外源抗氧化剂7-(4-氨基-1,2,4-三唑-5-)硫乙氧基黄酮及其意外乙酰化产物的合成

7-溴乙氧基黄酮与3-取代-4-氨基-1,2,4-三唑-5-硫醇类化合物缩合反应得到7-(4-氨基-1,2,4-三唑-5-)硫乙氧基黄酮,为了增加其脂溶性,将该类化合物进一步与乙酸酐回流反应12 h,得到的化合物不是预期的7-(3-取代-4-乙酰氨基-1,2,4-三唑-5-)硫乙氧基黄酮衍生物,而是7-[3-取代-4-(2-乙酰氧基)-乙亚氨基-1,2,4-三唑-5-]硫乙氧基黄酮,分别用红外、核磁共振氢谱及碳谱、质谱和元素分析对这4个乙酰化产物的结构进行了确证。以清除超氧自由基、羟自由基、亚硝基自由基和2,2-二苯基-1-苦味酰基自由基的活性及总还原能力为指标,测定比较了4个7-(3-取代-4-氨基-1,2,4-三唑-5-)硫乙氧基黄酮化合物及其意外乙酰化产物的体外抗氧化活性。结果表明,在测定浓度下,乙酰化衍生物7-[3-对甲氧苯基-4-(2-乙酰氧基)-乙亚氨基-1,2,4-三唑-5-]硫乙氧基黄酮较其前体抗氧化活性强。     

新型三唑席夫碱类化合物的合成及除草活性研究

用3-芳基-4-氨基-5-巯基-1,2,4-三唑与卤代烃发生烷基化反应,然后以乙酸为溶剂和催化剂,使之与不同取代基的芳香醛反应,合成了16个未经文献报道的标题化合物。通过IR、1HNMR和元素分析对所有化合物进行了结构表征,并对这些化合物进行了初步除草活性测试,结果表明大部分化合物表现出较好的除草活性,同时对该类席夫碱结构与活性的关系进行了探讨。     

五氟磺草胺中间体2-氨基-5,8-二甲氧基[1,2,4]三唑[1,5-c]嘧啶的合成研究

以甲氧基乙酸甲酯、甲酸乙酯和尿素为原料,经缩合、环化、三氯氧磷氯化、氨水取代得到2-氯-4-氨基-5-甲氧基嘧啶,然后与N-乙氧基羰基异硫氰酸酯反应、盐酸羟胺环化、甲氧基化得到目标产物2-氨基-5,8-二甲氧基[1,2,4]三唑[1,5-c]嘧啶。总收率27.2%。     

3-烷基-4-氨基-5-巯基-1,2,4-三唑衍生物的合成及表征

以3-烷基-4-氨基-5-巯基-1,2,4-三唑为起始原料,与1,2-二溴乙烷缩合制得双氨基三唑硫醚,再与取代的芳香醛在醋酸回流下缩合,即制得相应的三唑席夫碱类化合物.所得席夫碱类新化合物的结构均经FT-IR、1HNMR、MS和 13CNMR确证.     

α-(2,4-二氯-5-氟苯甲酰)-β-取代氨基丙烯酸酯的合成

以中间体2,4-二氯-5-氟苯甲酰乙酸甲酯为原料．通过与原甲酸三乙酯进行缩合,再与氨基化合物发生亲核取代反应,制备得到8种α-(2,4-二氯-5-氟苯甲酰)-β-取代氨基丙烯酸酯衍生物,并对它们的反应活性进行了研究。     

含三唑氮杂环结构的黄酮类外源抗氧化剂的合成与分析

7-溴乙氧基黄酮与3-取代-4-氨基-1,2,4-三唑-5-硫醇类化合物缩合反应得到7-(3-取代-4-氨基-1,2,4-三唑-5-)硫乙氧基黄酮,该类化合物进一步与乙酸酐反应得到其乙酰化衍生物,共设计合成了8个含N-取代三唑杂环结构的黄酮衍生物,分别用红外(IR)、核磁共振氢谱(~1H NMR)及碳谱(~(13)C NMR)、质谱(ESI-MS)、元素分析(EA)对化合物的结构进行了确证。测定了这些化合物抗氧化活性,包括清除超氧自由基(O_2~-·)、羟自由基(·OH)、亚硝基自由基(NO_2·)和2,2-二苯基-1-苦味酰基自由基(DPPH·)的活性及总还原能力。结果表明,在0.5mg/mL质量浓度时,多数化合物具有抗氧化活性,但均弱于对照芦丁和维生素C的抗氧化作用。     

3-(4-卤代苯氧基)甲基-5-环戊硫基-4-苯基-4H-1,2,4-三唑的合成及抑菌活性

以苄氧乙酸和异硫氰酸苯酯为原料,经肼解、环化制得中间体3-氯甲基-5-环戊硫基-4-苯基-4H-1,2,4-三唑后,再与对位卤素取代苯酚反应得到4个新型的标题化合物。其结构经红外、质谱、核磁共振氢谱及元素分析确认。初步生物活性研究结果表明,在实验浓度下该系列化合物表现出一定的杀菌活性。     

5,7-二甲基-N-芳基-1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺的合成

以5-氨基-3-巯基-1,2,4-三唑为原料,经氧氯化后分别与6个芳胺反应,得到5氨基-N-芳基1,2,4-三唑-3-磺酰胺,继而和乙酰丙酮于乙酸中环合,制得6个取代的1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺衍生物,同时讨论了胺解反应和环合反应的影响因素。所有目标产物的结构均经IR和1HNMR谱验证。     

嗪草酸甲酯关键中间体的合成新方法

5-氨基-2-氯-4-氟苯硫基乙酸甲酯是合成嗪草酸甲酯的关键中间体,目前合成该中间体的路线较多,但收率均不高。以3,4-二氯硝基苯为起始原料,经5步反应合成了中间体5-氨基-2-氯-4-氟苯硫基乙酸甲酯。     

5，7—二甲基—N—芳基—1，2，4—三唑[1，5—α]嘧啶—2—磺酰胺的合成

以5—氨基—3—巯基—1，2，4—三唑为原料，经氧氯化后分别与6个芳胺反应，得到5氨基—N—芳基1，2，4—三唑—3—磺酰胺，继而和乙酰丙酮于乙酸中环合，制得6个取代的1，2，4—三唑[1，5—α]嘧啶—2—磺酰胺衍生物，同时讨论了胺解反应和环合反应的影响因素。所有目标产物的结构均经IR和^1H NMR谱验证。     

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。