Nitric Acid → HCID 19100774, compound

HRID 1974960Notes

Reaction equation

HRID 1974960 reaction equation
[C:1]([NH:8][C:9]1[S:10][C:11]([C:17]([O-:19])=[O:18])=[C:12]([CH2:14][CH2:15][CH3:16])[CH:13]=1)([C:3]([O:5][CH2:6][CH3:7])=[O:4])=[O:2].[N+:20]([O-:23])(O)=[O:21].[C:24](OC(=O)C)(=O)[CH3:25]>C(Cl)Cl.C(O)(=O)C>[C:1]([NH:8][C:9]1[S:10][C:11]([C:17]([O:19][CH2:24][CH3:25])=[O:18])=[C:12]([CH2:14][CH2:15][CH3:16])[C:13]=1[N+:20]([O-:23])=[O:21])([C:3]([O:5][CH2:6][CH3:7])=[O:4])=[O:2]

Participants

6

Reactant 3

HCID 944Nitric AcidHCID 7918Acetic AnhydrideHCID 19100813HCID 19100813, compound

Product 1

HCID 19100774HCID 19100774, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
-10 °C

Procedure

A mixture of 2-ethoxalylamino-4-propylthiophene-5-carboxylate (9.0 g, 28.7 mmol) in 52 ml of acetic anhydride and 58 ml of methylene chloride was stirred in a dry nitrogen atmosphere and cooled to -10° C. A mixture of nitric acid (1.78 ml, d=1.52) in 40 ml of acetic acid was added dropwise during 0.5 hours. The reaction mixture was stirred at 0°-5° C. for 16 hours and poured into ice water. The organic phase was separated and carefully neutralized with saturated aqueous sodium hydrogen carbonate. The neutral organic phase was washed with water, dried (Na2SO4) and the solvent was evaporated. The residue was dissolved in methanol and water was added to favour precipitation. The precipitate was filtered off, washed with cold aqueous methanol and dried. Yield 4.77 g (46%) of ethyl 2-ethoxalylamino-3-nitro-4-propylthiophene-5-carboxylate. M.p. 73°-75° C. 1H-NMR (DMSO-d6, δ): 0.98 (t, 3H), 1.39 (t, 3H), 1.45 (t, 3H), 1.55 (hex, 2H), 3.20 (t, 2H), 4.31 (q, 2H), 4.38 (q, 2H), 12.02 (s, 1H).

Workup

  1. additionwas added dropwise during 0.5 hours
  2. stirringThe reaction mixture was stirred at 0°-5° C. for 16 hours
  3. customThe organic phase was separated
  4. washThe neutral organic phase was washed with water
  5. dry with materialdried (Na2SO4)
  6. customthe solvent was evaporated
  7. dissolutionThe residue was dissolved in methanol
  8. additionwater was added to favour precipitation
  9. filtrationThe precipitate was filtered off
  10. washwashed with cold aqueous methanol
  11. customdried

Sources & evidence

ORD record
ord-4308902c1a5d486989de3c8f095caaea
Source dataset
uspto-grants-1994_02
Patent number
US05284847

Reaction notes

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