cumyl trifluoroacetate | 7429-11-0

• 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: cumyl trifluoroacetate
• 英文别名: 2-Phenylpropan-2-yl trifluoroacetate；2-phenylpropan-2-yl 2,2,2-trifluoroacetate
• CAS: 7429-11-0
• 化学式: C₁₁H₁₁F₃O₂
• 分子量: 232.202
• InChiKey: ZTAXIADPXAFHGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  3
• 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：
  5

反应信息

• 作为反应物：
  描述：

  cumyl trifluoroacetate 在 sodium acetate 、 溶剂黄146 作用下， 以 乙醚 、 水 为溶剂， 生成 2-苯基-1-丙烯
  参考文献：
  名称：

  溶剂分解反应。循序渐进还是协调一致？

  摘要：

  2-Aryl-endo-2-norbornyl trifluoroacetates 11 溶剂分解得到很大一部分的氯化产物。氘标记研究表明，外氢仅在消除产物形成时丢失。因此排除了协同酯热解类型的机制。叔苄基三氟乙酸盐Ph(CH 3 )C(CONMe 2 )(OCOCF 3 ), 13 溶解以专门提供消除产物。β-CD 3 同位素对速率的影响为1.15。然而，当 Ph(CH 2 D)C(CONMe 2 )(OCOCF 3 ) 溶解时，消除产物的形成过程中存在较大的同位素效应 (2.5)

  DOI：

  10.1021/ja00058a018
• 作为产物：
  描述：

  2-苯基-2-丙醇 、 三氟乙酸酐 在 2,6-二甲基吡啶 作用下， 以 乙醚 为溶剂， 生成 cumyl trifluoroacetate
  参考文献：
  名称：

  Solvolytic elimination reactions of tertiary .alpha.-CSNMe2-substituted systems

  摘要：

  The tertiary benzylic alpha-CSNMe2-substituted p-nitrobenzoates and trifluoroacetates of general structure Ar(CH3)C(CSNMe2)(OCOR), 7 and 8, solvolyze to give exclusively elimination products H2C = C(CSNMe2)Ar. A Hammett study gave a nonlinear correlation. Variation in rate with solvent ionizing power was small for the unsubstituted trifluoroacetate derivative of 8, and the beta-CD3 isotope effect on rate was negligible. There is, however, a large isotope effect (2.5-2.8) in formation of the elimination product when Ph(CH2D)C(CSNMe2)(OCOCF3) solvolyzes. It is concluded that an intermediate must be involved since the product-determining step and the rate-determining step have differing isotope effects. The likely intermediate is an alpha-CSNMe2-substituted cation (as an ion pair), despite the fact that the reaction has few characteristics of a typical E1 reaction. Tertiary norbornyl, cyclohexyl, and 2-propyl alpha-CSNMe2-substituted systems also react to give exclusively elimination products at rates far in excess of alpha-CONMe2 analogues. It is suggested that alpha-CSNMe2 cations are also intermediates and that these cations undergo proton loss at an early ion pair stage. These cations are proposed to derive substantial stabilization by charge delocalization onto sulfur of the thiocarbonyl group. By way of contrast, the secondary system CH3CH(CSNMe2)(OCOCF3), 25, solvolyzes to give mainly a rearranged product CH3CH(CONMe2)(SCOCH3) via a k(DELTA) mechanism involving neighboring thiocarbonyl participation leading to a cyclized ion.

  DOI：

  10.1021/jo00032a051

文献信息

• Radical deoxygenation of tertiary alcohols via trifluoroacetates
  作者：Joong-Gon Kim、Dae Hyan Cho、Doo Ok Jang

  DOI：10.1016/j.tetlet.2004.02.109

  日期：2004.4

  Trifluoroacetates of tertiary alcohols undergo deoxygenation by Ph2SiH2 in the presence of (tBuO)2 in excellent yields of the deoxy products without affecting the stereochemistry at β-carbon.

  叔醇的三氟乙酸盐在（t BuO）2的存在下通过Ph 2 SiH 2进行脱氧，脱氧产物的收率极高，而不会影响β-碳的立体化学。
• Oxidative Trifluoroacetoxylation of 1°, 2°, and 3° Benzylic C(sp³)–H Bond Donors Using <i>N</i>-Trifluoroacetoxyquinuclidinium Salts under Photoredox Catalysis
  作者：Michael Hitt、Andrei N. Vedernikov

  DOI：10.1021/acs.orglett.2c02946

  日期：2022.10.28

  trifluoroacetate was prepared in situ from quinuclidine N-oxide and (CF3CO)2O. Except for some electron-poor substrates, this reagent allows for the high-yielding oxidative trifluoroacetoxylation of 1°, 2°, and 3° benzylic C–H bonds under photocatalytic conditions. The trifluoroacetoxylation of an ibuprofen methyl ester allowed the selective functionalization of a 2° benzylic C–H bond. For alkylbenzenes, hydrogen-atom

  N-三氟乙酰氧基奎宁环三氟乙酸盐由奎宁环N-氧化物和 (CF 3 CO) 2 O原位制备。除了一些缺电子底物外，该试剂允许 1°、2° 和 3° 的高产率氧化三氟乙酰氧基化光催化条件下的苄基 C-H 键。布洛芬甲酯的三氟乙酰氧基化允许 2° 苄基 C-H 键的选择性官能化。对于烷基苯，氢原子从苄基 C-H 键转移到奎宁环阳离子自由基被认为是决定反应产物的步骤。