Kinetics and mechanism of the reaction of benzoyl chloride with 4-(4′-N,N-dimethylaminostyryl)pyridine-N-oxide in toluene

The reaction of benzoyl chloride with 4-(4-N,N-dimethylaminostyryl)pyridine-N-oxide in toluene proceeds according to an addition—elimination mechanism. The rate and equilibrium constants of the individual steps were determined. An inhibiting effect of the substrate was detected.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 31, No. 5, pp. 316–318, September–October, 1995.     

Studies on Mechanisms and Blockade of Carcinogenic Action of Female Sex Hormones

Tumours of mice are induced by administration of Inj. Hydroxyprogesteroni Caproatis Co. (EP) in a practical subthreshold dose of carcinogenesis or 2. 5-5 times the human contraceptive dose (simply referred to as 2. 5- to 5-fold dose) combined with whole-body 0. 5 Gy gamma-ray irradiation. Malignant transformation of Syrian golden hamster embryo (SHE) cells is also induced by 5-fold dose of EP combined with 0. 3 Gy gamma-ray irradiation in vitro, thereby indicating that synergistic carcinogenesis can be obtained by combined use of physical and chemical carcinogens.The mechanisms of synergistic carcinogenesis have been further explained by cytogenetics, damage extent of the target cell DNA and production of free radicals. The Chinese traditional medicine with antioxidat-ing effect (Sulekang Capsule, SC), food additive--butylated hydroxyanisole (BHA) and green tea can effectively inhibit the carcinogenic effect of EP or EP combined with gamma rays in mice. They all have marked ability to scavenge or remove     

Action of Base on Methyl 6-Thio- (and 6-Deoxy-) 2-O-Methanesulfonyl-α-d-Glucopyranoside Derivatives1

Abstract

Treatment of methyl 4-O-benzoyl-3-O-tert-butyldiphenylsilyl-2-O-methanesulfonyl-6-thio-α-d-glucopyranoside (8) and its 6-deoxy analogue (11) with methanolic sodium methoxide, afforded methyl 2,3-anhydro-mannopyranoside derivatives as a consequence of an O₃ → O₄ TBDPS rearrangement. When the protecting group at C-3 was 2-methoxyethoxy methyl ether only deacylation and methanolysis of the methanesulfonyl group occurred.     

α-Amination of keto-nitrones via multihetero-Cope rearrangement employing an imidoyl chloride reagent

α-Aminations of ketone-derived nitrones have been developed via [3,3]-rearrangement of the intermediates generated upon condensation with imidoyl chlorides. Careful reagent selection provides synthetically attractive amino protecting groups. The enediamide or α'-carbamoyl enamide products can be hydrolyzed to the desired carbonyl, or exposed to electrophiles for further α-functionalization.     

Action of the Selenomorpholine Compounds on the Bacterium Growth by Microcalorimetry

The action of β-(N-selenomorpholine) ethyl phenyl ketone hydrochloride and 4-(N-selenomorpholine)-2-butanone hydro-chloride on Escherichia coli and Staphylococcus aureus was studied by microcalorimetry,Differences in their capacities to affect the metabolism of this bacterium were observed.The kinetics shows that the selenomorpholine compounds had action on the metabolism process of Escherichia coli and Staphylococcus aureus.The rate constant (k) of the studied bacterium in the presence of the drugs are concentration-dependant.The growth rate constants decrease with an increase in the mass of the selenomorpholine compounds ,but their relationship is different.As deduced from the rate constant(k) of the studied bacterium(in log phase )and the half inhibitory concentration (IC50),the experimental results reveal that the studied selenomorpholine compounds all have good antibiotic activity and better antibacterial activity on Staphylcoccus aureus than on Escherichia coli.     

Modifications based on coumarins. II. Synthesis ofα-monoglycerides of karatavic and galbanic acids and their phosphates

The synthesis has been performed of -monoglyceride derivatives of coumarins — karatavic and galbanic acids and their modified derivatives — phosphates. The structures of the compounds have been confirmed by IR, UV, PMR, and¹³C and³¹P NMR spectroscopies.A. B. Bekturov Institute of Chemical Sciences, Academy of Sciences of the Republic of Kazakhstan, Almaty Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 217–220, March–April, 1997.     

Structural defects in poly(vinyl chloride)—IV. Thermal degradation of vinyl chloride/acetylene copolymers

Vinyl chloride/acetylene copolymers have been prepared under subsaturation conditions. Copolymerization rates and molecular weights of the copolymers decrease with increasing concentration of acetylene in the monomer feed, indicating that acetylene is a retarder in vinyl chloride polymerization. The concentration of internal double bonds in the copolymers determined by ozonolysis increases with increasing amount of acetylene in the feed. Thermal degradation has been performed at 110 with solid samples and at 170° in solution under inert atmosphere. The extent of HCl loss as a function of time shows a rapid initial phase followed by a slower steady rate The initial dehydrochlorination rates are higher for copolymer samples containing higher concentrations of internal double bonds. Quantitative analysis of the u.v. and visible spectra of degraded copolymers shows that the sum of the concentration of polyenes with 4–12 conjugated double bonds increases rapidly in the first phase of degradation, but then decreases slowly, due to secondary reactions of polyene sequences.     

Microcalorimetric Study of the Action of Yb^3＋ ion on the Growth of Staphylococcus aureus

A microcalorimetric method was used to evaluate the action of Yb^3 ions onthe growth metabolism of Staphylococcus aureus.The power-time curves of the growth metabolism of Staphylo.coccus aureus and the action of Yb^3 ions were obtained by us-ing stopped-flow method at 37 ℃. For evaluation of the action,the growth rate constants ( k1 and k2) for the log phase 1, log phase 2, and the total heat effect (Qtotal) for Staphylococcus aureus were determined. The results show that Yb^3 ions at low concentrations have the stimnlatory effect on Staphylococcus au-reus and that Yb^3 ions at higher concentration could inhibit its growth.     

Thermodynamics of aqueous gallium chloride. Heats of solution and dilution at 25°C

The heat of solution of GaCl₃ and heats of dilution of single GaCl₃ solutions in water and of mixed GaCl₃−HCl solutions in HCl solutions (with a fixed HCl concentration of 0.1337 mol-kg⁻¹ HCl) up to 4 mol-kg⁻¹ GaCl₃ were measured at 25°C. While in the acid solutions hydrolysis is suppressed to below 0.5% of total gallium concentration, the measurements in water allow evaluation of the effect of hydrolysis on the relative enthalpy. The Pitzer interaction model for excess properties of aqueous electrolytes was used to interpret the change in relative enthalpy with concentration. Pitzer parameters were derived by statistical inference using ridge regression. Their physical significance is supported by the heat of solution data. The measurements yield the following results for standard heats of formation and Pitzer parameters for the relative molar enthalpy at 25°C: With these parameters the overall variance in the partial molar heat of solution at infinite dilution, extrapolated from the present experiments, is minimized to 0.35 kJ²-mol⁻², while the experimental apparent molar heats of dilution are reproduced on average within 2.7 kJ-mol⁻¹.     

Structural defects in poly(vinyl chloride)—V. Thermal and photodegradation of copolymers of vinyl chloride with various acetylene derivatives

Vinyl chloride has been copolymerized with various acetylene derivatives in bulk at 50. It has been shown by ozonolysis that these copolymers contain a significantly increased amount of internal double bonds. A comparison of the thermal and photodegradation behaviours of the copolymers has been made. The built-in double bonds show an effect on the reactivity of the adjacent allylic chlorine depending on the electron-withdrawing or repelling nature of the substituent. Among the comonomers investigated, copolymers containing 3-chloropropine have the least reactive defect sites, because of the electron-withdrawing chloromethyl substituent. On the contrary, the electron-repelling n-butyl group, built-in by using hexine-1 as comonomer, results in enhanced reactivity of the allylic chlorines.     

Physical–chemical properties of nickel analogs ionic liquid based on choline chloride

In this paper, a homogeneous, green analogs ionic liquid containing choline chloride and nickel chloride hexahydrate is formed. The structure of the analogs ionic liquid is preliminary investigated by Fourier transform infrared spectroscopy. It is shown that the nickel chloride hexahydrate bond via hydrogen bonds with choline chloride and urea. The physico-chemical properties of the analogs ionic liquid such as viscosity, conductivity, density, and thermal stability are measured as a function of temperature and composition. The thermal expansion coefficients (r), the molar Gibbs energy of activation (ΔG*) for viscous flow, the molar enthalpy of activation (ΔH*), and the molar entropy of activation (ΔS*) for viscous flow have been calculated. A straight-line equation is used to fit the density data while the Arrhenius equation is used to fit both viscosity and conductivity. Thermal stability of analogs ionic liquid was carried out from room temperature to 973.15 K. It indicates that analogs ionic liquid is stable from room temperature to 488.2 K.     

Studies on Agarofurans Ⅷ.Synthesis of the Metabolites of 4—Butyl—α—agarofuran

The structures of five metabolites (2-6) of agarofuran 1 were confirmed by synthesis. The configuration of the secondary hydroxyl in 7 was determined by Horeau′s method. The configuration of C-2 in compound 4 and 5 was determined by their stereochemistry and NMR.     

Conjugate additions on α-phenylthio-α,β-unsaturated oxazolines. Novel synthesis of 3,4-disubstituted coumarins.

Nucleophilic addition of organolithium, Grignard and hydride reagentsto α-phenylthio-α,β-unsaturated oxazolines is regioselective and occurs in a 1,4-fashion. This leads to a novel, versatile synthesis of polysubstituted coumarins.     

Propane transformations on aluminum chloride—cobalt chloride clusters: a quantum chemical study

Density functional PBE/TZ2p quantum chemical calculations of activated complexes and pathways of model catalytic transformations of propane under the action of aluminum chloride-cobalt chloride ionic bimetallic complexes were carried out. The formation of an intermediate with a broken C-C bond can occur on the cationic cluster CoAlCl₄ ⁺ characterized by the strongest coordination of propane molecule. The activation barrier to the reaction is ΔG = 25.0 kcal mol⁻¹. Activation of alkane C-H bonds follows the alkyl pathway involving the formation of bimetallic alkyl complexes. The interaction of activated hydrocarbon fragments bound to transition metal atoms in cobalt-chloroaluminate clusters can result in alkane metathesis products (in this case, ethane and a polymetallic cluster containing an extendedchain alkyl radical).     

Studies on Agarofurans Ⅱ.Stereoselective Synthesis of 1α-and 1β-Methyl Agarofuran

AgarOfuransPOssessbioactivityonthenervous-System('>.InordertoinvestigaetherelationbetWeenthesiteOfsubstituentsandthebioactivity,weplannedtointroducesubstitUentsontoseveralchosensites.HerewedescribetheSynthesisofla-andlp-methy1grofuran1and2,WhichhavenotbeenpreviouslyrePOrted.Thekeyintermediatesenroutetogrofuranland2wereenone3and4.OUrinitialroutewasreaCtionofdihydrocarvone(6)with3-pentene-2-one(1O)toaffordaAnxtUreof3and4withoutemPhasizingthestereochendStry(Schemel).ReduCtionofcarvone(5)…     

Microcalorimetric Studies of the Toxic Action of La^3＋ on Halobacterium Halobium R1 Growth

A microcalorimetric technique was used to evaluate the influence of La^3 on Halobacterium halobium R1 growth.By means of LKB-2277 bioactivity monitor,ampoule methos at 37℃,the thermogenic curves of Halobacterium halobium R1 growth were obtained.In order to analyze the results,the maximum power Pm and the growth rate constants k were determined,showing that values of Pm and k are linked to the concentration of La^3 .Addition of low concentration of La^3 can cause a decrease of the maximum heat production and growth rate constant.However,high concentration of La^3 may promote growth of Halobacterium halobium R1,but at much higher concentration of La^3 ,the growth of Halobacterium halobium R1 is inhibited again.For comparison,the shapes of Halobacterium halobium R1 cell were observed by means of transmission electron microscope.According to the thermogenic curves and TEM photos of Halobacterium halobium R1 under different conditions,it is clear that metabolic mechanism of Halobacterium halobium R1 growth is changed with the addition of La^3 .     

Influence of counteranions on catalytic ability of immobilized laccase in Cu-alginate matrices： Inhibition of chloride and activation of acetate

Laccase is a promising oxidase with environmental applications, such as lignin degradation and chlorophenol detoxification. Laccase immobilization can significantly improve physiochemical stability and reusability compared to the free enzymes. In this work, anion effect was investigated in entrapment of Cu-alginate matrix with five types of anions, including perchlorate(ClO4à), nitrate(NO3à), sulfate(SO42à), chloride(Clà), and acetate(CH3CO2à). Accordingly, chloride inhibition and acetate activation were detected in the o-tolidine kinetic experiments, while effects of the other three anions were much smaller. Such counteranion effects were also observed in the laccase-catalyzed biodegradation of 2,4-dichlorophenol. The results indicated that counteranions in the enzyme immobilization process are crucial for catalytic capacity, probably due to the competition with the carboxylate groups in alginate.Our results also imply that these anions might coordinate the copper cations in laccase.