α-neoclovene | 4545-68-0

• 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: α-neoclovene
• 英文别名: neoclovene；(1R,6S,7S)-2,6,8,8-tetramethyltricyclo[5.2.2.01,6]undec-2-ene
• CAS: 4545-68-0
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: ZCJQJJWNFDNQGZ-AEGPPILISA-N

物化性质

• 沸点：
  256.5±7.0 °C(Predicted)
• 密度：
  0.951 g/mL at 20 °C (lit.)
• 闪点：
  114 °C

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2902199090
• 安全说明：
  S23,S24/25
• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  α-neoclovene 在 manganese(IV) oxide 、 单过氧邻苯二甲酸 、 氯氟磺酰 、 氟磺酸 作用下， 以 甲醇 、 乙醚 、 正己烷 为溶剂， 反应 61.0h， 生成 (1R,4R,7R,11R)-8-oxo-1,3,4,7-tetramethyltricyclo<5.3.1.0^4,11>undec-2-ene
  参考文献：
  名称：

  Khomenko, T. M.; Korchagina, D. V.; Gatilov, Yu. V., Journal of Organic Chemistry USSR (English Translation), 1991, vol. 27, # 3.2, p. 516 - 524

  摘要：

  DOI：
• 作为产物：
  描述：

  isocaryophyllene 在 硫酸 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以235 mg的产率得到α-neoclovene
  参考文献：
  名称：

  在硫酸浸渍的 SiO2 和 Al2O3 存在下石竹烯的酸催化异构化

  摘要：

  在与硫酸浸渍的 Al2O3 和 SiO2 接触时进行石竹烯的转化，并确定所得混合物的组分。掌握这样的“标准”混合物极大地促进了精油和其他天然来源混合物的倍半萜成分成分的鉴定。用硫酸(H+-SiO2)浸渍的硅胶对石竹烯酸催化异构化的催化活性明显高于H+-Al2O3，与浓硫酸的活性相当。

  DOI：

  10.1007/s11172-018-2179-3

文献信息

• Reactions of caryophyllene, isocaryophyllene, and their epoxy derivatives with acetonitrile under ritter reaction conditions
  作者：O. I. Yarovaya、D. V. Korchagina、T. V. Rybalova、Yu. V. Gatilov、M. P. Polovinka、V. A. Barkhash

  DOI：10.1007/s11178-005-0065-6

  日期：2004.11

  Acid-catalyzed reactions between acetonitrile and caryophyllene, isocaryophyllene, caryophyllene 4β, 5α-epoxide, and isocaryophyllene 4β,5β-epoxide affording optically active amides with a tricyclic skeleton were investigated.

  研究了乙腈与石竹烯、异石竹烯、石竹烯4β,5α-环氧化物和异石竹烯4β,5β-环氧化物之间的酸催化反应，得到具有三环骨架的光学活性酰胺。
• Bridged ring systems. Part XV. Structure of neoclovene (2,6,8,8-tetramethyltricyclo[5,2,2,01,6]undec-2-ene)
  作者：W. Parker、R. A. Raphael、J. S. Roberts

  DOI：10.1039/j39690002634

  日期：——

  The structural elucidation of neoclovene (4), a new rearrangement product of caryophyllene, shows it to be 2,6,8,8-tetramethyltricyclo[5,2,2,01,6]undec-2-ene with the stereochemistry shown.

  一种新的石竹烯重排产物新丁香（4）的结构解析表明，它是2,6,8,8-四甲基三环[5,2,2,0 1,6 ]十一碳-2-烯，并显示了立体化学。
• The synthesis of neoclovene
  作者：T. F. W. McKillop、J. Martin、W. Parker、J. S. Roberts、J. R. Stevenson

  DOI：10.1039/j39710003375

  日期：——

  Neoclovene, a product from acid-catalysed rearrangement of caryophyllene, has been synthesised in such a manner as to demonstrate the probable intermediacy of a specific carbonium ion derived from (4S,7R)-3,3,7,11-tetramethyltricyclo[5,4,0,01,4]undecan-11-ol (24) in the formation of neoclovene from caryophyllene. This work also provides additional support for the relative configuration assigned to neoclovene.

  新氯烯是石竹烯酸催化重排的产物，其合成方式证明了源自 (4S,7R)-3,3,7,11-四甲基三环[5, 4,0,01,4]十一烷-11-醇 (24) 从石竹烯形成新丁烯。这项工作还为新氯烯的相关配置提供了额外的支持。
• Studies on the sesquiterpenoids of Panax ginseng C.A. Meyer. Isolation and structure determination of sesquiterpene alcohols, panasinsanols A and B.
  作者：HISAKATSU IWABUCHI、MASAHIRO YOSHIKURA、YOSHITOMI IKAWA、WASUKE KAMISAKO

  DOI：10.1248/cpb.35.1975

  日期：——

  Two sesquiterpene alcohols, panasinsanol A (1) and panasinsanol B (2), were isolated from the rootlets of Panax ginseng C. A. MEYER (Araliaceae) together with known sesquiterpene hydro-carbons, α-panasinsene (3), β-panasinsene (4), α-neoclovene (5), and β-neoclovene (6). The structures of 1 and 2 were established by spectral evidence, chemical correlations to congener hydrocarbons (3, 4, 5, and 6), and finally by their syntheses from (-) -β-caryophyllene. This is the first isolation of 1 from a natural source, and 2 is a novel panasinsane-type sesquiterpene.

  从人参（Araliaceae）的根茎中分离出两种倍半萜醇，即panasinsanol A（1）和panasinsanol B（2），以及已知的倍半萜烃，即α-panasinsene（3）、β-panasinsene（4）、α-neoclovene（5）和β-neoclovene（6）。1和2的结构通过光谱证据、与同系烃（3、4、5和6）的化学相关性，以及最终通过从（-）-β-石竹烯合成来确定。这是首次从天然来源分离出1，而2是一种新型的panasinsane型倍半萜。
• 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.