Tributylphosphine → HCID 66955245, compound
Reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([C:10]([F:13])([F:12])[F:11])[CH:3]=1.[F-].[Cs+].[CH2:16](P(CCCC)CCCC)[CH2:17]CC.C([Sn](CCCC)(CCCC)C=C)CCC.[F-].[K+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CCCCCC>[F:11][C:10]([F:13])([F:12])[C:4]1[CH:3]=[C:2]([CH:16]=[CH2:17])[CH:9]=[CH:8][C:5]=1[C:6]#[N:7]Participants
Reactant 5
Product 1
Reagents, catalysts & solvents 3
Conditions
- Temperature
- 80 °C
Procedure
To a mixture of 4-bromo-2-(trifluoromethyl)benzonitrile (500 mg, 2.000 mmol), cesium fluoride (668 mg, 4.40 mmol), tri-n-butylphosphine in hexane (0.347 mL, 0.120 mmol) and Pd2(dba)3 (36.6 mg, 0.040 mmol) in toluene (10 mL) was added tributyl(vinyl)stannane (0.587 mL, 2.000 mmol). The reaction mixture was heated at 80° C. overnight. Next, saturated KF solution was added and the resulting mixture was stirred 1 hour and then filtered. The filtrate was diluted with ethyl acetate and washed with H2O. The organic layer was dried with MgSO4, filtered, and concentrated. The solids were purified on a silica gel cartridge using an EtOAc/hexanes gradient to yield 450 mg of 2-(trifluoromethyl)-4-vinylbenzonitrile. 1H NMR (400 MHz, chloroform-d) δ ppm 7.79 (1H, s), 7.67 (1H, dd, J=7.91, 1.76 Hz), 7.40-7.45 (1H, m), 6.77 (1H, dd, J=17.58, 10.99 Hz), 5.97 (1H, d, J=17.58 Hz), 5.58 (1H, d, J=10.99 Hz)
Workup
- filtrationfiltered
- additionThe filtrate was diluted with ethyl acetate
- washwashed with H2O
- dry with materialThe organic layer was dried with MgSO4
- filtrationfiltered
- concentrationconcentrated
- customThe solids were purified on a silica gel cartridge
Sources & evidence
- ORD record
- ord-e264196197834eacbf75044cde6a94e1
- Source dataset
- uspto-grants-2013_03
- Patent number
- US08399451B2
Reaction notes
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