6,6-dimethyl-3-<(phenylthio)methyl>-2-cyclohexen-1-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: 6,6-dimethyl-3-<(phenylthio)methyl>-2-cyclohexen-1-one
• 英文别名: 6,6-Dimethyl-3-(phenylsulfanylmethyl)cyclohex-2-en-1-one
• 化学式: C₁₅H₁₈OS
• 分子量: 246.373
• InChiKey: CLSSORHVAPZLDX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4,4-二甲基-2-环己基-1-酮 在 三乙烯二胺 、 正丁基锂 、 silica gel 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 6,6-dimethyl-3-<(phenylthio)methyl>-2-cyclohexen-1-one
  参考文献：
  名称：

  Oxidative rearrangement of sulfur-containing tertiary allylic alcohols: synthesis of 2-cycloalkenones bearing 3-[(phenylthio)methyl] and 3-[2-alkyl-1,3-dithian-2-yl] substituents

  摘要：

  Substrate 1-[(phenylthio)methyl]-2-cycloalkenols 3a-d and 1-[2-alkyl-1,3-dithian-2-yl]cyclohexenols 1a-d were prepared by adding [(phenylthio)methyl]lithium and 2-lithio-2-alkyl-1,3-dithianes, respectively, in the 1,2-mode to various 2-cycloalkenones. The ranges of yields for the additions were 86-95% in the (phenylthio)methyl series and 69-88% in the dithiane series. A representative compound from each range of substrate tertiary allylic alcohols was then treated with a series of oxochromium(VI)-amine reagents such as pyridinium chlorochromate (PCC), pyridinium dichromate (PDC), the Collins reagent (CrO3.Pyr2), and 2,2'-bipyridinium chlorochromate (BPCC). The oxochromium(VI)-amine reagents effected conversions of the representative substrates to the corresponding 3-[(phenylthio)methyl]- and 3-[2-alkyl-1,3-dithian-2-yl]-2-cycloalkenones 4a-d and 2a-d which were measured by gas chromatographic-mass spectral analysis. When comparing the efficiency of the range of oxochromium(VI)-amine reagents, PCC was found to give the best conversions to the corresponding transposed alpha,beta-unsaturated carbonyl compounds in both series of substrates while the Jones reagent gave only decomposed material and no recovery of substrate. Distinct improvements on the initial PCC protocol using silica gel as an in situ adsorbent and promotion by ultrasound were then established with a range of substrate tertiary allylic alcohols while comparing sonicated versus nonsonicated experiments. The isolated yields of transposed products were found to be increased as much as 60 % in the dithiane series and 9 % in the (phenylthio)methyl series with the application of high-intensity ultrasound. Prolonged exposure of the substrate (3a) in the (phenylthio)methyl series to the PCC/silica reagent system resulted in the recovery of the corresponding sulfone (5), the identity of which was confirmed by selective oxidation of the transposed enone (4a) with m-chloroperbenzoic acid.

  DOI：

  10.1021/jo00063a011

文献信息

• Oxidative rearrangement of sulfur-containing tertiary allylic alcohols: synthesis of 2-cycloalkenones bearing 3-[(phenylthio)methyl] and 3-[2-alkyl-1,3-dithian-2-yl] substituents
  作者：Frederick A. Luzzio、William J. Moore

  DOI：10.1021/jo00063a011

  日期：1993.5

  Substrate 1-[(phenylthio)methyl]-2-cycloalkenols 3a-d and 1-[2-alkyl-1,3-dithian-2-yl]cyclohexenols 1a-d were prepared by adding [(phenylthio)methyl]lithium and 2-lithio-2-alkyl-1,3-dithianes, respectively, in the 1,2-mode to various 2-cycloalkenones. The ranges of yields for the additions were 86-95% in the (phenylthio)methyl series and 69-88% in the dithiane series. A representative compound from each range of substrate tertiary allylic alcohols was then treated with a series of oxochromium(VI)-amine reagents such as pyridinium chlorochromate (PCC), pyridinium dichromate (PDC), the Collins reagent (CrO3.Pyr2), and 2,2'-bipyridinium chlorochromate (BPCC). The oxochromium(VI)-amine reagents effected conversions of the representative substrates to the corresponding 3-[(phenylthio)methyl]- and 3-[2-alkyl-1,3-dithian-2-yl]-2-cycloalkenones 4a-d and 2a-d which were measured by gas chromatographic-mass spectral analysis. When comparing the efficiency of the range of oxochromium(VI)-amine reagents, PCC was found to give the best conversions to the corresponding transposed alpha,beta-unsaturated carbonyl compounds in both series of substrates while the Jones reagent gave only decomposed material and no recovery of substrate. Distinct improvements on the initial PCC protocol using silica gel as an in situ adsorbent and promotion by ultrasound were then established with a range of substrate tertiary allylic alcohols while comparing sonicated versus nonsonicated experiments. The isolated yields of transposed products were found to be increased as much as 60 % in the dithiane series and 9 % in the (phenylthio)methyl series with the application of high-intensity ultrasound. Prolonged exposure of the substrate (3a) in the (phenylthio)methyl series to the PCC/silica reagent system resulted in the recovery of the corresponding sulfone (5), the identity of which was confirmed by selective oxidation of the transposed enone (4a) with m-chloroperbenzoic acid.