Sodium hydride → 1-amino-1H-pyrrole-2,4-dicarbonitrile

HRID 73665Notes

Reaction equation

HRID 73665 reaction equation
[NH:1]1[CH:5]=[C:4]([C:6]#[N:7])[CH:3]=[C:2]1[C:8]#[N:9].[H-].[Na+].[NH2:12]OP(=O)(C1C=CC=CC=1)C1C=CC=CC=1>CN(C=O)C>[NH2:12][N:1]1[CH:5]=[C:4]([C:6]#[N:7])[CH:3]=[C:2]1[C:8]#[N:9]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 5759051H-Pyrrole-2,4-dicarbonitrileHCID 10955453O-(Diphenylphosphinyl)hydroxylamine

Product 1

HCID 552958981-amino-1H-pyrrole-2,4-dicarbonitrileYield 82%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of DMF (100 mL) was added 1H-pyrrole-2,4-dicarbonitrile (1.00 g, 8.54 mmol) followed by NaH, 60% dispersion in mineral oil (0.51 g, 12.8 mmol). The solution was stirred at rt for 15 min and then (aminooxy)(diphenyl)phosphine oxide (2.99 g, 12.8 mmol) was added, and the solution was heated to 80° C. for 2 h. Upon cooling to rt the solution was filtered washing with CH2Cl2. The solution was partially concentrated and a white precipitate formed which was filtered. The mother liquor was then evaporated under vacuum and subsequently purified by MPLC (Isco) 100% CH2Cl2 ramping to 9:1 v/v CH2Cl2-EtOAc. The resulting purified fractions were combined and concentrated in vacuo yielding 0.92 g of a white solid (6.98 mmol, yield 82%). 1H-NMR (DMSO-d6) (17.92 (d, J=1.8 Hz, 1H), 7.39 (d, J=1.9 Hz, 1H), 6.66 (s, 2H); MS [M+H]+=133.0; LCMS RT=0.96 min.

Workup

  1. temperaturethe solution was heated to 80° C. for 2 h
  2. temperatureUpon cooling to rt the solution
  3. filtrationwas filtered
  4. washwashing with CH2Cl2
  5. concentrationThe solution was partially concentrated
  6. customa white precipitate formed which
  7. filtrationwas filtered
  8. customThe mother liquor was then evaporated under vacuum
  9. customsubsequently purified by MPLC (Isco) 100% CH2Cl2 ramping to 9:1 v/v CH2Cl2-EtOAc
  10. customThe resulting purified fractions
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0b53212c63004bf2a8219cbb24a1be08
Source dataset
uspto-grants-2014_09
Patent number
US08829185B2

Reaction notes

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