2-(1-methoxyethyl)-1,1'-biphenyl

• 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: 2-(1-methoxyethyl)-1,1'-biphenyl
• 英文别名: 1-(1-Methoxyethyl)-2-phenylbenzene
• 化学式: C₁₅H₁₆O
• 分子量: 212.291
• InChiKey: RUEYHQWWYIDDJZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  二氢-3-(异十二碳烯基)呋喃-2,5-二酮 在 lithium aluminium tetrahydride 、 sodium hydride 作用下， 生成 2-(1-methoxyethyl)-1,1'-biphenyl
  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

• Visible-Light-Driven Organocatalytic Alkoxylation of Benzylic C–H Bonds
  作者：Chunbo Bo、Fei Chen、Qingqing Bu、Zhi-Hong Du、Min Li、Bin Dai、Ning Liu

  DOI：10.1021/acs.joc.2c02743

  日期：2023.3.17

  A variety of strategies for direct alkoxylation of the benzyl C–H bond have been developed toward the construction of benzyl ethers. The light-induced benzyl C–H bond alkoxylation provides an alternative strategy for the synthesis of these important intermediates. The photocatalyzed alkoxylation of the benzyl C–H bond has dominated by metal-catalyzed methods. Herein, we reported a light-driven organocatalytic

  已经开发了多种用于苄基 C-H 键直接烷氧基化的策略以构建苄基醚。光诱导的苄基 C-H 键烷氧基化为这些重要中间体的合成提供了一种替代策略。苯甲基 C-H 键的光催化烷氧基化反应以金属催化方法为主。在此，我们报道了一种光驱动的有机催化方法，通过使用 9,10-二溴蒽作为光催化剂并使用N2对苄基 C-H 键进行烷氧基化。-氟苯磺酰亚胺作为氧化剂。该反应在室温下进行，能够在 400 nm 光照射下将各种烷基联苯和偶联伙伴（包括各种醇和羧酸以及过氧化物）转化为所需产物。
• 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).