羟甲基苯基次膦酸的合成研究

本文以二氯苯膦(DCPP)、多聚甲醛和水为原料,采用两步法合成一种重要的磷系阻燃剂羟甲基苯基次膦酸。确定了优化反应条件,第一步为:在少量相转移催化剂存在下,于20℃反应6h,产率达到75.1%;第二步为:在130～140℃回流1h,经合适的溶剂重结晶,产率达83%。此工艺操作简便,能耗低,产率高。     

钯催化甲基苯基膦氢的不对称烷基化反应合成含膦手性中心化合物

研究了Pincer-钯催化的甲基苯基膦氢对卤代烃的不对称取代反应.以高收率、中等的立体选择性得到含膦手性中心的膦化合物,同时对反应的催化循环和可能的立体化学过程进行了探讨.     

苯丙氨酸酯类衍生物对映异构体的拆分

利用手性Ｃｈｉｒａｌｃｅｌ ＯＤ柱高效液相色谱对一系列苯丙氨酸酯类衍生物对映异构体进行了拆分，获得了良好的分离结果。讨论了化合物的结构对拆分效果的影响。     

超声波促进双(2,4,6-三甲基苯甲酰基)苯基氧化膦的合成

以苯基二氯化膦为主要原料,经还原取代、偶联、氧化三步反应合成了双(2,4,6-三甲基苯甲酰基)苯基氧化膦,收率70%,其结构经1HNMR和MS表征。改进了关键中间体苯基二钠化膦的合成方法,用微米钠粒取代碱金属锂、丁基锂等,大大节省了成本。     

Boc-L-甲基苯丙氨酸的合成与拆分

利用Boc-2-氨基丙二酸二乙酯和甲基苄溴为原料, 合成邻位、间位、对位甲基取代的Boc-苯丙氨酸乙酯, 经枯草杆菌蛋白酶拆分得到对应的Boc-L-甲基苯丙氨酸. 通过红外光谱、核磁共振、质谱及旋光度分析对3种物质的结构进行了表征.     

全甲基β-环糊精用于对映体拆分

合成了全甲基β－环糊精（熔点９８℃）,与用Ｃｙｃｌｏｌａｂ全甲基β－环糊精制备的色谱柱进行了比较。两者对乳酸乙酯、本乙烷有基本相同的手性选择性,但前者能罗好的拆分二氯菊酸甲酯顺、反对映体,并有较高的柱效性能,同时给出了全甲基β－环糊精对二十几种对映体的拆分结果。     

阻燃剂双（对—羧苯基）苯基氧化膦的合成新工艺

双（对－羧苯基）苯基氧化膦（ＢＣＰＰＯ）可用作聚酰胺［１,２］、聚酯［１,３］、聚苯并唑［４］等多种聚合物的反应型阻燃剂或阻燃单体以制得阻燃聚合物材料,它可同时赋予聚合物较好的阻燃性、抗静电性和染色性,较高的热稳定性和氧化稳定性以及较高的玻璃化转变...     

2-甲基-1-苯基丙胺的合成、拆分与结构表征

手性氨基醇由于原料来源广泛、便于合成,现已作为手性配体和手性助剂被广泛应用于不对称合成中。手性氨基烷基酚是许多抗生素和生物活性物质的主要成分,且在不对称催化和不对称诱导反应中取得了令人满意的效果。但自然界中氨基烷基酚贫乏,其合成和拆分也较困难。     

双(对-羧苯基)苯基氧化膦的合成

以苯、三氯化磷、甲苯为原料,通过Friedel - Crafts和氧化反应合成了高纯度(产率79.4%)的反应型阻燃单体--双(对-羧苯基)苯基氧化膦,其结构经IR,DSC及TG表征.第二步氧化反应时间为7 h.     

气相色谱-质谱法分析甲基苯基硅氧烷混合环体

用GC-MS对甲基苯基硅氧烷混合环体(Me2n-iPhiSinOn)样品进行分析,鉴定出了25个组分,其中包括甲基硅氧烷环体、含1个苯基的甲基硅氧烷环体以及含2个苯基的甲基硅氧烷环体。四甲基二苯基环三硅氧烷环体(Me4Ph2Si3O3)的2个异构体、六甲基二苯基环四硅氧烷环体(Me6Ph2Si4O4)的4个异构体都得到有效分离和归属,并且发现其各异构体的含量比例符合随机环化的理论值。同时对该混合环体的苯基/甲基比例以及苯基含量进行了计算,并得到氢谱的验证。     

dl-萘普生的简便合成及其光学异构体的拆分

萘普生(S)-(+)-2-(6-甲氧基-2-萘基)丙酸(1)是一种新型非甾体抗菌消炎药物,临床应用十分广泛,疗效显著^[1]。其分子结构中有一个不对称碳原子,S体比R体的药理作用要强28倍^[3]。     

手性亚砜类化合物的包结拆分

本文简要综述了手性亚砜类化合物的包结拆分研究,介绍了吡啶亚砜类化合物（包括苯并咪唑类抗胃溃疡药物）的包结拆分研究的最近进展。     

THE IMMOBILIZATION OF AMINOACYLASE AND THE RESOLUTION OF D,L-PHENYLALANINE

A polymer with suitable physical characters and matched functional groups was synthesized,and used as a supporter to immobilize aminoacylase. The results showed that this supporterhad high immobilizing capacity and high selectivity for aminoacylase. Immobilized amino-acylase had high specific activity. In this paper, we determine the physical and chemicalcharacters of aminoacylase for resolution of D,L--phenylalanine, including its optimum tem-perature, pH, ion concentration, activated ion, substrate concentration, thermal stability anddenaturation. The immobilized aminoacylase was used to resolve the D,L-phenylalaninecontinuously. Thc resolved products was separated and purified with ion-exchange resins. L-phenylalanine solution was concentrated by vacuum evaporation and its hydrochloride wasformed. Checking of final product with polarimeter showed high yield and purity.     

SYNTHESIS OF THE NOVEL CHIRAL POLYMERS WITH MULTIDENTATE LIGAND AND RESOLUTION OF DL-AMINO ACIDS

A new way for synthesizing styrenic type of chiral resins grafting to multidentate ligand has been found. The synthetic scheme is proved to be practical by means of elemental anaysis, IR spectra and metal adsorbility. The resolving power of the new chiral ligand resins coordinated with copper (Ⅱ) as stationary phases has been discussed based on HPLC, and some points of view about the compositions of mobil phase and mechanism of resolution are presented.     

高效液相色谱手性固定相法拆分DL—3,4—二羟基苯丙氨酸对映体

用高效液相色谱手性固定相法,以自行制备的两种Ｐｉｒｋｌｅ型手性固定相拆分的ＤＬ－３,４－二羟基苯丙氨酸对映体,均获得了良好的拆分效果。     

DL-苯丙氨酸-1-14C化学合成及酶促拆分

本文报道 DL-苯丙氨酸-1-(14)~C 的合成,并利用嗜热菌蛋白酶酶促拆分光学异构体。化学产率和放化产率一致,可达67%,标记化合物的放化纯度高于95%。     

SOLID STATE HIGH RESOLUTION ~(13)C NMR STUDY OF CHINESE MUDSTONE KEROGENS

Using ~(13)C CP MAS TOSS DD NMR, some rules governing the variations of structureparameter and fractional contents for various aliphatic carbon in the mudstone kerogensburied in different depths in China are first reported in this paper, and the preliminarystudies on their natural evolution as well for the formation of oil and gas have been made.The influence of T_(CP), T_(CH), f_(rsc) on quantity measurement of CP in kerogens is discussed.     

Attempt to Resolute Chiral Clusters by Optically Active Hydrazide

Due to the framework chirality optically active clusters can provide the proof that a cluster as a whole, and not one of its fragments, acts as a catalyst, most of the work have been directed to the synthesis of tetrahedron-type chiral clusters1-3. However, there remains another major problem to obtain the pure enantiomers. Although Vahrenkamp had obtained some pioneering results in this area before 19901, only several racemic chiral clusters have been separated into pure enantiomers until now…     

CHROMATOGRAPHIC RESOLUTION MECHANISM OF A TRIS(1, 10-PHENANTHROLINE)SILICON(IV) COMPLEX

Abstract

The ion-association constants between the optically active complex cations (A- or Δ-[Si(phen)₃]⁴⁺) and the resolving agent anions ([Sb₂[(+)-tart]_2-]^2-, tart = tartrate(4-) ion) were determined spectrophotometrically. Ion-association between the complex cation and the eluent union occurred in two steps and the stereoselective interaction was observed in the second step. The second-step association constant for the A-enantiomer (K ₂ = 1.41 × 10³) is larger than that for the Δ-enantiomer (K ₂ = 1.07 × 10³). The second-step association plays a dominant role in determining the elution order in column chromatographic resolution. The molecular mechanics calculations for the ion-associated species were performed to obtain information about the microscopic interaction between the ions. The total strain energy for the species containing the A-enantiomer is smaller than that for the Δ-enantiomer and this can explain the experimental finding that the A-enantiomer is eluted faster than the Δ-enantiomer.