4-(N,N-dimethylthiocarbamoyl)benzaldehyde | 134360-19-3

• 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: 4-(N,N-dimethylthiocarbamoyl)benzaldehyde
• 英文别名: 1,4-phthalaldehyde；4-formyl-N,N-dimethylbenzenecarbothioamide
• CAS: 134360-19-3
• 化学式: C₁₀H₁₁NOS
• 分子量: 193.269
• InChiKey: ICDZHEBVTJBFQU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  52.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(N,N-dimethylthiocarbamoyl)benzaldehyde 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 38.5h， 生成 Methanesulfonic acid (diethoxy-phosphoryl)-(4-dimethylthiocarbamoyl-phenyl)-methyl ester
  参考文献：
  名称：

  Variable electronic properties of the CSNMe2 thioamide group

  摘要：

  The sigma-I value for the CSNMe2 group has been determined and the value of 0.23 indicates that this group is inductively electron withdrawing. The effect of the p-CSNMe2 group on the solvolysis rate of cumyl chloride has also been determined and, relative to the p-H analogue, this group has a negligible effect on rate. p-CSNMe2 substitution slows the hydrolysis rate of substituted benzaldehyde dimethyl acetals. p-CSNMe2 substitution enhances the solvolysis rate of ArCH(OMs)PO(OEt)2. These variable rate effects on reactions involving cationic intermediates have been interpreted in terms of variable electronic properties of the CSNMe2 group. This group can be cation stabilizing, electroneutral, or cation destabilizing, depending on the charge demands of specific cations. This is a result of a conjugative interaction of CSNMe2 with a cationic center and resultant delocalization of positive charge onto sulfur. The importance of such conjugation is a function of the amount of transition-state charge developed on the carbon bearing the CSNMe2 group. The electronic effects of the amphielectronic p-CSNMe2 group are compared to the more conventional effects of CONMe2 and the m-CSNMe2 analogues.

  DOI：

  10.1021/jo00013a038
• 作为产物：
  描述：

  对溴苯甲醛 在 正丁基锂 、 硫酸 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 27.83h， 生成 4-(N,N-dimethylthiocarbamoyl)benzaldehyde
  参考文献：
  名称：

  Variable electronic properties of the CSNMe2 thioamide group

  摘要：

  The sigma-I value for the CSNMe2 group has been determined and the value of 0.23 indicates that this group is inductively electron withdrawing. The effect of the p-CSNMe2 group on the solvolysis rate of cumyl chloride has also been determined and, relative to the p-H analogue, this group has a negligible effect on rate. p-CSNMe2 substitution slows the hydrolysis rate of substituted benzaldehyde dimethyl acetals. p-CSNMe2 substitution enhances the solvolysis rate of ArCH(OMs)PO(OEt)2. These variable rate effects on reactions involving cationic intermediates have been interpreted in terms of variable electronic properties of the CSNMe2 group. This group can be cation stabilizing, electroneutral, or cation destabilizing, depending on the charge demands of specific cations. This is a result of a conjugative interaction of CSNMe2 with a cationic center and resultant delocalization of positive charge onto sulfur. The importance of such conjugation is a function of the amount of transition-state charge developed on the carbon bearing the CSNMe2 group. The electronic effects of the amphielectronic p-CSNMe2 group are compared to the more conventional effects of CONMe2 and the m-CSNMe2 analogues.

  DOI：

  10.1021/jo00013a038

文献信息

• Aqueous Compatible Protocol to Both Alkyl and Aryl Thioamide Synthesis
  作者：Jianpeng Wei、Yiming Li、Xuefeng Jiang

  DOI：10.1021/acs.orglett.5b03541

  日期：2016.1.15

  An efficient aqueous synthesis of thioamides through aldehydes, sodium sulfide, and N-substituted formamides has been developed. Both alkyl and aryl aldehydes are amenable to this protocol. N-Substituted formamides are essential for this transformation. Readily available inorganic salt (sodium sulfide) serves as the sulfur source in water, which makes this method much more practical and efficient.

  已经开发了通过醛，硫化钠和N-取代的甲酰胺的硫酰胺的有效的水性合成。烷基醛和芳基醛均适用于该方案。N-取代的甲酰胺对于该转化是必不可少的。现成的无机盐（硫化钠）是水中的硫源，这使该方法更加实用和有效。此外，已经建立了通过该方案对生物活性分子和衍生物进行后期修饰的方法。
• Variable electronic properties of the CSNMe2 thioamide group
  作者：Xavier Creary、Timothy Aldridge

  DOI：10.1021/jo00013a038

  日期：1991.6

  The sigma-I value for the CSNMe2 group has been determined and the value of 0.23 indicates that this group is inductively electron withdrawing. The effect of the p-CSNMe2 group on the solvolysis rate of cumyl chloride has also been determined and, relative to the p-H analogue, this group has a negligible effect on rate. p-CSNMe2 substitution slows the hydrolysis rate of substituted benzaldehyde dimethyl acetals. p-CSNMe2 substitution enhances the solvolysis rate of ArCH(OMs)PO(OEt)2. These variable rate effects on reactions involving cationic intermediates have been interpreted in terms of variable electronic properties of the CSNMe2 group. This group can be cation stabilizing, electroneutral, or cation destabilizing, depending on the charge demands of specific cations. This is a result of a conjugative interaction of CSNMe2 with a cationic center and resultant delocalization of positive charge onto sulfur. The importance of such conjugation is a function of the amount of transition-state charge developed on the carbon bearing the CSNMe2 group. The electronic effects of the amphielectronic p-CSNMe2 group are compared to the more conventional effects of CONMe2 and the m-CSNMe2 analogues.