二苯胺氯胂 | 578-94-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 中文名称: 二苯胺氯胂
• 中文别名: 10-氯-5,10-二氢吩吡嗪
• 英文名称: adamsite
• 英文别名: 10-Chlor-5,10-dihydro-phenarsazin；5-chloro-5,10-dihydrophenarsazine；10-chloro-5,10-dihydrophenarsazine；10-chloro-5,10-dihydrophenarsazinine；5,10-Dihydro-10-chlorphenarsazin；10-chloro-5H-phenarsazinine
• CAS: 578-94-9
• 化学式: C₁₂H₉AsClN
• 分子量: 277.585
• InChiKey: PBNSPNYJYOYWTA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.09
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

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、多倍体和有丝分裂的停滞。其他砷蛋白靶点的结合也可能导致DNA修复酶活性的改变、DNA甲基化模式的改变和细胞增殖的增加。(T1, A17)

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（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

• 储存条件：
  库房应保持通风、低温和干燥，并与其他氧化剂、酸类及食品分开储存和运输。

反应信息

• 作为反应物：
  描述：

  二苯胺氯胂 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲苯 为溶剂， 生成 Phenarsazin
  参考文献：
  名称：

  所谓的吩拉嗪的结构研究：吩拉嗪热生成的质谱证据

  摘要：

  维兰德和莱茵海默氏“吩嗪”的结构已被重新研究。建议的芳族结构3是不正确的，光谱和化学证据表明该化合物为10,10'-双（5,10-二氢菲拉嗪基）16。通过碱诱导的氯化氢消除来合成吩嗪3的尝试未成功。然而，质谱证据表明，吩吡嗪由任氯化氢或甲醇热消除从10-氯-5,10- dihydrophenarsazine形成7或10-甲氧基-5,10- dihydrophenarsazine 10分别。

  DOI：

  10.1016/0040-4020(75)80265-1
• 作为产物：
  描述：

  N-甲基二苯胺 生成 二苯胺氯胂
  参考文献：
  名称：

  Interaction of diarylamines and arsenic trichloride

  摘要：

  DOI：

  10.1021/jo00906a026

文献信息

• Identification of Degradation Products of Sea-Dumped Chemical Warfare Agent-Related Phenylarsenic Chemicals in Marine Sediment
  作者：Hanna Niemikoski、Martin Söderström、Harri Kiljunen、Anders Östin、Paula Vanninen

  DOI：10.1021/acs.analchem.9b04681

  日期：2020.4.7

  Previously unknown phenylarsenic chemicals originated from chemical warfare agents (CWAs) have been detected and identified in sediment samples collected from the vicinity of chemical munition dumpsites. Non-targeted screening by ultra-high performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS) was used for detection of 14 unknown CWA-related phenylarsenic chemicals. Methylated

  在从化学弹药垃圾场附近收集的沉积物样本中，已经检测到并鉴定了以前未知的源自化学战剂（CWA）的苯砷化学物质。通过超高效液相色谱-高分辨率质谱（UHPLC-HRMS）进行的非目标筛选用于检测14种未知的与CWA相关的苯基砷化学物质。在所有分析的沉积物样品中均检测到了Clark I / II，Adamsite和苯基二氯ar的甲基化形式，并基于合成化学物质对其进行了鉴定。此外，还检测了其他以前未知的CWA相关的苯基砷化学药品，并使用MS / HRMS技术阐明了它们的结构。根据质子化分子的相对同位素比并测量形成的碎片离子的精确质量，可以得出结论，其中一些未知的化学物质含有附着在砷原子上的硫原子。除此之外，一些样品还包含通过在芳香环上加成OH基而形成的化学物质。然而，尚不可能说出这些化学物质的形成方式，但最可能的原因是沉积物中海洋微生物的活动。据我们所知，以前从未从沉积物样品中检测到这些化学物质。这
• Arsinophosphonium Cations from Arsenium-phosphine and -bisphosphine Coordination Chemistry
  作者：Neil Burford、Paul J. Ragogna、Kendall Sharp、Robert McDonald、Michael J. Ferguson

  DOI：10.1021/ic050989w

  日期：2005.12.1

  A new 14pi-electron tricyclic organoarsenium cation (5-hydrophenarsazinium, AN, C12H9AsN+) has been prepared in situ and used as a Lewis acceptor with trimethylphosphine, triphenylphosphine, bis(diphenylphosphino)methane (dppm), bis(dimethylphosphino)methane (dmpm), and 1,4-bis(diphenylphosphino)benzene (dppb) ligands. Solid-state structures and spectroscopic characterization data are reported for

  一种新的14π电子三环有机砷阳离子（5-hydrophenarsazinium，AN，C12H9AsN +）已就地制备，并与三甲基膦，三苯基膦，双（二苯基膦基）甲烷（dpPM），双（二甲基膦基）甲烷（dmPM）一起用作Lewis受体。和1,4-双（二苯基膦基）苯（dppb）配体。报告了通式[AN-PMe3] +，[AN-PPh3] +，[AN-dpPM] +，[AN-dpPM-AN] 2 +，[AN- dmPM-AN] 2+和[AN-dppb-AN] 2+为四氯没食子酸盐。取决于反应化学计量，dpPM在一个或两个供体位点形成加合物。与阳离子类似络合物的结构比较提供了有趣的相似之处和不同之处。
• Synthesis of some nitrogen–arsenic heterocycles : 5,10-dihydro-5,10-o-benzenophenarsazine (azarsatriptycene), 10,11-dihydro-5-phenyl-5H-di-benzo[b,f][1,4]azarsepine, and 2,3-dihydro-1,2-diphenyl-1H-benz[c]-azarsole
  作者：R. A. Earley、M. J. Gallagher

  DOI：10.1039/j39700000158

  日期：——

  10,11-Dihydro-5-phenyl-5H-dibenzo[b,f][1,4]azarsepine (1) and 1,2-dihydro-1,2-diphenyl-1H-benz[c]azarsole (7) are formed in low yield in the reaction between o-lithio-N-(o-lithiobenzyl)aniline and dichloro(phenyl) arsine. Azarsatriptycene (12) is prepared by cyclising 10-(2-chlorophenyl)-5,10-dihydrophenarsazine with an excess of lithium diethylamide in ether. The triptycene is a neutral compound which

  10,11-二氢-5-苯基-5 H-二苯并[ b，f ] [1,4]阿塞西平（1）和1,2-二氢-1,2-二苯基-1 H-苯并[ c ] 7）在邻-硫代-N-（邻-硫代苄基）苯胺与二氯（苯基）a的反应中以低收率形成。通过将10-（2-氯苯基）-5,10-二氢吩嗪与过量的二乙酰胺锂在乙醚中环化来制备三氮杂蒽（12）。三萜是一种中性化合物，可抵抗季铵化，并且不受酸和碱的影响。通过在六甲基磷酰胺中用磺胺处理将砷碳键裂解，得到5,5'，10,10'-四氢-5,5'-二苯基-10,10'-氧二苯那嗪（10）。
• Phosphinopnictinophosphonium frameworks
  作者：Eamonn Conrad、Neil Burford、Ulrike Werner-Zwanziger、Robert McDonald、Michael J. Ferguson

  DOI：10.1039/b924918d

  日期：——

  Reactions of the cyclic tetraphosphine (CyP)4 with arsenium or stibenium cations (R2Pn+, Pn = As, Sb and R = Cl, Ph) give salts of the new cationic frameworks [(CyP)4(AN)]+, [(CyP)4(SbCl2)]+ and [(CyP)4}2(Sb2Cl2)]2+. The cations can be viewed as coordination complexes of a cyclophosphine ligand on a pnictenium cation, or a cyclo-2,3,4-triphosphino-1-pnictino-1-phosphonium cation, representing the first branched cyclic pnictogen framework, and examples of tertiary phosphonium centers with As–P or Sb–P bonds.

  四配位环状膦(CyP)4与胂鎓或銻鎓阳离子(R2Pn+，Pn = As，Sb 且 R = Cl，Ph)的反应生成了新的阳离子框架的盐类，即[(CyP)4(AN)]+、[(CyP)4(SbCl2)]+和[(CyP)4}2(Sb2Cl2)]2+。这些阳离子可以视为环状膦配体与镧系阳离子的配位复合物，或者是环-2,3,4-三膦-1-膦-1-膦鎓阳离子，代表了首个支化的环状膦框架，并展示了具有As–P或Sb–P键的三级膦中心实例。
• Heterocyclic arsinocarbynes <i>via</i> tandem transmetallation
  作者：Benjamin J. Frogley、Anthony F. Hill、Ryan M. Kirk

  DOI：10.1039/d1cc03015a

  日期：——

  Gold(I)-catalysed tandem transmetallation (Sn→Au→As) of the stannylcarbyne [W(≡CSnnBu3)(CO)2(Tp*)] (Tp* = hydrotris-(dimethylpyrazolyl)borate) with haloarsines gives direct access to a range of novel arsinocarbyne complexes, LnM≡CAsR2, including unusual heterocyclic phenarsazininyl and arsolyl examples.

  金( I )-催化的锡炔[W(≡CSn n Bu 3 )(CO) 2 (Tp*)]（Tp* = 氢三-（二甲基吡唑基）硼酸盐）与卤代胂的串联金属转移（Sn→Au→As）得到直接访问一系列新的胂碳炔配合物，L n M≡CAsR 2，包括不寻常的杂环 phenarsazininyl 和 arsolyl 例子。