4-Hydroxybenzaldehyde → Ethyl 6-(4-formylphenoxy)hexanoate

HRID 1797380Notes

Reaction equation

HRID 1797380 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.[CH2:10]([O:12][C:13](=[O:20])[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18]Br)[CH3:11].C([O-])([O-])=O.[K+].[K+]>CN(C=O)C>[CH2:10]([O:12][C:13](=[O:20])[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][O:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1)[CH3:11]

Participants

5

Reactant 3

HCID 1264-HydroxybenzaldehydeHCID 11430Potassium CarbonateHCID 117544Ethyl 6-bromohexanoate

Product 1

HCID 64294088Ethyl 6-(4-formylphenoxy)hexanoate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of 4-hydroxybenzaldehyde 1 (3, 0.60 kg, 4.91 mol), ethyl-6-bromohexanoate 2 (4, 1.10 kg, 4.91 mol), and K2CO3 (1.36 kg, 9.83 mol) in DMF (2 L) was stirred at 50° C. for 20 h. The mixture was filtered to remove remaining K2CO3. The resulting solution was concentrated in vacuo, diluted with EtOAc (3 L) and subsequently washed with saturated aqueous NaCl (3×1.5 L). The organic layer was dried (MgSO4), filtered and concentrated in vacuo to give an off white solid (3, 1.23 kg, 4.66 mol, 95%) with no need for further purification: M.p.: 33-35 ° C. 1H NMR (400 MHz, CDCl3) δ=9.87 (s, 1H), 7.81 (d, J=8.7, 2H), 6.97 (d, J=8.7, 2H), 4.12 (q, J=7.1, 2H), 4.04 (t, J=6.4, 2H), 2.33 (t, J=7.4, 2H), 1.82 (m, 2H), 1.69 (m, 2H), 1.53 (m, 2H), 1.25 (t, J=7.1, 3H); 13C NMR (400 MHz, CDCl3) δ=191.0, 173.7, 164.3, 132.1 (2C), 130.1, 114.9 (2C), 68.3, 60.5, 34.4, 29.0, 25.8, 24.8, 14.4; IR (film) ν=2941, 1719, 1688, 1595, 1579, 1509, 1466, 1392, 1307, 1252, 1213, 1155, 1108, 1030, 999, 832 cm−1; HRMS (MALDI-FTMS) m/z 287.1254 (287.1254 calculated for C15H20O4Na, (M+Na)+).

Workup

  1. filtrationThe mixture was filtered
  2. customto remove
  3. concentrationThe resulting solution was concentrated in vacuo
  4. additiondiluted with EtOAc (3 L)
  5. washsubsequently washed with saturated aqueous NaCl (3×1.5 L)
  6. dry with materialThe organic layer was dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give an off white solid (3, 1.23 kg, 4.66 mol, 95%) with no need
  10. customfor further purification

Sources & evidence

ORD record
ord-67095eb8ccaa48f88603e0c23c41efc0
Source dataset
uspto-grants-2006_04
Patent number
US07034147B2

Reaction notes

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