3-甲基-5-苯基-2-(3-氟苯基)吗啉盐酸盐合成及其抗实验性抑郁活性

1-(3-氟苯)-2-溴-1-丙酮在非质子极性溶剂中经胺化、环合反应,最后酸化,得到3-甲基-5-苯基-2-(3-氟基苯基)吗啉盐酸盐,总收率为70.6%。目标化合物结构经IR、1H NMR、MS测试技术确证。参照Porsolt法,使用小鼠强迫游泳药理实验模型,对所合成的化合物进行抗实验性抑郁药理活性研究。结果显示,此化合物具有良好的抗抑郁活性,值得进一步研究。     

西格列汀中间体新合成方法

L-门冬氨酸在氯化亚砜作用下选择性甲酯化生成L-门冬氨酸-4-甲酯盐酸盐,经二碳酸二叔丁酯保护氨基,再与N-甲基吗啉,氯甲酸叔丁酯低温下反应,加入硼氢化钠还原,得(3S)-3-(叔丁氧羰基氨基)-4-羟基丁酸甲酯,与对甲基苯磺酰氯反应后的产物继续与格式试剂(2,4,5-三氟苯基)溴化镁、溴化亚铜二甲硫醚反应,经氢氧化钠水解,调酸得化合物Boc-(R)-3-氨基-4-(2,4,5-三氟苯基)丁酸。     

11βHSD1抑制剂1-(4-三氟甲氧基苯甲酰基)-4-(4-甲氧基苯甲酰基)哌啶的合成研究

以4-甲氧羰基哌啶盐酸盐(1)和对三氟甲氧基苯甲酰氯(2)为起始原料,在三乙胺的作用下以92.7%的收率制得1-(4-三氟甲基苯甲酰基)-4-甲氧羰基哌啶(3);化合物(3)在羰基二咪唑与N,O-二甲基羟胺盐酸盐(4)作用下,以89.9%的收率制得1-(4-三氟甲氧基苯甲酰基)-4-(N-甲基-N-甲氧基羰基)哌啶(5);化合物(5)和4-甲氧基苯基溴化镁(6)偶联,以60.1%的收率制得化合物1-(4-三氟甲氧基苯甲酰基)-4-(4-甲氧基苯甲酰基)哌啶(7)。三步反应总收率50.0%。     

1-取代苯基-5-三氟甲基(二氟甲基)-4-吡唑甲酸的合成研究

对标题化合物的合成工艺进行了改进。以苯肼盐酸盐为原料,经中和、干燥之后与2-乙氧基亚甲基-4,4,4-三氟(-4,4-二氟)乙酰乙酸乙酯在四氢呋喃中关环。相比于文献中在质子溶剂或有水存在下的关环条件,本工艺可以高选择性地得到1-取代苯基-5-三氟甲基(二氟甲基)-4-吡唑甲酸乙酯。所得产物再经水解共得到20个目标产物,结构经~1HNMR、~(13)CNMR、HR-MS确证。     

3-甲基-2-(4-甲氧基苯基)吗啉盐酸盐的合成

以1-(4-甲氧基苯基)-2-溴-1-丙酮和乙醇胺为原料,在NMP溶剂中反应,经胺化、环合、还原、酸化得新型吗啉化合物3-甲基-2-(4-甲氧基苯基)吗啉盐酸盐,产率62.3%,新化合物结构经IR,1H NMR,MS测试技术确证。整个合成路线具有反应时间短、条件温和、收率高等优点。     

含氨基酸结构的磺酰胺衍生物合成与生物活性

采用分子杂交策略，设计合成15个氨基酸结构的磺酰胺衍生物进行抗菌活性评价。首先，苯磺酰氯与氨基酸反应制得苯磺酰氨基酸（中间体Ⅰ），然后，以芳香醛、亚磷酸酯、乙酸铵和三氟甲磺酸铝为原料，一锅法制得α-氨基膦酸酯（中间体Ⅱ），最后，中间体Ⅰ与Ⅱ缩合，制得目标物，经1H NMR 、13C NMR和MS确认结构。结果表明，该类化合物对大肠杆菌（E. coli）和耐氟喹诺酮大肠杆菌（FREC）活性最为显著。其中，化合物Ⅲb〔{(2-氟苯基) [2-(苯基磺酰氨基)苯丙酰氨基]甲基}膦酸二乙酯〕、Ⅲc〔{(2-氟苯基) [2-(苯基磺酰氨基)苯丙酰氨基]甲基}膦酸二乙酯〕、Ⅲh〔{(2-氟苯基) [2-(苯基磺酰基氨)异戊酰氨基]甲基}膦酸二乙酯〕和Ⅲm〔{(苯基) [2-(苯基磺酰基氨)乙酰氨基]甲基}膦酸二乙酯〕对E. coli的MIC（Minimum Inhibitory Concentration）均为16 μg/mL，化合物Ⅲn〔{(2-氟苯基) [2-(苯基磺酰氨基)乙酰氨基]甲基}膦酸二乙酯〕对E. coli的MIC为8 μg/mL，抗菌活性不低于对照药苯唑西林；化合物Ⅲb、Ⅲh、Ⅲm和Ⅲn对FREC的MIC分别为32、32、32和16 μg/mL，优于对照药苯唑西林和诺氟沙星。     

阿瑞匹坦的合成研究

以(2S,3R)-4-苄基-3-(4-氟苯基)-吗啉-2-醇、(R)-1-[3,5-二(三氟甲基)苯基]乙醇、5-氯甲基-2,4-二氢-[1,2,4]三唑-3-酮为主要原料,经5步反应合成阿瑞匹坦,总收率为23.90%。采用元素分析和1H-NMR分析技术,对产物的分子结构进行了表征。该路线操作简便,反应条件温和,适合工业化生产。     

4-取代的2-(2-氟-3-三氟甲基苯基)-1,3,4-噁二嗪-5-酮衍生物的合成及其生物活性

以2-氟-3-三氟甲基苯甲酰肼为起始原料,经与氯乙酰氯酰肼化,然后在碳酸钾的作用下进行环合,得到2-(2-氟-3-三氟甲基苯基)-1,3,4-噁二嗪-5-酮,最后通过与各种卤代烃反应,在4位N上引入不同基团,合成了18个未见报道的2-(2-氟-3-三氟甲基苯基)-1,3,4-噁二嗪-5-酮衍生物.所有化合物通过核磁共振鉴定,生物测试结果表明化合物1～化合物3对瓜类炭疽病具有较好的活性.     

2-吗啉醇盐酸盐的手性合成及晶体结构

以单一手性纯试剂与外消旋体化合物反应,合成了4对手性纯化合物(2R,3R,5S)-2-吗啉醇盐酸盐及其对映体(2S,3S,5R)-2-吗啉醇盐酸盐。其结构经IR、1HNMR、13CNMR及ESI-MS表征,利用X-射线单晶衍射法测定了其中一对对映体的空间构型。利用吗啉六元环椅式构象比船式构象稳定的特性,系统探讨了以构象稳定性促进目标化合物构型形成的手性化合物合成机制及规律,为手性化合物合成方法提供了新启示。     

含三氟甲基或3,4,5-三甲氧基二苯乙烯腈衍生物的制备及其活性研究

以4-三氟甲基苯甲酸和3,4,5-三甲氧基苯甲酸为原料合成出2-(4-(三氟甲基)苯基)乙腈和2-(3,4,5-三甲氧基苯基)乙腈,将其作为中间体和几种醛类合成一系列含4-三氟甲基及3,4,5-三甲氧基二苯乙烯腈衍生物。所合成的化合物通过氢谱、碳谱与高分辨质谱进行表征后用MTT法在12种细胞上测得其细胞增殖抑制率,其中(Z)-3-(4-丙氧基苯基)-2-(3,4,5-三甲氧基苯基)丙烯腈显示最好的抗癌活性及选择性抑制活性,经进一步研究发现通过抑制细胞迁移与抑制集落形成达到抗癌效果,具有进一步开发研究的价值。     

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.