3-((phenylthio)methyl)-2-cyclohexenone | 58775-66-9

• 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)methyl)-2-cyclohexenone
• 英文别名: 3-phenylthiomethylcyclohex-2-en-1-one；3-<(phenylthio)methyl>cyclohex-2-en-1-one；3-<(phenylthio)methyl>-2-cyclohexenone；3-<(phenylthio)methyl>-2-cyclohexen-1-one；3-[(Phenylsulfanyl)methyl]-2-cyclohexen-1-one；3-(phenylsulfanylmethyl)cyclohex-2-en-1-one
• CAS: 58775-66-9
• 化学式: C₁₃H₁₄OS
• 分子量: 218.32
• InChiKey: FJCONTIWLOOFSE-UHFFFAOYSA-N

物化性质

• 沸点：
  353.8±31.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  3-((phenylthio)methyl)-2-cyclohexenone 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以99%的产率得到3-<(phenylsulfonyl)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
• 作为产物：
  描述：

  1-<(phenylthio)methyl>-2-cyclohexen-1-ol 在 silica gel 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以75%的产率得到3-((phenylthio)methyl)-2-cyclohexenone
  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

• A Tandem Horner−Emmons Olefination−Conjugate Addition Approach to the Synthesis of 1,5-Disubstituted-6-azabicyclo[3.2.1]octanes Based on the AE Ring Structure of the Norditerpenoid Alkaloid Methyllycaconitine
  作者：David J. Callis、Noel F. Thomas、David P. J. Pearson、Barry V. L. Potter

  DOI：10.1021/jo9519672

  日期：1996.1.1

  A novel Horner-Emmons olefination conjugate addition reaction of N-acetylamides to form 1,5-disubstituted-6-azabicyclo[3.2.1]octanes with two bridgehead quarternary carbon centers is reported. This reaction is a key step in an approach to the synthesis of small ring analogues based on the AE ring structure of the Delphinium norditerpenoid, methyllycaconitine (MLA) (1). Initially, 3-(hydroxymethyl)cyclohex-2-en-1-one

  报道了一种新颖的N-乙酰酰胺的霍纳-埃蒙斯烯化共轭加成反应，形成带有两个桥头四元碳中心的1，5-二取代-6-氮杂双环[3.2.1]辛烷。该反应是基于Delphinium norditerpenoidoid，甲基lycaconitine（MLA）的AE环结构合成小环类似物的关键步骤。最初，选择3-（羟甲基）环己基-2-烯-1-酮（10）作为这些结构的起始材料，但事实证明生成效率低下。相反，3-[（（苯硫基）甲基]环己-2-烯-1-酮（6）和3-（1,3-二噻-2--2-基）环己-2-烯-1-酮（ 11）收成良好。随后进行氢氰化，缩酮化，还原，乙酰化，缩醛脱保护，和霍纳-埃蒙斯烯烃共轭加成反应形成1-[（（苯硫基）甲基] -5-[（乙氧羰基）甲基] -6-乙酰氨基-6-氮杂双环[3.2.1]辛烷（28），1-（1分别报道了，3-二噻二-2-基）-5-[（乙氧羰基）甲基] -6-乙酰基-6-氮杂双环[3
• Chemoselective behavior of enolate carbenes derived from dianions of enol thioacetals
  作者：Theodore Cohen、Lin Chen Yu

  DOI：10.1021/ja00347a047

  日期：1983.5
• Reactions of lithium bicyclo[1.1.0]butan-2-olates formed by carbenoid type decomposition of lithiothioacetal enolates. A novel concept for one-pot cyclopropanation of enones
  作者：Keith Ramig、M. Bhupathy、Theodore Cohen

  DOI：10.1021/jo00279a032

  日期：1989.9
• Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding
  作者：Mitsuru Shoji、Hiroki Imai、Isamu Shiina、Hideaki Kakeya、Hiroyuki Osada、Yujiro Hayashi

  DOI：10.1021/jo0355303

  日期：2004.3.1

  An oxidative dimerization reaction, involving the three successive steps of oxidation, 6pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6pi-electrocyclization.
• Lithiothioacetals as carbenoids. Highly selective one-flask conversion of cyclohex-2-en-1-ones to lithium bicyclo[1.1.0]butan-2-olate intermediates
  作者：Keith. Ramig、M. Bhupathy、Theodore. Cohen

  DOI：10.1021/ja00216a067

  日期：1988.4