二甲基胂 | 593-57-7

• 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: 二甲基胂
• 英文名称: dimethylarsine
• 英文别名: Dimethyl-arsin；Dimethylarsan；Arsine, dimethyl-；dimethylarsane
• CAS: 593-57-7
• 化学式: C₂H₇As
• 分子量: 105.999
• InChiKey: HBNBMOGARBJBHS-UHFFFAOYSA-N

物化性质

• 熔点：
  -136.1°C
• 沸点：
  36°C
• 密度：
  1.2080

计算性质

• 辛醇/水分配系数(LogP)：
  0.52
• 重原子数：
  3
• 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

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

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
• 危险品运输编号：
  UN 2845

反应信息

• 作为反应物：
  描述：

  二甲基胂 在 硫酸 作用下， 生成 dimethyl-arsine; sulfate
  参考文献：
  名称：

  Dehn; Wilcox, American Chemical Journal, 1906, vol. 35, p. 24

  摘要：

  DOI：
• 作为产物：
  描述：

  Dimethyl-(trimethylsilyl)-arsin 在 水 作用下， 生成 二甲基胂
  参考文献：
  名称：

  共价卤化物和质子试剂裂解硅-砷和锡-砷键

  摘要：

  研究了卤化物和质子试剂分别对Me 3 SiAsMe 2和Me 3 SnAsMe 2中的硅砷键和锡砷键的影响。卤素和共价卤化物总是引起硅砷键和锡砷键的裂变。

  DOI：

  10.1039/j19690001094

文献信息

• ADDITION OF FLUOROACETYLENES TO GROUP V HYDRIDES
  作者：W. R. Cullen、D. S. Dawson、G. E. Styan

  DOI：10.1139/v65-471

  日期：1965.12.1

  Compounds of the type R2EH react readily with CF3C≡CCF3 to give R2ECH(CF3)=C(CF3)H (E = N,P, As), and with CF3C≡CH to give R2ECH=CHCF3(E = N, As) and R2EC(CF3)=CH2 (E = As). The isomer distribution...

  R2EH 类型的化合物很容易与 CF3C≡CCF3 反应生成 R2ECH(CF3)=C(CF3)H (E = N,P, As)，与 CF3C≡CH 反应生成 R2ECH=CHCF3(E = N, As)和 R2EC(CF3)=CH2 (E = As)。异构体分布...
• Syntheses and Reactions of Arsenides, Stibides, and Bismuthides
  作者：G. O. DOAK、Leon D. FREEDMAN

  DOI：10.1055/s-1974-23306

  日期：——

  This review deals with the synthesis and preparative uses of metallic derivatives of primary and secondary arsines, stibines, and bismuthines. Reaction of these derivatives (usually called arsenides, stibides, and bismuthides) with organic halides has become an important synthetic pathway to tertiary arsines, stibines, and bismuthines. They have also proved useful for the preparation of organic compounds containing covalent bonds between arsenic or antimony and silicon, germanium, tin, or lead. A number of secondary arsines have been obtained by the reaction of arsenides of the type RAsHNa with alkyl halides. 1. The Cleavage of Triarylarsines or Triarylstibines with Alkali Metals. 2. The Cleavage of Diarsines, Bis[diarylarsenic] Oxides, and Arseno Compounds. 3. The Reaction of Secondary Arsines and Stibines with Organolithium Compounds or with Alkali Metals. 4. The Reaction of Primary Arsines with Sodium or Potassium. 5. The Reaction of Primary Arsines with Organolithium Reagents. 6. Reactions in which Haloarsines, Halostibines, or Halobismuthines react with an Alkali Metal. 7. Reactions of the Alkali Metal Arsenides M3As and (M2As)2 and the Alkali Metal Stibides M3Sb and (M2Sb)2 with Alkyl Halides. 8. Miscellaneous Reactions.

  这篇综述涉及了初级和次级肼、锑烷和铋烷的金属衍生物的合成及其制备应用。这些衍生物（通常称为砷化物、锑化物和铋化物）与有机卤化物的反应已成为合成三级肼、锑烷和铋烷的重要途径。它们在制备含砷或锑与硅、锗、锡或铅的共价键的有机化合物方面也已被证明是有用的。通过砷化物类型为RAsHNa与烷基卤化物的反应，已获得许多次级砷化物。 1. 三芳基肼或三芳基锑与碱金属的裂解。 2. 二肼、双[二芳基肼]氧化物和肼化合物的裂解。 3. 次级砷烷和锑烷与有机锂化合物或碱金属的反应。 4. 初级砷烷与钠或钾的反应。 5. 初级砷烷与有机锂试剂的反应。 6. 卤砷烷、卤锑烷或卤铋烷与碱金属的反应。 7. 碱金属砷化物M3As和(M2As)2以及碱金属锑化物M3Sb和(M2Sb)2与烷基卤化物的反应。 8. 其他反应。
• 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...
• Reaction of hexafluoroacetone with some arsenic compounds
  作者：W.R. Cullen、G.E. Styan

  DOI：10.1016/s0022-328x(00)84380-6

  日期：1965.8

  Hexafluoroacetone reacts with the arsines (CH3)2AsH and CH3AsH2 to give the compounds (CH3)2AsC(CF3)2OH and CH3(H)AsC(CF3)2OH respectively. The ketone also forms a fairly easily dissociated 1:1 complex with tetramethyldiarsine which reacts with hexafluoro-2-butyne to give a high yield of cis-(CH3)2AsC(CF3C(CF3)As(CH3)2. A cyclic structure is suggested for the complex.

  六氟丙酮与rs（CH 3）2 AsH和CH 3 AsH 2反应，分别得到化合物（CH 3）2 AsC（CF 3）2 OH和CH 3（H）AsC（CF 3）2 OH。酮还形成相当容易地解离1：1复合物与tetramethyldiarsine其与六氟发生反应2丁炔，得到高产率的顺式- （CH 3）2 ASC（CF 3 C（CF 3）如（CH 3）2个。建议该复合物具有循环结构。
• Demethylation of Methylated Arsenic Species during Generation of Arsanes with Tetrahydridoborate(1−) in Acidic Media
  作者：Karel Marschner、Stanislav Musil、Jiří Dědina

  DOI：10.1021/acs.analchem.6b00735

  日期：2016.6.21

  reaction of THB with HCl, H2SO4, and HClO4, while HG from CH3COOH or TRIS buffer after prereduction with l-cysteine resulted in the formation of only the corresponding hydrides. In the case of HNO3 formation of corresponding hydrides was preserved for MAsV and DMAsV but not for TMAsVO. The extent of demethylation strongly depends on concentration of the acid and THB. It can be strongly suppressed in

  挥发性氢化物（HG）生成过程中的脱甲基化，即通过四氢硼酸钠（1-）（THB）的反应，由单甲基砷酸（MAs V），二甲基砷酸（DMAs V）和三甲基ar氧化物（TMAs V O）形成非对应的a烷）在分析条件下用不同的酸进行了研究和表征。在THB与HCl，H 2 SO 4和HClO 4反应过程中发现MAs V，DMAs V和TMAs V O明显脱甲基，而CH 3 COOH或TRIS缓冲液中的HG预先还原为1则产生HG。-半胱氨酸导致仅形成相应的氢化物。在HNO 3的情况下，对于MAs V和DMAs V保留了相应的氢化物形成，对于TMA V O则没有保留。脱甲基化程度强烈取决于酸和THB的浓度。在HCl介质中，可以通过在THB与MAs V，DMAs V或TMAs V O反应之前用最佳浓度的酸部分水解THB来强力抑制它。看来脱甲基是由于THB特定水解产物的作用（最有可能是第一个和第二个）。