Intramolecular P=S and P=N Alkylation. General Method for Synthesizing 1,2-Heteraphosphacyclanes

Results have been generalized for investigations on the synthesis of 1,2-thiaphosphacyclanes by intramolecular P=S alkylation of -haloalkyl substituted compounds of four-coordinated phosphorus with a P=S bond. The method has been extended to nitrogen-containing analogs with a P=N bond. A new general method is proposed for the synthesis of 1,2-thia- and 1,2-azaphosphacyclanes.     

Alkaloids ofNitraria komarovii. IV. Total synthesis of komarovine and komarovidine

Two alkaloids of a new type — komarovine and komarovidine — have been isolated from the epigeal part of theNitraria komarovii. Their structures — 3-(quinolin-8'-yl)--carboline and 3-(quinolin-8'-yl)-5,6-dihydro--carboline, respectively — have been established by synthesis.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 192–195, March–April, 1981.     

Bisindoles. 32. Some activated diesters of 2,2-dihydroxycarbonyl-bis-(5-indolyl)sulfone and polyamides based thereon

Di-acyl halides of 2,2-dihydroxycarbonyl-bis(5-indolyl)sulfone, p-nitro-, pentachloro-, and 2,4-dinitrophenol have been used for the synthesis of activated diesters, polycondensation of which with diamines of different structures yielded polyamides containing indole fragments with free positions.For Communication 31, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1200–1202, September, 1993.     

Investigations of Imidazoles. 101. Synthesis of 2,3-Dihydroimidazo[1,2-a]pyrimidine from 2-Aminopyrimidine

Two novel preparative methods have been developed for the synthesis of 2,3-dihydroimidazo[1,2-a]pyrimidine from 2-aminopyrimidine. These are the reaction with 1,2-dibromoethane and also the reaction with ethylene chloro(bromo)hydrin, subsequent treatment of 1--hydroxyethyl-2-imino-1,2-dihydropyrimidine with thionyl chloride, and cyclization of the intermediate 1--chloroethyl-2-imino-1,2-dihydropyrimidine in the presence of sodium hydroxide.     

Pseudo-cross-conjugated mesomeric betaines. 1. Synthesis of pseudo-cross-conjugated mesomeric betaines from quinoxaline derivatives

A new method for the synthesis of pseudo-cross-conjugated mesomeric betainic heterocyclic compounds with an angular nitrogen atom has been developed consisting in the reaction of 1,4-dielectrophile — -carbethoxy-2-(3-chloro)quinoxalylacetonitrile with azoles. Experimental regularities have been studied and a reaction mechanism has been proposed including the stage of formation of an ylide from a quaternary azolium salt. A pseudo-crossconjugated mesomeric betainic heterocyclic compound containing a thiazole ring compound has been synthesized for the first time.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1528–1533, November, 1992.     

Withasteroids ofPhysalis. III. Physanolide and 4β-hydroxywithanolide E

Two withanolides have been isolated from the epigeal part ofPhysalis viscosa L. One of them with the compositions C₂₈H₃₈O₈ has been identified as 4-hydroxy-withanolide E, and for the second, which has been called physanolide, the structure of 14,17,20R-trihydroxy-1,4-dioxo-22R-witha-5,24-dienolide has been proposed on the basis of its UV, IR, PMR, and mass spectra, and also the results of a partial synthesis of 14-hydroxyandrost-5-ene-1,4,17-trione, obtained by its oxidation.Institute of the Chemistry of Plant Substances, Academy of Sciences of Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 187–192, March–April, 1981.     

Reaction of Naphtho- and Benzimidazolequinones with Enamines. Synthesis of Condensed Benzofurans and Indoles

The reaction of naphthoquinone with nitroenamines and the interaction of benzimidazolequinones with derivatives of -aminocrotonic ester have been studied. It was shown that in the first case only the synthesis of naphthofurans occurs but in the second imidazoindoles are formed.     

Transformed steroids. 133. Synthesis of 20-deoxysteroids with a tetrahydropyran ring E

The synthesis of 20-deoxy compounds — the precursors of the steroid pyranols and pyranones synthesized by the authors previously — has been effected from a steroid 20-ketotetrahydropyran by the hydrogenolysis of the corresponding ethylene dithioketal with Raney nickel. The¹H and¹³C NMR spectra have been studied in detail. Transformations of rings A and B via the epoxide or the 3,5-cyclosteroid have led to 3-acetoxy-16,23-epoxy-5H-21,24-dinorchol-5-en-6-one and 3-acetoxy-5-hydroxy-16,23-epoxy-21,24-dinorchol-5-en-6-one.N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 732–735, November–December, 1983.     

Alkoxy group facilitated ring closing metathesis (RCM) of acyclic 1,6-dienes. Convenient synthesis of non-racemic highly substituted cyclopentenols

Alkoxymethyl groups at the C-5 allylic position of 1,6-dienols have been found to accelerate RCM reactions significantly with the Grubbs’ catalyst PhCHRu(PCy₃)₂Cl₂. This phenomenon has been used for direct access to highly substituted cyclopentenols, potential intermediates in the synthesis of carbovir, abacavir and BCA.     

Beiträge zur Chemie der Pyrrolpigmente, 72. Mitt.

A strategy for the synthesis of bilatrienes-abc bridged between rings A and C has been developed and tested in case of a bibenzylethane bridging fragment. This strategy was then applied to the synthesis of a 2,3-dihydrobilatriene-abc bridged by a (S)-lysine moiety from ring A to ring C (positions 3 and 12) by means of peptide bonds between the two amino groups of lysine and the acetic and propionic acid side chains of the chromophoric unit. The two diastereomers resulting from the two chiral centers of the lysine residue and at position 3 of the chromophore were separated by chromatography.

     

Synthesis and some reactions of selenopheno[2,3-c]pyrylium salts

The catalytic acylation and subsequent heterocyclization of -acetonyl derivatives of selenophene have been investigated. Methods have been proposed for the synthesis of new heteroaromatic systems: salts of the selenopheno[2,3-c]pyrylium cation and of selenopheno[2,3-c]pyridine. Methods have been developed for the synthesis of selenophene-3-carbaldehydes and 3-acetonylselenophenes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 918–922, July, 1973.     

Bispyrazole[3,4-b∶4′,3′-e]pyrazines as. self-condensation products from 4,5-diaminopyrazoles

Bispyrazolo[3,4-b4,3-e]pyrazines have been obtained by self-condensation of 4,5-diaminopyrazoles and their structures confirmed by independent synthesis. The spectral data for these compounds is discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1222–1225, September, 1988.     

Phthalocyanines and related compounds: XXXVIII. Synthesis of symmetric taurine- and choline-substituted phthalocyanines

Procedures have been developed for the synthesis of a series of metal complexes derived from water-soluble anionic and cationic octa-4,5-carboxyphthalocyanine-taurine and choline conjugates.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1907–1911.Original Russian Text Copyright © 2004 by Mikhalenko, Soloveva, Lukyanets.For communication XXXVII, see [1].This revised version was published online in April 2005 with a corrected cover date.     

Studies of imidazo[1,2-a]benzimidazole derivatives. 21. Synthesis of haloketones in the imidazo[1,2-a] benzimidazole series

Methods for the synthesis of imidazo[1,2-a]benzimidazole haloketone derivatives have been investigated. It has been found that -bromoketone derivatives of this heterocycle can be prepared either by bromination of 3-acylimidazo[1,2-a]benz-imidazoles with bromine in glacial acetic acid or by acylation of 3-unsubstituted imidazo[1,2-a]benzimidazoles with haloanhydride derivatives of -bromoalkanoic acids. Treatment of imidazo[1,2-a]benzimidazoles with 3-chloropropionyl chloride results in the formation of imidazo[1,2-a]benzimidazolyl-3-propionyl chloride and bis(imidazo[1,2-a]benzimidazolyl)propan-3-one derivatives as side products. Reaction of 2-phenylimidazo[1,2-a]benzimidazoles with 3-bromopropionic acid in polyphosphoric acid gives benzocyclohepten[5,6:4,5]imidazo[1,2-a]benzimidazole derivatives.For Communication 20, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 339–345, March, 1986.     

Preparation and reactivity of metal-containing monomers. 11. Complexes of nickel(II), cobalt(II), and chromium(III) acrylates with 2,2′-dipyridyl and 1,10-phenanthroline

A procedure has been developed for the synthesis of complexes of nickel(II), cobalt(II), and chromium(III) with 2,2-dipyridyl and 1,10-phenanthroline. On the basis of data obtained by elemental analysis, DTA, IR and UV spectroscopy, and magnetochemistry, it has been established that the coordination unit for these compounds has an octahedral structure, and splitting parameters have been calculated in the approximation of O_h symmetry. It has been shown that, in comparison with the acrylate complexes, their saturated analogs have longer metal-ligand bonds and lower degrees of covalency.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2468–2474, November, 1989.     

New Routes to Oxindole Derivatives

A new, practical synthesis of the antirheumatic oxindole derivative, tenidap, has been elaborated. The new approach has initiated studies on the mechanism of the acylation reactions of oxindoles. Methods have been developed for the synthesis of 1-[alkoxy(or aryloxy)carbonyl]- and 1,3-di[alkoxy(or aryloxy)carbonyl]oxindoles starting from oxindoles. The route designed for tenidap has provided a facile access to several analogues, too.On another front, new reaction conditions are described, which turn Wenkerts synthesis of 3-alkyloxindoles (by Raney nickel induced alkylation of oxindoles with alcohols) into a highly efficient synthetic tool. The method has been extended to the synthesis of 3-alkyloxindoles from isatins and to the preparation of 3-(-hydroxyalkyl)oxindoles from oxindoles and isatins.     

Dextran derivatives I. Synthesis of O-aminoacyl derivatives of dextran

Conclusions 1. A method for the O-aminoacylation of dextran (polyglucin) has been proposed.2. The synthesis of O-aminoacyl derivatives of dextran containing residues of glycine, -aminoenanthic acid and N-acetyl-L-histidine has been effected.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 5, pp. 427–432, 1969     

Syntheses of some substituted sym-triazines

The synthesis of various -substituted propionimidic esters has been effected and the conditions of their conversion into the corresponding 2,4,6-triethyl-sym-triazine derivatives have been studied.     

Synthesis of the principal chain of the o-antigenic polysaccharides ofShigella flexneri. Communication 4. Synthesis of 1,3-di-o-acetyl-4,6-di-o-benzoyl-2-desoxy-2-phthalimido-D-glucopyranose and 1-o-acetyl-2-o-(3-o-acetyl-4,6-di-o-benzoyl-2-desoxy-2-phthalimido-β-D-glucopyranosyl)-3,4-di-o-benzoyl-L-rhamnopyranose

Conclusions Methyl-3-O-acetyl-4,6-di-O-benzoyl-2-desoxy-2-phthalimido--D-glucopyranoside and 1,3-di-O-acetyl-4,6-di-O-benzoyl-2-desoxy-2-phthalimido-D-glucopyranose have been obtained. These are conventional derivatives for the introduction of the 3-substituted 2-desoxy-2-amino--D-glucopyranose residue in oligosaccharide synthesis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1140–1145, May, 1985.For Communication 3, see [1].