Hi,

There is a book:

"The hydrolysis of acid amides"

By Reid, E.

From American Chemical Journal (1900), 24, 397.

A mass of data is tabulated showing the rates at which different amides are hydrolyzed in presence of hydrochloric acid or of barium hydroxide.

I haven't seen it, but it might have the data you want, even though it is >100 years old. I saw that it is available on EBay.

Bill

Hi

Here is another (labor intensive) way to get an answer: the separate references to the hydrolysis of Benzanilide and N-methylbenzamide. Somewhere in there you might find a reasonable answer. Unfortunately I didn't find a reference which showed data for both hydrolyses in the same paper.

Also, it is quite possible taht the two a ides hydrolyse by different mechanisms.

Bill

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Amide hydrolysis rates

Benzanilide

Kinetics of the hydrolysis of N-substituted amides. III. Benzanilide and p-substituted derivatives Full Text

By Cauzzo, Glulio; Mazzucato, Ugo; Foffani, Antonio

From Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti (1960), 29, 348-54. | Language: Unavailable, Database: CAPLUS

cf. CA 54, 23643g. Velocity of hydrolysis in acid and alk. medium was measured spectrophotometrically at 310-340 mμ by observing the amide absorbance. All tested compds. were synthesized by mixing in benzene an acid chloride with aniline in 1:1.5 molar ratio in the presence of NaHCO3, washing the ppt. with HCl and EtOH-Et2O, and crystg. from EtOH. The following p-RC6H4CONHC5H4R'-p were tested at 90° in 80% EtOH soln. (R, R', m.p., kH × 103, and kOH- × 103 in l. mole-1 min.-1 given): NO2, H, 210-11°, 1.31, 31.05; Cl, H, 194°, 1.36, 27.60; H, H, 160°, 1.21, 3.15; Me, H, 144-5°, 0.93, 1.78; OM...

Kinetics of the hydrolysis of carboxylic acid anilides. I. Effect of substituents on the rate of hydrolysis of benzanilideFull Text

By Mandyuk, V. F.; Lushina, N. P.

From Ukrainskii Khimicheskii Zhurnal (Russian Edition) (1966), 32(6), 607-9. | Language: Russian, Database: CAPLUS

The following data on the first-order hydrolysis of XC6H4NHBz in aq.-alc. H2SO4 are reported. The results fit the Hammett relation rather well and also vary with the acidity of the corresponding anilinium ion as shown by the following data (X, pKa of anilinium ion, k/k0, and k/k0 for hydrolysis of p-XC6H4NHO2SPh given): p-NO2, 1.02, 1.70, 1.46; p-Cl, 3.98, 1.20, 1.40; H, 4.58, 1.00, 1.00; p-Me, 5.12, 0.93, 0.75; p-MeO, 1.02, 0.74, 0.70. X, k × 104 at 80°sec-1, E kcal./mole, log PZ, ΔS‡ cal./degree mole; p-OMe, 0.0288, 23.8, 9.79, -14.1; m-OMe, 0.0430, 24.6, 10.8, - 11.1; p-Me, 0.0362, 24.6, ...

4. Hydrolysis of benzanilide and of the 4'-chloroanilide of benzoic acid Full Text

By Paluch, Karolina

From Roczniki Chemii (1965), 39(5), 755-6. | Language: Polish, Database: CAPLUS

Benzanilide (I) or 4'-chlorobenzanilide (II) (0.02 mole) in a soln. contg. 160 ml. H2O, 80 ml. EtOH, and 96 g. KOH refluxed for 5 hrs., ∼25 ml. EtOH distd., 30 ml. H2O added, ∼30 ml. amine distd., the mixt. treated with 30 ml. H2O and filtered, and the filtrate acidified with concd. HCl gave very pure benzoic acid, yield 91% from I, 89.7% from II.

5. Hydrolysis of N-aromatic substituted amides Full Text

By Owen, W. S.

From Mikrochimica et Ichnoanalytica Acta (1963), 19-22. | Language: English, Database: CAPLUS

cf. CA 57, 2024f. Amides of the general formula RCONHAr, where R is Me, Ph, a substituted phenyl group, PhNH, or a naphthyl group and Ar is H or an aryl group, and imides of aliphatic and aromatic dibasic acids are heated 8-20 min. with KOH pellets or NaOH pellets, the amine is distd., and the residue is acidified. Thus, 1.0-1.2 g. amide and 1.0-1.2 g. solid KOH or MeOH are placed in a hydrolysis tube, the mixt. is heated until all the amine distils, and the residue is acidified. Products obtained in this manner are (amine, amine b.p., acid, acid m.p. given): PhNH2, 183-4°, HOAc, -; o-MeC6H...

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N-Methylbenzamide

Acid hydrolysis of amides Full Text

By Bunton, Clifford A.; O'Connor, Charmian; Turney, T. A.

From Chemistry & Industry (London, United Kingdom) (1967), (43), 1835-6. | Language: English, Database: CAPLUS

The rate consts. for hydrolysis of benzamide, N-methylbenzamide, and N,N-dimethylbenzamide in HCl at 100° were measured and compared with calcd. values. Two mechanistic paths for the hydrolysis were given. The O exchange during hydrolysis at 100.4° between H2O and amides was examd.

. Alkaline hydrolysis of benzamide and N-methyl- and N,N-dimethylbenzamide Full Text

By Bunton, Clifford A.; Nayak, B.; O'Connor, Charmian

From Journal of Organic Chemistry (1968), 33(2), 572-5. | Language: English, Database: CAPLUS

The alk. hydrolyses of benzamide (I) and N-methylbenzamide, but not of N,N-dimethylbenzamide (II), are accompanied by extensive O exchange between water and the amide. The ratio of rate of exchange to hydrolysis for I decreases with increasing OH ion concn. and is greater in D2O than in H2O. For hydrolysis of I kH2O/kD2O is 1.4 and for II it is 0.88. These differences arise because of the solvent isotope effect upon partitioning of the tetrahedral intermediate derived from I. 25 references.

Structure, medium, and temperature dependence of acid-catalyzed amide hydrolysisFull Text

By Smith, Clinton R.; Yates, Keith

From Journal of the American Chemical Society (1971), 93(24), 6578-83. | Language: English, Database: CAPLUS

Kinetics of hydrolysis of benzamide, N-methylbenzamide, and N,N-dimethylbenzamide were studied in 5-60% aq. H2SO4 at 25-85°. The order of reactivity with N-Me substitution is primary > tertiary > secondary, and is due solely to variations in ΔH⧺ with structure. Water activity data for the above concn. and temp. range were calcd. from available emf. data and aH2O is a strongly temp.-dependent reaction variable. The kinetic acidity dependence and medium dependence of the activation parameters were analyzed using protonation and aH2O data appropriate to each kinetic temp. Calcd. ΔH⧺ values fo...

Solvent effects on the acid-catalyzed hydrolysis of benzamide, N-methylbenzamide, and N,N-dimethylbenzamide Full Text

By Bunton, C. A.; Farber, S. J.; Milbank, A. J. G.; O'Connor, Charmian J.; Turney, T. A.

From Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999) (1972), (12), 1869-75. | Language: English, Database: CAPLUS

The kinetics were detd. of hydrolysis of BzNH2 in HCl, H2SO4, HClO4, and H3PO4, of BzNHMe in HCl and H2SO4, and of BzNMe2 in HCl, H2SO4, and HClO4. The basicity consts. of these 3 amides were detd. in HCl and HClO4 and that of BzNH2 in H2SO4 also; these consts. were nonthermodynamic functions. The rate results fitted a 2-term equation. D isotope effects and Arrhenius parameters were measured. 18O exchange was not obsd. Measurements of the molar activity coeff. of unprotonated BzNMe2 showed that acids salt-in the amide but salts usually salt it out.

. Mechanism of the acid hydrolysis of benzamide, N-methylbenzamide, and N,N-dimethylbenzamide Full Text

By Vinnik, M. I.

From Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1978), (4), 799-807. | Language: Russian, Database: CAPLUS

Spectral data indicated that the title hydrolyses took place via formation of a complex (I) between H3O+ and the amide carbonyl. Hydrolysis in solns. not contg. salt additives could proceed by 2 routes; (a) via solvation of I by at least 1 H2O at the N atom; (b) via monomol. decompn. of I. Rate consts. of the various steps were detd.

Benzamide hydrolysis in strong acids - The last word Full Text

By Cox, Robin A.

From Canadian Journal of Chemistry (2008), 86(4), 290-297. | Language: English, Database: CAPLUS

Recently it has become apparent that the mechanism of amide hydrolysis in relatively dil. strong acid media is the same as the one obsd. for ester and benzimidate hydrolysis, two water mols. reacting with the O-protonated amide in the rate-detg. step. This is not the whole story, however, at least for benzamide, N-methylbenzamide, and N,N-dimethylbenzamide, since the obsd. rate consts. for these substrates deviate upwards from the obsd. excess acidity correlation lines at acidities higher than about 60% H2SO4, meaning that another, faster, reaction with a different mechanism is taking over at...

4. The mechanism of alkaline hydrolysis of amides: a comparative computational and experimental study of the hydrolysis of N-methylacetamide, N-methylbenzamide, and acetanilide Full Text

By Cheshmedzhieva, Diana; Ilieva, Sonia; Hadjieva, Boriana; Galabov, Boris

From Journal of Physical Organic Chemistry (2009), 22(6), 619-631. | Language: English, Database: CAPLUS

Theor. computations and exptl. kinetic measurements were applied in studying the mechanistic pathways for the alk. hydrolysis of three secondary amides: N-methylbenzamide, N-methylacetamide, and acetanilide. Electronic structure methods at the HF/6-31+G(d,p) and B3LYP/6-31+G(d,p) levels of theory are employed. The energies of the stationary points along the reaction coordinate were further refined via single point computations at the MP2/6-31+G(d,p) and MP2/6-311++G(2d,2p) levels of theory. The role of water in the reaction mechanisms is examd. The theor. results show that in the cases of ...

An interesting question! I do not know the answer but suspect that the the N-methyl benzamide will hydrolise more easily: Under acidic conditions, the electron withdrawing effect of the phenyl group in N-phenyl benzamide should mean that the degree of protonation on the amide carbonyl will be less than in N-methyl benzamide, which should result in a slower hydrolysis of the N-phenyl derivative. Under basic conditions, the electron withdrawing effect of the phenyl group in N-phenyl benzamide will increase the acidity of the NH proton leading to increased anion formation and a reduced rate of hydrolysis. I would be interested to hear other opinions.

Stephen Lindell has the right idea. I was looking into this, as I was worried about a side reaction. Stumbled across this paper handling it. EWG stabilizes anilides, EDG destabilizes to acidic hydrolysis. https://link.springer.com/content/pdf/10.1007%2FBF00768082.pdf