(-)-nopinone enol acetate | 28239-05-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (-)-nopinone enol acetate
• 英文别名: [(1R,5S)-6,6-dimethyl-2-bicyclo[3.1.1]hept-2-enyl] acetate
• CAS: 28239-05-6
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: NDZMNXNMVVXBAF-IUCAKERBSA-N

物化性质

• 沸点：
  249.2±7.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (-)-nopinone enol acetate 在 lead(IV) acetate 、 丙烷-1-硫醇 、 叔丁基锂 、 sodium hydride 作用下， 以 苯 为溶剂， 反应 23.5h， 生成 (-)-4-<2-Hydroxy-4-(1,1-dimethylheptyl)-6-methoxyphenyl>-6,6a-dimethylbicyclo<3.3.1>hept-3-en-2-one
  参考文献：
  名称：

  Synthesis of both enantiomers of nabilone from a common intermediate. Enantiodivergent synthesis of cannabinoids

  摘要：

  Both enantiomers of the synthetic cannabinoid nabilone (4) have been synthesized from a common intermediate, enone 7. Enone 7 was prepared by reaction of [2,6-dimethoxy-4-(1,1-dimethylheptyl)phenyl]lithium with (+)-apoverbenone (2), followed by PDC oxidation. Li/NH3 reduction of 7 gave saturated ketone 9, which, after ether cleavage to 10, afforded (6aS,10aR)-hexahydrodibenzopyran 15 on reaction with SnCl4. Isomerization to 6aR,10aR ketone 16 followed by ether cleavage gave the 6aR,10aR enantiomer of nabilone (4). The 6aS,10aS enantiomer of 4 (24) was prepared from 7 by ether cleavage to 18 and rearrangement to nonracemic tetrahydrodibenzopyran 20 using AlCl3. Dissolving metal reduction of 20 followed by ether cleavage gave the 6aS,10aS enantiomer of nabilone (24). A model sequence employing (2,6-dimethoxyphenyl)lithium at the first step was carried out and the structure of one of the intermediates, ketone 12, was established by X-ray crystallography. A new preparation of apoverbenone (2) has been developed.

  DOI：

  10.1021/jo00006a021
• 作为产物：
  描述：

  乙酸异丙烯酯 、 (1R)-(+)-诺蒎酮 在 对甲苯磺酸 作用下， 反应 5.0h， 以97.5%的产率得到(-)-nopinone enol acetate
  参考文献：
  名称：

  与双（亚乙基二硫代）四硫富瓦烯有关的新的手性有机硫供体

  摘要：

  已经合成了六种具有与BEDT-TTF相关结构的新的对映纯手性有机硫供体，用于制备有机金属，方法是从2 R，4 R-戊烷-2,4的双甲磺酸酯上进行双亲核取代。-二醇或通过环加成反应，然后在（+）-去甲酮的烯醇乙酸酯上消除乙酸。据报道其某些自由基阳离子三碘化物盐和TCNQ配合物的晶体结构。

  DOI：

  10.1016/j.tet.2010.06.034

文献信息

• Taming elemental fluorine: Indirect use of fluorine for the synthesis of α-fluoroketones[1]
  作者：Shlomo Rozen、Ynon Menahem

  DOI：10.1016/s0022-1139(00)85146-5

  日期：1980.7

  Fluorine and sodium trifluoroacetate react at −75° to produce a variety of fluoroxy-compounds. Although it is possible to direct the reaction towards the formation of CF3COOF or CF3CF2OF, mixtures may be used when only the electrophilic fluorine has to be attached to the molecule of interest. Such is the case of the reaction of enol-acetates with the mixture of the fluoroxy reagents. A wide variety

  氟和三氟乙酸钠在-75°下反应生成各种氟代化合物。尽管可以将反应引导至CF 3 COOF或CF 3 CF 2 OF的形成，但是当仅亲电氟必须连接到目标分子上时，可以使用混合物。烯醇-乙酸酯与氟代试剂混合物的反应就是这种情况。测试了多种化合物，包括类固醇和含有各种官能团。在大多数情况下，以良好至非常高的收率获得了所需的α-氟代酮。新的含氟化合物是编号为和的化合物。
• Oligomer-cannabinoid conjugates
  申请人：NEKTAR THERAPEUTICS

  公开号：US09155797B2

  公开（公告）日：2015-10-13

  The invention relates to (among other things) oligomer-cannabinoid conjugates and related compounds. A conjugate of the invention, when administered by any of a number of administration routes, exhibits advantages over previously administered un-conjugated cannabinoid compounds.

  这项发明涉及寡聚物-大麻素共轭物和相关化合物。根据本发明的共轭物，当通过多种给药途径之一进行给药时，表现出优于先前给药的非共轭大麻素化合物的优点。
• Novel Labelled Cannabinergic Ligands and Related Analogs
  申请人：Makriyannis Alexandros

  公开号：US20210300937A1

  公开（公告）日：2021-09-30

  Novel cannabinoid ligands represented by the general formulas I, II, and III and methods for preparation and use within which one or more of a fluorescent ligand, nitroxide spin label, metal chelate, biotin moiety, or group with enhanced polarity may be incorporated. The compounds can bind to and modulate the cannabinoid CB1 and CB2 receptors and thereby considered specific ligands for these receptors. Some of the disclosed compounds that bind to cannabinoid CB1 and CB2 receptors can exhibit tight or irreversible binding characteristics for these receptors. Due to the presence of the imaging/diagnostic and/or therapeutic functional groups including fluorescent groups, nitroxide spin labels, metal chelates, biotin moieties, and groups with enhanced polarity, the disclosed compounds may be useful as imaging/diagnostic tools and/or therapeutic agents.

  新型大麻素配体由一般公式I、II和III表示，以及用于制备和使用的方法，其中可以包含一个或多个荧光配体、亚硝基自旋标记、金属螯合物、生物素基团或具有增强极性的基团。这些化合物可以结合并调节大麻素CB1和CB2受体，因此被认为是这些受体的特异性配体。一些公开的结合到大麻素CB1和CB2受体的化合物可能表现出对这些受体的紧密或不可逆结合特性。由于含有成像/诊断和/或治疗功能基团，包括荧光基团、亚硝基自旋标记、金属螯合物、生物素基团和具有增强极性的基团，公开的这些化合物可能作为成像/诊断工具和/或治疗剂而有用。
• Selectivity in aromatic fluorination. Introduction of fluorine probes into nabilone
  作者：Marcus A. Tius、Joel K. Kawakami、W. Adam G. Hill、Alexandros Makriyannis

  DOI：10.1039/cc9960002085

  日期：——

  Selective fluorination of the aromatic ring of nabilone leads to functional analogues with diminished affinity for the CB1 receptor, thereby confirming the hypothesis that the phenolic hydroxy group is engaged in a hydrogen bonding interaction with the receptor.

  对纳比龙的芳香环进行选择性氟化，可得到对 CB1 受体亲和力减弱的功能类似物，从而证实了酚羟基与受体发生氢键相互作用的假设。
• Cannabinoids. 3. Synthetic approaches to 9-ketocannabinoids. Total synthesis of nabilone
  作者：Robert A. Archer、W. B. Blanchard、William A. Day、Douglas W. Johnson、E. R. Lavagnino、C. W. Ryan、Jack E. Baldwin

  DOI：10.1021/jo00433a020

  日期：1977.6