Facile Synthesis of Novel Pentofuranose Analogs of Phospha Sugar Derivatives

Novel pentofuranose analogs of phospha sugar derivatives were synthesized starting from 1-phenyl-2-phospholene 1-oxide ( 1 ). First, the allylic oxidation of 1-phenyl-2-phospholene 1-oxide ( 1 ) with CrO 3 in Ac 2 O-AcOH or 3-hydroxy-1-phenyl-2-phospholene ( 2 ) with MnO 2 afforded 1-phenyl-4-oxo-2-phospholene 1-oxide ( 3 ). The C-5 alkylation of 3 in the presence of NaH by using benzyl bromide or methyl iodide as electrophiles afforded the target title compounds.     

Polymerization of Acrolein by Imidazole

Polymerization of acrolein(AL) in the presence of imidazole(Im) has been investigated in tetrahydrofuran or methanol below room temperature. The polymers obtained, white or pale yellow powders, were found to be composed of vinyl polymer with one Im group attached and having an aldehyde side chain, of which 70–80 mole % of the aldehyde revealed bridge structure. The number-average molecular weight (M _n) of these polymers was determined to be in the range of 317 to 691. The rate of polmerization R_p was expressed by the equation, R + k[Im] [AL]².

The addition of water or dimethyl sulfoxide accelerated the polymerization reaction, while the presence of benzaldehyde or N,N'-dimethylformamide decreased R_p. The structure of addition products in the initial polymerization step was confirmed by IR and NMR spectra, and the observations of polymerization system was carried out by UV and NMR spectra. The polymerization mechanisms were discussed on the basis of these results.     

Kinetic Study of 1-β-Cyanoethyl Aziridine for Ring-Opening Polymerization Initiated with Alkyl Sulfate

The kinetics of the cationic polymerization of 1-β-cyanoethyl aziridine initiated 3-hydroxy- 1-propane sulfonic acid sultone and methyl tosylate have been studied. The course of polymerization involved the propagation stage and termination reaction due to the reaction between the growing chain and imino groups in the polymer chain. The propagation constants and termination constants were obtained. The enthalpies of activation for the propagation and termination reactions are ΔH_p? = 12.9 kcal/mol and ΔH_t? = 12.4 kcal/mol, and the entropies of activation are ΔS_p? = -31 cal/deg·mol and ΔS_t? = -39 cal/deg·mol. Otherwise, the polymerization initiated with methyl tosylate involved an early stage which was initiated very quickly.     

Kinetics of the Copolymerization of Methyl Vinyl Ketone and Acrylamide Initiated by the Adduct of Methyl Vinyl Ketone and Imidazole

N-(Butyl-3-one)imidazole acts as an initiating adduct which is formed in the anionic polymerization of methyl vinyl ketone (MVK) induced by imidazole (Im) and is directly formed from Im and the MVK monomer. The kinetics of the anionic homopolymerization of MVK and acrylamide (AAm) under argon in the presence of the adduct were investigated in tetrahydrofuran (THF). The rate of polymerization for the MVK system is expressed as R_p = k[Adduct] [MVK], where k = 3.1 × 10^?6 L/(mol·s)in THF at 30°C. The overall activation energy, E_a , was found to be 5.34 kcal/mol. The R_p for the AAm system is expressed as R_p = k[Adduct] [AAm], where k = 6.8 × 10^?6 L/(mol·s) in THF at 30°C, with E_a 7.78 kcal/mol. The mechanism of the polymerization induced by the initiator adduct is discussed on the basis of these results.     

Polymerization of N,N-Dimethylaminopropyl-Acrylamide Through Hydrogen Transfer Induced by the Propagation of the Polyacrolein Anion

The anionic polymerization of acrolein (AL) with N, N-dimethylamino-propylacrylamide (DMAPA) in the presence of water was investigated in tetrahydrofuran, benzene, and ethanol at 0°C in a nitrogen atmosphere. The resulting polymers were found to be essentially vinyl polymers with one DMAPA attached and an aldehyde side chain. From observations of the polymerization process by ¹H NMR, we find that polymerization was initiated by the hydroxyl anion formed in the thermodynamic equilibrium between the amine of DMAPA and water. The hydrogen transfer reaction of DMAPA was caused by the propagating poly-AL anion. On the other hand, the monomer reactivity ratios and the Q₂-e₂values of DMAPA were determined by the free-radical copolymerization of styrene (St, M₁) with DMAPA and AIBN as initiator.     

Mechanistic action of ferric oxide in the hydrosilylation of 1,6-divinyl(perfluorohexane) with trichlorosilane

In the hydrosilylation of 1,6-divinyl(perfluorohexane) (FDV) with trichlorosilane (TCS) in the presence of catalytic chloroplatinic acid (Pt-Cat) under an air atmosphere (0.99 MPa), a runaway reaction accompanied by a severe pressure release occurred when Fe₂O₃ was present as an impurity in the system. In this study, we investigated the mechanism of action of Fe₂O₃ on this hydrosilylation by monitoring the thermal behavior of TCS/FDV/Pt-Cat/Fe₂O₃ mixtures with various compositions, using an accelerating rate calorimeter (ARC). In the case of TSC/FDV/Pt-Cat, a typical hydrosilylation composition in the industrial process, heat release, possibly due to hydrosilylation, began at 90 °C. On the other hand, for TCS/FDV/Pt-Cat/Fe₂O, the heat release due to hydrosilylation was hardly observed, but abrupt heat and pressure releases occurred at higher temperatures (>170 °C). Like TCS/FDV/Pt-Cat/Fe₂O₃, TCS/FDV, which contain neither Pt-Cat nor Fe₂O₃, released heat and pressure at high temperatures (>210 °C), while the heat and pressure release rates were comparatively low. From these results, the runaway reaction may occur when hydrosilylation is prevented, and Fe₂O₃ behaves as a negative catalyst for hydrosilylation. In the FT-IR spectrum of TCS/FDV/Pt-Cat/Fe₂O₃ after heating, an absorption peak at approximately 1,710 cm^?1, which may be attributed to a carbonyl group, was observed. Thus, it is considered that the runaway reaction observed during the hydrosilylation results from the action of Fe₂O₃ as a negative catalyst for hydrosilylation as well as as an oxidation catalyst for the by-product generated from the reaction between TCS and FDV.     

Thermal behavior and dismantlability of adhesives containing various inorganic salts

As a fundamental study on the development of dismantlable adhesives containing chemically reactive materials, the thermal behavior and dismantlability of an epoxy adhesive containing one of the twenty-seven inorganic salts (chlorides, perchlorates, and nitrates) were observed. In the thermal behavior measured by the differential scanning calorimetry, epoxy adhesives with inorganic salts containing iron, copper, zinc, and aluminum cations released heats of reaction at lower temperatures than the adhesive alone or the adhesives with other inorganic salts. Since such inorganic salts were considered to be effective candidates as fillers in dismantlable adhesives, the adhesion strengths of their mixtures with the adhesive were observed after heat aging at 270 °C for 30 min. The results showed that both chloride and perchlorate salts specifically decreased the adhesion strength after heating. On the other hand, the effect of nitrate salts on the decrease in adhesion strength was low in comparison with the chloride and perchlorate salts.     

Synthesis of Optically Active Aromatic Ether Ketone Macrocycles Containing 2,2′-Dimethoxy-1,1′-binaphthyl-6,6′-diyl Moieties

Optically active aromatic ether ketone macrocycles containing 2,2′-dimethoxy-1,1′-binaphthyl-6,6′-diyl moieties were synthesized through electrophilic aromatic substitution reaction and stepwise nucleophilic aromatic substitution reactions. Structures of the resulting macrocycles were confirmed by NMR and matrix assisted laser desorption/ionization time of flight (MALDI-TOF) mass measurements.     

Aggregation Behavior of Pluronic-L64 in Presence of Sodium Dodecyl Sulphate in Water

The effect of sodium dodecyl sulfate (SDS) on the micellization and aggregation behavior of a poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) amphiphilic copolymer (Pluronic L64: EO₁₃ PO₃₀ EO₁₃) have been investigated by various techniques like, cloud point, viscosity, isothermal titration calorimetry (ITC), differential scanning calorimetry (DSC), fluorescence spectroscopy, room temperature phosphorescence (RTP), and small angle neutron scattering (SANS). Addition of SDS in L64 solutions shows mark alteration of different properties. We observed synergistic interaction between SDS and Pluronic L64. The changes in the critical micelle concentration (CMC), critical micelle temperature (CMT), cloud point (CP), micelle size, and shape has been correlated and reported in terms of structure dynamics and mechanics. The ITC titrations have been used to explore the different stages of binding and interactions of SDS with L64. The enthalpies of aggregation for copolymer-SDS aggregates binding, organizational change of bound aggregates, and the threshold concentrations of SDS in the presence of copolymer were estimated directly from ITC titration curves. The effect of temperature on enthalpy values has been reported in terms of different aggregation state. Fluorescence and RTP for L64 were used to investigate the change in micellar environment on the addition of SDS at different temperature. Appearance and shifting of SANS peaks have been used to monitor the size and inter micellar interaction on addition of SDS in L64 solution. Cloud point and viscosity elaborate the penetration of SDS molecule in L64 micelle and hence changing the micellar architect.     

Organochlorine Pesticides in Water,Sediment and Fish from the Nile River and Manzala Lake in Egypt

Abstract

To assess the risks of organochlorine pesticides discharged into the hydrospheric environment of Egypt, river and lake water, drinking water, suspended solids, sediments and fish were collected during 1993—1994 from the Nile River and Manzala Lake in Egypt and were transported to Japan for chemical analysis. Among different organochlorine pesticides analyzed, p,p′-DDE was the most predominant in fish (7.6 to 67 ng/g wet wt.), sediments (3.2 to 432 ng/g dry wt.) and suspended solids (5.3 tc 138 pg/L). However, in the dissolved phase of water samples HCH compounds predominated (α-HCH, 71 to 2,815 pg/L). Concentrations of organochlorine pesticides, except chlordane, were higher in Manzala Lake than in the River Nile. Concentrations of organochlorine pesticides in fish corresponded with those in sediments from each location. Comparison of organochlorine concentrations in Nile River water with those reported in earlier studies suggested a decrease in concentrations during the last decade. However, concentrations of p,p′-DDE has increased in fish. It appears that the release of this metabolite from contaminated sediment is the major source of p,p′-DDE in fish during recent years.