(2-Methyl-4-oxo-3-penta-2,4-dienylcyclopent-2-en-1-yl) 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;(2-methyl-4-oxo-3-penta-2,4-dienylcyclopent-2-en-1-yl) 3-(3-methoxy-2-methyl-3-oxoprop-1-enyl)-2,2-dimethylcyclopropane-1-carboxylate | 8003-34-7

• 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: (2-Methyl-4-oxo-3-penta-2,4-dienylcyclopent-2-en-1-yl) 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;(2-methyl-4-oxo-3-penta-2,4-dienylcyclopent-2-en-1-yl) 3-(3-methoxy-2-methyl-3-oxoprop-1-enyl)-2,2-dimethylcyclopropane-1-carboxylate
• 英文别名: (2-methyl-4-oxo-3-penta-2,4-dienylcyclopent-2-en-1-yl) 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;(2-methyl-4-oxo-3-penta-2,4-dienylcyclopent-2-en-1-yl) 3-(3-methoxy-2-methyl-3-oxoprop-1-enyl)-2,2-dimethylcyclopropane-1-carboxylate
• CAS: 8003-34-7
• 化学式: C43H56O8
• 分子量: 700.9
• InChiKey: VXSIXFKKSNGRRO-UHFFFAOYSA-N

物化性质

• 密度：
  0.84-0.86 g/cm3
• 闪点：
  75 °C
• 溶解度：
  氯仿：微溶；甲醇：微溶
• 物理描述：
  Pyrethrins, [solid] appears as colorless to white liquids (or tan dusts). Primarily a threat to the environment. Immediate steps should be taken to limit spread to the environment. Easily penetrate the soil, contaminate groundwater or nearby waterways. Toxic by inhalation, skin absorption and/or ingestion. Used as pesticide. Practically insoluble in water.
• 颜色/状态：
  Refined extract is pale yellow mobile oil; unrefined extract is a dark greenish brown viscous liquid; powder (ground flowers) is a tan color.
• 气味：
  Characteristic odor of carrier
• 沸点：
  338°F (Pyrethrin I), 392°F (Pyrethrin II), 279°F (Cinerin I), 361°F (Cinerin II)
• 蒸汽压力：
  VP: Essentially 0 torr at 20 °C
• 亨利常数：
  Henry's Law constant = 6.55X10-7 atm-cu m/mol at 25 °C (est)
• 稳定性/保质期：
  Pyrethrums are highly unstable in the presence of light, moisture, and air. Whole flowers decompose more slowly than ground flowers or dust. Stored powders lose about 20% of their potency in one year. The potency of the pyrethrums can best be preserved in sealed, lightproof containers kept at lower temperatures.
• 分解：
  170 °C at 0.01 kPa
• 腐蚀性：
  Non-corrosive

计算性质

• 辛醇/水分配系数(LogP)：
  8.27
• 重原子数：
  51
• 可旋转键数：
  16
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  113
• 氢给体数：
  0
• 氢受体数：
  8

ADMET

代谢

杀虫剂混合物中的酯类在大肠道和一定程度上在成年温血动物的体内通过水解迅速解毒。形成的菊花单羧酸随尿液排出。目前还没有研究使用现代方法证明拟除虫菊酯或其代谢物会在体内储存或随乳汁排出，但最近的研究已经开始描述拟除虫菊酯在大肠中经历的广泛代谢过程，主要在肝脏。各种有效成分经历显著不同的生物转化。到目前为止，还无法识别由酯类水解产生的许多化合物。

The esters constituting pyrethrum mixtures are rapidly detoxified by hydrolysis in the GI tract & to some extent in tissues of adult warm-blooded animals. The chrysanthemum monocarboxylic acid formed is excreted in urine. Pyrethrins or their metabolites are not known to be stored in body or ... excreted in milk, but no study of this matter has employed modern methods. ... recent studies have begun to describe ... extensive metabolism that pyrethrins undergo, mainly in liver. ... various active ingredients undergo significantly different biotransformation. ... So far it has not been possible to identify the ... numerous compounds that result from hydrolysis of the esters.

来源:Hazardous Substances Data Bank (HSDB)

代谢

拟除虫菊酯在摄入后据报道会在胃肠道中被灭活。在动物体内，拟除虫菊酯会迅速代谢成水溶性、无活性的化合物。

Pyrethrins are reportedly inactivated in the GI tract following ingestion. In animals, pyrethrins are rapidly metabolized to water soluble, inactive compounds. /Pyrethrins/

来源:Hazardous Substances Data Bank (HSDB)

代谢

基本上，除虫菊素和生物菊酯主要通过氧化酸部分的非丁烯基侧链和醇部分的不饱和侧链来分解，酯水解的作用不大，而对于其他拟除虫菊酯，酯水解占主导地位。这些反应可以在肝脏和血浆中发生，随后是羟基化和与葡萄糖醛酸或硫酸盐的结合，然后通过尿液排出。有许多因素会影响分解速率，尤其是立体特异性，反式异构体水解由酯酶催化，而顺式异构体水解由氧化酶催化的速率相对较低。顺式异构体的这种较慢分解可能有助于它们对哺乳动物的较高毒性，但它们对钠通道复合物的较高固有亲和力被认为是主要因素。代谢速率的另一个影响因素是α-氰基的存在，它减慢了水解和氧化。

Essentially, pyrethrum & allethrin are broken down mainly by oxidation of the isobutenyl side chain of the acid moiety & of the unsaturated side chain of the alcohol moiety with ester hydrolysis playing an unimportant part, whereas for the other pyrethroids ester hydrolysis predominates. These reactions can take place in both liver & plasma & are followed by hydroxylation & conjugation to glucuronides or sulfates, which are then excreted in the urine. A number of factors modify the rate of break- down, notably stereospecificity, with trans isomer hydrolysis being catalyzed by esterases but cis isomer hydrolysis being catalzyed at a rather lower rate by oxidases. This slower breakdown of cis isomers may contribute to their greater mammalian toxicity, but their higher inherent affinity for the sodium channel complex is thought to be the predominant factor. An addtl influence on the rate of metabolism is the presence of an alpha-cyano group, which slows both hydrolysis & oxidation.

来源:Hazardous Substances Data Bank (HSDB)

代谢

拟除虫菊酯在体内被广泛代谢，粪便和尿液中母体化合物的残留物仅占10%。已鉴定出六种代谢物，并提出了两条主要的代谢途径，第一条涉及双键和/或甲基基团的氧化，第二条涉及酯键的水解。拟除虫菊酯I主要通过氧化过程代谢，而拟除虫菊酯II则通过水解和氧化过程的结合代谢。

Pyrethrins are extensively metabolized, the residues of the parent compound in feces and urine representing only 10%. Six metabolites were identified and two major metabolic pathways were suggested, the first involving oxidation of the double-bond and/or the methyl groups and the second involving hydrolysis of the ester bond. Pyrethrins I are metabolized mainly through oxidative processes, while pyrethrins II are metabolized through a combination of hydrolytic and oxidative processes.

来源:Hazardous Substances Data Bank (HSDB)

代谢

在隔离和识别代谢物之后，确定了尿和粪便中代谢物的分布。在所有剂量下，尿液中的主要代谢物是菊花二羧酸。在粪便中，存在大量母化合物（在低剂量时小于10%），但另一种代谢物在所有剂量下最为普遍。这两种代谢物代表了超过三分之一的总放射性标记物被排泄。雄性和雌性大鼠以相似的方式代谢除虫菊素I，无论剂量如何，雄性和雌性之间的差异是数量上的，而不是质量上的。

After isolation and identification of the metabolites, the distribution of metabolites was determined in urine and feces. The major metabolite in urine at all doses was chrysanthemum dicarboxylic acid. In feces, a significant amount of parent compound was present (< 10% at the low dose), but another metabolite was the most prevalent at all doses. The two metabolites represented over one-third of the total excreted radiolabel. Male and female rats metabolized pyrethrins I in a similar manner, regardless of the dose, and the difference between males and females was quantitative rather than qualitative.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

癌症分类：有致癌性的提示性证据，但不足以评估对人类致癌的可能性/除虫菊酯/

Cancer Classification: Suggestive Evidence of Carcinogenicity, but Not Sufficient to Assess Human Carcinogenic Potential /Pyrethrins/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

A4：不能归类为人类致癌物。

A4: Not classifiable as a human carcinogen.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

TLV-A4

TLV-A4

来源:Occupational Safety and Health Administration (OSHA)

毒理性

• 健康影响

健康影响代码(s):HE3 - 慢性(累积)毒性-长期器官毒性，不包括神经、呼吸、血液或生殖系统 HE16 - 刺激-眼睛、鼻子、喉咙、皮肤-轻度 HE7 - 神经系统干扰-除麻醉外的神经系统效应

Health Effect Code(s):HE3 - Chronic (Cumulative) Toxicity---Long-term organ toxicity other than nervous, respiratory, hematologic or reproductive HE16 - Irritation-Eyes, Nose, Throat, Skin---Mild HE7 - Nervous System Disturbances---Nervous system effects other than narcosis

来源:Occupational Safety and Health Administration (OSHA)

毒理性

• 暴露途径

这种物质可以通过吸入、皮肤接触和摄入被身体吸收。

The substance can be absorbed into the body by inhalation, through the skin and by ingestion.

来源:ILO International Chemical Safety Cards (ICSC)

吸收、分配和排泄

拟除虫菊酯或其代谢物未被已知储存在体内或在乳汁中排出...

The pyrethrins or their metabolites are not known to be stored in the body or to be excreted in the milk...

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

拟除虫菊酯通过完整皮肤局部应用时可以被吸收。当动物接触到含有增效剂胡椒基丁氧基的拟除虫菊酯气溶胶时，这种组合很少或没有系统性吸收。/拟除虫菊酯/

Pyrethrins are absorbed through intact skin when applied topically. ... When animals were exposed to aerosols of pyrethrins with piperonyl butoxide being released into the air, little or none of the combination was systemically absorbed. /Pyrethrins/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

拟除虫菊酯或其代谢物未被知道会在体内储存或排泄在乳汁中...

The pyrethrins or their metabolites are not known to be stored in the body or to be excreted in the milk...

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 职业暴露等级：
  B
• 职业暴露限值：
  TWA: 5 mg/m3
• 危险等级：
  6.1(b)
• 立即威胁生命和健康浓度：
  5,000 mg/m3
• 危险品标志：
  Xn
• 安全说明：
  S13,S60,S61
• 危险类别码：
  R20/21/22,R50/53
• WGK Germany：
  3
• 危险品运输编号：
  UN 2810 6.1/PG 3
• RTECS号：
  UR4200000
• 海关编码：
  29400010
• 包装等级：
  III
• 危险类别：
  6.1(b)

制备方法与用途

除虫菊酯是制备蚊虫香的主要原料，源自菊科多年生草本植物除虫菊内含有的杀虫有效成分。主要有除虫菊酯Ⅰ和除虫菊酯Ⅱ两种，此外还有少量结构近似的瓜叶除虫菊酯Ⅰ、瓜叶除虫菊酯Ⅱ等。目前，人工已合成多种与天然除虫菊酯类似的化合物用作杀虫剂，并统称为拟除虫菊酯。

除虫菊酯为黄色粘稠油状液体，具有清香气味，不溶于水但可溶于多种有机溶剂。其稳定性较差，在碱性环境中易分解失效，强光或高温下也会迅速分解失效。主要剂型包括粉剂、乳油、气雾剂、油剂和蚊香等。除虫菊酯具有强力触杀作用，杀虫谱广，但残效期较短，主要用于防治卫生害虫及家畜害虫。对人畜非常安全，无药害、无残留，不污染农产品或环境。

除虫菊酯Ⅰ的毒性最强，瓜叶除虫菊酯次之，除虫菊酯Ⅱ再次之，而瓜叶除虫菊酯Ⅱ则最弱。FAO/WHO建议其日容许摄入量为0.04mg/kg体重（包括其他除虫菊酯）。大鼠口服1500mg/kg。

在食品方面，瑞典规定水果和蔬菜中除虫菊酯的最高容许浓度为1.0mg/kg；FAO/WHO则建议鱼(干)、未加工谷类中的最大容许浓度为3mg/kg，而对干果、干蔬菜、鲜果和鲜蔬菜以及花生米、核果，则规定为1mg/kg（包括其他除虫菊酯）。

图1：除虫菊酯主要成分——Ⅰ与Ⅱ的化学结构式

以上信息由Chemicalbook的晓楠编辑整理。

拟除虫菊酯是在除虫菊酯结构和生物活性基础上人工合成的，因其稳定性增强而被广泛用于农业及园艺领域。拟除虫菊酯分为类型I和II，其中类型II毒性大于类型I。氯菊酯是研究较早的一种不含氰基结构的拟除虫菊酯类杀虫剂，在防治农业害虫方面表现优异。

除虫菊为菊科植物白花除虫菊的干燥花序，含约1%除虫菊酯，具有良好的杀虫效果、击倒速度较快且毒性较低的优点。近年来人工合成的除虫菊酯类似物，如溴氰菊酯、氰戊菊酯等，因其杀虫谱广、对人畜毒性较低以及环境残留较少而被广泛使用。

除虫菊酯中毒机理：除虫菊酯可使机体神经细胞膜发生轻度去极化，增加复后电位，导致重复性后放电，影响Na+和K+通道的功能。此外，其增效剂能抑制和延缓代谢过程，从而增强毒性并延长体内药物作用时间。

类别：

• 农药
• 毒性分级：高毒
• 急性毒性：
  • 口服-大鼠 LD50: 200毫克/公斤
  • 口服-小鼠 LD50: 370毫克/公斤

可燃性危险特性：

• 可燃；火场释放辛辣刺激烟雾

储运特性：

• 库房通风低温干燥，与食品原料分开储运

灭火剂：

• 干粉、泡沫、砂土

职业标准：

• TWA 5毫克/立方米
• STEL 10毫克/立方米