(1R,3R)-((S)-2-methyl-4-oxo-3-((Z)-penta-2,4-dienyl)cyclopent-2-enyl) 3-((E)-3-methoxy-2-methyl-3-oxoprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate | 121-29-9

• 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: (1R,3R)-((S)-2-methyl-4-oxo-3-((Z)-penta-2,4-dienyl)cyclopent-2-enyl) 3-((E)-3-methoxy-2-methyl-3-oxoprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate
• 英文别名: [(1S)-2-methyl-4-oxo-3-penta-2,4-dienylcyclopent-2-en-1-yl] (1R,3R)-3-(3-methoxy-2-methyl-3-oxoprop-1-enyl)-2,2-dimethylcyclopropane-1-carboxylate
• CAS: 121-29-9
• 化学式: C₂₂H₂₈O₅
• 分子量: 372.5
• InChiKey: VJFUPGQZSXIULQ-NEWSRXKRSA-N

物化性质

• 比旋光度：
  D19 +14.7° (isooctane-ether)
• 沸点：
  bp0.007 192-193°
• 密度：
  1.12±0.1 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿（少许）、DMSO（少许）、甲醇（少许）
• 颜色/状态：
  Viscous liquid
• 蒸汽压力：
  3.98X10-7 mm Hg at 25 °C
• 稳定性/保质期：
  Oxidizes rapidly and becomes inactive in air.
• 旋光度：
  Specific optical rotation: -6 deg at 20 °C/D (diethyl ether, percentage concentration = 5%)
• 分解：
  When heated to decomp it emits acrid smoke and irritating fumes.
• 腐蚀性：
  Non-corrosive
• 折光率：
  Index of refraction: 1.5258 at 20 °C/D

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

ADMET

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/或甲基组的氧化，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进行代谢。

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

在给予大鼠口服(14)C-除虫菊素II后48小时内，53%的(14)C以呼出的二氧化碳形式回收。从尿液中回收的(14)C占7%...口服给药物质的一部分通过粪便排出，至少部分以代谢形式排出。已经从尿液中分离出三种化合物，并通过核磁共振和质谱鉴定。这三种化合物都是由除虫菊素I和II产生的。这三种化合物都是酸和醇部分氧化的结果，分子的主要结构保持完整。

... Within 48 hr of oral admin of (14)C-pyrethrin II to rats, 53% of the (14)C was recovered as exhaled carbon dioxide ... . The ... (14)C recovered from urine ... /was/ 7% ... some of the orally admin material is excreted in feces, at least partially in metabolized form. Three compounds have been isolated from urine & identified by NMR & mass spectra. All three are produced by ... pyrethrin I & II. All three are the result of oxidation of ... the acid & alcoholic moieties leaving the main structure of the molecule intact.

来源:Hazardous Substances Data Bank (HSDB)

代谢

口服放射性标记的除虫菊素I或除虫菊素II给大鼠后，产生了几个尿液代谢物。每一个代谢物都含有一个trans-2-羧基丙-1-烯基侧链，这是由除虫菊酸异丁烯基团的氧化或除虫菊酸甲氧基羰基团的水解产生的。此外，除虫菊素I和除虫菊素II的cis-2',4'-戊二烯基侧链在戊-2,4-二烯基团处被氧化，产生了cis-4',5'-二羟基戊-2'-烯基团，这个二醇的4'共轭物，或者是一个trans-2',5'-二羟基戊-3'-烯基团。

The oral administration of radio-labelled pyrethrin I, or pyrethrin II, to rats produced several urinary metabolites. Each contained a trans-2-carboxyprop-1-enyl side chain resulting from oxidation of the chrysanthemate isobutenyl group or hydrolysis of the pyrethrate methoxy-carbonyl group. Also, the cis-2',4'-pentadienyl side chain of pyrethrin I and pyrethrin II was oxidized at the penta-2,4-dienyl group to give a cis-4',5'-dihydroxypent-2'-enyl group, a 4' conjugate of this diol, or a trans-2',5'-dihydroxypent-3'-enyl group.

来源:Hazardous Substances Data Bank (HSDB)

代谢

The 2-甲基丙烯基团 of (S)-生物丙烯菊酯 (A) 和戊二烯基团 of 菊酯II被m-氯过氧苯甲酸在二氯甲烷中选择性地氧化，从A得到7,8-环氧物(1)，从菊酯II得到8',9'-和10',11'-环氧物的混合物(7和8)。这些环氧物在水酸中被水化成相应的二醇，以及其他由环丙基环开环或邻近双键迁移产生的羟基衍生物。通过二维核磁共振技术鉴定环氧和羟基衍生物。小鼠肝酶不能明显地水化环氧物1，但能迅速水化环氧物7和8，而双键不迁移。对菊酯I和II的微粒体代谢物的高效液相色谱分析确定了10',11'-二醇为主要代谢物，8',9'-二醇为次要产物。

The 2-methylpropenyl group of (S)-bioallethrin (A) and the pentadienyl group of pyrethrin II are selectively oxidized by m-chloroperoxybenzoic acid in dichloromethane to yield the 7,8-epoxide (1) from A and a mixture of the 8',9'- and 10',11'-epoxides (7 and 8) from pyrethrin II. These epoxides are hydrated in aqueous acid to the corresponding diols and other hydroxy derivatives produced by opening of the cycloprophyl ring or migration of the adjacent double bond. The epoxy and hydroxy derivatives are identified by two dimensional NMR techniques. Mouse liver enzymes do not detectably hydrate epoxide 1 but quickly hydrate epoxides 7 and 8 without migration of the double bond. HPLC analyses of the microsomal metabolites of pyrethrins I and II identify the 10',11'-diols as major metabolites and the 8',9'-diols as minor products.

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的致癌潜力/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

• 相互作用

胡椒基丁醚通过抑制负责在节肢动物中代谢除虫菊酯的水解酶，从而增强除虫菊酯的杀虫活性。当胡椒基丁醚与除虫菊酯结合使用时，后者的杀虫活性可增加2-12倍。

Piperonyl butoxide potentiates /insecticidal activity/ of pyrethrins by inhibiting the hydrolytic enzymes responsible for pyrethrins' metabolism in arthropods. When piperonyl butoxide is combined with pyrethrins, the insecticidal activity of the latter drug is increased 2-12 times /Pyrethrins/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 相互作用

在1000 ppm杀虫剂和10000 ppm氧化胡椒基丁的饮食水平下...在大鼠肝细胞中/肥大、边缘化和细胞质包涵体/仅在8天内就得到了很好的发展，但是...并没有达到最大值。变化与剂量成正比，并且与DDT产生的变化相似。这两种...的效果是累加的。/杀虫剂/

At dietary level of 1000 ppm pyrethrins & 10000 ppm piperonyl butoxide ... /enlargement, margination, & cytoplasmic inclusions in liver cells of rats/ were well developed in only 8 days, but ... were not maximal. Changes were proportional to dosage & similar to those produced by DDT. Effects of the 2 ... were additive. /Pyrethrins/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 相互作用

没有证据表明增效剂会增加拟除虫菊酯对哺乳动物的毒性。

There is no evidence that synergists incr toxicity of the pyrethrins to mammals. /pyrethrins/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 相互作用

抗氧化剂用于帮助保护拟除虫菊酯残留，包括微量的焦儿茶酚、焦酚和氢醌；1-苯基偶氮-2-萘酚用于防止阳光的影响。

Antioxidants used to help protect insecticidal residues of pyrethrins include minute concn of pyrocatechol, pyrogallol, & hydroquinone; 1-benzene-azo-2-naphthol is used to protect against the effects of sunlight.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

拟除虫菊酯经口服给药后从胃肠道吸收。在给予雄性大鼠3毫克/公斤口服的实验中，几乎完全吸收并在100小时内代谢完毕。尿液中没有观察到拟除虫菊酯，尽管存在大量的代谢物。在粪便中，观察到少量的原形拟除虫菊酯，同样伴随着代谢物。

Pyrethrins are absorbed from the gastrointestinal tract following oral administration. Studies in male rats receiving 3 mg/kg orally resulted in almost complete absorption and metabolism within 100 hours. No pyrethrin was observed in urine, although substantial quantities of metabolites were present. In feces, small quantities of the parent pyrethrin were observed, again accompanied by metabolites.

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)

吸收、分配和排泄

在给大鼠口服派瑞松II单次剂量后，53%的给药剂量以二氧化碳形式出现，7%出现在尿液中。在给予等效剂量的派瑞松I后，0.3%的剂量以二氧化碳形式被计算，46%的剂量通过尿液排出。

Following a single oral pyrethrin II dose to rats, 53% of the admin dose appeared as CO2 & 7% appeared in urine. After an equivalent dose of pyrethrin I, 0.3% could be accounted for as CO2 & 46% of the dose was eliminated in urine.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险等级：
  6.1(b)
• 危险品标志：
  Xn,N
• 安全说明：
  S13,S60,S61
• 危险类别码：
  R20/21/22
• 海关编码：
  29183000
• 危险品运输编号：
  UN 2902
• 包装等级：
  III
• 危险类别：
  6.1(b)

制备方法与用途

根据提供的信息,可以总结除虫菊素的几个关键点:

1. 除虫菊素主要存在于白花除虫菊花中,含量约为0.9-1.3%。

2. 生产方法:

   • 可用石油醚回流萃取、浓缩、脱蜡和脱色等步骤精制得到高纯度产品。
   • 或者使用混合溶剂抽提,如甲醇/煤油、石油醚/乙腈等。

3. 除虫菊素为神经毒剂,见光易分解。应避免阳光直射和高温保存。

4. 毒性:接触皮肤会引起刺痛感;大量摄入可引起全身症状如头痛、恶心等。

5. 主要用途:

   • 生产气雾杀虫剂
   • 制作蚊香
   • 制造动物香波
   • 用于绿色农药

6. 注意事项:

   • 避免与碱性农药混用
   • 施药时应尽量让药剂接触害虫

7. 使用方法:

   • 按照不同害虫类型选择合适的稀释倍数和施药时间
   • 喷洒在傍晚效果更好

8. 急救:无特殊解毒剂,主要对症治疗。