ω-(2-benzimidazolyl)perfluorinated carboxylic acids and their derivatives

A convenient method is proposed for the preparation of -(2-benzimidazolyl) perfluorinated carboxylic acids and their amides by condensation of o-phenylenediamine with imides of perfluorinated dicarboxylic acids. The transformations of the o-aminoanilides of the amides of the perfluorinated dicarboxylic acids were studied by thermal analysis and mass spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1262–1265, September, 1976.     

Efficient synthesis of 2-(trifluoromethyl)nicotinic acid derivatives from simple fluorinated precursors

Novel routes to 2-trifluoromethyl-nicotinic acid derivatives have been developed involving synthesis of the pyridine ring. These pyridyl compounds serve as key intermediates in the manufacture of the recently discovered COMT inhibitor, 3-(5-(3,4-dihydroxy-5-nitrophenyl)-1,2,4-oxadiazol-3-yl)-2-(trifluoromethyl)pyridine 1-oxide.     

Synthesis of derivatives of 2-hydroxyimino- and 2-alkoxyimino-3-(acylhydrazono)butanoic acids

Esters andN-methylamides of 2-hydroxyimino- and 2-alkoxyimino-3-(acylhydrazono)-butanoic acids were synthesized by condensation of acyl hydrazines with the corresponding alkyl 2-hydroxyimino- and 2-alkoxyimino-3-oxobutanoates andN-methyl-2-methoxyimino-3-oxobutanamide. The compounds obtained are analogs of strobilurins, fungicidal antibiotics. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 499–504, March, 1999.     

Cyclization ofα- andβ-(arylseleno)alkylcarboxylic acids and their derivatives

The cyclization of- and-(arylseleno)alkylcarboxylic acids in polyphosphoric acid was studied. It was found that-(arylseleno)alkylcarboxylic acids do not cyclize under those conditions in which cyclization of the analogous-(arylseleno)alkylcarboxylic acids does occur. A convenient method for the preparation of 2-methylselenonapthanone by the cyclization of-phenylselenopropionyl chloride is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 333–334, March, 1971.     

Molecular structures of quinuclidinic neurokinin antagonists: 2-(2-Phenylbenzylidene)-3-(2-X-benzylamino) derivatives

The solid-state molecular conformations and crystal structures of three analogues of the CP-96,345 molecule, an important nonpeptidic SP antagonist, namely the (±)-2-(3-phenylbenzilidene)-3-(2-benzylamino) quinuclidine, theo-chloro- and theo-methoxy-derivatives, have been determined by X-ray diffusion analyses and refined to finalR values of 0.055, 0.045, and 0.056, respectively. All three molecules in the solid state show the same disposition of the substituents of the double bond and differences in the conformation mainly caused by the need of releasing intramolecular strains and/or nonbonded interactions. The observed molecular structures are compared to the reported solid-state structure of the CP-96,345 and correlated to the biological activity as NK antagonists.     

A route to prostaglandin precursors from 1-(phenylthio)-2-octenyllithium.

The enolates generated by the conjugate addition of 1-(phenylthio)-2-octenyllithium to 4-$\text{tert}$-butoxycyclopent-2-en-1-one and <-crotonolactone react with methyl 7-halohept-5-ynoates in the presence of Ph₃SnCl to deliver products which may be converted into prostaglandin precursors.     

Synthetic route to 4-(2-aminoethyl)-5-hydroxyindole derivatives

In synthetic studies leading to the title compounds, application of the Claisen rearrangement of 5-allyloxyindole was investigated. Almost quantitative yields of Claisen rearrangement product were realized, and a strategy for oxidative cleavage of the allyl double bond to an indole-4-acetaldehyde derivative was developed. A new method for conversion of 2,3-dihydroindoles into indoles was utilized: air oxidation in a strongly basic environment. The Claisen rearrangement of allyloxyindoles is presented as a method having considerable potential utility in synthesis of a variety of polysubstituted indoles.     

Synthesis and metallation of 2-(pyridyl)benzoic acids and ethyl 2-(pyridyl)benzoates: a new route to azafluorenones

The ring deprotonation of 2-(2- and 4-pyridyl)benzoic acids using lithium dialkylamides in THF at rt, and the in situ cyclization afforded 4- and 2-azafluorenones, respectively. 1-Azafluorenone was obtained from ethyl 2-(3-pyridyl)benzoate using a similar protocol.     

Enzyme-catalyzed synthesis of (R)- and (S)-3-heteroaryl-3-hydroxy-propanoic acids and their derivatives

Starting from the racemic 3-benzofuranyl- and 3-benzo[b]thiophenyl-3-hydroxypropanoic acid ethyl esters as substrates, various multistep enzymatic procedures were developed for the efficient synthesis of the corresponding highly enantiomerically enriched (R)- and (S)-3-heteroaryl-3-hydroxypropanoic acids.     

New derivatives of coumarin: 2-(N-R-imino)-2H-1-benzopyrans

Methods of synthesizing previously unknown derivatives of coumarin — 2-(N-R-imino)-2H-1-benzopyrans, where R = Alk, Ar — are proposed. Possibilities of alternative synthetic schemes are discussed, and hypotheses concerning probable mechanisms of the reactions are formulated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 760–766, June, 1994. Original article submitted May 23, 1994.     

Chloromethyl derivatives of 3-furyl-3-(diethoxyphosphoryl)acrylic acids

Methoxymetyl derivatives of furoylphosphonates react with ethoxymethylenetriphenylphosphoranes to give phosphorylated (methoxymethylfuryl)acrylates. The reaction proceeds stereoselectively: phosphoryl and ester groups at the double bond are always trans-located. Treatment with dichloromethylmethyl ether and catalytic amount of zinc chloride converts the methoxymethyl group in the synthesized compounds into chloromethyl one. The ester group and the double bond are inert under these conditions.     

N1-(2-furoylmethyl) and N1-(5-nitro-2- furoylmethyl) derivatives of uracil and its 5-substituted derivatives

The corresponding N₁-(2-furoylmethyl) and N₁-(5-nitro-2-furoylmethyl) derivatives of uracil and its 5-substituted derivatives were obtained by the reaction of 2-bromo- and 5-nitro-2-bromoacetylfurans with uracil, 5-fluorouracil, and thymine. The structures of these compounds as N₁-substituted uracils were proved by a study of the UV spectra at various pH values. The computational method of expanding the UV spectra into individual bands was used.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1268–1270, September, 1971.     

2-(2-Hydroxyphenyl)imidazolidines and their O-phosphorylated derivatives

2-(2-Hydroxyaryl)imidazolidines were synthesized by reaction of aromatic carbonyl compounds with N,N′-dialkylethylenediamines. The title compounds were also prepared using the corresponding Schiff bases instead of carbonyl compounds. Phosphorylation of 2-(2-hydroxyphenyl)imidazolidines with phosphoryl and phosphorothioyl chlorides and phosphorochloridites was accomplished. The reaction of O-phosphorylsalicylaldehyde with N,N′-dialkylethylenediamines also afforded 2-(2-hydroxyphenyl)imidazolidines.     

Synthesis and spectral and luminescent properties of 4-(5-aryloxazoyl-2)benzoic acids and their derivatives

Condensation of acid chloride of monomethyl terephtalate with -aminomethyl-arylketones and subsequent cyclodehydration of the resulting amides in sulfuric acid or phosphorus oxychloride give rise to methyl 4-(5-aryloxazolyl-2)benzoates which led to the corresponding acids, acid chlorides, and amides. The effect of electron-withdrawing groups on the spectral and luminescent properties, as well as on the stability of substituted 2,5-diaryloxazoles toward UV irradiation has been investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1261–1264, September, 1986.     

Synthesis and anticancer activity evaluation of 3-(4-oxo-2-thioxothiazolidin-5-yl)-1H-indole-carboxylic acids derivatives

Abstract

A mild and efficient method for the synthesis of 1-oxo-9H-thiopyrano[3,4-b]indole-3-carboxylic acids and dimerized 3-(4-carboxy-1H-3-indolyl)-2-propenoic acids via alkaline hydrolysis of 3-(rhodanin-5-yl)-1H-indole-2-carboxylic acids derivatives was elaborated. Anticancer activity screening in NCI60-cell lines assay allowed identification of 5-fluoro-3-(4-oxo-2-thioxothiazolidin-5-ylidenemethyl)-1H-indole-2-carboxylic acid methyl ester 2a with significant antimitotic activity at micromolar and submicromolar concentrations.     

Syntheses and spectrophotometric studies of 2-(2-thiazolylazo)- and 2-(2-benzothiazolylazo)-5-dimethylaminobenzoic acids as analytical reagents: Determination of nickel

2-(2-ThiazolyIazo)-5-dimethylaminobenzoic acid (TAMB) and 2-(2-benzothiazolylazo)-5-dimethylaminobenzoic acid (BTAMB) have been synthesized, and their potential for determinations of metals has been studied spectrophotometrically. Both are extremely sensitive chromogenic reagents for the determination of nickel. Molar absorptivities in aqueous methanol are 0.95 × 10⁵ (TAMB) and 1.2 × 10⁵ (BTAMB). In aqueous methanol, at apparent pH 5–9.5, the system conforms to Beer's law for 0.05–0.5 ppm nickel; Cu, Cr, Co, Pd and Fe interfere, but they can easily be masked.