3-(phenylthio)heptan-4-one

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 3-(phenylthio)heptan-4-one
• 英文别名: Ethylphenylthiopentanone；3-phenylsulfanylheptan-4-one
• 化学式: C₁₃H₁₈OS
• 分子量: 222.351
• InChiKey: CDBLBHYIMIYDFF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl 2,2-dibromopropanoate 、 3-(phenylthio)heptan-4-one 、 碘甲烷 在 叔丁基锂 作用下， 以 四氢呋喃 、 正戊烷 、 六甲基磷酰三胺 为溶剂， 反应 18.5h， 以81%的产率得到(Z)-methyl 2-methyl-4-phenylthio-3-propyl-2-hexenoate
  参考文献：
  名称：

  The effects of C–S and C–Se bonds on torquoselectivity: stereoselective olefination of α-thio and α-selenoketones with ynolates

  摘要：

  Highly Z-selective olefination of acyclic alpha-thio and alpha-selenoketones with ynolates has been achieved, and the theoretical calculations of the transition states in the ring-opening of the intermediates, the beta-lactone enolates, revealed that the torquoselectivity was controlled by the secondary orbital interactions between the sigma orbital of the C-S bond or a lone pair orbital on the S and sigma* orbitals of the breaking C-O bond, and the sigma orbital of the breaking C-O bond or a lone pair orbital on the O on the ring and the sigma* orbitals of the C-S bond. The synthetic applications of the resulting olefins are also shown. (c) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.08.060
• 作为产物：
  描述：

  4-庚酮 、 Phenylsulfid-Kation-Radikal 在 tetrabutylammonium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 以26%的产率得到3-(phenylthio)heptan-4-one
  参考文献：
  名称：

  电产生的sulf阳离子R 1 -S +的亲电取代

  摘要：

  通过有机二硫化物的氧化而电生成的sulf阳离子R 1 -S +与酚，芳族醚和在α位带有氢原子的酮反应，得到烷基（芳基）硫烷基化合物。

  DOI：

  10.1016/s0040-4039(98)00871-5

文献信息

• Electrophilic substitutions with the electrogenerated sulfenium cation R1-S+
  作者：Quang Tho Do、Driss Elothmani、Georges Le Guillanton

  DOI：10.1016/s0040-4039(98)00871-5

  日期：1998.6

  The sulfenium cation R1-S+ electrogenerated by oxidation of organic disulfides, reacts with phenols, aromatic ethers and ketones bearing an hydrogen atom in α position, to give alkyl (aryl) sulfanyl compounds.

  通过有机二硫化物的氧化而电生成的sulf阳离子R 1 -S +与酚，芳族醚和在α位带有氢原子的酮反应，得到烷基（芳基）硫烷基化合物。
• The effects of C–S and C–Se bonds on torquoselectivity: stereoselective olefination of α-thio and α-selenoketones with ynolates
  作者：Takashi Yoshikawa、Seiji Mori、Mitsuru Shindo

  DOI：10.1016/j.tet.2009.08.060

  日期：2009.10

  Highly Z-selective olefination of acyclic alpha-thio and alpha-selenoketones with ynolates has been achieved, and the theoretical calculations of the transition states in the ring-opening of the intermediates, the beta-lactone enolates, revealed that the torquoselectivity was controlled by the secondary orbital interactions between the sigma orbital of the C-S bond or a lone pair orbital on the S and sigma* orbitals of the breaking C-O bond, and the sigma orbital of the breaking C-O bond or a lone pair orbital on the O on the ring and the sigma* orbitals of the C-S bond. The synthetic applications of the resulting olefins are also shown. (c) 2009 Elsevier Ltd. All rights reserved.