Methyl 4-(bromomethyl)-3-chlorobenzoate → HCID 67368455, compound

HRID 1184967Notes

Reaction equation

HRID 1184967 reaction equation
Br[CH2:2][C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][C:4]=1[Cl:13]>CO.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Cl:13][C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][C:3]=1[CH2:2][C:7]([O:9][CH3:10])=[O:8])[C:7]([O:9][CH3:10])=[O:8]

Participants

4

Reactant 1

HCID 22027761Methyl 4-(bromomethyl)-3-chlorobenzoate

Product 1

HCID 67368455HCID 67368455, compoundYield 58.6%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 887MethanolSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of methyl 4-(bromomethyl)-3-chlorobenzoate (10 g, 37.95 mmol) in MeOH (300 mL) was added TEA (4.2 mL, 30.36 mmol) and Pd(dppf)Cl2 (2.8 g, 3.8 mmol). The reaction was heated under 0.4 MPa CO pressure at 60° C. for 3 h, filtered and concentrated. The residue was purified by Combi-Flash (120 g silica gel, start PE/EA=10:0 to 5:1 by gradient, 60 mL/min, 60 min, 3.6 L total solvent volume) to afford product as a white solid (2.7 g, 29%). MS (ESI): m/z 243.0 [M+1]+.

Workup

  1. filtrationfiltered
  2. concentrationconcentrated
  3. customThe residue was purified by Combi-Flash (120 g silica gel, start PE/EA=10:0 to 5:1 by gradient, 60 mL/min, 60 min, 3.6 L total solvent volume)

Sources & evidence

ORD record
ord-8f48a2e3f60a4e7b89317bc38f835d3d
Source dataset
uspto-grants-2014_03
Patent number
US08669381B2

Reaction notes

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