1,4-Dioxane → 3-(Bromoacetyl)-6-methoxy-2-methylbenzonitrile
Reaction equation
Br[C:2]1[C:3]([CH3:12])=[C:4]([C:7]([O:10][CH3:11])=[CH:8][CH:9]=1)[C:5]#[N:6].C([Sn](CCCC)(CCCC)[C:18]([O:20]CC)=[CH2:19])CCC.O1CCOCC1.C1C(=O)N([Br:44])C(=O)C1>CCOC(C)=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Br:44][CH2:20][C:18]([C:2]1[C:3]([CH3:12])=[C:4]([C:7]([O:10][CH3:11])=[CH:8][CH:9]=1)[C:5]#[N:6])=[O:19]Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- 100 °C
Procedure
To a flask charged with 3-bromo-6-methoxy-2-methylbenzonitrile (0.98 g, 4.33 mmol) and a stir bar was added BIS(TRIPHENYLPHOSPHINE)PALLADIUM(II) CHLORIDE (0.152 g, 0.217 mmol), tributyl(1-ethoxyethenyl)stannane (2.35 g, 6.50 mmol), and dioxane (20 mL). The mixture was fitted with a condenser and purged three times with nitrogen, and heated to 100° C. for 3 hours. The reaction was cooled, and to the solution was added THF (16 mL) and water (8 mL). After cooling the solution to 0° C. with an ice bath, NBS (1.543 g, 8.67 mmol) was added into the reaction. The dark solution turned brownish orange within 5 minutes. TLC showed a more polar spot. The reaction was diluted with EtOAc (100 mL), washed with brine, dried over sodium sulfate, and purified by flash chromatography to afford the title compound.
Workup
- customThe mixture was fitted with a condenser
- custompurged three times with nitrogen
- temperatureThe reaction was cooled
- additionto the solution was added THF (16 mL) and water (8 mL)
- temperatureAfter cooling the solution to 0° C. with an ice bath
- washwashed with brine
- dry with materialdried over sodium sulfate
- custompurified by flash chromatography
Sources & evidence
- ORD record
- ord-87f8616120084d839a888a6c4b78f879
- Source dataset
- uspto-grants-2015_12
- Patent number
- US09206199B2
Reaction notes
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