HETEROCYCLIC SYSTEMS CONTAINING BRIDGE HEAD NITROGEN ATOM: REACTION OF 5-MERCAPTO-4H-IMIDAZO[4,5-e]- [2,1,3]BENZOTHIADIAZOLES AND 5,6-DIAMINO[2,1,3]BENZOTHIAZOLE WITH 3-(2-BROMOACETYL)COUMARINS

Condensation of 5-mercapto-4H-imidazo[4,5-e][2,1,3]benzothiadiazole (I) with various 3-(2-bromoacetyl)coumarins, followed by PPA cyclization of the intermediate ketones II, yielded 3-(2,8-dithia 1,3,5b, 9-tetraaza cyclopenta(b)-as-indacen-6-yl)chromen-2-ones III. Reaction of 5,6-diamino[2,1,3]benzothiadiazole with 3-(2-bromoacetyl)- coumarin in anhydrous ethanol containing fused sodium acetate gave the corresponding 2-coumarinyl 3,4-dihydro-1,4-pyrazino[5,6-e][2,1,3]benzothiadiazoles IV.     

Chemistry of 3-hetarylcoumarins. 2. 3-(2-thiazolyl)coumarins

3-(2-Thiazolyl)coumarins were obtained by the reaction of substituted salicylaldehydes with 2-thiazolylacetonitriles. Methylation, acylation, and aminomethylation were studied for the 7-hydroxy-substituted products.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1632–1644, November, 2004.     

2-Polyfluoroalkylchromones. 14. Synthesis of 4-chloro-3(5)-(2-hydroxyaryl)-5(3)-polyfluoroalkylpyrazoles

3-Chloro-2-polyfluoroalkyl- and 3-chloro-6-nitro-2-polyfluoroalkylchromones were synthesized. These compounds react with N₂H₄·2HCl on boiling in ethanol to form 4-chloro-3(5)-(2-hydroxyaryl)-5(3)-polyfluoroalkylpyrazoles.     

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins were prepared by reaction of substituted salicylaldehydes and hetarylacetonitriles. Alkylation and acylation of 3-hetaryl-7-hydroxycoumarins were studied. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 432–434, September–October, 2005.     

Microwave promoted one-pot synthesis of 3-(2''-amino-3''-cyano-4''-arylpyrid-6''-yl) coumarins

A facile procedure for the synthesis of 3-(2'-amino-3'-cyano-4'-arylpyrid-6'-yl) coumarins are being reported starting from 3-acetylcoumarin, aromatic aldehydes and malononitrile. The reactions were carded out on microwave irradiation in good yield with short time and easy work-up. The structures of all the compounds have been confirmed on the basis of their analytical, IR,1H NMR,and mass spectral data.     

Synthesis of 4-Hydroxy- and 4-Amino-2-Methyl-3-(2-Methylindol-3-Yl)methylquinolines and Their 6- and 8-Substituted Derivatives

A method has been developed for the synthesis of substituted 4-hydroxy- and 4-amino-2-methyl-3-(2-methylindol-3-yl)methylquinolines by treating the corresponding 4-hydroxy(chloro)-2-methyl-3-(3-oxobutyl)quinolines with phenylhydrazine hydrochloride. It was found that nucleophilic substitution occurred in the case of the 4-chloroquinolines together with subsequent rearrangement to give the 4-amino derivatives. The thiosemicarbazones of the corresponding 4-hydroxy-2-methyl-3-(3-oxobutyl)quinolines were also obtained.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 554–557, April, 2005.     

3-(2-Pyridyl)coumarins

3-(2-Pyridyl)coumarins were prepared by reaction of substituted salicylaldehydes and 2-pyridylacetonitrile. Benzylation, acylation, and aminomethylation of 7-hydroxy-3-(2-pyridyl)coumarin was studied. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 428–431, September–October, 2005.     

Reactivity of 3-formyl- and 3-cyanothiochromones toward some N- and C-nucleophiles. Novel synthesis of 3-substituted 2-aminothiochromones

The reactions of 3-formylthiochromone with o-phenylenediamines, o-aminobenzenethiol, and indoles proceeded at the aldehyde group to give 3-(benzimidazol-2-yl)thiochromone, 3-(benzothiazol-2-yl)thiochromone, and 3-di(indol-3-yl)methylthiochromones, respectively. 3-Formyl- and 3-cyanothiochromones react with primary aromatic amines and phenylhydrazine to give the corresponding anils and phenylhydrazones of 3-formyl- and 2-amino-3-formylthiochromones. The reaction of 3-cyanochromones with o-phenylenediamines gave 2-amino-3-[(2-aminophenyl)iminomethyl]-4H-chromen-4-ones.     

Reactions of 3-(4-Aryl-2-thiazolyl)- and 3-(2-Benzothiazolyl)-2-iminocoumarins with N-Nucleophiles

The reaction of 3-(4-aryl-2-thiazolyl)- and 3-(2-benzothiazolyl)-2-iminocoumarins with N-nucleophiles was studied. This reaction gives 2-N-substituted 3-(4-aryl-2-thiazolyl)- and 3-(2-benzothiazolyl)iminocourmarins. N-Nucleophiles such as arylamines, heterocyclic amines, and hydrazine derivatives undergo this reaction.     

Reaction of 2-(2-Azahetaryl)-4-chloro-3-oxobutyronitriles with Substituted Benzaldehyde Hydrazones. Unexpected Formation of 4-Arylideneamino-2-(1-R-benzimidazol-2-yl)-3-oxobutyronitriles

The reaction of 2-(2-azahetaryl)-3-oxo-4-chlorobutyronitriles with substituted benzaldehyde hydrazones gives 4-arylideneamino-2-(1-R-benzimidazol-2-yl)-3-oxobutyronitriles, the structures of which were proved using spectroscopic data, the results of elemental analysis, and through their chemical reactions. It was found that the reaction course depends on the basicity of the heterocyclic fragment in the starting nitrile. A likely mechanism for the process is proposed.     

Synthesis of Conjugated Systems Based on 3-(5-Methylfur-2-yl)-2-(3-oxobutyl)benzofurans

Methods were developed for the synthesis of 3-butyl-2-(3-oxobutenyl)benzofurans and 3-(3-furylbenzofuran-2-yl)acrylic acids on the basis of 3-furyl-2-(3-oxobutyl)benzofurans.     

One-Pot Synthesis of 1,3,4-Thiadiazin-5-yl-chromen-2-one Derivatives via Three-Component Reaction

An expeditious, one-pot reaction has been described for the preparation of 1,3,4-thiadiazin-5-yl-chromen-2-one derivatives. These compounds were synthesized by the reaction of 3-(2-bromoacetyl)coumarin with thiocarbohydrazide and various carbonyl compounds. The newly synthesized compounds were characterized by infrared, ¹H NMR, and mass spectra.     

Pd-catalyzed synthesis of 3-(diarylmethylene)-2-oxindoles and 3-(arylmethylene)-2-oxindoles

An efficient method for the stereoselective synthesis of 3-(diarylmethylene)-2-oxindoles and 3-(arylmethylene)-2-oxindoles via carbopalladation is described. In this approach, an Ugi-4-component reaction (4-CR) adduct was used as the starting material. A one-pot sequence involving intermolecular carbopalladation C-H activation/C-C bond formation efficiently afforded the oxindole derivatives.     

Investigation of 2,3'-Biquinolyl. 11. Regioselectivity in the Hydroxylation of 1-Alkyl-3-(2-quinolyl)quinolinium Halides

The hydroxylation of 1-alkyl-3-(2-quinolyl)quinolinium halides by an alkaline solution of K₃[Fe(CN)₆] in aqueous 1,4-dioxane leads to a mixture of 1-alkyl-3-(2-quinolyl)-1,2-dihydro-2-quinolones and 1-alkyl-3-(2-quinolyl)-1,4-dihydro-4-quinolones with predominance of the former. The use of the system of K₃[Fe(CN)₆]/Mg(OH)₂ in aqueous 1,4-dioxane leads to the regiospecific formation of 1-alkyl-3-(2-quinolyl)-1,4-dihydro-4-quinolones.     

Synthesis of （S）-2-（3-Arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）ethoxy]phenyl}propanoic Acids

The synthesis of （S）-2-（3-arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）etho- xy]phenyl}propanoic acids is described. Their structures were confirmed by ^1H-NMR.     

Bromination of 5-Substituted 3H-Furan-2-ones and 3H-Pyrrol-2-ones

The bromination of 5-alkyl(aryl)-3H-furan-2-ones and 5-alkyl(aryl)-3H-pyrrol-2-ones and also their derivatives takes place at the ethylene bond with the formation of 4-monobromo derivatives. N-Phenyl-3H-pyrrol-2-ones are brominated simultaneously at the ethylene bond of the heterocycle and at the phenyl substituent at the nitrogen atom.     

Reaction of 2-(2-oxoethylidene)furan-3(2H)-ones with isopropylidenehydrazides of aromatic carboxylic acids: Synthesis of 3-hydroxy-3-(2-oxoethyl)-2,3-dihydropyridazin-4(1H)-ones

3-Hydroxy-3-(2-oxoethyl)-6-phenyl-2,3-dihydropyridazin-4(1H)-ones were obtained by the reaction of methyl 3-oxo-5-phenylfuran-2(3H)-ylideneacetate or 2-[2-(4-chlorophenyl)-2-oxoethylidene]-5-phenylfuran-3(2H)-one with benzoic or p-nitrobenzoic isopropylidenehydrazides. Equilibrium C₍₅₎H and C₍₅₎H₂ tautomeric forms were detected in solutions of the 4-chlorophenyl derivatives in DMSO-d₆. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1156–1158, August, 2007.     

2-R-7-Hydroxy-8-methyl-3-(2-quinolyl)chromones

By condensation of 2-methyl resorcinol with 2-quinolyl acetonitrile, we have synthesized α-(2-quinolyl)-2,4-dihydroxy-3-methylacetophenone, which when reacted with carboxylic acid anhydrides followed by hydrolysis yields 2-R-7-hydroxy-8-methyl-3-(2-quinolyl)chromones.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 407–415, March, 2005.     

The Synthesis of 3-(2'-Hydroxybutyl) isobenzofuran-1 (3H)-one

l（3H】．Isobenzoturans（Dhthalldes】werereDortedtoexhibitawiderangeofbiologicalactivities．Forexample,3－n－butylphthallde（NB）exhibitsantlasthmatlc’,antlconvuls－ant“actlvltles．PenEandZhouhavestudiedonthemetabolismofNBPInrats‘．Theyfoundthat...     

Asymmetric synthesis of organoelemental analogs of natural compounds. 7. (2R,3S)-2-amino-3-hydroxy-5-phosphonovaleric acid

The reaction of the Ni(II) complex of the Schiff base of glycine with (S)-2-N-(N¹-benzylprolyl)-o-aminobenzophenone with diethyl-3-bromo-2-hydroxypropyl phosphonate yields the corresponding complex from which (2R, 3S)-2-amino-3-hydroxy-5-phosphonovaleric acid is separated with HCl.See [1] for Communication 6.Institute of Bioorganic Chemistry and Petrochemistry, Ukrainian Academy of Sciences, 252660 Kiev; N. A. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1172–1175, May, 1992.