含苯基硅氧烷的丙烯酸酯单体的组分分析

以甲基丙烯酸烯丙酯和1,1,5,5-四甲基-3,3-二苯基三硅氧烷为原料,硅氢加成得到含苯基硅氧烷的丙烯酸酯单体。采用核磁(1H-NMR)法表征了产物的封端基团,超高效液相色谱三重串联飞行时间质谱法(UPLC-QTof-MS)对不同封端基团产物的具体结构进行分析,鉴定出甲基丙烯酸-3-(1,1,5,5-四甲基-3,3-二苯基-5-甲基丙烯酰氧基三硅氧基)丙酯、1,1,5,5-四甲基-1,5-二(γ-甲基丙烯酰氧丙基)-3,3-二苯基三硅氧烷和甲基丙烯酸-3-(1,1,5,5-四甲基-5-丙基-3,3-二苯基三硅氧基)丙酯3个主要组分。建立了有机硅改性丙烯酸酯类功能材料的定性分析方法,对其进一步开发利用及其反应机理研究方面具有重要的指导意义。     

4-对羟基苯基-2-丁酮的合成

以生物质来源的对甲氧基苯甲醛(大茴香醛)为原料,经还原反应制备得到对甲氧基苄醇,经氯代反应制备得到对甲氧基氯苄,再与乙酰乙酸乙酯经取代反应制备得到2-乙酰基-3-(4-甲氧基苯基)丙酸乙酯,再经串联的水解、脱羧反应制备得到4-(4-甲氧基苯基)-2-丁酮,最后经脱甲基反应制备得到4-对羟基苯基-2-丁酮,总收率为60.7%。具有路线简捷、易于操作、环境友好、收率高等优点。     

高良姜中二苯基庚烷类化合物的高速逆流色谱分离制备

应用高速逆流色谱法(HSCCC)分离纯化了高良姜中3种二苯基庚烷类化合物。以正己烷-乙酸乙酯-甲醇-水(2:3:1.75:1, v/v/v/v)为两相溶剂系统,下相为固定相,上相为流动相,在主机转速为858 r/min、流速1.5 mL/min的条件下,从122.20 mg高良姜石油醚萃取物中经一步HSCCC分离可制备得到5R-羟基-7-(4-羟基-3-甲氧基苯基)-1-苯基-3-庚酮(7.37 mg)、7-(4-羟基-3-甲氧基苯基)-1-苯基-4E-烯-3-庚酮(9.11 mg)和1,7-二苯基-4E-烯-3-庚酮(15.44 mg),经高效液相色谱分析,纯度均大于93%,各化合物的结构由质谱和核磁共振氢谱、碳谱鉴定确证。该方法简便、快速、高效,可用于高良姜中二苯基庚烷类化合物的快速分离制备。     

甲基硅羟基封端硅树脂的合成及固化性能

将甲基三氯硅烷和二甲基二氯硅烷分别与二苯基二羟基硅烷反应得到1,1,5,5-四氯-1,5-二甲基-3,3-二苯基三硅氧烷(A)和1,1,5,5-四甲基-1,5-二氯-3,3-二苯基三硅氧烷(B)。按一定比例将(A)和(B)水解缩合得到完全是甲基硅羟基封端树脂(Ⅰ)。将甲基三氯硅烷和甲基三乙酰氯基硅烷分别处理一般共水解法硅封端树脂可得到另外两种甲基硅羟基封端树脂(Ⅱ)和(Ⅲ),将树脂Ⅰ、Ⅱ、Ⅲ与一般共水解法得到的具有相同R/Si和Ph/R(R代表甲基和苯基)的树脂(Ⅳ、Ⅴ、Ⅵ)进行固化试验,结果表明,甲基-硅羟基封端树脂(Ⅰ—Ⅲ)的固化速度为共水解法制得的以苯基硅羟基封端树脂(Ⅳ—Ⅵ)固化速度的两倍以上。     

新型海参硫酸软骨素葡萄糖受体及葡萄糖醛酸受体的高效合成

以D-葡萄糖为起始原料,经9步反应合成了2-O-苄基-3-O-烯丙基-1-O-对甲氧基苯基α-D-葡萄糖(9);将9的6-位伯羟基经叔丁基二苯基硅烷基(TBDPS)保护,首次合成了正交保护的新型葡萄糖受体2-O-苄基-3-O-烯丙基6-O-叔丁基二苯基硅烷基1-O-对甲氧基苯基α-D-葡萄糖(Ⅱ),总收率28.2%;将9的6-位伯羟基氧化糖醛酸化后,再经甲酯化,以25.0%的总收率首次合成了新型葡萄糖醛酸受体2-O-苄基-3-O-烯丙基-1-O-对甲氧基苯基α-D-葡萄糖醛酸甲酯(Ⅲ),化合物结构经¹H NMR,¹³C NMR, IR和HR-MS(ESI)表征。     

阳离子型UV光引发剂--三芳基硫鎓盐的合成

以硝基苯、浓硫酸、六氟磷酸钾和碘酸钾为原料,经氧化、取代、置换反应得到3,3′-二硝基二苯基碘六氟磷酸盐(2)。2与苯硫醚在苯甲酸铜的催化下合成了3-硝基苯基二苯基硫六氟磷酸盐(3)。3是一种新型的三芳基硫鎓盐阳离子UV光引发剂,其结构经UV,1H NMR,IR及MS确证。     

1,3,4-噁二唑三氮烯衍生物的合成及生物活性测定

利用拼合原理,将具有生物活性的三氮烯结构与1,3,4-噁二唑结构相拼合,设计合成了11个未见报道的1,3,4-噁二唑三氮烯衍生物.所合成化合物经1H NMR,IR和HRMS得到表征.用四甲基偶氮唑盐(MTT)法法评价了该类化合物对胃癌细胞(MGC803)和前列腺癌细胞(PC-3)的抑制作用,结果显示化合物2-[4-(3,3-二甲基三氮烯-1-基)苯基]-5-(4-甲氧基苯基)-1,3,4-噁二唑(b4)、2-[4-(3,3-二甲基三氮烯-1-基)苯基]-5-(2-甲氧基苯基)-1,3,4-噁二唑(b9)、2-[4-(3,3-二甲基三氮烯-1-基)苯基]-5-(3,4-甲叉二氧基苯基)-1,3,4-噁二唑(b10)、2-[4-(3,3-二甲基三氮烯-1-基)苯基]-5-(吡啶-4-基)-1,3,4-噁二唑(b11)对前列腺癌细胞的抑制作用强于典型三氮烯药物达卡巴嗪(DTIC),其IC50值分别为74.145,87.790,87.327和104.875μmol/L,而对胃癌细胞则几乎没有抑制作用.采用微量肉汤稀释法测试了该类化合物对大肠埃希菌(E.coli.)和金黄葡萄球菌(S.aureus)的抑制作用,结果显示这类化合物对这两种细菌并没有表现出抑制作用.     

6-取代苄硫基-3-(3,4,5-三甲氧基苯基)-1,2,4-三唑[3,4-b][1,3,4]噻二唑类化合物的合成与抑菌活性

以4-氨基-5-(3,4,5-三甲氧基苯基)-3-巯基-1,2,4-三唑为原料,环化得到6-巯基-3-(3,4,5-三甲氧基苯基)-1,2,4-三唑[3,4-b][1,3,4]噻二唑再与取代苄氯反应,得到9个6-取代苄硫基-3-(3,4,5-三甲氧基苯基)-1,2,4-三唑[3,4-b][1,3,4]噻二唑类衍生物3a～3i.其结构经IR,1H NMR,MS和元素分析确证.初步生物活性测试结果表明部分化合物有一定的杀菌活性.     

合成(±)顺式-3-(二氯乙烯基)-2,2-二甲基环丙烷羧酸的新方法

本文报道两种从5-氯-3,3-二甲基戊酸乙酯(4)合成(±)-顺式-3-(二氯乙烯基)-2,2-二甲基环丙烷羧酸(1)的方法.中间体4,4-二甲基-3,4-二氢-2-吡喃酮(3)是从化合物(4)经水解皂化,酸化和氧化得到3,3-二甲基戊醛酸甲酯(7),再皂化得到3,3-二甲基戊醛酸(8),然后环化得到;或者由化合物4经苯基硫醚化,氧化得到8,然后环化后得到.     

合成(±)顺式-3-(二氯乙烯基)-2,2-二甲基环丙烷羧酸的新方法

本文报道两种从5-氯-3,3-二甲基戊酸乙酯(4)合成±)-顺式-3-(二氯乙烯基)-2,2-二甲基环丙烷羟酸(±)的方法.中间体4,4-二甲基-3,4-二氢-2-吡喃酮(3)是从化合物(4)经水解皂化,酸化和氧得到3,3-二甲基戊醛酸甲酯(6),再皂化得到3,3-二甲基戊醛酸(8),然后环化得到;或者由化合物4经苯基硫醚化,氧化得到8,然后环化后得到.     

Grafting of Polymers onto a Crosslinked Polymer Carrying Carboxyl Groups as a Model Compound for Carbon Black

Abstract

A cation-exchange resin (a crosslinked polymer carrying carboxyl groups) was used as a model compound for carbon black, and the grafting of several polymers to the resin was investigated. Reaction of acyl chloride groups that had been placed on the ion-exchange resin with polymers having hydroxyl or amino groups, such as polypropylene glycol, polyethylene glycol, polybutadiene glycol, polyvinyl alcohol, silicone diol, silicone diamine, and polyethyleneimine, resulted in grafting to the ion-exchange resin. In further experiments, primary amino groups were placed on the cation-exchange resin by reaction of acyl chloride groups with ethylenediamine. It was found that ring-opening polymerization of γmethyl L-glutamate N-carboxyanhydride is initiated by the amino groups on the resin, and polypeptide was grafted from the cation-exchange resin. Therefore, the reactivity of carboxyl groups on the resin was found to be similar to that on carbon black. However, carboxyl groups on the resin failed to initiate the cationic polymerization of vinyl monomers, in contrast to those on carbon black. This suggested that the acidity of carboxyl groups on carbon black is greater than on the cation-exchange resin.     

Observation of 1,3-diketones formation in the reaction of bulky acyl chlorides with methyllithium

The formation of 1,3-diketones was observed in the reactions of bulky acyl chlorides with methyllithium. The reaction products depend on the steric hindrance around the carbonyl group of the acyl chloride and the electronic effect of the group(s) linked to the carbonyl. When the steric hindrance around the carbonyl group of the acyl chloride is big enough, the 1,3-diketone is the only product. In the case of the moderate hindrance around the carbonyl group of the acyl chloride, a moderate yield of 1,3-diketone is obtained and some tertiary alcohol is generated. When there is no steric hindrance around the carbonyl group of the acyl chloride, the tertiary alcohol is the only product. When the steric hindrance around the carbonyl group is moderate and an electron-donating group is connected to the carbonyl of the acyl chloride, all three products--ketone, 1,3-diketone and tertiary alcohol--can be isolated from the reaction mixture after long reaction times.     

聚苯乙烯基N-甲基-N-酰基磺酰胺树脂的制备及其作为酰基转移试剂在酰胺合成中的应用

聚苯乙烯基磺酰氯树脂(树脂1)与甲胺水溶液在吡啶的催化作用下反应，制备了N—甲基磺酰胺树脂(树脂2)．用酰氯在吡啶中与树脂2反应，得到N—酰基—N—甲基磺酰胺树脂(树脂3)．树脂3作为胺底物的酰基转移试剂，用来制备N—取代的酰胺，收率14～81％．树脂3可以有选择性地酰化乙醇胺中的氨基而不会使羟基酰化。     

Synthesis of non‐destructive amido group functionalized multi‐walled carbon nanotubes and their application in antistatic and thermal conductive polyetherimide matrix nanocomposites

Thermal conductive and antistatic polyetherimide (PEI) nanocomposites were fabricated by encapsulating non‐destructive amido group functionalized multi‐walled carbon nanotubes (MWCNTs) into the PEI matrix. Briefly, nearly half of acyl chloride groups in poly (acryloyl chloride) reacted with sodium azide and formed acyl azide groups, which could conjunct with MWCNTs via non‐destruction nitrenes addition reaction. The remaining acyl chloride groups in poly (acryloyl chloride) hydrolyzed into carboxyl groups, therefore COOH‐rich MWCNTs (MWCNTs@azide polyacrylic acid) were synthesized without serious damage to the MWCNTs. Then, MWCNTs@azide polyacrylic acid were then reacted with p‐Phenylene diamine (PPD) and transformed to amido group functionalized MWCNTs (MWCNTs@PPD). MWCNTs@PPD could participate into the in situ polymerization of PEI matrix, where the conjunction between bisphenol A dianhydride and amido groups on MWCNTs@PPD guaranteed the strong covalent bonding at the PEI/MWCNTs interface, which directly avoided the aggregation of MWCNTs. Owing to the non‐destructive modification of MWCNTs and tight matrix/filler interface, the volume electric and thermal conductivity of as‐prepared nanocomposites was up to 6.4 × 10^?8 S/cm (1.0 wt%, MWCNTs@PPD) and 0.43 W/(m · K) (4.0 wt%, MWCNTs@PPD), respectively. Copyright © 2016 John Wiley & Sons, Ltd.     

Chelating Ligands Tethered to Carbon Nanotubes

Summary: Carbon nanotubes offer an inert platform on which various species may be supported. A range of applications have been addressed using this approach. Anchoring sites on the nanotubes are usually groups introduced via an oxidative procedure. These groups provide convenient reactive functionality that can be accessed in a variety of ways. In this case, carboxyl functionality have been utilized to attach, through a linker, a good coordinating ligands, 1-10-phenanthroline. In the first instance, 1,10-phenanthroline was converted to the 5,6-epoxide by treatment with hypochlorite. The epoxide was opened in sulfuric acid to generate the 5-hydroxy compound. This, in turn, was treated with ethylene oxide in the presence of a base to provide the alkoxylated compound. The alcohol terminus, as the alkoxide, was used to couple the nanotubes by displacement of tosyl anion from the methylol ester. The carboxyl groups at the nanotubes surface were reduced to the corresponding alcohol and treated with p-toluenesulfonyl chloride in the presence of pyridine to generate the tosylate used for coupling. In a second approach the carboxyl groups were converted to the corresponding acid chloride which was treated with alkoxylated phenanthroline to achieve coupling via an ester linkage.     

丙酮酸及其衍生物的某些特异反应研究

合成了3个丙酮酸的衍生物.结果发现,2'-(N-苄氧羰基甘氨酰脯氨酰胺基)丙酮酸乙酯不稳定,该化合物可以通过自催化水解；与其他脂肪酸不同,丙酮酸与N,N-二异丙基碳二亚胺(DIC)反应形成稳定的加合物,该加合物对醇以及二级胺不敏感；在酰肼的作用下,1-氯-N,N,2-三甲基丙烯胺不能将丙酮酸转化为丙酮酰氯,而是得到2-羟基丙烯酸异丁基酯.     

脂质体的聚合反应（Ⅰ）：不饱和脂质体的单体合成

生物膜是由磷脂双分子层构成的基质和镶嵌或包埋在基质中的蛋白质所组成,脂质体与生物膜结构相似,但一般是热力学不稳定体系,为改善脂质体的稳定性,近年合成和制备了许多不饱和脂质体单体化合物和聚合脂质体。     

An ionizable chromophoric reagent for the analysis of primary amine-containing drugs by capillary electrophoresis

We found that ofloxacin acyl chloride is a potential chromophoric reagent for labeling amino analytes for capillary electrophoresis. Ofloxacin acyl chloride has a tertiary amino function in its structure and the derivatives from ofloxacin acyl chloride reacting with amino analytes can be ionized by an acid treatment and analyzed by simple capillary zone electrophoresis. Ofloxacin acyl chloride was used to derivatize model analytes (without chromophore) of amantadine (amino drug), tranexamic acid (non-protein amino carboxylic acid), glycine, and methionine (protein amino acids). The resulting derivatives were analyzed by capillary zone electrophoresis with ultraviolet detection (300 nm). The detection limits of the analytes studied were in the range of 1.0-2.5 microM (S/N = 3, injection 3 s). The precision (relative standard deviation) and accuracy (relative error) of the method for intra- and inter-day analyses of the analytes were respectively below 4.5% and 3.9%. Application of the method to the analysis of tranexamic acid in plasma proved feasible.     

Diastereoselective conjugate addition of 1-(α,β-unsaturated acyl)hydantoin with nucleophiles

A diastereomeric conjugate addition of dialkylaluminum chloride to 1-(α,β-unsaturated acyl)hydantoin provided the corresponding alkyl adduct with inducted chirality in the β-position. Treatment of 1-(α,β-unsaturated acyl)hydantoin with Gilman reagent in the presence of Lewis acid also gave the same product. In this reaction, diethylaluminum chloride was the most effective Lewis acid and the absolute configuration of the major adduct at the β-position of acyl group depended on the kinds of existing metals.     

N,N-二乙基蒎酮酸酰胺合成的研究

松节油的主要成分α-蒎烯在十二烷基硫酸钠的乳化作用下用高锰酸钾氧化,生成蒎酮酸。研究了氧化过程中各种反应因素的影响,得出较适宜的反应条件,蒎酮酸的收率在60%以上。蒎酮酸经过酰氯化后再和二乙胺反应,合成了可能有生物活性的N,N-二乙基蒎酮酸酰胺。