三甲基胂 | 593-88-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 中文名称: 三甲基胂
• 英文名称: trimethylarsine
• 英文别名: trimethylarsane
• CAS: 593-88-4
• 化学式: C₃H₉As
• 分子量: 120.026
• InChiKey: HTDIUWINAKAPER-UHFFFAOYSA-N

物化性质

• 熔点：
  -87,3°C
• 沸点：
  51°C
• 密度：
  1,124 g/cm3
• 闪点：
  -25°C
• 溶解度：
  溶于苯

计算性质

• 辛醇/水分配系数(LogP)：
  1.37
• 重原子数：
  4
• 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

砷主要通过吸入或摄入进入人体，其次是皮肤接触。进入人体后，砷会在全身分布，根据需要被还原成亚砷酸盐，然后通过亚砷酸盐甲基转移酶被甲基化成单甲基砷（MMA）和二甲基硅酸（DMA）。砷及其代谢物主要通过尿液排出体外。已知砷能诱导金属结合蛋白金属硫蛋白，金属硫蛋白通过结合砷和其他金属，使它们生物学上失活，并作为抗氧化剂，从而减少砷和其他金属的有毒效果。

Arsenic is absorbed mainly by inhalation or ingestion, as to a lesser extent, dermal exposure. It is then distributed throughout the body, where it is reduced into arsenite if necessary, then methylated into monomethylarsenic (MMA) and dimethylarsenic acid (DMA) by arsenite methyltransferase. Arsenic and its metabolites are primarily excreted in the urine. Arsenic is known to induce the metal-binding protein metallothionein, which decreases the toxic effects of arsenic and other metals by binding them and making them biologically inactive, as well as acting as an antioxidant. (L20)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

砒霜及其代谢物通过多种机制干扰ATP的产生。在柠檬酸循环层面，砒霜抑制了丙酮酸脱氢酶，并通过与磷酸竞争解耦了氧化磷酸化，从而抑制了与能量相关的NAD+还原、线粒体呼吸和ATP合成。过氧化氢的产生也增加了，这可能会形成活性氧物种和氧化应激。砒霜的致癌性受到砒霜与微管蛋白结合的影响，导致非整倍体、多倍体和有丝分裂停滞。其他砒霜蛋白质靶点的结合也可能导致DNA修复酶活性改变、DNA甲基化模式改变和细胞增殖。

Arsenic and its metabolites disrupt ATP production through several mechanisms. At the level of the citric acid cycle, arsenic inhibits pyruvate dehydrogenase and by competing with phosphate it uncouples oxidative phosphorylation, thus inhibiting energy-linked reduction of NAD+, mitochondrial respiration, and ATP synthesis. Hydrogen peroxide production is also increased, which might form reactive oxygen species and oxidative stress. Arsenic's carginogenicity is influenced by the arsenical binding of tubulin, which results in aneuploidy, polyploidy and mitotic arrests. The binding of other arsenic protein targets may also cause altered DNA repair enzyme activity, altered DNA methylation patterns and cell proliferation. (T1, A17)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌物分类

3, 无法归类其对人类致癌性的类别。(L135)

3, not classifiable as to its carcinogenicity to humans. (L135)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

砒霜中毒可能导致多系统器官衰竭死亡，可能是由于细胞坏死而非凋亡。砒霜也是一种已知的致癌物，尤其是在皮肤癌、肝癌、膀胱癌和肺癌中。

Arsenic poisoning can lead to death from multi-system organ failure, probably from necrotic cell death, not apoptosis. Arsenic is also a known carcinogen, esepcially in skin, liver, bladder and lung cancers. (T1, L20)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

口服（L2）；吸入（L2）；皮肤给药（L2）

Oral (L2) ; inhalation (L2); dermal (L2)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 症状

暴露于较低水平的砷可以导致恶心和呕吐，减少红白细胞的生产，心律异常，血管损伤和灼烧感。

Exposure to lower levels of arsenic can cause nausea and vomiting, decreased production of red and white blood cells, abnormal heart rhythm, damage to blood vessels, and a sensation of burn (T1).

来源:Toxin and Toxin Target Database (T3DB)

安全信息

• 危险等级：
  4.2
• 危险品标志：
  T,N
• 危险类别码：
  R11
• RTECS号：
  CH8800000
• 包装等级：
  I
• 危险类别：
  4.2
• 危险品运输编号：
  UN 1992

反应信息

• 作为反应物：
  描述：

  三甲基胂 在 溴 作用下， 以 乙醚 为溶剂， 反应 24.0h， 生成 Trimethylarsendibromid
  参考文献：
  名称：

  Reactions of dihalogenotriorgano-phosphorus, -arsenic and -antimony compounds with [Fe₂(CO)₉]. Single-crystal structures of the iron(III) complexes [(Ph₃PO)₂H][FeBr₄] and [Ph₄Sb][Fel₄]·Ph₃Sbl₂and of [Fe(CO)₃(Ph₃P)₂]

  摘要：

  The reaction of [Fe2(CO)9] with compounds of stoichiometry R3EX2 [R3E = Ph3P, (p-MeOC6H4)3P, Me2PhP, Me3As or Ph3Sb, X = I; R3E = Ph3P, Ph3As or Me3As, X = Br] has been investigated and shown to yield diverse products. A series of complexes with the ionic structure [R3EX][Fe(R3E)X3] [E = P, R3 = Ph3, Me2Ph or (p-MeOC6H4)3, X = I; R3E = Me3As; X = I or Br] has been obtained. The reaction of [Fe2(CO)9] with Ph3PBr2 and Ph3AsBr2, however, resulted in the formation of the iron(III) complexes [(Ph3E)2Br][FeBr4]. Hydrolysis of [(Ph3P)2Br][FeBr4] by trace quantities of water produces [(Ph3PO)2H][FeBr4], the crystal structure of which has been determined. Triphenylantimony diiodide reacted with [Fe2(CO)9] yielding the surprising ionic adduct [Ph4Sb][FeI4].Ph3SbI2, remarkable not only for the phenyl migration at the antimony atom, but also for the formation of the rare [FeI4]- anion from a zerovalent iron carbonyl complex. The reaction of [Fe2(CO)9] with the milder diphosphine tetraiodide, I2Ph2PCH2CH2PPh2I2, produced [Fe(CO)3(Ph2PCH2CH2PPh2)I][I3], a complex in which three CO ligands are retained.

  DOI：

  10.1039/dt9940003249
• 作为产物：
  描述：

  在 硫脲 作用下， 以 水 为溶剂， 以>99的产率得到三甲基胂
  参考文献：
  名称：

  Fournier, L.; Riess, J. G., Synthesis in Inorganic and Metal-Organic Chemistry, 1972, vol. 2, p. 53 - 55

  摘要：

  DOI：

文献信息

• Structural studies on organoarsenic(V) compounds by means of chlorine-35 nuclear quadrupole resonance spectroscopy
  作者：Keith B. Dillon、Roderick J. Lynch、Thomas C. Waddington

  DOI：10.1039/dt9760001478

  日期：——

  AsPh3Cl2 indicates that they have trigonal-bipyramidal structures in the solid state, with the phenyl groups occupying equatorial positions. The mono- and di-phenyl compounds are thought to be isostructural with the corresponding phosphorus compounds. Trichlorodimethylarsenic(V) and AsMe3Cl2 also have the trigonal-bipyramidal form in the solid, with the methyl groups occupying equatorial sites, unlike their

  对AsPhCl 4，AsPh 2 Cl 3和AsPh 3 Cl 2的35 Cl nqr研究表明，它们具有固态的三角双锥体结构，苯基占据了赤道位置。单苯基和二苯基化合物被认为与相应的磷化合物同构。三氯二甲基砷（V）和AsMe 3 Cl 2在固体中也具有三角双锥体形式，其中甲基占据了赤道位点，这与它们的离子性磷类似物不同。尝试通过氯化AsMeCl 2来合成AsMeCl 4会在低温下导致爆炸，并且如果存在的话，该化合物似乎极其不稳定。1：1制备了砷（v）化合物与路易斯酸X的加合物，例如BCl 3，SbCl 5或ICl；这些显示了预期的离子结构[AsR n Cl 4– n ] [XCl]。在阳离子，其中R = Me或pH值，类似于那些在类似鏻，硅烷和锗系列，并支持如（参与取代基效应d π）-Cl（p π）接合。还报告了化合物Ph 3 CCl，SiPh 3 Cl，GePh 2 Cl的氯35 nqr频率2和GePh
• PERFLUOROALKYL ARSENICALS: PART IV. SOME REACTIONS OF TRIFLUOROIODOMETHANE WITH ALKYL ARSINES
  作者：W. R. Cullen

  DOI：10.1139/v62-067

  日期：1962.3.1

  trimethylarsine. Trifluoroiodomethane also reacts with the compounds (CH3)2AsX (X = C6H5, Cl, I) and CH3AsI2 to give CH3As(CF3)2; and in most of these reactions the compound CH3As(CF3)I is also formed, which is converted to the compound CH3As(CF3)Cl by reaction with silver chloride.

  三氟碘甲烷与三乙基和三正丁基胂以及三正丁基膦反应生成 R2MCF3 型产物。七氟碘丙烷与三甲基胂的反应类似。三氟碘甲烷还与化合物 (CH3)2AsX (X = C6H5, Cl, I) 和 AsI2 反应生成 As(CF3)2；在大多数这些反应中，还会形成化合物 As( )I，通过与氯化银反应将其转化为化合物 As( )Cl。
• Kationische Stickstoff- und Arsen-koordinierte Titanocenbishexafluoroarsenat-Komplexe
  作者：P. Gowik、Th. Klapötke

  DOI：10.1016/0022-328x(91)86248-o

  日期：1991.1

  The reaction of Cp2Ti(AsF6)2 (1) in liquid sulfur dioxide with HCN, ICN, AsMe3, and As2Me4 afforded the new cationic titanocene complexes [Cp2TiHCN)2][AsF6]2 (2), [Cp2Ti(ICN)2][AsF6]2 (3), [Cp2Ti(AsMe3)2][AsF6]2 (4), and [Cp2Ti(As2Me4)]2[AsF6]4 (5) (Cp = η5-C5H5, Me = CH3). All compounds have been characterized by 1H NMR and IR spectroscopy. The dynamic 1H NMR spectrum of 5 shows a reversible temperature

  CP 2 Ti（AsF 6）2（1）在液态二氧化硫中与HCN，ICN，AsMe 3和As 2 Me 4的反应提供了新的阳离子钛茂配合物[CP 2 TiHCN）2 ] [AsF 6 ] 2（2），[CP 2 Ti（ICN）2 ] [AsF 6 ] 2（3），[CP 2 Ti（AsMe 3）2 ] [AsF 6 ] 2（4）和[CP 2的Ti（作为2我4）] 2 [ASF 6 ] 4（5）（CP =η 5 -C 5 H ^ 5中，Me = CH 3）。所有化合物均已通过1 H NMR和IR光谱进行了表征。动态1的1 H NMR光谱5示出了可逆温度依赖性由于六元的环反转杂环。
• Synthesis and solution multinuclear nuclear magnetic resonance studies of homoleptic copper(I) complexes of Group 15 donor ligands
  作者：Jane R. Black、William Levason、Mark D. Spicer、Michael Webster

  DOI：10.1039/dt9930003129

  日期：——

  spectra, have been recorded from CH2Cl2 solutions of the complexes over the temperature range 300–175 K, including the first reported 63Cu resonances from arsenic and antimony donor ligand compounds. The effects of ligand size and geometry upon the 63Cu NMR spectra are discussed and typical copper chemical-shift ranges for Group 15 donor ligand compounds established. The structure of [Cu(cis-Ph2AsCHCHAsPh2)2]PF6

  均纯络合物[CuL 4 ] Y（L = PMe 3，PMe 2 Ph，PMePh 2，PPh 3，PPh 2 H，PPhH 2，AsMe 3，AsMe 2 Ph，AsMePh 2，AsPh 3，SbMe 3，SbEt 3或SbPh 3； Y = PF 6或BF 4）和[Cu（L–L）2 ] Y [L–L = Me 2 P（CH 2）2 PMe 2，o -C 6 H 4（PMe 2）2，Ph 2 P（CH 2）n PPh 2（n = 1-4），顺式-Ph 2 PCH CHPPh 2，o -C 6 H 4（PPh 2）2，o -C 6 H 4（AsMe 2）2，顺式-Ph 2 AsCH CHAsPh 2，o -C 6 H 4（SbMe 2）2，Me由[Cu（MeCN） 4 ] Y和L或L–L制备了2 Sb（CH 2） 3 SbMe 2或Ph 2 Sb（CH 2） 3 SbPh 2 ]。在300–175
• Reactions of metal carbonyls. Part 7. Substitution reactions of decacarbonyldimanganese with tertiary phosphorus and arsenic ligands
  作者：Rolf H. Reimann、Eric Singleton

  DOI：10.1039/dt9760002109

  日期：——

  [Mn2(CO)8L2][L = PPh(OMe)2 and P(OMe)3]. Thermal reactions of [Mn2(CO)10] with an excess of L [L = PMePh2,PEtPh2,PMe2Ph, PPh(OMe)2, and P(OMe)3] in high boiling solvents give the hydrido-complexes mer-trans-[Mn(CO)3HL2] which are more conveniently prepared using Na[BH4] in refluxing ethanol. Treatment of the hydrides with HPF6 in acetonitrile gives the salts [Mn(CO)3(NCMe)L2][PF6]. Other cationic complexes of

  当L = PMe 2 Ph，AsMe 2 Ph和PMePh 2时，[Mn 2（CO）10 ]与L的热或光化学反应生成[Mn 2（CO）9 L] ，双轴取代的[Mn 2（CO）8 L 2 ]为L = PME 2 PH，PMePh 2，PPH（OME）2，和PPH 2（OME）和diequatorially取代的[锰2（CO）8大号2 ]为L = ASME 2 PH，ASET 3，和ASME 3。电导产物[Mn 2（AsMe 2 Ph）2（CO）8 ]与PPh（OMe）2和P（OMe）3进行配体交换，得到双轴[Mn 2（CO）8 L 2 ] [L = PPh（OMe）2和P（ OMe）3 ]。[Mn 2（CO）10 ]与过量的L [L = PMePh 2，PEtPh 2，PMe 2 Ph，PPh（OMe）2和P（OMe）3 ]在高沸点溶剂中的热反应产生氢化物-络合物聚体-反式- [锰（CO）3