Hydrochloric Acid → 4,5-Bis(4-methoxyphenyl)-2-(2,4-difluorophenylthio)imidazole

HRID 370770Notes

Reaction equation

HRID 370770 reaction equation
[F:1][C:2]1[CH:8]=[C:7]([F:9])[CH:6]=[CH:5][C:3]=1N.N([O-])=O.[Na+].Cl.[CH3:15][O:16][C:17]1[CH:22]=[CH:21][C:20]([C:23]2[N:24]=[C:25]([SH:36])[NH:26][C:27]=2[C:28]2[CH:33]=[CH:32][C:31]([O:34][CH3:35])=[CH:30][CH:29]=2)=[CH:19][CH:18]=1.[OH-].[Na+]>CN(C)C=O.[Cu]>[CH3:35][O:34][C:31]1[CH:32]=[CH:33][C:28]([C:27]2[N:26]=[C:25]([S:36][C:3]3[CH:5]=[CH:6][C:7]([F:9])=[CH:8][C:2]=3[F:1])[NH:24][C:23]=2[C:20]2[CH:21]=[CH:22][C:17]([O:16][CH3:15])=[CH:18][CH:19]=2)=[CH:29][CH:30]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 97092,4-DifluoroanilineHCID 14798Sodium HydroxideHCID 23668193Sodium NitriteHCID 178489021HCID 178489021, compound

Product 1

HCID 128323094,5-Bis(4-methoxyphenyl)-2-(2,4-difluorophenylthio)imidazoleYield 36.8%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 6228DimethylformamideSolvent

Procedure

At 0° a diazonium salt solution prepared from 2.58 g of 2,4-difluoroaniline, 1.58 g of sodium nitrite, and 10 ml of 6N hydrochloric acid is added dropwise to a solution of 6.25 g of 4,5-bis(4-methoxyphenyl)-2-mercaptoimidazole in a mixture of 240 ml of dimethylformamide, 10 ml of 2N sodium hydroxide solution, and 1.45 g of powdered copper. The solution becomes reddish brown under nitrogen evolution. The mixture is stirred for another 3 hours, the solution is concentrated under vacuum, and the residue is distributed between water and ethyl acetate. The organic solution is dried over sodium sulfate and concentrated to dryness under vacuum. The residue is subjected to column chromatography on 500 g of neutral aluminum oxide (activity stage II). Elution with acetone/hexan 2:3 yields 3.12 g of 4,5-bis(4-methoxyphenyl)-2-(2,4-difluorophenylthio)imidazole, having a melting point of 174°-176° after crystallization from hexane/ether and a melting point of 186°-188° after another crystallization from ethanol/ether.

Workup

  1. concentrationthe solution is concentrated under vacuum
  2. dry with materialThe organic solution is dried over sodium sulfate
  3. concentrationconcentrated to dryness under vacuum
  4. washElution with acetone/hexan 2:3

Sources & evidence

ORD record
ord-decf424f16c848838a27ff784accc34d
Source dataset
uspto-grants-1985_07
Patent number
US04528298

Reaction notes

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