Photochemical behaviour of dichlorprop [(+/-)-2-(2,4-dichlorophenoxy)propanoic acid] in aqueous solution

Aqueous solutions of dichlorprop were irradiated under different conditions of pH, wavelength and oxygenation. The photochemical behaviour was found to be complex and many photoproducts were formed. However, at low concentrations the main photoproducts were 4-chloropyrocatechol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol. Some other photoproducts were identified, namely 2-(4-chloro-2-hydroxyphenoxy)propanoic acid, 2-(3,5-dichloro-2-hydroxyphenyl)propanoic acid and 2,4-dichlorophenyl acetate. From comparison with results previously obtained with mecoprop [2-(4-chloro-2-methylphenoxy)propanoic acid] it appears that the presence of a chlorine atom in position 2 on the ring strongly modifies the photochemical behaviour.     

Different in-planta and ex-planta activities of 7-chloro-4-(2-[trifluoromethyl]phenoxy)quinoline against Pyricularia grisea due to volatilization

7-Chloro-4-[2-(trifluoromethyl)phenoxy]quinoline (L Y248908) strongly inhibits mycelial growth of Pyricularia grisea in ex-planta assays but, when applied to the foliage of rice seedlings, its protective and curative properties against P. grisea are poor. The principal cause for this difference was found to be volatilization of LY248908 from treated foliage. Variations in fungal sensitivity (due to strain or development stage) and compound loss due to translocation, sequestration, metabolism, or degradation were shown not to be significant.     

Factors favouring the choice of flamprop-methyl,methyl (±)-2-[N-(3-chloro-4-fluorophenyl)benzamido] propionate for the control of avena species in wheat

The post-emergence herbicide, methyl (±)-2-[N-(3-chloro-4-fluorophenyl)benzamido]-propionate, flamprop-methyl, showed good activity against oat with selectivity in wheat. It was superior in performance to flamprop-isopropyl and benzoylprop-ethyl already being marketed for wild oat control. It gave even more effective control of seed set in the oat than did the other compounds, prevented tiller growth and as a result of its higher activity was less dependent on crop competition. Selectivity of flamprop-methyl, however, was similar to that previously reported for related compounds, i.e. it was dependent on its rate of degradation and the subsequent detoxication of the biologically active acid to inactive conjugates. The rate of degradation of flamprop-methyl is comparable to that of benzoylprop-ethyl but the more active acid produced accounts for the improved performance of the former. The corresponding ethyl ester showed the highest rate of degradation and although generally comparable in performance to the methyl ester there was a tendency for the inhibition on the oat to last for a shorter period. Performance of flamprop-methyl is influenced by environmental factors such as temperature or water stress. These factors had an effect during the first 2 weeks after compound application, reducing the translocation of the active metabolite to its site of action and having a small but detectable effect on the amount of acid produced.     

Combined effects of wheat competition and 2,4-D amine on phenoxy herbicide resistant Raphanus raphanistrum populations

Phenoxy herbicides are integral to the control of Raphanus raphanistrum populations in Australian crop production systems, but the development of phenoxy resistant R. raphanistrum populations poses a major threat to the sustainability of these systems. In dose–response pot studies, phenoxy herbicide resistant R. raphanistrum populations, WARR12 and WARR20, suffered large biomass reductions following treatment with recommended or higher application rates of phenoxy herbicides. This indicates the presence of a weak resistance mechanism where treated plants, although surviving, are affected by these herbicides. Subsequently, the competitive ability of 2,4-D amine treated or untreated WARR12 and WARR20 populations with wheat was assessed using a target-neighbourhood experiment. The combination of wheat competition and 2,4-D amine application resulted in control of the resistant WARR12 population, but not the WARR20 population. Wheat crop competition alone resulted in large (>40%) biomass reductions of WARR12 and WARR20 populations. However, the application of the recommended rate of 2,4-D amine caused a large (>75%) reduction in WARR12 biomass, but had a reduced effect on WARR20 biomass. These studies possibly explain the largely successful control of R. raphanistrum populations being achieved with phenoxy herbicides in cropping systems across the Western Australia wheatbelt. However, the results also indicated that the strategy of combining crop competition with phenoxy herbicides for the control of this weed is likely to be an effective option in the short-term only.     

N-｛5-[1-(2,4-二氯苯氧)乙基]-1,3,4-噻二唑-2-基｝ -N''-芳酰基硫脲的合成及其生物活性

通过2-氨基-5- -1,3,4-噻二唑与芳酰基异硫氰酸酯反应,合成了12 个新的芳酰基硫脲,采用核磁共振氢谱、红外光谱和元素分析确证了它们的结构。初步的生物活性测定试验表明,部分化合物具有良好的植物生长调节活性,其中化合物 2c、2j 具有较好的生长素活性,其促进率分别为26.6%与26.9%,但不及对照β-吲哚乙酸。     

Effects of ametryn [2-(ethylamino)-4-(isopropylamino)-6-(methylthio)-s-triazine] on nitrate reductase activity and nitrite content of wheat (Triticum aestivum L.)

The objectives of this study were to show that: (a) a herbicide, such as ametryn, which interferes with the photosynthetic electron transport system, causes nitrite to accumulate in illuminated leaves and (b) that nitrite is toxic and contributes to the herbicidal damage and death of the plant. Tests were conducted on wheat seedlings grown on 5 mM nitrate, 5 mM ammonia, and zero nitrogen. Ametryn treatment decreased in vivo and in vitro nitrate reductase activity (NRA) within a 26-hr period. In vivo NRA decreased more rapidly than in vitro NRA. Compared with control tissue, only 3% in vivo NRA remained at the end of 26 hr. The in vivo assay conducted in light confirmed the inhibition of photosynthetic electron flow by ametryn within the leaf tissue. Nitrate-grown, ametryn-treated plants accumulated nitrite and, after 10 days were the only plants that were completely desiccated and dead. Ammonia- and zero-nitrogen, ametryn-treated plants did not accumulate nitrite, were only partially chlorotic after the 10-day period, and were still living. Low levels of NO_(X) (NO₂ and/or NO) emissions were demonstrated by nitrate-grown ametryn-treated plants.     

Absence of 3-(2,4-dichlorophenoxy)propionic acid in plants treated with 2,4-dichlorophenoxyacetic acid‡

Experiments were conducted to establish if the formation of 2.4-dichlorophenol (DCP) from 2.4-dichlorophenoxyacetic acid (2,4-D) in plants proceeds via 3-(2,4-dichtorophenoxy) propionic acid (2,4-DP) as an intermediate. Soybean (Glycine max (L.) Merr.), kidney bean (Phaseolus vtitgaris L.), pea (Pisum. sativum L.), smooth bromegrass (Bromus inermis Leyss.), wild oat (Avena fatua L.), yellow foxtail (Setaria glauca(L.) Beauv.), barley (Hordeum vulgare L.), timothy (Phleum pratense L.). and orchardgrass (Dactylis glomerata L.) were treated with equal weights of 2,4-D and 2,4-DP. After 3 days, all plants contained DCP; however, amounts were larger in plants treated with 2.4-DP than in those treated with 2,4-D. The 2.4-DP was absorbed from the leaf surface more efficiently than 2,4-D. No evidence was found for formation of 2,4-DP from 2,4-D in any of the plant species studied. L'absence de l'acide3-(2,4 dichlorophénoxy) propionique dans les plantes traitées avec I'acide 2,4-dichlorophénoxyacétique Des experiences ont été effectuées pour rechercher si la formation de 2,4-dichlorophénoI (DCP) dans les plantes, à partir de l'acide 2.4-dichlorophénoxy acétique (2,4-D) se produit par l'intermêdiaire de l'acide 3-(2,4-dichlorophenoxy) propionique. Le soja (Glycine max(L.) Merr.). le haricot (Phaseolus vuigaris L.), Ic pois (Pisum sativum L.), le brome (Bromus inermis Leyss.), la folle avoine (Avena fatua L.), la sétaire (Setaria glauca(L.) Beauv.). I'orge (Hordeum vulgare L.), la fléole (Phleum pratense L.) et le dactyle (Dactylis ghmerata L.) ont été traités par des poids égaux de 2.4-D et de 2,4-DP. Trois jours aprés, les plantes contenaient du DCP; toutefois, les quantités trouviés furent plus importantes dans les plantes traitées avec le 2,4-DP que dans celles traitées avec le 2,4-D. Le 2,4-DP a été absorbéà partir de la surface foliaire plus efficacement que le 2,4-D. La formation du 2,4-DP à partir du 2,4-D n'a pu être prouvée dans aucune des plantes étudiécs. Die Abwesenheit von 3-(2,4′Dichlorphenaxy)-propionsäure irt mil 2,4-Dichlorphenoxytesäure behandelten Pflanzen Es wurden Versuche durchgeführt um herauszufinden. ob die Bildung von 2,4-Dichlorphenol (DCP) aus 2.4-Dichlor-phenoxyessigsäure (2,4-D) in Pflanzen über 3-(2,4-Dichlor-phenoxy)-propionsaure (2,4-DP) als Zwischcnprodukt ver-läufl. Sojabohnen (Glycine max(L.) Merr.), Gartenbohnen (Phaseolus vutgaris L.), Erbsen (Pisum sativum L.), Wehrlose Trcspe (Bromus inermis Leyss.), Flughafer (Avena fama L.), Gelbe Borsienhirse (Setaria glauca(L.) Beauv.), Gerste (Hordetim vidgarc L.), Wiesenlieschgras (Phleum pratense L.) und Knaulgras (Dactylis ghmerata L.) wurden mit gleichen Mengen an 2,4-D und 2,4-DP behandelt. Nach drei Tagen enthielten alle PHanzen DCP; aber die Menge an DCP war in den mit 2,4-DP behandelten Pflanzen grosser als in den mit 2,4-D behandelten. 2,4-DP wurde von der Blatt-oberflache besser absorbiert als 2.4-D. In keiner der untersuchten Pflanzenarten konnte ein Hinweis für die Bildung von 2,4-DP aus 2,4-D gefunden werden.     

3-[2-(4-氯-苯基)-1-(3,3-二甲基-氧代-丁基)-乙烯基]-2-氰基亚胺-1,3-噻唑的合成研究

本文研究了3-[2-(4-氯-苯基)-1-(3,3-二甲基-氧代-丁基)-乙烯基]-2-氰基亚胺-1,3-噻唑的合成方法,对反应的各个步骤中的投料摩尔比、溶剂、温度和催化剂进行了对比,优化了反应步骤,总结出了产率较高的合成路径。设计合成了未见报道的新型噻唑衍生物类化合物。其结构经红外光谱、氢核磁共振和气质联用谱图确认,总收率为37.3%。该合成技术降低了成本,减轻了对环境的污染,具有很好的发展前景和市场竞争力。     

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%。     

N-羟基-N-2-[N-(4-氯苯基)-3-吡唑氧基甲基]-苯胺的合成

高效低成本合成N-羟基-N-2-[N-(4-氯苯基)-3-吡唑氧基甲基]-苯胺。以2-[(N-4-氯苯基)-1H-吡唑-3-基氧甲基]硝基苯和碳酸氢钠为原材料,5%Pt/C为催化剂,通入氢气还原得N-羟基-N-2-[N-(4-氯苯基)-3-吡唑氧基甲基]-苯胺,并对不同条件下的试验结果进行了分析。优化条件为氢气进气压力为0.2Mpa,5%Pt/C催化剂与2-[(N-4-氯苯基)-1H-吡唑-3-基氧甲基]硝基苯的配比为5∶60,温度为30℃,反应时间为4h。该反应条件下产物反应收率≥97%,含量≥97%,生产成本低、操作简便非常适合工业化生产。     

2-[4-(对氟苯基)噻唑-2-基]-3-羟基-3-烃氧基丙烯腈的合成及杀菌活性

为了寻找生物活性良好的噻唑基丙烯腈类化合物,利用2-氰甲基-4-(对氟苯基)噻唑( 3 )与取代氯甲酸酯( 4 )在碱存在下反应,合成了15个未见文献报道的2- -3-羟基-3-烃氧基丙烯腈化合物( 5 ),其结构经核磁共振氢谱、质谱和元素分析表征。初步杀菌活性测试结果表明:所有化合物在试验浓度下均具有一定的抑菌活性,尤其对炭疽病菌Colletotrichum gossypii表现出较好的抑制活性,在质量浓度25 mg/L下,所有化合物的抑制率均在50%以上,其中化合物 5a、5e、5g、5k、5n和5o 的抑制率在80%以上。     

The role of coleoptile on barban sensitivity between wild oat and wheat

Differential sensitivity of wild oat (Avena fatua L.) and wheat (Triticum aestivum L.) to barban (4-chloro-2-butynyl-m-chlorocarbanilate) was highest when barban was applied to the coleoptile. The coleoptile acts as a physical and physiological barrier to reduce the concentration of free barban in the stem section where the sensitive meristematic sites are located. Metabolism of barban was higher ïn the coleoptile of tolerant wheat than in that of susceptible wild oat. Free barban concentration was higher in the stem of wild oat than in the stem of wheat after 24 hr, but after 48 hr, concentrations were similar. The coleoptile appears to enhance the differential sensitivity to barban between wild oat and wheat.     

1-[2-苄氧基-2-(2,4-二氟苯基)乙基]-1H-1,2,4-三唑衍生物的合成及杀菌活性

以抗真菌药物益康唑为先导化合物,设计合成了17个1-((2-取代苄基) 氧基)-2-(2,4-二氟苯基) 乙基)-1H-1,2,4-三唑类目标化合物,其中14个为首次报道,其结构均经 1H NMR、13C NMR和HRMS确认。采用菌丝生长速率法测定了目标化合物对7种植物病原菌的抑制效果,并对毒力较高的化合物进行了其对水稻纹枯病和小麦条锈病的盆栽和田间药效试验,而且测定了其对水稻纹枯病菌麦角甾醇生物合成的抑制作用。结果表明:大多数目标化合物对测试病原菌菌丝生长有较强的抑制作用,尤其对水稻纹枯病菌和番茄早疫病菌的抑制作用最好,其中对水稻纹枯病菌的EC₅₀值均低于3 μmol/L,明显高于对照药剂苯醚甲环唑和益康唑;化合物 4a 、 4b 、 4c 、 4g 、 4i 和 4l 对番茄早疫病菌的EC₅₀值均低于10 μmol/L。在浓度为250 μmol/L时,化合物 4b 和 4i 对小麦条锈病的盆栽防效均超过70%,在有效剂量为240 g/hm2时,化合物 4b 对小麦条锈病的田间防效达到81.93%。而且,化合物 4b 和 4i 在100 μmol/L时可有效抑制水稻纹枯病菌麦角甾醇的生物合成,抑制效果在80%左右。     

Inhibition of ergosterol biosynthesis in Ustilago maydis by the fungicide 1-[2-(2, 4-dichlorophenyl)-4-ethyl-1, 3-dioxolan-2-ylmethyl]-1H-1, 2, 4-triazole

Inhibition of sporidial multiplication in cultures of Ustilago maydis by 1-[2-(2, 4-dichlorophenyl)-4-ethyl-1, 3-dioxolan-2-ylmethyl]-1H-1, 2, 4-triazole^a (CGA-64251), at concentrations of 0.1, 1.0 and 5.0 μg ml^?1, increased from about 15% during the first 4 h, to 58–70% during the subsequent 4 to 12-h period. Sporidia became swollen and highly branched in the presence of the fungicide. Total lipid content as a percentage of the dry weight was not affected after exposure of the sporidia to the fungicide at 0.1 or 5 μg ml^?1 for 4 h, but synthesis of ergosterol and other demethyl-sterols was inhibited by 87–92%. Large quantities of methyl-sterol precursors of ergosterol and of free fatty acids accumulated in the treated sporidia. Fungitoxicity of CGA-64251 is attributed to inhibition of ergosterol biosynthesis at the stage of sterol C-14 demethylation.     

Interaction between diclofop-methyl and 2,4-D in wild oat (Avena fatua L.) and cultivated oat (Avena sativa L.), and fate of diclofop-methyl in cultivated oat

Influence of 2,4-D on toxicity of diclofop-methyl to Avena sativa (cv. Selma) and Arena fatua at 2·5 leaf stage has been evaluated under controlled conditions. Effects of 2,4-D on the fate of diclofop-methyl in cultivated oat have also been studied. Mixture with 2,4-D reduced the toxicity of diclofop-methyl to both species. When applied immediately after diclofop-methyl treatment, 2,4-D still reduced herbicide toxicity to wild oat. This reduction was smaller in cultivated oat. and was only observed at higher phytotoxicity. No interaction was observed when a 10-day period separated the two applications. In mixture, 2,4-D enhanced diclofop-methyl penetration and diclofop acid conjugation in cultivated oat, and it slightly increased conjugation when applied separately. None of these effects clearly explain the reduction of diclofop-methyl toxicity by 2, 4-D in cultivated oat. Other processes are possibly involved and could be connected with the site of action of diclofop-methyl.     

Investigation of acute toxicity of (2,4-dichlorophenoxy)acetic acid (2,4-D) herbicide on crayfish (Astacus leptodactylus Esch. 1823)

The acute 96 h LC₅₀ of (2,4-dichlorophenoxy)acetic acid (2,4-D), a widely used agricultural herbicide, was determined on crayfish (Astacus leptodactylus Esch. 1823). Crayfish of 23.5 ± 1.49 g mean weight and 9.6 ± 0.21 cm mean length were selected for the bioassay experiments. The experiments were repeated three times, in 10 L tap water. The data obtained were statistically evaluated by the use of the E.P.A computer program based on Finney’s probit analysis method and the 96 h LC₅₀ value for crayfish was calculated to be 32.6 mg/L in a static bioassay test system. 95% lower and upper confidence limits for the LC₅₀ were 15.10-327.16. In conclusion, 2,4-D is highly toxic to crayfish, a non-target organism in the ecosystem. Water temperature was 23 ± 1 °C. Behavioral changes of crayfish were recorded for all herbicide concentrations.     

野燕麦发生量与小麦产量损失试验

野燕麦在内蒙古察右中旗年发生面积达２．６７万hm２左右，是影响小麦产量的重要因素之一。为了进一步了解野燕麦不同发生密度下对小麦产量的影响，为制定防除指标及防除措施提供科学依据，笔者进行了野燕麦不同密度对小麦产量影响的试验。１试验设计及方法１．１试验地点试验在察右中旗三道沟乡口子村和广昌隆乡东油房村进行。试验田土地平整、肥力均匀，历年野燕麦发生严重，密度高达５００株／m２以上。１．２试验设计于野燕麦苗期（小麦三叶至拔节前）人为控制野燕麦密度，拔除多余的野燕密度５０株／m２，③１００株／m２，④１５０株…     

Synthesis and Insecticidal Activity of Some New 3-[4(3H)-Quinazolinone-2-(yl)thiomethyl]-1,2,4- triazole-5-thiols

A series of 14 new 3-[4(3H)-quinazolinone-2-(yl)thiomethyl]-1,2,4-triazoles were prepared and characterized by elemental analyses, IR, [¹H] NMR and mass spectral data. Four of the compounds showed insecticidal activity equivalent to that of malathion against the adult stage of the blow fly (Chrysomyia albiceps). However, their activity against the larval stages of this insect species was considerably weaker.