O-phenyl 4-nitrophenyl dithiocarbonate | 149775-78-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: O-phenyl 4-nitrophenyl dithiocarbonate
• 英文别名: O-phenyl (4-nitrophenyl)sulfanylmethanethioate
• CAS: 149775-78-0
• 化学式: C₁₃H₉NO₃S₂
• 分子量: 291.351
• InChiKey: QNCDPPNPICZLMY-UHFFFAOYSA-N

物化性质

• 沸点：
  445.0±37.0 °C(Predicted)
• 密度：
  1.42±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  112
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-甲醛哌嗪 、 O-phenyl 4-nitrophenyl dithiocarbonate 以 乙醇 、 水 为溶剂， 生成
  参考文献：
  名称：

  Kinetics and mechanism of the aminolysis of O‐phenyl 4‐nitrophenyl dithiocarbonate in aqueous ethanol

  摘要：

  The reactions of the title substrate (1) with a series of secondary alicyclic amines are subjected to a kinetic investigation in 44 wt% ethanol-water, at 25.0 degrees C, ionic strength 0.2 M (KCl). Under amine excess over the substrate, pseudo-first-order rate coefficients (k(obs)) are obtained. Plots of k(obs) against [NH], where NH is the free amine, are nonlinear upwards,except the reactions of piperidine, which show linear plots. According to the kinetic results and the analysis of products, a reaction scheme is proposed with two tetrahedral intermediates, one zwitterionic (T+/-) and another anionic (T-), with a kinetically significant proton transfer from T+/- to an amine to yield T- (k(3) step). By nonlinear least-squarer fitting of an equation derived from the scheme to the experimental points, the rate microcoefficients involved in the reactions are determined. Comparison of the kinetics of the title reactions with the linear k(obs) vs. [NH] plots found in the same aminolysis of O-ethyl 4-nitrophenyl dithiocarbonate (2) in the same solvent shows that the rate coefficient for leaving group expulsion from T+/- (k(2)) is larger for 2 due to a stronger push by EtO than Pho. The k(3) value is the same for both reactions since both proton transfers are diffusion controlled. Comparison of the title reactions with the same aminolysis of phenyl 4-nitrophenyl thionocarbonate (3) in water indicates that iii the k(2) value is larger for the aminolysis of 1 due to the less basic nucleofuge involved and the small solvent effect on k(2), (ii) the k(3) value is smaller for the reactions of 1 due to the more viscous solvent, (iii) the rate coefficient for amine expulsion from T+/- (k(-1)) is larger for the aminolysis of 1 than that of 3 due to a solvent effect, and (iv) the value of the rate coefficient for amine attack (k(1)) is smaller for the aminolysis of 1 in aqueous ethanol, which can be explained by a predominant solvent effect relative to the electron-withdrawing effect from the nucleofuge. (C) 1999 John Wiley & Sons, Inc.

  DOI：

  10.1002/(sici)1097-4601(1999)31:12<839::aid-kin1>3.0.co;2-#
• 作为产物：
  描述：

  4-硝基苯硫醇 、 硫代氯甲酸苯酯 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 生成 O-phenyl 4-nitrophenyl dithiocarbonate
  参考文献：
  名称：

  Kinetics and mechanism of the aminolysis of O‐phenyl 4‐nitrophenyl dithiocarbonate in aqueous ethanol

  摘要：

  The reactions of the title substrate (1) with a series of secondary alicyclic amines are subjected to a kinetic investigation in 44 wt% ethanol-water, at 25.0 degrees C, ionic strength 0.2 M (KCl). Under amine excess over the substrate, pseudo-first-order rate coefficients (k(obs)) are obtained. Plots of k(obs) against [NH], where NH is the free amine, are nonlinear upwards,except the reactions of piperidine, which show linear plots. According to the kinetic results and the analysis of products, a reaction scheme is proposed with two tetrahedral intermediates, one zwitterionic (T+/-) and another anionic (T-), with a kinetically significant proton transfer from T+/- to an amine to yield T- (k(3) step). By nonlinear least-squarer fitting of an equation derived from the scheme to the experimental points, the rate microcoefficients involved in the reactions are determined. Comparison of the kinetics of the title reactions with the linear k(obs) vs. [NH] plots found in the same aminolysis of O-ethyl 4-nitrophenyl dithiocarbonate (2) in the same solvent shows that the rate coefficient for leaving group expulsion from T+/- (k(2)) is larger for 2 due to a stronger push by EtO than Pho. The k(3) value is the same for both reactions since both proton transfers are diffusion controlled. Comparison of the title reactions with the same aminolysis of phenyl 4-nitrophenyl thionocarbonate (3) in water indicates that iii the k(2) value is larger for the aminolysis of 1 due to the less basic nucleofuge involved and the small solvent effect on k(2), (ii) the k(3) value is smaller for the reactions of 1 due to the more viscous solvent, (iii) the rate coefficient for amine expulsion from T+/- (k(-1)) is larger for the aminolysis of 1 than that of 3 due to a solvent effect, and (iv) the value of the rate coefficient for amine attack (k(1)) is smaller for the aminolysis of 1 in aqueous ethanol, which can be explained by a predominant solvent effect relative to the electron-withdrawing effect from the nucleofuge. (C) 1999 John Wiley & Sons, Inc.

  DOI：

  10.1002/(sici)1097-4601(1999)31:12<839::aid-kin1>3.0.co;2-#

文献信息

• Novel aryloxy migrations in substituted diphenyldithiocarbonates under electron impact conditions
  作者：D. V. Ramana、P. Mahalakshmi、M. George

  DOI：10.1002/oms.1210280433

  日期：1993.4

  AbstractUnusual expulsion of ‘SO’ was observed from the molecular ions of substituted diphenyldithiocarbonates under electron impact conditions. An initial aryloxy migration to sulphur followed by further rearrangement is proposed for this process, based on the substituent effects. The diarylthioketone radical–cation structure assigned for the [M – SO] ion was confirmed through the collision‐activated dissociation B/E linked‐scan spectra.