(R)-α-cyano-3-phenoxybenzyl (R)-2-(4-chlorophenyl)isovalerate | 67614-33-9

• 物质功能分类: 化学试剂 - 有机试剂 - 酯类
• 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: (R)-α-cyano-3-phenoxybenzyl (R)-2-(4-chlorophenyl)isovalerate
• 英文别名: (R)-α-cyano-3-phenoxybenzyl (R)-2-(4-chlorophenyl)-3-methylbutyrate；(2R, αR)-fenvalerate；(2R,αR)-fenvalerate；(1R,2R)-fenvalerate；(R,R)-fenvalerate；[(R)-cyano-(3-phenoxyphenyl)methyl] (2R)-2-(4-chlorophenyl)-3-methylbutanoate
• CAS: 67614-33-9
• 化学式: C₂₅H₂₂ClNO₃
• 分子量: 419.908
• InChiKey: NYPJDWWKZLNGGM-BJKOFHAPSA-N

物化性质

• 沸点：
  538.9±50.0 °C(Predicted)
• 密度：
  1.21

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  59.3
• 氢给体数：
  0
• 氢受体数：
  4

ADMET

代谢

Esfenvalerate 通过口服途径容易被吸收，但通过皮肤吸收较少；吸收的敌百虫容易代谢和排泄。来自酸部分的主要尿液代谢物是 CPIA 葡糖苷酸、3-羟基-CPIA（游离和内酯）、2,3-羟基-CPIA 葡糖苷酸和 2-(4-氯苯基)-顺-2-丁二酸酐。来自醇部分的主要尿液代谢物是 3-(4'-羟基苯氧基)苯甲酸硫酸盐（给药放射活性的 16-24%）。其他代谢物包括 3-苯氧基苯甲酸（游离和甘氨酸和葡糖苷酸结合物）、3-(4'-羟基苯氧基)苯甲酸（游离和葡糖苷酸）和 3-(2'-羟基苯氧基)苯甲酸（游离和硫酸盐）。(A564)

Esfenvalerate is readily absorbed by the oral route, but less so dermally; absorbed deltamethrin is readily metabolized and excreted. The main urinary metabolites from the acid moiety are CPIA glucuronide, 3-hydroxy-CPIA (free and lactone), 2,3-hydroxy-CPIA glucuronide and 2-(4-chlorophenyl)-cis-2-butenedioic acid anhydride. The main urinary metabolite from the alcohol moiety is 3-(4'-hydroxyphenoxy)benzoic acid sulfate (16-24% of the administered radioactivity). Other metabolites included 3-phenoxybenzoic acid (free and glycine and glucuronide conjugates), 3-(4'-hydroxyphenoxy)benzoic acid (free and glucuronide) and 3-(2'-hydroxyphenoxy)benzoic acid (free and sulfate). (A564)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

I型和B型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的效果与DDT产生的效果非常相似，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、调节尼古丁乙酰胆碱传输、增强去甲肾上腺素的释放以及对钙离子的作用。它们还抑制钙通道和Ca2+，Mg2+-ATP酶。（T10，T18，L857）

Both type I and type II 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. They also inhibit calium channels and Ca2+, Mg2+-ATPase. (T10, 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Esfenvalerate的中毒迹象包括大量流涎和肺水肿，阵挛性癫痫，角弓反张（即脊柱向前弯曲，以至于仰卧的身体靠头部和脚跟支撑），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 esfenvalerate 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)

毒理性

• 症状

紧随接触异佛尔酮后，可能会出现皮肤麻木、瘙痒、灼热、刺痛、刺痛或温暖的感觉，这些感觉可能会持续几个小时。吸入或摄入大量异佛尔酮可能导致头晕、头痛、恶心、肌肉抽搐、体力下降和意识改变。接触后可能会出现麻痹。

Following dermal exposure to esfenvalerate, feelings of numbness, itching, burning, stinging, tingling, or warmth may occur, that could last for a few hours. Dizziness, headache, nausea, muscle twitching, reduced energy, and changes in awareness can result from inhalation or ingestion of large amounts of esfenvalerate. Paralysis can occur after exposure. (L857)

来源:Toxin and Toxin Target Database (T3DB)

安全信息

• 海关编码：
  2926909036

制备方法与用途

制备方法

制备氰戊菊酯通常采用一步法：首先将2-(对氯苯基)-3-甲基丁酸（α-异丙基对氯苯乙酸）用三氯化磷或五氯化磷等氯化成2-(对氯苯基)-3-甲基丁酰氯，然后与间苯氧基苯甲醛及氰化钠水溶液反应制得。国外曾采用正庚烷、石油醚、苯、甲苯作为溶剂，国内则多使用无溶剂法。

国外报道常采用相转移催化剂（如TEBA、TBA等四丁基溴化铵），而国内有些单位选择不添加催化剂。国内主要用此法生产，收率可达90%以上。

另一种方法是α-羟基磺酸钠法：以间苯氧基苯甲醛与亚硫酸氢钠加成的产物直接与氰化钠水溶液作用生成氰醇，并迅速与2-(对氯苯基)-3-甲基丁酰氯反应，生成氰戊菊酯。还有一种方法是α-溴代氰苄法：首先将间苯氧基氯化苄与氰化钠反应生成间苯氧基苯乙腈，然后在105～110℃回流条件下使氰苄与溴进行1～3小时的反应，再与丁酸作用，以K2CO3为缚酸剂、苯为溶剂、四丁基溴化铵为相转移催化剂、水为介质，在70～80℃下反应2小时制得。

用途简介

氰戊菊酯是一种广谱高效杀虫剂，作用迅速且击倒力强，主要用于防治棉花害虫（如棉铃虫、棉蚜等）、烟草、大豆、玉米、果树和蔬菜上的害虫。在使用上，每亩地一般施用有效成分4-10克即可防治棉花害虫；防治烟草害虫则需3-10克的有效成分；其他谷类作物的防治用量为2-10克的有效成分。

自氰氯苯苯醚菊酯商品化以来，因其高效的杀虫效果和较低的成本，在市场上迅速推广，并挤入了传统有机磷、有机氯杀虫剂的竞争领域。目前其主要应用于棉花种植，深受用户欢迎。由于它是拟除虫菊酯类杀虫剂中生产成本最低的一种，具有较强的市场竞争能力及良好的发展前景。

急性毒性方面，大鼠口服的半数致死量（LD50）为451毫克/千克，小鼠则在100-300毫克/千克之间。

反应信息

• 作为反应物：
  描述：

  (1S,2R/S)-fenvalerate 、 (R)-α-cyano-3-phenoxybenzyl (R)-2-(4-chlorophenyl)isovalerate 生成 来福灵
  参考文献：
  名称：

  AKETA, KOCHICHI;SUZUKI, YUKIO;OHNO, NOBUO;NAKAYAMA, ISAMU;KATO, TAKASHI

  摘要：

  DOI：
• 作为产物：
  描述：

  2-(4-氯苯基)-3-甲基丁酸 在 吡啶 、 氯化亚砜 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 反应 1.5h， 生成 (R)-α-cyano-3-phenoxybenzyl (R)-2-(4-chlorophenyl)isovalerate
  参考文献：
  名称：

  Development of an Immunoassay for the Pyrethroid Insecticide Esfenvalerate

  摘要：

  A competitive enzyme-linked immunosorbent assay was developed for the detection of the pyrethroid insecticide esfenvalerate. Two haptens containing amine or propanoic acid groups on the terminal aromatic ring of the fenvalerate molecule were synthesized and coupled to carrier proteins as immunogens. Five antisera were produced and screened against eight different coating antigens. The assay that had the least interference and was the most sensitive for esfenvalerate was optimized and characterized. The I-50 for esfenvalerate was 30 +/- 6.2 mu g/L, and the lower detection limit (LDL) was 3.0 +/- 1.8 mu g/L. The assay was very selective. Other pyrethroid analogues and esfenvalerate metabolites tested did not cross-react significantly in this assay. To increase the sensitivity of the overall method, a C-18 sorbent-based. solid-phase extraction (SPE) was used for water matrix. With this SPE step, the LDL of the overall method for esfenvalerate was 0.1 mu g/L in water samples.

  DOI：

  10.1021/jf981210m
• 作为试剂：
  描述：

  (1S,2R/S)-fenvalerate 在 (R)-α-cyano-3-phenoxybenzyl (R)-2-(4-chlorophenyl)isovalerate 作用下， 以 甲醇 为溶剂， 反应 81.5h， 生成 (R)-α-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate 、 来福灵
  参考文献：
  名称：

  Process for preparing (S)- alpha-cyano-3-phenoxybenzyl-(S)-2-(4-chlorophenyl)-isovalerate

  摘要：

  本发明涉及一种环保的工艺，用于从其对映体混合物(RS)-α-氰基-3-苯氧基苯甲酰-(S)-2-(4-氯苯基)异戊酸酯中制备(S)-α-氰基-3-苯氧基苯甲酰-(S)-2-(4-氯苯基)异戊酸酯。

  公开号：

  US20060128982A1

文献信息

• Crystalline phenylacetate enantiomer pair, and preparation of a pesticidal enantiomer pair
  申请人：SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

  公开号：EP0060580A1

  公开（公告）日：1982-09-22

  A pesticidal phenylacetate rich in the Y enantiomer pair is prepared by precipitating the novel intermediate crystalline phenylacetate X enantiomer pair in the presence of crystals of phenylacetate X from a solution of racemic phenylacetate and recovering the filtrate rich in the Y enantiomer pair. The phenylacetate X crystals are redissolved, epimerized and the resulting racemate recycled to improve the yield of phenylacetate Y enantiomer pair.

  从外消旋苯乙酸盐溶液中析出新型中间体结晶苯乙酸盐 X 对映体，在苯乙酸盐 X 晶体存在的情况下制备富含 Y 对映体的杀虫剂苯乙酸盐，并回收富含 Y 对映体的滤液。将苯乙酸 X 晶体重新溶解，进行外消旋化，并回收所产生的外消旋体，以提高苯乙酸 Y 对映体的产率。
• process for the preparation of optically-active cyanomethyl esters
  申请人：E.I. DU PONT DE NEMOURS AND COMPANY

  公开号：EP0109681A2

  公开（公告）日：1984-05-30

  Stereoisomerically-enriched cyanomethyl esters are prepared by treating a non-symmetrical ketene or an alpha-chiral carboxylic acid halide or reactive derivative thereof with an optically-active alphahydroxynitrile. Certain optically-active optionally substituted S-alphacyano-3-phenoxybenzyl alcohol intermediates are prepared by treating the corresponding aldehyde of ketone with a source of hydrogen cyanide in the presence of a substantially water-immiscible, aprotic solvent and a cyclo(D-phenylalanyl-D-histidine) as a catalyst.

  通过将非对称酮或α-手性羧酸卤化物或其活性衍生物与具有光学活性的α-羟腈进行处理，可制备立体异构体富集的氰甲基酯。某些具有光学活性的任选取代的 S-alphacyano-3-苯氧基苄醇中间体的制备方法是：在基本上不溶于水的壬烷溶剂和作为催化剂的环(D-苯丙氨酰-D-组氨酸)存在下，用氰化氢源处理相应的酮醛。
• Process for the preparation of optically-active cyanomethyl esters
  申请人：E.I. DU PONT DE NEMOURS AND COMPANY

  公开号：EP0291626A2

  公开（公告）日：1988-11-23

  Stereoisomerically-enriched cyanomethyl esters are prepared by treating a non-symmetrical ketene or an alpha-chiral carboxylic acid halide or reactive derivative thereof with an optically-active alpha-hydroxynitrile. Certain optically-active optionally substituted S-alpha-cyano-3-phenoxybenzyl alcohol intermediates are prepared by treating the corresponding aldehyde or ketone with a source of hydrogen cyanide in the presence of a substantially water-immiscible, aprotic solvent and a cyclo(D-phenylalanyl-D-histidine) as a catalyst.

  立体异构体富集氰基甲酯的制备方法是用光学活性的 α-羟腈处理非对称酮或α-手性羧酸卤化物或其活性衍生物。某些具有光学活性的任选取代的 S-α-氰基-3-苯氧基苄醇中间体的制备方法是：在基本上不溶于水的壬烷溶剂和作为催化剂的环(D-苯丙氨酰-D-组氨酸)存在下，用氰化氢源处理相应的醛或酮。
• Seed treatment with combinations of pyrethrins/pyrethroids and thiamethoxam
  申请人：Monsanto Technology, LLC

  公开号：EP1844655A2

  公开（公告）日：2007-10-17

  A method of preventing damage to the seed and/or shoots and foliage of a plant by a pest includes treating the seed from which the plant grows with a composition that includes a combination of thiamethoxam and at least one pyrethrin or synthetic pyrethroid which is selected from the group consisting of taufluvalinate, flumethrin, trans-cyfluthrin, kadethrin, bioresmethrin, tetramethrin, phenothrin, empenthrin, cyphenotrin, prallethrin, imiprothrin, allethrin and bioallethrin. The treatment is applied to the unsown seed. In another embodiment, the seed is a transgenic seed having at least one heterologous gene encoding for the expression of a protein having pesticidal activity against a first pest and the composition has activity against at least one second pest. Treated seeds are also provided.

  一种防止害虫对植物种子和/或嫩枝和叶片造成损害的方法，包括用一种组合物处理生长植物的种子，该组合物包括噻虫嗪和至少一种拟除虫菊酯或合成拟除虫菊酯的组合物，该拟除虫菊酯或合成拟除虫菊酯选自由氟虫腈组成的组、氟氯氰菊酯、反式氟氯氰菊酯、氯氰菊酯、生物除害菊酯、四氯氰菊酯、苯醚菊酯、氰戊菊酯、氯氰菊酯、炔丙菊酯、烯丙菊酯和生物烯丙菊酯。处理方法适用于未播种的种子。在另一个实施方案中，种子是转基因种子，具有至少一种异源基因，编码表达对第一种害虫具有杀虫活性的蛋白质，组合物对至少一种第二种害虫具有杀虫活性。还提供了经过处理的种子。
• Compositions and methods for deploying a transgenic refuge as a seed blend
  申请人：Head Graham

  公开号：US10036036B1

  公开（公告）日：2018-07-31

  Methods and compositions for deploying refuge seeds together with transgenic crop seeds are provided. The refuge seeds can be non-transgenic seeds of a similar variety to that of the transgenic crop seeds, or the refuge seeds can be a transgenic variety, but in either case lacking a transgenic trait conferring pest protection found in the transgenic crop seeds.

  本文提供了将避难种子与转基因作物种子一起播种的方法和组合物。保护种子可以是与转基因作物种子品种相似的非转基因种子，或者保护种子可以是转基因品种，但无论哪种情况，都缺乏转基因作物种子中具有害虫保护功能的转基因性状。