Five-membered dioxoheterocycles: XCIX. Reaction of 1-aryl-4-aroyl-5-methoxycarbonyl-1H-pyrrole-2,3-diones with indoles. Crystal and molecular structure of substituted 2-(indol-3-yl)pyrrole

1-Aryl-4-aroyl-5-methoxycarbonyl-1H-pyrrole-2,3-diones react with indole and 2-methylindole with the formation of methyl 1-aryl-3-aroyl-4-hydroxy-2-(1H-indol-3-yl)-5-oxo-2,5-dihydro-1H-pyrrole-2-carboxylates. Crystal and molecular structure of methyl 3-benzoyl-4-hydroxy-2-(2-methyl-1H-indol-3-yl)-5-oxo-1-phenyl-2,5-dihydro-1H-pyrrole-2-carboxylate was examined.     

Five-membered 2,3-dioxo heterocycles: LX. Reaction of 3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones with cyclic enehydrazino ketones. Crystalline and molecular structure of N-[3′-benzoyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6, 6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]-3-nitrobenzamide

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with N′-(5,5-dimethyl-3-oxocyclohex-1-en-1-yl)benzohydrazides to give the corresponding N-[3′-aroyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]benzamides. The molecular and crystalline structure of one of the products, N-[3′-benzoyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]-3-nitrobenzamide, was determined by X-ray analysis.     

Five-membered 2,3-dioxo heterocycles: XCI. Reaction of 3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones with dimedone. Crystalline and molecular structure of 3′-benzoyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6,6-dimethyl-6,7-dihydrospiro[1-benzofuran-3,2′-pyrrole]-2,4,5′(1′H,5H)-trione

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones reacted with 5,5-dimethylcyclohexane-1,3-dione to give 3′-aroyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6,6-dimethyl-6,7-dihydrospiro[1-benzofuran-3,2′-pyrrole]-2,4,5′(1′H,5H)-triones. The crystalline and molecular structures of 3′-benzoyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6,6-dimethyl-6,7-dihydrospiro[1-benzofuran-3,2′-pyrrole]-2,4,5′(1′H,5H)-trione were determined by X-ray analysis.     

Synthesis of substituted in benzene ring 4-[(2-aminophenyl)thio]-, 4-[(2-mercaptophenyl)amino]-2-methylquinolines and (4E)-4-[(2-mercaptophenyl)imino]-2-methyl-1,4-dihydroquinolines

By a reaction of 2-methyl-4-chloroquinolines with o-mercaptoaniline under various conditions synteses were performed of substituted in the benzene ring 4-[(2-aminophenyl)thio]-2-methylquinolines and (4E)-4-[(2-mercaptophenyl)imino]-2-methyl-1,4-dihydroquinolines that were respectively by isomerization or rearrangement converted into 4-[(2-mercaptophenyl)amino]-2-methylquinolines.     

3-methylthio-1,2-dithiolylium salts : Reaction with 4-hydroxy-6-methyl-2H-pyran-2-one and 4-hydroxycoumarin

The reaction of 4- and 5-aryl-3-methylthio-1,2-dithiolylium iodides with 4-hydroxy-6-methyl-2$\text{H}$-pyran-2-one and 4-hydroxycoumarin has been studied. 4-Substituted salts yielded 3-aryl-7-methyl-2-thioxo-2$\text{H}$,5$\text{H}$-pyrano [3,2-c]pyran-5-ones and 3-aryl-2-thioxo-2H,5H-pyrano[3,2-c]benzo[e]pyran-5-ones, respectively, whereas 5-substituted salts gave rise to 3-(5′-aryl-1′,2′-dithiol-3′-ylidene)-6-methyl-2$\text{H}$-pyran-2,4-diones and 3-(5′-aryl-1′,2′-dithiol-3′-ylidene)-2$\text{H}$-benzo [b]-pyran-2,4-diones.     

Ringschlussreaktionen von 1-(2-Aminophenyl)-1-phenyl-äthylenen durch Kondensation mit Phosgen

Cyclization of 1-(2-aminophenyl)-1-phenyl-ethylenes or 1-(2-aminophenyl)-1-phenyl-propenes (II) by condensation with phosgene led to 4-phenyl-carbostyrils (III) or 2-chloro-4-phenyl-quinolines (IV). Similarly, thiophosgene afforded 4-phenyl-thiocarbostyril. Treatment of 1-(2-aminophenyl)-2-methyl-1-p-tolyl-propene (VII) with phosgene led to the corresponding isocyanate IX, which cyclized in the presence of aluminum chloride with loss of a methyl group to 3-methyl-4-p-tolyl-carbostyril (III-6). However, 1-(2-aminophenyl)-2-methyl-1-phenyl-propene (VIII) treated with phosgene gave the isocyanate XI and 3-phenyl-3-isopropenyloxindole (X). Cyclization of the isocyanate XI with aluminium chloride led simultaneously to 3-methyl-4-phenyl-carbostyril (XIV), and with migration of a methyl group to 3-methylene-4-methyl-4-phenyl-3. 4-dihydro-carbostyril (XV).     

Features of reactions of polyfluorinated ethyl 4-oxo-2-pnenyl-4H-chromene-3-carboxylates with N-nucleophiles

Ethyl 5,6,7,8-tetrafluoro-4-oxo-2-phenyl-4H-chromene-3-carboxylate in reactions with primary amines is characterized by a chromone-coumarin rearrangement affording 3-[amino(phenyl)methylene]-6,7,8-trifluoro-2H-chromene-2,4(3H)-diones, and ethyl 4-oxo-2-phenyl-5,6,7,8-tetrafluoro-4H-chromene-3-carboxylate characteristically adds the amine at the C² site of the flavone furnishing 3-amino-3-phenyl-2-(2,3,4,5-tetrafluoro-6-hydroxybenzoyl)acrylates which depending on the substituent at the amino group are capable of intramolecular cyclization into 3-[(alkylamino)(phenyl)methylene]-5,6,7,8-tetrafluoro-2H-chromene-2,4(3H)-dione or in the case of benzylamine substituent, into ethyl 1-benzyl-5-hydroxy-4-oxo-2-phenyl-6,7,8-trifluoro-1,4-dihydroquinoline-3-carboxylate. The main process in the reaction of tri- and tetrafluoroflavones with secondary amine (1-methylpiperazine) is the nucleophilic substitution at the C⁷ of flavone. In the reaction with 1,2-phenylenediamine 3-[(2-aminophenyl)amino]-3-phenyl-2-(2,3,4,5-tetrafluoro-6-hydroxybenzoyl)acrylate was obtained from tetrafluoroflavone and 1H-benzimidazol-2-yl(3,4,5-trifluoro-2-hydroxyphenyl)methanone, from trifluoroflavone.     

Five-membered 2,3-dioxo heterocycles: CII. Spiro heterocyclization of 3-aroylpyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones by the action of tetrahydroquinoline

3-Aroylpyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones reacted with 1,2,3,4-tetrahydroquinoline to give 3-aroyl-4-hydroxy-1-(2-hydroxyphenyl)-5′,6′-dihydrospiro[pyrrole-2,1′-pyrrolo[3,2,1-ij]quinoline]-2′,5(1H,4′H)-diones.     

Synthesis of methyl (E)-2-[(3S,4S)-4-hydroxy-3-(pent-3-yloxy)-pyrrolidin-2-ylidene]propanoate and its unusual recyclization

Methyl (2E,4S,5S)-5-hydroxy-6-mesyloxy-2-methyl-4-(pent-3-yloxy)hex-2-enoate was synthesized from l-tartaric acid. Attempted substitution of the mesyloxy group by the reaction with NaN₃ directly led to methyl (E)-2-[(3S,4S)-4-hydroxy-3-(pent-3-yloxy)pyrrolidin-2-ylidene]propanoate. The latter on treatment with CF₃COOH and then NaOH gave methyl (2E)-2-methyl-4-[(S)-oxiran-2-yl]-4-(pent-3-yloxy)but-2-enoate.     

Synthesis of 3-(2-Oxo-2,3-dihydrobenzo[<Emphasis Type="Italic">b</Emphasis>]furan-3-ylidenehydrazono)-2,3-dihydrobenzo[<Emphasis Type="Italic">b</Emphasis>]furan-2-one

Reactions of benzophenone and fluoren-9-one hydrazones with (2-hydroxyphenyl)oxoacetic acid gave [carboxy(2-hydroxyphenyl)methylidenehydrazono](2-hydroxyphenyl)acetic acid which underwent intramolecular cyclization with formation of 3-(2-oxo-2,3-dihydrobenzo[bfuran-3-ylidenehydrazono)-2,3-dihydrobenzo[b]furan-2-one. The symmetric azine was also obtained by reactions of (2-hydroxyphenyl)oxoacetic acid with triphenylphosphoranylidenehydrazones derived from benzophenones, fluoren-9-one, and 1-methyl-2,3-dihydro-1H-indole-2,3-dione.     

One-pot synthesis of 3-(furan-2-yl)-4-hydroxy-2H-chromen-2-ones using K10 montmorillonite clay as heterogeneous catalyst

A facile and efficient one-pot synthesis of 3-(furan-2-yl)-4-hydroxy-2H-chromen-2-ones was developed. The reaction of ethyl 3-(2-hydroxyphenyl)-3-oxopropanoates and 2,5-dimethoxy-2,5-dihydrofuran were performed in presence of K10 Montmorillonite Clay heterogeneous catalyst under the solvent-free condition at 80?°C for 1?h, and followed by further converted to 3-(furan-2-yl)-4-hydroxy-2H-chromen-2-ones via refluxing in the alkaline EtOH solution for 0.5?h. The demonstrate method not only avoided the usage of any expensive transition-metals, but also eliminated the tedious intermediate purification. Moreover, due to the wide functional group tolerance, it could be applied to various substrates and gave product in good to excellent yields.     

Formation of 3-[amino(aryl)-methylidene]-1,3-dihydro-2H-indol-2-ones involving ring transformation of 2-aryl-5-(2-aminophenyl)-4-hydroxy-1,3-thiazoles

The reaction of 3-bromooxindole with substituted (hetero)aromatic thioamides in acetonitrile was studied. At room temperature the reaction preferably gives products of ring transformation i.e. 2-aryl-5-(2-aminophenyl)-4-hydroxy-1,3-thiazoles (3b-f,h) whereas at elevated temperature products of an Eschenmoser coupling reaction, i.e. 3-[amino(aryl)-methylidene]-1,3-dihydro-2H-indol-2-ones (2b-f), are formed exclusively. There exist only two exceptions (4-methoxy and 2-pyridinthioamide) in which the Eschenmoser coupling reaction always takes place giving 2a and 2g. Also N-methylation of the starting 3-bromooxindole completely prevents formation of thiazoles. The prepared thiazoles 3b-f are unstable in solution and they undergo slow ring transformation to 2b-f. The rate limiting step of this rearrangement involves cleavage of an intermediary thiirane ring, which is slowed down by electron-withdrawing substituents on the thioamide (ρ = ?1.15).     

Synthesis of 1-[3-methyl-2(3H)-benzazolon-5- or 6-yl]-4-{4-[cis-2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl-methyl)-1,3-dioxolan-4-yl]methyleneoxyphenyl}piperazines

Reactions of 3-methyl-6-[4-(4-hydroxyphenyl)-1-piperazinyl]-2(3H)-benzoxazolone, 3-methyl-6-[4-(4-hydroxy-phenyl)-1-piperazinyl]-2(3H)-benzothiazolone and 1,3-dimethyl-5-[4-(4-hydroxyphenyl)-1-piperazinyl]-2(3H)-benzimidazolone with cis-{[2-(2,4-dichlorophenyl) -2-(1H-imidazol-1-ylmethyl)]-1,3-dioxolan-4-yl}methyl meth-anesulfonate in the presence of sodium hydride furnish the title compounds.     

1′-Azido- and 1′-amino-1,3-dioxolan-4-ones

1,3-Dioxolanone alcohols, prepared via the addition of chiral lithium enolates of 1,3-dioxolan-4-ones to aldehydes, are suitable intermediates for the synthesis of chiral trisubstituted isoserines or trisubstituted 3-hydroxy-β-lactams. In particular, the methyl ester of 2-methyl-3-(2-furyl)isoserinic acid and two 3-methyl-3-hydroxy-β-lactams bearing either a 2-furyl or a phenyl substituent at C-(4) have been prepared. The (2R,3S) stereochemistry of the isoserine, and the (3R,4S) stereochemistry of the two β-lactams is that required for the synthesis of taxoid analogues having the side-chain with the proper (2′R,3′S) configuration.     

Syntheses on the basis of 2H-chromen-2-one and 2H-chromene-2-thione

4-Hydroxy-2H-chromen-2-one and 4-hydroxy-2H-chromene-2-thione reacted with allyl bromide, 1,1,3-trichloroprop-1-ene, and 1,3-dichlorobut-2-ene to give the corresponding ethers, which were oxidized to (2-oxo-2H-chromen-4-yloxy)acetic acid with potassium permanganate, and various derivatives of that acid were obtained. 3-(3,3-Dichloroprop-2-enyl)-7-hydroxy-4-methyl-2H-chromen-2-one and 3-(3,3-dichloroprop-2-enyl)-7-hydroxy-4-methyl-2H-chromene-2-thione were synthesized, and some their transformations were studied.     

Preparation and Structure of (E)-1-(3′-Hydroxy-2-Furanyl)-3-(3″-Hydroxy-4″-Methoxyphenyl)-2-Propen-1-One

Abstract

A facile procedure is presented for the synthesis of (E)-1-(3′-hydroxy-2′-furanyl)-3-(3″-hydroxy-4″-methoxyphenyl)-2- propen-1-one (6). Galactosylisomaltol (1) was condensed with isovanillin (2) under strong alkaline conditions at 25 [ddot]C to form (E)-1-(3′-O-β-D-galactopyranosyloxy-2′-furanyl)-3-(3″- hydroxy-4″-methoxyphenyl)-2-propen-1-one (4). (E)-1-(3′-hydroxy-2′-furanyl)-3-(3″-hydroxy-4″-methoxyphenyl)-2-propen-1-one (6) was obtained by acid hydrolysis of 4 in a 53.9% yield. This hetero-cyclic 2-propen-1-one was characterized on the basis of spectral data (IR and ¹H NMR), physicochemical properties, and conversion to a mono-O-acetyl derivative.     

Electron impact mass spectrometry of 3-hydroxy-3,4,5,6-tetrahydro-2H-[1]benzoxocines. A comparison with the behaviour of isomeric 2-hydroxymethyl-2,3,4,5-tetrahydro-[1]-benzoxepines and 1,2-epoxy-5-(2-hydroxyphenyl)pentane

The mass spectrometric behavior of 3-methyl-3-hydroxybenzoxocines has been studied in detail by means of linked scans and mass analyzed ion kinetic energy spectrometry. The structure of the molecular ion and the fragmentation processes are strictly related to the structure of the neutral moieties. The possible isomerization of 3-hydroxy-10-methoxy-3-methyl-3,4,5,6-tetrahydro-2H-[1]benzoxocine to 2-methyl-2-[3-(3′-methoxy-2′-hydroxy)phenyl]pentyloxirane and to 2-hydroxymethyl-9-methoxy-2-methyl-2,3,4,5-tetrahydro[1]benzoxepine is investigated.     

Reactions of 5-aryl-4-acyl-1-(4-hydroxyphenyl)-3-hydroxy-3-pyrrolin-2-ones with arylamines

The reaction of 5-(4-chlorophenyl)-4-benzoyl-1-(4-hydroxyphenyl)-3-hydroxy-3-pyrrolin-2-one with aromatic amines affords the corresponding 3-arylamino derivatives, and the reactions of 5-aryl-4-acetyl-1-(4-hydroxyphenyl)-3-hydroxy-3-pyrrolin-2-ones with p-toluidine yield 5-aryl-4-(1-p-tolylamino)ethylene-1-(4-hydroxyphenyl)pyrrolidin-2,3-diones.     

Reactions of 2- and 4-pyrones with secondary phosphine chalcogenides: a facile synthesis of functional phosphorylated pyrones

The oxidative cross-coupling between 4-hydroxy-6-methyl-2-pyrone or 3-hydroxy-2-methyl-4-pyrone and secondary phosphine chalcogenides proceeds in CCl₄/Et₃N under mild conditions (20–52 °С, 0.75–10 h) through the hydroxyl group to give O-(6-methyl-2-oxo-2H-pyran-4-yl) diorganylphosphinochalcogenoates or O-(2-methyl-4-oxo-4H-pyran-3-yl) diorganylphosphinochalcogenoates, in high yields.     

Transformations of 2-(3-Hydroxy-3-methyl-1-butynyl)adamantan-2-ol >Catalyzed by Acids

Reaction of 2-(3-hydroxy-3-methyl-1-butynyl)adamantan-2-ol with acetonitrile under Ritter reaction conditions is accompanied by isomerization and partial hydration where the water addition to the triple bond occurs nonselectively. As a result of reaction carried out in the presence of 8 equiv of sulfuric acid a mixture was obtained of N ²-[4-(1-acetylamino-2-adamantyl)-2-methyl-3-butyn-2-yl]acetamide, N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-2-oxo-3-butyl]-acetamide, and N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-1-oxo-3-butyl]acetamide in ~10:3:2 ratio. In the presence of 2 equiv of the acid the mixture obtained consisted of N ²-[4-(1-acetylamino-2-adamantyl)-2-methyl-3-butyn-2-yl]acetamide, N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-2-oxo-3-butyl]acetamide, and 1-(1-acetylamino-2-adamantyl)-3-methyl-2-buten-1-one in the same ratio. In Rupe reaction conditions we obtained instead of the expected ,-unsaturated ketones a mixture of 1-(1-hydroxy-2-adamantyl)-3-hydroxy-3-methylbutan-1-one and 1-(1-hydroxy-2-adamantyl)-3-hydroxy-3-methylbutan-2-one in a 5:3 ratio.