Acetic benzoic anhydride, hydrolysis

Bunton and Perry294 measured the rates of hydrolysis of acetic, benzoic, mesitoic, acetic-benzoic and acetic-mesitoic anhydrides in aqueous dioxan. They found that the hydrolyses of acetic, acetic-benzoic and benzoic an-... 

Acetyl )thiooxindole may be prepared by fusing together thio-oxindole and A,A -diphenylacetamidine to give the anil (217), which affords the acetyl compound on alkaline hydrolysis.573 Acetylation and benzoylation of thiooxindole are possible by using mixtures of acetic anhydride and sodium acetate or benzoic anhydride and sodium benzoate, respectively.575... 

Yet a further method of cleaving acetals is to treat them with acid anhydrides, such as acetic or benzoic anhydride, in the presence of hydrogen ions 95 equimolar amounts of acetal and anhydride give the aldehyde and the ester. Oximes, hydrazones, and Schiff bases can be obtained directly on acid hydrolysis of acetals in the presence of, e.g.9 hydroxylamine, hydrazine, or amines, respectively. 

Indole is acetylated at position 3 by acetic anhydride without a catalyst when vinyl acetate is used as reaction medium.557 Heating benzanilide and benzoic anhydride with polyphosphoric acid for 3 hours at 150° leads, after hydrolysis, to an 84% yield of p-aminobenzophenone.558 Trifluoroacetylation of azulenes has been reported by Anderson and Anderson.559... 

The conversion of pyridine 1-oxide into 2-acetoxypyridine (or into 2-hydroxypyridine by hydrolysis of this ester) by reaction with hot acetic anhydride is a valuable reaction " Benzoic anhydride produces a similar result, but acetic anhydride has naturally been used more often, and the reaction has been applied to several pyridine l-oxides 8, 863 When a halogen, hydroxyl, methoxycarbonyl or nitro group is present at C(3), hydroxylation occurs mainly at C(2) rather than C(6), whilst a methyl group directs substitution about equally to each position. With nicotinic acid... 

Pseudo-first-order rate constants (k bs) for alkaline hydrolysis of 2,4-dinitro-phenyl acetate (3) and octanoate (4) and benzoic anhydride (5) at 0.1 M total mixed surfactant solution of sodium dodecanoate (SDOD = C,H23C02Na) and sulfobetaines (SB3 - n = C H2, .iN+Me2(CH2)3S03-, n = 10, 12, 14, and 16) go through maxima at a mole fraction of SDOD (Xs od) of about 0.5 for 3 and 4 and 0.8 for 5P Quantitative treatment of kinetic data is carried out in terms of PP model with the following assumptions ... 

Esters have been prepared in 63-73% yields from several simple cycloalkyl and aryl alkyl ketones by reaction at room temperature with per-benzoic acid. The larger radical of the ketone appears as the alcohol fragment of the ester. Cyclic ketones are oxidized by potassium persulfate and sulfuric acid to esters from which o>-hydroxy aliphatic esters are obtained upon hydrolysis and reesterification. Peracetic acid in acetic anhydride converts salicylaldehyde to o-hydroxyphenyl formate (88%). ... 

The reaction of oarboxylate with various substrates is an example of a system which necessitates a careful search for products. Early examples of these reactions demonstrated that direct nucleophilic attack takes place. For example, using a dilatometric method, formate was found to catalyze strongly the hydrolysis of acetic anhydride whereas propionate and butyrate slow down the reaction (Kilpatrick, 1928). These results are attributable to mixed anhydride formation with the total rate being determined by the reactivity of the mixed anhydride. The reaction of acetate with 2,4-dinitrophenyl benzoate results in the formation of an unstable mixed anhydride, as was shown in an experiment in which 0 labeled acetate was used the benzoic acid product contains 75% of the O label (Bender and Neveu, 1958). The other 25 % of the O label is presumed to be lost to acetate by solvent attack at the benzoyl carbon if direct nucleophilic interaction is the sole path. 

Hydroxy-l,2-benziodoxole-3(l//)-one (104) is commercially available or can be easily prepared by direct oxidation of 2-iodobenzoic acid or by basic hydrolysis of 2-(dichloroiodo)benzoic acid [232,233,274]. A more recent preparative procedure for 104 involves the oxidation of 2-iodobenzoic acid with acetyl nitrate in acetic anhydride at room temperature followed by aqueous work-up [275]. In the 1980s benziodoxole 104 and other hydroxybenziodoxoles attracted considerable research interest due to their excellent catalytic activity in the cleavage of toxic phosphates and reactive esters. This activity is explained by a pronounced O-nucleophilicity of the benziodoxole anion 105 due to the a-effect [234,272,276]. Spectroscopic and kinetic mechanistic studies indicate that the highly unstable iodoxole derivatives, such as the phosphate 107, are reactive intermediates in catalytic cleavage of phosphates, as shown for the catalytic hydrolysis of a typical substrate 106 (Scheme 2.39) [277-279]. This mechanism was proved by the synthesis and reactivity studies of the phosphate intermediate 107. 

Experimental evidence for such nucleophilic catalysis is sununarized in Figure 7.27. Hydrolysis of 2,4-dinitrophenyl benzoate catalyzed by acetate ion labeled with on both oxygen atoms led to product in which both benzoic acid and acetic acid were labeled with 0, but about 75% of the label derived from one 0 in the reactant was found in the benzoate ion. The data were interpreted as evidence for the intermediacy of the mixed anhydride CH3CO2COC6H5. 

Products of degradation acetophenone, phenyl acetic acid, phenols, benzoic add, phthalic anhydride and phthalic acid end-groups chain session, photooxidative degradation of the isopropylidene bridge of BPA units, photooxidation of phthalimide units to phthalic anhydride end groups, hydrolysis of phthalic anhydride end groups ... 

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