Dimethylformamide → 6-Methoxy-5-formyl-2-naphthoic acid methyl ester

HRID 23227Notes

Reaction equation

HRID 23227 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:14]=[CH:13][C:12]2[C:7](=[CH:8][CH:9]=[C:10]([O:15][CH3:16])[CH:11]=2)[CH:6]=1)=[O:4].CN([CH:20]=[O:21])C.O=P(Cl)(Cl)Cl.C([O-])([O-])=O.[Na+].[Na+]>>[CH3:1][O:2][C:3]([C:5]1[CH:14]=[CH:13][C:12]2[C:7](=[CH:8][CH:9]=[C:10]([O:15][CH3:16])[C:11]=2[CH:20]=[O:21])[CH:6]=1)=[O:4]

Participants

5

Reactant 4

HCID 6228DimethylformamideHCID 10340Sodium CarbonateHCID 24813Phosphorus oxychlorideHCID 604020Methyl 6-methoxy-2-naphthoate

Product 1

HCID 118068606-Methoxy-5-formyl-2-naphthoic acid methyl esterYield 63%

Conditions

Temperature
80 °C

Procedure

To a stirred solution of 6-methoxy-2-naphthoic acid methyl ester (10.3 g, 47.6 mmol) in DMF (36.9 mL, 476 mmol) at 5° C. was added POCl3 (44.4 mL, 476 mmol) dropwise. The reaction mixture was heated to 80° C. After 2 days at this temperature, the reaction was poured into ice/H2O (400 mL). The solution was made basic with addition of solid Na2CO3. The resulting mixture was extracted with EtOAc (2×400 mL). The organic layer was washed with brine (80 mL) and dried (MgSO4). After concentration, the residue was recrystallized from MeOH:H2O to afford the product (7.30 g, 63%) as a solid; 1H NMR (DMSO-d6) δ3.91 (s, 3H), 4.11 (s, 3H), 7.72 (d, J=9.3 Hz, 1H), 8.10 (dd, J=2.0, 9.0 Hz, 1H), 8.53 (d, J=9.2 Hz, 1H), 8.66 (d, J=1.8 Hz, 1H), 9.17 (d, J=9.0 Hz, 1H), 10.76 (s, 1H).

Workup

  1. extractionThe resulting mixture was extracted with EtOAc (2×400 mL)
  2. washThe organic layer was washed with brine (80 mL)
  3. dry with materialdried (MgSO4)
  4. concentrationAfter concentration
  5. customthe residue was recrystallized from MeOH

Sources & evidence

ORD record
ord-f1d8492abde248a4a1a567b986cff609
Source dataset
uspto-grants-2005_02
Patent number
US06849761B2

Reaction notes

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