Hydrochloric Acid → 4-(Bromomethyl)-1-naphthaldehyde

HRID 587722Notes

Reaction equation

[Br:1][CH2:2][C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:6]([C:13]#N)=[CH:5][CH:4]=1.CC(C[AlH]CC(C)C)C.Cl.[OH2:25]>C1(C)C=CC=CC=1>[Br:1][CH2:2][C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:6]([CH:13]=[O:25])=[CH:5][CH:4]=1

Participants

Conditions

Temperature: 0 °C

Procedure

To a stirred solution of 4-(bromomethyl)-1-naphthonitrile (8 g, 33 mmol) in toluene (100 mL) at 0° C. was added dropwise DIBAL-H (1.0 M solution in toluene; 43 mL), and the reaction mixture was stirred at 0° C. for 1 h. 3 N HCl in water (50 mL) was added to the mixture until it became a white slurry and then additional 1 N HCl (20 mL) was added. The organic layer was collected and the aqueous layer was extracted with EtOAc (3×100 mL). The combined organic layer was dried over Na2SO4 and concentrated under reduced pressure. Purification by flash column chromatography (SiO2, 100-200 mesh; 5% EtOAc in petroleum ether) afforded the title compound as a white solid (7 g, 88%): mp 115-116° C.; 1H NMR (400 MHz, CDCl3) δ 10.41 (s, 1H), 9.35 (m, 1H), 8.22 (m, 1H), 7.90 (d, J=8.0 Hz, 1H), 7.75 (m, 3H), 4.95 (s, 2H); ESIMS m/z 248.88 ([M+H]+).

Workup

customThe organic layer was collected
extractionthe aqueous layer was extracted with EtOAc (3×100 mL)
dry with materialThe combined organic layer was dried over Na2SO4
concentrationconcentrated under reduced pressure
customPurification by flash column chromatography (SiO2, 100-200 mesh; 5% EtOAc in petroleum ether)

Sources & evidence

ORD record: ord-f44c6b39c8754fc9bc81e086bfd97ad6
Source dataset: uspto-grants-2016_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09226501B2

Reaction notes

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