2,4'-dihydroxy-3',5'-di-(tert-butyl)diphenyl | 131845-60-8

• 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'-dihydroxy-3',5'-di-(tert-butyl)diphenyl
• 英文别名: 2,6-Ditert-butyl-4-(2-hydroxyphenyl)phenol
• CAS: 131845-60-8
• 化学式: C₂₀H₂₆O₂
• 分子量: 298.425
• InChiKey: UFASMSWFPLKUIV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,4'-dihydroxy-3',5'-di-(tert-butyl)diphenyl 在 氢氧化钾 、 硫酸 、 potassium hexacyanoferrate(III) 作用下， 以 溶剂黄146 、 苯 为溶剂， 反应 15.0h， 生成 3,3',5,5'-tetra-tert-butyl-[1,1'-biphenyl]-2,4'-diol
  参考文献：
  名称：

  Unusual synthesis, structure, and thermochromic properties of novel sterically hindered cyclohexadienes

  摘要：

  Oxidation of 4-[alpha-morpholino-alpha-(2-hydroxyphenyl)]methyl-2,6-di-(tert-butyl)-phenol (I) follows an unusual course, with formal loss of the benzyl carbon atom, to give 2,6-di(tert-butyl)-4-morpholino-4-(2-hydroxyphenyl)cyclohexa-2,5-dienone (II), which is thermochromic in solution. This property is due to the dissociation of (II) into morpholine and 3',5'-di(tert-butyl)-2,4'-diphenoxyquinone. The structure of (II) was established directly by x-ray diffraction, which enabled its conformational features to be related to its thermochromic properties. An x-ray examination of 3,3',5,5'-tetra(tert-butyl)-2,4'-diphenoquinone (X), together with the direct synthesis of the thermochromic analog of (II) (2,6-di(tert-butyl)-4-morpholino-4-[2-hydroxy-3,5-di(tert-butyl)phenyl]cyclohexa-2,5-dienone) (XI) from (X) and morpholine, confirmed the proposed mechanism of thermochromic dissociation.

  DOI：

  10.1007/bf00961363
• 作为产物：
  描述：

  2,6-di(tert-butyl)-4-morpholino-4-(2-hydroxyphenyl)cyclohexa-2,5-dione 在 sodium dithionite 作用下， 以 乙醇 、 水 为溶剂， 以62%的产率得到2,4'-dihydroxy-3',5'-di-(tert-butyl)diphenyl
  参考文献：
  名称：

  Unusual synthesis, structure, and thermochromic properties of novel sterically hindered cyclohexadienes

  摘要：

  Oxidation of 4-[alpha-morpholino-alpha-(2-hydroxyphenyl)]methyl-2,6-di-(tert-butyl)-phenol (I) follows an unusual course, with formal loss of the benzyl carbon atom, to give 2,6-di(tert-butyl)-4-morpholino-4-(2-hydroxyphenyl)cyclohexa-2,5-dienone (II), which is thermochromic in solution. This property is due to the dissociation of (II) into morpholine and 3',5'-di(tert-butyl)-2,4'-diphenoxyquinone. The structure of (II) was established directly by x-ray diffraction, which enabled its conformational features to be related to its thermochromic properties. An x-ray examination of 3,3',5,5'-tetra(tert-butyl)-2,4'-diphenoquinone (X), together with the direct synthesis of the thermochromic analog of (II) (2,6-di(tert-butyl)-4-morpholino-4-[2-hydroxy-3,5-di(tert-butyl)phenyl]cyclohexa-2,5-dienone) (XI) from (X) and morpholine, confirmed the proposed mechanism of thermochromic dissociation.

  DOI：

  10.1007/bf00961363

文献信息

• Substituent‐Controlled Regiodivergent Palladium‐Catalyzed Annulative Dearomatization of Phenols toward Skeletally Diverse Spirocyclohexadienones
  作者：Hui‐Lin Mao、Jun Yu、Yi‐Ting Shen、Qiuyun Li、Wen‐Juan Hao、Bo Jiang

  DOI：10.1002/adsc.202300674

  日期：2023.9.19

  A palladium-catalyzed intermolecular dearomative formal [4+2] annulation of phenols with propargyl electrophiles is reported, enabling substituent-controlled regiodivergent synthesis of a wide range of skeletally diverse spirocyclohexadienones with good yields. The regiodivergence could be precisely controlled by adjusting the steric hindrance of O- and N-substituents from binucleophilic substrates

  报道了一种钯催化的苯酚与炔丙基亲电子试剂的分子间脱芳香形式[4+2]成环反应，使得取代基控制的区域发散合成多种骨架多样的螺环己二烯酮具有良好的产率。通过调节双亲核底物中O - 和N - 取代基的空间位阻可以精确控制区域发散，其中具有O - 亲核位点的底物被转化为螺[色烷-4,1'-环己烷]-2',5' -dien-4'-ones 具有完全的区域选择性和 ( Z )-选择性，而N-亲核试剂能够通过不同的区域发散过程来获得螺[环己烷-1,4'-喹啉]-2,5-dien-4-ones。
• Pd-Catalyzed Asymmetric Annulative Dearomatization of Phenols for Regio- and Enantioselective Synthesis of Spirocyclohexadienones
  作者：Hui-Lin Mao、Yu-Xin Wang、Xue Wang、Hai-Ying Wang、Wen-Juan Hao、Bo Jiang

  DOI：10.1021/acs.orglett.3c02051

  日期：2023.8.18

  A palladium-catalyzed asymmetric annulative dearomatization of phenols with butene dicarbonate is reported, enabling twofold decarboxylative allylation to regioselectively produce a range of spirocyclohexadienones with 29–95% yields and 74–99% ee. A catalytic dearomative formal [4 + 2] cyclization of 1,1′-biphenyl-2,4′-diols delivered spiro[chromane-4,1′-cyclohexane]-2′,5′-dien-4′-ones with high enantioselectivity

  据报道，钯催化的苯酚与丁烯二碳酸酯的不对称环环脱芳构化反应能够实现双重脱羧烯丙基化，从而区域选择性地产生一系列螺环己二酮，产率为 29-95%，ee 为 74-99%。1,1'-联苯-2,4'-二醇的催化脱芳香形式[4 + 2]环化生成螺[苯并二氢吡喃-4,1'-环己烷]-2',5'-二烯-4'-酮高对映选择性，而对映体富集的螺[环己烷-1,4'-喹啉]-2,5-二烯-4-酮是从2'-氨基-[1,1'-联苯]-4-醇开始生成的，为1， 4-双亲核试剂。
• KOMISSAROV, V. N.;UXIN, L. YU.;XARLANOV, V. A.;VETOSHKINA, L. V.;KONSTANT+, IZV. AN CCCP. CEP. XIM.,(1991) N, S. 1121-1129
  作者：KOMISSAROV, V. N.、UXIN, L. YU.、XARLANOV, V. A.、VETOSHKINA, L. V.、KONSTANT+

  DOI：——

  日期：——
• Synthesis and crystal structure of thermochroic 2,6-di-tert-butyl-4-dimethylamino-4-(2-hydroxyphenyl) cyclohexadien-2,5-one
  作者：S. M. Aldoshin、O. S. Filipenko、M. A. Novozhilova、L. O. Atovmyan、V. N. Komissarov、L. Yu. Ukhin

  DOI：10.1007/bf01172259

  日期：1991.8

  The compound 2,6-di-tert-butyl-4-dimethylamino-4-(2-hydroxyphenyl)cyclohexadien-2,5-one is synthesized and its structure is studied. The thermochromism of the compound is due to cleavage on excitation of the C(spiro)-N bond, which is lengthened to 1.512 angstrom under normal conditions, and O --> N proton transfer. A deeply colored diphenoquinone and dimethylamine are formed. The C(spiro)-N bond is lengthened due to mutual steric repulsion of the atoms bound to C4 and N.
• Biphenyl derivative, nerve cell degeneration repairing or protecting agent and process for preparing a phenyl derivative contained in the agent
  申请人：OTSUKA PHARMACEUTICAL CO., LTD.

  公开号：EP0382213B1

  公开（公告）日：1995-05-10