p-Toluenesulfonic acid monohydrate → 7-(2-Chloro-4,6-dimethylphenyl)-2-methyl-3-(1-propyl but-1-enyl)-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine

HRID 2416106Notes

Reaction equation

HRID 2416106 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[C:4]([CH3:9])[C:3]=1[N:10]1[CH2:15][CH2:14][CH2:13][C:12]2=[C:16]([C:20](O)([CH2:24][CH2:25][CH3:26])[CH2:21][CH2:22][CH3:23])[N:17]([CH3:19])[N:18]=[C:11]12.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[C:4]([CH3:9])[C:3]=1[N:10]1[CH2:15][CH2:14][CH2:13][C:12]2=[C:16]([C:20]([CH2:24][CH2:25][CH3:26])=[CH:21][CH2:22][CH3:23])[N:17]([CH3:19])[N:18]=[C:11]12

Participants

4

Reactant 2

HCID 521998p-Toluenesulfonic acid monohydrateHCID 101728344-[7-(2-Chloro-4,6-dimethylphenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridin-3-yl]heptan-4-ol

Product 1

HCID 692923867-(2-Chloro-4,6-dimethylphenyl)-2-methyl-3-(1-propyl but-1-enyl)-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridineYield 81.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

4-[7-(2-Chloro-4,6-dimethylphenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridin-3-yl]heptan-4-ol (594 mg) and p-toluenesulfonic acid monohydrate (74 mg) were combined in 13 mL toluene and the stirred mixture was heated to 110° C. for 11 h. The reaction mixture was then cooled to room temperature and partitioned between ethyl acetate and aqueous sodium bicarbonate. The aqueous phase was washed with additional ethyl acetate. The combined ethyl acetate was washed with brine, dried with magnesium sulfate, and concentrated. The residue was chromatographed on silica gel eluting with an acetone/hexane gradient to provide 461 mg of 7-(2-chloro-4,6-dimethylphenyl)-2-methyl-3-(1-propylbut-1-enyl)-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine, which was recrystallized from hexane, mp 86.7-88.2° C.

Workup

  1. temperatureThe reaction mixture was then cooled to room temperature
  2. custompartitioned between ethyl acetate and aqueous sodium bicarbonate
  3. washThe aqueous phase was washed with additional ethyl acetate
  4. washThe combined ethyl acetate was washed with brine
  5. dry with materialdried with magnesium sulfate
  6. concentrationconcentrated
  7. customThe residue was chromatographed on silica gel eluting with an acetone/hexane gradient

Sources & evidence

ORD record
ord-725faa40b36e4014b748b3d01b852937
Source dataset
uspto-grants-2004_11
Patent number
US06821984B2

Reaction notes

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