Condensation of methyl 2-chloro-3-(3-nitrophenyl)-2,3-epoxypropionate with 1,2-phenylene diamine

It is established that the -chloroepoxide methyl 2-chloro-3-(3-nitrophenyl)-2, 3-epoxypropionate, in contrast to its a-chloroketone isomer methyl 3-(3-nitrophenyl-3-chloro-2-oxopropionate, forms 2-(3-nitrophenyl-3methoxycarbonylquinoxaline in reaction with 1,2-phenylene diamine, whereas the condensation of the achloroketone with 1,2 phenylene diamine gives 3-(-chloro-3-nitrophenyl)-2-oxo-1,2-dihydroquinoxaline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1105-1108, August, 1994.     

Synthesis of cyanamides containing the phenothiazine fragment and their reactions with dialkyldithiophosphoric acids

Reaction of phenothiazine with dialkoxyphosphoryl or chlorosulfenyl isocyanide dichlorides has given 10-cyanophenothiazine, which adds dialkyldithiophosphoric acids at the CN bond. The addition products rearrange to 10-[N-(dialkoxythiophosphoryl) thiocarbamoyl]phenothiazines, which are prone to decompose to dialkoxythiophosphoryl isothiocyanates and phenothiazine, or on treatment with alkyl halides in the presence of base afford stable S-alkyl-N- dialkoxythiophosphoryl (l0-phenothiazinyl)isothioformamides. The reaction between 10-cyanophenothiazine and an excess of dithiophosphoric acids also affords 10-thiocarbamoylphenothiazine and tetraalkyl trithiopyrophosphates. An x-ray diffraction examination of the molecular structure of S-methyl-N-diisopropoxythiophosphoryl-(10-phenothiazinyl)isothioformamide has shown it to possess the Z-configuration. The dihedral angle formed by the benzene rings of the phenothiazine fragment is 125.7°. The products of the addition of dithiophosphoric acids to the CN bond of N,N-bis[2-(10-phenothiazinyl)-2-oxoethyl]cyanamide, obtained from 10-(chloroacety) phenothiazine and NaNHCN, also isomerize by 1,3S N migration of the thiophosphoryl group. Subsequent heterocyclization, with elimination of phenothiazine, affords 2-(dialkoxythiophosphorylimino)-3-[2-(10-phenothiazinyl)-2-oxoethyl]thiazolidin-5-ones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 451–460, February, 1991.     

Synthesis of 4,5-dih ydrofuran derivatives by the reaction of acetylace tone with conjugated alkenes

The reaction of the acetylacetonyl radical (generated from acetylacetone by the action of manganese acetate) with vinylacetylene, 2-vinylfuran, and butadiene Was studied. The reaction proceeds nonregioselectively with vinylacetylene: 3-acetyl-2-methyl-5-ethynyl- and 3-acetyl-2-methyl-5-(4-acetyl-5-methyl-2-furyl)-4,5-dihydrofurans in a ratio of 12.2 were isolated. The principal products in the reaction with 2-vinylfuran and butadiene were 3-acetyl-2-methyl-5-(2-furyl)- and 3-acetyl-2-methyl-5-vinyl-4,5-dihydrofurans.Communication 62 from the series Reactions of unsaturated compounds. See [1] for communication 61.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 884–887, July, 1980.     

Electronic spectra of α,β-unsaturated ketones — Indole derivatives

The electronic spectra of (3-indolyl)-, (1-methyl-3-indolyl)-, and (6-nitro-3-indolyl)-substituted ,-unsaturated ketones were measured and interpreted. 3-Indolyl and N-methyl-3-indolyl substituents have a considerable bathochromic effect as compared with the phenyl group in the investigated systems as a consequence of the electron-donor effect, which surpasses that for 4-anisyl, 2,4-dimethoxyphenyl, 2-furyl, 2-thienyl, and 2-selenienyl and differs only slightly from 2-pyrrolyl. The introduction of electron-donor substituents into the p position of the benzene ring of 1-(3-indolyl)-3-phenyl-1-propenone causes a red shift of the long-wave absorption band, the difference in frequencies of which correlates with the Hammett substituent constants. Except for compounds containing a nitro group,1-(3-indolyl)-3-aryl-3-propenones and their N-methyl derivatives fluoresce well in alcohol with _max >475 nm.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 949–953, July, 1972.     

2-Spiroanellated 1,3-Benzodioxoles from the Reaction of 2,3-Dihydro-1 H-pyrrol-3-ones with Tetrachloro-1,2-benzoquinone

Novel spiro[1,3-benzodioxole-2,2-(2,3-dihydro-1H-pyrrol-3-ones)] were obtained from 2-aminomethylene-2,3-dihydropyrrol-3(1H)-ones and tetrachloro-1,2-benzoquinone in ethanol at room temperature. However, in addition, 3,4-dichloro-7-methoxy-5-(4-methoxyphenyl)-5,10-dihydrophenazine-1,2-dione was formed in the reaction of 1-(4-methoxyphenyl)-2-(4-methoxyphenylaminomethylene)-4,5-diphenyl-1,2-dihydropyrrol-3-one with tetrachloro-1,2-benzoquinone.     

3-[ω-(2-Benzimidazolyl)alkyl]benzoxazolones

A new method for the preparation of -(3-benzoxazolonyl) butyric acids from sodium salts of benzoxazolones and -butyrolactone was developed. 3-[-(2-benzimidazolyl)alkyl]benzoxazolones were synthesized by the reaction of these acids and also (3-benzoxazolonyl)acetic and -(3-benzoxazolonyl)propionic acids with o-phenylenediamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 464–466, April, 1973.     

Radical Ions of a Bishomobinaphthylene Containing two 1,6-methano[10]annulene moieties: An ESR and ENDOR study

The radical cation and the radical anion of ‘syn’-cyclobuta[1,2-c:3,4-c′]di-1,6-methano[10]annulene (‘syn’-4a,12a:6a, 10a-bishomobinaphthylene; 3 ) have been characterized by their hyperfine data. The highly resolved ESR spectrum of $ 3^{+ \atop \dot{}} $ is dominated by a triplet splitting from the outer pair of methano β-protons (H_o). In contrast, the ESR spectrum of $ 3^{- \atop \dot{}} $ is poorly resolved with the largest coupling constants arising from perimeter α-protons. The different hyperfine features of $ 3^{+ \atop \dot{}} $ and $ 3^{- \atop \dot{}} $ are rationalized by MO models. The SOMO of $ 3^{+ \atop \dot{}} $ ψ_SA(b₁), has substantial LCAO coefficients of the same sign at the bridged atoms C(1), C(6), C(11), and C(16), whereas in the SOMO of $ 3^{- \atop \dot{}} $, ψ_SS(a₁), the four atoms lie in the vertical nodal planes. The large width and the reluctance to saturation of the lines in the ESR spectrum of $ 3^{- \atop \dot{}} $ are attributed to the near-degeneracy of the lowest antibonding MO's. Due to their similar nodal properties, the SOMO's of $ 3^{- \atop \dot{}} $ and the radical anions of binaphthylene ( 4 ), 1,6-methano[10]annulene ( 1 ), and naphthalene ( 2 ) are interrelated. Moreover, because the cyclic π-systems in 3 and 1 deviate in the same way from planarity, the effect of such distortions on the coupling constants, a_Hμ, of the perimeter α-protons in $ 3^{- \atop \dot{}} $ and $ 1^{- \atop \dot{}} $ should be comparable. Indeed, on going from $ 4^{- \atop \dot{}} $ to $ 3^{- \atop \dot{}} $, the |a_Hμ| values are reduced exactaly by half as much as the corresponding values on passing from $ 2^{- \atop \dot{}} $ to $ 3^{- \atop \dot{}} $, of which the cyclic π-systems are twice contained in $ 4^{- \atop \dot{}} $ and $ 3^{- \atop \dot{}} $ respectively.     

Lability of the β-diethylaminoethyl group under the conditions of the formation of a pyrrole ring via the Knorr synthesis

The corresponding 3-acetyl- and 3-H-pyrroles are formed along with 2,4-dimethyl-3-(-diethylaminoethyl)-5-carbethoxypyrrole in the condensation of 3-(-diethylaminoethyl)pentane-2,4-dione with isonitrosoacetoacetic (I) and isonitrosomalonic (II) esters.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1643–1645, December, 1973.     

Reaction of indoles and 2-ketoindolines with some aldehydes

3,5-Di-tert-butyl-4-hydroxybenzaldehyde reacts with indole and 2-methylindole to give di(3-indolyl)methane derivatives but reacts with 2-ketoindoline and 1-methyl-2-ketoindoline to give 3-arylidene-2-ketoindoline derivatives. 2-Ketoindolines form 3-(o-hydroxybenzylidene)-2-ketoindolines with salicylaldehyde. They react with aryglyoxals to give 3-(2-ketoindolinyl)-aroylcarbinols, which are dehydrated to 3-phenacylidene-2-ketoindolines under the influence of acetic acid. Both the starting carbinols and these products form spiro[(2-ketoindoline)-3,5-(3-aryl-²-pyrazolines)] on reaction with hydrazine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 40–44, January, 1973.     

Perfluorovinyl Morpholine and Perfluorovinyl Pyrrolidine with Nucleophiles and Electrophiles

In this study, both monofunctional and bifunctional nucleophiles, as well as the electrophile FNO, are reacted with perfluorovinyl amines. The perfluorovinyl amines CF?CF₂ and CF?CF₂ have been reacted with dimethylamine and diethylamine in the presence of small amounts of water to give CHFC(O)N(CH₃)₂ ( 1 ), CHFC(O)N(CH₃)₂ ( 2 ), and CHFC(O)N(C₂H₅)₂ ( 3 ). With perfluorovinyl pyrrolidine and perfluorovinyl morpholine, ethanolamine gives the cyclized products CHF ( 4 ) and CHF ( 5 ), respectively. Reaction of the vinyl amines with (CH₃)₃SiOCH₂CF₃ in the presence of catalytic amounts of CsF results in the formation of cis- ( 6 ) and trans- ( 7 ) CF?CF(OCH₂CF₃) and cis- ( 8 ) and trans- ( 9 ) CF?CF(OCH₂CF₃). The electrophile FNO reacts slowly with perfluorovinyl pyrrolidine and perfluorovinyl morpholine, and more rapidly with (CF₃)₃CCF?CF₂ to give CF(NO)CF₃ ( 10 ), CF(NO)CF₃ ( 11 ) and (CF₃)₃CF(NO)CF₃ ( 12 ), respectively. Single crystal X-ray analysis is used to confirm the identity of the product obtained from the controlled hydrolysis of the sultone of perfluorovinyl pyrrolidine as the sulfonic acid anhydride C(O)CF₂OS(O)₂OCF₂C(O) ( 13 ). The X-ray crystal structure of perfluorosuccinic acid monohydrate ( 14 ), which is obtained when the perfluorovinyl pyrrolidine sultone is hydrolyzed in excess water, is also reported for the first time.     

Synthesis and1H NMR and13C spectroscopy of L-arabinopyranosyl biosides

Conclusions The 3-0- and 4-0-trityl ethers of the acetates of methyl -L- arid methyl -L-arabinopyranosides were synthesized. The glycosylation of the ethers with the aid of 3,4-di-0-acetyl-1,2-0-(1-exo-cyano)ethylidene--L-arabinopyranose and the subsequent deacetylation of the synthesized products yielded the disaccharides: methyl 4-0-(-L-arabinopyranosyl)-,methyl 4-0-(-L-arabinopyranosyl)-, and methyl 3-0-(-L-arabinopyranosyl)--L-arabinopyranoside; and methyl 4-0-(-L-arabinopyranosyl)-, methyl 4-0-(-L-arabinopyranosyl)-, methyl 3-0-(-L-arabinopyranosyl)-, and methyl 3-0-(-L-arabinopyranosyl)--L-arabinopyranoside.The assignment of the signals in the PMR and¹³C NMR spectra of the synthesized arabinopyranosyl biosides was carried out, allowing the determination of the type and configuration of the glycosidic bond by means of which the arabinopyranose residues are linked in the oligo- and polysaccharide chains.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 200–209, January, 1986.     

Synthesis ofω-substituted 3-alkylorotic acids

3-(-Phthalimidoalkyl)-5-carbethoxymethylenehydantoins were synthesized by the reaction of-phthalimidoalkylureas with ethyl oxalacetate and then converted to 3-(-aminoalkyl)orotic acids. Condensation of the latter with 6-chloropurine yielded 3-[-(6-purinylamino)alkyljorotic acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 397–399, March, 1971.     

Reaction of benzylidene-2-naphthylamine with the ethyl ester of 3-pyridyl-β-oxopropionic acid

The reaction of benzylidene-2-naphthylamine with ethyl -(3-ethyl)--oxopropionate under various conditions gave the ethyl ester of -(2-naphthylamino)benzyl--(3-pyridyl)--oxopropionic acid, 1-(3-pyridyl)-3 phenylbenzo[f]quinoline, ethyl ester of 1-(3-pyridyl)-3-phenylbenzo[f]quinoline-2-carboxylic acid, and N-(2-naphthyl)amide of -(3-pyridyl)--oxopropionic acid. The IR, UV, and mass spectra of the products were studied and the pathways for their formation were discussed.Institute of Physical Organic Chemistry, Belorussian Academy of Sciences, Minsk 220603. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 807–810, June, 1996. Original article submitted December 30, 1995.     

Solvent-controlled regioselectivity in the ortho-palladation of benzylamines and intramolecular exchange in cyclopalladated ligands

Conclusions Cyclometallation of 1-(3,4-dimethoxyphenyl)-2-methyl-3-(4-nitrophenyl)-2-azapropane upon treatment with Pd(II) acetate occurs at the electron rich dimethoxy-substituted aromatic ring in CHCl₃ solution, and at the electron poor nitrophenyl ring in AcOH solution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 175–181, January, 1988.     

Isoquinoline derivatives

1-(3,4-Dimethoxyphenyl)-1-aminomethylcyclopentane (IV) was condensed with substituted phenylacetyl and benzpyl chlorides to synthesize 1-[R,R,R-phenylacet(benz)amidomethyl]-1-(3,4-dimethoxyphenyl)cyclopentanes (VI), which were converted to 1-[R,R,R-phenyl(benzyl)]-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline-4-spirocyclopentanes (IX) by cyclization and subsequent reduction. Reduction of VI yielded the corresponding secondary amines (VII). The compounds obtained were subjected to Chromatographic analysis. The IR spectra were investigated. Compounds VII and IX were subjected to pharmacological testing.See [6] for communication IV.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 637–640, May, 1971.     

Reaction of dialkylpyridines with styrene and mass-spectrometric behavior of the reaction products

The reaction of 2,4-dimethylpyridine with styrene gives 2-(3-phenyl-propyl)-4-methyl- and 2-methyl-4-(3-phenylpropyl) pyridine, but in the case of 2-methyl-5-ethylpyridine, the reaction gives only 2-(3-phenylpropyl)-5-ethylpyridine. The mass spectra of the compounds obtained have been studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1376–1378, October, 1984.     

Synthesis of tetrahydrodibenzodipyrazolo-[1,2,5,8,9,12]- and-[1,2,5,6,9,12]-hexaazacyclotetradecine derivatives

The reaction of nickel(II) nitrate with 4-(2-bromo-4-methyl-1-phenylazo)-3-amino-5-methy1-2-alkylpyrazoles by refluxing in dimethylformamide in the presence of K₂CO₃ followed by purification with a column filled with Al₂O₃ gave [1,10,11,20-tetrahydro-1, 11-dipropyl-3,8,13,18-tetramethyIdibenzo[c,j]dipyrazolo[3,4-f:3,4-m] [1,2,5,8,9,12]hexaazacyclotetradecinato(2-)-4,10,14,20]nickel and [1,14,15,20tetrahydro-1, 14-dipropyl-3,7,12,17-tetramethyldibenzo[c,j]dipyrazolo[4,3-g:3,4-m] [1,2,5,6,9,12]hexaazacyclotetradecinato(2-)-5,10,15,20]nickel, which were characterized by the results of elementary analysis and the IR, UV, PMR, and mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1097–1103, August, 1978.     

N-glycosides. 3. Reaction of 2,3-0-isopropylideneribofuranosylamine tosylate with 4-methyl-4-isothiocyanato-2-pentanone

The condensation of 2,3-0-isopropylideneribofuranosylamine tosylate with 4-methyl-4-isothiocyanato-2-pentanone in the presence of bases was studied. In pyridine the reaction gives a mixture of 3-(2,3-0-ispropylidene--D-ribofuranosyl)-4,6,6-trimethyl-1,2,3,6-tetrahydropyrimidine-2-thione and 3-(2,3-0-isopropylidene--D-ribofuranosyl)-4-methylene-6,6-dimethylhexahydropyrimidine-2-thione.See [1] for communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 244–246, February, 1984.     

Fused Polycyclic Nitrogen-Containing Heterocycles: VI. Pyrrolo[1,2-a]quinoxalines

3-(-Chlorobenzyl)-1,2-dihydroquinoxalin-2-one reacts with anions derived from acetylacetone, benzoylacetone, dibenzoylmethane, malononitrile, ethyl acetoacetate, and ethyl cyanoacetate to give the corresponding 3-(-R,R'CH-benzyl)-1,2-dihydroquinoxalin-2-ones which undergo intramolecular cyclocondensation to functionally substituted pyrrolo[1,2-a]quinoxalines on heating in boiling acetic acid. The reaction of 3-(-chloro-p-nitrobenzyl)-1,2-dihydroquinoxalin-2-one with acetylacetone anion directly leads to the corresponding pyrrolo[1,2-a]quinoxaline, without heating in acetic acid.     

Medium effect on the direction of the reaction of 3-chloro-1,3-diphenyl-1,2-propanedione with ortho-phenylenediamine

The reaction of 3-chloro-1,3-diphenyl-1,2-propanedione (I) with ortho-phenylenediamine in acetic acid gave 2-phenyl-3-(-chlorobenzyl)quinoxaline (II). This reaction in methanol with MeONa gave 2-(-hydroxybenzylidene)-3-phenyl-1,4-dihydroquinoxaline (VI).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1660–1662, July, 1991.