5-benzyloxycarbonyl-2-(2-bromo-acetyloxy)-pentandioic acid | 872139-37-2

• 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: 5-benzyloxycarbonyl-2-(2-bromo-acetyloxy)-pentandioic acid
• CAS: 872139-37-2
• 化学式: C₁₄H₁₅BrO₆
• 分子量: 359.173
• InChiKey: MCYCEUJDDYPQMG-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  21.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  89.9
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  5-benzyloxycarbonyl-2-(2-bromo-acetyloxy)-pentandioic acid 在 四丁基碘化铵 、 N,N-二异丙基乙胺 作用下， 以 4-甲基-2-戊酮 为溶剂， 以54%的产率得到(2S)-3,6-二氧代-1,4-二恶烷-2-丙酸苄酯; (2S)-3,6-二氧代-1,4-二氧六环-2-丙酸苄酯; (2S)-3,6-二氧代-1,4-二氧杂环己烷-2-丙酸苄酯
  参考文献：
  名称：

  Organo-Catalyzed Ring Opening Polymerization of a 1,4-Dioxane-2,5-dione Deriving from Glutamic Acid

  摘要：

  The (3S)-[(benzyloxycarbonypethyl)-1,4-dioxan-2,5-dione (BED) was prepared in four steps starting from glutamic acid and bromoacetyl bromide. According to X-ray diffraction analysis, the pendant functional group is located in equatorial position and points away from the six-membered ring. The organo-catalyzed ring-opening polymerization of BED was promoted with 4-dimethylaminopyridine (DMAP) and the combination of thiourea TUCy and (-)-sparteine. PolyBED samples of number-average molar mass M-n up to 36000 and narrow polydispersity (M-w/M-n < 1.25) were thereby prepared in a controlled manner under mild conditions (dichloromethane solution, 30 degrees C), as substantiated by size-exclusion chromatography, matrix-assisted laser desorption ionization time-of-flight-mass spectrometry (MALDI-TOF-MS) and nuclear magnetic resonance (NMR) spectroscopy. The pendant functional group does not interfere with the polymerization and BED was even found to be slightly more reactive than lactide. Despite the strongly dissymmetric substitution pattern of the 1,4-dioxan-2,5-dione core, the ensuing polyBED polymers present a random distribution of glycolic-[(benzyloxycarbonyl)ethyl]glycolic (gly glu) units, as supported by a H-1-C-13 HMBC 2D NMR experiment. The preparation of 1:1 adducts with n-pentanol confirmed that ring-opening of BED occurs almost indifferently on either of the endocyclic ester groups. Poly(alpha-hydroxyacids) featuring pendant carboxylic acids were finally obtained by acetylation of the terminal OH groups followed by hydrogenolysis.

  DOI：

  10.1021/bm100433c
• 作为产物：
  描述：

  L-谷氨酸 γ-苄酯 在 溶剂黄146 、 三乙胺 、 sodium nitrite 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 8.5h， 生成 5-benzyloxycarbonyl-2-(2-bromo-acetyloxy)-pentandioic acid
  参考文献：
  名称：

  Organo-Catalyzed Ring Opening Polymerization of a 1,4-Dioxane-2,5-dione Deriving from Glutamic Acid

  摘要：

  The (3S)-[(benzyloxycarbonypethyl)-1,4-dioxan-2,5-dione (BED) was prepared in four steps starting from glutamic acid and bromoacetyl bromide. According to X-ray diffraction analysis, the pendant functional group is located in equatorial position and points away from the six-membered ring. The organo-catalyzed ring-opening polymerization of BED was promoted with 4-dimethylaminopyridine (DMAP) and the combination of thiourea TUCy and (-)-sparteine. PolyBED samples of number-average molar mass M-n up to 36000 and narrow polydispersity (M-w/M-n < 1.25) were thereby prepared in a controlled manner under mild conditions (dichloromethane solution, 30 degrees C), as substantiated by size-exclusion chromatography, matrix-assisted laser desorption ionization time-of-flight-mass spectrometry (MALDI-TOF-MS) and nuclear magnetic resonance (NMR) spectroscopy. The pendant functional group does not interfere with the polymerization and BED was even found to be slightly more reactive than lactide. Despite the strongly dissymmetric substitution pattern of the 1,4-dioxan-2,5-dione core, the ensuing polyBED polymers present a random distribution of glycolic-[(benzyloxycarbonyl)ethyl]glycolic (gly glu) units, as supported by a H-1-C-13 HMBC 2D NMR experiment. The preparation of 1:1 adducts with n-pentanol confirmed that ring-opening of BED occurs almost indifferently on either of the endocyclic ester groups. Poly(alpha-hydroxyacids) featuring pendant carboxylic acids were finally obtained by acetylation of the terminal OH groups followed by hydrogenolysis.

  DOI：

  10.1021/bm100433c