1H-1,2,4-Triazole → 4-(1H-1,2,4-triazol-1-yl)benzaldehyde

HRID 1662989Notes

Reaction equation

F[C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.[NH:10]1[CH:14]=[N:13][CH:12]=[N:11]1.C(=O)([O-])[O-].[K+].[K+]>N1C=CC=CC=1.[Cu-]=O>[N:10]1([C:2]2[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=2)[CH:14]=[N:13][CH:12]=[N:11]1.[N:13]1([C:2]2[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=2)[CH:12]=[N:11][N:10]=[CH:14]1

Participants

Conditions

Temperature: 125 °C

Procedure

To a solution of 6.44 ml (60 mmol) of p-fluorobenzaldehyde in 40 ml of pyridine, 4.14 g (60 mmol) of 1,2,4-triazole, 0.286 g (2 mmol) of copper(I)oxide and 9.12 g (66 mmol) of potassium carbonate are succesively added at r.t. After stirring for 18 h at 125° C., the reaction mixture is concentrated under reduced pressure. The residue is diluted with CHCl3 and filtered through celite. The filtrate is concentrated and purified by flash column chromatography on silica gel (eluent: n-Hexane:AcOEt=4:1˜AcOEt only˜AcOEt:MeOH=20:1) to give 4-[1,2,4]triazol-1-yl-benzaldehyde as major product and 4-[1,3,4]triazol-1-yl-benzaldehyde as minor product. 1H-NMR (400 MHz, CDCl3): 7.61 (d, 2H, J=8.56 Hz), 8.09 (d, 2H, J=8.56 Hz), 8.59 (s, 1H), 10.10 (s, 1H) (minor product); 7.91 (d, 2H, J=7.07 Hz), 8.05 (d, 2H, J=7.07 Hz), 8.16 (s, 1H), 8.69 (s, 1H), 10.07 (s, 1H) (major product).

Workup

concentrationthe reaction mixture is concentrated under reduced pressure
additionThe residue is diluted with CHCl3
filtrationfiltered through celite
concentrationThe filtrate is concentrated
custompurified by flash column chromatography on silica gel (eluent: n-Hexane:AcOEt=4:1˜AcOEt only˜AcOEt:MeOH=20:1)

Sources & evidence

ORD record: ord-7aaa592ca692400d8cfaedce18a27d96
Source dataset: uspto-grants-2011_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08034810B2

Reaction notes

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