N-acetyl glycine ethyl dithioester | 77055-32-4

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: N-acetyl glycine ethyl dithioester
• 英文别名: Ethyl 2-acetamidoethanedithioate
• CAS: 77055-32-4
• 化学式: C₆H₁₁NOS₂
• 分子量: 177.291
• InChiKey: APZIDMYBKGCMAT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  86.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  在 吡啶 、 硫化氢 作用下， 反应 0.75h， 生成 N-acetyl glycine ethyl dithioester
  参考文献：
  名称：

  Modified method of synthesis of N-substituted dithioesters of amino acids and peptides in the Pinner reaction

  摘要：

  已开发出一种改进的合成氨基酸和肽二硫酯的方法。该合成是从腈中进行的。在二硫酯合成的Pinner步骤中，将硫醇加入到腈衍生物中，使用氢氟酸进行活化。描述了使用液体氢氟酸进行二硫酯合成的几个示例。描述了一些新型二硫酯，这些是用于共振拉曼光谱研究二硫酰基木瓜蛋白酶中间体的模型化合物。关键词：二硫酯，氨基酸，Pinner反应，HF，同位素。

  DOI：

  10.1139/v96-038

文献信息

• Resonance Raman spectroscopic evidence for an intramolecular interaction involving the amide and dithioester groups of <i>N</i>-acyl glycine ethyl dithioesters
  作者：A. C. Storer、Y. Ozaki、P. R. Carey

  DOI：10.1139/v82-032

  日期：1982.1.15

  The synthesis and resonance Raman spectra of several new N-acyl glycine ethyl dithioesters RC(=O)NH—CH₂—C(=S)SR are reported. The resonance Raman spectra of these compounds contain at least two peaks in the "C=S stretching region" between 1050 and 1200 cm⁻¹. The solvent, concentration, temperature, and excitation wavelength dependencies of these features have been investigated. The results obtained are consistent with two conformations of the dithioesters co-existing in solution with the conformational differences being controlled by rotational isomerism about one or both of the NH—CH₂ and CH₂—CS bonds. Strong support for the existence of more than one conformer in solution comes from the Raman spectrum of a single crystal of N-acetyl glycine ethyl dithioester. In the spectrum of the single crystal several Raman bands are absent compared to the spectrum of the dithioester in solution indicating that only one of the conformers found in the solution phase is retained in the crystal. In one of the conformers found in solution there is evidence for an intramolecular interaction between the amide group and the dithioester group. The exact nature of the intramolecular interaction is uncertain, although simple H-bonding and enethiol tautomerism have been eliminated as possibilities. Possible contributors to the interaction are dipole–dipole forces and amide π-electrons interacting through space with sulfur d_x orbitals. Both of these putative interactions would be modulated by rotational isomerism. Based on deuterium substitution experiments a resonance Raman band is identified in the 1050–1200 cm⁻¹ region which contains a contribution from the motion of the amide proton. The unexpected intensity enhancement of an amide mode is attributed to the amide–dithioester intramolecular interaction. The conformer exhibiting the intramolecular interaction is thought to closely resemble the conformation of the substrate in the active site of certain dithioester enzyme–substrate complexes.

  报道了几种新的N-酰基甘氨酸乙基二硫酯RC(=O)NH—CH₂—C(=S)SR的合成和共振拉曼光谱。这些化合物的共振拉曼光谱在“C=S伸展区”（1050至1200 cm⁻¹）至少包含两个峰。已经研究了这些特征的溶剂、浓度、温度和激发波长的依赖性。所得结果表明，溶液中存在两种二硫酯的构象，其构象差异由NH—CH₂和CH₂—CS键的旋转异构体控制。从N-乙酰基甘氨酸乙基二硫酯的单晶拉曼光谱中得到了溶液中存在多个构象的强有力支持。在单晶的光谱中，与溶液中的二硫酯光谱相比，有几个拉曼带消失，表明晶体中仅保留了溶液相中的一个构象。在溶液中发现的一个构象中，有证据表明酰胺基团与二硫酯基团之间存在分子内相互作用。分子内相互作用的确切性质尚不确定，尽管简单的氢键和烯硫醇互变异构已被排除为可能性。对于相互作用的可能贡献者包括偶极–偶极力和酰胺π-电子通过空间与硫d_x轨道相互作用。这两种假定的相互作用都将受到旋转异构体的调节。基于氘取代实验，确定了在1050–1200 cm⁻¹区域内的一个共振拉曼带，其中包含酰胺质子运动的贡献。对酰胺模式意外强度增强归因于酰胺–二硫酯分子内相互作用。认为展现分子内相互作用的构象与某些二硫酯酶–底物复合物活性位点中的底物构象非常相似。