4-Chloro-2-methyl-3-(1-methylethoxy)-2-cyclobutenone | 138151-56-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-Chloro-2-methyl-3-(1-methylethoxy)-2-cyclobutenone
• 英文别名: 4-chloro-3-(1-methylethoxy)-2-methyl-2-cyclobutenone；2-methyl-3-isopropoxy-4-chloro-2-cyclobutenone；4-Chloro-3-isopropoxy-2-methyl-2-cyclobutenone；4-Chloro-2-methyl-3-propan-2-yloxycyclobut-2-en-1-one
• CAS: 138151-56-1
• 化学式: C₈H₁₁ClO₂
• 分子量: 174.627
• InChiKey: SYGVFFMUAWQILL-UHFFFAOYSA-N

物化性质

• 沸点：
  258.2±40.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Chloro-2-methyl-3-(1-methylethoxy)-2-cyclobutenone 在 盐酸 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 作用下， 以 甲苯 为溶剂， 生成 3-Isopropoxy-2-methyl-cyclohepta-3,5-dienone
  参考文献：
  名称：

  Rhodium(I)-catalyzed intramolecular carbocyclic ring fusion: a new approach to medium-sized-ring ketones

  摘要：

  DOI：

  10.1021/ja00064a062
• 作为产物：
  描述：

  3-(1-methylethoxy)-4-methylcyclobut-3-ene-1,2-dione 在 四氯化碳 、 lithium tri-t-butoxyaluminum hydride 、 三苯基膦 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 4.5h， 生成 4-Chloro-2-methyl-3-(1-methylethoxy)-2-cyclobutenone
  参考文献：
  名称：

  通过区域控制结构的 4 位不饱和取代基环丁烯酮合成高度取代的芳烃

  摘要：

  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

  DOI：

  10.1021/ja00030a043
• 作为试剂：
  描述：

  4-acetoxy-1-methoxy-3-(1-methylethoxy)-2-phenyl-6-(tri-n-butylstannyl)naphthalene 在 tris(dibenzylideneacetone)dipalladium (0) 、 三(2-呋喃基)膦 、 4-Chloro-2-methyl-3-(1-methylethoxy)-2-cyclobutenone 作用下， 以 1,4-二氧六环 为溶剂， 反应 16.0h， 以7%的产率得到1-acetoxy-4-methoxy-2-(1-methylethoxy)-3-phenylnaphthalene
  参考文献：
  名称：

  General Synthetic Entry to Highly-Oxygenated, Angularly-Fused Polycyclic Aromatic Compounds

  摘要：

  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.

  DOI：

  10.1021/ja00117a009

文献信息

• 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.
• Benzannulation of stannylquinones. A new regiocontrolled construction of substituted naphtho- and anthraquinones
  作者：James P. Edwards、Damian J. Krysan、Lanny S. Liebeskind

  DOI：10.1021/ja00074a091

  日期：1993.10
• 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.