4-hydroxy(2',2',2'-2H3)acetophenone | 134334-11-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-hydroxy(2',2',2'-2H3)acetophenone
• CAS: 134334-11-5
• 化学式: C₈H₈O₂
• 分子量: 139.126
• InChiKey: TXFPEBPIARQUIG-FIBGUPNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.59
• 重原子数：
  10.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4-hydroxy(2',2',2'-2H3)acetophenone 在 palladium on activated charcoal 氘 作用下， 生成 4-(Ethyl-d5)phenol
  参考文献：
  名称：

  Supersonic jet studies of ethoxybenzenes: geometry of their minimum energy conformations

  摘要：

  Supersonic jet mass resolved excitation spectroscopy and MOPAC 5/AM1 calculations are employed to demonstrate that the minimum energy conformation of ethoxybenzene and a number of its ortho-unsubstituted (i.e., sterically unhindered) derivatives is the planar form for which tau-1(C(ortho)-C(ipso)-O-C-beta) = 0-degrees and tau-2(C(ipso)-O-C-beta-C-gamma) = 180-degrees. For 1-ethoxy-3-methylbenzene, two spectroscopic origin transitions are observed, one each for the conformations in which the C-beta-H2-C-gamma-H3 fragment is syn and anti to the C(3)-methyl substituent. For 1-ethoxy-4-ethylbenzene, a single origin transition is observed, as demonstrated by examination of two deuteriated derivatives.

  DOI：

  10.1021/jo00021a019
• 作为产物：
  描述：

  对羟基苯乙酮 在 氘氧化钠 、 重水 作用下， 生成 4-hydroxy(2',2',2'-2H3)acetophenone
  参考文献：
  名称：

  Supersonic jet studies of ethoxybenzenes: geometry of their minimum energy conformations

  摘要：

  Supersonic jet mass resolved excitation spectroscopy and MOPAC 5/AM1 calculations are employed to demonstrate that the minimum energy conformation of ethoxybenzene and a number of its ortho-unsubstituted (i.e., sterically unhindered) derivatives is the planar form for which tau-1(C(ortho)-C(ipso)-O-C-beta) = 0-degrees and tau-2(C(ipso)-O-C-beta-C-gamma) = 180-degrees. For 1-ethoxy-3-methylbenzene, two spectroscopic origin transitions are observed, one each for the conformations in which the C-beta-H2-C-gamma-H3 fragment is syn and anti to the C(3)-methyl substituent. For 1-ethoxy-4-ethylbenzene, a single origin transition is observed, as demonstrated by examination of two deuteriated derivatives.

  DOI：

  10.1021/jo00021a019

文献信息

• Unusual fragmentation of trimethylsilylated enols derived fromm- andp-hydroxyacetophenones
  作者：Rupert Kraus、Gerhard Spiteller

  DOI：10.1002/oms.1210241002

  日期：1989.10

  AbstractWhen 4‐hydroxyacetophenone is treated with MSTFA the corresponding bis‐trimethylsilylated enol ether (1a) is obtained. The mass spectrum of la is characterized by a [M – 1]+ base peak. Extensive deuteration experiments revealed that the hydrogen is mainly removed from a ring position, but originates also to some extent from the side chain (methylidene group) and even to a very small amount from the hydrogens of the methyl groups of the enolic trimethylsilyl group. A mechanism for this fragmentation behaviour is formulated.
• A New Procedure for Deconvolution of Inter-/Intramolecular Intrinsic Primary and α-Secondary Deuterium Isotope Effects from Enzyme Steady-State Kinetic Data
  作者：William S. McIntire、E. Thomas Everhart、John C. Craig、Vladislav Kuusk

  DOI：10.1021/ja984214g

  日期：1999.6.1

  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.