3-tert-butyl-trans-1,2-epoxycyclohexane | 81800-98-8

• 英文名称: 3-tert-butyl-trans-1,2-epoxycyclohexane
• 英文别名: (trans)-2-tertbutylcyclohexene oxide；(+/-)-trans-3-tert-butyl-1,2-epoxycyclohexane；γ-1,2-Epoxy-t-3-tert.-butylcyclohexan；t-3-tert-Butyl-c-1,2-epoxy-cyclohexan；(1S,2S,6R)-2-tert-butyl-7-oxabicyclo[4.1.0]heptane
• CAS: 81800-98-8
• 化学式: C₁₀H₁₈O
• 分子量: 154.252
• InChiKey: SFXWZOTYAVHTJO-HLTSFMKQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-tert-butyl-trans-1,2-epoxycyclohexane 在 chiral bicyclic diamine 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 6-(tert-butyl)cyclohex-2-en-1-ol
  参考文献：
  名称：

  Kinetic resolution of racemic epoxides using a chiral diamine catalyst

  摘要：

  The kinetic resolution of a variety of racemic epoxides has been performed using a chiral bicyclic diamine ligand. Using 5 mol% of catalyst very high selectivity could be achieved; both epoxide and the corresponding allylic alcohol could be obtained in up to 99% ee. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.05.017
• 作为产物：
  描述：

  N'-(2-(tert-butyl)cyclohexylidene)-4-methylbenzenesulfonohydrazide 在 正丁基锂 、 二甲基二环氧乙烷 作用下， 以 丙酮 为溶剂， 生成 3-tert-butyl-trans-1,2-epoxycyclohexane
  参考文献：
  名称：

  Diastereoselectivity in the Epoxidation of Substituted Cyclohexenes by Dimethyldioxirane^1,2

  摘要：

  Three series of compounds based on the cyclohexene framework. have been epoxidized by dimethyldioxirane. A pronounced dependence of epoxide diastereoselectivity on substituent has been observed. In addition there is a solvent influence on this stereoselectivity. The results have been explained by invoking steric, H-bonding, and dipole-dipole influences on the epoxide stereochemistry.

  DOI：

  10.1021/jo951864j

文献信息

• Steric and Electronic Effects in the Diastereoselective Catalytic Epoxidation of Cyclic Allylic Alcohols with Methyltrioxorhenium (MTO)
  作者：Waldemar Adam、Catherine M. Mitchell、Chantu R. Saha‐Möller

  DOI：10.1002/(sici)1099-0690(199904)1999:4<785::aid-ejoc785>3.0.co;2-#

  日期：1999.4

  Good cis selectivity is observed in the epoxidation of the cyclic allylic alcohols 2-cyclopentenol and 2-cyclohexenol due to a hydroxy-directing effect through hydrogen bonding; however, for 2-cycloheptenol and 2-cyclooctenol hydrogen bonding is ineffective and steric interactions cause a higher trans selectivity. The conformationally fixed cis- and trans-5-tert-butyl-2-cyclohexenols serve as suitable

  对于一系列的3-烷基取代的环己烯，已经评估了在用甲基三氧or /脲/过氧化氢加合物（MTO / UHP）进行环氧化时，烯丙基取代基的空间效应。的反式与取代基的大小选择性增加，并且非对映选择性遵循塔夫脱（的立体取代基常数的良好的线性相关性ë小号）或Charton（ν）。由于通过氢键的羟基引导作用，在环状烯丙基醇2-环戊烯醇和2-环己烯醇的环氧化中观察到良好的顺式选择性。但是，对于2-环庚烯醇和2-环辛烯醇，氢键无效，空间相互作用会导致更高的反式选择性。构象固定的顺式和反式-5-叔丁基-2-环己烯醇用作合适的底物，用于测量在这些环氧化反应中的氧转移的过渡态的二面角。因此，MTO / UHP氧化剂有利于一个准赤道有效氢键（羟基-组指向性）的羟基的结构，以类似于米氯过苯甲酸（米-CPBA）和二甲基二（DMD），和一个二面角约。建议130°。
• Iodoacetoxylation of 3-t-butylcyclohexene
  作者：Richard C. Cambie、Diana M. Gash、Peter S. Rutledge、Paul D. Woodgate

  DOI：10.1039/p19770001157

  日期：——

  Iodoacetoxylation of 3-t-butylcyclohexene with silver(I) acetate–iodine or thallium(I) acetate–iodine gives an ca. 3 : 1 mixture of t-2-iodo-t-3-t-butylcyclohexan-r-1-yl acetate and t-2-iodo-c-3-t-butylcyclohexan-r-1-yl acetate as the major products. The ratio is similar to that obtained for the major alcohols from reduction of the iodo-acetates with tri-n-butyltin hydride followed by lithium aluminium

  3-叔butylcyclohexene与银的Iodoacetoxylation（我）乙酸乙酯-碘或铊（我）乙酸乙酯-碘给出了一个CA。3：1混合物吨-2-碘-吨-3-叔butylcyclohexan- ř -1-基乙酸酯和吨-2-碘Ç -3-叔butylcyclohexan- ř乙酸-1-基酯为主要产品。该比率与通过先用氢化三正丁基锡，然后用氢化铝锂还原碘代乙酸盐获得的主要醇的比率相似，但是与由Fwardpel和Richer获得的由Woodward-Prévost制备的邻二醇的比率不同与3-叔丁基环己烯反应。通过显示双轴碘乙酸盐（2）的溶剂分解以非立体特异性方式进行来解释差异。
• Titanium-Catalyzed Heterogeneous Oxidations of Silanes, Chiral Allylic Alcohols, 3-Alkylcyclohexanes, and Thianthrene 5-Oxide: A Comparison of the Reactivities and Selectivities for the Large-Pore Zeolite Ti-β, the Mesoporous Ti-MCM-41, and the Layered Alumosilicate Ti-ITQ-2
  作者：Waldemar Adam、Avelino Corma、Hermenegildo García、Oliver Weichold

  DOI：10.1006/jcat.2000.3043

  日期：2000.12

  A comparative study of silane oxidation, olefin epoxidation, and thianthrene 5-oxide sulfoxidation with the oxidants Ti-β/H2O2, Ti-MCM-41/t-BuOOH, and Ti-ITQ-2/t-BuOOH provides the catalytic reactivity order Ti-β>Ti-MCM-41>Ti-ITQ-2. The steric constraints of the narrow channels make the Ti-β zeolite the most selective. For the more open structures of the Ti-MCM-41 and Ti-ITQ-2 hosts, such steric constraints

  用氧化剂Ti-β/ H 2 O 2，Ti-MCM-41 / t -BuOOH和Ti-ITQ-2 / t -BuOOH对硅烷氧化，烯烃环氧化和噻吨5氧化物硫氧化的比较研究提供了催化反应顺序为Ti-β> Ti-MCM-41> Ti-ITQ-2。狭窄通道的空间限制使Ti-β沸石具有最高的选择性。对于Ti-MCM-41和Ti-ITQ-2主体的更开放的结构，这种空间约束不太明显，因此，这些多相催化剂显示出较低的选择性。两者均通过类似于均相Ti（O i -Pr）4 / t的过渡结构激活t -BuOOH进行氧转移-BuOOH氧化剂。
• A Simple and Efficient Oxidation Procedure for the Synthesis of Acid-Sensitive Epoxides
  作者：Olga Bortolini、Marco Fogagnolo、Giancarlo Fantin

  DOI：10.1055/s-0028-1087999

  日期：2009.4

  A mild and straightforward epoxidation protocol based on sodium perborate as primary oxidant and sodium dehydrocholate as organomediator under homogeneous conditions is described. In particular, geraniol, linalool, 3-carene, and α-pinene are quantitatively converted into the corresponding 6,7-epoxides and trans-epoxides­, respectively. The bile acid salt is recovered from the reaction mixture and may be reused with unchanged efficiency and selectivity.

  描述了一种温和且简单的环氧化协议，基于过硼酸钠作为主要氧化剂，脱氢胆酸钠作为有机介质，在均相条件下进行。特别是，香草醇、芳樟醇、3-烯烃和α-蒎烯被定量转化为相应的6,7-环氧化物和反式环氧化物。胆盐从反应混合物中回收，并可重复使用，效率和选择性未改变。
• Bellucci,G. et al., Gazzetta Chimica Italiana, 1978, vol. 108, p. 643 - 650
  作者：Bellucci,G. et al.

  DOI：——

  日期：——