6-(1-Hydroxyethyl)-6-methylfulvene | 162143-86-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-(1-Hydroxyethyl)-6-methylfulvene
• 英文别名: 3-Cyclopenta-2,4-dien-1-ylidenebutan-2-ol
• CAS: 162143-86-4
• 化学式: C₉H₁₂O
• 分子量: 136.194
• InChiKey: VLZIOXVUIMYKHS-UHFFFAOYSA-N

物化性质

• 沸点：
  239.2±9.0 °C(predicted)
• 密度：
  1.035±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6-(1-Hydroxyethyl)-6-methylfulvene 在 5,10,15,20-tetrakisphenylporphyrin 、 氧气 、 potassium diazodicarboxylate 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 (1S,4R)-3-[2,3-Dioxa-bicyclo[2.2.1]hept-(7E)-ylidene]-butan-2-ol
  参考文献：
  名称：

  Unusual endoperoxide isomerizations: a convenient entry into 2-vinyl-2-cyclopentenones from saturated fulvene endoperoxides

  摘要：

  An unusual peroxide base-promoted isomerization is uncovered. Saturated endoperoxides derived from fulvenes give rise to 2-vinyl-2-cyclopentenones upon treatment with DBU in CH2CL2 in a one-pot reaction. This methodology is applied to a convenient synthesis of dihydrojasmone. Moreover, functional groups placed on the side chain at C-6 participate in the base-catalyzed isomerizations via conjugate attack at the enone moiety to give 2-cyclopentenones carrying oxygen heterocycles at C-2. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.07.107
• 作为产物：
  描述：

  3-羟基-2-丁酮 、 环戊二烯 在 四氢吡咯 作用下， 以85%的产率得到6-(1-Hydroxyethyl)-6-methylfulvene
  参考文献：
  名称：

  Scope and Limitations of Fulvene Syntheses. Preparation of 6-Vinyl-Substituted and -Functionalized Fulvenes. First Examples of Nucleophilic Substitution on a 6-(Chloromethyl)fulvene

  摘要：

  Very few 6-vinylfulvenes have previously been reported in the Literature. In a few cases where Little's procedure (using pyrrolidine as base) has been employed, most enones undergo conjugate attack by the cyclopentadienyl anion followed by either a retroaldol reaction or dihydropentalene formation. In several cases, Diels-Alder reaction of the enone with cyclopentadiene occurs rather than condensation. We have found that in cases where the Little procedure fails to give the desired 6-vinylfulvenes, the Thiele method using NaOH (or NaOMe in some cases) as base gives satisfactory results. In the latter instances, Michael attack is completely suppressed in all but one example. By appropriate choice of base, a variety of fulvenes carrying functional groups on the 6-alkyl position can be prepared. Some of these fulvenes have been shown to undergo further functional group transformations (e.g., nucleophilic substitutions); giving rise to derivatives bearing SR, S(O)R, N-3 or SCN groups.

  DOI：

  10.1021/jo00109a010

文献信息

• Scope and Limitations of Fulvene Syntheses. Preparation of 6-Vinyl-Substituted and -Functionalized Fulvenes. First Examples of Nucleophilic Substitution on a 6-(Chloromethyl)fulvene
  作者：Ihsan Erden、Fu-Pei Xu、Aladin Sadoun、Wyatt Smith、Greg Sheff、Madeleine Ossun

  DOI：10.1021/jo00109a010

  日期：1995.2

  Very few 6-vinylfulvenes have previously been reported in the Literature. In a few cases where Little's procedure (using pyrrolidine as base) has been employed, most enones undergo conjugate attack by the cyclopentadienyl anion followed by either a retroaldol reaction or dihydropentalene formation. In several cases, Diels-Alder reaction of the enone with cyclopentadiene occurs rather than condensation. We have found that in cases where the Little procedure fails to give the desired 6-vinylfulvenes, the Thiele method using NaOH (or NaOMe in some cases) as base gives satisfactory results. In the latter instances, Michael attack is completely suppressed in all but one example. By appropriate choice of base, a variety of fulvenes carrying functional groups on the 6-alkyl position can be prepared. Some of these fulvenes have been shown to undergo further functional group transformations (e.g., nucleophilic substitutions); giving rise to derivatives bearing SR, S(O)R, N-3 or SCN groups.
• Unusual endoperoxide isomerizations: a convenient entry into 2-vinyl-2-cyclopentenones from saturated fulvene endoperoxides
  作者：Ihsan Erden、Nüket Öcal、Jiangao Song、Cindy Gleason、Christian Gärtner

  DOI：10.1016/j.tet.2006.07.107

  日期：2006.11

  An unusual peroxide base-promoted isomerization is uncovered. Saturated endoperoxides derived from fulvenes give rise to 2-vinyl-2-cyclopentenones upon treatment with DBU in CH2CL2 in a one-pot reaction. This methodology is applied to a convenient synthesis of dihydrojasmone. Moreover, functional groups placed on the side chain at C-6 participate in the base-catalyzed isomerizations via conjugate attack at the enone moiety to give 2-cyclopentenones carrying oxygen heterocycles at C-2. (c) 2006 Elsevier Ltd. All rights reserved.