Toluene → Methyl 1-amino-1H-pyrrole-2-carboxylate

HRID 1511911Notes

Reaction equation

HRID 1511911 reaction equation
[CH3:1][O:2][C:3]([C:5]1[NH:6][CH:7]=[CH:8][CH:9]=1)=[O:4].CCC([O-])(C)C.[K+].C1(C)C=CC=CC=1.ClC1C=CC(C(O[NH2:32])=O)=CC=1>CN1C(=O)CCC1>[CH3:1][O:2][C:3]([C:5]1[N:6]([NH2:32])[CH:7]=[CH:8][CH:9]=1)=[O:4]

Participants

6

Reactant 4

HCID 1140TolueneHCID 136930Methyl pyrrole-2-carboxylateHCID 20504786O-4-ChlorobenzoylhydroxylamineHCID 23683543Potassium t-amylate

Product 1

HCID 14104599Methyl 1-amino-1H-pyrrole-2-carboxylate

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

To a stirred, ice/water cooled mixture of 1H-pyrrole-2-carboxylic acid methyl ester (425 mg, 3.40 mmol) in NMP (10 mL) was added a solution of potassium tert-pentoxide in toluene (2.30 mL, 3.90 mmol, 25 wt % solution); then the solid of O-4-chlorobenzoyl hydroxyamine (670 mg, prepared according to the literature: Parlanti, L Discordia, R. P.; Hynes, J. Jr.; Miller, M. M.; O'Grady, H. R.; Shi, Z. Org. Lett. 2007, 9(19) 3821-3824) was added in one portion; the cold bath was removed after addition completed, and the slurry was stirred at rt for 30 min. Subsequently, the reaction was quenched by addition of saturate sodium bicarbonate solution, then extracted with EtOAc, washed with brine; organic layers was dried over anhydrous sodium sulfate, filtered, concentrated and the residue was column purified to give the desired product (309 mg). 1H NMR (CDCl3, δ in ppm): 6.94 (t, 1H, J=2.3 Hz), 6.81 (dd, 1H, J=2.0 Hz, 4.0 Hz), 6.00 (dd, J=2.7 Hz, 4.3 Hz), 5.53 (br, s, 2H), 3.82 (s, 3H).

Workup

  1. addition2007, 9(19) 3821-3824) was added in one portion
  2. customthe cold bath was removed
  3. additionafter addition
  4. customSubsequently, the reaction was quenched by addition of saturate sodium bicarbonate solution
  5. extractionextracted with EtOAc
  6. washwashed with brine
  7. dry with materialorganic layers was dried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. custompurified

Sources & evidence

ORD record
ord-17634d2f348b4588b2efd011640eaab9
Source dataset
uspto-grants-2012_07
Patent number
US08217043B2

Reaction notes

Loading…