Trifluoroacetic acid → HCID 71150728, compound

HRID 407245Notes

Reaction equation

C(OC([N:8](C(OC(C)(C)C)=O)[C:9]1[CH:14]=C(C=O)[N:12]=[C:11]([C:17]([O:19][CH3:20])=[O:18])[C:10]=1[O:21][CH3:22])=O)(C)(C)C.COCCN(S(F)(F)F)CCOC.[C:43](O)([C:45]([F:48])(F)[F:46])=O.C([O-])(O)=O.[Na+]>C(Cl)Cl>[NH2:8][C:9]1[CH:14]=[C:43]([CH:45]([F:48])[F:46])[N:12]=[C:11]([C:17]([O:19][CH3:20])=[O:18])[C:10]=1[O:21][CH3:22]

Participants

Conditions

Temperature: 0 °C

Procedure

To a 0° C. solution of methyl 4-[bis(tert-butoxycarbonyl)amino]-6-formyl-3-methoxypyridine-2-carboxylate (0.279 g, 0.680 mmol) in CH2Cl2 (2.72 ml) was added DEOXO-FLUOR® (0.251 ml, 1.360 mmol). The mixture was stirred at 0° C. for 1 h (reaction completed based on TLC and LC). TFA (1 mL) was then added and the reaction mixture was allowed to slowly warm to room temperature and was stirred overnight. The mixture was poured into saturated NaHCO3 and extracted with EtOAc (2×). The combined organic layers were dried over MgSO4, filtered and concentrated. The residue was purified by flash column chromatography (ISCO, SiO2 12 g, hexanes/EtOAc 100:0 to 0:100 gradient) to afford methyl 4-amino-6-(difluoromethyl)-3-methoxypicolinate (89 mg, 0.383 mmol, 56.4% yield) as a white solid. ESIMS m/z 233 ([M+H]+); 1H NMR (400 MHz, CDCl3) δ 7.06 (s, 1H), 6.54 (t, J=55.4 Hz, 1H), 4.69 (s, 2H), 3.98 (s, 3H), 3.90 (s, 3H); 19F NMR (376 MHz, CDCl3) δ −114.65.

Workup

custom(reaction completed based on TLC and LC)
temperatureto slowly warm to room temperature
stirringwas stirred overnight
extractionextracted with EtOAc (2×)
dry with materialThe combined organic layers were dried over MgSO4
filtrationfiltered
concentrationconcentrated
customThe residue was purified by flash column chromatography (ISCO, SiO2 12 g, hexanes/EtOAc 100:0 to 0:100 gradient)

Sources & evidence

ORD record: ord-e9f593bd22a44499a75049b7f51555b5
Source dataset: uspto-grants-2014_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08754229B2

Reaction notes

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