Some aromatic derivatives of 1,4,7,10,13,16-hexaoxacyclooctadecane

Summary Some of the derivatives of polyglycoles were obtained just by reacting the -chlorhydrines with phenols, -naphtol and -naphtols in the presence of NaOH. Derivatives obtained were condensed with the ditosylates of polyethyleneglycoles in the presence of potassium tert-butoxide in THF and some asymmetrical mono and disubstituted hexaoxacyclooctadecanes were formed.Submitted for the fullfilment of Ph.D.degree in Organic Chemistry. Diyarbakir University, 1981     

1,4-二氢吡啶衍生物的手性拆分及不对称合成进展

1,4-二氢吡啶衍生物(1,4-DHPs)具有广泛的生物活性,是重要的钙离子拮抗剂,详细介绍了拆分法以及不对称合成法制备光活性1,4-二氢吡啶衍生物的研究进展。拆分有化学拆分和酶拆分两种,化学拆分法主要包括经典成盐法和形成非对映体酯法,用于拆分1,4-DHPs的酶有脂肪酶和蛋白酶两种。分析了几种方法的优缺点,提出了今后的发展方向。     

2-芳硫基咪唑啉酮衍生物的合成

通过膦亚胺与苯异氰酸酯的ava-Wittig反应制得碳二亚胺，应用碳二亚胺与硫酚（取代硫酚）反应制得8个新的2－芳硫基咪唑啉酮衍生物，并初步探讨了反应条件。     

Lipase-catalyzed synthesis of chiral triglycerides

Under certain reaction conditions, the acidolysis of tripalmitin with oleic acid using immobilized lipase from Rhizomucor miehei resulted in a higher level of monosubstituted oleoyldipalmitoyl (OPP) triglycerides than had been predicted according to kinetic modeling. The reaction products were subjected to chiral analysis by high-performance liquid chromatography (HPLC), which indicated that the enzyme was more active at the sn-1 position of the triglyceride than at the sn-3 position, resulting in synthesis of the chiral triglyceride 1-oleoyl-2,3-dipalmitoyl-sn-glycerol. A kinetic model was developed and was correlated with the HPLC method to provide a simple means to predict the stereoselectivity of lipase-catalyzed reactions. By using the model, the stereoselectivity of immobilized Rhizomucor miehei lipase was found to depend strongly on the initial water activity (a _w) of the reaction mixture, with greater selectivity occurring at lower a _w. The sn-1 selectivity was essentially maintained using various solvents, or without solvent, when a _w was kept constantly low. Variation in the fatty acid composition of the triglyceride indicated that shorter-chain fatty acids result in greater stereoselectivity, while variation of the chainlength of the free fatty acid indicated an enhancement by the longest chainlength. The stereoselectivity of this lipase was confirmed using a new ¹³C nuclear magnetic resonance method. By using immobilized R. miehei lipase at low a _w approximately 80% of the chiral triglyceride found in the reaction mixture was the sn-1 enantiomer, at high reaction conversion.     

Enzymatic resolution of planar chiral ferrocene derivatives

Racemic 3-methyl, 2-ethyl, 2-bromo, and 2-trimethylsilyl derivatives of formylferrocene were kinetically resolved by enantioselective reduction with a fermenting baker's yeast. Moreover, 2-methyl, 3-methyl, 2-ethyl, 2-bromo, and 2-trimethylsilyl derivatives of hydroxymethylferrocene were optically resolved with lipases by transesterification using vinyl esters.     

对甲酚衍生物催化氧化合成对羟基苯甲醛衍生物

阐述了对甲酚衍生物催化氧化合成对式苯甲醛衍生物的研究状况及近期研究动态,对Ｃｏ盐催化剂、Ｃｏ／Ｃｕ双金属催化剂以及其他催化剂对对甲酚衍生物选择性催化氧化的性能作一评述。     

新型手性胺类衍生物的合成

胺类化合物作为亲核试剂,与手性5-(S)-5-(L-孟氧基)-3,4-二溴-2(5H)呋喃酮通过不对称Michael加成-消除反应得到4个含手性中心的胺类衍生物,产率80%～93%。所有化合物均经IR、1HNMR、13CNMR、HRMS得到确证,为室温下方便地制备含多手性中心的胺类衍生物提供了一条可能的新途径。     

新型手性伪麻黄碱衍生物的合成

首次利用单一构型的伪麻黄碱作为亲核试剂与手性5-(S)-烷氧基-3,4-二卤-2-(5H)-呋喃酮在室温下反应,合成了4种新的单一构型的含手性中心的伪麻黄碱衍生物,产率68%~85%。这是对以往相关研究作了进一步的补充,使得麻黄碱和手性5-(S)-烷氧基-3,4-二卤-2-(5H)-呋喃酮反应体系的工作趋于完善。所有化合物均经IR、1HNMR、13CNMR、HRMS确证,为室温下方便地制备含单一构型的手性伪麻黄碱衍生物提供了一条新途径,也为新型麻黄碱类药物的开发打下基础。     

苯甲醛缩氨基硫脲类化合物的无溶剂合成

以液体苯甲醛和N4-苯基氨基硫脲为原料,浓盐酸作催化剂,室温条件下,在无溶剂条件下合成了4个苯甲醛缩氨基硫脲类化合物。产品经元素分析、红外光谱与核磁共振氢谱表征,确定为目标化合物。结果表明,无溶剂条件下的反应在2 h内产率达到90%,是合成该类化合物高产、低耗、绿色、环保的好方法。     

手性芳基醇的合成研究进展

综述了近年来手性芳基醇的合成研究情况,着重介绍了对羰基进行不对称加成来制取手性芳基醇的新进展。     

Electrochemical polymerization of chiral pyrrole derivatives in electrolytes containing chiral camphor sulfonic acid

N‐Substituted pyrrole derivatives with chiral side groups have been synthesized and electrochemically polymerized in acetonitrile containing tetrabutylammonium perchlorate (TBAClO₄) and (S)‐(+)‐camphor‐10‐sulfonic acid ((S)‐(+)‐CSA) or (R)‐(?)‐camphor‐10‐sulfonic acid ((R)‐(?)‐CSA). The resulting N‐substituted polypyrrole films were characterized by cyclic voltammetry, infrared, Raman and X‐ray photoelectron (XPS) spectroscopies. XPS results demonstrated that the as‐grown polymer films are preferably doped by CSA anions when the monomer and the CSA anion have the same optical rotation dispersion (ORD). Furthermore, the conductivities of the polymers synthesized in the media containing CSA with the same ORD of the corresponding monomers were measured to be about 2–10 times higher than those of polymers obtained from electrolytes without CSA. Copyright © 2004 Society of Chemical Industry     

两种手性吲哚啉衍生物的合成与表征

以(S)-吲哚啉-2-羧酸为原料,经氮甲基化、酯化、格氏反应合成了两个未见文献报道的手性吲哚啉衍生物(S)-(1-甲基-2-吲哚啉基)二苯基甲醇和(S)-2-(1-甲基-2-吲哚啉基)-1,3-二苯基-2-丙醇,总收率分别达86.5%和89.7%,产物结构经1HNMR、13CNMR、HRMS确证。     

生物催化技术在手性化合物合成中的应用

生物催化的手性合成是当今手性合成方法研究的热点和发展方向。本文综述了生物催化技术在手性化合物合成中的应用,并对其应用前景进行展望。     

Toward optimizing synthesis of nanostructured chiral polyaniline

We report here detailed investigation into optimizing the synthesis of chiral polyaniline nanofibers using an oligomer-assisted route. The effect of temperature, monomer concentration, nature of oligomer, and the rate of oxidant addition on the optical properties of the PANI nanofibers have been carefully determined. Our results indicate that the highest chirality is achieved under conditions that promote interaction of the chiral acid with the growing polymer chain. These chiral polyaniline nanofibers are thermally stable up to 90 °C and are found to be stable against repeated doping-dedoping cycles. The as-synthesized nanofibers are partially crystalline regardless of their chirality. This partial crystallinity may be responsible for their chemical and thermal stability.     

手性α-氨基酸的不对称合成

按合成方法综述了手性α-氨基酸的研究进展。简要介绍了手性拆分、L-氨基酸的高同系化、不对称烷基化、亚胺的不对称烷基化、脱氢氨基酸的不对称氢化等各种合成方法。对手性α-氨基酸合成的今后发展方向做了讨论。     

生物催化在手性化合物合成中的应用

介绍了生物催化手性化合物合成中使用的催化剂种类,生物催化手性合成方法在手性药物、手性化妆品及其它手性化合物合成中的应用,展望了这一方法在手性化合物合成方面的前景。     

对硝基杯芳烃衍生物的合成进展

对硝基杯芳烃是制备功能性杯芳烃重要中间体。从间接硝化和直接硝化两方面系统介绍了对硝基杯芳烃衍生物合成的最新进展，着重讨论了不同硝化方法和硝化试剂的特点。