[1-R-[1α(S),3α]]-2,2-dimethyl-3-(1,2,2,2,tetrabromoethyl)cyclopropane carboxylic acid cyano(3-phenoxyphenyl)methyl ester | 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
• 英文名称: [1-R-[1α(S),3α]]-2,2-dimethyl-3-(1,2,2,2,tetrabromoethyl)cyclopropane carboxylic acid cyano(3-phenoxyphenyl)methyl ester
• 英文别名: tralomethrin；RU 25474；[(1R,3S)-3-((1'RS)-1',2',2',2'-tetrabromoethyl)]-2,2-dimethylcyclopropanecarboxylic acid (S)-α-cyano-3-phenoxybenzyl ester；[(S)-cyano-(3-phenoxyphenyl)methyl] (1R,3S)-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-KAKFPZCNSA-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：
  在常温常压下，它保持稳定。
• 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/
• 保留指数：
  2968.1

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不活跃的酸和醇成分，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看到的相似易感性。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

拟除虫菊酯通常通过哺乳动物的酯水解、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，拟除虫菊酯在土壤和植物中相当快速地降解。分子上各个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)

代谢

赛百灵经口服给药后被很好地吸收，广泛代谢，并作为极性结合物在尿液中排出。主要的代谢途径正如预期，是通过酯键的水解。环丙烷-羧酸部分随后作为葡萄糖苷酸结合物通过尿液排出。

Cypermethrin has been shown to be well absorbed after oral administration, extensively metabolized, and eliminated as polar conjugates in urine. The main route of metabolism was, as anticipated, via hydrolysis of the ester linkage. The cyclopropane-carboxylic acid moiety is subsequently excreted via the urine as the glucuronide conjugate. (L857)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

识别和使用：三氯甲菊酯是一种固体。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（如三氯甲菊酯）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，通过作用于哺乳动物和/或昆虫的钠通道与外周和中枢神经系统的轴突相互作用。单次剂量就会在哺乳动物中产生毒性体征，如震颤、过度兴奋、流涎、舞蹈手足徐动症和瘫痪。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，如下肢神经轴突肿胀和/或断裂以及髓鞘退化。它们不会被认为会引起某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、增加行为效应、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、在雄性和雌性中皮炎和肌炎。在一项代际繁殖研究中，将三氯甲菊酯以0、0.75、3.0和12.0 mg/kg/天的剂量水平每天通过灌胃给予大鼠。在任何剂量水平下都没有发现对F0或F1代父母生殖性能的有害影响的证据。在F1幼崽的12 mg/kg/天组中注意到了出生时初始体重的降低。在F1和F2幼崽的哺育期间，在中剂量和高剂量组中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/天的剂量下体重下降。生态毒性研究：三氯甲菊酯对大型溞具有毒性，其LC50为0.15微克/升。在涂抹处理后的叶子接触1小时后，对蜜蜂没有毒性。

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

• 毒性总结

拟除虫菊酯通过延长神经细胞兴奋时钠通道门的开启阶段来发挥其作用。它们似乎与钠通道附近的膜脂质相结合，从而改变通道动力学。这阻止了神经中钠门的关闭，从而延长了膜电位恢复到静息状态的时间。重复的（感觉、运动）神经元放电和延长的负后电位产生了与DDT相似的效果，导致神经系统过度活跃，可能导致瘫痪和/或死亡。拟除虫菊酯的其他作用机制包括对抗γ-氨基丁酸（GABA）介导的抑制作用、调节尼古丁胆碱能传递、增强去甲肾上腺素的释放以及对钙离子的作用。(T18, L857)

Pyrethroids exert their effect by prolonging the open phase of the sodium channel gates when a nerve cell is excited. They appear to bind to the membrane lipid phase in the immediate vicinity of the sodium channel, thus modifying the channel kinetics. This blocks the closing of the sodium gates in the nerves, and thus prolongs the return of the membrane potential to its resting state. The repetitive (sensory, motor) neuronal discharge and a prolonged negative afterpotential produces effects quite similar to those produced by DDT, leading to hyperactivity of the nervous system which can result in paralysis and/or death. Other mechanisms of action of pyrethroids include antagonism of gamma-aminobutyric acid (GABA)-mediated inhibition, modulation of nicotinic cholinergic transmission, enhancement of noradrenaline release, and actions on calcium ions. (T18, L857)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌物分类

对人类不具有致癌性（未被国际癌症研究机构IARC列名）。

No indication of carcinogenicity to humans (not listed by IARC).

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

在高剂量下，可归因于特拉罗甲素的中毒迹象包括大量流涎和肺水肿，阵挛性惊厥，角弓反张（即脊柱向前弯曲，以至于仰卧的身体可以靠头和脚跟支撑），昏迷和死亡。在较低剂量下，常见的影响包括感觉异常和红斑。

At high doses, signs of poisoning attributable to tralomethrin include profuse salivation and pulmonary edema, clonic seizures, opisthotonos (i.e., the spine is bent forward such that a supine body rests on its head and heels), coma, and death. At lower doses, commonly observed effects include paresthesia and erythema. (L863)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

吸入 (L857)；口服 (L857)；皮肤接触 (L857)；眼睛接触 (L857)。

Inhalation (L857) ; oral (L857) ; dermal (L857) ; eye contact (L857).

来源:Toxin and Toxin Target Database (T3DB)

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。在大鼠中给予反式异构体：剂量：500毫克/千克；间隔20天；尿液36%；粪便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的快速生物降解（酯水解和氧化）可能是这一现象的主要因素......大多数拟除虫菊酯代谢物会迅速被排泄，至少部分通过肾脏。/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)
• 储存条件：
  0-6°C

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：

  [1-R-[1α(S),3α]]-2,2-dimethyl-3-(1,2,2,2,tetrabromoethyl)cyclopropane carboxylic acid cyano(3-phenoxyphenyl)methyl ester 生成 溴氰菊酯
  参考文献：
  名称：

  IRVING, S. N.;FRASER, T. E. M., J. AGR. AND FOOD CHEM., 1984, 32, N 1, 111-113

  摘要：

  DOI：

文献信息

• [EN] ACC INHIBITORS AND USES THEREOF<br/>[FR] INHIBITEURS DE L'ACC ET UTILISATIONS ASSOCIÉES
  申请人：GILEAD APOLLO LLC

  公开号：WO2017075056A1

  公开（公告）日：2017-05-04

  The present invention provides compounds I and II useful as inhibitors of Acetyl CoA Carboxylase (ACC), compositions thereof, and methods of using the same.

  本发明提供了化合物I和II，这些化合物可用作乙酰辅酶A羧化酶（ACC）的抑制剂，以及它们的组合物和使用方法。
• [EN] BICYCLYL-SUBSTITUTED ISOTHIAZOLINE COMPOUNDS<br/>[FR] COMPOSÉS ISOTHIAZOLINE SUBSTITUÉS PAR UN BICYCLYLE
  申请人：BASF SE

  公开号：WO2014206910A1

  公开（公告）日：2014-12-31

  The present invention relates to bicyclyl-substituted isothiazoline compounds of formula (I) wherein the variables are as defined in the claims and description. The compounds are useful for combating or controlling invertebrate pests, in particular arthropod pests and nematodes. The invention also relates to a method for controlling invertebrate pests by using these compounds and to plant propagation material and to an agricultural and a veterinary composition comprising said compounds.

  本发明涉及公式（I）中变量如索权和说明中所定义的自行车基取代异噻唑啉化合物。这些化合物对抗或控制无脊椎动物害虫，特别是节肢动物害虫和线虫方面具有用途。该发明还涉及一种通过使用这些化合物来控制无脊椎动物害虫的方法，以及包含所述化合物的植物繁殖材料、农业和兽医组合物。
• [EN] AZOLINE COMPOUNDS<br/>[FR] COMPOSÉS AZOLINE
  申请人：BASF SE

  公开号：WO2015128358A1

  公开（公告）日：2015-09-03

  The present invention relates to azoline compounds of formula (I) wherein A, B1, B2, B3, G1, G2, X1, R1, R3a, R3b, Rg1 and Rg2 are as defined in the claims and the description. The compounds are useful for combating or controlling invertebrate pests, in particular arthropod pests and nematodes. The invention also relates to a method for controlling invertebrate pests by using these compounds and to plant propagation material and to an agricultural and a veterinary composition comprising said compounds.

  本发明涉及式（I）的噁唑啉化合物，其中A、B1、B2、B3、G1、G2、X1、R1、R3a、R3b、Rg1和Rg2如权利要求和描述中所定义。这些化合物对抗或控制无脊椎动物害虫，特别是节肢动物害虫和线虫方面具有用途。该发明还涉及一种利用这些化合物控制无脊椎动物害虫的方法，以及包括所述化合物的植物繁殖材料、农业和兽医组合物。
• [EN] MICROBIOCIDAL OXADIAZOLE DERIVATIVES<br/>[FR] DÉRIVÉS D'OXADIAZOLE MICROBIOCIDES
  申请人：SYNGENTA PARTICIPATIONS AG

  公开号：WO2017157962A1

  公开（公告）日：2017-09-21

  Compounds of the formula (I) wherein the substituents are as defined in claim 1, useful as a pesticides, especially fungicides.

  式(I)的化合物，其中取代基如权利要求1所定义，作为杀虫剂特别是杀菌剂有用。
• Thieno-pyrimidine compounds having fungicidal activity
  申请人：Brewster Kirkland William

  公开号：US20070093498A1

  公开（公告）日：2007-04-26

  The present invention relates to thieno[2,3-d]-pyrimidine compounds having fungicidal activity.

  本发明涉及具有杀真菌活性的噻吩[2,3-d]-嘧啶化合物。