Nitric Acid → Dimethyl 4-acetamido-5-nitrophthalate

HRID 2400042Notes

Reaction equation

HRID 2400042 reaction equation
[C:1]([NH:4][C:5]1[CH:6]=[C:7]([C:15]([O:17][CH3:18])=[O:16])[C:8](=[CH:13][CH:14]=1)[C:9]([O:11][CH3:12])=[O:10])(=[O:3])[CH3:2].[N+:19]([O-])([OH:21])=[O:20]>C(Cl)Cl>[C:1]([NH:4][C:5]1[CH:6]=[C:7]([C:15]([O:17][CH3:18])=[O:16])[C:8](=[CH:13][C:14]=1[N+:19]([O-:21])=[O:20])[C:9]([O:11][CH3:12])=[O:10])(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 540173Dimethyl 4-acetamidophthalate

Product 1

HCID 14574474Dimethyl 4-acetamido-5-nitrophthalate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Dimethyl 4-acetamidophthalate (100.4 g, 0.400 mol) is added to fuming nitric acid (90%, 600 mL) at 0° C. to 5° C. When the addition is completed (0.5 hour), the mixture is stirred 2.5 hours at 0° C. to 10° C., combined with cold methylene chloride and shaken with crushed ice. The aqueous layer is separated and extracted further with methylene chloride. The combined organic layers are washed with ice water, sodium bicarbonate solution and cold water, dried (MgSO4) and concentrated in vacuo to give a solid residue. The residue is recrystallized twice from methanol to afford the title product I as orange-brown needles, mp 119°-120° C. The original mother liquor is concentrated in vacuo, and the residue is recrystallized several times from carbon tetrachloride to afford the title compound II as light yellow needles, mp 124°-125° C. The yield of compound I is 38.9 g (32.9%), and the yield of compound II is 33.1 g (28.1%).

Workup

  1. additionWhen the addition
  2. custom(0.5 hour)
  3. stirringshaken with crushed ice
  4. customThe aqueous layer is separated
  5. extractionextracted further with methylene chloride
  6. washThe combined organic layers are washed with ice water, sodium bicarbonate solution and cold water
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. customto give a solid residue
  10. customThe residue is recrystallized twice from methanol

Sources & evidence

ORD record
ord-e381cfe600594423bf213b93703c3603
Source dataset
uspto-grants-1995_09
Patent number
US05453415

Reaction notes

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