Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides

A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ³‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ³‐benziodoxolones are involved in these organocatalytic reactions.     

Novel,biodegradable, functional poly(ester‐carbonate)s by copolymerization of trans‐4‐hydroxy‐L‐proline with cyclic carbonate bearing a pendent carboxylic group

Water‐soluble poly(ester‐carbonate) having pendent amino and carboxylic groups on the main‐chain carbon is reported for the first time. This article describes the melt ring‐opening/condensation reaction of trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) with 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) at a wide range of molar fractions. The influence of reaction conditions such as catalyst concentration, polymerization time, and temperature on the number average molecular weight (M_n) and molecular weight distribution (M_w/M_n) of the copolymers was investigated. The polymerizations were carried out in bulk at 110 °C with 3 wt % stannous octoate as a catalyst for 16 h. The poly(ester‐carbonate)s obtained were characterized by Fourier transform infrared spectroscopy, ¹H NMR, differential scanning calorimetry, and gel permeation chromatography. The copolymers synthesized exhibited moderate molecular weights (M_n = 6000–14,700 g mol^?1) with reasonable molecular weight distributions (M_w/M_n = 1.11–2.23). The values of the glass‐transition temperature (T_g) of the copolymers depended on the molar fractions of cyclic carbonate. When the MBC content decreased from 76 to 12 mol %, the T_g increased from 16 to 48 °C. The relationship between the poly(N‐CBz‐Hpr‐co‐MBC) T_g and the compositions was in approximation with the Fox equation. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐MBC)s was evaluated from weight‐loss measurements and the change of M_n and M_w/M_n. Debenzylation of 3 by catalytic hydrogenation led to the corresponding linear poly(ester‐carbonate), 4 , with pendent amino and carboxylic groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2303–2312, 2004     

Self‐curable polyester by a reaction of glycidol with maleic anhydride

The controlled reaction of equimolar quantities of maleic anhydride and glycidol in dimethoxyethane gives soluble polyesters with one hydroxyl group in each repeating unit. The reaction proceeds with stepwise ring opening of the components and gives highly viscous clear solutions in relatively short periods. In the first step, monomaleate ester formation takes place around 80 °C. The ring opening of the oxirane group is the second step, and it occurs at 120 °C. The overall reaction is the formation of soluble polyesters with moderate molecular weights (6000–18,000), without the elimination of water. The soluble polyesters can be crosslinked tightly by direct heating at 190 °C without additional vinyl monomer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2549–2555, 2003     

新型卤代羟基三苯醚的合成与抑菌活性研究

设计合成了对(间、邻)苯二酚二(4-氯-2-羟基苯基)醚(4a～4c)及对(间、邻)苯二酚二(4-氯-5-溴-2-羟基苯基)醚(5a～5c)共6个卤代羟基三苯醚类化合物,其结构均经1H NMR,IR,MS和元素分析证实,并且对其抑菌活性进行了初步测试.结果表明:此类化合物大多在低浓度下对大肠杆菌、金黄色葡萄球菌、白色念珠菌、白色葡萄球菌、变形杆菌、卡他双球菌、青枯假单胞菌等具有良好的抗菌活性.     

CC14法合成α—羟基—α—甲基苯丙酮的研究

α 羟基 α 甲基苯丙酮 (ＰＨＭＰ)是一种性能优良的新型光引发剂 ,具有引发效率高、热稳定性好、耐黄变、无异味等优点[1,2 ] 。现有合成方法步骤多 ,产率低 ,后处理麻烦 ,操作复杂[3,4] ,且在反应过程中会产生ＨＣ1或ＨＢｒ等有毒副产物。本文研究了在相转移催化剂的作用下[5,6 ] ,ＣＣｌ4直接氯化水解生成α 羟基 α 甲基苯丙酮的新方法。该方法不仅减少了反应步骤 ,简化了操作 ,而且提高了产品质量。1　实验部分1 .1　仪器与试剂傅立叶红外光谱仪Ｐｅｒｋｉｎ Ｅｌｍｅｒ 1 71 0 ,ＷＸＳ 1型阿贝折光仪。异丁酸 ,ＳＯＣｌ2 ,苯 ,四氯化…     

从蓖麻油制取10-羟基癸酸的研究

本文报道了从蓖麻油制取10-羟基癸酸的研究,发现了从蓖麻油制取10-羟基癸酸的新的工艺路线和最佳的工艺条件,用氢氧化钠用量、2-辛醇量、反应时间和反应温度四因子三水平L_9(3~4)进行了正交试验,发现最佳工艺条件是:氢氧化钠(g)/蓖麻油(g):1.25:2-辛醇量(g)/蓖麻油(g):2:反应时间:6h;反应温度:180℃。在这一新的工艺路线和最佳工艺条件下,10-羟基癸酸产率可达75％。     

PEO／PBHE共混体系X射线散射研究

在聚环氧乙烷(PEO)/聚双酚A羟基醚(PBHE)共混体系中PEO是一个强质子受体,而PBHE是一个强质子给体,两者极易形成氢键,十分有利于形成互容对。笔者研究了PEO/PBHE共混体系的相容性,等温及非等温结晶动力学,本文根据Vonk提出的一维电子密度相关函数,分析了PEO/PBHE的SAXS现象,求得了共混体系的结晶度,片晶层厚度,过渡层厚度及长周期等结构参数。     

1-(2-羟基-5-硝基苯基)-重氮氨基偶氮苯与镍的显色反应及其分析应用

合成了新显色剂 1 - ( 2 -羟基 - 5 -硝基苯基 ) -重氮氨基偶氮苯 ( HNPDAAB) ,研究了该试剂与镍的显色反应条件。在 Triton X- 1 0 0存在下 ,镍与试剂生成 1∶ 1型深红色配合物 ,其表观摩尔吸光系数达 1 .5 8× 1 0 5L· mol- 1· cm- 1。 Ni2 + 的浓度在 0～9μg/2 5 m L范围内符合比耳定律。方法已应用于合金中微量镍的测定 ,结果满意     

A new oligosaccharide synthesis using special hydroxy protecting group

A new hydroxy protecting group for convenient preparation of oligosaccharide was developed using uni-chemo protection (UCP) concept. The UCP group was comprised of polymerized amino acid derivatives and protecting each hydroxyl groups by ester linkage. Depending on the polymerization degree, the hydroxyl groups were characterized and controlled. Using this protecting group, two kinds of sialyl-T analogues were successfully synthesized from same sugar parts merely by repeating Edman degradation and coupling.     

新显色剂1-羟基-2-(5-NO2-2-吡啶偶氮)-8-氨基-3,6-萘二磺酸与铜显色反应的研究

探讨了新显色剂 1-羟基-2-(5-NO2-2-吡啶偶氮)-8-氨基-3,6-萘二磺酸(简称5-NO2-PAH)与铜离子显色的适宜条件及其共存离子的影响,建立了 5-NO2-PAH测定铜的新显色反应体系.在 pH 7.0～10.0 范围内,铜与试剂形成稳定的 1∶2 配合物,其最大吸收峰位于 653 nm, 表观摩尔吸光系数εCu=4.68×104 L·mol-1·cm-1,铜的浓度在 0 μg/10 mL～14 μg/10 mL 范围内遵守比尔定律.方法已用于合金中铜的测定.