2-Hydroxy-6-carboxytetrahydropyran | 98485-61-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 2-Hydroxy-6-carboxytetrahydropyran
• 英文别名: 6-hydroxy-tetrahydro-pyran-2-carboxylic acid；6-Hydroxy-tetrahydro-pyran-2-carbonsaeure；6-Hydroxyoxane-2-carboxylic acid
• CAS: 98485-61-1
• 化学式: C₆H₁₀O₄
• mdl: MFCD18814869
• 分子量: 146.143
• InChiKey: DDEQHNYMFTWNMK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.833
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  7,8-二氧杂双环[3.2.1]辛烷-6-酮 在 水 作用下， 生成 2-Hydroxy-6-carboxytetrahydropyran
  参考文献：
  名称：

  Acylal hydrolysis. The pH-independent breakdown of 7-oxo-6,8-dioxabicyclo[3.2.1]octane

  摘要：

  The hydrolysis of the bicyclic acylal 7-oxo-6,8-dioxabicyclo[3.2.1]octane in water is rapid and pH independent from pH 1-12 (k0 = 6.0 x 10(-3) s-1 at 20-degrees-C). This reaction proceeds at nearly the same rate in D2O as in H2O (k(H2O)/k(D2O) = 1.1) and is uncatalyzed by buffer. Therefore, the reaction is a unimolecular breakdown to a resonance-stabilized oxocarbonium ion; i.e., the acylal is hydrolyzing like an acetal with a good leaving group and not like an ester. The H-1 and C-13 NMR spectra indicate a diaxial conformation for the substituents at C-1 and C-5 with moderate distortion of the tetrahydropyran ring. There is a large upfield shift for carbon at C-3 as compared with the corresponding carbon (C-4) of tetrahydropyran (8.8 ppm) or 2-ethoxytetrahydropyran (3.8 ppm). The rapid pH-independent unimolecular breakdown reaction is due to a relatively favorable DELTA-S* (-2.6 eu) and the lack of effective reversibility of that reaction.

  DOI：

  10.1021/jo00030a045

文献信息

• Notes: 6-Alkoxytetrahydropyran-2-carboxylates
  作者：J Brezinski、D Kubler、A Montagna

  DOI：10.1021/jo01093a618

  日期：1959.11
• Acylal hydrolysis. The pH-independent breakdown of 7-oxo-6,8-dioxabicyclo[3.2.1]octane
  作者：Thomas H. Fife、Ramesh Bembi

  DOI：10.1021/jo00030a045

  日期：1992.2

  The hydrolysis of the bicyclic acylal 7-oxo-6,8-dioxabicyclo[3.2.1]octane in water is rapid and pH independent from pH 1-12 (k0 = 6.0 x 10(-3) s-1 at 20-degrees-C). This reaction proceeds at nearly the same rate in D2O as in H2O (k(H2O)/k(D2O) = 1.1) and is uncatalyzed by buffer. Therefore, the reaction is a unimolecular breakdown to a resonance-stabilized oxocarbonium ion; i.e., the acylal is hydrolyzing like an acetal with a good leaving group and not like an ester. The H-1 and C-13 NMR spectra indicate a diaxial conformation for the substituents at C-1 and C-5 with moderate distortion of the tetrahydropyran ring. There is a large upfield shift for carbon at C-3 as compared with the corresponding carbon (C-4) of tetrahydropyran (8.8 ppm) or 2-ethoxytetrahydropyran (3.8 ppm). The rapid pH-independent unimolecular breakdown reaction is due to a relatively favorable DELTA-S* (-2.6 eu) and the lack of effective reversibility of that reaction.