反式-2-甲氧基-4-叔丁基环己酮 | 35394-07-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 反式-2-甲氧基-4-叔丁基环己酮
• 英文名称: trans-2-methoxy-4-tert-butylcyclohexanone
• 英文别名: trans-4-tert-butyl-2-methoxycyclohexanone；trans-4-t-butyl-2-methoxycyclohexanone；trans-2-Methoxy-4-tert.-butyl-cyclohexanon；trans-t-Butyl-4-methoxy-2-cyclohexanon；(2S,4R)-4-tert-butyl-2-methoxycyclohexan-1-one
• CAS: 35394-07-1；35394-08-2；145041-47-0；145041-48-1
• 化学式: C₁₁H₂₀O₂
• 分子量: 184.279
• InChiKey: WFIJQVZBLDECGE-SCZZXKLOSA-N

物化性质

• 沸点：
  245.9±33.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 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：

  反式-2-甲氧基-4-叔丁基环己酮 在 sodium hydroxide 、 dimethyl sulfide borane 、 双氧水 、 magnesium 作用下， 反应 4.0h， 生成 (1R^*,2S^*,4R^*)-1-(3-hydroxypropyl)-2-methoxy-4-tert-butylcyclohexanol
  参考文献：
  名称：

  烯丙基金属试剂向 2-甲氧基环己酮和四氢呋喃螺-（2-环己酮）的 1,2-加成中的 π-面非对映选择

  摘要：

  已经确定了几种烯丙基金属试剂和 Normant Grignard [ClMgO(CH2)3MgCl] 的 1,2-加成到 2-甲氧基环己酮和四氢呋喃螺-(2-环己酮) 的立体化学过程。在检测的六种底物中的四种中，存在一个 4-叔丁基作为构象锚。相邻的甲氧基取代基显示出能够有效参与螯合，尽管特殊情况可能另有规定。涉及烯丙基试剂作为水溶液中的亲核试剂的实验表明，水的存在不会抑制螯合控制的操作，这通常大大超过在无水介质中使用相应的镁、铈和铬试剂所能达到的效果。

  DOI：

  10.1021/ja9536835
• 作为产物：
  描述：

  4-叔丁基环己酮 在 亚碘酰苯 、 BF₄*Et₂O 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 26.0h， 生成 反式-2-甲氧基-4-叔丁基环己酮
  参考文献：
  名称：

  紫杉醇C，D环系统的合成：α-甲氧基酮的光解

  摘要：

  描述了用于合成紫杉醇的C和D环的模型系统，其涉及α-甲氧基酮的光解。紫杉醇常见的顺式稠合的氧杂环丁醇与新型的反式稠合的氧杂环丁烷一起形成。还描述了有关此过程的选择性以及机理假设的实验。

  DOI：

  10.1016/s0040-4020(01)91212-8

文献信息

• Aldol additions of pinacolone lithium enolate with ketones: reactivities governed predominantly by field effects
  作者：Goutam Das、Edward R. Thornton

  DOI：10.1021/ja00057a012

  日期：1993.2

  The relative reactivities of representative α- and β-heterosubstituted acyclic, cyclic (five- and six-membered), and aromatic ketones with the lithium enolate of pinacolone in diethyl ether at -78 o C were determined. The order of reactivitiesof monosubstituted acetones (MeCOCH 2 X) is X=Cl>OTBDMS>OMe>SMe>NMe 2 >CH 2 SM>H>Me and spans a range of 10 4

  测定了代表性的 α- 和 β- 杂取代的无环、环状（五元和六元）和芳香酮与频哪酮的烯醇锂在 -78 o C 的二乙醚中的相对反应性。单取代丙酮 (MeCOCH 2 X) 的反应性顺序为 X=Cl>OTBDMS>OMe>SMe>NMe 2 >CH 2 SM>H>Me，范围为 10 4
• An internally activated tin hydride with enhanced reducing ability
  作者：E. Vedejs、S. M. Duncan、A. R. Haight

  DOI：10.1021/jo00063a024

  日期：1993.5

  Tin hydride 1 is activated for nucleophilic hydride transfer and also for radical chain reduction, depending on solvent. The nucleophilic hydride pathway is favored in methanol, and 1 can be used as a selective reducing agent for ketones. Simple ketones are not reduced in aprotic solvents, but beta-hydroxy ketones are activated internally by the hydroxyl group and can be reduced in THF with good control of stereochemistry, as in the conversion from 7 to 9 (30:1 9:8). A catalytic version of the nucleophilic hydride reductions in methanol has been developed using PhSiH3 as the stoichiometric hydride source. Radical chain dehalogenations can also be achieved with 1 at room temperature and without added radical initiators. Simple xanthates are not reduced efficiently in the absence of an initiator, but the reaction proceeds in the presence of AIBN.
• Axial/equatorial populations in ?-hetero-substituted cyclohexanone Oximes andO-methyl oximes
  作者：Douglas S. Ribeiro、Paulo R. Olivato、Roberto Rittner

  DOI：10.1002/1097-458x(200008)38:8<627::aid-mrc680>3.0.co;2-m

  日期：2000.8

  Axial equatorial populations were determined for (E)-2-X-cyclohexanone oximes and O-methyl oxime ethers in chloroform by the Eliel method [X = F, Cl, Br, OCH3, N(CH3)(2), SCH3]. A novel approach is presented, which uses H-1 NMR data from the protons bonded to C-6. The conformational proportions were also obtained from the C-4 chemical shifts, the Z-isomer spectral parameters being taken as reference for calculation. For both series, all substituents adopt preferentially the axial conformation (86-96%), but the O-methyl oxime ethers present an enhanced axial population compared with the corresponding oximes, owing to the accepted occurrence of a pi(C=NOH)/sigma(CX)* stabilizing interaction. Copyright (C) 2000 John Wiley & Sons, Ltd.
• Axial/equatorial proportions for 2-substituted cyclohexanones
  作者：Ernani A. Basso、Carlos Kaiser、Roberto Rittner、Joseph B. Lambert

  DOI：10.1021/jo00079a035

  日期：1993.12

  Axial-equatorial conformational proportions have been measured for 2-substituted cyclohexanones in chloroform by the Eliel method for F, Cl, Br, I, MeO, MeS, Me2N, MeSe, and Me. For the first seven of these, at least five experimentally independent measurables were used and the resulting conformational preferences appear to be accurate to within 10%. Systematic errors degraded the results for MeSe and Me. For Me2N, the conformational preference also was measured for the first time at slow exchange in the low-temperature C-13 spectrum in several solvents. In chloroform, steric and polar effects contribute to the conformational preferences, with steric effects dominant for large groups such as I and MeS.
• Assistance du groupe méthoxyle en α d'un carbonyle dans le cours stérique de l'addition d'organométalliques insaturés
  作者：Danielle Guillerm-dron、Marie-Louise Capmau、Wladyslaw Chodkiewicz

  DOI：10.1016/s0040-4039(01)84233-7

  日期：1972.1