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.     

Fungicidal activity of 2-(1-alkenyl)-3-hydroxy-1,4-naphthoquinones and related compounds

The fungicidal activity of a series of 2-(1-alkenyl)-3-hydroxy-1,4-naphthoquinones and their acetates has been assessed against various fungi in vitro and against others, notably powdery mildews, in vivo, and the activity compared with that of analogous compounds bearing saturated side chains. Several of the compounds demonstrated a broad spectrum of activity in vitro. Whereas the presence of α-unsaturation in the side chain is essential for the in-vitro activity against the non-obligate fungi tested, it is of virtually no importance for the curative effect against Erysiphe graminis on barley. Only the corresponding acetates had activity against the latter pathogen.     

Allylamine antimycotics: Recent trends in structure—activity relationships and syntheses

Methods developed for the synthesis of terbinafine-related allylamine antimycotics are reviewed. The synthesis of the en-yne side chains were generally accomplished by means of organometallic reactions. The use of Pd⁰-catalysed coupling reactions allowed easy access to derivatives bearing sensitive side-chain substituents. As examples, four metabolites of terbinafine were prepared via this procedure. Investigations with the carbon analogue of terbinafine revealed that, within the allylamine antimycotics, the nitrogen appears to be necessary for penetration by the drug into the fungal cell. Replacement of the naphthalene moiety of terbinafine by optionally substituted benzo[b]thiophenes led to a number of derivatives with high antifungal activity. A series of benzo[b]thienyl compounds with the side chain at position 7 and different substituents at position 3 showed significantly increased activity against Candida albicans in vitro. In particular, the 3-chloro derivative with the allylamine side chain at position 7(SDZ 87–469) proved to be the most potent allylamine antimycotic reported to this date. Two novel types of lead structures, the homopropargylamines and the benzylamines show very high activity in vitro.     

Esterase isozymes in Lygus hesperus: Characterization and relationship with organophosphate resistance

Esterases of Lygus hesperus Knight from five field and one laboratory populations were separated by non-denaturing polyacrylamide gel electrophoresis and were characterized for inhibition and substrate specificity. There were six zones of esterase activity toward naphthyl ester substrates. Significant inter- and intra-populational polymorphisms were observed. All the isozymes were carbo-xylesterases that were sensitive to inhibition by paraoxon and insensitive to eserine or EDTA (ethylenedinitrilotetraacetic acid). Carboxylesterases from L. hesperus more readily hydrolysed naphthyl esters with short side chains. Molecular weight estimation by non-denaturing polyacrylamide gel electrophoresis revealed that Est-1, the specific band of older females and eggs, contained two enzymes with relative molecular masses of 140000 and 112000. The four esterase allozymes in Est-3 had an average relative molecular mass of approximately 106000. The frequency of one putative allozyme in Est-3 was directly correlated with the LC₅₀ values of trichlorfon (to which L. hesperus has become resistant). The developmental and distribution variability of the esterase isozymes are compared.     

The pyrethrins and related compounds part XL— structure-activity relationships of pyrethroidal esters with acyclic side chains in the alcohol component against resistant strains of housefly (Musca domestica)

Activities of a range of pyrethroidal esters, incorporating structural variations in all regions of the acid and alcohol components, have been measured against two fully characterised and homozygous resistant strains of Musca domestica (kdr and super-kdr). The results, limited in this paper to esters of alcohols with acyclic side chains, show the same level of uniform resistance as the kdr strain observed previously, across a range of acid and alcohol variations. Against the super-kdr strain, in contrast to the cyclic side chain set, resistance factors are barely higher than for the kdr strain. Against super-kdr flies, some dependence of resistance factor on the position of the side chain substituent was detected. Polyfluorobenzyl esters confer particularly low resistance factors.     

Design,synthesis and biological activities of new strobilurin derivatives containing substituted pyrazoles

BACKGROUND: Strobilurins are one of the most important classes of agricultural fungicides. To discover new strobilurin analogues with high activity, a series of new strobilurin derivatives containing substituted pyrazoles in the side chain were synthesised and bioassayed. RESULTS: The compounds were identified by ¹H NMR, IR, MS and elemental analysis. Preliminary bioassays indicated that some title compounds exhibited excellent fungicidal activities against Pseudoperonospora cubensis (Burk. & Curt.) Rostovsev and Erysiphe graminis DC f. sp. tritici Marchal, protecting cucumber and wheat at 6.25 and 1.56 mg L^?1 respectively, and showed a moderately high acaricidal activity against Tetranychus cinnabarinus (Boisd.) at 20 mg L^?1. The relationship between structure and biological activity is discussed in terms of effects of the substituent of the pyrazole ring. CONCLUSION: The present work demonstrates that strobilurin analogues with substituted phenylpyrazolylmethoxymethyl side chains can be used as possible lead compounds for further developing novel fungicides and acaricides. Copyright © 2009 Society of Chemical Industry     

Synthesis and insecticidal activity of lipophilic amides. Part 3: Influence of chain length and terminal group in N-(2-methylpropyl)-2,4-dienamides

Increasing the alkylene chain length in N-(2-methylpropyl)-ω-phenylalka-2,4-dienamides revealed in addition to the active compounds reported earlier a second peak of activity, but only against mustard beetles, with the tridecadienamide. Similar extension in the methyl-terminated series gave much weaker peaks, at different lengths for the two test species. Results with terminal vinyl compounds were intermediate, and indicated a specific functional role in the lethal process for the terminal unsaturation, with a possible contribution to steric flexibility and physical property optimisation from the longer chains. Synthetic samples of pellitorine and pipercide, natural products to which insecticidal activity has been ascribed, were only very weakly active in the present tests, but compounds with other groups on the ends of chains nearer the optimum length were more active.     

Structure—activity relationship for some substituted dialkyl vinyl phosphates

The biological activity against the house fly, Musca domestica L., is reported for a series of dialkyl 2-bromo-1-(2,4-dichlorophenyl)vinyl phosphates. Maximum activity and the lowest degree of synergism with piperonyl butoxide were found with the dimethyl ester. Good activity was also shown by the diethyl ester. Both these compounds, used at the same dose, inhibited fly-head acetylcholinesterase. Compounds with longer alkyl chains were less effective and did not inhibit acetylcholinesterase.     

Powdery mildew resistance in selections from moroccan barley landraces

Thirty barley landraces collected from Morocco in 1985 and 1989, and held in the Polish Gene Bank, IHAR, Radzików, Poland, were screened for resistance to powdery mildew. Fifteen tested landraces (50%) showed powdery mildew resistance reactions and 24 single plant lines were selected. Eighteen lines originating from 13 landraces were tested with 17 isolates of powdery mildew and another six lines originating from six landraces were tested with 23; the isolates were chosen according to their virulence spectra observed on the ‘Pallas’ isolines differential set. Three lines (E 1090-2-2, E 1110-3-2 and E 1077-1-1) showed resistance to all powdery mildew virulence genes prevalent in Europe. In 21 lines, unknown genes alone or in combination with specific ones were detected. Five different resistance alleles(Mlat, Mlal, Mla3, Mlg andMl(CP)) were postulated to be present in the tested lines, alone or in combination:Mlat was postulated to be present in nine (~38%) lines;Mlg andMl(CP) in two lines, andMla1 andMla3 in one tested line each. The use of newly identified sources of resistance in barley breeding as a means of controlling powdery mildew is discussed.     

The pyrethrins and related compounds part XXXIX— structure-activity relationships of pyrethroidal esters with cyclic side chains in the alcohol component against resistant strains of housefly (Musca domestica)

Activities of a range of pyrethroidal esters, incorporating structural variations in all regions of the acid and alcohol components, have been measured against two fully characterised and homozygous resistant strains of Musca domestica L. (kdr and super-kdr). The results, limited in this paper to esters of alcohols with cyclic side chains, indicate uniform resistance to the kdr strain across the whole range of structural variations. Against the super-kdr strain, while variation in the acid component has little effect, the resistance factor is sensitive to the nature of the alcohol component, in particular on whether it contains an α-cyano substituent.     

山东省危害核桃的链格孢属真菌鉴定及其系统发育

为了明确危害核桃的链格孢属Alternaria真菌种类,对34个供试菌株在PCA培养基上的培养特征、产孢表型、分生孢子特征等进行了研究,并采用ITS、OPA2-1和OPA1-3序列分析其系统发育。其中33个菌株为链格孢A.alternata,1个为细极链格孢A.tenuissima。链格孢:菌落灰色;孢子链短、分枝频繁,每条分枝含4～10个孢子;分生孢子多倒梨形,孢身平均25.6μm×7.4μm,横隔膜2～8个。细极链格孢:菌落褐色;孢子链长、少分枝,孢子链约含10个孢子;分生孢子多长椭圆形,孢身平均26.3μm×13.5μm,具柱状喙及假喙,主横隔膜1～6个,孢身中部的隔膜较粗。链格孢属真菌在遗传上有较大差异,ITS、OPA2-1和OPA1-3序列对链格孢小孢子种具有一定的区分作用,链格孢是危害核桃的主要链格孢属种。     

Metabolism of imazalil by wild-type and DMI-resistant isolates of Penicillium italicum

Metabolism of imazalil (1-[2-(2,4-dichlorophenyl)-2-(2-propenyloxy)ethyl]-1H-imidazole) inPenicillium italicum isolates with a wild-type sensitivity and with various degrees of resistance to sterol demethylation inhibitors was studied in liquid cultures. The metabolite 1-[2(2,4-dichlorophenyl)-2-(2,3-dihydroxypropyloxy)ethyl]-1H-imidazole (R42243) was detected in the culture filtrate after prolonged incubation. The metabolism occurred in the propenyl side chain of imazalil probably through epoxidation and hydratation. This is the first report of such a conversion of imazalil in fungi. R42243 was much less toxic toP. italicum than imazalil. Therefore, the metabolism can be regarded as a detoxification step. Both wild-type and resistant isolates metabolized imazalil, but metabolism by resistant isolates was faster than by the wild-type isolate. This is probably caused by a relatively strong inhibition of growth of the wild-type isolate by the fungicide. Results indicate that the detoxification of imazalil does not operate as a mechanism of resistance. This conclusion was confirmed by the fact that resistant isolates showed cross-resistance to miconazole and R42243, which had a similar structure as imazalil except for the propenyl side chain.     

The pyrethrins and related compounds. Part XXII. Preparation of isomeric cyano-substituted 3-phenoxybenzyl esters

Preparation of 3-phenoxybenzyl chrysanthemates and their dihalovinyl analogues substituted with a cyano group at the 2-, 6-, (R)-α-, or (S)-α- positions is described. The (R)- and (S)- isomers of α-cyano-3-phenoxybenzyl esters of 2,2-difluoro-, -dichloro-, and -dibromo-vinyl analogues of cis- and trans- chrysanthemic acid are separated chromatographically, as are the separate pairs of enantiomers of fenvalerate, (RS)-α- cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate. An optically active ester of α-cyano-3-phenoxybenzyl alcohol (obtained using D -oxynitrilase) with 2,2,3,3-tetramethylcyclopropanecarboxylic acid is synthesised.     

(Z)-3-hexenyl acetate and 1-undecanol increase male attraction to sex pheromone trap in Grapholita molesta (Busck) (Lepidoptera: Tortricidae)

The effects of host-plant volatiles (HPVs) on male oriental fruit moth, Grapholita molesta (Busck) (Lepidoptera: Tortricidae), and response to sex pheromone trap were studied in a pear orchard. Two HPVs compounds, (Z)-3-hexenyl acetate and 1-undecanol, combined with sex pheromone of G. molesta in traps were tested. The results showed that most of the male moths were captured in the traps baited with the sex pheromone combined with these two HPVs compounds than by the pheromone alone. Also, more males were captured by the trap containing pheromone plus (Z)-3-hexenyl acetate than by the one containing 1-undecanol. It appeared that these HPVs act as sex pheromone synergists to enhance the attraction of male G. molestato pheromone traps, since males were not captured in the traps baited only with (Z)-3-hexenyl acetate and/or 1-undecanol.     

Synthesis and bioactivity of some fluorine-containing benzoyl arylureas. Part I: Insecticidal-acaricidal products in which the aryl group bears a trifluoromethyl-substituted alkyl or alkenyl side chain

This paper reports the synthesis and the biological activity of benzoyl arylureas in which the aryl group bears a trifluoromethyl-substitiited alkyl or alkenyl side chain, R. The activity of these compounds has been evaluated on larvae of S. littoralis, A. aegypti, L. decemlineata and on the eggs of T. urticae. In general: (1) the optimum insecticidal activities are achieved when the substituents on the benzoyl moiety, R₁, and R₂, are 2,6-difluoro, the substituents on the aryl moiety, R₃, are 3,5-dichloro and R₁, is 4-(? CH?C(CI)CF₃); (2) the best acaricidal activity is shown when R₁, is 2-CI, R₂, and R₃, are hydrogen atoms and R₁, is 4-(? CH₂CH₂CH(CI)CF₃); (3) the best overall activity is displayed when R₁, is 2-CI, R₂ is hydrogen, R₃ is 3-chloro and R₁ is 4-(? CH₂CH₂CF₃).     

Response of susceptible and resistant peach-potato aphids Myzus persicae (Sulz.) to insecticides in leaf-dip bioassays

The response of susceptible (S), moderately resistant (R₁) and strongly resistant (R₂) peach-potato aphids, Myzus persicae (Sulz.) to organophosphorus, carbamate and pyrethroid insecticides was tested by a leaf-dip bioassay. The aphids were placed on potato leaves (dipped in insecticide solutions 1–2 or 24 h before infestation) and their mortality examined 48 h later. R₁ aphids were virtually susceptible to most of the carbamates, demephion and acephate, but were slightly to moderately resistant (2.1–9.4 times) to permethrin, cypermethrin and (S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (I), (NRDC 161), to 5,6,7,8-tetrahydro-2-methylquinolin-4-yl dimethylcarbamate (II), (Hoechst 25 682) and demeton-S-methyl. R₂ aphids resisted more strongly or very strongly (between 65 and 1280 times) the pyrethroids, demeton-S-methyl (×94), II (×83) and demephion (×9), and were slightly to moderately (2–5 times) resistant to acephate, pirimicarb, ethiofencarb and 2-(dimethylcarbamoyloxyimino)-3-methoxyimino-N,N- dimethylbutyramide (III), (DPX 3853). Both resistant strains were susceptible to nitrilacarb [4,4-dimethyl-5-(methylcarbamoyloxyimino)pentanenitrile] complex (1:1) with zinc chloride (IV), (AC 85 258). The implications of these results in terms of practical aphid control are discussed.     

Insecticidal activity of the pyrethrins and related compounds. VII. Insecticidal dihalovinyl analogues of cis and trans chrysanthemates

Eighteen esters of resolved cis- and trans-3-(2,2-difluoro, -dichloro or -dibromovinyl)-2,2-dimethylcyclopropanecarboxylic acids with 5-benzyl-3-furylmethyl, 3-phenoxybenzyl and α-cyano-3-phenoxybenzyl alcohols were prepared and evaluated for insecticidal activity against Musca domestica L. and Phaedon cochleariae Fab. Chlorine and bromine substituted esters are more active, in general, than those with fluorine, and in the most active esters, the cis isomer is more effective than the trans.     

RU-15525, a new pyrethroid with a very strong knockdown effect

(E)-5-Benzyl-3- furylmethyl (1-R),3-S)-2,2-dimethyl-3-(2,3,4,5-tetrahydro-2-oxothien-3-ylidenemethyl)cyclopropanecarboxylate or RU-15525 is a new pyrethroid. The action of this compound was tested on Musca domestica and Aedes aegypti and a very strong knockdown effect was observed in comparison with the knockdown effect of allethrin, bioallethrin and (S)-bioallethrin.     

Biological and biochemical aspects of the disruption of adult formation in Tribolium by a novel bis(thiocarbamate) R-31026 and the juvenoid R-20458

S,S-Di-isobutyl N ethylethylenebis(thiocarbamate) (R-31026) had a strong morphogenetic effect, acting by contact on the newly formed pupae of Tribolium confusum and Tribolium castaneum and thereby disrupting adult development. At a dietary concentration of 20 mg kg^?1, 95% of pupae of T. confusum produced pupa-adult intermediates; T. castaneum pupae were affected to a smaller extent. Topical application with 0.002 μg per 0–24-h-old pupa of T. confusum resulted in the formation of 88% malformed intermediates. The larvae brought into contact with R-31026 were not affected and pupated normally, hence the compound differs in its activity from that of a typical juvenile hormone compound. On the other hand, the pupal morphogenetic activity of R-31026 resembles that of the typical juvenoid compound 3-[5-(4-ethylphenoxy)-3-methylpent-3-enyl]-2,2-dimethyloxirane (R-20458). The progeny of the emerging adults from pupae treated with either R-20458 or R-31026 were strongly affected. The effective dosages were far below those required for pupal morphogenetic activity. Biochemical studies showed an increase in the soluble protein fraction during the pupal stage after treatment with either R-31026 or R-20458 indicating disturbances in protein build-up. The bis(thiocarbamate) R-31026 has more favourable practical properties than R-20458 for controlling agricultural insects, because it does not prolong the larval feeding stage.     

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.