Nitric Acid → 3-Acetoxy-4-(Acetylamino)-5-Nitrobenzoic Acid

HRID 1602800

Reaction equation

HRID 1602800 reaction equation
[C:1]([NH:4][C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[CH:7][C:6]=1[O:14][C:15](=[O:17])[CH3:16])(=[O:3])[CH3:2].CC(OC(C)=O)=O.[N+:25]([O-])([OH:27])=[O:26]>O1CCOCC1>[C:15]([O:14][C:6]1[CH:7]=[C:8]([CH:12]=[C:13]([N+:25]([O-:27])=[O:26])[C:5]=1[NH:4][C:1](=[O:3])[CH3:2])[C:9]([OH:11])=[O:10])(=[O:17])[CH3:16]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 7918Acetic Anhydride2×HCID 4938454-(Acetylamino)-3-acetoxybenzoic acid

Product 1

HCID 4938463-Acetoxy-4-(Acetylamino)-5-Nitrobenzoic AcidYield 89.9%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
0 °C

Procedure

Compound 102 (1.00 g, 4.21 mmol) was suspended with stirring in a mixture of Ac2O (8.33 mL, 8.99 g, 88.2 mmol) and dioxane (6.6 mL). This was cooled to 0° C., and a cold solution of the nitrating mixture made from Ac2O (3.33 mL, 3.59 g, 35.2 mmol) and concentrated HNO3 (3.33 mL) was slowly added to the mixture containing 102. The reaction mixture was then warmed to 30-35° C. until the reaction was complete as evidenced by TLC. The reaction mixture was poured onto ice/water (100 mL), extracted with EtOAc (4×50 mL), dried (NaSO4), and concentrated to dryness on a rotary evaporator to give crude 104 (1.05 g, 89.9%) as an oil. Trituration with CHCl3 gave a solid: mp 196-201° C. (dioxane/hexane).

Workup

  1. additionwas slowly added to the mixture
  2. additioncontaining 102
  3. temperatureThe reaction mixture was then warmed to 30-35° C. until the reaction
  4. additionThe reaction mixture was poured onto ice/water (100 mL)
  5. extractionextracted with EtOAc (4×50 mL)
  6. dry with materialdried (NaSO4)
  7. concentrationconcentrated to dryness on a rotary evaporator

Sources & evidence

ORD record
ord-ab628f2bfd6241b282ef57eece1e4f30
Source dataset
uspto-grants-1999_11
Patent number
US05985859

Linked notes

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