2-氨基-5-甲氧基-4-[3-(吡咯烷-1-基)丙氧基]苯胺合成

以2-氨基-4-羟基-5-甲氧基苯甲酸甲酯(化合物2)和1-(3-羟丙基)四氢吡咯(化合物3)为原料,通过光延反应得到2-氨基-5-甲氧基-4-[3-(吡咯烷-1-基)丙氧基]苯胺(化合物1).通过1H-NMR和ESI-MS对化合物1的结构进行了表征,并对反应条件进行了优化.确定的最佳的反应条件为:反应溶剂为四氢呋喃,n(化合物2)∶n(偶氮二甲酸二叔丁酯)∶n(化合物3)=1 ∶ 1.2 ∶ 2.0,n(三苯基膦)∶n(化合物2)=1∶1,反应时间为3h.在此反应条件下,化合物1的收率可达到65.4％.     

4,5-(2＇,3＇-二硫基-1,4-丁二醇)-1,3-二硫杂环戊烯-2-硫酮的合成研究

通过4,5-二硫基-1,3-二硫杂戊烯-2-硫酮(DMIT)的钠盐与2,3-二溴-1,4-丁二醇的反应成功的合成了题目化合物.比较了DMIT钠盐与DMIT锌配合物(DMIT)2Zn(NBu4)2的亲核反应能力,讨论了反应时间、反应温度、碱的用量等条件对反应的影响.并用IR、1HNMR、MS对目标化合物进行了表征.     

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。     

2-(4-氯苯甲基)苯并咪唑的合成及应用

以对氯苯乙腈和邻苯二胺为原料合成2-(4-氯苯甲基)苯并咪唑,讨论了影响反应产率的条件。     

9,10-二(β-萘基)蒽-2-硼酸的合成研究

以2-溴-9,10-二(β-萘基)蒽为原料,在低温条件下得到9,10-二(β-萘基)蒽-2-硼酸,并通过核磁共振、红外光谱分析、元素分析、质谱分析对其结构进行了确认和表征。并探讨了不同反应条件对收率的影响,确定了反应的最佳条件为:在-78℃下,以叔丁基锂作为锂试剂,以物质的量比为n(卤代芳烃)∶n(锂试剂)∶n(硼酸酯)=1∶5∶6,分别滴加叔丁基锂、硼酸三异丙酯,收率可达76.80%。     

烯烃复分解合成3-环戊烯-1,1-二甲醇的研究

以丙二酸二乙酯和3-氯丙烯为原料,经过亲核取代、烯烃复分解、酯还原三步反应合成了目标产物3-环戊烯-1,1-二甲醇。目标产物及中间体结构经~1HNMR、~(13)CNMR和ESI-MS确证。对关键步骤(烯烃复分解反应)的反应条件进行了考察,确定的最佳反应条件为:n(2,2-二烯丙基丙二酸二乙酯)∶n(Grubbs三代催化剂)=1∶0.03,反应溶剂为二氯甲烷,反应温度为25℃,反应时间为1.5h。     

N~1-(4-氨基丁基)-N~4-(9-蒽甲基)-1,4-丁二胺的合成

以N-叔丁氧羰基-1,4-丁二胺和N-(4-溴丁基)邻苯二甲酰亚胺为原料,经取代及保护两步反应合成N1-(4-邻苯二甲酰亚胺)丁基-N1,N4-二叔丁氧羰基-1,4-丁二胺(Ⅳ),然后肼解得N1-氨基丁基-N1,N4-二叔丁氧羰基-1,4-丁二胺(Ⅴ),3步反应总收率38%;Ⅴ与9-蒽甲醛缩合后用NaBH4还原,产物提纯后脱保护得目标产物N1-(4-氨基丁基)-N4-(9-蒽甲基)-1,4-丁二胺盐酸盐(Ⅶ),3步反应总收率约7 5%。化合物Ⅳ~Ⅶ的结构经13CNMR,1HNMR和ESI-MS确证,并对反应条件进行了初步优化。     

1-甲基-1H-苯并咪唑-4-硼酸的合成

以1-溴-3-氟-2-硝基苯为原料,经甲胺取代,锌粉还原,甲酸环化3步反应合成4-溴-1-甲基-1H-苯并咪唑,再与频哪醇硼酸酯在双(三环己基膦)二氯化钯催化下进行硼酸化,制得未见文献报道的目标化合物1-甲基-1H-苯并咪唑-4-硼酸,4步反应总收率27.4%。产品经MS和1H NMR确证。该合成工艺具有反应条件温和、操作简单的优点。     

(4-羟基-3-甲氧基苯基)（2-甲基哌啶-1-基）甲酮的合成

本文报道了（4-羟基-3-甲氧基苯基）（2-甲基哌啶-1-基）甲酮（1a）的合成。以4-羟基-3-甲氧基苯甲酸（2）和2-甲基哌啶（3）为原料,经缩合反应得到目标化合物（1a）。并考察该反应工艺,确定适宜的反应条件为：物料比为n(3)∶n(2)=1.8∶1、反应溶剂为N,N-二甲基甲酰胺、反应温度为40℃、反应时间为2h。在该条件下,产物（1a）收率达到88.6%。对该反应工艺的拓展应用发现,该条件同样适用于4-羟基-N,3-二甲氧基-N-甲基苯甲酰胺（1b）的合成,收率达到90.3%。产物结构经过1H NMR和13C NMR表征确证。     

(E)-1,8-二甲氧基-3-(3-氧代丁烯-1-基)-蒽-9,10-二酮的合成

以芦荟大黄素为原料,首先利用硫酸二甲酯对芦荟大黄素分子中的酚羟基进行选择性甲基化反应,合成1,8-二甲基氧芦荟大黄素,然后用氯铬酸吡啶盐(PCC)氧化甲基化的芦荟大黄素合成出1,8-二甲基氧芦荟大黄醛,最后使用丙酮和1,8-二甲基氧芦荟大黄醛进行Aldol缩合反应,合成了标题化合物,并用元素分析、质谱和1HNMR对所合成化合物的结构进行了表征。结果表明,使用丙酮作为溶剂,K2CO3为催化剂,在60~70℃下搅拌反应6~12 h,可以选择性、高产率得到1,8-二甲基氧芦荟大黄素。对于丙酮和1,8-二甲基氧芦荟大黄醛的Aldol缩合,超声波具有较好的促进效果。     

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.     

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.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.