Addition,elimination, exchange,and epimerization in nitro sulfones

Three reactions were studied in the diastereomers of 1‐(benzenesulfonyl)‐2‐nitro‐1‐phenylpropane ( 1A and 1B ) and briefly in related compounds: elimination of the benzenesulfonyl group, epimerization of one diastereomer to the other, and deuterium/hydrogen exchange at the methine group next to nitro in starting material. The two diastereomers showed quite different reactivity. The high melting diasteromer showed rapid elimination and some exchange. The low melting diastereomer (at approximately a half‐life) showed extensive epimerization, and elimination to the alkene, but little exchange. There is little effect of aromatic substituents on reaction course. The situation is complicated by re‐addition of benzenesulfinate to the alkene. The addition reaction was similar to elimination in agreement with the Principle of Microscopic Reversibility expectations. An electron transfer mechanism for addition is calculated to be comparatively favorable. Copyright © 2007 John Wiley & Sons, Ltd.     

取代二噁二唑硫醚及砜衍生物合成及抗菌活性

取代二噁二唑硫醚及砜衍生物合成及抗菌活性     

干相转换条件对致密皮层不对称膜结构及透气性能的影响

研究了挥发时间、温度等干相转换条件对聚芳醚砜致密皮层不对称膜形态结构、有效皮层厚度及氮、氢透过性能的影响．表明采用本铸膜液体系，在２０℃左右，很短的挥发时间内即可制得较理想的气体分离膜。     

Synthesis and Characterization of Metabolites and Potential Impurities of the Antiulcerative Drug Tenatoprazole

Tenatoprazole (Ulsacare^®) is a recently developed antiulcerative drug used for the treatment of both erosive and nonerosive gastroesophageal reflux disease. During the bulk synthesis of tenatoprazole, we have observed four impurities (tenatoprazole N‐oxide, tenatoprazole sulfone N‐oxide, N‐methyl tenatoprazole, and desmethoxy tenatoprazole) and two metabolites (tenatoprazole sulfide and tenatoprazole sulfone). The present work describes the synthesis and characterization of these impurities.     

Stereocontrolled Synthesis of 1,5‐Stereogenic Centers through Three‐Carbon Homologation of Boronic Esters

Allylic pinacol boronic esters are stable toward 1,3‐borotropic rearrangement. We developed a Pd^II‐mediated isomerization process that gives di‐ or trisubstituted allylic boronic esters with high E selectivity. The combination of this method with lithiation–borylation enables the synthesis of carbon chains that bear 1,5‐stereogenic centers. The utility of this method has been demonstrated in a formal synthesis of (+)‐jasplakinolide.     

Synthesis of pyridine-based poly(N-arylenebenzimidazole sulfone)

Poly（N-arylenebenzimidazole pyridine sulfone）（PNABIPS） has been prepared via the aromatic nucleophilic displacement reaction of 2,6-bis（2-benzimidazoly）pyridine（BBP） with bis（4-fluorophenyl） sulfone.BBP was synthesized by reaction of 2,6- pyridinedicarboxylic acid with 1,2-phenylenediamine in polyphosphoric acid.The chemical structure of BBP was confirmed by FTIR, HRMS,¹H NMR and ¹³C NMR.The characterization of the polymer was performed with FT-IR,¹H NMR,elemental analysis, GPC,XRD,DSC,TGA and solubility tests.The polymer was obtained in quantitative yield with M_n value 12,600 and M_w value 28,300,respectively.DSC and TGA measurements show that the glass transition temperature（T_g） is 312℃ and 5%weight loss temperature is 434℃ in nitrogen and 545℃ in air,respectively.In addition,the novel polymer exhibits good solubility,which can be dissolved in common organic solvent at room temperature.     

Stereoselective Synthesis of Allylic Amines by One-Pot Tandem Reaction of Acetylenic Sulfone,Grignard Reagent,and N-Tosylimine

Polysubstituted allylic amines were regio- and stereoselectively synthesized by a one-pot tandem reaction of Cu(I)-catalyzed carbomagnesiation of acetylenic sulfones and its further reaction with N-tosylimine.     

Synthesis,characterization, and blends of high temperature poly(arylether sulfone)s

The preparation of poly(4-oxy-1,4-phenylenesulfonyl-4,4′-biphenylene-4-sulfonylphenylene) (PBP) has been accomplished by the base mediated, polycondensation reaction between two biphenyl containing monomers. The bisphenol, 4,4′-bis[(4-hydroxyphenyl) sulfonyl]biphenyl (HSB), was reacted with 4,4′-bis[(4-chlorophenyl)sulfonyl]-biphenyl (CSB) in tetramethylene sulfone solvent. The highest mechanical properties and glass transition temperature was observed for polymer PBP with a reduced viscosity around 1.0 dL/g. Consequently, the current synthesis route provides polymer with higher properties than other historical preparative routes. Blends of PBP with a different poly(ether sulfone) were miscible based on the observance of a single glass transition temperature. The T_gs of the polymer blends exhibited an unusual positive deviation from the weighted linear averages of the components.     

Synthesis and characterization of poly(thioether ether sulfone imide)s derived from isomeric bis(chlorophthalimide)s and bis(4-mercaptophenyl) sulfone

A series of isomeric bis(chlorophthalimide)s (BCPIs) were conveniently prepared from 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, and mixtures thereof. Polymerization of BCPIs with bis(4-mercaptophenyl) sulfone (BMPS) proceeded smoothly in the presence of tributylamine, from which a class of isomeric poly(thioether ether sulfone imide)s (PTESIs) with inherent viscosities of 0.45-0.82 dL/g were obtained. The solubility, thermal stability, and mechanical properties of these polymers were characterized. Compared to the PTESIs derived from single BCPIs, i.e., 3,3′-, 3,4′-, or 4,4′-BCPIs, the PTESIs derived from mixed BCPIs showed better solubility and higher storage modulus. These PTESIs also demonstrated good thermal stability, giving only 5% weight loss at temperature of 490 °C in nitrogen atmosphere. The glass transition temperatures (T_gs) of these isomeric PTESIs were between 242 and 265 °C, and were increased with increasing of the ratio of 3-chlorophthalimide unit in the polymer backbone.     

Enantioselective synthesis of 1-vinyltetrahydroisoquinolines via Pd-catalyzed intramolecular asymmetric allylic amination reactions

1-Vinyltetrahydroisoquinolines serve as versatile intermediates for the synthesis of a variety of naturally occurring isoquinoline alkaloids. 1-Vinyl-6,8-dimethoxytetrahydroisoquinoline 4 and 1-vinyl-5,6,7-trimethoxytetrahydroisoquinoline 6 with >90% ee by means of Pd-catalyzed intramolecular asymmetric allylic amination reactions, using MPN and BOP ligands, developed in our laboratory. The fine-tuning capability of the MPN and BOP ligands has played a significant role in the optimization of enantioselectivity. Interesting substituent effect as well as solvent effect on the product selectivity and enantioselectivity was observed. Plausible mechanisms are proposed, which can accommodate various findings, including the critical importance of the activation of the trifluoroamide moiety through its coordination to the Lewis acidic Pd²⁺ metal center.