Translocation and degradation of pyrazosulfuron-ethyl in rice soil

BACKGROUND: Pyrazosulfuron‐ethyl {ethyl 5‐[(4,6‐dimethoxypyrimidin‐2‐ylcarbamoyl)‐sulfamoyl]‐1‐methylpyrazole‐4‐carboxylate} is a new rice herbicide belonging to the sulfonylurea group. This study reports the translocation of ¹⁴C‐pyrazosulfuron‐ethyl to rice plants and its degradation in rice‐planted and unplanted soil. RESULTS: Pyrazosulfuron‐ethyl did not show any appreciable translocation to rice shoots, as ¹⁴C‐activity translocated to the aerial portion never exceeded 1% of the initially applied ¹⁴C‐activity over a 25 day period. Results suggested that the dissipation of pyrazosulfuron‐ethyl from soils followed first‐order kinetics with a half‐life of 5.5 and 6.9 days in rice‐planted and unplanted soils respectively. HPLC analysis of the organic extract of soil samples showed the formation of three metabolites, namely ethyl 5‐(aminosulfonyl)‐1‐methyl‐1‐H‐pyrazole‐4‐carboxylate, 5‐[({[(4,6‐dimethoxy‐2 pyrimidinyl)‐amino]‐carbonyl} amino)‐sulfonyl]‐1‐methyl‐1H‐pyrazole‐4‐carboxylic acid and 2‐amino‐4,6‐dimethoxy pyrimidine, in both rice‐planted and unplanted soils. CONCLUSION: The study indicates that pyrazosulfuron‐ethyl was a short‐lived compound in the soil and was degraded relatively faster in rice‐planted soil than in unplanted soil. The herbicide did not show any appreciable translocation to rice plants. Copyright © 2011 Society of Chemical Industry     

Degradation rates in soil of 1-benzyltriazoies and two triazole fungicides

The degradation rates in soil of 1-benzyltriazole together with six analogues having substituents in the phenyl ring and two commercial triazole fungicides, PP450 and triadimefon, were determined at 15°C and 20 % soil water content. The order of degradation rates of the benzyltriazoles was H > 4-OCH₃ > 4-F>4-Cl.4-≥tert-C₄H_g3,4-diCl>3-CF₃. Thus, in general, persistence was enhanced by electron-withdrawing substituents and by lipophilic groups that increased sorption by soil. Of the commercial fungicides, PP450 was degraded very slowly (half-life 578 days) while triadimefon was quickly converted (half-life 15 days) to the corresponding alcohol, triadimenol, which in turn was degraded very slowly. The effects of temperature and soil water content on rate of degradation were studied for 1-benzyltriazole and 1-(4-fluorobenzyl)triazole. The rate of degradation of 1-benzyltriazole was more sensitive to soil temperature and water content than was that of 1 -(4-fluorobenzyl)triazole. The influence of these results on the input data required by models which simulate persistence in field soil is discussed.     

Degradation of the herbicide flamprop-isopropyl in soil under laboratory conditions

The degradation of the wild-oat herbicide flamprop-isopropyl, [isopropyl (±)-N-benzoyl-N-(3-chloro-4-fluorophenyl)alaninate], in four soils has been examined under laboratory conditions with sampling times of up to 45 weeks after treatment. The major degradation product of [¹⁴C]flamprop-isopropyl in all soils at up to 10 weeks after treatment was the carboxylic acid (±)-N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine. This compound in turn underwent degradation by loss of the benzoyl group and the propionic acid moiety, with evolution of [¹⁴C]carbon dioxide to form 3-chloro-4-fluoroaniline (CFA). The CFA was formed slowly in soil and occurred mainly as a bound form. There was evidence to show that the CFA was subsequently converted into other polar products. The time for depletion of 50% of the applied herbicide was approximately 10 weeks in sandy loam and medium loam soils, 11 weeks in a clay loam soil and 23 weeks in a peat soil.     

Metabolism of N-hydroxymethyl dimethoate and N-desmethyl dimethoate in bean plants

N-Hydroxymethyl [carbonyl-¹⁴C] dimethoate (0.43 ppm) and N-desmethyl [carbonyl-¹⁴C] dimethoate (0.50 ppm) were stem-injected into bean plants (Phaseolus vulgaris) in two separate experiments. Plants were harvested periodically, extracted, fractionated, and analyzed for metabolites. The resulting pattern of metabolites formed from the administration of these two compounds was different. Radioactivity was not detected in the organic fraction 2 days after N-desmethyl dimethoate administration. N-Desmethyl dimethoate was rapidly broken down to dimethoate carboxylic acid and other polar metabolites, then further degraded into materials which became part of the plant constituents. N-Hydroxymethyl dimethoate was quite stable in the plant. Most of the material not remaining as parent became rapidly conjugated and constant levels of conjugate were maintained. Very little radioactivity was bound in the plant marc. The metabolic pathway of these compounds is as follows: N-hydroxymethyl to the glucoside or N-desmethyl derivative; the N-desmethyl metabolite degrades primarily to the carboxylic acid but also to N-desmethyl dimethoxon, either of which in turn may be degraded to dimethoxon carboxylic acid. The conversion of -NHCH₂OH to -NH₂ is a slow reaction so that conjugation becomes the route of choice when the plant is treated with N-hydroxymethyl dimethoate.     

Mineralisation of the herbicide linuron by Variovorax sp. strain RA8 isolated from Japanese river sediment using an ecosystem model (microcosm)

BACKGROUND: Linuron is a globally used phenylurea herbicide, and a large number of studies have been made on the microbial degradation of the herbicide. However, to date, the few bacteria able individually to mineralise linuron have been isolated only from European agricultural soils. An attempt was made to isolate linuron‐mineralising bacteria from Japanese river sediment using a uniquely designed river ecosystem model (microcosm) treated with ¹⁴C‐ring‐labelled linuron (approximately 1 mg L^?1). RESULTS: A linuron‐mineralising bacterium that inhabits river sediment was successfully isolated. The isolate belongs to the genera Variovorax and was designated as strain RA8. Strain RA8 gradually used linuron in basal salt medium (5.2 mg L^?1) with slight growth. In 15 days, approximately 25% of ¹⁴C‐linuron was mineralised to ¹⁴CO₂, with 3,4‐dichloroaniline as an intermediate. Conversely, in 100‐fold diluted R2A broth, strain RA8 rapidly mineralised ¹⁴C‐linuron (5.5 mg L^?1) and more than 70% of the applied radioactivity was released as ¹⁴CO₂ within 3 days, and a trace amount of 3,4‐dichloroaniline was detected. Additionally, the isolate also degraded monolinuron, metobromuron and chlorobromuron, but not diuron, monuron or isoproturon. CONCLUSION: Although strain RA8 can grow on linuron, some elements in the R2A broth seemed significantly to stimulate its growth and ability to degrade. The isolate strictly recognised the structural difference between N‐methoxy‐N‐methyl and N,N‐dimethyl substitution of various phenylurea herbicides. Copyright © 2010 Society of Chemical Industry     

Degradation of the herbicide benzoylprop-ethyl in soil

The degradation of [¹⁴C] benzoyl prop ethyl (SUFFIX,^a ethyl N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate) in four soils has been studied under laboratory conditions. The major degradation product of benzoylprop ethyl at up to 4 months after treatment was its corresponding carboxylic acid (II). On further storage this compound became firmly bound to soil before it underwent a slow debenzoylation process which led to the formation of a number of products including N-3,4-dichlorophenylalanine (IV), benzoic acid, 3,4-dichloroaniline (DCA), which was mainly present complexed with humic acids, and other polar products. Although these polar products were not identified, they were probably degradation products of DCA, since they were also formed when DCA was added to soil. No 3,3′,4,4′-tetrachloroazobenzene (TCAB) was detected in any of the soils at limits of detectability ranging from 0.01-0.001 parts/million. Since N-3,4-dichlorophenylalanine (IV) and 3,4-dichloroaniline were transient degradation products of benzoylprop ethyl, the metabolism in soil of radiolabelled samples of these compounds was also studied. In these laboratory experiments the persistence of the herbicide increased as the organic matter content of the soil increased and the time for depletion of half of the applied benzoylprop ethyl varied from 1 week in sandy loam and clay loam soils to 12 weeks in a peat soil.     

Synthesis and fungicidal activity of tubulin polymerisation promoters. Part 1: pyrido[2,3‐b]pyrazines

BACKGROUND: The excellent fungicidal activity of [1,2,4]triazolo[1,5‐a]pyrimidines suggested the search for further analogues with improved properties. RESULTS: A series of novel trisubstituted pyrido[2,3‐b]pyrazines has been designed and prepared as 6,6‐biheterocyclic analogues of related 5,6‐bicyclic [1,2,4]triazolo[1,5‐a]pyrimidines. Their fungicidal activity was evaluated against the plant pathogens Puccinia recondita Rob. ex Desm. f. sp. tritici (Eriks.) CO Johnston (wheat brown rust), Mycosphaerella graminicola (Fuckel) Schroter (Septoria tritici Rob., leaf spot of wheat) and Magnaporthe grisea (Hebert) Barr (Pyricularia oryzae Cav., rice blast). Structure–activity relationship studies revealed the advantage of a fluoro substituent in position 6 and of a secondary amine in position 8. CONCLUSION: 8‐Amino‐7‐aryl‐6‐halogen‐substituted pyrido[2,3‐b]pyrazines have been prepared as 6,6‐biheterocyclic analogues of similarly substituted triazolopyrimidine fungicides. A concise four‐step synthesis route has been worked out to prepare these novel compounds from commercially available starting materials. [(R)‐(1,2‐Dimethylpropyl)]‐[6‐fluoro‐7‐(2,4,6‐trifluorophenyl)pyrido[2,3‐b]pyrazin‐8‐yl]amine showed excellent activity against three economically important phytopathogens. Copyright © 2009 Society of Chemical Industry     

The breakdown of the triazine herbicide cyanazine in soils and maize

Radioisotope techniques have been used to study the breakdown products that are formed from the herbicide cyanazine ( BLADEX )^a, 2-chloro-4-(1-cyano-1-methylethyl-amino)-6-ethylamino-1,3,5-triazine, in soils and in maize grown in the soils under indoor conditions. In soils of different types cyanazine broke down mainly by conversion of the nitrile group to amide ( II ) and then to an acid ( III ) followed by hydrolysis of the ring chlorine to hydroxyl ( IV ). Dealkylation reactions occurred to only a limited extent in soils. In maize plants grown in treated soils the hydrolysis products, the amide ( II ) and the hydroxy acid ( IV ) were detected as well as appreciable quantities of products ( VI ) and ( VIII ) formed from these by loss of the N-ethyl group. In plants the hydroxy acids ( IV ) and ( VIII ) were present in the free form and there was also evidence for conjugates which were not identified but could be converted to these hydroxy acids, ( IV ) and ( VIII ), on treatment with acids. In these indoor studies the major residues appear to be the hydroxy acid ( IV ) in soils and ( IV ) and its dealkylated analogue ( VIII ) in plants grown in treated soils. These compounds are not herbicides and are of a low order of toxicity to mammals.     

高效液相色谱法检测申嗪霉素在人参及其土壤中的残留

通过田间植株直接施药、定期采样后,采用高效液相色谱法检测人参及其土壤中申嗪霉素的残留量,研究了其在人参及田间土壤中的消解动态和最终残留量,并在室内模拟环境条件下,初步探讨了土壤类型及含水量、微生物、温度因素对其在土壤中降解的影响。结果表明:1%申嗪霉素悬浮剂在人参叶片及其田间土壤中的消解动态均符合一级动力学方程,消解半衰期分别为3.4和3.0d;以推荐高剂量有效成分用量18g/hm2(制剂用量为1.8kg/hm2)和推荐高剂量的1.5倍有效成分用量27g/hm2(制剂用量为2.7kg/hm2)2个施药剂量喷雾施药,距最后一次施药后7、14和21d采收的人参鲜根和干根中申嗪霉素的最终残留量均低于检测限(0.002mg/kg);室内模拟环境条件下,微生物作用增强、有机质含量高、温度升高和含水量增加,均可有效促进土壤中申嗪霉素的降解。     

New melanin biosynthesis inhibitors and their structural similarities

Relationships between their activities as blast control agents, and their abilities to inhibit mycelial melanisation on a nutrient agar, are described for 103 substituted benzothiazol-2(3H)-ones, benzoxazol-2(3H)-ones, indolin-2-ones, quinolin-2(1H)-ones, 1,2,3,4-tetrahydroquinolin-2-ones, benzo-1,4-thiazin-3(2H)-ones and benz-1,4-oxazin-3(2H)-ones, and some corresponding thiones. Several compounds in the respective series had a high protective activity and an antimelanisation activity against the blast fungus Pyricularia oryzae; furthermore, there was a good correlation in both of these activities, indicating that these compounds belong to the group of melanin biosynthesis inhibitors. Structural similarities of these compounds can be identified as follows: (a) having a benzo-bicyclic ring system; (b) containing a nitrogen atom in one ring at a position alpha to the benzene ring system; and (c) substitution, at the ring nitrogen atom, at the peri position in the aromatic ring relative to the nitrogen atom, and at the position alpha to the nitrogen atom in the ring system, with a double bond such as in carbonyl and thiocarbonyl groups. Among the compounds that have been proposed as melanin biosynthesis inhibitors, the chemical structures of tricyclazole, pyroquilon, 4,5-dihydro-4-methyltetrazolo[1,5-a]quinazolin-5-one (PP-389), [1,2,4]-triazolo[4,3-a]quinoline and 1-methylquinolin-2(1H)-one exhibit the structural similarities described above; however, 4,5,6,7-tetrachlorophthalide, 2,3,4,5,6-pentachlorobenzyl alcohol and N-substituted-2,3,4,5-tetrachloro-6-(hydroxymethyl)benzamides do not have such similarities in their chemical structures.     

Degradation of the herbicide flamprop-methyl in soil

The degradation of the wild oat herbicide flamprop-methyl [methyl DL -N-benzoyl-N-(3-chloro-4-fluorophenyl)alaninate] in four soils has been studied under laboratory conditions using ¹⁴C-1abelled samples. The flamprop-methyl underwent degradation more rapidly than its analogue flamprop-isopropyl. However, similar degradation products were formed, namely the corresponding carboxylic acid and 3-chloro-4-fluoroaniline. The latter compound occurred mainly as ‘bound’ forms although evidence was obtained of limited ring-opening to give [¹⁴C]carbon dioxide. The time for depletion of 50% of the applied herbicide was approximately 1-2 weeks in sandy loam, clay and medium loam soils and 2-3 weeks in a peat soil.     

The metabolism of the herbicide flamprop-methyl in rats and some comparative data for dogs,mice and rabbits

[¹⁴C]Flamprop-methyl administered orally to rats (3-4 mg kg^?1 body weight) was excreted mostly via the faeces (78.7 and 61.6% in males and females, respectively). Elimination was rapid and 90% of the dose of ¹⁴C was excreted in faeces and urine 0-48 h after dosing. The distribution of ¹⁴C between faeces and urine was different in males and females. No expired [¹⁴C]carbon dioxide was detected and less than 2% of the dose remained in the animals 4 days after dosing. The predominant metabolic pathway was hydrolysis of the ester bond to afford the carboxylic acid which was excreted unchanged and as its glucuronide conjugate. Aromatic hydroxylation occurred at the para- and meta-positions of the N-benzoyl ring. N-(3)-Chloro- 4-fluorophenyl-N-(3,4-dihydroxybenzoyl)-DL -alaninate was also formed. This hydroxylated form of flamprop-methyl was partially O-methylated at the 3-hydroxy group. Flamprop-methyl was also metabolised and eliminated rapidly by dogs, mice and rabbits. The last of these three species afforded very little aromatic hydroxylation and also differed from the others in that the metabolites were eliminated mostly in the urine. Aromatic hydroxylation lay in the order: male rat = female rat > dog= mouse>rabbit (female).     

The stability and degradation of a new biological pesticide,pyoluteorin

BACKGROUND: Pyoluteorin (Plt) is a polyketide metabolite produced by fluorescent Pseudomonas. It controls a wide range of pests, including bacteria, epiphytes and weeds. It could become widely used as a new biological pesticide. However, ignorance of the stability of Plt is an obstacle to its use. This work studied the stability of Plt and its degradation under different conditions, including temperature, pH and UV–visible light irradiation. RESULTS: Degradation of Plt followed first‐order reaction kinetics. The degradation rate increased with increased temperature. The derived activation energy was 11.06 J mol^?1 K^?1. Plt was relatively stable in neutral solutions, in contrast to acid and alkaline solutions. Visible irradiation had no obvious effect on Plt stability, while UV irradiation greatly decreased its half‐life to 3–4 days, in contrast to its half‐life of 25 days in the dark. CONCLUSION: Plt is relatively stable in pure water solutions and at room temperature, with a half‐life of more than 20 days. However, UV irradiation and acidic or alkaline solutions will enhance its degradation, reducing its half‐life by a factor of 0.1–0.3. Before Plt is widely used as a pesticide, it might be necessary to modify the structure of Plt to make it more stable. Copyright © 2009 Society of Chemical Industry     

Inhibition of the fucosterol-24(28)-epoxide cleavage enzyme of sitosterol dealkylation in Spodoptera littoralis larvae

The conversion of sitosterol into cholesterol and the effect of inhibitors on the dealkylation reaction has been studied in Spodoptera littoralis Boisd. Using a microsomal preparation from the midgut of the larvae [³H]fucosterol and [³H]fucosterol-24,28-epoxide were converted into desmosterol and cholesterol in vitro, and a series of inhibitors were tested using the latter substrate. Triadimefon [1-(4-chlorophenox)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one] strongly inhibited the cleavage enzyme at 2 μM. In a functional group study we observed that (i) the phenoxy substituent was more strongly inhibitory than the corresponding benzyl, and (ii) when the ketone is reduced to the secondary alcohol in either phenoxy or benzyl series, inhibition decreased markedly. In the benzyl series of compounds we found that (iii) a 2,4- or 2,6-dichlorophenyl gave greater inhibition than mono-, tri-, or pentachlorophenyl derivatives, and (iv) changing the heterocyclic ring gave activity in the order 2-pyridyl=3-pyridyl=imidazole>pyrazole>triazole. In the triazole series, substitution of the hetero ring did not abolish inhibition. When either triadimefon or 22,25-diazacholesterol was incorporated into a diet (1000 ppm) containing sitosterol plus campesterol as the only sterol supplements and fed to final larval instar insects, the weight of the insects throughout the instar was reduced and the duration of the instar increased. Insects reared from the early third-instar stage on such a diet containing amounts of triadimefon had reduced percentages of cholesterol and desmosterol in the final larval instar with a proportional increase in the sitosterol level. Thus, inhibition of side chain cleavage has been obtained in vitro and in vivo, but the high concentrations of inhibitor required preclude the enzyme as a target for a novel class of insecticide.     

Enhanced Mineralization of [14C]Atrazine in Kochia scoparia Rhizospheric Soil from a Pesticide-Contaminated Site

Mineralization of atrazine (6-chloro-N²-ethyl-N⁴-isopropyl-1,3,5- triazine-2,4-diamine) in soil treated with a mixture of atrazine and metolachlor (2-chloro-6′-ethyl-N-(2-methoxy-1-methylethyl)acet-o-toluidide at concentrations typical of point-source contamination (50 μg g⁻¹ each) was significantly greater (P<0·001) in rhizospheric soil from Kochia scoparia (L.) Roth., a herbicide-resistant plant, than in non-vegetated and control soils. Soils were collected from an agrochemical dealership contaminated with several herbicides, including atra-zine, metolachlor, trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine and pendimethalin (N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidene), at concentrations well exceeding the field application rates. Mineralization rates of ring-labeled atrazine in both rhizospheric and non-vegetated soils were quite high (>47% of the initial ¹⁴C applied after 36 days) compared to literature values. These results suggest that plants such as Kochia might be managed at pesticide-contaminated sites to help facilitate microbial degradation of wastes such as atrazine in soil.     

Oxidative degradation of chlortoluron,propiconazole, and metalaxyl in suspension cultures of various crop plants

The metabolism of chlortoluron, (N′-(3-chloro-4-methylphenyl)-N,N-dimethylurea), propiconazole (1-[2-(2′,4′-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole), and metalaxyl (dl-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl) alanine methyl ester) was investigated in suspension cultures of crop species for which differences in metabolism had been demonstrated at the intact plant level. Uptake and metabolism of chlortoluron by cultures of Italian rye-grass (Lolium multiflorum) was slow, the metabolites detected (42% of applied radioactivity after 13 days) being products of ring methyl oxidation and N-monodealkylation reactions. In sharp contrast, metabolism in a cotton (Gossypium hirsutum) suspension culture was extremely fast (72% after 4 hr) and was attributed to extensive N-didealkylation in addition to rapid ring methyl oxidation. This rate of metabolism also implied a very rapid uptake of chlortoluron by the cotton culture. ¹⁴C-labelled propiconazole became rapidly associated with cells of wheat (Triticum aestivum) and rice (Oryza sativa) following treatment of suspension cultures. Uptake was initially more rapid in the rice culture (36% of applied radioactivity after 8 h compared to 19% for wheat) which, together with a slower rate of metabolism, resulted in more unchanged propiconazole being associated with rice cells. On a parts-per-million basis these results indicated an apparent 10-fold accumulation of propiconazole in rice cells compared to 5-fold in the wheat culture. Propiconazole metabolite patterns were similar in cultures of both species and indicated side-chain hydroxylation as the principal pathway. Uptake of metalaxyl was slow in suspension cultures of both lettuce and potato (≅ 20% after 17 days). Subsequent metabolism was also slow but appeared to be limited by the poor rate of uptake. Both cultures were found to be similarly versatile with respect to metabolic attack on metalaxyl, which included ring methyl hydroxylation, aryl hydroxylation, ester cleavage, ether cleavage (O-dealkylation), and N-dealkylation (side-chain cleavage), the hydroxylation reactions being quatitatively the more important. The results for all three pesticides are compared to those obtained previously from studies with intact plants of the same species.     

Fate of [14C]diflubenzuron on cotton and in soil

Aqueous suspensions and oil emulsions of a commercial [¹⁴C]diflubenzuron (N-[[(4-chlorophenyl)amino]carbonyl]-2,6-difluorobenzamide) formulation (Dimilin W-25) remained on the leaf surface of greenhouse-treated plant tissues. Absorption, translocation, and metabolism of the [¹⁴C]diflubenzuron were not significant. Less than 0.05% of the applied ¹⁴C was found in newly developed plant tissues 28 days after spray treatment. [¹⁴C]Diflubenzuron was degraded in soil. After 91 days, biometer flask studies showed that 28% of the ¹⁴C incorporated into the soil as [¹⁴C]diflubenzuron was recovered as ¹⁴CO₂. Major dichloromethane-soluble soil residues were identified as unreacted [¹⁴C]diflubenzuron and [¹⁴C]4-chlorophenylurea. A minor unknown degradation product cochromatographed with 2,6-difluorobenzoic acid. Insoluble ¹⁴C-residues increased with time and represented 67.8% of the residual ¹⁴C in the soil 89 days after treatment. Cotton plants grown for 89 days in [¹⁴C]diflubenzuron-treated soil contained only 3% of the ¹⁴C applied to the soil. Small quantities of acetonitrile-soluble [¹⁴C]4-chlorophenylurea were isolated from the foliar tissues. Root tissues contained small amounts of [¹⁴C]diflubenzuron and trace quantities of a minor ¹⁴C-product that chromotographed similarly to 2,6-difluorobenzoic acid. Most of the ¹⁴C in the plant tissues (84–93%) was associated with an insoluble residue fraction 89 days after treatment.     

Design, synthesis, insecticidal activity and structure-activity relationship of 3,3-dichloro-2-propenyloxy-containing phthalic acid diamide structures

BACKGROUND: Phthalic acid diamide derivatives are among the most important classes of synthetic insecticides. In this study, a 3,3‐dichloro‐2‐propenyloxy group, the essential active group of pyridalyl derivatives, was incorporated into phthalic acid diamide derivatives with the aim of combining the active groups to generate more potent insecticides. RESULTS: Thirty‐one new phthalic acid diamides were obtained, and these were characterised by ¹H and ¹³C NMR. The structure of N²‐[1,1‐dimethyl‐2‐(methoxy)ethyl]‐3‐iodo‐N¹‐[4‐(3,3‐dichloro‐2‐propenyloxy)‐3‐(trifluoromethyl)phenyl]‐1,2‐benzenedicarboxamide was determined by X‐ray diffraction crystallography. The insecticidal activities of the compounds against Plutella xylostella were evaluated. The title compounds exhibited excellent larvicidal activities against P. xylostella. Structure‐activity relationships revealed that varying the combination of aliphatic amide and aromatic amide moieties, or the nature and position of substituent Y on the aniline ring, could aid the design of structures with superior performance. CONCLUSION: A series of novel phthalic acid diamides containing a 3,3‐dichloro‐2‐propenyloxy group at the 4‐position of the aniline ring were designed and synthesised. Structure‐activity relationships with the parent structure provided information that could direct further investigation on structure modification. Copyright © 2012 Society of Chemical Industry     

Factors influencing rates of degradation of an arylamide and a benzoic acid in subsoils

The kinetics of fundamental reactions (hydrolytic, oxidative and reductive) involved in the degradation of organic compounds such as pesticides in subsoils were investigated using the model compounds N‐(4‐nitrophenyl)propanamide and 4‐nitrobenzoic acid. The rates of hydrolysis of N‐(4‐nitrophenyl)propanamide were also measured in aqueous buffers, hydrolysis being extremely slow at neutral pH; its degradation in three soils was by microbially mediated hydrolysis, being very much faster than aqueous hydrolysis at the same pH. Rates of degradation of N‐(4‐nitrophenyl)propanamide in subsoils were initially up to thirty times slower than those in topsoil, and in some subsoils degradation showed a marked lag‐phase of between 72–144 h. For 4‐nitrobenzoic acid, a similar lag‐phase of slow degradation, followed by a phase of rapid degradation, was observed in both topsoils and subsoils. Remarkably, the rapid phases of degradation in subsoils often approached rates occurring in the corresponding topsoil. No reduction of the nitro group on either compound was observed, even in a water‐saturated subsoil. Sometimes there were differences in the length of the lag‐phases measured for replicate samples of subsoils; also, application of lower concentrations of 4‐nitrobenzoic acid generally gave rise to shorter lag‐phases. Partial sterilization of soils by azide greatly slowed breakdown of both compounds, confirming the important role of microbial degradation. Such behaviour is consistent with the variable build‐up of populations of micro‐organisms able to degrade the compound, smaller populations being able to deal rapidly with the lower concentrations. After applying a second dose of 4‐nitrobenzoic acid to soil, degradation was rapid but initially not as fast as the final rates during breakdown of the first treatment. Hence, soil may only partially retain the ability to degrade previously applied xenobiotics. Nonetheless it is noteworthy that, even in deep subsoils, indigenous microbial populations can rapidly adapt to degrade certain small organic molecules. © 2000 Society of Chemical Industry     

Synthesis and pesticidal activities of some substituted 1,2,4-triazines

A series of 5,6-diphenyl-3-substituted-thio-1,2,4-triazines ( II-V ) was prepared by treating 5,6-diphenyl-1,2,4-triazine-3-thiol ( I ) with corresponding electrophiles. Condensation of IV or V with 1,2-phenylenediamines gave 2-[(5,6-diphenyl-1,2,4-triazin-3-yl) thiomethyl-1H-benzimidazoles] ( VI ). IV was converted into its corresponding hydrazide ( VII ) by the action of hydrazine hydrate. N-Benzylidene derivatives ( VIII ) were prepared by the condensation of VII with appropriate aryl or heterocyclic aldehydes. The pesticidal activities of all the compounds thus synthesised were determined.