4-(Dimethylamino)-1,3-diphenoxy-3-buten-2-one | 170124-04-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-(Dimethylamino)-1,3-diphenoxy-3-buten-2-one
• CAS: 170124-04-6
• 化学式: C₁₈H₁₉NO₃
• 分子量: 297.354
• InChiKey: HTINJXROWCDAGM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.12
• 重原子数：
  22.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  38.77
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  4-(Dimethylamino)-1,3-diphenoxy-3-buten-2-one 在 对甲苯磺酸 、 三乙胺 作用下， 以 乙醚 、 苯 为溶剂， 反应 7.67h， 生成 4-(Butylthio)-1,3-diphenoxy-2-<(trimethylsilyl)oxy>-1,3-butadiene
  参考文献：
  名称：

  Synthesis of Functionalized Aryloxy 1,3-Butadienes and Their Transformation to Diaryl Ethers via Diels-Alder Cycloaddition Reactions

  摘要：

  The Diels-Alder reaction involving cycloaddition of aryloxy-substituted 1,3-butadienes with appropriate acetylenic electrophiles, followed by aromatization of the newly formed cyclohexadiene ring, has been used for the synthesis of diaryl ethers. The functionalized aryloxy 1,3-butadienes employed in this study were prepared by either of two methods: (1) methylenation of aryl esters via the Tebbe or related reagents, and (2) from 1-(aryloxy)-2-propanone by a sequence of formylation or alkylthio methlylenation, and subsequent enolsilylation. A tetrasubstituted butadiene containing two phenoxy groups at the 1 and 3 positions also was prepared by the latter method. The cycloaddition reactions of 2,3-dioxy-substituted dienes occurred in high yield, but, as expected, with no regioselectivity to furnish nearly equal mixtures of regioisomeric cycloadducts. In contrast, application of 1,2,3-trihetero-substituted dienes resulted in regiospecific cycloaddition reactions. Transformation of the cyclohexadiene cycloadducts to an aromatic ring was accomplished by dehydrogenation with DDQ or by elimination during the cycloaddition process of a molecule of an alkyl mercaptan. A chiral acetylenic ketone derived from D- or L-serine underwent condensation, without racemization, with aryloxy dienes to provide diaryl ethers related to the isodityrosine antibiotics.

  DOI：

  10.1021/jo00124a010
• 作为产物：
  描述：

  Bredereck 试剂 、 1,3-Diphenoxy-2-propanone 反应 20.0h， 以75%的产率得到4-(Dimethylamino)-1,3-diphenoxy-3-buten-2-one
  参考文献：
  名称：

  Synthesis of Functionalized Aryloxy 1,3-Butadienes and Their Transformation to Diaryl Ethers via Diels-Alder Cycloaddition Reactions

  摘要：

  The Diels-Alder reaction involving cycloaddition of aryloxy-substituted 1,3-butadienes with appropriate acetylenic electrophiles, followed by aromatization of the newly formed cyclohexadiene ring, has been used for the synthesis of diaryl ethers. The functionalized aryloxy 1,3-butadienes employed in this study were prepared by either of two methods: (1) methylenation of aryl esters via the Tebbe or related reagents, and (2) from 1-(aryloxy)-2-propanone by a sequence of formylation or alkylthio methlylenation, and subsequent enolsilylation. A tetrasubstituted butadiene containing two phenoxy groups at the 1 and 3 positions also was prepared by the latter method. The cycloaddition reactions of 2,3-dioxy-substituted dienes occurred in high yield, but, as expected, with no regioselectivity to furnish nearly equal mixtures of regioisomeric cycloadducts. In contrast, application of 1,2,3-trihetero-substituted dienes resulted in regiospecific cycloaddition reactions. Transformation of the cyclohexadiene cycloadducts to an aromatic ring was accomplished by dehydrogenation with DDQ or by elimination during the cycloaddition process of a molecule of an alkyl mercaptan. A chiral acetylenic ketone derived from D- or L-serine underwent condensation, without racemization, with aryloxy dienes to provide diaryl ethers related to the isodityrosine antibiotics.

  DOI：

  10.1021/jo00124a010