Carbolines

4-Substituted 3, 4-dihydro--carbolines (X–XVI) were obtained by the Beckman rearrangement of oximes of -(indolyl-3)ketones (I–IV, IX) under the action of phosphorus pentachloride in nitrobenzene. 3, 4-Dihydro--carbolines were converted into -carbolines (XV–XVII) on heating with Brown's palladium catalyst in ethylene glycol. Oximes containing the aryl group react on treatment with p-toluene sulfochloride in pyridine with the formation of the arilides of -(indolyl-3)propionic acids.For preliminary report, see [18].     

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.     

Transformed steroids. 180. Stereospecific transformation of 17Β-hydroxy-17α-ethynylsteroids into various 17α-substituted 17Β-ethynylsteroids

The use of a dicobalt hexacarbonyl protective group permitted us to carry out the stereospecific conversion of 17-hydroxy-17-ethynylsteroids into branched 17-R-substituted 17-ethynylsteroids (R-OH, OAc, OMe, NCS, and F).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 675–681, March, 1990.     

Synthesis of organocyclosiloxanes containing cyanoalkyl groups on the silicon atom

The cohydrolysis of-cyanoethyl- and-cyanopropylmethyldichlorosilanes with dimethyldichlorosilane has been studied and the optimum conditions ensuring the maximum yield of rings containing cyanoalhyl groups have been determined.B is(-cyanoethyl)hexamethylcyclotetrasiloxane,-cyanopropylpentamethylcyclotetrasiloxane, and bis(-cyanopropyl)hexamethylcyclotetrasiloxane have been obtained for the first time and characterized.     

Synthesis of some esters of α-acetoxy-Β,Β,Β-trichloroethylphosphonic acid

Summary By the reaction of dialkyl esters of -hydroxy, ,-trichloroethylphosphonic acid and acetic anhydride in the presence of a few drops of sulfuric acid, the dialkyl esters of -acetoxy-,,-trichloroethylphosphonic acid were obtained in high yields.     

Synthesis of homologs of p-phenoxystyrene

Conclusions Homologs of p-phenoxystyrene that had not been described in the literature have been synthesized: -methyl-p-phenoxystyrene, -ethyl-p-phenoxystyrene, ,-dimethyl-p-phenoxystyrene, -methyl-p-phenoxystyrene, and ,-dimethyl-p-phenoxy styrene.     

Crystallization,melting and spherulitic structure of Β-nucleated random propylene copolymers

The characteristics of crystallization, melting and spherulitic growth of a random propylene copolymer (PRC) containing small amount of ethylene were studied in the presence of a selective -nucleating agent (calcium pimelate). It was established that the products of isothermal and non-isothermal crystallization are very rich in -modification but have mixed polymorphic composition. The formation of -modification may be attributed to -transition on the surface of growing -spherulites resulting in -twin-spherulites. During melting of PRC of -modification, the characteristics observed with -nucleated propylene homopolymers, namely, a -recrystallization of recooled samples and separated melting of non-recooled samples (i.e. the melting memory effect), as well as a -recrystallization leading to a perfection of the structure within the -modification, are also demonstrated. The disturbance of regularity of the polymer chain highly reduces the tendency to -crystallization. In contrast to the observations with propylene homopolymers, the growth rate of -modification (G ) is higher than that of -modification (G ) and no critical crossover temperature can be found (T()=413 K) below whichG >G . The experimental results show that a partial disturbance of chain regularity by incorporation of comonomer units considerably reduces the tendency to -crystallization.This research was supported by the National Scientific Research Fund (OTKA), the author is grateful for it. Thanks are due to Professor Géza Bodor for his help in X-ray diffractometric investigations and to Ms. Tünde Lócska for her prudential technical assistance in the optical experiments.     

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.     

Mass spectrometric decomposition of Β-phenyloxiranecarboxylic esters

The electron-impact mass spectra of the E- and Z-isomers of the ,-methyl substituted esters of -phenyloxiranecarboxylic acids have been studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1310–1314, October, 1986.     

Study of the rotational isomerism about the C-O bond in six-membered secondary-tertiary diols

We have determined the spectroscopic characteristics, the dipole moments, and the Kerr constants of the stereoisomers of the secondary-tertiary diols of the cyclohexane and bicyclo [4.1.0]pentane series: 3,4-dihydroxy-3-carane (I), 3,4-dihydroxy-3-methylnorcarane (II), 3,4-dihydroxy-3-methylnorcarane (III), 4, 5-dihydroxy-3-methylcyclohexene (IV), 3,4-dihydroxy-3-carane (V), 3,4-dihydroxy-3-methylnorcarane (VI), 3, 4-dihydroxy-3-carane (VII), and 3,4-dihydroxy-4-methyl-3-carane (VIII). It was found that the cis diols are more polar than their trans isomers. It was shown by electrical and electrooptical methods that rotamers with a gauche orientation with respect to the tertiary C-O are stable relative to those containing the diol at the ordinary C-C bond of the ring.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 619–625, March, 1991.     

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.     

A study of nitrogen- and sulfur-containing heterocycles

The catalytic hydrogenation of N--cyanoacylureas and 1-alkyl-3--cyanoacylureas in the presence of hydrochlorides of aromatic amines has given N--arylaminoacryloyl-, 1-alkyl-3--arylaminoacryloyl-, N--alkyl--arylaminoacryloyl-, and 1-alkyl-3--alkyl--arylaminoacryloylureas. The action of N- -phenylaminoacryloyl- and 1-methyl -3- -phenylaminoacryloylureas of ethanolic hydrogen chloride has given uracil and 1-methyluracil.For Communication IX, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 847–850, June, 1970.     

Effects of medium and chemical modification on thermal characteristics of Β-lactoglobulin

The thermal properties of -lactoglobulin (-LG) were studied by differential scanning calorimetry (DSC) under different medium conditions.pH, neutral salts, protein perturbants, and polyols all affected the DSC characteristics of -LG. Acylation with fatty acids also changed the thermal properties, particularly peak width at half-height. The results suggest that the structural stability of -LG is controlled by non-covalent forces, particularly electrostatic and hydrophobic interactions. Disulfide bonds did not contribute to the thermal response of -LG. Fatty N-acyl-amino acids caused marked increases in thermal stability and decreases in denaturation enthalpy, and additional peaks were observed in the presence of some palmitoyl derivatives.Contribution No. 2310, Centre for Food and Animal Research.We thank D. Raymond for her excellent technical assistance.     

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.     

Direct nitration and acetylation of the furan nucleus of 1-alkyl-2-[Β -(2′-furyl) vinyl]-benzimidazoles

The direct nitration and acetylation of 1-methyl-, 1-ethyl-, and 1-benzyl-2-[-(2-furyl)vinyl]benzimidazoles has given the corresponding 1-alkyl- and 1-benzyl-2-[-(5-nitro-2-furyl)vinyl]benzimidazoles and 1-alkyl- and 1-benzyl-2-[-(5-acetyl-2-furyl)vinyl]benzimidazoles. The UV spectra of these compounds have been recorded and their ionization constants have been determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 832–834, June, 1970.     

The dimer of trifluoromethylthiirene

Conclusion The action of the hexaethyltriamide of phosphorous acid on disulfides containing an ,-dichloro-,,-trifluoroisopropyl group gives the dimer of trifluoromethylthiirene, namely, 2,5-bis(trifluoromethyl)p-dithiine. Oxidation of this dimer by the action of sulfuric acid gives a stable radical-cation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1160–1162, May, 1987.     

Reaction of Β-oxonitrones — Imidazoline and pyrroline derivatives — With nucleophilic reagents

The reaction of -oxonitrones — imidazoline derivatives — with hydroxylamine, phenylhydrazine, and semicarbazide takes place at the carbonyl group with retention of the nitrone group. Stable nitroxyl radicals — spiroimidazoisoxazole derivatives — are formed in the oxidation of -hydroximinonitrones. The recyclization of the -oxonitrones, which takes place in an acidic medium, as well as by the action of hydrazine and thiosemicarbazide, leads, respectively, to pyrroline and pyrazole derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 912–919, July, 1991.     

Bromide ion oxidation of various Pt surfaces

At variance with the absence of an orientation effect in the hydrogen evolution reaction, aclear difference in the electrocatalytic effect of various parts of the surface on bromide ion oxidation is observed.

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qv .

     

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.     

Investigation of nitrogen- and sulfur-containing heterocycles

The synthesis of two-ring 1,4-thiazine systems was previously accomplished on the basis of the reaction of o-amino mercapto derivatives of pyridine and pyrimidine with dicarbonyl compounds — halo -keto esters and halo -diketones. In the present paper it is shown that the primary products of this reaction are S--keto-alkylmercapto derivatives, which are subsequently cyclized to the corresponding hydroxy amino compounds. The latter are converted to N-acylamino-S--carbethoxy (keto)alkylmercapto derivatives under the influence of an alkaline agent. The indicated compounds were isolated and characterized [2, 3].See [1] for communication 36.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 250–253, February, 1979.