Antifungal activities of mono- and di-SCCl3 substituted compounds: Structure-activity correlations

The mono- and di-N-SCCl₃ substituted derivatives of lactams, cyclic urea, 5,5-diphenylhydantoin and 5-ethyl-5-phenylbarbituric acid were synthesized. Many of these compounds have not been reported previously. The antifungal activities were determined by spore germination method using Stemphylium sarcinaeforme, Monilinia fructicola, Helminthosporium maydis and Alternaria solani. Among the lactam and cyclic urea derivatives studied 1,3-bis(trichloromethylthio)-2-imidazolidinone appears to be the most active compound against S. sarcinaeforme, and has activity slightly below those of the commercial products captan and folpet. Among the diphenylhydantoin and phenobarbital derivatives the mono-SCCl₃ compounds appear to be more potent than the disubstituted compounds in most of the cases examined, but they are not as active as the imidazolidinone derivative. The antifungal activity appears to be highly dependent on the lipophilic character as measured by the 1-octanol/water partition coefficient. Since the bis-SCCl₃ compounds are less potent than the mono-substituted compounds in both of the series of compounds studied, it is evident that the whole molecule rather than any decomposition products of the N-SCCl₃ moiety is responsible for the fungitoxicity.     

The kinetics of insecticide action. Part IV: the in-vivo distribution of pyrethroid insecticides during insect poisoning

The distribution of pyrethroids in insects has been studied using a combination of mathematical modelling and experimental observation. This approach has resulted in the formulation of a physiological model of the pharmaco-kinetics of cypermethrin applied topically to larvae of Spodoptera littoralis. Development of this model from simpler two- and three-compartment models is described. Simple models, whilst capable of complex behaviour, consider only the average rates and magnitudes of pharmaco-kinetic processes over whole animals, and cannot account for differences in concentration of insecticide between individual tissues. This can be achieved by using physiological models, but these require more experimental information for their validation. Moreover, unless simplifying assumptions are made, analytical solutions are not feasible for the large number of equations necessary to define such models. The modelling studies prompted an investigation of (1) in-vivo binding of insecticide to insect tissues, (2) the sizes of body compartments, and (3) the factors which affect the distribution of toxicant between these compartments. Binding has a marked effect on pharmacokinetic profiles and may result in oscillatory behaviour. During poisoning, the total bound cypermethrin increases proportionally to the cube root of the elapsed time. This results in a rapid rate of increase over early elapsed times (< 3h) which slows to approach a more linear form thereafter. Average sizes for the body compartments of larvae of Spodoptera littoralis Boisd, and the steady-state distribution of cypermethrin in these compartments are described. Although the haemolymph, which acts as the main distributive phase during poisoning, forms the largest compartment by volume, it has a low affinity for cypermethrin and distribution reaches steady state within 5 min after topical application. The nerve cord (the target tissue), which is the smallest compartment, has the highest steady-state concentration of cypermethrin. The distribution of cypermethrin in larval tissues is related to the ratios of tissue dry matter to water content.     

Binding of organophosphate insecticides to lecithin: A proton magnetic resonance study

The interaction of four vinyl-type organophosphate insecticides with a phospholipid lecithin has been studied by proton magnetic resonance technique. The vinyl proton of organophosphate showed a low field chemical shift change when lecithin was added to a CCl₄ solution of the former. When organophosphate insecticide was added to a dilute solution of lecithin the choline protons peak also showed small chemical shift changes. These chemical shift changes suggest that the most probable binding site in the interaction involves a hydrogen bond formation between the vinyl proton and oxygen atom of phosphatidyl group of lecithin. Chemical shift data has been used to calculate the equilibrium constant of the interaction.     

Structure-activity study of herbicidal N-chloroacetyl-N-phenylglycine esters

N-Chloroacetyl-N-phenylglycine esters were shown to exert various degrees of growth inhibiting activity against young shoots of annual grasses. The activity against the rice plant and barnyard-grass was determined for 58 derivatives where either the aromatic substituent or ester moiety was modified. The structure-activity relationships were analyzed using physicochemical parameters of the molecule such as log P, σ, and E_s, and regression analysis. By comparing the correlations derived for the rice plant and barnyard-grass, the selectivity in herbicidal activity is discussed.     

新烟碱类杀虫剂抗药性研究进展

新烟碱类杀虫剂是一类新开发的杀虫剂。研究表明，害虫野外种群对其敏感性差弄较大，现已有多种害虫对吡虫啉和啶虫脒产生了抗性。初步研究显示，马铃薯叶甲对吡虫啉抗性以不完全隐性的常染色体遗传；抗性似不稳定，交互抗性谱随虫种而变化，抗性形成可能与多功能氧化酶和酯酶有关。合理轮用和高剂量杀死策略是治理其抗性的有效措施。     

多靶标杀虫剂——三氟苯嘧啶混配剂对水稻害虫的田间防治效果

基于兼治水稻害虫二化螟、稻纵卷叶螟和稻飞虱的杀虫单剂缺乏的现状,2014-2015年采用田间小区试验评价了三氟苯嘧啶与氯虫苯甲酰胺、溴氰虫酰胺、甲氧虫酰肼、茚虫威、阿维菌素或甲氨基阿维菌素苯甲酸盐混配以及吡蚜酮与氯虫苯甲酰胺混配对以上几种害虫的防治效果。结果表明,三氟苯嘧啶与氯虫苯甲酰胺混配最为理想,能有效控制二化螟、稻纵卷叶螟和稻飞虱为害;药后14~21d对二化螟和稻纵卷叶螟的防治效果分别为89.40%~93.62%和86.57%~90.81%,药后42d对稻飞虱的防治效果为77.60%~82.24%。其次为三氟苯嘧啶与溴氰虫酰胺混配,对二化螟和稻飞虱高效且兼治稻纵卷叶螟;药后14~21d对二化螟和稻纵卷叶螟的防治效果分别为80.43%~86.75%和67.31%~75.30%,药后42d对稻飞虱的防治效果为79.07%~84.30%。三氟苯嘧啶与甲氧虫酰肼、茚虫威、甲氨基阿维菌素苯甲酸盐或阿维菌素混配对稻飞虱高效,但难以有效控制二化螟和稻纵卷叶螟为害。而吡蚜酮与氯虫苯甲酰胺混配对二化螟和稻纵卷叶螟高效,但后期对稻飞虱的控制作用一般。在水稻生产实践中,使用三氟苯嘧啶与氯虫苯甲酰胺或溴氰虫酰胺混配,可有效控制二化螟、稻纵卷叶螟及稻飞虱为害。     

Structure-activity relationships in fungitoxicants related to triforine and chloraniformethan. Part IV: Evaluation of the predictive power of the Hansch analysis by the preparation and testing of further chloraniformethan analogues

Seven chloraniformethan analogues, which were predicted, on the basis of the quantitative Hansch analysis performed previously, to be as active as the parent compound against barley powdery mildew (Erysiphe graminis), were prepared. Their activity as leaf sprays against E. graminis was much lower than that calculated using the regression equations, indicating that the Hansch analysis is not a suitable method for predicting fungitoxicity in this chloraniformethan series of compounds.     

A theoretical study of discriminating parameters in metabolic resistance to insecticides

In the case where resistance to an insecticide is associated with increased metabolism of the insecticide, it should not be concluded that the resistance is due only to the increased metabolism (i.e. metabolic hypothesis). Here, we study theoretically the pharmacokinetic consequences of a resistance mechanism due to increased metabolism. We consider two cases: treatment with the initial dose D₀ applied to the susceptible strain and the treatment with the initial dose αD₀, with α>1, applied to the resistant strain. We show the conditions for which the metabolism hypothesis is conceivable. The time τ, from which the mortality of the susceptible strain is significantly higher than that of the resistant strain, is an important parameter in determining the validity of the metabolic hypothesis. The more τ increases, the more the conditions are favourable to this hypothesis. Our work suggests an approach to test the metabolic hypothesis from experimental results. © 1998 SCI     

Organosilane insecticides. Part II: Chemistry and structure—activity relationships

Silicon effectively substitutes for quaternary carbon in etofenpr ox-type insecticides; the resulting dimethyl-4-ethoxyphenyl-3-(4-fluoro-3-phenoxyphenyl)propylsilane is a broad-spectrum insecticide with extremely low toxicity to fish. Four regions of this new silane insecticide have been systematically altered. The methyl groups on silicon appear to be critical for activity. Replacement of the fluorine with hydrogen results in a substantial loss of activity. The aromatic rings of the phenoxyphenyl fragment are best tethered by oxygen or carbonyl, the methylene and nitrogen analogs being of very low toxicity to the test species. The activity ranking of the methylene and carbonyl tethers is opposite to that found for ester pyrethroids. The relationship of insecticidal activity to the aromatic substituent para to the silicon atom has been found to correlate with the molar refractivity of the substituent. Replacement of a tetra-substituted carbon atom with a silicon atom can simplify construction of test compounds and thus be advantageously used in the exploration of structure—activity relationships. A novel method for preparing allylbenzenes from aromatic aldehydes was also developed.     

美洲斑潜蝇幼虫对杀虫剂的敏感性研究

利用浸叶法测定了美洲斑潜蝇幼虫对１１种不同类型杀虫剂的敏感性。实验结果表明,齐墩螨素对美洲斑潜蝇具有较高的毒力,其ＬＣ_５０仅为０.０８１８ｍｇ／Ｌ,其次是菊酯类杀虫剂溴氰菊酯和高效氯氰菊酯。美洲斑潜蝇对有机磷杀虫剂马拉硫磷、敌敌畏、乙酰甲胺磷、氨基甲酸酯类杀虫剂灭多威和丁硫克百威具有较强的耐药性。     

Studies on pesticides based on coumarin IV: Synthesis and antifungal activity of twelve 4-(substituted phenoxy)methyl-6-methyl coumarins

Twelve 4-(substituted phenoxy)methyl-6-methyl coumarins were synthesised by the condensation of 4-chloromethyl-6-methyl coumarin with various phenols in the presence of potassium carbonate in dry acetone. The compounds were tested for their toxicity towards the mycelial growth of seven plant pathogenic fungi. Among the tested fungi, Pythium aphanidermatum, Colletotrichum falcatum, Drechslera oryzae, Alternaria alternata and Fusarium solani exhibited maximum sensitivity whereas Macrophomina phaseolina and Rhizoctonia solani were least sensitive to the test compounds. The 4-(4-tert-butylphenoxy)methyl and 4-(4-nitrophenoxy)methyl analogues possessed greatest toxicity towards the majority of the tested fungi.     

Structure-activity relationships in triorganotin biocides: The influence of the anionic radical

Bioassay data are reported for seven triorganotin compounds (R₃SnX), in which R=phenyl, cyclohexyl, or 2-methyl-2-phenylpropyl, and × is the anionic form of the organic chelating ligands quinolin-8-ol, quinoline-8-thiol, 1,3-diphenylpropane-1,3-dione, or 3-hydroxyflavone, when tested against an organophosphorus-resistant species of the two-spotted spider mite (Tetranychus urticae), the potato blight fungus (Phytophthora infestans), and the vine downy mildew fungus (Plasmopara viticola). The relationship between the activity and the co-ordination number of the tin atom is discussed, and it is shown that the anionic group × can, in some instances significantly affect the biological properties.     

Fungicidal activity and chemical constitution. XX. The activity of substituted 1,4-naphthohydroquinone esters and substituted 1,4-naphthoquinones against powdery mildews

Eleven 2-n-alkyl-, ten 2-n-alkyl-3-hydroxy- and ten 2-n-alkyl-2,3-epoxy-3-hydro-1,4-naphthoquinones, together with eighteen 1,4-naphthohydroquinone esters were tested as protectant fungicides against the apple and cucumber powdery mildews (caused by Podosphaera leucotricha and Sphaerotheca fuliginea respectively). In.general the former pathogen was more susceptible to compounds from all four series, the lowest 10⁵ED⁵⁰(M) being 0.7 for 2-n-octyl-2,3-epoxy-3-hydro-1,4 naphthoquinone.     

Occurrence of chlorinated hydrocarbon insecticides, southern Florida--1968-72.

The frequency with which chlorinated hydrocarbon insecticides appear in samples of southern Florida surface waters decreased sharply between 1968 and 1972. Sediment analyses attest to the earlier widespread use of chlordane, DDT, and dieldrin. Insecticide residues are more frequently detected in southern Florida than in other U.S. cropland soils. Transport of DDT, DDD, and DDE from the Everglades agricultural area into water conservation areas and undeveloped parts of the Everglades of southeastern Florida is facilitated by a system of water-management canals. Canal sediments within the urban area of southern Florida have high DDD, DDE, and dieldrin residue concentrations which may reflect local use of insecticides rather than their transport from adjacent agricultural areas.     

Structure-activity relationship study of alkynyl ether insecticide synergists and the development of MB-599 (verbutin)

Structure-activity relationships of aryl alkynyl synergists of the general formula of Ar-Q-R, where Q represents a bridging structure, were studied using a standardised testing system and Relative Potency values. Ethers, esters, oxime ethers, amides and amines were prepared and evaluated. The length of the R-alkynyl chain, the role of the bridge and the substitution of the aromatic ring were examined systematically. The most potent compounds possessed an aromatic ring connected via a bridge of three atoms to an alkynyl chain, forming together a linear side-chain of six atoms. Several highly potent compounds were synthesised of which one (MB-599; proposed common name verbutin) was selected for development as a selective insecticide synergist in crop protection. Its high potential at practical insecticide:synergist ratios makes possible the reduction of the total amount of insect-control chemicals applied, and its use as an additive to produce new formulations of existing insecticides makes it highly advantageous in resistance management, giving a new tool to sustain the effectiveness of a wide range of insecticides. A product containing a (1+1) mixture of verbutin and beta-cypermethrin was launched in Hungary in 2002.     

Note: Toxicity of some insecticides onBracon hebetor under laboratory conditions

Insecticides which were environmentally friendly and the least toxic, were screened against a laboratory strain ofBracon hebetor (Say) (Hymenoptera: Braconidae) for their suitability for release in IPM of cotton. Concentrations ranging from 1 to 1000 ppm of the formulated insecticides in acetone were applied in glass vials and also by a leaf method, whereby cotton leaves were dipped in aqueous solutions of the same concentrations of insecticides. Adult parasitoids were exposed in both methods. According to the LC₅₀ at 24 h exposure, Λ-cyhalothrin and spinosad were the most (7 and 5 ppm) and least (263 and 225 ppm) toxic in the vial and the leaf method, respectively, toB. hebetor. The possible use of the parasitoid for IPM of cotton is discussed. http://www.phytoparasitica.org posting July 20, 2006.     

长翅型与短翅型褐飞虱对杀虫剂的敏感性比较

采用稻苗浸渍法测定了长、短翅型褐飞虱对烯啶虫胺、环氧虫啶、呋虫胺、噻虫嗪、噻虫胺、吡虫啉、毒死蜱、敌敌畏、噻嗪酮、异丙威、吡蚜酮和醚菊酯的敏感性,并对其体内解毒酶活力进行了比较分析。结果表明:长翅型与短翅型褐飞虱若虫对新烟碱类杀虫剂呋虫胺、噻虫嗪、噻虫胺和吡虫啉的敏感性存在显著差异,长翅型比短翅型更敏感;相反,对于有机磷类杀虫剂毒死蜱,短翅型褐飞虱则更敏感;2种生物型对烯啶虫胺、环氧虫啶、敌敌畏、噻嗪酮、异丙威、吡蚜酮和醚菊酯的敏感性无显著差异。解毒酶相对比活力测定结果表明,长翅型褐飞虱若虫酯酶比活力显著高于短翅型,细胞色素P450单加氧酶比活力显著低于短翅型,而谷胱甘肽S-转移酶比活力无显著性差异。本研究结果可为褐飞虱的有效防控提供科学参考。     

Imidazoles III. Pesticidal screening of some substituted 1-hydroxyimidazoles

The screening of 30 substituted 1-hydroxyimidazoles as herbicides, anthelmintics, insecticides, bacteriostats, fungicides, coccidiostats and nematocides disclosed a broad spectrum of biological activity in all but two compounds. The most pesticidally active imidazoles carried an interdiazal benzenoid or heterocyclic aromatic ring substituent with a phenolic or potentially phenolic group attached thereto.     

Toxicity of biorational insecticides to Helicoverpa spp. (Lepidoptera: Noctuidae) and predators in cotton field

Field trials on upland cotton (Gossypium hirstum L.) during its reproductive phase were used to assess the toxicity of several biorational pesticides and chemicals to Helicoverpa armigera (Hübner) and H. puntigera Wallengren, as well as major predators at Dalby, Queensland, Australia. Moderate rate-dependent control was obtained in plots treated with neem (Azadirachta indica A. Juss) seed extract-azadirachtin (Aza) at rates of 30, 60 and 90 g/ha. Plots treated with Talstar EC (bifenthrin) applications achieved the best results, followed by treatment with alternation of chemicals (methomyl, bifenthrin, thiodicarb and endosulfan) and biorational insecticides (neem oil, azadirachtin and Bacillus thuringiensis kurstaki var. Berliner). Predators, including lady beetles, lacewings, spiders and predatory bugs, were insensitive to Aza, tooseendanin (Tsdn) andBT applications. In contrast, chemicals were very destructive of predators. All treatments provided some protection from infestation of H. armigera and H. puntigera. The effect of Aza on Helicoverpa spp. was reflected in a relatively higher yield of seed cotton harvested from Aza-treated plots compared with the control, but chemical control achieved significantly higher yields than any other treatment.