350-39-0

Upstream product

• 99-81-0 4-Nitrophenacyl bromide 
• 82961-74-8 5-[hydroxy(4-nitrophenyl)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione 
• 122-04-3 4-nitro-benzoyl chloride 
• 100-19-6 (4-nitrophenyl)ethanone 
• 74812-79-6 1-(4-nitrophenyl)-1-trimethylsilyloxyethylene 
• 1046785-21-0 4-(2-fluoro-1,1-dimethoxyethyl)-4-nitrobenzene 
• 67-56-1 methanol 
• 4203-31-0 2-diazo-1-(4-nitrophenyl)ethanone 
• 65220-26-0 1-azido-1-(4-nitrophenyl)ethene 
• 100-13-0 4-nitrostyrene 

Downstream Products

• 40733-89-9 (+/-)-2-fluoro-1-(4-nitrophenyl)ethanol 
• 1073056-12-8 (R)-2-fluoro-1-(4-nitrophenyl)ethanol 

Relevant academic research and scientific papers

α-Fluorotricarbonyl Derivatives as Versatile Fluorinated Building Blocks: Synthesis of Fluoroacetophenone, Fluoroketo Ester and Fluoropyran-4-one Derivatives

Fluorinated acyl-Meldrum's acid derivatives were synthesized by electrophilic fluorination of appropriate phenacyl Meldrum's acid substrates using Selectfluor. Reactions with water, ethanol, Grignard, and alkynyllithium reagents gave rise to the correspon

Fluorination of α-bromomethyl aryl ketones with fluorohydrogenate-based ionic liquids

Fluorination of α-bromomethyl aryl ketones using fluorohydrogenate-based ionic liquids as fluorinating reagent is described. Reaction of various α-bromomethyl aryl ketones (1a-g) with fluorohydrogenate-based ionic liquids such as EMIMF·(HF)2.3, PYR13F·(HF)2.3 or PYR14F·(HF)2.3 as a fluoride ion source in anhydrous THF led to the formation of the corresponding α-fluoromethyl aryl ketones (2a-g) in very good yield. Compared to alternative fluorinating agents for this reaction, fluorohydrogenate-based ionic liquids are safer to handle and have the potential to be less expensive and more selective.

Synthesis of α-Fluoroketones from Vinyl Azides and Mechanism Interrogation

An efficient and mild fluorination of vinyl azides for the synthesis of α-fluoroketones is described. The mechanistic studies indicated that a single-electron transfer (SET) and a subsequent fluorine atom transfer process could be involved in the reaction.

Synthesis of α-fluoroketones and α-fluoroenones in aqueous media

An efficient synthesis of α-fluoroketones via the nucleophilic fluorination of α-bromoketones in water with TBAF·3H2O as the fluorinating agent was developed in this paper. In addition, a simple and efficient synthesis of α-fluoroenones through the condensation of α-fluoroketones with aldehydes promoted by sodium hydroxide in water was also discovered.

Synthesis of enantiopure fluorohydrins using alcohol dehydrogenases at high substrate concentrations

The use of purified and overexpressed alcohol dehydrogenases to synthesize enantiopure fluorinated alcohols is shown. When the bioreductions were performed with ADH-A from Rhodococcus ruber overexpressed in E. coli, no external cofactor was necessary to obtain the enantiopure (R)-derivatives. Employing Lactobacillus brevis ADH, it was possible to achieve the synthesis of enantiopure (S)-fluorohydrins at a 0.5 M substrate concentration. Furthermore, due to the activated character of these substrates, a huge excess of the hydrogen donor was not necessary.

One-pot α-nucleophilic fluorination of acetophenones in a deep eutectic solvent

Two methods of nucleophilic fluorination to prepare α-fluoroacetophenones from α-bromoacetophenones by using KF with PEG-400 or TBAF with ZnF2 are described. On the fundamental of nucleophilic fluorination, a novel method of one-pot fluorination to prepare α-fluoroacetophenones directly from acetophenones in DES was developed.

Microwave assisted fluorination: an improved method for side chain fluorination of substituted 1-arylethanones

A two-step, one-pot microwave (MW) assisted fluorination of 1-arylethanones to their corresponding 1-aryl-2-fluoroethanones has been developed. The first step utilises Selectfluor as a fluorinating agent in methanol forming 1-aryl-2-fluoroethanones and their corresponding dimethyl acetals. In the second step, water is added and Selectfluor acts as a Lewis acid in the hydrolytic cleavage of the dimethyl acetals. Compared to the thermal synthesis, the MW assisted method leads to a reduction in reaction time both in the fluorination and for the dimethyl acetal cleavage. Moreover, the one-pot procedure reduces reagent and solvent consumption. The method is best suited for the preparation of 1-aryl-2-fluoroethanones containing substituents that deactivates electrophilic aromatic substitution, however highly electron deficient ketones such as 1-(3,5-dinitrophenyl)ethanone reacts more slowly. Reactions using electron rich aromatic ketones had a low regioselectivity, and also produced fluoroaromatic products.

Ruthenium-catalysed asymmetric transfer hydrogenation of para-substituted α-fluoroacetophenones

The first examples of asymmetric transfer hydrogenation of α-fluoroacetophenones are reported. Eight para-substituted α-fluoroacetophenones have been reduced using four catalytic systems constructed of [RuCl2(p-cymene)2]2 or [RuCl2(mesitylene)2]2 in combinations with each of the ligands (1R,2R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine ((R,R)-TsDPEN) and (1R,2R)-N-(p-toluenesulfonyl)-1,2-cyclohexanediamine ((R,R)-TsCYDN). All reactions were performed in both water and formic acid/triethylamine. The highest enantioselectivity was obtained using the (R,R)-TsDPEN ligand in a formic acid/triethylamine mixture, giving the (S)-1-aryl-2-fluoroethanols in high to moderate enantiomeric excess (97.5-84.5%). For this solvent system the presence of electron withdrawing groups in the para position reduced the enantioselectivity. Reactions performed in water generally gave lower enantioselectivity and reaction rate, although RuCl(mesitylene)-(R,R)-TsDPEN yielded the product alcohols with enantiomeric excess in the range of 95.5-76.5%.

Electrophilic and nucleophilic side chain fluorination of para-substituted acetophenones

para-Substituted α-fluoroacetophenones have been synthesised by three different routes. Electrophilic fluorination of trimethylsilyl enol ethers of acetophenones using Selectfluor (F-TEDA-BF4, 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis-(tetrafluoroborate)) gave high to moderate yield depending on the electronic properties of the substituents. F-TEDA-BF4 mediated fluorination of acetophenones in methanol resulted in a mixture of α-fluoroacetophenones and the corresponding 2-fluoro-1,1-dimethyl acetals. The dimethyl acetals were hydrolysed using trifluoroacetic acid in water to maximise the yield of the product. Nucleophilic fluorination of α-bromoacetophenones using tetrabutylammonium hydrogen bifluoride (TBABF) led to moderate yield when having electron-donating substituents, whereas low yields were experienced when more electron-withdrawing substituents were introduced.

Novel entry to aryl α-fluoromethyl ketones via sodium hydroxide-induced hydrolysis of fluorinated enol tosylates

Abstract: 1-Aryl-substituted 2,3,3-trifluoro-1-propenyl p-toluene-sulfonate 1 was smoothly hydrolyzed in a mixed solvent of dimethyl sulfoxide-water (1:1) in the presence of sodium hydroxide at 80 °C to afford the corresponding aryl α-monofluoromethyl ketones 2 in fair to good yields.