Nitric Acid → Methyl 4-(3-chloropropoxy)-5-methoxy-2-nitrobenzoate

HRID 631254Notes

Reaction equation

HRID 631254 reaction equation
[CH3:1][O:2][C:3](=[O:17])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH2:12][CH2:13][Cl:14])=[C:6]([O:15][CH3:16])[CH:5]=1.C(OC(=O)C)(=O)C.[N+:25]([O-])([OH:27])=[O:26]>C(O)(=O)C.C(OCC)(=O)C>[CH3:1][O:2][C:3](=[O:17])[C:4]1[CH:5]=[C:6]([O:15][CH3:16])[C:7]([O:10][CH2:11][CH2:12][CH2:13][Cl:14])=[CH:8][C:9]=1[N+:25]([O-:27])=[O:26]

Participants

6

Reactant 3

HCID 944Nitric AcidHCID 7918Acetic AnhydrideHCID 14407173Methyl 4-(3-chloropropoxy)-3-methoxybenzoate

Product 1

HCID 23032992Methyl 4-(3-chloropropoxy)-5-methoxy-2-nitrobenzoateYield 94%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

The intermediate from Step 1 (26.4 g, 102 mmol) was taken in acetic acid (185 mL) and acetic anhydride (15 mL) was added. The solution was cooled to 0° C. and 90% nitric acid (15 mL) was added. The reaction mixture was stirred for 10-15 minutes at ambient temperature, then heated to 50° C. for 3 hours. Completion of the reaction was monitored by LCMS. The reaction mixture was cooled and was diluted with ethyl acetate. The ethyl acetate layer was washed with aq. sodium bicarbonate, and concentrated to afford the pure compound 4-(3-chloro-propoxy)-5-methoxy-2-nitro-benzoic acid methyl ester (29.14 g, 94%) yellow solid. 1H NMR (300 MHz, DMSO-d6) δ 7.68 (s, 1H), 7.33 (s, 1H), 4.24 (t, 2H), 3.92 (s, 3H), 3.82 (s, 3H), 3.77 (t, 2H), 2.21 (q, 2H).

Workup

  1. temperatureheated to 50° C. for 3 hours
  2. temperatureThe reaction mixture was cooled
  3. washThe ethyl acetate layer was washed with aq. sodium bicarbonate
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-793ee83872c54031b4d8bc2c0c852d49
Source dataset
uspto-grants-2016_04
Patent number
US09320739B2

Reaction notes

Loading…