Hydrogen Sulfide → 4-Hydroxy-3-propylbenzenecarbothioamide

HRID 603511Notes

Reaction equation

HRID 603511 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[CH2:10][CH2:11][CH3:12].[SH2:13].C(NCC)C>CN(C=O)C>[OH:1][C:2]1[CH:9]=[CH:8][C:5]([C:6](=[S:13])[NH2:7])=[CH:4][C:3]=1[CH2:10][CH2:11][CH3:12]

Participants

5

Reactant 3

HCID 402Hydrogen Sulfide3×HCID 8021DiethylamineHCID 139876694-hydroxy-3-propylBenzonitrile

Product 1

HCID 1359745034-Hydroxy-3-propylbenzenecarbothioamideYield 93%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
7 °C

Procedure

A solution of 4-hydroxy-3-propylbenzonitrile (35.63 g, 0.221 mol) (Example 29 in DMF (300 mL) was saturated with hydrogen sulfide at rt (moderate flow over 45 min). Temperature was monitored (increase of about 7° C.). Diethylamine (45.73 mL, 0.442 mol) was added to the solution. The temperature rose to 10° C. and the already green reaction mixture became darker green. Hydrogen sulfide was passed through the solution for another 30 min (at this point the reaction temperature was 40° C.). The reaction mixture was warmed to 60° C. (gaseous evolution noted). Hydrogen sulfide was again passed through the solution at 60° C. over 2 h. The reaction mixture was cooled and stirred at rt for 54 h, and most of the solvent removed under reduced pressure. The resultant residue was partitioned between ethyl acetate (300 mL) and water (200 mL). The organic layer was washed with water (4×100 mL), then brine, and dried over sodium sulfate, filtered, and concentrated. The resultant orange oil was triturated in hexanes (300 mL) and ether (25 mL) to give a yellow solid (39.97 g, 93%) after drying for 1 h under suction. LC/MS m/z 196.1 (M+H)+, RT 2.16 min. 1H NMR (400 MHz, DMSO-d6) δ 9.94 (s, 1H), 9.44 (s, 1H), 9.14 (s, 1H), 7.73-7.65 (m, 2H), 6.73 (d, 1H), 2.51-2.47 (m, 2H), 1.59-1.50 (m, 2H), 0.90 (t, 3H).

Workup

  1. custom(moderate flow over 45 min)
  2. customrose to 10° C.
  3. customwas 40° C.
  4. temperatureThe reaction mixture was warmed to 60° C. (gaseous evolution noted)
  5. temperatureThe reaction mixture was cooled
  6. custommost of the solvent removed under reduced pressure
  7. customThe resultant residue was partitioned between ethyl acetate (300 mL) and water (200 mL)
  8. washThe organic layer was washed with water (4×100 mL)
  9. dry with materialbrine, and dried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe resultant orange oil was triturated in hexanes (300 mL)

Sources & evidence

ORD record
ord-b77fadb3c9d849a999d3f5d9e7ed9704
Source dataset
uspto-grants-2011_03
Patent number
US07906653B2

Reaction notes

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