Sodium Thiosulfate → Methyl 1-amino-1H-pyrrole-2-carboxylate

HRID 525019Notes

Reaction equation

HRID 525019 reaction equation
[H-].[Na+].[NH:3]1[CH:7]=[CH:6][CH:5]=[C:4]1[C:8]([O:10][CH3:11])=[O:9].C1C=CC(OP(O[NH2:29])(OC2C=CC=CC=2)=O)=CC=1.S([O-])([O-])(=O)=S.[Na+].[Na+]>CN(C=O)C.C(OCC)C>[NH2:29][N:3]1[CH:7]=[CH:6][CH:5]=[C:4]1[C:8]([O:10][CH3:11])=[O:9]

Participants

7

Reactant 4

HCID 24477Sodium ThiosulfateHCID 24758Sodium hydrideHCID 136930Methyl pyrrole-2-carboxylateHCID 44828816amino diphenyl phosphate

Product 1

HCID 14104599Methyl 1-amino-1H-pyrrole-2-carboxylateYield 82.5%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent3×

Conditions

Temperature
-5 °C

Procedure

Sodium hydride (4.40 g, 0.11 mol, 60% in hexanes) was suspended in DMF (550 ml) under nitrogen atmosphere. Once cooled at −5° C., methyl 1H-pyrrole-2-carboxylate (11.0 g, 0.09 mol) dissolved in DMF (182 ml) was dropwise added and vigorously stirred for 30. 277 ml more of DMF was added and then 0-(diphenylphosphoryl)hydroxylamine (32.8 g, 0.14 mol) was introduced into the reaction mixture. The reaction mixture was stirred at room temperature for 4 h. Once the reaction is over, 11 of saturated sodium thiosulfate solution (×5H2O) was added and the mixture was warmed to 80° C. for 1 h. Once at room temperature, 11 of ethyl ether was added and the phases separated. The aqueous phase was twice extracted with ethyl ether. The organic phase was washed with water and brine, dried over magnesium sulphate, filtered and the solvent evaporated under reduced pressure. 10.41 g (81.1% yield) of the final compound were obtained.

Workup

  1. additionwas dropwise added
  2. stirringThe reaction mixture was stirred at room temperature for 4 h
  3. additionwas added
  4. temperaturethe mixture was warmed to 80° C. for 1 h
  5. customthe phases separated
  6. extractionThe aqueous phase was twice extracted with ethyl ether
  7. washThe organic phase was washed with water and brine
  8. dry with materialdried over magnesium sulphate
  9. filtrationfiltered
  10. customthe solvent evaporated under reduced pressure

Sources & evidence

ORD record
ord-5e01967e773e4a0697505b526b5ba5b6
Source dataset
uspto-grants-2016_05
Patent number
US09340547B2

Reaction notes

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