2-hydroxy-4,4-dimethyl-6-tert-butylcyclohexa-2,5-diene-1-one | 122800-85-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-hydroxy-4,4-dimethyl-6-tert-butylcyclohexa-2,5-diene-1-one
• 英文别名: 2-Tert-butyl-6-hydroxy-4,4-dimethylcyclohexa-2,5-dien-1-one
• CAS: 122800-85-5
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: PAOZYHARMJADOX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-hydroxy-4,4-dimethyl-6-tert-butylcyclohexa-2,5-diene-1-one 在 硫酸 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以95%的产率得到4,5-二甲基-1,2-苯二酚
  参考文献：
  名称：

  Electronic and Steric Effects in the Dienone-Phenol Rearrangement of 2-Hydroxy- and 2-Alkoxycyclohexa-2,5-dien-1-ones

  摘要：

  A series of 4,4,6-trisubstituted-2-hydroxy- and -2-alkoxycyclohexa-2,5-dien-1-ones (7 and 8) were prepared, where the substituent at C-6 was H, CH3, Ph, tert-butyl, or Oft. In the acid-catalyzed dienone-phenol rearrangement of 7 and 8, the C-4 substituent migrates regioselectively to C-5, completely shunning the enol double bond, even though the substituents at C-6 are substantially larger than the OH or OMe groups situated at C-2. The C-5 regioselectivity in hydroxy dienones 7a-f and 8a,b, as well as the decreased rate of reaction in the case of dienone 7g, can be simply rationalized by considering the relative electron density at C-3 vs C-5 in the protonated form of ? or 8. Our results clearly indicate that the regioselectivity of the dienone-phenol rearrangement in these enolic systems is completely controlled by the electronic factors, which far outweigh any steric considerations.

  DOI：

  10.1021/jo00086a038
• 作为产物：
  描述：

  3-tert-butyl-5,5-dimethyl-2-cyclohexen-1-one 生成 2-hydroxy-4,4-dimethyl-6-tert-butylcyclohexa-2,5-diene-1-one
  参考文献：
  名称：

  FRIMER, ARYEH A.;GILINSKY-SHARON, PESSIA;ALJADEFF, GLADIS;GOTTLIEB, HUGO +, J. ORG. CHEM., 54,(1989) N0, C. 4853-4866

  摘要：

  DOI：

文献信息

• Superoxide anion radical (O2.bul.-)-mediated base-catalyzed autoxidation of enones
  作者：Aryeh A. Frimer、Pessia Gilinsky-Sharon、Gladis Aljadeff、Hugo E. Gottlieb、Judith Hameiri-Buch、Vered Marks、Rachel Philosof、Zilpa Rosental

  DOI：10.1021/jo00281a030

  日期：1989.9
• Superoxide anion radical (02.bul.-) mediated base-catalyzed autoxidation of .alpha.-keto enols
  作者：Aryeh A. Frimer、Pessia Gilinsky-Sharon、Gladis Aljadeff、Vered Marks、Zilpa Rosental

  DOI：10.1021/jo00281a031

  日期：1989.9
• FRIMER, ARYEH A.;GILINSKY-SHARON, PESSIA;ALJADEFF, GLADIS;GOTTLIEB, HUGO +, J. ORG. CHEM., 54,(1989) N0, C. 4853-4866
  作者：FRIMER, ARYEH A.、GILINSKY-SHARON, PESSIA、ALJADEFF, GLADIS、GOTTLIEB, HUGO +

  DOI：——

  日期：——
• FRIMER, ARYEH A.;GILINSKY-SHARON, PESSIA;ALJADEFF, GLADIS;MARKS, VERED;RO+, J. ORG. CHEM., 54,(1989) N0, C. 4866-4872
  作者：FRIMER, ARYEH A.、GILINSKY-SHARON, PESSIA、ALJADEFF, GLADIS、MARKS, VERED、RO+

  DOI：——

  日期：——
• Electronic and Steric Effects in the Dienone-Phenol Rearrangement of 2-Hydroxy- and 2-Alkoxycyclohexa-2,5-dien-1-ones
  作者：Aryeh A. Frimer、Vered Marks、Milon Sprecher、Pessia Gilinsky-Sharon

  DOI：10.1021/jo00086a038

  日期：1994.4

  A series of 4,4,6-trisubstituted-2-hydroxy- and -2-alkoxycyclohexa-2,5-dien-1-ones (7 and 8) were prepared, where the substituent at C-6 was H, CH3, Ph, tert-butyl, or Oft. In the acid-catalyzed dienone-phenol rearrangement of 7 and 8, the C-4 substituent migrates regioselectively to C-5, completely shunning the enol double bond, even though the substituents at C-6 are substantially larger than the OH or OMe groups situated at C-2. The C-5 regioselectivity in hydroxy dienones 7a-f and 8a,b, as well as the decreased rate of reaction in the case of dienone 7g, can be simply rationalized by considering the relative electron density at C-3 vs C-5 in the protonated form of ? or 8. Our results clearly indicate that the regioselectivity of the dienone-phenol rearrangement in these enolic systems is completely controlled by the electronic factors, which far outweigh any steric considerations.