D-胡椒酮 | 6091-50-5

• 物质功能分类: 有机原料 - 酮类化合物
• 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: D-胡椒酮
• 中文别名: (S)-3-甲基-6-(1-甲基乙基)-2-环己烯-1-酮
• 英文名称: (S)-(+)-piperitone
• 英文别名: (+)-piperitone；(+)-(4S)-Piperitone；d-Piperitone；(6S)-3-methyl-6-propan-2-ylcyclohex-2-en-1-one
• CAS: 6091-50-5
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: YSTPAHQEHQSRJD-VIFPVBQESA-N

物化性质

• 沸点：
  234.73°C (rough estimate)
• 密度：
  0.8899 (rough estimate)
• LogP：
  2.41
• 物理描述：
  Liquid
• 熔点：
  -29°C
• 溶解度：
  insoluble in water; soluble in alcohol
• 折光率：
  1.483-1.487

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

制备方法与用途

毒性

GRAS(FEMA)。

使用限量

• 软饮料：1.0～11.0 mg/kg
• 冷饮、糖果、焙烤制品：18.0 mg/kg

根据FDA (§172.515, 2000) 规定，使用时应适度为限。

反应信息

• 作为反应物：
  描述：

  D-胡椒酮 在 臭氧 、 双氧水 作用下， 以 甲醇 、 水 为溶剂， 反应 15.83h， 以86%的产率得到(2S)-2-异丙基-5-氧化己酸
  参考文献：
  名称：

  呋喃芬环戊二烯Diels-Alder方法制备（+）-茶色霉素：（+）-脱水茶色素的不对称全合成。

  摘要：

  尝试合成（+）-茶豆素的对映选择性全合成反应时，合成了（+）-脱水茶豆素。所提出的途径构成了呋喃烷方法，是所提出的生物合成的两种方法之一，可能涉及跨环的Diels-Alder（TADA）反应，以使该二萜生物上与呋喃类ran骨联系起来。合成工作的重点包括通过醛10和二硫代呋喃甲酸11的偶合组装手性，无环，三取代的呋喃28，通过闭环置换将其大环化为呋喃芬29E，达到四环中间体4的TADA反应和氢化物转移介导的氧转位作为对靶标的最终重排。很遗憾，

  DOI：

  10.1021/jo034123o
• 作为产物：
  描述：

  isopiperitenol 在 chromium(VI) oxide 作用下， 生成 D-胡椒酮
  参考文献：
  名称：

  3-Alkyl-p-menthan-3-ol derivatives: synthesis and evaluation of their physiological cooling activity

  摘要：

  Different 3-alkyl-p-methan-3-ol derivatives provide a strong physiological cooling effect with potential application as food and cosmetic additives. In order to investigate the influence of the chemical structure on the cooling sensation, the stereoselective syntheses of 29 different 3-alkyl-p-methan-3-ol derivatives were accomplished. All the compounds obtained are odorless and were evaluated by taste, considering two sensations: a cooling effect and bitterness. The results of this structure-activity relationship study highlight that compounds with a (1R,4S)-configuration are the isomers with the more intense cooling effect and lower bitterness. In addition, the structure of the 3-alkyl chain affected the latter properties. Increasing the chain length over two carbon atoms does not change the cooling power, but enhances the bitterness with the additional feature that the branched isomers are considerably more bitter than the linear ones. Overall, the 3-alkyl-p-menthan-3-ol isomers with the best quality in terms of high cooling power and low bitterness are (1R,4S)-3-(hydroxymethyl)-p-menthan-3-ol diasteroisomers (-)-38 and (-)-42. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.10.022

文献信息

• Highly stereoselective axial addition of ethynyl carbanions to the carbonyl of cyclohexenones
  作者：Gilbert Stork、Jeffrey M. Stryker

  DOI：10.1016/s0040-4039(01)99802-8

  日期：1983.1

  This communication reports that highly stereoselective axial addition of ethynyl anions is the normal result with conformationally defined conjugated cyclohexenones, in the absence of overriding steric factors.

  该通讯报道，在没有最重要的空间因素的情况下，高构象选择性的乙炔基阴离子轴向加成是构象确定的共轭环己酮的正常结果。
• Allyl‐Palladium‐Catalyzed Ketone Dehydrogenation Enables Telescoping with Enone α,β‐Vicinal Difunctionalization
  作者：Yifeng Chen、David Huang、Yizhou Zhao、Timothy R. Newhouse

  DOI：10.1002/anie.201704874

  日期：2017.7.3

  The telescoping of allyl‐palladium catalyzed ketone dehydrogenation with organocuprate conjugate addition chemistry allows for the introduction of aryl, heteroaryl, vinyl, acyl, methyl, and other functionalized alkyl groups chemoselectively to a wide variety of unactivated ketone compounds via their enone counterparts. The compatibility of the dehydrogenation conditions additionally allows for efficient

  烯丙基钯催化的酮脱氢与有机铜酸酯共轭加成化学的伸缩作用使芳基，杂芳基，乙烯基，酰基，甲基和其他官能化烷基可通过其对映异构体化学选择性地引入到各种未活化的酮化合物中。脱氢条件的相容性还允许中间烯醇与各种亲电试剂的有效捕集。通过与几个先前报告的多步骤序列进行比较，证明了该方法的实用性。
• Synthesis of Cyclic Enones by Allyl-Palladium-Catalyzed α,β-Dehydrogenation
  作者：David Huang、Yizhou Zhao、Timothy R. Newhouse

  DOI：10.1021/acs.orglett.7b03818

  日期：2018.2.2

  The use of allyl-palladium catalysis for the one-step α,β-dehydrogenation of ketones via their zinc enolates is reported. The optimized protocol utilizes commercially available Zn(TMP)2 as base and diethyl allyl phosphate as oxidant. Notably, this transformation operates under salt-free conditions and tolerates a diverse scope of cycloalkanones.

  报道了烯丙基钯催化通过酮的烯醇锌对酮进行α，β-脱氢的一步。优化后的协议利用市售的Zn（TMP）2作为碱，并使用磷酸二乙基烯丙酯作为氧化剂。值得注意的是，这种转化是在无盐条件下进行的，并能耐受各种环烷酮。
• Lewis acid-catalyzed intramolecular asymmetric ene reactions of chiral vinyl sulfoxide
  作者：Kunio Hiroi、Masayuki Umemura

  DOI：10.1016/s0040-4039(00)92084-7

  日期：1992.6

  sulfoxide served as an efficient chiral enophile in a Lewis acid-catalyzed intramolecular ene ractions. Use of diethylaluminum chloride as a catalyst provided extremely high stereoselectivity in this ene reaction. Based on the stereochemical results obtained, a mechanistic pathway for this asymmetric induction is presented.

  手性α-氰基乙烯基亚砜在路易斯酸催化的分子内烯作用中作为有效的手性亲烯剂。在该烯反应中，使用氯化二乙基铝作为催化剂提供了极高的立体选择性。基于获得的立体化学结果，提出了这种不对称诱导的机理途径。
• The Lewis acid-catalyzed intramolecular asymmetric ene reaction using a chiral α-cyanovinylic sulfoxide as an enophile
  作者：Kunio Hiroi、Masayuki Umemura

  DOI：10.1016/s0040-4020(01)80539-1

  日期：1993.2

  chiral enophile in a Lewis acid-catalyzed intramolecular ene reaction. Use of diethylaluminum chloride as a catalyst provided extremely high stereoselectivity in the ene reaction. The stereochemistry of the ene reaction products were determined by chemical correlation and the NMR spectral analysis. A mechanistic pathway for the asymmetric induction is presented on the basis of the stereochemical results

  手性α-氰基乙烯基亚砜在路易斯酸催化的分子内烯反应中可作为有效的手性亲烯剂。使用氯化二乙基铝作为催化剂在烯反应中提供了极高的立体选择性。烯反应产物的立体化学通过化学相关性和NMR光谱分析来确定。根据获得的立体化学结果，提出了一种用于不对称诱导的机制途径。