Sulfuric Acid → Tert-butyl 4-((methoxycarbonyl)methyl)benzoate

HRID 913242Notes

Reaction equation

HRID 913242 reaction equation
[CH3:1][O:2][C:3](=[O:14])[CH2:4][C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[CH:7][CH:6]=1.[CH3:15][C:16](=[CH2:18])[CH3:17].S(=O)(=O)(O)O>C(Cl)Cl>[CH3:1][O:2][C:3](=[O:14])[CH2:4][C:5]1[CH:13]=[CH:12][C:8]([C:9]([O:11][C:16]([CH3:18])([CH3:17])[CH3:15])=[O:10])=[CH:7][CH:6]=1

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 8255IsobutyleneHCID 138161444-(2-Methoxy-2-oxoethyl)benzoic acid

Product 1

HCID 57611856Tert-butyl 4-((methoxycarbonyl)methyl)benzoate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 4-(2-methoxy-2-oxoethyl)benzoic acid (0.87 g, 4.48 mmol) in methylene chloride (5 mL) was condensed isobutylene (approximately 20 mL) at −78° C. The solution was treated with 0.5 mL concentrated sulfuric acid and the solution was sealed in a stainless steel bomb and allowed to warm to ambient temperature for 6 hours. The solution was recooled to −78° C. and opened. The reaction was partitioned between 0.1M sodium hydroxide solution and diethyl ether. The organics were dried over sodium sulfate, filtered and evaporated. Purification by flash chromatography (0-35% ethyl acetate/hexanes) gave tert-butyl 4-(2-methoxy-2-oxoethyl)benzoate as a clear oil. 1H NMR (600 MHz, DMSO-d6) δ 7.81 (d, J=8.21 Hz, 2H), 7.35 (d, J=8.51 Hz, 2H), 3.75 (s, 2H), 3.56 (s, 3H), 1.51 (s, 9H); ESIMS calcd 251.1 (M++H), found 251.0 (M++H).

Workup

  1. customwas recooled to −78° C.
  2. customThe reaction was partitioned between 0.1M sodium hydroxide solution and diethyl ether
  3. dry with materialThe organics were dried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customPurification by flash chromatography (0-35% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-5bbb0c3efd744c64aa82e5ef8e54d520
Source dataset
uspto-grants-2011_09
Patent number
US08026260B2

Reaction notes

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