3,3'-dinitrothiobenzophenone S-oxide | 40490-41-3

• 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: 3,3'-dinitrothiobenzophenone S-oxide
• 英文别名: 1-Nitro-3-[(3-nitrophenyl)-sulfinylmethyl]benzene
• CAS: 40490-41-3
• 化学式: C₁₃H₈N₂O₅S
• 分子量: 304.283
• InChiKey: BIQRUDKLALMWBG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  110
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,3'-dinitrothiobenzophenone S-oxide 在 甲基三氧化铼(VII) 双氧水 作用下， 以 水 、 乙腈 为溶剂， 生成 3,3'-二硝基二苯甲酮
  参考文献：
  名称：

  Kinetics and Mechanism of the Methyltrioxorhenium-Catalyzed Sulfoxidation of Thioketones and Sulfines

  摘要：

  Kinetic studies have been carried out on the oxidation of thiobenzophenones and thiocamphor by hydrogen peroxide and on the second step in the sequence, oxidation of the resulting sulfines (Ar2C=S=O). The first reaction follows the pattern now common to methyltrioxorhenium/H2O2 reactions, in that the rate constant for the reaction between the peroxorhenium intermediate and the thioketone follows a Hammett; correlation such that electron-releasing substrates react more rapidly. The reaction constant is rho = -1.12. However, the plot of log(k(X)/k(H)) for the sulfines against 2 sigma, determined over the range -1.6 < 2 sigma < +1.5, is markedly U-shaped. This suggests a mechanism for the sulfines in which the direction of the electron flow in the transition state changes with the electron demand of the substituents on the sulfines. The product of oxidation of the sulfine is a transient sultine (from epoxidation of the C=S bond). It cannot be detected, however, because it so rapidly yields sulfur monoxide. The SO was oxidized to SO2 under these conditions rather than undergoing disproportionation to SO2 and S. Also, SO was trapped with a 1,3-diene as a thiophene-1-oxide.

  DOI：

  10.1021/jo990621e
• 作为产物：
  描述：

  3,3'-dinitrothiobenzophenone 在 甲基三氧化铼(VII) 双氧水 作用下， 以 水 、 乙腈 为溶剂， 生成 3,3'-dinitrothiobenzophenone S-oxide
  参考文献：
  名称：

  Kinetics and Mechanism of the Methyltrioxorhenium-Catalyzed Sulfoxidation of Thioketones and Sulfines

  摘要：

  Kinetic studies have been carried out on the oxidation of thiobenzophenones and thiocamphor by hydrogen peroxide and on the second step in the sequence, oxidation of the resulting sulfines (Ar2C=S=O). The first reaction follows the pattern now common to methyltrioxorhenium/H2O2 reactions, in that the rate constant for the reaction between the peroxorhenium intermediate and the thioketone follows a Hammett; correlation such that electron-releasing substrates react more rapidly. The reaction constant is rho = -1.12. However, the plot of log(k(X)/k(H)) for the sulfines against 2 sigma, determined over the range -1.6 < 2 sigma < +1.5, is markedly U-shaped. This suggests a mechanism for the sulfines in which the direction of the electron flow in the transition state changes with the electron demand of the substituents on the sulfines. The product of oxidation of the sulfine is a transient sultine (from epoxidation of the C=S bond). It cannot be detected, however, because it so rapidly yields sulfur monoxide. The SO was oxidized to SO2 under these conditions rather than undergoing disproportionation to SO2 and S. Also, SO was trapped with a 1,3-diene as a thiophene-1-oxide.

  DOI：

  10.1021/jo990621e

文献信息

• A Convenient Preparation of Sulfines (R₂CSO) from Thioketones
  作者：Ruili Huang、James H. Espenson

  DOI：10.1021/jo990967p

  日期：1999.9.1
• Kinetics and Mechanism of the Methyltrioxorhenium-Catalyzed Sulfoxidation of Thioketones and Sulfines
  作者：Ruili Huang、James H. Espenson

  DOI：10.1021/jo990621e

  日期：1999.8.1

  Kinetic studies have been carried out on the oxidation of thiobenzophenones and thiocamphor by hydrogen peroxide and on the second step in the sequence, oxidation of the resulting sulfines (Ar2C=S=O). The first reaction follows the pattern now common to methyltrioxorhenium/H2O2 reactions, in that the rate constant for the reaction between the peroxorhenium intermediate and the thioketone follows a Hammett; correlation such that electron-releasing substrates react more rapidly. The reaction constant is rho = -1.12. However, the plot of log(k(X)/k(H)) for the sulfines against 2 sigma, determined over the range -1.6 < 2 sigma < +1.5, is markedly U-shaped. This suggests a mechanism for the sulfines in which the direction of the electron flow in the transition state changes with the electron demand of the substituents on the sulfines. The product of oxidation of the sulfine is a transient sultine (from epoxidation of the C=S bond). It cannot be detected, however, because it so rapidly yields sulfur monoxide. The SO was oxidized to SO2 under these conditions rather than undergoing disproportionation to SO2 and S. Also, SO was trapped with a 1,3-diene as a thiophene-1-oxide.