4-Methylpyridine → alpha,alpha-Bis(4-fluorophenyl)-4-pyridineethanol

HRID 1709853Notes

Reaction equation

[N:1]1[CH:6]=[CH:5][C:4]([CH3:7])=[CH:3][CH:2]=1.C([Li])CCC.CCCCCC.[F:19][C:20]1[CH:34]=[CH:33][C:23]([C:24]([C:26]2[CH:31]=[CH:30][C:29]([F:32])=[CH:28][CH:27]=2)=[O:25])=[CH:22][CH:21]=1.[Cl-].[NH4+]>O1CCCC1>[F:19][C:20]1[CH:34]=[CH:33][C:23]([C:24]([C:26]2[CH:31]=[CH:30][C:29]([F:32])=[CH:28][CH:27]=2)([OH:25])[CH2:7][C:4]2[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=2)=[CH:22][CH:21]=1

Participants

Conditions

Temperature: -30 °C

Procedure

A solution of 27.8 g (0.30 mole) of 4-picoline in 400 ml of tetrahydrofuran and under an atmosphere of nitrogen was cooled to -30° C. in a dry-ice acetone bath. A solution of 2.5 moles n-butyllithium in hexane (119 ml, 0.30 mole) was added over 1 hr and the mixture was stirred for an additional 30 min at -30° C. The reaction mixture was allowed to warm to room temperature over 1.5 hr, and 66.7 g (0.30 mole) of 4,4'-difluorobenzophenone in 100 ml of tetrahydrofuran was added. The mixture was stirred for 2 hr and then was poured into an icy solution of ammonium chloride. A white solid was collected. The aqueous mixture was extracted with several portions of methylene chloride and the methylene chloride then removed in vacuo to give additional solid. The solid fractions were combined and recrystallized from a mixture of ether-hexane to give 63.14 g (67.9% yield) of title compound as a white, crystalline solid: mp 158°-159.5° C.

Workup

temperatureto warm to room temperature over 1.5 hr
stirringThe mixture was stirred for 2 hr
customA white solid was collected
extractionThe aqueous mixture was extracted with several portions of methylene chloride
customthe methylene chloride then removed in vacuo
customto give additional solid
customrecrystallized from a mixture of ether-hexane

Sources & evidence

ORD record: ord-eecf96a8b11e4d228594b448ceebf5ee
Source dataset: uspto-grants-1990_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04950674

Reaction notes

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