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Bromine → Ethyl 1-(2-acetoxyethyl)-4-bromopyrrole-2-glyoxalate

HRID 67113
Notes
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Reaction equation

HRID 67113 reaction equation
[Br:1]Br.[C:3]([O:6][CH2:7][CH2:8][N:9]1[CH:13]=[CH:12][CH:11]=[C:10]1[C:14](=[O:20])[C:15]([O:17][CH2:18][CH3:19])=[O:16])(=[O:5])[CH3:4].CCCCCC.C(OCC)(=O)C>ClCCl>[C:3]([O:6][CH2:7][CH2:8][N:9]1[CH:13]=[C:12]([Br:1])[CH:11]=[C:10]1[C:14](=[O:20])[C:15]([O:17][CH2:18][CH3:19])=[O:16])(=[O:5])[CH3:4]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 24408BromineHCID 12795013Ethyl 1-(2-acetoxyethyl)pyrrole-2-glyoxalateHCID 21226206Ethyl acetate hexane

Product 1

HCID 12795028Ethyl 1-(2-acetoxyethyl)-4-bromopyrrole-2-glyoxalateYield 56.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-75 °C

Procedure

Three ml (58.3 mmole) of bromine is added in a dropwise manner to a stirred solution of 14.77 g (58.3 mmole) of ethyl 1-(2-acetoxyethyl)pyrrole-2-glyoxalate in 200 ml anhydrous dichloromethane, cooled to -75° C. After the addition, the reaction is left at -75° C. for 2.5 hours and then the temperature is allowed to increase to room temperature. The solvent is removed in vacuo, dichloromethane is added to the residue and the solution is washed successively with water, 10% sodium bicarbonate solution and water. The organic phase is dried over sodium sulfate, and the solvent is removed in vacuo. The crude product thus obtained (18.3 g) is subjected to column chromatography on Florisil (1 Kg) using hexane-ethyl acetate (9:1) as the eluting solvent. There is thus obtained upon removal of the solvent, 10.9 g (56%) of ethyl 1-(2-acetoxyethyl)-4-bromopyrrole-2-glyoxalate as an oil having the following physical constants:

Workup

  1. additionAfter the addition
  2. temperatureto increase to room temperature
  3. customThe solvent is removed in vacuo, dichloromethane
  4. additionis added to the residue
  5. washthe solution is washed successively with water, 10% sodium bicarbonate solution and water
  6. dry with materialThe organic phase is dried over sodium sulfate
  7. customthe solvent is removed in vacuo
  8. customThe crude product thus obtained (18.3 g)

Sources & evidence

ORD record
ord-00fdc22f138741beb6add2da08e5184d
Source dataset
uspto-grants-1982_08
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04344943

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes