Benzoyl fluoride

Aminoacetone is a versatile starting material for many syntheses, particularly for the preparation of heterocycles. The present procedure describes a convenient method for its preparation in a form suitable for storage. The aminoacetone can be generated from aminoacetone semicarbazone hydrochloride in situ as needed. 

Department of Chemistry, College of Technology, Huddersfield, England present address, North Lindsey Technical College, Scunthorpe, England. 

Johnson, C. E. Dalgliesh, W. E. Harvey, and C. Buchanan, Amino-aldehydes and aminoketones, in E. H. Rodd, ed., Chemistry of Carbon Compounds, Vol. 1, Elsevier Publishing Company, 1951, Part A, p. 714. 

Submitted by George A. Olah and Stephen J. Kuhn 1 Checked by John A. Dupont and William D. Emmons 

Caution Anhydrous hydrogen fluoride is toxic and in contact with skin can cause serious burns. This preparation should be carried out in a well-ventilated hood. Rubber gloves and safely 

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Phosgene reacts exothermically with thiirane in two steps (Scheme 36) (77MI50602). 3,5-Dinitrobenzoyl chloride and benzoyl fluoride initiate polymerization of thiirane. A novel reaction of benzoyl isocyanate or trichloroacetyl isocyanate, which yields ethylenethiol derivatives from epithiochlorohydrin (2-chloromethylthiirane), 2-methylthiirane or cyclohexene episulfide, has been reported (Scheme 37) (71BAU2432). 

Fluorination of tetrachlorophthalic acid hemihydrate with an excess of sulfur tetrafluoride, or of tetrachlorophthalic anhydride with a sulfur tetrafluonde-hydro-gen fluoride reagent, provides an efficient synthesis of 4,5,6,7- tetrachloro-1,1,3,3-tetrafluorol,3-dihydroisobenzofuran. 3,4,5,6-Tetrachloro-2-(trifluoromethyl)-benzoyl fluoride is formed as a by-product [217] (equation 111). 

Phosphorus-nitrogen compounds containing alkylated amino groups can be cleaved by fluormatmg agents Phenyldifluorophosphine is formed from the reaction of A,MA, lV -tetramethylphenylphosphonous amide and benzoyl fluoride [79] (equation 17). 

The eliminaUon of carbon monoxide from nonfluonnated acyl fluorides, however, does not result in a fluonne compound Although it was claimed earlier that benzoyl fluoride can be converted into fluorobenzene by using tris(triphenyl-phosphme)rhodium chloride, recent studies proved that the product is benzene and not fluorobenzene [91]... 

Benzoyl fluoride, 46,3 Benzoy lhydrazine, 46, 85 Benzoyl peroxide, as catalyst for reaction of chloroform with as,as 1,5 cyclooctadiene, 47, 11 reaction with diethyl ethylmalonate, 46, 37... 

The Arbuzov reaction has been applied for the synthesis of fluorinated carbohydrates. 1,2 3,4-Di-O-isopropylidene-a-D-galactopyran-ose 6-(N,N-diethyl-P-methylphosphonamidite) was treated with ethyl fluoroacetate, to afford 6-deoxy-6-fluoro-l,2 3,4-di-O-isopropylidene-a-D-galactopyranose in 19% yield.241 The corresponding 6-deoxy-6-fluoride was obtained in 60% yield by treatment of l,2 3,4-di-0-isopropylidene-a-D-galactopyranose 6-(dipropylphosphinite) with hexafluoropropene.242 The mechanism of this reaction has been discussed.243,244 In contrast, treatment of 1,2 -.3,4-di-O-isopropylidene-a-D-galactopyranose 6-(tetraethylphosphorodiamidite) with benzoyl fluoride yielded the corresponding 6-benzoate, not the 6-deoxy-6-flu-oride expected.245... 

In addition to studying the behavior of benzoyl chloride. Cheek and Horine [72] have examined the reduction of benzoyl fluoride electrolysis of the latter compound affords benzyl benzoate, diphenyl-acetylene, stilbenol benzoate, and some polymers. Another feature of the reduction of benzoyl chloride is the possibility that both acyl radicals and acyl anions are involved as intermediates [71]. 

Benzoyl fluoride is a potent lachr)miator and is undoubtedly toxic. It is advisable to rinse all glassware with acetone followed by 10% aqueous ammonia before removing the glassware from the hood. 

Benzoyl fluoride can also be prepared by the reaction of anhydrous hydrogen fluoride or potassium fluoride with benzoic anhydride and by the halogen exchange of benzoyl chloride with alkali fluorides, such as NaF/ KF/ KHF2, Na2SiFe, or various other metal fluorides. ... 

The described procedure, first applied by Colson and Freden-hagen, is useful for the preparation of a wide variety of acyl fluorides. The yields are normally 80-90%. Some examples of acyl fluorides prepared are listed in Table I. Benzoyl fluoride can also be employed as a convenient source of acetyl fluoride by reaction with acetic acid. ... 

Benzophenone, 46, 36 N-(2-Benzothiazolyl)urea, 46, 72 Benzoyl chloride, reaction with hydrogen fluoride, 46, 4 Benzoyl fluoride, 46, 3 Benzoylhydrazine, 46, 8S Benzoyl peroxide, reaction with diethyl ethylmalonate, 45, 37 2-Benzyl-2-carbomethoxycyclopenta-none, 45, 7... 

More drastic conditions of temperature, pressure and time gave carbon as the product from both aromatic and aliphatic compounds. This carbon is an activated char with decolorizing properties. Tars, tarry substances, the oxides of carbon, and the usual products of the oxidation of aromatic compounds (dicarboxylic acids) were all conspicuous by their absence. Benzotrifluoride oxidized to benzoyl fluoride. The aliphatic compounds cyclohexane, methycyclohexane, n-heptane, etc., could be oxidized to carbon and water. 

Reaction of the 2-phenyl-4-(phosphoranylidene)-5(47/)-oxazolone 219 with alkyl halides gives 4-alkyl-2-phenyl-5(47/)-oxazolones 220 in good yields. Reaction of 219 with acyl iodides or bromides gives C-4- or O-acyl products 221 or 222. Reaction of 219 with acyl chlorides gives 4-(l-chloroalkylidene)-2-phenyl-5(47/)-oxazolones 224 that are Wittig-like products. The use of benzoyl fluoride gives rise to 4-(l-benzoyloxybenzylidene)-2-phenyl-5(47/)-oxazolone 223. These reactions are summarized in Scheme 7.68. 

To 70% HF/pyridine (5mL) in a polyethylene boitle was added benzoyl chloride (1.48g, 10.5 mmol). Evolution of HC1 was visible. The solution was stirred for 10 min, cooled to 0 C, and quenched with ice water (5 mL). It was then extracted with benzene, washed with ice-cold H20 (5mL) followed by brine, and dried (Na2S04). Evaporation of the solvent gave almost pure benzoyl fluoride which was further purified by distillation yield 1.25 g (92%) bp 149-160 C. 

Together with 2-(trifluoromethyl)benzoyl fluoride (23%). h Together with 4-(trifluoiomethyl)benzoyl fluoride (3%). 

Treatment of phthalimide with sulfur tetrafluoride and catalytic amounts of boron trifluoride gives 2-(trifluoromethyl)benzoyl fluoride (3) in reasonable yield.41... 

When heated with antimony(III) fluoride, l,l,3,3-tetrachIoro-l,3-dihydroisobenzofuran and its 5-substituted derivatives give a mixture of the corresponding 1,l,3.3-tetrafluoro-5-sub-stituted 1,3-dihydroisobenzofurans and 2-(trifluoromethyl)benzoyl fluorides with substituents R mainly in the 5-position.20 - 23... 

A reactor packed with FeCl3 supported on A1F3 was preactivated with HF. 2-(Methyl)benzoyl chloride (384 g h 2) and N2 were passed through with C12/HF for approx. 2 h. This gave a mixture (1.03 kg) containing 2-(trifluoromethyl)benzoyl fluoride (8) yield 612 g (70.4%) and a 2-(trifluoromethyl)chloro-benzoyl fluoride byproduct, the structure was not elucidated (13.4%). 

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