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.     

Mechanism of action of the 1,2,4-triazolo[1,5-a] pyrimidines

The substituted 1,2,4-triazolo[1,5-a]pyrimidines are a new class of highly active herbicides. Protection of Arabidopsis thaliana seedlings from triazolopyrimidine-induced injury by the branched-chain amino acids was observed. Acetolactate synthase (EC 4.1.3.18) was isolated and found to be quite sensitive to inhibition. I₅₀ values for inhibition of the enzyme from a number of plant sources show little variation and no correlation to whole-plant response, suggesting uptake, translocation and metabolism play key roles in modulating herbicidal activity. Further studies indicate that these chemicals are slow, tight-binding inhibitors that are readily dissociated by gel filtration. Some correlations between in-vitro activity and in-vivo activity were observed for ortho-substituted analogs on selected broadleaf species.     

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%。     

Synthesis and in-vitro antifungal activity of 6-trifluoromethylpyrazolo[3,4-d]pyrimidines

Thirty 6-trifluoromethylpyrazolo[3,4-d]pyrimidines were synthesised and tested for antifungal activity in vitro against ten phytopathogenic fungi of different taxonomic classes. Six of the compounds had noteworthy activity against Sclerotinia minor, Corticium solani and Phoma betae. The relationships between structure and activity are discussed on the basis of the present and previous studies.     

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.     

A possible mechanism for the selective herbicidal activity of iodide in relation to thiocyanate content

In an in vivo study, the rate of iodide oxidation by horseradish peroxidase was found to be reduced by the addition of ammonium thiocyanate to the system. The seleetive herbicidal activity of sodium iodide towards dwarf bean, pea, kale and cabbage was tested while the poicnlial ihioeyanale conteni of these platits was measured, A good relationship between inereasmg thiocyanale content and inereasing resistance to iodide was observed.     

An evaluation of the herbicidal and plant growth regulatory activity of a novel class of carbohydrate-derived 6,8-dioxabicyclo[3.2.1]octanes

Thirty-five carbohydrate-derived dioxabicyclo[3.2.l]octane derivatives have been tested for herbicidal and plant growth regulatory (PGR) activity in an Arabidopsis thaliana assay. Nine of these were herbicidal at concentrations of ? 16 μg ml^?1 in the growth medium. Three compounds, viz, 1,6-anhydro-3-deoxy-4-O-(2,6-dichlorobenzyl)-2-O-methyl-β-D-ribo-hexopyranose(I), its 4-O-benzyl analogue (II), and l,6-anhydro-2-azido-4-O-benzyl-2,3-dideoxy-β-D-ribo-hexopyranose (III) were very active herbicides, killing plants by the rosette stage at 1 μg ml^?1 or less. At lower rates, the herbicides acted as growth regulators, reducing growth rates of shoots and roots as well as flowering and seed-pod development. A further 14 compounds exerted PGR effects only, while 12 compounds were virtually inactive at 16 μg ml^?1, the highest rate tested. The ability of the active compounds to reduce seed viability on mature plants at sublethal concentrations was demonstrated in four cases.     

N-[2-(4,6-二甲氧基嘧啶-2-氧基)苯亚甲基]取代胺类衍生物的合成及除草活性

以水杨醛为原料,经取代、加成和消除反应合成了6个标题化合物(3a~3f),其中4个(3a~3d)为新化合物,其结构经核磁共振氢谱、质谱和元素分析确认。初步的除草活性测试结果表明,在有效成分150 g/hm2的剂量下,除化合物3f对稗草Echinochloa crus-galli的抑制率为55%外,其余5个化合物对供试杂草的抑制率均在80%以上,部分化合物对稗草、早熟禾Poa annua、反枝苋Amaranthus retroflexus或小藜Chenopodium album的抑制率达100%。     

阿魏酸衍生物的合成及其除草活性测定

为从天然产物中获取新的除草活性成分,通过化学合成的方法对分离自瓜果腐霉Pythium aphanidermatum代谢产物中的阿魏酸进行了结构改造,并采用小杯法,以马唐、马齿苋和播娘蒿为供试杂草对所得化合物进行了除草活性测定。结果显示:所合成的4-羟基-3-甲氧基肉桂酸乙酯、4-羟基-3-甲氧基肉桂酸邻氯苯胺、4-羟基-3-甲氧基肉桂酸酰肼、4-羟基-3-甲氧基肉桂酸叔丁酯和4-乙酰氧基-3-甲氧基肉桂酸5种化合物的回收率分别为96.81%、97.39%、82.20%、75.67%和98.29%。4-羟基-3-甲氧基肉桂酸酰肼和4-乙酰氧基-3-甲氧基肉桂酸对马齿苋胚根的抑制活性最强,IC50分别为87.50 mg/L和74.86 mg/L,其余3种活性相对较弱;4-羟基-3-甲氧基肉桂酸乙酯和4-乙酰氧基-3-甲氧基肉桂酸分别在500 mg/L和1 000 mg/L浓度下可完全抑制播娘蒿和马齿苋胚根、芽的生长,而4-羟基-3-甲氧基肉桂酸邻氯苯胺则在1 000 mg/L浓度下可完全抑制播娘蒿胚根的生长。表明在阿魏酸分子中的不同位点引入适当的基团结构可以提高或者降低阿魏酸分子的除草活性,并获得新的除草活性物质。     

Uptake and distribution of [14C]metalaxyl by detached tobacco leaves

When the petioles of detached tobacco leaves (10–17 cm²) were incubated in aqueous solutions containing [¹⁴C]metalaxyl, uptake of the fungicide was dependent on the temperature and photoperiod. Detached leaves took up 78% more [¹⁴C]metalaxyl at 26°C than at 16°C. The rate of uptake in the light at 21°C was linear, but after an additional 20h in the dark, there was only twice as much fungicide in the leaves. Different sized leaves contained the same amount of fungicide per cm² area. Uptake by detached leaves of the ¹⁴C-labelled anilide lactones ofurace and RE-26940 [2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)acet-2′,6′-xylidide] was similar to that of metalaxyl. At the concentration of metalaxyl (66 ng ml^?1) that controlled blue mould (Peronospora tabacina) on detached tobacco leaves, the amount of fungicide in the leaves was found to be 7.25 ng. Autoradiography showed that the distribution of [14C]metalaxyl in detached leaves after incubation for 23h was uniform, although higher concentrations of the label were present in the smaller veins of the leaves.     

环磺酮的除草活性及对玉米的安全性评价

为明确环磺酮在我国玉米田的应用技术和前景,采用温室盆栽法测定环磺酮的杀草谱和对常见杂草的除草活性以及对不同玉米品种的安全性,并通过田间药效试验验证其应用效果。结果表明,在100 g (a.i.)/hm²田间推荐剂量下进行茎叶处理时,环磺酮可以有效防除玉米田常见禾本科、莎草科和阔叶杂草,其中对反枝苋Amaranthus retroflexus、鳢肠Eclipta prostrata的活性较高,鲜重抑制率可达90%以上;对6种常见玉米田杂草稗Echinochloa crus-galli、马唐Digitaria sanguinalis、圆叶牵牛Ipomoea purpurea、反枝苋、碎米莎草Cyperus iria和青葙Celosia argentea的生长抑制中量GR₅₀分别为8.44、17.16、9.37、8.68、9.40和32.51 g (a.i.)/hm²,在供试剂量下环磺酮的除草活性均高于对照药剂硝磺草酮;田间推荐剂量下环磺酮对除黑糯301品种以外的11个玉米品种均较为安全,提高到2倍推荐剂量时,对不同玉米品种的生长抑制均增强;环磺酮对郑单958、珍珠糯8号、苏科甜1506和中糯2号4个玉米品种以及稗、马唐、圆叶牵牛、反枝苋、碎米莎草和青葙6种杂草之间均具有较好的选择性,选择性指数为10.40~29.14。田间药效试验表明,126 g (a.i.)/hm²环磺酮处理茎叶后第28天,对玉米田杂草稗、马唐、狗尾草Setaria viridis、香附子Cyperus rotundus、圆叶牵牛、空心莲子草Alternanthera philoxeroides的总株防效为86.51%,鲜重防效为87.81%,且对供试玉米品种彩甜糯102安全。     

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 .     

The metabolism of [14C] cymoxanil in the rat

A rat, given a single oral dose of [¹⁴C] cymoxanil, 1-(2-cyano-2-methoxyimino-[2-¹⁴C]-acetyl)-3-ethylurea, eliminated 91% of the radioactivity within 72 h. The urine contained 71%, the faeces 11%, and the expired air about 7% of the radiolabel; no ¹⁴C residue was found in the internal organs. Greater than 70% of the radioactivity in the urine was identified. The major metabolite was characterised as glycine, both free and conjugated, as hippuric acid and phenylaceturic acid [N-(phenylacetyl)-glycine], and probably in the form of polypeptides of low molecular weight. The other metabolites identified included 2-cyano-2-methoxyiminoacetic acid, 2-cyano-2-hydroxyiminoacetic acid and 1-ethylimidazolidine-2, 4, 5-trione. The minor metabolites included succinic acid and 2-oxoglutaric acid which indicated reincorporation of metabolic ¹⁴C. Cymoxanil, as such, was not detected in the urine.     

二氯喹啉草酮与二氯喹啉酸的除草活性及对水稻安全性的比较

采用整株生物测定法测定两种除草剂二氯喹啉草酮与二氯喹啉酸茎叶处理对水稻田杂草的生物活性及对水稻的安全性。结果表明:当二氯喹啉草酮和二氯喹啉酸有效成分剂量均为600 g/hm2时, 两种除草剂对稗属杂草、鳢肠的鲜重抑制率均高于94%, 其GR90为107.35~558.58 g/hm2; 对马唐和耳叶水苋的鲜重抑制率低于85%, 对抗二氯喹啉酸西来稗和千金子的鲜重抑制率低于50%; 不同的是二氯喹啉草酮对丁香蓼和异型莎草的鲜重抑制率分别为92.17%、94.33%, 均显著高于二氯喹啉酸(83.64%, 85.57%)。二氯喹啉草酮和二氯喹啉酸对1.5叶期水稻安全性差, 选择性指数为2.53~3.58; 对3.5叶期水稻安全, 选择性指数大于4, 各处理水稻鲜重与对照组之间无显著差异。本着高效、安全、经济的原则, 不推荐二氯喹啉草酮用于防除水稻田禾本科杂草, 仅对部分阔叶类和莎草科杂草发生严重的水稻田, 二氯喹啉草酮可以作为补充除草剂。     

A specific and sensitive assay to quantify the herbicidal activity of chloroacetamides

Based on a recently discovered property of chloroacetamide herbicides—the inhibition of the incorporation of oleic acid into sporopollenin of Scenedesmus acutus—a rapid quantitative test was developed for chloroacetamide-type herbicidal activity. In this test, algal cells are incubated for 3 h with [¹⁴C]oleic acid, saponified and the lipids (including non-saponifiable ones) extracted and discarded. The radioactivity incorporated into the residual non-lipid fraction is determined, and inhibition of this incorporation is used as a marker of chloroacetamide-type activity. Twenty-two agrochemical compounds were screened in this assay, which was found to be very sensitive, a 50% inhibition being reached with submicromolar herbicide concentrations. It is specific to chloroacetamides and related amides, since all these herbicides tested were potent inhibitors, while other herbicides were not. Highest inhibition was shown by cafenstrole followed by butachlor, fluthiamid, metazachlor, alachlor, dimethenamid, metolachlor and mefenacet. For these herbicides (with the exception of butachlor) sensitivity in the test was positively correlated (r=0·984) with their phytotoxic effect on the alga. © 1998 SCI     

N-苯基-2-(4,6-二甲氧基-2-嘧啶氧基)-6-氯-苄胺(ZJ1835)的除草活性研究

为明确新化合物N-苯基-2-(4,6-二甲氧基-2-嘧啶氧基)-6-氯-苄胺(ZJ1835)在棉花田的应用前景,就其对棉花的安全性、选择性、杀草谱和田间应用技术进行了研究。室内生物测定结果表明,ZJ1835对棉花生长初期有一定矮化作用,但不影响出苗和后期生长,在有效剂量225 g/hm2下对棉花安全性好;对不同棉花品种之间的安全性有一定差异,其中对王岳9913的安全性最好,其次为银山1号和福棉6号,对冀丰197安全性略差;该化合物在棉花与马唐、反枝苋之间的选择性系数分别为2.14和13.00,具有较好的选择性;多数田间常见杂草对其敏感,杀草谱较广。田间试验结果显示,ZJ1835在90～120 g/hm2有效剂量下对供试棉花安全性好,对棉田杂草总防效为82.1%～92.8%,具有一定的开发应用潜力。     

Influence of wetting agents on the foliar uptake and herbicidal activity of glufosinate

The influence of four different wetting agents on the foliar retention, uptake and herbicidal activity of the glutamine synthetase inhibitor, glufosinate, was examined in growth-chamber experiments on barley (Hordeum vulgare L. cv Roland) and barnyard grass (Echinochloa crus-galli (L.) P.B.) as test species. The non-formulated monoammomum salt, glufosinate-ammonium, was applied as a spray, either alone or mixed with a wetting agent. The dose rates of herbicide and wetting agent were 0.5 g a.i. litre^?1 and 2.0 g litre^?1, respectively, on barnyard grass, and 2.0 g a.i. litre^?1 and 60 g litre^?1, respectively, on barley. Herbicide damage, rated 10 days after spraying, was greatest when glufosinate was used with a sodium C₁₂/C₁₄-alcohol-diglycolether sulfate (FAEO-sulfate) and least with polyoxyethylene (POE)(8) tridecyl ether; intermediate effectiveness was obtained with a combination of herbicide and a POE(15) tridecyl ether or POE(15)-tallow amine. The activity of the target enzyme, glutamine synthetase, measured 2 h after spraying, was reduced most when FAEO-sulfate was present and least with POE(8) tridecyl ether. The behaviour of the glufosinate wetting agent solutions on plant foliage was analysed by measurements of spray retention, droplet contact angles and foliar uptake of [¹⁴C]glufosinate. The results led, for both grass species, to the conclusion that differential ability of the wetting agents to enhance the permeation of glufosinate from the leaf surface deposit into the leaf tissue was the main factor responsible for the differences in herbicidal effectiveness of the glufosinate/wetting agent combinations used in this study.