2-n-Butyl-4-chloro-3-methyl-2-cyclobutenone | 151664-21-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-n-Butyl-4-chloro-3-methyl-2-cyclobutenone
• 英文别名: 2-Butyl-4-chloro-3-methyl-2-cyclobutenone；2-Butyl-4-chloro-3-methylcyclobut-2-en-1-one
• CAS: 151664-21-0
• 化学式: C₉H₁₃ClO
• 分子量: 172.655
• InChiKey: YQFUEWPWZKSVNR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-n-Butyl-4-chloro-3-methyl-2-cyclobutenone 、 3-(Tri-n-butylstannyl)-3-cyclobutene-1,2-dione 2-(ethylene acetal) 在 二(氰基苯)二氯化钯 三(2-呋喃基)膦 作用下， 以 四氢呋喃 为溶剂， 以71%的产率得到4-n-Butyl-3-hydroxy-5-methylbenzocyclobutenedione 1-(ethylene acetal)
  参考文献：
  名称：

  A general, regioselective synthesis of substituted benzocyclobutenedione monoacetals

  摘要：

  A general, regioselective synthesis of substituted benzocyclobutenedione monoacetals is reported. Palladium-catalyzed coupling of a variety of 4-chlorocyclobutenones with 3-(tri-n-butylstannyl)-3-cyclobutene-1,2-dione 2-(ethylene acetal) and heating up to 70-100-degrees-C produces substituted benzocyclobutenedione monoacetals in good to excellent yields. Thia chemistry is presumed to proceed through palladium-catalyzed formation of a 3-(1-oxo-2-cyclobuten-4-yl)-3-cyclobutene-1,2-dione-2-(ethylene acetal) followed by a thermally induced ring opening to a dienyl ketene and subsequent six-electron electrocyclic ring closure and tautomerization. 2,3-Disubstituted 4-chlorocyclobutenones afford palladium intermediates which couple exclusively at the least-substituted allylic terminus. 2,3,4-Trisubstituted 4-chlorocyclobutenones have not been studied in detail; however, preliminary results suggest that regioselective allylic cross-coupling can be achieved. The methodology described provides an expedient and efficient route to previously difficult-to-prepare benzocyclobutenedione derivatives. These function as important synthetic intermediates in a variety of reactions developed in these and other laboratories.

  DOI：

  10.1021/jo00067a029
• 作为产物：
  描述：

  3-n-Butyl-4-methyl-3-cyclobutene-1,2-dione 2-(ethylene acetal) 在 盐酸 、 四氯化碳 、 二异丁基氢化铝 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 、 乙腈 为溶剂， 反应 1.92h， 生成 2-n-Butyl-4-chloro-3-methyl-2-cyclobutenone
  参考文献：
  名称：

  A general, regioselective synthesis of substituted benzocyclobutenedione monoacetals

  摘要：

  A general, regioselective synthesis of substituted benzocyclobutenedione monoacetals is reported. Palladium-catalyzed coupling of a variety of 4-chlorocyclobutenones with 3-(tri-n-butylstannyl)-3-cyclobutene-1,2-dione 2-(ethylene acetal) and heating up to 70-100-degrees-C produces substituted benzocyclobutenedione monoacetals in good to excellent yields. Thia chemistry is presumed to proceed through palladium-catalyzed formation of a 3-(1-oxo-2-cyclobuten-4-yl)-3-cyclobutene-1,2-dione-2-(ethylene acetal) followed by a thermally induced ring opening to a dienyl ketene and subsequent six-electron electrocyclic ring closure and tautomerization. 2,3-Disubstituted 4-chlorocyclobutenones afford palladium intermediates which couple exclusively at the least-substituted allylic terminus. 2,3,4-Trisubstituted 4-chlorocyclobutenones have not been studied in detail; however, preliminary results suggest that regioselective allylic cross-coupling can be achieved. The methodology described provides an expedient and efficient route to previously difficult-to-prepare benzocyclobutenedione derivatives. These function as important synthetic intermediates in a variety of reactions developed in these and other laboratories.

  DOI：

  10.1021/jo00067a029

文献信息

• Synthesis of .alpha.-Pyridone-Based Azaheteroaromatics by Intramolecular Vinylketene Cyclizations onto the C:N Bond of Nitrogen Heteroaromatics
  作者：Angela Gurski Birchler、Fuqiang Liu、Lanny S. Liebeskind

  DOI：10.1021/jo00104a033

  日期：1994.12

  Substituted quinolizin-4-ones and ring-fused alpha-pyridone derivatives have been synthesized by the construction of 2,3-disubstituted-4-(2-azaheteroaryl)-2-cyclobutenones followed by thermal rearrangment. 4-(2-Azaheteroaryl)-2-cyclobutenones have been prepared regioselectively by the addition of 2-lithioazaheteroaromatics to cyclobutenediones and by palladium catalyzed cross-coupling of 4-chloro-2-cyclobutenones with 2-tri-n-stannylazaheteroaromatics. The thermal transformation is proposed to occur by ring-opening of the cyclobutenone followed by intramolecular cyclization of the transient vinylketene onto the carbon-nitrogen double bond of the azaheteroaromatic. A variety of quinolizin-4-ones, imidazo [1,2-a]pyridin-5-ones, 1-oxopyrido[2,1-b]benzothiazoles, and thiazolo[3,2-a]pyridin-5-ones were prepared.