2-甲基-3-苯基-4-氯-3-环丁烯酮 | 16547-35-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-甲基-3-苯基-4-氯-3-环丁烯酮
• 英文名称: 2-methyl-3-phenyl-4-chloro-3-cyclobutenone
• 英文别名: 4-Chloro-2-methyl-3-phenyl-2-cyclobutenone；2-Chlor-3-phenyl-4-methyl-cyclobuten-(3)-on；4-Chloro-2-methyl-3-phenylcyclobut-2-enone；4-chloro-2-methyl-3-phenylcyclobut-2-en-1-one
• CAS: 16547-35-6
• 化学式: C₁₁H₉ClO
• mdl: MFCD03426974
• 分子量: 192.645
• InChiKey: KCZORHJIKJSKPH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.181
• 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-甲基-3-苯基-4-氯-3-环丁烯酮 在 二(氰基苯)二氯化钯 、 三(2-呋喃基)膦 吡啶 作用下， 反应 20.0h， 生成 1-Acetoxy-2,8-dimethyl-3-phenyldibenzothiophene
  参考文献：
  名称：

  Benzannulation of aromatic heterocycles. A regiocontrolled method for construction of substituted benzo- and dibenzofurans and benzo- and dibenzothiophenes

  摘要：

  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.

  DOI：

  10.1021/jo00065a017
• 作为产物：
  描述：

  1-丙烯基苯 在 氢氧化钾 、 硫酸 作用下， 以 乙醇 为溶剂， 生成 2-甲基-3-苯基-4-氯-3-环丁烯酮
  参考文献：
  名称：

  Stereochemical selectivities in the electrocyclic valence isomerizations of cyclobutenones and 2,4-cyclohexadienones

  摘要：

  DOI：

  10.1021/ja01024a031

文献信息

• A synthesis of highly substituted aromatics through regiocontrolled construction of cyclobutenones bearing unsaturated substituents at the 4-position
  作者：Damian J. Krysan、Angela Gurski、Lanny S. Liebeskind

  DOI：10.1021/ja00030a043

  日期：1992.2

  2,3-Substituted 4-chloro-2-cyclobutenones, prepared by regiospecific transformations of substituted cyclobutenediones, undergo palladium-catalyzed cross-coupling with vinyl- and arylstannanes and vinylzirconium reagents to form 4-R unsat -2-cyclobutenones. On thermolysis (100 o C), these substrates transform into substituted phenols in high yield. A pentasubstituted aromatic and a variety of tri- and

  2,3-取代的 4-氯-2-环丁烯酮，由取代的环丁烯二酮的区域特异性转化制备，经过钯催化与乙烯基和芳基锡烷以及乙烯基锆试剂交叉偶联，形成 4-R unsat -2-环丁烯酮。在热解 (100 o C) 时，这些底物以高产率转化为取代的苯酚。使用这种化学方法以区域特异性方式制备了五取代的芳香族化合物和各种三取代和四取代的芳香族化合物
• Collective Synthesis of Chiral Tetrasubstituted Cyclobutanes Enabled by Enantioconvergent Negishi Cross‐Coupling of Cyclobutenones
  作者：Min Yan、Qiang Zhou、Ping Lu

  DOI：10.1002/anie.202218008

  日期：2023.2.6

  Allylic substitution of readily available dichlorocyclobutenones and subsequent enantioconvergent Negishi coupling afforded 2,3,4-trisubstituted cyclobutenones. Further structural elaborations provided a group of 1,2,3,4-tetrasubstituted cyclobutanes with different stereochemical classes.

  容易获得的二氯环丁烯酮的烯丙基取代和随后的对映收敛 Negishi 偶联提供了 2,3,4-三取代的环丁烯酮。进一步的结构阐述提供了一组具有不同立体化学类别的 1,2,3,4-四取代环丁烷。
• 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.
• 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.
• 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.