研磨法合成双吲哚甲烷衍生物

以醛、吲哚为原料,在蒙脱土负载碘催化下研磨合成双吲哚甲烷衍生物。通过控制变量法筛选出最佳的催化剂及其用量、反应时间和原料物质的量比。得到最佳反应条件为:以蒙脱土负载碘催化剂,其用量为醛的15mol%,吲哚跟醛的物质的量比为2.0∶1.1,在室温下研磨20 min。得到最高产率为91.2%。此方法为双吲哚甲烷衍生物合成提供了一种高效、快速的合成路线     

蒙脱土负载碘催化-羰基二硫缩烯酮反应

以蒙脱土负载碘(MMT/I_2)为催化剂,将其用于催化α-羰基二硫缩烯酮的吲哚反应,合成了Ⅲa~Ⅲl 12个化合物,产物结构经NMR、FTIR进行了表征。并考察了反应温度、催化剂用量、原料物质的量比及反应时间对化合物Ⅲa产率的影响。结果表明:温度80℃、n(MMT/I2)∶n(3,3-二乙硫基苯丙烯酮)=0.1∶1.0[其中,n(MMT/I2)指有效负载在MMT上碘单质的物质的量,下同]、n(3,3-二乙硫基苯丙烯酮)∶n(吲哚)=1.0∶1.0、反应时间60 min时,产物3-吲哚基-3-乙硫基苯丙烯酮(Ⅲa)产率可达89.0%。催化剂循环使用4次,化合物Ⅲa产率仍可达86.0%。Ⅲa~Ⅲl的收率为79%~89%,此催化反应表现出良好的底物适用性。     

微波辐射固相合成5-(取代吲哚基-3-次甲基)(硫代)巴比妥酸

在无溶剂、无催化剂、微波辐射条件下,取代吲哚-3-甲醛与(硫代)巴比妥酸通过Knoevenagel缩合反应,合成了一系列5-(取代吲哚基-3-次甲基)(硫代)巴比妥酸。最佳反应条件为:n(吲哚-3-甲醛)∶n(巴比妥酸)=1.2∶1.0,微波辐射时间8 min,微波功率500 W,产率68.4%～82.8%。     

微波辅助法合成双吲哚甲烷衍生物

以吲哚、羰基化合物为原料,以路易斯酸固载蒙脱土为催化剂,微波辅助合成标题化合物。考察了溶剂、温度、反应时间、原料物质的量比及催化剂循环使用次数对产率的影响,最优条件下产率高达93.4%,催化剂循环3次产率仍可达71.0%,产物通过~1HNMR、IR、熔点进行表征。     

活性炭负载磷钨酸催化合成苯乙醛乙二醇缩醛

以活性炭负载磷钨酸作催化剂,对以苯乙醛和乙二醇为原料合成苯乙醛乙二醇缩醛的反应条件进行了研究.实验结果表明:活性炭负载磷钨酸是合成苯乙醛乙二醇缩醛的良好催化剂,较系统地研究了醛醇摩尔比、催化剂用量、反应时间诸因素对产率的影响.最佳反应条件为:n(苯乙醛)∶n(乙二醇)∶n(催化剂)=1∶1.2∶0.0034,带水剂环己烷12ml,反应时间90min.上述条件下,苯乙醛乙二醇缩醛的产率可达90.24%     

吲哚-3-羧酸的合成

介绍了吲哚-3-甲酸的合成工艺.研究了从吲哚经吲哚-3-甲醛合成吲哚-3-甲酸的合成工艺.采用吲哚为原料,DMF为溶剂和反应物,采用POCl3为氧化剂,首先合成吲哚-3-甲醛,然后用KMnO4氧化制得吲哚-3-甲酸.该法醛的产率可以达到90%以上,酸的产率也可以达到50%以上.     

磷酸二苯酯催化的2-吲哚甲烷胺衍生物的合成

以磷酸二苯酯为催化剂,3-甲基吲哚类化合物与亚胺通过Friedel-Crafts加成反应一步合成了具有广泛药理活性的2-吲哚基甲烷胺类化合物,对反应条件进行优化。结果表明,当n(3-甲基吲哚类)∶n(亚胺)∶n(磷酸二苯酯)=1.0∶2.0∶0.1,其中,磷酸二苯酯0.0025 mmol,1 mL无水二氯甲烷作溶剂,室温下反应0.5 h时,即可得到高收率2-吲哚基甲烷胺类衍生物（85%~90%）。产物经 1HNMR、13CNMR 和 HRMS 进行了结构确定。     

磷钨酸镍绿色催化合成缩醛的研究

用绿色催化剂磷钨酸镍催化合成了苯甲醛乙二醇缩醛,研究了催化剂用量、醛醇物质的量比、反应时间、带水剂用量、催化剂重复使用性能等因素对产率的影响。实验结果表明反应的最佳条件为:在苯甲醛0.2 mol、n(醛)∶n(乙二醇)=1.0∶1.5、m(NiPW)=0.8 g、反应温度86~90℃、反应时间为2.0 h、V(环己烷)=24 mL的条件下,产率可达到81.6%。     

新型光致变色螺吡喃化合物的合成及研究

将萘胺与羧基螺吡喃进行酰胺化得到了一种新型的螺吡喃衍生物，通过核磁共振氢谱进行了结构确认，对中间体羧基吲哚和最终产物SP-N的合成条件进行了条件优化。当醋酸用量为40 mL,反应时间为18 h时，中间体的产率达到最大为40.1%,当n(三乙胺)∶n(萘胺)为1.5∶1时，酰胺化反应产率达到最大38%。     

超声辅助蒙脱土负载路易斯酸催化合成喹喔啉衍生物

在超声辅助下,以蒙脱土负载氯化锌催化1,2-二羰基化合物与邻苯二胺反应合成喹喔啉类化合物。得出最佳条件为:苯偶酰与邻苯二胺的摩尔比为1.0∶1.0,蒙脱土负载氯化锌作催化剂、用量为苯偶酰的10%,乙醇作溶剂,超声时间5 min,反应温度30℃,产率可达80.3%~96.5%。所得化合物经过熔点、红外及核磁氢谱确认。     

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。