Trifluoro-acetic acid 4-(tert-butyl-dimethyl-silanyloxy)-2,3,5,6-tetramethyl-phenyl ester | 173069-11-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Trifluoro-acetic acid 4-(tert-butyl-dimethyl-silanyloxy)-2,3,5,6-tetramethyl-phenyl ester
• CAS: 173069-11-9
• 化学式: C₁₈H₂₇F₃O₃Si
• 分子量: 376.491
• InChiKey: BWDJEPOPESOHGJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.77
• 重原子数：
  25.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  Trifluoro-acetic acid 4-(tert-butyl-dimethyl-silanyloxy)-2,3,5,6-tetramethyl-phenyl ester 在 碳酸氢钠 作用下， 以 甲醇 、 水 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  Novel ipso-Substitution of p-Sulfinylphenols through the Pummerer-Type Reaction:  A Selective and Efficient Synthesis of p-Quinones and Protected p-Dihydroquinones

  摘要：

  The treatment of p-sulfinylphenols 3a-q with trifluoroacetic anhydride caused a Pummerer-type reaction on aromatic rings and concomitant desulfurization to give mixtures of the corresponding p-dihydroquinones 9 and p-quinones 10, which were subsequently oxidized under mild conditions to provide high yields of p-quinones 10. On the other hand, the treatment of p-(phenylsulfinyl)-phenyl ethers 6 with trifluoroacetic anhydride in the presence of styrene caused the direct ipso-substitution of the sulfinyl groups into trifluoroacetoxy groups, giving the protected dihydroquinones 14 in high yields. Both types of reactions were generally completed below room temperature within 1 h and compatible with various functional groups such as the allyl, carbonyl, ester, amide, and silyloxy groups. The preparation of the p-sulfinylphenols 3 and the silyl ethers 6 is also described through p-specific thiocyanation of phenols followed by the Grignard reaction and oxidation.

  DOI：

  10.1021/jo970418o
• 作为产物：
  描述：

  2,3,5,6-tetramethyl-4-(4-nitrophenyl)sulfinylphenol 在 咪唑 作用下， 以 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 30.5h， 生成 Trifluoro-acetic acid 4-(tert-butyl-dimethyl-silanyloxy)-2,3,5,6-tetramethyl-phenyl ester
  参考文献：
  名称：

  Novel ipso-Substitution of p-Sulfinylphenols through the Pummerer-Type Reaction:  A Selective and Efficient Synthesis of p-Quinones and Protected p-Dihydroquinones

  摘要：

  The treatment of p-sulfinylphenols 3a-q with trifluoroacetic anhydride caused a Pummerer-type reaction on aromatic rings and concomitant desulfurization to give mixtures of the corresponding p-dihydroquinones 9 and p-quinones 10, which were subsequently oxidized under mild conditions to provide high yields of p-quinones 10. On the other hand, the treatment of p-(phenylsulfinyl)-phenyl ethers 6 with trifluoroacetic anhydride in the presence of styrene caused the direct ipso-substitution of the sulfinyl groups into trifluoroacetoxy groups, giving the protected dihydroquinones 14 in high yields. Both types of reactions were generally completed below room temperature within 1 h and compatible with various functional groups such as the allyl, carbonyl, ester, amide, and silyloxy groups. The preparation of the p-sulfinylphenols 3 and the silyl ethers 6 is also described through p-specific thiocyanation of phenols followed by the Grignard reaction and oxidation.

  DOI：

  10.1021/jo970418o

文献信息

• Some Recent Advances in Pummerer-type Reactions
  作者：Yasuyuki Kita

  DOI：10.1080/10426509708545516

  日期：1997.1.1

  first successful Pummerer-type reaction of the aromatic ring. In this review, we describe 1) the asymmetric Pummerer-type rearrangement induced by an O-silylated ketene acetal, 2) the asymmetric Pummerer-type rearrangement induced by an ethoxy vinyl acetate, 3) the additive-Pummerer-type reaction, 4) the asymmetric Pummerer-type cyclization induced by an O-silylated ketene acetal, and 5) the aromatic

  亚砜与酸酐的普默勒重排是合成 α 取代硫化物的有用方法，从合成和机械的角度来看都引起了相当大的关注。近年来，我们开发了两种新颖且重要的Pummerer型反应；i) 具有高度对映体过量的手性非外消旋亚砜的不对称 Pummerer 型反应，以及 ii) 芳香环的第一个成功的 Pummerer 型反应。在这篇综述中，我们描述了 1) 由 O-甲硅烷基化乙烯酮缩醛引起的不对称 Pummerer 型重排，2) 由乙氧基乙酸乙烯酯引起的不对称 Pummerer 型重排，3) 添加剂-Pummerer 型反应，4)由O-甲硅烷基化乙烯酮缩醛诱导的不对称Pummerer型环化，
• Pummerer-type rearrangement on aromatic rings: an unprecedented ipso-substitution of the sulfinyl group of p-sulfinylphenyl ethers into oxygen functional groups leading to protected dihydroquinone derivatives
  作者：Shuji Akai、Kiyosei Iio、Yoshifumi Takeda、Hiroshi Ueno、Kayoko Yokogawa、Yasuyuki Kita

  DOI：10.1039/c39950002319

  日期：——

  The treatment of p-(phenylsulfinyl)phenyl ethers 1 with trifluoroacetic anhydride in the presence of styrene selectively caused the direct ipso-substitution of the sulfinyl groups by trifluoroacetoxy groups, giving the protected dihydroquinone derivatives 3 in high to quantitative yields.

  在苯乙烯存在下，用三氟乙酸酐处理对(苯亚磺酰基)苯基醚 1，可选择性地使亚磺酰基直接被三氟乙酰氧基取代，从而得到高产率至定量的受保护二氢醌衍生物 3。