Acetic Acid → 2-(Benzenesulfonyl)pyridine

HRID 1620797Notes

Reaction equation

HRID 1620797 reaction equation
Cl[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.[C:8]1([SH:14])[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.C([O-])([O-])=[O:16].[K+].[K+].C(O)(=O)C.[O-]Cl.[Na+].[OH-:28].[Na+]>O.CN(C=O)C>[C:8]1([S:14]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=2)(=[O:16])=[O:28])[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

9

Reactant 6

HCID 176Acetic AcidHCID 7969ThiophenolHCID 79772-ChloropyridineHCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 23665760Sodium Hypochlorite

Product 1

HCID 2898292-(Benzenesulfonyl)pyridineYield 86%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
40 °C

Procedure

Charge 2-chloropyridine (75 mL, 790 mmol), thiophenol (90 mL, 852 mmol), and DMF (450 mL) to a 2 L flask. Add K2CO3 (134.6 g, 962 mmol), then heat to 110° C. and stir for 18 hours. Filter the mixture, then rinse the waste cake with DMF (195 mL). The combined crude sulfide solution and rinses are transferred to a 5-L flask, and the waste filter cake is discarded. Glacial acetic acid (57 mL, 995 mmol) is added to the filtrate, then the solution is heated to 40° C., and 13 wt % NaOCl solution (850 mL, 1.7 mol) is added over 2 hours. After the reaction is complete, water (150 mL) is added, then the pH of the mixture adjusted to 9 with 20% (w/v) NaOH solution (250 mL). The resulting slurry is cooled to <5° C., stirred for 1.5 h, then filtered, and the cake washed with water (3×200 mL). The product wetcake is dried in a 55° C. vacuum oven to provide 2-benzene-sulfonyl pyridine (149 g, 676 mmol) in 86% yield: 1H NMR (500 MHz, CDCl3) δ 8.66 (d, J=5.5 Hz, 1H), 8.19 (d, J=7.7 Hz, 1H), 8.05 (m, 2H), 7.92 (ddd, J=9.3, 7.7, 1.6 Hz, 1H), 7.60 (m, 1H), 7.54 (m, 2H), 7.44 (m, 1H); IR (KBr) 788, 984, 1124, 1166, 1306, 1424, 1446, 1575, 3085 cm−1; MS (TOF) m/z 220.0439 (220.0427 calcd for C11H10NO2S, MH); Anal. calcd for C11H9NO2S: C, 60.26; H, 4.14; N, 6.39; S, 14.62. Found: C, 60.40; H, 4.02; N, 6.40; S, 14.76.

Workup

  1. filtrationFilter the mixture
  2. washrinse the waste cake with DMF (195 mL)
  3. customare transferred to a 5-L flask
  4. filtrationthe waste filter cake
  5. temperatureThe resulting slurry is cooled to <5° C.
  6. stirringstirred for 1.5 h
  7. filtrationfiltered
  8. washthe cake washed with water (3×200 mL)
  9. customThe product wetcake is dried in a 55° C. vacuum oven

Sources & evidence

ORD record
ord-304fb55ef10b40a78562f8eb5a056051
Source dataset
uspto-grants-2014_07
Patent number
US08772496B2

Reaction notes

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