New poly(amide-imide)s syntheses. XVII. Preparation and properties of poly(amide-imide)s derived from 3,3-Bis[4-(4-aminophenoxy)phenyl]phthalimidine and various bis(trimellitimide)s

A series of novel bis(phenoxy)phthalimidine-containing poly(amide-imide)s III were synthesized by the direct polycondensation of 3,3-bis[4-(4-aminophenoxy)phenyl]phthalimidine (BAPP) with various aromatic bis(trimellitimide)s in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s III , having inherent viscosities up to 1.36 dL/g, were obtained in quantitative yields. All resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 267–322°C and the 10% weight loss temperatures were above 490°C in nitrogen. Some properties of poly(amide-imide)s III were compared with those of the corresponding isomeric poly(amide-imide)s III′ prepared from 3,3-[4-(4-trimellitimidophenoxy)phenyl]-phthalimidine and various aromatic diamines. © 1996 John Wiley & Sons, Inc.     

三苯基咪唑富勒烯吡咯烷衍生物的合成及其紫外、荧光和光限幅性质的研究

通过1,3-偶极环加成合成了四种三苯基咪唑富勒烯吡咯烷衍生物3a～3d,用FT-IR,NMR,MS和元素分析进行其结构测定和表征;用循环伏安法测定了其电化学性质,结果表明,与参比化合物C60相比还原电位发生负移,更容易形成电子受体;用纳秒和飞秒激光研究了四种化合物的光限幅性质,结果表明化合物3a和3c的纳秒光限幅性质明显,而3b则观察不到光限幅现象,说明化合物中硝基的引入不利于光限幅效应.     

Synthesis,Characterization, X‐Ray Structural Analysis,and Iodination Ability of Benzyl(triphenyl)phosphonium Dichloroiodate

Benzyl(triphenyl)phosphonium dichloroiodate (BTPPICl₂), BnPh₃P⁺(ICl₂)^?, is easily synthesized in a nearly quantitative yield by the addition of BnPh₃P⁺Cl^? to a CH₂Cl₂ solution of iodine monochloride (ICl). BnPh₃P⁺Cl^? can be prepared by the reaction of Ph₃P and BnCl. The compound was characterized by physicochemical and spectroscopic methods (elemental analysis, FT‐IR, and ¹H‐NMR). The use of phosphonium counterion improves the quality of the BTPPICl₂ crystals. BTPPICl₂ crystallizes in the monoclinic system, and its crystal and molecular structure has been determined at 100(1) K by X‐ray diffraction. The structure was solved by the direct method and had refined R value of 0.0637 for 699 reflections (I>2σ(I)), space group P21/n with a=12.4700(3), b=13.2196(3), c=14.4580(3) Å, β=102.6340(10)°, V=2325.67(9) ų, and Z=4. The I‐atom is coordinated by two Cl‐atoms as ligands in a linear geometry. This compound is a versatile reagent for the efficient and selective iodination of organic substrates, in particular of aromatic phenols to the corresponding iodo compounds, under mild conditions. To assess the generality of method, a wide variety of phenols with electron‐donating and electron‐withdrawing substituents were studied. BTPPICl₂ is a mild iodination reagent, which offers a new avenue for an expeditious iodination of phenols. The inexpensive, relatively non‐toxic reagent, and mild conditions are the positive features of the procedure and reagent.     

One‐Pot,Four‐Component Synthesis of Fully Substituted 1,3,4‐Oxadiazole Derivatives from (Isocyanoimino)triphenylphosphorane,a Primary Amine,an Aromatic Carboxylic Acid,and Chloroacetone

The 1 : 1 imine intermediate 7 generated by the addition of a primary amine 2 to chloroacetone ( 1 ) is trapped by (isocyanoimino)triphenylphosphorane ( 4 ) in the presence of an aromatic carboxylic acid 3 and leads to the formation of the corresponding iminophosphorane intermediate 9 (Scheme 2). The 1,3,4‐oxadiazole derivatives 5 are then formed via an intramolecular aza‐Wittig reaction of the iminophosphorane intermediate 9 . The reactions were completed under neutral conditions at room temperature. The fully substituted 1,3,4‐oxadiazole derivatives 5 were produced in high yields (Table).     

Thermal behavior of poly(bisphenol A carbonate) in the presence of phosphorus compounds

To clarify the interaction between poly(bisphenol A carbonate) (PBAC) and phosphorus compounds such as triphenylphosphine oxide (TPPO), triphenyl phosphate (TPP), and resorcinol bis(diphenyl phosphate) (RDP), PBAC was heated in the presence of these phosphorus compounds at 240 °C for 2 h, and the resulting polymers were analyzed by ¹H NMR spectroscopy and gel permeation chromatography. When heated in the presence of TPPO, the PBAC sample decomposed extensively, resulting in a substantial decrease in molecular weight. On the other hand, thermal treatment in the presence of the phosphates increased the molecular weight. In both cases the molecular weight distribution became narrower. Thermal treatment of PBAC in the presence of both TPPO and TPP allowed us to control the molecular weight with a narrower distribution. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1069–1074, 2004     

Ionic liquids as novel solvents and catalysts for the direct polycondensation of N,N′‐(4,4′‐oxydiphthaloyl)‐bis‐L‐phenylalanine diacid with various aromatic diamines

Ionic liquids (ILs) are often considered green solvents capable of replacing traditional organic solvents and have been extensively studied in materials chemistry and catalysis. In this study, the direct polycondensation of N,N′‐(4,4′‐oxydiphthaloyl)‐bis‐L ‐phenylalanine diacid with various aromatic diamines was performed in IL media. The influence of various reaction parameters, including the nature of the IL cations and anions, the monomer structures, the reaction temperature, and the reaction time, on the yields and inherent viscosities of the resulting optically active poly(amide imide)s (PAIs) were investigated. Direct polycondensation successfully preceded in ILs and triphenyl phosphite (a condensing agent) without any additional extra components, such as LiCl and pyridine, which are used in similar reactions in ordinary molecular solvents. Therefore, ILs can act as both solvents and catalysts. Various high‐molecular‐weight, optically active PAIs were obtained in high yields with inherent viscosities ranging from 0.54 to 0.88 dL/g. This method was also compared with three other classical methods for the polycondensation of the aforementioned monomers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6545–6553, 2005     

Theoretical Investigations and Mechanisms of the Inclusion Processes of bi(3-sulfonatophenyl) (4-tert-butylphenyl) phosphine in the β-cyclodextrin

Quantum mechanical calculations on the bi(3-sulfonatophenyl) (4-tert-butylphenyl) phosphine/β-cyclodextrin inclusion complex (TPP/CD) are carried out using semiempirical quantum calculations. Inclusion process pathways described in the present work lead straight to the most probable structures of the 1:1 association. These investigations suggest that the most stable structure obtained is that where the aromatic ring bearing the tert-butyl (tBu) group is included into the hydrophobic cavity of the β-cyclodextrin from the side of the primary hydroxyl groups. Theoretical investigations of the Hartree-Fock level of the inter-proton proximity between the host and guest molecules in the inclusion complex and their corresponding electronic properties suggest a deep insertion of the tBu group into the cavity. The host-guest interaction energy of the complex at different levels of the insertion pathway is reported with the corresponding basis set superposition error (base). The host–guest association is thermodynamically stable when compared to the separated states and the calculated binding energy is 40.6 kcal mol⁻¹.     

Ruthenium(II) complexes containing bidentate Schiff bases and triphenylphosphine or triphenylarsine

Reactions of ruthenium(II) complexes [RuHX(CO)(EPh₃)₂(B)] (X = H or Cl; B = EPh₃, pyridine (py) or piperidine (pip); E = P or As) with bidentate Schiff base ligands derived by condensingo- hydroxyacetophenone with aniline,o- orp-methylaniline have been carried out. The products were characterized by analytical, IR, electronic and¹H-NMR spectral studies and are formulated as [Ru(X)(CO) (L)(EPh₃)(B)] (L = Schiff base anion; X = H or Cl; B = EPh₃, py or pip; E = P or As). An octahedral structure has been tentatively proposed for the new complexes. The new complexes were tested for their catalytic activities in the oxidation of benzyl alcohol to benzaldehyde.     

有机-无机杂化L-Rh/SiO2氢甲酰化催化剂的研究Ⅰ.PPh3-Rh/SiO2的催化性能及表征

 利用有机-无机杂化的概念,以三苯基膦直接修饰Rh/SiO2制备了PPh3-Rh/SiO2多相催化剂. 在浆态床烯烃氢甲酰化反应中,该催化剂在10 MPa,373 K温和条件下的活性和选择性远高于Rh/SiO2的活性和选择性,与相应的均相催化剂HRhCO(PPh3)3的性能相当,且具有易分离的优点. 31P MAS NMR和XPS技术表征结果表明,催化剂中的配体PPh3与高度分散的Rh之间存在配位作用,形成了兼具多相和均相催化性能的有机-无机杂化催化剂. 该催化剂对不同碳数烯烃的氢甲酰化反应都具有较好的催化性能.     

Reactions of tautomeric quaternary phosphonium salts based on triphenylphosphine and 3-phenylpropargyl bromide with nitrogen nucleophiles

Triphenyl(3-phenylprop-1-ynyl)phosphonium bromide (3) was isolated. This compound is a third isomer for the tautomeric system triphenyl(3-phenylpropadienyl)phosphonium bromide (1) triphenyl(3-phenylprop-2-ynyl)phosphonium bromide (2). Salts 1 and 2 smoothly react with secondary amines to give adducts with an ,-double bond, while salt 3 changes to an allene ylide. Addition of phenylhydrazine and triphenyl(phenylethynyl)phosphonium bromide to salts 1 and 2 and addition of dimethylformamide to salt 2 were performed.