Sulfuric Acid → tert-Butyl 3-acetylbenzoate

HRID 2300769Notes

Reaction equation

HRID 2300769 reaction equation
[O-]S([O-])(=O)=O.[Mg+2].OS(O)(=O)=O.[C:12]([C:15]1[CH:16]=[C:17]([CH:21]=[CH:22][CH:23]=1)[C:18]([OH:20])=[O:19])(=[O:14])[CH3:13].[C:24](O)([CH3:27])([CH3:26])[CH3:25].C([O-])(O)=O.[Na+]>C(Cl)Cl>[C:12]([C:15]1[CH:16]=[C:17]([CH:21]=[CH:22][CH:23]=1)[C:18]([O:20][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:19])(=[O:14])[CH3:13]

Participants

7

Reactant 5

HCID 1118Sulfuric AcidHCID 6386tert-ButanolHCID 24083Sulfuric acid magnesium salt (1:1)HCID 2203243-Acetylbenzoic acidHCID 516892Sodium Bicarbonate

Product 1

HCID 46941403tert-Butyl 3-acetylbenzoateYield 71.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

In a dry flask under nitrogen, MgSO4 (23.3 mmol) was suspended in CH2Cl2 (23 mL), the mixture was stirred vigorously as concentrated H2SO4 (5.85 mmol) was added dropwise. The resultant mixture was stirred for 20 min and 3-acetylbenzoic acid (5.84 mmol) was added in one portion followed by the dropwise addition of tert-butanol (29.3 mmol). This mixture was stoppered tightly and stirred at room temperature for 114 hours. Worked up by adding 100 mL saturated aqueous NaHCO3 and extracting 3× with 50 mL diethyl ether. The combined extracts were washed with brine, dried over MgSO4 and concentrated. Purified the residue by silica gel chromatography (90:10 hexanes:ethyl acetate) to yield 924 mg of the title compound. 1H NMR (500 MHz, CDCl3): δ 8.56 (m, 1H); 8.20 (m, 1H); 8.14 (m, 1H); 7.55 (t, J=7.6 Hz, 1H); 2.67 (s, 3H); 1.64 (s, 9H).

Workup

  1. additionwas added dropwise
  2. extractionextracting 3× with 50 mL diethyl ether
  3. washThe combined extracts were washed with brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. customPurified the residue by silica gel chromatography (90:10 hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-e1f8fbb219024e19a444de9c99b0d040
Source dataset
uspto-grants-2002_12
Patent number
US06498165B1

Reaction notes

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