Carbon Tetrachloride → HCID 10127912, compound

HRID 1269040Notes

Reaction equation

HRID 1269040 reaction equation
[CH:1]1([NH:6][C:7]2[N:12]=[C:11]([C:13]3[C:14]([C:22]4[CH:27]=[CH:26][N:25]=[C:24]([NH:28][CH:29]5[CH2:33][CH2:32][CH2:31][CH2:30]5)[N:23]=4)=[N:15][N:16]4[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=34)[CH:10]=[CH:9][N:8]=2)[CH2:5][CH2:4][CH2:3][CH2:2]1.C([Li])CCC.C(Cl)(Cl)(Cl)[Cl:40]>O1CCCC1>[Cl:40][C:21]1[N:16]2[N:15]=[C:14]([C:22]3[CH:27]=[CH:26][N:25]=[C:24]([NH:28][CH:29]4[CH2:33][CH2:32][CH2:31][CH2:30]4)[N:23]=3)[C:13]([C:11]3[CH:10]=[CH:9][N:8]=[C:7]([NH:6][CH:1]4[CH2:5][CH2:4][CH2:3][CH2:2]4)[N:12]=3)=[C:17]2[CH:18]=[CH:19][CH:20]=1

Participants

5

Reactant 3

HCID 5943Carbon TetrachlorideHCID 10238320HCID 10238320, compoundHCID 178418339Butyllithium

Product 1

HCID 10127912HCID 10127912, compoundYield 53%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

N-Cyclopentyl-N-(4-{2-[2-(cyclopentylamino)-4-pyrimidinyl]pyrazolo[1,5-a]pyridin-3-yl}-2-pyrimidinyl)amine (140 mg, 0.32 mmol) was dissolved in anhydrous tetrahydrofuran (5 mL). The resulting solution was cooled to −78° C., then n-butyllithium (0.99 mL, 1.6 mmol, 1.6 M in hexane) was added dropwise. The resulting dark solution was stirred at −78° C. for 20 minutes, then carbon tetrachloride (2 mL) was added. The reaction was stirred for additional 20 minutes and then quenched by the addition of water and allowed to warm to room temperature. The phases were separated and the aqueous phase extracted with ethyl acetate. The organics were combined, dried over magnesium sulfate, filtered and concentrated. Purification by silica gel chromatography (1:1 ethyl acetate:hexane) gave 80 mg (53%) of N-(4-{7-chloro-2-[2-(cyclopentylamino)-4-pyrimidinyl]pyrazolo[1,5-a]pyridin-3-yl}-2-pyrimidinyl)-N-cyclopentylamine as a foam. 1H NMR (CDCl3): δ 8.37 (d, 1H), 8.27 (d, 1H), 8.16 (d, 1H), 7.26 (t, 1H), 7.06 (d, 1H), 7.04 (m, 1H), 6.62 (d, 1H), 5.21 (d, 1H), 5.15 (d, 1H), 4.32 (m, 1H), 4.10 (m, 1H), 1.4–2.1 (m, 16H); MS m/z 475 (M+1).

Workup

  1. stirringThe reaction was stirred for additional 20 minutes
  2. customquenched by the addition of water
  3. temperatureto warm to room temperature
  4. customThe phases were separated
  5. extractionthe aqueous phase extracted with ethyl acetate
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by silica gel chromatography (1:1 ethyl acetate:hexane)

Sources & evidence

ORD record
ord-566523c972c54fea8e021c1dc78c9caf
Source dataset
uspto-grants-2007_04
Patent number
US07199120B2

Reaction notes

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