Ammonium Hydroxide → HCID 21075143, compound

HRID 1374246Notes

Reaction equation

HRID 1374246 reaction equation
[NH2:1]Cl.[NH4+].[Cl-].[NH4+].[OH-].[O-]Cl.[Na+].[C:10]([C:14]1[CH:15]=[C:16]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[NH:17][CH:18]=1)([CH3:13])([CH3:12])[CH3:11].[H-].[Na+]>CCOCC.CN(C=O)C>[C:10]([C:14]1[CH:15]=[C:16]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[N:17]([NH2:1])[CH:18]=1)([CH3:13])([CH3:11])[CH3:12]

Participants

9

Reactant 6

HCID 14923Ammonium HydroxideHCID 24758Sodium hydrideHCID 25423Monochloramine2×HCID 25517Ammonium ChlorideHCID 21075144HCID 21075144, compoundHCID 23665760Sodium Hypochlorite

Product 1

HCID 21075143HCID 21075143, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 6228DimethylformamideSolvent

Conditions

Temperature
-5 °C

Procedure

Preparation C7, Step 2: Preparation of monochloramine by the method of John Hynes, Jr., et al., J. Org. Chem., 2004, 69, 1368: NH4Cl (3 g, 56 mmol, was mixed in ether (110 mL) and cooled to −5° C. Concentrated NH4OH (4.7 mL) was then added followed by dropwise addition of bleach (Chlorox, 72 mL) over 15 minutes. The mixture was stirred for 15 minutes, the layers separated and the organic layer washed with brine. The organic layer was dried over powdered CaCl2 in the freezer for 1 h and used for the subsequent step immediately. Ethyl 4-tert-butyl-1H-pyrrole-2-carboxylate (1.67 g, 8.6 mmol, 1 eq) was dissolved in DMF. Sodium hydride (60% suspension in oil) (0.41 g, 10 mmol, 1.2 eq) was then added thereto cautiously and stirred for 45 minutes at RT under nitrogen. Monochloramine was then added (0.15M in ether, 68.4 mL, 10 mmol, 1.2 eq). The next morning, the reaction is quenched with saturated aqueous Na2S2O3, diluted with water and extracted into ether. The ether layer is dried, filtered and stripped to yield 3.19 g of ethyl 3-tert-butyl-1-aminopyrrole-5-carboxylate as a yellow oil which eventually crystallized as long needles. MS found: (M+H)+=211.34.

Workup

  1. customthe layers separated
  2. washthe organic layer washed with brine
  3. customThe organic layer was dried
  4. customfor 1 h
  5. stirringcautiously and stirred for 45 minutes at RT under nitrogen
  6. customThe next morning, the reaction is quenched with saturated aqueous Na2S2O3
  7. additiondiluted with water
  8. extractionextracted into ether
  9. dry with materialThe ether layer is dried
  10. filtrationfiltered

Sources & evidence

ORD record
ord-89559c3648c64ab2b5f1c1a29947b5e6
Source dataset
uspto-grants-2007_01
Patent number
US07163937B2

Reaction notes

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