Acetone → 4-{[3-Methyl-6-(methyloxy)-2-phenyl-1-naphthalenyl]oxy}benzoic acid

HRID 1992824Notes

Reaction equation

HRID 1992824 reaction equation
[CH3:1][C:2]1[C:3]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[C:4]([O:14][C:15]2[CH:22]=[CH:21][C:18]([CH:19]=[O:20])=[CH:17][CH:16]=2)[C:5]2[C:10]([CH:11]=1)=[CH:9][C:8]([O:12][CH3:13])=[CH:7][CH:6]=2.CC(C)=[O:31].S(=O)(=O)(O)N.Cl([O-])=O.[Na+]>O>[CH3:1][C:2]1[C:3]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[C:4]([O:14][C:15]2[CH:22]=[CH:21][C:18]([C:19]([OH:31])=[O:20])=[CH:17][CH:16]=2)[C:5]2[C:10]([CH:11]=1)=[CH:9][C:8]([O:12][CH3:13])=[CH:7][CH:6]=2

Participants

6

Reactant 4

HCID 180AcetoneHCID 5987Sulfamic AcidHCID 23668197Sodium ChloriteHCID 860871594-[(6-Methoxy-3-methyl-2-phenyl-1-naphthyl)oxy]benzaldehyde

Product 1

HCID 685346784-{[3-Methyl-6-(methyloxy)-2-phenyl-1-naphthalenyl]oxy}benzoic acidYield 80%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To 4-{[3-methyl-6-(methyloxy)-2-phenyl-1-naphthalenyl]oxy}benzaldehyde (8) (0.565 g, 1.53 mmol) was added a 2:1 acetone:H2O solution (21 mL). The turbid solution was cooled in an ice-water bath and sulfamic acid (0.158 g, 1.63 mmol, 1.06 eq) was added portionwise over several minutes. The reaction mixture was stirred for 5 min and sodium chlorite (80% tech. Grade) (0.185 g, 1.64 mmol, 1.07 eq) was added portionwise. The reaction mixture was stirred for 30 min. The acetone was removed in vacuo and the reaction mixture was partitioned between H2O and CH2Cl2. The organic phase was separated and the aqueous phase was extracted with CH2Cl2. The organic extracts were combined, dried over MgSO4, filtered, and the filtrate was concentrated to give the crude product. The crude product was purified by flash chromatography over SiO2 with CH2Cl2:MeOH (94:6) to give 0.47 g (80%) of the compound 16 as a gold-yellow amorphous solid. 1H NMR (400 MHz; DMSO-d6): δ 2.17 (s, 3H), 3.86 (s, 3H), 6.64 (d, J=8.7 Hz, 2H), 7.07 (dd, J=2.6 Hz, 9.2 Hz, 1H), 7.16 (m, 2H), 7.21-7.30 (m, 3H), 7.35 (d, J=2.4 Hz, 1H), 7.52 (d, J=9.1 Hz, 1H), 7.70 (m, 3H), 12.63 (br s, 1H). AP LRMS m/z 385 (M+H)+.

Workup

  1. temperatureThe turbid solution was cooled in an ice-water bath
  2. stirringThe reaction mixture was stirred for 30 min
  3. customThe acetone was removed in vacuo
  4. customthe reaction mixture was partitioned between H2O and CH2Cl2
  5. customThe organic phase was separated
  6. extractionthe aqueous phase was extracted with CH2Cl2
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationthe filtrate was concentrated
  10. customto give the crude product
  11. customThe crude product was purified by flash chromatography over SiO2 with CH2Cl2:MeOH (94:6)

Sources & evidence

ORD record
ord-9b93d3cb8fbd4c8bb6aacd618da624cf
Source dataset
uspto-grants-2010_01
Patent number
US07649093B2

Reaction notes

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