Nitric Acid → 3-(Benzyloxy)-6-methoxy-2-nitrobenzamide

HRID 922401Notes

Reaction equation

HRID 922401 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]([O:18][CH3:19])=[C:13]([CH:17]=1)[C:14]([NH2:16])=[O:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(OC(C)=O)=O.[N+:27]([O-])([OH:29])=[O:28]>>[CH2:1]([O:8][C:9]1[C:17]([N+:27]([O-:29])=[O:28])=[C:13]([C:12]([O:18][CH3:19])=[CH:11][CH:10]=1)[C:14]([NH2:16])=[O:15])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 3

HCID 944Nitric Acid2×HCID 7918Acetic AnhydrideHCID 215044235-(Benzyloxy)-2-methoxybenzamide

Product 1

HCID 867193593-(Benzyloxy)-6-methoxy-2-nitrobenzamide

Procedure

To a stirred mixture of 5-(benzyloxy)-2-methoxybenzamide (9, 0.365 g. 1.4 mmol) and Ac2O (1.2 mL) at 0° C. was added 70% HNO3 (0.14 mL, 2.1 mmol). The reaction mixture was warmed to room temperature and stirred for 1 h. Then 4.5 mL of 70% HNO3 precooled at −30° C. was added. The mixture was stirred at 0° C. for 1 h and was poured onto ice. The precipitate was collected, washed with water and dried in vacuo. Purification by silica gel chromatography eluting with 0-2.5% MeOH in CH2Cl2 afforded the title compound along with its regioisomer (0.34 g, 79%) as a yellow solid: 1H NMR (500 MHz, CDCl3) δ 7.73 (br s, 1H), 7.41-7.30 (m, 5H), 7.11 (d, J=9.2 Hz, 1H), 7.00 (d, J=9.2 Hz, 1H), 6.84 (br s, 1H), 5.15 (s, 2H), 3.91 (s, 3H); ESI MS m/z 303 [M+H]+.

Workup

  1. customprecooled at −30° C.
  2. additionwas added
  3. stirringThe mixture was stirred at 0° C. for 1 h
  4. additionwas poured onto ice
  5. customThe precipitate was collected
  6. washwashed with water
  7. customdried in vacuo
  8. customPurification by silica gel chromatography
  9. washeluting with 0-2.5% MeOH in CH2Cl2

Sources & evidence

ORD record
ord-dbcf8d4643c84c2190eedd4f972ef314
Source dataset
uspto-grants-2016_03
Patent number
US09278940B2

Reaction notes

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