Sulfuric Acid → HCID 9861204, compound

HRID 333009Notes

Reaction equation

HRID 333009 reaction equation
[CH3:1][S:2]([O:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[O:12][CH3:13])(=[O:4])=[O:3].[CH3:14][C:15]([CH3:20])=[CH:16][C:17]([OH:19])=[O:18].S(=O)(=O)(O)O>>[CH3:13][O:12][C:7]1[CH:8]=[CH:9][C:10]([C:15]([CH3:20])([CH3:14])[CH2:16][C:17]([OH:19])=[O:18])=[CH:11][C:6]=1[O:5][S:2]([CH3:1])(=[O:4])=[O:3]

Participants

4

Reactant 3

HCID 1118Sulfuric AcidHCID 109313-Methyl-2-butenoic acidHCID 1729096HCID 1729096, compound

Product 1

HCID 9861204HCID 9861204, compoundYield 23.4%

Conditions

Temperature
0 °C

Procedure

To a mixture of 2-methoxyphenyl methanesulfonate (Example 50b) (82 g, 406.4 mmol) and 3-methylbut-2-enoic acid (20.3 g, 203.2 mmol), was added concentrate sulfuric acid (11 mL, 96%, 206.3 mmol) at 0° C. The reaction mixture was stirred at 0° C. for 15 min, then heated to 70° C. and stirred under nitrogen overnight. Upon completion, the reaction was cooled to room temperature, quenched with ice water (500 mL) and extracted with ether (1×). The phases were separated, and the organic layer was washed with 2N NaOH (1×). The combined aqueous layers were acidified to pH 1 with 12N HCl at 0° C. and extracted with ether (1×). The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure to give the title compound as a red-brown oil (14.4 g, contained <20% 3-methylbut-2-enoic acid) 1H NMR (400 MHz, DMSO-d6) δ 1.33 (s, 6H), 2.53 (s, 2H), 3.31 (s, 3H), 3.79 (s, 3H), 7.08-7.31 (m, 3H), 11.87 (s, 1H).

Workup

  1. additionwas added
  2. temperatureheated to 70° C.
  3. stirringstirred under nitrogen overnight
  4. temperatureUpon completion, the reaction was cooled to room temperature
  5. customquenched with ice water (500 mL)
  6. extractionextracted with ether (1×)
  7. customThe phases were separated
  8. washthe organic layer was washed with 2N NaOH (1×)
  9. customwere acidified to pH 1 with 12N HCl at 0° C.
  10. extractionextracted with ether (1×)
  11. washThe organic layer was washed with brine
  12. dry with materialdried over Na2SO4
  13. filtrationfiltered
  14. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-0b4829aba08d4e4190379ea7a164e247
Source dataset
uspto-grants-2014_11
Patent number
US08877922B2

Reaction notes

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