Fatty-acid composition and secondary metabolites from slightly polar extracts of the aerial part of <Emphasis Type="Italic">Primula macrocalyx</Emphasis>

Flavones 2′,5′-dimethoxyflavone, 3′-methoxy-4′,5′-methylenedioxyflavone, 3′,4′-dimethoxyflavone, 5,6,2′,3′,6′-pentamethoxyflavone, and 5,6,2′,3′,5′,6′-hexamethoxyflavone; salicylates, methyl-4-methoxysalicylate and peonol; and bisbibenzyl polyphenol riccardin C were isolated for the first time from the acetone extract of the aerial part of Primula macrocalyx Bge. The content of free and total fatty acids was determined by GC and GC—MS. Palmitic (16:0), octadecatetraenoic 18:4 (6,9,12,15), linoleic 18:2 (9,12), and α-linolenic 18:3 (9,12,15) were the principal acids from the aerial part of Primula macrocalyx. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 457–460, September-October, 2008.     

Investigations on 2,3′-biquinolines. 18. New convenient one-pot synthesis of 1′-alkyl-1′,4′-dihydro-2,3′-biquinolyl-4′-thiones and their conversion into 1′-alkyl-1′,4′-dihydro-2,3′-biquinolyl-4′-ones

A method has been developed for the one pot synthesis of 1′-alkyl-1′,4′-dihydro-2.3′-biquinolyl-4′-thiones based on the reduction of 1-alkyl-3-(2-quinolyl)quinolinium halides with sodium borohydride and subsequent thiolation. 1′-Alkyl-1′,4′-dihydro-2,3′-biquinolyl-4′-ones were obtained in close to quantitative yield by the oxidation of 1′-alkyl-1′, 4′-dihydro-2,3′-biquinolyl-4′-thiones. For Part 17 see [1]. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 67–70, January, 2006.     

Investigations on 2,3′-Biquinoline. 17. Regioselectivity of the Halogenation of 2,3′-Biquinoline Derivatives

A method has been developed for the synthesis of bromo and chloro derivatives of 2,3′-biquinoline and 2,3′-biquinolones based on the bromination and chlorination in various media. It was found that the bromination of 2,3′-biquinoline in strongly acidic medium occurred on the 2-quinoline fragment and in weak acid on the 3-quinoline and that it takes place via a stage of formation of a dihydro derivative. 1′-Alkyl-1′, 4′-dihydro-2,3′-biquinolin-4′-ones and 1′-alkyl-1′,2′-dihydro-2,3′-biquinolin-2′-ones are halogenated at position 6′. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1372–1377, September, 2005.     

Investigation on 2,3′-biquinolyl series. 21. Reactions of 1′-alkyl-4′-aryl-1′,4′-dihydro-2,3t′-biquinolyls and 1′-alkyl-2′-aryl-1′,2′-dihydro-2,3′-biquinolyls with sulfur

A method has been developed for the synthesis of 2′-and 4′-aryl-2,3′-biquinolyls based on the reaction of 1′-alkyl-2′-aryl-1′,2′-dihydro-2,3′-biquinolyls and 1′-alkyl-4′-aryl-1′,4′-dihydro-2,3′-biquinolyls with sulfur in DMF. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1517–1519, October, 2006.     

Investigations on 2,3′-Biquinolyl. 16. The Regioselectivity of Reduction of 1-Alkyl-3-(2-quinolyl)quinolinium and 1,1′-Dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-biquinolyl Iodides Using Metallic Zinc,Lithium and Potassium

The reaction of 1-alkyl-3-(2-quinolyl)quinolinium iodides with excess zinc in THF gives a diastereomeric mixture of 1,1′-dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolyls. An excess of lithium in THF gives a mixture of 1′,2′-dihydro-2,3′-biquinolyl and 1′-alkyl-1′, 4′-dihydro-2,3′-biquinolyl with the former predominating. The reduction by lithium in THF of 1,1′-dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolyls leads to analogous products. Reduction of 1-alkyl-3-(2-quinolyl)quinolinium iodides by metallic potassium gives 1-alkyl-1′,4′-dihydro-2,3′-biquinolyls. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1208–1212, August, 2005.     

Synthesis of a Bifunctional 1,1′-Diphenyl-1,2,3,4-tetrahydroquinoline Derivative: 1,1′-Diphenyl-1,2,3,4,1′,2′,3′,4′-octahydro-6,6′-biquinolinyl-3,3′-diol

Summary. Intramolecular cyclization of N,N′-di(3-chloro-2-hydroxy)propyl-N,N′-diphenylbenzidine occurs to give bis-1,2,3,4-tetrahydroquinoline derivative 1,1′-diphenyl-1,2,3,4,1′,2′,3′,4′-octahydro-6,6′-biquinolinyl-3,3′-diol.     

Investigations on 2,3′-biquinoline series. 19. Regioselectivity of the reaction of 1,1′-dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolines with organomagnesium and organolithium compounds

1,1′-Dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolines react with organolithium and organo-magnesium compounds to form 1′-alkyl-2′-R-1′,2′-dihydro-2,3′-biquinolines. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, 224–226, February, 2006.     

Investigations of 2,3′-biquinolines 23. Synthesis of 1′-R-1′,4′-dihydro-2,3′-biquinolin-4′-ones by Claisen condensation

A method has been developed for the synthesis of 1′-R-1′,4′-dihydro-2,3′-biquinolin-4′-ones based on the interaction of quinaldine with N-alkyl-N-formylanthranilic acid methyl esters under the conditions of the Claisen condensation. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 409–410, March 2008.     

Synthesis, structures, and properties of spiro[6-azaperimidine-2,4′-cyclohexa-2′,5′-dien]-1′-one derivatives

The reaction of 5-amino-4-chloroquinolines with 4-amino-2,6-di-tert-butylphenol yielded derivatives of spiro[6-azaperimidine-2,4′-cyclohexa-2′,5′-dien]-1′-one, which exhibit photo-and thermochromic properties in solutions. The structure of 2′,6′-di-tert-butyl-5,7,9-trimethylspiro[6-aza,-2,3-dihydroperimidine-2,4′-cyclohexa-2′,5′-dien]-1′-one was established by X-ray diffraction study. The ring-chain isomerization of 2′,6′-di-tert-butyl-5,7-dimethyl-and 2′,6′-di-tert-butyl-5,7,8-trimethylspiro[6-aza-2,3-dihydroperimidine-2,4′-cyclohexa-2′,5′-dien]-1′-ones was studied by dynamic NMR spectroscopy. Deceased. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2028–2034, November, 1997.     

A novel compound from <Emphasis Type="Italic">Flos carthami</Emphasis> and its bioactivity

A novel compound, 4-{1′-hydroxy-1′-mercapto-1′-[1′′-2′′(N→O)-isoquinolyl]}yl-1-benzoic acid (1), together with six known compounds, 6-hydroxykaempferol-3-O-β-D-glucopyranoside (2), rutin (3), quercetin-3-O-β-D-glucopyranoside (4), kaempferol-3-O-β-D-glucopyranoside (5), cartormin (6), hydroxysafflor yellow A (7), were isolated by chromatography from the n-BuOH fraction of 50% ethanol extraction of Flos carthami. Their structures were elucidated on the basis of spectral analysis and comparison with published data. Among them, compound 1 was shown to possess a weak protective effect against cerebral ischemic damage in rats. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 339–341, May–June, 2009.     

Synthesis of conjugates of 2′,3′-dideoxynucleoside-5′-monophosphates with α-amino acids

Previously undescribed conjugates of 2′,3′-dideoxyuridine-5′-monophosphate-(L)-methoxytryptophylphosphoramidate (5) and 2′,3′-dideoxycytidine-5′-monophosphate-(L)-methoxytryptophylphosphoramidate (7) were isolated by a chemical enzymatic method in order to study their pharmacological properties and to prepare new medicinal preparations based on them. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 173–175, March–April, 2006.     

Pyridoxal-5′-phosphate-dependent catalytic antibodies

Cofactors—i.e., metal ions and coenzymes—extend the catalytic scope of enzymes and might have been among the first biological catalysts. They may be expected to efficiently extend the catalytic potential of antibodies. Monoclonal antibodies (MAbs) against N^α-phosphopyridoxyl-l-lysine were screened for 1) binding of 5′-phosphopyridoxyl amino acids, 2) binding of the planar Schiff base of pyridoxal-5′-phosphate (PLP) and amino acids, the first intermediate of all PLP-dependent reactions, and 3), catalysis of the PLP-dependent α, β-elimination reaction with β-chloro-D/L-alanine. Antibody 15A9 fulfilled all criteria and was also found to catalyze the cofactor-dependent transamination reaction of hydrophobic D-amino acids and oxo acids (k′ _cat=0.42 min⁻¹ with D-alanine at 25°C). No other reactions with either D- or L-amino acids were detected. PLP markedly contributes to catalytic effecacy—it is a 10⁴ times more efficient acceptor of the amino group than pyruvate. The antibody ensures reaction specificity, stereospecificity, and substrate specificity, and further accelerates the transamination reaction (k′ _cat(Ab)/k′ _cat(PLP)=5×10³). The successive screening steps simulate the selection criteria that might have been operative in the evolution of protein-assisted psyridoxal catalysis.     

Investigations on 2,3′-biquinolines 22. Novel and convenient method for the synthesis of benzo[5,6]indolizino-[2,1-<Emphasis Type="Italic">b</Emphasis>]quinolinium-13-thiolates and benzo-[5,6]indolizino[1,2-<Emphasis Type="Italic">c</Emphasis>]quinoline-6(5H)-thiones

We have developed a method of synthesis of benzo[5,6]indolizino[2,1-b]quinolinium-13-thiolates and 5,6-dihydrobenzo[5,6]indolizino[1,2-c]quinoline-6-thiones based on the reaction of the corresponding 1′, 2′-dialkyl-1′,2′-dihydro-2,3′-biquinolines and 1′,4′-dialkyl-1′,4′-dihydro-2,3′-biquinolines with sulfur in DMF. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 849–851, June, 2007.     

New flavanones from Scutellaria phyllostachya roots

The new natural flavanones (+)-5,2′-dihydroxy-6,6′,7-trimethoxyflavanone and (+)-5,2′-dihydroxy-6,6′,7,8-tetramethoxyflavanone in addition to the known flavones chrysin, norwogonin, and wogonin were isolated from Scutellaria phyllostachya roots. The structures of the isolated compounds were established using IR, UV and PMR spectra. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 24–25, January–February, 2008.     

Energy basis of recognition of base pair for platinum-based antitumour drug ZD0473 and cisplatin

Platinum-based antitumour drug ZD0473 was designed to reduce the cisplatin resistance to the tumor cells. In this paper, the mixed method of molecular mechanics and quantum chemistry, HF/lanl2dz// MM/uff and B3LYP/lanl2dz//6-31G*, are used to investigate the differences between four types of GG, 3′AG5′, 3′GA5′, and AA complexes, which are formed from four discrete DNA fragments recognized by ZD0473 and cisplatin. The results show that the binding interaction of both ZD0473 and cisplatin drugs with the GG base pair is much stronger than with other base pairs, namely the recognition capability of such drugs to the GG base pair is more considerable. Moreover, the interaction of four complexes of ZD0473 with DNA fragments is stronger than that of cisplatin with corresponding DNA fragments, which indicates the stronger binding capability of ZD0473 with DNA fragments and high antitumour activity of ZD0473. The main reason for easier forming of 3′GA5′ complex than the 3′AG5′ one is that the drug molecule prefers to bind with a single G base to form a monoligand compound firstly; then the con- figuration transformation from such monoligand compound to the bi-ligand one is limited.     

Synthesis and investigation of the stability of esters of 6′-carbamoylmethylthio-5′-cyano-1′,4′-dihydro-3,4′-and-4,4′-bipyridine-3′-carboxylic acids 1. Esters of 6′-carbamoylmethylthio-5′-cyano-1′,4′-dihydro-3,4′-bipyridine-3′-carboxylic acids

Esters of 6′-carbamoylmethylthio-5′-cyano-1′,4′-dihydro-3,4′-bipyridine-3′-carboxylic acids are obtained by the alkylation of piperidinium 3′-alkoxycarbonyl-5′-cyano-1′,4′-dihydro-3,4′-bipyridine-6′-thiolates with iodoacetamide. For an HPLC study of the stability of solutions of the abovementioned 1,4-dihydrobipyridines (solution pH 2.3–9.0) the appropriate esters of 6′-carbamoylmethylthio-5′-cyano-3,4′-bipyridine-3′-carboxylic acids and esters of 8-cyano-5-methyl(or phenyl)-3-oxo-7-pyridin-3-yl-2,3-dihydro-7H-thiazolo[3,2-a]pyridine-6-carboxylic acids were synthesized as reference compounds. Analysis by HPLC was carried out under conditions of reverse-phase chromatography. It was shown that solutions of the investigated compounds in a mixture of acetonitrile and phosphate buffer (pH 3.0–5.0) were stable for 1 month on storage protected from light. Under the action of light in all the solutions investigated irrespective of pH the formation occurs of the corresponding esters of 6′-carbamoylmethylthio-5′-cyano-3,4′-bipyridine-3′-carboxylic acids. The presence of esters of 8-cyano-5-methyl(or phenyl)-3-oxo-7-pyridin-3-yl-2,3-dihydro-7H-thiazolo[3,2-a]pyridine-6-carboxylic acids (no more than 4%) was detected only in 0.1% solutions of phosphoric acid (pH 2.3) under conditions of storage of the latter protected from light. A series of as yet unidentified products was detected in solutions of pH 7.0–9.0. Dedicated to E. Lukevics on his 70th birthday __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 59–68, January, 2007.     

Molecular recognition and supramolecular self-assemblies of (±)-2,2′-dihydroxy-1,1′-binaphthyl with aromatic aza compounds

Abstract  (±)-2,2′-dihydroxy-1,1′-binaphthyl (binol) co-crystallized with 1,10-phenanthroline-5,6-dione and acridine to afford co-crystals (Binol)·(1,10-phenanthroline-5,6-dione) 1 and (Binol)·(acridine)₂ 2, respectively. Co-crystal 1 crystallizes in space group P-42(1)c, with a = 14.9921(4), b = 14.9921(4), c = 20.8102(12) ?. Co-crystal 2 crystallizes in space group P2/c, with a = 17.8004(19), b = 10.0093(11), c = 19.393(2) ?, and α = γ = 90°, β = 103.187(2)°. In co-crystal 1, the components form an infinite 1D polar array; whereas in 2, the components form discrete three-component aggregates. Graphical abstract   Molecular recognition and supramolecular self-assemblies of (±)-2,2′-dihydroxy-1,1′-binaphthyl with aromatic aza compounds Baoming Ji, Shaobin Miao, Dongsheng Deng As a result of mutual recognition, (±)-binol with 1,10-phenanthroline-5,6-dione and acridine afforded co-crystals 1 and 2, respectively. In 1 the components form an infinite 1D polar array, whereas in 2 the components form discrete three-component aggregates.      

Heterogenous catalytic method for the synthesis of biquinolines and bipyridines

A method has been developed for the synthesis of 2,2′- and 3,3′-biquinolines and of 4,4′-bipyridine based on the coupling of 2- and 3-bromoquinoline or 4-bromopyridine using a Pd/C-hydrazine-KOH catalytic system. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1839–1840, December, 2008.     

Investigations in 2,3′-biquinoline series 24. Synthesis of 3-hetarylquinolines and their 1,4-dihydro derivatives under conditions of the Vilsmeier reaction

Methods have been developed for the synthesis of 2,3′-biquinolines, their 1′,4′-dihydro derivatives, 3-pyrid-2-ylquinolines, and 3-pyrazin-2-ylquinoline based on the interaction of hetarylethylenes and vinyl butyl ether with imidoyl chlorides and Vilsmeier complexes. Using the example of the synthesis of 3-hetarylquinolines and their dihydro derivatives the synthetic possibilities of the Vilsmeier method were shown for creating various bonds in different quinoline nuclei of the bisheterocyclic system. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1209–1215, August, 2008.     

Thermal decomposition of 2,2′-dipyridyl and 4,4′-dipyridyl complexes with rare-earth elements in air atmosphere

The present work provides data concerning thermal decomposition of 2,2′-dipyridyl(2-dipy) and 4,4′-dipyridyl(4-dipy) with rare-earth elements (Ln) based on literature and our own sustained studies which comprised about 100 complexes.

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Zusammenfassung Ausgehend von Literaturangaben und unseren eigenen Untersuchungen von mehr als 100 Komplexen liefert vorliegende Arbeit Angaben zur thermischen Zersetzung von 2,2′-Dipyridyl(2-dipy) und 4,4′-Dipyridyl(4-dipy) mit Seltenerdenelementen (Ln).