The activity of some pyrethroids against Periplaneta americana and Blattella germanica

The knockdown and contact killing actions of various pyrethroids were compared using Blattella germanica and Periplaneta americana. A wide range of knockdown activity was found; 5-benzyl-3-furylmethyl (1R)-cis-3-(dihydro-2-oxo-3-thienylidenemethyl)-2,2-dimethylcyclopropanecarboxylate (RU 15525) acted fastest, more rapidly than pyrethrins, against B. germanica as well as having a low LD₅₀ value. Topical application and direct spray tests showed that (S)-α-cyano-3-phenoxybenzyl (1R)-cir-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (NRDC 161) was more active as a killing agent, by an order of magnitude, than cismethrin, the next most active compound, and also had considerable knockdown activity. Piperonyl butoxide generally had little synergist effect. Female P. americana were over three times more tolerant than males to a range of insecticides applied topically. Residual knockdown action in the WHO resistance test was observed to provide baseline data. There was little overlap in speed of action between pyrethroids and other insecticides among the compounds tested.     

A Stable Synthetic Pyrethroid,NRDC 147, and the Control of Spodoptera littoralis

Abstract

Pyrethrins, the botanical insecticides and their synthetic analogues are well known for their power of producing very rapid paralysis (knockdown) in treated insects. The use of pyrethrins or synthetic analogues in agriculture to combat insect pests on field crops has been rather limited. The main reason for this is their non-persistence in field conditions. A recently developed synthetic pyrethroid NRDC 147, which is 10–100 times more stable in light than previous pyrethroids was tested in the laboratory and field against the Egyptian cotton leafworm Spodoptera littoralis (Boisd). Results indicate higher efficiency (LC₅₀ 320 ppm), compared with 460, 422, 1250, 180, 2150 and 265 ppm for cyolane, chlorpyrifos, leptophos, methomyl, monocrotophos and methamidophos respectively. The residual effect (LT₅₀) is more than 7 days in the field for NRDC 147, while it was 5.8, 6.8 and 4.2 for cyolane, leptophos and methamidophos.     

Comparison of symptomatic and neurophysiological activities of enantiomers of the insecticide 3-phenoxybenzyl 1-(4-ethoxyphenyl)-2,2-dichlorocyclopropane-1-carboxylate

The insecticidal activities of optical isomers of 3-phenoxybenzyl 1-(4-ethoxyphenyl)-2,2-dichlorocyclopropanecarboxylate and related compounds were measured with American cockroaches and their knockdown activities were evaluated with house flies. The activities of the S(?)-isomer of the dichlorocyclopropanecarboxylate were higher than those of the R(+)-isomer. The effects of the compounds on the inward membrane currents induced by a stepdepolarizing pulse in crayfish axonal membranes were examined under voltage clamp conditions by the sucrose gap method. The compounds induced a tail current upon step repolarization of the membrane. The tail current decayed to zero in each record, but developed with time after the start of application of the compound until a steady level was reached. The rate of decay of the tail current observed in axonal membranes treated with the S(?)-isomer was slower than with the R(+)-isomer. The rates of development of the tail current induced by the two isomers were not very different.     

Synthetic Pyrethroids: Their possible Role in the Control of Locusts and Leafworms

Abstract

The toxicity of a number of topically applied pyrethroids has been tested in the laboratory against three species of locusts and parathion-resistant and susceptible strains of the Egyptian cotton leafworm. Bioresmethrin, resmethrin and 5-benzyl-3-furylmethyl (+)-cis-chrysanthemate (NRDC 119) proved to be extremely active against one or more of these pests and there were small but noteworthy improvements with the synergists sesamex and TBTP. The field potential of the pyrethroids is discussed against the background of environmental problems associated with some of the insecticides in current use.     

Degradation of the pyrethroid cypermethrin NRDC 149 (±)-α-cyano-3-phenoxybenzyl (±)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and the respective cis-(NRDC 160) and trans- (NRDC 159) isomers in soils

The degradation of the pyrethroid insecticide cypermethrin and the geometric isomers NRDC 160 (cis-) and NRDC 159 (trans-) in three soils has been studied under laboratory conditions. Samples of the insecticides labelled separately with ¹⁴C in the cyclopropyl and benzyl rings were used. The rate of degradation was most rapid on sandy clay and sandy loam soils, 50% of the NRDC 160 and NRDC 159 applied to both soils being decomposed in 4 weeks and 2 weeks respectively. The major degradative route in all soils was hydrolysis of the ester linkage leading to the formation of 3-phenoxybenzoic acid and 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid; soil treated with the cis-isomer (NRDC 160) was found to contain both cis- and trans-isomer forms of the cyclopropanecarboxylic acid. Further degradation of these carboxylic acids was evident since ¹⁴CO₂ was released from cyclopropyl- and benzyllabelled cypermethrin in amounts equivalent to 24 and 38% of the applied radioactivity over a 22 week period. A minor degradative route was ring-hydroxylation of the insecticide to give an α-cyano-3-(4-hydroxyphenoxy)benzyl ester followed by hydrolysis of the ester bond. Under waterlogged conditions the rate of hydrolysis of cypermethrin on sandy loam soil was slower than under aerobic conditions and 3-phenoxybenzoic acid accumulated in the anaerobic soil.     

Quantitative structure-activity studies of substituted benzyl chrysanthemates: 5. Physicochemical substituent factors and neurophysiological effects in knockdown and lethal activities against the house fly

Knockdown and lethal activities of meta- and para-substituted benzyl (1R)-trans-chrysanthemates against the house fly were measured under synergistic conditions using piperonyl butoxide as an inhibitor of oxidative metabolism and NIA 16388 as an inhibitor of hydrolytic degradation. The variations in these activities were quantitatively analyzed in terms of physicochemical substituent effects using electronic, hydrophobic, and steric parameters of the aromatic substituents, and regression analysis. The most significant parameter in determining these activities is the steric bulkiness represented by the van der Waals voluem, the effect of which is highly specific to substituent positions. The substituent effects on knockdown and lethal activities against the house fly are shown to correspond well, respectively, with those on the convulsive and lethal activities against the American cockroach. The relationship between these symptomatic activities against the house fly and the neurophysiological activities determined by using excised nerve cords from American cockroaches were also quantitatively analyzed. Each house fly symptomatic activity was found to be analyzable by a linear combination of the neuroexcitatory and neuroblocking activity indices when the transport factor was separated by using the hydrophobicity parameter.     

Further studies of the degradation of the pyrethroid insecticide cypermethrin in soils

Studies of the degradation of the pyrethroid insecticide cypermethrin (NRDC 149) and its cis- and trans-isomers (NRDC 160 and NRDC 159, respectively), have been extended. In soils stored in the laboratory for up to 52 weeks, cypermethrin continued to be degraded by hydrolysis and oxidation. A previously unidentified product has now been identified as the dicarboxylic acid 3-(2, 2-dichlorovinyl)-1-methylcyclopropane-1, 2-dicarboxylic acid. Comparative experiments carried out under indoor and outdoor conditions showed that essentially the same products were formed under these different conditions. However, α-carboxy-3-phenoxybenzyl 3-(2, 2-dichlorovinyl)-2, 2-dimethyl-cyclopropanecarboxylate was one minor product detected only under outdoor conditions. Evidence is presented for the further degradation of bound residues arising in soil from cypermethrin treatments. There was limited uptake of the radiolabel into wheat grown in soil containing radiolabelled bound residues.     

Control of insects in cotton crops in africa with some pyrethroid

Cotton yield results are presented for trials in Senegal, the Ivory Coast, Chad and Morocco in which the pyrethroids permethrin, biopermethrin, 3-phenoxybenzyl (1R,cis)-3-(2,2-dichlorovinyl)-2, 2-dimethylcyclopropanecarboxylate (NRDC 167) and (S)-α-cyano-3-phenoxybenzyl (1R,1 S)-cis,trans-3-(2,2-dibromovinyl-2, 2-dimethylcy-clopropanecarboxylate (NRDC 156) were compared with the compounds currently used for insect control. NRDC 156 gave marked yield increases at rates as low as 12.5 g.a.i./ha, the other pyrethroids needing higher rates to give comparable results. Control of mites, Hemitarsonemus lata and Tetranychus urticae was not satisfactory, however.     

Effectiveness of the (+)-trans-chrysanthemic acid ester of (±)-allethrolone (bioallethrin) against four insect species

The activity of the (+)-trans-chrysanthemic acid ester of (±)-allethrolone (Bio-allethrin) is shown to be superior to that of the (±)-cis, trans-isomers (allethrin), against houseflies, two species of grain beetle and larvae of the yellow fever mosquito. The efficiency of the (+)-trans-isomer compares favourably with that of pyrethrins when each is used alone or with piperonyl butoxide.     

The metabolism of 1-naphthyl methylcarbamate by Periplaneta americana

The in vivo release of ¹⁴CO2 arising from decarbamoylation of l-naphthyl methyl [¹⁴C]carbamate (carbaryl) injected into male and female Periplaneta americana was measured over the range from 0.2 to 50 nmol carbaryl/g body weight. The amount of ¹⁴CO2 released was proportional to the dose of [¹⁴C]-carbaryl injected and was not significantly different between male and female cockroaches. Carbaryl was found to be more toxic to male (KD100, 12 nmol carbaryl/g) than female (KD100′ 57 nmol carbaryl/g) cockroaches, at any dose which caused knockdown, females showed a greater ability to recover from the toxic syndrome than did males. The [¹⁴C]-carbaryl metabolism (decarbamoylation) was temperature dependent and could be partially inhibited by sesamex, tri-orthocresyl phosphate and anoxia. Secondary effects of carbaryl poisoning were severe dehydration of the animals and in some cases abdominal swelling due to air being gulped into the crop. The amount of dehydration was essentially unaltered by the chemical inhibitors, but was partially reduced by anoxia and cooling. In the most severe cases of dehydration animals lost 18 % of their body water content.     

Disinsection of aircraft with pressure packs containing the pyrethroids,resmethrin and bioresmethrin

Pyrethrins and the pyrethroids, bioallethrin ((+) trans-chrysanthemic acid ester of (±) allethrolone), resmethrin* (5-benzyl-3-furylmethyl (±)-cis,trans-chrysanthemate) and bioresmethrin? (5-benzyl-3-furylmethyl (+)-trans-chrysanthemate) were compared for insecticidal activity against free-flying Aedes aegypti L. in a Peet-Grady chamber using kerosene solutions and an aerosol particle size. The relative potency for kill of female mosquitoes was 1; 2.3; 6.8; 8.0 respectively. In further experiments, resmethrin and bioresmethrin were compared as aerosol formulations in a Comet 4C aircraft using caged and fed female A. aegypti. Both compounds at 0.1% (by wt.) in pressure packs and 35 g of formulation per 100 m³ provided 99% kill. It is suggested that pressure packs containing 0.5% (by wt.) of either compound should be adequate for disinsection of passenger aircraft. However, bioresmethrin would appear to be the compound of choice in view of its greater biological efficiency under laboratory conditions, and consequent probable greater margin of kill in practice.     

A new pyrethroid-type ester with strong knockdown activity

Thirteen pyrethroid-type esters of substituted 1(or 3)-hydroxymethylimidazolidine-2, 4-dione were synthesised and their knockdown activities against houseflies, mosquitoes and cockroaches were examined. Knockdown activities of 2,4-dioxo-1-prop-2-ynylimidazolidin-3-ylmethyl esters in oil solutions were higher than those of known knockdown pyrethroids; three of the compounds also possessed strong knockdown and flushing-out activities against cockroaches.     

Insecticidal activity and microsomal metabolism of biooxidizable lindane analogs

The insecticidal activity of lindane analogs, in which some chlorine atoms were replaced by other groups susceptible to microsomal oxidative metabolism, was determined against mosquitos, house flies, and German cockroaches. When tested with a synergist, piperonyl butoxide, one of the methylthio analogs was as active as lindane, whereas several others were also highly active. By examining the ratio of synergized and unsynergized LD₅₀ values (synergistic ratio value), the highly insecticidal methylthio, methoxy, and methyl analogs appear to undergo metabolic detoxication effectively in house flies. By means of in vitro metabolism experiments using microsomal fraction from house fly abdomen, the methoxy, ethoxy, and methylthio analogs were shown to be metabolized rapidly at similar rates. The synergized insecticidal activities of these compounds against various insect species relate linearly with each other, suggesting that the oxidative degradation is inhibited by the synergist to a similar extent and that the transport process to the site of action is not a limiting factor in determining the relative insecticidal activity.     

Quantitative structure-activity studies of substituted benzyl chrysanthemates: 4. Physicochemical properties and the rate of progress of the knockdown symptom induced in house flies

A procedure to evaluate the knockdown activity of pyrethroids against house flies in which metabolic factors could be eliminated as far as possible was established. With piperonyl butoxide and NIA 16388 as the inhibitors of oxidative and hydrolytic metabolism, respectively, the “intrinsic” knockdown potencies of 22 substituted benzyl (1R)-trans-chrysanthemates and related compounds were determined 2.5–3 hr after topical application to house flies. From the intrinsic knockdown potency and the rate of progress of the knockdown symptom from the earliest stage of intoxication, a “penetration” rate constant was estimated by first-order kinetics using a two-compartment model. The rate constant was correlated quantitatively with the hydrophobic parameter of the molecule. The lower the hydrophobicity, the higher the rate constant within the range of compounds used in this study.     

The Pyrethrins and Related Compounds. Part XLI. Structure–Activity Relationships in Non-ester Pyrethroids against Resistant Strains of Housefly (Musca domestica L.)

A series of pyrethroids, related to NRDC 200 and etofenprox (MTI500) in which the central region is represented by a non-ester link, have been tested against one susceptible and two resistant strains (kdr and super-kdr) of houseflies (Musca domestica L.). A range of structural variations in the central region have been examined. Resistance factors mostly fell within narrow ranges for both resistant strains i.e. 10–50-fold resistance against kdr and 50–150-fold against super-kdr; thus no correlation of resistance with structural features was detectable for this region. Other changes examined were the substituent on the phenyl ring in the ‘acid’ component and the bridging group in the ‘alcohol’ component where small variations in response were observed. Examination of the effect of varying the ‘alcohol’ side chain was limited by lack of active analogues.     

Cross-Resistance to Imidacloprid in Strains of German Cockroach (Blattella germanica) and House Fly (Musca domestica)

The toxicity of a promising new insecticide, imidacloprid, was evaluated against several susceptible and resistant strains of German cockroach and house fly. Imidacloprid rapidly immobilized German cockroaches followed by a period of about 72 h during which some cockroaches recovered. After 72 h there was no further recovery. Imidacloprid-treated houseflies were immobilized more slowly than treated cockroaches, with the maximum effect observed after 72 h, and there was no recovery. Based upon 72-h LD₅₀ values imidacloprid was moderately toxic to German cockroaches (LD₅₀ values were 6–8 ng mg^-1) and had only low toxicity to house flies (LD₅₀ 140 ng mg^-1). Piperonyl butoxide (PBO) blocked the observed recovery in German cockroaches. PBO also greatly enhanced the 72-h LD₅₀ of imidacloprid from 43- to 59-fold in cockroaches and 86-fold in house flies. Two strains of German cockroach (Baygon-R and Pyr-R) showed >4-fold cross-resistance to imidacloprid. This cross-resistance could not be suppressed by PBO, suggesting that P450 monooxygenase-mediated detoxication is not responsible for this cross-resistance. Variation in the level of synergism observed with PBO (between strains) suggests the ‘basal’ level of monooxygenase-mediated detoxication of imidacloprid is quite variable between strains of German cockroach. The AVER and LPR strains of house fly showed significant cross-resistance to imidacloprid. PBO reduced the level of cross-resistance in AVER from >4·2-fold to 0·5-fold (i.e. the AVER strain LD₅₀ was half that of the susceptible strain when both were treated with PBO), but PBO did not suppress the cross-resistance in LPR. These data suggest monooxygenases are the mechanism responsible for cross-resistance to imidacloprid in AVER, but not in the LPR strain. © of SCI.     

Insecticidal properties of benzofuran-2-carboxylic acid derivatives

A series of amides and esters of substituted benzo[b]furan-2-carboxylic acids have been synthesised, and their activity against adult sweet potato weevils, Cylas formicarius elegantulus (Summer) studied. The topical insecticidal potency of these compounds was compared in acetone solution and in a mixture of piperonyl butoxide (PB) and acetone (0·05+99·95 by volume). The compounds were much more active when administered in the acetone/PB mixture, and exhibited 48-h LD₅₀ values ranging from 1·7 to 26·6 μg per insect. The most active compound, 2-(3,5-dimethylpyrazol-1-ylcarbonyl)-6-methoxy-3-methylbenzofuran, was equiactive with technical grade dimethoate (in acetone/PB) on a weight basis. © 1998 SCI     

Pyrethroid resistance and cross‐resistance in the German cockroach,Blattella germanica (L)

A German cockroach (Blatella germanica (L)) strain, Apyr‐R, was collected from Opelika, Alabama after control failures with pyrethroid insecticides. Levels of resistance to permethrin and deltamethrin in Apyr‐R (97‐ and 480‐fold, respectively, compared with a susceptible strain, ACY) were partially or mostly suppressed by piperonyl butoxide (PBO) and S,S,S,‐tributylphosphorotrithioate (DEF), suggesting that P450 monooxygenases and hydrolases are involved in resistance to these two pyrethroids in Apyr‐R. However, incomplete suppression of pyrethroid resistance with PBO and DEF implies that one or more additional mechanisms are involved in resistance. Injection, compared with topical application, resulted in 43‐ and 48‐fold increases in toxicity of permethrin in ACY and Apyr‐R, respectively. Similarly, injection increased the toxicity of deltamethrin 27‐fold in ACY and 28‐fold in Apyr‐R. These data indicate that cuticular penetration is one of the obstacles for the effectiveness of pyrethroids against German cockroaches. However, injection did not change the levels of resistance to either permethrin or deltamethrin, suggesting that a decrease in the rate of cuticular penetration may not play an important role in pyrethroid resistance in Apyr‐R. Apyr‐R showed cross‐resistance to imidacloprid, with a resistance ratio of 10. PBO treatment resulted in no significant change in the toxicity of imidacloprid, implying that P450 monooxygenase‐mediated detoxication is not the mechanism responsible for cross‐resistance. Apyr‐R showed no cross‐resistance to spinosad, although spinosad had relatively low toxicity to German cockroaches compared with other insecticides tested in this study. This result further confirmed that the mode of action of spinosad to insects is unique. Fipronil, a relatively new insecticide, was highly toxic to German cockroaches, and the multi‐resistance mechanisms in Apyr‐R did not confer significant cross‐resistance to this compound. Thus, we propose that fipronil could be a valuable tool in integrated resistance management of German cockroaches. © 2001 Society of Chemical Industry     

The use of piperonyl butoxide and MGK-264 to improve the efficacy of some plant-derived molluscicides

Synergism of an oil of Azadirachta indica, a powdered extract of Allium sativum bulbs and an oleoresin of Zingiber officinale rhizomes by piperonyl butoxide and MGK-264 was studied against the snails Lymnaea acuminata and Indoplanorbis exustus. The active components of these plant-derived molluscicides, respectively azadirachtin, allicin and [6]gingerol, were also combined with these synergists. Both piperonyl butoxide and MGK-264 enhanced the toxicity of all of the test compounds. The response of snails to the synergised mixtures was both time- and dose-dependent. © 1998 Society of Chemical Industry     

Insecticidal activity of synthetic 2-carboxylbenzofurans and their coumarin precursors

Several 2-carboxylbenzofurans and their coumarin precursors, compounds 1 – 6 , and the novel compound 7 were synthesized and their insecticidal activity studied using adult sweet potato weevils (Cylas formicarius elegantulus (Summer)) at 24 μg, 48 μg and 72 μg per insect in 0.5 ml litre^?1 piperonyl butoxide (PPB) in acetone. The order of toxicity of the compounds as judged by the percentage mortality at 24 μg per insect at 48 h was 2 (100%) > 6 (95%) > 7 (85%) > 4 (75%)) > 3 (65%) > 1 (60%) > 5 (45%) > piperonyl butoxide (0.0%). Compound 2 was equitoxic to 24 μg of technical grade dimethoate. When administered in acetone alone, however, the compounds were only moderately active (i.e. > 120 μg per insect was required for 60% mortality at 48 h). The test compounds were more active at lower doses (48–72 μg per insect) when dissolved in dimethylsulfoxide or in an oil extract obtained from the fruit of Blighia sapida Koenig.