Dimethylformamide → 1-(3-Bromophenyl)-3-chlorobutan-2-one

HRID 517550Notes

Reaction equation

HRID 517550 reaction equation
CN(C=O)C.[Br-].[Br:7][C:8]1[CH:9]=[C:10]([CH:13]=[CH:14][CH:15]=1)[CH2:11][Zn+].[Cl:16][CH:17]([CH3:21])[C:18](Cl)=[O:19]>C1(C)C=CC=CC=1.CCCCCC.CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:7][C:8]1[CH:9]=[C:10]([CH2:11][C:18](=[O:19])[CH:17]([Cl:16])[CH3:21])[CH:13]=[CH:14][CH:15]=1

Participants

8

Reactant 3

HCID 6228DimethylformamideHCID 1110192-Chloropropionyl chlorideHCID 178419771HCID 178419771, compound

Product 1

HCID 867114911-(3-Bromophenyl)-3-chlorobutan-2-oneYield 38%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of CuCN(LiCl)2 (2.5 mL, 2.500 mmol), DMF (0.194 mL, 2.5 mmol) and (3-bromobenzyl)zinc(II) bromide (5 mL, 2.5 mmol) was stirred at RT for 20 min. A solution of 2-chloropropanoyl chloride (0.244 mL, 2.5 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.087 g, 0.075 mmol) in toluene (5 mL) was added to the reaction mixture. After 45 min the reaction was diluted with hexane and EtOAc and solid silica gel was added. The mixture was stirred for 5 min and the solid was filtered. The organic layer was concentrated, and loaded to silica gel column chromatography for purification (0-30% EtOAc/Hexane) to afford a colorless liquid (246 mg, 38%). MS (ES+) C10H10BrClO requires: 260, 262, found: 261 263 [M+H]+(1:1).

Workup

  1. additionwas added
  2. stirringThe mixture was stirred for 5 min
  3. filtrationthe solid was filtered
  4. concentrationThe organic layer was concentrated
  5. customloaded to silica gel column chromatography for purification (0-30% EtOAc/Hexane)

Sources & evidence

ORD record
ord-fc912b58edfe488c8a0dd0b8c298eebc
Source dataset
uspto-grants-2015_08
Patent number
US09115120B2

Reaction notes

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