Synthesis of new 7H-1,3,4-thiadiazolo[3,2-a] [1,3,5] triazine-7-thiones as potential fungicides

A number of 2-aryl- and 2-aryloxymethyl-5-aryl-7H-1,3,4-thiadiazolo[3,2-a][1,3,5]triazine-7-thiones have been synthesised and their fungitoxicities determined in vitro against Aspergillus niger and Fusarium oxysporum. Two alternative routes for synthesis of the title compounds are described. Some of the compounds had activities comparable with that of the commercial fungicide mancozeb. Structure/activity relationships for the compounds are discussed.     

Suitability of weed species prevailing in Spanish vineyards as hosts for root-knot nematodes

Commercial vineyards in southern Spain were surveyed and sampled during October to December 2004 to determine the extent to which common weeds present were suitable hosts of root-knot nematodes infesting soils of those vineyards. Seven weed species commonly growing in grapevine soils in southern Spain were found infected by either Meloidogyne incognita or M. javanica: Amaranthus retroflexus (redroot pigweed), Anchusa azurea (ox-tongue), Chenopodium album (goosefoot), Erodium moschatum (musk stork’s bill), Malva rotundifolia (low mallow), Sinapis alba (white mustard), and Solanum nigrum (black nightshade). The host suitability of the weeds to root-knot nematodes was evaluated on the basis of root galling severity and nematode population densities in soil and roots. Also, the host–parasite relationship in these naturally Meloidogyne-infected weeds was examined. All the weed species in the study were considered suitable hosts for M. incognita and M. javanica because: (a) high Meloidogyne spp. populations occurred in roots and surrounding soil of the weed species; (b) the severity of root galling was high, and (c) well-established permanent feeding sites were observed in the histopathological studies of infected root tissues. In addition, this study presents the first reports of S. alba and A. azurea as hosts for M. incognita, and of E. moschatum as a new host for M. javanica, thus increasing the list of reported weed hosts for Meloidogyne spp. These results indicate that noticeable population densities of M. incognita and M. javanica can be maintained or increased in these weeds, at population levels higher than those previously reported for the same nematodes infecting grapevine roots. The weeds infesting vineyards thus represent an important source of inoculum of Meloidogyne spp., and furthermore may act as reservoirs of these nematodes which can be disseminated within or among vineyards by agricultural operations.     

Degradation of [14C]Terbuthylazine and [14C]Atrazine in Laboratory Soil Microcosms

The degradation and formation of major chlorinated metabolites of terbuthylazine and atrazine in three soils (loamy clay, calcareous clay and high clay) were studied in laboratory experiments using molecules labelled with ¹⁴C on the s-triazine ring. Soil microcosms were treated with the equivalent of 1 kg ha^-1 of herbicide and incubated in the dark for 45 days at 20(±1)°C. The quantity of [¹⁴C]carbon dioxide evolved in the soils treated with atrazine was negligible and could not be attributed to mineralization of the parent molecule. The mineralization of terbuthylazine accounted for 0·9–1·2% of the initial radioactivity. In the soils studied, the extrapolated half-lives varied from 88 to 116 days for terbuthylazine and 66 to 105 days for atrazine, with no significant differences for the three soils and the two molecules. The deethyl metabolites of the two s-triazines and the deisopropyl-atrazine metabolite appeared during the incubation in the three soils. The completely dealkylated metabolite was not detected in any of the soils. After 45 days of incubation, the non-extractable soil residues for the high clay, loamy clay and calcareous clay soils represented for terbuthylazine, 33·5, 38·3 and 43·1% and for atrazine, 19·8, 20·8 and 22·3% of the initial radioactivity. © 1997 SCI.     

Metabolism of [14C]parathion and [14C]paraoxon in isolated,perfused rat livers

Perfusion of ¹⁴C-(ring)-parathion or ¹⁴C-(ring)-paraoxon with blood through isolated, intact rat livers resulted in the rapid degradation of these insecticides. Degradation was negligible in the absence of rat liver (controls), thus demonstrating the capacity of the liver per se to effectively degrade these compounds. Of the total radiocarbon recovered after liver perfusion with [¹⁴C]parathion, 33 % could be attributed to unchanged [¹⁴C]parathion (similarly distributed between the liver and the blood) while 67.9 % was degraded to water soluble compounds and 2.5% was converted to organic soluble paraoxon and traces of p-nitrophenol. Nearly all of the [¹⁴C]paraoxon, however, was degraded by the intact rat liver, resulting in water soluble products that amounted to 98.5% of the total radiocarbon recovered. Unexplained losses of radiocarbon with the perfusion apparatus used were lower in the presence of rat liver which degraded the insecticides to more water soluble compounds. The water soluble degradation products produced from [¹⁴C]parathion and [¹⁴C]paraoxon were non-toxic to mosquito larvae (Aedes aegypti L.). These ring-labelled products were found to be conjugated p-nito-phenol. Nearly all of the water soluble radiocarbon was located in the perfused blood, while only small amounts (1.8 to 3.0% of recovered) were excreted via the bile or were associated with the liver tissue (1.3 to 1.8 % of recovered).     

Uptake and metabolism as mechanisms of selective herbicidal activity of the 1,2,4-triazolo[1,5-a] pyrimidines

In order to identify the factors providing the triazolopyrimidines with a wide range of selectivity amongst agriculturally important plant species, studies were made on the uptake and metabolism of a representative compound, N-(2,6-dichlorophenyl)-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine- 2-sulfonamide. This compound is much more phytotoxic to dicots than to monocots. Experiments showed that variations in leaf morphologies and geometries relative to spray applications resulted in different herbicide dosages applied to plant species used in selectivity evaluations. However, this parameter did not have a statistically significant correlation to herbicide selectivity measurements. Characterization of the metabolic pathways showed that the major herbicide metabolites involved methyl hydroxylation or hydroxylation of the aniline ring followed by glucose conjugation. Since these metabolites were not exclusive to either monocots or dicots, herbicide selectivity does not appear dependent on the pathway of metabolism. Studies on the kinetics of metabolism suggest instead that metabolic rate was important. Monocots metabolized the herbicide rapidly and generally were tolerant while the opposite was true of dicots.     

Weeds as alternative hosts for BSBV,BNYVV, and the vector Polymyxa betae (German isolate)

Journal of Plant Diseases and Protection - When grown in contaminated soil, several weed species proved to be alternative hosts for the Beet necrotic yellow vein virus (BNYVV), the Beet soil-borne...     

Binding of [14C]DDT and [14C]dicyclohexylcarbodi-imide to a lipoprotein of the membrane sector of mitochondrial ATpase

Intact mitochondria, isolated from red coxal muscle of the American cockroach (Periplaneta americana L.), were incubated in the presence of 1,1,1-trichloro-2,2-bis(4-chloro[¹⁴C]phenyl)ethane ([¹⁴C]DDT) to isolate a suspected binding site for DDT in the membrane sector of the mitochondrial ATPase. The requirements for the binding of DDT were compared with those for the binding of dicyclohexyl[¹⁴C]carbodi-imide([¹⁴C]DCCD), a potent inhibitory probe of mitochondrial ATPase activity. [¹⁴C]DDT appeared to bind to a proteolipid of the membrane sector, which also binds [¹⁴C]DCCD. Exchange experiments, with [¹⁴C]DCCD, [¹⁴C]DDT and unlabelled DDT at different concentrations, indicated that DDT and DCCD may be acting on a similar protein. This protein may act as the energy transducing protonophore required for the synthesis and hydrolysis of ATP in coupled mitochondria. Inhibition of mitochondrial ATPase activity may be a consequence of DDT and DCCD binding to this proteolipid protonophore, resulting in the disruption of energy transduction in muscle and nerve.     

Fate of [14C]daminozide and [14C]maleic hydrazide in American elm (Ulmus americana L.)

Radiolabelled daminozide and maleic hydrazide (MH) were injected into American elm seedlings, kept in nutrient solution, to determine their translocation pattern and metabolic fate. Both compounds were rapidly translocated to all parts of the plant. After 21 days, 13% of the applied ¹⁴C was exuded into the nutrient solution from the roots of the plants treated with MH. Using gel-filtration and thin-layer chromatographic techniques, it was determined that daminozide did not form any metabolite, and that MH was converted into a MH-sugar complex. A significant amount of ¹⁴C was unextractable from the plant tissue.     

Uptake and translocation of [14C]asulam and [14C]bromacil by roots of maize and bean plants

The uptake and translocation of ¹⁴C-ring-labeled asulam (methylsulfanilcarbamate) and bromacil (5-bromo-3-sec-butyl-6-methyluracil), were compared after root application to maize (Zea mays L.) and bean (Phaseolus vulgaris L.). Autoradiographs showed the distribution of bromacil throughout these and other plant species, and the retention of asulam in the roots. The recovery of both compounds in quantitative radioassays was between 90 and 100%. The absorption of bromacil and asulam was rather similar. Absorption of bromacil increased up to 20% of the applied dose in bean plants after 2 days of exposure, and up to 11% in maize plants after 4 days. Absorption of asulam in bean plants was 22% of the applied dose after 2 days, and 8% in maize plants after 4 days. The pattern of distribution of bromacil and asulam was completely different. After 4 h of exposure of the roots about half of the absorbed bromacil had accumulated in the shoots, while two-thirds or more was translocated to the shoots after exposure periods of 1 to 4 days. Not more than one-eighth of the absorbed asulam was found in the shoots. In consequence, the bromacil content in the transpiration stream relative to that in the ambient solution was much higher than that of asulam. The leakage of asulam from bean and maize roots into herbicide-free nutrient solution was lower than that of bromacil. The reasons for these differences are not yet clear. There was only some metabolism of asulam in maize, but not in bean plants. No metabolites of bromacil were detected in the two plant species.     

Sheep as vectors for branched broomrape (Orobanche ramosa subsp. mutelii [F.W. Schultz] Cout.) seed dispersal

Sheep can be vectors for the long‐distance dispersal of weeds when seed becomes attached and retained in wool or survives the gastrointestinal tract. This study aimed to determine an appropriate quarantine period for sheep that minimized the risk of the long‐distance dispersal of the seeds of branched broomrape (Orobanche ramosa L. subsp. mutelii [F.W. Shultz] Cout.), a parasitic weed. Experiments with penned sheep found that the seeds that were placed on the soil surface adhered to the wool on the thigh and belly of the sheep, with most of the seeds attaching to the feet. Most of the seeds that were applied to the belly and thigh wool detached within 2 days, although a small proportion was present after 7 days. The seeds that were introduced to the digestive tract via drenching had a peak voidance 2 days later and no seed was detected on Day 8. It is suggested that a 7 day quarantine period for sheep would be sufficient in order to reduce the risk of the internal transport of seed to acceptable levels, but a small risk of the external transport of seed on the fleece remains.     

Epidemiological importance of Solanum sisymbriifolium, S. nigrum and S. dulcamara as alternative hosts for Phytophthora infestans

Lesions of Phytophthora infestans were found on woody nightshade ( Solanum dulcamara ), black nightshade ( S. nigrum ) and S. sisymbriifolium during a nationwide late blight survey in the Netherlands in 1999 and 2000. Pathogenicity and spore production of P. infestans isolates collected from potato ( S. tuberosum ), S. nigrum , S. dulcamara and S. sisymbriifolium were determined on several host plant species, and oospore formation in naturally infected and inoculated foliage of hosts was quantified. The present population of P. infestans in the Netherlands is pathogenic on S. nigrum , S. dulcamara and S. sisymbriifolium . Oospores were produced in leaves of S. nigrum , S. dulcamara and S. sisymbriifolium following infection with A1 and A2 isolates. Therefore these plant species should be regarded as alternative hosts for the late blight pathogen. In the case of S. nigrum and S. dulcamara infection was a relatively rare event, suggesting that diseased plants do not significantly contribute to the overall late blight disease pressure present in potato-production areas. Oospore production in ageing S. nigrum and S. dulcamara plants in autumn, however, may generate a considerable source of (auto) infections in following years. Considerable numbers of sporangia and oospores were produced on S. sisymbriifolium following infection with P. infestans . Additional field infection data are needed to evaluate the epidemiological consequences of a commercial introduction of S. sisymbriifolium as a potato cyst nematode trap crop.     

青海东部小麦条锈菌转主寄主小檗资源调查与鉴定

 青海省是中国小麦条锈病的重要流行区。研究证实小檗是小麦条锈菌的转主寄主。然而,关于青海省分布的小檗能否作为小麦条锈菌转主寄主鲜有报道。本研究对青海东部的小檗资源进行调查,并对该地区小檗能否作为小麦条锈菌转主寄主进行了室内人工鉴定。结果表明:有10种小檗在青海东部常见且分布广泛,其中匙叶小檗、置疑小檗、松潘小檗、甘肃小檗和近似小檗,是小麦条锈菌的转主寄主小檗的新种类。本研究对进一步研究青海东部条锈菌有性生殖与毒性变异和小麦条锈病的流行奠定了基础。     

Studies on the mode of action of asulam,aminotriazole and glyphosate in Equisetum arvense L. (field horsetail). II: The metabolism of [14C]asulam, [14C]aminotriazole and [14C]glyphosate

The metabolism of [¹⁴C]asulam (methyl 4-aminophenylsulphonylcarbamate), [¹⁴C] aminotriazole (1H-1,2,4-triazol-3-ylamine) and [¹⁴C]glyphosate (N-(phosphonomethyl)glycine) were assessed in Equisetum arvense L. (field horsetail). Following application of the test herbicides (4mg?0.3 °Ci herbicide/shoot) to the shoots of 2-year-old pot-grown plants, the total recovery of ¹⁴C-label after 1 week and 8 weeks was high for all three herbicides (>80-0% of applied radioactivity). Asulam was persistent (>69-7% of recovered radioactivity) in both shoots and rhizomes. Sulphanilamide, a hydrolysis product of asulam, accounted for the remainder of the recovered radioactivity. Aminotriazole showed evidence of conjugation in shoots and rhizomes. The principal ¹⁴C-labelled component in shoots was composed of high proportions of aminotriazole (>76-3%) together with the metabolites: X (ninhydrin positive), β-(3-amino-1,2,4-triazolyl-1-)α-alanine, Y (diazotization positive) and various unidentified compounds. Rhizomes generally contained lower proportions of intact aminotriazole (>59.4%) together with the metabolites X,Y and unidentified compounds. The proportion of aminotriazole did not decrease with time in shoots or rhizomes; however, the ratio of metabolite X: Y moved in favour of Y as the interval after treatment increased. Glyphosate was extensively metabolised in shoots and rhizomes to yield aminomethylphosphonic acid (AMPA) and various unidentified compounds. Differential metabolism appears to be one of the factors which may govern the persistence and toxicity of the test herbicides in E. arvense.     

Studies on the mode of action of asulam,aminotriazole and glyphosate in Equisetum arvense L. (field horsetail). I: The uptake and translocation of [14c]asulam, [14C]aminotriazole and [14C]glyphosate

The uptake and translocation of [¹⁴C]asulam (methyl 4-aminophenyl-sulphonylcarbamate), [¹⁴C]aminotriazole (1-H-1,2,4-triazol-3-ylamine) and [¹⁴C]glyphosate (N-(phosphonomethyl)glycine) were assessed in Equisetum arvense L. (field horsetail), a weed of mainly horticultural situations. Under controlled-environment conditions, 21°C day/18°C night and 70% r. h., the test herbicides were applied to 2-month-old and 2-year-old plants. Seven days following the application of 0.07-0.09 °Ci (1.14mg) of the test herbicides to young E. arvense, the accumulation of ¹⁴C-label (as percentage of applied radioactivity) in the treated shoots, untreated apical and basal shoots was as follows: [¹⁴C]asulam, 13.2, 0.18 and 1.02%; [¹⁴C] aminotriazole, 67.2, 3.65 and 1-91%; [¹⁴C]glyphosate, 35.9, 0.06 and 0.11%. The equivalent mean values for the accumulation of ¹⁴C-label in 2-year-old E. arvense were [¹⁴C]asulam, 12.0, 1-15 and 1.74%; [¹⁴C]aminotriazole, 58.6, 9.44 and 4.12%; [¹⁴C]glyphosate, 33.1, 0.79 and 2.32%. In the latter experiment, test plants received 0.25-0.30 °Ci (4mg) of herbicide, they were assessed after a 14-day period and the experiment was carried out at 3-week intervals between 2 June and 25 August on outdoor-grown plants. Irrespective of test herbicide or time of application, very low levels of ¹⁴C-label accumulated in the rhizome system. Only 0.2% of the applied radioactivity was recovered in 2-year-old plants and 0.4% in 2-month-old plants. In the young plants [¹⁴C]asulam accumulated greater amounts and concentrations of ¹⁴C-label in the rhizome apices and nodes than [¹⁴C]aminotriazole or [¹⁴C]glyphosate treatments. Inadequate control of E. arvense under field conditions may be due to limited basipetal translocation and accumulation of the test herbicides in the rhizome apices and nodes.     

Synthesis and Evaluation of New Ethyl 2,3- Dihydro-3-oxoisothiazolo[5,4-b]pyridine- 2-alkanoate Derivatives as Potential Herbicides

Several ethyl 2,3-dihydro-3-oxoisothiazolo[5,4-b]pyridine-2-alkanoate derivatives were synthesized as herbicides. Only 5-methyl derivatives inhibited both hypocotyl and root growth in the lettuce (Lactuca sativa L.) seedling test at 100 mg litre^-1. Only ethyl propionate and valerate derivatives showed significant inhibition at 0·1 mg litre^-1, whereas ethyl acetate or butyrate derivatives were inactive. Contrary to unoxidized derivatives, the inhibitory effect of 1-oxide and 1,1-dioxide derivatives was strongly dependent on concentration; ethyl 2,3-dihydro-5-methyl-3-oxoisothiazolo[5,4-b]pyridine-2-propionate 1,1-dioxide inhibited 100% of germination at 100 mg litre^-1 and 45% of lettuce seedling growth at 0·1 mg litre^-1. Quantitative structure–inhibition of growth relationship analysis carried out by adaptive least-squares (ALS) method gave a good correlation with small and hydrophobic 5-substituents as well as with odd carbon-chain ethyl alkanoates in position 2. Active compounds did not show auxin-like activity from 0·1 to 100 mg litre^-1. © 1997 SCI.     

N-烷基-[1,2,3]苯并噻二唑-7-甲酰胺类化合物的合成及生物活性

合成了未见文献报道的 14个 N-烷基 - [1,2 ,3]苯并噻二唑 - 7-甲酰胺类化合物 ,所有新化合物经元素分析、1H NMR、IR确认 ,化合物 - 1表现出一定的诱导抗性活性。