trans-4-tert-butyl-2-fluorocyclohexanone | 23510-86-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-4-tert-butyl-2-fluorocyclohexanone
• 英文别名: trans-2-fluoro-4-tert-butylcyclohexanone；(2S,4R)-4-tert-Butyl-2-fluorocyclohexan-1-one
• CAS: 23510-86-3
• 化学式: C₁₀H₁₇FO
• 分子量: 172.243
• InChiKey: FDEQGSUXDUOCAO-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-4-tert-butyl-2-fluorocyclohexanone 在 potassium peroxomonosulphate 、 四丁基硫酸氢铵 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 10.0h， 生成 (3S,5R)-5-tert-Butyl-3-fluoro-oxepan-2-one
  参考文献：
  名称：

  烯烃与环氧乙烷的催化环氧化。2.氟代酮。

  摘要：

  DOI：

  10.1021/jo971781y
• 作为产物：
  描述：

  cis-2-fluoro-4-tert-butylcyclohexanone 在 盐酸 作用下， 以 乙醚 为溶剂， 生成 trans-4-tert-butyl-2-fluorocyclohexanone
  参考文献：
  名称：

  Axial/equatorial proportions for 2-substituted cyclohexanones

  摘要：

  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.

  DOI：

  10.1021/jo00079a035

文献信息

• Micellar-System-Mediated Direct Fluorination of Ketones in Water
  作者：Stojan Stavber、Gaj Stavber、Marko Zupan

  DOI：10.1055/s-0028-1087924

  日期：2009.3

  A micellar system was developed and applied for direct regioselective fluorination of a variety of cyclic and acyclic ketones to α-fluoroketones in water as reaction medium with Selectfluor F-TEDA-BF 4 as fluorinating reagent. The inexpensive ionic amphiphile sodium dodecyl sulfate (SDS) was found to be an excellent promoter for fluorofunctionalization of hydrophobic ketones without prior activation

  以Selectfluor F-TEDA-BF 4 为氟化剂，开发了一种胶束体系，并应用于在水中将各种环状和无环酮直接区域选择性氟化成α-氟代酮作为反应介质。发现廉价的离子两亲物十二烷基硫酸钠 (SDS) 是疏水酮氟官能化的极好促进剂，无需事先活化或使用酸催化剂。
• Taming elemental fluorine: Indirect use of fluorine for the synthesis of α-fluoroketones[1]
  作者：Shlomo Rozen、Ynon Menahem

  DOI：10.1016/s0022-1139(00)85146-5

  日期：1980.7

  Fluorine and sodium trifluoroacetate react at −75° to produce a variety of fluoroxy-compounds. Although it is possible to direct the reaction towards the formation of CF3COOF or CF3CF2OF, mixtures may be used when only the electrophilic fluorine has to be attached to the molecule of interest. Such is the case of the reaction of enol-acetates with the mixture of the fluoroxy reagents. A wide variety

  氟和三氟乙酸钠在-75°下反应生成各种氟代化合物。尽管可以将反应引导至CF 3 COOF或CF 3 CF 2 OF的形成，但是当仅亲电氟必须连接到目标分子上时，可以使用混合物。烯醇-乙酸酯与氟代试剂混合物的反应就是这种情况。测试了多种化合物，包括类固醇和含有各种官能团。在大多数情况下，以良好至非常高的收率获得了所需的α-氟代酮。新的含氟化合物是编号为和的化合物。
• High yield direct fluorofunctionalisation of ketones using AccufluorTM-NFTh fluorinating reagent
  作者：Stojan Stavber、Marko Zupan

  DOI：10.1016/0040-4039(96)00630-2

  日期：1996.5

  Direct regioselective conversion of a variety of cyclic and acyclic ketones to α-fluoroketones was achieved in high to excellent yield using 1-fluoro-4-hydroxy-1,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate) [AccufluorTM - NFTh] in acetonitrile solution.

  使用1-氟-4-羟基-1,4-二氮杂双环[2,2,2]辛烷双（四氟硼酸酯）[Accufluor TM -NFTh]在乙腈溶液中。
• Theoretical and Experimental Studies on the Baeyer−Villiger Oxidation of Ketones and the Effect of α-Halo Substituents
  作者：Friedrich Grein、Austin C. Chen、David Edwards、Cathleen M. Crudden

  DOI：10.1021/jo0513966

  日期：2006.2.1

  migration of the fluorinated substituent versus the alkyl substituent in fluoropentanone and fluoroacetone. These differences match remarkably well with the experimentally obtained ratios of oxidation at the fluorinated and nonfluorinated carbons in a series of aliphatic ketones (calculated, 0.3 kcal/mol, observed, 0.5 kcal/mol), which are reported herein. The migration of the chlorinated substituent is

  通过从头算和DFT计算研究了丙酮和3-戊酮的Baeyer-Villiger反应（包括其氟化和氯化衍生物）与过甲酸的反应。将结果与脂族氟和氯酮的Baeyer-Villiger氧化的实验结果进行比较。根据理论结果，即使在存在酸催化剂的情况下，对于所有底物而言，第一过渡态都是速率决定的。尽管将酸引入反应路径会导致第一过渡态（TS）的活化能急剧下降，但是一旦将熵包括在计算中，焓的损失就会消失。在所有被检查的底物中，戊酮通过最低的能量跃迁状态与过甲酸反应。戊烷酮的第二过渡态也最低，说明了另外的烷基的促进作用。有趣的是，在过渡态中仅存在很小的能量差异，从而导致氟代戊酮和氟代丙酮中的氟代取代基相对于烷基取代基发生迁移。这些差异与在实验中获得的一系列脂族酮（计算得出的0.3 kcal / mol，观察到的0.5 kcal / mol）在氟化碳和非氟化碳上的实验获得的氧化比非常吻合。氯化取代基的迁移明显比烷基迁移困难，第二过渡态的差异约为2
• Selective Nuclear Magnetic Resonance Experiments for Sign-Sensitive Determination of Heteronuclear Couplings: Expanding the Analysis of Crude Reaction Mixtures
  作者：Guilherme Dal Poggetto、João Vitor Soares、Cláudio F. Tormena

  DOI：10.1021/acs.analchem.0c02976

  日期：2020.10.20

  State-of-the-art nuclear magnetic resonance (NMR) selective experiments are capable of directly analyzing crude reaction mixtures. A new experiment named HD-HAPPY-FESTA yields ultrahigh-resolution total correlation subspectra, which are suitable for sign-sensitive determination of heteronuclear couplings, as demonstrated here by measuring the sign and magnitude for proton–fluorine couplings (JHF) from

  最先进的核磁共振（NMR）选择性实验能够直接分析粗制反应混合物。一项名为HD-HAPPY-FESTA的新实验可产生超高分辨率的全相关子谱，适用于杂核耦合的符号灵敏测定，如本文中通过测量主要原子和氢原子质子-氟偶合（J HF）的符号和强度所证明。两步反应的少量异构体产物，无需任何纯化。可以使用HD-HAPPY-FESTA测量51.5至-2.6 Hz范围内的质子-氟偶联，最小测量幅度为0.8 Hz。实验J HF值用于鉴定两种氟代酮中间体和四种氟代醇产物。将结果合理化，并与密度泛函理论（DFT）计算进行比较。将实验数据与文献中报道的耦合进行了比较，其中对纯样品进行了分析。