cis-2-fluoro-4-tert-butylcyclohexanone

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

  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
• 作为产物：
  描述：

  2-bromo-4-tert-butylcyclohexanone 在 氢氟酸 、 silver nitrate 作用下， 以 ammonium hydroxide 、 二甲基亚砜 为溶剂， 生成 cis-2-fluoro-4-tert-butylcyclohexanone
  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。
• Bench‐Stable Electrophilic Fluorinating Reagents for Highly Selective Mono‐ and Difluorination of Silyl Enol Ethers
  作者：Akiya Adachi、Kohsuke Aikawa、Yuichiro Ishibashi、Kyoko Nozaki、Takashi Okazoe

  DOI：10.1002/chem.202101499

  日期：2021.8.16

  the synthesis of fluorinated compounds have been intensively studied, recently. Development of practical fluorinating reagents is indispensable for this purpose. Herein, bench-stable electrophilic fluorinating reagents were synthesized as N-fluorobenzenesulfonimide (NFSI) substitutes. Reagents obtained by replacing one of the NFSI sulfonyl groups with an acyl group led to the highly selective monofluorination

  最近，人们对合成含氟化合物的有效方法进行了深入研究。为此，开发实用的氟化试剂是必不可少的。在此，工作台稳定的亲电子氟化试剂被合成为N-氟苯磺酰亚胺(NFSI) 替代品。通过用酰基取代 NFSI 磺酰基之一获得的试剂导致甲硅烷基烯醇醚的高度选择性单氟化，同时抑制了不希望的过度反应，即二氟化。另一方面，在 NFSI 苯磺酰基上带有吸电子取代基的试剂在无碱条件下有效地促进了甲硅烷基烯醇醚的二氟化。因此，单氟化和二氟化靶材料均由同一基材制备。
• 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。
• 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。