m-Chloroperbenzoic acid → 2-[4,4-bis(trifluoromethyl)-2-(4-fluorophenyl)-4,5-dihydro-1H-imidazol-5-ylidene]-1-(4-fluorophenyl)-1-ethanone

HRID 22305Notes

Reaction equation

HRID 22305 reaction equation
[F:1][C:2]([F:29])([F:28])[C:3]([C:24]([F:27])([F:26])[F:25])([C:5]1[NH:6][C:7]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)=[C:8]([C:10]2[CH:15]=[CH:14][C:13]([F:16])=[CH:12][CH:11]=2)[CH:9]=1)[NH2:4].ClC1C=CC=C(C(OO)=[O:38])C=1.C(=O)(O)[O-].[Na+]>C(Cl)(Cl)Cl>[F:29][C:2]([F:28])([F:1])[C:3]1([C:24]([F:25])([F:26])[F:27])[C:5](=[CH:9][C:8]([C:10]2[CH:15]=[CH:14][C:13]([F:16])=[CH:12][CH:11]=2)=[O:38])[NH:6][C:7]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)=[N:4]1

Participants

5

Reactant 3

HCID 70297m-Chloroperbenzoic acid2×HCID 516892Sodium BicarbonateHCID 10895067alpha,alpha-bis(trifluoromethyl)-4,5-bis(4-fluorophenyl)-1H-pyrrole-2-methanamine

Product 1

HCID 540378242-[4,4-bis(trifluoromethyl)-2-(4-fluorophenyl)-4,5-dihydro-1H-imidazol-5-ylidene]-1-(4-fluorophenyl)-1-ethanoneYield 20%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a solution of α,α-bis(trifluoromethyl)-4,5-bis(4-fluorophenyl)-1H-pyrrole-2-methanamine (5.0 g, 0.012 mole) in chloroform (100 mL) was added portionwise, m-chloroperbenzoic acid (MCPBA, 4.09 g, 0.024 mole). The reaction mixture was refluxed under nitrogen for one hour. Then additional MCPBA (2.05 g, 0.012 mole) was added and the mixture was refluxed for 1 hour. The solution was cooled to room temperature and poured into saturated sodium bicarbonate (200 ml). The organic layer was washed successively with saturated sodium bicarbonate solution, 10% sodium sulfite solution, water, and saturated sodium chloride solution, dried over magnesium sulfate and evaporated under vacuum. The residue was columned in silica gel eluted with hexane-ethyl acetate 20:1 then 10:1 to give the 2-[4,4-bis(trifluoromethyl)-2-(4-fluorophenyl)-4,5-dihydro-1H-imidazol-5-ylidene]-1-(4-fluorophenyl)-1-ethanone (1.02 g, 20%) as a yellow solid: mp 121°-123°; MS m/e 435 (M+ +H); 1H NMR (CDCl3 /TMS) δ 6.73(s,1H,C=CH), 7.17-7.30(m,4H,Harom), 8.00-8.10(m,4H,Harom), 11.80(s,1H,NH). Another product, N[2-(4-fluorophenyl)-4,5-dihydro-1-methyl-5,5-bis(trifluoromethyl)-1H-imidazol-5-yl]-N-methylacetamide (2.09 g, 56%) was also isolated as a solid: mp 114°-115°; MS m/e 437 (M+ +H); 1H NMR (CDCl3 /TMS) δ 2.57(s,2H,NH2), 3.87(s,1H,NH), 6.77(s,1H,C=CH), 6.90-7.03(m,4H,Harom), 7.23-7.40(m, 2H,Harom), 7.15-7.17(m,2H,Harom).

Workup

  1. temperatureThe reaction mixture was refluxed under nitrogen for one hour
  2. temperaturethe mixture was refluxed for 1 hour
  3. washThe organic layer was washed successively with saturated sodium bicarbonate solution, 10% sodium sulfite solution, water, and saturated sodium chloride solution
  4. dry with materialdried over magnesium sulfate
  5. customevaporated under vacuum
  6. washeluted with hexane-ethyl acetate 20:1

Sources & evidence

ORD record
ord-7056b392e99343b7abedb3db3bed6424
Source dataset
uspto-grants-1995_06
Patent number
US05428041

Reaction notes

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