N-bromobutanimide → 1-tert-butyl 2-methyl 3-bromo-1H-pyrrole-1,2-dicarboxylate

HRID 1478396

Reaction equation

HRID 1478396 reaction equation
[Br:1]N1C(=O)CCC1=O.[N:9]1([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:13][CH2:12][CH2:11][CH:10]1[C:14]([O:16][CH3:17])=[O:15]>C(Cl)(Cl)(Cl)Cl>[Br:1][C:11]1[CH:12]=[CH:13][N:9]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[C:10]=1[C:14]([O:16][CH3:17])=[O:15]

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 3941471-Tert-butyl 2-methyl pyrrolidine-1,2-dicarboxylate

Product 1

HCID 441898031-tert-butyl 2-methyl 3-bromo-1H-pyrrole-1,2-dicarboxylateYield 40%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
85 °C

Procedure

Synthesis was carried out according to the procedure reported: Hasse et al., Aust. J. Chem., 62(7):683-691 (2009). Crystallized (from water) N-bromo succinimide (100 g, 564 mmol) was added to a solution of 1-tert-butyl 2-methyl pyrrolidine-1,2-dicarboxylate (34.0 g, 148 mmol) in carbon tetrachloride (17 L). The resulting suspension was heated at 85° C. for 2 h. The reaction mixture was cooled to 0° C. and the precipitated succinimide removed by filtration. The filtrate was concentrated under reduced pressure. The dark orange oil obtained was subjected to column chromatography (REDISEP®, silica gel, 120 g, 10% EtOAc/hexanes), gave 1-tert-butyl 2-methyl 3-bromo-1H-pyrrole-1,2-dicarboxylate (18.0 g, 39.1%) as an orange color liquid. 1H NMR (400 MHz, CD3OD) 6 ppm: 1.53 (s, 9H), 3.32 (s, 3H), 6.46 (d, J=3.6 Hz, 1H), 7.44 (d, J=3.6 Hz, 1H).

Workup

  1. customSynthesis
  2. temperatureThe reaction mixture was cooled to 0° C.
  3. customthe precipitated succinimide removed by filtration
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. customThe dark orange oil obtained

Sources & evidence

ORD record
ord-38b9445e78fe4af6b295c3281e4f6693
Source dataset
uspto-grants-2016_08
Patent number
US09403834B2

Linked notes

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