Formation of 3,4-dihydro-α-carbolines from 2-aminoindole

In the condensation of 2-aminoindole with ,-unsaturated oxo compounds, in contrast to ordinary aromatic amines and a number of heterocyclic amines, the direction of cyclization is reversed. The general scheme of the reaction includes the reaction of the position of 2-aminoindole with the activated double bond of the oxo compound via a mechanism of the Michael type and condensation of the carbonyl group of the unsaturated carboline structure, which subsequently undergoes aromatization. The intermediate 3,4-dihydro--carbolines were produced and isolated; this made it possible in a number of cases to establish the structures of the final -carbolines. The structures of the 3,4-dihydro compounds were confirmed by the set of spectral characteristics. Data from the UV, IR, PMR, and mass spectra are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 945–951, pp. 945–951, July, 1977.     

EPR spectra and characteristics of metal-ligand bond in complexes of divalent copper with some amino acids

Electron paramagnetic resonance spectra were obtained in low-temperature glasses for a series of copper complexes with amino acids: glycine, - and -alanine, valine, leucine, histidine, serine. The ionicity coefficients ² and ₁ ² of the metal-ligand bond were calculated from the spin Hamiltonian constants and from optical data. The results are compared with the stability of the investigated complexes.     

Formation of ultra-thin films consisting of proteins or polysaccharides and syndiotactic-rich poly-vinyl alcohol mixtures adsorbed at air-solution interface

Ultra-thin films of syndiotactic-rich poly-vinyl alcohol (s-PVA) with several proteins and polysaccharides were prepared by the bubble and frame methods using a mixed dilute aqueous solution (1.5g/dL).The mixed amount of-cyclodextrin (-CD) was the largest among these proteins and polysaccharides giving a weight ratio (-CD/s-PVA) of 1. The ratios of silk fibroin(SF), lysozyme, pepsin, and pectin tos- PVA were 0.58, 0.40, 0.35, and 0.35, respectively. For the-CD/s-PVA and SF/s-PVA blend thin films, the phase separation was observed.     

Quinindines

It is shown that, together with -quinindane-9-carboxylic acid, the condensation of isatin with cyclopentanone in alkaline medium (Pfitzinger reaction) also affords , -dicyclopentylidenecyclopentanone and 3-cyclopentylidene--quinindane-9-carboxylic acid, the structure of which was confirmed by its NMR, IR, and UV spectra.     

Fluorinated Β-hydroxy-Β-carbomethoxy acids and photoreduction of their copper salts

Conclusions The methyl esters of fluorinated -keto acids enter into the Knoevenagel condensation with malonic acid and give fluorinated -hydroxy--carbomethoxy acids, which form copper salts with a ligand:copper composition=1:1. The Cu salts of fluorinated -hydroxy--carbomethoxy acids are photoreduced by alcohols in the presence of UV light to give -hydroxy--carbomethoxy acids and metallic Cu.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1896–1900, August, 1982.     

Nitration of 4-methyl-5,6-dihydro-2H-pyran and some aspects of the preparation and isomerization of nitrodihydropyrans

The reaction of 4-methyl-5,6-dihydro-2H-pyran with acetyl nitrate to give additive and substitutive nitration products has been examined. It is shown that the addition product, 4-acetoxy-4-methyl-3-nitro-tetrahydropyran, is deacylated on treatment with bases to give an ,-unsaturated nitro-compound which isomerizes under the reaction conditions to a ,-unsaturated nitro-compound. 4-Acetoxy-4-nitromethyltetrahydropyran behaves similarly.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 305–308, March, 1987.     

Perturbation calculation of oscillator strengths for the isoelectronic series of light atoms

Transition probabilities and oscillator strengths are calculated for the configurations 1s² 2sⁿ¹ and 1s² 2s^n1-1 2pⁿ²⁺¹, which are, respectively, of the form P=a/Z (1+/Z+) andf=/Z (1+/Z+). Numerical values are given fora, ,, and.     

Benzimidazole derivatives

-(1,3-Dimethyl-5-benzimidazolonyl)acrylic acid, -(1,3-dimethyl-5-benzimidazolonyl)propiolic acid, and 5-ethynyl-1,3-dimethylbenzimidazolone were synthesized via the Wittig reaction from 5-formyl-1,3-dimethylbenzimidazolone. The UV and IR spectra are presented.See [1] for communication XXV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 122–123, January, 1971.     

Some methoxy derivatives of 9-amino-6-nitroacridine

The reaction of the 2-, 3-, and 4-methoxy derivatives of 9-chloro-6-nitroacridine with-diethylamino--methylbutylamine and with-diethylamino--hydroxypropylainine in phenol has given the 2-, 3-, and 4-methoxy derivatives of 9-(-diethylamino--methylbutylamino)-6-nitroacridine and of 9-(-diethylamino--hydroxypropylamino)6-nitroacridine, respectively.     

Synthesis of polysaccharides. 11. Synthesis of α-(1 → 3)-L-rhamnan

Conclusions We synthesized the 4-0-acetyl-3-0-trityl-1,2-0-exo-cyanoethylidene--L-rhamnopyranose monomer, the polycondensation of which gave the regular polysaccharide -(1 3)-L-rhamnan.See [1] for Communication 10.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 196–200, January, 1981.     

Synthesis of 2-dimethylamino-3-substituted 2h-pyrans and study of their valence isomerization to δ-dimethylamino dienones

It is shown that 2-dimethylamino-3-isopropyl(3-dimethylamino)-2H-pyrans are formed in the condensation of aminal acetals of -isopropyl-or -dimethylamino--dimethylaminoacroleins with -dicarbonyl compounds. It was observed by means of ¹H and ¹³C NMR and UV spectroscopy that they do not undergo valence isomerization to -dimethylamino dienones. Under the influence of pulse photoexcitation the 2H-pyrans undergo reversible cleavage of the C-O bond and isomerization to the corresponding dienones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1325–1333, October, 1983.     

Studies in the field of synthetic dyes

-Acetanilidovinyl derivatives of the quinoline series have been synthesized, and their condensation with quaternary salts of heterocyclic bases has given 12 unsymmetrical carbocyanines.For communication LXVIII, see [12].     

Addition of hydrogen sulfide and mercaptans to Β,Β-dimethylvinyl vinyl ketone

Conclusions The nucleophilic addition of hydrogen sulfide or mercaptans to the unsubstituted vinyl group takes place when,-dimethylvinyl vinyl ketone is reacted with hydrogen sulfide or mercaptans.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2504–2509, November, 1967.     

Reaction of Β-arylacryloxiranes with phenyl azide. Synthesis and chemical transformations of Β-phenylamino-Β-arylacrylyloxiranes

The reaction of -arylacrylyloxiranes with phenyl azide by refluxing in dioxane or toluene leads to -phenylamino--aryl-acrylyloxiranes. Epoxypropionyl- and -hydroxypropionyltriazoles are also isolated when the reaction is carried out in the dark without heating. It is shown that -phenylamino--arylacrylyloxiranes undergo cyclization to 3(2H)-furanones in an acidic medium, whereas they are converted to 2,3-dihydro-4-pyridones under basic-catalysis conditions.Translated from Khimiya Geterotsiklicheskikh Soedineii, No. 8, pp. 1022–1027, August, 1988.     

Electronic spectra of α, Β-unsaturated diketone derivatives of thiophene

The electronic absorption spectra of ,-unsaturated diketone derivatives of thiophene of the p-dichalcone type have been studied. As a rule, these compounds have deeper colors than the monoketone thiophene analogs of the chalcones corresponding to them. Electron-donating substituents in the aromatic nucleus of 2,5-dicinnamoylthiophene and also the replacement of the phenyl radicals in them by heterocyclic radicals cause a bathochromic shift of the long-wave absorption maximum (frequency) which correlates satisfactorily with Hammett's constants. Some ketones with strong electron-donating groupings fluoresce under UV irradiation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 744–749, June, 1970.     

Carbolines

Anhydronium bases of 2-chloro--carbolines and 3,4-dihydro--carbolines are formed fay Beckmann rearrangement of - (3-indolyl) ketone oximes. In a number of cases the formation of anhydronium bases becomes the predominant process.See [1] for communication VII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 386–391, March, 1976.     

Binding energies of metal monocations to Β-lactones and Β-lactams. A theoretical study of cyclization effects

Ab initio calculations have been performed to study the association of-propiolactam and-propiolactone and their aliphatic analoguesN-methyl acetamide and methyl acetate with different metal monocations: Li⁺, Na⁺, Mg⁺, and Al⁺, in an effort to investigate cyclization effects on the gas-phase basicities of amides and esters, when the reference acid is not a proton. Similarly to what was found for protonation,N-methyl acetamide and-propiolactam are more basic than methyl acetate and-propiolactone, when the reference acids are the aforementioned metal monocations. However, cyclization effects on the corresponding binding energies for both kind of compounds do not parallel those observed for protonation energies, and-lactone is as basic as methyl acetate when the reference acid is Li⁺ and slightly more basic than methyl acetate when the attaching ion is Na⁺. This implies that when the interactions of the bases with the reference acids are essentially electrostatic the reactivity patterns change with respect to those observed when the interactions are essentially covalent.     

Reaction of Nitrosonium Tetrafluoroborate with Nitroxyl Radicals

It was established by means of multinuclear magnetic resonance method (¹H, ^{1 3}C, ^{1 9}F and ^{1 4}N) that reaction of 2,2,6,6-tetramethyl-4-R-piperidin-1-oxyl radicals (R = H, OH, OMe, OCOPh, NHCOMe) with nitrosonium tetrafluoroborate gave rise to the corresponding 2,2,6,6-tetramethyl-1-oxo-4-R-piperidinium tetrafluoroborates. Linear correlations were found between the chemical shifts of atoms H⁴, C⁴ of cations and respectively ₁-constants of substituents R and chemical shifts of C⁴ atom calculated from increments of substitution. The conformational features of the generated nitrosonium cations are considered on the grounds of vicinal coupling constants J _{H H} and quantum-chemical calculations by AM1 method.     

Synthesis of pyrylium salts by condensation of Β-chlorocinnamaldehydes with carbonyl compounds

A method is proposed for the synthesis of unsymmetrical unsubstituted pyrylium salts by condensation of -chlorocinnamaldehydes with methyl and methylene ketones and -dicarbonyl compounds in the presence of HClO₄ or Lewis acids. The probable scheme of the reaction is examined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1031–1035, August, 1974.     

Investigation on riboflavin analogs

Dinitrotrifluoromethyl-d-galactyl- and -hydroxyethyldihydrophenazines have been obtained for biological tests by the reaction of primary-secondary o-phenylenediamines with picryl chloride.For part IV, see [1].