Water → Methyl 4-(4-formyl-2-methoxyphenoxy)butanoate

HRID 33986

Reaction equation

HRID 33986 reaction equation
[O:1]=[CH:2][C:3]1[CH:11]=[CH:10][C:8]([OH:9])=[C:5]([O:6][CH3:7])[CH:4]=1.[CH3:12][O:13][C:14](=[O:19])[CH2:15][CH2:16][CH2:17]Br.C(=O)([O-])[O-].[K+].[K+].O>CN(C=O)C>[CH3:12][O:13][C:14](=[O:19])[CH2:15][CH2:16][CH2:17][O:9][C:8]1[CH:10]=[CH:11][C:3]([CH:2]=[O:1])=[CH:4][C:5]=1[O:6][CH3:7]

Participants

6

Reactant 4

HCID 962WaterHCID 1183VanillinHCID 11430Potassium CarbonateHCID 107604Methyl 4-bromobutyrate

Product 1

HCID 10753291Methyl 4-(4-formyl-2-methoxyphenoxy)butanoateYield 66%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of vanillin (47)(40.00 g, 262.89 mmol) and methyl-4-bromobutyrate (50.00 g, 276.18 mmol) in DMF (200 mL) was allowed to stir over potassium carbonate (51.53 g, 372.40 mmol) for 16 hours. Water was added to the reaction mixture at which time the product crystallised. The resulting mixture was filtered and dried in vacuo for 16 hours to afford the keto-ester (48) as a white solid (41.3 g, 66%). MP=57-59° C. 1H NMR (250 MHz, CDCl3) δ 9.80 (s, 1H), 7.46-7.40 (m, 2H), 6.97 (d, J=8.1 Hz, 1H), 4.16 (t, J=6.3 Hz, 2H), 3.92 (s, 3H), 3.70 (s, 3H), 2.57 (t, J=7.2 Hz, 2H), 2.20 (pent, J=6.7 Hz, 2H). 13C NMR (67.8 MHz, CDCl3) 188.2 (Cl), 173.7 (C12), 153.8 (Cquat.), 152.0 (Cquat.), 144.1 (Cquat.), 125.8 (Cmethine), 110.3 (C3), 108.5 (C6), 69.0 (C9), 57.0 (C8), 52.2 (C13), 30.6 (C11), 24.5 (C10). It was decided to adopt the numbering system shown in the figure below for the molecule for ease of peak assignment in 13C NMR.

Workup

  1. customcrystallised
  2. filtrationThe resulting mixture was filtered
  3. customdried in vacuo for 16 hours

Sources & evidence

ORD record
ord-44a5e748fd264f4bbf8f4ac6744d97fd
Source dataset
uspto-grants-2008_09
Patent number
US07429658B2

Linked notes

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