利用季铵盐催化剂提高地亚农收率

以嘧啶醇和O，O-二乙基硫代磷酰氯（简称氯化物）为原料，在相转移催化剂作用下合成地亚农，考察了影响反应的因素。结果表明；选用苄基基乙基氯化铵做相转移催化剂，0.1mol嘧啶醇用1.0g催化剂，溶剂选用甲苯，嘧啶醇和氯化物的物质的量比为1：1.1，收率可以达到94%。     

二氯化物直接氨化制甲胺磷中间体酰胺

O,O-二甲基硫代磷酰胺(篇称酰胺),是生产甲胺磷的中间体。现今国内外的生产工艺多是先由三氯硫磷和甲醇反应生成O-甲基硫代磷酰二氯(简称二氯化物)。二氯化物用液碱脱氯生成O,O-二甲基硫代磷酰氯(简称一氯化物)。一氯化物再和氨水反应,制成酰胺。由此制备酰胺,不但工艺路线较长,而且     

O,O-二乙基硫代磷酰氯合成路线的对比与分析

本文对O,O—二乙基硫代磷酰氯生产的三氯硫磷法和五硫化二磷法两条合成路线进行了分析比较指出天津农药厂将工业化生产装置由三氯硫磷法改为五硫化二磷法,系为我国第一个建成的高温氯化的工业装置其产品纯度达95％,收率达70％。     

水溶剂法合成高效杀虫剂毒死蜱的研究

研究了"一锅法"合成毒死蜱的新工艺。以2,3,5,6-四氯吡啶和液碱为原料,一步制得3,5,6-三氯吡啶醇钠,3,5,6-三氯吡啶醇钠和O,O-二乙基硫代磷酰氯反应得到目标产物,报道了一种用三元复合催化剂催化合成毒死蜱的新方法,探讨了采用水溶剂法合成毒死蜱的适宜的工艺条件,毒死蜱的收率、质量分数分别达到95%和97%以上,并采用IR、1H NMR对该化合物的结构进行了表征。     

相转移催化合成N—取代硫代磷酰胺二乙酯

用乙基氯化物（Ｏ，Ｏ－二乙基硫代磷酰氯）与不同的胺反应，以碳酸钾作缚酸剂、季铵盐作相转移催化剂，合成了六种Ｎ－取代硫代磷酰胺二乙酯，其结构经ＩＲ、ＮＭＲ和元素分析证实。     

在水介质中用相转移催化剂合成蝇毒磷

为了降低蝇毒磷[O,O-二乙基-O-(3-氯-4-甲基香豆素-7-基)硫逐磷酸酯]的合成成本,减少污染,采用水为溶剂研究了相转移催化剂的类型与用量、缚酸剂、反应温度和反应时间对O,O-二乙基硫代磷酰氯与3-氯-4-甲基-7-羟基香豆素(香豆素)酯化反应的影响。小试结果表明,以4-二甲氨基吡啶(DMAP)为相转移催化剂,碳酸钾为缚酸剂,催化剂用量n(DMAP)∶n(香豆素)=1∶40,在40℃反应1h,蝇毒磷收率和含量均可达到95%;含催化剂的液体复用4次,蝇毒磷收率仍高达90.3%。车间500L反应釜中试结果表明,蝇毒磷单釜收率可达93%,含量高于96%。     

醇碱法合成甲基氯化物的改进试验

O,O——二甲基硫代磷酰氯(以下简称一氯),是硫代磷酸酯型多种有机磷农药的主要中间体。综合有关文献报导,其合成方法有以下几条路线: 1.甲醇与三氯硫磷反应。 2CH_3OH+PSCl_3→(CH_3O)_2PSCl+2HCl 该路线多采用氢氧化钠或吡啶作为脱酸剂。     

相转移催化合成N－取代硫代磷酰胺二乙酯

用乙基氯化物（Ｏ，Ｏ－二基硫代磷酰氯）与不同的胺反应，以碱酸钾作缚酸剂、季铵盐作相转移催化剂，合成了六种Ｎ－取代硫代磷酰胺二乙酯，其结构经ＩＲ、ＮＭＲ和元素分析证实。     

P_2S_5法制乙基氯化物新工艺

0,0-二乙基硫代磷酰氯(简称氯化物)是有机磷农药的重要中间体。现有两种生产工艺,其一是以无水乙醇与三氯硫磷为原料合成,称之为三氯硫磷法;其二是以P_2S_5代PSCl_3,称之为P_2S_5法。     

凝聚态合成毒死蜱

采用3,5,6-三氯吡啶-2-醇钠(简称醇钠)和O,O-二乙基硫代磷酰氯(简称乙基氯化物),在凝聚态条件下合成了毒死蜱。研究了物料配比、催化剂组成及用量、反应温度、反应时间等因素对醇钠转化率的影响。最佳合成工艺条件为:醇钠与乙基氯化物的摩尔比为1∶1.05,催化剂组成为:4-(N,N-二甲基)胺基吡啶(缩写DMAP)与烧碱的重量比为1∶13,投料量为醇钠重量的0.5%,反应温度10～25℃,反应时间120min。醇钠的最佳转化率为98.6%,收率为98.6%。     

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.     

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.     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.     

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.