Synthesis and fungitoxic activity of 5‐aryl‐1‐formyl‐4,5‐dihydro‐3‐(2‐hydroxyphenyl)‐1H‐pyrazoles and their complexes

Cyclization of 3‐aryl‐1‐(2‐hydroxyphenyl)prop‐2‐en‐1‐ones with hydrazine hydrate in refluxing formic acid afforded the title ligands, 5‐aryl‐1‐formyl‐4,5‐dihydro‐3‐(2‐hydroxyphenyl)‐1H‐pyrazoles (HL¹–HL⁴, Ar = Ph, 4‐CH₃O‐C₆H₄‐, 2‐furyl, 2‐thienyl). Reaction of HL¹–HL⁴ with the divalent metal ions, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺, afforded novel complexes of the type [ML₂] (M = metal ion; L = deprotonated ligand) which were characterized by elemental analyses, molecular weight determinations, molar conductances, magnetic moments and electronic and infrared spectral data. The ligands behaved as tridentate, coordinating through the phenolic oxygen after deprotonation, N‐2 of the pyrazole ring and oxygen of the 1‐formyl group. The ligands and their complexes were evaluated for growth‐inhibiting activity against four phytopathogenic fungi. Macrophomina phaseoli was generally most sensitive followed by Alternaria alternata and Colletotrichum falcatum while Fusarium oxysporum was least sensitive to the tested compounds. The ligand HL¹ and its complexes showed the best activity against the fungi tested. © 2000 Society of Chemical Industry     

Activity of the botanical aphicides 1,5‐diphenyl‐1‐pentanone and 1,5‐diphenyl‐2‐penten‐1‐one on two species of Aphididnae

1,5‐Diphenyl‐1‐pentanone (A) and 1,5‐diphenyl‐2‐penten‐1‐one (B) are natural products extracted for the first time from Stellera chamaejasme. Laboratory bioassay showed that the two products have strong contact activity and very good anti‐feedant activity against Aphis gossypii and Schizaphis graminum. Both products showed dose‐dependent relationships for both forms of activity against the two aphids, the contact activity of B being about twice that of A. Both products were inferior to methomyl in contact activity but superior in anti‐feedant activity against the two aphids. This is the first report of aphicidal activity in these two compounds, which may represent a new class of aphicide. © 2001 Society of Chemical Industry     

Differentially expressed genes in dicamba‐resistant and dicamba‐susceptible biotypes

In an ongoing effort to investigate the mechanism of auxinic herbicide resistance in Kochia scoparia (kochia), polymerase chain reaction‐based cDNA suppression subtractive hybridization was used to identify genes that are differentially expressed between dicamba‐resistant (HRd) and dicamba‐susceptible (S1) kochia biotypes in response to herbicide treatment. Both the HRd and S1 adaptor‐ligated cDNAs were used in separate hybridizations in order to generate biotype‐specific clones. A total of 710 cDNAs, representing putative differentially expressed mRNAs, were isolated and subjected to further screening. The false‐positive cDNAs were removed by conducting two colony hybridizations and at least one Northern hybridization. Differential or biotype‐specific expression was confirmed for six clones each from the HRd and S1 plants. The S1‐related genes were constitutively expressed at higher levels than in the HRd plants, but none had significant sequence similarity to known genes. Among the HRd‐related genes, HRd‐88 had 42% amino acid sequence identity to a conserved domain within thiol peptidases, which might be involved in auxin‐regulated gene expression. The constitutively expressed and inducible (by the dicamba treatment) HRd‐39 had 40% identity and 60% similarity to a domain from the Fe(II)/α‐ketoglutarate‐dependent hydroxylase superfamily. The HRd‐39 gene product had the characteristics of an enzyme that is able to detoxify dicamba via oxidative hydroxylation and thus its overexpression might confer the dicamba resistance phenotype.     

Surfactant‐induced deposit structures in relation to the biological efficacy of glyphosate on easy‐ and difficult‐to‐wet weed species

BACKGROUND: Typical active ingredient (AI) residue patterns are formed during droplet drying on plant surfaces owing to the interaction of spray solution characteristics and leaf micromorphology. Currently, comparatively little is known about the influence of AI deposit patterns within a spray droplet residue area on the penetration and biological efficacy of glyphosate. A scanning electron microscope with energy dispersive X‐ray microanalysis has been used to characterise residue patterns and to quantify the area ultimately covered by glyphosate within the droplet spread area. RESULTS: The easy‐to‐wet weed species Stellaria media L. and Viola arvensis L., as well as the difficult‐to‐wet Chenopodium album L. and Setaria viridis L., differing in their surface micromorphology, have been used. Rapeseed oil ethoxylates (RSO 5 or RSO 60) were added to glyphosate solutions to provide different droplet spread areas. Addition of RSO 5 enhanced droplet spread area more than RSO 60, and both caused distinct glyphosate residue patterns. The biological efficacy of treatment solutions showed no significant correlation with the area ultimately covered by glyphosate. CONCLUSION: The results have implications on herbicide uptake models. This study shows that droplet spread area does not correspond to the area ultimately covered by glyphosate, and that the latter does not affect glyphosate phytotoxicity. Copyright © 2009 Society of Chemical Industry     

Adsorption and degradation of thiazopyr in compost‐amended and non‐amended soils

Adsorption and degradation of thiazopyr on two unamended soils and a soil amended annually during 8 years with compost were studied under laboratory conditions and compared with the results obtained on soils amended with fresh sewage sludge compost. The adsorption isotherms fitted the Freundlich equation well and a marked sorption increase was found in amended soils. Degradation data followed first‐order kinetics and thiazopyr had a half‐life of about 75 days at 25 °C and 60% water‐holding capacity of soil. The addition of fresh compost markedly decreased the rate of thiazopyr degradation, whereas the compost mineralised in the field after annual additions had only a small influence. Incubation studies with sterile soils showed a very significant decrease of the degradation rate, indicating that degradation by micro‐organisms was the main pathway of thiazopyr degradation in the soils studied. © 2001 Society of Chemical Industry     

Phototransformation of metoxuron [3‐(3‐chloro‐4‐methoxyphenyl)‐1,1‐dimethylurea] in aqueous solution

UV irradiation of metoxuron in aerated aqueous solution at 254 nm or between 300 and 450 nm led initially to an almost specific photohydrolysis of the C–Cl bond, resulting in the formation of 3‐(3‐hydroxy‐4‐methoxyphenyl)‐1,1‐dimethylurea (MX3) and hydrogen chloride. The quantum yield was determined to be 0.020 (±0.005) in solutions irradiated at 254 nm. Five minor photoproducts were also identified, in particular the dihydroxydimethoxybiphenyl derivatives resulting from the phototransformation of MX3. Irradiation increased the toxicity of an aqueous solution of metoxuron to the marine bacterium Vibrio fischeri. © 2001 Society of Chemical Industry     

Segregation of non‐target‐site resistance to herbicides in multiple‐resistant Alopecurus myosuroides plants

Non‐target‐site resistance (NTSR) comprises a set of mechanisms conferring resistance to multiple modes of action. Investigation of the number of loci involved in NTSR will aid in the understanding of these resistance mechanisms. Therefore, six different multiple herbicide‐resistant Alopecurus myosuroides plants with different herbicide history were crossed in two generations with a susceptible wild type. Seeds from the backcrossing generation were studied for their segregation rate for resistance to five herbicides with four different modes of action (HRAC groups C₂, A, B and K₃). Taking into account that NTSR is a set of quantitative traits, the numbers of loci controlling NTSR were estimated using a normal mixture model fitted by the NLMIXED procedure of SAS. Each herbicide was controlled by a different number of loci comparing the six plants. In most of the cases, chlorotoluron resistance was controlled by one locus, whereas resistance to fenoxaprop‐P‐ethyl needed one or two loci. Resistance to pinoxaden was in all plants conferred by two loci. Cross‐resistance of fenoxaprop‐P‐ethyl and pinoxaden was found in all backcrossings, indicating that at least one of the two loci is responsible for both resistances. Resistance to mesosulfuron + iodosulfuron was conferred by a minimum of two loci. Results indicated that a minimum of five different loci can be involved in a multiple NTSR plant. Furthermore, the plant‐specific accumulation of NTSR loci was demonstrated. Such behaviour should be taken into account when evaluating the development and further spread of herbicide resistance.