D-(—)－樟脑磺内酰胺合成方法的改进

D- ( - ) -樟脑磺内酰胺是重要的手性助剂 ,由于它具有刚性骨架结构 ,在不对称合成中空间效应明显 ,立体选择性高 ,所得产物光学纯度一般都大于 90 % e .e .,而且合成它的原料 D- ( ) -樟脑磺酸易得 ,D- ( - ) -樟脑磺内酰胺经结晶即可纯化 ,并可回收再利用 ,因而被广泛用于不对称合成反应中 ,如 Die ls- Alde r反应 [1]、1 ,4—加成反应 [2 ] 、Mannich反应 [3] 、α,β—二羟基化反应 [4] 、催化氢化反应[5 ] 、共轭加成反应 [6 ] 、成杂环反应 [7] 、环丙烷化反应 [8] 等。本文报道合成 D- ( - ) -樟脑磺内酰胺的新方法 ,对反应试剂…     

手性CBS催化剂的研究进展

CBS催化剂是不对称还原反应中重要的手性催化剂,广泛应用于不对称合成领域中极重要的手性配体与手性中间体以及生物活性物质和天然物质的合成,具有巨大的市场潜力。CBS催化剂的制备通常是以(R/S)-脯氨酸为原料,先经某些反应保护氨基与羧基后进行格氏反应,之后脱去保护基团得前驱体(R/S)-α,α′-二苯基-2-吡咯烷甲醇,再与硼烷或其衍生物进行反应而得到。对CBS催化剂的制备方法、在有机合成中的应用、不对称催化反应的机理及其负载化进行了概述。     

手性羰基(η6-芳烃)铬配合物在不对称合成中的应用

综述了手性羰基(η^6—芳烃)铬配合物在氢化反应、烷基化反应、取代反应、硼氢化反应、Diels—Alder反应等不对称合成中的应用。     

国内资料文摘(83059～83082)

用不对称合成方法制取光学活性的除虫菊酯,但是,合成产物的光学收得率均不高,大约20%～30%。本文报道了合成两种不对称铜络合物试剂,樟脑磺酸铜(Ⅰ)和双[N-α-苯乙基水杨醛亚胺]铜Ⅱ。并以此作为不对称合成的催化剂,开展不对称合成的研究工作。即对重氮醋酸酯进行放氮反应,生成的卡宾对碳碳双键进行加成环化反应,最后,制得了具有一定化学活性的顺式二氯菊酸。     

不对称催化反应合成手性药物的研究进展

综述了不对称催化反应在手性药物合成中的应用,包括不对称催化氢化、不对称催化氧化、不对称催化环丙烷化、不对称催化羰基化和羰基的不对称催化还原。介绍了L-多巴、(S)-萘普生、薄荷醇、(S)-心得安、(S)-阿替洛尔、二肽抑制剂Cilastatin、氟西汀、布洛芬的合成工艺和Sharpless环氧化(AE反应)、不对称双羟基化(AD反应)、不对称羟氨化(AA反应)三种典型的不对称催化氧化反应。展望了不对称催化反应在手性药物合成中的发展方向。     

手性相转移催化剂的合成和不对称诱导效应Ⅳ--手性双季铵盐

以(-)—苯丙氨酸、( )．樟脑酸和(-)—氯霉素为原料,合成了3种手性双季铵相转移催化剂,它们在α-羟基苯乙酸的合成中显示良好的催化作用和一定的不对称诱导效应。     

(S)-(+)-萘普生的催化不对称合成研究进展

对近10年来非甾体消炎镇痛药物(S)-(+)-萘普生的催化不对称合成方法进行了综述,重点介绍了不对称催化氢化反应、不对称氢氰化反应、不对称二羟基化反应和不对称交叉偶合反应等不对称合成技术的新进展.其中特别对不对称催化氢化反应中催化剂的高活性、高选择性以及分离回收方法的研究进展作了评述,指出了均相催化剂的多相化是今后的研究方向.同时提出了(S)-(+)-萘普生的催化不对称合成技术今后研究中需要解决的关键问题.     

维生素A和E的化学合成

综述了砜化物、Ｗｉｔｔｉｇ、Ｋｎｏｅｖｅｎａｇｌｅｌ和Ｇｒｙｇｎａｒｄ反应缩合法合成视黄醇以及ｄ－α生育酚及其主环和侧链不对称合成的新近研究进展。     

α-脱氢氨基酸衍生物的不对称催化氢化研究进展

α-脱氢氨基酸及其衍生物是不对称催化氢化反应中研究的最早的一类底物。这类化合物不但易于合成,更重要的是氢化产物α-氨基酸具有重要的生物活性,有着广泛的应用α-脱氢氨基酸酯的不对称催化氢化反应还被用作模型反应,以评价新的手性配体的催化活性和手性诱导效果。目前,已有很多手性膦配体在该反应中取得了优秀的催化活性和对映选择性。     

超临界二氧化碳中的不对称合成反应研究进展

本文主要介绍超临界二氧化碳中的不对称合成反应,如不对称氢甲酰化反应、碳碳双键不对称催化反应、碳氮双键的不对称催化还原、不对称D-A反应、不对称酶催化合成反应的研究进展。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料，介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比，介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序，对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

Inorganic/organic nanocomposite coatings: The next step in coating performance

Inorganic/organic hybrid materials have considerable promise and are beginning to become a major area of research for many coating usages, including abrasion and corrosion resistance. Our primary approach is to prepare the inorganic phase in situ within the film formation process of the organic phase. The inorganic phase is introduced via sol-gel chemistry into a thermosetting organic phase. By this method, the size, periodicity, spatial positioning, and density of the inorganic phase can be controlled. An important aspect of the inorganic/organic hybrid materials is the coupling agent. The initial task of the coupling agent is to provide uniform mixing of the oligomeric organic phase with the sol-gel precursors, which are otherwise immiscible. UV-curable inorganic/organic hybrid systems have the advantages of a rapid cure and the ability to be used on heat sensitive substrates such as molded plastics. Also, it is possible to have better control of the growth of the inorganic phase using UV curing. It is our ultimate goal to completely separate the curing of inorganic and organic phases to gain complete control over the morphology, and hence optimization of “all” the coating properties. Thus far, it has been found that concomitant UV curing of the inorganic and organic phases using titanium sol-gel precursors afforded nanocomposite coatings which completely block the substrate from UV light while maintaining a transparent to visible light. Also, it has been found that the morphology of the inorganic phase is highly dependent on the concentration and reactivity of the coupling agent. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Some Large Wood-Boring Beetles in Southeastern USA

Ethanol and α-pinene were tested as attractants for large wood-boring pine beetles in Alabama, Florida, Georgia, North Carolina, and South Carolina in 2002–2004. Multiple-funnel traps baited with (−)-α-pinene (released at about 2 g/d at 25–28°C) were attractive to the following Cerambycidae: Acanthocinus nodosus, A. obsoletus, Arhopalus rusticus nubilus, Asemum striatum, Monochamus titillator, Prionus pocularis, Xylotrechus integer, and X. sagittatus sagittatus. Buprestis lineata (Buprestidae), Alaus myops (Elateridae), and Hylobius pales and Pachylobius picivorus (Curculionidae) were also attracted to traps baited with (−)-α-pinene. In many locations, ethanol synergized attraction of the cerambycids Acanthocinus nodosus, A. obsoletus, Arhopalus r. nubilus, Monochamus titillator, and Xylotrechus s. sagittatus (but not Asemum striatum, Prionus pocularis, or Xylotrechus integer) to traps baited with (−)-α-pinene. Similarly, attraction of Alaus myops, Hylobius pales, and Pachylobius picivorus (but not Buprestis lineata) to traps baited with (−)-α-pinene was synergized by ethanol. These results provide support for the use of traps baited with ethanol and (−)-α-pinene to detect and monitor common large wood-boring beetles from the southeastern region of the USA at ports-of-entry in other countries, as well as forested areas in the USA.