A. Compound Ia (0.7183 g., 0.002 mole) was dissolved in 30 ml. of 0.2 N. sodium hydroxide, and the solution was kept under nitrogen. At time intervals aliquots of the solution were acidified
with acetic acid and titrated with iodine. Five minutes after dissolution 66% of the S-benzoyl group was removed; after 15 minutes almost l00%. The rest of the solution was acidified with sulfuric acid, and after oxidation with iodine the solution was extracted with ethyl acetate. The ethyl acetate layer was washed with water until the water extract became neutral to congo red paper, dried over sodium sulfate and concentrated to a small volume in vacuo. Upon the addition of cyclohexylamine to the solution, N,N"-biscarbobenzoxy-L-cystine cyclohexylamine salt separated. The yield of product recrystallized from ethanol was 35%, calculated on the basis of the amount of Ia used; m.p. 183 oC (reported183 oC).
B. Compound Ia (0.001 mole) was dissolved in 20 ml. of aqueous 2 N ammonia. The solution was kept under nitrogen and was worked up as in case A. Fifteen minutes after dissolution, 51% of the S-benzoyl group was split off; after 30 minutes, 95% was removed.
Saponification of the S-acetyl group of Id by procedure A as described for Ia was almost complete after 2 minutes; for a complete ammonolysis of the S-acetyl group (procedure B) approx. 12 minutes was required.