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Acetonitrile → 3-methyl-1-[4-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]cyclobutylacetonitrile

HRID 1692953
Notes
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Reaction equation

HRID 1692953 reaction equation
[CH3:1][CH:2]1[CH2:5][C:4]([CH2:28][C:29]#[N:30])([N:6]2[CH:10]=[C:9]([C:11]3[C:12]4[CH:19]=[CH:18][N:17](COCC[Si](C)(C)C)[C:13]=4[N:14]=[CH:15][N:16]=3)[CH:8]=[N:7]2)[CH2:3]1.C(#N)C.F[B-](F)(F)F.[Li+].[OH-].[NH4+]>O>[CH3:1][CH:2]1[CH2:3][C:4]([CH2:28][C:29]#[N:30])([N:6]2[CH:10]=[C:9]([C:11]3[C:12]4[CH:19]=[CH:18][NH:17][C:13]=4[N:14]=[CH:15][N:16]=3)[CH:8]=[N:7]2)[CH2:5]1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 14923Ammonium HydroxideHCID 4298216Lithium tetrafluoroborateHCID 670172343-methyl-1-[4-(7-[2-(trimethylsilyl)ethoxy]methyl-7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]cyclobutylacetonitrile

Product 1

HCID 442322273-methyl-1-[4-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]cyclobutylacetonitrile

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
100 °C

Procedure

To a mixture of 3-methyl-1-[4-(7-[2-(trimethylsilyl)ethoxy]methyl-7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]cyclobutylacetonitrile (0.5 g, 0.001 mol) in acetonitrile (8.07 mL, 0.154 mol) and water (0.70 mL, 0.039 mol) was added lithium tetrafluoroborate (1.10 g, 0.0114 mol). The solution was warmed to reflux at 100° C. over 5 days. Charged 7.2 M of ammonium hydroxide in water (0.59 mL) in portions over a period of 5 minutes at rt adjusting pH to 9-10. The reaction mixture was stirred for 2 h at rt. The reaction was filtered and the filtrate was diluted with acetonitrile, water and MeOH and purified with prep. HPLC (XBridge C18 column, eluting with a gradient of acetonitrile/water containing 0.15% NH4OH) to give the first isomer with retention time 1.057 min, LCMS calculated for C1-6H17N6(M+H)+: 293.2; Found: 293.3. 1H NMR (500 MHz, CDCl3): δ 10.07(1H, br s), 8.88 (1H, s), 8.45 (1H, s), 8.34 (1H, s), 7.43 (1H, d, J=3.5 Hz), 6.85 (1H, d, J=3.5 Hz), 3.16 (2H, s), 2.77 (2H, m), 2.55 (1H, m), 2.43 (2H, m), 1.24 (3H, d, J=6.5 Hz) ppm; then the second isomer with retention time 1.107 min; LCMS calculated for C16H17N6(M+H)+: 293.2; Found: 293.3. 1H NMR (500 MHz, CDCl3): δ 10.21(1H, br s), 8.89 (1H, s), 8.61 (1H, s), 8.37 (1H, s), 7.44 (1H, d, J=3.5 Hz),6.86 (1 H, d, J =3.5 Hz), 3.07 (2H, s), 3.05 (2H, m), 2.61 (1H, m), 2.26 (2H, m), 1.25 (3H, d, J=7.0 Hz) ppm.

Workup

  1. temperatureThe solution was warmed
  2. filtrationThe reaction was filtered
  3. additionthe filtrate was diluted with acetonitrile, water and MeOH
  4. custompurified with prep
  5. washHPLC (XBridge C18 column, eluting with a gradient of acetonitrile/water containing 0.15% NH4OH)
  6. customto give the first isomer with retention time 1.057 min, LCMS

Sources & evidence

ORD record
ord-373922bbcf124a8fa94373cb7915edff
Source dataset
uspto-grants-2012_04
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08158616B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes