Synthesis and herbicidal activity of new oxazinone herbicides with a long-lasting herbicidal activity against Echinochloa oryzicola

Chemical modification of the herbicide 1-[2-(benzothiazol-2-yl)isopropyl]-4-methyl-3-phenyl-5H-pyrrolin-2-one (MI-2826) has revealed a new oxazinone herbicide, 3-[2-(7-chlorobenzothiazol-2-yl)isopropyl]-2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxazin-4-one (MI-3069), for use in paddy fields. In comparing the phyototoxicity of the two herbicides to transplanted rice, the latter was superior to the former and kept the same predominant characteristic to control Echinochloa oryzicola Vasin for a long period of time owing to its long-lasting residual effect.     

Increased herbicidal activity of triazine herbicides by piperonyl butoxide

Piperonyl butoxide (PB) is a known Synergist which enhances the activity of insecticides by inhibiting their biotransformation to less active products. We have evaluated the possible use of PB as a herbicide synergist using triazine herbicides in sensitive, tolerant, and resistant plants. The effects of PB, triazine herbicides, and their combinations were examined in whole plants as well as in chloroplasts isolated from triazine-sensitive (S) and -resistant (R) weed biotypes. PB itself, applied postemergence (0.1–0.5%, v/v), was slightly toxic to the plants tested. However, foliar application of PB combined with atrazine, terbutryn or prometryn to maize seedlings significantly increased the phytotoxicity of the herbicides. Low rates of atrazine, prometryn, and terbutryn in a tank-mixture with PB, effectively controlled Solatium nigrum L. and Abutilon theophrasli Medik. PB enhanced atrazine efficacy in both S and R biotypes of Lolium rigidum Gaud. The synergistic effect of PB was evident also in vitro when atrazine and methabenzthiazuron were used to inhibit photosystem II electron transport in chloroplasts isolated from resistant weeds. These data demonstrate the potential of PB as a herbicide synergist and its possible utilization as an aid for improving the activity of triazine herbicides in sensitive, tolerant and resistant plants.     

单嘧磺酯钠盐的合成及除草活性

单嘧磺酯是新型超高效磺酰脲类除草剂,为了寻找生物活性与之相当、环境友好的同类药剂,室温条件下用单嘧磺酯与氢氧化钠在水中反应合成了单嘧磺酯钠盐,其结构经核磁共振氢谱、红外、质谱及元素分析确认。室内生物测定结果显示,单嘧磺酯钠盐与其母体单嘧磺酯对马唐Digitaria ciliaris、稗草Echinochloa crusgalli、苋菜Amaranthus retroflexus和藜Chenopodium aldum的除草活性基本相当。     

Synthesis and herbicidal activity of new benzenesulfonylureas

A series of benzenesulfonylurea derivatives possessing a branched hydroxymethyl moiety as an ortho-substituent were synthesized and found to have interesting herbicidal activity under submerged paddy conditions.     

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。     

Alkylating reactivity and herbicidal activity of chloroacetamides

The relationship between S- and N-alkylating reactivity and herbicidal activity within a series of chloroacetamides, including several commercial herbicides and newly synthesised analogues was studied. The S-alkylating reactivity of selected chloroacetamides, as well as those of atrazine and chlorfenprop-methyl, was determined by in vitro GSH conjugation at a ratio of GSH to alkylating agent of 25:1. A spectrophotometric reaction using 4-(4-nitrobenzyl)pyridine was used to characterise the N-alkylating reactivity of the chemicals. Our results indicate that a reduced level of N-alkylating reactivity correlates with an improved herbicidal efficacy at a practical rate. However, the phytoxicity of the molecules is not simply dependent on chemical reactivities, but strictly related to the molecular structure, indicating that lipophilicity, uptake, mobility and induction of detoxifying enzymes may also be decisive factors in the mode of action.     

Synthesis and herbicidal activity of phenyl-substituted benzoylpyrazoles

A novel series of substituted 3-phenyl benzoylpyrazoles were prepared and tested as potential grass herbicides. The targeted materials were prepared by three newly developed synthetic routes, which allowed a comprehensive study of the SAR (structure-activity relationships) of this series. The best combination of grass weed activity (Avena fatua L, Setaria viridis (L) Beauv and Alopecurus myosuroides Huds) and wheat selectivity was obtained with an alkoxy group in the 4-position of the phenyl ring. Activity was further enhanced by the presence of tert-butyl on the pyrazole and a methyl group at the C-2 position of the benzoyl moiety. The alkoxy-substituted 3-phenylbenzoylpyrazoles are a novel class of herbicides with potential utility for control of important grass weeds in cereals.     

5-氧代三酮类化感物质及其衍生物的合成和除草活性

为评价5-氧代三酮类化感物质AB5046A和AB5046B及其衍生物的除草活性,以均三酚为起始原料合成了天然化合物AB5046A和AB5046B,同时合成了13个2-脂肪酰基和2-芳香甲酰基衍生物,并采用小杯法和平皿法测定了它们及其衍生物对油菜和稗草的生物活性。结果表明：所建立的合成方法仅通过5步反应即可分别以36%和28%的较高收率合成AB5046A和AB5046B,包括：（1）均三酚通过部分氢化还原和酸性离子交换树脂以83%的产率转化为3-乙氧基-5羟基-环己烯酮;（2）通过对羟基氯甲基甲醚保护,以80%的产率得到酮,（3）经3 mol/L HCl去乙基,进一步在4-N,N-二甲基氨基吡啶（DMAP）/二环己基碳二亚胺（DCC）条件下与相应等量羧酸缩合,分别以77%和71%的产率得到二酮,（4）~（5）随后在三甲基碘硅烷/4A分子筛条件下反应,分别以83%和70%的产率完成AB5046A和AB5046B的合成。AB5046A和AB5046B及其衍生物具有明显的除草活性,油菜和稗草表现出白化和褪绿特征,其中在100 μg/mL浓度下,AB5046A和AB5046B对油菜的根长抑制率均为43.9%,对稗草的株高抑制率则为38.6%和53.2%。在合成的13个衍生物中,5-羟基保护的衍生物2-正辛酰基-3-羟基-5-氧甲氧基甲基-2-环己烯酮（TM-6）对油菜和稗草的抑制率分别达到70.2%和62.5%,除草活性较2个天然产物明显提高,可以作为除草剂先导结构进行优化。     

四唑啉酮衍生物的除草活性及代谢研究进展

四唑啉酮衍生物在医药、农药和材料领域具有广泛的研究和应用价值,特别是在除草活性方面。对两类四唑啉酮衍生物的研发过程、除草活性和代谢方面的研究进展进行了综述,对其发展趋势和应用前景进行了展望。     

Synthesis and herbicidal activity of substituted tetrahydronaphthalenes: I

This paper reports the synthesis and the biological activity of substituted 6-alkyl-1,2,3,4-tetrahydro-1,1-dimethylnaphthalenes in which the substituents at the 5- and/or 7-position are varied with a multitide of functional groups. These compounds exhibited pre-emergent herbicidal activity which was a function of the electron-withdrawing ability and the size of the groups substituted at the 5- and/or 7-position. Nitro and/or nitrile groups at these positions tended to optimize activity.     

Synthesis and herbicidal activity of 3-substituted toxoflavin analogs

We investigated the synthesis and herbicidal activity of 23 toxoflavin analogs, 1a–w, in which aromatic rings (R) were introduced into the C-3 position. In paddy field conditions, 1k (R=2-CF₃–C₆H₄) and 1w (R=2-thienyl) showed excellent herbicidal activity. Under upland field conditions, we found that toxoflavin analogs 1a (R=C₆H₅), 1n (R=2-CH₃O–C₆H₄), and 1p (R=4-CH₃O–C₆H₄) exhibited wide herbicidal spectrum against Echinochloa crus-galli (L) var. crus-galli (ECHCG), Chenopodium album, and Amaranthus viridis (AMAVI). The analog with the 2-fluoro group on benzene ring 1b also showed high herbicidal activity against both ECHCG and AMAVI.     

嘧啶联吡唑甲酰胺类化合物的合成及除草活性

设计合成了一系列结构新颖的嘧啶联吡唑甲酰胺类化合物5a~5o,其结构均经过1H NM R和MS分析确证。初步生物活性测试结果表明:在有效成分150 g/hm2剂量下苗后茎叶喷雾处理时,化合物(R)-N-[1-(4-氯苯基)乙基]-3-二氟甲基-1-(4,6-二甲氧基嘧啶-2-基)-1H-吡唑-4-甲酰胺(5c)、N-[1-(4-氯苯基)乙基]-1-(4,6-二甲氧基嘧啶-2-基)-N-甲基-3-三氟甲基-1H-吡唑-4-甲酰胺(5i)和N-[1-(4-氯苯基)乙基]-1-(4,6-二甲氧基嘧啶-2-基)-3-三氟甲基-1H-吡唑-4-甲酰胺(5k)对繁缕Stellaria media的抑制率高达90%以上;而同样剂量下苗前土壤喷雾处理时,化合物N-[1-(4-氯苯基)乙基]-3-二氟甲基-1-(4,6-二甲氧基嘧啶-2-基)-1H-吡唑-4-甲酰胺(5b)和5c对繁缕的抑制率达100%。该类结构化合物有望作为除草先导化合物进行开发。     

4-取代嘧啶基苯磺酰脲类化合物的合成与除草活性

为了探寻磺酰脲类除草剂的构效关系,以单嘧磺隆和单嘧磺酯为先导化合物,在嘧啶环上引入取代苯基,设计合成了16个新型单取代嘧啶磺酰脲衍生物,其结构均经过核磁共振氢谱、质谱和元素分析确证。盆栽试验结果表明:在1.5 kg/hm2时,大部分化合物对供试杂草具有一定的抑制活性,其中对双子叶杂草的活性高于对单子叶杂草的活性,但均不及先导化合物的活性。     

异香豆素噁二唑类化合物的合成及除草活性

为了寻找具有较高除草活性的异香豆素类化合物,设计合成了16个新型异香豆素噁二唑类化合物4a～4p,其结构均经核磁共振氢谱、碳谱及高分辨质谱确证。初步除草活性测定结果表明,部分目标化合物在500 mg/L下对马唐Digitaria sanguinalis L.和反枝苋Amaranthusretroflexus L.具有一定的除草活性,其中化合物4j（4-[5-（4-氯-苯基）-[1,2,4]二唑-3-基]-3-己基-6,7-二甲氧基异香豆素）的活性最好,对马唐和反枝苋的致死率分别为64%和62%。     

具除草活性放线菌的分离和形态学鉴定

从土壤中分离得到17株放线菌,其中JL27菌株的发酵液上清液对反枝苋萌发抑制率达90％,对苘麻萌发抑制率达96．7％;JL12菌株的发酵液上清液对反枝苋萌发抑制率为19．67％,对苘麻萌发抑制率达100％。JL27菌株属链霉菌属金色类群。     

Synthesis and herbicidal activity of novel heterocyclic protoporphyrinogen oxidase inhibitors

Protox inhibitors are applied as foliar sprays, thus causing very rapid cellular collapse and desiccation of many troublesome weeds in the presence of light. In many respects, they appear to be ideal herbicides, because they act rapidly and do not harm mammals under normal conditions. The main limitation to their widespread adoption is that few crops are naturally resistant to them. Crop tolerance has mainly been pursued with the synthesis of the cyclic imide classes containing 5- and 6-membered heterocycles, including pyrazole, pyridazine, 1,2,4-triazine, triazolinone and trifluoromethyluracil derivatives. Because of their structural novelties and biological performance, active investigations on heterocyclic protox inhibitors have been carried out in our laboratories and we have found 3-arylpyrroles to be a new class of light-activated, membrane-disrupting herbicides. They are active on both grass and broadleaf weeds at low rates. The synthesis and structure-activity relationships are presented.     

丙炔氟草胺除草活性及对棉花的安全性

丙炔氟草胺是一种以原卟啉原氧化酶为作用标靶的N-苯基肽酰亚胺类除草剂。为探究其在棉花田的应用前景,通过温室盆栽法对丙炔氟草胺的杀草谱、除草活性及其对棉花的安全性进行了测定。结果表明:丙炔氟草胺对棉田常见阔叶杂草有较好防效,处理剂量为有效成分15 g/hm2时,对马齿苋Portulaca oleracea、反枝苋Amaranthus retroflexus、藜Chenopodium album、小藜Chenopodium serotinum和鳢肠Eclipta prostrata的鲜重防效均高于90%,对野油菜Rorippa indica、苣荬菜Sonchus arvensis、小飞蓬Conyza canadensis、龙葵Solanum nigrum、马唐Digitaria sanguinalis和牛筋草Eleusine indica等的鲜重防效高于80%;丙炔氟草胺对棉田4种常见阔叶杂草马齿苋、反枝苋、龙葵和藜的除草活性均显著高于二甲戊灵;丙炔氟草胺在鲁棉研28号与马齿苋、反枝苋、龙葵和藜之间的选择性指数依次为79.1、38.1、32.1和112.6,均显著高于二甲戊灵的12.0、9.9、5.8和9.2;鲁棉研37号、鑫秋4号与杂草间的选择性指数,与鲁棉研28号的相近。试验结果表明,丙炔氟草胺可作为棉田苗前防除阔叶杂草的候选药剂之一。     

除草活性细菌SY9的筛选与发酵条件研究

从沈阳玉米田土壤中分离筛选出一株细菌SY9,其代谢产物对反枝苋种子萌发具有明显抑制活性,抑制率达85%.研究发现该菌最佳摇瓶发酵培养基为NYBD,最佳培养基配方为牛肉膏15g,蔗糖10g;最佳发酵培养条件为接菌量1%、起始pH值6.5、装液量40 ml/250ml、发酵温度28℃、摇瓶培养72 h.     

Synthesis and herbicidal activity of 1,4-benzoxazin-3-one sulfonylureas

A series of 1,4-benzoxazin-3-ones with a sulfonylurea group attached at either the 5 or 8 position have been synthesised and found to show moderate herbicidal activity. Similarly, a series of 1,4-benzothiazin-3-ones, including some of the related S-oxides and S-dioxides, with a sulfonylurea group linked at the 8 position, have been prepared and been found to be herbicidal. In both series of compounds many substituent variations were made but none of the compounds showed any useful crop selectivities.