Ethylene Glycol → 3-(4-methoxyphenyl)sulfanylbenzoic Acid

HRID 2253522Notes

Reaction equation

HRID 2253522 reaction equation
C(=O)([O-])[O-].[K+].[K+].I[C:8]1[CH:9]=[C:10]([CH:14]=[CH:15][CH:16]=1)[C:11]([OH:13])=[O:12].C(O)CO.[CH3:21][O:22][C:23]1[CH:28]=[CH:27][C:26]([SH:29])=[CH:25][CH:24]=1.Cl>O.C(OCC)(=O)C.CC(O)C>[CH3:21][O:22][C:23]1[CH:28]=[CH:27][C:26]([S:29][C:8]2[CH:9]=[C:10]([CH:14]=[CH:15][CH:16]=2)[C:11]([OH:13])=[O:12])=[CH:25][CH:24]=1

Participants

9

Reactant 5

HCID 174Ethylene GlycolHCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 120603-Iodobenzoic acidHCID 127654-Methoxybenzenethiol

Product 1

HCID 112424193-(4-methoxyphenyl)sulfanylbenzoic AcidYield 85%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3776IsopropanolSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

Cu(I) iodide (10 mg, 0.05 mmol), potassium carbonate (414 mg, 3.0 mmol) and 3-iodobenzoic acid (248 mg, 1.0 mmol) were charged into a screw-capped test tube with Teflon-lining. The tube was evacuated and backfilled with argon (3 cycles). 2-Propanol (1.0 mL, bench grade solvent without degassing and pre-drying), ethylene glycol (111 μL, 2.0 mmol, bench grade solvent) and 4-methoxythiophenol (123 μL, 1.0 mmol) were added by syringes at room temperature. The tube was heated to 80° C. and stirred for 24 hours. The reaction mixture was then allowed to reach room temperature. Ethyl acetate (˜5 mL), water (˜10 mL) and dil. HCl were added to reach pH 3-4. The reaction mixture was extracted with ethyl acetate (2×10 mL) and CH2Cl2 (2×10 mL). The combined organic phase was passed through a short pad of silica (0.5 cm diameter×1 cm height). Solvent was removed and the yellow residue was redissolved in minimum amount of CH2Cl2. Hexane was added slowly and the solution was stand overnight at room temperature. White crystal was obtained as the titled product (221 mg, 85% yield). Rf=0.2 (hexane/ethyl acetate=2/1) (Note: same Rf value as the starting material). Melting point; 121-123° C. 1H NMR (CDCl3, 300 MHz) δ 10.68 (brs, 1 H), 7.86 (s, 1 H), 7.82 (dt, 1 H, J=1.8 Hz, 6.6 Hz), 7.42 (dt, 2 H, J=2.1 Hz, 8.7 Hz), 7.28-7.31 (m, 2 H), 6.90 (dt, 2 H, J=2.1 Hz, 8.7 Hz), 3.83 (s, 3 H). 13C NMR (CDCl3, 75 MHz) δ 172.0, 160.3, 140.3, 136.1, 132.8, 130.2, 129.2, 129.1, 127.4, 123.1, 55.7. IR (neat, cm−1) 2964 (broad), 2943, 2902, 2875, 2856, 2840, 2813, 2360, 2342, 1688. MS (EI) m/z (relative intensity) 260 (100). Anal. Cald. for C14H12O3S, Cald. C: 64.60, H: 4.65; Found C: 64.52, H: 4.68.

Workup

  1. customThe tube was evacuated
  2. customto reach room temperature
  3. extractionThe reaction mixture was extracted with ethyl acetate (2×10 mL) and CH2Cl2 (2×10 mL)
  4. customSolvent was removed
  5. dissolutionthe yellow residue was redissolved in minimum amount of CH2Cl2
  6. additionHexane was added slowly
  7. waitthe solution was stand overnight at room temperature

Sources & evidence

ORD record
ord-e2199bbc784c48689fb4fa228cdef2fa
Source dataset
uspto-grants-2008_01
Patent number
US07323608B2

Reaction notes

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