S-(1,2-二氯乙烯基)硫代乙酸酯 | 213845-16-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硫代羧酸及其衍生物
• 中文名称: S-(1,2-二氯乙烯基)硫代乙酸酯
• 英文名称: S-(1,2-Dichlorovinyl)thioacetate
• 英文别名: S-(1,2-dichloroethenyl) ethanethioate
• CAS: 213845-16-0
• 化学式: C₄H₄Cl₂OS
• 分子量: 171.047
• InChiKey: JBOVMXBELSAETQ-UHFFFAOYSA-N

物化性质

• 沸点：
  189.3±40.0 °C(Predicted)
• 密度：
  1.403±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.54
• 重原子数：
  8.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  胞嘧啶 、 S-(1,2-二氯乙烯基)硫代乙酸酯 以 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 N⁴-(Chlorothioacetyl)cytosine
  参考文献：
  名称：

  Chlorothioketene, the Ultimate Reactive Intermediate Formed by Cysteine Conjugate β-Lyase-Mediated Cleavage of the Trichloroethene Metabolite S-(1,2-Dichlorovinyl)-l-cysteine, Forms Cytosine Adducts in Organic Solvents, but Not in Aqueous Solution

  摘要：

  Chlorothioketene has been suggested as a reactive intermediate formed by the cysteine conjugate beta-lyase-mediated cleavage of S-(1,2-dichlorovinyl)-L-cysteine, a minor metabolite of trichloroethene. Halothioketenes are highly reactive, and their intermediate formation may be confirmed by reactions such as cycloadditions and thioacylations of nucleophiles. A precursor of chlorothioketene, S-( 1,2-dichlorovinyl)thioacetate, is readly accessible by the reaction of dichloroethyne with thioacetic acid. In presence of base, S-(1,2-dichlorovinyl)thioacetate is cleaved to chlorothioketene. Chlorothioketene is not stable at room temperature and was characterized after transformation to stable products by reaction with compounds such as cyclopentadiene, N,N-diethylamine, and ethanol. In organic solvents, the cleavage of S-(1,2-dichlorovinyl)thioacetate in the presence of cytosine results in N-4-acetylcytosine, N-4-(chlorothioacetyl)cytosine, and small amounts of 3-(N-4-thioacetyl)cytosine. No reaction products were seen with guanosine, adenosine, and thymidine under identical conditions. When cytosine was reacted with S-(1,2-dichlorovinyl)thioacetate in aqueous solutions, only N-4-acetylcytosine was formed. N-4-(Chlorothioacetyl)cytosine and 3-(N-4-thioacetyl)cytosine were not detected even when using a very sensitive method, derivatization with pentafluorobenzyl bromide and electron capture mass spectrometry with a detection limit of 50 fmol/mu L of injection volume. Aqueous solutions of DNA cleave S-(1,2-dichlorovinyl)thioacetate to give N-4-acetyldeoxycyticline in DNA, but chlorothioketene adducts of deoxynucleosides were also not detected in these experiments. These results confirm the electrophilic reactivity of chlorothioketene toward nucleophilic groups of DNA constituents in inert solvents but also demonstrate that the formation of DNA adducts under physiological conditions likely is not efficient. Therefore, DNA adducts may not represent useful biomarkers of exposure and biochemical effects for trichloroethene.

  DOI：

  10.1021/tx980084d
• 作为产物：
  描述：

  Dichloroethyne etherate 、 硫代乙酸 以 正己烷 为溶剂， 反应 1.0h， 生成 S-(1,2-二氯乙烯基)硫代乙酸酯
  参考文献：
  名称：

  Chlorothioketene, the Ultimate Reactive Intermediate Formed by Cysteine Conjugate β-Lyase-Mediated Cleavage of the Trichloroethene Metabolite S-(1,2-Dichlorovinyl)-l-cysteine, Forms Cytosine Adducts in Organic Solvents, but Not in Aqueous Solution

  摘要：

  Chlorothioketene has been suggested as a reactive intermediate formed by the cysteine conjugate beta-lyase-mediated cleavage of S-(1,2-dichlorovinyl)-L-cysteine, a minor metabolite of trichloroethene. Halothioketenes are highly reactive, and their intermediate formation may be confirmed by reactions such as cycloadditions and thioacylations of nucleophiles. A precursor of chlorothioketene, S-( 1,2-dichlorovinyl)thioacetate, is readly accessible by the reaction of dichloroethyne with thioacetic acid. In presence of base, S-(1,2-dichlorovinyl)thioacetate is cleaved to chlorothioketene. Chlorothioketene is not stable at room temperature and was characterized after transformation to stable products by reaction with compounds such as cyclopentadiene, N,N-diethylamine, and ethanol. In organic solvents, the cleavage of S-(1,2-dichlorovinyl)thioacetate in the presence of cytosine results in N-4-acetylcytosine, N-4-(chlorothioacetyl)cytosine, and small amounts of 3-(N-4-thioacetyl)cytosine. No reaction products were seen with guanosine, adenosine, and thymidine under identical conditions. When cytosine was reacted with S-(1,2-dichlorovinyl)thioacetate in aqueous solutions, only N-4-acetylcytosine was formed. N-4-(Chlorothioacetyl)cytosine and 3-(N-4-thioacetyl)cytosine were not detected even when using a very sensitive method, derivatization with pentafluorobenzyl bromide and electron capture mass spectrometry with a detection limit of 50 fmol/mu L of injection volume. Aqueous solutions of DNA cleave S-(1,2-dichlorovinyl)thioacetate to give N-4-acetyldeoxycyticline in DNA, but chlorothioketene adducts of deoxynucleosides were also not detected in these experiments. These results confirm the electrophilic reactivity of chlorothioketene toward nucleophilic groups of DNA constituents in inert solvents but also demonstrate that the formation of DNA adducts under physiological conditions likely is not efficient. Therefore, DNA adducts may not represent useful biomarkers of exposure and biochemical effects for trichloroethene.

  DOI：

  10.1021/tx980084d