4-Methyl-4-nitro-1-phenyl-3-(pyridin-3-yl)pentan-1-one → HCID 12621421, compound

HRID 1730157Notes

Reaction equation

HRID 1730157 reaction equation
[CH3:1][C:2]([N+:20]([O-])=O)([CH3:19])[CH:3]([C:13]1[CH:14]=[N:15][CH:16]=[CH:17][CH:18]=1)[CH2:4][C:5]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)=O>[Zn].C(O)(=O)C>[CH3:1][C:2]1([CH3:19])[C@@H:3]([C:13]2[CH:14]=[N:15][CH:16]=[CH:17][CH:18]=2)[CH2:4][C@H:5]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[NH:20]1

Participants

4

Reactant 1

HCID 126213674-Methyl-4-nitro-1-phenyl-3-(pyridin-3-yl)pentan-1-one

Product 1

HCID 12621421HCID 12621421, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalyst2×HCID 176Acetic AcidSolvent

Procedure

A solution of 44.7 g. of 4-methyl-4-nitro-3-(3-pyridyl)-valerophenone in 420 ml. of glacial acetic acid is heated at 60° C. with stirring and treated portionwise with 44.7 g. of zinc dust. After 1 hour, an additional 44.7 g. of zinc dust are added and the reaction mixture is left to react for an additional hour. The cooled reaction mixture is filtered, the filter residue washed with glacial beingnabled acetic acid and the filtrate evaporated under reduced pressure. The residue is taken up in 400 ml. of water and made alkaline with potassium carbonate. The reaction mixture is extracted three times with 200 ml. of ethyl acetate each time, the organic phase is washed twice with water, dried over sodium sulfate and evaporated under reduced pressure. The resulting residue is crystallized with isopropyl ether and there is obtained a product with a melting point of 60°-61° C. The mother liquors are chromatographed on a 50-fold amount of silica gel with ether/diethylamine (95.5) and, after crystallization with isopropyl ether, there is obtained trans-3-(2,2-dimethyl-5-phenyl-3-pyrrolidinyl)-pyridine, with a melting point of 57°-58° C. A methanolic solution of the base product is treated with a methanolic solution of oxalic acid to obtain pH 6. The obtained crystals are washed with ether and the oxalate of the product with a melting point of 224°-225° C. is obtained.

Workup

  1. additiontreated portionwise with 44.7 g
  2. waitthe reaction mixture is left
  3. customto react for an additional hour
  4. customThe cooled reaction mixture
  5. filtrationis filtered
  6. washthe filter residue washed with glacial beingnabled acetic acid
  7. customthe filtrate evaporated under reduced pressure
  8. extractionThe reaction mixture is extracted three times with 200 ml
  9. washof ethyl acetate each time, the organic phase is washed twice with water
  10. dry with materialdried over sodium sulfate
  11. customevaporated under reduced pressure
  12. customThe resulting residue is crystallized with isopropyl ether
  13. customthere is obtained a product with a melting point of 60°-61° C
  14. customThe mother liquors are chromatographed on a 50-fold amount of silica gel with ether/diethylamine (95.5)
  15. customafter crystallization with isopropyl ether

Sources & evidence

ORD record
ord-73c8661bfb96491595043ddd3f148b2f
Source dataset
uspto-grants-1976_11
Patent number
US03991197

Reaction notes

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