1-芳基-1,4-二氢-4-氧-6-甲基哒嗪-3-羧酸酯的合成

为探索哒嗪酮羧酸酯的简便合成方法 ,通过亚磷酸二烷基酯与 1-芳基 - 1,4 -二氢- 4 -氧 - 6 -甲基哒嗪 - 3-羧酸 (摩尔比为 2∶ 1)在 120～ 130℃下共热 4 h,得到 7个收率 63%～85%的哒嗪酸烷基酯。     

4-取代-2-[(3-三氟甲基)-苯乙烯基]-1,3,4-噁二嗪-5-酮的合成及其生物活性

以3-(3-三氟甲基苯基)-丙烯酸为起始原料,设计并合成了14个4-取代-2-(3-三氟甲基)苯乙烯基-1,3,4-噁二嗪-5-酮衍生物,其化学结构经核磁共振氢谱及元素分析确证。初步的生物活性测定结果表明,该类化合物具有良好的杀虫活性,其中化合物 D-2,D-3,D-4,D-8 在质量浓度为50 mg/L时,对淡色库蚊Culex pipiens pallens的致死率分别为91.7% ,86.1% ,85.5%和93.9%。     

新型N-芳基-2-((5-((4,6-二甲基嘧啶-2-基)硫甲基)-1,3,4-噻二唑-2-基)硫)乙酰胺类化合物的合成及杀菌活性

为寻找新型杂环活性化合物,通过活性亚结构拼接,以硫脲和乙酰丙酮为起始原料合成4,6-二甲基嘧啶-2-硫醇,随后经酯化、肼化、环化和缩合反应,设计并采用微波辅助合成了10个新型N-芳基-2-（（5-（（4,6-二甲基嘧啶-2-基）硫甲基）-1,3,4-噻二唑-2-基）硫）乙酰胺类化合物,其结构通过核磁共振氢谱和碳谱、红外光谱、质谱及元素分析确认。初步生物活性测试结果表明,在50 mg/L下,大部分目标化合物对植物病原真菌具有一定的抑制活性,其中化合物8h对黄瓜炭疽病菌Colletotrichum orbiculare的抑制率达77.3%。     

1-（4-氯苯基）-3-吡唑醇的合成工艺

以对氯苯肼为原料经环合、氯化,合成1-（4-氯苯基）-3-吡唑醇。本文研究了其合成工艺和投料比、反应温度、反应时间,催化剂用量和溶剂种类对收率的影响。用IR、1HNMR表征了其结构,在最优条件下,1-（4-氯苯基）-3-吡唑醇合成的总收率为68．35％,含量为98．5％,该路线简单经济,条件温和,收率高,适合工业化生产。     

3-苄基-5-(1-(2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-氨基咪唑啉-4-酮类化合物的合成及杀菌活性

为寻找高活性的杀菌化合物,在前期合成5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-氨基咪唑啉-4-酮类化合物的基础上进行结构修饰,在咪唑啉-4-酮的3-位引入苄基,设计并合成了一系列未见文献报道的化合物,其结构经过核磁共振氢谱 (1H NMR)、碳谱 (13C NMR) 及高分辨质谱 (HR-ESI-MS) 确证。经高效液相色谱 (HPLC) 分析显示,Z-构型中间体化合物 6 在酸性条件下会发生氮质子化开环再环化,转化为E-构型化合物 7 。离体杀菌活性测定结果表明,3-位苄基的引入改善了该类化合物的杀菌活性,其中化合物 (E)-3-苄基-5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-(4-甲氧基苯基) 氨基-咪唑啉-4-酮 ( 9c ) 和 (E)-3-苄基-5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-(4-氟苯基) 氨基-咪唑啉-4-酮 ( 9h ) 对油菜菌核病菌的EC₅₀ 值分别为14.3和21.1 mg/L。活体杀菌活性测试结果显示,在400 mg/L下化合物 9c 对于黄瓜霜霉病和小麦白粉病的防治效果分别为 80%和85%。     

吡啶衍生物研究(V):2-[(2-氯吡啶)-4-基]-5-芳胺基-1,3,4-噻二唑的合成及杀菌活性

合成了一系列 2 - [(2 -氯吡啶 ) - 4 -基 ]- 5-芳胺基 - 1,3,4 -噻二唑类化合物 ,其结构经元素分析、1H NMR、和 13 C NMR确认。初步生物活性测定表明 ,合成化合物对某些真菌生长表现出较好的抑制活性 ,如 I- 0 2在 50 0 μMg· m L-1剂量下对水稻纹枯病菌生长的抑制率达87.5%。     

吡啶衍生物研究(V):2-[(2-氯吡啶)-4-基]-5-芳胺基-1,3,4-噻二唑的合成及杀菌活性

合成了一系列 2 - [(2 -氯吡啶 ) - 4 -基 ]- 5-芳胺基 - 1,3,4 -噻二唑类化合物 ,其结构经元素分析、1H NMR、和 13 C NMR确认。初步生物活性测定表明 ,合成化合物对某些真菌生长表现出较好的抑制活性 ,如 I- 0 2在 50 0 μg· m L-1剂量下对水稻纹枯病菌生长的抑制率达87.5%。     

2-氰基-3-取代胺基(或甲硫基)-3-(2-氯-5-吡啶甲胺基)-丙烯酸酯类化合物的合成及生物活性

作者曾模拟新烟碱类杀虫剂的化学结构,合成了一系列含2-氯-5-吡啶甲基的双氰基取代烯酮缩胺类化合物,并对其进行了生物活性测定,发现部分化合物显示了较好的杀虫和除草活性[1],特别是除草活性引起我们的兴趣。为进一步研究此结构类型的化合物的合成及生物活性,我们以酯基替代前文所述化合物中的一个氰基,并保留新烟碱杀虫剂nitenpyram类似物的骨架[2]。由于这种结构与作为光合作用光系统II(PSII)电子传递抑制剂的氰基丙烯酸酯类化合物很相似[3],该类化合物可能会有更好的除草效果。我们依此设计,合成了2-氰基-3-(2-氯-5-吡啶甲胺基)-3-甲…     

2-(4-羟基苯氧基)-6-氯-喹喔啉的合成新方法

以2,6-二氯喹喔啉、对苯二酚、液碱为原料,优化操作过程,于三元体系中合成2-(4-羟基苯氧基)-6-氯喹喔啉,收率达到96％以上.     

N-1,3,4-噁二唑基-N′-对溴苯氧乙酰基硫脲的合成及其抑菌活性

从对溴苯氧乙酸出发,先合成中间体酰基异硫氰酸酯,该中间体与2-氨基-5-芳基-1,3,4口-恶二唑反应合成了10个新的苯氧乙酰基硫脲类化合物,其结构经元素分析、红外光谱、核磁共振氢谱和质谱确认。初步生物活性测试结果表明,在50mg/L浓度下,所有目标化合物对水稻纹枯病菌Rhizatonia solani和黄瓜灰霉病菌Botrytis cinereapers的抑制率均达85%以上,部分化合物对黄瓜灰霉病菌的抑制率达100%。     

新一代烟碱类杀虫剂呋虫胺及中间体合成新工艺的研究

本文以丙二酸二乙酯为原料,在乙醇钠条件下与氯乙酸乙酯反应生成乙烷-1,2,2-三羧酸乙酯,再用硼氢化钠还原得2-羟基-1,4-丁二醇,在对甲苯磺酸的催化下脱水环合成3-羟甲基四氢呋喃,再与对甲苯磺酰氯、三乙胺反应生成3-四氢呋喃甲基对甲苯磺酸酯;甲醛水溶液、甲基硝基胍、甲胺水溶液在乙醇中反应生成1,5-二甲基-2-硝基亚胺六氢-1,3,5-三嗪;3-四氢呋喃甲基对甲苯磺酸酯与1,5-二甲基-2-硝基亚胺六氢-1,3,5-三嗪反应生成呋虫胺。     

Synergism of organophosphorus insecticides by diethyl maleate and related compounds in house flies

The toxicity of several organophosphorus and one carbamate insecticide for house flies is enhanced by simultaneous administration of diethyl maleate. Synergism factors vary from 2 to 116 and are strongly dependent on the combination of strain and insecticide studied. In general, it seems that thiono compounds are less synergized than their oxon analogs. Comparison of some analogs of maleic acid esters showed that the diethyl ester was not the most active compound. trans-Phenylbutenone was found to be a good alternative for diethyl maleate. Both diethyl maleate and trans-phenylbutenone deplete glutathione in the flies, but this depletion per se is certainly not the most important mode of action. In vitro experiments made clear that sufficient glutathione remained to permit a substantial insecticide degradation rate. Moreover, treatment of the flies with diethyl maleate 2–4 hr before the insecticide application resulted in a partial or complete disappearance of synergism in a period in which the glutathione concentration in the flies was still very low. Apart from this effect on the glutathione levels in the insect tissues it appeared from further experimental work in vitro that both compounds had a direct inhibitory effect on glutathione-dependent transferase(s) as well as on oxidative enzymes involved in insecticide degradation. The contribution of these reactions to the eventual synergism factor is discussed.     

Penetration of clopyralid and related weak acid herbicides into and through isolated cuticular membranes of Euonymus fortunei

A model system consisting of chemically isolated cuticular membranes placed on agar was used to study the penetration of various formulations of ¹⁴C-labelled clopyralid, fluroxypyr, triclopyr, picloram, and 2,4-D into and through cuticular membranes. Clopyralid, commercially formulated as the acid, or 1-decyl ester was rapidly absorbed after 12 h by isolated cuticles of Euonymus fortunei. There was less absorption of the monoethanolamine and potassium salt formulations when compared to the acid and 1-decyl ester. However, in terms of the absorbed ¹⁴C-activity that partitioned into the agar, there was no difference between the acid and salt formulations with approximately 90% being partitioned after 48 h. Conversely, the 1-decyl ester formulation of clopyralid was retained in the cuticle; less than 5% of the absorbed fraction was recovered in the agar after 48 h. When the acid forms of clopyralid, fluroxypyr, triclopyr, picloram, and 2,4-D were compared, there was little or no difference in absorption among the herbicides. However, the ¹⁴C-activity from clopyralid partitioned the most (90%) and triclopyr the least (50%) into the agar. When ester formulations of clopyralid, fluroxypyr, and triclopyr were compared, at least 95% of the ¹⁴C-activity was absorbed 24 h after application. However, of the amount absorbed, significantly more of the butoxyethyl ester of triclopyr (36%) partitioned into the agar than did the 1-decyl ester of clopyralid (6%) or the 1-methylheptyl ester of fluroxypyr (5%). Differential retention of various herbicide formulations in this model system may explain, in part, the differences in absorption and translocation among radiolabelled clopyralid formulations observed in previous research (Kloppenburg & Hall, 1990).     

广宁红花油茶广寄生开花结实特性与防控药剂

广宁红花油茶作为重要的油茶作物,在种植过程中受到广寄生的严重危害。为阻断广寄生的传播和蔓延,为广寄生的防控提供技术支撑,对广寄生开花结实特性与防控药剂开展了研究。对广东省樟木头林场广寄生开花结实动态的定点监测结果表明：广寄生的花期为7月-12月,果实成熟期为9月-翌年2月,花果期长达7个月以上。通过喷淋法研究4种植物生长调节剂对广寄生及寄主广宁红花油茶生长的影响,以筛选防控广寄生的化学制剂。结果表明：选用的30%胺鲜·乙烯利水剂、5%萘乙酸水剂、50%丁酰肼可溶性粉剂及0.1%S-诱抗素水剂4种植物生长调节剂对广宁红花油茶上的广寄生均有一定的防控作用,其中30%胺鲜·乙烯利水剂的防控效果显著优于其他药剂,1∶400的处理防效最优,且未对红花油茶产生明显药害。     

Structure—activity relationship for some substituted dialkyl vinyl phosphates

The biological activity against the house fly, Musca domestica L., is reported for a series of dialkyl 2-bromo-1-(2,4-dichlorophenyl)vinyl phosphates. Maximum activity and the lowest degree of synergism with piperonyl butoxide were found with the dimethyl ester. Good activity was also shown by the diethyl ester. Both these compounds, used at the same dose, inhibited fly-head acetylcholinesterase. Compounds with longer alkyl chains were less effective and did not inhibit acetylcholinesterase.     

阿魏酸衍生物的合成及其除草活性测定

为从天然产物中获取新的除草活性成分,通过化学合成的方法对分离自瓜果腐霉Pythium aphanidermatum代谢产物中的阿魏酸进行了结构改造,并采用小杯法,以马唐、马齿苋和播娘蒿为供试杂草对所得化合物进行了除草活性测定。结果显示:所合成的4-羟基-3-甲氧基肉桂酸乙酯、4-羟基-3-甲氧基肉桂酸邻氯苯胺、4-羟基-3-甲氧基肉桂酸酰肼、4-羟基-3-甲氧基肉桂酸叔丁酯和4-乙酰氧基-3-甲氧基肉桂酸5种化合物的回收率分别为96.81%、97.39%、82.20%、75.67%和98.29%。4-羟基-3-甲氧基肉桂酸酰肼和4-乙酰氧基-3-甲氧基肉桂酸对马齿苋胚根的抑制活性最强,IC50分别为87.50 mg/L和74.86 mg/L,其余3种活性相对较弱;4-羟基-3-甲氧基肉桂酸乙酯和4-乙酰氧基-3-甲氧基肉桂酸分别在500 mg/L和1 000 mg/L浓度下可完全抑制播娘蒿和马齿苋胚根、芽的生长,而4-羟基-3-甲氧基肉桂酸邻氯苯胺则在1 000 mg/L浓度下可完全抑制播娘蒿胚根的生长。表明在阿魏酸分子中的不同位点引入适当的基团结构可以提高或者降低阿魏酸分子的除草活性,并获得新的除草活性物质。     

THE HYDROLYSIS OF 2,4-DICHLOROPHENOXY- ACETATE ESTERS TO 2,4-DICHLOROPHENOXYACETIC ACID IN SASKATCHEWAN SOILS

Summary. The hydrolysis of the iso-propyl, n-butyl and iso-octyl esters of 2,4-dichloro-phenoxyacetic acid to the free acid was studied in aqueous solutions and on three prairie soils. The esters were analysed using electron-capture gas chromatography following extraction from solution with benzene, and from soils, using either 10% aqueous aceto-nitrile or a 2:1 mixture of benzene and iso-propanol.
Ester hydrolysis in 0·1 n sodium hydroxide solution was very rapid, more than 50% of all the esters being hydrolysed in less than 1 min. In 0·1 n sodium carbonate solution the times for 50% hydrolysis at 25°C were < 5, 5 and 30 min for the n-butyl, iso-propyl and iso-octyl esters respectively. In distilled water negligible hydrolysis occurred over a 5 h period.
The iso-propyl and n-butyl esters underwent a very facile hydrolysis on soils. Shaking the treated soils with 0·1 M calcium chloride solution for 30 min at 25°C resulted in extensive hydrolysis to the acid as determined spectrophotometrically. Under similar conditions negligible hydrolysis of the iso-octyl ester occurred.
After 1·5 h at 25±1°C on soils at their wilting point moisture levels, and greater, less than 15% of the applied iso-propyl or n-butyl esters could be recovered using either extraction procedure, indicating rapid hydrolysis to the acid. After 24 h no iso-propyl or n-butyl ester residues could be detected in any of the soils. Loss of the iso-octyl ester was slower under these conditions with approximately 20–30% of the ester remaining after 24 h, and 10% after 48 h.
L'hydrolyse des esters de 2,4 dichlorophénoxyacétates en acide 2,4 dichlorophénoxyacétique dans les sols du saskatchewan.     

Kinetic efficiency of mutant carboxylesterases implicated in organophosphate insecticide resistance

Resistance to organophosphorus (OP) insecticides in Lucilia cuprina arises from two mutations in carboxylesterase E3 that enable it to hydrolyse the phosphate ester of various organophosphates, plus the carboxlyester in the leaving group in the case of malathion. These mutations are not found naturally in the orthologous EST23 enzyme in Drosophila melanogaster. We have introduced the two mutations (G137D and W251L) into cloned genes encoding E3 and EST23 from susceptible L. cuprina and D. melanogaster and expressed them in vitro with the baculovirus system. The ability of the resultant enzymes to hydrolyse the phosphate ester of diethyl and dimethyl organophosphates was studied by a novel fluorometric assay, which also provided a sensitive titration technique for the molar amount of esterase regardless of its ability to hydrolyse the fluorogenic substrate used. Malathion carboxylesterase activity was also measured. The G137D mutation markedly enhanced (>30-fold) hydrolysis of both classes of phosphate ester by E3 but only had a similar effect on the hydrolysis of dimethyl organophosphate in EST23. Introduction of the W251L mutation into either gene enhanced dimethyl (23-30-fold) more than diethyl (6-10-fold) organophosphate hydrolysis and slightly improved (2-4-fold) malathion carboxylesterase activity, but only at high substrate concentration.     

The rational design of the optically active wild oat herbicide L-flamprop-isopropyl

An esterase, that has been partially purified from oat tissues, catalyses the hydrolysis of the wild oat herbicide benzoylprop-ethyl and of the related esters of N-benzoyl-N-(3-chloro-4-fluorophenyl)-DL -alanine, including flamprop-methyl and flampropisopropyl. The enzyme is virtually stereospecific for the L -isomers in the racemic mixtures. Hydrolysis of flamprop-methyl in oat tissues shows similar enantiomeric discrimination, but the ethyl and isopropyl ester analogues are converted in vivo to the free acid with very little overall stereoselectivity. Oat tissues must, therefore, contain another enzyme, labile to isolation, that acts on the D -isomers of the higher esters. This was confirmed by showing that it is possible to manipulate the stereoselectivity of the de-esterification of the ethyl ester in vivo by selective inhibition of either the L -isomer pathway with paraoxon (diethyl 4-nitrophenyl phosphate), or the D -isomer route with piperonyl butoxide. The relationship of these findings to the superior herbicidal performance of the L -isomers of these esters, relative to their racemates, is discussed.     

Physiological interactions between the herbicide EPTC and selected analogues of the antidote naphthalic anhydride on two hybrids of maize

The efficacies of nine structural analogues of the herbicide antidote naphthalene-1,8-dicarboxylic acid anhydride (naphthalic anhydride, NA) for the protection of maize (Zea mays L. cv. DeKalb XL72AA and DeKalb XL67) against injury by the herbicide S-ethyl dipropyl(thiocarbamate) (EPTC) were elevated under greenhouse conditions. The chemical analogues of NA tested were: acenaphthenequinone (ACQ); 4-aminonaphthalene-1,8-dicarboxylic acid anhydride (NH₂NA); 1,8:4,5-naphthalenetetracarboxylic acid dianhydride (NDiA); naphthalene- 1,8-carboximide (NHNA); 4-chloronaphthalene-1,8-dicarboxylic acid anhydride (C1NA); biphenyl-2,2′-dicarboxylic acid anhydride (diphenic anhydride; DA); 2-phenylglutaric anhydride (PGA); phthalic anhydride (PHA); phenalen-1-one (PA). Pre-plant incorporated applications of EPTC at 2.2, 4.5, 6.7, and 9.0 kg ha^?1 were highly toxic to XL67 maize. Appreciable injury to XL72AA maize by EPTC was observed only with the high rates of EPTC (6.7 and 9.0 kg ha^?1). Of the analogues tested PGA and PA were very toxic and inhibited germination of both maize hybrids. NA, ACQ, NH₂NA, NDiA, NHNA, C1NA, DA, and PHA applied as seed dressings at 5.0 and 10 g per kg of seed offered satisfactory protection to XL72AA maize against EPTC rates higher than 6.7 kg ha^?1. The same antidotes significantly antagonised the EPTC activity against XL67 maize but the overall protection obtained was partial and not agronomically important. The presence of the dicarboxylic anhydride group and of at least one aromatic ring attached directly to the anhydride appeared to be essential for the exhibition of protective activity by the structural analogues of NA. NA was slightly toxic to both hybrids of maize and chlorination of NA increased the phytotoxicity of this molecule. A genetic component that is present in the thiocarbamate-tolerant XL72AA hybrid but absent from the thiocarbamate-susceptible XL67 hybrid of maize appeared to be important for the phytotoxic activity of EPTC and may be involved in the protective activity of NA and its structural analogues.