Tert-Butylamine → HCID 10127447, compound

HRID 1296728Notes

Reaction equation

HRID 1296728 reaction equation
[CH:1]1([NH:6][C:7]2[N:12]=[C:11]([C:13]3[C:14]([C:24]4[CH:29]=[CH:28][C:27]([F:30])=[CH:26][CH:25]=4)=[N:15][N:16]4[C:21]=3[CH:20]=[CH:19][N:18]=[C:17]4SC)[CH:10]=[CH:9][N:8]=2)[CH2:5][CH2:4][CH2:3][CH2:2]1.ClC1C=C(C=CC=1)C(OO)=O.[C:42]([NH2:46])([CH3:45])([CH3:44])[CH3:43]>ClCCl.O>[C:42]([NH:46][C:17]1[N:16]2[N:15]=[C:14]([C:24]3[CH:29]=[CH:28][C:27]([F:30])=[CH:26][CH:25]=3)[C:13]([C:11]3[CH:10]=[CH:9][N:8]=[C:7]([NH:6][CH:1]4[CH2:2][CH2:3][CH2:4][CH2:5]4)[N:12]=3)=[C:21]2[CH:20]=[CH:19][N:18]=1)([CH3:45])([CH3:44])[CH3:43]

Participants

6

Reactant 3

HCID 6385Tert-Butylamine2×HCID 70297m-Chloroperbenzoic acid2×HCID 10173307HCID 10173307, compound

Product 1

HCID 10127447HCID 10127447, compoundYield 14%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of N-cyclopentyl-4-[2-(4-fluorophenyl)-7-(methylsulfanyl)pyrazolo[1,5-c]pyrimidin-3-yl]pyrimidin-2-amine (40 mg, 0.095 mmol) in dichloromethane (2 mL) was added 3-chloroperoxybenzoic acid (12 mg, 0.14 mmol) and the reaction mixture stirred at room temperature for 1 hour. t-Butylamine (3 mL) was added and heated to reflux for 3 hours. The reaction was allowed to cool and diluted with water. The mixture was extracted with ethyl acetate and the organic phase washed with brine before being concentrated under vacuum. The residue was purified by silica gel chromatography eluting with SO/5 acetone in dichloromethane to yield a 1:1 mixture of starting material and product. The residue was dissolved in dichloromethane (2 mL) and 3-chloroperoxybenzoic acid (18 mg, 0.21 mmol) was added. The mixture was stirred for 2 hours and then t-butylamine (3 mL) was added. The reaction mixture was stirred for 3 hours, diluted with water, extracted with ethyl acetate, washed with brine, concentrated, and the residue purified by silica gel chromatography eluting with 5% acetone in dichloromethane to yield N-(tert-butyl)-3-[2-(cyclopentylamino)pyrimidin-4-yl]-2-(4-fluorophenyl)pyrazolo[1,5-c]pyrimidin-7-amine (6 mg, 14%), 1H NMR (CDCl3): δ 8.02 (d, 1H), 7.72 (d, 1H), 7.60 (dd, 2H), 7.47 (d, 1H), 7.13 (t, 2H), 6.42 (s, 1H), 6.25 (d, 1H), 5.14 (bs, 1H), 4.28 (m, 1H), 2.04 (m, 2H), 1.45–1.78 (m, 15H). MS m/z 446 (M+1).

Workup

  1. temperatureheated
  2. temperatureto reflux for 3 hours
  3. temperatureto cool
  4. extractionThe mixture was extracted with ethyl acetate
  5. washthe organic phase washed with brine
  6. concentrationbefore being concentrated under vacuum
  7. customThe residue was purified by silica gel chromatography
  8. washeluting with SO/5 acetone in dichloromethane
  9. customto yield
  10. additiona 1:1 mixture of starting material and product
  11. stirringThe mixture was stirred for 2 hours
  12. stirringThe reaction mixture was stirred for 3 hours
  13. extractionextracted with ethyl acetate
  14. washwashed with brine
  15. concentrationconcentrated
  16. customthe residue purified by silica gel chromatography
  17. washeluting with 5% acetone in dichloromethane

Sources & evidence

ORD record
ord-7ad20545356c41f8babf54f49094a4ff
Source dataset
uspto-grants-2007_07
Patent number
US07247626B2

Reaction notes

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