Synthesis of aromatic polyethers by scholl reaction. VIII. On the polymerizability of 1,5-bis(phenoxy)pentanes and 1,5-bis(phenylthio)pentane

The synthesis and the oxidative polymerization of 1,5-bis(phenoxy)pentane, 1,5-bis(phenoxy)pentane substituted with various electron-donating groups, and 1,5-bis(phenylthio)pentane is described. The polymers derived from methyl substituted 1,5-bis(phenoxy)pentane monomers contain diphenyl methane, 1,2-diphenylethane, and benzyl chloride structural units. The mechanism for the generation of these structural units is presented. It consists of the proton transfer reactions from the cation-radical propagating species and subsequent reactions of the resulting benzyl radicals. The polymerizability of monomers with 1,5-pentanedioxy group is lower than that of the monomers with diphenyl sulfone group. This dissimilarity was attributed to the difference between both the reactivity and the concentration of the cation-radical propagating species resulted from these two classes of monomers.     

Studies on the thermotropic liquid crystalline polycarbonates. II. Synthesis and properties of fully aromatic liquid crystalline polycarbonates

Four series of fully aromatic polycarbonates were prepared by using melt polycondensation from various novel phenylene diphenyl dicarbonates: 1,4-phenylenc diphenyl dicarbonate, 1,3-phenylene diphenyl dicarbonate, methyl-1,4-phenylene diphenyl dicarbonate, and chloro-1,4-phenylene diphenyl dicarbonate with various diols—4,4′-biphenyl diol, hydroquinone, 2,7-naphthalene diol and 1,5-naphthalene diol, respectively. The thermotropic liquid crystalline properties of synthesized polycarbonates were investigated by: (1) examination of the melt birefringence and stir opalescence by a polarizing microscope equipped with a heating stage, (2) characterization by a differential scanning calorimeter (DSC), and (3) analysis of the wide angle x-ray diffraction. It was found that the 1,3-phenylene unit is compensated for the nonlinearity of the carbonate group, and polycarbonates which contain this bent shape unit showed excellent wide mesophase transition in this study. © 1993 John Wiley & Sons, Inc.     

手性双噁唑啉配体的合成进展

总结了近年来用于不对称催化的各种双噁唑啉配体的合成方法,包括丙二酸酯类、酒石酸类、吡啶类、联苯、联萘及二茂铁类等多种双噁唑啉配体的合成.另外,还讨论了苯甲醚类、二联苯噁二唑类、联苯胺类与氮杂类等新型双噁唑啉配体的合成.     

由Diels-Alder反应合成新型热稳定性含硅双马来酰亚胺──合成及表征

由Ｄｉｅｌｓ－Ａｌｄｅｒ反应合成新型热稳定性含硅双马来酰亚胺──合成及表征郝建军,江璐霞,蔡兴贤（四川联合大学材料科学与工程学院高分子材料系,成都,６１００６５）关键词双马来酰亚胺,有机硅,Ｄｉｅｌｓ－Ａｌｄｅｒ反应,合成,表征采用单体扩链增韧［１］...     

Radical alkylphosphanylation of olefins with stannylated or silylated phosphanes and alkyl iodides

Intermolecular conjugate radical addition reactions of secondary and tertiary alkyl radicals derived from the corresponding alkyl iodides to activated olefins such as α,β-unsaturated esters, amides, imides, nitriles, and sulfones are described. The adduct radicals are trapped by either diphenyl(trimethylstannyl)phosphane or the commercially available diphenyl(trimethylsilyl)phosphane as chain transfer reagents to give the corresponding phosphanylated products in moderate to good yields. The overall process comprises a C-C followed by a C-P bond formation.     

Preparation and Properties of a Thermoplastic Partially Crystalline Polyimide in the Oriented State

Russian Journal of Applied Chemistry - Polyamido acids derived from 4,4′-bis(4-aminophenoxy)diphenyl (diamine) and 1,3-bis(3′,4-dicarboxyphenoxy)benzene dianhydride were synthesized in...     

α-(2-噻唑基脲基)膦酸二苯酯的合成

报道了一种简便的合成取代脲基膦酸酯的通用的新方法。在二氯甲烷中,三乙胺为缚酸剂的条件下,α-氨基膦酸二苯酯与三聚光气反应形成α-异氰酸基膦酸酯2,2不经分离,直接与2-氨基(苯并)噻唑加成得到α-(2-噻唑基脲基)膦酸二苯酯3,产率55.0%-88.9%。     

Retro-ene reactions in heterocyclic synthesis. II. A facile synthetic method for 4-hydroxy-2-pyridones

Schiff's bases 1 derived from ketones and t-butylamine reacted with diphenyl malonate, diphenyl methyl-malonate and diphenyl phenylmalonate to give 4-hydroxy-2-pyridones 4–6 . Schiff's bases b on reaction with trimethyl methanetricarboxylate afforded 4-hydroxy-3-methoxycarbonyl-2-pyridones 12 .     

Cinchona-derived thiourea catalyzed hydrophosphonylation of ketimines—an enantioselective synthesis of α-amino phosphonates

A highly enantioselective addition of diphenyl phosphite to ketimines derived from isatins has been developed employing bifunctional thiourea-tertiary amine organocatalysts. A variety of isatins derived ketimines react well with diphenyl phosphite in the presence of Cinchona-derived thiourea (epiCDT) to provide biologically important chiral 3-substituted 3-amino-2-oxindoles (3a–l) in good yield (up to 88%) and good enantioselectivity (up to 97% ee). The three-component version of the reaction through a domino aza-Wittig/phospha-Mannich sequence has successfully been explored.     

Physicochemical Investigation on a Chelate Polymer

Coordination polymers of Cu(II), Ni(II), Co(II), and Mn(II) with a poly-Schiff base derived from methylene bis-salicylaldehyde (MBSAL) and diamino diphenyl ether (DDE) have been prepared. Magnetic susceptibility, visible and IR spectra, and thermal and electrical conductivities of the chelates have been studied and probable structures assigned to the chelates.     

离子液体中聚碳酸酯光盘的降解-碳酸二苯酯的回收

利用多种氯化铝离子液体和氯化铝离子液体/无机酸体系为反应介质,考察了 较温和条件下废旧聚碳酸酯光盘的降解行为。实验结果表明,在酸性的甲基丁基咪 唑盐的氯化铝离子液体/硫酸介质中,常压,100 ℃条件下,可将废旧聚碳酸酯光 盘有效地降解,主要产物为碳酸二苯酯。反应72 h后,收率为63%。     

Synthesis and properties of films of a polyimide filled with ferromagnetic nanoparticles

Film-forming polyimide nanocomposites containing 5 to 20 wt % nanoparticles were prepared from ferromagnetic Fe/Fe₃O₄ nanoparticles and a polyimide derived from 4,4′-bis(4-aminophenoxy)diphenyl sulfone and 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride. The mechanical properties and magnetization of the nanocomposite samples were studied in relation to the nanoparticle concentration.     

New methods and reagents in organic synthesis, 24. A new synthesis of prumycin as an application of the direct c-acylation using diphenyl phosphorazidate (DPPA)

The 5-substituted 4-methoxycarbonyloxazole $\text{5}$ derived from L-serine derivative $\text{3}$ using diphenyl phosphorazidate (DPPA) has been converted to a 2,4-diaminosugar antibiotic, prumycin.     

P-C Bond formation via direct and three-component conjugate addition catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)

The direct addition of P(O)-H bonds (dialkyl phosphites and diphenyl phosphonite) across various activated alkenes was catalyzed effectively by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). This is a mild, rapid and efficient protocol to generate P-C bonds. This simple procedure allows a series of dialkyl alkylphosphonates and trisubstituted phosphine oxides to be prepared in high yields. Further investigation resulted in a convenient one-pot, three-component reaction containing diphenyl phosphonite, malononitrile and an aldehyde.     

Antibiotics from algae—XXVIII: Cleavage of high molecular phlorotannin derivatives from the brown alga fucus vesiculosus L

A mixture of various high molecular weight phenols containing phlorotannins was extracted from the brown alga Fucus vesiculosus, and phase transfer catalytically methylated in the presence of Adogen 464. Aromatic ether chains of permethylated phlorotannins and of a few low molecular weight model compounds were cleaved with sodium in liquid ammonia. A number of methoxylated phenols, biphenyls, diphenyl ethers and phenoxy-biphenyls were isolated from the mixture of cleavage products. Analysis of these cleavage products proves the occurrence of the substitution patterns already known for low molecular weight phlorotannins consisting of polyhydroxyphenols derived from phloroglucinol and indicates the presence of additional substitution patterns in high molecular phlorotannins.     

Asymmetric hydrogenation of quinolines catalyzed by iridium complexes of BINOL-derived diphosphonites

A chiral diphosphonite, derived from BINOL and with an achiral diphenyl ether backbone, is an excellent ligand for the Ir-catalyzed asymmetric hydrogenation of quinolines; achiral P-ligands serving as possible additives (ee = 73-96%).     

The thermal degradation of polysiloxanes—Part 4: Poly(dimethyl/diphenyl siloxane)

Poly(dimethyl/diphenyl siloxanes) have been prepared with a range of phenyl group contents both from mixtures of dimethyl and diphenyl cyclic siloxanes and from cyclic siloxanes in which both dimethyl and diphenyl structures are present. Attempts to prepare poly(diphenyl siloxane) with a reasonably high molecular weight were unsuccessful.The products of degradation of the poly(dimethyl/diphenyl siloxanes) are benzene and complex mixtures of cyclic oligomers which have been separated, identified and analysed. The characteristics of the formation of these products are discussed in relation to the degradation reactions which occur in poly(dimethyl siloxane), poly(methyphenyl siloxane) and poly(dimethyl/methylphenyl siloxane) and which have been described previously.     

Controlled sulfonation of poly(arylene ether sulfone)s and poly(arylene ether ketone)s with different molecular structures for polymer electrolyte membranes

Poly(arylene ether sulfone) copolymers derived from 9,9-bis(4-hydroxyphenyl)fluorene, bisphenol S and 4,4′-difluorodiphenylsulfone and poly(arylene ether ketone) copolymers derived from 4-phenoxybiphenyl, diphenyl ether and isophthaloyl chloride were prepared as precursor polymers for sulfonation reaction in which sulfonic groups are introduced quantitatively into specified positions. Sulfonation reaction for these two series of copolymers by concentrated sulfuric acid was successfully carried out to give sulfonated polymers with controlled positions and degree of sulfonation. Thermal stability, moisture absorption and proton conductivity for these two series of copolymers were measured and the results were compared to those of perfluorosulfonic acid polymers.     

Synthesis of poly(aryl ether ketone)s containing diphenyl moieties by electrophilic Friedel–Crafts solution polycondensation

A new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), was prepared by Friedel–Crafts reaction of 4‐bromobenzoyl chloride and diphenyl, followed by condensation with potassium phenoxide. Novel poly(ether ketone ketone) (PEKK)/poly(ether ketone diphenyl ketone ether ketone ketone) (PEKDKEKK) copolymers were synthesized by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of diphenyl ether (DPE) and BPOBDP, in the presence of anhydrous aluminum chloride and N‐methyl‐pyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers obtained were characterized by various analytical techniques such as FT‐IR, DSC, TGA, and wide‐angle X‐ray diffraction (WAXD). The results showed that the resulting copolymers exhibited excellent thermal stability due to the existence of diphenyl moieties in the main chain. The glass transition temperatures are above 152°C, the melting temperatures are above 276°C, and the temperatures at a 5% weight loss are above 548°C in nitrogen. The copolymers with 50–70 mol% BPOBDP had tensile strengths of 101.5–102.7 MPa, Young's moduli of 3.23–3.41 GPa, and elongations at break of 12–17%. All these copolymers were semicrystalline and insoluble in organic solvents. Copyright © 2008 John Wiley & Sons, Ltd.     

瑞香狼毒中灭蚜活性物质的结构鉴定

报道从瑞香狼毒(StellerachamaejasmeL.)根中发现分离到2个显示高农药活性化合物，能有效杀灭农业重要害虫蚜虫，经波谱及元素分析，确定其结构为1,5-二苯基-1-戊酮(1)和1,5-二苯基-2-烯-1-戊酮(2)。