4-(2-Furyl)-3-isopropoxy-4-methoxy-2-methyl-2-cyclobutenone | 141462-31-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 4-(2-Furyl)-3-isopropoxy-4-methoxy-2-methyl-2-cyclobutenone
• 英文别名: 4-(Furan-2-yl)-4-methoxy-2-methyl-3-propan-2-yloxycyclobut-2-en-1-one
• CAS: 141462-31-9
• 化学式: C₁₃H₁₆O₄
• 分子量: 236.268
• InChiKey: IKWRYAPECFOHIF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  48.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-(2-Furyl)-3-isopropoxy-4-methoxy-2-methyl-2-cyclobutenone 在 lithium aluminium tetrahydride 、 氯化铵 、 三氟乙酸酐 作用下， 生成 4-呋喃-2-基-4-甲氧基-2-甲基-环丁-2-烯酮
  参考文献：
  名称：

  A strategy for generalization of the regiospecific synthesis of substituted quinones from cyclobutenediones

  摘要：

  Documented within is a straightforward protocol for the synthesis of generally substituted benzoquinones and ring-fused quinones. Previously, the crucial issue of quinone substituent regiochemistry was resolved at the stage of addition of an unsaturated carbon nucleophile to a cyclobutenedione by using either symmetrically substituted cyclobutenediones or 3-alkoxy (or amino)-4-substituted-3-cyclobutenediones. In the former case there are no regioisomeric quinones formed, while in the latter, through resonance delocalization, the alkoxy (or amino) substituent renders one of the two carbonyl groups less reactive and directs the incoming nucleophile to the other. The placement of a wide variety of substituents about the quinone ring periphery has now been solved by the less restrictive strategy of sequential introduction of substituents onto a cyclobutenedione core. The chemistry commences with 3-isopropoxy-4-substituted-3-cyclobutene-1,2-diones. Addition of an aromatic, heteroaromatic, or alkenyl nucleophile to the more reactive carbonyl group provides 4-hydroxy-4-R(unsat)-2-cyclobutenones, which are protected as the methyl ethers by treatment with MeI/Ag2O/K2CO3 in MeCN. A second nucleophile is added, again in a 1,2-sense, providing highly substituted 3-isopropoxy-2-cyclobutenols that are arranged to cyclobutenones under acidic conditions. The resulting cyclobutenones are converted into substituted quinones by thermolysis at 140-degrees-C in o-xylene followed by oxidative workup with ceric ammonium nitrate. The substitution pattern about the quinone core is rigorously controlled by the sequence of introduction of the substituents.

  DOI：

  10.1021/jo00042a009
• 作为产物：
  描述：

  3-(1-methylethoxy)-4-methylcyclobut-3-ene-1,2-dione 在 正丁基锂 、 四甲基乙二胺 、 potassium carbonate 、 silver(l) oxide 作用下， 以 乙腈 为溶剂， 反应 5.0h， 生成 4-(2-Furyl)-3-isopropoxy-4-methoxy-2-methyl-2-cyclobutenone
  参考文献：
  名称：

  A strategy for generalization of the regiospecific synthesis of substituted quinones from cyclobutenediones

  摘要：

  Documented within is a straightforward protocol for the synthesis of generally substituted benzoquinones and ring-fused quinones. Previously, the crucial issue of quinone substituent regiochemistry was resolved at the stage of addition of an unsaturated carbon nucleophile to a cyclobutenedione by using either symmetrically substituted cyclobutenediones or 3-alkoxy (or amino)-4-substituted-3-cyclobutenediones. In the former case there are no regioisomeric quinones formed, while in the latter, through resonance delocalization, the alkoxy (or amino) substituent renders one of the two carbonyl groups less reactive and directs the incoming nucleophile to the other. The placement of a wide variety of substituents about the quinone ring periphery has now been solved by the less restrictive strategy of sequential introduction of substituents onto a cyclobutenedione core. The chemistry commences with 3-isopropoxy-4-substituted-3-cyclobutene-1,2-diones. Addition of an aromatic, heteroaromatic, or alkenyl nucleophile to the more reactive carbonyl group provides 4-hydroxy-4-R(unsat)-2-cyclobutenones, which are protected as the methyl ethers by treatment with MeI/Ag2O/K2CO3 in MeCN. A second nucleophile is added, again in a 1,2-sense, providing highly substituted 3-isopropoxy-2-cyclobutenols that are arranged to cyclobutenones under acidic conditions. The resulting cyclobutenones are converted into substituted quinones by thermolysis at 140-degrees-C in o-xylene followed by oxidative workup with ceric ammonium nitrate. The substitution pattern about the quinone core is rigorously controlled by the sequence of introduction of the substituents.

  DOI：

  10.1021/jo00042a009

文献信息

• A strategy for generalization of the regiospecific synthesis of substituted quinones from cyclobutenediones
  作者：Lanny S. Liebeskind、Kenneth L. Granberg、Jing Zhang

  DOI：10.1021/jo00042a009

  日期：1992.7

  Documented within is a straightforward protocol for the synthesis of generally substituted benzoquinones and ring-fused quinones. Previously, the crucial issue of quinone substituent regiochemistry was resolved at the stage of addition of an unsaturated carbon nucleophile to a cyclobutenedione by using either symmetrically substituted cyclobutenediones or 3-alkoxy (or amino)-4-substituted-3-cyclobutenediones. In the former case there are no regioisomeric quinones formed, while in the latter, through resonance delocalization, the alkoxy (or amino) substituent renders one of the two carbonyl groups less reactive and directs the incoming nucleophile to the other. The placement of a wide variety of substituents about the quinone ring periphery has now been solved by the less restrictive strategy of sequential introduction of substituents onto a cyclobutenedione core. The chemistry commences with 3-isopropoxy-4-substituted-3-cyclobutene-1,2-diones. Addition of an aromatic, heteroaromatic, or alkenyl nucleophile to the more reactive carbonyl group provides 4-hydroxy-4-R(unsat)-2-cyclobutenones, which are protected as the methyl ethers by treatment with MeI/Ag2O/K2CO3 in MeCN. A second nucleophile is added, again in a 1,2-sense, providing highly substituted 3-isopropoxy-2-cyclobutenols that are arranged to cyclobutenones under acidic conditions. The resulting cyclobutenones are converted into substituted quinones by thermolysis at 140-degrees-C in o-xylene followed by oxidative workup with ceric ammonium nitrate. The substitution pattern about the quinone core is rigorously controlled by the sequence of introduction of the substituents.