3-methoxy-2,4,5-trimethylbenzyl bromide | 158549-29-2

• 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: 3-methoxy-2,4,5-trimethylbenzyl bromide
• 英文别名: 3-(Bromomethyl)-2,5,6-trimethylanisole；1-(Bromomethyl)-3-methoxy-2,4,5-trimethylbenzene
• CAS: 158549-29-2
• 化学式: C₁₁H₁₅BrO
• 分子量: 243.143
• InChiKey: VDAPTNGSQUNXPI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-methoxy-2,4,5-trimethylbenzyl bromide 在 溴 作用下， 以 二氯甲烷 为溶剂， 反应 4.5h， 以100%的产率得到2-bromo-5-methoxy-3,4,6-trimethylbenzyl bromide
  参考文献：
  名称：

  Synthesis and Antioxidant Profile of all-rac-α-Selenotocopherol

  摘要：

  all-rac-alpha-Selenotocopherol (6c) has been synthesized in 11 steps in 6.6% total yield. Key steps include chloromethylation to approach the persubstituted aromatic 9b and cyclization of alcohol precursor 10 by radical homolytic substitution at selenium to form the selenotocopherol heterocycle. Determination of the OH bond dissociation enthalpy (BDE) of 6c by electron paramagnetic resonance (EPR) equilibration techniques gave a value of 78.1 +/- 0.3 kcal mol(-1), approximately I kcal mol(-1) higher than that of a-tocopherol. Kinetic studies performed by measuring oxygen uptake of the induced oxidation of styrene in the presence of an antioxidant showed that selenotocopherol (6c) was a slightly poorer inhibitor than (x-tocopherol, in agreement with the BDE values. In contrast to simpler setenotocopherol analogues, 6c was not regenerable in the presence of a stoichiometric coreductant in a two-phase lipid peroxidation model.

  DOI：

  10.1021/jo052133e
• 作为产物：
  描述：

  3-cyano-2,5,6-trimethylphenol 在 氢氧化钾 、 lithium aluminium tetrahydride 、 三溴化磷 、 potassium carbonate 、 乙二醇 作用下， 以 四氢呋喃 、 乙醚 、 水 、 丙酮 为溶剂， 反应 53.5h， 生成 3-methoxy-2,4,5-trimethylbenzyl bromide
  参考文献：
  名称：

  Synthesis and Antioxidant Profile of all-rac-α-Selenotocopherol

  摘要：

  all-rac-alpha-Selenotocopherol (6c) has been synthesized in 11 steps in 6.6% total yield. Key steps include chloromethylation to approach the persubstituted aromatic 9b and cyclization of alcohol precursor 10 by radical homolytic substitution at selenium to form the selenotocopherol heterocycle. Determination of the OH bond dissociation enthalpy (BDE) of 6c by electron paramagnetic resonance (EPR) equilibration techniques gave a value of 78.1 +/- 0.3 kcal mol(-1), approximately I kcal mol(-1) higher than that of a-tocopherol. Kinetic studies performed by measuring oxygen uptake of the induced oxidation of styrene in the presence of an antioxidant showed that selenotocopherol (6c) was a slightly poorer inhibitor than (x-tocopherol, in agreement with the BDE values. In contrast to simpler setenotocopherol analogues, 6c was not regenerable in the presence of a stoichiometric coreductant in a two-phase lipid peroxidation model.

  DOI：

  10.1021/jo052133e

文献信息

• Nuclear versus Side-Chain Bromination of Methyl-Substituted Anisoles by N-Bromosuccinimide
  作者：Gert-Jan M. Gruter、Otto S. Akkerman、Friedrich Bickelhaupt

  DOI：10.1021/jo00095a023

  日期：1994.8

  The reactions of methyl-substituted anisoles with N-bromosuccinimide in CCl4 are reported. In the absence of a catalyst and under irradiation, some of these substrates undergo nuclear bromination in competition with the well-known side-chain bromination. With 2-methylanisole and with 2,6-dimethylanisole, nuclear bromination is not observed, whereas with 3,5-dimethylanisole, nuclear bromination at the 4-position is the dominating reaction. Investigation of the reactivity of several other methyl-substituted anisoles revealed the following general trend: methyl-substituted anisoles are attacked at the position para to the methoxy group rather than at the side chain when (at least) two methyl groups are present at positions 3 and 5. When positions 2 and 6 are both occupied, nuclear bromination is retarded; in 2,6-dimethylanisole and in 2,3,6-trimethylanisole, only side-chain bromination is observed. In contrast, in 2,3,5,6-tetramethylanisole, the 4-position is sufficiently reactive to be brominated, because the decrease in reactivity by the presence of two methyl groups at positions 2 and 6 is overruled by the two additional methyl groups at positions 3 and 5; as a result, both nuclear and side-chain bromination occur. The observed chemospecificity can be rationalized by a difference in mechanism: the side-chain bromination is a radical reaction, while the nuclear bromination is an electrophilic aromatic substitution reaction, which is so far contrary to expectation, as irradiation had been expected to favor radical processes.
• Gruter Gert-Jan M., Akkerman Otto S., Bickelhaupt Friedrich, J. Org. Chem, 59 (1994) N 16, S 4473- 4481
  作者：Gruter Gert-Jan M., Akkerman Otto S., Bickelhaupt Friedrich

  DOI：——

  日期：——
• WO2022272133A2
  申请人：——

  公开号：WO2022272133A2

  公开（公告）日：2022-12-29
• Synthesis and Antioxidant Profile of all-<i>r</i><i>ac</i>-α-Selenotocopherol
  作者：David Shanks、Riccardo Amorati、Maria Grazia Fumo、Gian Franco Pedulli、Luca Valgimigli、Lars Engman

  DOI：10.1021/jo052133e

  日期：2006.2.1

  all-rac-alpha-Selenotocopherol (6c) has been synthesized in 11 steps in 6.6% total yield. Key steps include chloromethylation to approach the persubstituted aromatic 9b and cyclization of alcohol precursor 10 by radical homolytic substitution at selenium to form the selenotocopherol heterocycle. Determination of the OH bond dissociation enthalpy (BDE) of 6c by electron paramagnetic resonance (EPR) equilibration techniques gave a value of 78.1 +/- 0.3 kcal mol(-1), approximately I kcal mol(-1) higher than that of a-tocopherol. Kinetic studies performed by measuring oxygen uptake of the induced oxidation of styrene in the presence of an antioxidant showed that selenotocopherol (6c) was a slightly poorer inhibitor than (x-tocopherol, in agreement with the BDE values. In contrast to simpler setenotocopherol analogues, 6c was not regenerable in the presence of a stoichiometric coreductant in a two-phase lipid peroxidation model.