heptadeuteriotoluene | 71013-72-4

• 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: heptadeuteriotoluene
• 英文别名: toluene-d7；1,2,3,4,5-pentadeuterio-6-dideuteriomethyl-benzene；2,3,4,5,6,α,α-heptadeuterio-toluene；Heptadeuterotoluol；1,2,3,4,5-pentadeuterio-6-(dideuteriomethyl)benzene
• CAS: 71013-72-4
• 化学式: C₇H₈
• 分子量: 99.0849
• InChiKey: YXFVVABEGXRONW-QMUWOJKRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  heptadeuteriotoluene 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 为溶剂， 反应 20.0h， 生成 苄基溴-d7
  参考文献：
  名称：

  Guthrie, Robert D.; Shi, Buchang, Journal of the American Chemical Society, 1990, vol. 112, # 8, p. 3136 - 3139

  摘要：

  DOI：
• 作为产物：
  描述：

  苯基氯-d7 在 三正丁基氢锡 作用下， 生成 heptadeuteriotoluene
  参考文献：
  名称：

  Effect of the internal rotation of the CHD₂group on the aliphatic CH stretching mode of the toluenes C₆H₅CHD₂and C₆D₅CHD₂in solid crystalline phases

  摘要：

  The infrared and Raman spectra of the toluenes C6H5CHD2 and C6D5CHD2in the aliphatic CH stretching mode range have been recorded in a large temperature range (17 to 165 K) for both crystalline phases α and β. At very low temperature, the β form spectra show three bands; each of them is assigned to the vibration of a CH oscillator localized in a different site. Three groups of bands are also observed in the α phase spectra: a single band at higher frequency and two doublets at lower frequency. This splitting is assigned to the existence of two types of molecules in the unit cell, involving six different CH vibrators. A quantum theory of these spectra is carried out, assuming an anharmonic coupling of the CH stretching mode with the CHD2 torsion. As a consequence of this coupling, in the adiabatic approximation, the vibrational energy depends on the conformation and can be considered as an additional torsional potential. This latter has no ternary symmetry so that the total torsional potential has three principal unequal wells that correspond to three different locations of the CH oscillator. Therefore, no tunneling effect appears, which is in agreement with the classical interpretation. Furthermore, this theory ascribes the temperature dependence of the relative intensities of the νCH bands to the population density of the first torsional levels in the vibrational ground state and suggests that, at very low temperature, the isotopic system gets ordered. At higher temperature, a strong relaxation of the νCH vibration bands is observed. This relaxation is much stronger than that of the aromatic ring modes. Thus the relaxation process is essentially due to the influence of the anharmonic coupling between the CH stretching mode and the τCHD2 mode. Two mechanisms are considered: the first one involves Markovian jumps of the system from an equilibrium position to another one, the second one involves fluctuations of the CH vibration around each of these equilibrium positions. NMR and neutron scattering data have already been analyzed on the basis of the first process. Starting from the residence times so determined, the computations show that this mechanism is an efficient relaxation process, but indicate that it is not sufficient to fit the experimental profiles. This fit is obtained rather by using the second model with parameters of reasonable physical values; thus, the second process is also efficient. A better treatment of the relaxation process would be to elaborate; it would have to include both mechanisms and to take into account motions of the methyl group with different amplitudes.

  DOI：

  10.1063/1.443567

文献信息

• Organopotassium‐Catalyzed Silylation of Benzylic C(<i>sp</i>³)−H Bonds
  作者：Baptiste Neil、Lamine Saadi、Louis Fensterbank、Clément Chauvier

  DOI：10.1002/anie.202306115

  日期：2023.8

  Benzylsilanes have found increasing applications in organic synthesis as bench‐stable synthetic intermediates, yet are mostly produced by stoichiometric procedures. Catalytic alternatives based on the atom‐economical silylation of benzylic C(sp³)−H bonds remain scarcely available as specialized directing groups and catalytic systems are needed to outcompete the kinetically‐favored silylation of C(sp²)−H bonds. Herein, we describe the first general and catalytic‐in‐metal undirected silylation of benzylic C(sp³)−H bonds under ambient, transition metal‐free conditions using stable tert‐butyl‐substituted silyldiazenes (tBu−N=N−SiR₃) as silicon source. The high activity and selectivity of the catalytic system, exemplified by the preparation of various mono‐ or gem‐bis benzyl(di)silanes, originates from the facile generation of organopotassium reagents, including tert‐butylpotassium.

  摘要苄基硅烷作为稳定的合成中间体，在有机合成中的应用日益广泛，但大多是通过化学计量法生产的。基于苄基 C（sp3）-H 键原子经济硅烷化的催化替代品仍然很少，因为需要专门的定向基团和催化系统才能与动力学上有利的 C（sp2）-H 键硅烷化竞争。在本文中，我们首次介绍了以稳定的叔丁基取代的硅二氮（tBu-N=N-SiR3）为硅源，在无过渡金属的环境条件下，对苄基 C(sp3)-H 键进行的通用金属内催化非定向硅烷化反应。该催化系统的高活性和高选择性源于有机钾试剂（包括叔丁基钾）的简便生成，以制备各种单苄基或双苄基（二）硅烷为例。
• Formation of deuterium atoms in the pyrolysis of toluene-d8 behind shock waves. Kinetics of the reaction C7D8 + H .fwdarw. C7D7H + D
  作者：V. Subba Rao、Gordon B. Skinner

  DOI：10.1021/j150663a035

  日期：1984.9