2,4-diphenyl-4-hydroxy-3-methoxy-2-cyclobuten-1-one | 137395-33-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,4-diphenyl-4-hydroxy-3-methoxy-2-cyclobuten-1-one
• 英文别名: 4-hydroxy-3-methoxy-2,4-diphenylcyclobut-2-en-1-one
• CAS: 137395-33-6
• 化学式: C₁₇H₁₄O₃
• 分子量: 266.296
• InChiKey: YRPPQOFTANTCOB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.51
• 重原子数：
  20.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2,4-diphenyl-4-hydroxy-3-methoxy-2-cyclobuten-1-one 在 吡啶 、 氯化亚砜 、 silver(l) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 12.17h， 生成 4-isopropoxy-3-methoxy-2,4-diphenyl-2-cyclobuten-1-one
  参考文献：
  名称：

  Synthesis of p-chlorophenols (and -naphthols) from the thermal rearrangement of 4-chlorocyclobutenones

  摘要：

  A systematic study of the reaction of 4-hydroxycyclobutenones with thionyl chloride is reported. A useful model evolves from this study which allows the prediction of the site of chlorination for unsymmetrical examples. The chlorination is envisaged to involve the corresponding homoaromatic carbocation, and the site of chlorination takes place preferentially at the position substituted with the greater cation-stabilizing substituent. Specifically, this follows the general order of allyl > benzyl > alkyl > propargyl. The 4-chlorocyclobutenones prepared in this study were shown to be useful synthetic precursors to highly substituted chlorophenols and chloronaphthols.

  DOI：

  10.1021/jo00027a057
• 作为产物：
  描述：

  苯基锂 、 3-methoxy-4-phenylcyclobutenedione 以 四氢呋喃 为溶剂， 反应 0.25h， 以80%的产率得到2,4-diphenyl-4-hydroxy-3-methoxy-2-cyclobuten-1-one
  参考文献：
  名称：

  Synthesis of p-chlorophenols (and -naphthols) from the thermal rearrangement of 4-chlorocyclobutenones

  摘要：

  A systematic study of the reaction of 4-hydroxycyclobutenones with thionyl chloride is reported. A useful model evolves from this study which allows the prediction of the site of chlorination for unsymmetrical examples. The chlorination is envisaged to involve the corresponding homoaromatic carbocation, and the site of chlorination takes place preferentially at the position substituted with the greater cation-stabilizing substituent. Specifically, this follows the general order of allyl > benzyl > alkyl > propargyl. The 4-chlorocyclobutenones prepared in this study were shown to be useful synthetic precursors to highly substituted chlorophenols and chloronaphthols.

  DOI：

  10.1021/jo00027a057

文献信息

• Synthesis and Thermal Rearrangements of 4-Allyl-4-arylcyclobutenones
  作者：Ralf Tiedemann、Philip Turnbull、Harold W. Moore

  DOI：10.1021/jo990052a

  日期：1999.5.1

  The synthesis and thermolysis of 4-allyl-4-arylcyclobutenones are detailed. Allylcyclobutenones were prepared through the trapping of the cyclobutenonium cation generated by treatment of 4-hydroxycyclobutenones with Lewis acids. A study of the nucleophilic trapping revealed the following mechanistic highlights: the most likely intermediate is the cyclobutenonium cation, the regioselectivity of the allylation reaction is dictated by attack at the site most suited to stabilize the cation, and the rate of allylation is dependent on carbocation formation. Thermolysis of 4-allyl-4-arylcyclobutenones made possible a study of the competitive [2 + 2] cycloaddition and 6 pi electrocyclization. A judicious choice of substituents allows some control of the selectivity between the two pathways. The substituents control this selectivity through a combination of imposed electronics in the dienylketene intermediate, the relative ketenophilicity of the 4-position substituent, and the relative contortion substituents in the 2- and S-positions impose on the transition state of the respective ring-closure processes. The scope of the cyclobutenonium cation trapping with silylated carbon nucleophiles was explored, producing 4-allenylcyclobutenones from the use of propargylsilane and 4-spirocyclobutenones from triisopropylsilane. Thermolysis studies of these precursors are also detailed.
• XU, SIMON L.;MOORE, HAROLD W., J. ORG. CHEM., 54,(1989) N7, C. 4024-4026
  作者：XU, SIMON L.、MOORE, HAROLD W.

  DOI：——

  日期：——
• Synthesis of p-chlorophenols (and -naphthols) from the thermal rearrangement of 4-chlorocyclobutenones
  作者：Simon L. Xu、Harold W. Moore

  DOI：10.1021/jo00027a057

  日期：1992.1

  A systematic study of the reaction of 4-hydroxycyclobutenones with thionyl chloride is reported. A useful model evolves from this study which allows the prediction of the site of chlorination for unsymmetrical examples. The chlorination is envisaged to involve the corresponding homoaromatic carbocation, and the site of chlorination takes place preferentially at the position substituted with the greater cation-stabilizing substituent. Specifically, this follows the general order of allyl > benzyl > alkyl > propargyl. The 4-chlorocyclobutenones prepared in this study were shown to be useful synthetic precursors to highly substituted chlorophenols and chloronaphthols.