Chlorfenapyr 溴虫腈 虫螨腈

溴虫腈

溴虫腈，英文名称Chlorfenapyr，商品名除尽悬浮剂，中文通用名虫螨腈。是由美国氰胺公司开发成功的一种新型杂环类杀虫、杀螨、杀线虫剂。随着国家高毒农药替代政策的出台和人们环保意识的提高，作为的无公害农产品病虫防治推荐农药品种的代表，低毒高效的溴虫腈的应用越来越广泛。

名称： 溴虫腈 溴虫腈结构式
俗名： 除尽、虫螨腈
CAS号： 122453-73-0
分子式： C15H11BrClF3N2O
分子量： 437.2
物理性状： 白色结晶

产品特点：
虫螨腈又叫溴虫腈，属芳基吡咯类化合物，对害虫具有胃毒和一定的触杀作用及内吸活性。对钻蛀、刺吸式口器害虫和害螨的防效优异，持效期中等，其杀虫机理是阻断线粒体的氧化磷酰化作用。产品为10%悬浮剂。

使用方法：
防治十字花科蔬菜上的小菜蛾、甜菜夜蛾、亩用10%悬浮剂34-50毫升，对水40-50千克喷雾，药效可维持15天左右。每个生长季节使用不宜超过2次。可与顺式氯氰菊酯混用，或与氟铃脲、高效氯氟氰菊酯轮用，
可增强杀卵效果。

毒性：
对鱼和蜜蜂毒性较高，使用时应注意防护。

作用机理
溴虫腈是一种杀虫剂前体，其本身对昆虫无毒杀作用。昆虫取食或接触溴虫腈后在昆虫体内，溴虫腈在多功能氧化酶的作用下转变为具体杀虫活性化合物，其靶标是昆虫体细胞中的线粒体。使细胞合成因缺少能量而停止生命功能，打药后害虫活动变弱，出现斑点，颜色发生变化，活动停止，昏迷，瘫软，最终导致死亡。

制剂特点
第一，除尽杀虫谱广，经大田多年试验及实际应用表明，对鳞翅目、同翅目、鞘翅目等目中的70多种害虫都有极好的防效，尤其对蔬菜抗性害虫中的小菜蛾、甜菜夜蛾、斜纹夜蛾、美洲斑潜蝇、豆野螟、蓟马、红蜘蛛等特效。
第二，除尽属仿生农药，毒性低，杀虫速度快，用药1小时即可杀灭害虫，当天防效即达85%以上。
第三，击破抗性，除尽作用机理独特，与其它杀虫剂作用机理不同，无交互抗性，对抗药性严重的害虫同样高效。特别对有机磷、氨基甲酸脂、菊酯、几丁质合成抑制剂类杀虫剂产生抗性的害虫和螨类有很好的效果。
第四，持效期特别长，在防治抗性害虫上可控制15-20天，防治红蜘蛛残效期长达35天，可彻底解除菜农“三天一遍药”的劳苦。
第五，适用范围广，可用于蔬菜、果树、观赏植物等，可广泛用于防治棉花、蔬菜、柑桔、葡萄和大豆等多种作物上的害虫和螨类，药效比灭多威、乙酰甲胺磷等常规药剂高4-16倍。也可用于防治白蚁。
第六，渗透性强，叶面喷雾，有效成份可渗透至叶背，杀虫更为彻底。
第七，环保型产品，除尽为天然筛选的吡咯类物质，对人体及牲畜十分安全。尤其适合在出口产品、高品质产品使用。
第八，经过近两年的示范推广，全国各大城市将溴虫睛选定为无公害蔬菜的首选农药。
第九，除尽虽然一次用药投入较高，但因杀虫谱广，防治彻底，控制时间长，按每亩累计成本仍比用其他杀虫剂合算。

使用方法：
溴虫腈有一定的杀卵作用，结合害虫的预测预报工作，建议在害虫的产孵高峰，或卵孵高峰喷雾能起到良好的防治效果。
由于溴虫腈在植物体内具有良好的局部传导性，可以从叶片的一面渗透传导至另一面，故对害虫取食的叶片的背面也可以得到同样的效果。
药后1-3天内防效90-100%，药后15天药效仍可稳定在90%，推荐亩用量30-40毫升，安全间隔期15-20天。
一般对抗性害虫如小菜蛾，夜蛾类每亩用30毫升，即1支（10毫升）用1桶水（10-12千克水），常规喷雾，对高龄大虫应增加用量。

注意事项
1．除尽具有长持效控制害虫种群的特点，为达最佳防效推荐在卵孵盛期或在低龄幼虫发育初期使用。
2．除尽具有胃毒和触杀的双重作用，施药时要均匀的将药液喷到叶面害虫取食部位或虫体上。
3．除尽不宜与其他杀虫剂混用，提倡与其他不同作用机制的杀虫剂交替使用，如卡死克等，每季作物建议使用次数不超过2次。
4．傍晚施药更有利药效发挥。

理化性质
化学名称： 4-溴基-2-(4-氯苯基)-1-(乙氧基甲基)-5-(三氟甲基)吡咯-3-腈
英文名称： 4－Bromo-2-(p-chloropenyl)-1-(ethoxymethyl-5-(trifluoromethyl)pyrrle-3-carbonitrile
CA登记号： 122453-73-0
分子式： C15H11BrClF3N2O
分子量： 407.62
性状： 纯品为白色或类白色油性粉末
熔点： 100～101℃
溶解性： 溶于丙酮、乙醚、二甲亚砜、四氢呋喃、乙腈，醇、甲苯、二甲苯等有机溶剂，不容于水。
酸碱性： 中性，pH 6～8
含量： 98.00---99.50%
毒性： 大鼠急毒(口服) LD50 441～1152mg/Kg
兔急性经皮剂量LD50 ≧2000 mg/Kg
兔眼刺激轻微
日本鲤鱼 LC50=0.5ppm
经改进的Ames试验及中国仓鼠卵巢试验表明无制突变性
药害： 溴虫腈原药溶于丙酮和水中（1︰1），试验浓度1000ppm时，对棉苗和利马豆无药害。

chlorfenapyr
Insecticide, acaricide
IRAC 13; arylpyrrole

NOMENCLATURE
Common name chlorfenapyr (BSI, pa ISO, ANSI)
IUPAC name 4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile
Chemical Abstracts name 4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile
CAS RN [122453-73-0] Development codes AC 303,630; CL 303,630 (both Cyanamid); MK-242 (Mitsubishi Chemical)

PHYSICAL CHEMISTRY
Mol. wt. 407.6 M.f. C15H11BrClF3N2O Form White solid. M.p. 100-101 ºC V.p. <1.2 ´ 10-2 mPa (20 ºC) KOW logP = 4.83 S.g./density 0.355 (24 ºC) Solubility Practically insoluble in water. Soluble in acetone, diethyl ether, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, and alcohols. Stability In air DT50 0.88 d (10.6 h, calc.). In water (direct photodegradation) DT50 4.8-7.5 d. Stable to hydrolysis (pH 4, 7 and 9).

COMMERCIALISATION
History Developed by American Cyanamid Co. (now BASF AG). Manufacturers BASF

APPLICATIONS
Biochemistry Oxidative removal in vivo of the N-ethoxymethyl group generates the active species, which is a mitochondrial uncoupler. Mode of action Insecticide and acaricide with mainly stomach and some contact action. Exhibits good translaminar but limited systemic activity in plants. Uses Control of many species of insects and mites, including those resistant to carbamate, organophosphate and pyrethroid insecticides and also chitin-synthesis inhibitors, in cotton, vegetables, citrus, top fruit, vines and soya beans. Among pests resistant to conventional products which are controlled by chlorfenapyr are Brevipalpus phoenicis (leprosis mite), Leptinotarsa decemlineata (Colorado potato beetle), Helicoverpa spp., Heliothis spp., Plutella xylostella (diamond-back moth) and Tetranychus spp. Also control of many species of structural and household Formicidae (especially Camponotus, Iridomyrmex, Monomorium, and Solenopsis), Blattellidae (especially Blatta, Blattella, Periplaneta and Supella spp.), Kalotermitidae (especially Incisitermes) and Rhinotermitidae (especially Reticulitermes, Coptotermes, Heterotermes) at use rates of between 0.125 to 0.50% a.i. w/w. Phytotoxicity No phytotoxicity observed at field use rates. Formulation types EC; SC. Selected products: 'Phantom' (professional pest control) (BASF); 'Pylon' (BASF)

OTHER PRODUCTS
'Alert' (citrus, cotton) (BASF); 'Chu-Jin' (China) (BASF); 'Grizli' (E. Europe) (BASF); 'Intrepid' (Europe) (BASF); 'Kotetsu' (Japan) (BASF, Nihon Nohyaku); 'Pirate' (cotton) (BASF); 'Rampage' (S.E. Asia) (BASF); 'Secure' (ornamentals) (BASF); 'Stalker' (BASF) mixtures: 'Oonata' (+ fluacrypyrim) (Nippon Soda)

ANALYSIS
Product by glc. Residues by hplc. Details from BASF.

MAMMALIAN TOXICOLOGY
Oral Acute oral LD50 for male rats 441, female rats 1152 mg tech./kg. Skin and eye Acute percutaneous LD50 for rabbits >2000 mg/kg. Moderate eye irritant; non-irritating to skin (rabbits). Inhalation LC50 for rats 1.9 mg tech./l air. Other Non-mutagenic in the Ames, CHO/HGPRT, mouse micronucleus and unscheduled DNA synthesis tests. Toxicity class WHO (a.i.) II; EPA (formulation) III (240 g/l 'Pylon', 'Phantom')

ECOTOXICOLOGY
Birds Acute oral LD50 for mallard ducks 10, bobwhite quail 34 mg/kg. LC50 (8 d) for mallard ducks 9.4, bobwhite quail 132 ppm. Fish LC50 (48 h) for carp 500 mg/l. LC50 (96 h) for rainbow trout 7.44, bluegill sunfish 11.6 mg/l. Daphnia LC50 (96 h) 6.11 mg/l. Algae EC50 for Selenastrum capricornutum 132 ppb. Bees LD50 0.2 mg/bee. Worms NOEC (14 d) for Eisenia foetida 8.4 mg/kg.

ENVIRONMENTAL FATE
Animals In rats, >60% of orally administered chlorfenapyr was excreted primarily through faeces within 24 hours. The absorbed residues were metabolised via N-dealkylation, dehalogenation, hydroxylation and conjugation. Parent and less polar metabolites were found in egg, milk and tissues such as fat and liver. Metabolism in hens and goats is similar to that in rats, however in these species, 80% of orally administered chlorfenapyr was rapidly excreted. Un-excreted residues were present in kidney and liver. At the potential maximum dietary burden, all residues are <0.01 ppm. Chlorfenapyr is the only significant residue component. Plants In cotton, citrus, tomato, lettuce and potato, chlorfenapyr is dealkylkated to the insecticidally active component (AC 303268) or debrominated to less toxic metabolites. Chlorfenapyr does not translocate out of treated plant parts. Parent compound is the prominent residue. Soil/Environment In soil, chlorfenapyr is the major residue. Debromination to a less toxic metabolite is the primary route; dealkylation is not a primary route of degradation in soil. Koc >10 000 ml/g, indicating chlorfenapyr is likely to be strongly bound in soils. In water DT50 (direct photodegradation) 4.8-7.5 d; stable to hydrolysis at pH 4, 7 and 9.