Water → 7-Chloro-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridine-3-carbaldehyde

HRID 2214955Notes

Reaction equation

HRID 2214955 reaction equation
CN(C)[CH:3]=[O:4].P(Cl)(Cl)(Cl)=O.[Cl:11][C:12]1[N:17]2[N:18]=[C:19]([C:21]3[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=3)[CH:20]=[C:16]2[CH:15]=[CH:14][CH:13]=1.O>ClCCl>[Cl:11][C:12]1[N:17]2[N:18]=[C:19]([C:21]3[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=3)[C:20]([CH:3]=[O:4])=[C:16]2[CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 4

HCID 962WaterHCID 6228DimethylformamideHCID 24813Phosphorus oxychlorideHCID 111841947-Chloro-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridine

Product 1

HCID 221748437-Chloro-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridine-3-carbaldehydeYield 95%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

N,N-Dimethylformamide (100 mL) was cooled to 0° C. and treated with phosphorous oxychloride (5.7 mL, 60.8 mmol). After the addition was complete, the mixture was warmed to room temperature and stirred for 1 hour. To this was added 7-chloro-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridine (10.0 g, 40.5 mmol) and the resultant solution was stirred overnight Water was added, followed by dichloromethane. The aqueous layer was extracted with dichloromethane. The combined organics were washed with brine, dried over magnesium sulfate, filtered and concentrated. The residue was recrystallized from diethyl ether and hexanes to give 7-chloro-2-(4-fluorophenyl)pyrazolo[1,5-α]pyridine-3-carbaldehyde (10.6 g, 95%) as a fluffy white solid. 1H NMR (CDCl3): δ 10.07 (s, 1H), 8.37 (d, 1H), 7.78 (m, 2H), 7.48 (t, 1H), 7.20 (m, 3H); 19F NMR (CDCl3) δ−111.25; MS m/z 275 (M+1); Anal. Calcd for C14H8ClFN2O: C, 61.22; H, 2.94; N. 10.20. Found: C, 61.34; H. 2.90; N. 10.15; mp 212–213° C. (decomp.).

Workup

  1. additionAfter the addition
  2. additionwas added
  3. extractionThe aqueous layer was extracted with dichloromethane
  4. washThe combined organics were washed with brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was recrystallized from diethyl ether and hexanes

Sources & evidence

ORD record
ord-653fd1558c83419096c18be289209224
Source dataset
uspto-grants-2006_09
Patent number
US07109209B2

Reaction notes

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