m-Chloroperbenzoic acid → HCID 178517607, compound

HRID 1296713Notes

Reaction equation

HRID 1296713 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:8]2[C:16]([C:17]3[CH:22]=[CH:21][N:20]=[C:19]([NH:23][CH:24]4[CH2:28][CH2:27][CH2:26][CH2:25]4)[N:18]=3)=[C:15]3[N:10]([C:11](SC)=[N:12][CH:13]=[CH:14]3)[N:9]=2)[CH:5]=[CH:6][CH:7]=1.Cl[C:32]1[CH:33]=[C:34](C=CC=1)[C:35](OO)=[O:36].[Na].[O-:43]CCCC.[Na+:48]>ClCCl.C(OCC)(=O)C.C(O)CCC>[O-:36][CH2:35][CH2:34][CH2:33][CH3:32].[Na+:48].[Cl:1][C:2]1[CH:3]=[C:4]([C:8]2[C:16]([C:17]3[CH:22]=[CH:21][N:20]=[C:19]([NH:23][CH:24]4[CH2:28][CH2:27][CH2:26][CH2:25]4)[N:18]=3)=[C:15]3[N:10]([C:11]([OH:43])=[N:12][CH:13]=[CH:14]3)[N:9]=2)[CH:5]=[CH:6][CH:7]=1

Participants

9

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 5360545SodiumHCID 10151314HCID 10151314, compoundHCID 23669364Sodium n-butylate

Product 2

HCID 23669364Sodium n-butylateHCID 178517607HCID 178517607, compoundYield 26%

Reagents, catalysts & solvents 3

HCID 2631-ButanolSolventHCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a cold (0° C.) solution of 4-[2-(3-chlorophenyl)-7-(methylthio)pyrazolo[1,5-c]pyrimidin-3-yl]-N-cyclopentylpyrimidin-2-amine (90 mg, 0.206 mmol) in dichloromethane (10 mL) was added m-chloroperoxybenzoic acid (54 mg, 0.313 mmol). The reaction mixture was stirred 1.5 hours at 0° C. then diluted with dichloromethane and washed with saturated aqueous sodium bicarbonate. The organic layer was washed with water and brine, then dried over magnesium sulfate. Filtration and concentration provided a crude oil. In a separate flask, a solution of sodium butoxide was prepared by reacting sodium (35 mg, 1.52 mmol) with n-butanol (2 mL). The sodium butoxide solution was added to the crude oil and the resulting solution was heated in a sealed tube at 120° C. for 16 hours. The reaction mixture was cooled and concentrated in vacuo. The resulting oil was partitioned between water and ethyl acetate. The organic layer was washed with water and brine, then dried over magnesium sulfate. Filtration and concentration provided a crude oil which was diluted with ethyl acetate (˜5 mL). Upon standing 7 hours, a solid had precipitated, which was collected on a filter to provide 2-(3-chlorophenyl)-3-[2-(cyclopentylamino)-4-pyrimidinyl]pyrazolo[1,5-c]pyrimidin-7-ol (22 mg, 26%) as a pale yellow solid. 1H NMR (CDCl3) δ 8.00 (d, 1H), 7.60 (s, 1H), 7.42 (d, 1H), 7.36 (d, 1H), 7.30 (d, 1H), 7.25 (s, 1H), 7.14 (d, 1H), 7.02 (d, 1H), 6.24 (d, 1H), 4.19 (m, 1H), 1.99 (m, 2H), 1.78–1.42 (m, 6H); MS m/z 407 (M+1).

Workup

  1. washwashed with saturated aqueous sodium bicarbonate
  2. washThe organic layer was washed with water and brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationFiltration and concentration
  5. customprovided a crude oil
  6. temperaturethe resulting solution was heated in a sealed tube at 120° C. for 16 hours
  7. temperatureThe reaction mixture was cooled
  8. concentrationconcentrated in vacuo
  9. customThe resulting oil was partitioned between water and ethyl acetate
  10. washThe organic layer was washed with water and brine
  11. dry with materialdried over magnesium sulfate
  12. filtrationFiltration and concentration
  13. customprovided a crude oil which
  14. waitUpon standing 7 hours
  15. customa solid had precipitated
  16. customwhich was collected on
  17. filtrationa filter

Sources & evidence

ORD record
ord-774e3cca36fc422ab2734991553c8574
Source dataset
uspto-grants-2007_07
Patent number
US07247626B2

Reaction notes

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