Ammonia → M-Phenylenediamine

Participants

Reaction Conditions

Reaction Steps

A mixture of 105.7 g (2.71 moles) of sodamide and 337 cc of xylene containing 1.0 cc of oleic acid was placed in a liter Magne Drive, equipped as described in Example 15. The autoclave was closed, purged of air with nitrogen and pressurized to 100 psig with nitrogen (pressure relief valve was set at 100 psig). The sodamide slurry was heated with stirring to 190° C. and 191.7 g (2.06 moles) of 2-picoline was started adding from a Fisher-porter pressure bottle. The addition was completed over a period of 84 minutes within a temperature range of 188°-198° C. During the addition, ammonia and hydrogen were evolved and passed through the pressure relief valve. The reaction mixture was heated about 10 minutes longer, cooled to 40° C. and hydrolyzed with 200 cc of water. After adding 50 cc of ispropanol, the aqueous phase was separated. It was extracted twice, each time with 60 cc of a solution of 2 volumes of xylene to 1 volume of isopropanol. The original oil layer and extracts were combined and distilled to recover 37.7 g of 2-picoline. 48.7 g of 2-amino-6-methylpyridine and 72.8 g of material boiling from 212° C. at 102 mm to 220° C. at 104 mm. The material was a solid at room temperature and analyzed 90% pure by GLC. An analytical sample (m.p. 63.4°-64.6° C.) was prepared by recrystallization from isopropanol. The NMR spectra was identical with m-phenylenediamine. Anal. Calc'd. for C6H8N2 : C, 66.67; H, 7.41; N, 25.92. Found: C, 66.90; H, 7.21; N, 26.08. The N,N'-diacetyl-m-phenylenediamine derivative was prepared, m.p. 190°-191° C. Literature m.p. is 191° C. Beilstein 13, (1), 13. The yield of m-phenylenediamine, based on 2-picoline recovered, was 36.6%. The amination of 2-picoline at atmospheric pressure under standard Chichibabin conditions gives little if an m-phenylenediamine. The m-phenlenediamine is a rubber curing agent and is also valuable as a corrosion inhibitor.

Provenance & Evidence