SYNTHESIS OF SPIRO [1,3-BENZODIOXOLE-2,4′-(3′H) QUINAZOLINES]

Abstract

In the present investigation, the authors could obtain a new series of spiranes (1) through the reaction of the high potential quinone tetrachloro-o-benzoquinone with 2-aryl-3-phenyl-3H-quinazoline-4-thiones. Thus, 2,3-diphenyl- (2a), 2-p-tolyl-3-phenyl- (2b) and 2-p-anisyl-3-phenyl- (2c)-3H-quinazoline-4-thiones react readily with tetrachloro-o-benzoquinone, in boiling toluene, to give the corresponding spiro-1,3-benzodioxole-2,4′-(3′H)-quinazolines (1a-c), respectively.     

Pesticide‐conjugated polyacrylate nanoparticles: novel opportunities for improving the photostability of emamectin benzoate

Emamectin benzoate, a macrocyclic lactone, can be used in low quantities to control arthropod pests, effectively. However, its poor photostability prevents its further use. To delay its photodegradation, novel acrylate‐type polymeric nanoparticles were synthesized and tested as materials for improving pesticide photostability. N‐acylated emamectin benzoate was synthesized via bonding emamectin benzoate to acrylamide. The resulting pesticide, containing the double bond linkage –C=C–N–, was copolymerized with butyl acrylate and methyl methacrylate by the emulsion polymerization method. The refined polymers were characterized by Fourier transform infrared spectroscopy spectroscopy, and result illustrated the pesticide was conjugated to the polymers. Atomic force microscope and dynamic light scattering analyses were also used for determining the average particle diameters of pesticide–polymer conjugates. Photostability tests showed that the nanoparticles obtained exhibited greatly improved photostability. Additionally, the laboratory toxicity tests demonstrated that the insecticidal effects of the novel emamectin benzoate formulation were better than those of the control pesticide formulation (emamectin benzoate EC). Copyright © 2012 John Wiley & Sons, Ltd.     

Radiation-Induced,Solid-State Polymerization of Derivatives of Methacrylic Acid. XI. Aspects of the Polymerization of Methacrylic Acid by γ-Irradiation

Aspects of the radiation-induced polymerization of methacrylic acid in the crystalline state have been investigated and utilized to evaluate the mechanism of polymerization. In particular, results for post-irradiation polymerization at 0°C after radiation doses of 0.1 to 2.0 Mrad support the concepts of Lando and Semen that chain initiation essentially all commences at the same time, that chain propagation continues without termination, and that termination of nonpropagating radicals proceeds simultaneously.     

Crystallization Behavior of the System Poly(L-lactic Acid) and Pentaerythrityl Tetrabromide

Differential scanning calorimetry has been used to study the thermal crystallization of poly(L-lactic acid) (PLLA) and pentaerythrityl tetrabromide mixtures at different compositions. The melting temperature-composition phase diagram of the system reveals that PLLA forms a simple eutectic with pentaerythrityl tetrabromide, with a eutectic composition of 46% (w/w) of PLLA and a eutectic temperature of 422 K. Investigation of the microstructures obtained after removal of the diluent from the eutectic using scanning electron microscopy shows that the simultaneous crystallization of PLLA and the diluent proceeded in such a way that the diluent rods are the leading phases.     

Synthesis,Electrical Conductivity,Spectral and Thermal Stability Studies on Poly(aniline-co-o-nitroaniline)

o-Nitroaniline units were incorporated in the polyaniline backbone through copolymerization with aniline. The copolymers were synthesized for 1:3 and 1:1 molar ratios of aniline and o-nitroaniline in acidic medium using potassium persulphate as oxidant and their properties were compared with that of polyaniline. The polymers showed less electrical conductivity than polyaniline. Unlike polyaniline, the presence of nitro group caused higher frequency dependence of electrical conductivity. Electronic spectra showed a blue shift in both the band of the copolymers due to the decrease in the extent of conjugation leading to lower conductivity, which could also be explained in terms of a decrease of delocalization of electron as evinced from electron para magnetic resonance (EPR) data. Thermo gravimetric analysis (TGA) revealed that copolymer derived from 1:1 molar ratio showed comparable thermal stability with polyaniline and the one derived from 1:3 molar ratios is thermally less stable than polyaniline. Activation energies for thermal degradation were estimated using Broido equation. The temperature dependence of electrical conductivity suggested charge transport is mainly through variable range hopping.     

FT-RAMAN SPECTROSCOPIC STUDY OF THE FORMATION OF POLYENES DURING THERMAL DEGRADATION OF POLY(VINYL CHLORIDE) AND POLY (N-VINYL-2-PYRROLIDONE) BLENDS

In situ degradation of poly(vinyl chloride)/poly (N-vinyl-2- pyrrolidone) (PVC/PVP) blends has been studied by Fourier-transform Raman spectroscopy. PVP acts as a destabilizer in the thermal degradation of PVC as manifested by the reduction of temperature for the onset of degradation and the time the polymer is held at a particular temperature for this onset. Increasing the amount of PVP in the blends decreases the dehydrochlorination temperature and time. In blends containing high PVP concentrations, polyene bands dominate over nondegraded PVC bands. Maximum polyene lengths of around 35 were achieved. High PVP ratios and prolonged degradation at higher temperatures resulted in a decrease in mean polyene length due to crosslinking and oxidative scission.     

Thermal Degradation of HDPE in a Batch Pressure Reactor: Reaction Time and Mechanical Stirring Effect

The effect of reaction time and mechanical stirring on thermal degradation of high density polyethylene(HDPE) was studied at 350°C under nitrogen atomosphere in a batch pressure reactor. Changes in molecular weight(MW), molecular weight distribution (MWD), and crystalline behaviors of the degraded products were investigated by gel chromatography (GPC) and differential scanning calorimetry (DSC). It was found that MWD curves all shifted toward lower molecular weight with increasing reaction time, with both the extent of the movement and its showing a rapid initial drop and then leveling off. In a short period of reaction time, the MW, MWD and crystalline behaviors of the degraded products were affected notably by the mechanical stirring. The of the degraded products without stirring was lower than that of products with stirring in the same time, which should be related to the large difference of temperature distributions in the reactor. When the reaction time reached 4 h, the of the degraded products had dropped to about 5 × 10³g/mol from about 3 × 10⁵g/mol for the original , and the product did not show the melting and crystallization behaviors of high density polyethylene again.