Zur Kenntnis des m,m′-Divinylazobenzols und des m,m′-Divinylazoxybenzols

Ohne Zusammenfassung     

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.     

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。     

Optimisation of pressurised liquid extraction for the determination of p,p′-DDT and p,p′-DDE in aged contaminated Ethiopian soils

The effectiveness of extracting p,p′-DDT and p,p′-DDE from aged contaminated soil samples by means of pressurized liquid extraction (PLE) was evaluated. Two soil samples, which were contaminated more than 10 years ago, were used in the investigation. The static extraction time was optimised and then validated against the total sum of target analytes obtained from multiple sequential extractions. The PLE results were also compared with Soxhlet extraction (SOX). PLE for 3×10 min at 100 °C was proven to be more exhaustive than SOX in the determination of p,p′-DDE from both soil samples. In the case of p,p′-DDT, PLE was found to be equally as exhaustive as SOX. Additionally, most of the previous PLE investigations used hazardous organic solvents such as n-hexane, toluene and dichloromethane mixed with acetone, whereas in this investigation the less toxic solvent combination n-heptane/acetone has been employed.     

Synthesis of p,p ′-Phenolphthaleinbis(trimellitic) Dianhydride

p,p′-Phenolphthalein-bis(trimellitic) dianhydride was obtained by the reaction of diacetyloxyphenolphthalein with trimellitic anhydride. The structure of the new compound was proved by elementary analysis, infrared spectroscopy, and acid value determination. The course of acidolysis reaction was examined in the temperature range of 240–280°C. The compound obtained is a powder having a melting point of 135–138° C, has high thermal stability, and is easily soluble in many organic solvents and low-molecular epoxy resins. Application of p,p′-phenolphthalein-bis(trimellitic) dianhydride in synthesis of soluble polyester-imides and as a hardening agent for low molecular weight epoxy resins is proposed.     

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.     

Donor-acceptor interaction of p,p′-dimethoxystilbene with α,β-dinitrostilbene

A study was carried out on the interactions of the Z and E forms of the indicated stilbenes in all four possible combinations. Charge transfer complexes are formed and only Z-p,p-dimethoxystilbene converts to its E form.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 210–211, January, 1992.     

Processable Heat-Resistant Polymers. IX. Synthesis and Properties of Polyamideimide from N-(p-Carboxy Phenyl) Trimellitimide and p,p′-Di-(amino Phenyl) Sulfone

A novel polyamideimide was synthesized by reacting p,p′-di-(amino phenyl) sulfone and N-(p-carboxy phenyl) trimellitimide or its diacid chloride derivative. The polymer was found to be soluble in highly polar solvents. The polymer was characterized by elemental analyses and IR spectrum. It is found to be amorphous and of low molecular weight. The polymer is fairly thermostable, having a T of 210–220°C. Thermogravimetric determination revealed that the polymer underwent 17% weight loss at 375°C in air. The dielectric constant of the polymer at 1 kHz was 3.74 at 30°C. The electrical conductivity of the polymer was also measured.     

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.     

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.     

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.     

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.