7443-34-7

Upstream product

• 7360-39-6 1-acetoxy-4-tert-butylcyclohexene 
• 98-53-3 4-tercbutyl-cyclohexanone 
• 19980-19-9 4-t-butyl-1-trimethylsilyloxy-1-cyclohexene 
• 1076-82-0 2-bromo-4-tert-butylcyclohexanone 
• 1544-02-1 cis-4-(1,1-dimethylethyl)-2-fluorocyclohexanone 

Downstream Products

• 1544-02-1 trans-2α-fluoro-4-t-butylcyclohexanone 
• 19626-82-5 2t-Fluor-4c-tert.-butyl-1r-cyclohexanol 
• 19626-82-5 2c-Fluor-4c-tert.-butyl-1r-cyclohexanol 
• 19626-82-5 2t-Fluor-4t-tert.-butyl-1r-cyclohexanol 

Relevant academic research and scientific papers

Micellar-system-mediated direct fluorination of ketones in water

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-BF4 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 or use of acid catalysts. Georg Thieme Verlag Stuttgart.

Bench-Stable Electrophilic Fluorinating Reagents for Highly Selective Mono- and Difluorination of Silyl Enol Ethers

Efficient methods for 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 of silyl enol ethers with suppression of undesired overreaction, that is, difluorination. On the other hand, reagents bearing electron-withdrawing substituents at NFSI benzenesulfonyl groups efficiently facilitated the difluorination of silyl enol ethers under base-free conditions. Thus, both mono- and difluorinated target materials were prepared from the same substrate.

Selective Nuclear Magnetic Resonance Experiments for Sign-Sensitive Determination of Heteronuclear Couplings: Expanding the Analysis of Crude Reaction Mixtures

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 major and minor isomer products of a two-step reaction without any purification. Proton-fluorine couplings ranging from 51.5 to -2.6 Hz could be measured using HD-HAPPY-FESTA, with the smallest measured magnitude of 0.8 Hz. Experimental JHF values were used to identify the two fluoroketone intermediates and the four fluoroalcohol products. Results were rationalized and compared with the density functional theory (DFT) calculations. Experimental data were further compared with the couplings reported in the literature, where pure samples were analyzed.

Fluorination of ketones using iodotoluene difluoride

Fluorination of ketones was achieved by the reaction of silyl enol ethers with iodotoluene difluoride in the presence of BF3·OEt 2 and a Et3N·HF complex. Georg Thieme Verlag Stuttgart.

High yield direct fluorofunctionalisation of ketones using accufluor - NFTh fluorinating reagent

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) [Accufluor - NFTh] in acetonitrile solution. Copyright

The conformation of 2-fluoroethanol - is intramolecular hydrogen bonding important?

The conformations of 2-fluoroethanol (FE) and trans-4-tert-butyl-cis-2-fluorocyclohexanol (1) have been investigated by FT-IR and 1H NMR spectroscopy and the methyl ether of 1 (3) by 13C NMR spectroscopy.The energies of the conformations of FE, its methyl ether, cis-2-fluorocyclohexanol (4) and its methyl ether (5) were investigated by molecular mechanics (MMPMI) calculations.FE and its methyl ether were investigated by ab initio calculations (MP2/6-31++G**//MP2/6-31++G*).The results were all consistent with a dominance (>90percent) of the gauche rotamer around the CH2CH2 fragment in FE.Furthermore, the gauche rotamer around the CH2OH bond of FE with the hydroxyl proton pointing towards the fluorine atom was also a major component making the conformation Gg' the most important one.However, from the conformations of the methyl ethers 1-fluoro-2-methoxyethane and 3 it was concluded that an intramolecular hydrogen bond was not important for this dominance.Other interactions e.g. the repulsive forces between the lone pair electrons of the oxygen atom and the fluorine atom, were found to be more important than a hydrogen bond for the conformational composition around the C-O bond.The rotamer distribution around the CH2CH2 bond was found to be the result of the gauche effect.

Axial/equatorial proportions for 2-substituted cyclohexanones

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 13C 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.

Obtention d'α-fluorocetones par oxydation anodique de derives d'enol.

To obtain fluoroketones without the use of electrophilic fluorinating reagents, we have carried out the anodic oxidation of enol esters and enol ethers in acetonitrile/Et3N, 3HF solution.With enol esters the main product is a fluoroketone or an acetoxyketone respectively, depending on the structure of the starting compound.The enol ether cation-radicals seemed to be less reactive towards H2F3- ions than the corresponding enol ester ones.

TAMING ELEMENTAL FLUORINE: INDIRECT USE OF FLUORINE FOR THE SYNTHESIS OF α-FLUOROKETONES

Fluorine and sodium trifloroacetate react at -75 deg to produce a variety of fluoroxy-compounds.Although it is possible to direct the reaction towards the formation of CF3COOF or CF3CF2O, mixtures may be used when only the electrophilic fluorine has to be