3,5-dimethoxybenzyl pivalate | 157843-81-7

• 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: 3,5-dimethoxybenzyl pivalate
• 英文别名: (3,5-Dimethoxyphenyl)methyl 2,2-dimethylpropanoate
• CAS: 157843-81-7
• 化学式: C₁₄H₂₀O₄
• 分子量: 252.31
• InChiKey: ODDWUIWNOHATAX-UHFFFAOYSA-N

物化性质

• 沸点：
  335.5±27.0 °C(Predicted)
• 密度：
  1.052±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,5-dimethoxybenzyl pivalate 在 bis(1,5-cyclooctadiene)nickel (0) 、 sodium formate 、 1,2-双(二环己基磷基)-乙烷 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以91%的产率得到3,5-二甲氧基甲苯
  参考文献：
  名称：

  镍催化的简单甲酸钠可对C–O键进行高效选择性加氢

  摘要：

  开发了镍催化的甲酸钠对C–O化合物的加氢反应。各种催化剂，即芳基，烯基，新戊酸苄基酯，甚至芳基醚，都可以通过将镍催化剂的负载量降至0.5 mol％有效地还原。反应性官能团，例如CC双键，羰基，CN，MeS和卤素基团是可以忍受的。该反应可用于复杂分子的修饰并大规模进行。

  DOI：

  10.1039/c7cc08709h
• 作为产物：
  描述：

  3,5-二甲氧基苯甲酸 在 吡啶 、 diborane(6) 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 2.0h， 生成 3,5-dimethoxybenzyl pivalate
  参考文献：
  名称：

  The Photochemistry of Methoxy-Substituted Benzyl Acetates and Benzyl Pivalates: Homolytic vs Heterolytic Cleavage

  摘要：

  The multiple methoxy-substituted benzyl acetates (3g-i) and benzyl pivalates (4g-i) have been photolyzed in methanol solution. The products of these reactions are derived from two critical intermediates; the benzyl radical/acyloxy radical pair and the benzyl cation/carboxylate anion pair. As predicted by the meta effect, the yield of ion-derived product, the methyl ether in this case, was enhanced by the presence of the m-methoxy groups. The yield of ether, for the acetate esters, varied from 2% for the 4-methoxy-substituted ester to 66% for the 3,4,5-trimethoxy-substituted ester. In contrast, the yield of ether, for the pivalate esters, varied from <1% for the 4-methoxy-substituted ester to 20% for the 3,4,5-trimethoxy-substituted one. The meta effect does not explain these differences; electron transfer converting the radical pair to the ion pair is still an important pathway in the mechanism for ion formation. A quantitative analysis of the yield of the ethers was done in order to obtain the electron-transfer rate constants. This analysis revealed that the yield of the ethers was higher than expected based on previous results for other substituted benzyl acetates. A possible explanation for this discrepancy is that internal return of the radical pair to starting material for the acetate esters is more efficient than for the pivalate esters. Also, the esters 3k and 3l, were prepared to study the effect of electron-withdrawing groups in the meta position. For these esters, the benzylic cleavage reactions were inefficient and an isomerization reaction, the benzvalene rearrangement, was competitive.

  DOI：

  10.1021/jo00098a016

文献信息

• Nickel-catalyzed synthesis of (E)-olefins from benzylic alcohol derivatives and arylacetonitriles via C–O activation
  作者：Jing Xiao、Jia Yang、Tieqiao Chen、Li-Biao Han

  DOI：10.1039/c5cc10005d

  日期：——

  An efficient Ni-catalyzed synthesis of (E)-olefins using the readily available benzylic alcohol derivatives and arylacetonitriles is described. This transformation should proceed via a tandem process involving nickel-catalyzed cross coupling via C–O activation and subsequent stereoselective E2 elimination.

  描述了一种高效的镍催化合成方法，使用易得的苄基醇衍生物和芳基乙腈合成(E)-烯烃。这种转化应该通过涉及镍催化的交叉偶联，通过C-O活化和随后的立体选择性E2消除的串联过程进行。
• Metal-Free Reductive Cleavage of Benzylic Esters and Ethers: Fragmentations Result from Single and Double Electron Transfers
  作者：Eswararao Doni、Steven O'Sullivan、John A. Murphy

  DOI：10.1002/anie.201208066

  日期：2013.2.18

  The mechanisms for the reductive cleavage of benzylic esters and ethers by neutral organic electron donor 1 are different (see scheme). Products isolated from the cleavage of benzylic ethers result from the transfer of two electrons, without the intermediacy of benzyl radicals, which are believed to be intermediates in the reductive cleavage of benzylic esters.

  中性有机电子给体1对苄基酯和醚进行还原性裂解的机理是不同的（请参见方案）。从苄基醚的裂解中分离出的产物是由两个电子的转移产生的，而没有苄基的中间体，而苄基被认为是苄基酯的还原裂解的中间体。
• Pincock J.A., Wedge P.J., J. Org. Chem., 59 (1994) N 19, 5587-5595
  作者：Pincock J.A., Wedge P.J.

  DOI：——

  日期：——