(2-methyl-3-phenylphenyl)methyl (Z)-(1RS,3SR)-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate | 82657-04-3

• 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 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2-methyl-3-phenylphenyl)methyl (Z)-(1RS,3SR)-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate
• 英文别名: (2-methyl-3-phenylphenyl)methyl (1R,3S)-3-[(E)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate
• CAS: 82657-04-3；83322-02-5；87648-90-6；87680-56-6；99267-18-2；107538-31-8；107538-32-9；107538-33-0；107538-34-1；131100-77-1
• 化学式: C₂₃H₂₂ClF₃O₂
• 分子量: 422.875
• InChiKey: OMFRMAHOUUJSGP-ONQPXKCRSA-N

物化性质

• 熔点：
  68-71°C
• 沸点：
  453.2±45.0 °C(Predicted)
• 密度：
  d25 1.212 g/ml
• 闪点：
  165 °C
• 溶解度：
  二甲基亚砜：100 mg/mL（236.48 mM）
• LogP：
  7.300 (est)
• 物理描述：
  Bifenthrin is an off-white to pale tan waxy solid with a very faint slightly sweet odor. Used as a broad spectrum insecticide.
• 颜色/状态：
  Light brown viscous oil
• 气味：
  Very faint, slightly sweet odor
• 蒸汽压力：
  1.78X10-3 mPa at 20 °C /1.335X10-8 mm Hg/
• 稳定性/保质期：
  Stable for two years at 25 °C and 50 °C /technical bifenthrin/ ... stable 21 days at pH 5-9 (21 °C).
• 分解：
  When heated to decomposition it emits toxic vapors of /fluoride/ and /chloride/.

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

ADMET

代谢

雄性和雌性大鼠单次口服剂量为4和35 mg/kg的(14)C-联苯菊酯，其酸部分或醇部分带有放射性碳标记。(14)C迅速通过粪便和尿液排出，(14)C通过粪便和尿液排出的比率分别为66-83%和13-25%。...主要的粪便代谢物在酸部分或醇部分带有完整的酯键，并带有羟基，例如羟甲基联苯菊酯、4'-OH-联苯菊酯和3'-或4'-OH-羟甲基联苯菊酯。还检测到了来自单羟基化和双羟基化母化合物的酯裂解产物。另一方面，尿液中的大多数代谢物是酯裂解产物，如4'-OH-BPacid (4'-羟基-2-甲基-3-苯基苯甲酸)、BPacid (2-甲基-3-苯基苯甲酸)、4'-OH-BPalcohol (4'-羟基-2-甲基-3-苯基苄醇)、dimethoxy-BPacid、4'-methoxy BPacid、dimethoxy BPalcohol、BPalcohol、TFPacid [3-(2-氯-3,3,3-三氟-1-丙烯基-2,2-二甲基环丙烷甲酸]、顺式和反式羟甲基TFPacid。主要的代谢途径被认为是酯键的水解、酸部分甲基基团和苯基的3'-和4'-位置的氧化以及O-甲基化。认为会发生结合反应；然而，没有详细的信息可用。

Male and female rats were treated with (14)C-bifenthrin labeled in the acid or alcohol moiety at single oral doses of 4 and 35 mg/kg. (14)C was rapidly excreted into feces and urine, and the excretion rates of the (14)C to feces and urine were 66-83% and 13-25%, respectively. ... The major fecal metabolites possessed intact ester linkage hydroxylated in the acid or alcohol moiety such as hydroxymethyl-bifenthrin, 4'-OH-bifenthrin, and 3'- or 4'-OH-hydroxymethyl bifenthrin. Ester-cleaved products derived from mono- and dihydroxylated parent compounds were also detected. On the other hand, the majority of urinary metabolites were ester-cleaved products such as 4'-OH-BPacid (4'-hydroxy-2-methyl-3-phenylbenzoic acid), BPacid (2-methyl-3-phenylbenzoic acid), 4'-OH-BPalcohol (4'-hydroxy-2-methyl-3-phenylbenzyl alcohol), dimethoxy-BPacid, 4'-methoxy BPacid, dimethoxy BPalcohol, BPalcohol, TFPacid [3-(2-chloro-3,3,3-trifluoro-1-propenyl-2,2-dimethyl-cyclopropanecarboxylic acid], cis- and trans-hydroxymethyl TFPacid. The major metabolic pathways are considered to be hydrolysis of ester linkage, oxidation at the methyl group of the acid moiety and at the 3'- and 4'-positions of the phenyl group, and O-methylation. The conjugation reactions are considered to take place; however, detailed information is not available.

来源:Hazardous Substances Data Bank (HSDB)

代谢

最快的水解和氧化发生在带有反式取代基的初级醇酯上，因为它们会迅速受到水解和氧化的攻击。对于所有次级醇酯和初级醇顺式取代的环丙烷甲酸酯，氧化攻击是主要形式。/拟除虫菊酯/

Fastest breakdown is seen with primary alcohol esters of trans-substituted acids since they undergo rapid hydrolytic and oxidative attack. For all secondary alcohol esters and for primary alcohol cis-substituted cyclopropanecarboxylates, oxidative attack is predominant. /Pyrethroids/

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

bifenthrin是一种拟除虫菊酯类杀虫剂，在鱼类体内具有雌激素作用。然而，据文献报道，bifenthrin在ER-CALUX（雌激素受体）细胞系中具有抗雌激素作用。我们研究了是否是由于代谢物的形成导致这种不一致性。我们将Menidia beryllina（内陆银鱼）暴露于10 ng/L bifenthrin、10 ng/L 4-羟基bifenthrin以及10 ng/L bifenthrin和25 ug/L Piperonyl butoxide（PBO）——一种P450抑制剂的环境中。与bifenthrin/PBO暴露的幼体相比，暴露于代谢物的幼体雌激素介导的蛋白水平（卵黄蛋白）显著更高，而单独暴露于bifenthrin的则处于中间水平（与两者均无显著差异）。这表明代谢物是bifenthrin体内雌激素作用的主要贡献者。

Bifenthrin, a pyrethroid pesticide, is estrogenic in vivo in fishes. However, bifenthrin is documented to be anti-estrogenic in vitro, in the ER-CALUX (estrogen receptor) cell line. We investigated whether metabolite formation is the reason for this incongruity. We exposed Menidia beryllina (inland silversides) to 10 ng/L bifenthrin, 10 ng/L 4-hydroxy bifenthrin, and 10 ng/L bifenthrin with 25 ug/L piperonyl butoxide (PBO) - a P450 inhibitor. Metabolite-exposed juveniles had significantly higher estrogen-mediated protein levels (choriogenin) than bifenthrin/PBO-exposed, while bifenthrinalone was intermediate (not significantly different from either). This suggests that metabolites are the main contributors to bifenthrin's in vivo estrogenicity.

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)

毒理性

• 致癌性证据

癌症分类：C组可能的人类致癌物

Cancer Classification: Group C Possible Human Carcinogen

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 相互作用

一种新颖的两层分析方法是用来对I型和II型拟除虫菊酯对Hyalella azteca的相互作用进行特征描述和量化。使用标准化的水柱毒性测试，对双甲脒、氯菊酯、氟氯菊酯和高效氯氟氰菊酯进行了所有可能的二元组合测试，共计六个实验。所有混合物都进行了4天的致死性分析，其中六个混合物中的两个（氯菊酯-双甲脒和氯菊酯-氟氯菊酯）进行了亚慢性10天的致死性和对游泳活动力和生长的亚致死效应测试。混合物最初使用回归分析来分析相互作用，然后与浓度加和（CA）和独立作用（IA）的加和模型进行比较，以进一步描述混合物反应。在六个测试混合物中的两个（氟氯菊酯-双甲脒和氟氯菊酯-氯菊酯）中，负面相互作用（拮抗作用）仅在急性4天致死性终点显著。在这两种情况下，混合物反应在CA和IA的加和模型之间。所有其他混合物在4天致死性上是加和的，双甲脒-氯菊酯和氟氯菊酯-氯菊酯在亚慢性10天致死性和亚致死反应上也是加和的。

A novel two-tiered analytical approach was used to characterize and quantify interactions between Type I and Type II pyrethroids on Hyalella azteca using standardized water column toxicity tests. Bifenthrin, permethrin, cyfluthrin and lambda-cyhalothrin were tested in all possible binary combinations across six experiments. All mixtures were analyzed for 4 d lethality, and two of the six mixtures (permethrin-bifenthrin and permethrin-cyfluthrin) were tested for subchronic 10 d lethality and sublethal effects on swimming motility and growth. Mixtures were initially analyzed for interactions using regression analyses, and subsequently compared to the additive models of Concentration Addition (CA) and Independent Action (IA) to further characterize mixture responses. Negative interactions (antagonistic) were significant in two of the six mixtures tested, including cyfluthrin-bifenthrin and cyfluthrin-permethrin, but only on the acute 4d lethality endpoint. In both cases mixture responses fell between the additive models of CA and IA. All other mixtures were additive across 4 d lethality, and bifenthrin-permethrin and cyfluthrin-permethrin were also additive on subchronic 10 d lethality and sublethal responses.

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，增强了除虫菊酯的杀虫活性。当胡椒基丁醚与除虫菊酯结合时，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。变化与剂量成正比，并且与DDT产生的变化相似。这两种...的效果是叠加的。/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

三种氨基甲酸酯类(甲萘威、甲硫威、嘧啶胺)和一种拟除虫菊酯类(联苯菊酯)杀虫剂作为纯化学品和商业制剂进行了研究，以揭示商业制剂中添加剂和溶剂可能产生的毒性效应，并评估细胞应激反应作为一种防御机制。毒性效应在A549细胞上进行评估，该细胞来源于人肺癌，通过测量(1)导致生长速率下降的阈值浓度(LOEC)，(2)不杀死细胞但停止生长的亚致死浓度(SC)，以及(3)几种应激蛋白的表达水平，即HSP27、HSP72/73、HSP90、GRP78和GRP94。与纯活性分子相比，使用商业制剂时LOEC出现在较低的浓度，即Dicarzol(甲萘威)、Lannate20(甲硫威)和Talstar或Kiros EV(联苯菊酯)。Talstar和Kiros中分别存在的丙二醇和丙二醇单甲醚并不解释这些商业制剂的高毒性，也不会增强联苯菊酯的毒性。当细胞暴露于4种不同商业制剂的混合物时，观察到添加剂而非协同的有害效应...所有杀虫剂都能使GRP78上调，商业制剂更有效地触发应激反应。这表明杀虫剂和商业制剂中的添加剂破坏了内质网的功能。相反，发现所有杀虫剂都能使HSP72/73下调。这似乎与细胞质中蛋白质合成减少有关，是内质网未折叠蛋白反应的结果。事实上，已知抑制内质网N-连接糖基化的曲古霉素，被发现能诱导GRP78过表达和HSP72/73低表达之间的类似反向关系。发现GRP94的表达在高浓度联苯菊酯商业制剂中增加，HSP27降低。甲硫威和Lannate20仅诱导HSP90的下调。

Three carbamate (formetanate, methomyl, pyrimicarb) and one pyrethroid (bifenthrin) insecticides were investigated both as pure chemicals and as commercial formulations in order to unveil possible toxic effects of additives and solvents present in the commercial formulations and to evaluate the cellular stress response as a defense mechanism. Toxic effects were evaluated on A549 cells, derived from a human lung carcinoma, by measuring (1) threshold concentrations leading to a decrease of the growth rate (LOEC), (2) sublethal concentrations (SC) which arrested growth without killing the cells, and (3) expression levels of several stress proteins, i.e., HSP27, HSP72/73, HSP90, GRP78, and GRP94. As compared to the pure active molecule, LOEC appeared at lower concentrations when using the commercial formulations, i.e., Dicarzol (formetanate), Lannate20 (methomyl) and Talstar or Kiros EV (bifenthrin). Propylene glycol and propylene glycol monomethyl ether, respectively, present in Talstar and kiros, do not account for the high toxicity of these commercial formulations and do not potentiate the toxicity of bifenthrin. Additive but not synergistic adverse effects were observed when cells are exposed to a mixture of 4 different commercial formulations ... GRP78 was up-regulated by all the insecticides, commercial preparations being more efficient to trigger the stress reaction. This suggests that insecticides and additives present in commercial formulations disrupt ER functions. Conversely, HSP72/73 was found to be down-regulated by all the insecticides. This seems to be related with a decrease of protein synthesis in the cytosol, as a result of the ER unfolded protein response. Indeed, tunicamycin, known to inhibit N-linked glycosylation in the ER, was found to induce a similar inverse correlation between GRP78 overexpression and HSP72/73 under-expression. Expression of GRP94 was found to be increased and HSP27 lowered by the highest concentrations of bifenthrin commercial formulations. Methomyl and Lannate20 only induced an under-expression of HSP90.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

雄性和雌性大鼠单次口服给予4和35毫克/千克的(14)C-联苯菊酯，标记在酸部分或醇部分。(14)C迅速排泄到粪便和尿液中，(14)C的粪便和尿液排泄率分别为66-83%和13-25%。在脂肪中发现的残留物最高，低剂量给药后略高于1 ppm，高剂量给药后雄性和雌性分别为8和16 ppm。其他器官的残留水平在大多数情况下，低剂量给药后<0.2 ppm，高剂量给药后<1 ppm。

Male and female rats were treated with (14)C-bifenthrin labeled in the acid or alcohol moiety at single oral doses of 4 and 35 mg/kg. (14)C was rapidly excreted into feces and urine, and the excretion rates of the (14)C to feces and urine were 66-83% and 13-25%, respectively. Highest residues were found in the fat, with values of slightly more than 1 ppm after low-dose administration and 8 and 16 ppm in males and females, respectively, after application of the high dose. Residue levels in other organs were in most cases <0.2 ppm after low-dose administration and <1 ppm after high-dose administration.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在大鼠口服给药0.5 mg/kg/天的(14)C-联苯菊酯70天后，检查了大鼠的组织残留物。平均来看，(14)C浓度在脂肪中达到9.6 ppm，皮肤中1.7 ppm，肝脏中0.4 ppm，肾脏中0.3 ppm，卵巢中1.7 ppm，坐骨神经中3.2 ppm，全血中0.06 ppm，血浆中0.06 ppm。在停止给药后，分析又额外进行了85天（排泄阶段）。从(14)C排泄中估计出脂肪、皮肤、肝脏、肾脏、卵巢和坐骨神经的半衰期分别为51天、50天、19天、28天和40天。对脂肪的分析揭示，母体化合物在脂肪中的(14)C残留物中占了大部分（65-85%）。

The tissue residues /of rats/ were examined after oral administration of (14)C-bifenthrin at 0.5 mg/kg/day for 70 days. The peak (14)C concentrations on an average were 9.6 ppm in fat, 1.7 ppm in skin, 0.4 ppm in liver, 0.3 ppm in kidney, 1.7 ppm in ovaries, 3.2 ppm in sciatic nerve, 0.06 ppm in whole blood, and 0.06 ppm in plasma. Analyses were extended for an additional 85 days following cessation of dosing (depuration phase). Half-lives of 51 days (fat), 50 days (skin), 19 days (liver), 28 days (kidney), and 40 days (ovaries and sciatic nerve) were estimated from (14)C-depuration. Analysis of the fat revealed that the parent chemical accounted for a majority (65-85%) of the (14)C-residues in fat.

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。

Pyrethrins are absorbed through intact skin when applied topically. /Pyrethrins/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

双甲脒在大鼠口服、吸入和静脉给药后的药代动力学进行了描述。此外，还介绍了通过口服和吸入途径的拟除虫菊酯类化合物急性毒性。将雄性大鼠分为几组，通过口服灌胃给药3.1 mg/kg（每千克1毫升玉米油，临界急性口服基准剂量下限，BMDL）以及等效剂量的吸入（0.018 mg/L）持续4小时。在给药开始后的2、4、6、8和12小时，测量了血浆和大脑中双甲脒的浓度。血浆中双甲脒的最大浓度为361 ng/mL或0.853 uM（口服）和232 ng/mL或0.548 uM（吸入），在大脑中为83和73 ng/g。口服灌胃给药后的浓度-时间曲线下面积（AUC）值为1969 h ng/mL（血浆）和763 h ng/mL（大脑），吸入后的值为1584 h ng/mL（血浆）和619 h ng/mL（大脑）。静脉给药的结果是血浆和大脑的表观末端半衰期（t1/2）分别为13.4小时和11.1小时，血浆和大脑的AUC0-∞值分别为454和1566 h ng/mL。血浆的清除率为37 mL/min/kg。口服给药后的血浆和大脑浓度峰值通常略高（大约14%）。双甲脒的吸入给药避免了肝脏的首过效应，没有导致血浆或大脑中暴露增加。消除半衰期与其他拟除虫菊酯类化合物相当，表明生物积累潜力较小。

... The pharmacokinetics of bifenthrin in the rat after oral, inhalation and intravenous administration is described. Pyrethroid acute toxicity via oral and inhalation routes is also presented. Groups of male rats were dosed by oral gavage at 3.1 mg/kg in 1 mL/kg of corn oil (the critical, acute, oral benchmark dose lower limit, BMDL) and at an equivalent dose by inhalation (0.018 mg/L) for 4 hr. At 2, 4, 6, 8 and 12 hr after dosing initiation, blood plasma and brain bifenthrin concentrations were measured. The maximum concentrations of bifenthrin in plasma were 361 ng/mL or 0.853 uM (oral) and 232 ng/mL or 0.548 uM (inhalation), and in brain they were 83 and 73 ng/g. The area under the concentration versus time curve (AUC) values were 1969 h ng/mL (plasma) and 763 h ng/mL (brain) following oral gavage dosing, and 1584 h ng/mL (plasma) and 619 h ng/mL (brain) after inhalation. Intravenous dosing resulted in apparent terminal half-life (t1/2 ) values of 13.4 h (plasma) and 11.1 h (brain) and in AUC0-infinity values of 454 and 1566 h ng/mL for plasma and brain. Clearance from plasma was 37 mL/min/kg. Peak plasma and brain concentrations were generally a little higher after oral dosing (by ca 14%). Inhalation administration of bifenthrin did not cause increases in exposure in plasma or brain by avoiding first-pass effects in the liver. The elimination t1/2 was comparable with other pyrethroids and indicated little bioaccumulation potential. ...

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

这项研究评估了 bifenthrin 在成年雄性长埃文斯大鼠体内的口服处置和生物利用度。在处置研究中，通过口服灌胃给大鼠给予 bifenthrin（0.3 或 3 毫克/千克），并连续牺牲（0.25 小时到 21 天）。收集血液、肝脏、大脑和脂肪组织。在生物利用度研究中，从颈静脉插管的大鼠中连续收集血液（0.25 到 24 小时），这些大鼠通过口服（0.3 或 3 毫克/千克）或静脉注射（0.3 毫克/千克）给予 bifenthrin。提取组织并使用高效液相色谱-串联质谱（HPLC-MS/MS）分析 bifenthrin。口服给药后，血液和肝脏中的 bifenthrin 浓度在 1-2 小时达到峰值，两种组织的浓度分别约为 90 ng/mL（或 g）和 1000 ng/mL（或 g），对于 0.3 毫克/千克和 3 毫克/千克的剂量。Bifenthrin 从血液和肝脏中迅速清除。大脑浓度在 4-6 小时达到峰值，并且低于两种剂量的血液浓度（12 和 143 ng/g）。脂肪组织中的 bifenthrin 在收集的时间点 8（157 ng/g）和 24（1145 ng/g）小时对于 0.3 毫克/千克和 3 毫克/千克的剂量达到峰值，并且在口服给药后 21 天仍保持。静脉给药后，血液中的 bifenthrin 浓度双指数下降，分布半衰期为 0.2 小时，消除半衰期为 8 小时。Bifenthrin 的生物利用度大约为 30%。这些 bifenthrin 的处置和动力学数据可能减少对这种拟除虫菊酯类杀虫剂风险评估的不确定性。

... This study evaluated the oral disposition and bioavailability of bifenthrin in the adult male Long-Evans rat. In the disposition study, rats were administered bifenthrin (0.3 or 3 mg/kg) by oral gavage and serially sacrificed (0.25 hr to 21 days). Blood, liver, brain and adipose tissue were removed. In the bioavailability study, blood was collected serially from jugular vein cannulated rats (0.25 to 24 hr) following oral (0.3 or 3 mg/kg) or intravenous (0.3 mg/kg) administration of bifenthrin. Tissues were extracted and analyzed for bifenthrin by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Bifenthrin concentration in blood and liver peaked 1-2-hr post-oral administration and were approximately 90 ng/mL (or g) and 1000 ng/mL (or g) for both tissues at 0.3 and 3 mg/kg, respectively. Bifenthrin was rapidly cleared from both blood and liver. Brain concentrations peaked at 4-6 hr and were lower than in blood at both doses (12 and 143 ng/g). Bifenthrin in adipose tissue peaked at the collected time points of 8 (157 ng/g) and 24 (1145 ng/g) hr for the 0.3 and 3 mg/kg doses, respectively and was retained 21 days post-oral administration. Following intravenous administration, the blood bifenthrin concentration decreased bi-exponentially, with a distribution half-life of 0.2 hr and an elimination half-life of 8 hr. Bifenthrin bioavailability was approximately 30%. These disposition and kinetic bifenthrin data may decrease uncertainties in the risk assessment for this pyrethroid insecticide.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险等级：
  6.1(b)
• 危险品标志：
  Xn
• 安全说明：
  S13,S16,S36/37,S60,S61
• 危险类别码：
  R20/21/22,R50/53
• WGK Germany：
  3
• 海关编码：
  29162090
• 危险品运输编号：
  UN 2588
• RTECS号：
  GZ1227800
• 包装等级：
  III
• 危险类别：
  6.1(b)

制备方法与用途

概述

联苯菊酯是70-80年代迅速发展起来的一种新型拟除虫菊类农用杀虫剂，广泛应用于全球各地。该农药对人和畜的毒性中等，在土壤中有很高的亲合作用，具有极高的杀虫活性，能够通过胃毒和触杀作用防治多种害虫。

毒性

联苯菊酯原药对大鼠急性经口LD50为54.5毫克/公斤，兔急性经皮LD50大于2000毫克/千克。该药对大鼠、兔皮肤及眼睛无刺激和致敏作用，在动物饲喂试验中未表现出致癌、致畸或致突变性。但在鱼类等水生生物中的毒性较高，蓝鳃翻车鱼LC50为0.35微克/升（96小时），虹鳟鱼LC50为0.15微克/升（96小时），水蚤LC50为0.16微克/升（48小时）。野鸭和鹌鹑的急性经口LD50浓度分别为1280毫克/千克饲料（8天）和4450毫克/千克饲料（8天）。

化学性质

联苯菊酯是一种灰白色固体，熔点68-70.6℃（工业品为61-66℃），相对密度1.210（25℃），蒸气压为2.4×10^-5帕斯卡，闪点165℃。该物质能溶于丙酮、氯仿、二氯甲烷、甲苯和乙醚，可稍溶于庚烷和甲醇，不溶于水。其分配系数（正辛醇/水）高达1000000。在常温下，原药稳定时间超过一年，在天然日光照射下的半衰期为255天，在土壤中则为65至125天。

用途

联苯菊酯是一种高效、广谱的拟除虫菊酯类杀虫剂和杀螨剂，主要通过触杀作用和胃毒作用控制害虫。它适用于防治棉铃虫、红铃虫、茶尺蠖、茶毛虫、苹果或山楂红蜘蛛、桃小食心虫、菜蚜、菜青虫、小菜蛾等害虫。例如，在防治棉铃虫和红铃虫时，通常在第二代至第三代卵盛期，幼虫蛀入蕾铃前，或在防治棉红蜘蛛时，应在成螨和若螨发生期使用10%乳油3.4～6毫升/100平方米，对水7.5～15公斤或4.5～6毫升/100平方米，对水7.5公斤进行喷雾。此外，它还可兼治棉蚜、造桥虫、卷叶虫和刺蛾等害虫。

生产方法

联苯菊酯可通过两种主要制备方法获得：

• 方法一：首先由2-苯基苯甲酸与SOCl2反应生成2-苯基苯甲酰氯，再与二甲基甲酰胺反应生成相应的2-苯基苯甲酰胺。然后使用氢化锂铝还原得到2-苯基二甲苄胺。将此化合物与CH3I反应制得相应的铵盐，并经异构化后与氯甲酸乙酯反应，最终制得2-甲基-3-苯基氯苄。最后，在KOH存在下于乙腈中回流16小时制备得到联苯菊酯。

• 方法二：由3,3-二甲基-1-烯戊酸2-甲基-3-苯基溴苄经缩合、环合和脱氯化氢制得。

类别

• 农药
• 毒性分级：剧毒
• 急性毒性：口服 - 大鼠 LD50: 54.5毫克/公斤
• 可燃性危险特性：易燃；燃烧时产生有毒的氯化物和氟化物气体
• 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、泡沫或砂土

反应信息

• 作为产物：
  描述：

  (2-methyl-3-phenylphenyl)methyl (1RS,3SR)-3-(2,2-dichloro-3,3,3-trifluoro-1-hydroxypropyl)-2,2-dimethylcyclopropanecarboxylate 在 三乙胺 、 锌 作用下， 以 乙醚 为溶剂， 反应 12.0h， 生成 (2-methyl-3-phenylphenyl)methyl (Z)-(1RS,3SR)-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate
  参考文献：
  名称：

  Practical, Stereocontrolled Synthesis of Polyfluorinated Artificial Pyrethroids

  摘要：

  本文介绍了基于 CF3CCl2ZnCl 的醛加成法制备多氟合成拟除虫菊酯的实用立体控制方法。锌试剂可与 3-甲酰基-2,2-二甲基环丙烷羧酸盐 (6) 反应，生成相应的加合物。这些加合物经乙酰化后再次用锌还原，得到 (1R*，3S*)-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基环丙烷羧酸盐 (12)。(1R*, 3R*)异构体是由 2,2-二氯-1,1,1-三氟-5-甲基-4-己烯-3-醇通过重氮乙酰化、Cu(II)催化的分子内碳烯加成，最后通过锌还原得到的。获得 12 及其 (Z)- 吡咯烷卤素同系物的另一种方法是在 6 的 CHO 基上添加 1-卤代-2,2-二氟乙烯基，然后进行区域和立体选择性卤化。

  DOI：

  10.1246/bcsj.60.4385

文献信息

• Practical ways from aldehydes to 2-chloro-1,1,1-trifluoro-2-alkenes and 2-chloro-1,1-difluoro-1-alken-3-ols
  作者：Makoto Fujita、Tamejiro Hiyama

  DOI：10.1016/s0040-4039(00)84873-x

  日期：1986.1
• Practical, Stereocontrolled Synthesis of Polyfluorinated Artificial Pyrethroids
  作者：Makoto Fujita、Kiyosi Kondo、Tamejiro Hiyama

  DOI：10.1246/bcsj.60.4385

  日期：1987.12

  Practical and stereocontrolled approaches to polyfluorinated synthetic pyrethroids based on aldehyde addition of CF3CCl2ZnCl are described. The zinc reagent was allowed to react with 3-formyl-2,2-dimethylcyclopropanecarboxylates (6) to give the corresponding adducts. These were acetylated and then reduced again with zinc to afford (1R*, 3S*)-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylates (12). The (1R*, 3R*)-isomer was derived from 2,2-dichloro-1,1,1-trifluoro-5-methyl-4-hexen-3-ol by diazoacetylation, Cu(II)-catalyzed intramolecular carbene addition, and finally by the zinc reduction. An alternative access to 12 and its halogen homologues of the (Z)-pyrethroids involves addition of 1-halo-2,2-difluoroethenyl group across the CHO group of 6 and subsequent regio- and stereoselective halogenation.

  本文介绍了基于 CF3CCl2ZnCl 的醛加成法制备多氟合成拟除虫菊酯的实用立体控制方法。锌试剂可与 3-甲酰基-2,2-二甲基环丙烷羧酸盐 (6) 反应，生成相应的加合物。这些加合物经乙酰化后再次用锌还原，得到 (1R*，3S*)-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基环丙烷羧酸盐 (12)。(1R*, 3R*)异构体是由 2,2-二氯-1,1,1-三氟-5-甲基-4-己烯-3-醇通过重氮乙酰化、Cu(II)催化的分子内碳烯加成，最后通过锌还原得到的。获得 12 及其 (Z)- 吡咯烷卤素同系物的另一种方法是在 6 的 CHO 基上添加 1-卤代-2,2-二氟乙烯基，然后进行区域和立体选择性卤化。