1-Butanol → 4-Butoxy-2-nitrobenzoic acid

HRID 2426645Notes

Reaction equation

HRID 2426645 reaction equation
F[C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[C:4]([N+:11]([O-:13])=[O:12])[CH:3]=1.S(=O)(=O)(O)O.C(OCC)(=O)C.[CH2:25]([OH:29])[CH2:26][CH2:27][CH3:28]>>[CH2:25]([O:29][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[C:4]([N+:11]([O-:13])=[O:12])[CH:3]=1)[CH2:26][CH2:27][CH3:28]

Participants

5

Reactant 4

HCID 2631-ButanolHCID 1118Sulfuric AcidHCID 8857Ethyl Acetate2×HCID 27374164-Fluoro-2-nitrobenzoic acid

Product 1

HCID 211054734-Butoxy-2-nitrobenzoic acid

Conditions

Temperature
110 °C

Procedure

A solution of 4-fluoro-2-nitrobenzoic acid (1.81 g) in butanol (20 ml) was mixed with sulfuric acid (3 ml) and stirred at 110° C. for 4 hours. Ethyl acetate (100 ml) was added, and the mixture was washed with saturated sodium bicarbonate solution (3×50 ml), dried with sodium sulfate, filtered and concentrated in vacuo. The residue (2.2 g) was added dropwise at −10° C. to a sodium butoxylate solution prepared from butanol (20 ml) and sodium hydride (2.18 g) at −10° C. under argon and then stirred for 20 hours. Ethyl acetate (100 ml) was added, and the mixture was washed with water (2×50 ml), dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by preparative HPLC. The butyl 4-butoxy-2-nitrobenzoate was hydrolyzed with sodium hydoxide (5N; 100 ml) in ethanol at room temperature for 3 hours. The mixture was acidified with hydrochloric acid (10N; 100 ml) and extracted with dichloromethane, and the organic phase was dried over sodium sulfate, filtered and concentrated. This resulted in the product with the molecular weight of 239.23 (C11H13NO5); MS (ESI): 240 (M+H+).

Workup

  1. washthe mixture was washed with saturated sodium bicarbonate solution (3×50 ml)
  2. dry with materialdried with sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. additionThe residue (2.2 g) was added dropwise at −10° C. to a sodium butoxylate solution
  6. customprepared from butanol (20 ml) and sodium hydride (2.18 g) at −10° C. under argon
  7. stirringstirred for 20 hours
  8. washthe mixture was washed with water (2×50 ml)
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe residue was purified by preparative HPLC
  13. waitThe butyl 4-butoxy-2-nitrobenzoate was hydrolyzed with sodium hydoxide (5N; 100 ml) in ethanol at room temperature for 3 hours
  14. extractionextracted with dichloromethane
  15. dry with materialthe organic phase was dried over sodium sulfate
  16. filtrationfiltered
  17. concentrationconcentrated
  18. customThis resulted in the product with the molecular weight of 239.23 (C11H13NO5)

Sources & evidence

ORD record
ord-3c593af404e84c4b81670d60ea4ee510
Source dataset
uspto-grants-2011_06
Patent number
US07968550B2

Reaction notes

Loading…