dimethylmonothioarsinic acid | 754217-65-7

• 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
• 英文名称: dimethylmonothioarsinic acid
• 英文别名: DMMTA^V；Dimethylthioarsinic acid；hydroxy-dimethyl-sulfanylidene-λ5-arsane
• CAS: 754217-65-7
• 化学式: C₂H₇AsOS
• 分子量: 154.065
• InChiKey: YBGVNEGTAKTTKS-UHFFFAOYSA-N

物化性质

• 沸点：
  200.6±23.0 °C(Predicted)
• 溶解度：
  DMSO（微溶）、水（微溶）

计算性质

• 辛醇/水分配系数(LogP)：
  0.88
• 重原子数：
  5
• 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：
  52.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  dimethylmonothioarsinic acid 在 谷胱甘肽 作用下， 以 phosphate buffer 为溶剂， 反应 12.0h， 生成 二甲基卑胂酸 、 dimethyldithioarsinic acid
  参考文献：
  名称：

  Theoretical Calculations and Reaction Analysis on the Interaction of Pentavalent Thioarsenicals with Biorelevant Thiol Compounds

  摘要：

  To obtain a rational understanding of the extraordinary interaction of pentavalent thioarsenicals with biorelevant thiol compounds, we carried out ab initio calculations on related arsenic compounds and discussed the correlation between the distribution of observed arsenic species in actual reaction systems and the corresponding calculated reaction enthalpies. Previously, it was considered that pentavalent arsenicals do not form thiol conjugates. However, the dimethylmonothioarsinic acid-glutathione conjugate (DMMTA(v)-GSH) was recentry reported as the first stable conjugate of a pentavalent arsenical with a thiol compound. We carried out detailed analysis of the DMMTAv-GSH formation reaction and demonstrated that this conjugate could be formed nonenzymatically under weakly acidic conditions. On the basis of the ab initio calculations, this conjugation was an exothermic reaction (Delta H = -4.85 kcal/ mol) and gave the minimum energy point during the reaction sequence of DMMTA(v) with a thiol compound. However, in the case of dimethylarsinic acid (DMA(v)), a corresponding oxo acid to DMMTAv, conjugation with a thiol compound is an endothermic reaction (Delta H = +0.06 kcal/mol). The minimum energy point of the reaction sequence of DMAv with a thiol compound was the formation of a trivalent dimethylarsinous acid (DMA(III))-GSH conjugate. Because the formation of arsenic-sulfur bonds is one of the major mechanisms for arsenic toxicity, these energetic results could account for the extraordinary behaviors and toxicities of thioarsenicals in vivo and in vitro in comparison with those of the corresponding oxo acids.

  DOI：

  10.1021/tx700346z
• 作为产物：
  描述：

  dimethylarsinosulfenyl iodide 在 水 作用下， 以 氘代甲醇 为溶剂， 反应 3.0h， 生成 dimethylmonothioarsinic acid
  参考文献：
  名称：

  本生二硫化二甲胂 Me2As(S)-S-AsMe2 与碘的反应：二甲基胂亚硫基碘 Me2As-SI 的制备和性质

  摘要：

  本生的二硫化物 Me2As(S)-S-AsMe2 (1) 与碘反应得到新型二甲基胂亚硫基碘化物 Me2As-SI (3) 尽管理论计算表明 AsV 化合物 Me2As(S)-I (4) 更多在气相中稳定。油状产品在 +4 °C 和 –20 °C 下作为 CDCl3 溶液在纯品和溶液中稳定至少 15 天。光、H2O、H2O2 和 Zn 粉尘（但不是 NaI 或 Ag）分解了它。化合物 3 不与 Ph3N 相互作用，它与 Ph2NH 和 PhNH2 相互作用但不反应。3被哌啶分解，与吡啶和4-二甲氨基吡啶相互作用生成Me2As-SS-AsMe2(2)和I2，形成电荷转移络合物Base·I2，而Et3N分解3，分离出3Et3N·2I2。3被Ph3P和(Me2N)3P完全脱硫，部分被(PhO)3P和(PhS)3P脱硫。3与(Me2N)3P的反应，(PhS)3P 和 (EtO)3P 很复杂。从 AsIII

  DOI：

  10.1002/zaac.201500096

文献信息

• Possible differences in the mechanism of malignant transformation of HaCaT cells by arsenite and its dimethyl metabolites, particularly dimethylthioarsenics
  作者：Jiayuan Mao、Qianlei Yang、Makoto Miyazawa、Motofumi Miura、Luna Wang、Haixuan Xia、Koichi Kato、Kenzo Yamanaka、Yan An

  DOI：10.1016/j.jtemb.2020.126544

  日期：2020.9

  confirmed human carcinogen, arsenic can cause skin cancer, lung cancer, etc. However, its carcinogenic mechanism is still unclear. In recent years, the oxidative stress hypothesis has become widely accepted. In mammals it has been found that arsenic can be converted to dimethylarsinous acid (DMAIII) and dimethylmonothioarsinic acid (DMMTAV) through a series of methylation and redox reactions. DMAIII

  背景技术砷已被证实是人类致癌物，可引起皮肤癌，肺癌等。然而，其致癌机理仍不清楚。近年来，氧化应激假说已被广泛接受。在哺乳动物中，已发现砷可通过一系列甲基化和氧化还原反应转化为二甲基ar亚磺酸（DMAIII）和二甲基单硫代ar氨酸（DMMTAV）。DMAIII和DMMTAV具有剧毒。方法将人类角质形成细胞（HaCaT）暴露于不同浓度的NaAsO2（IAsIII），DMMTAV和DMAIII中24小时。测量了活性氧（过氧化氢和超氧化物），氧化损伤标记（8-羟基脱氧鸟苷和丙二醛）和抗氧化剂标记（谷胱甘肽和超氧化物歧化酶）。此外，在HaCaT细胞和无细胞系统中测量了亚砜硫。结果在相同剂量的DMMTAV和DMAIII处理组中，HaCaT细胞中的过氧化氢和超氧化物水平高于IAsIII处理组。在相同剂量下，DMMTAV和DMAIII治疗组的8-OHdG和MDA水平也高于IAsIII治疗组。然而，在DMM
• The Reaction of Bunsen's Cacodyl Disulfide, Me₂As(S)-S-AsMe₂, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide, Me₂As-S-I
  作者：Panayiotis V. Ioannou、Dimitris G. Vachliotis、Athanassios Chrissanthopoulos

  DOI：10.1002/zaac.201500096

  日期：2015.6

  Bunsen's cacodyl disulfide, Me2As(S)-S-AsMe2 (1), reacted with iodine giving the novel dimethylarsinosulfenyl iodide, Me2As-S-I (3) although theoretical calculations indicated that the AsV compound Me2As(S)-I (4) was more stable in the gas phase. The oily product was stable neat and as a solution in CDCl3 at +4 °C and –20 °C for at least 15 d. Light, H2O, H2O2, and Zn dust, but not NaI or Ag, decomposed

  本生的二硫化物 Me2As(S)-S-AsMe2 (1) 与碘反应得到新型二甲基胂亚硫基碘化物 Me2As-SI (3) 尽管理论计算表明 AsV 化合物 Me2As(S)-I (4) 更多在气相中稳定。油状产品在 +4 °C 和 –20 °C 下作为 CDCl3 溶液在纯品和溶液中稳定至少 15 天。光、H2O、H2O2 和 Zn 粉尘（但不是 NaI 或 Ag）分解了它。化合物 3 不与 Ph3N 相互作用，它与 Ph2NH 和 PhNH2 相互作用但不反应。3被哌啶分解，与吡啶和4-二甲氨基吡啶相互作用生成Me2As-SS-AsMe2(2)和I2，形成电荷转移络合物Base·I2，而Et3N分解3，分离出3Et3N·2I2。3被Ph3P和(Me2N)3P完全脱硫，部分被(PhO)3P和(PhS)3P脱硫。3与(Me2N)3P的反应，(PhS)3P 和 (EtO)3P 很复杂。从 AsIII
• Theoretical Calculations and Reaction Analysis on the Interaction of Pentavalent Thioarsenicals with Biorelevant Thiol Compounds
  作者：Noriyuki Suzuki、Hua Naranmandura、Seishiro Hirano、Kazuo T. Suzuki

  DOI：10.1021/tx700346z

  日期：2008.2.1

  To obtain a rational understanding of the extraordinary interaction of pentavalent thioarsenicals with biorelevant thiol compounds, we carried out ab initio calculations on related arsenic compounds and discussed the correlation between the distribution of observed arsenic species in actual reaction systems and the corresponding calculated reaction enthalpies. Previously, it was considered that pentavalent arsenicals do not form thiol conjugates. However, the dimethylmonothioarsinic acid-glutathione conjugate (DMMTA(v)-GSH) was recentry reported as the first stable conjugate of a pentavalent arsenical with a thiol compound. We carried out detailed analysis of the DMMTAv-GSH formation reaction and demonstrated that this conjugate could be formed nonenzymatically under weakly acidic conditions. On the basis of the ab initio calculations, this conjugation was an exothermic reaction (Delta H = -4.85 kcal/ mol) and gave the minimum energy point during the reaction sequence of DMMTA(v) with a thiol compound. However, in the case of dimethylarsinic acid (DMA(v)), a corresponding oxo acid to DMMTAv, conjugation with a thiol compound is an endothermic reaction (Delta H = +0.06 kcal/mol). The minimum energy point of the reaction sequence of DMAv with a thiol compound was the formation of a trivalent dimethylarsinous acid (DMA(III))-GSH conjugate. Because the formation of arsenic-sulfur bonds is one of the major mechanisms for arsenic toxicity, these energetic results could account for the extraordinary behaviors and toxicities of thioarsenicals in vivo and in vitro in comparison with those of the corresponding oxo acids.