Reactions with benzoyl fluoride

Benzoyl chloride, reaction with hydrogen fluoride, 45, 4... 

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... 

Kinetic studies of the acylation of imidazoles with benzoyl halides and sulfonyl halides have been carried out. In acetonitrile, benzoyl fluoride reacts with imidazole in a mixed third- and fourth-order reaction i.e., the rate-determining transition state contains the acid fluoride and two or three molecules of imidazole. With benzoyl chloride in benzene a second-order equation is followed similar to the aroylation of anilines ... 

Kinetic studies of the acylation of imidazoles with benzoyl halides and sulfonyl halides have been carried out. In acetonitrile, benzoyl fluoride reacts with imidazole in a mixed third- and fourth-order reaction ... 

The reactions of perfluoroisobutene with sodium salts of malonic esters are difficult to control, owing to rearrangement and base catalysed cyclization, but when the complex BFs NEts is used as HF acceptor, condensation is readily controlled (see Scheme 15 and p. 99) and yields of up to 50% of allene (39) obtained. Antimony pentaliuoride catalyses the electrophilic addition of acid fluorides to 1,1-difluoro- and trifluoro-ethylene. Propiophenones, PhCO CHX-CFs (X = H or F), are obtained from benzoyl fluoride, but with acetyl fluoride, further condensation occurs, and trifluoroethylene yields the jS-diketone, CF3-CHF-CO-CH2Ac. ... 

Acylation of alkenes can also be similarly effected with SbFs. Reaction of acetyl fluoride with trifluoroethylene produces 1,1,1,2-tetrafluorohexane-3,5-dione in 40% yield. When antimony pentafluoride is used in excess (more than 6 molar equivalents), 1,1,1,2-tetrafluorobutan-3-one is formed as a side product. Benzoyl fluoride reacts with dilluoroethy lene to form the expected ketone in 39% yield. a, 3-Unsaturated carboxylic acid fluorides have also been used in reactions with perfluoroalkenes. In these cases, a,p-unsaturated ketones are obtained (eq 17). Enol acetates of perfluoroisopropyl methyl ketone and perfluoro-f-butyl methyl ketone react with acetyl fluoride to provide the corresponding p-diketones (eq IS). ... 

Benzotrichloride is a chemical iatermediate used to produce two significant products. Partial hydrolysis or reaction with benzoic acid yields benzoyl chloride, whereas chlorination and subsequent reaction with hydrogen fluoride yields -chlorobenzotrifluoride [98-56-6]. 

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). 

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... 

Hydrazoic acid reaction with cyclobu-tanecarboxyhc acid, 47, 28 Hydrogenation of t butylazidoacetate to glycme ( butyl ester, 46,47 Hydrogen bromide 46, 43 reaction with y butyrolactone, 46, 43 Hydrogen fluoride anhydrous, precautions in use of, 46, 3 in preparation of mtromum tetra-fluoroborate 47, 57 reaction with benzoyl chloride, 46,4 with boron tnfluonde in conversion of p cymene to m cymene, 47, 40 in bromofluorination of 1 heptene, 46, 11... 

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... 

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. ... 

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. 

Uranium(VI) fluoride in l,l,2-trichloro-l,2,2-trifluoroethane at 0°C oxidizes12 aldehydes to acid fluorides in moderate yields (e.g., heptanoyl fluoride from heptaldehyde in 47% yield, benzoyl fluoride from benzaldehyde in 40% yield) benzaldehyde gives methyl benzoate and benzaldehyde dimethyl acetal when the reaction mixture is worked up by quenching with methanol.13... 

Stoichiometry (28) is followed under neutral or in alkaline aqueous conditions and (29) in concentrated mineral acids. In acid solution reaction (28) is powerfully inhibited and in the absence of general acids or bases the rate of hydrolysis is a function of pH. At pH >5.0 the reaction is first-order in OH but below this value there is a region where the rate of hydrolysis is largely independent of pH followed by a region where the rate falls as [H30+] increases. The kinetic data at various temperatures both with pure water and buffer solutions, the solvent isotope effect and the rate increase of the 4-chloro derivative ( 2-fold) are compatible with the interpretation of the hydrolysis in terms of two mechanisms. These are a dominant bimolecular reaction between hydroxide ion and acyl cyanide at pH >5.0 and a dominant water reaction at lower pH, the latter susceptible to general base catalysis and inhibition by acids. The data at pH <5.0 can be rationalised by a carbonyl addition intermediate and are compatible with a two-step, but not one-step, cyclic mechanism for hydration. Benzoyl cyanide is more reactive towards water than benzoyl fluoride, but less reactive than benzoyl chloride and anhydride, an unexpected result since HCN has a smaller dissociation constant than HF or RC02H. There are no grounds, however, to suspect that an ionisation mechanism is involved. 

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