The synthesis of 5- and 6-hydroxy-2-methylisoquinuclidine

The reduction of the isomeric 5,6-epoxy-2-carboethoxyisoquinuclidines with lithium aluminum hydride afforded 5- and 6-hydroxy-2-methylisoquinuclidine. Contrary to expectation essentially single epimers were obtained for each alcohol.     

Synthesis and modeling study of (2S,5R,6R)- and (2S,5R,6S)-6-hydroxy- 8-(1-decynyl)-benzolactam-V8 as protein kinase C modulators

[structures: see text] Both (2S,5R,6R)- and (2S,5R,6S)-6-hydroxy-8-(1-decynyl)benzolactam-V8 were designed and synthesized as PKC modulators. Biological assays reveal the (6R)-ligand to be 20-fold more potent than its (6S)-counterpart in binding to PKC alpha.     

Synthesis and properties of 7-hydroxy-8-phenylxanthine and its derivatives. Disproportionation to derivatives of 8-phenylxanthine and 6-amino-5-nitrosouracil

8-Phenyl, 8-(p-methoxyphenyl) and 8-(p-chlorophenyl)-7-hydroxyxanthine were synthesized by ring closure of 6-amino-5-nitrosouracil with benzaldehyde, p-methoxybenzaldehyde and p-chlorobenzaldehyde, respectively. The disproportionation of these products to the corresponding 8-phenylxanthines and 6-amino-5-nitrosouracil was studied. The dependence of the rate of the reaction on the various substituents was studied. The disproportionation reaction is inhibited by the polarophilic ethyl acetylenedicarboxylate and enhanced by phosphate.     

1-Methyl-2-[2-(8-hydroxy-5-chinolyl)vinyl]-8-hydroxychinoliniumchlorid

Ohne Zusammenfassung     

Preparation of 1-aminomethylenemercapto derivatives of 2, 4, 6, 8-tetrathiaadamantane and adamantane

1-Aminomethylenemercapto derivatives of 3, 5, 7, 9, 9-pentamethyl-2, 4, 6, 8-tetrathiaadamantane and adamantane were obtained by aminomethylation of 3, 5, 7, 9, 9-pentamethyl-2, 4, 6, 8-tetrathiaadamantane-l-thiol and adamantane-1-thiol.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 658–660, May, 1976.     

Preparation,characterization, reactivities and electrochemistry of some homo- and heterodinuclear complexes of 2-hydroxy-5- methylbenzene-1,3-dicarbaldehyde and 1,3-diacetyl- 2-hydroxy-5-methylbenzene

Homo- and heterodinuclear complexes of composition [M₂L₂](ClO₄)₂·4H₂O, [CuML₂](ClO₄)₂·nH₂O (M = Ni, Co or Mn; L = L¹ or L²) and [CuML²Cl₂]·2H₂O (M = Ni or Co) have been synthesized with the dinucleating ligands 2-hydroxy-5-methyl- benzene-1,3-dicarbaldehyde (HL¹) and 1,3-diacetyl-2-hydroxy-5-methylbenzene (HL₂). These compounds have been characterized and their chemical reactivities investigated. The electrochemical behaviour of [M₂L₂²](ClO₄)₂·4H₂O and [CuML₂²](ClO₄)₂·nH₂O complexes have been examined in acetonitrile and dimethyl sulfoxide using Hg and Pt electrodes. The cyclic voltammograms obtained with a Hg electrode show quasi-reversible electron transfers for both metal centres that often get complicated due to decomplexation of metal ions and adsorption phenomena. On a Pt electrode irreversible electron transfers occur at more negative potentials.     

Synthesis of (+)-(R)-5-hydroxy-6-hydroxymethyl-7-methoxy-8-methylflavanone

The synthesis of (+)-(R)-5-hydroxy-6-hydroxymethyl-7-methoxy-8-methylflavanone is described. A new chromylation method of β-ketosulfoxide 9 leading to the Michael acceptor 12 has been developed. Dilithium tetrachlorocuprate was shown to be a very efficient catalyst for the conjugate addition reaction of phenyl magnesium bromide to the α,β-unsaturated sulfoxide 12. The instability of the obtained adducts 10 represents a limitation in terms of yield. It was confirmed that the natural flavanone leridol does not possess the structure of title compound 1.     

Enzymatic resolution of 5-hydroxy- and 8-hydroxy-2-tetralols using immobilized lipases

(R)-2-Tetralol (R)-2a, (R)-5-hydroxy-2-tetralol (R)-2b and (R)-8-hydroxy-2-tetralol (R)-2c, which are key intermediates in the synthesis of pharmacologically active 2-aminotetralins 3, were prepared in moderate to very high enantiomeric excess (up to 99% ee) by enzymatic resolution of the corresponding racemic butyrates rac-1a, rac-1b and rac-1c, respectively, using lipases immobilized on octyl agarose. This methodology is an alternative to the microbial reduction of 2-tetralones.     

Conversions of 5-hydroxy-5, 6-dihydro-4H-1, 2, 5-oxadiazines

Oxidation of 5-hydroxy-5, 6-dihydro-4H-1, 2, 5-oxadiazines leads to the formation of 6H-1,2, 5-oxadiazine-5-oxides. Acid treatment of 5, 6-dihydro-4H-1, 2, 5-oxadiazines and 6H-1, 2, 5-oxadiazine-5-oxides results in heterocyclic-ring contraction with the formation of imidazole 3-oxides and 1-hydroxyimidazole 3-oxides. The structures of the products are established by their spectral properties and confirmed by independent synthesis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1264–1266, September, 1970.     

Synthesis and investigation of 2-(2-quinolyl)-5, 6-benzocinchoninic acid and its derivatives

2-(2-Quinolyl)- and 2-(4-phenyl-2-quinolyl)-5,6-benzocinchoninic acids were synthesized, and their derivatives were obtained and decarboxylated. The UV and IR spectra of the compounds were studied, and it was found that all of the new compounds form colored Cu(I) complexes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 239–241, February, 1973.     

Synthesis and Alkylation of 4-(2-Chlorophenyl)-3-cyano-6-hydroxy-5-(2-thienoyl)-6-trifluoromethylpiperidin-2-thione

4-(2-Chlorophenyl)-3-cyano-6-hydroxy-5-(2-thienoyl)-6-trifluoromethylpiperidin-2-thione, which was used for the synthesis of 2-allylthio-4-(2-chlorophenyl)-3-cyano-6-hydroxy-5-(2-thienoyl)-6-trifluoromethyl-1,4,5,6-tetrahydropyridine, was obtained by the reaction of 2-thienoyltrifluoroacetone with 2-chlorophenylphenylmethylenecyanothioacetamide or with a mixture of 2-chlorobenzaldehyde and cyanothioacetamide in the presence of N-methylmorpholine. The molecular and crystal structure of the piperidinthione have been established by X-ray crystallography.     

The autorecycling oxidation of benzylamine by synthetic 8-hydroxy-5-deazaflavin derivatives

Various 8-hydroxy-5-deazaflavin derivatives were synthesized as the model compounds of coenzyme F₄₂₀-These compounds oxidized benzylamine to benzaldehyde more efficiently than the corresponding 8-unsubstituted 5-deazaflavins.     

Cyanine dyes from derivatives of 4-, 5-, and 6-trifluoromethylindolenines

The synthesis of 2,3-dimethyl-5- and -6-trifluoromethylindoles and 2,3,3-trimethyl-4-, -5-, and -6-trifluoromethylindolenines, from which quaternary salts, as well as indocarbo- and di- and tricarbocyanine dyes were obtained, is described. The effect of the introduction of a trifluoromethyl group in the 4, 5, and 6 positions on the color of the indocyanine dyes is examined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 47–51, January, 1982.     

Indolizines. 6. Relative reactivities of isomeric 6-, 7-, and 8-ethoxycarbonylindolizine derivatives

The kinetics of the alkaline hydrolysis of 2-phenyl-6-, -7-, and -8-ethoxycarbonylindolizines were studied. The rate constants for the hydrolysis of these compounds and the indexes of the dissociation constants of 2-phenylindolizine-6-,-7-, and -8-carboxylic acids were determined by spectrophotometry. The indexes of the electronic structures and reactivities of 2-methyl-6-, -7-, and -8-ethoxycarbonylindolizines were calculated from theory.See [1] for Communication [5].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 627–633, May, 1979.     

C nucleosides II. Preparation of 2-β-d-ribofuranosylbenzothiazole, 5-β-D-ribofuranosyltetrazole,and 5-β-glycosyl-1,3,4-oxadiazole derivatives

The conversion of 5--D-ribofuranosyl cyanides to the corresponding 2--ribofuranosylbenzothiazoles (under the influence of 2-aminothiophenol) and to 5--glycosyltetrazoles (by reaction with sodium azide and ammonium chloride) is described. It is shown that acylation of the latter structures with acetic anhydride or benzoyl chloride is a convenient method for the synthesis of 5--glycosyl-1,3,4-oxadiazoles.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 893–896, July, 1978.