1-甲基-2,4,5-三硝基咪唑(MTNI)的合成

以4-硝基咪唑为原料,经硝化、热重排、甲基化等反应合成1-甲基-2,4,5-三硝基咪唑(MTNI),总收率19.4%,纯度>98%,经红外光谱、核磁共振、元素分析等方法表征其结构。研究了反应温度、反应时间等因素对1-甲基-2,4-二硝基咪唑(MDNI)合成及收率的影响,得到了较优的工艺条件:n(2,4-二硝基咪唑)∶n(碘甲烷)=5∶9,反应温度40~45℃,反应时间8h。对硝化反应条件进行了研究,确定了适宜反应时间为1h,反应温度为95℃。     

1-甲基-2，4，5-三硝基咪唑合成工艺优化

以咪唑为原料,通过两步硝化制得1,4-二硝基咪唑,然后在氯苯中热重排得2,4-二硝基咪唑,将2,4-二硝基咪唑进-步硝化并制得2,4,5-三硝基咪唑的钾盐,最后将钾盐甲基化,得到1-甲基-2,4,5-三硝基咪唑（MTNI）,收率23％。采用红外光谱、元素分析、核磁共振的方法对其结构进行表征。用DSC进行了热分解研究。优化了2,4-二硝基咪唑的合成工艺：反应温度为123±2℃,反应时间为6h,n（1,4-二硝基咪唑）：n（氯苯）=1：9。改进了前两步硝化条件和2,4,5-三硝基咪唑钾盐的合成工艺。     

1-甲基-2,4,5-三硝基咪唑的合成新工艺

以N-甲基咪唑为原料,经过两步硝化反应得到1-甲基-2,4,5-三硝基咪唑(MTNI),并用红外光谱、核磁共振、元素分析对其结构进行了表征.研究了发烟硝酸与发烟硫酸的体积比、加料顺序、反应时间、温度对1-甲基-2,4-二硝基咪唑(2,4-MDNI)和MTNI收率的影响.结果表明,当一段硝化采用正加法加料,发烟硝酸与发烟硫酸的体积比1:2,二段硝化采用反加法加料,发烟硝酸与发烟硫酸的体积比1:4,反应时间2h,反应温度110～115℃时,产物得率较高.     

不敏感炸药1-甲基-2,4,5-三硝基咪唑的合成

以咪唑为原料,通过两步硝化制得1,4-二硝基咪唑,然后在氯苯中热重排得2,4-二硝基咪唑,将2,4-二硝基咪唑进一步硝化并制得2,4,5-三硝基咪唑的钾盐,最后将钾盐甲基化,得到1-甲基-2,4,5-三硝基咪唑.采用红外光谱、元素分析、核磁的方法对其结构进行表征.用DSC进行了热分解研究.同时优化了2,4-二硝基咪唑的重排工艺:反应温度为120℃～125℃.反应时间为4h,1,4-二硝基咪唑和氯苯的物质的量比为1:30.对2,4,5-三硝基咪唑不稳定性进行了分析.     

不敏感炸药1-甲基-294，5-三硝基咪唑的合成

以咪唑为原料,通过两步硝化制得1,4-二硝基咪唑,然后在氯苯中热重排得2,4-二硝基咪唑,将2,4-二硝基咪唑进一步硝化并制得2,4,5-三基咪唑的钾盐,最后将钾盐甲基化,得到1-甲基-2,4,5-三硝基咪唑。采用红外光谱、元素分析、核磁的方法对其结构进行表征。用DSC进行了热分解研究。同时优化了2,4-二硝基咪唑的重排工艺：反应温度为120℃-125℃,反应时间为4h,1,4-二硝基咪唑和氯苯的物质的量比为1：30。对2,4,5-三硝基咪唑不稳定性进行了分析。     

N-苄基-2,4-二硝基咪唑的合成及其亲核取代反应

以2,4-二硝基咪唑为原料,经N-苄基保护合成出N-苄基-2,4-二硝基咪唑,并研究了其亲核取代反应,结果表明-N3、-F、-OCH3可以高收率的取代2位硝基,产物经核磁、质谱、元素分析进行了表征。     

3-（2,4-二甲基-3-戊氧基）邻苯二腈的合成

以3-硝基邻苯二腈、2,4-二甲基-3-戊醇、氢化钠为原料,进行赖因德斯—林格反应缩合,合成目标化合物——3-（2,4-二甲基-3-戊氧基）邻苯二腈,主要探讨了原料摩尔比、反应温度、滴加时间对产品质量和收率的影响。确定了较优反应条件;3-硝基邻苯二腈与2,4-二甲基-3-戊醇钠的摩尔比为1∶1.25,反应温度为0℃,滴加时间为3 h,反应时间2 h,反应收率为87%。通过熔点,HNMR确证目标产物的化学结构。     

1,1-二甲硫基-2-硝基乙烯的合成

研究了以硝基甲烷和二硫化碳为原料,合成1,1-二甲硫基-2-硝基乙烯。考察了反应温度、反应时间、甲基化试剂、溶剂、投料比等对于反应产物的影响,得到优化工艺条件为:反应温度35℃,反应时间3h。以硫酸二甲酯为甲基化试剂,常温下反应时间3 h,重结晶得1,1-二甲硫基-2-硝基乙烯,收率为84%,产物通过IR、1H-NMR鉴定。     

N-(5-氨基-2,4-二乙氧基苯基)苯甲酰胺的合成

以2,4-二乙氧基-5-硝基苯胺(DEANB)为原料,先经酰化反应得到N-(2,4-二乙氧基-5-硝基苯基)苯甲酰胺(DEBNB),最后经还原得到蓝色基BB的同分异构体N-(5-氨基-2,4-二乙氧基苯基)苯甲酰胺(DEBAB)。DEBNB的较佳合成条件:n(DEANB):n(苯甲酰氯)=1∶1.25,丙酮和水作溶剂,K2CO3作缚酸剂,反应温度0℃,反应时间1 h,收率90.95%,HPLC纯度98.35%;产品DEBAB的较佳合成条件:Fe粉为还原剂,n(DEBNB):n(铁粉)=1∶4,水和乙醇作溶剂,反应时间5 h,反应温度80℃,收率89.93%,HPLC纯度98.96%。     

相转移催化合成1-(2,4-二氯苯基)-2-(1-咪唑基)-乙醇的研究

以1-(2,4-二氯苯基)-2-氯-乙醇和咪唑为原料,采用聚乙二醇-400作相转移催化剂合成了1-(2,4-二氯苯基)-2-(1-咪唑基)-乙醇。通过正交试验法考察了催化剂用量、反应温度、反应时间等因素对1-(2,4-二氯苯基)-2-(1-咪唑基)-乙醇收率的影响,确定了最佳的工艺条件。结果表明,聚乙二醇-400使反应选择性高、条件温和、操作简便,收率可达84.6%。     

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.