Suggested Improvement in the Ing−Manske Procedure and Gabriel Synthesis of Primary Amines: Kinetic Study on Alkaline Hydrolysis of N-Phthaloylglycine and Acid Hydrolysis of N-(o-Carboxybenzoyl)glycine in Aqueous Organic Solvents

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Abstract
A slight modification of the Gabriel synthesis of primary amines is suggested on the basis of the observed and reported values of rate constants for the alkaline and acid hydrolyses of phthalimide, phthalamic acid, benzamide, and their N-substituted derivatives. The suggested procedure requires shorter reactions time and milder acid−base reaction conditions compared with the conventional acid−base hydrolysis in the Gabriel synthesis. A slight modification in the Ing−Manske procedure is also suggested. Pseudo-first-order rate constants, kobs, for hydrolysis of N-phthaloylglycine, NPG, decrease from 24.1 × 10-3 to 7.72 × 10-3 and 6.12 × 10-3 s-1 with increasing acetonitrile and 1,4-dioxan contents, respectively, from 2 to 50% v/v (all the percentages given in the paper are vol %), while increasing the organic cosolvents content from 50 to 80% increases kobs from 7.72 × 10-3 to 19.7 × 10-3 s-1 for acetonitrile and from 6.12 × 10-3 to 52.8 × 10-3 s-1 for 1,4-dioxan, in aqueous organic solvents containing 0.004 M NaOH at 35 °C. The rate constants for NPG hydrolysis decrease from 2.11 × 10-2 to 1.19 × 10-4 s-1 with increasing MeOH content from 2 to 84%, in aqueous organic solvents containing 2% MeCN and 0.004 M NaOH at 35 °C.

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