Iodine → (R)-5-tert-butyl-3-((tetrahydrofuran-2-yl)methyl)thiazol-2(3H)-imine hydroiodide

HRID 78546

반응식

HRID 78546 반응식
[CH3:1][C:2]([CH3:7])([CH3:6])[CH2:3][CH:4]=O.[O:8]1[CH2:12][CH2:11][CH2:10][C@@H:9]1[CH2:13][NH2:14].[S-:15][C:16]#[N:17].[K+].[I:19]I.S(S([O-])=O)([O-])(=O)=O.[Na+].[Na+]>C(#N)C.C(OCC)(=O)C.ClCCl>[IH:19].[C:2]([C:3]1[S:15][C:16](=[NH:17])[N:14]([CH2:13][C@H:9]2[CH2:10][CH2:11][CH2:12][O:8]2)[CH:4]=1)([CH3:7])([CH3:6])[CH3:1]

참가 물질

9

반응물 5

HCID 807IodineHCID 763353,3-DimethylbutanalHCID 516872Potassium thiocyanateHCID 656671Sodium PyrosulfiteHCID 2734124(R)-(-)-Tetrahydrofurfurylamine

생성물 1

HCID 67303544(R)-5-tert-butyl-3-((tetrahydrofuran-2-yl)methyl)thiazol-2(3H)-imine hydroiodide수율 50%

시약·촉매·용매 3

HCID 6342Acetonitrile용매HCID 6344Dichloromethane용매HCID 8857Ethyl Acetate용매

실험 절차

To a solution of 3,3-dimethylbutanal (9.90 g, 99 mmol) in acetonitrile (60 mL) were added molecular sieves (8 g) and (R)-(tetrahydrofuran-2-yl)methanamine (10 g, 99 mmol). The reaction mixture was stirred at room temperature for 24 hr and then filtered. To the filtrate was added potassium thiocyanate (12.78 g, 131 mmol). The temperature was adjusted to 50° C. and the mixture was stirred until the solids were dissolved. Then, iodine (25.09 g, 99 mmol) was added to the mixture and stirred at 50° C. for 24 hr. The reaction mixture was cooled, and to the mixture was added sodium metabisulfite (20%, 100 mL) and stirred for 30 min. The organic layer was separated. The aqueous layer was washed with dichloromethane (3×40 mL). The combined organic extracts were dried with sodium sulfate, filtered and concentrated to obtain the crude product as a yellow solid. The residue was taken into dichloromethane (20 mL) and ethyl acetate (80 mL) was added, the mixture was warmed to 40° C., sonicated, and left in the refrigerator overnight. The solid was collected and washed with cold ethyl acetate to obtain the title compound as a white solid (18.2 g, 50%). 1H NMR (300 MHz, DMSO-d6) δ ppm 1.27 (s, 9H) 1.48-1.61 (m, 1H) 1.78-1.93 (m, 2H) 1.94-2.07 (m, 1H) 3.62-3.71 (m, 1H) 3.76-3.84 (m, 1H) 3.92-4.08 (m, 2H) 4.11-4.20 (m, 1H) 7.19 (s, 1H) 9.39 (s, 2H); MS (DCI/NH3); m/z 241 (M+H)+.

후처리

  1. filtrationfiltered
  2. customwas adjusted to 50° C.
  3. stirringthe mixture was stirred until the solids
  4. dissolutionwere dissolved
  5. stirringstirred at 50° C. for 24 hr
  6. temperatureThe reaction mixture was cooled
  7. stirringstirred for 30 min
  8. customThe organic layer was separated
  9. washThe aqueous layer was washed with dichloromethane (3×40 mL)
  10. dry with materialThe combined organic extracts were dried with sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customto obtain the crude product as a yellow solid
  14. additionwas added
  15. temperaturethe mixture was warmed to 40° C.
  16. customsonicated
  17. waitleft in the refrigerator overnight
  18. customThe solid was collected
  19. washwashed with cold ethyl acetate

출처 및 근거

ORD 기록
ord-a22e0716ec9441c0a38ee6ca6fc48eed
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08841334B2

연결된 노트

불러오는 중…