Ethanethiol → 11-(Ethylthio)undecanoic acid

HRID 1461004Notes

Reaction equation

HRID 1461004 reaction equation
Br[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][C:12]([OH:14])=[O:13].[CH2:15]([SH:17])[CH3:16].[OH-].[K+]>C(O)C.C(OCC)(=O)C>[CH2:15]([S:17][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][C:12]([OH:14])=[O:13])[CH3:16]

Participants

6

Reactant 3

HCID 6343EthanethiolHCID 14797Potassium HydroxideHCID 1781211-Bromoundecanoic acid

Product 1

HCID 12209911-(Ethylthio)undecanoic acidYield 8.2%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

11-Bromoundecanoic acid (1 g, 3.77 mmol, Aldrich) was added to a solution of ethanethiol (0.279 mL, 3.77 mmol, Aldrich) and potassium hydroxide (0.486 g, 8.66 mmol) in absolute ethanol (40 mL) and refluxed for 5 hr under a nitrogen atmosphere. After cooling and acidification with HC1, solvent was removed under reduced pressure to give a white solid. The solid was dissolved in ethyl acetate and extracted with water. The organic phase was dried over sodium sulfate, filtered and the solvent removed under reduced pressure. The product was purified by silica column chromatography using increasing concentrations of ethyl acetate in hexane for elution. The product eluted at 25% ethyl acetate/hexane. Solvent was removed under reduced pressure to yield 11-(ethylthio)-undecanoic acid (76 mg, 8%), mp 58-61° C.; 1H NMR (300 MHz, CDC13) δ 1.24 (t, 3H, J=7.4, CH3), 1.20-1.40 (bm, 12 H, methylene envelope), 1.48-1.67 (bm, 4H, S-CH2 -CH2COO-CH2 -CH2), 2.33 (t, 2H, J=7.5, CH2 -COOH), 2.49 (t, 2H, J=7.4, S-CH2 -CH2), 2.51 (q, 2H, J=7.4, S-CH2 -CH2), 10.5 (br, 1H, COOH); 13C NMR (75.4 MHz, CDC13) δ 14.88, 24.70, 25.98, 28.97, 29.08, 29.24*, 29.38, 29.48, 29.69, 31.73, 34.11, 180.05; MS, m/z 246 (M+, 50), 217 (COOH(CH2)10S+, 7), 199 (100), 181 (7), 167 (7), 149 (6), 117 (7), 101 (9), 97 (9), 87 (14), 83 (18), 75 (54), 69 (29), 62 (18), 55 (37).

Workup

  1. temperaturerefluxed for 5 hr under a nitrogen atmosphere
  2. temperatureAfter cooling
  3. customacidification with HC1, solvent was removed under reduced pressure
  4. customto give a white solid
  5. extractionextracted with water
  6. dry with materialThe organic phase was dried over sodium sulfate
  7. filtrationfiltered
  8. customthe solvent removed under reduced pressure
  9. customThe product was purified by silica column chromatography
  10. temperatureusing increasing concentrations of ethyl acetate in hexane
  11. washfor elution
  12. washThe product eluted at 25% ethyl acetate/hexane
  13. customSolvent was removed under reduced pressure

Sources & evidence

ORD record
ord-d47a7a46e5f941279d80d77ee719061c
Source dataset
uspto-grants-1991_12
Patent number
US05073571

Reaction notes

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