Pesticidal properties of parthenin (from Parthenium hysterophorus) and related compounds

Eleven sesquiterpene lactone derivatives of parthenin ( 1 ), obtained from wild feverfew, Parthenium hysterophorus, were prepared by chemical and photochemical transformations. The compounds tested were a pyrazoline adduct ( 2 ) of parthenin, its cyclopropyl ( 3 ) and propenyl ( 4 ) derivatives, anhydroparthenin ( 5 ), a dihydro‐deoxygenated product ( 6 ), a formate ( 7 ) and its corresponding alcohol ( 8 ) and acetate ( 9 ), a rearranged product ( 10 ), lactone ( 11 ) and hemiacetal ( 12 ). All these derivatives, along with parthenin, were tried for their antifeedant action against sixth‐instar larvae of Spodoptera litura, for insecticidal activity against the adults of store grain pest Callosobruchus maculatus, for phytotoxic activity against Cassia tora, and for nematicidal activity against the juvenile stage‐II (J₂) of the root knot nematode Meloidogyne incognita. Antifeedent bioassay revealed that parthenin is moderately antifeedant. Among the derivatives, the saturated lactone ( 11 ) was found to be about 2.25 times more active than parthenin. The pyrazoline adduct ( 2 ) was found to be the most effective as an insecticide, with LC₅₀ values after 24, 48 and 72 h of 96, 43 and 32 mg litre⁻¹, respectively, which are comparable with neem extract. Compound 4 was found to be the most effective inhibitor of germination and seedling growth of C tora, with ID₅₀ values for germination, plumule length and radicle length of 136, 326 and 172 compared with 364, 738 and 427 mg litre⁻¹, respectively, for parthenin. Compound 10 was found to be the most effective in terms of nematicidal activity. The LC₅₀ values for this compound were 273 and 104 mg litre⁻¹, respectively, after 48 and 72 h compared with 862 and 512 mg litre⁻¹ observed for parthenin after 48 and 72 h. © 2001 Society of Chemical Industry     

Laboratory Evaluation of the Novel Naturally Derived Compound Spinosad against Ceratitiscapitata

Laboratory studies were conducted to determine the effect of the naturally derived compound spinosad on Ceratitis capitata Wied. (Diptera, Tephritidae). The organophosphate fenthion was used as a standard. Direct dose-dependent mortality and reduced fecundity were observed in oral treatment of adults with spinosad. The LC₉₀ values 14 h and seven days after treatment were 19·50 and 0·49 mg litre⁻¹ respectively. Fenthion was less active (the LC₅₀ eight days after treatment was 1·17 mg litre⁻¹) and did not affect the fecundity of the fly. Adults were also very susceptible to spinosad and fenthion via residual contact. For spinosad, 100% mortality was recorded 48 h after treatment for a dose of 10 mg litre⁻¹. Spinosad was more effective than fenthion in suppressing larval development when neonate larvae were reared on treated diet supplemented with a range of concentrations from 0·02 to 0·83 mg kg⁻¹ diet. Last-instar larvae were much less susceptible to spinosad or fenthion when exposed via dipping or when they pupated in treated medium and both products had similar performance. A lack of ovicidal activity was observed in direct egg-treatments with spinosad but significant reductions from 1 mg litre⁻¹ onwards were recorded for fenthion.     

DPX-MP062—a potent compound for controlling the Egyptian cotton leafworm Spodoptera littoralis (Boisd.)

The effects of DPX-MP062 [methyl 7-chloro-2,3,4a,5-tetrahydro-2-[methoxycarbonyl(4-trifluoromethoxyphenyl)carbamoyl] indeno[1,2-e][1,3,4] oxadiazine-4a-carboxylate] a broad-spectrum insecticide with a novel mode of action, on the Egyptian cotton leafworm, Spodoptera littoralis, were studied in laboratory experiments. Egg hatch was affected by high concentrations (125 mg AI litre^-1) of DPX-MP062. Larvae that hatched from treated eggs were significantly affected at concentrations of 12·5 mg AI litre^-1 and greater. Larvae were fed castor bean leaves treated with DPX-MP062; 1st-instar larvae were the most susceptible development stage. Pupation and adult formation were determined in assays with 5th-instar larvae. There was strong suppression of adult formation; 65 and 91% at 0·5 and 0·75 mg AI litre^-1, respectively. Highly affected larvae died before pupation; slightly affected ones reached pupation 2–4 days later, were smaller than larvae in the untreated control, and were sometimes unable to develop into normal adults. Comparatively high concentrations (50 and 100 mg AI litre^-1) of the test compound were necessary to affect adults by ingestion, but no effects from contact application could be determined at a concentration of 100 mg AI litre^-1. © 1998 Society of Chemical Industry     

Depression of the minimum concentration of methyl bromide effective against diapausing warehouse moth larvae at 15°c by prior exposure at a moderate concentration

Warehouse moth (Ephestia elutella) larvae in diapause were exposed at 15°C to methyl bromide at 8 mg litre^?1 for 14.5 h and then immediately exposed at a lower concentration. The exposure at 8 mg litre^?1 killed 44–69% of the larvae treated. Subsequent concentrations down to 1.1 mg litre^?1 obeyed Haber's rule (concentration × time= k, a constant for mortality), but a higher concentration-time product (ct) was required for over 90% kill at 0.8 mg litre^?1. Only concentrations down to 1.9 mg litre^?1 obey Haber's rule if there is no prior exposure at a higher concentration. Although minimum effective concentrations are lower at 15°C than at 25°C, exposure at a higher concentration depresses the subsequent level to a similar extent at each temperature. The contribution to the efficacy of a treatment, of low concentrations persisting at the end of fumigation, is thus likely to be even greater at moderate to low temperatures than at 25°C. The implications for the development of resistance to methyl bromide are discussed.     

Susceptibility pattern and development of resistance in the diamondback moth,Plutella xylostella L,to Bacillus thuringiensis Berl var kurstaki in India

Base‐line susceptibility for six‐day‐old larvae of the diamondback moth, Plutella xylostella, against Bacillus thuringiensis var kurstaki (Biobit^®) was studied by a cabbage leaf disc dip bioassay technique. Diamondback moth from 13 locations in seven different states spread over a distance of about 3000 km longitudinally was used for these studies. Forty‐eight‐hour LC₅₀ values varied from 1.0 to 10.97 mg AI litre⁻¹. Further investigations on the development of resistance under laboratory conditions showed an increase in LC₅₀ from 2.76 (for unselected F₁ generation) to 5.28 mg AI litre⁻¹ (for selected F₉ generation), using a selection concentration of 6.4 mg AI litre⁻¹. This suggested a possibility of the development of resistance under field conditions if there were to be extensive and indiscriminate use of B thuringiensis. These findings are discussed in relation to integrated pest management and the mechanisms of resistance in resistance management tactics. © 2000 Society of Chemical Industry     

Sensitivity of European Plasmopara viticola populations to cymoxanil

Between 1995 and 1997, 278 grape downy mildew (Plasmopara viticola) populations originating from European vineyards were characterised for their sensitivity to cymoxanil in a leaf-disc assay. The sensitivity profile revealed a wide distribution, with minimum inhibitory concentrations (MIC) ranging from 10 to more than 800 mg litre⁻¹. EC₅₀ values ranged from 1 to more than 800 mg litre⁻¹ with an average of 125 mg litre⁻¹. The sensitivity distribution was stable between 1995 and 1997. Surprisingly, populations from Portugal appeared significantly more sensitive than those from France or Italy, which could not be linked to differential cymoxanil usage in these countries. P viticola populations collected outside Europe and never exposed to cymoxanil appeared significantly more sensitive than exposed European populations, with an average EC₅₀ value of 10 mg litre⁻¹. The level of sensitivity of European P viticola populations was relatively unaffected by the number of cymoxanil applications made during a season or by the number of years of cymoxanil use. No link was found between the level of sensitivity in the leaf-disc assay and the level of performance of the cymoxanil mixtures used in the fields where the populations originated. Specific field trials conducted in Italy and Portugal have shown that the performance of cymoxanil-based mixtures remained good even on populations of the grape downy mildew fungus characterised as less sensitive in the leaf-disc assay. While there are no baseline sensitivity data for pre-commercialisation P viticola populations, the results of our study suggest that a shift in sensitivity (12.5-fold) may have occurred in some areas since introduction of cymoxanil on grapes nearly 20 years ago. Because cymoxanil is never used alone, it is difficult to determine whether or not practical resistance is occurring in European vineyards. © 1999 Society of Chemical Industry     

Effect of temperature on the toxicity of low concentrations of methyl bromide to diapausing larvae of the warehouse moth Ephestia elutella (Hübner)

The performance of low concentrations of methyl bromide against diapausing larvae of Ephestia elutella at 15 and 25°C was assessed in extended exposure periods. At concentrations of 1.9 mg litre^?1 and below, test batches required higher concentration-time (ct) products for 100% kill at 25°C than at 15°C. The minimum concentration at which the concentration: time relationship still applied was between 1.3 and 1.9 mg litre^?1 at 15°C, whereas at 25°C it was between 2.7 and 4.0 mg litre^?1. For many individuals within each population sample, however, lower concentrations at moderate dosage levels remained lethal. At 25°C, a ct product of about 90 mg litre^?1 h gave between 53 and 77% kill at 6.1, 4.0, 2.7 and 1.9 mg litre^?1. The trends observed suggest that the most tolerant members of the population have an enhanced ability to detoxify methyl bromide at the higher temperature. The implications of the results for the build-up of resistance and for practical control measures are discussed.     

Laboratory and field evaluation of spinosad against the gypsy moth,Lymantria dispar

The toxicity of the naturally derived insecticide spinosad was tested against the gypsy moth, Lymantria dispar. Bioassays using red oak leaf disks, treated with spinosad in a Potter spray tower, yielded an LC₅₀ value of 0.0015 µg AI cm⁻² (3‐day exposure; 13‐day evaluation; 2nd instar larvae). Applied to foliage to run‐off in the laboratory (potted red oak seedlings) and the field (4 m‐tall birch trees), spinosad effectively controlled 2nd instar larvae at concentrations ranging from 3 to 50 mg litre⁻¹. Toxicity in the laboratory, and efficacy and persistence in the field, were comparable to those achieved with the insecticide permethrin. Laboratory studies supported field observations that control was achieved in part by knockdown due to paralysis. In addition, laboratory results demonstrated that crawling contact activity may play an important role in field efficacy; 50% of treated larvae were paralyzed 16 h after a 2‐min crawling exposure to glass coated with a 4 mg litre⁻¹ spinosad solution. © 2000 Society of Chemical Industry     

The algaecidal activity of some substituted 1,3-diphenylureas, 1-phenyl-3-(2-pyridyl)ureas and the corresponding thioureas

Twelve ureas and thioureas with 1,3-diphenyl- and 1-phenyl-3-(2-pyridyl) were tested as potential herbicides in a simple screen against two species of algae Chlorella fusca and Anabaena variabilis. Several were shown to inhibit growth at 100 mg litre^?1 but only 1-[2,4-bis(azidosulphonyl)phenyl]-3-(2-pyridyl)urea and 1,3-bis(4-isopropyl- idenehydrazinosulphonylphenyl)thiourea showed any activity at 1 mg litre^?1. This compares with the well-established urea herbicide diuron which, in identical tests, gives similar inhibition of growth at concentrations as low as 0.01 mg litre^?1.     

Laboratory studies with antifeedants against larvae of Boarmia (Ascotis) selenaria on alfalfa

The antifeedant effect of five organotin compounds (fentin acetate, fentin hydroxide, fentin chloride, cyhexatin and fenbutatin oxide) and of three other compounds known to possess antifeeding activity (guazatine triacetate, 4′-chloroacetophenone isobutyrylhydrazone and thiram) was investigated by feeding treated alfalfa to larvae of Boarmia selenaria. The three fentins and cyhexatin were highly active at 0.1 g litre^?1, the order of activity at this concentration being fentin chloride > fentin hydroxide > fentin acetate ? cyhexatin, whereas the other compounds were practically inactive at either this or a somewhat higher concentration (0.5 g litre^?1). Guazatine triacetate had a concentration-independent antifeedant effect at much higher concentrations (5–20 g litre^?1).     

Glutamic oxaloacetic transaminase (GOT) and glutamic pyruvic transaminase (GPT) enzyme activities in different tissues of Sarotherodon mossambicus (Peters) exposed to a carbamate pesticide,carbaryl

The activity levels of glutamic oxaloacetic transaminase (GOT) and glutamic pyruvic transaminase (GPT) enzymes were estimated in liver, muscle and brain tissues of the fish, Sarotherodon mossambicus (Peters), which had been exposed to sub-lethal (3 mg litre⁻¹) and lethal (25 mg litre⁻¹) concentrations of the carbamate insecticide carbaryl. Based on the results obtained, the changes in GOT and GPT levels in liver, muscle and brain following different periods of sub-lethal and lethal carbaryl exposures suggested that S mossambicus showed adaptive elevation in the activity levels of the two aminotransferase enzymes in the tissues, thereby probably aiding gluconeogenesis through transamination of glucogenic amino acids to meet the energy demand under carbaryl toxicity. © 1999 Society of Chemical Industry     

Effect of short exposures to a high concentration on the subsequent toxicity of low concentrations of methyl bromide to diapausing larvae of the warehouse moth,Ephestia elutella (Hübner)

Ephestia elutella larvae in diapause were exposed at 25°C to methyl bromide at 12 mg litre^?1 for 3.5 or 7.5 h and then immediately exposed to a lower concentration. The minimum effective concentration (that at which Haber's rule, concentration × time = k, a constant for mortality, still applied) was about 3 mg litre^?1 in tests with no previous exposure toa high concentration, but it was about 2.5 mg litre^?1 for individuals surviving a 3.5 h exposure to 12 mg litre^?1, and was about 1.6 mg litre^?1 for those surviving a 7.5 h exposure to 12 mg litre^?1. These exposures to 12 mg litre^?1, respectively, killed 2–20% and 50–75% of larvae exposed, and hence the smaller the proportion of survivors of exposure to a high concentration, the lower the minimum effective concentration needed against them. Thus the low concentration persisting at the end of a practical fumigation should contribute significantly to the success of the treatment and be much more effective than any similar low concentration present soon after the introduction of gas.     

Effect of ABT on the activity and rate of degradation of isoproturon in susceptible and resistant biotypes of Phalaris minor and in wheat

The effect of the monooxygenase inhibitor, 1-aminobenzotriazole (ABT) on isoproturon phytotoxicity and metabolism was studied in resistant (R) and susceptible (S) biotypes of Phalaris minor and in wheat (Triticum aestivum). Addition of ABT (2·5, 5 and 10 mg litre^-1) to isoproturon (0·25, 0·5, 1, 2 and 4 mg litre^-1) in the nutrient solution significantly enhanced the phytotoxicity of isoproturon against the R biotype. Isoproturon at 0·25 mg litre^-1 reduced the dry weight (DW) of the S biotype by 77%, whereas the R biotype required 4·0 mg litre^-1 for similar reduction. Addition of 10 mg litre^-1 of ABT to the 0·25 mg litre^-1 isoproturon caused 71 and 82% reduction in DW of R and S biotypes, respectively. Wheat was more sensitive to the mixture of isoproturon and ABT than the R biotype of P. minor. Reduced concentrations of ABT in the mixture from 10 to 2·5 mg litre^-1 increased the DW of the R biotype more than that of the S biotype. The R biotype metabolised [¹⁴C]isoproturon at a faster rate than the S biotype. ABT (5 mg litre^-1) inhibited the degradation of [¹⁴C]isoproturon in both biotypes of P. minor and in wheat. In the presence of ABT, about half of the applied [¹⁴C]isoproturon remained as parent herbicide in all the three species after two days. The metabolites were similar in the R and S biotypes and wheat as determined by co-chromatography with reference standards and mass spectroscopy (MS). ABT inhibited the appearance of the hydroxy and monomethyl metabolites and their conjugates in all the test plants. These results suggest that the activity of the enzymes responsible for the degradation of isoproturon is greater in the R than in the S biotype of P. minor, resulting in its rapid detoxification. Incorporation of the monooxygenase inhibitor ABT into the nutrient solution greatly inhibited the degradation of [¹⁴C]isoproturon in the R biotype and increased its phytotoxicity. Both hydroxylation and N-dealkylation reactions were found to be sensitive to ABT; inhibition of hydroxylation was greater than that of demethylation. Since ABT could not completely suppress isoproturon degradation, it is possible that more than one monooxygenase is involved. © 1998 SCI     

Synthesis and Evaluation of New Ethyl 2,3- Dihydro-3-oxoisothiazolo[5,4-b]pyridine- 2-alkanoate Derivatives as Potential Herbicides

Several ethyl 2,3-dihydro-3-oxoisothiazolo[5,4-b]pyridine-2-alkanoate derivatives were synthesized as herbicides. Only 5-methyl derivatives inhibited both hypocotyl and root growth in the lettuce (Lactuca sativa L.) seedling test at 100 mg litre^-1. Only ethyl propionate and valerate derivatives showed significant inhibition at 0·1 mg litre^-1, whereas ethyl acetate or butyrate derivatives were inactive. Contrary to unoxidized derivatives, the inhibitory effect of 1-oxide and 1,1-dioxide derivatives was strongly dependent on concentration; ethyl 2,3-dihydro-5-methyl-3-oxoisothiazolo[5,4-b]pyridine-2-propionate 1,1-dioxide inhibited 100% of germination at 100 mg litre^-1 and 45% of lettuce seedling growth at 0·1 mg litre^-1. Quantitative structure–inhibition of growth relationship analysis carried out by adaptive least-squares (ALS) method gave a good correlation with small and hydrophobic 5-substituents as well as with odd carbon-chain ethyl alkanoates in position 2. Active compounds did not show auxin-like activity from 0·1 to 100 mg litre^-1. © 1997 SCI.     

Synthesis and insecticidal activity of novel 1,3,4-oxadiazolin-5-one and pyrazolin-5-one derivatives

A series of novel 2-(2,4,6-trisubstituted phenyl)-1,3,4-oxadiazolin-5-one derivatives and 3-(2,4,6-trichlorophenyl)pyrazolin-5-one derivatives were synthesized and evaluated for insecticidal activity. It was found that a moderately bulky alkyl group, such as a tert-butyl group, on the heterocyclic ring, and a trifluoromethyl group on the benzene ring were optimal substituents on the molecule. The oxygen atom in the oxadiazoline ring was essential for insecticidal activity. Of the compounds assayed, 4-tert-butyl-2-(2,6-dichloro-4-trifluoromethylphenyl)-1,3,4-oxadiazolin-5-one gave the highest activity against Nephtotettix cincticeps, with an LC₅₀ value of 0.51 mg litre⁻¹. © 1999 Society of Chemical Industry     

Effect of Hydrogen Cyanide and Carbonyl Sulphide on the Germination and Plumule Vigour of Wheat

Several factors which may influence the germination of wheat fumigated with hydrogen cyanide or carbonyl sulphide were investigated. Dosages of hydrogen cyanide ranged from 10 mg litre⁻¹ for 24-h exposure up to 150 mg litre⁻¹ for 96-h exposure. Dosages of carbonyl sulphide ranged from 25 mg litre⁻¹ for 24-h exposure up to 500 mg litre⁻¹ for 72-h exposure. The experiments were conducted on wheat of 11·4, 13·8 and 15·7% moisture content. The higher levels of these fumigants exceed those needed for control of insects in wheat. Germination was not diminished and may have been slightly enhanced with hydrogen cyanide, but was diminished by high levels of carbonyl sulphide in the drier wheat. The plumule length was reduced following all dosages of hydrogen cyanide, but only after high dosages of carbonyl sulphide, especially on the driest wheat. It is concluded that hydrogen cyanide and carbonyl sulphide could be used to control insects in wheat without affecting seed viability, provided that concentrations are carefully controlled.     

Effect of fipronil seed treatments on the germination and early growth of rice

Fipronil seed treatments were evaluated to determine whether they directly influence germination and subsequent seedling growth in rice (Oryza sativa L). Continuous seed exposure to fipronil (four days) at 2 000 mg litre⁻¹ significantly impaired germination (P < 0.001). When exposure was restricted to a 1-h period 48 h after the initiation of germination, early post-germination growth was also impaired (assessment two days after exposure, P < 0.05). The proportion of seeds satisfying our criteria for normal germination fell by 2.3 and 2.6% respectively across 17 cultivars. Cultivar effects were highly significant (P < 0.001). When exposure to fipronil (2 000 mg litre⁻¹) was restricted to 2 h at initial seed wetting no significant growth impairment occurred. No significant differences (P > 0.05) were found between shoot lengths or root system dry weights of control plants and plants developing from seed exposed continuously (two days) to fipronil at rates of up to 2 000 mg litre⁻¹ during germination and harvested nine days after sowing. Treating germinated seed with fipronil for 1 h immediately prior to sowing at rates of up to 4 000 mg litre⁻¹ did not result in significant changes (P < 0.05) in plant growth parameters at either nine or 25 days after sowing. No evidence of fipronil having a direct phytostimulatory effect on rice was obtained. © 1999 Society of Chemical Industry     

Anthelmintic Actions of the Cyclic Depsipeptide PF1022A and its Electrophysiological Effects on Muscle Cells of Ascaris suum

The cyclic depsipeptide PF1022A, given orally to mice, showed very good anthelmintic activity against Heligmosomoides polygyrus and Heterakis spumosa at 50 mg kg⁻¹. In vitro, PF1022A was very active against Trichinella spiralis and had good activity against Nippostrongylus brasiliensis at 1 μg ml⁻¹. An 18-membered enniatin analogue, JES 1798, showed good activity only against N. brasiliensis at 10 μg ml⁻¹. The optical antipode of PF1022A had poor activity even at 100 μg ml⁻¹. The effects of PF1022A on the membrane potential and input conductance of somatic muscle of Ascaris suum were examined using a two-microelectrode current-clamp technique. PF1022A did not antagonize the effects of the selective nicotinic agonist levamisole. PF1022A and an analogue, JES 1798, but not the PF1022A antipode, produced a small time-dependent increase in input conductance associated with no potential change. The increase in input conductance did not occur in the Cl⁻-free bathing solution, suggesting that the increase in input conductance was mediated by Cl⁻ ions. The addition of high concentrations of Ca²⁺ to the preparation after the addition of PF1022A did not lead to production of Ca²⁺-activated Cl⁻ channels, suggesting that its mode of action was not that of a Ca²⁺ ionophore. The mechanism by which the cyclic depsipeptide might increase the Cl⁻ conductance is discussed.     

Fungicidal activity of the polyamine analogue,keto-putrescine

The polyamine analogue, keto-putrescine, was shown to provide substantial control of infections by six economically important plant pathogens, with EC₅₀ values ranging between 57 and 82 mg litre^?1. However, keto-putrescine was relatively less effective in vitro against Phytophthora infestans, Pyricularia oryzae and Pyrenophora avenae, with EC₅₀ values ranging from 145 to 340 mg litre^?1. In contrast, the polyamine analogue N-acetylputrescine had to effect on in-vitro growth of P. avenae or P. oryzae or infection of barley seedlings with powdery mildew. When P. avenae was grown in the presence of keto-putrescine, there were small, insignificant reductions in ornithine decarboxylase activity, with more substantial, significant reductions in S-adenosylmethionine decarboxylase activity. These changes were accompanied by a 43% reduction in spermidine concentration and increased concentrations of spermine and cadaverine.     

Activity against plant pathogenic fungi of phomalactone isolated from Nigrospora sphaerica

Phomalactone, 5,6‐dihydro‐5‐hydroxy‐6‐prop‐2‐enyl‐2H‐pyran‐2‐one, produced by the fungus Nigrospora sphaerica, was tested in vitro against nine plant pathogenic fungi, and specifically inhibited the mycelial growth of Phytophthora infestans, with an MIC value of 2.5 mg litre^?1. Its inhibitory activities against sporangium and zoospore germination of P infestans were similar to those against Phytophthora capsici. In vivo, at 100 and 500 mg litre^?1, it reduced the development of tomato late blight caused by P infestans. © 2001 Society of Chemical Industry