Hydrochloric Acid → (3-Aminophenyl)-2-pyridinylmethanone

HRID 2231747Notes

Reaction equation

HRID 2231747 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]([C:9]1[CH:10]=[C:11]([NH:15]C(C2C=CN3C=2CSC3C2C=NC=CC=2)=O)[CH:12]=[CH:13][CH:14]=1)=[O:8].[N+](C1C=C(C=CC=1)C(C1C=CC=CN=1)=O)([O-])=O.Cl>C(O)C>[NH2:15][C:11]1[CH:10]=[C:9]([CH:14]=[CH:13][CH:12]=1)[C:7]([C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][N:1]=1)=[O:8]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 125057027693-37-4HCID 19911334HCID 19911334, compound

Product 1

HCID 10726618(3-Aminophenyl)-2-pyridinylmethanone

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
20 °C

Procedure

The 2-(3-aminobenzoyl)pyridine may be prepared as follows: Stannous chloride in the dihydrate form (63 g) is added, at a temperature in the vicinity of 3° C., to a suspension of 2-(3-nitrobenzoyl)pyridine (19 g) in a 3.7N solution (360 cc) of hydrogen chloride in ethanol, in the course of 45 minutes. The suspension obtained is stirred at a temperature in the vicinity of 4° C. for 1 hour and 30 minutes, at a temperature in the vicinity of 20° C. for 1 hour and 30 minutes and then at a temperature in the vicinity of 80° C. for 1 hour and 30 minutes. The solvent is evaporated off under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature in the vicinity of 50° C. The residue is taken up with distilled water (200 cc). The aqueous solution is adjusted to a pH in the region of 11 by adding an aqueous 10N sodium hydroxide solution at a temperature in the vicinity of 25° C., saturated with sodium chloride and then extracted 3 times with diethyl ether (600 cc in total). The ether extracts are combined, washed 3 times with a saturated aqueous sodium chloride solution (300 cc in total), dried over anhydrous magnesium sulphate, treated with decolourizing charcoal (0.5 g), filtered and concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature in the vicinity of 40° C. A crude product (15.8 g) is obtained, which is chromatographed on an 8 cm diameter column containing silica (0.02-0.045 mm; 500 g). Elution is carried out with a mixture of cyclohexane and ethyl acetate (50:50 by volume) at a pressure of 0.4 bar (40 kPa), collecting 400 cc fractions. The first 7 fractions are discarded. The following 7 fractions are combined and concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature in the vicinity of 50° C. 2-(3-Aminobenzoyl) pyridine (12 g) in the form of a red oil is thereby obtained and it is used in the subsequent syntheses.

Workup

  1. customThe suspension obtained
  2. waitat a temperature in the vicinity of 80° C. for 1 hour
  3. custom30 minutes
  4. customThe solvent is evaporated off under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature in the vicinity of 50° C
  5. additionby adding an aqueous 10N sodium hydroxide solution at a temperature in the vicinity of 25° C.
  6. extractionsaturated with sodium chloride and then extracted 3 times with diethyl ether (600 cc in total)
  7. washwashed 3 times with a saturated aqueous sodium chloride solution (300 cc in total)
  8. dry with materialdried over anhydrous magnesium sulphate
  9. additiontreated with decolourizing charcoal (0.5 g)
  10. filtrationfiltered
  11. concentrationconcentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature in the vicinity of 40° C
  12. customA crude product (15.8 g) is obtained
  13. customwhich is chromatographed on an 8 cm diameter column
  14. additioncontaining silica (0.02-0.045 mm; 500 g)
  15. washElution
  16. additionis carried out with a mixture of cyclohexane and ethyl acetate (50:50 by volume) at a pressure of 0.4 bar (40 kPa)
  17. customcollecting 400 cc fractions
  18. concentrationconcentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature in the vicinity of 50° C

Sources & evidence

ORD record
ord-8f531e229c684c55b7536203b106047a
Source dataset
uspto-grants-1988_11
Patent number
US04783472

Reaction notes

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