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N,N'-Dimethylethylenediamine → Gsk-2798745

HRID 715539
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HRID 715539 반응식
Cl[C:2]1[N:3]=[CH:4][C:5]([C:8]([OH:11])([CH3:10])[CH3:9])=[N:6][CH:7]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].[CH3:20][C@:21]1([CH2:32][N:33]2[C:37]3[CH:38]=[C:39]([C:42]#[N:43])[CH:40]=[CH:41][C:36]=3[N:35]=[CH:34]2)[CH2:31][CH2:30][CH2:29][C@:23]2([O:27][C:26](=[O:28])[NH:25][CH2:24]2)[CH2:22]1.CNCCNC>C(Cl)Cl.O.N.CO.[Cu]I.O1CCOCC1>[OH:11][C:8]([C:5]1[N:6]=[CH:7][C:2]([N:25]2[CH2:24][C@@:23]3([CH2:29][CH2:30][CH2:31][C@@:21]([CH2:32][N:33]4[C:37]5[CH:38]=[C:39]([C:42]#[N:43])[CH:40]=[CH:41][C:36]=5[N:35]=[CH:34]4)([CH3:20])[CH2:22]3)[O:27][C:26]2=[O:28])=[N:3][CH:4]=1)([CH3:10])[CH3:9]
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참가 물질

11

반응물 4

HCID 8070N,N'-DimethylethylenediamineHCID 62657Potassium Phosphate, TribasicHCID 712269671-(((5S,7S)-7-methyl-2-oxo-1-oxa-3-azaspiro[4.5]decan-7-yl)methyl)-1H-benzo[d]imidazole-6-carbonitrileHCID 867175962-(5-Chloropyrazin-2-yl)propan-2-ol

생성물 1

HCID 71227359Gsk-2798745

시약·촉매·용매 6

HCID 24350
Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)
촉매
HCID 222Ammonia용매
HCID 887Methanol용매
HCID 962Water용매2회
HCID 6344Dichloromethane용매
HCID 312751,4-Dioxane용매

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온도
100 °C

실험 절차

Two identical reactions were set up: To a 1 L flask containing 2-(5-chloropyrazin-2-yl)propan-2-ol (18.29 g, 106 mmol) was added reagents in the following order: first potassium phosphate tribasic (36.0 g, 170 mmol), followed by 1-(((5S,7S)-7-methyl-2-oxo-1-oxa-3-azaspiro[4.5]decan-7-yl)methyl)-1H-benzo[d]imidazole-6-carbonitrile (27.5 g, 85 mmol). Next 1,4-dioxane (424 mL) was added followed by N1,N2-dimethylethane-1,2-diamine (7.47 g, 85 mmol). To the resulting white slurry was added copper(I) iodide (8.07 g, 42.4 mmol). The slurry was put under nitrogen and heated to 100° C. (Reaction 1=44 h, Reaction 2=68 h). After completion, the mixture was cooled to RT, diluted with DCM and water and 7N NH3 in MeOH and allowed to stir for 10 min. The layers were separated and the aqueous layer was extracted with DCM (2×). The combined DCM extracts were diluted with 7N NH3 in MeOH (300 mL) (to remove residual copper ions), and then washed with water (2×500 mL), and dried over Na2SO4, filtered, and concentrated. Each residue was purified on the ISCO: 4×330 g silica, 0-10% MeOH/DCM over 10 CV. Fractions containing product were concentrated, dissolved in DCM, and washed one final time with water/7N NH3 in MeOH to remove any leftover copper. The resulting layers were separated, the aqueous layer extracted with DCM (2×), and the combined DCM extracts were dried over Na2SO4, filtered, and concentrated. The residue was then azeotroped with MeCN (300 mL) and then diluted to a volume of ˜650 mL. The solution was heated to 70° C. (all solids went into solution affording a yellow solution), then allowed to cool to RT with stirring and crystals started to form. After stirring at RT for ˜2 h, the slurry was diluted with 2 L water. Stirring was continued overnight before the slurry was filtered and the solids dried under reduced pressure to 1-(((5S,7S)-3-(5-(2-hydroxypropan-2-yl)pyrazin-2-yl)-7-methyl-2-oxo-1-oxa-3-azaspiro[4.5]decan-7-yl)methyl)-1H-benzo[d]imidazole-6-carbonitrile (71.3 g, 91%) as a white solid. MS (m/z) 461.2 (M+H+) 1H NMR (400 MHz, DMSO-d6) δ 9.18 (s, 1H), 8.59 (s, 1H), 8.47 (s, 1H), 8.37 (s, 1H), 7.82 (d, J=8.28 Hz, 1H), 7.58 (d, J=8.28 Hz, 1H), 5.41 (s, 1H), 4.16 (br. s., 2H), 3.77-3.96 (m, 2H), 1.98 (d, J=7.03 Hz, 1H), 1.82-1.93 (m, 1H), 1.72 (d, J=14.56 Hz, 2H), 1.58-1.67 (m, 2H), 1.28-1.57 (m, 8H), 1.06 (s, 3H). MS (m/z) 461.0 (M+H+).

후처리

  1. additionwas added reagents in the following order
  2. custom(Reaction 1=44 h, Reaction 2=68 h)
  3. temperatureAfter completion, the mixture was cooled to RT
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with DCM (2×)
  6. additionThe combined DCM extracts were diluted with 7N NH3 in MeOH (300 mL) (to remove residual copper ions)
  7. washwashed with water (2×500 mL)
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customEach residue was purified on the ISCO
  12. additionFractions containing product
  13. concentrationwere concentrated
  14. dissolutiondissolved in DCM
  15. washwashed one final time with water/7N NH3 in MeOH
  16. customto remove any leftover copper
  17. customThe resulting layers were separated
  18. extractionthe aqueous layer extracted with DCM (2×)
  19. dry with materialthe combined DCM extracts were dried over Na2SO4
  20. filtrationfiltered
  21. concentrationconcentrated
  22. customThe residue was then azeotroped with MeCN (300 mL)
  23. additiondiluted to a volume of ˜650 mL
  24. temperatureThe solution was heated to 70° C. (all solids
  25. customaffording a yellow solution),
  26. temperatureto cool to RT
  27. stirringwith stirring
  28. customto form
  29. stirringAfter stirring at RT for ˜2 h
  30. stirringStirring
  31. waitwas continued overnight before the slurry
  32. filtrationwas filtered
  33. dry with materialthe solids dried under reduced pressure to 1-(((5S,7S)-3-(5-(2-hydroxypropan-2-yl)pyrazin-2-yl)-7-methyl-2-oxo-1-oxa-3-azaspiro[4.5]decan-7-yl)methyl)-1H-benzo[d]imidazole-6-carbonitrile (71.3 g, 91%) as a white solid

출처 및 근거

ORD 기록
ord-6c3a56f205094dcabf60a4a0c24f7d9f
출처 데이터셋
uspto-grants-2015_11
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09187464B2

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