tetramethyldiarsine | 471-35-2

• 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
• 英文名称: tetramethyldiarsine
• 英文别名: Tetramethyl-diarsin；Kakodyl；Cacodyl；dimethylarsanyl(dimethyl)arsane
• CAS: 471-35-2
• 化学式: C₄H₁₂As₂
• 分子量: 209.982
• InChiKey: RSKPLCGMBWEANE-UHFFFAOYSA-N

物化性质

• 熔点：
  -6°
• 沸点：
  bp760 165°
• 密度：
  1.4470

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  6
• 可旋转键数：
  1
• 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

砒霜主要通过吸入或摄入被吸收，较少程度上通过皮肤接触。然后它被分布到全身，如果需要，它会被还原成亚砷酸盐，然后通过亚砷酸盐甲基转移酶甲基化成单甲基砷（MMA）和二甲基硅酸（DMA）。砒霜及其代谢物主要通过尿液排出。已知砒霜能诱导金属结合蛋白金属硫蛋白，通过绑定砒霜和其他金属并使其生物活性失效，以及作为抗氧化剂的作用，从而减少砒霜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

砷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，砷抑制了丙酮酸脱氢酶，并通过与磷酸竞争，解偶联氧化磷酸化，从而抑制了与能量相关的NAD+的还原、线粒体呼吸和ATP的合成。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。砷的致癌性受到砷与微管蛋白结合的影响，这会导致非整倍体、多倍体和有丝分裂停滞。其他砷蛋白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, 其对人类致癌性无法分类。

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而死亡，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（L2）

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

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 症状

暴露在较低水平的砒霜下可能导致恶心和呕吐，减少红白细胞的生产，心律异常，血管损伤，以及一种感觉。

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

来源:Toxin and Toxin Target Database (T3DB)

反应信息

• 作为反应物：
  描述：

  tetramethyldiarsine 生成 三甲基胂
  参考文献：
  名称：

  Dehn; Williams, American Chemical Journal, 1908, vol. 40, p. 120

  摘要：

  DOI：
• 作为产物：
  描述：

  右旋苯甘氨酸 生成 tetramethyldiarsine
  参考文献：
  名称：

  Paneth; Loleit, Journal of the Chemical Society, 1935, p. 370

  摘要：

  DOI：

文献信息

• 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。
• DIMETHYLTRIFLUOROACETYLARSINE AND RELATED COMPOUNDS
  作者：W. R. Cullen、G. E. Styan

  DOI：10.1139/v66-180

  日期：1966.5.15

  not available

  不可用

• Reactions of diarsines with bi- and tri-metallic carbonyl complexes containing cobalt
  作者：Nick Choi、Gráinne Conole、Jason D. King、Martin J. Mays、Mary McPartlin、Caroline L. Stone

  DOI：10.1039/a906611j

  日期：——

  Reaction of the diarsines As2R4 (R = Me or Ph) with alkyne-bridged dicobalt hexacarbonyl complexes leads to products with bridging (AsR2)2O ligands and to the production of simple AsR3 substituted complexes; alkylidyne tricobalt nonacarbonyl complexes exhibit parallel reactivity with As2R4. Thermolysis of the complex [Co2(μ-PhCCPh)μ-(AsMe2)2O}(CO)4] gives the tetra-substituted complex, [Co2(μ-PhCCPh)μ-(AsMe2)2O}2(CO)2]. Reaction of the heterometallic complex [(OC)3Coμ-C2(CO2Me)2}MoCp(CO)2] with As2Ph4 affords [(HO)Ph2As}(OC)2Coμ-C2(CO2Me)2}MoCp(CO)2], supporting the suggestion of a possible hydrolytic mechanism for the formation of the (AsR2)2O bridged complexes.

  二砷化物As2R4（R = Me或Ph）与炔桥联二钴六羰基配合物的反应产生了具有桥联(AsR2)2O配体的产物，以及生成简单的AsR3取代配合物；烷基亚砜三钴壬羰基配合物表现出平行的反应性。复杂配合物[Co2(μ-PhCCPh)μ-(AsMe2)2O}(CO)4]的热分解产生了四取代配合物，[Co2(μ-PhCCPh)μ-(AsMe2)2O}2(CO)2]。异金属配合物[(OC)3Coμ-C2(CO2Me)2}MoCp(CO)2]与As2Ph4反应生成[(HO)Ph2As}(OC)2Coμ-C2(CO2Me)2}MoCp(CO)2]，支持了(AsR2)2O桥联配合物形成的可能水解机制的建议。
• PERFLUOROALKYL ARSENICALS: PART IX. SOME REACTIONS OF COMPOUNDS CONTAINING As–As BONDS
  作者：W. R. Cullen、N. K. Hota

  DOI：10.1139/v64-174

  日期：1964.5.1

  C6H5As(CF3)I, and C6H5AsI2. C6H5As(CF3)I and AgCl yield C6H5As(CF3)Cl. The compounds CF2=CFX react with (CH3)2As—As(CH3)2 under mild conditions to give 1:1 adducts (CH3)As—CF2CFX—As(CH3)2 (X = CF3, Br). Some (CH3)2As—CF=CF2 is produced when X = Br and is the major product when X = I. When X = F a 1:4 adduct (CH3)2As—(CF2CF2)4—As(CH3)2 is probably formed on ultraviolet irradiation. (CH3)2As—As(CH3)2 reacts

  砷苯与 CF3I 反应生成 C6H5As(CF3)2、C6H5As(CF3)I 和 C6H5AsI2。C6H5As(CF3)I 和 AgCl 生成 C6H5As(CF3)Cl。化合物 CF2=CFX 在温和条件下与 (CH3)2As-As(CH3)2 反应生成 1:1 加合物 (CH3)As-CF2CFX-As(CH3)2 (X = CF3, Br)。当 X = Br 时产生一些 (CH3)2As-CF=CF2，当 X = I 时是主要产物。当 X = F 时，1:4 加合物 (CH3)2As-(CF2CF2)4-As(CH3)2 是可能是在紫外线照射下形成的。(CH3)2As-As(CH3)2 与 CF3C≡CCF3 反应生成顺式和反式 (CH3)2AsC(CF3)=C(CF3)As(CH3)2 并生成 (CH3)2AsF 和 。
• Reaction of bis(trifluoromethyl)diazomethane with trimethyl-3,3,3-trifluoropropynyltin, trimethyltin hydride, and related compounds
  作者：W. R. Cullen、M. C. Waldman

  DOI：10.1139/v70-311

  日期：1970.6.15

  Bis(trifluoromethyl)diazomethane (1) reacts with the compounds (CH3)3MC≡CCF3 (M = Ge, Sn) to give the cyclopropenes . Cyclopropenes are also obtained from the reaction of 1 with the acetylenes RC≡C...

  双（三氟甲基）重氮甲烷 (1) 与化合物 (CH3)3MC≡CCF3 (M = Ge, Sn) 反应生成环丙烯。环丙烯也可从 1 与乙炔 RC≡C...

表征谱图