(2'-methylbiphenyl-2-yl)(phenyl)methanone | 183313-50-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: (2'-methylbiphenyl-2-yl)(phenyl)methanone
• 英文别名: [2-(2-Methylphenyl)phenyl]-phenylmethanone；[2-(2-methylphenyl)phenyl]-phenylmethanone
• CAS: 183313-50-0
• 化学式: C₂₀H₁₆O
• 分子量: 272.346
• InChiKey: HFQRCOSOCGBPCK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2'-methylbiphenyl-2-yl)(phenyl)methanone 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 以79%的产率得到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
• 作为产物：
  描述：

  2-(2-甲氧基苯基)-4,4-二甲基-2-噁唑啉 在 盐酸 、 sodium hydroxide 作用下， 生成 (2'-methylbiphenyl-2-yl)(phenyl)methanone
  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

• Efficient Cross-Coupling of Aryl Chlorides with Arylzinc Reagents Catalyzed by Amido Pincer Complexes of Nickel
  作者：Li Wang、Zhong-Xia Wang

  DOI：10.1021/ol701927g

  日期：2007.10.1

  The nickel-catalyzed Negishi cross-coupling reaction of aryl chlorides with arylzinc compounds was investigated. The nickel complexes with the amido pincer type of ligands exhibited high catalytic activity and good functional group tolerance.

  研究了芳基氯化物与芳基锌化合物的镍催化Negishi交叉偶联反应。具有酰胺钳型配体的镍配合物表现出高催化活性和良好的官能团耐受性。
• Intramolecular reactivity of arylcarbenes: Biphenyl-2-ylcarbenes
  作者：Michael Dorra、Klaus Gomann、Michael Guth、Wolfgang Kirmse

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

  日期：1996.9

  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).