3-methylenethiochroman-4-one | 143565-15-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫铬烷
• 英文名称: 3-methylenethiochroman-4-one
• 英文别名: 3-Methylene-thiochroman-4-one；3-methylidenethiochromen-4-one
• CAS: 143565-15-5
• 化学式: C₁₀H₈OS
• 分子量: 176.239
• InChiKey: KZRWHAQFFFDEIR-UHFFFAOYSA-N

物化性质

• 熔点：
  157-158 °C(Solv: acetone (67-64-1))
• 沸点：
  309.4±42.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.1
• 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：

  吲哚 、 3-methylenethiochroman-4-one 在 C₄₅H₅₅O₄P 作用下， 以 氯苯 为溶剂， 反应 40.0h， 以89%的产率得到
  参考文献：
  名称：

  手性螺磷酸催化的Friedel-Crafts共轭加成/对映选择性质子化反应

  摘要：

  产生α-手性中心的不对称Friedel-Crafts共轭加成反应具有挑战性，因为构型确定步骤是高活性烯醇中间体的质子转移反应。在本文中，我们报道了手性螺环磷酸催化将吲哚和吡咯高度对映选择性的Friedel-Crafts共轭加成到环外烯酮上的方案。该方案为具有重要的手性中心的合成重要的含吲哚的环状酮提供了一种简单，有效的方法，并且在宽范围的底物范围内具有高收率（高达99％）和高对映选择性（高达98％ee）的特征。密度泛函理论计算表明，螺磷酸最初通过充当布朗斯台德酸来催化加成反应，然后通过充当手性质子转移穿梭物来催化烯醇中间体的对映选择性质子转移反应。本文所述的对映体控制策略可广泛应用于其中质子转移是构象确定步骤的其他加成反应。

  DOI：

  10.1021/acscatal.9b01502
• 作为产物：
  描述：

  2-(烯丙基硫基)苯甲酰氯 在 sodium tetrahydroborate 作用下， 以 苯 为溶剂， 反应 2.0h， 生成 3-methylenethiochroman-4-one
  参考文献：
  名称：

  Photoinduced Free Radical Chemistry of the Acyl Tellurides: Generation, Inter- and Intramolecular Trapping, and ESR Spectroscopic Identification of Acyl Radicals

  摘要：

  Acyl tellurides are prepared in good to excellent yield by the reaction of sodium aryl tellurides with acyl chlorides, or mixed anhydrides, and are found to be moderately air-stable substances. In contrast to previous literature reports, acyl tellurides of aryl and vinyl carboxylic acids are found to be excellent sources of acyl radicals on photolysis with a simple white light source. The acyl radicals so generated may be trapped intermolecularly by dichalcogenides, or by TEMPO in excellent yield. Trapping by N-tert-butyl-alpha-phenyl nitrone produces a stable nitroxide radical which has been characterized by ESR spectroscopy. The very efficient trapping of acyl radicals by acyl tellurides themselves is demonstrated by a crossover experiment. Acyl tellurides are shown to participate in very efficient radical cyclization reactions onto alkenes with the formation of five-, six-, and eight-membered rings. The immediate products of the cyclizations onto alkenes are alpha-[(aryltelluro)methyl] ketones and the chemistry of these relatively unstable species is briefly described. Treatment with hydrogen peroxide affords alpha-methylene ketones in high yield. When elimination of the aryl telluro group is not possible the alpha-[(aryltelluro)methyl] ketones are stable species that may subsequently be employed in further radical chain reactions, for example with tributyltin hydride and methyl acrylate. Cyclization onto alkynes yields alpha-[(aryltelluro)methylene] ketones which are stable species and which take part in substitution reactions with higher order cuprates or with diphenyl diselenide.

  DOI：

  10.1021/ja00099a011

文献信息

• Efficient α-Methylenation of Carbonyl Compounds in Ionic Liquids at Room Temperature
  作者：J. Rodrigues、Juliana Vale、Daniel Zanchetta、Paulo Moran

  DOI：10.1055/s-0028-1087389

  日期：——

  The application of several 1-butyl-3-methylimidazolium (BMIM) salt ionic liquids as solvent in the α-methylenation of carbonyl compounds at room temperature is reported. The ionic liquid [BMIM][NTf2] gave a clean reaction in a short time and good yields of several α-methylene carbonyl compounds. This ionic liquid was reused without affecting the reaction rates or yields over seven runs.

  报道了几种1-丁基-3-甲基咪唑鎓（BMIM）盐离子液体在常温下对羰基化合物进行α-亚甲基化的溶剂应用。离子液体[BMIM][NTf2]在短时间内提供了干净的反应和多种α-亚甲基羰基化合物的高产率。这种离子液体在连续七次使用中重复使用，未影响反应速率或产率。
• The chemistry of acyl tellurides: generation and trapping of acyl radicals, including aryltellurium group transfer
  作者：Chen Chen、David Crich、Aristotle Papadatos

  DOI：10.1021/ja00047a066

  日期：1992.10
• Chiral Spiro Phosphoric Acid-Catalyzed Friedel–Crafts Conjugate Addition/Enantioselective Protonation Reactions
  作者：Yi-Pan Li、Zi-Qi Li、Biying Zhou、Mao-Lin Li、Xiao-Song Xue、Shou-Fei Zhu、Qi-Lin Zhou

  DOI：10.1021/acscatal.9b01502

  日期：2019.7.5

  indole-containing cyclic ketones with an α-chiral center and features with high yields (up to 99%) and high enantioselectivities (up to 98% ee) for a broad substrate scope. Density functional theory calculations suggest that the spiro phosphoric acid initially catalyzed the addition reaction by acting as a Brønsted acid and then catalyzed an enantioselective proton-transfer reaction of the enol intermediate

  产生α-手性中心的不对称Friedel-Crafts共轭加成反应具有挑战性，因为构型确定步骤是高活性烯醇中间体的质子转移反应。在本文中，我们报道了手性螺环磷酸催化将吲哚和吡咯高度对映选择性的Friedel-Crafts共轭加成到环外烯酮上的方案。该方案为具有重要的手性中心的合成重要的含吲哚的环状酮提供了一种简单，有效的方法，并且在宽范围的底物范围内具有高收率（高达99％）和高对映选择性（高达98％ee）的特征。密度泛函理论计算表明，螺磷酸最初通过充当布朗斯台德酸来催化加成反应，然后通过充当手性质子转移穿梭物来催化烯醇中间体的对映选择性质子转移反应。本文所述的对映体控制策略可广泛应用于其中质子转移是构象确定步骤的其他加成反应。
• Photoinduced Free Radical Chemistry of the Acyl Tellurides: Generation, Inter- and Intramolecular Trapping, and ESR Spectroscopic Identification of Acyl Radicals
  作者：David Crich、Chen Chen、Jae-Taeg Hwang、Hongwei Yuan、Aristotle Papadatos、Robert I. Walter

  DOI：10.1021/ja00099a011

  日期：1994.10

  Acyl tellurides are prepared in good to excellent yield by the reaction of sodium aryl tellurides with acyl chlorides, or mixed anhydrides, and are found to be moderately air-stable substances. In contrast to previous literature reports, acyl tellurides of aryl and vinyl carboxylic acids are found to be excellent sources of acyl radicals on photolysis with a simple white light source. The acyl radicals so generated may be trapped intermolecularly by dichalcogenides, or by TEMPO in excellent yield. Trapping by N-tert-butyl-alpha-phenyl nitrone produces a stable nitroxide radical which has been characterized by ESR spectroscopy. The very efficient trapping of acyl radicals by acyl tellurides themselves is demonstrated by a crossover experiment. Acyl tellurides are shown to participate in very efficient radical cyclization reactions onto alkenes with the formation of five-, six-, and eight-membered rings. The immediate products of the cyclizations onto alkenes are alpha-[(aryltelluro)methyl] ketones and the chemistry of these relatively unstable species is briefly described. Treatment with hydrogen peroxide affords alpha-methylene ketones in high yield. When elimination of the aryl telluro group is not possible the alpha-[(aryltelluro)methyl] ketones are stable species that may subsequently be employed in further radical chain reactions, for example with tributyltin hydride and methyl acrylate. Cyclization onto alkynes yields alpha-[(aryltelluro)methylene] ketones which are stable species and which take part in substitution reactions with higher order cuprates or with diphenyl diselenide.