tert-butylbenzene-phenyl-d5 | 56247-40-6

• 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: tert-butylbenzene-phenyl-d5
• 英文别名: t-Butyl-(pentadeuterobenzol)；tert-butyl-pentadeuterio-benzene；1-Tert-butyl-2,3,4,5,6-pentadeuteriobenzene
• CAS: 56247-40-6
• 化学式: C₁₀H₁₄
• 分子量: 139.181
• InChiKey: YTZKOQUCBOVLHL-UPKDRLQUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tert-butylbenzene-phenyl-d5 、 以 四氢呋喃 为溶剂， 生成 叔丁基苯 、
  参考文献：
  名称：

  平衡同位素效应的线性自由能关系

  摘要：

  The solution electron affinities of a series of monosubstituted phenyl-d5 benzenes relative to their perprotiated analogues were measured via electron paramagnetic resonance studies. The equilibrium constant for the electron transfer X-C6H5.- + X-C6D5 half-arrow-right-over-half-arrow-left X-C6H5 + X-C6D5.-, where X = H, C6D5, CN, NO2, OCH3, tert-butyl, was found to be less than unity for all cases. However, this equilibrium constant is closer to unity for those systems where the substituent is electron withdrawing in nature, and it deviates further from unity for those systems that have an electron-donating group as the substituent. A linear free energy relationship was found, and the positive rho value (0.34) is presumably due to the fact that there is a smaller excess charge and spin density from the antibonding electron in the area of the molecule where isotopic substitution takes place, for those systems where the sigma value of the substituent is positive.

  DOI：

  10.1021/j100155a075
• 作为产物：
  描述：

  叔丁基苯 在 6-甲基烟酸甲酯 、 1,1,1,3,3,3-六氟-2-丙烷 、 palladium diacetate 、 silver fluoride 、 N-乙酰甘氨酸 作用下， 反应 24.0h， 生成 tert-butylbenzene-phenyl-d5
  参考文献：
  名称：

  钯催化芳烃非定向后期 C-H 氘化

  摘要：

  我们描述了钯催化的芳烃非定向后期氘化。关键方面包括使用D 2 O作为方便且容易获得的氘源以及发现含有N-酰基磺酰胺基团的高活性N,N-二齿配体。报道的方案通过可逆的 C-H 激活步骤实现了高度的氘掺入，并具有非凡的官能团耐受性，允许复杂底物的氘化。各种药学相关基序和相关支架的后期同位素标记就是例证。我们预计这种方法以及其他应用将被证明作为药物开发过程和机制研究的有用工具。

  DOI：

  10.1021/jacs.1c08233

文献信息

• Hidden Brønsted Acid Catalysis: Pathways of Accidental or Deliberate Generation of Triflic Acid from Metal Triflates
  作者：Tuan Thanh Dang、Florian Boeck、Lukas Hintermann

  DOI：10.1021/jo201631x

  日期：2011.11.18

  The generation of a hidden Bronsted acid as a true catalytic species in hydroalkoxylation reactions from metal precatalysts has been clarified in case studies. The mechanism of triflic acid (CF3SO3H or HOTf) generation starting either from AgOTf in 1,2-dichloroethane (DCE) or from a Cp*RuCl2/AgOTf/phosphane combination in toluene has been elucidated. The deliberate and controlled generation of HOTf from AgOTf and cocatalytic amounts of tert-butyl chloride in the cold or from AgOTf in DCE at elevated temperatures results in a hidden Bronsted acid catalyst useful for mechanistic control experiments or for synthetic applications.
• Effect of Solvent and Ancillary Ligands on the Catalytic H/D Exchange Reactivity of Cp*Ir^III(L) Complexes
  作者：Matthew C. Lehman、J. Brannon Gary、Paul D. Boyle、Melanie S. Sanford、Elon A. Ison

  DOI：10.1021/cs400420n

  日期：2013.10.4

  The reactivity of a series of Cp*Ir-III(L) complexes that contain a diverse set of ancillary ligands, L, (L = PMe3, N-heterocyclic carbene, NHC = 1,3-dimethylimidazol-2-ylidene, aqua, 4-t-butylpyridine, and 4-(2,4,6-tris-(4-t-butylphenyl)pyridinium)pyridine tetrafluoroborate) has been, examined in catalytic H/D exchange reactions between C6H6 and a series of deuterated solvents (methanol-d(4), acetic acid-d(4), and trifluoroacetic acid-d(1)). These studies demonstrate that (1) the mechanism of catalytic H/D exchange is significantly influenced by the nature of the solvent; (2) electron-donating ligands (PMe3, NHC) promote the formation of Ir hydrides in methanol-d(4), and these are critical intermediates in catalytic H/D exchange processes, and (3) weak/poorly donating ligands (4-t-butylpyridine, 4-(2,4,6-tris-(4-t-butylphenyl)pyridinium)pyridine tetrafluoroborate and aqua) can support efficient H/D exchange catalysis in acetic acid-d(4).
• Palladium-Catalyzed Nondirected Late-Stage C–H Deuteration of Arenes
  作者：Mirxan Farizyan、Arup Mondal、Sourjya Mal、Fritz Deufel、Manuel van Gemmeren

  DOI：10.1021/jacs.1c08233

  日期：2021.10.13

  We describe a palladium-catalyzed nondirected late-stage deuteration of arenes. Key aspects include the use of D2O as a convenient and easily available deuterium source and the discovery of highly active N,N-bidentate ligands containing an N-acylsulfonamide group. The reported protocol enables high degrees of deuterium incorporation via a reversible C–H activation step and features extraordinary functional

  我们描述了钯催化的芳烃非定向后期氘化。关键方面包括使用D 2 O作为方便且容易获得的氘源以及发现含有N-酰基磺酰胺基团的高活性N,N-二齿配体。报道的方案通过可逆的 C-H 激活步骤实现了高度的氘掺入，并具有非凡的官能团耐受性，允许复杂底物的氘化。各种药学相关基序和相关支架的后期同位素标记就是例证。我们预计这种方法以及其他应用将被证明作为药物开发过程和机制研究的有用工具。
• A linear free energy relationship for an equilibrium isotope effect
  作者：Cheryl D. Stevenson、Glenn C. Wehrmann、Richard C. Reiter

  DOI：10.1021/j100155a075

  日期：1991.1.1

  The solution electron affinities of a series of monosubstituted phenyl-d5 benzenes relative to their perprotiated analogues were measured via electron paramagnetic resonance studies. The equilibrium constant for the electron transfer X-C6H5.- + X-C6D5 half-arrow-right-over-half-arrow-left X-C6H5 + X-C6D5.-, where X = H, C6D5, CN, NO2, OCH3, tert-butyl, was found to be less than unity for all cases. However, this equilibrium constant is closer to unity for those systems where the substituent is electron withdrawing in nature, and it deviates further from unity for those systems that have an electron-donating group as the substituent. A linear free energy relationship was found, and the positive rho value (0.34) is presumably due to the fact that there is a smaller excess charge and spin density from the antibonding electron in the area of the molecule where isotopic substitution takes place, for those systems where the sigma value of the substituent is positive.