2-Methyl-2-butene → 5-(1,1-Dimethylethyl)salicylic acid

HRID 2425579Notes

Reaction equation

HRID 2425579 reaction equation
[C:1]([C:5]1[CH:6]=[CH:7][C:8]([OH:13])=[C:9]([CH:12]=1)[CH:10]=[O:11])([CH3:4])([CH3:3])[CH3:2].CC(=CC)C.P([O-])(O)(O)=[O:20].[Na+].Cl([O-])=O.[Na+]>O1CCCC1.O.C(OCC)(=O)C.C(O)(C)(C)C>[C:1]([C:5]1[CH:6]=[CH:7][C:8]([OH:13])=[C:9]([CH:12]=1)[C:10]([OH:20])=[O:11])([CH3:4])([CH3:2])[CH3:3]

Participants

9

Reactant 4

HCID 105532-Methyl-2-buteneHCID 14750905-tert-ButylsalicylaldehydeHCID 23668197Sodium ChloriteHCID 23672064Monosodium phosphate

Product 1

HCID 852815-(1,1-Dimethylethyl)salicylic acidYield 128.7%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

5-tert-Butyl-2-hydroxy-benzaldehyde (1.4 g, 6.0 mmol, prepared according to Smith W. E. J. Org. Chem. 1972, 37, 3972-3973) was taken up in 30 mL of a 2M solution of 2-methyl-2-butene in tetrahydrofuran. t-Butanol (30 mL) was added. Sodium dihydrogenphosphate (2.6 g, 18.8 mmol) and sodium chlorite (1.4 g, 12.3 mmol) were then added as a solution in 12 mL of water. The reaction mixture was stirred at room temperature for 2 h. It was diluted with ethyl acetate and washed with 1N hydrochloric acid. The aqueous layers were extracted three times with ethyl acetate. The combined organic layers were washed with a saturated solution of Na2S2O3, brine, and dried over anhydrous magnesium sulfate. The solids were filtered off, and the filtrate was concentrated to give 5-tert-butyl-2-hydroxy-benzoic acid (1.5 g, quant.), which was used in the next step without further purification.

Workup

  1. washwashed with 1N hydrochloric acid
  2. extractionThe aqueous layers were extracted three times with ethyl acetate
  3. washThe combined organic layers were washed with a saturated solution of Na2S2O3, brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationThe solids were filtered off
  6. concentrationthe filtrate was concentrated

Sources & evidence

ORD record
ord-b9740e3698394c7f9db485794a951faf
Source dataset
uspto-grants-2011_06
Patent number
US07964724B2

Reaction notes

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