Transformations of 4-chloro-o-toluidine in soil: Generation of coupling products by one-electron oxidation

Four coupling products formed by one-electron oxidation of 4-chloro-o-toluidine were isolated from soil samples after 90 days of incubation with [¹⁴C]chlordimeform (200 mg/kg). The metabolic compounds were identified as 4,4′-dichloro-2,2′-dimethyl-azobenzene, 4-chloro-6-nitro-o-toluidine, N-(4-chloro-o-tolyl)-2-methyl-p-benzoquin-one monoimine and 2-(4-chloro-o-toluidino)-N-(4-chloro-o-tolyl)-6-methyl-p-benzo-quinone monoimine, respectively. Mechanisms of formation and possible significance of these substances as indicators for metabolic pathways to mineralisation of aniline derivatives are discussed. The chlordimeform soil concentrations (70–100 mg/kg) necessary for the formation of the azobenzene and the benzoquinone monoimines are at least 10 times higher than those occurring after actual field application.     

The insecticidal and anticholinesterase activities of O,O-diethyl O-4-(2,2-disubstituted vinyl)phenyl phosphates and phosphorothioates

A series of O,O-diethyl O-4-(2,2-disubstituted-vinyl)phenyl phosphorothioates and phosphates was synthesised and examined for anticholinesterase activity to housefly and bovine erythrocyte ChE, and also for their toxicity to Musca domestica and Triatoma infestans. The synthesised phosphates were potent anticholinesterases and stronger inhibitors of housefly acetylcholinesterase than bovine erythrocyte acetyl-cholinesterase. Satisfactory correlation was obtained between the anticholinesterase activity and the Hammett σ^? constants against both enzymes, but it was not significantly improved by introducing a term for the Hansch π constant. The phosphorothioates showed poor and variable toxicity to M. domestica. On T. infestans, the only compound that showed some toxicity was the di(acetyl)-substituted product [O-4-(2-acetyl-3-oxobut-1-enyl)phenyl O,O-diethyl phosphorothioate]. For comparative studies, some commercial products were also assayed on T. infestans.     

Light-induced transformations of tribenuron-methyl in aqueous solution

Tribenuron-methyl a sulfonylurea herbicide, readily photodegraded in aqueous solution under sunlight and UV light. The photoproducts identified were N-methyl-4-methoxy-6-methyl-1,3,5-triazine-2-amine, methyl 2-(aminosulfonyl) benzoate, o-benzoic sulfimide, N-(4-methoxy-6-methyl1,3,5-triazin-2-yl)-N-methyl urea and N-(2-carbomethoxyphenyl)-N-(4-methoxy-6-methyl-1,3,5triazin-2-yl)-N′-methyl urea. The rate of photodegradation of tribenuron-methyl in different types of water followed first-order kinetics with significant correlation coefficient, increased with increase in pH and was also dependent upon the dissolved impurities. © 1999 Society of Chemical Industry     

Conversion of [14C]buturon in soil and leaching water under outdoor conditions

[¹⁴C]Buturon, a urea herbicide, was sprayed on soil and winter wheat as an aqueous formulation (2.98 kg/ha) under outdoor conditions. Three months after application, a total of 49.2% of the applied radiocarbon was recovered: 46.9% in the soil, 0.3% in the leaching water (depth > 50 cm), and 2.0% in the plants. Radioactive residues in the soil were distributed to a depth of 50 cm and decreased with increasing depth of the soil. An average of 47% of the radioactivity present in the soil could be extracted with cold chloroform; by this extraction method, the formation of artefacts was avoided. Between one and two thirds of the extracted radioactivity was unchanged buturon. In the soil extracts, the following eight conversion products were isolated and identified by combined gas chromatography/mass spectrometry: N-(p-chlorophenyl)-N-methyl-O-methyl carbamate; N-(p-chlorophenyl)-O-methyl carbamate; N-(p-chlorophenyl)-N′-methyl-N′-isobutenyl-urea; N-(p-chlorophenyl)-N′-methyl-urea, N-(p-chlorophenyl)-N′-methyl-N′-isobutenylol-urea; p-chloroaniline in “biologically bound” form; N-(p-chlorophenyl)-N′-methyl-N′-methoxyisobutenyl-urea; and N-(p-chlorophenyl)-N′-methyl-N′-ethoxyisobutenyl-urea. In the leaching water, which contained only 0.005–0.006 mg/liter of radioactive substances, the following three conversion products were isolated and identified by gas chromatography/mass spectrometry: p-chloroformanilide; N-(p-chlorophenyl)-N-methyl-O-methyl carbamate; and an N-hydroxyphenyl-N′-methyl-N′-isobutinyl-urea. The results are discussed in relation to the factors responsible for the formation of these products.     

Comparative studies on chlorpyrifos and methyl parathion induced oxidative stress in different parts of rat brain: Attenuation by antioxidant vitamins

Organophosphate (OP) pesticides are among the most widely used synthetic chemicals for controlling a wide variety of pests. Chlorpyrifos (o,o′-diethyl-o-3,5,6-trichloro-2-pyridyl phosphorothionate, CPF) is among the leading OP pesticides used extensively throughout the world including India while methyl parathion (o,o-di methyl-o-p-nitrophenyl phosphorothioate, MPT) another OP compound, widely used as insecticide and acaricide to control many biting or sucking pests of agricultural crops. Present study was carried out to compare the chronic toxicity of CPF and MPT, their potential to generate oxidative stress and ameliorating effects of antioxidant vitamins in brain of rats. Results of the present study clearly demonstrated that the oral exposure of CPF or MPT, generated oxidative stress in different parts of rat brain consequently accumulating malondialdehyde (MDA) and 4-hydroxynonanal (4HNE), the two major end products of lipid peroxidation, in all the three brain regions i.e. fore-, mid- and hind-brain. The levels of hydrogen peroxide (H₂O₂) were also increased in all the three brain regions when compared with control. CPF and MPT exposure caused decrease in the levels of reduced glutathione (GSH) and increase in the levels of oxidized glutathione (GSSG) in all the three brain regions. The increase in the levels of MDA, 4HNE, H₂O₂ and GSSG was less pronounced when CPF or MPT was given to the rats fed with a mixture of vitamin A, E and C. The present findings clearly show that oral intake of a mixture of vitamin A, E and C protects the rats from MPT or CPF induced oxidative stress and suggest that this treatment alleviates the toxicity of these pesticides to a greater extent.     

Studies on residues and the metabolic pathway of methidathion in tomato fruit

The residues and metabolism of methidathion [S-(2, 3-dihydro-5-methoxy-2-oxo-1, 3, 4-thiadiazol-3-ylmethyl) O, O-dimethyl phosphorodithioate] and its secondary metabolites: demethyl-methidathion [S-(2, 3-dihydro-5-methoxy-2-oxo-1, 3, 4-thiadiazol-3-ylmethyl) O-methyl O-hydrogen phosphorodithioate] ( IV ), the sulphide (2,3-dihydro-5-methoxy-3-methylthiomethyl-1,3,4-thiadiazol-2-one) ( I ), tsulphoxide(2,3-dihydro-5-methoxy-3- methylsulphinylmethyl-1,3,4-thiadiazol-2-one) ( II ) and the sulphone (2,3-dihydro-5-methoxy-3-methylsulphonylmethyl-1,3,4-thiadiazol-2-one ( III ) were studied in laboratory-treated tomato fruit. The metabolites and residues of methidathion were determined for the applied doses of 1, 7 and 14 mg of methidathion kg^?1 of fruit. Methidathion was metabolised extensively over a 14-day period. The amount of metabolites formed was a function of both the applied dose as well as the time after application. Major water-soluble metabolites were found to be IV and the cysteine conjugate S-(2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl)-L-cysteine ( VI ). The chloroform-soluble metabolites were identified as the oxygen analogue of methidathion [S-(2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl) O, O-dimethyl phosphorothioate] ( V ), the sulphoxide II , and the hydroxy compound 2,3-dihydro-3-hydroxymethyl-5-methoxy-1,3,4-thiadiazol-2-one. The oxygen analogue of methidathion ( V ) was found in small amounts, corresponding to <5% of the added methidathion. Demethyl-methidathion ( IV ) appeared to be a precursor in the formation of the cysteine conjugate VI . The sulphide I seemed to be more reactive in forming the cysteine conjugate than the sulphoxide II or the sulphone III .     

Studies on the induction of rat uterine ornithine decarboxylase by DDT analogs. I. Comparison with estradiol-17β activity

The effect of DDT analogs and estradiol-17β on uterine ornithine decarboxylase activity in the immature intact and ovariectomized rat was studied. Pretreatment with various doses of o,p′DDT [1-(o-chlorophenyl)-1-(p-chlorophenyl)-2,2,2-trichloroethane] or estradiol-17β caused a marked increase in the specific activity of ornithine decarboxylase in the 20,000g supernatant fraction of uterine homogenates but not in liver homogenates. Doses as low as 0.5 mg of o,p′DDT or 0.002 μg of estradiol-17β stimulated uterine ornithine decarboxylase activity in the ovariectomized rat. The peaks of activity after treatment with o,p′ DDT and estradiol-17β occurred at 6 and 5 hr, respectively. The level of ornithine decarboxylase activity in untreated groups was consistently lower in ovariectomized rats than in intact immature animals. Treatment with o,p′ DDT (10 mg/100 g body weight) of ovariectomized and intact immature rats demonstrated at 131-fold and an about 20-fold increase in uterine ornithine decarboxylase activity, respectively. Treatment of ovariectomized rats with cycloheximide or actinomycin D effectively blocked the increase in ornithine decarboxylase caused by o,p′ DDT. Similar results were obtained with cycloheximide in the intact immature rat. Animals subjected to both adrenalectomy and ovariectomy demonstrated an increase in ornithine decarboxylase activity when treated with either estradiol-17β or o,p′ DDT. Dose-response curves obtained for estradiol-17β and o,p′ DDT suggest a similar mechanism of action for the two compounds. Graphic analysis of the dose-response curves for estradiol-17β and o,p′ DDT demonstrated an ED₅₀ of 0.038 μg/100 g body weight and 1.8 mg/100 g body weight, respectively. The examination of various DDT analogs in intact and ovariectomized animals showed that o,p′ DDT was the most potent inducer of ornithine decarboxylase. The order of decreasing potency of DDT analogs was o,p′ DDT, o,p′ DDD. p,p′ DDT, p,p′ DDD, and p,p′ DDE.     

Activity of two pyrethroids against blackfly larvae,determined by a simple laboratory technique

A simple laboratory technique for determining the activity of two pyrethroids (5-benzyl-3-furyImethyl DL-cis, trans-chrysanthemate and 5-benzyl-3-furylmethyl D-trans-chrysanthemate) against blackfly larvae (Simulium ornatum) is described. The results showed that the pyrethroids alone or with piperonyl butpxide were of similar activity to Abate (O,O,O',O'-tetramethyl O,O'-thiodi-p-phenylene phosphor-othioate) and Dursban (O,O-diethyl O-3,5,6-trichloro-2-pyridylphosphorothioate), insecticides of known activity against blackfly larvae. However, the pyrethroids cause rapid larval detachment in running water, and may be of value in controlling these insects when used in conjunction with another insecticide.     

Synthesis,spectral properties and insecticidal,acaricidal and ovicidal activities of some O-(1,5-disubstituted- 6-oxo-12H-pyridazin-4-yl) phosphorothioates

A synthesis of O,O-dialkyl, O-alkyl O-2-chloroethyl (or O-2-ethoxyethyl) O-(1,5-disubstituted-6-oxo-1H-pyridazin-4-yl) phosphorothioates is described. Infrared, Raman and ultraviolet spectra of the compounds prepared are interpreted. The wave-numbers of the v(C? C) bands were correlated with substituent constants. Good linear correlations of v(C? O) with σ, σ^F, σ_I and σ_R were observed for compounds containing various substituents in the neighbourhood of the keto group of the pyridazinone ring. The insecticidal, acaricidal and ovicidal activities of O-(ethyl or isopropyl), O-(alkyl, 2-chloroethyl, or 2-ethoxyethyl) O-(5-methoxy-1-methyl-6-oxo-1H- pyridazin-4-yl) phosphorothioates, O-ethyl O-isopropyl O-(5-methoxy-1-substituted-6-oxo-1H-pyridazin-4-yl) phosphorothioates and O-ethyl O-isopropyl O-(1-methyl-5-substitutedd-oxo-1H-pyridazin-4-yl) phosphorothioates are reported together with the toxicity of some of these compounds to rats.     

Interaction between the factor delaying penetration of insecticides and the desethylation mechanism of resistance in organophosphorus-resistant houseflies

The desethylation (gene a) and penetration delaying (pen) factors of resistance to organophosphorus insecticides isolated by genetical methods from the diazinon-selected SKA strain of houseflies (Musca domestica L.) were inbred into a strain whose resistance was compared with that of flies with single factors of resistance and the SKA strain. Pen alone decreases kill marginally, and gene a alone raises LD₅₀ to 1·4–48 times that of susceptible flies, depending on the insecticide. The two factors together increase resistance greatly to many organophosphorus insecticides (up to 5–10 times or more to diazinon, malathion-ethyl and chlorthion-ethyl than of flies with gene a only) indicating that the two factors interact. Interaction is greater against the thionates than the corresponding phosphates, probably because pen delays entry of thionates more than of the corresponding phosphates. The role in resistance of each factor when hetero-and homo-zygous, and the reasons for interaction, are discussed.     

Shift of allelochemicals from Sorghum halepense in the soil and their effects on the soil's bacterial community

Johnsongrass (Sorghum halepense [L.]Pers.), an exotic invasive weed in China, secretes the phenolic compounds, p‐hydroxybenzoic acid (p‐HBA) and p‐hydroxybenzaldehyde (p‐HBAL), as the dominant allelochemicals in the root exudates. To better understand how these two allelochemicals affect the soil microbial community in the rhizosphere of S. halepense, the fate of these compounds in the invaded soil and the effect of these phytotoxins on the soil bacterial community were evaluated. The concentrations of the allelochemicals in the soil were determined by a high‐performance liquid chromatography‐ultraviolet/photodiode array after 1, 2, 4, 6, 12 and 24 h of treatment. MiSeq sequencing was undertaken to understand how the bacterial populations in the soil were affected by the allelochemicals. The HPLC results indicated that p‐HBA was degraded by the microorganisms that were present in the soil after 1 h and disappeared after 6 h of incubation. The compound, p‐HBAL, initially was converted to p‐HBA and then the p‐HBA broke down, disappearing after 12 h of incubation in non‐sterile soil. Both p‐HBA and p‐HBAL were stable under sterile soil conditions for up to 24 h. The relative abundance of Proteobacteria was significantly inhibited. However, those of Acidobacteria, Chloroflexi, Verrucomicrobia and Cyanobacteria were increased by the p‐HBAL treatment. These findings suggest that allelochemicals from S. halepense might affect the bacterial community composition in the soil.     

Application of energy-filtering electron microscopy (EFEM) for analysis of hydrogen peroxide and lignin in epidermal walls of cucumber leaves triggered by acibenzolar-S-methyl treatment prior to inoculation with Colletotrichum orbiculare

Hydrogen peroxide (H₂O₂) and lignin induced by acibenzolar-S-methyl (ASM) during the expression of systemic acquired resistance (SAR) of cucumber plants against the fungus Colletotrichum orbiculare was analysed with electron microscopy and energy-filtering electron microscopy (EFEM). ASM pretreatment consistently led to the blockage of appressorial penetration pegs into leaves at early stages after inoculation, whereas the fungus was able to grow into the vascular tissue after distilled water pretreatment. The blocked pegs, seen frequently at epidermal pectin layers in leaves of ASM-treated plants, were surrounded by abundant electron-dense amorphous material and dots. These were identified as lignin, based on their appearance and high reactivity with KMnO₄. Lignin first appeared as an amorphous material at pectin layers, and then as dots in some areas of the material. The results showed that ASM caused SAR in leaves via faster formation of lignin within 1 day after inoculation. After CeCl₃ treatment to detect H₂O₂, H₂O₂-reactive products (cerium perhydroxides) were seen near ASM-induced lignin formation sites in pectin layers. EFEM analysis showed that Ce and O were located at the same sites as the lignin dots, suggesting that lignin was associated with sources of H₂O₂ generation. The results indicate that the faster H₂O₂ generation and lignification induced by ASM were the potential causes of SAR.     

Photodegradation of fenarimol

The photodegradation of aqueous alcoholic solutions of fenarimol at λ ≥ 250 nm has been examined. UV irradiation of an aqueous methanolic solution for 24 h yielded two photoproducts, identified as 2,4′‐dichlorobenzil and p‐chlorobenzoic acid, while irradiation of a solution in aqueous isopropanol yielded p‐chlorobenzoic acid and two additional products identified as 2,4′‐dichlorobenzophenone and o‐chlorobenzoic acid. A mechanism for the formation of the photoproducts is suggested. © 2000 Society of Chemical Industry     

A novel series of O,O-diethyl O-(1,3-disubstituted-1,2,4-triazol-5-yl) phosphorothioates. Part II. Quantitative structure–activity relationships

The in-vivo toxicity data of 33 O,O-diethyl O-(1-alkyl-3-R″-1,2,4-triazol-5-yl) phosphorothioates, reported in Part I of this series, were subjected to multiregression analyses for the following organisms: Leptinotarsa decemlineata (larvae), Macrosiphum euphorbiae (aphids), Culex pipiens (adults), Spodoptera littoralis (larvae) and the rat. The activities were found to depend mainly on the steric parameters of R″, these being best expressed by the values L, B₁ and B₄ of the computer program STERIMOL. It was shown that there were different steric requirements for each species and these are discussed. The predictive values of the best equations were also estimated.     

Metabolism of 1,1-bis-(p-ethoxyphenyl)-2-nitropropane in the house fly and the cluster caterpillar

Some aspects of the metabolism of a new insecticide, 1,1-bis-(p-ethoxyphenyl)-2-nitropropane have been investigated in the house fly, Musca domestica and the cluster caterpillar, Spodoptera litura. In the house fly the compound was deethylated and after 24 hr exposure, 1-(p-ethoxyphenyl)-1-(p-hydroxyphenyl)-2-nitropropane and 1,1-bis-(p-hydroxyphenyl)-2-nitropropane were isolated. From evidence given below it is probable that conjugates of these compounds were also present. Feeding of the insecticide to S. litura resulted in the excretion of mainly unchanged insecticide although a small percentage was converted to a polar compound tentatively identified as 1,1-bis-(p-hydroxyphenyl)-2-propanone.     

Inhibition of aflatoxin production in Aspergillus flavus by pyrazolines and pyrazoles

A new series of 1,3,5-triarylpyrazolines, obtained from 3, 4-dichloroacetophenone, were readily dehydrogenated by tetrachloro-o-benzoquinone at room temperature to the pyrazoles. The spectra and fluorescence of the compounds are discussed. The pyrazolines and pyrazoles did not significantly affect the mycelial growth of 19 fungal isolates, but at low concentrations, they inhibited aflatoxin production by Aspergillus flavus.     

Mechanism of inhibition reaction of acetylcholinesterase by phenyl N-methylcarbamates: Separation of hydrophobic,electronic, hydrogen bonding and proximity effects of aromatic substituents

The association equilibrium constant, $\text{1}\text{K}{}_{\mathrm{d}}$, and the carbamylation constant, k₂, of 53 o-, m-, and p-substituted phenyl N-methylcarbamates with bovine erythrocyte acetylcholinesterase were determined. The $\text{1}\text{K}{}_{\mathrm{d}}$ value varied 1000-fold, whereas the k₂ value did not depend upon the nature and position of substituents. The variation in $\text{log}\text{(}\text{1}\text{K}{}_{\mathrm{d}}\text{)}$ was analyzed using free energy related substituent parameters and regression analyses. The effect of substituents at o-, m-, and p-positions was nicely separated into hydrophobic, electronic, hydrogen bonding, and proximity (steric and field electronic for o-substituents) factors. The physicochemical significance of these factors was established by comparison with those for model organic reactivities. The mechanism of the whole reaction process was elucidated in terms of physical organic chemistry.     

Insect glutathione S-transferase: Separation of transferases from fat bodies of American cockroaches active on organophosphorus triesters

Several glutathione S-transferases which catalyze the conjugation of reduced glutathione with organophosphorus triesters were separated from fat bodies of adult female American cockroaches, Periplaneta americana (L.). Two transferases (I, V) were active on diazinon and three transferases (II, III, IV) were active on methyl parathion. The transferase (I) active on the pyrimidinyl moiety of diazinon was distinguishable from the other transferases on the O-methyl portion of methyl parathion, as shown by chromatographic properties, and additionally it was almost inactive or less active on 3,4-dichloronitrobenzene, methyl iodide, p-nitrobenzyl chloride, trans-cinnamaldehyde, and 1,2-epoxy-3-(p-nitrophenoxy)propane. Transferase II had high activities with “aryl” and “aralkyl” compounds, transferase III with “epoxide” and “alkene,” and transferase IV with “alkyl,” “aryl,” and “aralkyl” compounds. This indicated that the transferases had overlapping substrate specificities. The molecular weight was 35,000–37,000 for both of the enzymes active on methyl parathion and diazinon. The pH optima with methyl parathion and diazinon were about 8.5 and 6.5, respectively. At a glutathione concentration of 5 mM, Michaelis constants were 0.28 and 0.13 mM for methyl parathion and diazinon, respectively.     

新型含2(1H)-喹啉酮的甲氧基丙烯酸酯类

以(E)-2-[2'-(bromo-methyl)phenyl]3-甲氧基丙烯酸甲酯和2(1H)-喹啉酮类化合物为原料,通过醚化等反应,合成了11个新型含2(1H)-喹啉酮结构的甲氧基丙烯酸酯类化合物,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,部分目标化合物对烟草赤星病菌Alternaria alternata等6种病原菌具有一定的抑菌活性,其中5a对水稻稻瘟病菌Pyricularia grisea的抑菌率达100%。     

Polymerization of 1-naphthol and related phenolic compounds by an extracellular fungal enzyme

An extracellular phenol oxidase was isolated from the culture filtrate of the fungus Rhizoctonia praticola by gel filtration on Sephadex G-200. The enzyme catalyzed the polymerization of 1-naphthol to dimeric, trimeric, tetrameric, and pentameric compounds as determined by mass spectrometry. One product with a molecular weight of 286 was identified as 4,4′-bi-1-naphthol. Other compounds that were dimerized or polymerized by the enzyme were phenol, o-methoxyphenol (guaiacol), p-methylphenol (p-cresol), 2,6-dimethoxyphenol, and 1,3- and 1,5-dihydroxynaphthalene. The product from 2,6-dimethoxyphenol was isolated and identified as 3,5,3′,5′-tetramethoxydiphenoquinone.