4-三氟甲基苯乙酸的合成新方法

以4-三氟甲基苯胺为原料,经重氮化、Grignard反应、Wolff-Kishner-黄鸣龙还原反应制得标题化合物.研究表明:n(Mg)∶n(4-三氟甲基溴苯)∶n(草酸二乙酯)=1.2∶1∶1.5、反应温度为50～60 ℃、n(4-三氟甲基苯乙酮酸乙酯)∶n(水合肼)=1∶1.2,总收率68.4%,并通过~1HNMR对中间体及产物进行了结构确证.     

5-乙酰胺甲基-3-[3-氟-4-（1-哌嗪基苯基）]异噁唑啉的合成

以3,4-二氟苯甲醛、盐酸羟胺为原料,经缩合反应、氯代反应制得3,4-二氟苯肟氯代物（3）;以烯丙基胺为原料经乙酰化反应制得乙酰烯丙基胺（4）;化合物3与化合物4经环合反应、哌嗪取代反应合成终产物5-乙酰胺甲基-3-[3-氟-4-（1-哌嗪基苯基）]异噁唑啉（呈）。总收率为30．2％,纯度为99．1％（HPLC）。     

2-氟-4-三氟甲基苯乙腈的合成研究

以2-氟-4-三氟甲基溴苯为起始原料,先经甲酰化和醛基还原反应"一锅法"合成了2-氟-4-三氟甲基苄醇,继而以氯取代反应合成了2-氟-4-三氟甲基苄氯,最后经氰化反应合成了2-氟-4-三氟甲基苯乙腈。经优化后,4步反应总收率为88. 8%,气相色谱测得产品含量为99. 2%,是一个适合工业生产的工艺路线。     

3-乙氧基-4-{[3-(三氟甲基)苯基]氨基}环丁-3-烯-1,2-二酮的合成

以3-三氟甲基苯胺和方酸二乙酯等为原料,依次经过酯化和氨解反应合成了目标化合物3-乙氧基-4-{[3-(三氟甲基)苯基]氨基}环丁-3-烯-1,2-二酮.中间体及目标化合物结构经11HNMR和MS表征,并考察了影响目标化合物收率的主要因素.确定氨解反应的适宜条件为:n(3-三氟甲基苯胺)∶n(方酸二乙酯)=1.1∶1;...     

1-烯丙基-6-氯-7-甲基-1,4-二氢喹喔啉-2,3-二酮的合成

设计并合成了化合物1 烯丙基 6 氯 7 甲基 1,4 二氢喹喔啉 2,3 二酮,该化合物主要用于一系列新型NMDA受体拮抗剂的制备。反应以1 氯 4 氟 2 甲基苯为原料,在浓硫酸溶液中采用硝酸钾硝化得1 氯 4 氟 2 甲基 5 硝基苯,收率94 0%,将1 氯 4 氟 2 甲基 5 硝基苯与烯丙胺反应,三乙胺为缚酸剂,回流反应合成烯丙基 (4 氯 5 甲基 2 硝基 苯基) 胺,收率为81 0%,然后使用铁粉高收率还原所得的硝基化合物(收率为95 0%),再与二水合草酸在c(HCl)=2mol/L的盐酸中进行环合反应合成目的化合物1 烯丙基 6 氯 7 甲基 1,4 二氢喹喔啉 2,3 二酮(收率为90 6%),反应总收率为65 5%。     

微波促进下N-(3-氯-4-氟苯基)-7-氟-6-硝基-4-喹唑啉胺的合成

以2-溴-4-氟-5-硝基苯甲腈为原料,CuI为催化剂,在微波促进下与3-氯-4-氟苯胺进行加成反应后,再与甲酰胺发生串联的胺化和缩合环化反应合成抗癌药Afatinib(阿法替尼)和Dacomitinib(达克替尼)的关键中间体N-(3-氯-4-氟苯基)-7-氟-6-硝基-4-喹唑啉胺,并对反应条件进行了优化。结果表明:在Cu I用量为20%(以2-溴-4-氟-5-硝基苯甲腈的物质的量为基准,下同)和微波促进下,n(2-溴-4-氟-5-硝基苯甲腈):n(3-氯-4-氟苯胺)=1:1,回流反应20 min,制备得到2-溴-N-(3-氯-4-氟苯基)-4-氟-5-硝基苯甲脒,收率93.8%;在Cu I与4-羟基-L-脯氨酸用量均为10%〔以2-溴-N-(3-氯-4-氟苯基)-4-氟-5-硝基苯甲脒的物质的量为基准,下同〕和微波促进下,n〔2-溴-N-(3-氯-4-氟苯基)-4-氟-5-硝基苯甲脒〕:n(甲酰胺)=1:2,80℃反应10min,以96.4%的收率得到目标产物N-(3-氯-4-氟苯基)-7-氟-6-硝基-4-喹唑啉胺。     

2-(4′-羟基苯氧基)-3-氯-5-三氟甲基吡啶的合成

以对苯二酚与2,3-二氯-5-三氟甲基吡啶单醚化合成精吡氟氯禾灵的重要中间体2-(4′-羟基苯氧基)-3-氯-5-三氟甲基吡啶。探讨并得到了反应的最佳工艺条件:K2CO3为缚酸剂,二甲基亚砜和甲苯为溶剂,n(2,3-二氯-5-三氟甲基吡啶)∶n(对苯二酚)∶n(K2CO3)=1∶2∶1.08,不需要脱水。在回流条件下加入2,3-二氯-5-三氟甲基吡啶并反应5 h。在此条件下,2,3-二氯-5-三氟甲基吡啶的转化率100%,产品的选择性大于98%。     

1-氨甲基-2-萘酚类化合物的合成

为了高效简便合成1-氨甲基-2-萘酚类化合物,选择以β-萘酚、醛和胺为起始原料,在有机小分子三氟甲磺酸脯氨酸盐的催化下,一锅法合成了该类化合物。重点考察了不同有机小分子催化剂以及不同溶剂对该反应的影响,确定了适宜的反应条件为:n(β-萘酚):n(醛):n(胺):n(三氟甲磺酸脯氨酸盐)=1:1:1.1:0.1,于二氯甲烷溶剂中回流反应。同时,合成的系列目标化合物,结构经过熔点、IR、~1H-NMR、~(13)C-NMR和MS确认。此外,还将该方法应用于α-萘酚及芳胺中,合成了相应的产物,并探讨了可能的反应机理。     

4-氯-2,5二氟苯甲酸的合成

提出了一种以2,5-二氟苯胺为原料,经Sandmeyer反应、溴化和格氏反应三步得到4-氟-2,5-二氟苯甲酸的合成方法.其中溴化反应的最佳反应条件为:n(2-氯1,4-二氟苯):,你、n(溴素)=1:1.13,n(2-氯1,4-二氟苯):n(无水三氯化铁)=1:0.03,溴化反应温度为30℃,反应时间为5h.三步总摩...     

一锅法合成N-[4-氯-3-(三氟甲基)苯基]-N-′(4-甲基苯基)脲

以4-氯-3-三氟甲基苯胺、固体光气和4-甲基苯胺为原料,一锅法合成了标题化合物。考察了投料次序、原料配比、温度对这一反应的影响,优化了反应条件。产物结构经元素分析、IR、1HNMR确证。     

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。