Trifluoroacetic acid → 4-(2,4-Difluorobenzyloxy)pyridine-1-oxide

HRID 1831973Notes

Reaction equation

HRID 1831973 reaction equation
[F:1][C:2]1[CH:16]=[C:15]([F:17])[CH:14]=[CH:13][C:3]=1[CH2:4][O:5][C:6]1[CH:11]=[CH:10][NH:9][C:8](=O)[CH:7]=1.ClN1C(=[O:24])CCC1=O.C(#N)C.O.FC(F)(F)C(O)=O>CN(C)C=O>[F:1][C:2]1[CH:16]=[C:15]([F:17])[CH:14]=[CH:13][C:3]=1[CH2:4][O:5][C:6]1[CH:11]=[CH:10][N+:9]([O-:24])=[CH:8][CH:7]=1

Participants

6

Reactant 4

HCID 6422Trifluoroacetic acidHCID 31398ChlorosuccinimideHCID 18373917Acetonitrile--water (1/1)HCID 220503904-(2,4-difluorobenzyloxy)-1H-pyridin-2-one

Product 1

HCID 220502194-(2,4-Difluorobenzyloxy)pyridine-1-oxide

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

4-[(2,4-difluorobenzyl)oxy]-pyridin-2 (1H)-one (from Step 2) (8.60 g, 36.3 mmol) was stirred in 150 ml dimethylformamide and treated with N-chlorosuccinimide (5.4 g, 39.9 mmol). After 15 hours, the precipitate was collected by filtration (5.11 g, 52%) yeilding a lustrous white solid. The mother liquor was diluted to 500 ml with diethyl ether, providing 2.47 g (25%) in a second crop. 1H-NMR (400 MHz, DMSO-d6) δ 11.87 (s, 1H), 7.60 (quartet, J=6.34 Hz, 1H), 7.43 (d, J=7.58 Hz, 1H), 7.31 (dt, J=10.08, 2.21 Hz, 1H), 7.14 (dt, J 8.65, 1.79 Hz, 1H), 6.44 (d, J=7.49 Hz, 1H), 5.28 (s, 1H). 19F-NMR (400 MHz, DMSO-d6) δ−109.58 (quintet, J=7.75 Hz, 1F), −113.68 (quartet, J=8.68 Hz, 1F). LC/MS tr=4.47 minutes (0-95% acetonitrile/water, 0.05% trifluoroacetic acid, over 6 minutes at 1 ml/min with detection at 254 nm, at 50° C.) ES-MS m/z 272, 274 3:1 (M+H).

Workup

  1. filtrationthe precipitate was collected by filtration (5.11 g, 52%) yeilding a lustrous white solid
  2. additionThe mother liquor was diluted to 500 ml with diethyl ether
  3. customproviding 2.47 g (25%) in a second crop

Sources & evidence

ORD record
ord-230243f3e6f34ac3866b98e85b1b82b5
Source dataset
uspto-grants-2006_06
Patent number
US07067540B2

Reaction notes

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