1-[Chloromethyl-(4-methoxyphenyl)phosphoryl]-4-methoxybenzene | 13685-40-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-[Chloromethyl-(4-methoxyphenyl)phosphoryl]-4-methoxybenzene
• CAS: 13685-40-0
• 化学式: C₁₅H₁₆ClO₃P
• 分子量: 310.717
• InChiKey: RFSGPGMKNLETQV-UHFFFAOYSA-N

物化性质

• 熔点：
  120-121 °C(Solv: carbon tetrachloride (56-23-5))
• 沸点：
  178-184 °C(Press: 0.01 Torr)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-[Chloromethyl-(4-methoxyphenyl)phosphoryl]-4-methoxybenzene 在 sodium hydroxide 、 三氯硅烷 、 1-羟基苯并三唑 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 95.5h， 生成 S-[bis(4-methoxyphenyl)phosphanylmethyl] (2S)-2-acetamidopropanethioate
  参考文献：
  名称：

  Staudinger Ligation of Peptides at Non-Glycyl Residues

  摘要：

  The Staudinger ligation provides a means to form an amide bond between a phosphinothioester and azide. This reaction holds promise for the ligation of peptides en route to the total chemical synthesis of proteins. (Diphenylphosphino) methanethiol is the most efficacious of known reagents for mediating the Staudinger ligation of peptides, providing high (> 90%) isolated yields for equimolar couplings in which a glycine residue is at the nascent junction. Surprisingly, the yields are lower (< 50%) for non-glycyl couplings due to an aza-Wittig reaction that diverts the reaction toward a phosphonamide byproduct. Here, the partitioning of the reaction toward Staudinger ligation (and away from the aza-Wittig reaction) is shown to increase with increasing electron density on phosphorus. This electron density can be tuned either by installing functional groups on the phenyl substituents of (diphenylphosphino) methanethiol or by changing the polarity of the solvent. Installing p-methoxy groups and using a solvent of low polarity (such as toluene or dioxane) provide especially high (> 80%) isolated yields for the ligation of two non-glycyl residues. These conditions retain the high chemoselectivity of the reaction and do not lead to a substantial change in reaction rate. The traceless Staudinger ligation is now poised to enable the iterative ligation of peptides with little regard for their sequence, as well as the synthesis of amide bonds for other purposes.

  DOI：

  10.1021/jo0620056
• 作为产物：
  描述：

  (hydroxymethyl)di-p-anisylphosphine oxide 在 五氯化磷 作用下， 以 苯 为溶剂， 反应 0.5h， 以82%的产率得到1-[Chloromethyl-(4-methoxyphenyl)phosphoryl]-4-methoxybenzene
  参考文献：
  名称：

  Patsanovskii, I. I.; Ishmaeva, E. A.; Sundukova, E. N., Journal of general chemistry of the USSR, 1986, vol. 56, # 3, p. 501 - 509

  摘要：

  DOI：

文献信息

• Tsvetkov, E. N.; Tkachenko, S. E.; Yarkevich, A. N., Bulletin de la Societe Chimique de France, 1988, # 2, p. 339 - 341
  作者：Tsvetkov, E. N.、Tkachenko, S. E.、Yarkevich, A. N.

  DOI：——

  日期：——
• Tkachenko, S. E.; Yarkevich, A. N.; Tsvetkov, E. N., Doklady Chemistry, 1990, vol. 315, # 1.3, p. 334 - 337
  作者：Tkachenko, S. E.、Yarkevich, A. N.、Tsvetkov, E. N.、Galkin, V. I.、Sayakhov, R. D.、et al.

  DOI：——

  日期：——
• PATSANOVSKIJ, I. I.;ISHMAEVA, EH. A.;SUNDUKOVA, E. N.;YARKEVICH, A. N.;TS+, ZH. OBSHCH. XIMII, 1986, 56, N 3, 567-576
  作者：PATSANOVSKIJ, I. I.、ISHMAEVA, EH. A.、SUNDUKOVA, E. N.、YARKEVICH, A. N.、TS+

  DOI：——

  日期：——
• Staudinger Ligation of Peptides at Non-Glycyl Residues
  作者：Matthew B. Soellner、Annie Tam、Ronald T. Raines

  DOI：10.1021/jo0620056

  日期：2006.12.1

  The Staudinger ligation provides a means to form an amide bond between a phosphinothioester and azide. This reaction holds promise for the ligation of peptides en route to the total chemical synthesis of proteins. (Diphenylphosphino) methanethiol is the most efficacious of known reagents for mediating the Staudinger ligation of peptides, providing high (> 90%) isolated yields for equimolar couplings in which a glycine residue is at the nascent junction. Surprisingly, the yields are lower (< 50%) for non-glycyl couplings due to an aza-Wittig reaction that diverts the reaction toward a phosphonamide byproduct. Here, the partitioning of the reaction toward Staudinger ligation (and away from the aza-Wittig reaction) is shown to increase with increasing electron density on phosphorus. This electron density can be tuned either by installing functional groups on the phenyl substituents of (diphenylphosphino) methanethiol or by changing the polarity of the solvent. Installing p-methoxy groups and using a solvent of low polarity (such as toluene or dioxane) provide especially high (> 80%) isolated yields for the ligation of two non-glycyl residues. These conditions retain the high chemoselectivity of the reaction and do not lead to a substantial change in reaction rate. The traceless Staudinger ligation is now poised to enable the iterative ligation of peptides with little regard for their sequence, as well as the synthesis of amide bonds for other purposes.
• Patsanovskii, I. I.; Ishmaeva, E. A.; Sundukova, E. N., Journal of general chemistry of the USSR, 1986, vol. 56, # 3, p. 501 - 509
  作者：Patsanovskii, I. I.、Ishmaeva, E. A.、Sundukova, E. N.、Yarkevich, A. N.、Tsvetkov, E. N.

  DOI：——

  日期：——