Insecticidal activity of the pyrethrins and related compounds X 5-benzyl-3-furylmethyl 2,2-dimethyicyclopropanecarboxylates with ethylenic substituents at position 3 on the cyclopropane ring

The insecticidal activities against houseflies (Musca domestica L.) and mustard beetles (Phaedon cochleariae Fab.) of the chrysanthemate bioresmethrin, and of 31 related 5-benzyl-3-furylmethyl 2,2-dimethylcyclopropanecarboxylates with alkenyl, alkadienyl or alkoxycarbonylalkenyl substituents at position 3 of the cyclopropane ring are compared to determine the relative influence of the isobutenyl sidechain (as in chrysanthemates) and of the other side chains. Several substituents, in particular (E)- or (Z)-butadienyl or -pentadienyl, give considerably greater activity than isobutenyl but alkoxycarbonyl compounds are less potent.     

The pyrethrins and related compounds. XVII. Preparation of the insecticide bioresmethrin (5-benzyl-3-furylmethyl (+)-trans-chrysanthemate) and related compounds labelled with deuterium or tritium on the furan ring

2-²H-5-Benzyl-3-furylmethyl esters exclusively are obtained from an exchange reaction of the parent esters with deuterium oxide and a trace of acid (n.m.r. and mass spectrometric control). Similarly, with tritiated water, 6 insecticidal esters of 5-benzyl-3-furylmethyl alcohol give the corresponding [2-³H]esters, each with specific activity of approx. 500 mCi/mmol.     

Insecticidal activity of the pyrethrins and related compounds. IX. 5-benzyl-3-furylmethyl 2,2-dimethylcyciopropanecarboxylates with non-ethylenic substituents at position 3 on the cyclopropane ring

The insecticidal activities against houseflies (Musca domestica L.) and mustard beetles (Phaedon cochleariae Fab.) of 29 new 5-benzyl-3-furylmethyl 2,2-dimethyl-cyclopropane-carboxylates are compared with those of the corresponding chrysanthe-mate (bioresmethrin) to assess the influence of non-ethylenic and isobutenyl substituents at position 3 of the cyclopropane ring. Of the new groups investigated, only 3-methoxyiminomethyl gives equal or enhanced activity; 3-(2-furyl) esters are moderately effective, but 3-phenyl and 3-alkoxycarbonyl compounds show weak activity. A 3-(2,2,2-trihaloethyl) compound was more active than compounds with other saturated groups, such as isobutyl.     

Investigating the potential of selected natural compounds to increase the potency of pyrethrum against houseflies Muscadomestica (Diptera: Muscidae)

BACKGROUND: A study was undertaken to determine the efficacy of seven natural compounds compared with piperonyl butoxide (PBO) in synergising pyrethrum, with the intention of formulating an effective natural synergist with pyrethrum for use in the organic crop market. RESULTS: Discriminating dose bioassays showed PBO to be significantly more effective at synergising pyrethrum in houseflies than the seven natural compounds tested, causing 100% mortality in insecticide‐susceptible WHO and resistant 381zb strains of housefly. The most effective natural synergists against WHO houseflies were dillapiole oil, grapefruit oil and parsley seed oil, with 59, 50 and 41% mortality respectively, compared with 18% mortality with unsynergised pyrethrum. Against 381zb houseflies, the most effective natural synergists were parsley seed oil and dillapiole oil. Esterase inhibition by the natural compounds and PBO in vitro showed no correlation with pyrethrum synergism in vivo, whereas the inhibition of oxidases in vitro more closely correlated with pyrethrum synergism in vivo. CONCLUSION: Dillapiole oil and parsley seed oil showed the greatest potential as pyrethrum synergists. PBO remained the most effective synergist, possibly owing to its surfactant properties, enhancing penetration of pyrethrins. The results suggest the involvement of oxidases in pyrethroid resistance in houseflies, with the efficacy of synergists showing a high correlation with inhibition of oxidases. Copyright © 2011 Society of Chemical Industry     

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.     

3-苄基-5-(1-(2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基)亚乙基)-2-氨基咪唑啉-4-酮类化合物的合成及杀菌活性

为寻找高活性的杀菌化合物,在前期合成5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-氨基咪唑啉-4-酮类化合物的基础上进行结构修饰,在咪唑啉-4-酮的3-位引入苄基,设计并合成了一系列未见文献报道的化合物,其结构经过核磁共振氢谱 (1H NMR)、碳谱 (13C NMR) 及高分辨质谱 (HR-ESI-MS) 确证。经高效液相色谱 (HPLC) 分析显示,Z-构型中间体化合物 6 在酸性条件下会发生氮质子化开环再环化,转化为E-构型化合物 7 。离体杀菌活性测定结果表明,3-位苄基的引入改善了该类化合物的杀菌活性,其中化合物 (E)-3-苄基-5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-(4-甲氧基苯基) 氨基-咪唑啉-4-酮 ( 9c ) 和 (E)-3-苄基-5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-(4-氟苯基) 氨基-咪唑啉-4-酮 ( 9h ) 对油菜菌核病菌的EC₅₀ 值分别为14.3和21.1 mg/L。活体杀菌活性测试结果显示,在400 mg/L下化合物 9c 对于黄瓜霜霉病和小麦白粉病的防治效果分别为 80%和85%。     

Toxicity of pyrethroids to larvae of the egyptian cotton leafworm,Spodoptera littoralis (Boisd.). I. Relative toxicities and knockdown activities of benzyl,and 5-benzyl-3-furylmethyl,cyclopropanecarboxylates

The contact toxicity of ten pyrethroids to larvae of Spodoptera littoralis (Boisd.) was investigated by topical application, and symptoms observed for different combinations of dose and time. Several compounds were sufficiently active to suggest that they may prove useful for the control of populations in the field. Structure and activity are discussed with particular reference to time-dose-response relationships: speed of action is related to both chemical structure and applied dose.     

粉纹夜蛾离体细胞对Bt Cry1Ac毒素的抗性发展及其交互抗性

以CrylAc活性毒素逐代筛选抗性粉纹夜蛾离体细胞BTI-TN-5B1抗性发展速度呈S形曲线，经56代选择后，抗性比上升至1280倍。在去除选择压力后，抗性比逐渐下降。低水平抗性细胞抗性衰退较快，而高水平抗性细胞抗性衰退较缓慢。抗性比衰退至1．5倍的细胞在复筛后抗性比恢复较快。抗性细胞对苏云金杆菌工程菌GC-91(BtGC-91)、苏云金杆菌鲇泽亚种(B.t.atoazai)和苏云金杆菌库斯塔克亚种(B．t．kurstaki)的复合毒素晶体的活性毒素都具有较高的交互抗性，但对农药无交互抗性，对杆状病毒的敏感性也没发生变化。     

Metabolism of 2-[methoxy(methylthio)phosphinylimino]-3-ethyl-5-methyl-1,3-oxazolidine in the cotton plant and houseflies

The metabolism of 2-[methoxy(methylthio)phosphinylimino]-3-ethyl-5-methyl-1,3-oxazolidine (Stauffer R-16,661), a new experimental insecticide, was investigated in the cotton plant, houseflies, and in in vitro enzymatic and model oxidation systems. The principal metabolite isolated both in vivo and in vitro proved to be the 4-keto derivative of R-16,661. The structure of this metabolite was confirmed by PMR and mass spectral analysis. Toxicological examination showed that the 4-keto metabolite was approximately equal to R-16,661 in toxicity to the white mouse but was substantially less toxic to the housefly.     

粉纹夜蛾离体细胞对Bt Cry1Ac毒素的抗性发展及其交互抗性

以Cry1Ac活性毒素逐代筛选抗性粉纹夜蛾离体细胞BTI-TN-5B1,抗性发展速度呈S形曲线,经56代选择后,抗性比上升至1 280倍.在去除选择压力后,抗性比逐渐下降.低水平抗性细胞抗性衰退较快,而高水平抗性细胞抗性衰退较缓慢.抗性比衰退至1.5倍的细胞在复筛后抗性比恢复较快.抗性细胞对苏云金杆菌工程菌GC-91(Bt GC-91)、苏云金杆菌鲇泽亚种(B.t.awazai)和苏云金杆菌库斯塔克亚种(B.t.kurstaki)的复合毒素晶体的活性毒素都具有较高的交互抗性,但对农药无交互抗性,对杆状病毒的敏感性也没发生变化.     

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 pyrethrins and related compounds. Part XXXVII. synthesis and insecticidal properties of new 1-aryl-1-(3-arylpropyl and -propenyl)cyclopropanes (non-ester pyrethroids)

New routes to the title compounds, involving improved conditions for the cyclopropanation, and a new method of constructing the central three-carbon unit (based on the coupling of a Grignard reagent with an allylic acetate) give access to products for which the previously reported route was not satisfactory. For the new route, a synthesis of 5-bromo-2-fluoro-diphenyl ether was developed. Previously deduced relationships between structure and insecticidal activity apply for the new compounds: alkenes are generally more active than corresponding alkanes; substitution at the 3- or 4-position (but not the 2-) of the 1-aryl group can enhance activity. In addition, some fluorine-containing substituents lead to high activity.     

Degradation of the pyrethroid insecticide WL 41706, (±)-α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate,in soils

The degradation of the insecticide WL 41706, (±)-α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate, (I), in two soils from Spain and one from the UK has been studied in the laboratory. Samples of (I) labelled separately with ¹⁴C in the benzyl ring (uniform labelling) and at C₍₁₎ of the cyclopropyl ring were used. The insecticide underwent degradation by hydrolysis at the cyano group to form the amide and carboxylic acid analogues. However, the major degradative route was hydrolysis at the ester linkage leading initially to the formation of 3-phenoxy-benzoic acid and 2,2,3,3-tetramethylcyclopropanecarboxylic acid. When a sandy clay soil was treated with [benzyl^?14C]-WL 41706 under balance conditions, ¹⁴CO₂ was evolved at a steady rate and 16 % of the applied radiolabel was detected as ¹⁴CO₂ over a 26 week period. The rate of degradation of I was most rapid on a moist sandy clay (loss of 50 % initial quantity in 4 weeks) but it was considerably slower on dry sandy clay and moist clay soils (> 16 weeks). Under flooded, anaerobic conditions the rate of hydrolysis of the insecticide was slower than under aerobic conditions and the 3-phenoxybenzoic acid and 2,2,3,3-tetramethylcyclopropanecarboxylic acid were found to accumulate over the 24 weeks of the experiment.     

The pyrethrins and related compounds. XIX Geometrical and optical isomers of 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acid and insecticidal esters with 5-benzyi-3-furylmethyi and 3-phenoxybenzyl alcohols

Esters of 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acid with appropriate alcohols are more active insecticides than the corresponding 3-isobutenyl compounds (chrysanthemates). (±)-Cis and (±)-trans forms of the dichloro acid are obtained by fractional crystallisation of the mixed acids or by hydrolysis of the ethyl esters separated by fractional distillation. The (±)-cis and (±)-trans acids are resolved into their (+)- and (-)-forms with α-methyl-benzylamine and threo-l-p-nitrophenyl-2-N,N-dimethyiamino-propane-1,3-diol respectively. As for the corresponding chrysanthemates, the (+)-cis and (+)-trans acids give esters more active as insecticides than their enantiomers.     

Activity of adjuvants in ‘aliette’ against Botryotinia fuckeliana (botrytis cinered) and their cross-resistance with benzimidazole fungicides

‘Aliette’, a formulation of the fungicide fosetyl-aluminium, is moderately active in vitro against the ascomycete Botryotinia fuckeliana (Botrytis cinerea). In contrast, fosetyl-aluminium and related chemicals, such as phosphonic acid and sodium phosphonate, have low efficacy, although it is enhanced by media with low phosphate content. This indicates that the effectiveness of ‘Aliette’ against B. fuckeliana is not due to fosetyl-aluminium but to adjuvants included in the formulation. The genetic basis of differences in sensitivity to ‘Aliette’ was investigated in field and laboratory isolates of B. fuckeliana. Genetic analysis showed that reduced sensitivity to ‘Aliette’ always co-segregated with resistance to benzimidazole fungicides in meiotic progeny of sexual crosses. This indicates that differences in sensitivity to ‘Aliette’ in B. fuckeliana are due to the major gene Mbcl of resistance to benzimidazole fungicides and active adjuvant(s) present in ‘Aliette’ are linked to benzimidazoles by cross-resistance.     

The metabolism of the pyrethroid insecticide (±)-α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethyl-cyclopropanecarboxylate,WL 41706, in the rat

The metabolism of the pyrethroid insecticide α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate (WL 41706) has been studied in rats using two forms of ¹⁴C-labelling (benzyl- and cyclopropyl-). Excretion of benzyl^?14C was rapid, 57% of the administered dose being eliminated in the urine 48 h after treatment and 40% in the faeces. No significant sex difference was observed. The amount of radioactivity excreted via expired gases was 0.005% of the administered dose and less than 1.5% of the dose remained in the animals 8 days after treatment. The mean percentage recovery of administered dose was 104% for male rats and 97% for female rats. Urinary and faecal metabolites from these rats, and from rats dosed similarly with [cyclopropyl^?14C]-WL 41706 were studied. The rapid metabolism of WL 41706 is due to efficient cleavage of the ester bond by rats in vivo to afford 2,2,3,3-tetramethylcyclopropanecarboxylic acid (partly as glucuronide) and the 3-phenoxybenzyl moiety. Before this cleavage occurs, however, about half of the intake suffers aryl hydroxylation giving the α-cyano-3-(4-hydroxyphenoxy)benzyl ester, part of which is excreted in the bile as a conjugate(s) and part of which is cleaved and eliminated as the O-sulphate of 3-(4-hydroxyphenoxy)benzoic acid and the glucuronide of 2,2,3,3-tetramethylcyclopropanecarboxylic acid. A minor amount of hydroxylation occurs at a trans-methyl group on the cyclopropane acid moiety. The metabolism of WL 41706 by rat liver occurs mainly in the microsomes and mainly via oxidative processes.     

Relative solubilities of bifenox and 1-naphthylacetic acid (NAA) in plant cuticles and in selected pure or aqueous glycol additives

The driving force for foliar penetration is the product of the partition coefficient (K) between the cuticle and the formulation residue, and the concentration of the active ingredient in the spray residue. Ethylene glycols and polyethylene glycols (PEGs) are often contained in commercial formulations, because they are good solvents and not toxic. Since they are humectants, the water content of the formulation residue varies with humidity of the air. At 25°C and 65% relative humidity PEG 400 contains about 50% water. The partition coefficients for the lipophilic herbicide, bifenox, increased with increasing water content of the ethylene glycols and PEGs, such that log K was a linear function of the mass fraction of water or PEG. The K value was about 0·5 for the system cuticle/pure PEG and 27500 for the system cuticle/water. When PEG contained 50% water, K was only 110. Partition coefficients of bifenox between cuticle and ‘Tween’ 80 depended also on humidity, having values of 0·75 in cuticle/pure ‘Tween’ 80 and 29·1 when ‘Tween’ 80 contained 50% water. With 1-naphthylacetic acid (NAA), which is a weak acid, partition coefficients also depended on water content of PEG 400, but a maximum curve was obtained. The maximum partition coefficient (211) was observed with a mixture of 30% PEG 400 and 70% water, which corresponded to a humidity of 88%. We suggest that this is due to an effect of PEG 400 on the ionisation of NAA. Our data demonstrate that partition coefficients are affected by humidity, because solubilities of lipophilic compounds and weak acids in PEG/water mixtures vary greatly with the water content. This in turn affects driving forces, mainly by the effect of humidity on partition coefficient. With non-ionisable lipophilic compounds, partition coefficients, driving forces and rates of foliar uptake therefore increase with increasing humidity. © 1998 SCI     

Selectivity and mode of action of ethyl (±)-2-(N-benzoyl-3,4-dichloroamiino)propionate in the control of Arena fatua in cereals

The activity of foliar applications of ethyl (±)-2-(N-benzoyl-3,4-dichloroanilino)—propionate(benzoylprop-ethyl)to oat was dependent upon its degradation to the biologically active acid (benzoylprop). The acid, unlike benzoylprop-ethyl, showed some movement via the phloem from the foliage to the stem where it inhibited stem elongation through an effect on cell expansion. The resulting stunted wild plants oat were unable to compete successfully with the cereal crop. Selectivity of the herbicide was dependent on its relative rate of de-esterification, and the subsequent detoxication of the acid to inactive conjugates. De-esterification was fastest in oat and slowest in wheat. The rate of detoxication in wheat prevented the accumulation of the acid to phytotoxic levels but in oat, although the rate of detoxication was higher, it failed to prevent the occurrence of phytotoxic levels of benzoylprop. In barley de-esterification was slower than in oat, and detoxication again failed to prevent some accumulation of the acid.     

Factors favouring the choice of flamprop-methyl,methyl (±)-2-[N-(3-chloro-4-fluorophenyl)benzamido] propionate for the control of avena species in wheat

The post-emergence herbicide, methyl (±)-2-[N-(3-chloro-4-fluorophenyl)benzamido]-propionate, flamprop-methyl, showed good activity against oat with selectivity in wheat. It was superior in performance to flamprop-isopropyl and benzoylprop-ethyl already being marketed for wild oat control. It gave even more effective control of seed set in the oat than did the other compounds, prevented tiller growth and as a result of its higher activity was less dependent on crop competition. Selectivity of flamprop-methyl, however, was similar to that previously reported for related compounds, i.e. it was dependent on its rate of degradation and the subsequent detoxication of the biologically active acid to inactive conjugates. The rate of degradation of flamprop-methyl is comparable to that of benzoylprop-ethyl but the more active acid produced accounts for the improved performance of the former. The corresponding ethyl ester showed the highest rate of degradation and although generally comparable in performance to the methyl ester there was a tendency for the inhibition on the oat to last for a shorter period. Performance of flamprop-methyl is influenced by environmental factors such as temperature or water stress. These factors had an effect during the first 2 weeks after compound application, reducing the translocation of the active metabolite to its site of action and having a small but detectable effect on the amount of acid produced.     

Lack of cross-resistance to Mtx1 from Bacillus sphaericus in B. sphaericus-resistant Culex quinquefasciatus (Diptera: Culicidae)

The toxicities of Mtx1 toxin against dipteran and lepidopteran species have been evaluated in this study. It was shown that Mtx1 has little or no toxicity to the tested lepidopteran species, but has moderate-level toxicity to Aedes albopictus Skuse (Diptera: Culicidae) and high-level toxicity to both susceptible and binary toxin-resistant Culex quinquefasciatus Say (Diptera: Culicidae). The LC(50) values of Mtx1 against a susceptible C. quinquefasciatus colony SLCq and two resistant colonies RLCq1/C3-41 and RLCq2/IAB59 selected in the laboratory with Bacillus sphaericus (Mayer & Neide) strains C3-41 and IAB59 respectively were 0.508, 0.854 and 0.675 mg L(-1) respectively. The data indicate that Mtx1 has a different mode of action from the binary toxin, and that it could be an alternative toxin to delay or overcome resistance development to binary toxin in C. quinquefasciatus.