cis-3-acetoxy-1,8-cineole

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: cis-3-acetoxy-1,8-cineole
• 英文别名: exo-1,3,3-trimethyl-2-oxabicyclo<2.2.2>octan-5-ol acetate；(1RS,3RS,4SR)-3-acetoxycineole；(+/-)-exo-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-5-yl acetate；(±)-5-acetoxyeucalyptol；(+/-)-exo-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-yl ethanoate；[(1S,4R,5S)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-yl] acetate
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: LUYHJKNQBUWCNY-SCVCMEIPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cis-3-acetoxy-1,8-cineole 在 porcine liver esterase 、 4-二甲氨基吡啶 作用下， 以 phosphate buffer 、 二氯甲烷 为溶剂， 反应 28.0h， 生成 (+)-exo-1,3,3-trimethyl-2-oxabicyclo[2.2.2]oct-5-yl-(S)-α-methoxyphenylacetate
  参考文献：
  名称：

  Enzymatic resolution of the 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane (1,8-cineole) system

  摘要：

  Regioselective oxidation of 1,8-cineole 1 with chromyl acetate according to a literature procedure gave the bicyclic 2-ketocineole 8 as the major product along with the symmetrical diketocineole 9. The bicyclic monoketone was reduced with lithium aluminum hydride followed by exposure to acetyl chloride/DMAP to afford the exo-acetate (+/-)-4b. Pig liver esterase (PLE)-mediated hydrolysis of the racemic acetate provided the alcohol (-)-2b (45%) together with its antipodal acetate (+)-4b (43%) in greater than 99% enantiomeric purity, as determined by analysis of the Mosher's ester derivatives. Iodination of the alcohol exo-(+)-2b, obtained by hydrolysis of the resolved actetate with iodine/triphenylphosphine/imidazole, provided the corresponding endo iodide (-)-12a, which was easily dehydro halogenated with DBU under solvent-free conditions to provide the corresponding cineolene (-)-6 in an overall yield of 6 and 99%. e.e. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00313-0
• 作为产物：
  描述：

  桉叶油醇 在 吡啶 、 chromium(VI) oxide 、 sodium tetrahydroborate 、 乙酸酐 、 溶剂黄146 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 87.0h， 生成 cis-3-acetoxy-1,8-cineole
  参考文献：
  名称：

  肉桂醛衍生物的除草活性

  摘要：

  精油及其成分具有作为生态可接受的农药的潜力，也可能具有新颖的作用方式。在这项工作中，制备了大多数桉树油中主要成分天然单萜1,8-cineole 3和1,4-cineole 4的羟基和酯衍生物，并针对一年生黑麦草（黑麦草）进行了芽前除草活性。和萝卜（萝卜）变种 Long Scarlet（Long Scarlet）在基于实验室的生物测定法中进行了研究。1,8-桉树脑，桉树油和所有衍生物对一年生黑麦草和萝卜均表现出剂量依赖性的除草活性，其中许多衍生物相对于1,8-桉树脑和高桉树脑的桉树油具有更好的除草活性。与它们相关的羟基-桉树脑和羧酸相比，未观察到桉树脑酯衍生物的活性增加。没有观察到桉树脑酯衍生物的羧酸部分的亲脂性与除草活性之间的关系。结果表明这些桉树脑衍生物可能是环境可接受的除草剂。

  DOI：

  10.1021/jf101827v

文献信息

• Experimental and theoretical insights into the formation of weak hydrogen bonds and H⋯H bonding interactions in the solid-state structure of two eucalyptol derivatives
  作者：Carolina E. Galvez、Oscar E. Piro、Gustavo A. Echeverría、Norma Lis Robles、José O. G. Lezama、Sankaran Venkatachalam Sankaran、Subbiah Thamotharan、Margarita B. Villecco、María del H. Loandos、Diego M. Gil

  DOI：10.1039/d2nj00428c

  日期：——

  C–H⋯O hydrogen bonds and H⋯H bonding interactions. These interactions have also been described and studied energetically using DFT calculations. The nature and strength of these intermolecular contacts have been rationalized by using several computational tools including molecular electrostatic potential (MEP) surfaces, natural bond orbital analysis (NBO), Bader's theory of atoms in molecules (QTAIM)

  两种桉树脑衍生物，即 1,3,3-trimethyl-2-oxabicycle[2.2.2]oct-5-yl acetate ( 4 ) 和 1,3,3-trimethyl-2-oxabicycle[2.2.2]oct-5 ,8-乙酸酯 ( 6 ) 已被合成和表征。它们的晶体结构已通过单晶 X 射线衍射方法解析，表明这两种化合物的分子构象是由桉树醇部分甲基的 H 原子与 O- 之间的分子内 C-H⋯O 键稳定的。乙酰氧基原子。此外，我们通过使用 Hirshfeld 表面分析及其相关的二维指纹图对稳定两种结构的晶体堆积的分子间相互作用进行了详细研究。分析表明化合物的固态结构4和6主要通过C-H⋯O氢键和H⋯H键相互作用来稳定。还使用 DFT 计算大力描述和研究了这些相互作用。这些分子间接触的性质和强度已通过使用多种计算工具进行了合理化，包括分子静电势 (MEP) 表面、自然键轨道分析 (NBO)、Bader
• Enantiomeric Purity and Odor Characteristics of 2- and 3-Acetoxy-1,8-cineoles in the Rhizomes of <i>Alpinia </i><i>g</i><i>alanga</i> Willd.
  作者：Kikue Kubota、Yuki Someya、Reiko Yoshida、Akio Kobayashi、Tetsu-ichiro Morita、Hiroyuki Koshino

  DOI：10.1021/jf9807465

  日期：1999.2.1

  (S)-(+)-O-methylmandelate esters of trans- and cis-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5- and 6-ols (2- and 3-hydroxy-1,8-cineoles) were prepared, and eight diastereomers were separated. The absolute configuration of the asymmetric carbons of the cineole moiety of each diastereomer was determined by H-1 NMR data according to the Mosher theory. Each mandelate was reduced with LiAlHe4 to obtain optically pure hydroxy-1,8-cineoles, this being followed by acetylation to afford optically pure acetoxy-1,8-cineoles. These acetates were subjected to chiral GC, using a cyclodextrin column, and the enantiomeric purity of trans- and cis-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5- and 6-yl acetates in the aroma concentrate from the rhizomes of Alpinia galanga was determined as 93.9 (5S), 19.4 (5R), 63.5 (6R), and 100 (6R) % cc, respectively. The aroma character of each enantiomer was also evaluated by GC-sniffing.
• Regiospecific functionalization of the monoterpene ether 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane (1,8-cineole). Synthesis of the useful bridged .gamma.-lactone 1,3-dimethyl-2-oxabicyclo[2.2.2]octan-3 .fwdarw. 5-olide
  作者：Margarita V. De Boggiatto、Carola S. De Heluani、Ines J. S. De Fenik、Cesar A. N. Catalan

  DOI：10.1021/jo00384a023

  日期：1987.4
• Enzymatic resolution of the 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane (1,8-cineole) system
  作者：Frederick A. Luzzio、Damien Y. Duveau

  DOI：10.1016/s0957-4166(02)00313-0

  日期：2002.6

  Regioselective oxidation of 1,8-cineole 1 with chromyl acetate according to a literature procedure gave the bicyclic 2-ketocineole 8 as the major product along with the symmetrical diketocineole 9. The bicyclic monoketone was reduced with lithium aluminum hydride followed by exposure to acetyl chloride/DMAP to afford the exo-acetate (+/-)-4b. Pig liver esterase (PLE)-mediated hydrolysis of the racemic acetate provided the alcohol (-)-2b (45%) together with its antipodal acetate (+)-4b (43%) in greater than 99% enantiomeric purity, as determined by analysis of the Mosher's ester derivatives. Iodination of the alcohol exo-(+)-2b, obtained by hydrolysis of the resolved actetate with iodine/triphenylphosphine/imidazole, provided the corresponding endo iodide (-)-12a, which was easily dehydro halogenated with DBU under solvent-free conditions to provide the corresponding cineolene (-)-6 in an overall yield of 6 and 99%. e.e. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Herbicidal Activity of Cineole Derivatives
  作者：Allan F. M. Barton、Bernard Dell、Allan R. Knight

  DOI：10.1021/jf101827v

  日期：2010.9.22

  dose-dependent herbicidal activity against annual ryegrass and radish with many of the derivatives showing improved herbicidal activity relative to 1,8-cineole and high-cineole eucalyptus oil. Increased activity of cineole ester derivatives compared to their associated hydroxy-cineole and carboxylic acid was not observed. No relationship between lipophilicity of the carboxylic acid portion of cineole ester derivatives

  精油及其成分具有作为生态可接受的农药的潜力，也可能具有新颖的作用方式。在这项工作中，制备了大多数桉树油中主要成分天然单萜1,8-cineole 3和1,4-cineole 4的羟基和酯衍生物，并针对一年生黑麦草（黑麦草）进行了芽前除草活性。和萝卜（萝卜）变种 Long Scarlet（Long Scarlet）在基于实验室的生物测定法中进行了研究。1,8-桉树脑，桉树油和所有衍生物对一年生黑麦草和萝卜均表现出剂量依赖性的除草活性，其中许多衍生物相对于1,8-桉树脑和高桉树脑的桉树油具有更好的除草活性。与它们相关的羟基-桉树脑和羧酸相比，未观察到桉树脑酯衍生物的活性增加。没有观察到桉树脑酯衍生物的羧酸部分的亲脂性与除草活性之间的关系。结果表明这些桉树脑衍生物可能是环境可接受的除草剂。