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     

Multiple resistance across glufosinate,glyphosate, paraquat and ACCase‐inhibiting herbicides in an Eleusine indica population

An Eleusine indica population was previously reported as the first global case of field‐evolved glufosinate resistance. This study re‐examines glufosinate resistance and investigates multiple resistance to other herbicides in the population. Dose–response experiments with glufosinate showed that the resistant population is 5‐fold and 14‐fold resistant relative to the susceptible population, based on GR₅₀ and LD₅₀ R/S ratio respectively. The selected glufosinate‐resistant subpopulation also displayed a high‐level resistance to glyphosate, with the respective GR₅₀ and LD₅₀ R/S ratios being 12‐ and 144‐fold. In addition, the subpopulation also displayed a level of resistance to paraquat and ACCase‐inhibiting herbicides fluazifop‐P‐butyl, haloxyfop‐P‐methyl and butroxydim. ACCase gene sequencing revealed that the Trp‐2027‐Cys mutation is likely responsible for resistance to the ACCase inhibitors examined. Here, we confirm glufosinate resistance and importantly, we find very high‐level glyphosate resistance, as well as resistance to paraquat and ACCase‐inhibiting herbicides. This is the first confirmed report of a weed species that evolved multiple resistance across all the three non‐selective global herbicides, glufosinate, glyphosate and paraquat.     

Synthesis and insecticidal activity of new 3-benzylfuran-2-yl N,N,N',N'-tetraethyldiamidophosphate derivatives

BACKGROUND: A series of 3-benzylfuran-2-yl N,N,N',N'-tetraethyldiamidophosphate derivatives were synthesized as potential new agents to control insects. Their structures were confirmed on the basis of IR, NMR and MS analyses. RESULTS: Ten 3-benzylfuran-2-ylN,N,N',N'-tetraethyl derivatives were prepared from the compound furan-2-yl N' (N,N,N',N'-tetraethyldiamidophosphate). The contact toxicity of all derivatives, at a dose of 10 microg mg(-1) insect, was evaluated against four insect species, Ascia monuste orseis Latr. (Lepidoptera: Pyralidae), Diaphania hyalinata (L.) (Lepidoptera: Pyralidae), Sitophilus zeamais Mots. (Coleoptera: Bruchidae) and Solenopsis saevissima (Smith) (Hymenoptera: Formicidae). The mortality range observed for some derivatives, such as 3-(3-methylbenzyl)furan-2-yl N,N,N',N'-tetraethyldiamidophosphate (82.5% mortality against D. hyalinata; 100% mortality against S. saevissima), was comparable with that of the commercial insecticide chlorpyrifos-methyl. The biological activity of the derivatives depended on the substitution pattern of the benzylic ring. Furan-2-yl N,N,N',N'-tetraethyldiamidophosphate, furan-2-yl N,N-diethylamidochlorophosphate and difuran-2-yl N,N-diethylamidophosphate were also evaluated, displaying, in some cases, activity comparable with that of chlorpyrifos-methyl (90%, 100% and 97.5% respectively against A. monuste orseis). Considerable activity was observed for some furan-2(5H)-ones evaluated. CONCLUSION: Ten 3-benzylfuran-2-yl N,N,N',N'-tetraethyldiamidophosphate derivatives were synthesized and fully characterized from a chemical point of view. The results obtained from the biological assays indicate that this class of compounds can be utilized for the design of new substances endowed with insecticidal activity.     

Synthesis, crystal structure and biological activity of aryl [(N,N'-diacyl-N'-tert-butylhydrazino)thio]methylcarbamates

A series of novel aryl [(N,N'-diacyl-N'-tert-butylhydrazino)thio]methylcarbamates were synthesized by the reaction of aryl (chlorothio)methylcarbamates with N,N'-diacyl-N-tert-butylhydrazines in the presence of sodium hydride. X-Ray single crystal diffraction of 2-isobutylphenyl [(N,N'-dibenzoyl-N'-tert-butylhydrazino)thio]methylcarbamate demonstrated the presence of N-S-N bonding. All of the compounds exhibited excellent larvicidal activities. Toxicity assays indicated that the products had knockdown activities of aryl methylcarbamates at higher concentrations and insect growth regulator activities of diacylhydrazines at lower concentrations.     

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.     

Synthesis and herbicidal activity of novel alpha,alpha,alpha-trifluoro-m-tolyl pyridazinone derivatives

A series of novel alpha,alpha,alpha-trifluoro-m-tolyl pyridazinone derivatives was synthesised. Herbicidal activities of the two intermediate compounds and 15 pyridazinone derivatives were evaluated through barnyardgrass and rape cup tests and Spirodela polyrrhiza (L.) Schleiden tests. Selected compounds were also evaluated under greenhouse conditions. Bleaching activities were observed at 10 microg ml(-1) and some compounds exhibited herbicidal activities at a rate of 300 g ha(-1). The relationship between crystal structures and herbicidal activities is discussed through a comparison of two compounds (5a and 5f).     

Cycloate,an inhibitor of fatty acid elongase,modulates the metabolism of very‐long‐side‐chain alkylresorcinols in rye seedlings

BACKGROUND: Cycloate inhibits the biosynthesis of very‐long‐chain fatty acids, the essential constituents of plant waxes and suberin. Fatty acids also serve as precursors of aliphatic carbon chains in resorcinolic lipids, which play a fundamental role in the plant defence system against fungal pathogens. In this study, the effect of cycloate on the biosynthesis of 5‐n‐alkylresorcinols in rye seedlings (Secale cereale L.) grown under various light and thermal conditions was examined. RESULTS: The content of alkylresorcinols biosynthesised in rye was generally increased by the herbicide in both green and etiolated plants. The presence of cycloate also affected patterns of alkylresorcinol homologues in plants grown at 15 and 22 °C; very‐long‐side‐chain compounds were less abundant, whereas both short‐chain saturated and unsaturated homologues were generally accumulated. No cycloate‐related effects caused by homologue pattern modifications were observed at elevated temperature. CONCLUSION: This study extends present understanding of the mode of action of thiocarbamate herbicides. Cycloate markedly affected the biosynthesis of very‐long‐side‐chain resorcinolic lipids in rye seedlings, confirming the existence of parallels in both fatty acid and alkylresorcinol biosynthetic pathways. The observed cycloate‐driven accumulation of 5‐n‐alkylresorcinols may improve the resistance of cereals to infections caused by microbial pathogens. Copyright © 2009 Society of Chemical Industry     

Ovicidal,larvicidal and juvenilizing activity of a picolinephenoxyanilide against Cydia pomonella

N‐(4‐phenoxyphenyl)‐2‐pyridinecarboxamide (1) was synthesized from commercially available materials and its ovicidal and larvicidal activity against Cydia pomonella (L) was tested. The compound showed a LC₅₀ of 0.98 mg ml⁻¹ when eggs less than 24 h were sprayed using a Potter Tower, but it had no effect when eggs older than this were sprayed. The compound did not have larvicidal activity when larvae were treated with 1200 µg g⁻¹. However, the larval head capsules were smaller than those in the controls when treated at this concentration. To assess its possible juvenile‐hormone‐like activity, the compound was topically applied to young pupae of Tribolium confusum duVal, where it produced clear juvenilization effects, which were dependent on the applied dose. © 2000 Society of Chemical Industry     

Isoflucypram,the first representative of a new succinate dehydrogenase inhibitor fungicide subclass: Its chemical discovery and unusual binding mode

Succinate dehydrogenase inhibitors (SDHIs) have played a crucial role in disease control to protect cereals as well as fruit and vegetables for more than a decade. Isoflucypram, the first representative of a newly installed subclass of SDHIs inside the Fungicide Resistance Action Committee (FRAC) family of complex II inhibitors, offers unparalleled long‐lasting efficacy against major foliar diseases in cereals. Herein we report the chemical optimization from early discovery towards isoflucypram and the first hypothesis of its altered binding mode in the ubiquinone binding site of succinate dehydrogenase. © 2020 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Comparison of crop and weed height,for potential differentiation of weed patches at harvest

Weeds and weed control are major production costs in global agriculture, with increasing challenges associated with herbicide‐based management because of concerns with chemical residue and herbicide resistance. Non‐chemical weed management may address these challenges but requires the ability to differentiate weeds from crops. Harvest is an ideal opportunity for the differentiation of weeds that grow taller than the crop, however, the ability to differentiate late‐season weeds from the crop is unknown. Weed mapping enables farmers to locate weed patches, evaluate the success of previous weed management strategies, and assist with planning for future herbicide applications. The aim of this study was to determine whether weed patches could be differentiated from the crop plants, based on height differences. Field surveys were carried out before crop harvest in 2018 and 2019, where a total of 86 and 105 weedy patches were manually assessed respectively. The results of this study demonstrated that across the 191 assessed weedy patches, in 97% of patches with Avena fatua (wild oat) plants, 86% with Raphanus raphanistrum (wild radish) plants and 92% with Sonchus oleraceus L. (sow thistles) plants it was possible to distinguish the weeds taller than the 95% of the crop plants. Future work should be dedicated to the assessment of the ability of remote sensing methods such as Light Detection and Ranging to detect and map late‐season weed species based on the results from this study on crop and weed height differences.     

Nematodes network too: diversity,abundance and dispersal via plant produce trade networks

The dispersal of invasive species, such as plant pests, can have major economic, environmental and social impacts worldwide. Movement of plant pests from farms to both foreign and domestic markets is facilitated by trade networks, such as plant produce trade networks. While many potential pathways of invasive plant pest entry are regulated, few studies have examined the diversity, abundance and dispersal of soil microorganisms, such as nematodes, on plant produce while en route between origin and destination to quantify the risk of invasive plant pest introductions via these pathways. Here it is shown that a large range and number of live nematodes are dispersing locally and nationally via plant produce trade networks, with the potential to also move internationally. Up to 98% of samples tested carried free‐living nematodes and up to 40% carried plant‐parasitic forms. Diversity of nematodes varied between countries and regions, and numbers on samples generally decreased with increasing distance from the farm to market. These findings may have implications for plant biosecurity surveillance as well as human health. Moreover, nematodes provide a model for other potentially invasive species dispersing via plant produce trade networks.     

Biodegradation of methylthio-s-triazines by Rhodococcus sp. strain FJ1117YT, and production of the corresponding methylsulfinyl, methylsulfonyl and hydroxy analogues

A novel bacterial strain FJ1117YT was isolated from an enrichment culture with the herbicide simetryn. The isolate was capable of degrading the herbicide supplied as the sole sulfur source in an aquatic batch culture. The strain FJ1117YT was identified as that belonging to Rhodococcus sp. on the basis of comparative morphology, physiological characteristics and comparison of the 16S rRNA gene sequence. The biodegradation pathway of simetryn was established by isolating the methylsulfinyl analogue as the first metabolite and by identification of the methylsulfonyl intermediate and the hydroxy analogue by liquid chromatography-mass spectrometry (LC-MS) and/or nuclear magnetic resonance (NMR) analysis. The results indicate that the methylthio group was progressively oxidised and hydrolysed by the strain FJ1117YT. The same strain is also able to metabolise other methylthio-s-triazines such as ametryn, desmetryn, dimethametryn and prometryn through similar pathways.     

Effect of application timing and method on efficacy and phytotoxicity of 1,3-D, chloropicrin and metam-sodium combinations in squash plasticulture

BACKGROUND: Metam-sodium, 1,3-dichloropropene (1,3-D) and chloropicrin are widely used soil fumigants. Combined application of metam-sodium and 1,3-D + chloropicrin is intended to improve efficacy and broaden spectrum of control, but little is known about the effect on crop safety. This study aimed to evaluate the effects of application timing of fumigant combinations on soilborne pest and disease control (nematodes, soil fungi and weeds) and growth of squash. Two separate tests with chisel-injected and drip-applied fumigant combinations and plant-back times ranging from 1 to 4 weeks were conducted in Tifton, GA, USA, in spring and fall 2002. RESULTS: Fumigant combinations using 1,3-D, chloropicrin and metam-sodium were as effective as methyl bromide in controlling Meloidogyne incognita (Kofoid & White) Chitwood, Pythium irregulare Buis., Rhizoctonia solani Kühn and Cyperus esculentus L. Chisel-applied combinations were more effective in terms of root-knot nematode control than drip-applied combinations. Root-knot nematode reduced squash yields by up to 60%. Phytotoxicity problems and lower yields were observed during spring, especially following 1,3-D + chloropicrin and when plant-back periods were shorter. CONCLUSION: The main problem with fumigant alternatives to methyl bromide may not be reduced efficacy but, in particular for 1,3-D products, loss of flexibility in terms of longer plant-back periods.     

Synthesis, characterization, absolute structural determination and antifungal activity of a new chlorinated aromatic avenaciolide analogue

BACKGROUND: Avenaciolide, a natural product isolated from Aspergillus avenaceus H. Smith, possesses several interesting biological properties, such as antifungal and antibacterial activities and inhibition of glutamate transport in mitochondria. In a study aiming to discover new compounds with antifungal activity, a bis‐γ‐lactone analogous to avenaciolide was prepared and characterized by elemental analysis, mass spectrometry, and infrared and NMR spectroscopy. RESULTS: The absolute structures of this compound and of the synthetic precursor (also a bis‐γ‐lactone) were determined by X‐ray diffraction analysis. The bis‐γ‐lactones synthesized crystallize in the orthorhombic space group P2₁2₁2₁, and the crystal packings are supported by C? H···O hydrogen bonds. The compound showed antifungal activity against Colletotrichum gloeosporioides (Penz.) Penz. & Sacc., while the synthetic precursor was inactive under the in vitro test conditions employed. CONCLUSION: The results indicate that it is not only the bis‐γ‐lactone skeleton that is important to antifungal activity. The latter also depends on the presence of the exocyclic double bond possibly due to a Michael addition type reaction with the fungal enzymes. Copyright © 2008 Society of Chemical Industry     

Nematicidal activity of anion transport blockers against Meloidogyne incognita, Caenorhabditis elegans and Heterorhabditis bacteriophora

BACKGROUND: Because methyl bromide has been phased out as a soil sterilant, new nematicides are urgently needed. Four different chemical classes of organic acids acting as anion transport (AT) blockers were tested against a free-living nematode, Caenorhabditis elegans Maupas, a plant-parasitic nematode, Meloidogyne incognita (Kofoid and White) Chitwood, and an entomopathogenic nematode, Heterorhabditis bacteriophora Poinar, in toxicity bioassays. The materials tested were DIDS (4,4'-diisothiocyanatostilbene-2,2'-disulfonic acid), 9-AC (anthracene-9-carboxylic acid), NPPB [5-nitro-2-(3-phenylpropylamino)benzoic acid] and IAA-94 (indanyloxyacetic acid). RESULTS: All the compounds showed slowly developing nematicidal activity against second-stage juveniles of M. incognita and adults of C. elegans, but not against H. bacteriophora infective-stage juveniles. The LC(50) values of these compounds were < 50 mg L(-1) after 48 and 72 h incubation, while at 168 h incubation the LC(50) values were < 10 mg L(-1) for both sensitive species. Across both species and time, the LC(50) values generally differed no more than twofold among the four compounds tested in this study. In contrast, none of the compounds (200 mg L(-1)) caused more than control mortality to H. bacteriophora, even after 168 h of incubation. CONCLUSION: These compounds are potential leads for commercial nematicides. The insensitivity to H. bacteriophora is consistent with the natural exposure of this nematode to DST (3,5-dihydroxy-4-isopropylstilbene), a stilbene produced by its symbiotic bacterium. Based on the known activity of the compounds used in this study, it is suggested that anion transporters form the probable target sites for DIDS, 9-AC, NPPB and IAA-94 in nematodes.