1,4-Dioxane → HCID 59651817, compound
Reaction equation
[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][C:3]=1[F:10].C([Sn](CCCC)(CCCC)[C:16]([O:18]CC)=[CH2:17])CCC.O1CCO[CH2:31][CH2:30]1>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:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]([O:18][CH2:16][CH3:17])[O:7][CH2:30][CH3:31])=[CH:4][C:3]=1[F:10]Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 130 °C
Procedure
To a solution of 4-bromo-3-fluorobenzaldehyde (1.00 g, 4.9 mmol) in dioxane (10.0 mL) was added tributyl(1-ethoxyvinyl)stannane (1.7 mL, 5.2 mmol) and Pd(PPh3)2Cl2 (0.069 g, 0.099 mmol). The resulting solution was purged with argon for 2 min and then heated (microwave) in a sealed tube at 130° C. for 30 min. The cooled reaction solution was filtered through a plug of silica gel (eluting with 80 mL EtOAc), and the filtrate was concentrated in vacuo. Chromatographic purification of the residue (ISCO, 40 g, 0-30% EtOAc/Hex) afforded 1-bromo-4-(diethoxymethyl)-2-fluorobenzene as a light yellow oil. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 9.98 (s, 1H), 7.81 (t, J=7.5 Hz, 1H), 7.65 (d, J=7.5 Hz, 1H), 7.57 (d, J=11.0 Hz, 1H), 4.90 (d, J=2.0 Hz, 1H), 4.58 (s, 1H), 3.94 (q, J=7.0 Hz, 2H), 1.42 (t, J=6.8 Hz, 3H).
Workup
- customThe resulting solution was purged with argon for 2 min
- customThe cooled reaction solution
- filtrationwas filtered through a plug of silica gel (eluting with 80 mL EtOAc)
- concentrationthe filtrate was concentrated in vacuo
- customChromatographic purification of the residue (ISCO, 40 g, 0-30% EtOAc/Hex)
Sources & evidence
- ORD record
- ord-0984f92d6975442e840a9a959bd7bb38
- Source dataset
- uspto-grants-2011_04
- Patent number
- US07919519B2
Reaction notes
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