Cyclopropyl 4-fluorophenyl ketone → 1,1'-(4-Chloro-1-butenylidene)bis[4-fluorobenzene]

HRID 50988Notes

Reaction equation

[CH:1]1([C:4]([C:6]2[CH:11]=[CH:10][C:9]([F:12])=[CH:8][CH:7]=2)=O)[CH2:3][CH2:2]1.[F:13][C:14]1[CH:19]=[CH:18]C([Mg]Br)=CC=1.[Cl:22][CH2:23][CH2:24][CH:25]=C(C1C=CC=CC=1)C1C=CC=CC=1>C1COCC1>[F:12][C:9]1[CH:8]=[CH:7][C:6]([C:4]([C:1]2[CH:3]=[CH:2][C:14]([F:13])=[CH:19][CH:18]=2)=[CH:25][CH2:24][CH2:23][Cl:22])=[CH:11][CH:10]=1

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of cyclopropyl-(4-fluorophenyl)ketone (520 mg, 3.17 mmol) in THF (10 mL) was added 4-fluorophenyl magnesium bromide dropwise at 0° C. under N2 atmosphere. The reaction mixture was stirred for 1 h at 0° C., quenched by addition of brine and extracted with Et2O. The organic layer was then washed with NaHCO3 saturated aqueous solution and brine. It was then dried over MgSO4, filtered, concentrated in vacuo to give crude bis(4-fluorophenyl)-cyclopropylmethanol. It was used for ring opening reaction by following the procedure for formation of 4-chloro-1,1-diphenyl-1-butene without further purification. 1,1-Bis(4-fluorophenyl)-4-chloro-1-butene (780 mg, 88%) was obtained as a colorless oil. 1H NMR (CDCl3, 300 MHz) δ2.57 (q, 2H, J=6.9 Hz), 3.58 (t, 2H, J=6.9 Hz), 6.04 (t, 1H, J=7.3 Hz), 6.92-7.21 (m, 8H) ppm.

Workup

customquenched by addition of brine
extractionextracted with Et2O
washThe organic layer was then washed with NaHCO3 saturated aqueous solution and brine
dry with materialIt was then dried over MgSO4
filtrationfiltered
concentrationconcentrated in vacuo
customto give crude bis(4-fluorophenyl)-cyclopropylmethanol
customIt was used for ring opening reaction
customwithout further purification

Sources & evidence

ORD record: ord-14a486f563ac43d38a555df41f92d179
Source dataset: uspto-grants-2004_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06713471B1

Reaction notes

Loading…