Picolinic acid → Diethyl 2-(4-bromo-2-methoxyphenyl)malonate
Reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[C:4]([O:9][CH3:10])[CH:3]=1.C([C:13](CC)([C:17]([O-:19])=[O:18])[C:14]([O-:16])=[O:15])C.C(=O)([O-])[O-].[Cs+].[Cs+].N1C=CC=[CH:30][C:29]=1C(O)=O.O1CCO[CH2:39][CH2:38]1>[Cu]I>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH:13]([C:17]([O:19][CH2:38][CH3:39])=[O:18])[C:14]([O:16][CH2:29][CH3:30])=[O:15])=[C:4]([O:9][CH3:10])[CH:3]=1Participants
7
Reactant 5
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 55 °C
Procedure
A mixture of 4-bromo-1-iodo-2-methoxybenzene (1100 mg, 3.5 mmol), diethylmalonate (1240 mg, 7.70 mmol), cesium carbonate (1830 mg, 5.60 mmol), 2-picolinic acid (62 mg, 0.39 mmol), copper (I) iodide (34 mg, 0.18 mmol), and dioxane (7 ml) was stirred at 55° C. for 2 days. A very heavy slurry formed, LCMS indicates that the starting iodoarene is about 70% consumed. The mixture was cooled to room temperature and diluted with 30 mL of water and extracted with ethyl acetate. The extract was washed with water, brine, dried over magnesium sulfate, and concentrated to obtain the title compound which was about 60% pure by LCMS and was used for the next step without purification. GCMS (ES+) 344 (M+).
Workup
- customA very heavy slurry formed
- customconsumed
- temperatureThe mixture was cooled to room temperature
- additiondiluted with 30 mL of water
- extractionextracted with ethyl acetate
- washThe extract was washed with water, brine
- dry with materialdried over magnesium sulfate
- concentrationconcentrated
Sources & evidence
- ORD record
- ord-38b3b7a36d8e469bbab438dd1175e3be
- Source dataset
- uspto-grants-2016_07
- Patent number
- US09394285B2
Reaction notes
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