Sulfuric Acid → HCID 71346087, compound

Participants

Reaction Steps

2,6-Diaminopyridine hemisulfate (DAPH) was prepared as follows. To a 5-L round-bottomed flask equipped with a means of temperature control and a liquid addition funnel was added water (deionized, 2 L) and 2,6-diaminopyridine (DAP 500 g) and the mixture stirred to form a solution. Sulfuric acid (96%, 334 g) the stoichiometric amount) was added at a rate to raise and then to maintain a temperature of 45° to 55° C. An exotherm resulted when the sulfuric acid was added. The solution became brown during the reaction, probably due to the generation of small quantities of water-soluble oxidation products of DAP. Off-white crystals of 2,6-diaminopyridene hemisulfate (DAPH or DAP.½H2SO4) precipitated out as the sulfuric acid was added. The end-point pH was adjusted to between about pH 3 to about pH 5, preferably to a pH about 4. Any necessary final adjustment was by small supplemental additions of sulfuric acid to lower the pH or by small supplemental additions of DAP to raise the pH. The reaction mixture was then cooled to room temperature and filtered. The wet crystalline filter cake was washed once with water (800 mL) and once with industrial denatured 2 T ethanol (ethanol denatured with 7.5% toluene and containing 7.5% water) or water (800 mL). The crystals were then dried in a vacuum oven at 75° C. and 30.5 kPa. At 25° C., the solubility of DAP Hemisulfate in water was about 1.5% and in ethanol less than 0.15%. Thus, in a series of preparations, the water filtrate and washes, which contained small amounts of dissolved DAPH, optionally may be reused in subsequent preparations to maximize yield. With this recycle, the yield of DAPH was 98-99%.

Provenance & Evidence