(E)-2,2-dimethyl-4-methyl-4-hexen-3-ol | 223140-41-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-2,2-dimethyl-4-methyl-4-hexen-3-ol
• 英文别名: (4E)-2,2,4-trimethylhex-4-en-3-ol；(E)-2,2,4-trimethylhex-4-en-3-ol
• CAS: 223140-41-8
• 化学式: C₉H₁₈O
• 分子量: 142.241
• InChiKey: WJZKVWPADJARMV-VOTSOKGWSA-N

物化性质

• 沸点：
  168.4±8.0 °C(Predicted)
• 密度：
  0.844±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  (E)-2,2-dimethyl-4-methyl-4-hexen-3-ol 在 Celite 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以75%的产率得到(4E)-2,2,4-trimethylhex-4-en-3-one
  参考文献：
  名称：

  Design, Synthesis and Olfactory Properties of 2-Substituted 2-tert-Butyl-5-­methyl-2,5-dihydrofurans: seco-Derivatives of Theaspiranes

  摘要：

  具有明显黑加仑香味的两种次级锡兰螺环烷，2-叔丁基-5-甲基-2-丙基-2,5-二氢呋喃（7）和2-叔丁基-5-甲基-2-丙基四氢呋喃（8），通过包括格氏反应、林德拉氢化和环化，随后可选择钯催化的氢化反应的合成序列合成。该序列经过修改，用于合成含氧化合物2-(2'-叔丁基-5'-甲基四氢呋喃-2'-基)丙烷-2-醇（9）和3-(2'-叔丁基-5'-甲基四氢呋喃-2'-基)丁烷-2-酮（10）。第一次修改特色是三甲基硅醚保护以及由于空间位阻所需的乙炔部分的逐步构建。在第二次修改中，使用2-丁烯-2-基作为潜在的3-羟基丁烯-1-烯-2-基功能性，并通过SN2环闭合引入立体中心，利用围绕三级羟基的空间约束。至于母体化合物7和9，含氧次级锡兰螺环烷的香味向木质调性转变。相似的非对映异构体9a甚至具有典型的广藿香特征，而其对映体10a和10b在嗅觉特性上有显著差异。

  DOI：

  10.1055/s-2005-918404
• 作为产物：
  描述：

  反式-2-甲基-2-丁烯醛 、 叔丁基锂 以 四氢呋喃 为溶剂， 反应 4.0h， 以25%的产率得到(E)-2,2-dimethyl-4-methyl-4-hexen-3-ol
  参考文献：
  名称：

  Regio- and Diastereoselective Ene Reaction of 4-Phenyl-1,2,4-triazoline-3,5-dione with Chiral Allylic Alcohols and Their Derivatives

  摘要：

  Chiral allylic alcohols la-e reacted with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) in CH2Cl2 to produce 3-amino-1-alken-4-ols 2 and 3 in 78-89% yields, with 68-90% diastereomeric excess (de) in favor of the three isomer. Chiral allylic ethers If,g and acetates Ih,i gave similar yields but lower de (34-66%). Reaction of allylic alcohols 6a-e with PTAD in CH2Cl2 produced 1,3-regioisomers 7 and 8 exclusively in 33-65% yields without apparent diastereoselectivity, except when R-1 was a Bu-t group, in which case only syn product 7 was formed. However, when 6a or 6c was subjected to reaction with PTAD in a polar solvent, up to 88% de was observed. Reaction of allylic ethers 6f,g and acetates 6h,i with PTAD in CH2Cl2 also produced 7 and 8 exclusively with improved yields (56-96%) and diastereoselectivity (50-100% de in favor of the syn isomer).

  DOI：

  10.1021/jo980835g

文献信息

• Design, Synthesis and Olfactory Properties of 2-Substituted 2-<i>tert</i>-Butyl-5-­methyl-2,5-dihydrofurans: <i>seco</i>-Derivatives of Theaspiranes
  作者：Philip Kraft、Kasim Popaj、Agnese Abate

  DOI：10.1055/s-2005-918404

  日期：——

  Two seco-theaspiranes with pronounced blackcurrant notes, 2-tert-butyl-5-methyl-2-propyl-2,5-dihydrofuran (7) and 2-tert-butyl-5-methyl-2-propyltetrahydrofuran (8), were synthesized by a synthetic sequence consisting of Grignard reaction, Lindlar ­hydrogenation, and cyclization followed by optional Pd-catalyzed hydrogenation. The sequence was modified for the synthesis of the oxygenated analogs 2-(2′-tert-butyl-5′-methyltetrahydrofuran-2′-yl)propan-2-ol (9) and 3-(2′-tert-butyl-5′-methyltetrahydrofuran-2′-yl)butan-2-one (10). The first modification featured trimethyl­silyl ether protection and stepwise construction of the alkyne moiety necessitated by steric hindrance. In the second modification, a but-2-en-2-yl group was utilized as latent 3-hydroxybut-1-en-2-yl functionality, and the steric constraint around the tertiary hydroxy group was exploited to introduce a stereocenter by SN2 ring closure. As for the parent compounds 7 and 9, the odor of the oxygenated seco-­theaspiranes was shifted towards a woody tonality. The like-diastereo­mer 9a even had a typical patchouli profile, and the ­enantiomers 10a and 10b differed significantly in their olfactory properties.

  具有明显黑加仑香味的两种次级锡兰螺环烷，2-叔丁基-5-甲基-2-丙基-2,5-二氢呋喃（7）和2-叔丁基-5-甲基-2-丙基四氢呋喃（8），通过包括格氏反应、林德拉氢化和环化，随后可选择钯催化的氢化反应的合成序列合成。该序列经过修改，用于合成含氧化合物2-(2'-叔丁基-5'-甲基四氢呋喃-2'-基)丙烷-2-醇（9）和3-(2'-叔丁基-5'-甲基四氢呋喃-2'-基)丁烷-2-酮（10）。第一次修改特色是三甲基硅醚保护以及由于空间位阻所需的乙炔部分的逐步构建。在第二次修改中，使用2-丁烯-2-基作为潜在的3-羟基丁烯-1-烯-2-基功能性，并通过SN2环闭合引入立体中心，利用围绕三级羟基的空间约束。至于母体化合物7和9，含氧次级锡兰螺环烷的香味向木质调性转变。相似的非对映异构体9a甚至具有典型的广藿香特征，而其对映体10a和10b在嗅觉特性上有显著差异。
• Regio- and Diastereoselective Ene Reaction of 4-Phenyl-1,2,4-triazoline-3,5-dione with Chiral Allylic Alcohols and Their Derivatives
  作者：Ay-Hua Gau、Guey-Liang Lin、Biing-Jiun Uang、Fen-Ling Liao、Sue-Lein Wang

  DOI：10.1021/jo980835g

  日期：1999.4.1

  Chiral allylic alcohols la-e reacted with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) in CH2Cl2 to produce 3-amino-1-alken-4-ols 2 and 3 in 78-89% yields, with 68-90% diastereomeric excess (de) in favor of the three isomer. Chiral allylic ethers If,g and acetates Ih,i gave similar yields but lower de (34-66%). Reaction of allylic alcohols 6a-e with PTAD in CH2Cl2 produced 1,3-regioisomers 7 and 8 exclusively in 33-65% yields without apparent diastereoselectivity, except when R-1 was a Bu-t group, in which case only syn product 7 was formed. However, when 6a or 6c was subjected to reaction with PTAD in a polar solvent, up to 88% de was observed. Reaction of allylic ethers 6f,g and acetates 6h,i with PTAD in CH2Cl2 also produced 7 and 8 exclusively with improved yields (56-96%) and diastereoselectivity (50-100% de in favor of the syn isomer).