Methylthiourea → HCID 22911797, compound

HRID 1378611Notes

Reaction equation

HRID 1378611 reaction equation
Br[CH:2]([C:12]1[CH:17]=[CH:16][C:15]([S:18]([CH3:21])(=[O:20])=[O:19])=[CH:14][CH:13]=1)[C:3]([C:5]1[CH:10]=[CH:9][C:8]([F:11])=[CH:7][CH:6]=1)=O.[CH3:22][NH:23][C:24]([NH2:26])=[S:25]>C(O)C>[F:11][C:8]1[CH:9]=[CH:10][C:5]([C:3]2[N:26]=[C:24]([NH:23][CH3:22])[S:25][C:2]=2[C:12]2[CH:17]=[CH:16][C:15]([S:18]([CH3:21])(=[O:20])=[O:19])=[CH:14][CH:13]=2)=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 2723704MethylthioureaHCID 112340792-Bromo-1-(4-fluorophenyl)-2-(4-(methylsulfonyl)phenyl)ethanone

Product 1

HCID 22911797HCID 22911797, compoundYield 39%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 2-bromo-1-(4-fluorophenyl)-2-(4-methylsulfonylphenyl)ethanone (Example 26, Step 2) (0.355 g, 0.959 mmol) in ethanol (10 mL) in a 25 mL round bottom flask was added N-methylthiourea (0.086 g, 0.959 mmol). The solution was heated to reflux for 14 hours and cooled to room temperature. The resulting suspension was concentrated in vacuo, suspended in ethyl acetate (100 mL) and washed with NaHCO3 saturated solution (3×10 mL), dried over sodium sulfate and filtered. Isooctane was added to the filtrate until the solution became cloudy yielding a pale yellow fluffy solid which was collected by vacuum filtration. This solid was dissolved in methylene chloride and washed with sodium carbonate solution (10% solution), dried over sodium sulfate, and concentrated yielding a solid. This solid was recrystallized from methylene chloride-isooctane yielding 4-(4-fluorophenyl)-5-(4-methylsulfonylphenyl)-2-methylaminothiazole (0.135 g, 39%) as a pale yellow powder: mp 243°-244° C.; 1HNMR 400 mHz 7.90 (q, J=4.76 Hz, 1 H), 7.81 (d, J=8.50 Hz, 2 H), 7.49-7.43 (m, 2 H), 7.41 (t, J=8.70 Hz, 2 H), 7.19 (t, J=8.95 Hz, 2 H), 3.22 (s, 3 H), 2.90 (d, J=4.80 Hz, 3 H); MS (FAB) m/z 363 (M+H). HRMS Δ=-0.2 mmu.

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux for 14 hours
  3. concentrationThe resulting suspension was concentrated in vacuo
  4. washwashed with NaHCO3 saturated solution (3×10 mL)
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. additionIsooctane was added to the filtrate until the solution
  8. customyielding a pale yellow fluffy solid which
  9. filtrationwas collected by vacuum filtration
  10. dissolutionThis solid was dissolved in methylene chloride
  11. washwashed with sodium carbonate solution (10% solution)
  12. dry with materialdried over sodium sulfate
  13. concentrationconcentrated
  14. customyielding a solid
  15. customThis solid was recrystallized from methylene chloride-isooctane

Sources & evidence

ORD record
ord-8cb26804246b4d1c8474dff72d9b37c3
Source dataset
uspto-grants-1997_09
Patent number
US05668161

Reaction notes

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