α-trideuteriomethyl-4-methyl-benzyl alcohol | 56248-27-2

• 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: α-trideuteriomethyl-4-methyl-benzyl alcohol
• CAS: 56248-27-2
• 化学式: C₉H₁₂O
• 分子量: 139.17
• InChiKey: JESIHYIJKKUWIS-BMSJAHLVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.05
• 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：
  0.33
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  α-trideuteriomethyl-4-methyl-benzyl alcohol 在 五氟化锑 、 氟磺酸 作用下， 以 various solvent(s) 为溶剂， 生成
  参考文献：
  名称：

  Deuterium isotope effects on the carbon-13 chemical shifts of carbocations

  摘要：

  DOI：

  10.1021/ja00544a010
• 作为产物：
  描述：

  d3-4-methylacetophenone 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 α-trideuteriomethyl-4-methyl-benzyl alcohol
  参考文献：
  名称：

  Effects of deuterium substitution on the rates of organic reactions. XI. .alpha.- and .beta.-Deuterium effects on the solvolysis rates of a series of substituted 1-phenylethyl halides

  摘要：

  DOI：

  10.1021/ja01004a037

文献信息

• β-Deuterium kinetic isotope effects for identity processes: bromide ion substitution at 1-bromo-1-arylethanes and 2-bromooctane
  作者：Allan R. Stein

  DOI：10.1139/v94-227

  日期：1994.8.1

  While deuterium kinetic isotope effects for solvolyses have been extensively studied, other nucleophilic substitutions have received less attention, and identity processes, that is, substitutions where the nucleophile and leaving group are the same, have rarely been examined. Identity reactions must pass through a truly symmetrical stage, a transition state or an intermediate, so that data will be of interest to both theoretical and experimental chemists. Values of k_H/k_D have been determined by polarimetry for bromide exchange– racemization at ArCHBrCH₃/CD₃ (Ar = C₆H₅,4-Br- and 4-Me-C₆H₄, and 3,4,-dimethyl-C₆H₃) in acetone, acetonitrile, and nitromethane. Observed values are analogous to values seen in solvolyses. They range from 1.01 to 1.35 and, in some cases, increase markedly as the concentration of Bu₄NBr decreases. Solvolyses are either first order or pseudo first order whereas plotting observed racemization rate versus [Bu₄NBr] allows separation of first- and second-order components; those species giving more stable carbocations in the more dipolar solvents, the systems showing k_H/k_D variation with Br⁻ concentration, alone show an appreciable first-order component. The second-order k_H/k_D ratio averages 1.062 ± −0.018 at temperatures ranging from 25 to 50 °C for all substrates in the three solvents, very analogous to the values seen for racemization of 1,1,1-d₃-2-bromooctane or solvolysis of ethyl substrates but considerably lower than the typical solvolysis values of 1.15–1.25 for secondary, and 1.35–1.5 for tertiary substrates. The first-order k_H/k_D values obtained are higher, 1.1–1.5. These and other results are discussed.

  尽管已经广泛研究了溶剂解离中氘动力学同位素效应，但其他亲核取代反应受到的关注较少，而同一过程，即亲核取代反应中亲核试剂和离去基团相同的反应则很少被研究。同一反应必须经过一个真正对称的阶段，一个过渡态或一个中间体，因此这些数据将对理论化学家和实验化学家都具有兴趣。通过极化测定已确定了在丙酮、乙腈和硝基甲烷中对ArCHBrCH₃/CD₃（Ar = C₆H₅、4-Br- 和 4-Me-C₆H₄，以及 3,4,-dimethyl-C₆H₃）进行溴化物交换-消旋化的k_H/k_D值。观察到的数值类似于在溶剂解离中观察到的数值。它们的范围从1.01到1.35，在某些情况下，随着Bu₄NBr浓度的降低而显著增加。溶剂解离要么是一阶的，要么是伪一阶的，而绘制观察到的消旋化速率与[Bu₄NBr]的图表允许分离一阶和二阶组分；那些在极性溶剂中产生更稳定的碳阳离子的物种，那些显示与Br⁻浓度变化有关的k_H/k_D变化的系统，仅显示明显的一阶组分。在温度范围从25到50°C的三种溶剂中，所有底物的二阶k_H/k_D比率平均为1.062 ± -0.018，这与1,1,1-d₃-2-溴辛烷的消旋化或乙基底物的溶解反应所见的数值非常类似，但远低于二级底物的典型溶解数值1.15-1.25和三级底物的1.35-1.5。得到的一阶k_H/k_D值较高，为1.1-1.5。这些和其他结果进行了讨论。
• The Ei Reaction of Substituted<i>threo</i>- and<i>erythro</i>-1-Phenylethyl Phenyl Sulfoxides
  作者：Toshiaki Yoshimura、Eiichi Tsukurimichi、Yukihiko Iizuka、Hironobu Mizuno、Hiroshi Isaji、Choichiro Shimasaki

  DOI：10.1246/bcsj.62.1891

  日期：1989.6

  Substituted (RS,SR)-1-phenylethyl phenyl sulfoxides (threo) (XC6H4S(O)CH(CH3)C6H4Y) and some substituted (RR,SS)-sulfoxides (erythro) were prepared and kinetic investigation for the thermal decomposition was carried out at 80.0, 90.0, and 100.0 °C in dioxane. Hammett plots for threo-XC6H4S(O)CH(CH3)C6H5 gave positive ρ-values (ρX=0.60–0.64 at three temperatures), while those for threo- and erythro

  制备了取代的 (RS,SR)-1-苯乙基苯基亚砜 (threo) (XC6H4S(O)CH(CH3)C6H4Y) 和一些取代的 (RR,SS)-亚砜 (erythro) 并进行了热分解动力学研究在二恶烷中分别在 80.0、90.0 和 100.0 °C 下进行测试。苏式-XC6H4S(O)CH(CH3)C6H5 的哈米特图给出了正 ρ 值（三种温度下的 ρX=0.60–0.64），而苏式和赤式 C6H5S(O)CH(CH3)C6H4Y 的哈米特图给出了正的 ρ 值（ρX=0.60–0.64）尽管取代基的影响很小，但在 m-OCH3 取代基处形成带有底部的线条。同时，在所有温度下都观察到苏-和赤-C6H5S(O)CH(CD3)C6H4Y（Y=H，p-OMe，m-Cl）（kH⁄kD=4-6）的大动力学同位素效应。所有亚砜的活化能在 104-121 kJ mol-1 的范围内，而激活熵相对较大（7-37
• Solvolysis of 1-alkyl-1-chloro-1-(4-methyl)phenylmethanes. Nucleophilic solvent intervention and extendedYBnCl scale
  作者：Kwang-Ting Liu、Lih-Wie Chang、Der-Gann Yu、Png-Shao Chen、Ju-Ta Fan

  DOI：10.1002/(sici)1099-1395(199712)10:12<879::aid-poc879>3.0.co;2-k

  日期：1997.12

  The solvolysis of 1-alkyl-1-chloro-1-(4-methyl)phenylmethanes (4a-d) in aqueous acetone, aqueous ethanol, aqueous methanol and ethanol-trifluoroethanol was studied. Grunwald-Winstein-type correlation analysis using the Y-BnCl scale suggests significant nucleophilic solvent intervention in the ease of 1-chloro-1-(4-methyl)phenylethane (4a). Increasing bulkiness of the 1-alkyl substituent from methyl (4a) to ethyl (4b), to isopropyl (4c) and to tert-butyl (4d) resulted in a gradual change to limiting S(N)1 mechanisms. The observed excellent linear correlations with Y-BnCl and the good solubility in high-water-containing binary solvents made 4d a suitable reference standard For deriving more Y-BnCl values. A positive azide salt effect was realized in the solvolysis of 4a but not 4d. A small decrease in the beta-deuterium kinetic Isotope effect from 4a to 1-chloro-1-(4-methoxyphenyl)propane (5) suggested the presence of additional stabilization of the benzylic cationic transition state. However, no relationship between k(CH3)/k(CD3) and the solvent effect was found. The superiority of employing the Y-BnCl scale over the combination of Y-Cl and I scales in the mehanistic study was observed. (C) 1997 John Wiley & Sons, Ltd.
• Effects of deuterium substitution on the rates of organic reactions. XI. .alpha.- and .beta.-Deuterium effects on the solvolysis rates of a series of substituted 1-phenylethyl halides
  作者：V. J. Shiner、W. E. Buddenbaum、B. L. Murr、G. Lamaty

  DOI：10.1021/ja01004a037

  日期：1968.1
• Deuterium isotope effects on the carbon-13 chemical shifts of carbocations
  作者：Kenneth L. Servis、Feng-Fang Shue

  DOI：10.1021/ja00544a010

  日期：1980.11