Hydrolysis of triasulfuron,metsulfuron‐methyl and chlorsulfuron in alkaline soil and aqueous solutions

The hydrolysis of triasulfuron, metsulfuron‐methyl and chlorsulfuron in aqueous buffer solutions and in soil suspensions at pH values ranging from 5.2 to 11.2 was investigated. Hydrolysis of all three compounds in both aqueous buffer and soil suspensions was highly pH‐sensitive. The rate of hydrolysis was much faster in the acidic pH range (5.2–6.2) than under neutral and moderately alkaline conditions (8.2–9.4), but it increased rapidly as the pH exceeded 10.2. All three compounds degraded faster at pH 5.2 than at pH 11.2. Hydrolysis rates of all three compounds could be described well with pseudo‐first‐order kinetics. There were no significant differences (P = 0.05) in the rate constants (k, day⁻¹) of the three compounds in soil suspensions from those in buffer solutions within the pH ranges studied. A functional relationship based on the propensity of nonionic and anionic species of the herbicides to hydrolyse was used to describe the dependence of the ‘rate constant’ on pH. The hydrolysis involving attack by neutral water was at least 100‐fold faster when the sulfonylurea herbicides were undissociated (acidic conditions) than when they were present as the anion at near neutral pH. In aqueous buffer solution at pH > 11, a prominent degradation pathway involved O‐demethylation of metsulfuron‐methyl to yield a highly polar degradate, and hydrolytic opening of the triazine ring. It is concluded that these herbicides are not likely to degrade substantially through hydrolysis in most agricultural alkaline soils. © 2000 Society of Chemical Industry     

Synthesis and insecticidal and acaricidal activity of new N-(α-substituted phenoxybenzyl)-4-pyrimidinamines

A new class of insecticides and acaricides containing N-(α-substituted phenoxybenzyl)-4-pyrimidinamines as core structure were synthesized and their insecticidal and acaricidal potencies assessed. Among these, both the N-(3 or 4-phenoxybenzyl)-4-pyrimidinamine showed remarkable activity against diamondback moth, Plutella xylostella L., brown rice planthopper, Nilaparvata lugens (Stal) and two-spotted spider mite, Tetranychus urticae Koch. The potency of the new pyrimidinamines was particularly increased when a methyl, ethyl, iso-propyl, or cyclopropyl group was introduced at the α-position of benzyl moiety and it was evident that a single (+) optical isomer is more active than its antipode. Structure-activity relationships are discussed.     

Hydrolyse chimique acide du metsulfuron méthyle

Chemical acidic hydrolysis of metsulfuran methyl The chemical degradation of metsulfuron methyl in acidic aqueous solution involved two pathways: hydrolysis of the urea function and hydrolysis of methoxy radical. Decrease of pH (6 to 1) strongly increased activity but selectivity remained unchanged. Increase of temperature (25 to 55°C) enhanced the rate of reaction (E_A= 84 kj mol^?1) and favoured the urea function hydrolysis. Other factors (presence of various transition metals cations, humic acids or clays) were generally of limited effect, sometimes the rate of reaction was affected.     

Effects of pyrethroid structure on rates of hydrolysis and oxidation by mouse liver microsomal enzymes

Studies on the metabolism rates of 44 pyrethroids and 24 model compounds in mouse liver microsomal systems serve to divide the substrates into three groups based on their ease of hydrolysis and oxidation. Primary alcohol esters of trans-substituted cyclopropanecarboxylic acids are most rapidly metabolized with hydrolysis generally serving as the major component of the total metabolism rate. Although hydrolyzed slowly or not at detectable rates, the primary alcohol cis-substituted cyclopropanecarboxylates, tetramethylcyclopropanecarboxylates, and p-chlorophenyl-α-isopropylacetates are rapidly oxidized. The highly insecticidal α-cyano-3-phenoxybenzyl esters are least susceptible to metabolic attack due to both reduced esterase rates attributable to α substitution in the alcohol moiety and reduced oxidase rates for which no adequate explanation is currently available. Other structural modifications in the acid and alcohol moieties are less important in determining the metabolism rates. The substrate specificities of the microsomal esterases and oxidases are compared with in vivo pyrethroid structure-biodegradability relationships.     

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%.     

Synthesis and insecticidal activity of new pyrethroids

BACKGROUND: Pyrethroids are among the most potent pesticides known, with great potential for structural variation with retention or enhancement of potency. The simple methyl ester is easier to prepare (at least one step shorter) than the more complex pyrethroids modified on the alcohol moiety. The objective was to synthesise methyl esters of pyrethroid acids containing an aromatic ring on the acid moiety and evaluate their biological activity against Ascia monuste orseis Latr., Tuta absoluta Meyrick, Periplaneta americana (L.), Musca domestica L. and Sitophilus zeamais (Motsch.). RESULTS: The synthetic sequence required seven steps: protection of the hydroxyl groups of D ‐mannitol, diol oxidative cleavage with sodium metaperiodate, alkene formation by Wittig reaction with methoxycarbonylmethylidene(triphenyl)phosphorane, cyclopropanation, acetal hydrolysis with perchloric acid and oxidative cleavage with sodium metaperiodate gave methyl (1S, 3S)‐3‐formyl‐2,2‐dimethylcyclopropane‐1‐carboxylate. The final step comprised reaction of the aldehyde with five different aromatic phosphorus ylides to give the pyrethroids. CONCLUSION: An efficient and versatile synthesis of ten new pyrethroid methyl esters has been accomplished from the readily available D ‐mannitol in seven steps. All compounds showed insecticidal activity, and methyl (1S, 3S)‐3‐[(Z)‐2‐(4‐chlorophenyl)vinyl]‐2,2‐dimethylcyclopropane‐1‐carboxylate was the most active, killing 90% of A. monuste orseis and 100% of T. absoluta and P. americana. Copyright © 2009 Society of Chemical Industry     

In vitro activity of isothiocyanates against Fusarium graminearum

Isothiocyanates are biotoxic degradation products formed as a result of enzymatic hydrolysis of glucosinolates present in Brassica species. The application of biofumigant Brassica crops, as an alternative crop protection method for soilborne pathogens and pests is increasingly gaining interest. However, little is known of the potential of biofumigation to reduce the inoculum of Fusarium species affecting cereals. The aim of this study was to evaluate the antifungal activity of five isothiocyanates, namely allyl, benzyl, ethyl, 2-phenylethyl and methyl isothiocyanates, against germination and growth of Fusarium graminearum under in vitro conditions. Aromatic isothiocyanates were more inhibitory than the aliphatic isothiocyanates against mycelial growth, whereas the reverse was observed for conidial germination. Among the tested isothiocyanates, allyl and methyl isothiocyanates were more efficient overall, showing lower ED₅₀ values (35–150 mg/L) for conidial germination and mycelial radial growth. The findings suggest that Brassica plants containing allyl and methyl glucosinolates could have a suppressive effect, reducing the inoculum of F. graminearum in soil prior to cereal production.     

Suppression of Food Intake in Triatoma infestans by N-Substituted Methyl Maleamates

A series of methyl esters of N-substituted (Z)- and (E)-maleamic acids were synthesized and their effect on food intake measured on fifth-instar nymphs of Triatoma infestans. Suppression of food intake was found only for the (Z)-isomers. The initial reaction rate of the synthesized compounds with glutathione (GSH) was calculated from the reaction in vitro of the (Z)-isomers. No reaction was observed with the (E)-isomers. Good correlation between the suppression of food intake, measured by its ED₅₀ (effective dose that inhibited feeding of 50% of the population) and the initial reaction rate with GSH and the hydrophobic parameter π, was found. © of SCI.     

2-取代苯并咪唑类化合物的合成及其抑菌活性

以甲基酮、草酸二乙酯或草酸二甲酯、盐酸羟胺和水合肼为原料,通过缩合、环合、水解等反应,将取代吡唑环、异 NFDA1 唑环引入苯并咪唑的2位,设计合成了13个未见文献报道的2-取代苯并咪唑类衍生物,其结构经红外、电喷雾串联质谱(ESI-MS)和核磁共振氢谱确证。初步生物活性测试结果表明,在100 mg/L质量浓度下,所有目标化合物对6种供试病原菌均具有一定的抑菌活性,其中2-吡唑取代的化合物 2a~2d 对苹果炭疽病菌Glomerella cingulata的抑制率在80%以上,2-异 NFDA1 唑取代的化合物 4a 对番茄早疫病菌 Alternaria solani 、苹果炭疽病菌和水稻稻瘟病菌 Magnaport hegrisease 的抑制率达100%。     

Pyrethroid insecticides derived from substituted biphenyl-3-ylmethanols

The synthesis of a series of mono- and disubstituted biphenyl-3-ylmethyl esters of 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid is described. The bioactivity of these compounds against Spodoptera eridania, Epilachna varivestis, Oncopeltus fasciatus, Acrythosiphon pisum and Tetranychus urticae is presented and discussed. Substitution of fluorine, chlorine and methyl groups in the 2-position of the biphenyl ring generally led to an increase in activity over the unsubstituted parent biphenyl ester. In addition, pyrethroid esters derived from these 2-substituted biphenyl-3-ylmethanols appeared to have a broader spectrum of activity than ‘classical’ pyrethroids. For example, the (1RS)-cis-3-(2,2-dichlorovinyl)-2, 2-dimethylcyclopro-panecarboxylic acid ester of 2-methylbiphenyl-3-ylmethanol was acaricidal, while maintaining a level of activity against other insects that was equal to or greater than cis-permethiin. Biological data on other esters of this novel alcohol are also presented.     

Effect of soil physical factors on methyl iodide and methyl bromide

Production and importation of methyl bromide is scheduled to be banned by 2001. Methyl iodide was evaluated as a possible replacement soil fumigant. The effects of soil moisture, temperature, soil texture and fumigation time on the efficacy of methyl iodide for the control of two common weeds, Abutilon theophrasti and Lolium multiflorum, were characterized and compared with those of methyl bromide. The optimal soil moisture for methyl iodide to kill both weed species in sandy soils was 14% water content (w/w). Greater efficacy was obtained when the temperature during fumigation was above 20°C. Compared to methyl bromide, the efficacy of methyl iodide was more consistent in different soils. Time to 100% mortality of weeds was 24 h for methyl iodide fumigation and 36 h for methyl bromide when 200 μM of fumigant was used. On a molar basis methyl iodide was consistently more effective than methyl bromide across the range of environmental factors tested. In terms of application technology and spectrum of activity, methyl bromide can be directly replaced by methyl iodide. © 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.     

Evaluation of methyl iodide as a soil fumigant in container and small field plot studies

Methyl iodide was evaluated as a soil fumigant as a potential replacement for the widely used soil fumigant methyl bromide. In container trials, methyl iodide was significantly more effective than methyl bromide against the plant parasitic nematodes Meloidogyne incognita, Heterodera schachtii and Tylenchulus semipenetrans and the plant pathogenic fungus Rhizoctonia solani. In small field plots, soil populations of root-knot nematodes were no longer detected after methyl iodide fumigation at an application rate of 112 kg ha^-1. However, after growing a susceptible lima bean host for two months, substantial root-knot galling occurred, while Rhizobium nodulation was absent. At 168 kg ha^-1 of methyl iodide, root-knot galling was reduced to less than 1%, and no Pythium propagules were recovered on selective detection media. These efficacy data support the conclusion that methyl iodide is a likely candidate for replacing methyl bromide as a soil fumigant. © 1998 SCI.     

Methyl bromide in natural fresh waters: Hydrolysis and volatilisation

The effect of some physical factors on the processes (hydrolysis, volatilisation) regulating the persistence of methyl bromide in fresh surface waters was investigated to complement previous research. It has been confirmed that electromagnetic radiation in the visible field has no influence on the hydrolysis kinetics of the fumigant. The removal of methyl bromide by volatilisation from stirred and ventilated solutions appears to be of greater importance in practice. It has been shown that under these conditions the half-life is directly proportional to the liquid depth. Without stirring volatilisation is greatly reduced, due to the low diffusivity of methyl bromide in the aqueous phase.     

Synthesis and structure–activity relationships for anticipated molluscicidal activity of some 2-amino-5-substituted pyridine derivatives

A series of 2-amino-5-substituted pyridine derivatives was synthesized and their molluscicidal activity against white garden, Theba pisana (Müller), and brown garden, Helix aspersa (Müller), snails was investigated by two methods of application. Some of these compounds showed strong activity under laboratory conditions against the two types of snail. T pisana was more sensitive to the tested compounds than H aspersa. The most effective compounds were 2-amino-5-(benzotriazole-1-ylmethyl)-3-methylpyridine, 2-amino-5-[1-(benzotriazole-1-yl)nonyl]-3-methylpyridine and 2-[(1,2,4-triazole-1-ylmethyl)amino]-3-methylpyridine which exhibited high molluscicidal activity. The toxicity results are discussed in relation to the chemical structures. © 1999 Society of Chemical Industry     

氟氯吡啶酯与双氟磺草胺复配的田间除草效果及其对作物安全性评价

氟氯吡啶酯属于人工合成激素类除草剂全新类别,是芳香基吡啶甲酸类家族的第1位成员,为明确其作用特点、除草活性、与双氟磺草胺复配后的除草效果以及对小麦和后茬作物的安全性,连续2年分别于小麦越冬前和返青初期施药,在冬小麦田进行了田间试验。结果表明,7.5 g/L氟氯吡啶酯EC在7.5 g/hm2用量下,对猪殃殃、播娘蒿防效较好,2次施药末次调查对猪殃殃防效为96.5%和100%,对播娘蒿防效为94.1%和81.1%;对麦瓶草防效较差,末次调查为57.1%和27.9%,对麦家公无效。复配制剂20%氟氯吡啶酯·双氟磺草胺WG在15、20、30 g/hm2用量下,对猪殃殃、播娘蒿、麦瓶草防效均较好,株防效为90.5%~100%,对麦家公防效略差,越冬前施药株防效为78.8%~98.6%,返青初期施药株防效为20.9%~82.5%;末次调查时杂草总鲜重防效为90.1%~98.2%,2次施药结果差异不显著。小麦田喷施该复配制剂15~45 g/hm2剂量,对小麦安全,未见任何药害症状;且对后茬作物玉米、大豆、花生、棉花、谷子均安全。     

Kinetics and mechanism of the hydrolysis of imidacloprid

The kinetics of the hydrolysis of imidacloprid were studied at different pH values and under various temperatures. Imidacloprid was found to be stable in acidic and neutral water, but readily hydrolysed in alkaline water. The main hydrolysis product was found to be 1-[(6-chloro-3-pyridinyl)methyl]-2-imidazolidone, and a mechanism for its formation is proposed. © 1999 Society of Chemical Industry     

Synthesis and insecticidal evaluation of N-substituted 2-nitroiminoimidazolidines

N-substituted and N,N′-disubstituted 2-nitroiminoimidazolidines were prepared from 2-nitroiminoimidazoline. The feeding-contact and systemic activities as insecticides of some of these new compounds have been evaluated. © 1998 Society of Chemical Industry     

Pesticides and the Honey Bee

Abstract

In wheat fields, irrigated with treated sewage water, the performance of six herbicides: bromoxynil/MCPA; bentazon/ dichlorprop; diclofop‐methyl; tralkoxydim; pendimethalin and bromophenoxim; and some their combinations were assessed at two different locations around the city of Riyadh. The common weeds include: Lolium spp.; Phalaris spp.; Avena spp.; Malva spp.; Chenopodium spp. and others. The best weed control treatments were: bentazon/dichlorprop followed by bromoxynil/MCPA for the broad‐leaved, and diclofop‐methyl followed by tralkoxydim for the grassy weeds. The combinations of bromoxynil/MCPA with either pendimethalin or tralkoxydim were far more effective against the broad‐leaved weeds, and significantly improved the wheat growth and yield, compared with the single treatments. However, bromoxynil/MCPA combination with diclofop‐methyl was less effective against the grassy and broad‐leaved weeds than each of them. Bromophenoxim showed an effective control of the whole weeds, with appreciable improvement in the wheat growth and yield.     

Dimethoxypyrimidines as novel herbicides. Part 4. Quantitative structure–activity relationships of dimethoxypyrimidinyl(thio)salicylic acids

The activity of a number of O-(4,6-dimethoxypyrimidin-2-yl)salicylic acids and their thio analogs inhibiting acetolactate synthase (ALS) preparation was measured. The effects of substituents on the salicylic-benzene ring on the inhibitory activity were analyzed quantitatively with physicochemical substituent parameters. For 6-substituted (thio)salicylic acids, the activity was shown to vary parabolically with the ‘intramolecular’ steric parameter ( E_s ). In addition, the higher steric dimension of substituents in terms of the STERIMOL width or length parameter lowered the activity. The field-inductive electron-withdrawing property of the 6-substituents in terms of the Swain–Lupton–Hansch F was favorable for the activity of salicylic acid series. In 5-substituted salicylic acids, the activity was increased by electron-donating substituents with smaller size. The relationships between ALS inhibitory and herbicidal activities were also analyzed with some weed species. Both pre- and post-emergence activities against barnyard grass, Echinochloa crus-galli, were linearly related to the ALS inhibitory activity after allowing for the hydrophobic factor that may contribute to the transport processes. Those against two broad-leaved weed species, Polygonum convolvulus and Abutilon theophrasti were linearly related to the in-vitro activity with no significant participation of the hydrophobic factor. © 1998 SCI