Ethyl Acetate → HCID 59548029, compound

HRID 1915036Notes

Reaction equation

[Br:1][C:2]1[N:3]=[CH:4][C:5]([NH:8][C:9]2[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][C:10]=2[N+:19]([O-])=O)=[N:6][CH:7]=1.[NH4+].[Cl-].CCOC(C)=O>C1COCC1.O.[Fe]>[NH2:19][C:10]1[CH:11]=[C:12]([CH:17]=[CH:18][C:9]=1[NH:8][C:5]1[CH:4]=[N:3][C:2]([Br:1])=[CH:7][N:6]=1)[C:13]([O:15][CH3:16])=[O:14]

Participants

Conditions

Temperature: 65 °C

Procedure

Into a 250 mL 3-necked roundbottom flask, was placed a solution of methyl 4-(5-bromopyrazin-2-ylamino)-3-nitrobenzoate (x) (5.0 g, 14.2 mmol) in THF (75 mL). This was followed by the addition of a solution of NH4Cl (3.8 g, 71 mmol) in H2O (25 mL). To the above was added Fe (4.0 g, 71 mmol) in several batches, while warming to a temperature of 65° C. The resulting solution was allowed to react for 3 hours at 65° C. The reaction progress was monitored by TLC (EtOAc/PE=1:2). Undissolved material was removed by filtration. The filtrate was extracted three times with 200 mL of EtOAc and the organic layers were combined and dried (Na2SO4). After removal of the solvent, the residue was separated by silica gel chromatography eluting with a mixture of PE/EtOAc (starting at 10:1 and proceeding through 5:1, 3:1, and 2:1, v/v) to afford the product methyl 3-amino-4-(5-bromopyrazin-2-ylamino)benzoate (xi) (3.4 g, yield 74%) as a yellow solid.

Workup

customInto a 250 mL 3-necked roundbottom flask, was placed
customto react for 3 hours at 65° C
customUndissolved material was removed by filtration
extractionThe filtrate was extracted three times with 200 mL of EtOAc
dry with materialdried (Na2SO4)
customAfter removal of the solvent
customthe residue was separated by silica gel chromatography
washeluting with a mixture of PE/EtOAc (

Sources & evidence

ORD record: ord-1f0a6f7cd84341e9a823a150ef83e86e
Source dataset: uspto-grants-2013_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08614321B2

Reaction notes

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