Polymerization of 1,2-epoxy-4-epoxyethylcyclohexane

Radiation-induced polymerization of 1,2-epoxy-4-epoxyethylcyclohexane (EECH) has been carried out at different temperatures in solid and liquid states. Activation energy was calculated from Arrhenius plot and ionic mechanism was proposed. Molecular weights for some polymer samples were determined by cryscopic method and compared with their intrinsic viscosities. Cationic polymerization of EECH initiated by BF₃ · O(C₂H₅)₂ and anionic polymerization initiated by NaOH are also studied. Two epoxy rings can be opened for polymerization selectively by radiation, but not by chemical initiators. The expected polyether structure was observed from the IR spectrum. Polymers obtained were shown to be amorphous from X-ray photographs.     

Electrochemical study of 1,2-Naphthoquinone-4-sulphonate and 1,2-Naphthoquinone semicarbazone

Summary A study of the electrochemical characteristics of 1,2-naphthoquinone-4-sulphonate, sodium salt, and of the semicarbazone of 1,2-naphthoquinone (Naftazone) was carried out using d.c., a.c. and d.p. polarography and cyclic voltammetry. Changes in the waves as a function of concentration and pH indicate evidence of adsorption phenomena at the potential of the reduction wave. These techniques also indicate the formation of a mercury derivative in the case of Naftazone. The quantitative determination of these two compounds is possible by polarography. Limits of detection are 5×10^–6 and 5×10^–8 M, respectively.

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Elektrochemische Untersuchung von 1,2-Naphthochinon-4-sulfonat und 1,2-Naphthochinon-semicarbazon

Zusammenfassung Die elektrochemischen Eigenschaften von 1,2-Naphthochinon-4-sulfonat und -semicarbazon (Naftazon) wurden mit Hilfe der Gleichstrom-, Wechselstrom und Differentialpuls-Polarographie sowie der cyclischen Voltammetrie untersucht. Veränderungen an den Stufen in Abhängigkeit von Konzentration und pH-Wert deuten auf Adsorptionsvorgänge beim Potential der Reduktionsstufe hin. Im Falle von Naftazon wurde die Bildung eines Quecksilberderivats nachgewiesen. Beide Substanzen können polarographisch mit Nachweisgrenzen von 5×10^–6 bzw. 5 × 10^–8 M bestimmt werden.

     

Synthesis of 1,2-dialkyl-4-pyrazolidinols

Condensation of 1,2-dialkylhydrazines with epichlorohydrin affords 1,2-dialkyl-4-pyrazolidinols in moderate yield.     

Reactions of 4-hydroxy-4-methyl-2-pentynonitrile with 1,2-ethanediol

The reaction of 1,2-ethanediol with 4-hydroxy-4-methyl-2-pentynonitrile in the presence of a catalytic amount of metallic sodium or triethylamine leads to 2,5-dihydro-5,5-dimethyl-2-imino-4-(2-hydroxyethoxy)furan.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1671–1673, July, 1991.     

Condensation of 1,2-dihydro-7-methoxy-4-vinylnaphthalene with 3,5-dimethyl-3-cyclopentene-1,2-dione

Summary Unlike 2-(3,4-dihydro-6-methoxy-1-naphthyl)ethenol acetate (I) [4-(2-acetoxyvinyl)-1,2-dihydro-7-methoxy-naphthalene], the diene of analogous structure -1,2-dihydro-7-methoxy-4-vinylnaphthalene (III)-in condensation with 3,5-dimethyl-3-cyclopentene-1,2-dione (II) forms an adduct (IV) which contains a 15- and not a 17-keto group. The orientation in the diene condensation is determined by the presence, or absence, of an electronegative substituent in the 1-position of the diene of type (III).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1058–1061, June, 1965     

Beiträge zur Chemie des Phosphors. 111. 1,2-Dichlor-1,2-di-tert-butyldiphosphan

Contributions to the Chemistry of Phosphorus. 111. 1,2-Dichloro-1,2-di-tert-butyl-diphosphane The reaction of tri-tert-butyl-cyclotriphosphane, (t-BuP)₃, with phosphorus(V) chloride (molar ratio 1:2) leads to the title compound Cl(t-Bu)P? P(t-Bu)Cl ( 1 ), which is remarkably stable against disproportionation reactions. As the first 1,2-dichloro-1,2-diorganyldiphosphane, 1 has been isolated in a pure state and was thoroughly characterized. At room temperature, 1 exists in a mixture of the d,l and meso form (about 20:80). The mutual repulsion of the negative polarized Cl atoms and their preferred gauche arrangement to the free electron pairs of neighboured P atoms leads to a gauche-conformation of the lone electron pairs in the d,l- and to a trans-conformation in the meso-configuration.     

Optically active 4-substituted cis-1,2-diphenylethylene oxides and related 1,2-diphenylethane diols

Erythro 1-(4′-chlorophenyl)- and 1-(4′-methylphenyl)-2-phenylethane diols with [1S:2R] and [1R:2S] absolute stereochemistry were synthesized and converted to the corresponding 4′-substituted [1S:2R] and [1R:2S] cis-stilbene oxides by the following sequence: formation of 2-methoxydioxalanes, conversion to halohydrins and cyclization to cis epoxides. Substantial amounts of optically active 4′-substituted trans-stilbene oxides were also produced. The enzyme epoxide hydrase stereoselectivity adds water at the [S] carbon atom of the cis-stilbene oxides with inversion of configuration to produce [R:R] diols. Facile enzymatic resolution of cis - 1 - (4′ - nitrophenyl) - 2 - phenylethylene oxide was achieved. Optical properties, including CD spectra of the above compounds are described.     

Reaction of 4-methyl-1,2-phenylenediamine with acetoacetic ester

Depending on the reaction conditions, 4-methyl-1,2-phenylenediamine reacts with acetoacetic ester to form 4,7(or 8)-dimethyl-2,3-dihydro-1H-1,5-benzodiazepinones or 5(or 6)-methyl-1-isopropenylbenzimidazolones. During acid catalysis under mild conditions, the more basic diamine group initially reacts with acetoacetic ester to form ethyl 3-(2-amino-4-toluidino)-crotonate, which subsequently can be converted to the corresponding benzodiazepinone and 2,5-dimethylbenzimidazole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1556–1560, November, 1971.     

Facile Synthesis of 1,2-Dialkyl-3-Phenyl-4-Quinolinones

The synthesis of 1,2-dialkyl-3-phenyl-4-quinolinones (1) is readily accomplished by a low-temperature reaction of an N-alkylisatoic anhydride with the therraodynamic potassium enolate of phenyl-acetone. The reaction has also been extended to encompass the synthesis of the more complex 2-(3-hydroxy-propyl)-3-(4-fluorophenyl)-1-methyl-4(1H)-quinolinone (10).     

Esters of (1,2, 5-trimethyl-4-hydroxy-4-piperedyl)- and phenyl-(1,2, 5-trimethyl-4-hydroxy-4-piperidyl) acetic acids

The methyl ester of a new hydroxy acid of the piperidine series (-phenyl--(1,2, 5-trimethyl-4-hydroxy 4-piperidyl)acetic acid) has been prepared. Ethyl -(1,2, 5-trimethyl-4-hydroxy-4-piperidyl)acetate has been converted into the substituted pyridine, 1,1-diphenyl-2-(2-5-dimethyl-4-pyridyl)ethylene.     

A Novel Approach to 2,2-Disubstituted 1,2-Dihydro-4-phenylquinolines

The reaction of 2-(1-phenylvinyl)aniline and 4-chloro-2-(1-phenylvinyl)aniline with acetophenone derivatives, 1-(naphthalen-1-yl)ethanone and 1-(furan-2-yl)ethanone in toluene at 110–115° with toluene-4-sulfonic acid as a catalyst leads in good-to-excellent yields to the 2,2-disubstituted 1,2-dihydro-4-phenyl-quinolines 1–18 (Scheme 1, Table). The structure of the new racemic 1,2-dihydroquinolines 1–18 is determined by NMR spectroscopy. A reaction mechanism proceeding via a 6π-electrocyclic rearrangement of 2-(1-phenylvinyl)anils 19 as the key step is proposed for the formation of these compounds (Scheme 1). The scope and limitations of the novel methods are discussed (Scheme 2).     

Polyimides derived from 1,2-bis(4-aminophenoxy)propane

The diamine 1,2-bis(4-aminophenoxy)propane, containing the flexible 1,4-dioxa-2-methylbutyl-ene unit, was synthesized. Polyimidization was carried out with 5,5′-[2,2,2-trifluoro-(trifluoromethyl)ethylidine]bis-1,3-isobenzofurandione in m-cresol employing toluene as azeotroping agent to yield a polyimide that was soluble in a variety of solvents and had an inherent viscosity of 0.84 dL/g in N,N-dimethylformamide. Poly(amic acid) formation with pyromellitic dianhydride, 4,4′-carbonyldiphthalic anhydride, and 5,5′-[ethanediylbis(oxy)]-bis-1,3-isobenzofurandione was carried out in N,N-dimethylformamide with imidization completed by heating at 160°C for 24 h under vacuum. All of the polyimides exhibited a 5% weight loss in air and in helium by 420°C.     

4-[（Furan-2-ylmethylene）-amino]-1,5- dimethyl-1,2-dihyl-1,2-dihydo-pyrazol-3-one

1 INTRODUCTION Antipyrine (2,3-dimethyl-1-phenyl-5-pyrazolone) and its derivatives exhibit a wide range of biological activities and applications[1～3]. Antipyrine shows mi- nimal protein binding and is rapidly and complete- ly absorbed from the gastrointestinal tract and exten- sively metabolized by the cytochrome P450 liver en- zymes[4]. Estimates of half-life and systemic clear- ance of antipyrine have been used for the in vivo as- sessment of hepatic drug oxidation in different spe- c…     

Synthesis of derivatives of dihydro-1,2-oxazine and tetrahydro-1,2-diazine from (4-chlorobutanoyl)-alkoxybenzenes

The reaction of (4-chlorobutanoyl)alkoxybenzenes with hydroxylamine and 2,4-dinitrophenylhydrazine gave dihydro-1,2-oxazines and tetrahydro-1,2-diazines, respectively.Institute of Petrochemical Processes, Academy of Sciences of the Republic of Azerbaijan, 370025 Baku. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1685–1687, July, 1992.