歧化松香树脂酸乙烯酯组成与结构的研究

本文研究了国产歧化松香乙烯酯的组成与各组分的分子结构，结果表明国产歧化松香乙烯酯的主要成分是二氢枞酸和脱氮枞酸的乙烯酯，二者重量比为3∶4；其乙烯酯上的乙烯基在核磁共振谱图中呈现为很好的ABX系统；因为二氢枞酸有三个异构体，所以仅用光谱方法无法确定二氧枞酸乙烯酯环内双键的位置。     

ATRP法合成聚去氢枞酸丙烯酸乙二醇酯的研究

本研究从歧化松香中提取的去氢枞酸(DHA)出发,经酰氯化后与丙烯酸(2-羟基)乙酯反应,合成了去氢枞酸丙烯酸乙二醇酯(DHAAGE);并以此为单体,2-溴-异丁酸乙酯(EBr-iB)为引发剂,CuBr/2,2'-联吡啶(2,2'-bipyridine)为催化体系,在90 oC下,利用原子转移聚合(ATRP)法制备了聚去氢枞酸丙烯酸乙二醇酯(PDHAAGE).利用FT-IR、1H-NMR和GPC对所制备的单体和聚合物进行了表征,同时考察了单体转化率随聚合反应时间的变化.结果表明,聚合反应动力学曲线呈良好线性关系,表观聚合速率常数kp′为3.6 ×10-7 s-1;所得聚合物的分子量分布很窄.     

Synthesis of Dehydroabietic Acid (2-Acryloyloxy) Ethyl Ester in Ionic Liquids

A simple ionic liquid methodology for the synthesis of a novel derivative of dehydroabietic acid is described. 1-Butyl-3-methylimidazolium tetrafluoroborate [bmim]BF₄, a typical ionic liquid, was used as an efficient and environmentally benign solvent in the synthesis of dehydroabietic acid (2-acryloloxy) ethyl ester by O-acylation reaction of dehydroabietic acid chloride with 2-hydroxyethyl acrylate. This new method showed the advantages of mild reaction conditions, short reaction times, good yields, and recyclable solvent.     

Synthesis of Di- and Triterpenoid Ferrocenyltriazoles

Ferrocene conjugates with a lupane triterpenoid linked through a triazole ring and C₃ or C₆ hydrocarbon tether were synthesized by reaction of ferrocenylalkylazides with betulonic acid propargyl ester. Analogous conjugates were obtained from dehydroabietic acid propargyl ester.     

Polymers from 12-hydroxymethyltetrahydroabietic acid and its vinyl and acrylate esters

12-Hydroxymethyltetrahydroabietic acid has been homopolymerized by melt condensation and homopolyester has been obtained. Vinyl 12-hydroxymethyltetrahydroabietate has been prepared from 12-hydroxymethyltetrahydroabietic acid by vinyl interchange procedure with vinyl acetate, and has been homopolymerized, copolymerized with vinyl chloride, vinyl acetate, and terpolymerized with styrene and acrylonitrile. The acrylate ester of 12-hydroxymethyltetrahydroabietic acid also has been prepared from 12-hydroxymethyltetrahydroabietic acid and acrylyl chloride. The acrylate thus obtained has been homopolymerized and copolymerized with vinyl chloride and vinyl acetate. Polymers thus obtained have been characterized.     

Regioselective lipase-catalyzed acylation of 41-desmethoxy-rapamycin without vinyl esters

Selective lipase-catalyzed acylation of 41-desmethoxyrapamycin has been achieved with a quaternary carboxylic acid avoiding the use of vinyl ester activation. Among the acyl donors investigated, the novel butanedione-monooxime and the N-acetylhydroxamate ester proved to be the most efficient donors, comparable in reactivity to the undesired vinyl ester and allowing selective, preparative acylation on gram scale in excellent yields. These new donors are proposed as sustainable and process-friendly alternatives to the widely used vinyl ester substrate activation in lipase-catalyzed acylations of secondary alcohols.     

褐煤树脂中游离酸的化学组成与结构特征

对云南潦浒、寻甸、吉林舒兰褐煤树脂中游离酸的化学组成及结构特征进行了对比研究。结果显示,潦浒和寻甸游离树脂酸主要是由云 氢松香酸组成,其它三环二萜酸,如松脂酸、三达松脂酸、氢化松香酸、松香酸以及五环三萜酸均有分布,但含量低。正构烷酸Ｃ１２￣Ｃ２８也存在着分布,且集中在Ｃ１６、Ｃ１８和Ｃ２０上,低碳数支链烷酸也被检出。因此,去氢松香酸是潦浒寻甸游离树脂酸的特征代表物,与此相反,舒半游离树脂酸则主要     

A novel synthesis of vinyl esters from vinylversatate-10

Vinylversatate-10 (VV10)¹ has successfully been used to synthesise a large number of lower vinyl esters by transvinylation in presence of mercuric acetate and sulfuric acid. The synthesis of vinylhalo esters proceeds with more difficulty. It has been observed that neither Hg(OAc)₂ nor H₂SO₄ alone is capable of initiating the transvinylation. Furthermore, it has been found that a molar ratio 2:1 of VV10 to carboxylic acid is sufficient to drive the reaction to the right by continuous distillation of the vinyl ester formed, and as a result a high yield of vinyl ester is obtained. A mechanism for this reaction and for the formation of side products has been proposed.     

Stepwise unidirectional synthesis of oligo phenylene vinylenes with a series of monomers. Use in plastic solar cells

Four new monomers for directional stepwise synthesis of oligophenylenevinylenes (OPVs) (4-{2-[4-(5,5-dimethyl[1,3]dioxan-2-yl)-2,5-dipropoxyphenyl]vinyl}benzyl)phosphonic acid diethyl ester, (5-{2-[4-(5,5-dimethyl[1,3]dioxan-2-yl)-2,5-dipropylphenyl]vinyl}thiophene-2-ylmethyl)phosphonic acid diethyl ester, (5-{2-[4-(5,5-dimethyl[1,3]dioxan-2-yl)-2,5-dipropoxyphenyl]vinyl}thiophene-2-ylmethyl)phosphonic acid diethyl ester, and (7-{2-[4-(5,5-dimethyl[1,3]dioxan-2-yl)-2,5-dipropylphenyl]vinyl}benzo[1,2,5]thiadiazol-4-ylmethyl)phosphonic acid diethyl ester have been prepared. Trimeric OPVs were then synthesized and tested as active materials in photovoltaic cells. Conversion efficiencies in the range of 0.5-1% were obtained in blends with the soluble C(60) derivative PCBM. A terpyridine end-functionalized trimer and a heterotrimer with a mixed composition of monomers were also prepared.     

脱氢枞酸及其衍生物生物活性的研究进展

脱氢枞酸是一种从松香中分离出来的具有三环二萜结构的树脂酸,具有广泛的生物活性,在医药、工业、农业等领域具有重要的用途。本文综述了脱氢枞酸衍生物在抑菌、抗病毒、K离子通道开启、抗肿瘤等生物活性方面的研究进展,展望了脱氢枞酸衍生物的研究和应用前景。     

去氢枞酸蔗糖酯的溶剂法合成

松香主要成分是二萜树脂酸(C29H29COOH,含量约为90％),可用作表面活性剂的合成原料。将松香树脂酸与蔗糖进行酯化反应,即可合成松香-蔗糖基非离子表面活性剂。目前关于高级脂肪酸蔗糖酯和松香基表面活性剂的研究有许多报道,但有关松香蔗糖酯的研究报道极少,工艺极不成熟,且都使用未经改性的松香,结构中仍保留两个易氧化的双键,不利于长时间储存和使用。从歧化松香中分离提纯去氢枞酸,     

导数光谱法测定松香中枞酸和脱氢枞酸

本文用导数光谱法对松香中枞酸和脱氢枞酸的测定进行了方法研究和比较,并用四阶导数光谱对几种不同松香中枞酸和脱氢枞酸进行了同时测定,结果令人满意。该法灵敏度高,能较好地消除背景干扰。相对标准偏差0.17％;枞酸回收率99.17％;脱氢枞酸回收率96.27％。     

Analysis of nonvolatile oxidation products of polypropylene. III. Photodegradation

The nonvolatile oxidation products of photodegraded polypropylene have been analyzed by infrared spectroscopy and chemical reactions. The major functional group is ester followed by vinyl alkene, then acid. In comparison, thermally oxidized polypropylene contains relatively more aldehyde, ketone, and γ-lactone and much less ester and vinyl alkene. Photodegraded polyethylene contains mostly vinyl alkene followed by carboxylic acid. Gel-permeation chromatography (GPC) determined the decrease in polypropylene molecular weights with exposure time. A calculation determined that there is one functional group formed per chain scission; in thermal oxidation there are two groups formed per scission.     

A convergent approach to gamma-carbonyl vinyl boronates

Gamma-carbonyl vinyl boronates can be prepared by a visible light induced radical chain addition of an S-acyl dithiocarbonate (xanthate) to the pinacol ester of vinyl boronic acid, followed by treatment with base.     

分子量规整聚p-乙烯基苯甲酸及苯乙烯p-乙烯基苯甲酸两嵌段共聚物的合成

当两嵌段共聚物为由性质不同的规制 (Ｗｅｌｌ ｄｅｆｉｎｅｄ)分子量两链段所构成时 ,在只对其中一链段为良溶剂的选择性溶剂中 ,它能够自组装形成尺寸均一的胶束 .胶束的形态与共聚物的组成、浓度、溶剂的性质等关系密切[1] .因此 ,两嵌段共聚物的合成颇被关注[2 ] .这一性质使得嵌段共聚物在分子识别、药物和其他物质的输送、基因疗法、水系涂料、污染物的除去、催化剂以及传感器等方面展示着潜在的应用前景 .规制分子量的两嵌段共聚合物的合成主要通过阴离子、阳离子、开环易位、基团转移等活性或可控聚合来实现 .但是这些方法受到单体…     

对位取代二苯乙烯衍生物的合成和非线性光学性质

合成了反式-4-[N-（乙氧基羰基-4"-硝基苯基）-N'-乙基氨基]-4'-(二甲基氨 基)二苯乙烯(DMANHAS)和三个新有机化合物。用核磁、红外以及元素分析进行了表 征。测试了紫外吸收光谱、单光子荧光光谱和双光子荧光光谱。在800nm的飞秒脉 冲激光激发下,反式-4-（N-羟乙基-N'-乙基氨基）-4'-(二甲基氨基)二苯乙烯 (DMAHAS)和反式-4-(N-羟乙基-N'-乙基氨基)-4'-(二乙基氨基)二苯乙烯(DEAHAS) 均发出较强的蓝紫色上转换荧光,荧光峰分别位于436和440nm,而DMANHAS和反式- 4-[N-(乙氧基羰基-4"-硝基苯基)-N'-乙基氨基]-4'-（二乙基氨基）二苯乙烯 (DEANHAS)没有荧光。     

脂肪族二酸二烷基双去氢枞基双噁二唑的合成及除草活性

以去氢枞酸为原料,制备去氢枞酸酰氯.以脂肪族二酸为原料,经过脂肪族二酸二乙酯得到脂肪族二酸二酰肼.脂肪族二酸二酰肼与去氧枞酸酰氯在相转移催化下反应得到N,N＇-二去氢枞酰基取代脂肪族二酸二酰肼,再脱水环合,得到5个标题化合物脂肪族二酸二烷基双去氢枞基双噁二唑.通过元素分析,IR,MS,1H NMR和13C NMR对所合成的新化合物进行了结构表征.初步的除草活性测试表明,化合物6b～6e在100 μg/mL浓度下对油菜的胚根生长具有良好的抑制作用,抑制率均超过80％.     

Amides of Dehydroabietic Acid Based on 5-Aminooxoindoles and Their Transformation Products

Chemistry of Natural Compounds - Amides of dehydroabietic acid based on 5-aminooxoindoles were synthesized. Further transformations of the oxoindole-functionalized dehydroabietic acid derivatives...     

Synthesis and photopolymerization of novel multifunctional vinyl esters

Novel mono‐ and multifunctional vinyl ester monomers containing thioether groups were synthesized via an amine‐catalyzed Michael addition reaction between vinyl acrylate and multifunctional thiols. Using photo‐differential scanning calorimetry and real‐time Fourier transform infrared (RTIR) spectroscopy, the polymerization kinetics and oxygen inhibition of the homopolymerizations of the vinyl ester monomers were investigated. The effect of the vinyl ester and thioether group on acrylate/vinyl ester and thiol/vinyl ester copolymerizations was determined using real‐time IR spectroscopy to monitor polymerization rates of acrylate, vinyl, and thiol groups simultaneously. Polymerization of the vinyl esters used was found to be relatively insensitive to oxygen inhibition. We propose that the thioether group is responsible for reducing oxygen inhibition by a series of chain transfer/oxygen‐scavenging reactions. In polymerization of a acrylate/vinyl ester mixture both in nitrogen and in air, the vinyl ester monomer significantly enhances the polymerization rates and the conversion of the acrylate double bonds via plasticization of the crosslinked matrix and reduction of inhibition by oxygen. Ultimately, the vinyl ester monomer is incorporated into the polymer network. Thiol/vinyl ester free‐radical copolymerization is much faster than either thiol/allylether copolymerization or vinyl ester homopolymerization. The electron‐rich vinyl ester double bonds ensure rapid copolymerization with thiol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4424–4436, 2004     

(Meth)acrylate vinyl ester hybrid polymerizations

In this study, vinyl ester monomers were synthesized by an amine catalyzed Michael addition reaction between a multifunctional thiol and the acrylate double bond of vinyl acrylate. The copolymerization behavior of both methacrylate/vinyl ester and acrylate/vinyl ester systems was studied with near‐infrared spectroscopy. In acrylate/vinyl ester systems, the acrylate groups polymerize faster than the vinyl ester groups resulting in an overall conversion of 80% for acrylate double bonds in the acrylate/vinyl ester system relative to only 50% in the bulk acrylate system. In the methacrylate/vinyl ester systems, the difference in reactivity is even more pronounced resulting in two distinguishable polymerization regimes, one dominated by methacrylate polymerization and a second dominated by vinyl ester polymerization. A faster polymerization rate and higher overall conversion of the methacrylate double bonds is thus achieved relative to polymerization of the pure methacrylate system. The methacrylate conversion in the methacrylate/vinyl ester system is near 100% compared to only ～60% in the pure methacrylate system. Utilizing hydrophilic vinyl ester and hydrophobic methacrylate monomers, polymerization‐induced phase separation is observed. The phase separated domain size is in the order of ～1 μm under the polymerization conditions. The phase separated domains become larger and more distinct with slower polymerization and correspondingly increased time for diffusion. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2509–2517, 2009