2，3，4，5—四氟苯甲酸的合成与应用

医药中间体2,3,4,5-四氟苯甲酸有四氯苯酐法、2,3,4,5-四氟苯甲醇法、邻苯二腈法、1,2,3,4-四氟苯法和八氯萘法等五条不同的合成路线,其中四氯苯酐法和邻苯二腈法是适合工业化生产的路线。2,3,4,5-四氟苯甲酸的主要用途是合成洛美沙星、司氟沙星、氟罗沙星、氧氟沙星、左氟沙星和芦氟沙星等第三代喹诺酮药物。目前,以2,3,4,5-四氟苯甲酸为原料合成的第三代喹诺酮药物在世界市场的年销售额达数百亿美元,并以每年近20％的速度增长。我国已有小批量试制产品生产,但质量不稳定,成本高;制药厂生产所需原料主要依靠进口。2,3,4,5-四氟苯甲酸已成为我国有机中间体生产企业亟待开发的重要品种。     

2，3，45—四氟苯甲酸的制备方法

2,3,4,5-四氟苯甲酸是一种重要的药物中间体,在药物合成过程中得到广泛应用,尤其是制备第三代喹诺酮类抗菌药物如左旋氧氟沙星、氟罗沙星、洛美沙星、卢氟沙星和斯帕沙星的重要原料。     

2,3,5,6-四氟苯甲酸的制备及应用研究进展

综述了2,3,5,6-四氟苯甲酸的制备方法,并对这些方法进行概括和评述.同时,对2,3,5,6-四氟苯甲酸在合成喹诺酮类药物领域的应用作了归纳总结,并展望其在含氟液晶、氟树脂等领域的应用及发展前景,以期对对2,3,5,6-四氟苯甲酸的制备和应用有较全面的认识.     

2,3,4,5-四氟苯胺的制备

研究了2,3,4,5 四氟苯胺的制备工艺。以N 苯基四氟邻苯二甲酰亚胺为原料,酸式水解得到四氟邻苯二甲酸、经甲苯脱水生成四氟邻苯二甲酸酐、与氨水反应得到2 羧基四氟苯甲酰胺、再经霍夫曼降解及脱羧反应得到目标化合物2,3,4,5 四氟苯胺,总收率为43%。目标化合物结构经质谱和核磁验证。     

喹诺酮化合物5，7-二氨基-1-环丙基-6，8-二氟-1，4-二氢-4-氧代喹啉-3-羧酸的合成研究

研究5,7-二氨基-1-环丙基-6,8-二氟-1,4-二氢-4-氧代喹啉-3-羧酸（1）的合成路线和工艺。原料2,3,4,5-四氟苯甲酸经硝化、酰氯化、缩合,水解脱羧等多步反映得到中间体2,中间体2与叔丁胺亲核取代后,酸水解,氢化还原得到目标化合物。     

2，3，5，6-四氟苯甲醇的合成

经氟代、水解脱羧、酯化、还原等步骤合成了杀虫剂四氟苯菊酯的重要中间体2，3，5，6，-四氟苯甲醇，改进了氟代反应的无水操作和反应条件，产物四氟对苯二甲腈纯度高达98．3％，通过加入水参与反应改进了水解反应，使水解和脱羧由两步反应变为一步，且产物为只脱一个羧基的2，3，5，6-四氟苯甲酸，收率可以高达925％，用相对价廉的NaBH4/I2体系还原2，3，5，6-四氟苯甲酸甲酯以52.3％的收率得到了目标产物，总收率29．6％。     

麻保沙星的合成工艺研究

介绍了一种麻保沙星的绿色合成工艺。以2,3,4,5-四氟苯甲酸为原料,经酰氯化后与3-(N-甲基-甲酰肼基)-丙烯酸乙酯偶联、环合,与4-甲基哌嗪缩合、水解、环合,氨水中和得到目标产物,总收率为47.7%。与传统工艺相比,该法原料易得,实验步骤少,收率高,操作简单,具有一定的工业化前景。     

四氟苯甲酸的制备方法及其在新型氟喹诺酮抗菌药物中的应用

介绍了采用间苯二甲腈与四氯苯酐两种原料路线制备四氟苯甲酸的方法 ,对四氟苯甲酸在新型氟喹诺酮类抗菌药物中的应用进行了综述。     

液质联用法测定2,3,4,5-四氟苯甲酸示踪剂研究与应用

氟苯甲酸类示踪剂因其环境友好、稳定性好、无放射性等优点,具有极好应用前景。针对目前检测方法存在问题,研究了2,3,4,5-四氟苯甲酸示踪剂痕量检测方法。采用三重串联四极杆液质联用仪(Agilent G6410),ZORBAX SB-C18色谱柱(2.1 mm×50 mm,1.8μm),乙腈-甲酸水溶液为流动相,质谱应用电喷雾(ESI)离子源和负离子多反应监测(MRM)方式,在碰撞电源80 V、碰撞能6 V的条件下,1.0～200μg/L浓度范围内线性关系良好,R²=0.999 9。该方法已在渤海油田成功应用17井次。     

用于识别卤素阴离子的单体和聚合物以及制备方法

正一种用于识别卤素阴离子的单体N-(对乙炔基)-苯基-2-X-四氟苯甲酰胺(X=F,Cl,Br,I)、聚合物、及其单体和聚合物的制备方法,该方法采用对氨基苯乙炔和六氟苯甲酸为主要起始原料,以N,N-二甲基-4-氨基吡啶为催化剂,终合成了目标小分子化合物N-(对乙炔基)-苯基-2-X-四氟苯甲酰     

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.