N,N-Dimethylaniline → tert-Butyl 7beta-(2',2',3'-trichlorobutylideneamino)-3-methyl-3-cephem-4-carboxylate

HRID 638383Notes

Reaction equation

HRID 638383 reaction equation
[NH2:1][C@@H:2]1[C:17](=[O:18])[N:4]2[C:5]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])=[C:6]([CH3:9])[CH2:7][S:8][C@H:3]12.C([C:23]([C:25](Cl)(Cl)[Cl:26])=O)CCC.[CH3:29]N(C)C1C=CC=CC=1.S(Cl)(Cl)=O.[CH2:42]([Cl:44])[Cl:43]>>[Cl:43][C:42]([Cl:44])([CH:25]([Cl:26])[CH3:23])[CH:29]=[N:1][C@@H:2]1[C:17](=[O:18])[N:4]2[C:5]([C:10]([O:12][C:13]([CH3:14])([CH3:16])[CH3:15])=[O:11])=[C:6]([CH3:9])[CH2:7][S:8][C@H:3]12

Participants

6

Reactant 5

HCID 949N,N-DimethylanilineHCID 6344DichloromethaneHCID 24386Thionyl ChlorideHCID 10869362t-Butyl 7beta-amino-3-methyl-3-cephem-4-carboxylateHCID 539370051,1,1-Trichlorohexan-2-one

Product 1

HCID 13669180tert-Butyl 7beta-(2',2',3'-trichlorobutylideneamino)-3-methyl-3-cephem-4-carboxylateYield 100%

Procedure

To a solution of tert-butyl 7β-amino-3-methyl-3-cephem-4-carboxylate (1.35 g, 5.00 mmol) in methylene chloride (30 ml) was added dropwise under ice-cooling butyl chloral (2,2,3-trichlorobutanal) (0.63 ml, 5.0 mmol). The reaction mixture was stirred at room temperature for 10 minutes, was allowed to cool to -20° C., N,N-dimethylaniline (3 ml) was added thereto and then thionyl chloride (0.5 ml) was added dropwise. After stirring under ice-cooling for 1.5 hours, the reaction mixture was poured into ice-water (40 ml), extracted with methylene chloride (30 ml, twice). The organic layer was washed successively with an ice-cooled saturated aqueous solution of potassium hydrogen sulfate (30 ml, twice), ice-water (30 ml), an ice-cooled saturated aqueous solution of sodium hydrogen carbonate (30 ml) and ice-water (30 ml) and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give 2.13 g (100%) of the title compound as a pale yellow foamy substance.

Workup

  1. temperatureto cool to -20° C.
  2. stirringAfter stirring under ice-
  3. temperaturecooling for 1.5 hours
  4. extractionextracted with methylene chloride (30 ml
  5. washThe organic layer was washed successively with an ice-
  6. temperaturecooled saturated aqueous solution of potassium hydrogen sulfate (30 ml
  7. temperaturetwice), ice-water (30 ml), an ice-cooled saturated aqueous solution of sodium hydrogen carbonate (30 ml) and ice-water (30 ml)
  8. dry with materialdried over anhydrous magnesium sulfate
  9. distillationThe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-63852b633b3a4d299dd1ce4815239cf1
Source dataset
uspto-grants-1985_12
Patent number
US04560750

Reaction notes

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