Sodium Hydroxide → 3-Bromo-5-chloropyridin-2-amine

HRID 974225Notes

Reaction equation

C([O-])(=O)C.[Na+].[NH2:6][C:7]1[CH:12]=[CH:11][C:10]([Cl:13])=[CH:9][N:8]=1.[Br:14]Br.[OH-].[Na+]>C(O)(=O)C.O>[NH2:6][C:7]1[C:12]([Br:14])=[CH:11][C:10]([Cl:13])=[CH:9][N:8]=1

Participants

Conditions

Temperature: 43 °C

Procedure

An acetic acid (400 mL) suspension of sodium acetate (57.1 g, 0.696 mol) and 2-amino-5-chloropyridine (89.5 g, 0.696 mol) was treated with a solution of bromine (35.9 mL, 0.696 mol) in acetic acid (15 mL) over a period of 1.25 hours with gentle warming to 43° C. The resulting orange slurry was then cooled to 15° C. and filtered to provide a solid which was subsequently dissolved in water, basified (pH 8.5) with 1N NaOH, and extracted with ethyl acetate (5×150 mL). The combined organic layers were washed with 10% sodium bisulfite (2×150 mL), dried over magnesium sulfate, and condensed to give 102.1 g (70.7%) of a yellow solid, m.p. 83-85° C.: IR(CHCl3) 3683, 3504, 3401, 2987, 2482, 2392, 1608, 1571, 1544, 1455, 1389, 1316, 1207, 1127, 1057, 1026, 895, 881, 650, 607, 249, 236 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 5.20 (br s, 2H), 7.70 (d, 1H), J=2.2 Hz), 8.0 (d, 1H, J=2.2 Hz); 13C NMR (CDCl3) δ 104.08, 120.33, 139.62, 145.24, 154.10; exact mass calculated for C5H4N2BrCl=205.9246. High resolution mass spec. 205.9246.

Workup

temperatureThe resulting orange slurry was then cooled to 15° C.
filtrationfiltered
customto provide a solid which
extractionextracted with ethyl acetate (5×150 mL)
washThe combined organic layers were washed with 10% sodium bisulfite (2×150 mL)
dry with materialdried over magnesium sulfate, and condensed

Sources & evidence

ORD record: ord-cad83a7b3f3640a094cc7412b347593c
Source dataset: uspto-grants-1991_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05068333

Reaction notes

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