Investigations of 2,3′-biquinolyl. 9. Reaction of 1′,4′-dihydro-2,3′-biquinolyl with organolithium compounds

The 1,4-dihydro-2,3-biquinolyl reacts with organolithium compounds to form the mixture of 4-R-1,4-dihydro-2,3-biquinolyls and 2-R-1,2-dihydro-2,3-biquinolyls in the ratio analogous to the conversion in the series of 2,3-biquinolyl. The utilization of the complex, the organolithium compound-TMEDA, in this process leads, after treatment of the reaction mixture with water, exclusively to 2-R-1,2-dihydro-2,3-biquinolyls. Treatment with methyl iodide leads to 1-methyl-2-R-1,2-dihydro-2,3-biquinolyls.     

Friedel-Crafts Polymers. I. Self-Polycondensation of 4,4′-Dichloromethyldiphenyl Ether

Friedel-Crafts self-polycondensation of 4,4′-dichloromethyl-diphenyl ether (DDE) is studied under various experimental conditions. These polymer samples are infusible and are insoluble in all solvents. The polymer samples, PDs, are characterized by elemental analysis, IR spectral study, and by TGA. Polymer reaction products of one polymer sample are prepared by subjecting it to Friedel-Crafts reaction with excess benzene and by treating it with triethylamine. Both the polymer reaction products are found to be less stable than the parent polymer sample.     

Bisindoles. 31. Synthesis of new derivatives of 2,5′- and 3,5′-bis-1H-indoles

Using p-aminoacetophenone as starting material, new derivatives of 2,5- and 3,5-bis-1H-indoles containing amino, nitro, acetyl, and ester groups have been prepared.For Communication 30, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1194–1199, September, 1993.     

Spirophosphoranes D′ α-Cetoacides. Structure Cristalline. Induction Asymetrique

Des couples d'énantiomères diastéréoisomères de spirophosphoranes ont été préparés en faisant réagir le trichlorophosphane sur l'acide céto-2-glutarique. Par cristallisation sélective, un couple a été isolé dont la structure a été déterminée par diffraction des rayons X. Les sels de triéthylammonium de thiolo et sélénospirophosphoranes ont été obtenus en faisant réagir le soufre ou (et) le sélénium sur les spirophosphoranes préparés à partir des acides phénylpyruvique et céto-2-glutarique. Tous ces résultats ont été rationalisés par des calculs semi-empiriques.     

Thermal Degradation of Polymers. IV. Poly-2,2′-(m-phenylene)-5,5′-bibenzimidazole

The thermal decomposition of poly-2,2′-(m-phenylene)-5,5′-bibenzimidazole has been investigated at temperatures to 916°C. Mass-spectrometric thermal analysis (MTA), supported by elemental analysis of residues at various stages of a thermogravimetric analysis, was used to determine product distribution as a function of temperature. Below 550°C, the major product is water. Above 550°C, degradation of the heterocyclic structure to hydrogen cyanide, ammonia, carbon monoxide, and water begins. Hydrogen and methane probably are formed from decomposition and condensation of the carbocyclic structure. Activation energies for the formation of each major product were derived from the MTA data. The average of these is somewhat temperature-dependent but agrees within experimental error with the value of 44 ± 11 kcal obtained from isothermal kinetics. A mechanism involving initial hydrolysis of the polymer to an amine-substituted polyamide is postulated. Subsequent homolytic reactions account for formation of the major products.     

Investigations in the region of 2,3′-biquinoline. 3. Synthesis of 2′-alkyl(aryl)-1′,2′-dihydro-2,3′-biquinolines and 2′-alkyl(aryl)-2,3′-biquinolines

A method was developed for the synthesis of 2-alkyl(aryl)-1,2-dihydro-2,3-biquinolines, based on the addition of organolithium compounds to 2,3-biquinoline in the presence of tetramethylethylenediamine. Their oxidation with manganese dioxide led to 2-alkyl(aryl)-2,3-biquinolines.For Communication 2, see [1].Stavropol State University, Stavropol 355009, Russia. Russian Chemical-Technology University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 350–354, March, 1998.     

Aromatische Spirane, 23. Mitt.: Darstellung von unsymmetrisch substituierten Dimethyl-2,2′-Spirobiindan-1,1′-dionen

Summary Both spirodiketones7 and8 were obtained as a mixture (56:44) by treatment of dicarbonic acid5 with polyphosphoric acid (PPA).5 was accessible from dimethylester3, synthesized byretro-Claisen reaction between1 and2. In the same way,30 was obtainedvia 27. The preparation of the pure spiro compounds7 and8, resp., was achieved by aldol reaction between9 and10 or9 and16, resp. Short treatment of the resulting compounds11 and17 with diazomethane yielded the methylbenzoates12 and18. Prolonged reaction (several hours) gave the pyrazole compounds14 and19, resp., which were also obtained (several days) from phthalides14 and20. The latter were formed from the benzylidene compounds11 and17, resp., by heating.11 and17 (after hydrogenation to15a and21a) were cyclized either withPPA or thermically to the spiro compounds7 and8. The main product20 was cyclized thermically to8 after reduction with zinc to a mixture of21a and8 (20:75).

     

Studies in the area of 2,3′-biquinolyl. 1. Arylation and hetarylation of 2,3′-biquinolyl dianion

The 2,3-biquinolyl dianion, when reacting with aryl- and hetaryl halides, forms arylation products at the 4 position, and treatment of these products with alkyl halides or water yields 1-alkyl-4-aryl-1,4-dihydro-2,3-biquinolyls or 4-aryl-1,4-dihydro-2,3-biquinolyls, respectively. Oxidation of the latter yields 4-aryl-2,3-biquinolyls. The cation dependence of the arylation reaction is demonstrated.Stavropol' State University, Stavropol' 355009. Russian Chemical Engineering University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1094–1099, August, 1997.     

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.     

8,8′-Bis(diphenylphosphinomethyl)-1,1′-binaphthyl. Synthese und Konformation

Summary The title compound3 was prepared from 8,8-Bis(bromomethyl)-1,1-binaphthyl (1) in two steps in approx. 10% overall yield. The crystal structure of the intermediate phosphinoxide2 was determined. Attempts to prepare chelate complexes of3 with Ni(II) or Pd(II) failed.

     

Transformations of β-d-xylofuranosyl nucleosides. Synthesis of 3′-azido-3′-deoxythymidine

A modified synthesis of 3′-azido-3′-deoxythymidine starting fromD-xylose is proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2062–2063, October, 1998.     

Vinyl Polymerization. CLXVII. Vinyl Polymerization Initiated with p-Methoxy p′-nitrobenzoyl Peroxide

It was described in the literature that p-methoxy-p′-nitrobenzoyl peroxide decomposed homolytically in benzene, but heterolytically in acetone. However, in the present study the polymerizations of styrene and acrylonitrile were found to proceed always through radical mechanism in benzene, dimethylformamide, or acetone. And in the above various solvents, the rate of polymerization was found to be almost equal.     

Studies on Flavans. III. The Total Synthesis of (±)-7,4′-Dihydroxy-3′-methoxyflavan, (±)-7,3′-Dihydroxy-4′-methoxyflavan,and (±)-7,4′-Dihydroxyflavan

Abstract

The first total synthesis of (±)-7,3′-dihydroxy-4′-methoxyflavan (1) and (±)-7,4′-dihydroxy-3′-methoxyflavan (2), along with the synthesis of (±)-7,4′-dihydroxyflavan (3), three naturally occurring flavans, were described. The key step is the cyclization of 1,3-diaryl-1-propanol by BF₃·Et₂O.     

Untersuchungen über Phenthiazinderivate, 13. Mitt.: Derivate des 10-(2′-Hydroxy-3′-amino-propyl)-phenthiazins

Ohne Zusammenfassung     

The electron-donating properties of 2,2′-bipyridine. Charge-transfer studies

Molecular charge-transfer complexes of 2,2′-bipyridine with iodine and tetracyanoethylene have been investigated. The formation constants of these complexes were determined at different temperatures and the thermodynamic functions, ΔH_f and ΔS_f were calculated. The spectra and stability of the complexes were discussed and interpreted.     

干扰素的功能表达机理——Ⅹ.ATP对ppp A2′p5′A2′p5′A受体的拮抗作用

pppA2′p5′A2′p5′A(2′-5′P_3A_3)受体可能是第一个寡核苷酸受体。但ATP能与2′-5′P_3A_3竞争此受体,那么ATP的作用是什么呢?本文证明ATP虽然对巨噬细胞的结合具有饱和性和可逆性,似乎是2′-5′P_3A_3受体的一个配基,但ATP并不能提高巨噬细胞的吞噬功能,而且当ATP和2′-5′P_3A_3同时作用于巨噬细胞时,ATP反而抑制2′-5′P_3A_3~′对巨噬细胞的生物效应。如果ATP先与巨噬细胞作用占据了2′-5′P_3A_3所要结合的位点后,再加2′-5′P_3A_3时,则2′-5′P_3A_3的结合能力和引起的生物学效应都明显地被阻断了,这表明,2′-5′P_3A_3的作用是通过它的受体而发挥的,ATP则可能是2′-5′P_3A_3受体的一个拮抗剂。     

4-Hydroxy-2-quinolones 146. Synthesis and structure of 1,1′-diallyl-4,4′-dihydroxy-1H,1′ H-[3,3′]biquinolinyl-2,2′-dione

The methyl ester of N-allyl-2-methoxycarbonylsuccinanilic acid is partially converted to 1,1′-diallyl-4,4′-dihydroxy-1H,1′H-[3,3t′]biquinolinyl-2,2′-dione in refluxing toluene in the presence of metallic sodium. A possible mechanism for the occurrence of these chemical processes is discussed. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1033–1038, July, 2008.     

Investigations in the region of 2,3′-biquinolyl 4. Alkylation of the dianion of 2,3′-biquinolyl

With alkyl chlorides and alkyl phenyl ethers the dianion of 2,3-biquinolyl forms the products from alkylation at position 4. Their treatment with alkyl halides or water gives 1, 4-dialkyl-1, 4-dihydro-2,3-biquinolyls or 4-alkyl-1,4-dihydro-2,3-biquinolyls respectively.For communication 3, see [1].Stavropol State University, Stavropol, Russia 355009. Russian Chemical Technology University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1214–1217, September, 1998.     

2,2′-Dialkoxy, 2,2′-dihydroxy,and 2,2′-diamino derivatives of 1,1′-azobenzimidazole. The first synthesis of heterocyclic tetrazenes by means of a nucleophilic substitution reaction

2,2-Dimethanesulfonyl-1,1-azobenzimidazole is prepared by the oxidation of 1-amino-2-methanesulfonylbenzimidazole with lead tetraacetate. The reaction of this tetrazene with alkali in DMSO, with sodium alkoxides in the corresponding alcohol or ammonia, or with primary or secondary amines leads to the formation of 2,2-dihydroxy, 2,2-dialkoxy, or 2,2-diamino derivatives of 1,1-azobenzimidazole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 190–193, February, 1992.