4-Hydroxybenzaldehyde → 4-Formylphenyl 4-(heptyloxy)benzoate

HRID 923551Notes

Reaction equation

HRID 923551 reaction equation
[CH2:1]([O:8][C:9]1[CH:17]=[CH:16][C:12]([C:13]([OH:15])=[O:14])=[CH:11][CH:10]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH3:7].C(Cl)(=O)C(Cl)=O.O[C:25]1[CH:32]=[CH:31][C:28]([CH:29]=[O:30])=[CH:27][CH:26]=1>C(Cl)Cl.CN(C=O)C>[CH2:1]([O:8][C:9]1[CH:17]=[CH:16][C:12]([C:13]([O:15][C:25]2[CH:32]=[CH:31][C:28]([CH:29]=[O:30])=[CH:27][CH:26]=2)=[O:14])=[CH:11][CH:10]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH3:7]

Participants

6

Reactant 3

HCID 1264-HydroxybenzaldehydeHCID 65578Oxalyl chlorideHCID 85154p-Heptoxybenzoic acid

Product 1

HCID 17122224-Formylphenyl 4-(heptyloxy)benzoateYield 67.8%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

Prepared using General Procedure 2: To a stirring solution of 4-(heptyloxy)benzoic acid (1.0 g, 4.23 mmol) in DCM (10 mL) were added DMF (1 drop) and oxalyl chloride (0.47 mL, 5.5 mmol). The reaction mixture was stirred at room temperature for 1 h. Solvent was evaporated under high vacuum. DCM (10 mL) was added and the reaction mixture evaporated again to dryness. The residue was dissolved in DCM (10 mL) then added to a stirring mixture of 4-hydroxy benzaldehyde (0.56 g, 4.6 mmol) and TEA (0.706 mL, 5.07 mmol) in DCM (5 mL) at 0° C. The reaction mixture was allowed to stir at room temperature for 2 h. The reaction mixture was quenched with NaHCO3 (10 mL). The aqueous phase was extracted with DCM and the combined organic phases were dried over MgSO4 and concentrated to give 977 mg (62%) of 4-formylphenyl 4-(heptyloxy)benzoate INT-12 which was used in the next step without purification. LCMS-ESI (m/z) calculated for C21H24O4: 340; found 341 [M+H]+, tR=11.91 min (Method 2). 1H NMR (400 MHz, DMSO) δ 10.03 (s, 1H), 8.19-7.91 (m, 4H), 7.63-7.41 (m, 2H), 7.24-7.01 (m, 2H), 4.09 (t, J=6.5 Hz, 2H), 1.86-1.62 (m, 2H), 1.50-1.07 (m, 8H), 0.87 (t, J=6.9 Hz, 3H).

Workup

  1. customPrepared
  2. customSolvent was evaporated under high vacuum
  3. additionDCM (10 mL) was added
  4. customthe reaction mixture evaporated again to dryness
  5. dissolutionThe residue was dissolved in DCM (10 mL)
  6. stirringto stir at room temperature for 2 h
  7. customThe reaction mixture was quenched with NaHCO3 (10 mL)
  8. extractionThe aqueous phase was extracted with DCM
  9. dry with materialthe combined organic phases were dried over MgSO4
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-459a2e39ca9d4a8cb4422878d9165d52
Source dataset
uspto-grants-2016_03
Patent number
US09278910B2

Reaction notes

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