Dimethyl Disulfide → tert-butyl 1-(4-chlorophenyl)-2-(2,4-dichlorophenyl)-5-methylsulfanyl-1H-imidazole-4-carboxylate

HRID 2215067Notes

Reaction equation

HRID 2215067 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH:12]=[C:11]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[N:10]=[C:9]2[C:20]2[CH:25]=[CH:24][C:23]([Cl:26])=[CH:22][C:21]=2[Cl:27])=[CH:4][CH:3]=1.[Li+].CC([N-]C(C)C)C.[CH3:36][S:37]SC.[NH4+].[Cl-]>C1COCC1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:12]([S:37][CH3:36])=[C:11]([C:13]([O:15][C:16]([CH3:17])([CH3:18])[CH3:19])=[O:14])[N:10]=[C:9]2[C:20]2[CH:25]=[CH:24][C:23]([Cl:26])=[CH:22][C:21]=2[Cl:27])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 12232Dimethyl DisulfideHCID 25517Ammonium ChlorideHCID 2724682Lithium diisopropylamideHCID 11270197tert-butyl 1-(4-chlorophenyl)-2-(2,4-dichlorophenyl)-1H-imidazole-4-carboxylate

Product 1

HCID 21948987tert-butyl 1-(4-chlorophenyl)-2-(2,4-dichlorophenyl)-5-methylsulfanyl-1H-imidazole-4-carboxylateYield 90%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a cooled (−20° C.) and magnetically stirred solution of tert-butyl 1-(4-chlorophenyl)-2-(2,4-dichlorophenyl)-1H-imidazole-4-carboxylate (10.59 g, 25.0 mmol), in anhydrous THF (100 ml) was added LDA (15.0 ml, 2 M solution in heptane/THF, 30.0 mmol) and the resulting mixture was stirred for 1 hour under N2. A solution of (CH3S)2 (2.7 ml, 30.0 mmol) in THF (20 ml) was added and the resulting solution was successively stirred at −40° C. for 1 h, allowed to attain room temperature and stirred for another 16 h. A saturated aqueous NH4Cl solution (250 ml) was added and the resulting solution was extracted twice with ethyl acetate (EtOAc). The combined organic layers were washed with water, dried over MgSO4, filtered and concentrated to give tert-butyl 1-(4-chlorophenyl)-2-(2,4-dichlorophenyl)-5-methylsulfanyl-1H-imidazole-4-carboxylate in 90% yield as an oil which slowly solidified; 1H-NMR (200 MHz, CDCl3) δ 1.66 (s, 9H), 2.28 (s, 3H), 7.05 (br d, J˜8 Hz, 2H), 7.25 (dd, J=8 and 2 Hz, 1H), 7.28 (d, J=2 Hz, 1H), 7.32–7.41 (m, 3H).

Workup

  1. stirringthe resulting solution was successively stirred at −40° C. for 1 h
  2. customto attain room temperature
  3. stirringstirred for another 16 h
  4. extractionthe resulting solution was extracted twice with ethyl acetate (EtOAc)
  5. washThe combined organic layers were washed with water
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-3524d4aaf9e140ab813e8a6e98ce74b1
Source dataset
uspto-grants-2006_09
Patent number
US07109216B2

Reaction notes

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