肌醇的生产工艺改进与应用拓展

肌醇是附加值很高的精细化工产品，是治疗心血管疾病、肝硬化等疾病的药物原料，还可用作营养药物、饲料添加剂等。目前国际市场肌醇供不应求，且消费量仍在增另，我国具有生产肌醇的优势，应积极改进传统工艺、增强国际竞争力。本主要介绍了肌醇的生产工艺的改进和应用的拓展等。     

分离对映体的旋光性固定相的研制

在自然界往往只有某种形式的旋光异构体才具有生物活性或只有某种光学异构体才有生理作用。如在肽合成、药物合成及不对称化合物的合成工作中都要求对对映体进行有效的分离测定。由于光谱、质谱等方法在对映体的分辨上没有特征,而旋光度法的分辨能力又很低,因此色谱方法,尤其是旋光性固定相的分离方法,显示了优越性。1966年Gil-Av等人首先开发了氨基酸衍生物的旋光性固定相,而后又发展了多种旋光性固定相,如二肽、二胺类及酰脲等等。目前用气相色谱法已成功地分离了氨基酸、胺类、氨基醇类、醣类等对映体,其中Bayer等人提出的以聚硅氧烷为基质的Chirasil-val固定相,因为使用温度较高,选择性较好,目前已成为普遍使用的一种旋光固定相。     

L—抗坏血酸—2—硫酸酯盐的合成

以焦硫酸钾为酯化剂，以嘴啶为溶剂合成了Ｌ－抗坏血酸的稳定衍生物－Ｌ－抗坏血酸－２－硫酸酯二卤。该衍生物具有弱酸性，在燕碱中稳定合成方法操作简便，收率高。     

L-抗坏血酸-2-硫酸酯盐的合成

以焦硫酸钾为酯化剂，以吡啶为溶剂合成了Ｌ－ 抗坏血酸的稳定衍生物 Ｌ－ 抗坏血酸－ ２ － 硫酸酯二钾盐。该衍生物具有弱酸性，在弱碱中稳定。合成方法操作简便，收率高。     

植酸和肌醇的生产工艺

植酸,化学名为环己六醇六磷酸酯,又称肌醇六磷酸酯.国外已广泛应用于食品、医药、化工、电镀、环保等领域,其应用范围和用量还在不断增加.美、日、苏等国已将之列为重要原料产品,国内正在推广应用.肌醇,化学名为环已六醇,其本身及其衍生物为治疗肝病及心血管疾病的药物.两     

5-取代海因的消旋过程对化学酶法制备D-氨基酸的影响

海因酶是化学酶法制备光学活性氨基酸的关键酶，今研究通过采用不同旋光性的底物进行了海因酶底物光学特异性的研究，结果表明，本体系采用的海因酶是D－海因酶，具有严格的光学选择性，提出了L－海因消旋是以混旋海因制备D－氨基酸的重要限速步骤，以L－5－甲基海因为对象，研究了L－海因的消旋过程，对其动力学过程进行了分析，研究表明，L－海因消旋符合一级反应动力学过程，并结合实验提出增高温度和pH值均有助于提高转化效率。     

肌醇生产中蛋白质的危害及去除

本文从肌醇工业生产的实际出发，阐述了蛋白质等杂质对肌醇质量、得率以及原辅材料消耗造成的影响，针对肌醇中蛋白质等杂质的特点，作者在不改变原生产流程，不增添设备的前提下，采用锡山市新宇化工厂生产的净化剂ＦＮＯ－１０，在去除蛋白质方面取得了明显的效果，不但提高了肌醇的质量，而且提高了肌醇得率，减少了辅助材料的消耗，降低了生产成本。     

（R）—环氧丙醇的制备

(R)-环氧丙醇1是旋光性甘油衍生物和氨基丙醇类药物等有机合成和药物合成的重要试剂。对1虽然有文献提出可由丙烯醇不对称环氧化制备,但很难得到光学纯的产品。我们参考有关文献,用廉价的 D-甘露醇为原料,通过缩酮保护,氧化断链,还原,磺酰化,水解,环化等6步反应制得光学纯(R)-环氧丙醇。反应式如下:     

肌醇生产中蛋白质的危害及去除

从肌醇工业生产的实际出发，阐述了蛋白质等杂质对肌醇质量、得率以及原辅材料消耗造成的影响。针对肌醇中蛋白质等杂质的特点，在不改变原生产流程，不增添设备的前提下，采用锡山市新宇化工厂生产的净化剂ＦＮＯ－１０，在去除蛋白质方面取得了明显的效果，不但提高了肌醇的质量，而且提高了肌醇得率，减少了辅助材料的消耗，降低了生产成本。     

肌醇生产中蛋白质的危害及去除

阐述了蛋白质等杂质对肌醇质量，得率以及原辅助材料消耗造成的影响，针对肌醇中蛋白质等杂质的特点，在不改变原生产流程，不增添设备前提下，采用净化剂ＦＮＯ－１０，在去除蛋白质方面取得了明显的效果，不但提高了肌醇的质量，而且提高了肌醇得率，减少了辅助材料的消耗，降低了生产成本。     

Synthesis, characterization and photoconductive properties of optically active methacrylic polymers bearing side-chain 9-phenylcarbazole moieties

The synthesis of two novel optically active monomers containing 9-phenylcarbazole moieties, such as (S)-(+)-2-methacryloyloxy-N-[4-(9-carbazolyl)phenyl]succinimide [(S)-(+)-MCPS] and (S)-(+)-3-methacryloyloxy-N-[4-(9-carbazolyl)phenyl]pyrrolidine [(S)-(+)-MCPP], is described. Each monomer has been radically homopolymerized to afford the corresponding optically active polymeric derivatives, which have been fully characterized. Their spectroscopic, thermal and photoconductive properties were compared to those of the new achiral homopolymer poly[N-(2-methacryloyloxyethyl)-N-[4-(9-carbazolyl)phenyl]ethylamine] {poly[MCPE]}, devised as an optically inactive macromolecular model compound, as well as to analogue polymeric derivatives containing side-chain optically active carbazolyl moieties. The chiroptical properties of the chiral polymers are quantitatively higher than in the corresponding monomers. Owing to the substantially stereoirregular structure of the main chain, this suggests that the overall optical activity is mainly due to conformational dissymmetry of the macromolecules. Spectroscopic evidence suggests the presence in all polymeric derivatives of dipole-dipole interactions between the 9-phenylcarbazolyl chromophores, occurring as a consequence of their anchorage to the polymer backbone, which favours their aggregation and justifies their high decomposition temperatures.     

联萘酚纳米孔道配位聚合物催化剂的研究进展

纳米多孔材料可用作催化剂、气体储存材料和光电子器件,是目前新型多孔材料的研究热点之一。手性联萘酚配体所修饰的催化剂是一种很优异的C2轴对称手性诱导源,可以催化各种α,β-不饱和羰基化合物,具有良好的催化活性和对映选择性。本文对由手性联萘酚类配体所修饰的小分子催化剂、聚合物负载的催化剂和自负载催化剂,在不饱和羰基化合物催化不对称环氧化反应中的应用进行了综述。本文介绍了对手性联萘酚纳米多孔配位聚合物的研究。     

Optically active photochromic methacrylic polymers with controlled average molecular weight and defined end-groups by atom transfer radical polymerization

We report a new approach based on atom transfer radical polymerization (ATRP) to produce optically active polymers containing azoaromatic moieties in the side chain with controlled average molecular weights, that can be used to investigate the conformational origin of chirality in this class of synthetic materials. The ATRP technique has been successfully applied to the synthesis of a series of optically active photochromic homopolymers poly[(S)-3-methacryloyloxy-1-(4-azobenzene)pyrrolidine] {poly[(S)-MAP]}, containing a chiral group of one prevailing configuration interposed between the methacrylic moiety and the photochromic azoaromatic chromophore. By just changing the duration of the polymerization process, macromolecules having distinct average chain lengths with low polydispersity values and well defined end-groups have been obtained.Optical activity and thermal properties of the resulting polymeric derivatives result to depend on their average molecular weight. In particular, a dependence of optical rotation and circular dichroism on chain-length has been evidenced.     

Chemo-enzymatic synthesis of optically active polymeric prodrug of naproxen, ketoprofen and ibuprofen

A combined enzymatic resolution and chemical polymerization strategy has been used to create optically active polymeric prodrugs. (S)-Naproxen, (S)-ketoprofen and (S)-ibuprofen derivatives were obtained in excellent optical purity and high yield by enzymatic resolution after optimization of reaction conditions. Each optically active monomer was subjected to free radical polymerization with methyl methacrylate. The obtained optically active polymeric prodrugs bearing (S)-naproxen, (S)-ketoprofen or (S)-ibuprofen residue were characterized by IR, NMR and GPC. The effect of molar ratio of naproxen vinyl ester to methyl methacrylate on the polymerization was also investigated. This methodology is useful to provide a facile and clean route to optically active macromolecular prodrugs.     

Optisch aktive O-Silyl-β-dicarbonylverbindungen. IV. Transsilylierungsreaktionen

Optically Active O-Silyl-β-dicarbonyl Compounds. IV. Transsilylation Reactions The relationship between the structure of O-silyl-β-dicarbonyl compounds and their tendency to transsilylation reactions is studied by gas chromatography. It is shown that the silyl derivatives of β-diketones and β-dicarboxylic acid diesters easily undergo intermolecular mutual transsilylation reactions. The same compounds quickly transfer silyl groups to free β-dicarbonyl compounds. On the contrary, with silyl derivatives of β-keto esters, o-acylphenols and salicylic acid esters no transsilylation reaction could be observed, and the transfer of silyl groups from O-silyl-β-keto esters to free β-keto esters is only very slow. The ease of transsilylation reactions of O-silyl-β-dicarbonyl compounds correlates with the velocity of racemization of optically active O-silyl-β-dicarbonyl compounds of the same structure. Therefore, we assume that intermolecular transsilylation reactions with inversion of configuration are the main reason for the racemization of optically active O-silyl-β-dicarbonyl compounds. However, no connection could be found between the tendency to transsilylation reactions and the stereochemistry of the reactions of optically active O-silyl-β-dicarbonyl compounds with LiAlH₄ which is also dependent on the structure of these compounds.     

Asymmetrisch katalysierte Additionen von Thiolen an α-Aminoacrylsäure- Derivate und Nitroolefine

Asymmetrically Catalyzed Additions of Thiols to Derivatives of α-Aminoacrylic Acid and Nitroolefins Benzylmercaptane and other thiols were asymmetrically added, under the catalytic influence of optically active bases (preferently cinchona alkaloids), to the double bond of methyl α-phthalimidoacrylate or 2-ethyl-4-methylene-1,3-oxazolin-5-one to give optically active derivatives of cysteine in optical yields upto 54%. Similar asymmetric additions of SH-compounds were performed also with 2-nitrostyrene and 1-phenyl-2-nitropropene.     

脂肪酶在催化合成光学活性农药中的应用

脂肪酶作为天然的手性催化剂，具有高立体选择性、作用底物广泛、催化反应条件温和的特点，在不对称合成、光学活性化合物及天然产物的合成领域具有广泛的用途。本文介绍了脂肪酶的催化特性及在合成不谱活性农药中的应用。     

生物催化制备光学活性4-氯-3-羟基丁酸酯研究进展

综述了生物催化制备光学活性4-氯-3-羟基丁酸酯(CHBE)的研究进展,介绍了生物催化外消旋体拆分和不对称还原方法制备光学活性CHBE的研究现状,重点阐述了反应介质选择、辅助底物和添加剂的选择、细胞热处理等一些控制不对称还原4-氯-3-氧代丁酸酯(COBE)立体选择性的方法。对生物催化制备光学活性CHBE的工业化前景进行了展望。     

金鸡纳碱及其衍生物在不对称Mannich反应中的应用

不对称Mannich反应是一种应用最广泛的合成光学活性的手性氨基酸衍生物的方法,近几年基于金鸡纳碱及其衍生物的有机小分子催化的不对称Mannich反应成为国内外研究的热点,本文简要介绍了金鸡纳碱及其衍生物在不对称Mannich反应中的应用。     

Macromolecular Conjugates of 4- and 8-Aminoquinoline Compounds

Some members of 4-aminoquinolines and 8-aminoquinolines have been found to provide adjuvant effects when used in combination with anti-cancer drugs. The clinical co-administration of active anti-cancer drugs with other drugs acting as potentiating agents has shown considerable merits when compared to a single-drug administration. Anti-cancer drugs are often toxic when delivered straight, but the bio-reversible drug conjugation of anticancer drugs to water-soluble macromolecular carriers has proved to enhance the therapeutic effectiveness of anticancer drugs. Following facilitated pharmacokinetics pathways, the conjugates, acting as pro-drugs, will release the active drug species in the transformed target cells and their designs are geared towards reducing pharmacological barriers of toxicity, drug resistance and poor bioavailability encountered with currently used anti-cancer drugs. This paper describes the synthesis of water-soluble macromolecular carriers containing 4- and 8-aminoquinolines that are bio-reversibly anchored with cytotoxic drugs. The conjugates and co-conjugates are isolated as water soluble solids and characterized by NMR-spectroscopy.