Synthesis of new 3,4-di-and 1,2,3,4-tetrahydroquinazolin-4-one derivatives and X-ray diffraction study of crystal solvates of 3-methylsulfonylamino-2-(2-methylsulfonylaminophenyl)-1,2,3,4-tetrahydroquinazolin-4-one

The reactions of hydrazide, mesyl hydrazide, succinyl hydrazide, and maleyl hydrazide of anthranilic acid with carbonyl compounds were studied, and new di-and tetrahydroquinazolin-4-one derivatives were prepared. The structure of one reaction product, viz., 3-methylsulfonylamino-2-(2-methylsulfonylaminophenyl)-1,2,3,4-tetrahydroquinazolin-4-one, was established by X-ray diffraction study of two crystal solvates of this compound. The characteristic features of the crystal packings of these solvates are discussed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1183–1191, July, 2006.     

4-苯乙炔苯酐封端聚酰亚胺树脂的合成与性能研究

使用3,3′,4,4′-二苯醚四酸二酐(ODPA)、3,3′,4,4′-联苯四酸二酐(BPDA)、1,3-双(4-氨基苯氧基)苯(1,3,4-APB)、3,4′-二氨基二苯醚(3,4′-ODA)和反应性封端剂4-苯乙炔苯酐(4-PEPA)合成了设计分子量为5000的系列苯乙炔基封端的聚酰亚胺低聚物,并使用XRD、DSC、TGA、FT-IR、DMA和流变仪等对低聚物的化学结构、热性能和熔体性能,固化后树脂的热性能和力学性能进行了测试.研究结果表明基于ODPA的低聚物具有低的熔体粘度和良好的熔体粘度稳定性,固化后的树脂具有很高的热失重温度,较高的玻璃化转变温度以及良好的力学性能尤其是高的断裂伸长率(>10%);基于BPDA的低聚物具有一定的结晶性,其结晶熔融温度与苯乙炔基固化交联温度相近,影响了材料的成型工艺性能.     

Synthesis and Absorption Properties of Some 4-Thioaryl-1,8-naphthalimides and 4-Thioaryl-7H-benzimidazo-[2,1-a]-benz-[d,c]-isoquinolin-7-one Derivatives

A series of novel 4-thioaryl-1,8-naphthalimide derivatives were synthesized using 4-chloro-1,8-naphthalic anhydrid and arylthioles as starting materials. 4-thioaryl-1,8-naphthalic anhydride was treated with different primary amines and o-phenylene diamine or 1,2-diaminoethene to produce 4-thioaryl-1,8-naphthalimides and 4-thioaryl-7 H-benzimidazo-[2,1-a]-benz-[d,c]-isoquinolin-7-one derivatives, respectively. The UV/VIS absorption properties are discussed.     

Rearrangements in Spiro-λ4-sulfane Chemistry

The reactions of possible spiro-λ⁴-sulfane precursor diaryl sulfoxides with dehydrating agents have been studied resulting in the formation of cyclic anhydride, spiro-λ⁴-sulfane, cyclic sulfonium-ylide, lactam-sulfoxide, cyclic sulfonimide and cyclic sulfilimine type of intermediates or products. The structures of the intermediates or products depend on the functional groups attached to the aryl rings at ortho positions and on the reaction conditions applied.     

Crystallizable Polyphenylacetylene-Preparation and Solution Properties

The molecular weight distribution (MWD) of crystallizable polyphenylacetylene prepared near room temperature in the presence of ferric acetylacetonate and triethylaluminum was determined through use of fractions characterized by vapor pressure osmometry and gel permeation chromatography (GPC). The number- and weight-average molecular weights (M _n and M _w) are both less than the molecular weight corresponding to the maximum of the weight distribution function, which lacks a high molecular weight tail. M _wandM _n is less than is consistent with models allowing for chain termination characteristic of vinyl polymers. GPC elution volumes are much less than those characteristic of polystyrene of similar molecular weight, and the Mark-Houwink exponent is high (2.4 for M _v 4800 to 6800). These data indicate more rodlike behavior than for polystyrene of equivalent molecular weight. The MWD and other data suggest intramolecular chain termination, possibly associated with the molecule's tendency to form paramagnetic defect states.     

Swelling Ratios and Rates of Sulfonation of Solvent Modified Copolymers of Styrene Cross-Linked with Pure m-and Pure p-Divinylbenzene

Solvent-modified (toluene) copolymers have been prepared from styrene cross-linked with commercial divinylbenzene, m-divinylbenzene, and p-divinylbenzene at divinyl monomer contents of 16 mole % and 32 mole % at F_M = 0.50. The resultant copolymers have been characterized by swelling-ratio determinations and rates of sulfonation at 60 and 80°C. The solvent-modified 16 mole % cross-linked copolymers sulfonated at rates slightly greater than those characterizing the 8 mole % cross-linked copolymers prepared in the absence of diluent. The order of decreasing sulfonation rates for both the conventional 8 mole % cross-linked systems and for the solvent-modified 16 mole % cross-linked copolymers is commercial divinylbenzene/styrene, p-divinylbenzene/styrene, m-divinylbenzene styrene. The 32 mole % cross-linked systems exhibit a different order of decreasing sulfonation rates: commercial divinylbenzene/styrene, m-divinylbenzene/styrene, p-divinylbenzene/styrene. The swelling ratios of the 32 mole % solvent-modified copolymers were comparable to those of the conventional 8 mole % cross-linked systems.     

Deep eutectic solvents and glycerol: a simple,environmentally benign and efficient catalyst/reaction media for synthesis of N-aryl phthalimide derivatives

Abstract

Deep eutectic solvents (DES) and glycerol have been successfully employed as efficient catalysts/reaction media in the synthesis of N-aryl phthalimide derivatives from phthalic anhydride and primary aromatic amines. The DES prepared from choline chloride and malonic acid proved to be an efficient catalyst whereas glycerol and the DES of choline chloride and urea played a dual role of catalyst and solvent. These mixtures are biodegradable, nontoxic, and cost-effective thereby providing a good industrial alternative to conventional methods. These methods gave products in moderate to high yields with good recyclability of catalyst/solvent at least up to five consecutive runs.     

Mild,Rapid, and Inexpensive Microwave-Assisted Synthesis of Allylic and Propargylic Esters

A variety of allylic and propargylic esters were rapidly prepared via microwave heating of their corresponding mixed anhydride derived from pivaloyl chloride. The reaction conditions were modified to account for the sterics of the alcohol and the electronics of the carboxylic acid.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

RuCl3 · xH2O: A New Efficient Catalyst for Facile Preparation of 1,1‐Diacetates from Aldehydes

An efficient, facile preparation of aldehyde 1,1‐diacetates (acylals) in excellent yields catalyzed by RuCl₃ · xH₂O is described. Ketones do not react under these conditions.     

Micellar Effects on the Oxidation of d‐Glucose by Chromic Acid in Perchloric Acidic Medium

Kinetics of the reaction between d‐glucose and Cr(VI) in the absence and presence of surfactant micelles have been studied by a spectrophotometric method in aqueous‐acidic solutions of perchloric acid. It was observed that the reaction has a nonautocatalytic followed by an autocatalytic pathway. The rate of the initial stage increases with increase in [glucose], [HClO₄] and temperature. Due to precipitation, the effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) could not be studied whereas the oxidation is catalyzed by anionic micelles of sodium dodecyl sulfate (SDS) and nonionic micelles of Triton X‐100 (TX‐100). The results are discussed in terms of the pseudo‐phase kinetic model. Activation parameters are evaluated and a mechanism consistent with the results is proposed. A rate law for the reaction has also been derived. The redox reaction occurs through a Cr(VI)→Cr(IV) path.