Comparison of physiological effects of fluazifop-butyl and sethoxydim on oat (Avena sativa L.)

Laboratory experiments were conducted to compare the physiological effects of two herbicides: fluazifop-butyl {butyl ( RS )-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]-propionate} and sethoxydim {(±)-2-[1-(ethoxyimino)butyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one} on oat ( Avena sativa L. cv. Zenshin). The herbicides strongly inhibited growth of oat and induced chlorosis at the basal part of shoots and ethylene production from the seedlings. The phytotoxicity of these herbicides in oat seedlings was alleviated by 2,4-D (2,4-dichlorophenoxyacetic acid), but not by IAA (indole-3-acetic acid). Coleoptile elongation induced by 2,4-D or IAA was inhibited by fluazifop-butyl and sethoxydim, suggesting both herbicides possess the activity to inhibit this auxin action. Fluazifop (free acid) and sethoxydim inhibited proton excretion from oat roots but fluazifop-butyl did not. This proton excretion was not restored by 2,4-D or IAA. Furthermore, cellular electrolyte leakage in oat shoots was increased by both herbicides, indicating that the membrane permeability was increased. We conclude that fluazifop-butyl and sethoxydim may have the same mechanism of action which leads to disruption of membrane integrity, although fluazifop-butyl acts as a free acid after hydrolysis (fluazifop).     

Effects of fluazifop-butyl on shoot growth and rhizome buds of Elymus repens (L.) Gould

A series of glasshouse experiments was conducted to evaluate the activity of fluazifop-butyl, butyl 2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy] propionate, against Elymus repens. Foliar applications of doses 0·25–1·0 kg ha^?1 consistently gave better control than did soil applications. The most obvious phytotoxic symptoms were chlorosis and necrosis, beginning with the youngest leaves 5–6 days after spraying, which spread to all leaves within 2 weeks. Translocation was measured by defoliating plants at different times after spraying and assessing regrowth and by evaluating rhizome-bud viability. At low doses (0·125 and 0·25 kg ha^?1) translocation to rhizomes occurred mainly between 6 and 48 h. When fluazifop-butyl was sprayed at a dose range of 0·125–1·0 kg ha^?1, at least 90% of the rhizome buds had accumulated a lethal dose within 72 h of spraying. In another experiment, with a dose of 0·25 kg ha^?1, 31, 72 and 92% of rhizome buds were found to be non-viable when sampled 2, 24 and 48 h respectively after spraying. At 1·0 kg ha^?1 all the buds had accumulated sufficient herbicide to prevent sprouting 48 h after spraying.     

Catalytic hydrolysis of diclofop-methyl on Ca-, Na- and K-montmorillonites

The decomposition of the herbicide diclofop-methyl (methyl (RS)-2-(4-(2,4-dichlorophenoxy)phenoxy)propionate), on homoionic Ca-, Na- and K-montmorillonite in hydroalcoholic suspension was investigated. The results show that the solvolysis of the pesticide affords two products: diclofop (RS)-2-(4-(2,4-dichlorophenoxy)phenoxy)propionic acid) and diclofop-ethyl (ethyl (RS)-2-(4-(22,4-dichlorophenoxy)phenoxy)propionate). The former is always the main product of hydrolysis on the Ca-, Na- and K-clays, whereas the latter, arising from a transesterification reaction, is favoured only by the presence of Ca-and Na-clays. The solvolysis reaction follows the adsorption of the herbicide on the clay, as evidenced by the shift of the IR stretching value of the ester group of the molecule, depending on the polarising power of the saturating ions.     

Aerobic soil metabolism of flupyrazofos

To elucidate the fate of flupyrazofos [O,O-diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phosphorothionate] in soil, an aerobic soil metabolism study was carried out for 60 days with [¹⁴C]flupyrazofos applied at a concentration of 0·38 μg g^-1 to a loamy soil. The material balance ranged from 103·5% to 86·9% and the half-life of [¹⁴C]flupyrazofos was calculated to be 13·6 days. The metabolites identified during the study were 1-phenyl-3-trifluoromethyl-5-hydroxypyrazole (PTMHP) and O,O-diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phosphate (flupyrazofos oxon), with maximum levels of 9·8% and 1·6% of applied radiocarbon, respectively. Evolved [¹⁴C]carbon dioxide accounted for up to 5·3% of applied radiocarbon and no volatile products were detected during the study. Non-extractable ¹⁴C-residue reached 31·6% of applied material at 60 days after treatment and radiocarbon was distributed almost evenly in humin, humic acid and fulvic acid fraction. © 1998 Society of Chemical Industry     

A root bioassay procedure for the determination of chlorsulfuron, diclofop acid and sethoxydim residues in soils

Measurement of the root lengths of pre-ger-minated oat seedlings (Avena sativa L. var. Sioux) grown in the dark in treated soils was used to assay residues of diclofop acid (2-[4-(2,4-dichloro-phenoxy)phenoxy]propionate) and sethoxydim (2-[1-(ethoxyimino)-butyl]-5-[2-(ethylthio)-propy]-3-hydroxy-2-cyclohexene-1-one). Similar measurements involving maize seedlings (Zea Mays L. var. Sunny Vee) were also used to determine residues of the herbicide chlorsulfuron (2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbony]benzenesulfonamide) in soils. The procedure appeared to be reproducible with residues of chlorsulfuron, diclofop acid and sethoxydim being detectable at amounts of 0.001, 0.2 and 0.05 μg g^?1 respectively.     

N-甲氧基-N- 苯基氨基甲酸甲酯的合成及生物活性研究

为了寻找新的高效的Strobilurin类杀菌剂,以1-取代基-3-三氟甲基吡唑啉-5-酮与N-甲氧基-N-(2-溴甲基苯基)氨基甲酸甲酯反应,合成了系列新型N-甲氧基-N- 苯基氨基甲酸甲酯化合物 (IV1~IV13) ,其结构经IR、1H NMR、LC/MS及元素分析确认。生物活性测定结果表明,该类化合物在50 mg/L下对稻瘟病菌Pyricularia oryzae、黄瓜灰霉病菌Botrytis cinerea、小麦白粉病病菌Erysiphe graminis等具有较高的抑菌活性,如 IV13 对稻瘟病菌P.oryzae 的抑制率达94.0%.     

Control of Sorghum halepense (L.) Pers. in cotton with post-emergence herbicides and trifluralin

A field experiment was conducted in 1981 and 1982 to evaluate five post-emergence herbicides applied alone or following a preplant incorporated application of trifluralin for the control of Sorghum halepense (L.) Pers. in cotton (Gossypium hirsutum). One application of the methyl ester of haloxyfop [methyl 2- (4- ((3-chloro-5-trifluoromethyl)-2-pyridinyl)oxy)phenoxy)pro-panoate], trifluralin plus the ethyl ester of DPX-Y6202 [ethyl[2-[-4-(6-chloro-2-quinoxalinyl)oxy]phenoxy]propionate], the butyl ester of fluazifop and trifluralin plus haloxyfop resulted in over 90% control of S. halepense just prior to harvest in 1981 and 1982. Sorghum halepense control was similar whether the post-emergence herbicides were applied alone or following preplant incorporated trifluralin at 0.8 kg ha^?1. La lutte contre Sorghum halepense (L.) Pers. en culture de cotonnier moyennant des herbicides de post-levée et la trifluraline Une expérience a été installée en plein champ en 1981 et 1982 dans le but d'évaluer cinq herbicides de post-levée, appliqués seuls ou suite à la trifluraline incorporée avant le semis, dans la lutte contre Sorghum halepense (L.) Pers. en culture de cotonnier (Gossypium hirsutum). Une seule application de l'haloxyfop ester de méthyle [méthyle 2-(4-((3-chloro-5- (trifluorométhyle)-2-pyridinyle) oxy)phénoxy)propanoate], de trifluraline + DPX-Y6202 ester d'éthyle (éthyle[2-[4-(6-chloro-2-quinoxalinyle)oxy]phénoxy)propionate), de l'ester butylique du fluazifop et de trifluraline + haloxyfop a permis en 1981 et 1982 une bonne maîtrise (90%) de S. halepense juste avant la récolte. La maîtrise de Sorghum halepenseétait semblable, que les herbicides de postlevée aient été précédés ou non d'une application de trifluraline à 0,8 kg ha^?1 incorporée avant le semis. Bekämpfung von Sorghum halepense (L.) Pers. in Baumwolle mit Nachauflaufherbiziden und Trifluralin In den Jahren 1981 und 1982 wurden Feldversuche zur Bekämpfung von Sorghum halepense (L.) Pers. in Baumwolle (Gossypium hirsutum) mit fünf Nachauflaufherbiziden durchgeführt. Die Herbizide wurden allein oder nach einer vor der Baumwollsaat erfolgten Einarbeitung von Trifluralin appliziert. Eine Applikation des Methylesters von Haloxyfop [Methyl-2-(4-((3-chloro-5-(trifluormethyl)-2-pyridinyl)oxy)phenoxy)propanoat]. Von Trifluralin + Aethylester von DPX-Y 6202 [Aethyl[2-[-4-(6-chlor-2-quinoxalinyl)oxy)phenoxy)propionat], des Butylesters von Fluazifop und Trifluralin + Haloxyfop ergaben in beiden Jahren kurz vor der Ernte eine über 90 ige Kontrolle von S. halepense. Der Bekämpfungserfolg war ähnlich, gleichgültig ob die Herbizide allein oder nach der Einarbeitung von Trifluralin (0,8 kg ha^?1) appliziert worden waren.     

Synthesis and fungicidal activity against Pyricularia oryzae of 6-(1,2,4-triazol-4-yl) chromone and -1-thiochromone derivatives

A series of novel 6-(1,2,4-triazol-4-yl) chromone and -1-thiochromone (benzo[b]thiazin-4-one) derivatives was obtained by cyclisation via thiosemicarbazides which were prepared by reaction of hydrazines and the corresponding isothiocyanates. Their fungicidal activity was evaluated against the rice blast fungus Pyricularia oryzae. Of this series, 2,5,8-trimethyl-6-(1-propyl-5-thioxo-3-trifluoromethyl-1,2,4-triazol-4-yl) chromone, 6-(1-butyl-5-thioxo-3-trifluoromethyl-1,2,4-triazol-4-yl)-2,5,8-trimethylchromone, 6-(1-hexyl-3-methyl-5-thioxo-1,2,4-triazol-4-yl)-2,5,8-trimethylchromone and 6-(1-allyl-5-thioxo-3-trifluoromethyl-1,2,4-triazol-4-yl)-2,5,8-trimethylchromone were highly active (pEC₅₀>6·0). Structure–activity relationship studies using the capacity factor k′ as a hydrophobicity index suggested that the log k′ optimum for 2,5,8-trimethyl-chromone and -1-thiochromone derivatives was around 1·0, equivalent to a log P_ow value of c. 4·4. © 1998 SCI     

Analysis of soils for diclofop-methyl and diclofop

A method is described for the analysis of soils for residues of the herbicide diclofop-methyl, methyl (RS)-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate, and its breakdown product diclofop, (RS)-2-[4-(2,4-dichlorophenoxy)phenoxy]propionic acid. Diclofop-methyl undergoes hydrolysis in the soil to diclofop, which also has herbicidal activity. A procedure, using a 1% phosphoric acid solution for extraction purposes, has been developed and gives good recoveries of both diclofop-methyl and diclofop at the 0.5 and 0.05 mg kg^?1 levels. After methylation, gas-liquid chromatography with electron-capture detection is used to determine total residue concentrations.     

The cyclization transformation of the sulfonylurea herbicide flupyrsulfuron in the soil of winter wheat crops

The synthesis of 1-(4,6-dimethoxypyrimidine-2-yl)-7-trifluoromethyl-1,2,3,4-tetrahydropyrido [2,3-d]pyrimidin-2,4-dione has been carried out in such a way that the dimethoxypyrimidine substituent was unambiguously in position 1 of the pyrido[2,3-d]pyrimidine ring. This regioisomer was obtained by cyclization with phosgene of 2-(4,6-dimethoxypyrimidin-2-ylamino)-6-trifluoromethylnicotinamide which had previously been ionized with sodium hydride. It was shown to be identical to the metabolite generated in the soil of winter wheat crops treated previously with the sulfonylurea herbicide flupyrsulfuronmethyl [(methyl 2-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-6-trifluoromethylnicotinate]. The position of the dimethoxypyrimidine substituent had not previously been assigned unambiguously to positions 1 or 3 of the pyrido[2,3-d]pyrimidine ring. The regioisomer was also identical to the cyclization compound generated chemically from flupyrsulfuron in a sterile water buffer at pH 9. The metabolism pathways of flupyrsulfuron in soil are discussed in the light these structure determinations and compared with the soil metabolism pathways frequently observed with other sulfonylurea herbicides.     

The metabolism of the herbicide flamprop-methyl in wheat

The metabolism of the wild oat herbicide flamprop-methyl, methyl (±)-2-[N-(3-chloro-4-fluorophenyl)benzamido]propionate, in spring wheat grown to maturity has been studied under glasshouse and outdoor conditions. [¹⁴C]-Flamprop-methyl labelled separately in the halophenyl ring and the carbonyl of the benzoyl group was used. The major metabolite formed in plants was the corresponding carboxylic acid, II, which also occurred as conjugates. Other minor metabolites detected under glasshouse conditions only were the 3- and 4-hydroxybenzoyl analogues of flamprop-methyl and 3′-chloro-4′-fluorobenzanilide. The soil in which the plants were grown contained residues comprising mainly flamprop-methyl and II together with smaller amounts of unidentified polar material.     

Persistence studies with the herbicide sethoxydim in prairie soils

The persistence of [¹⁴C]sethoxydim (2-[1-(ethoxyimino)butyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexene-1-one) at the 2 μg g^?1 level was studied under laboratory conditions in three soils at 20°C and 85% of their field capacity moistures. Following extraction of the soils with methanol, the herbicide remaining was determined using radiochemical techniques. Loss of radioactivity was more rapid on moist clay loam and sandy loam, where the half-lives were 12 days, than on heavy clay in which the half-life was 26 days. Loss of radioactivity from air-dried soils (15% of field capacity) was negligible with over 94% of the applied activity being recovered after 28 days. The persistence of sethoxydim at a rate of 1 kg ha^?1 was investigated under field conditions using small plots at three prairie locations for 3 successive years. Using an oat-root bioassay procedure, no residues were detected in the 0–10 cm depths of any soils, any year, in September following May treatments.     

土壤和水中氰氟草酯及其代谢物的分析方法

建立了一种简易而实用的残留分析方法 ,用于检测土壤与水中氰氟草酯及其 3种代谢产物 ,即(R)-2-[4-(4-氰基-2-氟苯氧基)苯氧基]-丙酸(ACID)、 (R)-2-[4-(4-氨基甲酰基-2-氟苯氧基)苯氧基]-丙酸(AMIDE)、(R)-2-[4-(4-羧基-2-氟苯氧基)苯氧基]-丙酸 (DIACID)。该方法仅用高效液相色谱法的梯度洗脱程序即可将 4种化合物有效分离 ,省去了需将氰氟草酯 (母体)衍生化反应再用气相色谱法检测这一复杂步骤。同时 ,该方法的添加回收率高。较低的 p H值对提高 4种化合物的提取效率很重要。     

Interception and persistence of parathion and fenvalerate on cotton plants as a function of application method

Parathion (O,O-diethyl O-4-nitrophenyl phosphorothioate) and fenvalerate [(RS)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate] were applied by controlled droplet applicators (CDAs) and conventional hydraulic nozzles in refined soybean oil, soybean oil + water, or water, to mature cotton plants (Gossypium hirsutum L.) as ULV (ultra-low volume, < 5 litre ha^?1), VLV(very low volume, 5-50 litre ha^?1), or LV(low volume, 50–200 litre ha^?1) carrier rates. The use of CDA or soybean oil applied as ULV and VLV sprays did not produce greater deposition or persistence for either insecticide during the 49-h test period following application. In general, insecticide persistence was greatest when applied with water or soybean oil + water as LV sprays using the conventional TX8 hydraulic nozzle.     

Synthesis and herbicidal activity of new oxazinone herbicides with a long-lasting herbicidal activity against Echinochloa oryzicola

Chemical modification of the herbicide 1-[2-(benzothiazol-2-yl)isopropyl]-4-methyl-3-phenyl-5H-pyrrolin-2-one (MI-2826) has revealed a new oxazinone herbicide, 3-[2-(7-chlorobenzothiazol-2-yl)isopropyl]-2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxazin-4-one (MI-3069), for use in paddy fields. In comparing the phyototoxicity of the two herbicides to transplanted rice, the latter was superior to the former and kept the same predominant characteristic to control Echinochloa oryzicola Vasin for a long period of time owing to its long-lasting residual effect.     

Synthesis and characterization of synthetic analogs of cinnacidin, a novel phytotoxin from Nectria sp

BACKGROUND: The novel natural product cinnacidin was isolated from a fungal fermentation extract of Nectria sp. DA060097. The compound was found to contain a cyclopentalenone ring system with an isoleucine subunit linked through an amide bond. Initial biological characterization of cinnacidin suggested promising herbicidal activity. RESULTS: Two synthetic analogs, (2S,3S)-2-[(3RS,3aSR,6aRS)-3-methoxy-4-oxo-3,3a,4,5,6,6a-hexahydropentalen-1-ylcarbamoyl]-3-methylvaleric acid and benzyl (2S,3S)-2-[(3RS,3aSR,6aRS)-3-methoxy-4-oxo-3,3a,4, 5,6,6a-hexahydropentalen-1-ylcarbamoyl]-3-methylvalerate, were prepared for further characterization, and their herbicidal activities were compared with that of cinnacidin. CONCLUSIONS: The synthetic compounds were highly phytotoxic on a range of weeds. Based on the symptoms in treated plants, the mode of action of these compounds is suggested to be similar to that of coronatine and jasmonic acid. Coronatine was more active against warm-season grasses, while the cinnacidin benzyl ester analog was more effective on cool-season grasses. In a seedling growth bioassay conducted on bentgrass, the cinnacidin analog was equivalent in activity to coronatine.     

Steric structure–activity relationships of the rice blasticide,S-2900 (diclocymet)

The four diastereomers of 2-cyano-N-[1-(2,4-dichlorophenyl)ethyl]-3,3-dimethyl-butyramide were prepared by a direct HPLC separation with chiral columns. The [(S)acid, (R)amine]-isomer (was the most antifungal among the diastereomers tested. Because of the lability of the clinical group in the acid moiety, the (RS)-(R)-isomer is being developed as a rice blasticide. (S-2900, proposed common name diclocymet).     

Absorption,translocation and metabolism of the herbicide naproanilide in tobacco

Naproanilide [2-(2-naphthyloxy)propionanilide] has a high activity against dicotyledonous weeds in rice fields, but is very safe to rice. This study was designed to clarify the absorption and translocation of radiolabelled naproanilide in tobacco plants and the metabolism in tobacco callus. The results indicated that naproanilide is translocated easily to the upper part of tobacco plants. Distribution of radioactivity in tobacco plants at the 7th day was shown to be 0.88, 0.24 and 0.03%, and at the 14th day 1.71, 1.86 and 2.32% of the total activities of [¹⁴C]naproanilide in root, stem and leaf, respectively. When compared to earlier results obtained with rice, the translocation rate in tobacco is much higher and might therefore contribute a possible mechanism of herbicidal selectivity. Metabolites including NOP [2-(2-naphthyloxy)propionic acid], NOPM [methyl 2-(2-naphthyloxy)propionate], 2-naphthol, 2,3-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol and 2-hydroxy-1,4-naphthoquinone were identified in tobacco callus by co-chromatography.     

Degradation of the herbicide [14C]-diclofop-methyl in soil under different conditions

The degradation of the herbicide diclofop-methyl, ( ± )-methyl 2-[4-(2,4-dichloro-phenoxy)phenoxy]propionate, was investigated in two agricultural soils under aerobic and anaerobic conditions. Using two differently labelled forms of [¹⁴C]-diclofop-methyl the qualitative as well as the quantitative formation of extractable metabolites was followed for 64 days. The mineralisation of the uniformly labelled aromatic rings was pursued by monitoring the ¹⁴CO₂ generated for 25 weeks. As a first step of the degradation a very rapid hydrolysis of the ester bond was detected under all conditions. Diclofop, the corresponding substituted propionic acid formed, was extensively degraded under aerobic conditions, the final product being ¹⁴CO₂. As an intermediate, a compound later identified by GLC/MS to be 4-(2,4-dichlorophenoxy)phenol, was found in the extracts. Furthermore, traces of six other unknown metabolites were detected. Under anaerobic conditions the degradation proceeded to a small extent. At most 3% of the applied radioactivity was accounted for by the degradation product 4-(2,4-dichlorophenoxy)phenol. No other metabolite, including ¹⁴CO₂, was observed, implying lack of any further degradation.     

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%。