硝胺类含能化合物ADNQ和APX的合成及热性能

以硝基胍(NQ)为原料,经硝化合成了中间体1,2–二硝基胍(DNQ),然后与碳酸铵反应得到1,2–二硝基胍铵(ADNQ);DNQ与碳酸氢钾进行酸碱中和反应得到1,2–二硝基胍钾(PDNQ),最后在碘化钠和18–冠–6醚相转移催化剂的作用下与1,3–二氯–2–硝氨基氮杂丙烷进行取代反应合成了1,7–二氨基–1,7–二硝氨基–2,4,6–三硝基–2,4,6–三氮杂庚烷(APX)。采用红外光谱、核磁、质谱以及元素分析等进行了中间体与目标化合物的结构表征;采用差示扫描量热(DSC)、热重(TG)等手段研究了目标化合物的热性能。     

9H-吲哚[4,5-b]并嘧啶类衍生物的合成研究

7-甲(乙)基吲哚酮(1a,1b)与制备好的Vilsmeier-Haack试剂反应合成2-氯-3-甲酰基-7-甲(乙)基吲哚(2a,2b)和2-氯-3-乙酰基-7-甲(乙)基吲哚(3a,3b);将2a,2b,3a,3b N甲基化得4a-4b,5a-5b,再将以上化合物与硝酸胍反应,以良好的收率合成吲哚并嘧啶类化合物(6a-6b,7a-7b),在此基础上探究与氨基胍反应尝试得到闭环化合物。以上制备过程具有反应条件温和、后处理简单等优点,为制备吲哚并嘧啶类化合物提供了简单方法。     

生物催化轴手性化合物的不对称合成进展

轴手性化合物是许多天然产物、药物中间体、手性配体的核心骨架,在手性化合物中占有重要地位。与金属催化剂催化的不对称化学偶联反应等化学方法相比,生物催化方法具有选择性高、反应条件温和、环保等优势。随着酶的改造等关键技术的快速发展,酶催化轴手性化合物的合成成为新的研究热点与难点。从动力学拆分(kinetic resolution,KR)、动态动力学拆分(dynamic kinetic resolution,DKR)以及去对称化(desymmetrization)等不对称合成方法入手,综述了生物催化轴手性化合物的合成领域的主要研究成就,并阐述了此方向的发展前景、应用及存在的问题。     

三种稠环硝胺化合物的爆炸性能估算及其硝化母体化合物的合成

以乙二醛、硝基胍为原料,经两步环化反应合成了含能稠环化合物6-硝亚氨基咪唑烷并[4,5-e]呋咱并[3,4-b]哌嗪(化合物4),并优化了其合成条件,总收率52.2%(文献值29.4%)。以乙二醛、尿素为原料,经两步环化反应合成了稠环化合物5-硝亚氨基咪唑烷并[4,5-d]咪唑烷酮(化合物5)。以乙二醛和1,1-二氨基-2,2-二硝基乙烯(FOX-7)为原料,通过两步环化反应得到了一种新型含能稠环化合物6-偕二硝基乙烯基咪唑烷并[4,5-e]呋咱并[3,4-b]哌嗪化合物(化合物6)。用IR、NMR、MS和元素分析对3种稠环和中间体的结构进行了表征。基于化合物4、5、6设计了3种新型稠环硝胺化合物的结构。用Gaussian 98程序和VLW方程计算了3种稠环的理化性能和爆轰性能。结果表明,3种稠环硝胺化合物的计算密度分别为2.03、2.08、2.07g/cm3,理论爆速分别为9 928、9 672、10 109m/s。     

含有氨基酸结构单元的手性γ-丁内酯衍生物的合成及结构表征

在K_2CO_3和相转移催化剂TBAB存在下,氨基酸酯与手性源(R)-5-(l-氧基)-2(5H)-呋喃酮于室温下反应,得到一系列具有氨基酸结构组分的手性γ-丁内酯化合物。所有合成化合物的结构通过红外、核磁共振、高分辨质谱等进行了确认,并通过底物结构、反应规律以及产物的核磁共振氢谱分析,确认了新形成手性中心的绝对构型。     

手性合成、手性拆分在分析分离科学及医药学中的应用

简要介绍了手性合成、手性拆分及应用。重点介绍了:(1)手性合成及手性拆分在分析分离科学中的应用;(2)含氧侧链三唑类抗真菌活性化合物的合成及在医药学中的应用;(3)酸性记忆效应对环糊精手性固定相的手性分离及应用。并对手性化学的发展进行了展望。     

生物催化C—N成键反应合成手性胺的研究进展

生物催化C—N键的成键反应主要是用于合成手性胺类化合物,它广泛应用于食品、精细化学品和药物中间体的制备过程中。酶法生产手性胺具有高对映体选择性、转化率和时空产率的特点。主要介绍了C—N键成键的三种方式,分别为还原胺化反应、氢胺化反应和转氨化反应。并根据不同的反应类型对相关的酶进行了归纳总结。     

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。     

新型手性相转移催化剂N-苄基溴化奎宁的合成及应用

通过对天然手性物质进行修饰合成手性相转移催化剂N-苄基溴化奎宁,并对目标分子2,5-二甲基-4-(3-硝基苯)-1,4-二氢吡啶-3-甲酸乙酯-5-甲酸甲酯(nitrendipine)进行不对称催化合成,并通过红外光谱和核磁共振氢谱对化合物进行了表征,用X射线单晶衍射法测定了该化合物的晶体结构。     

手性磺酰胺的合成及在苯乙酮的不对称氢转移反应中的应用

以辛可宁为原料,经Mitsunobu反应合成了9-氨基(9-脱氧)表辛可宁,然后分别与8-喹啉磺酰氯、苯磺酰氯、对甲基苯磺酰氯、对氯苯磺酰氯反应,合成了4个手性磺酰胺化合物.对这些磺酰胺在苯乙酮的不对称氢转移反应中的催化性能进行了考察,在80℃下反应,当n(苯乙酮):n(手性磺酰胺Ru(Ⅱ)配合物):n(氢氧化钾)=50:1:2.5时,获得的最大转化率为96.0%.     

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.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

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.     

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.     

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。