Hydrochloric Acid → 5-Dibutylamino-2-methoxy-benzaldehyde

HRID 1989813Notes

Reaction equation

Br[C:2]1[CH:3]=[CH:4][C:5]([O:14][CH3:15])=[C:6]([CH:8]2[O:13]CCCO2)[CH:7]=1.[CH2:16]([NH:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH2:17][CH2:18][CH3:19].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.Cl.[OH-].[Na+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:16]([N:20]([CH2:21][CH2:22][CH2:23][CH3:24])[C:2]1[CH:3]=[CH:4][C:5]([O:14][CH3:15])=[C:6]([CH:7]=1)[CH:8]=[O:13])[CH2:17][CH2:18][CH3:19]

Participants

Conditions

Temperature: 25 °C

Procedure

2-(5-Bromo-2-methoxy-phenyl)-[1,3]dioxane (40 mmol), di-n-butylamine (48 mmol), Pd2(dba)3 (0.2 mmol, 1 mol % Pd), P(o-tol)3 (0.6 mmol) and Na-t-OBu (68 mmol) was stirred in degassed toluene (60 mL) at 80° C. for 18 h. The darkbrown mixture was poured into icecold hydrochloric acid (1 M, 200 mL) and stirred vigorously for 2 hours at 25° C. The solution was cooled to 0° C. and pH was adjusted to 9 using 6M NaOH(aq) and extracted with Et2O (4×100 mL). The organic phase was dried (Na2SO4) and the solvent was removed under reduced pressure. The resulting crude oil purified by flash chromatography using EtOAc/n-heptane (1:4, v/v) as eluent. The product was isolated as yellow oil in 46% yield.

Workup

temperatureThe solution was cooled to 0° C.
extractionextracted with Et2O (4×100 mL)
dry with materialThe organic phase was dried (Na2SO4)
customthe solvent was removed under reduced pressure
customThe resulting crude oil purified by flash chromatography
customThe product was isolated as yellow oil in 46% yield

Sources & evidence

ORD record: ord-8261bab93a224a1980c3988478e40b97
Source dataset: uspto-grants-2010_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07642367B2

Reaction notes

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