Sodium Hydroxide → 3'-Chloro-4-(1,3-dimethyl-1H-pyrazol-4-ylmethyl)-3,4,5,6-tetrahydro-2H-[1,2']bipyrazine

HRID 220493Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 220493
[Cl:1][C:2]1[C:3]([N:8]2[CH2:13][CH2:12][NH:11][CH2:10][CH2:9]2)=[N:4][CH:5]=[CH:6][N:7]=1.[CH3:14][N:15]1[CH:19]=[C:18]([CH:20]=O)[C:17]([CH3:22])=[N:16]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[OH-].[Na+]>ClCCCl>[Cl:1][C:2]1[C:3]([N:8]2[CH2:9][CH2:10][N:11]([CH2:20][C:18]3[C:17]([CH3:22])=[N:16][N:15]([CH3:14])[CH:19]=3)[CH2:12][CH2:13]2)=[N:4][CH:5]=[CH:6][N:7]=1

Komponenten

6

Edukt 4

HCID 14798Sodium HydroxideHCID 8472851,3-dimethyl-1H-pyrazole-4-carbaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 140864382-Chloro-3-(piperazin-1-yl)pyrazine

Produkt 1

HCID 866416563'-Chloro-4-(1,3-dimethyl-1H-pyrazol-4-ylmethyl)-3,4,5,6-tetrahydro-2H-[1,2']bipyrazine

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 111,2-DichloroethaneLösungsmittel

Versuchsvorschrift

To a solution of 3′-chloro-3,4,5,6-tetrahydro-2H-[1,2′]bipyrazinyl (3 g, 15.1 mmol, 1 eq) and 1,3-dimethyl-1H-pyrazole-4-carbaldehyde (2.0 g, 16.6 mmol, 1.1 eq) in DCE (75 mL) add sodium triacetoxyborohydride (4.8 g, 22.6 mmol, 1.5 eq) and stir at room temperature over the weekend. Add 2 N sodium hydroxide (100 mL), separate the layers, extract the aqueous layer twice with DCM (75 mL), dry (magnesium sulfate), filter, concentrate and purify (silica gel chromatography, eluting with 0:100 to 10:90 methanol:DCM). Combine only the fractions which contain the main component and concentrate to give the title preparation as a viscous yellow oil (2.14 g, 46%). Combine all other fractions which contain main component plus impurities, concentrate then repeat the chromatography step to recover further material (1.6 g, 35%, total yield 81%). MS (ES): m/z=307.1 [M+H]+.

Aufarbeitung

  1. customseparate the layers
  2. extractionextract the aqueous layer twice with DCM (75 mL)
  3. dry with materialdry (magnesium sulfate)
  4. filtrationfilter
  5. concentrationconcentrate
  6. custompurify
  7. wash(silica gel chromatography, eluting with 0:100 to 10:90 methanol:DCM)
  8. concentrationconcentrate
  9. customto give the title
  10. concentrationconcentrate
  11. customto recover further material (1.6 g, 35%, total yield 81%)

Quellen und Nachweise

ORD-Eintrag
ord-5005bcbbeed644e2a116426aeaf1ce57
Quelldatensatz
uspto-grants-2012_06
Patentnummer
US08202873B2

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