4-异丙烯基-3-异丙氧基-2-异丙基-4-甲氧基-环丁-2-烯酮 | 1027247-54-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯酯类
• 中文名称: 4-异丙烯基-3-异丙氧基-2-异丙基-4-甲氧基-环丁-2-烯酮
• 英文名称: 4-Methoxy-2-propan-2-yl-3-propan-2-yloxy-4-prop-1-en-2-ylcyclobut-2-en-1-one
• CAS: 1027247-54-6
• 化学式: C₁₄H₂₂O₃
• 分子量: 238.327
• InChiKey: ZQSQCTNTRDIJKF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-异丙烯基-3-异丙氧基-2-异丙基-4-甲氧基-环丁-2-烯酮 在 吡啶 、 lithium aluminium tetrahydride 、 三氟乙酸酐 作用下， 生成 4-Methoxy-2-propan-2-yl-4-prop-1-en-2-ylcyclobut-2-en-1-one
  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-Isopropoxy-4-isopropyl-3-cyclobutene-1,2-dione 、 2-溴丙烷 、 三氟甲烷磺酸甲酯 生成 4-异丙烯基-3-异丙氧基-2-异丙基-4-甲氧基-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