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

HRID 1764864Notes

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-4e124def13ee466a8f60a41d545914be
Source dataset: uspto-grants-2007_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: USRE039679E1

Reaction notes

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