Sodium Hydroxide → diethyl 1-amino-1H-pyrrole-2,4-dicarboxylate

HRID 877658Notes

Reaction equation

HRID 877658 reaction equation
[Cl-].[NH4+:2].[OH-].[NH4+].Cl[O-].[Na+].[NH:8]1[CH:12]=[C:11]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH:10]=[C:9]1[C:18]([O:20][CH2:21][CH3:22])=[O:19].[OH-].[Na+].NCl>CC(OC)(C)C.CN(C=O)C>[NH2:2][N:8]1[CH:12]=[C:11]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH:10]=[C:9]1[C:18]([O:20][CH2:21][CH3:22])=[O:19]

Participants

9

Reactant 6

HCID 14798Sodium HydroxideHCID 14923Ammonium HydroxideHCID 25423MonochloramineHCID 25517Ammonium ChlorideHCID 12711558Diethyl 1H-pyrrole-2,4-dicarboxylateHCID 23665760Sodium Hypochlorite

Product 1

HCID 68291368diethyl 1-amino-1H-pyrrole-2,4-dicarboxylateYield 95%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 15413tert-Butyl methyl etherSolvent2×

Conditions

Temperature
-20 °C

Procedure

To a flask was added MTBE (2 L) and ammonium chloride (60 g, 1.13 mol). The reaction was cooled to −20° C. Then concentrated aq ammonium hydroxide (160 mL) was added to the reaction followed by slow addition of commercial-grade sodium hypochlorite solution (149 g, 1.5 L). After addition, the reaction was stirred at −20° C. for additional 30 minutes. The MTBE layer was separated and washed with brine and dried over Na2SO4. In a separate flask under nitrogen was added diethyl 1H-pyrrole-2,4-dicarboxylate (40 g, 190 mmol) and dry DMF (400 mL). The reaction was cooled to 0° C. whereupon sodium hydroxide (190 mmol) was added portionwise to the reaction. The reaction was stirred at 0° C. for additional 1 hour before it was cooled to −20° C. At this time, the previously prepared MTBE solution of chloramine was added slowly to the reaction and the reaction was stirred at −20° C. for 1 hour. The reaction was quenched with saturated sodium thiosulfate solution. The organic layer of the reaction was separated and washed with water and brine, dried over sodium sulfate, filtered and concentrated to yield 40 g (95%) of the title compound. H1 NMR (400 MHz, CDCl3) δ ppm: 7.48 (1H, d, J=1.6 Hz), 7.24 (1H, d, J=1.6 Hz), 5.65 (2H, s), 4.32-4.23 (4H, merging quartets), 1.367-1.32 (6H, merging triplets). LCMS (condition A) m/z=227.2 +ve.

Workup

  1. additionAfter addition
  2. customThe MTBE layer was separated
  3. washwashed with brine
  4. dry with materialdried over Na2SO4
  5. additionwas added portionwise to the reaction
  6. stirringThe reaction was stirred at 0° C. for additional 1 hour before it
  7. temperaturewas cooled to −20° C
  8. stirringthe reaction was stirred at −20° C. for 1 hour
  9. customThe reaction was quenched with saturated sodium thiosulfate solution
  10. customThe organic layer of the reaction was separated
  11. washwashed with water and brine
  12. dry with materialdried over sodium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-553d85023add48e796dcf1efc4fc9b0a
Source dataset
uspto-grants-2015_03
Patent number
US08987268B2

Reaction notes

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