2-环丁烯-1-酮,4-氯-2,3-二乙基- | 148962-09-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-环丁烯-1-酮,4-氯-2,3-二乙基-
• 英文名称: 4-Chloro-2,3-diethyl-2-cyclobutenone
• 英文别名: 4-Chloro-2,3-diethylcyclobut-2-EN-1-one
• CAS: 148962-09-8
• 化学式: C₈H₁₁ClO
• mdl: MFCD18813567
• 分子量: 158.628
• InChiKey: VPAJWVXIYDTMCX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.625
• 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：

  5-trimethylsilyl-6-(tri-n-butylstannyl)-benzo-1,4-cyclobutenone 、 2-环丁烯-1-酮,4-氯-2,3-二乙基- 在 tris-(dibenzylideneacetone)dipalladium(0) 、 三(2-呋喃基)膦 作用下， 以 1,4-二氧六环 为溶剂， 以95%的产率得到2,3-Diethyl-1-hydroxy-anthraquinone
  参考文献：
  名称：

  Benzannulation of stannylquinones. A new regiocontrolled construction of substituted naphtho- and anthraquinones

  摘要：

  DOI：

  10.1021/ja00074a091
• 作为产物：
  描述：

  二氯乙酰氯 、 3-己炔 在 铜 、 锌 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以75%的产率得到2-环丁烯-1-酮,4-氯-2,3-二乙基-
  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

• A synthesis of substituted 2-pyrones by carbonylative cross-coupling-thermolysis of 4-halocyclobutenones with alkenyl-, aryl-, and heteroarylstannanes
  作者：Lanny S Liebeskind、Jianying Wang

  DOI：10.1016/s0040-4020(01)87262-8

  日期：1993.1

  Palladium catalyzed carbonylative cross-coupling of 4-chloro-2,3-disubstituted-2-cyclobutenones with alkenyl-, aryl-, and heteroaryltin reagents and thermolysis provides a general method for the synthesis of 2,3,6-trisubstituted-2-pyrones. The reaction is regiospecific, coupling occurring preferentially at the 4-position of the cyclobutenone.
• General Synthetic Entry to Highly-Oxygenated, Angularly-Fused Polycyclic Aromatic Compounds
  作者：Sangho Koo、Lanny S. Liebeskind

  DOI：10.1021/ja00117a009

  日期：1995.3

  A convergent and efficient synthesis of highly-oxygenated, angularly-fused polycyclic aromatic compounds has been developed. Nucleophilic addition of [4-(tri-n-butylstannyl)phenyl]lithium to a 3,4-disubstituted-cyclobutene-1,2-dione followed by appropriate protection of the hydroxyl group and thermal rearrangement of the O-protected addition product generated a 1,4-dioxygenated-2,3-disubstituted-6-(tri-n-butylstannyl) naphthalene. Stille coupling of the 6-(tri-n-butylstannyl)naphthalene with a 4-chloro-2,3-disubstituted-2-cyclobutenone and thermolysis of the coupled product gave highly-oxygenated phenanthrenes. An isomeric series of compounds was generated from [3-(tri-n-butylstannyl)phenyl]lithium. Substituted phenanthrenes at higher overall levels of oxygenation were prepared by (1) thermolysis of the adduct obtained by addition of a lithiated naphthalene, generated by Sn --> Li exchange from a 1,4-dioxygenated-2,3-disubstituted-6-(tri to a cyclobutenedione or (2) thermolysis of the double adducts generated by reaction of 2 equiv of a cyclobutenedione with either 1,4-dilithiobenzene or 1,3 dilithiobenzene. Phenanthrenes at lower levels of oxygenation were prepared by the palladium-catalyzed cross-coupling/thermolysis of 2 equivalents of a 4-chlorocyclobutenone with either 1,4-bis(tri-n-butylstannyl)benzene or 1,3-bis(tri-n-butylstannyl)benzene.
• 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.
• Benzannulation of aromatic heterocycles. A regiocontrolled method for construction of substituted benzo- and dibenzofurans and benzo- and dibenzothiophenes
  作者：Lanny S. Liebeskind、Jianying Wang

  DOI：10.1021/jo00065a017

  日期：1993.6

  4-Chloro-2,3-disubstituted-2-cyclobutenones undergo palladium-catalyzed cross-coupling with oxygen and sulfur heteroaryl tin reagents, and upon thermolysis at 100-degrees-C, good to high yields of substituted benzannulated heteroaromatics are formed. Relying on the control inherent in the construction of 4-chloro-2,3-disubstituted-2-cyclobutenones, regioisomeric substituted heteroaromatics are easily prepared.
• A general, regioselective synthesis of substituted benzocyclobutenedione monoacetals
  作者：James P. Edwards、Damian J. Krysan、Lanny S. Liebeskind

  DOI：10.1021/jo00067a029

  日期：1993.7

  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.