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N,N'-Dimethylethylenediamine → ethyl 4-[1-methyl-6-(pyridin-2-ylmethoxy)-1H-pyrrolo[2,3-b]pyridin-3-yl]-3-oxopiperazine-1-carboxylate

HRID 1622895
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HRID 1622895 반응식
[O:1]=[C:2]1[NH:7][CH2:6][CH2:5][N:4]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:3]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].Br[C:22]1[C:30]2[C:25](=[N:26][C:27]([O:31][CH2:32][C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][N:34]=3)=[CH:28][CH:29]=2)[N:24]([CH3:39])[CH:23]=1.CNCCNC>O1CCOCC1.[Cu]I.O>[CH3:39][N:24]1[C:25]2=[N:26][C:27]([O:31][CH2:32][C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][N:34]=3)=[CH:28][CH:29]=[C:30]2[C:22]([N:7]2[CH2:6][CH2:5][N:4]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:3][C:2]2=[O:1])=[CH:23]1
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8

반응물 4

HCID 8070N,N'-Dimethylethylenediamine2회HCID 62657Potassium Phosphate, TribasicHCID 13190471Ethyl 3-oxopiperazine-1-carboxylateHCID 678161163-Bromo-1-methyl-6-(2-pyridylmethoxy)pyrrolo[2,3-b]pyridine2회

생성물 1

HCID 67817855ethyl 4-[1-methyl-6-(pyridin-2-ylmethoxy)-1H-pyrrolo[2,3-b]pyridin-3-yl]-3-oxopiperazine-1-carboxylate수율 45.5%

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매2회HCID 962Water용매HCID 312751,4-Dioxane용매

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온도
100 °C

실험 절차

Ethyl 3-oxo-piperazine-1-carboxylate (161.4 g, 937.2 mmol), copper(I) iodide (27.65 g, 145.20 mmol) and potassium phosphate (tribasic, n-hydrate) (205.1 g, 937.2 mmol) is charged into a glass reactor at room temperature under nitrogen. A solution of 3-bromo-1-methyl-6-(pyridin-2-ylmethoxy)-1H-pyrrolo[2,3-b]pyridine (210 g, 660.0 mmol) in 1,4-dioxane (2.73 L) is added, followed by N,N′-dimethylethane-1,2-diamine (24.34 g; 270.6 mmol). The reaction mixture is heated to 100° C. and stirred for 20 h. Further copper(I) iodide (10.06 g, 52.80 mmol) and N,N′-dimethylethane-1,2-diamine (10.95 g, 105.6 mmol) is added and the reaction stirred for a further 23 h. The reaction mixture is combined with a smaller batch made in a similar manner starting with 23.68 g of 3-bromo-1-methyl-6-(pyridin-2-ylmethoxy)-1H-pyrrolo[2,3-b]pyridine. The mixture is cooled to room temperature, then poured into water (4.2 L) and extracted with EtOAc (3×1.7 L). The organic extracts are combined and washed with 3% w/w aqueous ammonia (3×400 mL), then water (2×2 L), then brine (600 mL), and dried over sodium sulphate, filtered and concentrated in vacuo. The residue is purified by column chromatography on silica, eluting with 50 to 100% EtOAc in isohexane. The appropriate fractions are combined, evaporated and recrystallized from ethanol (525 mL). The solid is dried to give the title compound (125.6 g, 0.3 mol). MS (m/z): 410.1 (M+1). 1H-NMR (400 MHz, CDCl3): δ 1.31 (t, 3H), 3.72 (s, 3H), 3.80-3.78 (t, 2H), 3.86 (t, 2H), 4.22 (q, 2H), 4.34 (s, 2H), 5.59 (s, 2H), 6.71 (d, 1H), 7.01 (s, 1H), 7.20 (dd, 1H), 7.49 (d, 1H), 7.70-7.66 (m, 2H), 8.60 (d, 1H). DSC (onset) mp=143.42° C.

후처리

  1. stirringthe reaction stirred for a further 23 h
  2. temperatureThe mixture is cooled to room temperature
  3. extractionextracted with EtOAc (3×1.7 L)
  4. washwashed with 3% w/w aqueous ammonia (3×400 mL)
  5. dry with materialwater (2×2 L), then brine (600 mL), and dried over sodium sulphate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue is purified by column chromatography on silica
  9. washeluting with 50 to 100% EtOAc in isohexane
  10. customevaporated
  11. customrecrystallized from ethanol (525 mL)
  12. customThe solid is dried

출처 및 근거

ORD 기록
ord-12da2ccd0b9746b6a619e42163580096
출처 데이터셋
uspto-grants-2014_07
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08778946B2

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