(4-Cyanophenyl)thiourea → HCID 22911871, compound

HRID 1378616Notes

Reaction equation

HRID 1378616 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.[C:22]([C:24]1[CH:29]=[CH:28][C:27]([NH:30][C:31]([NH2:33])=[S:32])=[CH:26][CH:25]=1)#[N:23]>C(O)C>[C:22]([C:24]1[CH:25]=[CH:26][C:27]([NH:30][C:31]2[S:32][C:2]([C:12]3[CH:17]=[CH:16][C:15]([S:18]([CH3:21])(=[O:20])=[O:19])=[CH:14][CH:13]=3)=[C:3]([C:5]3[CH:10]=[CH:9][C:8]([F:11])=[CH:7][CH:6]=3)[N:33]=2)=[CH:28][CH:29]=1)#[N:23]

Participants

4

Reactant 2

HCID 2757973(4-Cyanophenyl)thioureaHCID 112340792-Bromo-1-(4-fluorophenyl)-2-(4-(methylsulfonyl)phenyl)ethanone

Product 1

HCID 22911871HCID 22911871, compoundYield 53.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 2-bromo-1-(4-fluorophenyl)-2-(4-methylsulfonylphenyl)ethanone (Example 26, Step 2) (0.413, 1.11 mmol) in ethanol (10 mL) in a 25 mL round bottom flask was added N-(4-cyanophenyl)thiourea (0.207 g, 1.17 mmol). The solution was heated to reflux (24 hours) and the reaction was cooled to room temperature. The resulting suspension was concentrated in vacuo, suspended in methylene chloride (100 mL) and washed with sodium carbonate solution (10%, 3×20 mL), brine (1×20 mL), dried over sodium sulfate, filtered and concentrated yielding a solid. This solid was flash chromatographed (1:1, hexane:ethyl acetate with 1% acetic acid). The resulting product was recrystallized from methylene chloride and isooctane yielding 2-(4-cyanophenylamino)-4-(4-fluorophenyl)-5-(4-methylsulfonylphenyl)thiazole (0.266 g, 53%) as a pale yellow solid: mp 273°-274° C.; 1HNMR (DMSO d6) 400 mHz 10.98 (s, 1 H), 7.86 (d, J=8.32 Hz, 2 H), 7.83 (d, J=9.05 Hz, 2 H), 7.76 (d, J=8.80 Hz, 2 H), 7.55-7.47 (m, 4 H), 7.21 (t, J=8.80 Hz, 2 H), 3.22 (s, 3 H); MS m/z 450 (M+H). HRMS Δ=2.6 mmu.

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux (24 hours)
  3. concentrationThe resulting suspension was concentrated in vacuo
  4. washwashed with sodium carbonate solution (10%, 3×20 mL), brine (1×20 mL)
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customyielding a solid
  9. customchromatographed (1:1, hexane:ethyl acetate with 1% acetic acid)
  10. customThe resulting product was recrystallized from methylene chloride and isooctane

Sources & evidence

ORD record
ord-baa7ab97b3074ef7a721894855400b83
Source dataset
uspto-grants-1997_09
Patent number
US05668161

Reaction notes

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