Acetamidine monohydrochloride → 5-Bromo-2-methylpyrimidine-4-carboxylic acid

HRID 1399926Notes

Reaction equation

[Na].[O-]CC.[Na+].Cl.[C:7]([NH2:10])(=[NH:9])[CH3:8].[C:11]([OH:19])(=[O:18])/[C:12](=[C:14](\[CH:16]=O)/[Br:15])/Br>C(O)C>[Br:15][C:14]1[C:12]([C:11]([OH:19])=[O:18])=[N:9][C:7]([CH3:8])=[N:10][CH:16]=1

Participants

Conditions

Temperature: 50 °C

Procedure

Sodium (356 mg, 15.5 mmol) was carefully added to ethanol (5.9 mL) to prepare sodium ethoxide solution in ethanol. The above freshly prepared sodium ethoxide in ethanol solution (3.5 mL) was added to a stirred suspension of acetamidine hydrochloride (0.91 g, 9.69 mmol). The mixture was warmed to 50° C., then the heating bath was removed and a solution of mucobromic acid (1 g, 3.87 mmol) in ethanol was added dropwise at a rate which maintained a constant temperature, followed by a further sodium ethoxide in ethanol solution (2 mL). After cooling, the mixture was filtered and evaporated to a residue which was shaken vigorously with hydrochloric acid (2 M×2.4 mL). The brown precipitate was filtered and washed with cold water, then freeze-dried to give 5-bromo-2-methylpyrimidine-4-carboxylic acid (350 mg, 42%) as a brown solid. LCMS: 218 [M+1]+, 1H NMR (400 MHz, DMSO-d6): δ 2.62 (s, 3H), 9.03 (s, 1H).

Workup

customthe heating bath was removed
temperaturemaintained a constant temperature
temperatureAfter cooling
filtrationthe mixture was filtered
customevaporated to a residue which
filtrationThe brown precipitate was filtered
washwashed with cold water
customfreeze-dried

Sources & evidence

ORD record: ord-34e25231488d4579a87b449a57d910a5
Source dataset: uspto-grants-2014_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08906909B2

Reaction notes

Loading…