Unsaturated lactones

New, biologically active pyrazole derivatives containing an unsaturated -lactone ring were obtained by condensation of 2-(1-etboxycarbonyl-1,3-diketopropyl)-2-buten-4-olides with phenylhydrazine and hydrazine hydrate. A number of transformations of the resulting pyrazole-3-carboxylic acid esters were realized.See [1] for communication XXXIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1611–1614, December, 1978.     

New synthesis of 2,4-dimethylfuro[3,2-<Emphasis Type="Italic">c</Emphasis>]quinolines

Thermal cyclization of ethyl -(2-chloro-2-propenyl)--arylaminocrotonates in mineral oil afforded the corresponding substituted 2,4-dimethylfuro[3,2-c]quinolines instead of the expected 4-hydroxy-2-methyl-3-(2-chloro-2-propenyl)quinolines.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004, pp. 1397–1398.Original Russian Text Copyright © 2004 by Avetisyan, Aleksanyan, Pivazyan.     

ESR study of the free radicals formed in the photolysis of α-ketofluorosulfates

ESR spectroscopy was used to establish that the UV irradiation of -ketofluorosulfates containing an OSO ₂ F group at a tertiary carbon atom gives radicals formed upon cleavage of the C-OSO ₂ F bond. If the OSO ₂ F group is attached to a primary or secondary carbon atom, we observe ordinary photodecomposition with cleavage of the acyl—carbon bond. The ESR spectra of the new radicals were studied. Replacement of fluorine by the OSO ₂ F group in the trifluoromethyl radical leads to compression of the radical site. Branched -oxoperfluoroalkyl radicals are not heteroallylic and the unpaired electron is localized largely on the carbon atom. The [(CF ₃ ) ₂ CF] ₂ C(O)CF ₃ radical is stable in the air.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 757–761, March, 1992.     

Oxidative coupling of aromatic compounds with trimethylbenzylsilane by the action of MoCl5

Conclusions The benzylation of aromatic compounds was carried out efficiently under mild conditions by the action of trimethylbenzylsilane in the presence of MoCl₅, AlCl₃, or WCl₆ with the formation of the corresponding diarylmethanes. The benzylation in the presence of MoCl₅ conforms to behavior typical of electrophilic substitution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1868–1870, August, 1987.     

Synthesis of Derivatives of (4-Methyl-2-Quinolylthio)acetic and (4-Methyl-2-Quinolylthio)propionic Acids

An efficient synthesis has been developed for derivatives of (4-methyl-2-quinolylthio)acetic and (4-methyl-2-quinolylthio)propionic acids by the reaction of 4-methyl-2-thioxoquinoline with methyl methacrylate, the amide of methacrylic acid, acrylonitrile, ethyl bromoacetate, and ethyl acrylate. The hydrolysis of the resultant intermediates by (quinolylthio)acetic and (quinolylthio)propionic acids gave the corresponding acid products, which are also formed in the reaction of 4-methyl-2-thioxoquinoline with chloroacetic and acrylic acids. The reaction of 4-methyl-2-thioxoquinoline with allyl bromide was studied. The potassium permanganate oxidation of the resultant 2-allylthio-4-methylquinoline led to (4-methyl-2-quinolylthio)acetic acid.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 403–406, April, 2005.     

Structure of 22-deoxocucurbitacins isolated fromBryonia alba andEcbalium elaterium

22-Deoxocucurbitacin D (II), dihydrocucurbitacin B, cucurbitacin L, and the previously unknown rhamnoglucosyl-22-deoxo-16,23-epoxycucurbitosides A (III) and B (IV) have been isolated from the roots ofBryonia alba and identified. Glucoside (III) has also been identified in the fruit ofEcbalium elaterium L.A. L. Mndzhoyan Institute of Fine Organic Chemistry, Academy of Sciences of the Armenian SSR, Erevan, Translated from Khimiya Prirodnyk Soedinenii, No. 5, pp. 679–687, September–October, 1985.     

Synthesis of acetylenic derivatives of 1,4-dioxane

Cyclic ketals — 2,5-dimethyl-2,5-bis(4-penten-2-ynyloxy)-1,4-dioxane and 2,5-dimethyl-2,5-bis(3-phenyl-2-propynyloxy)-1,4-dioxane — were isolated in the reaction of propargyl alcohol with vinyl- and phenylethynylcarbinols in the presence of HgO-BF₃.O(C₂H₅)₂ catalytic system.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1029–1030, August, 1986.     

Synthesis and Transformations of 4-(4-Ethoxycarbonylphenylamino)- and 4-(2-Carboxyphenylamino)quinolines

Synthesis was performed of 4-(4-ethoxycarbonylphenylamino)- and 4-(2-carboxyphenylamino)-2-methylquinolines by reaction of 2-methyl-4-chloroquinoline with anesthesin and anthranilic acid. In concentrated sulfuric acid 4-(2-carboxyphenylamino)-2-methylquinoline underwent cyclization into 6-hydroxy-7-methylquinolino[3,2-c]quinoline, and the alkaline hydrolysis of 4-(4-ethoxycarbonylphenyl-amino)quinoline afforded 2-methyl-4-(4-carboxyphenylamino)quinoline.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 786–787.Original Russian Text Copyright © 2005 by Avetisyan, Aleksanyan, Ambartsumyan.