共查询到19条相似文献,搜索用时 78 毫秒
1.
2.
3.
天冬酰胺叔丁酯的改良合成 总被引:1,自引:0,他引:1
在多肽和蛋白质的结构及功能研究中,天冬酰胺(Asn)备受关注.在α-螺旋结构的肽链中,天冬酰胺往往处于C-末端,通过其侧链形成的氢键限制构象任意改变,使螺旋结构稳定[1].-CH2CONH2侧链还可作为糖肽的键合点[2],后者在细胞识别方面起着重要作用.近来又发现天冬酰胺叔丁酯与芳香醛形成亚胺后,可与另一氨基酸的酰氯缩合,生成二肽的同时伴随天冬酰胺的环化,形成四氢嘧啶酮的环状结构[3],为天冬酰胺在多肽合成中的应用开辟了新途径. 应用天冬酰胺合成多肽时,经常涉及天冬酰胺羧基的保护.甲酯和乙酯等酯基保护基在脱保护时会导致侧链脱水形成腈类副产物.叔丁酯比较稳定,在大多数形成肽键的缩合反应条件下不分解,必要时又可方便地在三氟乙酸中脱去保护,是理想的保护基.但是,叔丁酯的制备相对比较困难.由于叔丁基的空间位阻,酸催化下由叔丁醇和氨基酸直接酯化通常得不到预期的产物.采用激烈的酯化条件又可能导致氨基酸消旋化.为克服这些困难,一般以异丁烯作酯化剂,在酸催化剂存在下与氨基酸反应制备叔丁酯.…… 相似文献
4.
5.
6.
7.
研究了过氧化苯甲酸叔丁酯的热分解动力学及不同包装规格下的自加速分解温度(SADT),利用C600微量热仪测试了过氧化苯甲酸叔丁酯的热分解特征,得到升温速率分别为0.1 K/min、0.2 K/min、0.5 K/min、1 K/min下热流随时间的变化曲线,并使用Friedman等转化率法对所得的实验数据进行分析处理,得到了过氧化苯甲酸叔丁酯的分解反应活化能、指前因子等热动力学参数,推算了不同包装规格的过氧化苯甲酸叔丁酯的SADT。结果表明TBPB分解活化能及指前因子随转化率变化而变化,活化能范围为42-135.5 kJ/mol,指前因子范围为0.25-33.5,在25L聚乙烯桶包装下的SADT为59℃,50L下为52℃,200L下为46℃。 相似文献
8.
9.
拟除虫菊酯类和酰基硫脲类化合物具有很好的杀虫 ,杀菌及植物生长调节活性[1 - 3] 。本文采用有效基团拼接方法 ,以拟除虫菊酯类化合物的活性部分即取代菊酸为母体 ,以酰基硫脲为骨架 ,并将叔丁基引入到该结构中 ,设计合成了 4种N 叔丁胺基羰基 N 取代菊酰硫脲类化合物。结构经1 HNMR ,IR和元素分析表征 ,初步的生物活性测定结果表明该类化合物具有较好的生物活性合成路线为 ,其结构简式如下发 :1 实验部分1 1 仪器和试剂XT4A型显微熔点测定仪 ;Nicolet5DXFT IR型红外光谱仪 (KBr压片 ) ;joelFX 90Q型超导核磁仪 (CDCl3作溶… 相似文献
10.
以甲基丙烯酸-3-(三甲氧基硅基)丙酯(MPS)修饰的SiO2胶体粒子为种子,甲基丙烯酸叔丁酯(tBMA)为单体、十二烷基硫酸钠(SDS)为乳化剂,采用种子乳液聚合法制备了SiO2/聚甲基丙烯酸叔丁酯的核壳复合微粒。微粒经水解后形成具有pH敏感性的无机/有机复合微粒。研究了影响核壳复合微粒形态结构的因素,结果发现,控制SiO2种子乳液的质量分数在1.5%~2%,可避免聚合过程中生成纯聚甲基丙烯酸叔丁酯乳胶粒子;反应体系中乳化剂SDS的用量超过质量分数0.3%时,易形成纯聚合物乳胶粒子;SDS用量低于质量分数0.15%时,生成的核壳复合微粒易产生团聚;单体和交联剂用量升高,核壳复合微粒的壳层厚度增加,用量过高会导致核壳复合微粒出现团聚现象,并且有纯聚合物乳胶粒子生成。采用TEM、NMR和FTIR及接触角测试技术分析结果表明,复合微粒是由SiO和聚甲基丙烯酸叔丁酯组成的核壳结构微粒。 相似文献
11.
A simple method for the determination of methyl tert-butyl ether (MTBE) in gasoline has been developed. The separation of MTBE from other analytes was controlled by the use of gas chromatography–mass spectrometry in the full scan mode using the characteristic primary, secondary and tertiary ions m/z 73, 57 and 43. The sample mass spectrum did not show any superimposition of other analytes. The separation from the common gasoline component 2-methylpentane was sufficient for reliable quantitation. An application of the developed conditions using gas chromatography with flame ionization detection was performed by the analysis of regular, euro super, super premium unleaded and ‘Optimax’ gasoline from petrol stations in the area of Frankfurt/Main, Germany. Regular unleaded gasoline shows an average MTBE content of 0.4% (w/w), whereas the MTBE content in euro super gasoline varies between 0.4 and 4.2% (w/w). The blending of MTBE to super premium has increased from 8.2% (w/w) in 1998 to 9.8% (w/w) on average in 1999. The recently introduced gasoline ‘Optimax’ shows an average MTBE content of 11.9% (w/w). The presented method might also be used for the analysis of other ethers, such as ethyl tert-butyl ether, which requires the use of another internal standard. 相似文献
12.
13.
The first total synthesis of isoquinolinone alkaloid marinamide 1 and its methyl ester 2 was described. The key steps involved a regioselective Frieclel-Crafts reaction of 1-benzyl-1H-pyrrole to form the intermediate 8. 相似文献
14.
15.
A novel method is proposed to synthesize new mesoporous silica containing amine groups (MPSA), and it was further employed to modify bismaleimide‐dialllyl bisphenol (BD)/cyanate ester (CE) resin to form novel MPSA/BD/CE hybrids; in addition, the typical properties of MPSA/BD/CE were systematically investigated. Results show that these hybrids have very low dielectric constant and loss as well as good thermal properties. Compared with BD/CE resin, all hybrids have not only decreased dielectric constant and loss but also similar dependence of dielectric properties on frequency over the whole frequency from 10 to 106 Hz. Specifically, with the addition of MPSA to BD/CE resin, the dielectric constant reduces from 3.5 to 3.0, and the dielectric loss is only 85% of that of BD/CE resin. Note that all hybrids show better thermal resistance (reflected by higher glass transition temperature, decreased maximum degradation rate, and higher char yield at 800°C) than BD/CE resin. All these differences in macro‐properties are attributed to the different structure between MPSA/BD/CE hybrids and BD/CE resin. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
16.
Rosin glycerin ester and its bromide were prepared from natural renewable rosin, glycerin and liquid bromine which were first
subjected to an esterification reaction, followed by an addition reaction. Their structures were characterized by an infrared
(IR) spectrum and their thermal resistance was conducted with thermal gravity (TG) and differential scanning calorimetry (DSC).
It showed that the bromide in the rosin glycerin ester decomposed faster than the ester; hence it may be used as fire-resistant
material. 相似文献
17.
以7-苯乙酰氨基-3-氯甲基头孢烷烯酸对甲氧基苄酯(GCLE)和吡啶为原料合成头孢他啶中间体7-苯乙酰氨基-3-吡啶甲基头孢-4-羧酸对甲氧苄酯,用高效液相色谱仪监测了吡啶与GCLE碘取代物在二氯甲烷、丙酮、四氢呋喃、乙酸乙酯和DMF混合液中的亲核取代反应,反应的动力学行为可用SN2机理来解释。在一定的溶剂中不同温度的速率常数可用Arrhenius方程很好的关联。根据Arrhenius方程求得了指前因子,进一步讨论了该反应的溶剂效应,得出在不同溶剂中亲核取代反应顺序为:乙酸乙酯-DMF混合液>二氯甲烷>四氢呋喃>丙酮。 相似文献
18.
Grzegorz Lewandowski 《Reaction Kinetics and Catalysis Letters》2002,77(2):325-334
The reaction rate at the initial period during the epoxidation of 2-methyl-2-pentene with tert-butyl hydroperoxide in the presence of Mo(CO)6 as catalyst varies linearly in the range of lower concentrations of olefin, hydroperoxide and catalyst. The reaction is losing the first order character in the region of higher concentrations due to the inhibition with the reaction products. This finds the confirmations in a discrepancy between the concentration and the instantaneous (temporal) reaction order. 相似文献