1,1'-Thiocarbonyldiimidazole → HCID 57554365、化合物

HRID 1895579ノート

反応式

HRID 1895579 の反応式
[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]

参加物

4

反応物 2

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

生成物 1

HCID 57554365HCID 57554365、化合物

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

反応条件

温度
60 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-cdf0b0b8774242b2a5a2674fe7f99871
出典データセット
uspto-grants-2013_08
特許番号
US08513462B2

反応ノート

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