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 1826956

반응식

HRID 1826956 반응식
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

참가 물질

7

반응물 4

HCID 280Carbon Dioxide2회HCID 13181,10-PhenanthrolineHCID 11360216HCID 11360216, 화합물HCID 178418339Butyllithium2회

생성물 1

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

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매HCID 8078Cyclohexane용매

반응 조건

온도
-78 °C

실험 절차

3-Bromo-7-(2-chloro-4,6-dimethylphenyl)-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.

후처리

  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

출처 및 근거

ORD 기록
ord-b9f578d523a14461965a4b6495eb049f
출처 데이터셋
uspto-grants-2006_05
특허 번호
US07053103B2

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