2,6-dimethylphenoxide | 25117-01-5

• 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: 2,6-dimethylphenoxide
• 英文别名: 2,6-Dimethylphenolate
• CAS: 25117-01-5
• 化学式: C₈H₉O
• 分子量: 121.159
• InChiKey: NXXYKOUNUYWIHA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  23.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,6-dimethylphenoxide 在 过氧化苯甲酰 作用下， 以 四氢呋喃 、 四氯化碳 、 乙醇 、 苯 为溶剂， 反应 39.0h， 生成 9,18-(ethylenedioxy)-2,11-dithia<3.3>metacyclophane
  参考文献：
  名称：

  Synthesis and conformational study of 9,18-(ethylenedioxy)-2,11-dithia[3.3]metacyclophane: the propelling behavior of the three bridges in a [3.4.3](1,2,3)cyclophane

  摘要：

  A general approach which involved first the introduction of the central oxy or dioxy bridge and subsequent intramolecular coupling reactions to form the two thia bridges was employed in the syntheses of the 1,2,3-triply bridged cyclophanes 2, 3, and 4. The attempted routes to potential precursors of 2 were unsuccessful while the tetrabromide 16 could be synthesized. Intramolecular cyclizations of the latter, however, failed to yield 4, possibly due to unfavorable stereochemistry of the intermediate leading to the second intramolecular coupling reaction. The tetrabromide 18, with a central bridge of an appropriate length, successfully led to the formation of 3. The conformational behavior of 3 was analyzed by dynamic H-1 NMR spectroscopy. The ethylenedioxy bridge is believed to adopt the symmetrical ''boat'' conformation. All three bridges, however, undergo unrestricted pseudorotation, represented by free conformational interconversion 3b reversible 3c, at room temperature. A relatively frozen conformation 3b (3c) was observed at the low-temperature limit. Flipping processes of the ethylenedioxy bridge and the two thia bridges are found to be interdependent, resulting in an overall propelling process with a common conformational barrier estimated at ca. 45 kJ mol-1.

  DOI：

  10.1021/jo00001a050
• 作为产物：
  描述：

  2,6-二甲基苯酚 在 sodium hydroxide 作用下， 以 四氢呋喃 为溶剂， 生成 2,6-dimethylphenoxide
  参考文献：
  名称：

  Synthesis and conformational study of 9,18-(ethylenedioxy)-2,11-dithia[3.3]metacyclophane: the propelling behavior of the three bridges in a [3.4.3](1,2,3)cyclophane

  摘要：

  A general approach which involved first the introduction of the central oxy or dioxy bridge and subsequent intramolecular coupling reactions to form the two thia bridges was employed in the syntheses of the 1,2,3-triply bridged cyclophanes 2, 3, and 4. The attempted routes to potential precursors of 2 were unsuccessful while the tetrabromide 16 could be synthesized. Intramolecular cyclizations of the latter, however, failed to yield 4, possibly due to unfavorable stereochemistry of the intermediate leading to the second intramolecular coupling reaction. The tetrabromide 18, with a central bridge of an appropriate length, successfully led to the formation of 3. The conformational behavior of 3 was analyzed by dynamic H-1 NMR spectroscopy. The ethylenedioxy bridge is believed to adopt the symmetrical ''boat'' conformation. All three bridges, however, undergo unrestricted pseudorotation, represented by free conformational interconversion 3b reversible 3c, at room temperature. A relatively frozen conformation 3b (3c) was observed at the low-temperature limit. Flipping processes of the ethylenedioxy bridge and the two thia bridges are found to be interdependent, resulting in an overall propelling process with a common conformational barrier estimated at ca. 45 kJ mol-1.

  DOI：

  10.1021/jo00001a050

文献信息

• Antihydrophobic Cosolvent Effects for Alkylation Reactions in Water Solution, Particularly Oxygen versus Carbon Alkylations of Phenoxide Ions
  作者：Ronald Breslow、Kevin Groves、M. Uljana Mayer

  DOI：10.1021/ja012293h

  日期：2002.4.1

  nucleophile, using its oxygen n electrons to avoid loss of conjugation. The geometry of alkylation of aniline is very different, involving packing (stacking) of the aniline ring onto the phenyl ring of a benzyl group in the benzylation reaction. The alkylation of phenoxide ions by benzylic chlorides can occur both at the phenoxide oxygen and on ortho and para positions of the ring. Carbon alkylation occurs

  抗疏水性助溶剂（例如乙醇）会增加疏水性分子在水中的溶解度，并且它们还会影响涉及疏水性表面的反应速率。在碳氢化合物的简单反应中，例如 1,3-环戊二烯的 Diels-Alder 二聚反应，速率和溶解度数据直接反映了过渡态的几何形状，其中一些疏水表面变得隐藏。在涉及极性基团的反应中，例如酚盐离子的烷基化或烷基卤化物的 S(N)1 电离，水中的助溶剂也会产生其他影响。然而，疏水表面的溶剂化仍然很重要。通过使用结构-反应性关系，并比较乙醇和 DMSO 作为溶剂的影响，可以理清这些影响。疏水溶剂化的 ab initio 计算机模型加强了这些结论。结果是苯氧离子作为亲核试剂的合理过渡态，使用其氧 n 电子来避免共轭损失。苯胺烷基化的几何结构非常不同，包括在苄基化反应中将苯胺环堆积（堆积）到苄基的苯环上。苯甲酰氯对苯氧离子的烷基化可以发生在苯氧氧和环的邻位和对位。碳烷基化发生在水中，但不发生在非极性有机
• Antihydrophobic Cosolvent Effects in Organic Displacement Reactions
  作者：Ronald Breslow、Kevin Groves、M. Uljana Mayer

  DOI：10.1021/ol990037s

  日期：1999.7.1

  presence of antihydrophobic cosolvents such as ethanol and DMSO, which lower the energies of nonpolar surfaces. The rate effects reflect changes both in the solvation of nonpolar surfaces and also in the solvation of polar groups. The effects have been sorted out for some displacement reactions, revealing the geometry of an interesting branching reaction whose two paths show different antihydrophobic effects

  可以通过降低乙醇和DMSO等疏水性助溶剂的存在来改变水中的反应速率，从而降低非极性表面的能量。速率效应反映了非极性表面的溶剂化和极性基团的溶剂化的变化。已经对一些置换反应的影响进行了分类，揭示了有趣的支化反应的几何结构，其两条路径显示出不同的抗疏水作用。
• Ainscough, Eric W.; Bingham, Alistair G.; Brodie, Andrew M., Journal of Chemical Research - Part S
  作者：Ainscough, Eric W.、Bingham, Alistair G.、Brodie, Andrew M.、Englebretsen, Darren R.、Husbands, June M.

  DOI：——

  日期：——
• Skeletal rearrangements preceding CO loss from metastable phenoxymethylene ions derived from phenoxyacetic acid and anisole
  作者：Tineke A. Molenaar-Langeveld、Steen Ingemann、Nico M. M. Nibeering

  DOI：10.1002/oms.1210281031

  日期：1993.10

  AbstractThe loss of CH2˙ from the molecular ion of phenoxyacetic acid and the expulsion of an H˙ atom from ionized anisole lead to phenoxymethylen ions, which fragment predominantly by CO loss on the microsecond time‐scale. Carbon‐13 labelling reveals that ∼90% of the CO molecules expelled from the metastable ions derived from phenoxyacetic acid incorporate the carbon atom from the 1‐position of the phenyl group of the parent compound, whereas the residual CO molecules contain one of the other carbon atoms of the aromatic ring. The 2‐fluoro‐ and 2‐methylphenoxymethylene ions derived from the appropriate aryloxyacetic acids behave similarly, i.e. the carbon atom of the methylene group of the parent compound is not incorporated in the expelled CO molecules. In contrast, ∼45% of the CO molecules eliminated from the metastable phenoxymethylene ions formed from ionized anisole contain the carbon atom of the methyl group, while the remaining part contains the carbon atom from the 1‐position of the phenyl ring of the parent compound. This result is taken as evidence for the occurrence of a skeletal rearrangement of the anisole molecular ion leading to an interchange between the carbon atom of the methyl group and the carbon atom at the 1‐position of the ring. The elimination of CO from the metastable ions generated from either phenoxyacetic acid or anisole gives rise to a composite metastable peak. Conclusive evidence as to the formation of [C7H7O]+ isomers other than the phenoxymethylene ion is not obtained, indicating that the composite metastable peak is a result of two competing reactions both leading to CO loss. Possible mechanisms of these reactions are discussed together with the mechanism of the skeletal rearrangement of the molecular ion of anisole prior to H˙ loss.
• Hunter, A.; Renfrew, M.; Taylor, John A., Journal of the Chemical Society. Perkin transactions II, 1993, # 10, p. 1703 - 1704
  作者：Hunter, A.、Renfrew, M.、Taylor, John A.、Whitmore, James M. J.、Williams, Andrew

  DOI：——

  日期：——