1,2-亚苯基双(二甲基砷化氢) | 13246-32-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1,2-亚苯基双(二甲基砷化氢)
• 英文名称: ortho-phenylenebis(dimethylarsine)
• 英文别名: 1,2-Bis(dimethylarsino)benzene；(2-dimethylarsanylphenyl)-dimethylarsane
• CAS: 13246-32-7
• 化学式: C₁₀H₁₆As₂
• 分子量: 286.08
• InChiKey: HUBWRAMPQVYBRS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.61
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 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，其次是通过皮肤接触。然后它被分布到全身，如果有必要，它会还原成亚砷酸盐，然后通过亚砷酸盐甲基转移酶被甲基化成单甲基砷（MMA）和二甲基硒酸（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，通过结合砒霜和其他金属并使它们生物活性失效，同时充当抗氧化剂，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+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。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, 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)

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  1,2-亚苯基双(二甲基砷化氢) 以 乙醇 为溶剂， 生成 trans-{Co(o-C6H4(AsMe2)2)2I2}I
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Co: SVol.B1, 139, page 308 - 310

  摘要：

  DOI：
• 作为产物：
  描述：

  二甲基胂 、 邻二氯苯 生成 1,2-亚苯基双(二甲基砷化氢)
  参考文献：
  名称：

  11-Membered macrocycles containing the diarsa moiety

  摘要：

  DOI：

  10.1021/ja00543a018

文献信息

• The synthesis of vicinal bis(dimethylarsino) compounds
  作者：Robert D. Feltham、H.Gary Metzger

  DOI：10.1016/s0022-328x(00)87418-5

  日期：1971.12

  bis(dimethylarsino)acetylene, and 1-bromo-1,2-bis(dimethylarisno)ethylene. NaAs(C6H5)2, and NaP(C6H5)2 react with 8-dichloroquinoline to give 8-(diphenylarsino)quinoline and 8-(diphenylphosphino)quinoline, respectively. An improved synthesis of cis-1,2-bis(dimethylarsino)ethylene by hydroboration of bis(dimethylarsino)acetylene is also reported. The proton NMR and mass spectra of these novel arsine compounds

  已研究了NaAs（CH 3）2与邻-Cl 2（C 6 H 4）之间的反应，并鉴定出以下产物：（CH 3）2 AsH，o -[（CH 3）2 As] 2 [C 6 H 4 ]，（CH 3）3 As，（CH 3）2 As（C 6 H 5），5,10-二甲基-5,10-二氢ar蒽和甲基双[邻-（二甲基ar基）苯基] ar。NaAs（CH 3）2和CIS -1,2-二氯乙烯给出的混合物中的顺式-和反式-1,2-双（二甲胂基）乙烯，1,2-同时二溴乙烯产量双（二甲胂基）乙炔，和1-溴-1,2- -双（二甲基芳基）乙烯。NaAs（C 6 H 5）2和NaP（C 6 H 5）2与8-二氯喹啉反应，分别得到8-（二苯基di基）喹啉和8-（二苯基膦基）喹啉。还报道了通过双（二甲基ar基）乙炔的氢硼化而改进的顺式-1,2-双（二甲基ar基）乙烯的合成。讨论了这些新颖的砷化氢化合物的质子核磁共振和质谱。
• 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。
• 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 low-valent metal complexes with fluorocarbons. Part XVII. Tertiary arsine–nickel complexes
  作者：Jane Browning、M. Green、F. G. A. Stone

  DOI：10.1039/j19710000453

  日期：——

  (PhMe2As)4Ni to give (PhMe2As)2[graphic omitted]. The complex [o-C6H4(AsMe2)2][graphic omitted], prepared from 1,5-C8H12[graphic omitted], reacts with (CF3)2CO and with (CF3)2CNH to form the five-membered ring compounds [o-C6H4(AsMe2)2] [graphic omitted] (X = O or NH). Bis-(π-2-methylallyl)nickel and tetrafluoroethylene react to form a complex containing two C2F4 groups per nickel atom.

  用四氟乙烯或三氟乙烯处理L 4 Ni [L ＝ PhAsMe 2，L 2＝o- C 6 H 4（AsMe 2）2 ]分别得到稳定的化合物[省略图示]和[省略图示]。氯和溴代三氟乙烯与（PhMe 2 As）4 Ni反应，得到乙烯基化合物（PhMe 2 As）2 Ni（CF：CF 2）X（X = Cl或Br）。类似地，1,1-二氯-2,2-二氟乙烯和1,2-二氯-1,2-二氟乙烯得到（PhMe 2 As）2 Ni（CCl：CF 2）Cl和（PhMe2 As） 2 Ni（CF：CFCl）Cl分别为顺式和反式乙烯基异构体的混合物。六氟丁酸酯-1，3-二烯与（PhMe 2 As） 4 Ni反应，得到（PhMe 2 As） 2 [省略图示]。由1，5-C 8 H 12 [省略图]制备的络合物[ o -C 6 H 4（AsMe 2） 2 ] [省略图]与（CF 3） 2 CO和（CF 3） 2反应。 CNH形成五元环化合物[
• Eight coordinate 1,2-bis(dimethylarsino) and 1,2-bis(dimethylphosphino)-benzene complexes of uranium tetrachloride, UCl4[(1,2-Me2E)2C6H4]2 where E is As or P
  作者：Sergio S. Rozenel、Peter G. Edwards、Mark A. Petrie、Richard A. Andersen

  DOI：10.1016/j.poly.2016.04.024

  日期：2016.9

  uranium crystallize in the tetragonal crystal system in space group I 4 ¯ 2m, in which the geometry is a D2d-dodecahedron. In solution the uranium complexes do not exchange with added free ligand on the NMR time scale but they undergo bidentate ligand exchange on the chemical time scale. The 31P1H} NMR chemical shifts of UI4(diphos)2 and UX4(dmpe)2, X = Cl, Br, I range from 1500 to 2100 ppm and are strongly

  摘要制备并表征了1,2-双（二甲基亚砷基）苯，MCl4（diars）2（其中M为Th或U）和1,2-双（二甲基膦基）苯，UCl4（diphos）2的八个配位化合物。铀的两个配位配合物在I 4×2m空间群的四方晶系中结晶，其中几何形状为D2d-十二面体。在溶液中，铀络合物在NMR时标上不与添加的游离配体交换，但在化学时标上进行二齿配体交换。UI4（diphos）2和UX4（dmpe）2的31P 1H} NMR化学位移，X = Cl，Br，I为1500至2100 ppm，并强烈依赖于温度。