Synthesis of new functionally substituted fullerenopyrrolidines

New fullerenopyrrolidines were synthesized by the three-component reactions of fullerene C₆₀, N-methylglycine, and aromatic aldehydes, viz., N,N-bis(2-chloroethyl)-4-aminobenzaldehyde, N-(2-chloroethyl)-N-methyl-4-aminobenzaldehyde, indole-3-carbaldehyde, 4-phenylbenzaldehyde, and anthracene-9-carbaldehyde. The structures of the resulting compounds were established by spectroscopic methods.     

Synthesis and alkylation of new 3-functionally substituted carbo[c]fused pyridin-2-ones(thiones)

By condensation of 2-acyl-1-(morpholin-4-yl)cycloalkenes with CH-acids new 3-functuinally substituted carbo[c]fused pyridin-2-ones(thiones) were synthesized. N, 1-Diphenyl-5, 6, 7, 8-tetrahydroisoquinoline-3-thione under the action of acrylonitrile and alkyl halides suffered a selective S-alkylation.     

Synthesis of functionally substituted 2-cyanoacrylates

The conditions for the Knoevenagel synthesis of 2-cyanoacrylates containing double and triple bonds in the alkoxycarbonyl group have been studied. It was found that the esters are formed in 10–70 % yields by the condensation of the respective cyanoacetates with formaldehyde in the 11 ratio in the presence of piperidine, followed by the pyrolysis of the oligomers formedin vacuo at 170–200 °C in the presence ofpara-toluenesulfonic acid. The compounds synthesized readily undergo polymerization at room temperature and can be used as the basis for thermostable rapidly polymerizing adhesives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 646–649, April, 1994.     

Synthesis and structural study of new substituted chiral sulfamoyl oxazolidin-2-ones

The synthesis of new series of oxazolidinones having sulfonamide moieties is described. These compounds are synthesized in good yield starting prochiral 1,3-dichloro-2-propanol and chlorosulfonyl isocyanate. This strategy involves the formation of carboxylsulfamide by carbamoylation–sulfamoylation reaction followed by intermolecular cyclization. In order to determine the enantioselectivity during the cyclization step, X-ray studies of products are performed.     

Synthesis of new unsaturated derivatives of functionally substituted 2-imino-2,5-dihydrofurans

5,5-Substituted 2-imino-4-methyl-2,5-dihydrofuran-3-carbonitriles reacted with aromatic aldehydes to give the corresponding 5,5-substituted 2-imino-4-(2-R-vinyl)-2,5-dihydrofuran-3-carbonitriles. The latter were converted into hydrochlorides which were hydrolyzed to 3-cyano-4-(2-R-vinyl)-2,5-dihydrofuran-2-ones whose condensation with malononitrile afforded dicyanomethylidene derivatives.     

Synthesis and structure of substituted 3,4-dihydropyridin-2-ones

The condensation of benzylideneacetonacetic ester with cyanoacetamide in the presence of triethylamine yielded 3-carbamoyl-3,4-dihydropyridin-2-one, while the condensation of arylidenecyanoacetamides with -aminocrotonic ester in acetic acid yielded 3-cyano-3,4-dihydropyridin-2-ones. It was established by NMR spectroscopy that 3-cyano-4-R-5-ethoxycarbonyl-6-methyl-3,4-dihydropyridin-2-ones exist in solutions in the form of a mixture of cis- and trans-stereoisomers in a 101 ratio.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1504–1508, November, 1984.     

Synthesis of 4,5-bifunctionally substituted imidazolidin-2-ones

It is shown that the reaction of readily available 4,5-dihydroxyimidazolidin-2-ones with hydrazoic or p-toluenesulfinic acid takes place stereo- and regioselectively and leads to the formation of 4,5-diazido- or 4,5-di(p-tolylsulfonyl)imidazolidin-2-ones. The example of 4,5-diazidoimidazolidin-2-one is used to demonstrate the possibility of using compounds of this type for stereoselective introduction of substituents into the 4 and 5 positions of the imidazole ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1645–1649, December, 1993.     

Synthesis of functionally substituted benzaldehydes

A new method of synthesis of functionally substituted benzaldehydes by catalytic debromometoxylation of dibromomethylarenes with benzaldehyde dimethyl acetal has been suggested. Anhydrous zinc chloride has been used as a catalyst. Being soft Lewis acid, it formed no strong complex with aldehyde group and other functional groups. The initial acetal has been readily recovered by the treatment of benzaldehyde isolated from the reaction mixture with trimethyl orthoformate.     

Synthesis of functionally substituted cyanoacetates

Some new cyanoacetates were synthesized and characterized. They are precursors for -cyanoacrylates used as rapidly polymerized, cold-hardening adhesives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 523–525, March, 1993.     

Synthesis of substituted thienopyrimidine-4-ones

The parallel solution-phase synthesis of more than 3000 substituted thienopyrimidin-4-ones has been accomplished. Key reactions include assembly of the 2-thioxopyrimidin-4-one ring by condensation of isomeric aminothiophenecarboxylates or their appropriate reactive derivatives (isothiocyanates or dithiocarbamates) with the corresponding isothiocyanates or amines. The libraries from libraries were then obtained in good yields and purities using solution-phase alkylation and acylation methodologies. Simple manual techniques for parallel reactions using special CombiSyn synthesizers were coupled with easy purification procedures (crystallization from the reaction mixtures) to give high-purity final products. The scope and limitations of the developed approach are discussed.     

Synthesis of functionally substituted 5-phenylthiazoles

The reaction of esters and amides of 3-phenyl-3-chloro-2-oxopropionic acid with thioamides and thiourea gave new 5-phenylthiazoles.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2854–2856. December, 1990.     

Synthesis of functionally substituted isoxazole and isothiazole derivatives

Acylation of benzene and toluene with 5-phenyl- and 5-(p-tolyl)isoxazole-3-carbonyl chlorides gave 5-phenyl(or p-tolyl)isoxazol-3-yl phenyl(or p-tolyl)ketones which were reduced to the corresponding alcohols with sodium tetrahydridoborate in propan-2-ol. Selective reduction of the carboxy group in 4,5-dichloroisothiazole-3-carboxylic acid was achieved by the action of BH₃, and the aldehyde group in 4-formyl-2-methoxyphenyl 5-arylisoxazole-3-carboxylates and 4,5-dichloroisothiazole-3-carboxylates was reduced to hydroxymethyl group with sodium triacetoxyhydridoborate in benzene. Acylation of the resulting hydroxymethyl derivatives with 5-arylisoxazole- and 4,5-dichloroisothiazole-3-carbonyl chlorides afforded the corresponding esters containing two azole fragments in their molecules.     

Synthesis of novel functionally substituted pyridazines and oxazines

Acetone 1,3-di(phenylhydrazone) reacts with arylidenemalononitriles in the presence of piperidine to give the coressponding 3,3′-carbonylbispyridazine derivatives. Under the same reaction conditions dioxime reacts with arylidenemalononitriles to give the corresponding 3,3′-carbonylbis-1,2-oxazines. Dioxime reacts with primary aromatic amines and formalin in a molar ratio of 1:1:2 to give 1-arylidene-3,5-dihydroxyimino-piperidine-4-ones. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1223–1229, August, 2008.     

Synthesis and some transformations of functionally substituted lactones

Reactions of functionally substituted unsaturated five- and six-membered cyanolactones with α- and β-hydroxy ketones in the presence of sulfuric acid gave substituted 2-oxofuran- and 2-oxopyran-3-carboxamides. Hydrolysis of some keto amides thus obtained afforded the corresponding carboxylic acids, and reactions with hydrazines and semicarbazides led to hydrazones and semicarbazones at the side-chain oxo group.     

Synthesis and properties of functionally substituted 1,2-azolidines

Results of investigations on the synthesis and properties of functionally substituted 1,2-azolidines are reviewed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 829–850, June, 1992.     

Synthesis of substituted 1-benzazepin-2-ones via ring-closing olefin metathesis

The 1-benzazepin-2-one ring system is an important structural feature of marketed drugs, clinical candidates, and other bioactive molecules. We have developed a new benzazepinone synthesis that employs ring-closing olefin metathesis as a key step. This route provides efficient access to substituted benzazepinones that are difficult to synthesize via existing procedures.