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

反応式

HRID 916213 の反応式
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

参加物

7

反応物 4

HCID 280Carbon Dioxide2 回HCID 13181,10-PhenanthrolineHCID 11360216HCID 11360216、化合物HCID 178418339Butyllithium2 回

生成物 1

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

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8078Cyclohexane溶媒

反応条件

温度
-78 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-38d726860a234b598209de457ed4f2de
出典データセット
uspto-grants-2007_09
特許番号
US07268146B2

関連ノート

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