4-Methyl-2-((trimethylsilyl)ethynyl)phenyl acetate | 183589-21-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: 4-Methyl-2-((trimethylsilyl)ethynyl)phenyl acetate
• 英文别名: [4-methyl-2-(2-trimethylsilylethynyl)phenyl] acetate
• CAS: 183589-21-1
• 化学式: C₁₄H₁₈O₂Si
• 分子量: 246.381
• InChiKey: DUXZBSGSACOWPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Methyl-2-((trimethylsilyl)ethynyl)phenyl acetate 在 potassium fluoride dihydrate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 以8.35 g的产率得到2-ethynyl-4-methylphenyl acetate
  参考文献：
  名称：

  Benzofurans or Isochromenes via the Ring-Opening Cyclization of Cyclopropene Derivatives with Organolithiums

  摘要：

  A new and efficient approach to benzocycles from cyclopropene derivatives is described. Deprotection by organolithiums and subsequent ring-opening cyclization of the related 2-cyclopropenyl phenyl or benzyl acetates generated benzofurans and isochromenes in one pot.

  DOI：

  10.1021/ol2032009
• 作为产物：
  描述：

  2-碘-4-甲基苯酚 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 1,4-二氧六环 为溶剂， 反应 6.0h， 生成 4-Methyl-2-((trimethylsilyl)ethynyl)phenyl acetate
  参考文献：
  名称：

  Palladium-Catalyzed Reaction of o-Ethynylphenols, o-((Trimethylsilyl)ethynyl)phenyl Acetates, and o-Alkynylphenols with Unsaturated Triflates or Halides:  A Route to 2-Substituted-, 2,3-Disubstituted-, and 2-Substituted-3-acylbenzo[b]furans

  摘要：

  The reaction of o-ethynylphenols 3 with a wide variety of unsaturated halides or triflates 6 in the presence of Pd(OAc)(2)(PPh(3))(2), CuI, and Et(3)N (procedure A) gives 2-vinyl- and 2-arylbenzo[b]furans 7, in good to high yield, through a palladium-catalyzed coupling followed by an in situ cyclization step. Small amounts of 2,3-disubstituted-benzo[b]furans 8 are usually isolated as side products. In some cases, however, compounds 8 are generated in significant yield or even as the main products. The formation of 8 can be prevented by employing alternative procedures (B and C) that use o-((trimethylsilyl)ethynyl)phenyl acetates 5 as starting building blocks. Procedure B is based on the palladium-catalyzed reaction of 5 with 6 in the presence of Pd(PPh(3))(4), Et(3)N, and n-Bu(4)NF, followed by the hydrolysis of the resultant coupling derivative 12 under basic conditions. Procedure C affords 7 through an in situ coupling/cyclization of 5 with 6 in the presence of Pd(PPh(3))(4) and KOBu(t). The utilization of o-alkynylphenols 9 as the starting alkynes in the palladium-catalyzed reaction with 6 leads to the formation of 2,3-disubstituted-benzo[b]furans 13 through an annulation process promoted by sigma-vinyl- and sigma-arylpalladium complexes generated in situ. The best results in this case are obtained by using KOAc and Pd(PPh(3))(4). In the presence of KOAc and Pd(PPh(3))(4), and under an atmosphere of carbon monoxide, the reaction of o-alkynylphenols with 6 provides 2-vinyl- and 2-aryl-3-acylbenzo[b]furans 14.

  DOI：

  10.1021/jo961051a

文献信息

• Palladium-Catalyzed Reaction of <i>o</i>-Ethynylphenols, <i>o</i>-((Trimethylsilyl)ethynyl)phenyl Acetates, and <i>o</i>-Alkynylphenols with Unsaturated Triflates or Halides:  A Route to 2-Substituted-, 2,3-Disubstituted-, and 2-Substituted-3-acylbenzo[<i>b</i>]furans
  作者：Antonio Arcadi、Sandro Cacchi、Mario Del Rosario、Giancarlo Fabrizi、Fabio Marinelli

  DOI：10.1021/jo961051a

  日期：1996.1.1

  The reaction of o-ethynylphenols 3 with a wide variety of unsaturated halides or triflates 6 in the presence of Pd(OAc)(2)(PPh(3))(2), CuI, and Et(3)N (procedure A) gives 2-vinyl- and 2-arylbenzo[b]furans 7, in good to high yield, through a palladium-catalyzed coupling followed by an in situ cyclization step. Small amounts of 2,3-disubstituted-benzo[b]furans 8 are usually isolated as side products. In some cases, however, compounds 8 are generated in significant yield or even as the main products. The formation of 8 can be prevented by employing alternative procedures (B and C) that use o-((trimethylsilyl)ethynyl)phenyl acetates 5 as starting building blocks. Procedure B is based on the palladium-catalyzed reaction of 5 with 6 in the presence of Pd(PPh(3))(4), Et(3)N, and n-Bu(4)NF, followed by the hydrolysis of the resultant coupling derivative 12 under basic conditions. Procedure C affords 7 through an in situ coupling/cyclization of 5 with 6 in the presence of Pd(PPh(3))(4) and KOBu(t). The utilization of o-alkynylphenols 9 as the starting alkynes in the palladium-catalyzed reaction with 6 leads to the formation of 2,3-disubstituted-benzo[b]furans 13 through an annulation process promoted by sigma-vinyl- and sigma-arylpalladium complexes generated in situ. The best results in this case are obtained by using KOAc and Pd(PPh(3))(4). In the presence of KOAc and Pd(PPh(3))(4), and under an atmosphere of carbon monoxide, the reaction of o-alkynylphenols with 6 provides 2-vinyl- and 2-aryl-3-acylbenzo[b]furans 14.
• Benzofurans or Isochromenes via the Ring-Opening Cyclization of Cyclopropene Derivatives with Organolithiums
  作者：Yu Liu、Shengming Ma

  DOI：10.1021/ol2032009

  日期：2012.2.3

  A new and efficient approach to benzocycles from cyclopropene derivatives is described. Deprotection by organolithiums and subsequent ring-opening cyclization of the related 2-cyclopropenyl phenyl or benzyl acetates generated benzofurans and isochromenes in one pot.