Sulfamic Acid → 6-(Benzyloxy)-5-nitropicolinic Acid

HRID 509398Notes

Reaction equation

[CH2:1]([O:8][C:9]1[N:14]=[C:13]([CH:15]=[O:16])[CH:12]=[CH:11][C:10]=1[N+:17]([O-:19])=[O:18])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.S(=O)(=O)([OH:22])N.[O-]Cl=O.[Na+].CCOC(C)=O>CC(C)=O.O.CCCCCC>[CH2:1]([O:8][C:9]1[N:14]=[C:13]([C:15]([OH:22])=[O:16])[CH:12]=[CH:11][C:10]=1[N+:17]([O-:19])=[O:18])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

Conditions

Temperature: 0 °C

Procedure

To a cooled (0° C.) stirred mixture of 6-(benzyloxy)-5-nitropicolinaldehyde (0.5 g, 0.0019 mol) in acetone:water (1:1, 5 mL), was added sulphamic acid (280 mg, 0.00029 mol, Aldrich) and NaClO2 (260 mg, 0.00029 mol, Aldrich). The reaction mixture was stirred for 2 h at the same temperature. After completion of the reaction (monitored by TLC, 10% EtOAc in hexane), the reaction mixture was quenched with water (2 mL) and extracted with EtOAc (20 mL×3). The organic layers were combined, dried over anhydrous sodium sulfate, and purified by column chromatography, silica gel (60-120 mesh) using 5-9% EtOAc in petroleum ether as an eluent to give the title compound. 1H NMR (400 MHz, CDCl3) δ: 13.80 (br. s., 1H), 8.45 (d, J=8.1 Hz, 1H), 7.96 (d, J=8.1 Hz, 1H), 7.51 (d, J=7.2 Hz, 2H), 7.44-7.36 (m, 3H), 5.62 (s, 2H).

Workup

stirringThe reaction mixture was stirred for 2 h at the same temperature
customthe reaction mixture was quenched with water (2 mL)
extractionextracted with EtOAc (20 mL×3)
dry with materialdried over anhydrous sodium sulfate
custompurified by column chromatography, silica gel (60-120 mesh)

Sources & evidence

ORD record: ord-16f1c755301d4a4e8f8485dd6cd60dd2
Source dataset: uspto-grants-2015_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09096527B2

Reaction notes

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