(1S,2R,5R,6R,9R)-2,6,10,10-tetramethyltricyclo<7.2.0.0^2,5>undecan-6-ol | 131830-35-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2R,5R,6R,9R)-2,6,10,10-tetramethyltricyclo<7.2.0.0^2,5>undecan-6-ol
• 英文别名: 1R,4R,5R,8R,9S-5,8-cyclocaryophyllan-4-ol；(1S,2R,5R,6R,9R)-2,6,10,10-tetramethyltricyclo[7.2.0.02,5]undecan-6-ol
• CAS: 131830-35-8
• 化学式: C₁₅H₂₆O
• 分子量: 222.371
• InChiKey: CPLGPDHGFNXBOA-BUONHZGMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  (1S,2R,5R,6R,9R)-2,6,10,10-tetramethyltricyclo<7.2.0.0^2,5>undecan-6-ol 、 3,5-二硝基苯甲酰氯 在 吡啶 作用下， 反应 6.0h， 以49%的产率得到3',5'-dinitrobenzoic acid (1S,2R,5R,6R,9R)-2,6,10,10-tetramethyltricyclo<7.2.0.0^2,5>undec-6-yl ester
  参考文献：
  名称：

  Rearrangement of (-)-.beta.-Caryophyllene. A Product Analysis and Force Field Study

  摘要：

  The rearrangement of (-)-beta-caryophyllene (1) with sulfuric acid in ether has been reinvestigated. In the early stage, a multitude of products is formed. Of these, fourteen hydrocarbons (3, 4, 6-17) and four alcohols (5, 18-20) were obtained pure. From the very beginning, the tricycloundecenes 15-17 accumulate quickly. This indicates that a previously unknown rearrangement of 1 by protonation of the exocyclic double bond followed by transannular ring closure is a main reaction, and that the conformation beta alpha is involved. Three hydrocarbons (3, 4, 8) and three alcohols (5, 18, 19) proved to be stable. They are the main components in the late stage. A complete rearrangement scheme followed from a force field analysis using MMP2. First, all conformations up to 4 kcal above the global minimum of each product and each carbenium ion necessary for its formation were detected automatically using the search program HUNTER. Second, the conformation favoring a specific transformation was searched for. For transannular cyclizations, the conformation with the shortest distance between the atoms to be bound and, for ring openings and 1,2-shifts, the conformation with the smallest dihedral angle between the empty p-orbital and the bond to be broken were selected. In all cases, the selection criteria proved valid: The stereochemistry of the conformations selected matched the stereochemistry of the products observed. On the basis of the results presented, a fully automated search prog ram for favorable rearrangement paths may be developed.

  DOI：

  10.1021/ja00141a009
• 作为产物：
  描述：

  (1R,2S,5R,9S)-1,4,4-trimethyl-8-methylenetricyclo<7.2.0.02,5>undecane 在 lithium aluminium tetrahydride 、 2甲4氯丁酸 、 potassium hydrogencarbonate 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 (1S,2R,5R,6R,9R)-2,6,10,10-tetramethyltricyclo<7.2.0.0^2,5>undecan-6-ol
  参考文献：
  名称：

  Rearrangement of (-)-.beta.-Caryophyllene. A Product Analysis and Force Field Study

  摘要：

  The rearrangement of (-)-beta-caryophyllene (1) with sulfuric acid in ether has been reinvestigated. In the early stage, a multitude of products is formed. Of these, fourteen hydrocarbons (3, 4, 6-17) and four alcohols (5, 18-20) were obtained pure. From the very beginning, the tricycloundecenes 15-17 accumulate quickly. This indicates that a previously unknown rearrangement of 1 by protonation of the exocyclic double bond followed by transannular ring closure is a main reaction, and that the conformation beta alpha is involved. Three hydrocarbons (3, 4, 8) and three alcohols (5, 18, 19) proved to be stable. They are the main components in the late stage. A complete rearrangement scheme followed from a force field analysis using MMP2. First, all conformations up to 4 kcal above the global minimum of each product and each carbenium ion necessary for its formation were detected automatically using the search program HUNTER. Second, the conformation favoring a specific transformation was searched for. For transannular cyclizations, the conformation with the shortest distance between the atoms to be bound and, for ring openings and 1,2-shifts, the conformation with the smallest dihedral angle between the empty p-orbital and the bond to be broken were selected. In all cases, the selection criteria proved valid: The stereochemistry of the conformations selected matched the stereochemistry of the products observed. On the basis of the results presented, a fully automated search prog ram for favorable rearrangement paths may be developed.

  DOI：

  10.1021/ja00141a009

文献信息

• Tkachev, A. V., Journal of Organic Chemistry USSR (English Translation), 1990, vol. 26, # 8.1, p. 1476 - 1479
  作者：Tkachev, A. V.

  DOI：——

  日期：——
• TKACHEV, A. V., ZH. ORGAN. XIMII, 26,(1990) N, S. 1706-1710
  作者：TKACHEV, A. V.

  DOI：——

  日期：——
• Rearrangement of (-)-.beta.-Caryophyllene. A Product Analysis and Force Field Study
  作者：Lutz Fitjer、Andreas Malich、Carola Paschke、Sabine Kluge、Ralf Gerke、Beate Rissom、Joerg Weiser、Mathias Noltemeyer

  DOI：10.1021/ja00141a009

  日期：1995.9

  The rearrangement of (-)-beta-caryophyllene (1) with sulfuric acid in ether has been reinvestigated. In the early stage, a multitude of products is formed. Of these, fourteen hydrocarbons (3, 4, 6-17) and four alcohols (5, 18-20) were obtained pure. From the very beginning, the tricycloundecenes 15-17 accumulate quickly. This indicates that a previously unknown rearrangement of 1 by protonation of the exocyclic double bond followed by transannular ring closure is a main reaction, and that the conformation beta alpha is involved. Three hydrocarbons (3, 4, 8) and three alcohols (5, 18, 19) proved to be stable. They are the main components in the late stage. A complete rearrangement scheme followed from a force field analysis using MMP2. First, all conformations up to 4 kcal above the global minimum of each product and each carbenium ion necessary for its formation were detected automatically using the search program HUNTER. Second, the conformation favoring a specific transformation was searched for. For transannular cyclizations, the conformation with the shortest distance between the atoms to be bound and, for ring openings and 1,2-shifts, the conformation with the smallest dihedral angle between the empty p-orbital and the bond to be broken were selected. In all cases, the selection criteria proved valid: The stereochemistry of the conformations selected matched the stereochemistry of the products observed. On the basis of the results presented, a fully automated search prog ram for favorable rearrangement paths may be developed.