Allyl bromide → HCID 66980187, compound

HRID 1423324Notes

Reaction equation

HRID 1423324 reaction equation
[H-].[Na+].[CH3:3][Si:4]([CH3:54])([CH3:53])[CH2:5][CH2:6][O:7][CH2:8][N:9]([CH2:45][O:46][CH2:47][CH2:48][Si:49]([CH3:52])([CH3:51])[CH3:50])[C:10]1[N:15]2[N:16]=[CH:17][C:18]([C:19]3[CH:20]=[N:21][C:22]4[C:27]([CH:28]=3)=[CH:26][C:25]([F:29])=[CH:24][CH:23]=4)=[C:14]2[N:13]=[C:12]([NH:30][CH:31]2[CH2:36][CH2:35][N:34]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:33][CH2:32]2)[C:11]=1[Br:44].[CH2:55](Br)[CH:56]=[CH2:57]>CN(C=O)C.O>[CH2:57]([N:30]([C:12]1[C:11]([Br:44])=[C:10]([N:9]([CH2:8][O:7][CH2:6][CH2:5][Si:4]([CH3:3])([CH3:53])[CH3:54])[CH2:45][O:46][CH2:47][CH2:48][Si:49]([CH3:51])([CH3:50])[CH3:52])[N:15]2[N:16]=[CH:17][C:18]([C:19]3[CH:20]=[N:21][C:22]4[C:27]([CH:28]=3)=[CH:26][C:25]([F:29])=[CH:24][CH:23]=4)=[C:14]2[N:13]=1)[CH:31]1[CH2:32][CH2:33][N:34]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:35][CH2:36]1)[CH:56]=[CH2:55]

Participants

6

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 66980176HCID 66980176, compound

Product 1

HCID 66980187HCID 66980187, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

At 0° C., NaH (60%, 40.2 mg, 1.00 mmol) was added in one portion to a solution of tert-butyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-6-bromo-3-(6-fluoroquinolin-3-yl)pyrazolo[1,5-a]pyrimidin-5-ylamino)piperidine-1-carboxylate (205 mg, 0.25 mmol) in DMF (6 mL). After stirring at room temperature for 30 min, the mixture was cooled to 0° C. and allyl bromide (60.8 mg, 0.50 mmol) was added dropwise. The mixture was stirred at room temperature overnight and then diluted with H2O and then extracted with ethyl acetate (×2). The combined organic layers were washed with brine and dried with Na2SO4. Evaporation and purification by column chromatography afforded tert-butyl 4-(allyl(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-6-bromo-3-(6-fluoroquinolin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)amino)piperidine-1-carboxylate: LCMS tR=1.99 Min (5 min run, UV254nm), Mass calculated for M+855.3, observed LC/MS m/z 856.3 (M+H).

Workup

  1. temperaturethe mixture was cooled to 0° C.
  2. stirringThe mixture was stirred at room temperature overnight
  3. extractionextracted with ethyl acetate (×2)
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried with Na2SO4
  6. customEvaporation and purification by column chromatography

Sources & evidence

ORD record
ord-ec5b6b7914b747aa98ac6b7741218861
Source dataset
uspto-grants-2015_01
Patent number
US08927562B2

Reaction notes

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