Synthesis and nuclear magnetic resonance analysis of starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers

A new biodegradable starch graft copolymer, starch‐g‐poly(1,4‐dioxan‐2‐one), was synthesized through the ring‐opening graft polymerization of 1,4‐dioxan‐2‐one onto a starch backbone. The grafting reactions were conducted with various 1,4‐dioxan‐2‐one/starch feed ratios to obtain starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers with various poly(1,4‐dioxan‐2‐one) graft structures. The microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was characterized in detail with one‐ and two‐dimensional NMR spectroscopy. The effect of the feed composition on the resulting microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3417–3422, 2004     

Synthesis and characterization of novel perfluorinated polyimides with 3D‐controlled structures for photonic applications

We have designed and synthesized novel perfluorinated polyimides with 3D controlled structure. At first, we successfully developed the new synthetic routes to diamines with pendant bulky perfluorinated aromatic units in a multi‐step synthetic procedure. Novel perfluorinated polyimides were prepared in a two‐step reaction in N‐methyl‐2‐pyrrolidinone (NMP) solution: The first step was for the synthesis of polyamic acids (PAAs) and the second reaction was for the imidization of PAA. The polymer yield was over 89% and the inherent viscosity of PAAs was in the range of 0.24–0.36 dL/g. The thin films were prepared by spin‐coating the PAA solution in NMP onto various substrates such as a Si wafer or a KBr pellet, dried at 80 °C and further cured at 230 °C. The resultant polyimides are thermally stable over 400 °C. The refractive index and birefringence of the resultant polyimides are 1.5858–1.6452 and 0.01–0.005, respectively. The refractive index of polyimide decreases with increasing the fluorine content. The copolymerization and the ether linkages into the backbone reduce the birefringence of polyimides. Surprisingly, the pendant ether linkage is not a crucial factor in reducing the polyimide birefringence. Their birefringence is comparatively very low, compared with that of previous polyimides. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1326–1342, 2006     

Melting behaviors,crystallization kinetics,and spherulitic morphologies of poly(butylene succinate) and its copolyester modified with rosin maleopimaric acid anhydride

This article investigated the melting behaviors, crystallization kinetics, and spherulitic morphologies of poly(butylene succinate) (PBS) and its copolyester (PBSR) modified with rosin maleopimaric acid anhydride, using wide‐angle X‐ray diffraction, differential scanning calorimeter (DSC), and polarized optical microscope. Subsequent DSC scans of isothermally crystallized PBS and PBSR exhibited two melting endotherms, respectively, which was due to the melt‐recrystallization process occurring during the DSC scans. The equilibrium melting point of PBSR (125.9 °C) was lower than that of PBS (139 °C). The commonly used Avrami equation was used to describe the isothermal crystallization kinetics. For nonisothermal crystallization studies, the model combining Avrami equation and Ozawa equation was employed. The result showed a consistent trend in the crystallization process. The crystallization rate was decreased, the perfection of crystals was decreased, the recrystallization was reduced, and the spherulitic morphologies were changed when the huge hydrogenated phenanthrene ring was added into the chain of PBS. The activation energy (ΔE) for the isothermal crystallization process determined by Arrhenius method was 255.9 kJ/mol for PBS and 345.7 kJ/mol for PBSR. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 900–913, 2006     

Acetic anhydride as a synthetic reagent

Acetic anhydride has been used widely in synthetic organic chemistry, especially in syntheses and transformations of heterocyclic compounds. These utilities are reviewed under the following classification.     

Synthesis of pyrimido[4,5-e][1,4]oxazepin-5-ones

Eighteen novel pyrimido[4,5-e][1,4]oxazepin-5-ones were prepared directly via the reaction of either ethyl 4-chloro-2-phenyl-5-pyrimidinecarboxylate (Ia) or ethyl 4-chloro-2-m-chlorophenyl-5-pyrimidinecarboxylate (Ib) with a variety of substituted 2-(alkylamino)ethanols. A typical example was the preparation of 8,9-dihydro-9-methyl-2-phenylpyrimido[4,5-e][1,4]-oxazepin-5(7H)-one (IIa) from the reaction of Ia with 2-(methylamino)ethanol. Hydrolytic cleavage of the lactone ring in IIa with sodium hydroxide solution, followed by acidification with hydrochloric acid afforded 4-[(2-hydroxyethyl)methylamino]-2-phenyl-5-pyrimidinecarboxylic acid (IV). Reactions of IIa with concentrated ammonium hydroxide or hydrazine also caused cleavage of the lactone ring, giving the corresponding amide (V) or hydrazide (VI), respectively. Structural assignments were supported by infrared and nuclear magnetic resonance spectra.     

Synthesis of 5,6,8,9,14,14a-hexahydroisoquino[1,2-b][3]benzazepines

Syntheses of 5,6,8,9,14,14a-hexahydroisoquino[1,2-b][3]benzazepine-2,3,11,12-tetrol and related compounds are described. Key steps involve an initial construction of the isoquinoline ring under the Bischler-Napieralski conditions, which is followed by the building of the azepine ring via an intramolecular lactam formation on to the isoquinoline nucleus.     

Synthesis of 1,2,3,4,8,9,10,11-octahydro-[1,4] diazepino[6,5,4-jk ]earbazole and related compounds

1,2,3,4,8,9,10,11-Octahydro[1,4]diazepino[6,5,4-jk]earbazole (VIa) was synthesized from 2,3,4,5-tetrahydro-1H-benzodiazepine (la) via the route shown in Scheme 1. Other compounds which were prepared similarly are 3-acetyl-6-chloro-1,2,3,4,8,9,10,11-octahydro[1,4]diazepino-[6,5,4-jk]carbazole(Vb) and 3-methyl-1,2,3,4,8,9,10,11-octahydro[1,4]diazepino[6,5,4-jk]carb-azole (VIII). Chemical transformations which were carried out with VI and 3-acetyl-1,2,3,4,8,9, 10,11-octahydro[1,4]diazepino[6,5,4-jk]carbazole (Va) are also described.     

One-step preparation of highly concentrated well-stable gold colloids by direct mix of polyelectrolyte and HAuCl4 aqueous solutions at room temperature

Highly concentrated, well-stable gold colloids can be prepared directly from an amine-bearing polyelectrolyte-HAuCl4 aqueous solution at room temperature. It is found that increasing molar ratio of polyelectrolyte to gold leads to increasing particle size. UV-vis spectra, transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS) were used to characterize the products thus formed.