Microwave Assisted Conversion of Oximes and Semicarbazones to Carbonyl Compounds Using Benzyltriphenylphosphonium Peroxymonosulfate

Summary.  Benzyltriphenylphosphonium peroxymonosulfate in the presence of catalytic amounts of bismuth chloride was found to be an efficient and mild reagent for the oxidative cleavage of oximes and semicarbazones to the corresponding carbonyl compounds under microwave irradiation. Corresponding author. E-mail: haji@cc.iut.ac.ir Received March 4, 2002; accepted (revised) April 8, 2002     

Synthesis and characterization of new optically active poly(amide‐imide)s containing epiclon and L‐methionine moieties in the main chain

Epiclon [3a,4,5,7a‐tetrahydro‐7‐methyl‐5‐(tetrahydro‐2,5‐dioxo‐3‐furanyl)‐1,3‐isobenzofurandione] (1) was reacted with L ‐methionine (2) in acetic acid and the resulting imide‐acid 3 was obtained in high yield. The diacid chloride 4 was prepared from diacid derivative 3 by reaction with thionyl chloride. Thermostable poly(amide‐imide)s containing epiclon structure were synthesized by reacting of diacid chloride 4 with various aromatic diamines. Polymerization reaction was performed by two conventional methods: low temperature solution polycondensation and short period reflux conditions. In order to compare conventional solution polycondensation reaction methods with microwave‐assisted polycondensation, the reactions were also carried out under microwave conditions with a small amount of o‐cresol that acts as a primary microwave absorber. The reaction mixture was irradiated for 6 min with 100% radiation power. Several new optically active poly(amide‐imide)s with inherent viscosity ranging from 0.15 to 0.36 dl/g were obtained with high yield. All of the above polymers were fully characterized by ¹H‐NMR, FT‐IR, elemental analyses and specific rotation techniques. Some structural characterizations and physical properties of these new optically active poly(amide‐imide)s are reported. Copyright © 2005 John Wiley & Sons, Ltd.     

Preparation and characterization of new thermally stable and optically active poly(ester‐imide)s by direct polycondensation with thionyl chloride in pyridine

4,4′‐hexafluoroisopropylidene‐2,2‐bis‐(phthalic acid anhydride) (1) was reacted with L ‐methionine (2) in acetic acid and the resulting N,N′–(4,4′‐hexafluoroisopropylidenediphthaloyl)‐bis‐L ‐methionine (4) was obtained in high yield. The direct polycondensation reaction of this diacid with several aromatic diols such as bisphenol A (5a), phenolphthalein (5b), 1,4‐dihydroxybenzene (5c), 4,4′‐dihydroxydiphenyl sulfide (5d), 4,6‐dihydroxypyrimidine (5e), 4,4′‐dihydroxydiphenyl sulfone (5f) and 2,4′‐dihydroxyacetophenone (5g) was carried out in a system of thionyl chloride and pyridine. Expecting that the reaction with thionyl chloride in pyridine might involve alternative intermediates different from an acyl chloride, the polycondensation at a higher temperature favorable for the reaction of the expected intermediate with nucleophiles was attempted, and a highly thermally stable poly(ester‐imide) was obtained by carrying out the reaction at 80°C. All of the above polymers were fully characterized by ¹H‐NMR, ¹⁹F‐NMR FT‐IR spectroscopy, elemental analysis and specific rotation. Some structural characterization and physical properties of these optically active poly(ester‐ imide)s are reported. Copyright © 2006 John Wiley & Sons, Ltd.     

The effects of reactive organoclay on the thermal, mechanical, and microstructural properties of polymer/layered silicate nanocomposites based on chiral poly(amide-imide)s

Considering the importance of the nanocomposites, the present work focuses on some new hybrid materials prepared by introducing reactive organoclay (OC) into the chiral poly(amide-imide) (PAI) matrix. At first, Cloisite Na⁺ was modified with protonated l-isoleucine amino acid. Then, PAI containing phenylalanine was synthesized via solution polycondensation of chiral diacid chloride with 4,4′-diaminodiphenylsulfone and was characterized with Fourier transform infrared (FTIR) and ¹H NMR techniques. At last, PAI/OC nanocomposite films containing 2, 5, 10, and 15 % of OC were prepared via solution intercalation method. The effect of OC dispersion and the interaction between OC and polymer chains on the properties of nanocomposites were investigated using FTIR, X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, tensile testing of thin films, and thermogravimetry analysis techniques. The thermal stability of hybrids such as the decomposition temperature and mass residue at 800 °C was improved. Mechanical data indicated improvement in the tensile strength of the nanocomposites with OC loading up to 10 wt%. The transparency of the hybrid films was investigated by means of UV–Vis spectra.     

Microwave Irradiation for Accelerating Synthesis of New Chiral Nanostructured Poly(amide-imide)s Having a Thiazole Pendant Group

Microwave irradiation was used to accelerate the polycondensation of a new thiazole-containing diamine with several chiral diacids. Polymerization reactions were carried out in molten tetrabutylammonium bromide as a green molten salt medium and triphenyl phosphite as the homogenizer. A series of new compounds were characterized by Fourier transform-infrared spectroscopy, nuclear magnetic resonance spectroscopy, and elemental analysis techniques. The polymeric samples showed high thermal stability with decomposition temperature being above 360°C; they were in a nanoscale size and were assembled uniformly and randomly in a sponge-like morphology.     

An Efficient Method for Production and Storage of Unstable S-Nitrosothiols Under Mild and Heterogeneous Condition with Sodium Nitrite and Oxalic Acid Dihydrate

Thiols can be readily converted to their corresponding nitrosothiols with a combination of oxalic acid and sodium nitrite in t-butanol at room temperature (26-30°C). The reaction mixture could be solidified with decreasing its temperature to, 15°C and was stored for several days without any destruction of the nitrosothiols.     

Supported Nitric Acid on Silica Gel and Polyvinyl Pyrrolidone (PVP) as an Efficient Oxidizing Agent for the Oxidation of Urazoles and Bis-urazoles

A method for the oxidation of a good range of urazoles and bis-urazoles to the corresponding triazolinediones by supported nitric acid on silica gel (SiO₂-HNO₃) and/or polyvinyl pyrrolidone (PVP-HNO₃) is described. Reactions have been carried out heterogeneously at room temperature in dichloromethane with good to excellent yields.     

Reinforcement of poly(vinyl alcohol) with chiral poly(amide-imide)s nanoparticles containing S-valine under simple ultrasonic irradiation method

Nanostructured amino acid containing poly(amide-imide) (PAI) was synthesized from the direct polycondensation reaction of 2–(3,5–diaminophenyl)–benzimidazole and N,N′–(pyromellitoyl)–bis–phenylalanine diacid under green condition by using tetrabutylammonium bromide as molten ionic liquid. Field emission scanning electron microscopy images show that the average diameter of polymeric nanoparticles with spherical shape was around 20–35 nm. In the next step, these polymeric nanoparticles were used as nano-fillers for reinforcement of poly(vinyl alcohol) (PVA) for the first time. Bionanocomposite of PVA and various compositions of PAI nanoparticles were produced through ultrasound-assisted technique. Fourier transform infrared spectroscopy, x-ray diffraction, field emission scanning electron microscopy, and thermogravimetric analysis were utilized to characterize the obtained hybrid materials, morphology, and properties. Results of thermal properties indicated that the thermal stability is enhanced. The improvement of thermal properties was attributed to the homogeneous and good dispersion of PAI nanoparticles in the PVA matrix and the strong hydrogen bonding between O–H groups of PVA and the carbonyl of amide and imide groups of the used PAI nanoparticles.     

Insertion of fluorophore dyes between Cloisite Na+ layered for preparation of novel organoclays

The aim of this study was to obtain novel photo-functional organomontmorillonites from the intercalation reaction of Cloisite Na⁺ and fluorescent dyes of auramine O, and safranin T in an aqueous solution. The insertion of surfactants in the interlamellar space of nanoclay was followed by Fourier transform infrared spectroscopy and X-ray measurements. An X-ray diffraction analysis established that incorporation of the organic dye cations into the Cloisite Na⁺ expands remarkably the mineral interplanar distances from 1.17 to 1.83–1.97 nm. Field emission scanning electron microscopy was used to study the morphology of the synthesized organoclays. The thermal behavior of the novel hybrid materials was investigated by thermogravimetric analysis and the results show that the organo modified clays verify stepwise decomposition corresponding to initial weight loss from residual water desorption, followed by decomposition of the fluorescent dyes and the dehydroxylation of structural water of the clay layers. Fluorescence properties of the cationic dyes, auramine O, and safranin T incorporated in the clay have significant differences from their behavior in organic solvents and water and the results show that both dyes exhibit a significant fluorescence emission at room temperature when adsorbed in clay.     

Opportunities and Challenges in the Use of TiO2 Nanoparticles Modified with Citric Acid to Synthesize Advanced Nanocomposites Based on Poly(amide-imide) Containing N,N′-(Pyromellitoyl)-bis-L-leucine Segments

In this study, the goal was the preparation, characterization, and surface morphology of poly(amide-imide)/TiO₂-citric acid nanocomposites (PAI/TiO₂-CA NCs). Owing to the high surface energy and tendency for agglomeration, the surface of TiO₂ nanoparticles was modified with citric acid. Then poly(amide-imide) was synthesized by direct polycondensation reaction of N,N′-(pyromellitoyl)-bis-L-leucine diacid with 4,4′-diaminodiphenylmethane by triphenyl phosphite and tetra-n-butylammonium bromide as a green medium. The attained polymer and modified TiO₂ nanoparticles were used to prepare PAI/TiO₂-CA NCs through ultrasonic irradiation. The resulting PAI/TiO₂-CA NC was characterized with FT-IR spectroscopy, X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis.