4-(2H2)methylanisole | 131088-93-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-(2H2)methylanisole
• 英文别名: 1-(dideuteriomethyl)-4-methoxybenzene
• CAS: 131088-93-2
• 化学式: C₈H₁₀O
• 分子量: 124.151
• InChiKey: CHLICZRVGGXEOD-DICFDUPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.0
• 重原子数：
  9.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  4-(2H2)methylanisole 在 氢溴酸 作用下， 生成 4-(2H2)methylphenol
  参考文献：
  名称：

  A New Procedure for Deconvolution of Inter-/Intramolecular Intrinsic Primary and α-Secondary Deuterium Isotope Effects from Enzyme Steady-State Kinetic Data

  摘要：

  The A(2)B(2) flavocytochrome p-cresol methylhydroxylase (PCMH) from Pseudomonas putida oxidizes 4-methylphenol (p-cresol) to 4-hydroxybenzyl alcohol in a process requiring scission of an a-C-H bond with concomitant reduction of covalently bound FAD in each A subunit. Values of k(cat)/K were determined from steady-state kinetic data for the reactions of PCMH with the following substrates: 4-methylphenol, 4-(H-2(1))methylphenol, 4-(H-2(2))methylphenol, and 4-(H-2(3))methylphenol. A procedure was devised to extract the intrinsic primary deuterium and intrinsic alpha-secondary deuterium kinetic isotope effects from these values of k(cat)/K. The primary effect, P, is 6.71 +/- 0.08, and the secondary effect, S, is 1.013 +/- 0.014. The magnitudes of these effects are discussed in terms of an early or late transition state, hydrogen tunneling, coupled motion between the leaving and remaining hydrogens of the methyl group, and a H- expulsion mechanism versus a substrate radical mechanism versus a covalent substrate-FAD intermediate mechanism. The reaction of 4-ethylphenol with PCMH produces 4-vinylphenol and (-)-S-1-(4-hydroxyphenyl)ethanol (similar to 100% enantomeric excess). The evidence indicates that these are formed from a common intermediate, presumably a p-quinone methide. From the partition ratios for the formation of the alcohol and 4-vinylphenol from 4-ethylphenol, 4-(1',1'-H-2(2))ethylphenol, and 4-(2',2',2'-H-2(3))ethylphenol, the primary isotope effect for conversion of the p-quinone (2',2',2' 2H3)methide to 4-(2',2'-H-2(2))vinylphenol was estimated to be about 2, and the a-secondary isotope effect for conversion of p-quinone (1'-H-2(1))methide to 1-(4-hydroxyphenyl)-(1'-H-2(1))ethanol was found to be inverse (=0.83), as expected for sp(2) to sp(3) hybridization change at the alpha-carbon. Values of k(cat)/K were determined for 4-ethylphenol, R,S-(+/-)-4-(1'-H-2(1))ethylphenol (abbreviated R,S-D), S-(-)-4-(1'-H-2(1))ethylphenol (S-D), R-(+)4-(1'-H-2(1))ethylphenol (R-D), and 4-(1',1'-H-2(2))ethylphenol (D2). The (D2)(k(cat)/K) value was found to be 5.1-6.1, the same as determined in an earlier study. Unexpectedly, the values for (R,S-D)(k(cat)/K), (S-D)(k(cat)/K), and (R-D)(k(cat)/K) were all about the same (similar to 1.7), indicating that then is nearly an equal probability for pro-R or pro-S C-H bond scission. An apparent flux ratio for the pro-S path/pro-R path was estimated to be 0.78 +/- 0.02. The same procedure devised to determine values for P and S for 4-methylphenol was used to determine these values for the 4-ethylphenol reaction (commitment to catalysis = 0); P = 5.98 +/- 0.12 and S = 0.967 +/- 0.021. These values are essentially the same as those determined for 4-methylphenol. Thus, the chemical mechanisms for both substrates are assumed to be similar.

  DOI：

  10.1021/ja984214g
• 作为产物：
  描述：

  rac-[α-(2)H]-p-methoxybenzyl alcohol 在 吡啶 、 硼氘化锂 、 氯化亚砜 作用下， 生成 4-(2H2)methylanisole
  参考文献：
  名称：

  Holland, Herbert L.; Brown, Frances M.; Conn, Morgan, Journal of the Chemical Society. Perkin transactions II, 1990, # 10, p. 1651 - 1655

  摘要：

  DOI：

文献信息

• Selectivity Control in Photocatalytic Transfer Hydrogenation of Bio‐based Aldehydes
  作者：Hongmei Fu、Haijun Chen、Beibei Gao、Tianliang Lu、Yunlai Su、Lipeng Zhou、Meijiang Liu、Hongji Li、Xiaomei Yang

  DOI：10.1002/cctc.202200120

  日期：2022.7.7

  Hydrodeoxygenation and reductive etherification of biomass-derived aldehydes were realized on the same Pd/TiO2 photocatalyst via photocatalytic transfer hydrogenation using aliphatic alcohols as hydrogen donor, and the selectivity was easily switched by the substrate concentration.

  在同一Pd/TiO 2光催化剂上，以脂肪醇为供氢体，通过光催化转移氢化，实现了生物质醛的加氢脱氧和还原醚化，选择性容易通过底物浓度进行切换。
• HOLLAND, HERBERT L.;BROWN, FRANCES;M.;CONN, MORGAN, J. CHEM. SOC. PT 2. PERKIN TRANS.,(1990) N0, C. 1651-1655
  作者：HOLLAND, HERBERT L.、BROWN, FRANCES、M.、CONN, MORGAN

  DOI：——

  日期：——