Synthesis and Antimicrobial Activity of Methyl (2 Z )-4-Aryl-2-{4-[(4,6-dimethylpyrimidin-2-yl)sulfamoyl]phenylamino}-4-oxobut-2-enoates and Their Silver Salts

A series of new methyl (2Z)-4-aryl-2-{4-[(4,6-dimethylpyrimidin-2-yl)-sulfamoyl]phenylamino}-4-oxobut-2-enoates was synthesized by the reaction of methyl esters of aroylpyruvic acids with 2-(4-aminobenzenesulfamido)-4,6-dimethylpyrimidine in a mixture of acetic acid–ethanol (1 : 1). The obtained 4-oxobut-2-enoates reacted with silver nitrate in ethanol–DMF (2 : 1) to form their silver salts. The antimicrobial activity of the compounds was studied.     

Synthesis of methyl 4-aryl-2-{[4-(carbamimidoylsulfamoyl)- phenyl]amino}-4-oxobut-2-enoates

Methyl aroylpyruvates reacted with 4-amino-N-carbamimidoylbenzene-1-sulfonamide in acetic acid–ethanol (1: 1) to give methyl 4-aryl-2-{[4-(carbamimidoylsulfamoyl)phenyl]amino}-4-oxobut-2-enoates which were found to exist in solution as mixtures of Z and E isomers.     

Chemistry of iminofurans: IX. Synthesis and cyclization of (2<Emphasis Type="Italic">Z</Emphasis>)-2-{(2<Emphasis Type="Italic">Z</Emphasis>)-2-[2-(3-R-adamantan-1-yl)-2-oxoethylidene]hydrazinyl}-4-(het)aryl-4-oxobut-2-enoic acids

1-(3-R-adamantan-1-yl)-2-[(triphenyl-λ⁵-phosphanylidene)hydrazinylidene]ethanone reacted with 4-aryl(hetaryl)-2,4-dioxobutanoic acids to give 2-{2-[2-(3-R-adamantan-1-yl)-2-oxoethylidene]hydrazinyl}-4-aryl(hetaryl)-4-oxobut-2-enoic acids which were shown to exist in solution as mixtures of Z- and E-isomeric enehydrazine tautomers. The products underwent cyclization to 3-{[2-(3-R-adamantan-1-yl)-2-oxoethylidene]- hydrazinylidene}-5-aryl(hetaryl)furan-2(3H)-ones.     

Chemistry of iminofurans: XI. Synthesis,structure, and cyclization of 4-substituted 2-(aroylhydrazinylidene)-4-oxobutanoic acids

Aromatic hydrazides reacted with 4-aryl-2-hydroxy-4-oxobut-2-enoic and 2-hydroxy-5,5-dimethyl- 4-oxohex-2-enoic acids to give 4-aryl-2-(2-aroylhydrazinylidene)-4-oxobutanoic and 5,5-dimethyl-2-(aroylhydrazinylidene)- 4-oxohexanoic acids. The products were found to exist in solution as mixtures of Z/E-hydrazinylidene and cyclic dihydropyrazole tautomers, and they underwent intramolecular cyclization to 5-aryland 5-tert-butyl-3-(aroylhydrazinylidene)furan-2(3H)-ones by the action of acetic anhydride.     

Functionalization of methyl 3-acetyl-5-[(methoxycarbonyl)amino]-2-methyl-1<Emphasis Type="Italic">H</Emphasis>-indole-1-carboxylate

Oxidative heterocyclization of methyl 3-{1-[2-(carbamoylhydrazinylidene)]ethyl}-2-methyl-5-[(methoxycarbonyl)amino]-1H-indole-1-carboxylate by the action of selenium dioxide in acetic acid and heating of the corresponding thiosemicarbazone in boiling acetic anhydride gave 1,2,3-selenadiazole and 2,3-dihydro-1,3,4-thiadiazole derivatives, respectively. Methyl 3-acetyl-2-methyl-5-[(methoxycarbonyl)amino]-1H-indole-1-carboxylate reacted with selenium dioxide in dioxane–water (30: 1) at 80?90°C to form methyl 5-[(methoxycarbonyl)amino]-2-methyl-3-(2-oxoacetyl)-1H-indole-1-carboxylate whose condensation with o-phenylenediamine afforded methyl 2-methyl-5-[(methoxycarbonyl)amino]-3-(quinoxalin-2-yl)-1H-indole-1-carboxylate.     

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.     

Iminofurans chemistry: IV. Synthesis and structure of 2-<Emphasis Type="Italic">N</Emphasis>-aryl-substituted derivatives of 2-amino-4-aryl-4-oxobut-2-enoic and 2-amino-5,5-dimethyl-4-oxohex-2-enoic acids

Reactions of arylamines with 4-aryl-2-hydroxy-4-oxobut-2-enoic and 2-hydroxy-5,5-dimethyl-4-oxohex-2-enoic acids gave rise to 4-aryl-2-arylamino-4-oxobut-2-enoic and 2-aryl-amino-5,5-dimethyl-4-oxohex-2-enoic acids that existed in solutions as Z- and E-isomers or in a ring form as 3-arylamino-5-tert-butyl-5-hydroxyfuran-2(5H)-ones. The probable cyclization mechanism of these compounds into 5-R-3-arylimino-3H-furan-2-one derivatives was considered.     

Synthesis and reactions of 3-(3-ethoxycarbonyl-1-phenyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-4-yl)propenic acid

The reaction of ethyl 4-formyl-1-phenyl-1H-pyrazole-3-carboxylate with the malonic acid led to the formation (2E)-3-(3-ethoxycarbonyl-1-phenyl-1H-pyrazol-4-yl)propenic acid. In reactions of this acid chloride with 4-amino-5-aryl(hetaryl)-4H-1,2,4-triazole-3-thiols were obtained ethyl 4-[(E)-2-{3-aryl(hetaryl)[1,2,4]triazolo[3,4-b][1,3,4]thiadiazol-6-yl}ethenyl]-1-phenyl-1H-pyrazoe-3-carboxylates, with 5-aryltetrazoles, ethyl 4-[(E)-2-(5-aryl-1,3,4-oxadiazol-2-yl)-ethenyl]-1-phenyl-1H-pyrazole-3-carboxylates, with 1-(2-hydroxy-3,5-dimethylphenyl) followed by the Baker-Venkataraman rearrangement and the cyclization, ethyl 4-[(E)-2-(6,8-dimethyl-4-oxo-4Hchromen-2-yl)ethenyl]-1-phenyl-1H-pyrazole-3-carboxylate.     

Derivatives of α,β-dehydroamino acids: V. Intramolecular cyclization of 2-{2-[(<Emphasis Type="Italic">Z</Emphasis>)-1-Benzamido-2-phenylvinyl]acetamidomethyl}benzimidazole

Reaction of 4-benzylidene-2-phenyl-1,3-oxazol-5(4H)-one with 2-(1H-benzimidazol-2-yl)ethaneamine led to the formation of 2-{2-[(Z)-1-benzamido-2-phenylvinyl]acetamidomethyl}benzimidazole that in a reaction with hexamethyldisilazane in DMF gave 5-benzylidene-1-(1H-benzimidazol-2-yl)-2-phenyl-3,5-dihydro-4H-imidazol-4-one. In the presence of K₂CO₃ in dioxane the reaction with hexamethyldisilazane resulted in the product of intramolecular addition, N-(4-benzyl-3-oxo-1,2,3,4-tetrahydropyrazino[1,2-a]-benzimidazol-4-yl)benzamide     

Microwave-assisted synthesis of 1-{2-[(1-benzyl-1<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazol-4-yl)methoxy]phenyl}-3-(3-aryl-1-phenyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-4-yl)prop-2-en-1-ones and their antimicrobial activity

A series of new (E)-1-{2-[(1-benzyl-1H-1,2,3-triazol-4-yl)methoxy]phenyl}-3-(3-aryl-1-phenyl-1H-pyrazol-4-yl)prop-2-en-1-ones (3a–3i) has been synthesized via copper-catalyzed 1,3-dipolar azide-alkyne cycloaddition reaction (CuAAC) of benzyl azide with substituted (E)-3-(3-aryl-1-phenyl-1H-pyrazol-4-yl)-1-[2-(prop-2-ynyloxy)phenyl]prop-2-en-1-ones (2a–2i). The synthesized compounds have been characterized by their IR, ^lH, ¹³C NMR spectra, and mass spectroscopy data. All the compounds have been screened for antimicrobial activity.     

Reaction of 2-methylquinoline with 3-phenylprop-2-ynenitrile in the KOH—H<Subscript>2</Subscript>O system

The reaction of 2-methylquinoline with 3-phenylprop-2-ynenitrile in the presence of water (0—25 °C, 20 mol.% KOH, 5 equiv. H₂O) is accompanied by the loss of aromaticity of the quinoline nucleus and results in double functionalization of the molecule at the nitrogen atom and the methyl group. Two 2-cyano-1-phenylethenyl groups were introduced into the molecule to form (2E,4E)-4-{1-[(Z)-2-cyano-1-phenylethenyl]quinolin-2(1H)-ylidene}-3-phenylbut-2-enenitrile in 59—67% yield. This reaction is stereoselective: the N-2-cyano-1-phenylethenyl-substituent has the Z-configuration, while the 1,3-diene moiety at the methyl group has the E,E-configuration. (2E)-3-Phenyl-4-(quinolin-2-yl)but-2-enenitrile that formed as a by-product (0—24% yields) is formally the addition product of the methyl group of the quinoline substrate at the acetylenic bond.     

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 methyl 4-aryl-4-oxo-2-[(4-sulfamoylphenyl)amino]but-2-enoates and their reaction with ninhydrin

The reaction of methyl 4-aryl-2,4-dioxobut-2-enoates with 4-aminobenzenesulfonamide in acetic acid–ethanol (1: 1) afforded methyl (2Z)-4-aryl-4-oxo-2-(4-sulfamoylanilino)but-2-enoates which reacted with ninhydrin in glacial acetic acid to give 3-aroyl-4-(4-sulfamoylanilino]-5H-spiro[furan-2,2′-indene]-1′,3′,5-triones.     

Acylation of Fischer’s Base with Methyl Aroylpyruvates

Methyl (Z)-4-aryl-2-hydroxy-4-oxobut-2-enoates (methyl aroylpyruvates) reacted with 1,3,3-trimethyl- 2-methylidene-2,3-dihydro-1H-indole (Fischer’s base) to give (2Z,5E)-1-aryl-3-hydroxy-5-(1,3,3-trimethyl-2,3-dihydro-1H-indol-2-ylidene)pent-2-ene-1,4-diones.     

Reaction of <Emphasis Type="Italic">N</Emphasis>-(carbamimidoyl)thiourea with 1-benzoyl-2-phenylacetylene

1-Benzoyl-2-phenylacetylene reacted with N-(carbamimidoyl)thiourea in glacial acetic acid saturated with 20% HBr to give (4,6-diphenyl-2H-1,3-thazin-2-ylidene)guanidine hydrobromide. The reaction of the same compounds in anhydrous ethanol in the presence of sodium ethoxide led to the formation of N-(4,6-diphenylpyrimidin-2-yl)thiourea. Bis(3-oxo-1,3-diphenylprop-1-en-1-yl) sulfide and 1-benzoyl-2-ethylsulfanyl-2-phenylethylene were isolated in the reactions of 1-benzoyl-2-phenylacetylene with N-(carbamimidoyl)thiourea and N-(carbamimidoyl)-S-ethylisothiuronium bromide, respectively, in anhydrous methanol.     

Cyclization of trifluoro-<Emphasis Type="Italic">N</Emphasis>-(prop-2-yn-1-yl)methanesulfonamides to <Emphasis Type="Italic">N</Emphasis>-(hydroxymethyl)-1,2,3-triazoles

Three-component heterocyclizations of trifluoro-N-(prop-2-yn-1-yl)methanesulfonamide, trifluoro-N-pheny-N-(prop-2-yn-1-yl)methanesulfonamide, and trifluoro-N,N-di(prop-2-yn-1-yl)methanesulfonamide with formaldehyde and sodium azide afforded N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-, N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-N-phenyl-, and N,N-bis{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}trifluoromethanesulfonamides as the major products together with minor 1-(hydroxymethyl)-1H-1,2,3-triazole isomers.     

4-aryl-2-hydroxy-4-oxobut-2-enoic acids <Emphasis Type="Italic">N</Emphasis>-(2-pyridyl)amides in reactions with diazo compounds

Reactions of 4-aryl-2-hydroxy-4-oxobut-2-enoic acids N-(2-pyridyl)amides with diazomethane, diazoethane, diaryldiazomethanes, and diazofluorene lead to the formation of 2-alkoxy-4-aryl-4-oxobut-2-enoic acids N-(2-pyridyl)amides, 3-aroyl-5-methylpyrazole-4-carboxylic acids N-(2-pyridyl)amides, and 3-alkoxy-3-(2-aryl-2-oxoethyl)-2,3-dihydro-2-oxoimidazo[1,2-a]pyridines. The composition and structure of compounds obtained depend on the nucleophilic nature of the diazo compound and on the character of substituents in the aryl and pyridine parts of the substrate.     

Azolyl-substituted 1,2,3-triazoles

Huisgen reaction of (E)-1,5-diarylpent-2-en-4-yn-1-ones and (E)-1,5-diarylpent-1-en-4-yn-3-ones afforded 1-aryl-3-(5-aryl-1H-1,2,3-triazol-4-yl)prop-2-en-1-ones and 3-aryl-1-(5-aryl-1H-1,2,3-triazol-4-yl)-prop-2-en-1-ones, respectively. (E)-1-Aryl-3-(5-phenyl-1H-1,2,3-triazol-4-yl)prop-2-en-1-ones reacted with hydrazine hydrate and phenylhydrazine to give 72–93% of 4-(3-aryl-4,5-dihydro-1H-pyrazol-5-yl)-5-phenyl-1H-1,2,3-triazoles which underwent dehydrogenation on heating in boiling acetic acid with formation of the corresponding pyrazole derivatives. The molecular structures of (E)-3-phenyl-1-(5-phenyl-1H-1,2,3-triazol-4-yl)prop-2-en-1-one and 4-[3-(4-methylphenyl)-1-phenyl-4,5-dihydro-1H-pyrazol-5-yl]-5-phenyl-1H-1,2,3-triazole were studied by X-ray analysis. 4-(3-Aryl-4,5-dihydro-1H-pyrazol-5-yl)-5-phenyl-1H-1,2,3-triazoles showed toxicity against Daphnia magna.     

Stereoselective synthesis of (<Emphasis Type="Italic">Z</Emphasis>,<Emphasis Type="Italic">E</Emphasis>)-bis(2-chloroethenyl)tellanes

A procedure for the stereoselective synthesis of dichloro[(Z)-2-chloro-2-phenylethenyl][(4E)-5- chlorooct-4-en-4-yl]-λ⁴-tellane and [(Z)-2-chloro-2-phenylethenyl][(4E)-5-chlorooct-4-en-4-yl]tellane has been developed on the basis of anti-addition of tellurium tetrachloride–phenylacetylene monoadduct to oct-4-yne.     

Preparation of stereochemically pure <Emphasis Type="Italic">E</Emphasis>- and <Emphasis Type="Italic">Z</Emphasis>-alkenoic acids and their methyl esters from bicyclo[<Emphasis Type="Italic">n</Emphasis>.1.0]alkan-1-ols. Application in the synthesis of insect pheromones

Oxidative cleavage of exo- and endo-alkyl- and hydroxyalkyl-substituted bicyclo[n.1.0]alkan-1-ols with (diacetoxy-λ³-iodanyl)benzene gave the corresponding methyl alkenoates exclusively with E or Z configuration of the double bond. This reaction was used as the key stage in the syntheses of stereoisomerically pure components of pest insect pheromones: (E)-dodec-9-en-1-yl acetate (European pine shoot moth Rhyacionia buoliana), (Z)-tetradec-11-en-1-yl acetate (European oak leafroller Tortrix viridana), and (3E,8Z,11Z)-tetradeca-3,8,11-trien-1-yl acetate (tomato leafminer Tuta absoluta).