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 2113786Notes

Reaction equation

HRID 2113786 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 (2-1; 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 fractions were 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 compound 3-1 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 fractions were 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-25dac7cd91e543899d8e28a5a6b54e40
Source dataset
uspto-grants-2008_10
Patent number
US07432283B2

Reaction notes

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