diethyl [13C2]-cyanomethylphosphonate | 441015-64-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: diethyl [13C2]-cyanomethylphosphonate
• 英文别名: diethyl ((cyano‐¹³C)methyl‐¹³C)phosphonate
• CAS: 441015-64-1
• 化学式: C₆H₁₂NO₃P
• 分子量: 179.118
• InChiKey: KWMBADTWRIGGGG-MPOCSFTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.78
• 重原子数：
  11.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  59.32
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  diethyl [13C2]-cyanomethylphosphonate 、 3-(2-acetoxyethyl)-6-methyl-8-(2,6,6-trimethyl-1-cyclohexenyl)-octa-3,5,7-trien-2-one 以 四氢呋喃 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  Synthesis and vibrational analysis of a locked 14-s-cis conformer of retinal.

  摘要：

  A 12-N-ethano retinal Schiff base is synthesized to study the vibrational properties of a C-14-C-15 s-cis conformer of retinal. The synthesis of the 12-N-ethano retinal Schiff base and seven of its isotopomers is described. Raman and FTIR spectra of this compound and its isotopic derivatives are analyzed and the normal mode assignments compared to MNDO normal coordinate calculations. The frequency of the C-14-C-15 stretch at 1096 cm-1 is approximately 100 cm-1 below typical values for s-trans conformers of retinal polyenes, supporting previous arguments that s-cis conformers will have characteristically low frequencies for the C-C stretch of the s-cis bond (Smith et al., Proc. Natl. Acad. Sci. U.S.A. 1986, 83, 967-971). Deuteriation at the 15-position produces two modes at 950 and 1044 cm-1 that contain C-15D rock character. The elevated frequency (1044 cm-1) of the high-frequency component is a marker band for the C=N syn geometry and confirms an earlier analysis of the sensitivity of the C-15D rock frequency to Schiff base configuration (Ames et al., Biochemistry 1989, 28, 3681-3687). This work on retinals with chemically defined configuration and conformation provides a basis for further analysis of the geometry of these bonds in retinal-containing pigments.

  DOI：

  10.1021/ja00053a023
• 作为产物：
  描述：

  乙腈-13C2 、 氯磷酸二乙酯 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.42h， 以89%的产率得到diethyl [13C2]-cyanomethylphosphonate
  参考文献：
  名称：

  Synthesis of isotopically labeled all-trans retinals for DNP-enhanced solid-state NMR studies of retinylidene proteins

  摘要：

  已经合成了三种含有多个13C标记的全反式视黄醛，用于增强动态核极化固态魔角旋转核磁共振研究新型微生物视黄基膜蛋白，包括蛋白紫质和通道紫质。合成方法允许在环取代基和多烯链的不同位置上特异性地引入13C标记，以探测环取向和发色团在基态和光中间体中与蛋白质的相互作用等结构特征。[10-18-13C9]-全反式视黄醛（1b）、[12,15-13C2]-全反式视黄醛（1c）和[14,15-13C2]-全反式视黄醛（1d）分别从乙基2-氧环己烷羧酸酯（5）或β-紫罗兰酮（4）开始，经过12步、8步和7步线性合成得到。

  DOI：

  10.1002/jlcr.3576

文献信息

• The Preparation of All-Trans Uniformly ¹³C-Labeled Retinal via a Modular Total Organic Synthetic Strategy. Emerging Central Contribution of Organic Synthesis toward the Structure and Function Study with Atomic Resolution in Protein Research
  作者：Alain F. L. Creemers、Johan Lugtenburg

  DOI：10.1021/ja012368h

  日期：2002.6.1

  Uniformly [C-13(20)]-labeled all-trans-retinal (1) has been prepared via a convergent modular total organic strategy with high isotope incorporation (>99%) and without isotope dilution starting from commercially available 99% enriched C-13-labeled starting materials. For this purpose we have developed a strategy that is based on four different modules: [1,2,3,4,(3-CH3)- C-13(5)]-4-(diethylphosphono)-3-methyl-2-butenenitrile (3), [1,2,3,4-C-13(4)]-ethyl acetoacetate (7), [U-C-13(5)]-4-bromo-2-methyl-2-butene (13), and [U-C-13(10)]-2,6,6-trimethylcyclohex-2-ene-1-ylcarbonitrile (16). This scheme permits the synthesis of the full cassette of all isotopomers with C-13-labels at any position or combination of positions by using different C-13-labeled starting materials. In addition, modifications of the synthesized modules will give access to a broad range of chemically modified C-13-labeled retinoids and carotenoids. This modular strategy enables the synthesis of multifold and uniformly stable isotopically labeled (bio) macro molecules that can be used for studying proteins with atomic resolution, providing detailed functional information of the studied biological system.