tert-Butyl acrylate → 3-((3-Tert-butoxy-3-oxopropylthio)methyl)benzoic acid

HRID 1407949Notes

Reaction equation

HRID 1407949 reaction equation
[SH:1][CH2:2][C:3]1[CH:4]=[C:5]([CH:9]=[CH:10][CH:11]=1)[C:6]([OH:8])=[O:7].[C:12]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])(=[O:15])[CH:13]=[CH2:14].C1CCN2C(=NCCC2)CC1>C(#N)C>[C:17]([O:16][C:12](=[O:15])[CH2:13][CH2:14][S:1][CH2:2][C:3]1[CH:4]=[C:5]([CH:9]=[CH:10][CH:11]=1)[C:6]([OH:8])=[O:7])([CH3:20])([CH3:19])[CH3:18]

Participants

5

Reactant 3

HCID 15458tert-Butyl acrylateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 113211893-(mercaptomethyl)benzoic acid

Product 1

HCID 665867133-((3-Tert-butoxy-3-oxopropylthio)methyl)benzoic acid

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

Into a 500-mL round-bottom flask, was placed a solution of 3-(mercaptomethyl)benzoic acid (12 g, 71.43 mmol, 1.00 equiv) in acetonitrile (200 mL), and tert-butyl acrylate (60 mL), DBU (21.7 g, 142.76 mmol, 2.00 equiv). The resulting solution was stirred overnight at 80° C. in an oil bath. The resulting mixture was concentrated under vacuum. The resulting solution was diluted with 200 mL of water and adjusted to pH 2˜3 with 10% hydrochloric acid. The resulting solution was extracted with 3×200 mL of ethyl acetate and the organic layers combined. The mixture was dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was applied onto a silica gel column and eluted with petroleum ether/ethyl acetate (50:1). This resulted in 10.5 g (47%) of 3-((3-tert-butoxy-3-oxopropylthio)methyl)benzoic acid as red oil. 1H-NMR (300 MHz, CDCl3, ppm): δ 8.08 (s, 1H), 8.04 (d, J=7.8 Hz, 1H), 7.62 (d, J=7.8 Hz, 1H), 7.46 (t, 1H), 3.81 (s, 2H), 2.68 (t, 2H), 2.50 (t, 2H), 1.48 (s, 9H). MS (ES, m/z): 295 [M−H]—.

Workup

  1. customInto a 500-mL round-bottom flask, was placed
  2. concentrationThe resulting mixture was concentrated under vacuum
  3. additionThe resulting solution was diluted with 200 mL of water
  4. extractionThe resulting solution was extracted with 3×200 mL of ethyl acetate
  5. dry with materialThe mixture was dried over anhydrous sodium sulfate
  6. concentrationconcentrated under vacuum
  7. washeluted with petroleum ether/ethyl acetate (50:1)
  8. customThis resulted in 10.5 g (47%) of 3-((3-tert-butoxy-3-oxopropylthio)methyl)benzoic acid as red oil

Sources & evidence

ORD record
ord-1a3ee7f631bf44debb1a9860e67adccb
Source dataset
uspto-grants-2014_12
Patent number
US08916569B2

Reaction notes

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