Triclopyr 绿草定

草定

CAS号: 55335-06-3
英文名称： triclopyr
化学名称： (3,5,6-三氯-2-吡啶基)氧乙酸 ；[(3,5,6-trichloro-2-pyridyl)oxy]acetic acid
其他名称：盖灌能；盖灌林；定草酯；盖世龙
分子式： C7H4Cl3NO3
分子量： 256.47

结构式：

理化性质：　 原药外观为白色固体，熔点148-150℃，蒸汽压（25℃）0.168mPa。分解温度为290℃。24.5℃时水中的 溶解度为 430-440mg/L，溶於乙醇、丙酮、正辛醇，难溶於其他普通有机溶剂；在通常贮藏条件下稳定，对水解稳定，但容易被光分解，12小时内损失50%。在土壤中半衰期为46d。

毒性： 原药大鼠急性经口毒性LD50：雌性630mg/kg，雄性729mg/kg，家兔急性经皮LD50为350mg/kg，对家兔皮肤无刺激作用，对眼睛有轻度刺激。

作用特点及杀草谱：　本品可被植物的叶和根吸收，并转移到植株．90g(a.i.)/ha与2，4-滴或敌稗混用，可防除稻田和小麦田（不能用于大麦田）杂草；也可用于种植园（如油棕和橡胶），用125～250g(a.i.)/ha可防除覆盖植物，用0.72～10kg(a.i.)/ha，可防除泽兰属及其它主要杂草；在牧场中，用l～2kg(a.i.)/ha可防除一年生和多年生草本杂草；以2～4kg/ha可防除悬钩子属和其它木本杂草；在森林中，用于造林前除草灭灌，维护防火线，扶育松树及林分改造。可防除胡枝子、榛材、蒙古柞、黑桦、椴、山杨、山刺玫、榆、蒿、柴胡、桔梗、地榆、铁线莲、婆婆纳、草木樨、唐松草、蕨、槭、柳、珍珠梅、蚊子草、走马芹、玉竹、柳叶绣菊、红丁香、金丝桃、山梅花、山顶子、稠李、山梨、香蒿。幼林抚育用量为1kg有效成分/hm2 ，造林前及防火线为1.95kg有效成分/hm2 。注意对松树和云杉严格控制剂量，超过1kg/hm2 易产生药害。2～8kg/ha，用于工业区除草，放牧地除草用量为0.24～10kg/ha．

剂型：A：绿草定三乙銨盐（原药）。 B：绿草定丁氧基乙酯（原药）；绿草定丁氧乙酯61.6%乳油.，绿草定三乙胺盐44.4%水剂.

生产方法：1、由2，3，5，6-四氯吡啶水解为3，5，6-三氯-2-羟基吡啶再与碳酰氯反应制得。

2、以三氯乙酰氯、丙烯腈和氯乙酸酯为主要原料制备绿草定酸。.该方法首先由三氯乙酰氯和丙烯腈制备三氯吡啶酚钠,再由三氯吡啶酚钠和氯乙酸甲酯制备绿草定酸,

生产情况：浙江东风化工有限公司，浙江永农化工有限公司；利尔化学股份有限公司（400t/a）；武汉远城集团有限公司；浙江奥复托化工有限公司；迈克斯（如东）化工有限公司（在建，400t/a）；山东大成农药股份有限公司；江苏化工农药集团有限公司（200t/a）

价格：绿草定原药价格约10.5美元/公斤。（09.10）

triclopyr
Herbicide
HRAC O WSSA 4; pyridinecarboxylic acid

NOMENCLATURE
triclopyr
Common name triclopyr (BSI, E-ISO, F-ISO, ANSI, WSSA); no name (Eire)
IUPAC name 3,5,6-trichloro-2-pyridyloxyacetic acid
Chemical Abstracts name [(3,5,6-trichloro-2-pyridyl)oxy]acetic acid
CAS RN [55335-06-3] Development codes Dowco 233 (Dow)

triclopyr-butotyl
CAS RN [64700-56-7] Development codes M 4021 (Agrimont)

triclopyr-triethylammonium
CAS RN [57213-69-1], formerly [69653-73-2]

PHYSICAL CHEMISTRY
triclopyr
Mol. wt. 256.5 M.f. C7H4Cl3NO3 Form Fluffy, colourless solid. M.p. 150.5 ºC B.p. Decomposes at 208 ºC V.p. 0.2 mPa (25 ºC, vapour pressure balance) KOW logP = 0.42 (pH 5), -0.45 (pH 7), -0.96 (pH 9) Henry 9.77 ´ 10-5 Pa m3 mol-1 (calc.) S.g./density 1.85 (21 ºC). Solubility In water 0.408 (purified), 7.69 (pH 5), 8.10 (pH 7), 8.22 (pH 9) (all in g/l, 20 ºC). In acetone 581, acetonitrile 92.1, hexane 0.09, toluene 19.2, dichloromethane 24.9, methanol 665, ethyl acetate 271 (all in g/l). Stability Stable under normal storage conditions and to hydrolysis, but subject to photodecomposition, DT50 <12 h. pKa 3.97

triclopyr-butotyl
Mol. wt. 356.6 M.f. C13H16Cl3NO4 Henry 2.50 ´ 10-2 Pa m3 mol-1 (calc.)

triclopyr-triethylammonium
Mol. wt. 357.7 M.f. C13H19Cl3N2O3 Henry 1.16 ´ 10-9 Pa m3 mol-1 (calc.)

COMMERCIALISATION
History Herbicide reported by B. C. Byrd et al. (Proc. West. Soc. Weed Sci., 1975, 28, 44). Introduced by Dow Chemical Co. (now Dow AgroSciences). Triclopyr-triethylammonium was first registered in 1979, as a herbicide for use on non-crop areas and in forestry. Triclopyr-butotyl was subsequently registered in 1980. Manufacturers Agriphar; Aimco; Dow AgroSciences; Gharda; Punjab; Sharda

APPLICATIONS
Biochemistry Synthetic auxin (acting like indolylacetic acid). Mode of action Selective systemic herbicide, rapidly absorbed by the foliage and roots, with translocation throughout the plant, accumulating in meristematic tissue. Induces auxin-type responses in susceptible species (mainly broad-leaved weeds, grass weeds being unaffected at normal application rates).

triclopyr
Uses Control of woody plants and many broad-leaved weeds (e.g. nettles, docks, brambles, gorse, broom) in grassland, uncultivated land, industrial areas, coniferous forests, plantation crops, and rice fields. In plantation crops (oil palm, rubber) at 125-250 g a.e./ha for covercrop maintenance, and at 0.72-1.0 kg a.e./ha to control Eupatorium odoratum and other problem plants; in pastures at 1-2 kg/ha to control annual and perennial herbaceous weeds, and at 2-4 kg/ha against Rubus spp. and other woody plants; in forestry at 4-8 kg/ha for site preparation, and at 1.5-2.0 kg/ha for conifer release; for industrial sites at 2-8 kg/ha; in rangeland at 0.24-1.0 kg/ha. Phytotoxicity Clovers are sensitive, as also are larch, lodgepole pine, ornamentals, and edible crops. Selected products: 'Trident' (Agriphar)

triclopyr-butotyl
Formulation types EC. Selected products: 'Garlon 4' (Dow AgroSciences)

triclopyr-triethylammonium
Selected products: 'Garlon 3A' (Dow AgroSciences)

OTHER PRODUCTS
triclopyr
Mixtures: 'Stampir' (+ propanil) (Dow AgroSciences); 'Nu-Shot' (+ 2,4-D+ dicamba) (Nufarm UK); 'Starmix' (+ glyphosate) (Nichimen) Discontinued products: 'Convoy' * (Nufarm Whyte); 'Rely' * (Hoechst) mixtures: 'Broadshot' * (+ 2,4-D+ dicamba) (Cyanamid); 'Fettel' * (+ dicamba+ mecoprop) (Zeneca)

triclopyr-butotyl
'Pathfinder II' (Dow AgroSciences); 'Remedy' (Dow AgroSciences); 'Timbrel' (Dow AgroSciences); 'Turflon' (Dow AgroSciences); 'Triptic 48' (United Phosphorus Ltd) mixtures: 'Crossbow' (+ 2,4-D-butotyl) (Dow AgroSciences); 'Doxstar' (+ fluroxypyr-meptyl) (Dow AgroSciences); 'Grazon 90' (+ clopyralid) (Dow AgroSciences); 'Pastor' (+ clopyralid+ fluroxypyr-meptyl) (Dow AgroSciences); 'Togar BT' (+ picloram-isoctyl) (Dow AgroSciences); 'Broadsword' (+ 2,4-D-2-ethylhexyl+ dicamba) (dicamba as butotyl ester) (United Phosphorus Ltd) Discontinued products: 'Exetor' * (Dow AgroSciences); 'Rely' * (Dow AgroSciences) mixtures: 'Access' * (+ picloram-isoctyl) (Dow AgroSciences)

triclopyr-triethylammonium
'Grandstand' (Dow AgroSciences) mixtures: 'Confront' (+ clopyralid) (clopyralid also as triethylammonium salt) (Dow AgroSciences); 'Redeem' (+ clopyralid) (clopyralid as triethylammonium salt) (Dow AgroSciences); 'Xrm-5202 Premium' (+ 2,4-D+ clopyralid) (2,4-D and clopyralid as triisopropanolammonium salts) (Riverdale)

ANALYSIS
Product analysis by hplc. Residues determined by glc. Details available from Dow AgroSciences.

MAMMALIAN TOXICOLOGY
triclopyr
Oral Acute oral LD50 for male rats 692, female rats 577 mg/kg. Skin and eye Acute percutaneous LD50 for rabbits >2000 mg/kg. Mild eye irritant; non-irritating to skin (rabbits). Inhalation LC50 (4 h) for rats >256 ppm. NOEL (2 y) for rats 3.0 mg/kg b.w. daily, for mice 35.7 mg/kg b.w. daily. ADI 0.005 mg/kg b.w. Toxicity class WHO (a.i.) III; EPA (formulation) III

ECOTOXICOLOGY
triclopyr
Birds Acute oral LD50 for mallard ducks 1698 mg/kg. Dietary LC50 (8 d) for mallard ducks >5000, Japanese quail 3278, bobwhite quail 2935 mg/kg. Fish LC50 (96 h) for rainbow trout 117, bluegill sunfish 148 mg/l. Daphnia LC50 (48 h) 133 mg/l. Algae EC50 (5 d) for Selenastrum capricornutum 45 mg/l. Bees Non-toxic to bees; contact LD50 >100 mg/bee.

ENVIRONMENTAL FATE
Animals In mammals, following oral administration, excretion is primarily via the urine as the unchanged compound. For details of minor urinary metabolites, see C. Timchalk et al., Toxicology, 1990, 62, 71. Plants In plants, DT50 c. 3-10 d. The main metabolite is 3,5,6-trichloro-2-methoxypyridine. Soil/Environment In soil, fairly rapid degradation by microbial activity, with an average half-life of 46 d, depending on soil and climatic conditions. The major degradation product is 3,5,6-trichloro-2-pyridinol (which has a soil half-life of 30-90 d), with a smaller amount of 3,5,6-trichloro-2-methoxypyridine. Koc c. 59 ml/g; Kd c. 87 (unaged samples), c. 225 (aged) ml/g.