Benzaldehyde → 3-Chloro-4-ethoxybenzoic acid

HRID 710412Notes

Reaction equation

HRID 710412 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[OH:10])[CH:5]=[O:6].[CH2:11](I)[CH3:12].C([O-])([O-])=[O:15].[K+].[K+].C(=O)C1C=CC=CC=1.[O-][Mn](=O)(=O)=O.[K+]>O.O1CCOCC1.O>[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[O:10][CH2:11][CH3:12])[C:5]([OH:15])=[O:6]

Participants

8

Reactant 5

HCID 240BenzaldehydeHCID 6340IodoethaneHCID 11430Potassium CarbonateHCID 170223-Chloro-4-hydroxybenzaldehydeHCID 516875Potassium Permanganate

Product 1

HCID 7209893-Chloro-4-ethoxybenzoic acidYield 83%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 218864351,4-Dioxane--water (1/1)Solvent

Procedure

A mixture of 3-chloro-4-hydroxybenzaldehyde (0.4 g, 2.55 mmol), EtI (0.31 ml) and K2CO3 (0.421 g; 3.1 mmol) was stirred overnight at room temperature. The mixture was diluted 100 ml with H2O and extracted with EtOAc (50 ml). The organic layer was separated and dried over MgSO4 and filtered. The filtrate was evaporated to dryness to give the crude product (0.41 g, 87%) used as such in next step. 1H-NMR (CDCl3) 1.49 (tr, 3H, J=6.96 Hz); 4.18 (q, 2H, J=6.99, 13.97 Hz); 6.98 (d, 1H, J=8.49 Hz); 7.72 (dd, 1H, J=1.94, 8.46 Hz); 7.87 (d, 1H, J=1.95 Hz); 9.82 (s, 1H). The above benzaldehyde (0.4 g 2.16 mmol) was dissolved in a mixture of dioxane: H2O (30:10) and to it KMnO4 (0.341 g; 2.16 mmol) was added at room temperature and the mixture was stirred for 1 h. The solvent was evaporated and the residue was diluted to 100 ml with EtOAc and the mixture was filtered through a silica gel bead. The filtrate was evaporated to dryness to give the title compound (0.36 g, 83%), as creamy solid. 1H-NMR (DMSO-d6) 2.44 (tr, 3H, J=6.99 Hz); 5.11 (q, 2H, J=13.95 Hz); 6.96 Hz); 7.88 (d, 1H, J=8.55 Hz), 8.9 (d, 1H, J=8.55 Hz); 9.5 (m, 1H).

Workup

  1. extractionextracted with EtOAc (50 ml)
  2. customThe organic layer was separated
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. customThe filtrate was evaporated to dryness
  6. customto give the crude product (0.41 g, 87%)
  7. additionwas added at room temperature
  8. stirringthe mixture was stirred for 1 h
  9. customThe solvent was evaporated
  10. additionthe residue was diluted to 100 ml with EtOAc
  11. filtrationthe mixture was filtered through a silica gel bead
  12. customThe filtrate was evaporated to dryness

Sources & evidence

ORD record
ord-463b5edd32204e1e811ac4aaa8ec34fb
Source dataset
uspto-grants-2015_11
Patent number
US09181182B2

Reaction notes

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