四溴菊酯 | 66841-25-6

• 物质功能分类: 化学农药原药 - 杀虫剂 - 拟除虫菊脂杀虫剂
• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: 四溴菊酯
• 中文别名: 四溴菊酸；四溴氟菊酯；溴氯氰聚酯；溴氯氰菊酯
• 英文名称: α-cyano-3-phenoxy-benzyl 2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate
• 英文别名: tralomethrin；scout；α-cyano-3-phenoxybenzyl 2,2-dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylate；3'-phenoxy-α-cyanobenzyl 2,2-dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylate；[cyano-(3-phenoxyphenyl)methyl] 2,2-dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropane-1-carboxylate
• CAS: 66841-25-6
• 化学式: C₂₂H₁₉Br₄NO₃
• 分子量: 665.014
• InChiKey: YWSCPYYRJXKUDB-UHFFFAOYSA-N

物化性质

• 熔点：
  143℃
• 沸点：
  185～190℃ (0.1mmHg)
• 密度：
  1.70 g/cm3 (20℃)
• 颜色/状态：
  Orange-yellow solid
• 闪点：
  26 °C
• 溶解度：
  1.20e-07 M
• 蒸汽压力：
  3.6X10-11 mm Hg at 25 °C
• 稳定性/保质期：

  Stable for 6 months at 50 °C. Acidic media reduce hydrolysis and epimerization.

• 旋光度：
  Specific rotation: +21 deg to +27 deg (50 g/l toluene).
• 分解：
  When heated to decomposition it emits toxic vapors of /nitrogen oxides/ and /bromides/

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  59.3
• 氢给体数：
  0
• 氢受体数：
  4

ADMET

代谢

哺乳动物对拟除虫菊酯的相对抗性几乎完全归因于它们能够迅速将拟除虫菊酯水解为其无活性的酸和醇成分，因为直接注射到哺乳动物的中央神经系统会导致与昆虫中观察到的相似易感性。恒温生物的一些额外抗性也可以归因于拟除虫菊酯的作用负温度系数，这意味着在哺乳动物体温下毒性较低，但主要效果是代谢性的。拟除虫菊酯的代谢消除非常迅速，这意味着通过静脉注射的毒性很高，通过较慢的口服吸收毒性适中，而通过皮肤吸收的毒性通常很低。/拟除虫菊酯/

The relative resistance of mammals to the pyrethroids is almost wholly attributable to their ability to hydrolyze the pyrethroids rapidly to their inactive acid and alcohol components, since direct injection into the mammalian CNS leads to a susceptibility similar to that seen in insects. Some additional resistance of homeothermic organisms can also be attributed to the negative temperature coefficient of action of the pyrethroids, which are thus less toxic at mammalian body temperatures, but the major effect is metabolic. Metabolic disposal of the pyrethroids is very rapid, which means that toxicity is high by the intravenous route, moderate by slower oral absorption, and often unmeasureably low by dermal absorption. /Pyrethroids/

来源:Hazardous Substances Data Bank (HSDB)

代谢

合成拟除虫菊酯在哺乳动物体内通常通过酯水解、氧化和结合进行代谢，并且没有在组织中积累的趋势。在环境中，合成拟除虫菊酯在土壤和植物中相当快地降解。分子上不同位点的酯水解和氧化是主要的降解过程。/拟除虫菊酯/

Synthetic pyrethroids are generally metabolized in mammals through ester hydrolysis, oxidation, and conjugation, and there is no tendency to accumulate in tissues. In the environment, synthetic pyrethroids are fairly rapidly degraded in soil and in plants. Ester hydrolysis and oxidation at various sites on the molecule are the major degradation processes. /Pyrethroids/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

识别和使用：Tralomethrin 是一种固体。它以前被用作杀虫剂。人类暴露和毒性：吸入拟除虫菊酯类化合物（如 Tralomethrin）的临床表现可能是局部或全身性的。局限于上呼吸道的局部反应包括鼻炎、打喷嚏、喉咙痒、口腔粘膜水肿，甚至喉粘膜水肿。下呼吸道的局部反应包括咳嗽、气短、喘息和胸痛。在敏感患者中，急性暴露会引起类似哮喘的反应。慢性暴露的个体可能会出现胸痛、咳嗽、呼吸困难、支气管痉挛的过敏性肺炎。动物研究：合成拟除虫菊酯是神经毒素，通过在哺乳动物和/或昆虫的钠通道上相互作用，作用于外周和中央神经系统的轴突。单次剂量就会在哺乳动物中产生毒性迹象，如震颤、过度兴奋、流涎、舞蹈病样运动和瘫痪。在接近致死剂量水平，合成拟除虫菊酯会导致神经系统短暂变化，如坐骨神经轴突肿胀和/或断裂以及髓鞘退行性变。它们不会被认为会引起由一些有机磷化合物诱导的迟发性神经毒性。在为期2年的小鼠研究中，以10 mg/kg/天的剂量观察到以下效果：增加死亡率、增加行为影响、皮肤病变、增加食物和水的消耗、增加尿量、肝和肾重量暂时增加、皮肤炎和肌炎在雄性和雌性中。在一项代际繁殖研究中，Tralomethrin 以剂量0、0.75、3.0和12.0 mg/kg/天通过灌胃方式每天给药给大鼠。在任何剂量水平下都没有发现对F0或F1父母生殖性能的有害影响的证据。在F1幼崽中，12 mg/kg/天组的幼崽出生时初始体重（出生时）有所下降。在F1和F2幼崽的哺乳期间，中剂量和高剂量组观察到与剂量相关的幼崽体重下降，而母体大鼠在3和12 mg/kg/天时体重下降。生态毒性研究：Tralomethrin 对 D. magna 有毒性，LC50 为 0.15 ug/L。在处理后1小时接触处理的叶子的蜜蜂中它不具有毒性。

IDENTIFICATION AND USE: Tralomethrin is a solid. It was formerly used as an insecticide. HUMAN EXPOSURE AND TOXICITY: The clinical manifestations of inhalation exposure to pyrethrins, such as tralomethrin, can be local or systemic. Localized reactions confined to the upper respiratory tract include rhinitis, sneezing, scratchy throat, oral mucosal edema, and even laryngeal mucosal edema. Localized reactions of the lower respiratory tract include cough, shortness of breath, wheezing, and chest pain. An asthma-like reaction occurs with acute exposures in sensitized patients. Hypersensitivity pneumonitis characterized by chest pain, cough, dyspnea, and bronchospasm may occur in an individual chronically exposed. ANIMAL STUDIES: Synthetic pyrethroids are neuropoisons acting on the axons in the peripheral and central nervous systems by interacting with sodium channels in mammals and/or insects. A single dose produces toxic signs in mammals, such as tremors, hyperexcitability, salivation, choreoathetosis, and paralysis. At near-lethal dose levels, synthetic pyrethroids cause transient changes in the nervous system, such as axonal swelling and/or breaks and myelin degeneration in sciatic nerves. They are not considered to cause delayed neurotoxicity of the kind induced by some organophosphorus compounds. In 2 year mouse study at 10 mg/kg/day the following effects were observed: increased mortality, increased behavioral effects, skin lesions, increased food and water consumption, increased urine volume, transient increase in liver and kidney weights, dermatitis and myositis in male and female. In a generation reproduction study tralomethrin was administered daily by gavage to rats at dose levels of 0, 0.75, 3.0, and 12.0 mg/kg/day. No evidence of adverse effects on reproductive performance of either male or the female F0 or F1 parents were noted at any dose levels. Some signs of decreased initial body weight (at birth) were noted in the F1 pups in the 12 mg/kg/day group. Dose-related decreases in pup weights were observed during lactation in the F1 and F2 pups in the mid- and high- dose groups while the parent rats showed decreases in body weight at 3 and 12 mg/kg/day. ECOTOXICITY STUDIES: Tralomethrin was toxic to D. magna, with LC50 of 0.15 ug/L. It was not toxic to bees contacting treated foliage 1 hr after application.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 副作用

神经毒素 - 其他中枢神经系统神经毒素

Neurotoxin - Other CNS neurotoxin

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

毒理性

• 毒性数据

LCLo（大鼠）= 286 毫克/立方米/4小时

LCLo (rat) = 286 mg/m3/4h

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

毒理性

• 相互作用

拟除虫菊酯类农药解毒……在苍蝇中很重要，可能因添加增效剂……如有机磷或氨基甲酸酯……而延迟……以确保致死效果。……拟除虫菊酯类农药

/Pyrethroid/ detoxification ... important in flies, may be delayed by the addition of synergists ... organophosphates or carbamates ... to guarantee a lethal effect. ... /Pyrethroid/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

立即用肥皂和水清洗皮肤...如果出现刺激或感觉异常症状，应寻求医生的治療。由于拟除虫菊酯的挥发显然是导致面部感觉异常的原因，因此应采取严格措施（通风、戴防护面罩和头罩）以避免面部和眼睛接触到蒸汽。维生素E油制剂（dL-α-生育酚醋酸酯）在预防和停止感觉异常反应方面具有独特的效果。它们适用于现场条件下的皮肤涂抹。玉米油也有一定效果，但可能的副作用以及持续使用使其不太合适。凡士林的效果不如玉米油。氧化锌实际上会加剧反应。/拟除虫菊酯/

Decontaminate the skin promptly with soap and water ... . If irritant or paresthetic effects occur, obtain treatment by a physician. Because volatilization of pyrethroids apparently accounts for paresthesia affecting the face, strenuous measures should be taken (ventilation, protective face mask and hood) to avoid vapor contact with the face and eyes. Vitamin E oil preparations (dL-alpha tocopheryl acetate) are uniquely effective in preventing and stopping the paresthetic reaction. They are safe for application to the skin under field conditions. Corn oil is somewhat effective, but possible side effects with continuing use make it less suitable. Vaseline is less effective than corn oil. Zinc oxide actually worsens the reaction. /Pyrethroids/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

当放射性拟除虫菊酯通过口服方式给予哺乳动物时，它会被动物的小肠吸收并分布到所有被检查的组织中。在大鼠中给予顺式异构体：剂量：500毫克/千克；间隔20天；尿液占36%，粪便占64%，总计100%。/拟除虫菊酯/

When radioactive pyrethroid is administered orally to mammals, it is absorbed from intestinal tract of the animals and distributed in every tissue examined. Excretion of radioactivity in rats admin trans-isomer: dosage: 500 mg/kg; interval 20 days; urine 36%; feces 64%; total 100%. /Pyrethroids/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

尽管有限的吸收可能是某些拟除虫菊酯类低毒性的原因，但通过哺乳动物肝脏酶（酯水解和氧化）的快速生物降解可能是这种现象的主要因素...大多数拟除虫菊酯代谢物会迅速被肾脏至少部分排出。/拟除虫菊酯/

Although limited absorption may account for the low toxicity of some pyrethroids, rapid biodegradation by mammalian liver enzymes (ester hydrolysis and oxidation) is probably the major factor responsible for this phenomenon ... Most pyrethroid metabolites are promptly excreted, at least in part, by the kidneys. /Pyrethroids/

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险等级：
  6.1(b)
• 危险品标志：
  N,Xn
• 安全说明：
  S26,S60,S61
• 危险类别码：
  R36/38,R22,R50/53
• WGK Germany：
  3
• 危险品运输编号：
  UN 2588
• 包装等级：
  III
• 危险类别：
  6.1(b)

制备方法与用途

作用机理

拟除虫菊酯类杀虫剂具有触杀和胃毒作用，性质稳定且持效期长。对某些害虫的毒性甚至高于溴氰菊酯。

应用

四溴菊酯广泛用于防治鞘翅目、同翅目及直翅目害虫，尤其适用于禾谷类、棉花、玉米、果树、烟草、蔬菜和水稻上的鳞翅目害虫。其推荐使用量为0.075～1.95g有效成分/100m²。

合成方法

四溴菊酯可通过以下反应制备：

二溴菊酸与溴在20℃条件下加成，再经过氯化亚砜转化为四溴菊酰氯，并最终与α-氰基间苯氧基苯甲醇合成四溴菊酯。具体步骤可参见制备方法一、二和三。

毒性

四溴菊酯对雄大鼠的急性经口LD₅₀为99.2mg/kg，雌大鼠为157.2mg/kg；兔急性经皮LD₅₀>2000mg/kg；大鼠急性吸入LC₅₀为0.286mg/kg（4小时）。对兔皮肤和眼睛有轻微刺激作用。长期试验结果显示，大鼠、小鼠和狗的每日无作用剂量分别为0.75mg/kg、3mg/kg 和1mg/kg。未发现四溴菊酯具有致畸性，也不影响生殖功能。致癌试验结果为阴性。对虹鳟鱼、蓝鳃鱼及水蚤的毒性较低，分别在LC₅₀ 0.0016mg/L（96小时）、0.0043mg/L（96小时）和38mg/L（48小时）。鹌鹑急性经口LD₅₀>2510mg/kg。蜜蜂接触LD₅₀为0.00012mg/只。

化学性质

四溴菊酯为黄色至橘黄色树脂状物质，相对密度在20℃时约为1.7，蒸气压低（25℃下约为1.73×10⁻¹¹Pa），旋光度+21°～+27°（50g/L甲苯溶液）。该化合物可溶于丙酮、二甲苯、甲苯、二氯甲烷和二甲基亚砜等有机溶剂，在水中溶解度为70mg/L。在室温下，即使放置6个月也不会分解，并对光稳定无腐蚀性。

用途

拟除虫菊酯类杀虫剂通过抑制离子通道关闭能力干扰调节钠离子流的离子通道，导致神经细胞产生过度兴奋最终死亡，从而达到杀死害虫的目的。

生产方法

制备四溴菊酯的方法包括：

• 方法一：在四氯化碳溶剂中，二溴菊酸与溴反应生成四溴菊酸，再经转化得到四溴菊酰氯，最终与α-氰基间苯氧基苯甲醇合成目标产物。
• 方法二：通过多种途径高产率获得的二氯菊酰氯和溴化反应制备四溴菊酯。
• 方法三：利用溴氰菊酯在四氯化碳存在下加溴直接生成四溴菊酯。

反应信息

• 作为反应物：
  描述：

  四溴菊酯 生成 溴氰菊酯
  参考文献：
  名称：

  COLE, L. M.;CASIDA, J. E.;RUZO, L. O., J. AGR. AND FOOD CHEM., 1982, 30, N 5, 916-920

  摘要：

  DOI：

文献信息

• Insecticidal resin coating film
  申请人：MITSUI TOATSU CHEMICALS, Inc.

  公开号：EP0257415A1

  公开（公告）日：1988-03-02

  An insecticidal resin coating film comprising a combination of an acrylonitrile and/or methacrylonitrile copolymer resin and an insecticidal component selected from the group consisting of specified compounds exhibits an insecticidal effect, since the compound is kept on the surface of the coating film in a state capable of exhibiting its insecticidal effect for a long period of time.

  杀虫树脂涂膜由丙烯腈和/或甲基丙烯腈共聚物树脂和从特定化合物组成的组中选出的杀虫成分组合而成，具有杀虫效果，因为化合物在涂膜表面保持的状态能够长时间显示其杀虫效果。
• STABLE SOLID PESTICIDAL PREPARATION
  申请人：Sumitomo Chemical Company, Limited

  公开号：EP0304492A1

  公开（公告）日：1989-03-01

  A stable solid pesticidal preparation which contains a benzyl ester type synthetic pyrethroid having a cyano group in α-position and an organophosphate compound as effective ingredients supported on a mineral carrier, with at least one weakly acidic salt of an alkali or alkaline earth metal being incorporated therein.

  一种稳定的固体杀虫剂制剂，含有一种苄酯类合成拟除虫菊酯，其 α 位有一个氰基，以及一种有机磷化合物作为有效成分，以矿物载体为支撑，其中至少含有一种碱金属或碱土金属的弱酸性盐。
• Sustained release pesticidal or plant growth regulating composition
  申请人：SUMITOMO CHEMICAL COMPANY, LIMITED

  公开号：EP0646314A1

  公开（公告）日：1995-04-05

  There are discolsed a pesticidal composition containing a water-insoluble alginate, which is prepared by treating a solid composition containing (a) a pesticidally active ingredient which is a pest-controlling active ingredient or a plant growth-regulating active ingredient and (b) an alginic acid or a water-soluble alginate with an aqueous solution containing a divalent or polyvalent cation which can convert said alginic acid or water-soluble alginate into a water-insoluble alginate. Also disclosed is a pesticidal composition containing a water-insoluble alginate, which is prepared by coating a solid substance containing the pesticidally active ingredient with a water-insoluble alginate. The composition of the invention has excellent sustained-release effects of the pesticidally active ingredient.

  本发明公开了一种含有水不溶性藻酸盐的杀虫组合物，其制备方法是将含有(a) 杀虫活性成分（一种害虫控制活性成分或植物生长调节活性成分）和(b) 藻酸或水溶性藻酸盐的固体组合物用含有二价或多价阳离子的水溶液处理，该阳离子可将所述藻酸或水溶性藻酸盐转化为水不溶性藻酸盐。本发明还公开了一种含有水不溶性海藻酸盐的杀虫组合物，其制备方法是将含有杀虫活性成分的固体物质包覆在水不溶性海藻酸盐上。本发明的组合物具有优异的农药活性成分持续释放效果。
• Residual control of parasites by long-acting shampoo formulations
  申请人：LABORATOIRES VIRBAC

  公开号：EP0714601A1

  公开（公告）日：1996-06-05

  The invention relates to shampoo compositions comprising a detergent and at least one active compound selected from juvenile hormone-like nitrogen containing heterocyclic compounds, other insect growth regulators such as methoprene or fenoxycarb, synthetic pyrethroids and mixtures thereof, wherein the dose of the active compound is sufficient for leaving on the haircoat of a warm-blooded animal after rinse out the shampoo an ovicidally and/or insecticidally and/or acaricidally residual effective amount against ectoparasites of said compound. Such shampoo compositions are useful for a residual control of ectoparasites on warm-blooded animals.

  本发明涉及由洗涤剂和至少一种活性化合物组成的洗发水组合物，这些活性化合物选自含杂环化合物的稚虫激素样氮、其他昆虫生长调节剂如甲氧苄啶或唑螨酯、合成除虫菊酯及其混合物，其中活性化合物的剂量足以在洗发水冲洗后在温血动物的毛发上残留有效量的卵杀螨剂和/或杀虫剂和/或杀螨剂。这种洗发水组合物可用于温血动物体外寄生虫的残留控制。
• Dry pesticidal composition
  申请人：SUMITOMO CHEMICAL COMPANY, LIMITED

  公开号：EP0699389A2

  公开（公告）日：1996-03-06

  This invention relates to a dry pesticidal composition containing an active ingredient for controlling pests, a surfactant, a modified starch, a carbonate and a solid acid, wherein said constituents of said composition are combined together by means of a water-soluble polymer which is soluble in a volatile solvent. The composition has sufficient hardness and high solubility in water.

  本发明涉及一种干农药组合物，其中含有一种用于控制害虫的活性成分、一种表面活性剂、一种变性淀粉、一种碳酸盐和一种固体酸，所述组合物中的所述成分通过一种可溶于挥发性溶剂的水溶性聚合物结合在一起。该组合物具有足够的硬度和较高的水溶性。

表征谱图