Reaction of 1,5-diarylpenta-1,4-dien-3-ones with methyl 1-bromocycloalkanecarboxylates and zinc

Methyl 1-bromocyclopentane-, 1-bromocyclohexane- and 1-bromocycloheptanecarboxylates react with zinc and 1,5-diarylpenta-1,4-dien-3-ones to form 10-aryl-8-(2-arylethenyl)-7-oxaspiro[4.5]dec-8-en-6-ones, 5-aryl-3-(2-arylethenyl)-2-oxaspiro[5.5]undec-3-en-1-ones, and 5-aryl-3-(2-arylethenyl)-2-oxaspiro[5.6]-dodec-3-en-1-ones, respectively.     

Reaction of methyl 1-bromocycloalkanecarboxylates with zinc and 2,6-bis(arylmethylene)cyclohexanones

Methyl 1-bromocyclopentane-, 1-bromocyclohexane-, and 1-bromocycloheptanecarboxylates react with zinc and 2,6-bis(arylmethylene)cyclohexanones to afford 4-aryl-8-(arylmethylene)-5,6,7,8-tetrahydrospiro[chromene-3,1′-cyclopentan]-2(4H)-ones, 4-aryl-8-(arylmethylene)-5,6,7,8-tetrahydrospiro[chromene-3,1′-cyclohexan]-2(4H)-ones, and 4-aryl-8-(arylmethylene)-5,6,7,8-tetrahydrospiro[chromene-3,1′-cycloheptan]-2(4H)-ones, respectively.     

Reactivity of N-(omega-haloalkyl)-beta-lactams with regard to lithium aluminium hydride: novel synthesis of 1-(1-aryl-3-hydroxypropyl)aziridines and 3-aryl-3-(N-propylamino)propan-1-ols

The reactivity of 4-aryl-1-(2-chloroethyl)azetidin-2-ones and 4-aryl-1-(3-bromopropyl)azetidin-2-ones with regard to lithium aluminium hydride has been evaluated for the first time. 4-Aryl-1-(2-chloroethyl)azetidin-2-ones were transformed into novel 1-(1-aryl-3-hydroxypropyl)aziridines through an unprecedented conversion of beta-lactams into 2,3-unsubstituted aziridine derivatives. Unexpectedly, 4-aryl-1-(3-bromopropyl)azetidin-2-ones underwent dehalogenation towards 3-aryl-3-(N-propylamino)propan-1-ols upon treatment with LiAlH(4). 1-(1-Aryl-3-hydroxypropyl)aziridines were further elaborated by means of ring opening reactions using benzyl bromide in acetonitrile towards 3-aryl-3-[N-benzyl-N-(2-bromoethyl)amino]propan-1-ols and using aluminium(iii) chloride in diethyl ether, affording 3-aryl-3-[N-(2-chloroethyl)amino]propan-1-ols.     

Reaction of 3-Aryl-1-(2-methyloxiran-2-yl)prop-2-en-1-ones with Tosylhydrazine

It was established that the reaction of 3-aryl-1-(2-methyloxiran-2-yl)prop-2-en-1-ones with tosylhydrazine leads to 3-[(E)-2-arylvinyl]-4-methyl-1-tosyl-1H-pyrazoles and 3-aryl-1-(2-methyloxiran-2-yl)-3-tosylpropan-1-ones. The latter are formed as a result of rearrangement of the intermediate hydrazino alcohols and/or addition of p-toluenesulfinic acid during reductive degradation of the tosylhydrazine. It was shown that the reaction of 3-aryl-1-(2-methyloxiran-2-yl)-3-tosylpropan-1-ones with an excess of tosylhydrazine leads to 3-(2-aryl-2-tosylethyl)-4-methyl-1-tosyl-1H-pyrazoles. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1481–1489, October, 2005.     

Reactions of 4-acyl-1-alkoxyaryl-5-aryl-3-hydroxy-2,5-dihydro-1H-pyrrol-2-ones with nucleophilic reagents

4-Acetyl-1-alkoxyaryl-5-aryl-3-hydroxy-2,5-dihydro-1H-pyrrol-2-ones reacted with amines to give 1-alkoxyaryl-5-aryl-4-(1-R-aminoethylidene)pyrrolidine-2,3-diones. Reactions of amines with 4-benzoyl-substituted analogs involve nucleophilic attack on the C³ atom in the heteroring to produce the corresponding 3-R-amino-1-alkoxyaryl-5-aryl-4-benzoyl-2,5-dihydro-1H-pyrrol-2-ones. Reactions of the title compounds with hydrazine hydrate, regardless on the substituent on C₄, afforded 4-aryl-3-methyl(phenyl)-5-[2(4)-methoxyphenyl]-4,6-dihydropyrrolo[3,4-c]pyrazol-6-ones.     

First synthesis of 1-aryl-4,4-dichlorobut-3-en-1-ones. The electrochemical reduction of 1-aryl-4,4,4-trichlorobut-2-en-1-ones as a key step

The first method for the synthesis of 1-aryl-4,4-dichlorobut-3-en-1-ones is reported. Treatment of acetophenones with anhydrous chloral leads to 1-aryl-4,4,4-trichloro-3-hydroxybutan-1-ones in near quantitative yields. These compounds were efficiently dehydrated with either sulfuric or p-toluenesulfonic acid to give 1-aryl-4,4,4-trichlorobut-2-en-1-ones, which were selectively converted to the title compounds in fair to quantitative yields by electrochemical reduction. The X-ray crystallographic structure of 4,4-dichloro-1-(4-methoxyphenyl)but-3-en-1-one has been determined. The preferential formation of β,γ-unsaturated ketones with total exclusion of the corresponding α,β-unsaturated isomers has been discussed with the aid of HF and B3LYP density functional theory methods.     

Reactions of 1-aryl-2-bromo-3,4,4-trichlorobut-3-en-1-ones with some nucleophilic reagents

Reactions of 2-bromo-1-phenyl- and 2-bromo-1-(4-methylphenyl)-3,4,4-trichlorobut-3-en-1-ones with morpholine and diethylamine are accompanied by prototropic allylic rearrangement, leading to 3-amino-1-aryl-2-bromo-4,4-dichlorobut-2-en-1-ones as mixtures of E and Z isomers. The title compounds react with hydrazine, hydroxylamine, and thiourea to give the corresponding 5-aroyl-4-methoxypyrazoles, 3-aryl-5-hydroxyiminomethyl-4-methoxyisoxazoles, and 2-amino-4-aryl-5-trichlorovinylthiazoles.     

Reactions of zinc enolates derived from 1-aryl-2-bromo-alkanones and 1-aryl-2-bromo-2-phenylethanone with 3-aroyl-6-bromochromen-2-ones and 2-benzoylbenzo[f]chromen-3-one

3-Aroyl-6-bromochromen-2-ones and 2-benzoylbenzo[f]chromen-3-one reacted with zinc enolates derived from 1-aryl-2-bromoalkanones and 1-aryl-2-bromo-2-phenylethanone to give, respectively, 4-(1-alkyl-2-aryl-2-oxoethyl)-3-aroyl-6-bromochroman-2-ones and 1-(2-aroyl-1-methyl-2-oxoethyl)-2-benzoyl-1,2-dihydrobenzo[f]chromen-3-ones as a single stereoisomer. Treatment with acetic anhydride of the intermediate product obtained from 3-benzoyl-6-bromochromen-2-one and [1-(4-chlorophenyl)-2-phenylethen-1-yloxy]-zinc(II) bromide resulted in the formation of 3-(1-acetoxy-1-phenylmethylidene)-6-bromo-4-[2-(4-chlorophenyl)-2-oxo-1-phenylethyl]chroman-2-one.     

Reactions of 1-(4-aminosulfonylphenyl)-5-aryl-4-aroyl-3-hydroxy-3-pyrrolin-2-ones with arylamines and hydrazine hydrate

Depending on the reaction condition, 1-(4-aminosulfonylphenyl)-5-aryl-4-aroyl-3-hydroxy-3-pyrrolin-2-ones reacted with aromatic amines to yield 3-arylamino-3-pyrrolin-2-ones or 4-[aryl (arylamino) methylene]tetrahydropyrrole-2,3-diones. Reactions of 1-(4-aminosulfonylphenyl)-5-aryl-4-aroyl-3-hydroxy-3-pyrrolin-2-ones with hydrazine hydrate afforded pyrrolo[3,4-c]pyrazol-6-ones.     

Five-membered 2,3-dioxo heterocycles: LXXXIX. Reaction of methyl 1-aryl-3-cinnamoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with (E)-4-arylaminopent-3-en-2-ones. Crystalline and molecular structure of 9-acetyl-4-cinnamoyl-3-hydroxy-1-(4-methoxyphenyl)-8-methyl-7-phenyl-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-dione

Methyl 1-aryl-3-cinnamoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 4-benzylamino- and 4-arylaminopent-3-en-2-ones to give 1-aryl-7-benzyl- and 1,7-diaryl-9-acetyl-4-cinnamoyl-3-hydroxy-8-methyl-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-diones. The crystalline and molecular structures of 9-acetyl-4-cinnamoyl-3-hydroxy-1-(4-methoxyphenyl)-8-methyl-7-phenyl-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-dione were studied by X-ray analysis.     

Sulfanyl chloride induced heterocyclization of N-(pyrazolyl)styrylacetamides

Heterocyclization of N-(pyrazol-3-yl)styrylacetamides with arenesulfenyl chlorides yields the corresponding tetrahydrofuran-2-iminium perchlorates isolable after chromatography as trans-5-aryl-4-(arylthio)tetrahydrofuran-2-ones and 5-aryl-4-(arylthio)-1-(pyrazol-3-yl)pyrrolidin-2-ones, with the latter predominating. N-(Pyrazol-4-yl)styrylacetamides react under analogous conditions to give 5-aryl-4-(arylthio)-1-(pyrazol-4-yl)pyrrolidin-2-ones, 4-aryl-3-(arylthio)-4-chloro-N-(1-methylpyrazol-4-yl)butanamides, and tetrahydrofuran-2-iminium perchlorates which, when chromatographed, produce 5-aryl-4-(arylthio)dihydrofuran-2(3H)-ones and 4-aryl-3-(arylthio)-4-methoxy-N-(1-methyl-1H-pyrazol-4-yl)butanamides.     

Reformatsky Reaction of Methyl 1-Bromocyclopentane-1-carboxylate with 1-Aryl-3-(2-hydroxyphenyl)prop-2-en-1-ones

Russian Journal of Organic Chemistry - Reformatsky reaction of methyl 1-bromocyclopentanecarboxylate with 1-aryl-3-(2-hydroxyphenyl)-prop-2-en-1-ones afforded 6-substituted...     

Reaction of methyl 1-bromocyclopentane- and 1-bromocyclohexanecarboxylates with zinc and 2-arylmethylidene-2,3-dihydro-1<Emphasis Type="Italic">H</Emphasis>-inden-1-ones or 2-arylmethylidene-3,4-dihydronaphthalen-1(2<Emphasis Type="Italic">H</Emphasis>)-ones

Methyl 1-bromocyclopentanecarboxylate and methyl 1-bromocyclohexanecarboxylate reacted with zinc and 2-arylmethylidene-2,3-dihydro-1H-inden-1-ones or 2-arylmethylidene-3,4-dihydronaphthalen-1(2H)-ones to give 4′-aryl-4′,5′-dihydro-2′H-spiro[cyclopentane(cyclohexane)-1,3′-indeno[1,2-b]pyran]-2′-ones or 4-aryl-5,6-dihydrospiro[benzo[h]chromene-3,1′-cyclopentane(cyclohexane)]-2(4H)-ones, respectively.     

New Dipyrrinonols Derived from 2,3-Dihydro-1H-pyrrol-3-ones

Summary. The reaction of 2-aminomethylene-2,3-dihydropyrrol-3(1H)-ones with ethyl bromoacetate, chloroacetonitrile, or dilute HCl gave rise to a series of methine dyes, namely 1-aryl-2-[3-hydroxy-1-aryl-4,5-diphenyl-1H-pyrrol-2-yl]methylene-4,5-diphenyl-2,3-dihydropyrrol-3(1H)-ones.     

Synthesis of aryl 2-(2-imidazolyl)ethyl ketones

The Claisen-Schmidt condensation of 1-(triphenylmethyl)-2-imidazolecarboxaldehyde with acetophenones yielded 1-aryl-3-[1-(triphenylmethyl)-2-imidazolyl]propen-1-ones 7 . Selective catalytic hydrogenation over platinum of 7 furnished 1-aryl-3-(2-imidazolyl)-1-propanones 8 . An alternate synthesis of 8 started with sodium borohydride reduction of 7 to give allylic alcohols, 1-aryl-3-[1-(triphenylmethyl)-2-imidazolyl]-2-propen-1-ols 10 , which were rearranged by hot aqueous sodium to 8 . Acid hydrolysis of 8 provided the title compounds and triphenylmethanol.     

Reformatsky reaction of methyl 1-bromocycloalkane-1-carboxylates with phenyl-and benzoylhydrazones derived from aromatic aldehydes

Reformatsky reagents obtained from methyl 1-bromocyclohexane-and 1-bromocyclopentane-1-carboxylates reacted with aromatic aldehyde phenyl-and benzoylhydrazones to give 3-aryl-2-phenylamino-2-azaspiro[3.5]nonan-, 3-aryl-2-phenylamino-2-azaspiro[3.4]octan-, 3-aryl-2-benzoylamino-2-azaspiro[3.5]-nonan-, and 3-aryl-2-benzoylamino-2-azaspiro[3.4]octan-1-ones, respectively. The reaction of furan-2-carbaldehyde phenylhydrazone with methyl 1-bromocyclohexane-1-carboxylate and zinc led to the formation of 4-(2-furyl)-2-phenyl-2,3-diazaspiro[4.5]decan-1-one.     

A convenient synthesis of 1-aryl-3-methyl-1,2,4-triazolin-5-ones from the reaction between acetone arylhydrazones and acetyl isocyanate

The reaction of acetone arylhydrazones with acetyl isocyanate gave the corresponding 4-acetyl-1-aryl-3,3-dimethyl-1,2,4-triazolidin-5-ones which eliminated acetone upon acidic hydrolysis to give 1-aryl-3-methyl-1,2,-4-triazolin-5-ones. The above transformation can be achieved in one pot by a simple solvent swap.     

Heterocyclic compounds from 3,3-dimercapto-1-aryl-2-propen-1-ones. Note 1. 4-Ary1-1,3-dihydro-2H-1,5-benzodiazepine-2-thiones

A series of new 4-aryl-1,3-dihydro-2H-1,5-benzodiazepine-2-thiones ( 3 ) has been synthesized by condensing the 3,3-dimercapto-1-aryl-2-propen-1-ones with o-phenylenediamine. The structure was established by the results of acid cleavage and by nmr spectra. The alkylation of compounds 3 gave 2-alkylthio-4-aryl-3H-1,5 benzodiazepines ( 10 ).     

Electrophilic intramolecular cyclization of functional derivatives of unsaturated compounds: VIII. Cyclization of 4-aryl-<Emphasis Type="Italic">N</Emphasis>-(thiophen-3-yl)but-3-enamides by the action of polyphosphoric acid and chlorosulfanylarenes

Intramolecular cyclization of 4-aryl-N-(thiophen-3-yl)but-3-enamides on heating in polyphosphoric acid afforded 8-aryl-4,6,7,8-tetrahydro-5H-thieno[3,2-b]azepin-5-ones and 5-aryl-1-(thiophen-3-yl)pyrrolidin-2-ones. Cyclofunctionalization of the title compounds with (chlorosulfanyl)benzene and 4-(chlorosulfanyl)-toluene led to the formation of 8-aryl-7-arylsulfanyl-4,6,7,8-tetrahydro-5H-thieno[3,2-b]azepin-5-ones or their mixtures with 5-aryl-4-arylsulfanyltetrahydrofuran-2-ones. 1-(Chlorosulfanyl)-4-nitrobenzene reacted with 4-(4-methylphenyl)-N-(thiophen-3-yl)but-3-enamide and 4-(4-fluorophenyl)-N-(thiophen-3-yl)but-3-enamide to give 5-(4-methylphenyl)-4-(4-nitrophenylsulfanyl)-1-(thiophen-3-yl)pyrrolidin-2-one and 5-(4-fluorophenyl)-4-(4-nitrophenylsulfanyl)tetrahydrofuran-2-one, respectively.     

Reaction of Methyl 1-Bromocyclohexanecarboxylate with Zinc and 3-Aryl-1-(2-hydroxyphenyl)prop-2-en-1-ones

Russian Journal of Organic Chemistry - The reaction of 3-aryl-1-(2-hydroxyphenyl)prop-2-en-1-ones with methyl 1-bromocyclohexanecarboxylate and zinc resulted in the isolation, after hydrolysis of...