Carbon Dioxide → 7-(2-chloro-4,6-dimethylphenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine-3-carboxylic acid

HRID 916213

Reaktionsgleichung

Reaktionsgleichung von HRID 916213
Br[C:2]1[N:3]([CH3:20])[N:4]=[C:5]2[C:10]=1[CH2:9][CH2:8][CH2:7][N:6]2[C:11]1[C:16]([CH3:17])=[CH:15][C:14]([CH3:18])=[CH:13][C:12]=1[Cl:19].N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.C([Li])CCC.[C:40](=[O:42])=[O:41]>O1CCCC1.C1CCCCC1>[Cl:19][C:12]1[CH:13]=[C:14]([CH3:18])[CH:15]=[C:16]([CH3:17])[C:11]=1[N:6]1[CH2:7][CH2:8][CH2:9][C:10]2=[C:2]([C:40]([OH:42])=[O:41])[N:3]([CH3:20])[N:4]=[C:5]12

Komponenten

7

Edukt 4

HCID 280Carbon Dioxide2×HCID 13181,10-PhenanthrolineHCID 11360216HCID 11360216, VerbindungHCID 178418339Butyllithium2×

Produkt 1

HCID 221362637-(2-chloro-4,6-dimethylphenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine-3-carboxylic acid

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittelHCID 8078CyclohexaneLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

3-Bromo-7-(2-chloro-4,6-dimethyl phenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine (1.46 g) and a few crystals of 1,10 phenanthroline were dissolved in 25 mL of dry tetrahydrofuran and chilled to −78° C. under an atmosphere of argon. Then a 2.0 M solution of n-butyllithium in cyclohexane was added dropwise until the dark color of the phenanthroline/organolithium complex persisted. Then an additional 2.05 mL of the n-butyllithium solution was added. After 10 minutes, carbon dioxide, generated from dry ice, was bubbled through the reaction mixture for 5 minutes. After the reaction mixture had been stirred at −78° C. for 5 minutes, the cooling bath was removed and the mixture was allowed to warm for 5 minutes before being quenched by the addition of water. The mixture was combined with ethyl acetate and water, acidified with dilute hydrochloric acid, and the phases separated. The ethyl acetate was dried with magnesium sulfate and concentrated. The residue was chromatographed on silica gel eluting with an acetone/hexane gradient to provide 1.11 g of 7-(2-chloro-4,6-dimethylphenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine-3-carboxylic acid, mp 247.8-248.3° C.

Aufarbeitung

  1. customwas bubbled through the reaction mixture for 5 minutes
  2. customthe cooling bath was removed
  3. temperatureto warm for 5 minutes
  4. custombefore being quenched by the addition of water
  5. customthe phases separated
  6. dry with materialThe ethyl acetate was dried with magnesium sulfate
  7. concentrationconcentrated
  8. customThe residue was chromatographed on silica gel eluting with an acetone/hexane gradient

Quellen und Nachweise

ORD-Eintrag
ord-38d726860a234b598209de457ed4f2de
Quelldatensatz
uspto-grants-2007_09
Patentnummer
US07268146B2

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