3-Cyanopyridine → 3-(3-Fluorobenzoyl)pyridine

HRID 1904640Notes

Reaction equation

Br[C:2]1[CH:3]=[C:4]([F:8])[CH:5]=[CH:6][CH:7]=1.C([Li])(C)(C)C.CCCCC.[C:19]([C:21]1[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=1)#N.[OH-:27].[Na+]>CCOCC.O>[F:8][C:4]1[CH:3]=[C:2]([CH:7]=[CH:6][CH:5]=1)[C:19]([C:21]1[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=1)=[O:27]

Participants

Conditions

Temperature: 15 °C

Procedure

A solution of 3-bromofluorobenzene (25.0, 0.143 mol) in ether (250 ml) was cooled to -78° C. and stirred during the dropwise addition of a 2.3 M solution of tert-butyllithium in pentane (62 ml, 0.143 mol). After the addition was completed, stirring was continued for 15 minutes and a solution of 3-cyanopyridine (14.9 g, 0.143 mol) in ether (125 ml) was added dropwise. The resulting mixture was allowed to warm to 15° C. and a solution of 12 N HC1 (36 ml) in H2O (90 ml) was added dropwise. After the resulting light yellow solution had stirred for 30 minutes, 10% NaOH was added to give a pH of 10, and the ether layer was separated. The aqueous phase was extracted twice with ether, the combined ether extracts were concentrated and the residue was distilled to yield 21.3 g (74%) of 3-(3-fluorobenzoyl)pyridine bp: 112°-128° C./59.99 Nm-2.

Workup

additionAfter the addition
stirringAfter the resulting light yellow solution had stirred for 30 minutes
customto give a pH of 10
customthe ether layer was separated
extractionThe aqueous phase was extracted twice with ether
concentrationthe combined ether extracts were concentrated
distillationthe residue was distilled

Sources & evidence

ORD record: ord-7838e7defaf743f59db19fd4a1bac480
Source dataset: uspto-grants-1989_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04839371

Reaction notes

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