3-(2',2'-dimethyl-6'-methylidenecyclohexyl)-1-propanol | 95452-04-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(2',2'-dimethyl-6'-methylidenecyclohexyl)-1-propanol
• 英文别名: 3-(2,2-dimethyl-6-methylene-cyclohexyl)-propan-1-ol；3-(2,2-Dimethyl-6-methylen-cyclohexyl)-propan-1-ol；Cyclohexanepropanol, 2,2-dimethyl-6-methylene-；3-(2,2-dimethyl-6-methylidenecyclohexyl)propan-1-ol
• CAS: 95452-04-3
• 化学式: C₁₂H₂₂O
• 分子量: 182.306
• InChiKey: FKUIYDFLMWSYME-UHFFFAOYSA-N

物化性质

• 沸点：
  123-124 °C(Press: 12 Torr)
• 密度：
  0.90±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  3-(2',2'-dimethyl-6'-methylidenecyclohexyl)-1-propanol 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 生成 alpha,2,2-三甲基-6-亚甲基-环己烷丙醇
  参考文献：
  名称：

  Studies on the Synthesis of Acanthodoral and Nanaimoal:  Evaluation of Cationic Cyclization Routes

  摘要：

  Intramolecular Lewis acid-promoted reactions of alpha,beta-unsaturated ketone 6 and aldehydes 7 and 8 were examined as potential routes to acanthodoral (1), a structurally interesting natural product. Ketone 6 afforded ene product 22 exclusively, and both 7 and 8 gave mixtures of bicyclic aldehydes 3 and 26 and tricyclic aldehyde 25. The latter most likely results from 7 by intramolecular cyclization of the alkene onto the Lewis acid-activated carbonyl moiety affording carbocation 31 followed by a 1,2-hydride shift and ring closure. Starting from 8, tricyclic aldehyde 25 apparently forms by cyclization to cation 35 and ring closure to cyclobutane 36, followed by ring opening to 31, the same cation as formed in reactions of 7. Nanaimoal (3) results from loss of H+ from 31, and bicyclic aldehyde 26 may be formed in a similar manner or by a concerted ene reaction. The configuration of 25 establishes that the stereochemistry of the initial cyclization to 31 precludes the possible use of this strategy for the synthesis of acanthodoral. However, acid-promoted cyclization of allylic alcohol 23 efficiently gives diene 29 which undergoes selective hydroboration/oxidation to afford nanaimoal.

  DOI：

  10.1021/jo9610568
• 作为产物：
  描述：

  4-(2,2-二甲基-6-亚甲基环己基)丁烷-2-酮 在 sodium hydroxide 、 lithium aluminium tetrahydride 、 碘 作用下， 以 乙醚 为溶剂， 反应 3.0h， 生成 3-(2',2'-dimethyl-6'-methylidenecyclohexyl)-1-propanol
  参考文献：
  名称：

  光化学反应。第139次交流。酰基硅烷的光化学：1.硅氧烷形成与γ-H提取†

  摘要：

  描述了酰基硅烷1和相应的甲基酮2的合成和光解。在n，π*激发下，甲硅烷基酮1和甲基酮2进行Norrish II型反应，包括γ-H吸收并断裂成二烯12和丙酮（20）或酰基硅烷26。甲基酮2而不是酰基硅烷1异构化为环丁醇（21A - D）。此外，化合物1显示出典型的酰基硅烷发生重排为甲氧化卡宾中间体c的光化学行为。将c插入烯醇28的OH-ond导致化合物13。但是，H 2 O最初捕集甲硅烷氧基碳烯c会导致化合物16 – 18的形成。作为次要光解产物1，化合物14和（Ž） - 15形成; 但是，在气相热解（520°）下的1，化合物14和（E / Z15）以92％的总收率获得。酰基硅烷1在较小程度上也经历了Norrish I型裂解，从而生成了酸19。

  DOI：

  10.1002/hlca.19840670711

文献信息

• �ber die fl�chtigen Bestandteile des grauen Ambra. 3. Mitteilung. Isolierung und Identifizierung von ?-Cyclohomogeraniol im grauen Ambra. Synthese von l,l-Dimethyl-2-(?-hydroxy�thyl)-3-methylen-cyclohexan (?-Cyclo-homo-geraniol) und l,l-Dimethyl-2-(?-hydroxypropyl)-3-methylen-cyclohexan
  作者：C. F. Seidel、M. Stoll

  DOI：10.1002/hlca.19570400650

  日期：——

  In good agreement with previous oxydation results, it is shown that the volatile non-ketonic fractions of gray amber contain mainly γ-Cyclo-homo-geraniol.

  与先前的氧化结果非常吻合，表明灰琥珀色的挥发性非酮级分主要包含γ-环-均-香叶醇。
• SCHELLER, M. E.;FREI, B., HELV. CHIM. ACTA, 1984, 67, N 7, 1734-1747
  作者：SCHELLER, M. E.、FREI, B.

  DOI：——

  日期：——
• Studies on the Synthesis of Acanthodoral and Nanaimoal:  Evaluation of Cationic Cyclization Routes
  作者：Thomas A. Engler、Mohammed Hashmat Ali、Fusao Takusagawa

  DOI：10.1021/jo9610568

  日期：1996.1.1

  Intramolecular Lewis acid-promoted reactions of alpha,beta-unsaturated ketone 6 and aldehydes 7 and 8 were examined as potential routes to acanthodoral (1), a structurally interesting natural product. Ketone 6 afforded ene product 22 exclusively, and both 7 and 8 gave mixtures of bicyclic aldehydes 3 and 26 and tricyclic aldehyde 25. The latter most likely results from 7 by intramolecular cyclization of the alkene onto the Lewis acid-activated carbonyl moiety affording carbocation 31 followed by a 1,2-hydride shift and ring closure. Starting from 8, tricyclic aldehyde 25 apparently forms by cyclization to cation 35 and ring closure to cyclobutane 36, followed by ring opening to 31, the same cation as formed in reactions of 7. Nanaimoal (3) results from loss of H+ from 31, and bicyclic aldehyde 26 may be formed in a similar manner or by a concerted ene reaction. The configuration of 25 establishes that the stereochemistry of the initial cyclization to 31 precludes the possible use of this strategy for the synthesis of acanthodoral. However, acid-promoted cyclization of allylic alcohol 23 efficiently gives diene 29 which undergoes selective hydroboration/oxidation to afford nanaimoal.
• Photochemical reactions. 139th Communication. Photochemistry of acylsilanes: 1. Siloxcarbene formationversus ?-H-abstraction
  作者：Markus E. Scheller、Bruno Frei

  DOI：10.1002/hlca.19840670711

  日期：1984.11.7

  the silyl ketone 1 as well as the methyl ketone 2 undergo a Norrish type II reaction involving γ-H-abstraction and fragmentation to the diene 12, and acetone (20) or the acylsilane 26, respectively. The methyl ketone 2, but not the acylsilane 1, isomerizes to cyclobutanols (21A-D). Additionally, compound 1 shows photochemical behavior typical of acylsilanes undergoing rearrangement to the siloxycarbene

  描述了酰基硅烷1和相应的甲基酮2的合成和光解。在n，π*激发下，甲硅烷基酮1和甲基酮2进行Norrish II型反应，包括γ-H吸收并断裂成二烯12和丙酮（20）或酰基硅烷26。甲基酮2而不是酰基硅烷1异构化为环丁醇（21A - D）。此外，化合物1显示出典型的酰基硅烷发生重排为甲氧化卡宾中间体c的光化学行为。将c插入烯醇28的OH-ond导致化合物13。但是，H 2 O最初捕集甲硅烷氧基碳烯c会导致化合物16 – 18的形成。作为次要光解产物1，化合物14和（Ž） - 15形成; 但是，在气相热解（520°）下的1，化合物14和（E / Z15）以92％的总收率获得。酰基硅烷1在较小程度上也经历了Norrish I型裂解，从而生成了酸19。