4-tert-Butyl-2-(2-propenyl)cyclohexanone | 4861-78-3

• 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
• 英文名称: 4-tert-Butyl-2-(2-propenyl)cyclohexanone
• 英文别名: 2-allyl-4-tert-butylcyclohexanone；4-Tert-butyl-2-prop-2-enylcyclohexan-1-one
• CAS: 4861-78-3
• 化学式: C₁₃H₂₂O
• 分子量: 194.317
• InChiKey: ISONXJGBQIJAEM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-tert-Butyl-2-(2-propenyl)cyclohexanone 在 吡啶 、 4-二甲氨基吡啶 、 三丁基膦 、 三氟甲磺酸三甲基硅酯 、 碳酸氢钠 、 臭氧 作用下， 以 二氯甲烷 为溶剂， 反应 31.0h， 生成 (1R^*,3R^*,5S^*,7R^*)-7-tert-Butyl-11-acetoxy-12-(methoxycarbonyl)-2-oxatricyclo<6.3.1.0^1,5>dodec-11-ene
  参考文献：
  名称：

  Neighboring group participation in Lewis acid-promoted [3 + 4] and [3 + 5] annulations. The stereocontrolled synthesis of tricyclic ethers

  摘要：

  A variety of 1,4- and 1,5-keto aldehydes derived from cycloalkanes are coupled with the bis(trimethylsilyl) enol ether of methyl acetoacetate in the presence of either TMSOTf or TrSbCl6 to generate tricyclic ethers. The reactions proceed with excellent regiochemical control by a mechanism involving neighboring group participation. This mechanism involves initial formation of a bicyclic oxocarbenium ion intermediate from the keto aldehyde substrates. The geometries of selected bicyclic intermediates have been optimized using the AM1 method allowing successful prediction of the stereochemical outcomes in the cyclization in most cases. Epimerization of alpha-chiral keto aldehyde substrates does not appear to occur in these Lewis acid-promoted annulation reactions.

  DOI：

  10.1021/jo00074a018
• 作为产物：
  描述：

  4-叔丁基环己酮N,N-二甲基腙 在 sodium periodate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 水 为溶剂， 反应 40.5h， 生成 4-tert-Butyl-2-(2-propenyl)cyclohexanone
  参考文献：
  名称：

  Neighboring group participation in Lewis acid-promoted [3 + 4] and [3 + 5] annulations. The stereocontrolled synthesis of tricyclic ethers

  摘要：

  A variety of 1,4- and 1,5-keto aldehydes derived from cycloalkanes are coupled with the bis(trimethylsilyl) enol ether of methyl acetoacetate in the presence of either TMSOTf or TrSbCl6 to generate tricyclic ethers. The reactions proceed with excellent regiochemical control by a mechanism involving neighboring group participation. This mechanism involves initial formation of a bicyclic oxocarbenium ion intermediate from the keto aldehyde substrates. The geometries of selected bicyclic intermediates have been optimized using the AM1 method allowing successful prediction of the stereochemical outcomes in the cyclization in most cases. Epimerization of alpha-chiral keto aldehyde substrates does not appear to occur in these Lewis acid-promoted annulation reactions.

  DOI：

  10.1021/jo00074a018

文献信息

• Cerium(IV)-Catalyzed Deprotection of Acetals and Ketals under Mildly Basic Conditions
  作者：István E. Markó、Ali Ates、Arnaud Gautier、Bernard Leroy、Jean-Marc Plancher、Yannick Quesnel、Jean-Christophe Vanherck

  DOI：10.1002/(sici)1521-3773(19991102)38:21<3207::aid-anie3207>3.0.co;2-i

  日期：1999.11.2

  Smooth and quantitative deprotection of a wide range of acetals and ketals [Eq. (a); R, R(1)=alkyl, aryl, H] under neutral to mildly basic conditions was achieved with catalytic quantities of cerium ammonium nitrate (CAN). The reaction conditions are compatible with a variety of sensitive functional groups, and aldehydes can be liberated from acetals without being oxidized to the corresponding carboxylic

  各种缩醛和缩酮的平滑定量脱保护[Eq。（一种）; R，R（1）=烷基，芳基，H]在中性至弱碱性条件下用催化量的硝酸铈铵（CAN）实现。反应条件与各种敏感的官能团相容，并且醛可以从缩醛中释放出来而不会被氧化为相应的羧酸。
• Intramolecular sulfur-ylide additions to ketones. A cyclopentane annulation1
  作者：J.K. Crandall、H.S. Magaha、R.K. Widener、G.A. Tharp

  DOI：10.1016/0040-4039(80)80145-6

  日期：1980.1

  Various 2-(3′-phenylthiopropyl)cycloalkanones were prepared from the corresponding cyclic ketones and subjected to S-alkylation by triethyloxonium tetrafluoroborate followed by potassium -butoxide treatment to give bicyclic epoxides with new five-membered carbocycles. A related cyclization to a six-membered ring was also observed.

  由相应的环状酮制备各种2-（3'-苯硫基丙基）环烷酮，并通过四氟硼酸三乙基氧鎓进行S-烷基化，然后用丁醇钾处理，得到具有新的五元碳环的双环环氧化物。还观察到六元环的相关环化。
• Octahydrobenzofurane und Octahydrochromene - Verfahren zur Herstellung und ihre Verwendung als Duftstoffe
  申请人：Symrise AG

  公开号：EP2848611A1

  公开（公告）日：2015-03-18

  Die Erfindung betrifft neue Verbindungen der Formel mit R = -H, -methyl, ethyl, O-methyl oder O-ethyl, R1= -H, -methyl, ethyl, O-methyl oder O-ethyl und n = 1 oder 2, deren Verwendung als Duftstoffe, bevorzugte Mischungen, Konsumgüter enthaltend diese Verbindungen und deren Herstellung.

  本发明涉及式如下的新化合物 式中 R＝-H、-甲基、乙基、O-甲基或 O-乙基、 R1＝-H、-甲基、乙基、O-甲基或 O-乙基，以及 n = 1 或 2、 它们作为香料的用途、优选混合物、含有这些化合物的消费品及其制备方法。
• Intramolecular sulfur ylide additions to ketones
  作者：Jack K. Crandall、H. Steve Magaha、Mark A. Henderson、Rexford K. Widener、Gregg A. Tharp

  DOI：10.1021/jo00148a025

  日期：1982.12
• CRANDALL, J. K.;MAGAHA, H. S.;HENDERSON, M. A.;WIDENER, R. K.;THARP, G. A+, J. ORG. CHEM., 1982, 47, N 27, 5372-5380
  作者：CRANDALL, J. K.、MAGAHA, H. S.、HENDERSON, M. A.、WIDENER, R. K.、THARP, G. A+

  DOI：——

  日期：——