Synthesis of Jasminaldehyde by Solid-Liquid Phase Transfer Catalysis Without Solvent,Under Microwave Irradiation

α-n-amylcinnamaldehyde (jasminaldehyde) was obtained with 82 % yield by solid-liquid phase transfer catalysis without solvent within 3 days at room temperature. By use of domestic microwave irradiation, the same yield was obtained within 1 minute at a power of 600 W.     

On the rate of convergence for central limit theorems of sojourn times of Gaussian fields

The aim of this paper is to control the rate of convergence for central limit theorems of sojourn times of Gaussian fields in both cases: the fixed and the moving level. Our main tools are the Malliavin calculus and the Stein method, developed by Nualart, Peccati and Nourdin. We also extend some results of Berman to the multidimensional case.     

Regioselective Hydrolysis of Cocaine and A Convenient Acylation Procedure by Benzoylecgonine

Regioselective hydrolysis of cocaine led, according to the reaction conditions, either to benzoylecgonine or to ecgonine methyl ester. Acylation with benzoylecgonine was readily achieved when benzotriazolyloxytrisdimethylamino-phosphonium (BOP) was used as a coupling agent.     

Internal Transfer Reactions in the Copolymerization of Vinyl Acetate with Chlorinated Monomers

In the copolymerization of vinyl acetate (A) with either vinyl chloride (C) or vinylidene chloride (V), an internal transfer (backbiting) reaction—of the C- or V-ended radi-cals on an antepenultimate A unit—is proposed to be responsible for the deviation of the copolymerization kinetics from the Lewis and Mayo theory. The deviations disappear if A is replaced by isopropenylacetate [I_p], Then one gets, for the I_p -C copolymerization. r_{I p} =0.35 and :r_c=2.4, and for I -V copolymerization, r_{I p}=0.13 and r_v=5.9. The internal transfer reaction causes the formation of branches which may be evidenced by NMR analysis of constant composition suspension A-C copolymers. A kinetic scheme is proposed and the corresponding reactivity ratios derived r_A=0.29, r_c=1.60, r=0.3 (radical resulting from the transfer reaction), and k_T=1500 (rate constant of the transfer reaction at 50°C). The distribution of branches is calculated together with the sequence distribution functions for the .A. or Cunits.     

Synthesis and Application of Epoxidized Natural Rubber

Abstract

North Vietnamese NR latexes were successfully epoxidized using peracetic acid at moderate temperature and pH range. The epoxide contents of pure epoxidized natural rubber (ENR) are from 5 to 70 mol%. The ENR products were characterized and determined by spectral and thermal analysis besides the chemical titration. Conditions of longlasting or excessive temperature, or high acidic pH led to side ring opened products, proved easily by IR, ¹H-NMR, and DSC analysis. The ENR were vulcanized using a semiefficient system. The epoxidation increased the adhesion between rubber and tire cord and metal. This effect becomes stronger beyond 25 mol% and tends to be limited at over 60 mol%. The ENRs were used to formulate special-purpose adhesives. The shear strength of the adhesive ranges from 32 to 45 kg/cm² for bonding rubber to nylon and rubber to metal, respectively.     

Redox‐responsive core cross‐linked micelles of poly(ethylene oxide)‐b‐poly(furfuryl methacrylate) by Diels‐Alder reaction for doxorubicin release

Redox‐responsive core cross‐linked (CCL) micelles of poly(ethylene oxide)‐b‐poly(furfuryl methacrylate) (PEO‐b‐PFMA) block copolymers were prepared by the Diels‐Alder click‐type reaction. First, the PEO‐b‐PFMA amphiphilic block copolymer was synthesized by the reversible addition‐fragmentation chain transfer polymerization. The hydrophobic blocks of PFMA were employed to encapsulate the doxorubicin (DOX) drug, and they were cross‐linked using dithiobismaleimidoethane at 60 °C without any catalyst. Under physiological circumstance, the CCL micelles demonstrated the enhanced structural stability of the micelles, whereas dissociation of the micelles took place rapidly through the breaking of disulfide bonds in the cross‐linking linkages under reduction environment. The core‐cross‐linked micelles showed fine spherical distribution with hydrodynamic diameter of 68 ± 2.9  nm. The in vitro drug release profiles presented a slight release of DOX at pH 7.4, while a significant release of DOX was observed at pH 5.0 in the presence of 1,4‐dithiothreitol. MTT assays demonstrated that the block copolymer did not have any practically cytotoxicity against the normal HEK293 cell line while DOX‐loaded CCL micelles exhibited a high antitumor activity towards HepG2 cells. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3741–3750     

Cinchona based squaramide catalysed enantioselective Michael addition of α-nitrophosphonates to aryl acrylates: enantioselective synthesis of quaternary α-aminophosphonates

Several cinchona based squaramide catalysts were applied to the asymmetric Michael addition of α-nitroethylphosphonates to acrylic acid aryl esters, resulting in high yields and enantioselectivities. The absolute configuration of one of the quaternary α-nitrophosphonate adducts was deduced from its experimental and calculated CD spectra. The adducts were reduced to their cyclic aminophosphonates by catalytic hydrogenation.