4-Hydroxybenzaldehyde → m-PEG4-benzaldehyde

HRID 2245205Notes

Reaction equation

HRID 2245205 reaction equation
Cl[CH2:2][CH2:3][O:4][CH2:5][CH2:6][O:7][CH2:8][CH2:9][O:10][CH3:11].[OH:12][C:13]1[CH:20]=[CH:19][C:16]([CH:17]=[O:18])=[CH:15][CH:14]=1.C([O-])([O-])=O.[K+].[K+].C1OCCOCCOCCOCCOCCOC1>C1COCC1.O>[O:12]([C:13]1[CH:20]=[CH:19][C:16]([CH:17]=[O:18])=[CH:15][CH:14]=1)[CH2:2][CH2:3][O:4][CH2:5][CH2:6][O:7][CH2:8][CH2:9][O:10][CH3:11]

Participants

7

Reactant 4

HCID 1264-HydroxybenzaldehydeHCID 11430Potassium CarbonateHCID 2855718-Crown-6HCID 5478521-Chloro-3,6,9-trioxadecane

Product 1

HCID 10061559m-PEG4-benzaldehydeYield 71.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

Chloride 603 (26 g, 0.14 mol, 1.3 equiv) and p-hydroxybenzaldehyde (13 g, 0.11 mol, 1 equiv) were dissolved in dry THF (40 mL). K2CO3 (15 g, 0.11 mol, 1 equiv) was added followed by 18-crown-6 (3.0 g, 11 mmol, 0.11 equiv) and KI (0.20 g, 1.2 mmol, 0.01 equiv). The reaction mixture was stirred at reflux for 48 h. The resulting mixture was cooled to room temperature, and water (200 mL) was added. The product was extracted with 3×350 mL portions of ethyl acetate and the combined organic layers were dried and concentrated. The oil was loaded onto a silica gel column and eluted with a 1:9 mixture of ethyl acetate/hexane, followed by a ratio of 1:4, 3:7, 4:1 of ethyl acetate/hexane and finally washed with ethyl acetate to afford 21 g (70%) of 604 as a clear oil. IR(cm−1): 1697 (s), 1165 (s). 1H NMR (400, CDCl3): δ 3.36 (s, 3), 3.54 (t, 2, J=4.6), 3.63-3.68 (m, 4), 3.72-3.75 (m, 2), 3.88 (t, 2, J=4.8), 4.20 (t, 2, J=4.8), 7.01 (d, 2, J=8.8), 7.82 (d, 2, J=8.8), 9.87 (s, 1). 13C NMR (CDCl3): δ 58.86, 67.59, 69.29, 70.40, 70.47, 70.71, 71.73, 114.71, 129.84, 131.76, 163.69, 190.63. Calcd: [M+H]+ (C14H21O5) m/z=269.13889. Found FAB-HRMS: [M+H]+ m/z=269.134487. Anal. Calcd. for C14H20O5: C, 62.67; H, 7.51. Found: C, 62.47; H, 7.74.

Workup

  1. temperatureat reflux for 48 h
  2. extractionThe product was extracted with 3×350 mL portions of ethyl acetate
  3. customthe combined organic layers were dried
  4. concentrationconcentrated
  5. washeluted with a 1:9 mixture of ethyl acetate/hexane
  6. washfinally washed with ethyl acetate

Sources & evidence

ORD record
ord-6b01c3f9df384b2bb9f0fccac534bb08
Source dataset
uspto-grants-2010_03
Patent number
US07683041B2

Reaction notes

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