trans-1,1,1-Trifluorododec-3-en-2-one | 136808-16-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-1,1,1-Trifluorododec-3-en-2-one
• 英文别名: (E)-1,1,1-trifluorododec-3-en-2-one；1,1,1-Trifluoro-3-dodecen-2-one
• CAS: 136808-16-7
• 化学式: C₁₂H₁₉F₃O
• 分子量: 236.277
• InChiKey: MKNFAGQTRLXRAV-MDZDMXLPSA-N

物化性质

• 沸点：
  215.8±40.0 °C(Predicted)
• 密度：
  1.010±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  trans-1,1,1-Trifluorododec-3-en-2-one 在 三氟甲磺酸三甲基硅酯 、 magnesium 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 14.5h， 生成 (E)-2-(trifluoromethyl)undeca-1,3-diene
  参考文献：
  名称：

  使用Peterson Olefination方法对全氟烷基酮进行亚甲基化

  摘要：

  据报道，操作上简单，廉价且快速的途径是将多种三氟甲基酮进行烯化以生成3,3,3-三氟甲基丙烯。使用彼得森烯化方法，该反应使烯烃产物的收率良好至极佳，并且可以在不纯化β-羟基甲硅烷基中间体的情况下进行。该反应可以扩展至其他全氟烷基取代基，并且易于扩大规模。所制备的烯烃可以容易地转化成多种其他的含全氟烷基的化合物。

  DOI：

  10.1021/jo402577n
• 作为产物：
  描述：

  1,1,1-trifluorododec-3-yn-2-one 在 lithium aluminium tetrahydride 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 11.0h， 生成 trans-1,1,1-Trifluorododec-3-en-2-one
  参考文献：
  名称：

  Synthesis of and Analysis of Thiol Additions to .beta.-Alkyl-.alpha.,.beta.-unsaturated Trifluoromethyl Ketones

  摘要：

  A series of beta-alkyl-alpha,beta-unsaturated trifluoromethyl ketones have been prepared from the corresponding alpha-acetylenic trifluoromethyl ketones. The addition of sulfur nucleophiles was shown by chemical and F-19 NMR studies to proceed exclusively by 1,4-addition with no indication of any 1,2-addition products. The unsaturated trifluoromethyl ketones have been shown to be effective inhibitors of rat cytosolic glutathione-S-transferase.

  DOI：

  10.1021/jo00084a009

文献信息

• Synthesis of αβ-Unsaturated Trifluoromethyl Ketones from 4-Dimethylamino-1,1,1-trifluorobut-3-ene-2-one by Addition of Grignard Reagents
  作者：Rebecca J. Andrew、John M. Mellor

  DOI：10.1016/s0040-4020(00)00597-4

  日期：2000.9

  such as dimethylamine and they react with Grignard reagents to give αβ-unsaturated trifluoromethyl ketones in good yield by 1,4-addition followed by elimination. The generality of this procedure is contrasted with reactions based either on the use of organolithium nucleophiles, or the use of 4-alkoxy-αβ-unsaturated trifluoromethyl ketones as electrophilic partners.

  通过4-乙氧基-1,1,1-三氟丁-3-烯-2-酮与胺（如二甲胺）反应可获得烯胺酮，它们与格氏试剂反应生成αβ-不饱和三氟甲基酮，产率高，产率为1,4。 -添加，然后消除。该方法的一般性与基于使用有机锂亲核试剂或基于4-烷氧基-αβ-不饱和三氟甲基酮作为亲电子试剂的反应形成对比。
• Regiospecific and diastereoselective aldol reaction of chiral N-sulfinyl metalloenamines with α,β-unsaturated trifluoromethyl ketones: Asymmetric synthesis of tertiary trifluoromethyl allylic carbinols
  作者：Zhen-Jiang Liu、Fan Zhang、Jin-Tao Liu

  DOI：10.1016/j.jfluchem.2011.09.002

  日期：2012.1

  Regiospecific and diastereoselective aldol type reaction of chiral N-sulfinyl metalloenamines with α,β-unsaturated trifluoromethyl ketones was reported, which affords the corresponding tertiary trifluoromethyl allylic carbinols in high yields with good diastereoselectivities (dr up to 90:10). The reduction of the condensation product 3a with LiBHEt3 and Catecholborane provides CF3-substituted syn-

  报道了手性N-亚磺酰基金属烯胺与α，β-不饱和三氟甲基酮的区域专一性和非对映选择性的醛醇型反应，该反应可高收率地提供相应的叔三氟甲基烯丙基甲醇，其非对映选择性良好（dr高达90:10）。用LiBHEt 3和邻苯二甲硼烷还原缩合产物3a可提供高产率的CF 3取代的顺式和反-1,3-氨基醇5a和5b，具有优异的非对映选择性（dr> 99：1）。
• Asymmetric synthesis of either diastereomer of trifluoromethylated allylic amines by the selective reduction of trifluoromethyl α,β-unsaturated N-tert-butanesulfinyl ketoimines
  作者：Zhen-Jiang Liu、Jin-Tao Liu

  DOI：10.1039/b810459j

  日期：——

  Regio- and diastereoselective reduction of chiraltrifluoromethyl α,β-unsaturated N-tert-butanesulfinyl ketoimines 1 was achieved by choosing appropriate reducing agent and either diastereomer of the corresponding trifluoromethylated allylic amines was obtained with good yield and excellent diastereoselectivity (up to >99 : 1 dr).

  通过选择适当的还原剂，实现了手性三氟甲基δ,δ-不饱和 N-叔丁基亚磺酰酮亚胺 1 的区域和非对映选择性还原，并获得了相应的三氟甲基烯丙基胺的非对映异构体，且收率高，非对映选择性极佳（达 >99 : 1 dr）。
• Studies on Trifluoromethyl Ketones. VII. Ene Reaction of Trifluroacetaldehyde and Its Application for Synthesis of Trifluoromethyl Compounds.
  作者：Keizo OGAWA、Takabumi NAGAI、Masahiko NONOMURA、Toshiyuki TAKAGI、Mayumi KOYAMA、Akira ANDO、Takuichi MIKI、Itsumaro KUMADAKI

  DOI：10.1248/cpb.39.1707

  日期：——

  As an extension of our studies on the ene reaction of trifluoromethyl ketones, the ene reaction of trifluoroacetaldehyde was examined. The aldehyde reacted with various ene compounds as a good enophile in the presence of Lewis acids, among which methylaluminum dichloride workded best, though polymerization of the aldehyde caused by the Lewis acid among which methylaluminum dichloride worked best, though polymerization of the aldehyde caused by the Lewis acid often lowered the isolation yields of the ene reaction. The ene reaction products were successfully oxidized to trifluoromethyl β, γ-unsaturated ketones with Dess Martin reagent. Reduction of the ene reaction products followed by oxidation with Jones reagent gave saturated trifluoromethyl ketones. The β, γ-unsaturated ketone rearranged on thermolysis to an α, β-unsaturated ketone. These ketones obtained were converted to otehr types of trifluoromethyl compounds. Thus, the ene reaction of trifluoroacetaldehyde provides a versatile method for synthesis of many types of trifluoromethyl compounds. During this derivatization, a trifluoromethyl group was found to behave as a much larger substituent than a decyl group.

  作为三氟甲基酮烯化反应研究的延伸，我们还研究了三氟乙醛的烯化反应。在路易斯酸（其中二氯化甲基铝的效果最好）存在的情况下，该醛作为一种良好的亲烯烃与各种烯化合物发生反应，但路易斯酸引起的醛聚合往往会降低烯反应的分离产率。使用 Dess Martin 试剂成功地将烯酮反应产物氧化为三氟甲基 β、γ-不饱和酮。烯反应产物还原后再用琼斯试剂氧化，得到饱和的三氟甲基酮。β、γ-不饱和酮在热分解过程中重新排列为 α、β-不饱和酮。得到的这些酮又转化为其他类型的三氟甲基化合物。因此，三氟乙醛的烯化反应为合成多种类型的三氟甲基化合物提供了一种通用方法。在这一衍生过程中，发现三氟甲基的取代基比癸基大得多。
• Methylenation of Perfluoroalkyl Ketones using a Peterson Olefination Approach
  作者：Trevor A. Hamlin、Christopher B. Kelly、Robin M. Cywar、Nicholas E. Leadbeater

  DOI：10.1021/jo402577n

  日期：2014.2.7

  An operationally simple, inexpensive, and rapid route for the olefination of a wide array of trifluoromethyl ketones to yield 3,3,3-trifluoromethylpropenes is reported. Using a Peterson olefination approach, the reaction gives good to excellent yields of the alkene products and can be performed without purification of the β-hydroxysilyl intermediate. The reaction can be extended to other perfluoroalkyl

  据报道，操作上简单，廉价且快速的途径是将多种三氟甲基酮进行烯化以生成3,3,3-三氟甲基丙烯。使用彼得森烯化方法，该反应使烯烃产物的收率良好至极佳，并且可以在不纯化β-羟基甲硅烷基中间体的情况下进行。该反应可以扩展至其他全氟烷基取代基，并且易于扩大规模。所制备的烯烃可以容易地转化成多种其他的含全氟烷基的化合物。