2-甲基-2'-[羟基(苯基)甲基]联苯 | 1059502-57-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 中文名称: 2-甲基-2'-[羟基(苯基)甲基]联苯
• 英文名称: 2-methyl-2'-[hydroxyl(phenyl)methyl]biphenyl
• 英文别名: 2-methyl-2-((hydroxy)phenylmethyl)biphenyl；[2-(2-Methylphenyl)phenyl]-phenylmethanol
• CAS: 1059502-57-6
• 化学式: C₂₀H₁₈O
• 分子量: 274.362
• InChiKey: WQVSVBBCLKEBII-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-甲基-2'-[羟基(苯基)甲基]联苯 在 五氯化磷 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以56%的产率得到2-(α-chlorophenylmethyl)-2'-methylbiphenyl
  参考文献：
  名称：

  Intramolecular reactivity of arylcarbenes: Biphenyl-2-ylcarbenes

  摘要：

  Biphenyl-2-ylcarbenes, 2-ArC(6)H(4)CR, were generated photolytically and thermally from diazo precursors. Cyclization, leading to fluorenes, competes with capture of the carbenes by methanol but proceeds faster than intramolecular hydrogen shifts (with R = Me) and intermolecular C-H insertion reactions (with R = H in cyclohexane). By comparison of product ratios with kinetic data for related carbenes from the literature, the cyclization rate is estimated as ca 10(11) s(-1). The intramolecular reactivity of biphenyl-2-ylcarbenes is nor significantly attenuated by variation of R (R = H, Me, Ph). Very minor effects of triplet sensitization and methanol quenching indicate that fluorenes arise from spin-equilibrated biphenyl-2-ylcarbenes, presumably from the singlet state. When Ar = mesityl, the carbene predominantly inserts into C-H bonds of the 2'-methyl groups, giving rise to a dihydrophenanthrene. Formation of a fluorene derivative, by formal insertion into C-C bonds, occurs as a minor process. This unprecedented reaction points to intervention of an o-xylylene in which the methyl group migrates. Laser flash photolysis (LFP) of 2-PhC(6)H(4)CN(2)Ph generates a transient absorption which is due to the T-0-->T-n transition of 9-phenylfluorene rather than to the presumed o-xylylene. On LFP of 2-ArC(6)H(4)CN(2)Ph in trifluoroethanol-acetonitrile, protonation of the carbenes gives rise to carbocations, 2-ArC(6)H(4)CH(+)Ph. The transient absorption spectra of these cations are strongly influenced by twisting about the Ar-Ar bond (Ar = Ph < o-tolyl < mesityl) whereas the rates of nucleophilic capture vary only slightly. Biphenyl-2-ylcarbenium ions (Ar = R = Ph) cyclize more slowly than the analogous carbenes, by a factor of greater than or equal to 10(4).

  DOI：

  10.1002/(sici)1099-1395(199609)9:9<598::aid-poc825>3.0.co;2-l
• 作为产物：
  描述：

  邻甲苯基溴化镁 在 盐酸 、 sodium hydroxide 、 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 2-甲基-2'-[羟基(苯基)甲基]联苯
  参考文献：
  名称：

  Intramolecular reactivity of arylcarbenes: Biphenyl-2-ylcarbenes

  摘要：

  Biphenyl-2-ylcarbenes, 2-ArC(6)H(4)CR, were generated photolytically and thermally from diazo precursors. Cyclization, leading to fluorenes, competes with capture of the carbenes by methanol but proceeds faster than intramolecular hydrogen shifts (with R = Me) and intermolecular C-H insertion reactions (with R = H in cyclohexane). By comparison of product ratios with kinetic data for related carbenes from the literature, the cyclization rate is estimated as ca 10(11) s(-1). The intramolecular reactivity of biphenyl-2-ylcarbenes is nor significantly attenuated by variation of R (R = H, Me, Ph). Very minor effects of triplet sensitization and methanol quenching indicate that fluorenes arise from spin-equilibrated biphenyl-2-ylcarbenes, presumably from the singlet state. When Ar = mesityl, the carbene predominantly inserts into C-H bonds of the 2'-methyl groups, giving rise to a dihydrophenanthrene. Formation of a fluorene derivative, by formal insertion into C-C bonds, occurs as a minor process. This unprecedented reaction points to intervention of an o-xylylene in which the methyl group migrates. Laser flash photolysis (LFP) of 2-PhC(6)H(4)CN(2)Ph generates a transient absorption which is due to the T-0-->T-n transition of 9-phenylfluorene rather than to the presumed o-xylylene. On LFP of 2-ArC(6)H(4)CN(2)Ph in trifluoroethanol-acetonitrile, protonation of the carbenes gives rise to carbocations, 2-ArC(6)H(4)CH(+)Ph. The transient absorption spectra of these cations are strongly influenced by twisting about the Ar-Ar bond (Ar = Ph < o-tolyl < mesityl) whereas the rates of nucleophilic capture vary only slightly. Biphenyl-2-ylcarbenium ions (Ar = R = Ph) cyclize more slowly than the analogous carbenes, by a factor of greater than or equal to 10(4).

  DOI：

  10.1002/(sici)1099-1395(199609)9:9<598::aid-poc825>3.0.co;2-l

文献信息

• Selective Monolithiation of Dibromobiaryls Using Microflow Systems
  作者：Aiichiro Nagaki、Naofumi Takabayashi、Yutaka Tomida、Jun-ichi Yoshida

  DOI：10.1021/ol8015572

  日期：2008.9.18

  Selective monolithiation of dibromobiaryls, such as 2,2'-dibromobiphenyl, 4,4'-dibromobiphenyl, 2,7-dibromo-9,9-dioctylfluorene, 2,2'-dibromo-1,1'-binaphthyl, and 5,5'-dibromo-2,2'-bithiophene, with 1 equiv of n-butyllithium followed by the reaction with electrophiles was achieved using a microflow system by virtue of fast micromixing and precise temperature control. Sequential introduction of two

  二溴联芳基的选择性单锂化反应，例如2,2'-二溴联苯，4,4'-二溴联苯，2,7-二溴-9,9-二辛基芴，2,2'-二溴-1,1'-联萘和5，使用微流系统，通过快速微混合和精确的温度控制，获得了具有1当量正丁基锂的5'-dibromo-2,2'-联噻吩，然后与亲电试剂反应。使用由四个微混合器和四个微管反应器组成的微流系统，还可以实现基于此方法的两种不同亲电试剂的顺序引入。
• Synthesis of unsymmetrically substituted biaryls via sequential lithiation of dibromobiaryls using integrated microflow systems
  作者：Aiichiro Nagaki、Naofumi Takabayashi、Yutaka Tomida、Jun-ichi Yoshida

  DOI：10.3762/bjoc.5.16

  日期：——

  A microflow system consisting of micromixers and microtube reactors provides an effective method for the introduction of two electrophiles onto dibromobiaryls. Selective monolithiation of dibromobiaryls, such as 2,2′-dibromobiphenyl, 4,4′-dibromobiphenyl, 2,7-dibromo-9,9-dioctylfluorene, 2,2′-dibromo-1,1′-binaphthyl, and 2,2′-dibromobibenzyl with 1 equiv of n-butyllithium followed by the reaction with electrophiles was achieved using a microflow system by virtue of fast micromixing and precise temperature control. Sequential introduction of two different electrophiles was achieved using an integrated microflow system composed of four micromixers and four microtube reactors to obtain unsymmetrically substituted biaryl compounds.

  一个微流系统由微混合器和微管反应器组成，为双溴联苯引入两个亲电试剂提供了有效的方法。通过选择性的双溴联苯单烷基化，如2,2′-双溴联苯、4,4′-双溴联苯、2,7-双溴-9,9-二辛基芴、2,2′-双溴-1,1′-联萘和2,2′-双溴联苯基苄，使用1当量的正丁基锂后与亲电试剂反应，利用微流系统实现了通过快速微混合和精确温度控制。使用由四个微混合器和四个微管反应器组成的集成微流系统，实现了两种不同亲电试剂的顺序引入，以获得非对称取代联苯化合物。