7Th international congress of pesticide chemistry

A series of 2-(1,3-dimethyl-4-substituted-5-pyrazolyl)sulfonylimino-5,7-disubstituted-2H-1,2,4-thiadiazolo[2,3-a]pyrimidines was synthesized and tested for herbicidal effects. The compounds showed potent activity and improved selectivity to rice when compared with analogous sulfonylurea derivatives.     

Hydrolytic activation/decomposition pathways of herbicidally active ethyl 5-[N-(5,7-dimethoxy-2H-1,2,4- thiadiazolo[2,3-a] pyrimidin-2-ylidene)sulfamoyl]-1,3- dimethylpyrazole-4-carboxylate

Potent herbicidal ethyl 5-[N-(5,7-dimethoxy2H-1,2,4-thiadiazolo-[2,3-a] pyrimidin-2-ylidene)sulfamoyl]-1,3-dimethylpyrazole-4-carboxylate (I) was hydrolyzed under weakly basic conditions to afford a sulfonylurea (VII) , a 2-pyrimidylcyanamide (IV) and a mercaptopyrazole (VI) . The formation of these products was explained by nucleophilic attack at the 1 and 2-positions of the 1,2,4-thiadiazolo[2,3-alpyrimidine ring. This is believed to mimic the process which occurs on application to the plant. I appears to be a pro-pesticide for the sulfonylurea, VII .     

2-(5,7-二甲基-1,2,4-三唑[1,5-a]嘧啶-2-硫代)乙酰胺类化合物的合成及除草活性

以芳胺或取代稠杂环胺、氯乙酰氯和2-巯基-5,7-二甲基-1,2,4-三唑[1,5a-]嘧啶为原料,合成了8个含稠杂环及芳环的三唑并嘧啶类新化合物,结构经1H NMR,M S和IR确证,初步测定了该类化合物在室温下对稗草等3种禾本科杂草和反枝苋等3种阔叶杂草芽前芽后的抑制率,结果表明:有6个化合物在有效剂量75g/hm2下的抑制率超过80%。     

2-(5,7-二甲基-1,2,4-三唑[1,5-a]嘧啶-2-硫代)乙酰胺类化合物的合成及除草活性

以芳胺或取代稠杂环胺、氯乙酰氯和2-巯基-5,7-二甲基-1,2,4-三唑 嘧啶为原料,合成了8个含稠杂环及芳环的三唑并嘧啶类新化合物,结构经1H NMR, MS 和IR确证,初步测定了该类化合物在室温下对稗草等3种禾本科杂草和反枝苋等3种阔叶杂草芽前芽后的抑制率,结果表明:有6个化合物在有效剂量75 g/hm2下的抑制率超过80%。     

2H-1,2,4-噻二唑并[2,3-a]嘧啶衍生物的合成及除草活性研究(Ⅱ)

取代苯氧乙酸及其衍生物、酰基硫脲[1]和2H-1,2,4-噻二唑并嘧啶类化合物[2]都是具有很好生物活性的母体结构。前文[3]曾报道了2H-1,2,4-噻二唑并[2,3-a]嘧啶的苯甲酰亚胺衍生物的合成及除草活性测定。为了寻找高效、高选择性的新型除草剂,本文以2-氯苯氧乙酰异硫氰酸酯1为创制源合成了未见文献报道的4个2和4个3。化合物2和3的结构经元素分析、IR和1HNMR确证。合成路线如下:OCH2CNCSOCl NNH2NXZY丆lOCH2CNHOCSNHNNXZY　　　　　　　1　　　　　　　　　　　　　　　　　　　　　　　2Br2NNYZXNSOCH2CNOCl32/3abcdXCH…     

三氟羧草醚类似物的合成及除草活性

以2,5-二羟基苯甲酸甲酯和三氟羧草醚为起始原料,设计合成了3个系列20个新的三氟羧草醚类似物,通过核磁共振氢谱、碳谱对其结构进行了表征。分别采用小杯法和室内盆栽法测定了目标化合物的除草活性。结果表明,化合物 III-02 [5-(2-氯-4-三氟甲基苯氧基)-2-硝基苯甲酸-(6-甲基苯并噻唑-2-基)酯]对单子叶杂草的除草活性明显高于对照药剂三氟羧草醚,其对稗草Echinochloa crusgalli和马唐Digitaria sanguinalis根茎生长的EC₅₀值分别为2.03、0.93 μg/mL和1.49、0.52 μg/mL;在有效成分100 g/hm2的施药剂量下,化合物 III-02 对单子叶杂草稗草、马唐及狗尾草Setaria viridis的防治效果均在85%以上,明显高于三氟羧草醚,对阔叶杂草马齿苋Portulaca oleracea、反枝苋Amaranthus retroflexus及苘麻Abutilon theophrasti的防治效果可达100%。初步构效关系表明,2-硝基苯甲酰衍生物的除草活性明显优于其2-甲氧基衍生物,三氟羧草醚苯甲酸酯衍生物对单子叶杂草的除草活性明显高于其苯甲酰胺衍生物。     

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.     

Herbicidal efficacy and selectivity of pyribenzoxim in turfgrasses

Three field trials were conducted from 2003–2004 at Utsunomiya University, Japan, to evaluate the safety and herbicidal activity of pyribenzoxim (benzophenone O -[2,6-bis[(4,6-dimethoxy-2-pyrimidinyl)oxybenzoyl]oxime) in turfgrass. Pyribenzoxim showed a high level of safety in bentgrass ( Agrostis palustris Huds.) and zoysiagrass ( Zoysia matrella ) ≤ 300 g ai ha⁻¹ and it controlled various major grass weeds, including annual bluegrass ( Poa annua L.), large crabgrass ( Digitaria sanguinalis L.), and green foxtail ( Setaria viridis L.), and broadleaf weeds, including common dandelion ( Taraxacum officinale Weber), horseweed ( Erigeron canadensis L.), shepherd's-purse ( Capsella bursa-pastoris (L.) Medic.), common chickweed ( Stellaria media L.), common lambsquarters ( Chenopodium album L.), creeping woodsorrel ( Oxalis corniculata L.), and common dayflower ( Commelina communis L.) by fall or spring application. In comparison with bispyribac-sodium (sodium 2,6-[bis(4,6-dimethoxy-2-pyrimidin-2-yl)oxy]benzoate), pyribenzoxim showed a higher safety level in bentgrass and a stronger herbicidal activity on grass weeds; in particular, annual bluegrass and large crabgrass.     

New herbicidal derivatives of 1,2,4-triazolo [1,5-a] pyrimidine

Two new structural classes of herbicide have been discovered which are based on the 1,2,4-triazolo[1,5-a]pyrimidine ring system. These compounds are related to the known herbicidal sulfonylureas and imidazolinones and other studies have shown that they have a similar mode of action, involving the inhibition of branched-chain amino acid biosynthesis, the site of action being the enzyme acetolactate synthase. The design, synthesis and structure- activity relationships of these new classes of compounds are described.     

吡唑酰胺基脲类化合物的合成及除草活性

根据活性结构拼接原理,以1-甲基-3-乙基-5-吡唑甲酰肼为起始原料,设计合成了19个新吡唑酰胺基脲类衍生物,其结构均经过核磁共振氢谱、红外光谱、质谱和元素分析确证。生物活性测试结果表明:大部分化合物对双子叶杂草苘麻Abutilon theophrasti、反枝苋Amaranthus retroflexus以及凹头苋A.ascedense显示出较好的除草活性及选择性,如在2 250 g/hm2的剂量下,3i在苗后和苗前处理时,对苘麻和反枝苋的抑制率都达到了100%。复筛的结果表明,在375 g/hm2下,3i对双子叶杂草表现出中等除草活性。     

牡丹皮提取物除草活性初步研究

为明确牡丹皮(Cortex Moutan Radicis)的除草活性并初步探索其活性成分分离条件,采用平皿法、土壤喷雾法及茎叶喷雾法测定了牡丹皮不同极性溶剂萃取物对反枝苋Amaranthus retroflexus和稗Echinochloa crus-galli的除草活性。平皿法测定结果显示,在1 mg/mL浓度下,牡丹皮正丁醇萃取物的除草活性最强,对反枝苋幼根和幼茎的抑制率分别为67.88%和65.71%,对稗草幼根和幼茎的抑制率分别为68.72%和71.32%;毒力测定结果表明,牡丹皮正丁醇萃取物对反枝苋幼根和幼茎的IC₅₀分别为12.28 mg/L和19.67 mg/L,对稗草幼根和幼茎的IC₅₀分别为43.35 mg/L和72.79 mg/L。土壤喷雾法和茎叶喷雾法测定结果显示,在5 mg/mL浓度下,牡丹皮正丁醇萃取物对反枝苋和稗草的鲜重抑制率最高,其中土壤喷雾法对反枝苋和稗草的鲜重抑制率分别为81.43%和83.18%;茎叶喷雾法对两种杂草的鲜重抑制率分别为80.83%和83.65%。由此可见,牡丹皮的除草活性成分主要集中在正丁醇...     

New 2-phenyl-4,5,6,7-tetrahydro-2H-indazole derivatives as paddy field herbicides

A series of 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives containing various substituted isoxazolinylmethoxy groups at the 5-position of the benzene ring were synthesized and their herbicidal activities assessed under greenhouse and flooded paddy conditions. Among them, compounds having a phenyl or cyano substituent at the 3-position of the 5-methyl-isoxazolin-5-yl structure demonstrated good rice selectivity and potent herbicidal activity against annual weeds at 16-63 g AI ha(-1) under greenhouse conditions. Field trials indicated that these two compounds controlled a wide range of annual weeds rapidly with a good tolerance on transplanted rice seedlings by pre-emergence application. They showed a low mammalian and environmental toxicity in various toxicological tests.     

新型原卟啉原氧化酶抑制剂Y11049的作用特性

为明确新型原卟啉原氧化酶 (PPO) 抑制剂Y11049 [化学名称为 2-((6-氟-5-(3-甲基-2,6-二氧代-4-三氟甲基-3,6-二氢嘧啶-1(2H)-基)苯并[d]噻唑-2-基)硫代)丙酸乙酯] 的作用特性,本研究以同类型药剂苯嘧磺草胺为对照,选择对Y11049敏感的几种阔叶杂草为测试靶标,采用室内生物测定法,分别研究了环境温度、光照强度、模拟降雨及杂草叶龄对Y11049除草活性的影响,以及Y11049在黄瓜和苘麻植株中的吸收传导特性。结果表明:在有效成分3.75、7.5、15及30 g/hm2剂量下,在15~35 ℃ 范围内,Y11049对绿穗苋的除草活性与温度呈显著正相关;强光照 (8427 lx) 条件下,有效成分60 g/hm2的Y11049对牵牛的鲜重抑制率为95.2%,显著高于中等光照 (4200 lx) 和低光照 (5 lx) 条件下的抑制率,说明其为需光型;于施药后4 h模拟降雨,Y11049 对苘麻的鲜重抑制率与无降雨处理之间无显著差异;在有效成分30 g/hm2剂量下,Y11049芽前土壤处理对苘麻和反枝苋无活性,对芽后2~8叶期苘麻和反枝苋的鲜重抑制率分别为86.0%~98.6%和86.5%~97.9%,表明其施药适期较长。Y11049可通过根、茎、叶及芽吸收进入植物体内,但传导能力较弱;其作用特性整体与苯嘧磺草胺相近。研究表明,新型PPO抑制剂 Y11049 在防除非耕地阔叶杂草方面具有较好的应用前景,但以选择温度适宜的晴天施药为宜,且由于其作用方式为触杀,在非耕地应用时需要足够的喷液量以保证均匀喷施于杂草表面。结果可为Y11049的开发应用提供理论依据。     

利用96孔板建立除草剂微量活体筛选方法初探

以马唐、稗草、反枝苋3种杂草为指示植物,采用96孔板建立了化合物除草活性微量活体筛选方法。从6种培养基中筛选出最适合3种指示杂草生长的Ⅰ号培养基,以传统盆栽法为对照,进行了96孔板苗前处理微量活体筛选方法(以下简称96孔板法)的研究。结果表明:96孔板法以指示杂草的株高受抑制情况作为评价指标较为合适;3种供试除草剂采用96孔板法对3种指示杂草所表现出的杀草活性要高于盆栽法;乙氧氟草醚、二甲戊灵、氟乐灵盆栽法的EC50和EC90值分别是96孔板法的1.44~21.47倍和1.47~32.84倍;采用96孔板法,乙氧氟草醚对马唐和反枝苋、二甲戊灵对稗草的活性最高,EC50值分别为0.79、0.73和0.45 μg/mL,EC90值也分别只有3.13、1.72和1.36 μg/mL。96孔板法达到了微量、敏感、节省时间和空间的要求,是发现先导化合物除草活性较适宜的微量活体筛选方法。     

吡啶衍生物研究(IX):N-(1-甲氧羰基)乙基-N-[5-(2-氯吡啶-4-基)-1,3,4-噻二唑-2-基]酰胺的合成及除草活性

为了进一步研究前期发现的除草先导化合物2-仲丁氨基-5-(2-氯吡啶-4-基)-1，3，4-噻二唑(BCPT)的结构-活性关系并提高其除草活性，设计并合成了一系列N-(1-甲氧羰基)乙基-N-[5-(2-氯吡啶-4-基)-1，3，4-噻二唑-2-基]酰胺类化合物。其苗后除草活性测定结果表明，所有化合物的活性都远低于BCPT本身。说明BCPT可能具有与传统酰胺类除草剂不同的作用机制。     

Novel 3,3a,5,9b-tetrahydro-2H-furo[3,2-c][2] benzopyran derivatives: synthesis of chiral glycol benzyl ether herbicides

Novel tricyclic 3,3a,5,9b-tetrahydro-2H-furo[3,2-c][2]benzopyran (TFB) derivatives were synthesized, and their herbicidal activities were elucidated. They were synthesized from D-glucose as a natural chiral source. The formation of the TFB skeleton was achieved by a Friedel-Crafts type intramolecular cyclization of methyl 5-deoxy-2,3-O-dibenzyl-5-C-methyl-D-xylofranosides. The intramolecular cyclization was dependent upon the electronic effects of the substituents at the C-2 benzyloxy group of methyl xylofranosides. Some TFBs exhibited a remarkable herbicidal activity to annual paddy weeds, such as Echinochloa sp, without injury to the rice.     

Dimethoxypyrimidines as Novel Herbicides. Part 1. Synthesis and Herbicidal Activity of Dimethoxyphenoxyphenoxypyrimidines and Analogues

A number of 6-(4-phenoxyphenoxy)pyrimidines and triazines were synthesized and their herbicidal activity was measured. Compounds with the methoxy groups at the 2- and 4-positions on the pyrimidine and triazine rings exhibited high herbicidal activity. Introduction of a substituent into the 5-position of the pyrimidine ring diminished the activity. In the phenoxyphenoxy substructure at the 6-position, the central ether bond can be replaced by a methylene group without loss of activity. The optimum substituent on the terminal phenyl ring was 3-trifluoromethyl. The compounds showed a strong Hill reaction inhibition, but unfortunately showed poor selectivity between weeds and crops.     

Investigation of an emulsifiable oil adjuvant and its components on the activity of a new grass herbicide by factorial experimentation

The herbicidal activity of a new compound [(±)-(EZ}-2-[1-allyloxy-imino)propyr]-3-hydroxy-6-(4-cyanophenyl)cyclohex-2-ene-1-one] (I) , selective to broad-leaf plants, and partially selective in some cereal crops was enhanced by an emulsifiable paraffinic oil (HVI 60E). In order to determine the amount of HVI 60E to be applied with an emulsifiable concentrate of I (IE) a factorial herbicidal assay involving six concentrations of I and five concentrations of HVI 60E (both sets including zero concentration) was conducted to obtain response surfaces of herbicidal activity. The total selectivity of IE in broad-leaf species remained for all HVI 60E concentrations. The activity against grass weeds, except Poa annua L., increased markedly with increasing HVI 60E concentration and enhancement of performance of IE by HVI 60E in broad-leaf crops could be pursued without fear of crop phytotoxicity. However, the increases in activity against grass weeds were accompanied by increases in phytotoxicity against cereal crops. The response surfaces of Echinochloa crus-galli(L.) Beauv. and Zea mays L. were coincident and this result terminated further testing in this outlet. However, the response surfaces of Avena fatua L. and Triticum aestivum L. were reasonably well separated. Further tests in this outlet and in broad-leaf crops are planned around optimum cost-performance ratios derived from combinations with cost-response surfaces. The results of a further lest showed that both components (oil and emulsifier) of HVI 60E were approximately equivalent in adjuvant enhancement activity and so, on cost grounds, a crop oil (low emulsifier content) would be preferred over a crop oil concentrate (high emulsifier content).     

Evaluation of novel sulfonylurea derivatives with a fused heterocyclic moiety as paddy herbicides that control sulfonylurea‐resistant weeds

Herbicidal activity and acetolactate synthase (ALS) inhibition of sulfonylurea derivatives with a fused heterocyclic moiety bonded to a sulfonyl group were investigated. Some compounds that had an imidazo[1,2‐b]pyridazine moiety substituted at the 2‐position by chlorine or methyl controlled sulfonylurea‐resistant (SU‐R) weeds and showed inhibitory activity to ALS prepared from SU‐R Schoenoplectus juncoides shoot. There was a correlation between in vitro and whole‐plant herbicidal activity of the compounds mentioned above against SU‐R Schoenoplectus juncoides. Among them 1‐(2‐chloro‐6‐propylimidazo[1,2‐b]pyridazin‐3‐ylsulfonyl)‐3‐(4,6‐dimethoxypyrimidin‐2‐yl)urea, propyrisulfuron, was selected for further evaluation. Propyrisulfuron effectively controlled paddy weeds at doses of 70 and 140 g a.i. ha^?1 with good rice selectivity in a field trial.     

含稠杂环结构的螺环丁烯内酯类化合物的合成及杀菌活性

为了发现更高杀菌活性的螺环丁烯内酯类化合物并分析该类化合物的构效关系，设计并合成了一系列未见文献报道的含咪唑并噻唑、咪唑并噻嗪和咪唑并噻嗪酮等稠杂环结构的螺环丁烯内酯类化合物，其结构通过核磁共振氢谱 (1H NMR)、碳谱 (13C NMR)及高分辨质谱 (HRMS)确证。离体杀菌活性测试结果表明，化合物 5f 和 6f 对油菜菌核病菌的EC₅₀值分别为33.2和29.8 mg/L，优于对照药剂咪唑菌酮(46.8 mg/L)，化合物 7b 和 7e 对辣椒疫霉的EC₅₀值分别为45.8和43.5 mg/L，优于咪唑菌酮(50.7 mg/L)，与先导化合物相比，其杀菌活性高于2-甲硫基衍生物，低于2-芳氨基衍生物，表明稠杂环的引入可以提高化合物的杀菌活性，而结构中的NH片段对杀菌活性具有关键作用。