Effect of the alkyl chain length of 1,1′-binaphthyl esters in lipase-catalyzed amidation

Lipase-catalyzed amidation of 2-[2-(ethoxycarbonyl)ethyl]-1,1′-binaphthyl [(±)-3] yielded optically active (S)-3 and 2-[2-(2-cyanoethylaminocarbonyl)ethyl]-1,1′-binaphthyl [(R)-6a] with high enantiomeric excess. For these lipase-catalyzed amidations, the optimal alkyl chain length between the binaphthyl ring and the ester group was determined to be an ethylene spacer.     

Synthesis,optical properties,and spectral stability of chiral dendronized binaphthyl‐containing polyfluorene derivatives

A new kind of chiral dendronized binaphthyl‐containing random polyfluorene derivatives bearing different contents (3.2–14.9 mol %) of Fréchet's polyether dendritic wedges have been designed and synthesized through a versatile Pd‐catalyzed Suzuki polycondensation. Their properties have been investigated by NMR, TGA, DSC, CD, UV–vis, and photoluminescence and compared to those of poly(9,9‐dihexylfluorene) ( PF ). It was found that attachment of Fréchet's dendritic wedges into the main chain enhanced the emission efficiency and thermal stability of the copolymers. Furthermore, different from PF , good to excellent spectral stabilities in the solid state were proven for all the dendronized chiral copolymers after a thermal annealing under air at 200 °C. The second‐generation dendronized polymer P3 bearing about 15 mol % of dendritic pendants exhibited high quantum yields in both solutions and films, and excellent thermal oxidative stability. These results demonstrated that the combination of the twisted nonplanar binaphthyl and the sterically demanding dendron could efficiently suppress the intermolecular packing and aggregation at much lower dendron contents compared to other reported dendronized polyfluorenes. Additionally, the investigation of circular dichroism spectra of these chiral dendronized polymers showed a strong Cotton effect at long wavelength (378–384 nm), indicating that the chirality of binaphthyl unit was transferred to the whole polyfluorene backbone. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 886–896, 2008     

Polyimides from isomeric oxydiphthalic anhydrides

2,2′,3,3′‐Oxydiphthalic dianhydride (2,2′,3,3′‐ODPA) and 2,3,3′,4′‐ODPA were synthesized from 3‐chlorophthalic anhydride with 2,3‐xylenol and 3,4‐xylenol, respectively. Their structures were determined via single‐crystal X‐ray diffraction. A series of polyimides derived from isomeric ODPAs with several diamines were prepared in dimethylacetamide (DMAc) with the conventional two‐step method. Matrix‐assisted laser desorption/ionization time‐of‐flight spectra showed that the polymerization of 2,2′,3,3′‐ODPA with 4,4′‐oxydianiline (ODA) has a greater trend to form cyclic oligomers than that of 2,3,3′,4′‐ODPA. Both 2,2′,3,3′‐ODPA and 2,3,3′,4′‐ODPA based polyimides have good solubility in polar aprotic solvents such as DMAc, dimethylformamide, and N‐methylpyrrolidone. The 5% weight‐loss temperatures of all polyimides were obtained near 500 °C in air. Their glass‐transition temperatures measured by dynamic mechanical thermal analysis or differential scanning calorimetry decreased according to the order of polyimides on the basis of 2,2′,3,3′‐ODPA, 2,3,3′,4′‐ODPA, and 3,3′,4,4′‐ODPA. The wide‐angle X‐ray diffraction of all polyimide films from isomeric ODPAs and ODA showed some certain extent of crystallization after stretching. Rheological properties revealed that polyimide (2,3,3′,4′‐ODPA/ODA) has a comparatively lower melt viscosity than its isomers, which indicated its better melt processability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3249–3260, 2003     

Inclusion by a substituted binaphthyl host: structures and kinetics of desolvation

The host compound 2,2′-bis(hydroxydiphenylmethyl)-1,1′-binaphthyl displays a remarkably constant conformation, which is governed chiefly by an intramolecular O–H…O hydrogen bond. Its inclusion compound with chloroform has been characterised and the dehydration product affords the corresponding oxepine with significantly different conformation.     

Synthesis and properties of polyimides from 4,4′-binaphthyl-1,1′,8,8′-tetracarboxylic dianhydride

4,4′-Binaphthyl-1,1′,8,8′-tetracarboxylic dianhydride was synthesized from 4-chloro-1,8-naphthalic anhydride and polymerized with aromatic and pliphatic diamines in m-cresol or N-methyl-2-pyrrolidinone (NMP). The polyimides, except for two derived from p-phenylenediamine and hydrazine, are soluble in 1,1,2,2-tetrachloroethane and NMP. Their intrinsic viscosities ranged from 0.36 to 2.20 dL/g. The polymers showed excellent thermal and thermooxidative stabilities and displayed weak glass transition temperatures. Young's moduli of some polymer films were in the range of 2.5 and 5.4 GPa at 30°C. The aliphatic polyimides exhibited a stronger fluorescence than the aromatic polyimides. © 1995 John Wiley & Sons, Inc.     

Colorless poly(ether-imide)s deriving from 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride(BPADA) and aromatic bis(ether amine)s bearing pendent trifluoromethyl groups

A series of poly(ether-imide)s (III) characterized by colorless, highly solubility was synthesized from 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride(BPADA) and various fluorinated aromatic diamines (I_a-h) in DMAc via polycondensation to form poly(amic acid) (II), followed by chemical (C) and thermal (H) imidization. These polymers had inherent viscosities ranging from 0.60 to 1.3 dL/g. These polyimides were highly soluble in a variety of organic solvent such as amide-type, ether-type and chlorinated solvents. Moreover, these poly(ether-imide) films were almost colorless, with an ultraviolet-visible absorption cutoff wavelength below 390 nm and low b* value (a yellowness index) of 4.6-18.0. The III series showed strength tensile of 72-101 MPa, elongation at break of 11-25%, initial modulus of 1.5-2.0 GPa. The glass transition temperature (T_g) of III_a-h were in the range of 202-267 °C, and the decomposition temperature above 493 °C and left 40-65% char yield at 800 °C in nitrogen. They had the lower dielectric constants of 3.39-3.72 (1 MHz) and moisture absorptions in the range of 0.11-0.40%.     

Preparation and properties of imide‐containing elastic polymers from elastic polyureas and pyromellitic dianhydride

A new approach to obtain imide‐containing elastic polymers (IEPs) via elastic and high‐molecular‐weight polyureas, which were prepared from α‐(4‐aminobenzoyl)‐ω‐[(4‐aminobenzoyl)oxy]‐poly(oxytetramethylene) and the conventional diisocyanates such as tolylene‐2,4‐diisocyanate(2,4‐TDI), tolylene‐2,6‐diisocyanate(2,6‐TDI), and 4,4′‐diphenylmethanediisocyanate (MDI), was investigated. IEP solutions were prepared in high yield by the reaction of the polyureas with pyromellitic dianhydride in N‐methyl‐2‐pyrrolidone (NMP) at 165°C for 3.7–5.2 h. IEPs were obtained by the thermal treatment at 200°C for 4 h in vacuo after NMP was evaporated from the resulting IEP solutions. We assumed a mechanism of the reaction via N‐acylurea from the identification of imide linkage and amid acid group in IEP solutions. NMR and FTIR analyses confirmed that IEPs were segmented polymers composed of imide hard segment and poly(tetramethylene oxide) (PTMO) soft segment. The dynamic mechanical and thermal analyses indicated that the IEPs prepared from 2,6‐TDI and MDI showed a glass‐transition temperature (T_g ) at about −60°C, corresponding to T_g of PTMO segment, and suggested that microphase‐separation between the imide segment and the PTMO segment occured in them. TGA studies indicated the 10% weight‐loss temperatures (T₁₀) under air for IEPs were in the temperature range of 343–374°C. IEPs prepared from 2,6‐TDI and MDI showed excellent tensile properties and good solvent resistance. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 715–723, 2000     

Highly enantioselective addition of in situ prepared arylzinc to aldehydes catalyzed by a series of atropisomeric binaphthyl-derived amino alcohols

The direct addition of in situ prepared arylzinc to aldehydes with chiral binaphthyl-derived amino alcohols as catalysts can afford optically active diarylmethanols in high yields and with excellent enantioselectivities (up to 99 % ee, ee = enantiomeric excess). By using a single catalyst, both enantiomers of many pharmaceutically interesting diarylmethanols can be obtained by the proper combination of various arylzinc reagents with different aldehydes; this catalytic system also works well for the phenylation of aliphatic aldehydes to give up to 96 % ee.     

苝二酸酐与嘧啶衍生物的氢键组装

Semi-empirical AM1 method was used to study 1:1 and 1:2 hydrogen bond complexes formed with perylene dianhydride and pyridine derivatives. The weak interaction energy become bigger as the number of hydrogen bonds increases. The donor groups on the host and electron-withdrawing groups on the guest molecules favor hydrogen bonding interactions, and the formation of hydrogen bonding leads to electron density flow from the host to the guest molecules. Electronic spectra of these complexes were computed using INDO/SCI method. Blue-shift of the electronic absorption spectra for the complexes, comparing that of the host,takes place, and the first peaks for different complexes changed slightly. These are in agreement with the experimental results. The cause of blue-shift was discussed, and the electronic transitions were assigned based on theoretical calculations. The potential curve of double proton transfer in the complex was calculated, and the transition state and activated energy relative to the N-H bond were obtained.     

Synthesis and properties of poly(ether imide)s derived from 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride and aromatic diamines

A new naphthalene unit-containing bis(ether anhydride), 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride, was synthesized in three steps starting from the nucleophilic nitrodisplacement reaction of 2,6-dihydroxynaphthalene and 4-nitrophthalonitrile in N,N-dimethylformamide (DMF) solution in the presence of potassium carbonate, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). High-molar-mass aromatic poly(ether imide)s were prepared using a conventional two-step polymerization process from the bis(ether anhydride) and various aromatic diamines. The intermediate poly(ether amic acid)s had inherent viscosities of 0.65–2.03 dL/g. The films of poly(ether imide)s derived from two rigid diamines, i.e. p-phenylenediamine and benzidine, crystallized during the thermal imidization process. The other poly(ether imide)s belonged to amorphous materials and could be fabricated into transparent, flexible, and tough films. These aromatic poly(ether imide) films had yield strengths of 104–131 MPa, tensile strengths of 102–153 MPa, elongation to break of 8–87%, and initial moduli of 1.6–3.2 GPa. The glass transition temperatures (T_g's) of poly(ether imide)s were recorded in the range of 220–277°C depending on the nature of the diamine moiety. All polymers were stable up to 500°C, with 10% weight loss being recorded above 550°C in both air and nitrogen atmospheres. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1657–1665, 1998