Sodium hydride → HCID 13240319, compound

HRID 1649595Notes

Reaction equation

HRID 1649595 reaction equation
[H-].[Na+].[C:3]1([C:9]2[N:10]=[N:11][C:12](=[O:14])[CH:13]=2)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[H][H].S(O[CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][O:34][C:35]([C:37]1[CH:38]([C:49]2[CH:54]=[CH:53][CH:52]=[C:51]([Cl:55])[C:50]=2[Cl:56])[C:39]([C:45]([O:47][CH3:48])=[O:46])=[C:40]([CH3:44])[NH:41][C:42]=1[CH3:43])=[O:36])(C1C=CC(C)=CC=1)(=O)=O>CN(C)C=O>[C:3]1([C:9]2[NH:10][N:11]=[C:12]([O:14][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][O:34][C:35]([C:37]3[CH:38]([C:49]4[CH:54]=[CH:53][CH:52]=[C:51]([Cl:55])[C:50]=4[Cl:56])[C:39]([C:45]([O:47][CH3:48])=[O:46])=[C:40]([CH3:44])[NH:41][C:42]=3[CH3:43])=[O:36])[CH:13]=2)[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1

Participants

6

Reactant 4

HCID 24758Sodium hydrideHCID 18519594HCID 18519594, compoundHCID 86739134HCID 86739134, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 13240319HCID 13240319, compoundYield 43.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

0.51 g (12 mmole) of 55% sodium hydride in mineral oil was suspended in 10 ml of N,N-dimethylformamide, to which was added gradually 2.40 g (15 mmole) of 3-phenyl-5-pyrazolone with stirring at room temperature. After evolution of hydrogen had ceased, to this solution was added dropwise 20 ml of a solution of 6.10 g (10 mmole) of the 1,4-dihydro-2,6-dimethyl-4-(2,3-dichlorophenyl)-3-methoxycarbonylpyridine-5-carboxylic acid 6-tosyloxyhexyl ester obtained in the above Step i in N,N-dimethylformamide, and stirring with heating at 60° C. was continued for 4 hours. The resultant reaction mixture was poured into 150 ml of ice water, and the separated product was extracted with 50 ml of ethyl acetate. This ethyl acetate solution was washed with 50 ml of water three times, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain a brown oily residue. This residue was chromatographed on a silica gel column using a chloroform-methanol mixed solution as an eluent, and the eluate fractions containing the intended compound were concentrated under reduced pressure to obtain crystals. These crystals were recrystallized from a mixed solution of benzene-hexane to obtain 2.63 g (yield 43.9%) of the 1,4-dihydro-2,6-dimethyl-4-(2,3-dichlorophenyl)-3-methoxycarbonylpyridine-5-carboxylic acid 6-(5-phenyl-3-pyrazolyloxy)hexyl ester.

Workup

  1. stirringstirring
  2. temperaturewith heating at 60° C.
  3. customThe resultant reaction mixture
  4. extractionthe separated product was extracted with 50 ml of ethyl acetate
  5. washThis ethyl acetate solution was washed with 50 ml of water three times
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customto obtain a brown oily residue
  9. customThis residue was chromatographed on a silica gel column
  10. additionthe eluate fractions containing the intended compound
  11. concentrationwere concentrated under reduced pressure
  12. customto obtain crystals
  13. customThese crystals were recrystallized from a mixed solution of benzene-hexane

Sources & evidence

ORD record
ord-33d2d242782540c3ba76dc0dee4874db
Source dataset
uspto-grants-1983_11
Patent number
US04418197

Reaction notes

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