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.     

O,O′-二烃基 N-[α-芳氧乙(丙)酰基]硫代磷酰肼的合成与除草活性

通过芳氧乙(丙)酸与O,O'-二烃基硫代磷酰肼的缩合反应合成了8个未见报道的标题化合物,利用红外光谱、核磁共振、质谱和元素分析确定了化合物的结构。生物活性测试结果表明:目标化合物具有很好的选择性除草活性,其中化合物 3a、3b、3g和3h 对单子叶植物稗草和双子叶植物油菜均有较好的抑制作用,特别是对油菜的抑制作用尤为明显,其效果接近、有些甚至优于对照化合物2,4-D。     

A mechanism for the formation of bis-glutathione conjugates of propargyl alcohol

Our earlier research clearly revealed glutathione (GSH) conjugation as a major pathway for the metabolism of propargyl alcohol (2-propyn-1-ol) in rats and in mice. The identification of the metabolite 3,3-bis[(2-acetylamino-2-carboxyethyl)thio]-1-propanol (I) and its congeners represented the first example of multi-glutathione addition to a triple bond, and invoked further research to determine the mechanism for bis-conjugation. To determine whether GSH conjugated directly with propargyl alcohol or after oxidation of the latter to 2-propynal, urinary metabolites from rats administered deuterium-labeled propargyl alcohol were characterized. Following TLC separation and HPLC purification, mass spectrometry was used to show a single mass unit increase for metabolite I over that of the chemically synthesized standard. This result indicates that conjugation of propargyl alcohol with GSH to form the bis-conjugates occurred after initial oxidation to 2-propynal, a reaction that is analogous to a Michael addition.     

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.     

S-cysteinyl-hydroxychlorpropham: Formation of the S-cysteinyl conjugate of isopropyl-3′-chloro-4′-hydroxycarbanilate in oat (Avena sativa L.)

Isopropyl-3′-chlorocarbanilate (chlorpropham) forms phenolic metabolites, isopropyl-3′-chloro-4′-hydroxycarbanilate (I), and isopropyl-5′-chloro-2′-hydroxycarbanilate (II), in several plant species. In oat, which is a chlorpropham-susceptible plant, I was converted to an S-cysteinyl-conjugate (III). The reaction in vitro was catalyzed by a partially purified, soluble enzyme. The formation of III by the enzyme preparation and by oat shoot sections was compared. Mass spectral data indicated the presence of an aryl-thioether bond, and chloro-, hydroxy-, and isopropylcarbanilate groups in III. The results of this investigation indicate that III was isopropyl-[(2-amino-2-carboxyethyl)thio]-chloro-hydroxycarbanilate (S-cysteinyl-hydroxychlorpropham).     

靶标酶在研究杀虫活性构效关系中的应用

运用已建立的乙酰胆碱酯酶(AChE) 活力分析规范化筛选模型, 研究N-甲基取代苯基氨基甲酸酯类化合物和含硅氨基甲酸酯类新系列化合物与AChE 酶抑制中量( I50)构效关系的规律, 并以CA SAR 软件进行Q SAR 分析, 所得结果迅速反馈给化学合成, 为高效低毒新杀虫剂的创制提供有益的信息和科学依据。     

Design,synthesis and structure–activity relationships of novel ALS inhibitors

The paper describes the biophore models of sulfonylurea, imidazolinone, triazolopyrimidinesulfonamide and 5‐pyrimidyltriazolo‐3‐sulfonamides established by the Apex‐3D method. A series of N‐phenylsulfonyl‐N ′‐(thiadiazol‐2‐yl)oxamides and three types of triazolopyrimidinesulfonamide were synthesised and their herbicidal activities determined to assess the validity of the model. In general, the model gave useful leads to activity, although the actual level was not always predicted accurately. In only a few cases did compounds predicted as being active prove to be inactive in the bioassay, and compounds with little or no activity were clearly indicated. As a result of this work, the compound N,N ′‐[1‐(5,7‐dimethyl‐1,2,4‐triazolo[1,5‐a]pyrimidin‐2‐yl‐thio)butane‐2,3‐di‐imino]bis(2‐chlorobenzenesulfonamide) was selected as showing good activity against a range of species, and will be used as a lead for further development. © 2000 Society of Chemical Industry     

Quantification of plasma and egg 4,4'-dinitrocarbanilide (DNC) residues for the efficient development of a nicarbazin-based contraceptive for pest waterfowl

Urbanization and associated landscaping has increased the abundance of year-round habitat for waterfowl, resulting in vegetation damage, loss of recreational activities, air transportation mishaps and health hazards. As part of a research program to develop socially acceptable techniques for management of pest bird populations, we are evaluating nicarbazin as a contraceptive in pest and surrogate avian species. As reproductive studies with Canada Geese (Branta canadensis) are tedious due to the difficulty of conducting controlled field studies and/or breeding geese in captivity, we evaluated the effects of oral nicarbazin administration on the production and hatchability of chicken eggs. Blood plasma and egg DNC concentrations were correlated to contraceptive efficacy. Subsequent studies are being conducted with geese to determine the diet nicarbazin concentration required to produce the desired blood and plasma DNC concentrations. This approach permits the expeditious evaluation of formulations and dosing regimes by simply monitoring blood DNC concentrations in target species.     

Studies of the New Herbicide KIH-6127. Part II. Synthesis and Herbicidal Activity of 6-Acyl Pyrimidin-2-yl Salicylates and Analogues against Barnyard Grass

The method reported previously (Part I) was employed to prepare a variety of novel 6-acylsalicylates as key intermediates. 6-Acylpyrimidin-2-yl salicylates (2-acyl-6-[(4,6-disubstituted pyrimidin-2-yl)oxy]benzoate derivatives: Type 1), the closely related phthalide compounds (3-alkyl-7-[(4,6-dimethoxypyrimidin-2-yl)oxy]phthalide derivatives: Type 2) and the ketal derivatives of 2-acyl-6-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoates (Type 3) were synthesized and their herbicidal activities measured. Methyl 2-acetyl-6-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate gave excellent control of barnyard grass with a promising profile as a prototype rice herbicide.     

7‐(4,6‐Dimethoxypyrimidinyl)oxy‐ and ‐thiophthalides as novel herbicides: Part 1. CGA 279 233: a new grass‐killer for rice

A series of novel types of 7‐(4,6‐dimethoxypyrimidin‐2‐yl)oxy ‐ and ‐thio‐3‐methyl‐1 (3H)‐isobenzofuranones were discovered at Dr R Maag AG. From the thio‐isobenzofuranyl series, CGA 279 233—BSI‐proposed common name pyriftalid—was chosen for further development as a grass herbicide for use in rice. General synthetic approaches to these new phthalic acid‐derived compounds are given, with emphasis on the synthesis of pyriftalid and its physico‐chemical behaviour. © 2001 Society of Chemical Industry     

Synthesis and insecticidal activities of novel oxime ether pyrethroids

A series of novel 2-methylthio-3'/4'-substituted acetophenone oxime O-ethers were synthesized by the reaction of the corresponding acetophenone oximes with halides of pyrethroid alcohols in the presence of sodium hydroxide and phase-transfer catalysis or with triethyl quaternary ammonium salts of halides of pyrethroid alcohols in the presence of sodium hydroxide. These compounds showed notable insecticidal activity against Homopteran and Lepidopteran pests. 2-Methylthio-4'-fluoroacetophenone oxime O-[(2-methylbiphenyl-3-yl)methyl] ether was more effective than the commercial insecticides chlorfenapyr and fenvalerate.     

吡啶衍生物研究(II)3-(4-吡啶基)-4-烃基-1,2,4-三唑啉-5-硫酮的合成及生物活性

本文研究合成了十七个 3- (4-吡啶基 ) - 4 -烃基 - 1,2 ,4 -三唑啉 - 5-硫酮化合物 ,并归属了它们的1HNMR和 13 CNMR。生物活性测定结果表明 ,合成化合物均具有一定的杀菌和除草活性 ,但植物生长促进活性较差     

Inhibitory effects of furanone metabolites of a rhizobacterium, Pseudomonas jessenii, on phytopathogenic Aphanomyces cochlioides and Pythium aphanidermatum

An antagonistic rhizobacterium, Pseudomonas jessenii EC-S101, isolated from the rhizosphere of spinach, produces two related secondary metabolites, 3-[(1 R )-hydroxyoctyl]-5-methylene-2(5 H )-furanone (4,5-didehydroacaterin) (1) and 3-[(1 R )-hydroxyhexyl]-5-methylene-2(5 H )-furanone (2). This study demonstrated their in vitro inhibitory effects, in particular those of (1), against Aphanomyces cochlioides AC-5 and Pythium aphanidermatum PA-5. The compounds inhibited radial growth and induced morphological abnormalities characterized by hyperbranching and periodic swelling in AC-5 and PA-5 hyphae, respectively. Staining with rhodamine-phalloidin, which binds to plasma-membrane-associated filamentous-actin (F-actin), revealed that tip-specific actin filaments were remodelled into a plaque-like form at an early stage of encounter (up to 24 h) with (1) or (2), whereas at later stages of encounter (48 h), the plaques were eliminated, reflecting the disorganization of actin arrays in the morphologically abnormal AC-5 and PA-5 hyphae. A similar response of actin disorganization was observed in AC-5 and PA-5 hyphae upon treatment with latrunculin B (3), an actin-assembly inhibitor produced by a sea sponge. It is suggested that (1) and (2) caused actin disorganization and their inhibitory activities were comparable to that of (3). Further ultrastructural observations substantiated abnormal functioning and delocalization of F-actin-linked cell organelles.     

Insecticidal activity and nicotinic acetylcholine receptor binding of dinotefuran and its analogues in the housefly, Musca domestica

The insecticidal activity of dinotefuran and 23 related compounds against the housefly, Musca domestica (L) was measured by injection with metabolic inhibitors. Dinotefuran was less active than imidacloprid and clothianidin by a factor of 10 in molar concentrations. Their binding activities to the fly-head membrane preparation were measured by using [125I]alpha-bungarotoxin ([125I]alpha-BGTX) and [3H]imidacloprid ([3H]IMI) as radioligands. The activity of some selected compounds measured with [3H]IMI was 10(4)-fold higher than that measured with [125I]alpha-BGTX. With [3H]IMI as a radioligand, dinotefuran was 13-fold less active than imidacloprid. The inhibitory effect of dinotefuran on the binding of [3H]IMI to the membrane preparation was in a competitive manner. Quantitative analysis of the insecticidal activity of the test compounds with the binding activity measured with [3H]IMI showed that the higher the binding activity, the higher was the insecticidal activity.     

Feeding‐deterrent activity of α‐asarone isomers against some stored Coleoptera

All isomers of α‐asarone [(E)‐4‐prop‐1‐enyl‐1,2,5‐trimethoxybenzene] were tested for their feeding deterrent activity against adults of Sitophilus granarius and Tribolium confusum and larvae of Trogoderma granarium and Tribolium confusum. (E)‐2‐prop‐1‐enyl‐1,3,5‐trimethoxybenzene exhibited the strongest deterrent activity against all the species tested. The total coefficients of deterrency for this compound were 140.6 and 169.7 for Tribolium confusum adults and larvae, respectively, and 144.9 and 104.6 for larvae of Trogoderma granarium and adults of Sitophilus granarius, respectively. © 2000 Society of Chemical Industry     

Synthesis and bioactivity of some new N-aryl/alkyl/cyclohexyl-N'-(2,3-dihydro-2-oxo-4H-benz[e][1,3,2]oxazaphosphorin-2-yl) ureas

Several new substituted oxazaphosphorinyl urea derivatives of the type RR'P(O)NHC(O)NHR' were synthesized from alpha-(3-chloro-4-fluoroanilino)-o-cresol by reaction with chlorides of aryl/alkyl/cyclohexyl carbamidophosphoric acids in the presence of triethylamine at 0-50 degrees C. Their significant insecticidal and antimicrobial activity and promotion of Rhizobium bacteria growth in the soil without effect on the host tissue suggests their possible commercial application as ecofriendly pesticides and antimicrobial agents.     

Soil metabolism of flupyrsulfuron in winter wheat crops

The sulfonylurea herbicide flupyrsulfuron was applied post‐emergence in March at the rate of 10 g a.i. ha^?1 on winter wheat crops. In the 0–8 cm surface soil layer of the crops grown on sandy loam and loam soils, the flupyrsulfuron half‐life was 64 and 40 days respectively. Flupyrsulfuron and its metabolites were not detected during both crops or 1 month after crop harvest in the 8–15 and 15–20 cm soil layers. Soil degradation of flupyrsulfuron successively generated the cyclization products 1‐(4,6‐dimethoxypyrimidine‐2‐yl)‐2,4‐diketo‐7‐trifluoromethyl‐1,2,3,4‐tetrahydropyrido[2,3‐d]pyrimidine 2 and N‐(4,6‐dimethoxypyrimidine‐2‐yl)‐N‐(3‐methoxycarbonyl‐6‐trifluoromethylpyridine‐2‐yl)‐amine 3 , which were the main metabolites of flupyrsulfuron in soil. Hydrolysis of 3 successively generated N‐(4,6‐dimethoxypyrimidine‐2‐yl)‐N‐(3‐car‐ boxylic acid‐6‐trifluoromethylpyridine‐2‐yl)‐amine 4 and N‐(4‐methoxy‐6‐hydroxypyrimidine‐2‐yl)‐N‐(3‐carboxylic acid‐6‐trifluoromethylpyridine‐2‐yl)‐amine 5 . Low and temporary concentrations of 2‐sulfonamido‐3‐carbomethoxy‐6‐trifluoromethyl‐pyridine 6 and 2‐amino‐4,6‐dimethoxypyrimidine 7 were observed. Bioassays with sugarbeet as test plants indicated that 2, 3, 4, 5, 6 and 7 had herbicide activities corresponding to 100%, 80%, 75%, 75%, 75% and 15% of that of flupyrsulfuron respectively. The metabolites thus extended the herbicidal protection given by flupyrsulfuron and explain the high herbicidal protection given by the low dose of flupyrsulfuron applied. One month after the harvest of the winter wheat, no more significant residue of flupyrsulfuron or of its metabolites was detected in soil.     

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     

啶酰菌胺等8种杀菌剂对烟草叶斑病菌的生物活性

采用生物测定方法分析了烟草叶斑病菌Didymella segeticola在菌丝生长阶段对8种杀菌剂(啶酰菌胺、苯醚甲环唑、丙环唑、氟硅唑、多菌灵、咪鲜胺、菌核净和代森锰锌)的敏感性,同时通过离体叶片法测定了8种杀菌剂对烟草叶斑病的保护和治疗作用。结果表明：供试8种杀菌剂对D. segeticola菌丝生长表现出不同的抑制活性,同时对其引起的病害具有一定的保护和治疗作用。抑菌活性最强的是啶酰菌胺,其平均EC₅₀值为(0.047 0±0.012 0) mg/L;其次依次为苯醚甲环唑[(0.079 0±0.005 0) mg/L]、咪鲜胺[(0.29±0.08) mg/L]、丙环唑[(0.69±0.12) mg/L]、菌核净[(1.08±0.33) mg/L]、多菌灵[(1.22±0.29) mg/L]、氟硅唑[(1.38±0.07)mg/L];代森锰锌的抑菌活性最弱[(22.80±10.51) mg/L]。进一步研究表明,氟硅唑、苯醚甲环唑、丙环唑、啶酰菌胺、菌核净和多菌灵对烟草叶斑病保护作用较强,25 mg/L药剂质量浓度处理下防效均>82%;100 mg/...     

Synthesis and characterization of synthetic analogs of cinnacidin, a novel phytotoxin from Nectria sp

BACKGROUND: The novel natural product cinnacidin was isolated from a fungal fermentation extract of Nectria sp. DA060097. The compound was found to contain a cyclopentalenone ring system with an isoleucine subunit linked through an amide bond. Initial biological characterization of cinnacidin suggested promising herbicidal activity. RESULTS: Two synthetic analogs, (2S,3S)-2-[(3RS,3aSR,6aRS)-3-methoxy-4-oxo-3,3a,4,5,6,6a-hexahydropentalen-1-ylcarbamoyl]-3-methylvaleric acid and benzyl (2S,3S)-2-[(3RS,3aSR,6aRS)-3-methoxy-4-oxo-3,3a,4, 5,6,6a-hexahydropentalen-1-ylcarbamoyl]-3-methylvalerate, were prepared for further characterization, and their herbicidal activities were compared with that of cinnacidin. CONCLUSIONS: The synthetic compounds were highly phytotoxic on a range of weeds. Based on the symptoms in treated plants, the mode of action of these compounds is suggested to be similar to that of coronatine and jasmonic acid. Coronatine was more active against warm-season grasses, while the cinnacidin benzyl ester analog was more effective on cool-season grasses. In a seedling growth bioassay conducted on bentgrass, the cinnacidin analog was equivalent in activity to coronatine.