tert-Butyl isothiocyanate → 2-(tert-Butylamino)-5,6-dichloro-1H-benzimidazole

HRID 610454

反応式

HRID 610454 の反応式
[Cl:1][C:2]1[C:7]([Cl:8])=[CH:6][C:5]([NH2:9])=[C:4]([NH2:10])[CH:3]=1.[C:11]([N:15]=[C:16]=S)([CH3:14])([CH3:13])[CH3:12].C1(N=C=NCCN2CCOCC2)CCCCC1.C1(C)C=CC(S([O-])(=O)=O)=CC=1>N1C=CC=CC=1>[C:11]([NH:15][C:16]1[NH:9][C:5]2[CH:6]=[C:7]([Cl:8])[C:2]([Cl:1])=[CH:3][C:4]=2[N:10]=1)([CH3:14])([CH3:13])[CH3:12]

参加物

6

反応物 4

HCID 11544tert-Butyl isothiocyanateHCID 792974,5-Dichloro-1,2-phenylenediamineHCID 849981-Cyclohexyl-3-(2-morpholinoethyl)carbodiimideHCID 85570p-Toluenesulfonate

生成物 1

HCID 229954272-(tert-Butylamino)-5,6-dichloro-1H-benzimidazole収率 27%

試薬・触媒・溶媒 1

HCID 1049Pyridine溶媒3 回

反応条件

温度
80 °C

実験手順

4,5-Dichlorophenylene diamine (8.0 g, 45.2 mmol) (Aldrich, Milwaukee, Wis.) was combined with tert-butyl isothiocyanate (6.3 mL, 49.7 mmol) (Aldrich, Milwaukee, Wis.) in anhydrous pyridine (100 mL). The solution was heated at 80° C. for 1 h under nitrogen. 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-ρ-toluene-sulphonate (24.9 g, 58.8 mmol) (Fluka Chemika) was added along with anhydrous pyridine (90 mL). This solution was heated at 90° C. for 2.5 h. The pyridine. was removed by rotoevaporation, and the residue was dissolved in ethyl acetate (300 μM) and extracted with water (4×100 mL). The ethyl acetate layer was treated with decolorizing carbon and washed through a silica gel filter pad (4×8 cm, 230-400 mesh) using ethyl acetate. The crude product was purifed on a silica gel column (5×16 cm, 230-400 mesh) using (1:4) ethyl acetate:hexane. Crude fractions were repurified on a second identical column using (1:3) ethyl acetate: hexane. Pure fractions from the two columns were combined to give a tan solid (3.13 g, 12.1 mmol, 27%); m.p. 219-221° C.; MS (API+): m/z (rel. intensity) 258 (100, M+1); 1H NMR (DMSO-d6) d 10.31 (s, 1H, NH), 7.31 (s, 2H, Ar-H), 6.61 (s, 1H, NH), 1.38 (s, 9H, t-butyl).

後処理

  1. temperatureThis solution was heated at 90° C. for 2.5 h
  2. customwas removed by rotoevaporation
  3. dissolutionthe residue was dissolved in ethyl acetate (300 μM)
  4. extractionextracted with water (4×100 mL)
  5. additionThe ethyl acetate layer was treated with decolorizing carbon
  6. washwashed through a silica gel
  7. filtrationfilter pad (4×8 cm, 230-400 mesh)
  8. customCrude fractions were repurified on a second identical column

出典と根拠

ORDレコード
ord-d7703aeae8804a399e9e2ec64b7a8fa5
出典データセット
uspto-grants-1999_12
特許番号
US05998605

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