异佛尔酮腈亚胺化反应动力学研究

异佛尔酮腈(IPN)与氨反应生成异佛尔酮腈亚胺和水,此反应是可逆反应,其逆反应为席夫碱的水解反应。为了获得IPN的亚胺化反应动力学方程,以IPN和氨气为原料、甲醇为溶剂,考察了303.15~333.15 K下氨腈摩尔比β=5、13、21的亚胺化反应。采用气相色谱分析,测定了IPN的浓度随时间的变化,数据拟合获得了氨腈比1、产物初始浓度为零、恒容条件下亚胺化的反应速率方程。结果表明,反应焓变△H为-17.417 kJ·mol-1;正反应的表观活化能Ea为23.043 kJ·mol-1,指前因子ka0为8.804×103 L·(mol·s)-1;逆反应的表观活化能Eb为40.461 kJ·mol-1,指前因子kb0为5.638×106 L·(mol·s)-1。对获得的动力学方程进行了验证,转化率的实验值与计算值符合较好。获得的动力学方程为深入研究IPN的亚胺化提供了重要的参考,为工业化提供了相应的指导。     

1-苯基环丙基甲腈及衍生物的合成

合成了1-苯基环丙基甲腈及其衍生物。以苯乙腈为研究模型,考察了超声功率、温度、搅拌速率、时间对反应的影响,优化反应条件为:超声功率300 W、反应温度25℃、搅拌速率150 rpm、反应时间1.5 h,此时苯乙腈转化率达99.5%、产物收率达99.2%。该体系应用于1-苯基环丙基甲腈衍生物的合成,原料转化率≥92.3%,产物选择性≥92.2%。该体系用于杂环腈的转化,以噻吩-2-乙腈为原料合成了1-(噻吩-2-基)环丙烷甲腈,原料转化率为95.2%,产物选择性为97.8%。     

20-二胺的合成

以20-二酸为原料,经氨化反应合成20-二腈中间体后,再以乙醇为溶剂,兰尼镍(Raney Ni)为催化剂,加氢后合成20-二胺。氨化反应始温为280-340℃,终温为420℃,氨化时间为5 h时转化率最高。加氢反应温度为130℃,压力为4.9 MPa,催化剂质量分数为1.75％时,转化率达85.7％,20-二胺纯度达97.6％。产物经红外光谱分析及化学分析,初步确定为目标产物。     

曼尼希改性异佛尔酮二胺环氧固化剂性能研究

选用苯酚、壬基酚、甲醛等试剂,对脂环族胺异佛尔酮二胺（IPDA）进行曼尼希反应改性,然后研究了其产物的固化性能,探究了较佳的反应条件以及反应配比对产物性能,如胺值、色泽、黏度等影响。合成的固化剂与环氧主料、增韧剂以及其他助剂复配制得的浇注料,具有较快的固化速率和较好的物理化学性能。凝胶时间为1．7h,弯曲强度可达74．6MPa,压缩强度可达58．2MPa。     

液相法合成异佛尔酮反应研究

研究以丙酮为原料液相法合成异佛尔酮的液相缩合反应动力学。考察了以氢氧化钠为催化剂时,催化剂浓度、压力、温度、反应时间对反应的影响,结果表明该反应温度215～220℃、丙酮与水质量比3∶1、催化剂用量0.13 mol NaOH、压力3.8～4.5 MPa下反应3 h为最优反应条件。     

酰亚胺二羧酸的合成研究

以偏苯三酸酐(TMA)为原料,分别与4,4'-二氨基二苯醚、4,4'-二氨基二苯甲烷、1,6-己二胺反应,得到三种含酰亚胺结构的二羧酸产物(DIDA-a、DIDA-b、DIDA-c)。利用傅里叶红外光谱(FT-IR)、核磁共振氢谱(1H NMR)对酰亚胺二羧酸的结构进行表征。通过单因素实验,考察溶剂用量、反应时间、反应温度和反应物摩尔比对二酸产物收率的影响,得出DIDA-a的优化合成条件:偏酐起始浓度1.11mol/L,酰亚胺化反应时间6h,酰亚胺化反应温度140℃,TMA和二胺摩尔比2.05;DIDA-b的优化合成条件:偏酐起始浓度1.05mol/L,酰亚胺化反应时间5.5h,酰亚胺化反应温度145℃,TMA和二胺摩尔比2.02;DIDA-c的优化合成条件:偏酐起始浓度0.95mol/L,酰亚胺化反应时间5h,酰亚胺化反应温度135℃,TMA和二胺摩尔比2.03。     

四氢环戊二烯三聚体的合成

双环戊二烯与环戊二烯反应,经两步合成了标题化合物。考察了环戊二烯与双环戊二烯反应中温度、压力、反应时间及溶剂用量对转化率和环戊二烯三聚体收率的影响,最佳条件220℃,0.5 MPa,m(溶剂)∶m(原料)为50%,反应4 h,双环戊二烯转化率85.4%,环戊二烯三聚体收率76.5%。考察了环戊二烯三聚体加氢反应中催化剂用量、温度、氢气压对反应的影响,在m(Raney Ni)∶m(原料)为25%,90℃,4.0 MPa的最佳条件下反应540 min,收率99.6%。两步反应总收率76.2%,产物经质谱、红外光谱等进行了表征。     

烟酮合成条件的优化

文章研究了30%的双氧水在不同pH、溶剂、温度和催化剂条件下氧化异佛尔酮为2,3-氧化异佛尔酮的反应,同时优化出了后者分别在浓盐酸或硫酸作用下水解得到烟酮的最佳条件。该合成方法收率比文献报道有所提高。     

用溴酸钾-硫酸体系制备3-溴-4-氯苯腈

采用溴酸钾为溴化试剂,以对氯苯腈为底物,合成了未见文献报道的化合物3-溴-4-氯苯腈。对此反应的主要参数进行了条件优化。最佳反应条件为:n(对氯苯腈)∶n(溴酸钾)=1∶1.2,在25℃条件下反应7 h,产物纯度≥99.0%,收率85.3%。其结构经红外和核磁氢谱分析确证。     

6-2-氨丙基-2,3-二氢苯并呋喃的合成工艺研究

以3-甲氧基苯甲醛为原料,经亨利反应、还原硝基和双键、氨基保护、傅-克酰基化、脱甲基、环合、羰基还原等反应,合成目的产物6-2-氨丙基-2,3-二氢苯并呋喃。并对硝基和双键的还原反应、傅-克酰基化和脱甲基反应的工艺条件进行了优化,得出较佳工艺条件：(1) 还原反应：反应温度40 ℃,氢气压力4.0 MPa,Raney-Ni质量为化合物2的质量的8 %,产物收率为78.6 %;（2）合成化合物6的较佳工艺条件：反应温度45 ℃,n(氯乙酰氯)：n(化合物4)=1.4：1,反应时间为6 h,产物的收率为68.8 %。     

Sapindaceae,cyanolipids, and bugs

Scentless plant bugs (Heteroptera: Rhopalidae) are so named because adults of the Serinethinae have vestigial metathoracic scent glands. Serinethines are seed predators of Sapindales, especially Sapindaceae that produce toxic cyanolipids. In two serinethine species whose ranges extend into the southern United States,Jadera haematoloma andJ. sanguinolenta, sequestration of host cyanolipids as glucosides renders these gregarious, aposematic insects unpalatable to a variety of predators. The blood glucoside profile and cyanogenesis ofJadera varies depending on the cyanolipid chemistry of hosts, and adults and larvae fed golden rain tree seeds (Koelreuteria paniculata) excrete the volatile lactone, 4-methyl-2(5H)-furanone, to which they are attracted.Jadera fed balloon vine seeds (Cardiospermum spp.) do not excrete the attractive lactone. Loss of the usual heteropteran defensive glands in serinethines may have coevolved with host specificity on toxic plants, and the orientation ofJadera to a volatile excretory product could be an adaptive response to save time.Mention of a commercial product does not consititute an endorsement by the USDA.     

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.     

2008～2009年世界塑料工业进展

收集了2008年7月～2009年6月世界塑料工业的相关资料,介绍了2008～2009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、环氧树脂、不饱和聚酯树脂)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。     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

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.