Diisopropylethylamine → 1-Vinyl-4-cyano-3-methoxybenzene

HRID 1480530Notes

Reaction equation

Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([O:10][CH3:11])[CH:3]=1.[CH:12](N(C(C)C)CC)(C)[CH3:13].C([Sn](CCCC)(CCCC)C=C)CCC>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:12]([C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([O:10][CH3:11])[CH:3]=1)=[CH2:13]

Participants

Conditions

Temperature: 90 °C

Procedure

To a solution of 4-bromo-2-methoxybenzonitrile (−0.5 g, 2.36 mmol, 1.0 eq) in toluene (12 mL) was added diisopropylethylamine (0.61 g, 0.82 mL, 4.72 mmol, 2.0 eq), and tributyl(vinyl)tin (1.12 g, 1.03 mL, 3.54 mmol, 1.5 eq). The reaction mixture was degrassed by bubbling agron through the mixture. Tetrakis(triphenylphosphine)palladium (0.10 g, 0.12 mmol, 0.05 eq) was added and the reaction further degassed before heating to 90° C. for 16 hours. The reaction was cooled and partitioned between EtOAc (100 mL) and NaHCO3 (100 mL). The organics were washed with brine (80 mL), dried (Na2SO4) and concentrated under reduced pressure. MPLC (5→30% EtOAc-hexane) yielded the title compound (0.343 g, 91%) as a white solid; 1H nmr (CDCl3) δ 7.56-7.53 (2H, m, ArH-5, H-6), 6.92 (1H, d, J 9.0 Hz, ArH-2), 6.59 (1H, dd, J 17.5, 11.0 Hz, CH═CH2), 5.63 (1H, d, J 17.5 Hz, CH═CH2 trans), 5.23 (1H, d, J 11.0 Hz, CH═CH2 cis), 3.91 (3H, s, OCH3); m/z 160 [M+H]+.

Workup

customby bubbling agron through the mixture
customthe reaction
customfurther degassed
temperatureThe reaction was cooled
custompartitioned between EtOAc (100 mL) and NaHCO3 (100 mL)
washThe organics were washed with brine (80 mL)
dry with materialdried (Na2SO4)
concentrationconcentrated under reduced pressure

Sources & evidence

ORD record: ord-17b4914a2a9b4e798679e04c317221c2
Source dataset: uspto-grants-2016_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09409884B2

Reaction notes

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