丁香酚杂质C(EP) | 103475-43-0

• 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
• 中文名称: 丁香酚杂质C(EP)
• 英文名称: caryophyllene oxide
• 英文别名: (1R,4S,6S,10S)-4,12,12-trimethyl-9-methylidene-5-oxatricyclo[8.2.0.04,6]dodecane
• CAS: 103475-43-0
• 化学式: C₁₅H₂₄O
• 分子量: 220.355
• InChiKey: NVEQFIOZRFFVFW-CXTNEJHOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 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：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  丁香酚杂质C(EP) 生成 (1S,5R,6R,9R)-6,10,10-trimethyl-2-methylidenebicyclo[7.2.0]undecan-5-ol
  参考文献：
  名称：

  TKACHEV, A. V., ZH. ORGAN. XIMII, 25,(1989) N, S. 122-132

  摘要：

  DOI：
• 作为产物：
  描述：

  β-caryophyllene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以13 mg的产率得到丁香酚杂质C(EP)
  参考文献：
  名称：

  Antimicrobial Agents fromHeterotheca inuloides

  摘要：

  通过生物测定定向分馏，从 Heterotheca inuloides（一种墨西哥药用植物，当地称为 "山金车"）的干燥花中分离出四种倍半萜 1 - 4，作为抗菌剂。7-Hydroxy-3,4-dihydrocadalin (3) 和 7-hydroxycadalin (4) 对革兰氏阳性细菌具有很强的抗菌活性，最低抑菌浓度为 6.25 至 12.5 µg/ml。值得注意的是，7-羟基-3,4-二氢蟾蜍甙对耐甲氧西林金黄色葡萄球菌（MRSA）具有杀菌活性，最低杀菌浓度（MBC）为 12.5 µg/ml。

  DOI：

  10.1055/s-2006-959462

文献信息

• Transannular Cyclization of Epoxycaryophyllenes Catalyzed by TiIII: An Efficient Synthesis of Tricyclo[6.3.0.02,5]undecanes
  作者：Alejandro F. Barrero、M. Mar Herrador、José F. Quílez del Moral、Pilar Arteaga、Elena M. Sánchez、Jesús F. Arteaga、Maria Piedra

  DOI：10.1002/ejoc.200600159

  日期：2006.8

  The transannular cyclization of epoxycaryophyllenes 2–7 catalyzed by TiIII has been investigated. This cyclization led to alcohols 8–15, all of them possessing a tricyclo[6.3.0.02,5]undecane skeleton. All of these compounds present pleasant aromatic properties. The cyclization takes place with high yields (> 80 %) and via the αα or ββ conformation of the intermediate radical I. (© Wiley-VCH Verlag

  已经研究了由 TiIII 催化的环氧石竹烯 2-7 的跨环环化。这种环化导致醇 8-15，它们都具有三环 [6.3.0.02,5] 十一烷骨架。所有这些化合物都具有令人愉悦的芳香特性。通过中间基团 I 的 αα 或 ββ 构象，环化以高产率 (> 80 %) 发生。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• Thermoconversion of Caryophyllene- to Farnesene-Type Sesquiterpenes. Short access to the enantiomers of (6RS,7RS)- and (6RS,7SR)-6,7-epoxy-6,7-dihydro-?-farnesenes
  作者：Wolfgang K. Giersch、Andr� F. Boschung、Roger L. Snowden、Karl H. Schulte-Elte

  DOI：10.1002/hlca.19940770106

  日期：1994.2.9

  Flash-vacuum thermolysis of the four diastereoisomeric 5,6-epoxy-5,6-dihydro-caryophyllenes 1–4 at 500–550°/0.1–0.7 Torr leads to the hitherto unreported enantiomers of (6RS,7RS)- and (6RS,7SR)-6,7-epoxy-6,7-dihydro-β-farnesenes ((±)-5 and (±)-6, resp.). In particular, (+)-5 is formed in 45% yield (ca. 90% ee) and is, thus, an attractive chiral building block for natural-product synthesis.

  在500-550°/ 0.1-0.7 Torr下对4个非对映异构体5,6-环氧-5,6-二氢-石竹烯1-4进行的闪蒸-真空热解反应导致迄今未报道的（6 RS，7 RS）对映体和（6 RS，7 SR）-6,7-环氧-6,7-二氢-β-法呢烯（（±）-5和（±）-6，分别）。特别地，（+）- 5以45％的产率（约90％ee）形成，并且因此是用于天然产物合成的有吸引力的手性构件。
• Mechanism-Based Design and Optimization of a Catalytic Electrophilic Cyclopropanation without Diazomethane
  作者：Augustin A. S. W. Tchawou、Mihai Raducan、Peter Chen

  DOI：10.1021/acs.organomet.6b00531

  日期：2017.1.9

  Iodomethylboron compounds, either the trifluoroborate or a boronic ester, cyclopropanate electron-rich olefins and unprotected allylic alcohols with Pd catalysts according to a novel, designed catalytic cycle. Proposed intermediates in a "diverted Heck" mechanism are observed by means of spectroscopic studies and by isolation and X-ray crystallographic characterization, which together with reaction kinetics point to a separation of rate-determining and product-determining steps, and a mechanism-based optimization of the yield, selectivity, and scope of the catalytic electrophilic cyclopropanation. The reaction with crystalline, air-stable, nonhygroscopic, and nontoxic reagents provides an alternative to Simmons Smith-type reactions, as well as cyclopropanation procedures that require the use of diazomethane.
• Biomimetic Syntheses of the Neurotrophic Natural Products Caryolanemagnolol and Clovanemagnolol
  作者：Xu Cheng、Nicole L. Harzdorf、Travis Shaw、Dionicio Siegel

  DOI：10.1021/ol100214x

  日期：2010.3.19

  Separate short and modular syntheses of the isomeric natural products caryolanemagnolol and clovanemagnolol have been achieved starting from commercially available (-)-caryophyllene. The postulated biosynthetic pathways guided the syntheses of the neuro regenerative small molecules allowing their assembly in as few as two steps.
• Stereochemistry of 14-hydroxy-β-caryophyllene and related compounds
  作者：Alejandro F. Barrero、José Molina、J. Enrique Oltra、Joaquín Altarejos、Armando Barragán、Armando Lara、Margot Segura

  DOI：10.1016/0040-4020(95)00104-g

  日期：1995.3

  The isomerization of beta-caryophyllene (3), under treatment with SeO2, is described. Chemical correlations, between 3 and 14-hydroxy-beta-caryophyllene (6) from Juniperus oxycedrus, are established. High resolution H-1 NMR spectra and analysis by molecular mechanics of 3, 6 and 14-acetoxy-beta-taryophyllene (1) indicate the existence of two conformational isomers, beta alpha and beta beta, in each compound. At 25 degrees C, the beta alpha conformer predominates in 3 and 7 but the beta beta conformer predominates in 6. The higher percentage of 6 beta beta possibly derives from an intramolecular hydrogen bond. The treatment of 3, 6 and 7 with m-CPBA generates, in each case, two diastereomeric 4,5-epoxi-derivatives. The epoxides obtained from 6 have been isolated and analysed separately.