Five-membered 2,3-dioxo heterocycles: LXXX. Recyclization of 1H-pyrrole-2,3-diones into pyrazolo[1,5-a]pyrimidines by the action of pyrazolamine. Crystalline and molecular structure of substituted pyrazolo[1,5-a]pyrimidine

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 3-methyl-4-phenyl-1H-pyrazol-5-amine to give methyl 7-arylcarbamoyl-6-aroyl-2-methyl-3-phenylpyrazolo[1,5-a]-pyrimidine-5-carboxylates. The molecular and crystalline structures of methyl 6-benzoyl-7-(4-chlorophenylcarbamoyl)-2-methyl-3-phenylpyrazolo[1,5-a]pyrimidine-5-carboxylate were studied by X-ray analysis.     

Synthesis of 5-(aroylamino)-2-methyl-2H,-1,2,4-thiadiazol-3-ones by oxidative cyclization of 1-aroyl-5-methyl-2-thiobiurets

5-Aroylamino-2-methyl-2H-1,2,4-thiadiazol-3-ones 3 have been synthesized by oxidative cyclization of 1-aroyl-5-methyl-2-thiobiurets 2 with hydrogen peroxide in an alkaline solution. The needed 1-aroyl-5-methyl-2-thiobiurets 2 have been obtained through the addition of methylurea to the corresponding aroyl isothiocyanates.     

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.     

Five-membered 2,3-dioxo heterocycles: LV. Reaction of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrole-2-carboxylates with ethyl 3-arylaminobut-2-enoates

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with ethyl 3-aryl-aminobut-2-enoates to give the corresponding ethyl 1,7-diaryl-4-aroyl-3-hydroxy-8-methyl-2,6-dioxo-1,7-diazaspiro[4.4]nona-3,8-diene-9-carboxylates.     

Imidazo[2,1-b]thiazolium salts based on 2-phenylamino-4-methylthiazole

Alkylation of 2-phenylamino-4-methylthiazole with substituted phenacyl bromides led to the synthesis of hydrobromides of 2-phenylimino-3-(p-R-phenacyl)-4-methylthiazoles. It was shown that, depending on the conditions of the cyclization of the last, 3-methyl-6-aryl-7-phenyl- or 3-methyl-5-aroyl-6-alkyl-7-phenylimidazo[2,1-b]thiazolium bromides can be synthesized. The spectral characteristics of the compounds synthesized were studied.Chernigov Technological Institute, Chernigov 250027. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 833–836, June, 1997.     

Five-membered 2,3-dioxo heterocycles: CIII. Spiro heterocyclization of 4,5-diaroyl-1H-pyrrole-2,3-diones with 3-aminobut-2-enenitrile

1-Aryl-4,5-diaroyl-1H-pyrrole-2,3-diones reacted with 3-aminobut-2-enenitrile to produce 1,6-diaryl-4-aroyl-3-hydroxy-8-methyl-2-oxo-1,7-diazaspiro[4.4]nona-3,6,8-triene-9-carbonitriles.     

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-dioxoheterocycles: LVIII. Reaction of methyl 1-Aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrol-2-carboxylates with substituted 1-methyl-3,4-dihydroisoquinolines. New approach to the synthesis of steroid 13-azaanalogs

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with substituted 1-methyl-3,4-dihydroisoquinolines with the formation of substituted 3-oxo-2,3,5,6-tetra-hydropyrrolo[2,1-a]-isoquinoline-2-spiro-2′-(1-aryl-3-aroyl-4-hydroxy-5-oxo-2,5-dihydro-1H-pyrroles). A new approach was developed to the synthesis of 13-azagonanes, substituted benzo[f]pyrrolo[2,1-a]isoquinoline-9-spiro-2′-pyrroles.     

Identification of some isomeric 3,5-unsymmetrically substituted 1-aroyl-pyrazole derivatives by NMR spectroscopy

The ¹H and ¹³C nmr chemical shifts are used for the structural assignment of isomeric 1-aroyl-4,5-dihydro-5-hydroxy-4,4-dimethyl-1H-pyrazoles 1 unsymmetrically substituted with phenyl or methyl in the 3,5-positions of the pyrazole ring. The ¹H nmr spectra of 1-aroyl- or 1-acetyl-4-methyl-1H-pyrazoles 2 are useful in structure elucidation of unsymmetrically 3- or 5-methyl substituted derivatives.     

Conversion of 3-Carbethoxy-4-methyl Coumarin Derivatives into Several New Annelated Coumarin Derivatives

The reaction of ethyl esters of 4-methyl-2-oxo-2H-l-benzo(naphtho) pyran.3-carboxylic acids (1) with aromatic aldehy-des in the presence of piperidine yielded 4-styryl-3-carboxami-dopiperidyl connmrin derivatives 4. The reaction of hydrazlne hydrate with 1 gave acetophenone hydrozone derivatives 5 and acetophenone azine derivatives 6. The reaction of 1 with prima-ry amines afforded compomlds 7—9. And the treatment of la with Grignard reagents afforded 3-aroyl-4-methyl coumarin derivatives 10.     

Alkylation of 3-cyano-4-methoxymethyl-6-methyl-2(1h)-pyridone by active halomethylene compounds. The molecular structure of 3-amino-2-benzoyl-4-methoxymethyl-6-methylfuro[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridine

The alkylation of 3-cyano-4-methoxymethyl-6-methyl-2(1H)-pyridone by active halomethylene compounds has been studied. It was shown that the reaction of the pyridone with methyl- and ethylchloroacetates and phenacyl and p-bromophenacyl bromides occurs to give N- and O-structural isomers. Only the N-derivatives are separated from the reaction mixture when the pyridone is alkylated with iodoacetamide. It was found that 2-aroylmethyl-3-cyano-4-methoxymethyl-6-methylpyridines cyclize in the presence of KOH to 3-amino-2-aroyl-4-methoxymethyl-6-methylfuro[2,3-b]pyridines. The molecular structure of 3-amino-2-benzoyl-4-methoxymethyl-6-methylfuro[2,3-b]pyridine has been studied using an X-ray analytical method.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1670–1682, November, 2004.     

Synthesis,stereochemistry, and isomeric transformations of cis- and trans-1,2-dimethyl-4-aryl-5-aroyl-2-imidazolines

The corresponding trans- and cis-1,2-dimethyl-4-aryl-5-aroyl-2-imidazolines were obtained from complexes of cis- and trans-1-methyl-2-aryl-3-aroylaziridines with BF₃ by heating with acetonitrile. The reaction proceeds with inversion of the configuration of the starting 3-aroylaziridines. In the presence of bases the complexes of cis-1,2-dimethyl-4-aryl-5-aroyl-2-imidazolines readily undergo isomerization to the corresponding trans analogs. The structures of the products were established on the basis of the IR, PMR, and mass spectra and the results of elementary analysis. The configurations of the compounds were determined by means of the Overhauser nuclear effect.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 952–957, July, 1981.     

Acetylenic ketones. Part V. Reaction of acetylenic ketones with thiourea and some of its derivatives

Aroylphenylacetylenes (I) reacted with thiourea and S-benzylisothiourea to give 4,6-diaryl-pyrimidine-2(1H)thiones (IV) and α-aroyl-β-benzylmercaptostyrenes (X), respectively. Methyla-tion and acetylation of the thiones (IV) gave the corresponding S-methyl- (V) and S-acetyl- (VI) derivatives, respectively. The oxidation of these thiones gave the corresponding disulfide derivatives (VII). Reaction of α-aroyl-β-benzylmercaptostyrenes (X) with hydrazine hydrate and phenylhydrazine gave 3(5)-aryl-5(3)-phenylpyrazoles (XI) and 3-aryl-1,5-diphenylpyrazoles (XIII), respectively. Reaction of aroylphenylacetylenes (1) with N-allylthiourea gave 1-allyl-4,6-diaryl-pyrimidine-2-thiones (XVI).     

Five-membered 2.3-dioxo heterocycles: LXVIII. Three pathways in the reaction of methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with 3-amino-5,5-dimethylcyclohex-2-en-1-one

Methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 3-amino-5,5-dimethylcyclohex-2-en-1-one having no substituent on the nitrogen atom to give 3-aroyl-4-arylamino-6′,6′-dimethyl-6′,7′-dihydro-5H-spiro[furan-2,3′-indole]-2′,4′,5′(1′H,5′H)-triones or methyl 12-aroyl-11-aryl-9-hydroxy-5,5-dimethyl-3,10-dioxo-8,11-diazatricyclo[7.2.1.0^2,7]dodec-2(7)-ene-1-carboxylates. The latter underwent thermal recyclization to 3′-aroyl-1′-aryl-4′-hydroxy-6,6-dimethyl-6,7-dihydrospiro[indole-3,2′-pyrrole]-2,4,5′(1H,1′H,5H)-triones.     

Reactions of zinc enolates derived from 1-aryl-2,2-di-bromoalkanones with 2-acyl-3H-benzo[f]chromen-3-ones, 6-bromo-2-oxochromene-3-carboxamides, and 3-oxo-3H-benzo-[f]chromene-2-carboxamides

Zinc enolates derived from substituted 1-aryl-2,2-dibromoalkanones reacted with 2-acyl-3H-benzo-[f]chromen-3-ones to give 1-alkyl-1-aroyl-1a-acyl-1a, 9c-dihydro-1H-3-oxacyclopropa[c]phenanthren-2-ones which were formed as a single stereoisomer. Reactions of the same zinc enolates with 6-bromo-2-oxo-chromene-3-carboxamides (piperidides and morpholides) afforded 1-aroyl-6-bromo-1-alkyl-1a-piperidino-(morpholino)carbonyl-1a,7b-dihydrocyclopropa[c]chromen-2-ones with high stereoselectivity. Likewise, 1-benzoyl-1-methyl-1a-morpholinocarbonyl-1a, 9c-dihydro-1H-3-oxacyclopropa[c]phenanthren-2-one was obtained by reac-tion with 3-oxo-3H-benzo[f]chromene-2-carboxylic acid morpholide.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004, pp. 1399–1404.Original Russian Text Copyright © 2004 by V. Shchepin, Kalyuzhnyi, Silaichev, Russkikh, R. Shchepin, Ezhikova, Kodess.This study was performed under financial support by the Russian Foundation for Basic Research (project no. 04-03-96 036).     

Facile synthesis of fluorine-containing [4-aryl-4,5-dihydro-5-imino-1,3,4-thiadiazol-2-ylaryl]methanone, 2-amino-4-aryl-5-arylazothiazoles and 3-aroyl-4-acetyl/benzoyl-5-methyl-1-phenylpyrazoles through N-aryl-α-oxo-α-arylethanehydrazonoyl bromide

N-Aryl-α-oxo-α-arylethanehydrazonoyl bromides 2 react with potassium thiocyanate in ethanol leading to the formation of [4-aryl-4,5-dihydro-5-imino-1,3,4-thiadiazol-2-ylaryl]methanone 5 in quantitative yield. Treatment of 2 with thiourea and β-diketones affords 2-amino-4-aryl-5-arylazothiazoles 4 and 3-aroyl-4-acetyl/benzoyl-5-methyl-1-phenylpyrazoles 6 in 65–70 and 60–70% yields respectively. Compound 5 has also been subjected to acetylation and chloroacetylation. All the compounds are characterized by their analytical and spectral (ir, ¹H-nmr and ms) data. Mass fragmentation patterns of these compounds are discussed.     

Steric effect of ortho-substituents of 1-phenyl-3-methyl-4-aroyl-5-pyrazolones on the synergic extraction of lutetium with trioctylphosphine oxide

The substituent effect of ortho-substituted 4-aroyl derivatives of 1-phenyl-3-methyl-5-pyrazolones (HA) on the adduct formation reaction between their lutetium chelates and a neutral ligand, trioctylphosphine oxide (TOPO, L), in benzene was studied using a liquid-liquid extraction system. The lutetium 4-aroyl-5-pyrazolonates react with TOPO to form LuA₃L and LuA₃L₂ types of adducts. An obvious steric hindrance of the terminal group on the adduct formation reaction was observed. Linear relationships between the acid dissociation constant of the ortho-substituted 4-aroyl-5-pyrazolone derivatives and those of the corresponding benzoic acids, between the extraction constants of lutetium and the acid dissociation constants of pyrazolones and between the adduct formation constants of TOPO and the acid dissociation constants of pyrazolones could be obtained.     

The solvent extraction of europium and barium with 1-aryl-3-methyl-4-aroyl-5-pyrazolones

Eleven 1-aryl-3-methyl-4-aroyl-5-pyrazolone derivatives were synthesized. Their acid dissociation constants were determined spectrophotometrically; there was a linear relationship between them and Hammett's σ values. Europium and barium ions were readily extracted into benzene and n-octyl alcohol, respectively, at very low pH.     

Reaction of 3-benzylidene-2,4-pentanedione and 3-methoxymethylene-2,4-pentanedione with aroylhydrazines

Aroylhydrazines 2 reacted with 3-benzylidene-2,4-pentanedione ( 1 ) to give 1-aroyl-3,5-dimethyl-1H-pyrazoles 5 and benzaldehyde aroylhydrazones 6 . From the reaction of 3-methoxymethylene-2,4-pentanedione ( 7 ) with aroylhydrazines 2 the unknown N-aroyl-4-acetyl-1H-pyrazoles 9 were exclusively isolated in good yields.     

Five-membered 2,3-dioxo heterocycles: LXXV. Reaction of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with 1,3-diphenylguanidine. Crystalline and molecular structure of 9-Benzoyl-8-hydroxy-2-imino-6-(4-methylphenyl)-1,3-diphenyl-1,3,6-triazaspiro-[4.4]non-8-ene-4,7-dione

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 1,3-diphenylguanidine to give the corresponding 6-aryl-9-aroyl-8-hydroxy-2-imino-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4,7-diones. The molecular and crystalline structures of 9-benzoyl-8-hydroxy-2-imino-6-(4-methylphenyl)-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4,7-dione were determined by X-ray analysis.