KINETICS OF POLYMERIZATION OF ACRYLONITRILE INITIATED BY VANADIUM(V)-THIOUREA REDOX SYSTEM

The kinetics of polymerization of acrylonitrile (AN) initiated by quinquevalent vanadium (V~(5+))-thiourea (TU) redox system has been investigated in aqueous nitric acid in the temperature range from 30 to 50℃. The polymerization rate (R_p) can be expressed as follows: In the copolymerization of acryionitrile with methyl acrylate (MA), the reactivity ratios were found to be 1.0 and 1.1, respectively. The experimental observations suggest that the initiating species is probably a complex consisting of a central ion of Lewis acid-VO_2~+ and the ligands of Lewis bases-acrylonitrile, thiourea, and nitrate anions, while the initiating system in lower concentration, the polymerization of acrylonitrile does not occur if the thiourea is acidified prior to its reaction with quinquevalent vanadium. This indicates that the primary radicals (or the monomeric radicals in the present article) are produced by associated thiourea rather than isothlourea.     

18-冠-6与Eu(fod)3+在CCl4中的化学平衡及其配合物的结构

在室温下测定了CCl_4溶液中,18-冠-6的亚甲基、Eu(fod)的t—丁基质子的PMR化学位移与溶液组成的相互关系。提出了生成配合物RS,R_2S,R_2,R_3(S为18-冠-6,R为Eu(fod)_3)的模式。求得了平衡常数值(升/摩):K_1=[RS]/([R][S])=2.O×10~5,K_2=[R_2S]/([R][RS])=1.0×10~3,Q_1=[R_2]/[R]~2=4.2×10~2,Q_2=[R_3]/([R_2][R])=4.0×10~1。并测得在配合物RS,R_2S中18-冠-6质子的平均化学位移分别为4.90,10.84(ppm,相对于纯18-冠-6); 在配合物R,R_2,R_3,RS,R_2中t-丁基质子平均化学位移分别为1.53,2.33,0.54,1.02,2.42(ppm,相对于TMS)。 根据配合物的化学位移值,并考虑分子及分子轨道的对称性、位阻等因素提出了配合物R_2,RS,R_2S的可能的结构模型。     

Thionation of the monoacetal of pentacyclo[5.4.0.0.0.0]undecane-8,11-dione

As part of a programme to synthesize thione derivatives with pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane moieties it was decided to sulfurize the monoacetal 6 of pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane-8,11-dione 2. Unexpectedly the diol 9 was isolated as the product.     

Installation of carbon chain onto 2-cyclohexene-1,4-diol monoacetate

Alkylation of cyclohexenyl monoacetate 1 with R₂Cu(CN)(MgCl)₂ or RMgBr/CuCN (cat.) in Et₂O produced trans 1,2-isomers 4, while arylation and alkenylation of 1 was accomplished with lithium borates 5 and a nickel cat. to afford trans 1,4-isomers 3 selectively. Furthermore, several transformations of the products were carried out to demonstrate synthetic advantages of the present reactions.     

Redox troponization of (η5-cyclopentadienyl)(η4-4-menthyl-4-exo-trichloromethylcyclohexa-2,5-dien-1-one)rhodium as a novel approach to the synthesis of metal-coordinated nonbenzenoid aromatics of the tropone seriesas a novel approach to the synthesis of metal-coordinated nonbenzenoid aromatics of the tropone series

The possibility of redox troponization of a gem-polyhalomethylated semiquinoid system, π-coordinated to a metal atom, was shown in relation to the reaction of (η⁵-cyclopentadienyl)(η⁴-4-menthyl-4-exo-trichloromethylcyclohexa-2,5-dien-1-one)rhodium with Pd(PPh₃)₄. The reaction occurs with retention of the metal coordination affording a sevenmembered organometallic derivative of the nonbenzoid aromatic series, namely, (η⁵-cyclopentadienyl)(η⁴-4-chloro-5-menthylcyclohepta-2,4,6-trien-1-one)rhodium, whose structure was established by means of elemental analysis, NMR, and mass-spectral data. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1255–1256, June, 1998.     

Validated Enantioselective LC Method, with Precolumn Derivatization with Marfey’s Reagent, for Analysis of the Antiepileptic Drug Pregabalin in Bulk Drug Samples

An enantioselective high-performance liquid chromatographic method, with precolumn derivatization with Marfey’s chiral reagent, sodium 2,4-dinitro-5-fluorophenyl-l-alanine amide, has been developed for resolution of the enantiomers of a new antiepileptic drug, pregabalin, in the bulk drug. The diastereomers of the pregabalin enantiomers were resolved to baseline on a reversed-phase ODS column with a 60:40 (v/v) mixture of aqueous 0.2% triethylamine (pH adjusted to 3.5 with dilute orthophosphoric acid) and acetonitrile as mobile phase. Resolution between the diastereomers was not less than five. The method was extensively validated and proved to be robust. The calibration plot was indicative of an excellent linear relationship between response and concentration over the range 750 (LOQ) to 7,500 ng L⁻¹ for the R enantiomer. The limits of detection and quantification of the R enantiomer were 250 and 750 ng L⁻¹, respectively, for an injection volume of 10 μL. Recovery of the R enantiomer from bulk drug samples of pregabalin ranged from 97.5 to 101.76%. Solutions of pregabalin in water and in the mobile phase were found to be stable for at least 48 h. The method was found to be suitable and accurate for quantitative determination of the R enantiomer in the bulk drug. It can be also used to test the stability of samples of pregabalin.     

Chemical analysis for small amounts of horseradish peroxidase using “porphyrinogen” as a chromogenic reagent

The properties of porphyrinogen as a new chromogenic reagent were examined. 5,10,15,20-Tetrahydro-tetraphenylporphyrinogen (TPPN) is changed to 5,10,15,20-tetraphenylporphine (TPP) by the oxidative reaction involving six electrons, and its formation of the porphine ring significantly increased the absorbance in the Soret band.The horseradish peroxidase (HRP) accelerated the oxidative reaction as a catalyst and the increment of absorbance depended upon the increase in the concentration of HRP. The reaction proceeded in the presence of dissolved oxygen and in the neighborhood of pH 7. Based on these findings, a chemical analysis by catalytic action using HRP was developed.In the procedure for this determination, the difference in absorbance at 419 nm (ΔA₄₁₉=A_s−A_b, where A_s and A_b are the absorbances of the sample solution containing HRP and the blank solution without HRP after 30 min, respectively), was measured. The determination range of HRP, which was obtained from the ΔA₄₁₉—HRP concentration curve, was 0.05-1.0 mg/l. The relative standard deviation in the median of the calibration curve was 3.19% (seven determinations), and the detection limit (S/N=3) was 29 ng/l. Furthermore, when the proposed method was applied to the enzyme immunoassay, bisphenol A (BPA) was selectively and sensitivity determined.     

Oxidative Transformations of Organic Compounds Mediated by Redox Molecular Sieves

Zeolites are viewed by some as the “philosopher's stone” of modern chemistry.^[1] They are more or less indispensable in oil refining and petrochemicals manufacture where they are widely applied as solid acid catalysts. More recently attention has been focused on their use in the manufacture of fine chemicals. The synthetic utility of zeolites and related molecular sieves (zeotypes) has been considerably extended by the incorporation of redox metals into their frameworks. The resulting redox molecular sieves catalyze a variety of selective oxidations under mild conditions in the liquid phase. Their structural diversity–including variation of the redox metal, incorporation of metal complexes, and the size and polarity of the micropores–provides the possibility of designing tailor-made solid catalysts (“mineral enzymes”) for liquid-phase oxidations with clean oxidants such as O₂, H₂O₂, and RO₂H. Hence, they have enormous potential in industrial organic synthesis as environmentally friendly alternatives to traditional oxidations employing inorganic oxidants in stoichiometric amounts. A primary aim of this review is to familiarize organic chemists with the synthetic potential of redox molecular sieves. An outline of their synthesis, structures, and chemical properties, highlighting their unique advantages, is followed by a discussion of general (mechanistic) features that influence the choice of a suitable catalyst for a particular type of oxidation. The main part of the review deals with the oxidation of various substrates of synthetic interest–such as alkanes, alkenes, (alkyl)arenes, alcohols, and amines–and emphasizes the advantages of redox molecular sieves (including selectivity and stability) over their homogeneous counterparts. New directions towards truly biomimetic solid catalysts, for example zeolite-encapsulated chiral metal complexes as heterogeneous catalysts for asymmetric oxidations, are high-lighted.     

Synthesis of new diheteroarylcarbazoles: a facile and simple route of 3,6-di(pyrazol-4-yl)carbazoles

A short and facile route to the synthesis of new 3,6-di(pyrazol-4-yl)carbazoles is reported. Dipyrazolylcarbazoles were synthesized in two steps from 3,6-diacetylcarbazoles through a Vilsmeier reaction which led to the formation of carbazolyl-β-chlorovinyl aldehydes, followed by cyclization with hydrazine hydrate. The reaction of the Vilsmeier reagent with hydrazones of diacetylcarbazoles yielded the corresponding pyrazole dicarbaldehydes in good yields.