丙酸,2,2-二甲基-,(3,4,5-trimethoxyphenyl)甲基酯 | 157843-82-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 丙酸,2,2-二甲基-,(3,4,5-trimethoxyphenyl)甲基酯
• 英文名称: 3,4,5-Trimethoxybenzyl pivalate
• 英文别名: (3,4,5-Trimethoxyphenyl)methyl 2,2-dimethylpropanoate
• CAS: 157843-82-8
• 化学式: C₁₅H₂₂O₅
• 分子量: 282.337
• InChiKey: OQKKWNAUPINCEP-UHFFFAOYSA-N

物化性质

• 沸点：
  351.8±37.0 °C(Predicted)
• 密度：
  1.070±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  丙酸,2,2-二甲基-,(3,4,5-trimethoxyphenyl)甲基酯 以20%的产率得到
  参考文献：
  名称：

  Pincock J.A., Wedge P.J., J. Org. Chem., 59 (1994) N 19, 5587-5595

  摘要：

  DOI：
• 作为产物：
  描述：

  3,4,5-三甲氧基苯甲醛 在 吡啶 、 sodium tetrahydroborate 作用下， 以 甲醇 、 苯 为溶剂， 生成 丙酸,2,2-二甲基-,(3,4,5-trimethoxyphenyl)甲基酯
  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

• 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。
• PRECIPITATION PROMOTER AND PRECIPITATION METHOD IN WHICH SAME IS USED
  申请人：AJINOMOTO CO., INC.

  公开号：US20170320904A1

  公开（公告）日：2017-11-09

  Precipitation promoters, which are an organic compound having one or more linear aliphatic hydrocarbon groups having not less than 10 carbon atoms, wherein the aliphatic hydrocarbon group has not less than 20 carbon atoms in total are useful for precipitating an organic compound protected by an organic group having one or more aliphatic hydrocarbon groups having not less than 10 carbon atoms from a solvent.

  沉淀促进剂是一种有机化合物，具有一个或多个线性脂肪烃基，至少含有10个碳原子，其中脂肪烃基总计含有不少于20个碳原子，对于从溶剂中沉淀具有一个或多个脂肪烃基，至少含有10个碳原子的有机基保护的有机化合物是有用的。
• Precipitation promoter and precipitation method in which same is used
  申请人：AJINOMOTO CO., INC.

  公开号：US10464966B2

  公开（公告）日：2019-11-05

  Precipitation promoters, which are an organic compound having one or more linear aliphatic hydrocarbon groups having not less than 10 carbon atoms, wherein the aliphatic hydrocarbon group has not less than 20 carbon atoms in total are useful for precipitating an organic compound protected by an organic group having one or more aliphatic hydrocarbon groups having not less than 10 carbon atoms from a solvent.

  沉淀促进剂是具有一个或多个碳原子数不少于 10 个的线性脂肪烃基的有机化合物，其中脂肪烃基的碳原子总数不少于 20 个，可用于从溶剂中沉淀受具有一个或多个碳原子数不少于 10 个的脂肪烃基的有机基团保护的有机化合物。
• 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：——
• The Photochemistry of Methoxy-Substituted Benzyl Acetates and Benzyl Pivalates: Homolytic vs Heterolytic Cleavage
  作者：J. A. Pincock、P. J. Wedge

  DOI：10.1021/jo00098a016

  日期：1994.9

  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.