N,N-Dimethylaniline → HCID 13669176, compound

HRID 638382Notes

Reaction equation

HRID 638382 reaction equation
[NH2:1][C@@H:2]1[C:33](=[O:34])[N:4]2[C:5]([C:17]([O:19][CH:20]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)=[O:18])=[C:6]([CH2:9][S:10][C:11]3[N:15]([CH3:16])[N:14]=[N:13][N:12]=3)[CH2:7][S:8][C@H:3]12.[Br:35][C:36]([Br:41])([CH2:39][Br:40])[CH:37]=O.CN(C)C1C=CC=CC=1.S(Cl)(Cl)=O.S([O-])(O)(=O)=O.[K+]>C(Cl)Cl>[Br:35][C:36]([Br:41])([CH2:39][Br:40])[CH:37]=[N:1][C@@H:2]1[C:33](=[O:34])[N:4]2[C:5]([C:17]([O:19][CH:20]([C:27]3[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=3)[C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)=[O:18])=[C:6]([CH2:9][S:10][C:11]3[N:15]([CH3:16])[N:14]=[N:13][N:12]=3)[CH2:7][S:8][C@H:3]12

Participants

7

Reactant 5

HCID 949N,N-DimethylanilineHCID 24386Thionyl ChlorideHCID 931082,2,3-TribromopropanalHCID 516920Potassium bisulfateHCID 12873516(6R,7R)-Benzhydryl 7-amino-3-((1-methyl-1H-tetrazol-5-ylthio)methyl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate

Product 1

HCID 13669176HCID 13669176, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-20 °C

Procedure

To a solution of benzhydryl 7β-amino-3-(1-methyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylate (2.473 g, 5.000 mmol) in methylene chloride (35 ml) was added under ice-cooling a solution of 2,2,3-tribromopropanal (1.474 g, 5.000 mmol) in methylene chloride (5 ml) and the mixture was stirred for 20 minutes. The reaction mixture was cooled to -20° C., N,N-dimethylaniline (3.5 ml) was added thereto and then thionyl chloride (0.5 ml, 6.9 mmol) was added dropwise. After stirring under ice-cooling for 2 hours, the reaction mixture was poured into a mixture of a saturated aqueous solution of potassium hydrogen sulfate (100 ml) with ice (100 g) followed by extraction with methylene chloride (400 ml, twice). The methylene chloride layer was washed successively with an ice-cooled saturated aqueous solution of potassium hydrogen sulfate (200 ml) and then ice-water (200 ml). Thereafter, the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was crystallized with the addition of ethyl acetate (20 ml). The crystalline substance was recovered by filtration, washed with a small volume of ice-cooled methylene chloride and dried under reduced pressure to yield 2.720 g (71%) of the title compound as a pale yellow crystal. This product gradually decomposed with coloration at 90° C. and higher.

Workup

  1. stirringAfter stirring under ice-
  2. temperaturecooling for 2 hours
  3. extractionfollowed by extraction with methylene chloride (400 ml
  4. washThe methylene chloride layer was washed successively with an ice-
  5. temperaturecooled saturated aqueous solution of potassium hydrogen sulfate (200 ml)
  6. dry with materialThereafter, the organic layer was dried over anhydrous magnesium sulfate
  7. distillationThe solvent was distilled off under reduced pressure
  8. customthe residue was crystallized with the addition of ethyl acetate (20 ml)
  9. filtrationThe crystalline substance was recovered by filtration
  10. washwashed with a small volume of ice-
  11. temperaturecooled methylene chloride
  12. customdried under reduced pressure

Sources & evidence

ORD record
ord-0dac488d28fd45f6ae4fb8fe23233db9
Source dataset
uspto-grants-1985_12
Patent number
US04560750

Reaction notes

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