Pyridine-2-carbonitrile → HCID 178420129, compound

HRID 558035Notes

Reaction equation

HRID 558035 reaction equation
C[Si]([CH:5]=[N+:6]=[N-:7])(C)C.C([Li])CCC.[C:13]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][N:16]=1)#[N:14].[F-].[K+].C(=O)(O)[O-].[Na+]>Cl.C(O)C.CCOCC>[N:6]1[CH:5]=[C:13]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][N:16]=2)[NH:14][N:7]=1

Participants

9

Reactant 5

HCID 7522Pyridine-2-carbonitrileHCID 167693TrimethylsilyldiazomethaneHCID 516892Sodium BicarbonateHCID 522689Potassium FluorideHCID 178418339Butyllithium

Product 1

HCID 178420129HCID 178420129, compoundYield 60%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidCatalystHCID 702EthanolSolventHCID 3283Diethyl EtherSolvent

Procedure

A 250 ml reaction flask is dried under vacuum and baked by fire and then cooled by nitrogen gas flow. 50 ml of anhydrous ether is added into the flask and (trimethylsilyl)diazomethane (6 ml, 12.0 mmol) is also added. At −78° C., n-butyl lithium agent (6 ml, 14.4 mmol) is added. After reacting for 0.5 hrs, 2-cyanopyridine (1.04 g, 10.0 mmol) is added. The reaction is then carried out for 12 hrs. After the reaction is finished, ether extraction is carried out and the organic layer is collected and then concentrated to obtained white solids. The white solids are placed in a 50 ml reaction flask, potassium fluoride (0.58 g, 10.0 mmol) is added, 10 ml of ethanol is added, and a few drops of hydrochloride are added. Hot reflux is carried out for 2 hrs. After the reaction is finished, the reaction solution is neutralized by saturated sodium bicarbonate solution. Ether extraction is carried out and the organic layer is collected and then concentrated to obtain white solids. After purified by silicone chromatographic column, the product pytz is obtained. The yield is about 60%. 1H NMR (500 MHz, CDCl3): δ 8.70 (s, 1 H), 8.36 (s, 1 H), 7.99 (s, 1 H), 7.82 (t, 1 H, J=8.0 Hz), 7.32-7.29 (m, 1 H). HRMS (EI) m/z:calculated value C7H6N4 146.0592; experimental value 146.0593.

Workup

  1. customA 250 ml reaction flask
  2. customis dried under vacuum and baked by fire
  3. temperaturecooled by nitrogen gas flow
  4. additionis also added
  5. waitThe reaction is then carried out for 12 hrs
  6. extractionether extraction
  7. customthe organic layer is collected
  8. concentrationconcentrated
  9. customto obtained white solids
  10. additionis added
  11. temperatureHot reflux
  12. waitis carried out for 2 hrs
  13. extractionEther extraction
  14. customthe organic layer is collected
  15. concentrationconcentrated
  16. customto obtain white solids
  17. customAfter purified by silicone chromatographic column
  18. customthe product pytz is obtained

Sources & evidence

ORD record
ord-e83691d9f39c4a33a601e1ca70e00ca3
Source dataset
uspto-grants-2011_11
Patent number
US08062767B2

Reaction notes

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