(3aRS,5aSR,9aRS,9bSR)-dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan | 3738-00-9

• 物质功能分类: 有机原料 - 醚类化合物及其衍生物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并呋喃类
• 英文名称: (3aRS,5aSR,9aRS,9bSR)-dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan
• 英文别名: (+/-)-5β,8α-Ambrox；(3aR,5aS,9aR,9bS)-3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzofuran
• CAS: 3738-00-9；6790-58-5；67844-43-3；68365-88-8；68365-89-9；100679-85-4；105561-31-7；108945-29-5；119818-38-1；122566-15-8；122566-16-9；122566-18-1；124578-52-5；131831-61-3；131831-62-4；131831-63-5；133907-53-6；138283-79-1；138283-80-4；145164-17-6
• 化学式: C₁₆H₂₈O
• 分子量: 236.398
• InChiKey: YPZUZOLGGMJZJO-WMHQRMGPSA-N

物化性质

• 熔点：
  75-76 °C
• 沸点：
  273.9±8.0 °C(Predicted)
• 密度：
  0.939±0.06 g/cm3(Predicted)
• LogP：
  5.41

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  17
• 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：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2932999099

制备方法与用途

生产方法主要采用紫苏醇作为起始原料。

反应信息

• 作为产物：
  描述：

  3-oxo-5-(2,6,6-trimethyl-cyclohex-2-enyl)-pentanoic acid methyl ester 在 吡啶 、 sodium tetrahydroborate 、 四氯化锡 、 sodium hydride 、 对甲苯磺酸 、 臭氧 、 对甲苯磺酰氯 、 calcium chloride 作用下， 以 乙醚 、 硝基甲烷 、 二甲基亚砜 、 xylene 为溶剂， 反应 34.25h， 生成 (3aRS,5aSR,9aRS,9bSR)-dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan
  参考文献：
  名称：

  5β-Ambrox中的构型-气味关系

  摘要：

  已经合成了Ambrox®的四种可能的A / B顺式非对映异构体，并通过X射线和NMR分析确定了它们的构型和构象。仅5β-ambrox（= 1,2,3a，4,5,5β，6,7,8,9,9a，9bα-十二烷基氢化-3aβ，6,6,9aβ-四甲基萘[2,1- b ]呋喃; 5）具有与Ambrox®相当的气味质量。因此，已证实C（8）（= C（3a））和C（10）（= C（9a））上的取代基的1,3- synperiplanar / diaxial构象是特定气味的强制性结构元素。

  DOI：

  10.1002/hlca.19900730717

文献信息

• Internal Nucleophilic Termination in Acid-Mediated Polyene Cyclizations. Part 3
  作者：Roger L. Snowden、Jean-Claude Eichenberger、Simon Linder、Philippe Sonnay

  DOI：10.1002/hlca.200490155

  日期：2004.7

  Treatment of the unsaturated allenic alcohols (E)-7, (Z)-7, 10, 13, and 19 with an excess of FSO3H in 2-nitropropane at −90° to −30° afforded, in 68–85% yield, diastereoisomer mixtures of racemic tricyclic ethers 14a–d and 20a–d, respectively (Schemes 3 and 5), with high stereoselectivity (see Table and Scheme 6). These stereospecific transformations represent the first reported examples of an acid-mediated

  不饱和丙二烯醇的处理（ë） - 7，（Ž） - 7，10，13，和19与过量的FSO 3中2-硝基丙烷H在-90°〜-30°，得到，在68-85％外消旋三环醚14a – d和20a – d的高收率，非对映异构体混合物（方案3和5），具有高立体选择性（参见表和方案6））。这些立体有择的转化代表了酸介导的多烯环化的首次报道实例，其中烯烃是引发基团，而烯丙醇用作内部终止剂。与我们之前的工作非常相似，我们假设一个非同步过程，其中环化的立体化学过程由中间环己基阳离子的构象结构控制（参见方案3和6）。此外，感官特性14C和20C，外消旋二脱氢和脱氢甲基类似物，分别，已知的加臭剂的艾姆罗克斯®（（ - ） - 4F），是简要地讨论。
• Internal nucleophilic termination in biomimetic acid mediated polyene cyclizations: stereochemical and mechanistic implications. Synthesis of (.+-.)-Ambrox and its diastereoisomers
  作者：Roger L. Snowden、Jean Claude Eichenberger、Simon M. Linder、Philippe Sonnay、Christian Vial、Karl H. Schulte-Elte

  DOI：10.1021/jo00029a031

  日期：1992.1

  Treatment of 10 structurally related trienols and dienols 5-8 with an excess of fluorosulfonic acid in 2-nitropropane at -90-degrees-C afforded, in 74-87% yield, diastereoisomeric mixtures of the odoriferous norlabdane oxides 9-15 ((-)-9 (Ambrox) is a naturally occurring ambergris odorant). These transformations represent examples of efficient biomimetic acid-mediated cyclizations in which the hydroxyl group serves as the internal nucleophilic terminator. The stereochemical outcome of these kinetically controlled processes has been analysed in detail, and mechanistic hypotheses consistent with the results have been proposed. For the four acyclic trienols 5, the major reaction pathway can be rationalized by a totally synchronous process involving three internal anti additions via chair or skew-boat conformations of the nascent cyclohexane rings. An alternative explanation postulates a non-synchronous process in which ring closure to an intermediate cyclohexyl cation is followed by rapid cyclization, directed by a strong kinetic preference for equatorial C-C and C-O ond formation. In contrast, for the monocyclic dienols 6-8 only a nonsynchronous process, involving prior protonation of the cyclohexenyl bond, is fully consistent with the results. In the nonsynchronous processes, the orientation of the side chain vicinal to the cyclohexyl cation directs the stereochemical course of the cyclization. For the acyclic trienols, this factor is predetermined by the configuration of the C(7) = C(8) bond, whereas, for the acyclic trienols, this factor is predetermined by the configuration of the C(7) = C(8) bond, whereas, for the monocyclic dienols, this orientation is determined by the stereoselective axial protonation of the cyclohexenyl bond in 6, or by the distribution of cyclohexene and cyclohexane conformers in 7 and 8, respectively. In the cases studied, it is clear that conformational inversion of the six-membered ring is slower than cyclization and thus ensures that an equatorial side chain leads to a trans A/B ring junction in the cyclization product, whereas an axial side chain affords a cis A/B ring junction.