Formic Acid → HCID 86681245, compound

HRID 1848271Notes

Reaction equation

HRID 1848271 reaction equation
C(OC(=O)C)(=O)C.[CH:8]([OH:10])=O.[N+:11]([C:14]1[CH:20]=[C:19]([O:21][CH:22]2[CH2:25][O:24][CH2:23]2)[CH:18]=[CH:17][C:15]=1[NH2:16])([O-:13])=[O:12]>>[N+:11]([C:14]1[CH:20]=[C:19]([O:21][CH:22]2[CH2:23][O:24][CH2:25]2)[CH:18]=[CH:17][C:15]=1[NH:16][CH:8]=[O:10])([O-:13])=[O:12]

Participants

4

Reactant 3

HCID 284Formic AcidHCID 7918Acetic AnhydrideHCID 86681244HCID 86681244, compound

Product 1

HCID 86681245HCID 86681245, compoundYield 51%

Conditions

Temperature
60 °C

Procedure

A stirred mixture of acetic anhydride (15 mL, 161 mmol) and formic acid (6 mL, 161 mmol) was heated at 60° C. for 5 h. The mixture was cooled to rt, then 2-nitro-4-(oxetan-3-yloxy)aniline (1.69 g, 8.02 mmol) was added and the mixture was heated at 70° C. for 15 h. The mixture was cooled to rt and concentrated under reduced pressure. The residue was partitioned between EtOAc and saturated aq NaHCO3. The organic layer was separated, dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography eluting with a gradient of 20% EtOAc in hexanes to 100% EtOAc to afford N-(2-nitro-4-(oxetan-3-yloxy)phenyl)formamide (967 mg, 51%) as a yellow solid. 1H NMR (500 MHz, DMSO-d6) δ 10.36 (br s, 1H), 8.29 (m, 1H), 7.85 (d, J=8.9 Hz, 1H), 7.36 (d, J=1.8 Hz, 1H), 7.24 (dd, J=9.0, 3.0 Hz, 1H), 5.38 (pentet, J=4.9 Hz, 1H), 4.92-4.94 (m, 2H), 4.53-4.56 (m, 2H).

Workup

  1. temperatureThe mixture was cooled to rt
  2. temperaturethe mixture was heated at 70° C. for 15 h
  3. temperatureThe mixture was cooled to rt
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was partitioned between EtOAc and saturated aq NaHCO3
  6. customThe organic layer was separated
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by silica gel flash chromatography
  11. washeluting with a gradient of 20% EtOAc in hexanes to 100% EtOAc

Sources & evidence

ORD record
ord-0465381bd7fa430c899b946f78ade968
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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