4-氯-alpha,alpha-二甲基苄醇 | 1989-25-9

• 物质功能分类: 有机原料 - 醇、酚、酚醇类化合物及衍生物
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 4-氯-alpha,alpha-二甲基苄醇
• 英文名称: 4-chlorocumyl alcohol
• 英文别名: 2-(4-chlorophenyl)propan-2-ol；2-(4-chlorophenyl)-2-propanol；2-(4-Chlor-phenyl)-propan-2-ol；<4-Chlor-phenyl>-dimethyl-carbinol；(4-Chlor-phenyl)-dimethylcarbinol
• CAS: 1989-25-9
• 化学式: C₉H₁₁ClO
• mdl: MFCD11870102
• 分子量: 170.639
• InChiKey: JQZCRSDZIWKYBF-UHFFFAOYSA-N

物化性质

• 熔点：
  31-32 °C
• 沸点：
  92-96 °C
• 密度：
  1.144±0.06 g/cm3(Predicted)
• 溶解度：
  溶于甲醇

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.333
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

安全信息

• 海关编码：
  2906299090
• 储存条件：
  室温且干燥

反应信息

• 作为反应物：
  描述：

  4-氯-alpha,alpha-二甲基苄醇 在 乙醇 、 铂 作用下， 生成 1-氯-4-丙-2-基苯
  参考文献：
  名称：

  The Coupling Action of the Grignard Reagent. V. The Influence of the Halogen Atom of the Reagent

  摘要：

  DOI：

  10.1021/ja01334a057
• 作为产物：
  描述：

  对氯甲基苯乙烯 在 氧气 、 potassium carbonate 、 异丙醇 作用下， 150.0 ℃ 、400.01 kPa 条件下， 反应 12.0h， 以99%的产率得到4-氯-alpha,alpha-二甲基苄醇
  参考文献：
  名称：

  Isopropanol as a hydrogen source for single atom cobalt-catalyzed Wacker-type oxidation

  摘要：

  第一个以单原子钴催化剂在二氧化碳下利用异丙醇作为氢源进行的Wacker型氧化反应的示例被建立。

  DOI：

  10.1039/d0cy00409j

文献信息

• Oxidation of Tertiary Aromatic Alcohols to Ketones in Water
  作者：Dengfeng Chen、Yuchen Zhang、Xingyu Pan、Fei Wang、Shenlin Huang

  DOI：10.1002/adsc.201800612

  日期：2018.9.17

  A new rosin‐based amphiphile enables the oxidation of tertiary aromatic alcohols in water under mild conditions. The oxidation process is mediated by β‐scission of alkoxy radicals. Our catalyst system including the surfactant, catalysts, and water can be easily recycled within the same reaction vial.

  一种新的基于松香的两亲物能够在温和条件下氧化水中的芳族叔醇。氧化过程是由烷氧基的β断裂介导的。我们的催化剂体系，包括表面活性剂，催化剂和水，可以在同一反应瓶中轻松回收。
• Kinetics and Mechanism of Acid Catalysed Hydration of α-Methylstyrenes
  作者：Oldřich Pytela、Bronislav Trlida

  DOI：10.1135/cccc20071025

  日期：——

  Twelve para-substituted α-methylstyrenes with substituents H, CH₃, CF₃, CH₃O, CH₃S, F, Cl, Br, CH₃CO, CH₃SO₂, CN a NO₂ were synthesised; additionally, the acid catalysed hydration kinetics of these compounds were measured in sulfuric acid in a concentration range c from 0.017 to 9.58 mol l^-1, at 25.0 °C. The observed rate constants obtained were used to construct the kinetic acidity function and calculate the catalytic rate constants. Based on the evaluation of the acidity function kinetic dependence on acid medium concentration, and the substituent effects of acid catalysed hydration of α-methylstyrenes on the catalytic rate constants, the mechanism of acid catalysed hydration was verified. The mechanism involves the addition of a proton to the double bond of α-methylstyrene in the rate-limiting reaction step denoted as A-SE2. No evident difference was found between the effects of the acid medium on the acid catalysed hydration of styrenes and α-methylstyrenes, which indicates very similar activity coefficients of the reactants, and of the transition state of both substrates. The substituent effects evaluation shows that the rate-limiting step of the reaction consists in the addition of a proton to the substrate. The carbocation formation in the transition state of this reaction step proceeds roughly half-way compared with the extent of the carbocation formation by cumyl chloride hydrolysis. The obtained carbocation is in particular stabilised by the substituents with +M effect, while the influence of the substituents with -M and I effects is significantly smaller.

  十二种带有取代基H、CH₃、CF₃、CH₃O、CH₃S、F、Cl、Br、CH₃CO、CH₃SO₂、CN和NO₂的α-甲基苯乙烯被合成；此外，在浓度范围从0.017到9.58摩尔/升的硫酸中，测量了这些化合物的酸催化水合动力学。所得到的观察速率常数被用来构建动力学酸度函数并计算催化速率常数。通过评估酸性函数动力学对酸性介质浓度的依赖性，以及α-甲基苯乙烯的酸催化水合反应的取代基效应对催化速率常数的影响，验证了酸催化水合的机理。该机理涉及在速率限制的反应步骤中向α-甲基苯乙烯的双键加入质子，被标记为A-SE2。在酸性介质对苯乙烯和α-甲基苯乙烯的酸催化水合的影响之间没有明显差异，这表明反应物和两种底物的过渡态的活性系数非常相似。取代基效应评估显示，反应的速率限制步骤在向底物加入质子时发生。与叔丁基氯化物水解形成的碳正离子相比，该反应步骤的过渡态中的碳正离子形成大致进行了一半。所得到的碳正离子特别受到具有+M效应的取代基的稳定作用，而具有-M和I效应的取代基的影响则明显较小。
• Selective reaction of benzyl alcohols with HI gas: Iodination, reduction, and indane ring formations
  作者：Shoji Matsumoto、Masafumi Naito、Takehisa Oseki、Motohiro Akazome、Yasuhiko Otani

  DOI：10.1016/j.tet.2017.11.009

  日期：2017.12

  Reactions of benzyl alcohols with HI in solvent-free conditions were examined. Three types of reactions (iodination, reduction, and ring formation) occurred depending on the degree of crowding around the benzyl position and the benzylic stabilization of substrates. Results also showed that the ring formation to give indanes proceeded efficiently when HI was used, and that compounds with electron-rich

  在无溶剂条件下检查了苄醇与HI的反应。发生三种类型的反应（碘化，还原和成环），具体取决于围绕苄基位置的拥挤程度和底物的苄基稳定性。结果还表明，当使用HI时，形成茚满的环的形成有效地进行，并且具有富电子芳族环的化合物以良好的收率得到茚满衍生物。
• Tertiary alkoxyl radicals from 3-alkoxythiazole-2(3H)-thiones
  作者：Christine Schur、Nina Becker、Uwe Bergsträßer、Thomas Gottwald、Jens Hartung

  DOI：10.1016/j.tet.2010.12.071

  日期：2011.3

  2-methyl-5-phenylpent-2-oxyl to 2-hydroxy-2-methyl-5-phenylpent-5-yl radical isomerization (1,5-H-atom shift; k=0.4–1.5×108 s−1). The reactions pose key steps in synthesis of 2,2,5-substituted tetrahydrofurans and 2-bromo-3-alkoxybicyclo[2.2.1]heptanes. Stereoselectivity in 5-exo-trig cyclization (2,5-cis) and intermolecular addition (exo/endo>99:1), originates from torsional strain in transition structures of alkoxyl

  这项研究涉及的合成叔- Ø烷基thiohydroxamates及其作为叔-烷氧基自由基前体。将叔烷氧基自由基用于机理研究中，以确定（i）对双环[2.2.1]庚烯（k = 1×10 7  M -1  s -1），（ii）2-的对氯枯基氧基自由基的速率常数苯基己-5-烯-2-氧基自由基-5-外- TRIG -cyclization（ķ顺式= 3×10 9 小号-1，ķ反式= 1×10 9 小号-1）和（iii）2-甲基-5-苯基戊-2-氧基转变为2-羟基-2-甲基-5-苯基戊-5-基的自由基异构化（1,5-H原子位移；k = 0.4-1.5 ×10 8  s -1）。该反应是合成2,2,5-取代的四氢呋喃和2-溴-3-烷氧基双环[2.2.1]庚烷的关键步骤。5- exo - trig环化（2,5-cis）和分子间加成（exo / endo > 99：1）的立体选择性源自烷氧基自由基反应过渡结构中的扭转应变。
• Synthesis of Isochromene and Related Derivatives by Rhodium-Catalyzed Oxidative Coupling of Benzyl and Allyl Alcohols with Alkynes
  作者：Keisuke Morimoto、Koji Hirano、Tetsuya Satoh、Masahiro Miura

  DOI：10.1021/jo201923d

  日期：2011.11.18

  The straightforward synthesis of isochromene derivatives and related cyclic ethers is achieved by the rhodium-catalyzed oxidative coupling of α,α-disubstituted benzyl and allyl alcohols with alkynes. The hydroxy groups effectively act as the key function for the regioselective C–H bond cleavage.

  异戊二烯衍生物和相关环醚的直接合成是通过铑催化的α，α-二取代的苄基和烯丙醇与炔烃的氧化偶联。羟基有效地充当了区域选择性C–H键裂解的关键功能。

表征谱图