N,N,N-Tributylbutan-1-aminium fluoride--hydrogen fluoride (1/1/2) → (2z)-3-Fluoro-3-[4-(2-pyrimidinyl)phenyl]-2-propenal
Reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[N:3][C:2]=1[C:7]1[CH:12]=[CH:11][C:10]([C:13]#[C:14][CH:15]=[O:16])=[CH:9][CH:8]=1.CCCC[N+](CCCC)(CCCC)CCCC.[FH:34].F.[F-]>C(OCC)(=O)C>[F:34]/[C:13](/[C:10]1[CH:11]=[CH:12][C:7]([C:2]2[N:3]=[CH:4][CH:5]=[CH:6][N:1]=2)=[CH:8][CH:9]=1)=[CH:14]\[CH:15]=[O:16]Participants
Conditions
- Temperature
- 110 °C
Procedure
A mixture of 3-[4-(2-pyrimidinyl)phenyl]-2-propynal (210 mg, 1.01 mmol, prepared as described in Reference Example 300) and tetrabutylamonium dihydrogentrifluoride (50 wt % in 1,2-dichloroethane, 1.8 g, 3.0 mmol) was heated to 110° C. for 4 h. The cooled reaction mixture was diluted with ethyl acetate (30 mL), washed with aq. sat. NaHCO3 (30 mL) and brine (30 mL), and filtered through a plug of SiO2 (5 g). The SiO2 plug was rinsed with additional ethyl acetate (30 mL) and the combined filtrates were concentrated. Purification by chromatography (SiO2, 97:3 dichloromethane/ethyl acetate) provided 116 mg (51%) of the title compound as a colorless solid. MS 229 (M+H)+. Also isolated were (2Z)-3-chloro-3-[4-(2-pyrmidinyl)phenyl]-2-propenal (10 mg, 4%, MS 245, 247 (M+H)+) and recovered starting material (15 mg, 7%).
Workup
- customThe cooled reaction mixture
- washwashed with aq. sat. NaHCO3 (30 mL) and brine (30 mL)
- filtrationfiltered through a plug of SiO2 (5 g)
- washThe SiO2 plug was rinsed with additional ethyl acetate (30 mL)
- concentrationthe combined filtrates were concentrated
- customPurification by chromatography (SiO2, 97:3 dichloromethane/ethyl acetate)
Sources & evidence
- ORD record
- ord-b250371f928d40f498bb924ae478b6b8
- Source dataset
- uspto-grants-2004_11
- Patent number
- US06825170B2
Reaction notes
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