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     

Photolysis of chlorsulfuron and metsulfuron-methyl in methanol

Photolysis of chlorsulfuron and metsulfuron-methyl was studied in methanol under UV light. Their rates of primary photolysis followed first-order kinetics. The main photoproducts were identified as 2-methoxy-4-methyl-1,3,5-triazin-6-amine, 2-chloro-benzenesulfonamide and methyl 2-(aminosulfonyl)benzoate, which entailed the cleavage of the two N–C ureic bonds. Further photolysis of benzenesulfonamide derivatives involved oxidation of −NH₂, cyclisation with loss of CH₃OH, and scission of the C–S bond A trace of methyl o-mercaptobenzoate was also detected. The corresponding photolysis pathways of chlorsulfuron and metsulfuron-methyl were tentatively proposed. © 1999 Society of Chemical Industry     

Kinetics and products of the hydrolysis of 3,4-dihydroprecocene I 3,4-epoxide in aqueous organic solvents

The hydrolysis of 3, 4-dihydroprecocene I 3, 4-epoxide (3, 4-dihydro-7-methoxy-2, 2-dimethyl-3, 4-epoxy-2H-benzo[b]pyran), the putative ultimate cytotoxin of the insect growth regulator precocene I (7-methoxy-2, 2-dimethyl-2H-benzo[b]pyran), has been studied and found to exhibit first-order kinetics [k = 0.17 s^?1 in 10 mm-phosphate buffer pH 7.0, containing 1, 4-dioxane (1 + 1 by volume), ionic strength 0.1]. Plots of log k versus pH, and k versus buffer concentration, suggest that the reaction is subject to both specific and general acid catalysis. High-performance liquid chromatography showed the reaction products to be predominantly the corresponding stereoisomeric diols (3, 4-dihydro-7-methoxy-2, 2-dimethyl-2H-benzo[b]pyran-3, 4-diol), the trans : cis ratio of which varied from 1.8: 1 to 2.2: 1 but was constant over the pH range 6-8, at a given buffer concentration. The results indicate that acid-catalysed hydration of 3, 4-dihydroprecocene I 3, 4-epoxide is an S_N1 reaction, involving a trigonally hybridised carbocation at C4, even at physiological pH. Similar studies on 3, 4-dihydroiso-precocene I 3, 4-epoxide (3, 4-dihydro-6-methoxy-2, 2-dimethyl-3, 4-epoxy-2H-benzo-[b]pyran), a biologically inactive isomer of 3, 4-dihydroprecocene I 3, 4-epoxide suggest that an S_NI mechanism also contributes to its hydrolysis, but the rate constant is 4000 times lower than that for 3, 4-dihydroprecocene I 3, 4-epoxide. Knowledge of the reactivity and mechanism of reaction of such compounds forms an important part of the basis for rational prediction of biological activity in precocene analogues, and hence their possible use as pest control agents.     

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.     

Iron(III) photo-induced degradation of isoproturon: correlation between degradation and toxicity

The degradation of isoproturon photoinduced by Fe(III) was investigated under both artificial and solar light. The monomeric species Fe(OH)2+ present under the experimental conditions ([Fe(III)] = 3 x 10(-4) M) is the main Fe(III) species responsible for the degradation of isoproturon. The process involves the attack on the pollutant by OH radicals generated by irradiation of Fe(OH)2+. The major primary photoproducts were identified; they accumulate in the solution medium before being degraded. The toxicity of the solution to marine bacterium Vibrio fisheri (Beijerinck) Lehmann & Neumann was monitored during the degradation process. It increased in the early stages of the reaction and, among the photoproducts, the N-formyl derivative appeared to be the major product responsible for the increase in toxicity.     

Direct and induced phototransformation of mecoprop [2‐(4‐chloro‐2‐methylphenoxy)propionic acid] in aqueous solution

Mecoprop was irradiated under various conditions of pH, oxygenation and wavelengths in order to study the reactions involved in the phototransformation. Four main photoproducts were identified: 2‐(4‐hydroxy‐2‐methylphenoxy)propionic acid ( I ), o‐cresol ( II ), 2‐(5‐chloro‐2‐hydroxy‐3‐methylphenyl)propionic acid ( III ) and 4‐chloro‐o‐cresol ( IV ). When the anionic form of mecoprop was irradiated between 254 nm and 310 nm (UV‐C or UV‐B), I was the main photoproduct. At 254 nm its formation initially accounted for more than 80% of the transformation. It has not previously been reported in the literature. The reaction results from a heterolytic photohydrolysis. Product II accounted for only a low percentage of the transformation. The stoichiometry was different with the molecular form: the main photoproduct, III , resulted from a rearrangement after a homolytic scission. Products I, II and IV were also formed as minor photoproducts. Some other minor photoproducts were also identified. In contrast, IV was the main photoproduct under sunlight irradiation or when solutions were irradiated in near‐UV light (UV‐A). This wavelength effect is attributed to the involvement of an induced phototransformation; IV is also the main photoproduct when the phototransformation is induced by Fe( III ) perchlorate or nitrite ions. In usual environmental conditions the excitation of the molecular form is negligible and the phototransformation is mainly due to induced photoreactions. © 2000 Society of Chemical Industry     

除草剂噻吩磺隆的合成

以氯甲酸甲酯和2-羧甲基-3-磺酰氨基噻吩为起始原料合成除草剂噻磺隆的方法。原料2-羧甲基-3-磺酰氨基噻吩与氯甲酸甲酯生成2-甲氧羰基-3-磺酰氨基甲酸甲酯噻吩, 再与2-氨基-4-甲氧基-6-甲基均三嗪反应生成噻吩磺隆。避免了异氰酸酯路线和光气法的种种缺点,具有收率高、含量高、成本低的特点。以2-羧甲基-3-磺酰氨基噻吩计,总收率为77．73％,原药纯度达到93．6％。     

Phototransformation of the insecticide hydramethylnon in aqueous systems

Sunlight irradiation of hydramethylnon in aqueous media of different pH values resulted in 80-94% transformation within 10h. The rate of disappearance of the insecticide was affected marginally by the initial pH of the reaction medium. After 10 h irradiation, eight photoproducts were formed. Three products were isolated as pure crystalline substances and the structures of two of these (I & III) were characterised by mass and NMR spectroscopy. The reaction mechanisms involved in the formation of photoproducts are discussed.     

Photolysis of Diuron

The major photoproducts observed in the photolysis of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] ( 2 ) in aqueous solution resulted from a heterolytic substitution of chlorine by OH (photohydrolysis). A wavelength effect was observed: at 254 nm the formation of 3-(4-chloro-3-hydroxyphenyl)-1,1-dimethylurea ( 3 ) accounted for more than 90% of the conversion, whereas when the solution was irradiated in ‘black light’ (85% of photons emitted at 365 nm, about 7% at 334 nm), the major photoproduct was 3-(3-chloro-4-hydroxyphenyl)-1,1-dimethylurea ( 4 ). The presence of methanol favoured the photoreduction into 3-(3-chlorophenyl)-1,1-dimethylurea ( 5 ). Completely different reactions were observed when 2 was irradiated in dry aerobic conditions on silica. They resulted from elimination or oxidation of methyl groups. The main photoproducts initially formed were 3-(3,4-dichlorophenyl)-1-methyl urea ( 6 ) and 3-(3,4-dichlorophenyl)-1-formyl-1-methylurea ( 7 ). In the second stage ( 6 ) was transformed into (3,4-dichlorophenyl)-urea ( 8 ) and 3-(3,4-dichlorophenyl)-1-formylurea ( 9 ); some other minor products such as monuron ( 1 ) were also identified. The formation rate of 6 and 7 was much slower on clay (montmorillonite or kaolin) than on silica. In contrast with products 6 and 8 , the formation of 7 and 9 needed the presence of oxygen: they did not appear when diuron was irradiated in deoxygenated C₂Cl₃F₃. It can be concluded that the photolysis of diuron is highly dependent on the conditions of irradiation. © 1997 SCI.     

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.     

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 .     

Photochemistry of parathion in the plant cuticle environment: Model reactions in the presence of 2-propanol and methyl 12-hydroxystearate

On UV-irradiation (λ > 280 nm), photodegradation of parathion dissolved in 2-propanol took place mainly by reduction of the phenylnitro group. The photoreduction intermediates so formed then combined, yielding primarily azoxyparathion which, upon further irradiation, rearranged into 2-hydroxyazoparathion. When parathion was irradiated in the presence of the cutin acid 12-hydroxystearic acid (as the methyl ester), azoparathion, azoxyparathion and 2-hydroxyazoparathion were the dominant photoproducts if the reaction was performed in thin-layer films of the 12-hydroxystearate. Irradiation of parathion dissolved in a solution of the 12-hydroxystearate in cyclohexane yielded mainly paraoxon. Furthermore, in all experiments, photolysis of the P—O ester bonds of the parent compound as well as of the photoproducts was observed at low levels.     

Kinetics and hydrolysis mechanism of chlorsulfuron and metsulfuron-methyl

In acidic media, hydrolysis of chlorsulfuron and metsulfuron-methyl occurs via two consecutive reactions which were followed by ultraviolet spectrophotometry. For these two reactions, the pseudo-first-order rate constants increase proportionally to the concentration of hydronium ion in the more acidic media and to the square of this concentration at higher pH values. A kinetic study by HPLC shows that the first reaction leads to the formation of 4-methoxy-6-methyl-1,3,5-triazin-2-amine and (o-chlorophenylsulfonyl) carbamic acid for chlorsulfuron or (o-methoxycarbonylphenylsulfonyl) carbamic acid for metsulfuronmethyl. The second reaction is the conversion of these sulfonylcarbamic acids to sulfonamides and carbon dioxide. The complete lack of saccharin and of o-sulfamoyl benzoic acid proves that the ester function of the methoxycarbonyl group is stable. The lack of general acid-base catalysis and a solvent deuterium isotope effect less than unity are consistent with a rate-determining cleavage of the protonated substrate. In the basic pH range (10–14) a single reaction occurs, the nucleophilic substitution of the methoxy group on the triazine by a hydroxide group.     

Photolysis of organophosphorus insecticides on soil surfaces

Photolysis on soil surfaces of the organophosphorus insecticides diazinon, methidathion and profenofos was studied under artificial sunlight conditions. All three compounds were readily degraded under the conditions used. The rate of degradation decreased in the order diazinon, profenofos, methidathion and was always greater in moist than in dry soil. The same order of stability was also observed from photolysis studies in aqueous solution. The major photolysis products identified were 2-isopropyl-6-methylpyrimidin-4-ol from diazinon, 5-methoxy-3H-1,3,4-thiadiazol-2-one from methidathion and 4-bromo-2-chlorophenol and 4-bromo-2-chlorophenyl ethyl hydrogen phosphate from profenofos. The same compounds were formed in hydrolysis studies and also upon photodecomposition in aqueous solutions of diazinon and methidathion. Profenofos, however, showed a different photolytic reaction in aqueous systems, forming O-(2-chlorophenyl) O-ethyl S-propyl phosphorothioate. Soil photolysis studies together with hydrolysis experiments could be a useful quick method for obtaining early information on the chemical breakdown products which are to be expected in the soil environment.     

Synthesis and insecticidal and acaricidal properties of some 5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl phosphorus esters. III

A series of new 5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl phosphorus esters, which was prepared by phosphoroylation of 5-methoxy-1-methyl-6-oxo-1H-pyri-dazin-4-ol, is described. Many of the compounds showed high insecticidal and acaricidal activity.     

Photolysis of fluchloralin in aqueous methanol

The photodegradation of fluchloralin by UV irradiation or sunlight in aqueous methanolic solution has been examined. In the presence of titanium dioxide five photoproducts were obtained, but only four in its absence. One photoproduct, 2, 2'-azoxy-bis(alpha,alpha,alpha-trifluoro-6-nitro-p-toluidine) is reported for the first time as a metabolite of fluchloralin. In natural sunlight the rate of degradation was higher than in UV light and titanium dioxide had almost no effect on the rate of degradation.     

Photolysis of dimepiperate in aqueous solution

Dimepiperate, S-(1-methyl-1-phenylethyl) piperidine-1-carbothioate ( I ) was degraded in aqueous solution by ultraviolet irradiation into piperidine ( II ), α-methylstyrene ( III ), acetophenone ( IV ), and formaldehyde ( V ). The reaction followed first-order kinetics. In sunlight the reaction occurred only in the presence of a sensitiser and afforded the same four photolytic degradation products. In the absence of oxygen the herbicide was converted much more rapidly, but yielded only ( II ) and ( III ) as products. A mechanism which accounts for the formation of the photoproducts is proposed.     

New fluoro intermediates for herbicidal sulfonylureas

New pyrimidine and triazine intermediates for herbicidal sulfonylureas are prepared as follows: 2,4-dichloro-6-methylpyrimidine is converted via a halogenation, halogen exchange and substitution sequence to 2-amino-4-trifluoromethyl-6-trifluoromethoxypyrimidine. New fluoromethyl-triazines are available starting from guanidine, trichloroacetonitrile and difluoroacetic anhydride, or alternatively from thiocarbamoyl guanidine and chlorodifluoroacetic ester ring closure. To obtain new o-fluoroalkyl-benzenesulfonamide precursors, o-chlorobenzaldehyde was fluorinated with sulfur tetrafluoride, or a bromobenzene derivative was subjected to a substitution reaction with sodium pentafluoropropionate. Sulfonylureas derived from trifluoromethylpyrimidines with an m-methylthio substituent are selective post-emergence herbicides in cotton, presumably due to sulfone metabolization. Selectivity in wheat is obtained by combining 4-methoxy-6-trifluoromethylpyrimidine with a lipophilic difluoromethyl-benzenesulfonamide moiety. Also in the difluoromethyl-triazine series, the combination with the difluoromethyl-benzenesulfonamide moiety is a good choice for wheat selectivity. Chlorodifluoromethyl- and trifluoromethyltriazines, however, combine better with an aromatic ester for best activity and selectivity in wheat. Selected compounds are undergoing broad field tests in wheat.     

Studies on photodegradation of chlorimuron-ethyl in soil

Photolysis of chlorimuron-ethyl was studied on a soil surface under sunlight and UV light. Eight photoproducts were isolated and characterised by spectroscopic methods. Major photoproducts are formed by cleavage of the sulfonylurea bridge and minor products are formed via dechlorination, hydrolysis and cyclisation. The rates of photodegradation of chlorimuron-ethyl on different soils followed first-order rate kinetics, with half lives of 22·3 h, 9·4 h, 4·9 h (UV) and 20·7 days, 11·1 days and 11·1 days (sunlight) for alluvial, red and laterite soils, respectively. The differences in rates of photodegradation were dependent upon the soil pH. © 1997 SCI     

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.