1,1'-Thiocarbonyldiimidazole → HCID 57554365, compound

HRID 2066047Notes

Reaction equation

HRID 2066047 reaction equation
[CH3:1][S:2]([CH:5]([C:7]1[CH:8]=[CH:9][C:10]([C:13]([F:16])([F:15])[F:14])=[N:11][CH:12]=1)[CH3:6])(=[NH:4])=[O:3].[C:17](N1C=CN=C1)([N:19]1[CH:23]=[CH:22][N:21]=[CH:20]1)=[S:18]>C(#N)C>[CH3:1][S:2](=[O:3])([CH:5]([C:7]1[CH:12]=[N:11][C:10]([C:13]([F:15])([F:16])[F:14])=[CH:9][CH:8]=1)[CH3:6])=[N:4][C:17]([N:19]1[CH:23]=[CH:22][N:21]=[CH:20]1)=[S:18]

Participants

4

Reactant 2

HCID 802641,1'-Thiocarbonyldiimidazole2×HCID 592186285-[1-(Methylsulfonimidoyl)ethyl]-2-(trifluoromethyl)pyridine

Product 1

HCID 57554365HCID 57554365, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 5-[1-(methylsulfonimidoyl)ethyl]-2-(trifluoromethyl)pyridine (E) (400 mg, 1.59 mmol) in acetonitrile (5 mL), 1,1′-thiocarbonyldiimidazole (353 mg, 1.59 mmol, 1 eq) was added and stirred over night. A second aliquot of 1,1′-thiocarbonyldiimidazole (71 mg, 0.317 mmol, 0.2 eq) was added and the mixture heated to 60° C. for two hours. The solvent was removed under reduced pressure, the residue dissolved in CHCl3 and washed five times with water. The organic phase was dried (Na2SO4) and chloroform was removed under reduced pressure. N-(Methyl(oxo){1-[6-(trifluoromethyl)-3-pyridinyl]ethyl}-λ6-sulfanylidene)-1H-imidazole-1-carbothioamide (Y) was obtained as an orange-brown residue, which was dried in the high vacuum over night (371 mg, 1.02 mmol, 64%). A 1:1 mixture of diastereomes with a purity of 94% was observed by UPLC-UV/ELSD and NMR, which was sufficient for subsequent conversions. Higher purities were obtained by filtration of the residue through a plug of silica (7.5% MeOH in CHCl3). 1H NMR (CDCl3, 400 MHz): δ=1.83 (d, J=7.1 Hz, 1.5H, CHCH3, diastereomer 1); 1.86 (d, J=7.1 Hz, 1.5H, CHCH3, diastereomer 2); 2.86 (s, 1.5H, S—CH3, diastereomer 1); 2.89 (s, 1.5H, S—CH3, diastereomer 2); 4.32 (q, J=7.1 Hz, 0.5H, CHCH3, diastereomer 1); 4.37 (q, J=7.1 Hz, 0.5H, CHCH3, diastereomer 2); 7.68-7.85 (m, 2H, Ar), 7.97-8.14 (m, 2H, Ar), 8.67-8.82 (m, 2H, Ar), UPLC-MS (ESI+): mass calc'd for C13H12F3N4OS2 (M+H+): 363.0. Found 363.1, UPLC-MS (ESI−) mass calc'd for C13H14F3N4OS2 (M−H+): 361.0. Found 361.1.

Workup

  1. customThe solvent was removed under reduced pressure
  2. dissolutionthe residue dissolved in CHCl3
  3. washwashed five times with water
  4. dry with materialThe organic phase was dried (Na2SO4) and chloroform
  5. customwas removed under reduced pressure

Sources & evidence

ORD record
ord-23ebaa403d1c4aed87a57b62870289b8
Source dataset
uspto-grants-2012_10
Patent number
US08288589B2

Reaction notes

Loading…