HomeMCPWorkbenchSkills
HomeWorkbenchNotificationsMe
llms.txt · MCP GuidePrivacy Policy · Terms of Service · Supportv1.8.0
  1. Home
  2. /Reaction

Sodium hydride → 3-bromo-N-(5-cyanopyridin-2-yl)-N-(oxetan-3-yl)pyrazolo[1,5-a]pyridine-5-carboxamide

HRID 539581
Notes
Print preview

Reaction equation

HRID 539581 reaction equation
[Br:1][C:2]1[CH:3]=[N:4][N:5]2[CH:10]=[CH:9][C:8]([C:11]([OH:13])=O)=[CH:7][C:6]=12.C(Cl)(=O)C(Cl)=O.[O:20]1[CH2:23][CH:22]([NH:24][C:25]2[CH:32]=[CH:31][C:28]([C:29]#[N:30])=[CH:27][N:26]=2)[CH2:21]1.[H-].[Na+]>ClCCl.CN(C)C=O>[Br:1][C:2]1[CH:3]=[N:4][N:5]2[CH:10]=[CH:9][C:8]([C:11]([N:24]([C:25]3[CH:32]=[CH:31][C:28]([C:29]#[N:30])=[CH:27][N:26]=3)[CH:22]3[CH2:21][O:20][CH2:23]3)=[O:13])=[CH:7][C:6]=12
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 4

HCID 24758Sodium hydrideHCID 65578Oxalyl chlorideHCID 457896763-Bromopyrazolo(1,5-a)pyridine-5-carboxylic acidHCID 867202576-(Oxetan-3-ylamino)nicotinonitrile

Product 1

HCID 867202583-bromo-N-(5-cyanopyridin-2-yl)-N-(oxetan-3-yl)pyrazolo[1,5-a]pyridine-5-carboxamideYield 20%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent3×

Procedure

To a solution of 3-bromopyrazolo[1,5-a]pyridine-5-carboxylic acid (I-7, 240 mg, 1 mmol) in dichloromethane (10 mL) was added oxalyl chloride (0.25 mL) and catalytic amounts of anhydrous dimethylformamide at rt. The reaction mixture was stirred for 30 minutes and subsequently the solvent was removed under reduced pressure. To the residual acid chloride was added a solution of 6-(oxetan-3-ylamino)nicotinonitrile (I-25, 175 mg, 1 mmol) in dichloromethane (10 mL). The resulting reaction mixture was quickly transferred to a microwave vial and NaH (60% in mineral oil) (191 mg, 5 mmol) was added. The vial was heatedin a microwave oven at 80° C. for 3 h. The reaction mixture was diluted with dichloromethane (15 mL) and subsequently washed with water, sat. NaHCO3 solution and brine. The organic layer was dried over Na2SO4 and the solvent was removed under reduced pressure. The resulting crude product was purified by column chromatography over silica gel (chloroform/MeOH, 0-10% EtOAc) to afford 75 mg (20%) of 3-bromo-N-(5-cyanopyridin-2-yl)-N-(oxetan-3-yl)pyrazolo[1,5-a]pyridine-5-carboxamide (I-26) as a brown solid. 1H NMR (400 MHz, CDCl3) δ 8.45 (d, J=7.0 Hz, 1H), 8.16 (s, 1H), 8.02 (t, J=7.90 Hz, 1H), 7.53 (d, J=0.8 Hz, 1H), 7.33-7.31 (m, 1H), 6.90-6.87 (m, 1H), 6.43 (d, J=10.1 Hz, 1H), 4.67-4.62 (m, 1H), 4.52-4.43 (m, 2H), 4.25-4.19 (m, 1H), 4.03-3.98 (m, 1H); ESI-LC/MS (m/z): [M+H]+ 398.13, [(M+2)+H]+ 400.08, RT 1.25 min.

Workup

  1. customsubsequently the solvent was removed under reduced pressure
  2. customThe resulting reaction mixture
  3. additionwas added
  4. waitThe vial was heatedin a microwave oven at 80° C. for 3 h
  5. washsubsequently washed with water, sat. NaHCO3 solution and brine
  6. dry with materialThe organic layer was dried over Na2SO4
  7. customthe solvent was removed under reduced pressure
  8. customThe resulting crude product was purified by column chromatography over silica gel (chloroform/MeOH, 0-10% EtOAc)

Sources & evidence

ORD record
ord-07b83297c55443a4a82f7dd706acd8e5
Source dataset
uspto-grants-2014_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08871754B2

Reaction notes

Loading…

On this pageParticipantsProcedureWorkupSources & evidenceReaction notes