1,1,1-trifluoro-4,4,-dimethyl-5-phenyl-3-pentanone | 642040-27-5

• 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: 1,1,1-trifluoro-4,4,-dimethyl-5-phenyl-3-pentanone
• 英文别名: 1,1,1-trifluoro-4,4-dimethyl-5-phenyl-3-pentanone；1,1,1-trifluoro-4,4-dimethyl-5-phenylpentan-3-one
• CAS: 642040-27-5
• 化学式: C₁₃H₁₅F₃O
• 分子量: 244.257
• InChiKey: OFALLGGDEMXHNU-UHFFFAOYSA-N

物化性质

• 沸点：
  256.7±35.0 °C(Predicted)
• 密度：
  1.118±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,1,1-trifluoro-4,4,-dimethyl-5-phenyl-3-pentanone 在 三氯化铝 、 三正丁胺 、 dimethyl sulfide borane 、 四氯化钛 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 6.75h， 生成 4-(1,1-dimethyl-2-phenylethyl)-2,2-dimethyl-5,6-bis(trifluoromethyl)-[1,3]dioxane
  参考文献：
  名称：

  Dipole Interaction-Controlled Stereoselectivity in Aldol Reaction of α-CF₃ Enolate with Fluoral

  摘要：

  [GRAPHICS]The stereoselectivity of a reaction is generally determined by minimizing steric repulsion. However, the aldol reaction of alpha-CF3-ketone (Z)-enolate with fluoral anomalously gave an anti-aldol through a sterically demanding transition state, because of the strong dipole interaction of the two CF3 groups. We have thus disclosed a paradigm shift from steric to electronic control of reaction stereoselectivity.

  DOI：

  10.1021/ol0358307
• 作为产物：
  描述：

  三氟碘甲烷 、 (3,3-Dimethyl-4-phenylbut-1-en-2-yl)oxy-trimethylsilane 在 diethylzinc 、 air 、 三乙基硼 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 25.0h， 以54%的产率得到1,1,1-trifluoro-4,4,-dimethyl-5-phenyl-3-pentanone
  参考文献：
  名称：

  通过用二烷基锌活化使酮甲硅烷基烯醇醚自由基三氟甲基化。

  摘要：

  [反应：见正文]酮甲硅烷基烯醇醚的自由基三氟甲基化反应可得到高产率的α-CF（3）酮，并具有广泛的酮基底物，包括无环酮和环戊酮。使用二烷基锌活化甲硅烷基烯醇醚是有效的自由基三氟甲基化的关键。

  DOI：

  10.1021/ol0611301

文献信息

• Zn-mediated rhodium-catalyzed α-trifluoromethylation of ketones via silyl enol ethers
  作者：Kazuyuki Sato、Takashi Yuki、Atsushi Tarui、Masaaki Omote、Itsumaro Kumadaki、Akira Ando

  DOI：10.1016/j.tetlet.2008.04.030

  日期：2008.5

  The treatment of silyl enol ethers of ketones with CF3–I and Et2Zn in the presence of RhCl(PPh3)3 in DME gave α-trifluoromethyl ketones in good yields. The reaction can be widely applicable to silyl enol ethers derived from aliphatic or aromatic ketones. In the absence of the rhodium catalyst, the reaction was very slow and the yields were quite poor.

  在DME中，在RhCl（PPh 3）3存在下，用CF 3 –I和Et 2 Zn处理酮的甲硅烷基烯醇醚可得到高产率的α-三氟甲基酮。该反应可广泛应用于衍生自脂族或芳族酮的甲硅烷基烯醇醚。在没有铑催化剂的情况下，反应非常缓慢并且收率很差。
• Dialkylzinc-accelerated α-Trifluoromethylation of Carbonyl Compounds Catalyzed by Late-transition-metal Complexes
  作者：Yuichi Tomita、Yoshimitsu Itoh、Koichi Mikami

  DOI：10.1246/cl.2008.1080

  日期：2008.10.5

  Trifluoromethylation of ketone silyl enol ethers is found to be significantly accelerated by late-transition-metal catalysts and dialkylzincs to give α-trifluoromethyl ketones in good yields. Addition of dialkylzinc is the key to the high yielding α-trifluoromethylation of carbonyl compounds.

  发现后过渡金属催化剂和二烷基锌显着加速了酮甲硅烷基烯醇醚的三氟甲基化，以良好的产率生成α-三氟甲基酮。二烷基锌的加成是羰基化合物高产率α-三氟甲基化的关键。
• Radical Trifluoromethylation of Titanium Ate Enolate
  作者：Yoshimitsu Itoh、Koichi Mikami

  DOI：10.1021/ol047565a

  日期：2005.2.1

  The radical trifluoromethylation of ketone titanium ate enolates gave alpha-CF3 ketones in good yields. The use of excess amount of LDA and Ti(OiPr)4 in the preparation of titanium ate enolates is the key to the efficient radical trifluoromethylation. [reaction: see text]

  酮钛酸酯烯酸酯的自由基三氟甲基化以良好的产率得到了α-CF3酮。在制备钛酸酯烯醇化物中使用过量的LDA和Ti（OiPr）4是有效的自由基三氟甲基化的关键。[反应：看文字]
• Radical trifluoromethylation of Ti ate enolate: possible intervention of transformation of Ti(IV) to Ti(III) for radical termination
  作者：Yoshimitsu Itoh、Koichi Mikami

  DOI：10.1016/j.jfluchem.2006.03.011

  日期：2006.5

  The radical trifluoromethylation of ketone Ti ate enolates gave α-CF3 ketones in good yields. The use of excess amount of LDA and Ti(OiPr)4 in the preparation of Ti ate enolates is the key to the efficient radical trifluoromethylation. Theoretical studies on the spin density of the Ti(IV) ate ketyl radical intermediate suggest the involvement of transformation from Ti(IV) ate ketyl radical intermediates

  酮的Ti的自由基三氟甲基化烯醇化物吃了α-CF 3吨酮以良好的收率。在钛酸酯烯酸酯的制备中使用过量的LDA和Ti（O i Pr）4是有效的自由基三氟甲基化的关键。Ti（IV）酯酮基自由基中间体的自旋密度的理论研究表明，在自由基终止步骤中涉及从Ti（IV）酯酮基自由基中间体向Ti（III）物种的转化。
• Radical trifluoromethylation of ketone Li enolates
  作者：Yoshimitsu Itoh、Koichi Mikami

  DOI：10.1016/j.tet.2006.03.115

  日期：2006.7

  It has generally been believed that highly basic Li enolates cannot be applied as substrates for radical trifluoromethylation due to defluorination of the alpha-CF3 product. However, Li enolates can be in fact employed for radical trifluoromethylation. Moreover, the reaction is extremely fast and the minimum reaction time is only similar to 1 s. (c) 2006 Elsevier Ltd. All rights reserved.