4-Hydroxybenzaldehyde → 4-(2,2-Diethoxyethoxy)benzaldehyde

HRID 1370202Notes

Reaction equation

HRID 1370202 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.C([CH:12](CC)[C:13]([OH:15])=[O:14])C.Br[CH2:19][CH:20]=O.C(=O)([O-])[O-].[K+].[K+].[C:28]1(C)C=CC=C[CH:29]=1>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[CH2:28]([O:15][CH:13]([O:14][CH2:19][CH3:20])[CH2:12][O:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1)[CH3:29]

Participants

7

Reactant 4

HCID 1264-HydroxybenzaldehydeHCID 1140TolueneHCID 11430Potassium CarbonateHCID 86586421Bromoacetaldehyde diethyl acetate

Product 1

HCID 187608894-(2,2-Diethoxyethoxy)benzaldehydeYield 79%

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolvent

Procedure

Under nitrogen, a mixture of 4-hydroxybenzaldehyde (1.71 g, 14 mmol), bromoacetaldehyde diethyl acetate (37.4 g, 190 mmol), tetrabutylammonium bromide (0.61 g, 1.9 mmol) and potassium carbonate (26.1 g, 190 mmol) in 100 mL of toluene was refluxed for 2.5 days. After cooling the mixture was dissolved in water and extracted with dichloromethane. The organic layers were dried over magnesium sulfate and concentrated. The residue was purified by column chromatography (eluent: hexanes/ethyl acetate) to give 4-(2,2-diethoxyethoxy) benzaldehyde as a colorless oil (2.60 g, 79%). The title compound was prepared from 4-(2,2-diethoxyethoxy) benzaldehyde and rhodanine according to the procedure of Intermediate 15 as a yellowish solid; 1H NMR (300 MHz, DMSO-d6) δ 1.14(t, J=7.1 Hz, 6 H), 3.50-3.80 (m, 4 H), 4.04(d, J=5.0 Hz, 2 H), 4.05-4.30(m, 2 H), 6.06 (t, J=5.0 Hz, 1 H), 7.14 (d, J=9.0 Hz, 2 H), 7.60 (d, J=9.0 Hz, 2 H), 7.63(s, 1 H); MS (ES) m/z:351.7 ((M−H)−, 100%); HRMS Calcd. for C16H20NO4S2 (MH+): 353.0775. Found: 353.0757.

Workup

  1. temperaturewas refluxed for 2.5 days
  2. temperatureAfter cooling the mixture
  3. extractionextracted with dichloromethane
  4. dry with materialThe organic layers were dried over magnesium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography (eluent: hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-fb4dcae5aa8e4d7b9e20264c1074210e
Source dataset
uspto-grants-2003_06
Patent number
US06583140B2

Reaction notes

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