X-ray studies, IR, ¹H-NMR and LCMS mass spectral analysis.     

Synthesis of methyl 7-aryl(hetaryl,cyclohexenyl)-10,10-dimethyl-8-oxo-7,8,9,10,11,12-hexahydrobenzo[<Emphasis Type="Italic">b</Emphasis>][1,7]phenanthroline-9-carboxylates

Three-component condensation of quinolin-5-amine with methyl 2,2-dimethyl-4,6-dioxocyclohexane-1-carboxylate and aromatic (heteroaromatic) aldehydes or cyclohex-3-ene-1-carbaldehyde gave previously unknown 1,7-phenanthroline derivatives. The reactions in butan-1ol were characterized by 100% regioselectivity but low stereoselectivity, and mixtures of cis- and trans-isomeric methyl 7-aryl(hetaryl, cyclohexenyl)-10,10-dimethyl-8-oxo-7,8,9,10,11,12-hexahydrobenzo[b][1,7]phenanthroline-9-carboxylates were obtained at a ratio of ∼45: 55.     

Synthesis and Structure of 4-Indolyl-5-(thieno[3,2-<Emphasis Type="Italic">b</Emphasis>]pyrrol-6-yl)imidazoles

A procedure was proposed for regioselective acylation of methyl 2-methyl-4H-thieno[3,2-b]-pyrrole-5-carboxylate with 2-(3-indolyl)-2-oxoacetyl chloride. Reactions of the resulting methyl 6-[2-(3-indolyl)-1,2-dioxoethyl]-2-methyl-4H-thieno[3,2-b]pyrrole-5-carboxylate with aromatic aldehydes and ammonium acetate in acetic acid afforded the corresponding methyl 6-[2-aryl-4-(3-indolyl)imidazol-5-yl]-2-methyl-4H-thieno[3,2-b]pyrrole-5-carboxylates. The structure of methyl 6-[2-(4-chlorophenyl)-4-(3-indolyl)imidazol-5-yl]-2-methyl-4H-thieno[3,2-b]pyrrole-5-carboxylate was studied by X-ray analysis.     

Spirobisheterocyclization of 5-(Methoxycarbonyl)-1<Emphasis Type="Italic">H</Emphasis>-pyrrol-2,3-diones by the action of enaminoesters. Crystal and molecular structure of 1,7-diazaspiro[4.4]nonane

1-Aryl-4-aroyl-5-(methoxycarbonyl)-1Н-pyrrole-2,3-diones react with methyl 4-aryl-2-(arylamino)-4-oxobut-2-enoates with the formation of methyl 1,7-diaryl-4,9-diaroyl-3-hydroxy-2,6-dioxo-1,7-diazaspiro[4.4]nona-3,8-diene-8-carboxylates.     

Five-membered 2,3-dioxo heterocycles: CV. Reaction of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with methyl 2-arylamino-4-(2-naphthyl)-4-oxobut-2-enoates. Crystal and molecular structure of substituted 1,7-diazaspiro[4.4]nonane

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with methyl 2-arylamino-4-(2-naphthyl)-4-oxobut-2-enoates to give methyl 1,7-diaryl-4-aroyl-3-hydroxy-9-(2-naphthalen-2-ylcarbonyl)-2,6-dioxo-1,7-diazaspiro[4.4]nona-3,8-diene-8-carboxylates.     

Reactions of 3,5-dibromo-1-(thiiran-2-ylmethyl)-1,2,4-triazole with NH-azoles

Reactions of 3,5-dibromo-1-(thiiran-2-ylmethyl)-1,2,4-triazole with 3,5-dimethylpyrazole, 1,3-dimethyl-3,7-dihydropurine-2,6-dione, 3,5-dibromo-1,2,4-triazole, 2,4,5-tribromoimidazole, and 2-chlorobenzimidazole lead to the formation of 5-azolylmethyl-2-bromo-5,6-dihydrothiazolo[3,2-b]-1,2,4-triazoles. In the case of 8-bromo-1,3-dimethyl-3,7-dihydropurine-2,6-dione the intermediate thiolate anion undergoes cyclization into 7-[(3,5-dibromo-1,2,4-triazol-1-yl)methyl]-1,3-dimethyl-6,7-dihydrothiazolo[2,3-f]purine-2,4(1H,3H)-dione. The structure of reaction products depends on the relative rate of substitution of leaving groups in the reagents.     

Thermolysis of 1-(methylideneamino)-1<Emphasis Type="Italic">H</Emphasis>-pyrrole-2,3-diones. Synthesis of pyrazolooxazines by [4 + 2]-cycloaddition of azomethine imines to alkenes

Thermolysis of methyl 3-acyl-1-[(diphenylmethylidene)amino]-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates generates 4-acyl-1-(diphenylmethylidene)-3-(methoxycarbonyl)-1H-pyrazol-1-ium-5-olates which react with alkenes to give methyl 3-acyl-7,7-diphenyl-6,7-dihydro-5H-pyrazolo[5,1-b][1,3]oxazine-2- carboxylates. The product structure was confirmed by X-ray analysis.     

Aldehydes of furan series in the synthesis of 1,7-phenanthroline derivatives

By condensation of quinolin-5-amine with 5-arylfuran-2-carbaldehydes and cyclohexane-1,3-dione or dimedone new compounds were synthesized, 10,10-dimethyl-7-(5-arylfuran-2-yl)-9,10,11,12-tetrahydrobenzo[b][1,7]phenanthrolin-8(7H)-ones unsubstituted in the position 10.     

Reaction of 4-Aryl-1-(4-oxo-3,4-dihydrothieno-[2,3-d]pyrimidin-2-yl)thiosemicarbazides with Dimethyl Acetylenedicarboxylate

4-Aryl-1-(4-oxo-3,4-dihydrothieno[2,3-d]pyrimidin-2-yl)thiosemicarbazides react with dimethyl acetylenedicarboxylate in methanol to give the corresponding methyl {3-aryl-4-oxo-2-[(4-oxo-3,4-dihydro-thieno[2,3-d]pyrimidin-2-yl)hydrazono]-1,3-thiazolidin-5-ylidene}acetates, whereas in dioxane methyl 5-aryl-amino-2-methoxycarbonylmethyl-3-(4-oxo-3,4-dihydrothieno[2,3-d]pyrimidin-2-yl)-2,3-dihydro-1,3,4-thiadiazole-2-carboxylates are mainly formed.     

A novel synthesis of aryl tethered imidazo[4,5-b]pyrazin-2-ones through in situ ring construction and contraction

An innovative synthesis of aryl tethered 1,3-dimethylimidazo[4,5-b]pyrazin-2-ones 4 and 6 has been delineated through base catalyzed ring transformation of 6-aryl-4-(piperidin-1-yl)-2H-pyran-2-one-3-carbonitriles 1 and methyl 6-aryl-4-methylsulfanyl-2H-pyran-2-one-3-carboxylates 5 with 7-acetyl-1,3-dimethyllumazine 2 with subsequent ring contraction of the fused pyrimidine to an imidazole ring. An additional product, methyl [6-(1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazo[4,5-b]pyrazin-5-yl)-4-thiophen-2-ylpyran-2-ylidene]acetate 8b, was also isolated from the reaction of 5 and 2, as a minor constituent.     

Fused polycyclic nitrogen-containing heterocycles: IX. Synthesis and molecular structure of methyl 3-(2-R-5-phenylthiazol-4-yl)-7-phenyl-7<Emphasis Type="Italic">H</Emphasis>-[1,2,4]triazolo-[3,4-<Emphasis Type="Italic">b</Emphasis>][1,3,4]thiadiazine-6-carboxylates

4-Amino-3-(2-R-5-phenylthiazol-4-yl)-1,2,4-triazole-5-thiones react with methyl 3-chloro-2-oxo-3-phenylpropionate to give methyl 3-(2-R-5-phenylthiazol-4-yl)-7-phenyl-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine-6-carboxylates. According to the X-ray diffraction data, the thiazole ring in the products is planar, while the thiadiazine ring has a distorted unsymmetrical boat conformation. Depending on the substituent in the thiazole ring, methyl 3-(2-R-5-phenylthiazol-4-yl)-7-phenyl-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine-6-carboxylates in crystal give rise to different supramolecular structures, lamellar and cylindrical.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004, pp. 1358–1365.Original Russian Text Copyright © 2004 by Mamedov, Mustakimova, Gubaidullin, Litvinov, Levin.     

Some chemical transformations of alkyl (4-aminophenyl)carbamates

Azo coupling of diazonium salts derived from alkyl (4-aminophenyl)carbamates with ethyl α-methylacetoacetate gave ethyl 5-alkoxycarbonylamino-1H-indole-2-carboxylates. The condensation of aminophenylcarbamates with aromatic aldehydes in ethanol afforded the corresponding Schiff bases. Cyclohexyl {4-[(4-methoxyphenyl)methylidene]aminophenyl}carbamate reacted with chloroacetyl chloride in dioxane in the presence of triethylamine to produce cyclohexyl {4-[3-chloro-2-(4-methoxyphenyl)-4-oxoazetidin-1-yl]phenylcarbamate, and the reaction of benzyl {4-[(4-nitrophenyl)methylidene]aminophenyl}carbamate with sulfanylacetic acid in DMF led to the formation of benzyl {4-[2-(4-nitrophenyl)-4-oxo-1,3-thiazolidin-3-yl]-phenyl}carbamate.     

Synthesis of pyrazolo[3,4-c][1,2]thiazin-4(3H)-one 2,2-dioxides,new heterocycles

The reaction of substituted ethyl 5-aminopyrazole-4-carboxylates with two equivalents of methanesul-fonyl chloride gave the substituted ethyl 5-[bis(methylsufonyl)amino]-1H.-pyrazole-4-carboxylates II . Removal of one of the methanesulfonyl groups, followed by alkylation of the ethyl 5-[(methylsulfonyl)amino]-1H-pyrazole-4-carboxylates III with methyl iodide produced the substituted ethyl 5-[methyl(methylsulfonyl)amino]-1H-pyrazole-4-carboxylates IV . Treatment of IV with sodium hydride gave the 7-substituted 1,7-dihydro-1-methylpyrazolo[3,4-c][1,2]thiazin-4(3H)-one 2,2-dioxides V .     

Synthesis of heterocycles from arylation products of unsaturated compounds: XVIII. 5-Arylfuran-2-carboxylic acids and their application in the synthesis of 1,2,4-thiadiazole, 1,3,4-oxadiazole,and [1,2,4]triazolo[3,4-<Emphasis Type="Italic">b</Emphasis>][1,3,4]thiadiazole derivatives

Arylation of furan-2-carboxylic acid or its methyl ester with arenediazonium chlorides in the presence of copper(II) chloride gave the corresponding 5-arylfuran-2-carboxylic acids or methyl 5-arylfuran-2-carboxylates. 5-Arylfuran-2-carbonyl chlorides reacted with potassium thiocyanate and then with 5-methyl-1,2-oxazol-3-amine to give 5-aryl-N-[3-(2-oxopropyl)-1,2,4-thiadiazol-5-yl]furan-2-carboxamides as a result of recyclization of intermediate isoxazolylthiourea derivatives. The reactions of 5-arylfuran-2-carbonyl chlorides with 5-(2-furyl)-1H-tetrazole involved opening of the tetrazole ring with elimination of nitrogen molecule and led to the formation of 2-(5-arylfuran-2-yl)-5-(2-furyl)-1,3,4-oxadiazoles. 3-Substituted 6-(5-arylfuran-2-yl)-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazoles were obtained by condensation of 5-arylfuran-2-carboxylic acids with 5-substituted 4-amino-4H-1,2,4-triazole-3-thiols in phosphoryl chloride.     

Synthesis of new functionally substituted hetarylcarbamates from methyl {4-[(2<Emphasis Type="Italic">E</Emphasis>)-3-(4-methoxyphenyl)-prop-2-enoyl]phenyl}carbamate

Three-component condensation of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2-enoyl]phenyl}- carbamate with ninhydrin and L-proline in methanol–water (10: 1) afforded methyl {4-[1,3-dioxo-1′- (4-methoxyphenyl)-1,1′,2′,3,5′,6′,7′,7a′-octahydrospiro[indene-2,3′-pyrrolizin]-2′-ylcarbonyl]phenyl}carbamate. Heating of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2-enoyl]phenyl}carbamate with isatin and benzylamine in methanol gave methyl {4-[4′-(4-methoxyphenyl)-2-oxo-5′-phenyl-1,2-dihydrospiro[indole-3,2′-pyrrolidin]-3′-ylcarbonyl]phenyl}carbamate. The condensation of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2- enoyl]phenyl}carbamate with sarcosine and 11H-indeno[1,2-b]quinoxalin-11-one generated in situ from ninhydrin and o-phenylenediamine in boiling ethanol led to the formation of methyl {4-[4′-(4-methoxyphenyl)-1′-methyl-11,11a-dihydro-5aH-spiro[benzo[b]phenazine-6,2′-pyrrolidin]-3′-ylcarbonyl]phenyl}carbamate.     

Synthesis of 1-azaxanthones by condensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with 3-(cyano)benzopyrylium triflates and subsequent domino ‘retro-Michael/nitrile-addition/heterocyclization’ reaction

Functionalized 1-azaxanthones (5-oxo-5H-[1]-benzopyrano[2,3-b]pyridines) were prepared by TMSOTf-mediated condensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with 3-cyanochromones and subsequent base-mediated domino ‘retro-Michael/nitrile-addition/heterocyclization’ reaction.     

Synthesis of 1-(1,3-dialkyl-2-oxo-2,3-dihydro-1<Emphasis Type="Italic">H</Emphasis>-imidazo-[4,5-<Emphasis Type="Italic">b</Emphasis>]pyridin-5-yl)-5-oxopyrrolidine-3-carboxylic acids

Nitration of 2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one gave its 5-nitro derivative which was subjected to alkylation with dimethyl sulfate, diethyl sulfate, and benzyl(dimethyl)phenylammonium chloride. The resulting 1,3-dimethyl-, 1,3-diethyl-, and 1,3-dibenzyl-5-nitro-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones were reduced to the corresponding 1,3-dialkyl-5-amino-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones, and the latter reacted with itaconic acid to produce 1-(1,3-dialkyl-2-oxo-2,3-dihydro-1H-imidazo[4,5-b]pyridin-5-yl)-5-oxopyrrolidine-3-carboxylic acids. 1-(2-Oxo-2,3-dihydro-1H-imidazo[4,5-b]pyridin-5-yl)-5-oxopyrrolidine-3-carboxylic acid was obtained by analogous reaction with 5-amino-2,3-dihydro-1H-imidazo[4,5-b]-pyridin-2-one.     

Synthesis of 7-iodo(arylsulfanyl)methyl-7,8-dihydro-[1,3]thiazolo[2,3-i]purinium pentaiodide (perchlorates) and their transformation into 4-amino-5-(1,3-thiazol-2-yl)imidazole derivatives

Intramolecular electrophilic cyclization of 6-allylsulfanylpurine by the action of iodine and arenesulfenyl chlorides gave 7-iodomethyl-7,8-dihydro[1,3]thiazolo[2,3-i]purin-6-ium pentaiodide and 7-arylsulfanylmethyl-7,8-dihydro[1,3]thiazolo[2,3-i]purin-6-ium perchlorates, respectively. 7-Iodomethyl-7,8-dihydro-[1,3]thiazolo[2,3-i]purin-6-ium iodide reacted with sodium and potassium alkoxides to produce alkyl N-[5-(4-methyl-1,3-thiazol-2-yl)-1H-imidazol-4-yl]formimidates, and its reaction with secondary cyclic amines afforded 5-(4-methyl-1,3-thiazol-2-yl)-N-[morpholin-4-yl(or piperidin-1-yl)methylidene]-1H-imidazol-4-amines. Successive treatment of 7-arylsulfanylmethyl-7,8-dihydro[1,3]thiazolo[2,3-i]purin-6-ium perchlorates with sodium acetate and morpholine led to the formation of 5-(4-arylsulfanylmethyl-4,5-dihydro-1,3-thiazol-2-yl)-N-(morpholin-4-ylmethylidene)-1H-imidazol-4-amines.