Water → Ethyl 5-bromo-2-formyl-1-(2-trimethylsilylethoxymethyl)-1H-pyrrol-3-carboxylate

HRID 2097485Notes

Reaction equation

HRID 2097485 reaction equation
[Br:1][C:2]1[N:6]([CH2:7][O:8][CH2:9][CH2:10][Si:11]([CH3:14])([CH3:13])[CH3:12])[C:5]([CH2:15][O:16]C)=[C:4]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH:3]=1.ClCCl.O.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1(C)C=CC=CC=1>[Br:1][C:2]1[N:6]([CH2:7][O:8][CH2:9][CH2:10][Si:11]([CH3:14])([CH3:12])[CH3:13])[C:5]([CH:15]=[O:16])=[C:4]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 6344DichloromethaneHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 66602785ethyl 5-bromo-2-methoxymethyl-1-(2-trimethylsilylethoxymethyl)-1H-pyrrol-3-carboxylate

Product 1

HCID 86627038Ethyl 5-bromo-2-formyl-1-(2-trimethylsilylethoxymethyl)-1H-pyrrol-3-carboxylateYield 99.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To 450 g (1.15 mol) of ethyl 5-bromo-2-methoxymethyl-1-(2-trimethylsilylethoxymethyl)-1H-pyrrol-3-carboxylate obtained in Reference example 15-(e) were added 5.4 L of dichloromethane and 540 ml of water, and then, 363 g (1.60 mol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was added to the mixture by dividing it into several portions at room temperature. The mixture was stirred at room temperature for 30 minutes, and then, refluxed for 6 hours. After completion of the reaction, 450 g of Celite and 2.5 L of toluene were added to the reaction suspension, the mixture was stirred at room temperature for 30 minutes, and insoluble material was removed by filtration. The organic layer obtained by separating the filtrate was washed successively with a saturated aqueous solution of sodium hydrogencarbonate, and with a saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 430 g of the title compound as a pale brownish oil substantially quantitatively.

Workup

  1. customat room temperature
  2. temperaturerefluxed for 6 hours
  3. additionwere added to the reaction suspension
  4. stirringthe mixture was stirred at room temperature for 30 minutes
  5. custominsoluble material was removed by filtration
  6. customThe organic layer obtained
  7. customby separating the filtrate
  8. washwas washed successively with a saturated aqueous solution of sodium hydrogencarbonate
  9. dry with materialwith a saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-61e731717ea84c40a84d95f0b9041036
Source dataset
uspto-grants-2013_05
Patent number
US08450319B2

Reaction notes

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