右旋苯甘氨酸 | 75-74-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 中文名称: 右旋苯甘氨酸
• 中文别名: 四甲铅；四甲[基]鉛；四甲基铅
• 英文名称: Tetramethylblei-(IV)
• 英文别名: Tetramethylblei；Tetramethyl-plumban；Bleitetramethyl；tetramethyl lead；Tetramethyllead；tetramethylplumbane
• CAS: 75-74-1
• 化学式: C₄H₁₂Pb
• 分子量: 267.339
• InChiKey: XOOGZRUBTYCLHG-UHFFFAOYSA-N

物化性质

• 熔点：
  -27.5°C
• 沸点：
  110°C
• 密度：
  1.3 g/mL at 25 °C
• 闪点：
  37.7°C
• 物理描述：
  Tetramethyllead appears as colorless liquid, dyed red, orange or blue. Has a slight musty odor. Used as an antiknock additive for gasolines; component of mixed alkyl leads for gasoline additives. (EPA, 1998)
• 颜色/状态：
  Colorless liquid (/often/ dyed red, orange, or blue /for use in coimmercial gasoline/)
• 气味：
  Fruity odor
• 溶解度：
  In water, 15 mg/L at 25 °C
• 蒸汽密度：
  6.5 (EPA, 1998) (Relative to Air)
• 蒸汽压力：
  26 mm Hg at 20 °C
• 稳定性/保质期：

  在常温常压下稳定，应避免与强氧化剂和强酸接触。

• 自燃温度：
  254 °C
• 分解：
  Temperatures above 100 °C (212 °F) cause decomposition and development of pressure that may cause containers to burst.
• 燃烧热：
  -5290 Btu/lb = -2940 cal/g = -123x10-5 J/kg (est)
• 汽化热：
  55.5 Btu/lb = 30.8 cal/g = 1.29x10+5 J/kg (estimated)
• 电离电位：
  8.50 eV
• 折光率：
  Index of refraction: 1.5120 at 20 °C

计算性质

• 辛醇/水分配系数(LogP)：
  1.95
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

有机铅化合物最终被代谢为无机铅，后者储存在骨骼中...烷基铅化合物通过细胞色素P-450催化的氧化脱烷基反应在肝脏中积极代谢...四乙基铅和四甲基铅...分别代谢为高度神经毒性的代谢物三乙基铅和三甲基铅。在兔肝中，该反应由细胞色素P-450依赖的单加氧酶系统催化...烷基铅完全氧化为无机铅也会在大鼠、小鼠和兔中发生。/有机铅/

Organic lead cmpd are ultimately metabolized to inorganic lead and the latter is stored in the bones ... Alkyl lead cmpd are actively metabolized in the liver through oxidative dealkylation catalyzed by cytochrome P-450 ... Tetraethyl and tetramethyl lead ... are metabolized to the highly neurotoxic metabolites triethyl and trimethyl lead, respectively. In rabbit liver, the reaction is catalyzed by a cytochrome P-450-dependent monooxygenase system ... Complete oxidation of alkyl lead to inorganic lead also occurs in rat, mouse and rabbit. /Organic lead/

来源:Hazardous Substances Data Bank (HSDB)

代谢

四甲基铅（TML）的代谢速度比四乙基铅（TEL）慢，因此被认为比TEL的毒性小一些；然而，TML比TEL更易挥发，因此可能更容易通过呼吸道吸收。

Tetramethyl lead (TML) is metabolized more slowly than tetraethyl lead (TEL) to the trialkyl derivative and hence is considered somewhat less toxic than TEL; however, it is more volatile than TEL and thus probably is more available for respiratory absorption.

来源:Hazardous Substances Data Bank (HSDB)

代谢

... 四乙基铅和四甲基铅在体内发生氧化脱烷基反应。体内产生的任何无机铅的分布模式与摄入的无机铅相同，但母体化合物和中间脱烷基产物在分布上却有很大差异，并且与它们的亲脂性相符。在大鼠和家兔中，双烷基铅是尿液中发现的主要代谢物。四烷基铅也会以无机铅的形式随粪便排出，这是代谢的最终产物。

... Tetraethyl lead and tetramethyl lead are oxidatively dealkylated in the body. Any inorganic lead produced endogenously is distributed in the same pattern as admin inorganic lead, but the parent cmpd and the intermediate dealkylated products are distributed quite differently and in accordance with their lipophilicity ... In rats and rabbits, dialkyl lead is the major metabolite found in urine. Tetraalkyl leads would also be excreted in the feces as inorganic lead, the end product of metabolism ...

来源:Hazardous Substances Data Bank (HSDB)

代谢

通常情况下，血液中的铅含量略有升高，但在某些中毒病例中几乎正常。在反复吸汽油的情况下，血液中的铅含量很高。血铅水平与中毒严重程度之间没有密切的相关性。铅的尿排泄明显增加... /有机铅/

The concentration of lead in blood varies, in general, it is slightly elevated but in some cases of poisoning it is nearly normal. In cases of repeated gasoline sniffing the content of lead in blood is high. No close correlation exists between blood lead levels and the severity of intoxication. The urinary excretion of lead is increased markedly ... /Organic lead/

来源:Hazardous Substances Data Bank (HSDB)

代谢

在兔子中，单次静脉注射9.9毫克/千克四甲基铅（7.7毫克/千克铅）后，尿液中排出的铅化合物混合物大约由73%的二甲基铅、19%的三甲基铅、6%的无机铅和2%的四甲基铅组成。注射后第7天，尿液中的排出物完全由三甲基铅组成。在注射了39.7毫克/千克四甲基铅（30.8毫克/千克铅）的兔子中，注射后第一天尿液中的总铅排出物大约由67%的二甲基铅、14%的三甲基铅、17%的无机铅和2%的四甲基铅组成，而注射后第7天大约由8%的二甲基铅、74%的三甲基铅、17%的无机铅和1%的四甲基铅组成。在这两组兔子中，注射后7天内通过粪便排出的总铅完全是无机铅。在同一时期内，1到3%的注射剂量四甲基铅通过尿液排出，7到19%通过粪便排出。

... In rabbits, after a single iv dose of 9.9 mg/kg tetramethyl lead (7.7 mg/kg lead), the mixture of lead cmpd excreted in urine was composed of about 73% dimethyl lead, 19% trimethyl lead, 6% inorganic lead and 2% tetramethyl lead on the day following injection. The excretion on day 7 was entirely composed of trimethyl lead. In rabbits injected with 39.7 mg/kg tetramethyl lead (30.8 mg/kg lead), total urinary lead excretion was composed of about 67% dimethyl lead, 14% trimethyl lead, 17% inorganic lead and 2% tetramethyl lead on the day following admin and about 8% dimethyl lead, 74% trimethyl lead, 17% inorganic lead and 1% tetramethyl lead on day 7 after dosing. In both groups of rabbits, total lead excretion in feces during the 7 days after injection was entirely composed of inorganic lead. During the same period, 1 to 3% of either admin dose of tetramethyl lead was excreted in the urine and 7 to 19% in the feces.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

铅模仿其他生物学上重要的金属，如锌、钙和铁，作为许多它们各自酶促反应的辅因子与之竞争。例如，铅已被证明能竞争性地抑制钙与钙调蛋白的结合，干扰神经递质的释放。它对NMDA受体和蛋白激酶C表现出类似的竞争性抑制，这损害了脑微血管的形成和功能，并改变了血脑屏障。铅还通过阻碍多巴胺合成的调节和阻止乙酰胆碱的诱发释放来影响神经系统。然而，其主要作用机制是通过抑制δ-氨基酮酸脱水酶，这是一种在血红素生物合成中至关重要的酶，而血红素是血红蛋白所需的必要辅因子。(T4, A20, A22, L136)

Lead mimics other biologically important metals, such as zinc, calcium, and iron, competing as cofactors for many of their respective enzymatic reactions. For example, lead has been shown to competitively inhibit calcium's binding of calmodulin, interferring with neurotransmitter release. It exhibits similar competitive inhibition at the NMDA receptor and protein kinase C, which impairs brain microvascular formation and function, as well as alters the blood-brain barrier. Lead also affects the nervous system by impairing regulation of dopamine synthesis and blocking evoked release of acetylcholine. However, it's main mechanism of action occurs by inhibiting delta-aminolevulinic acid dehydratase, an enzyme vital in the biosynthesis of heme, which is a necesssary cofactor of hemoglobin. (T4, A20, A22, L136)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

对于无机铅化合物的致癌性，人类的证据有限。对于有机铅化合物的致癌性，人类的证据不足。在实验动物中，对于无机铅化合物的致癌性有充分的证据……在实验动物中，对于有机铅化合物的致癌性证据不足……无机铅化合物可能对人类具有致癌性（2A组）。有机铅化合物对人类的致癌性无法分类（3组）。工作组注意到，有机铅化合物在人类和动物中至少部分代谢为离子铅。由于有机铅生成的离子铅存在于体内，预计它将表现出与无机铅相关的毒性。

There is limited evidence in humans for the carcinogenicity of inorganic lead cmpd. There is inadequate evidence in humans for the carcinogenicity of organic lead cmpd. There is sufficient evidence in exptl animals for the carcinogenicity of inorganic lead cmpd ... There is inadequate evidence in exptl animals for the carcinogenicity of organic lead cmpd ... Inorganic lead cmpd are probably carcinogenic to humans (Group 2A). Organic lead cmpd are not classifiable as to their carcinogenicity to humans (Group 3). The working group noted that organic lead cmpd are metabolized, at least in part, to ionic lead both in humans and animals. The the extent that ionic lead, generated from organic lead, is present in the body, it will be expected to exert the toxicities associated with inorganic lead.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

铅、铅化合物：合理预期为人类致癌物

Lead, lead compounds: Reasonably anticipated to be a human carcinogen

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

有机铅化合物无法归类为对人类的致癌性（第3组）。在有机铅化合物部分代谢为离子铅的程度上，它们预计会表现出与无机铅（第2A组，可能对人类致癌）相关的毒性。

Organic lead compounds are not classifiable as to their carcinogenicity to humans (Group 3). To the extent that organic lead compounds are metabolized in part to ionic lead, they are expected to exert the toxicities associated with inorganic lead (Group 2A, probably carcinogenic to humans). (L135)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

铅是一种神经毒素，已知会导致大脑损伤和认知能力下降，特别是在儿童中。铅暴露可能导致肾病，以及诸如高血压和贫血等血液疾病。铅还表现出生殖毒性，可能导致流产和减少精子产生。

Lead is a neurotoxin and has been known to cause brain damage and reduced cognitive capacity, especially in children. Lead exposure can result in nephropathy, as well as blood disorders such as high blood pressure and anemia. Lead also exhibits reproductive toxicity and can results in miscarriages and reduced sperm production. (L21)

来源:Toxin and Toxin Target Database (T3DB)

吸收、分配和排泄

... /IT WAS/ 发现人类血液中的铅浓度几乎不受呼出气中四甲基铅（TML）水平的影响。

... /IT WAS/ FOUND THAT BLOOD LEAD CONCN /IN MAN/ WERE LITTLE AFFECTED BY LEVELS OF ... TETRAMETHYL LEAD (TML) IN EXPIRED AIR.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

像四甲基铅这样的有机形式会通过完整的皮肤被迅速吸收。

... ORG FORMS SUCH AS ... TETRAMETHYL LEAD ARE ABSORBED QUICKLY THROUGH INTACT SKIN ... .

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

每周5次，连续20周，以0.001-1.08毫克/千克体重的四甲基铅(TML)对大鼠进行口服给药，导致铅在大鼠的肝脏、肾脏、大脑、睾丸和其他器官中沉积。四乙基铅(TEL)和TML在组织中的铅分布不同，且随着剂量、给药方案和暴露动物性别而变化。

REPEATED ORAL DOSES OF ... 0.001-1.08 MG/KG BODY WT OF TETRAMETHYL LEAD (TML) TO RATS 5 TIMES PER WK FOR 20 WK RESULTED IN DEPOSITION OF LEAD IN LIVER, KIDNEY, BRAIN, TESTIS & OTHER ORGANS. DISTRIBUTION OF LEAD IN TISSUES DIFFERED BETWEEN TETRAETHYL LEAD (TEL) & TML & VARIED WITH DOSE, DOSE SCHEDULE & SEX OF EXPOSED ANIMALS.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

六只狗每天暴露于4、12、23或44毫克/立方米的四甲基铅(TML)环境7小时，最长可达100天，平均尿铅浓度从0.6到4.0毫克/升不等，且在更高暴露水平下尿铅浓度更高，但并未呈现出明确的剂量反应关系。

... SIX DOGS /EXPOSED/ DAILY FOR 7 HR TO 4, 12, 23 OR 44 MG/CU M OF TETRAMETHYL LEAD (TML) FOR UP TO 100 DAYS, & AVG URINARY LEAD CONCN RANGED FROM 0.6 TO 4.0 MG/L, BEING HIGHER FOR GREATER EXPOSURE LEVELS WITHOUT A CLEAR DOSE RESPONSE RELATIONSHIP.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 职业暴露等级：
  D
• 职业暴露限值：
  TWA: 0.075 mg/m3 [skin]
• 危险等级：
  6.1(a)
• 立即威胁生命和健康浓度：
  40 mg Pb/m3
• 安全说明：
  S26,S28,S36/37/39,S45,S53,S60,S61
• 危险类别码：
  R38,R61,R33,R26/27/28,R10,R50/53,R62
• 危险类别：
  6.1(a)
• 危险品运输编号：
  UN 1649
• 储存条件：
  常温下应存放在阴凉、通风的地方。

SDS

第一部分：化学品名称

制备方法与用途

生产方法
在金属钠的存在下，Pb与CH₃Cl作用，然后进行蒸馏。

类别 有毒物品

毒性分级 高毒

急性毒性

• 口服 - 大鼠 LD₅₀: 105 毫克/公斤
• 吸入 - 小鼠 LC₅₀: 8.5 克/立方米（30 分钟）

爆炸物危险特性 与空气混合可爆

可燃性危险特性 可燃；火场释放有毒含铅烟雾

储运特性 库房通风、低温干燥；与氧化剂、食品分开储运

灭火剂 水、砂土、泡沫、二氧化碳

职业标准

• 时间加权平均容许浓度（TLV-TWA）: 0.15 毫克/立方米（铅）
• 短时间接触容许浓度（STEL）: 0.23 毫克/立方米（铅）

反应信息

• 作为反应物：
  描述：

  右旋苯甘氨酸 在 乙醇 、 mercury dichloride 作用下， 生成 氯化甲基汞
  参考文献：
  名称：

  DE565609

  摘要：

  公开号：
• 作为产物：
  描述：

  氯甲烷 在 lead 、 lead(II) iodide 作用下， 生成 右旋苯甘氨酸
  参考文献：
  名称：

  Method of making lead alkyls

  摘要：

  公开号：

  US02414058A1
• 作为试剂：
  描述：

  乙烷 在 右旋苯甘氨酸 作用下， 800.0~1100.0 ℃ 、2.53 kPa 条件下， 生成 甲基自由基
  参考文献：
  名称：

  Eltenton, Journal of Chemical Physics, 1947, vol. 15, p. 465

  摘要：

  DOI：

文献信息

• 1,1-Organoboration of Trimethyl-l-propynyltin Using Diorganoboryl-Substituted Ferrocenes
  作者：Bernd Wrackmeyer、Udo Dörfler、Wolfgang Milius、Max Herberhold

  DOI：10.1515/znb-1996-0615

  日期：1996.6.1

  The reactions of various diorganoborylferrocenes, Fc -BR₂ [1, R = Me (a), Et (b), ⁱPr (c), ^tBu (d), Ph (f), R₂B = 9-borabicyclo[3.3.1]nonyl (e)] and 1,1′-bis(9-borabicyclo[3.3.1]nonyl)- ferrocene (2) with trimethyl-l-propynyltin (3) were studied, and the products of the 1,1- organoboration were characterized as the alkenyltin compounds 4 -6 by ¹H, ¹¹B, ¹³C and ¹¹⁹Sn NMR. In the cases of 1a - 1d and If, there is competition between the transfer of a ferrocenyl group and the other organyl groups R from boron to carbon, whereas in the case of the 9-borabicyclo[3.3.1]nonane derivatives 1e and 2, the enlargement of the bicyclic system takes place selectively (compounds 4e and 6). The molecular structure of the product 6, obtained from the reaction between the 1,1′-diborylated ferrocene 2 and two equivalents of 3, was determined by single crystal X-ray analysis (space group P2₁/c monoclinic; Z = 4, a = 958.3(2), b = 1610.4(3), c = 2405.3(5) pm and β = 90.33(3)°)

  标题：摘要 研究了各种二有机硼基二茂铁，Fc-BR2 [1，R = Me（a），Et（b），iPr（c），tBu（d），Ph（f），R2B = 9-硼杂双环[3.3.1]壬基（e）]和1,1'-双（9-硼杂双环[3.3.1]壬基）-二茂铁（2）与三甲基-1-丙炔基锡（3）的反应，并将1,1-有机硼化的产物表征为烯基锡化合物4-6，通过1H，11B，13C和119Sn NMR进行表征。在1a-1d和1f的情况下，存在从硼到碳的一铁茂基团和其他有机基团R之间的竞争，而在9-硼杂双环[3.3.1]壬烷衍生物1e和2的情况下，选择性地发生双环系统的扩大（化合物4e和6）。通过单晶X射线分析确定了从1,1'-二硼基化二茂铁2和两当量3反应得到的产物6的分子结构（空间群P21/c单斜；Z = 4，a = 958.3(2)，b = 1610.4(3)，c = 2405.3(5) pm和β = 90.33(3)°）。
• Trifluormethylsubstituierte plumbane. Synthese, eigenschaften und NMR-Spektren der verbindungen (CF3)nPbR4-n (n = 1–3) und (C
  作者：R. Eujen、A. Patorra

  DOI：10.1016/0022-328x(92)88006-5

  日期：1992.10

  Trifluoromethylated derivatives of lead, (CF3)nPbR4-n (n = 1–3; R = CH3, C2H5), have been prepared by a stepwise halide/CF3 exchange from (CF3)nPbR3-nX (n=O–2) and donor-stabilized (CF3)2Cd. Upon treatment of CF3PbR3 and (CF3)2PbR2 with halides under mild conditions, selective cleavage of the PbC(H) bond and formation of the corresponding alkyl(trifluoromethyl)haloplumbanes were achieved, whereas

  铅的三氟甲基化衍生物（CF 3）n PbR 4- n（n = 1-3; R = CH 3，C 2 H 5），是通过从（CF 3）n PbR逐步进行卤化物/ CF 3交换制得的3- n X（n = O-2）和施主稳定的（CF 3）2 Cd。处理CF 3 PbR 3和（CF 3）2 PbR 2时用卤化物在温和的条件下，PbC（H）键的选择性裂解和相应的烷基（三氟甲基）卤代铅烷的形成得以实现，而仅用（CF 3）3 PbMe（CF 3）2 PbMeX得到了。对于系统PbR 4 /（CF 3）n E（E = Hg，Ge，Sn），（CF 3）4 Sn是最有效的CF 3转移试剂，观察到烷基和三氟甲基的直接交换。所有化合物均通过振动，质谱和多核NMR光谱表征。NMR耦合常数n J（207已确定了PbE）（E = 19 F，1 H，13 C），其随溶剂和取代基的变化而变化，并确定了它们的绝对符号。之间发现线性关系1
• Unstable intermediates. Part 165. Radicals in irradiated organolead compounds: an electron spin resonance study
  作者：Robert J. Booth、Stephen A. Fieldhouse、Haydn C. Starkie、Martyn C. R. Symons

  DOI：10.1039/dt9760001506

  日期：——

  the parent radical anions. The electron-loss centres are thought to be the corresponding cations, with the hole largely confined to the halogen atoms. Irradiated PbMe3Cl gives a similar anionic centre in methanolic solution, but the pure material gives largely Me˙ and PbMe2(ĊH2)Cl radicals. Irradiated PbMe4 and PbEt4 pure or in toluene at 77 K. give centres thought to be PbR3˙ radicals having g⊥≈ 2

  PbPh的曝光3 Cl和PbBrPh 3至60钴γ射线在77K产生了具有中心207 Pb和35 Cl或81个溴超精细耦合常数与预期父自由基阴离子是一致的。电子损失中心被认为是相应的阳离子，空穴主要局限在卤素原子上。辐照的PbMe 3 Cl在甲醇溶液中给出了相似的阴离子中心，但纯净的材料在很大程度上给出了Me P和PbMe 2（2H 2）Cl自由基。辐照的PbMe 4和PbEt 4纯的或在77K给定中心甲苯认为是PBR 3个具有˙自由基克⊥听，说：2.1和克∥听，说：1.9，异常大的各向异性207的Pb超精细耦合常数。此外，PbMe 4给出了一个中心认为是[PbMe 4 ] - ˙两者生成R和PbMe 3（CH 2）或PBET 3（CHME）。辐照的Pb 2 Ph 6仅给出一个明确定义的顺磁中心，初步确定为母体阴离子。
• Selectivity factors in the electrophilic cleavages of tetraalkyllead compounds
  作者：Nye A. Clinton、Hugh C. Gardner、Jay K. Kochi

  DOI：10.1016/s0022-328x(00)89971-4

  日期：1973.8

  The rates of electrophilic cleavage of CH3Pb and CH3CH2Pb bonds in various methyl/ethyl tetraalkyllead compounds are examined. The reactivity of a given alkylPb linkage is highly dependent on the substitution pattern on the cationic trialkyllead leaving group, in which an ethyl group is approximately twice as effective as a methyl group in enhancing the rate. A method is developed for obtaining

  CH的电切割的速率3 Pb和CH 3 CH 2 Pb各种甲基键被检查/乙基四烷基化合物。给定的烷基Pb键的反应性高度依赖于阳离子三烷基铅离去基团上的取代方式，其中乙基在提高速率上的效率约为甲基的两倍。一种方法，用于获得CH的相对反应性开发3 Pb和CH 3 CH 2从竞争研究恒定的离去基团的条件下Pb债券电切割。
• Reactions of bis(trifluoromethyl)mercury: the synthesis and properties of methyl(trifluoromethyl)-stannanes and -plumbanes
  作者：Reint Eujen、Richard J. Lagow

  DOI：10.1039/dt9780000541

  日期：——

  reactions of Hg(CF3)2 with Group 4 organometallic compounds MMe4(M = Si,Ge,Sn, or Pb), MMe3(CF3)(M = Sn or Pb), and M2R6(M = Si or Sn, R = Me; M = Ge, Sn, or Pb, R = Ph) have been investigated. Exchange of one CF3, group with a methyl group occurs for SnMe4, SnMe3(CF3), and PbMe4; the lead derivative reacts much more readily than the tin compound. Cleavage of the metal-metal bond with formation of MR3(CF3)

  Hg（CF 3）2与4族有机金属化合物MMe 4（M = Si，Ge，Sn或Pb），MMe 3（CF 3）（M = Sn或Pb）和M 2 R 6（M ＝ Si或Sn，R ＝ Me； M ＝ Ge，Sn或Pb，R ＝ Ph）已被研究。SnMe 4，SnMe 3（CF 3）和PbMe 4发生一个CF 3基与甲基的交换。铅衍生物比锡化合物更容易反应。对于Sn 2 Me 6，已经实现了金属-金属键的裂解以及MR 3（CF 3）的形成但是对于Si 2 Me 6和六苯基衍生物却不发生。研究了PbMe 3（CF 3）与溴，氯化氢和水的反应及其热稳定性。讨论了第4组混合三氟甲基-甲基衍生物的光谱性质。

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