Ammonium Hydroxide → HCID 59853585, compound

HRID 1177039Notes

Reaction equation

HRID 1177039 reaction equation
[Cl-].[NH4+:2].[OH-].[NH4+].[CH3:5][O:6][C:7]([C:9]1[NH:10][CH:11]=[C:12]([C:14]#[N:15])[CH:13]=1)=[O:8].[H-].[Na+].NCl>C(OCC)C.CN(C)C=O>[CH3:5][O:6][C:7]([C:9]1[N:10]([NH2:2])[CH:11]=[C:12]([C:14]#[N:15])[CH:13]=1)=[O:8]

Participants

8

Reactant 5

HCID 14923Ammonium HydroxideHCID 24758Sodium hydrideHCID 25423MonochloramineHCID 25517Ammonium ChlorideHCID 109864094-CYANO-1H-PYRROLE-2-CARBOXYLIC ACID METHYL ESTER

Product 1

HCID 59853585HCID 59853585, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 6228DimethylformamideSolvent

Conditions

Temperature
-5 °C

Procedure

Solid ammonium chloride (5.8 g, 109.4 mmol) was suspended in diethyl ether (300 mL) and the suspension was cooled to −5° C. To this were added 29.56% aqueous ammonium hydroxide solution (16 mL) and 6.15% aqueous bleach solution (“Chlorox”, 240 mL) over a period of 15 min. The mixture was stirred for 30 min at −5° C. and then the layers were separated. The organic layer was washed with brine, filtered over sodium sulfate and stored over solid calcium chloride at −5° C. 4-Cyano-1H-pyrrole-2-carboxylic acid methyl ester (Example 15a, 1.09 g, 7.265 mmol) was dissolved in N,N-dimethylformamide (30 mL) and a 60% dispersion of sodium hydride in mineral oil (0.378 g, 9.445 mmol) was added. After stirring for 1 h at 25° C., the above ˜0.36 M solution of monochloramine in ether (26 mL, 9.445 mmol) was added and stirred for 2 h at 25° C. The reaction was quenched with saturated aqueous sodium thiosulfate solution followed by water. The layers were separated and the aqueous layer was extracted with diethyl ether. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to afford the crude desired product, 1-amino-4-cyano-1H-pyrrole-2-carboxylic acid methyl ester, which was used in the next step without further purification. 1H NMR (400 MHz, CDCl3) δ: 3.88 (3H, s), 5.67 (2H, bs), 7.07 (1H, d, J=1.7 Hz), 7.37 (1H, d, J=1.7 Hz).

Workup

  1. customthe layers were separated
  2. washThe organic layer was washed with brine
  3. filtrationfiltered over sodium sulfate
  4. customstored over solid calcium chloride at −5° C
  5. stirringAfter stirring for 1 h at 25° C.
  6. stirringstirred for 2 h at 25° C
  7. customThe reaction was quenched with saturated aqueous sodium thiosulfate solution
  8. customThe layers were separated
  9. extractionthe aqueous layer was extracted with diethyl ether
  10. dry with materialThe combined organic layers were dried over sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-88df910971444cdca61879008650788c
Source dataset
uspto-grants-2010_11
Patent number
US07842838B2

Reaction notes

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