Sodium Chloride → HCID 88790938, compound

HRID 1448032Notes

Reaction equation

HRID 1448032 reaction equation
[CH2:1]=[C:2]1[O:6][C:4](=[O:5])[CH2:3]1.[Br:7]Br.[NH2:9][CH:10]1[C:42](=[O:43])[N:12]2[C:13]([C:26]([O:28][CH:29]([C:36]3[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=3)[C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)=[O:27])=[C:14]([C:17]3[S:18][C:19]([NH:22][C:23](=[O:25])[CH3:24])=[N:20][N:21]=3)[CH2:15][S:16][C@H:11]12.[Cl-].[Na+]>ClCCl.N1C=CC=CC=1>[Br:7][CH2:6][C:2](=[O:1])[CH2:3][C:4]([NH:9][CH:10]1[C:42](=[O:43])[N:12]2[C:13]([C:26]([O:28][CH:29]([C:36]3[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=3)[C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)=[O:27])=[C:14]([C:17]3[S:18][C:19]([NH:22][C:23](=[O:25])[CH3:24])=[N:20][N:21]=3)[CH2:15][S:16][C@H:11]12)=[O:5]

Participants

7

Reactant 4

HCID 5234Sodium ChlorideHCID 12661DiketeneHCID 24408BromineHCID 70583915HCID 70583915, compound

Product 1

HCID 88790938HCID 88790938, compoundYield 58%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent4×

Conditions

Temperature
0 °C

Procedure

In 10.5 ml of dichloromethane there were dissolved 2.1 g of diketene and, under stirring, a solution of 4.00 g of bromine in 12.5 ml of dichloromethane was added dropwise at a temperature not exceeding -20° C. After the dropwise addition was completed, the mixture was maintained at 0° C. for 10 minutes. Separately, 0.5 g of benzhydryl 7-amino-3-(5-acetylamino-1,3,4-thiadiazol-2-yl)-3-cephem-4-carboxylate was suspended in 15 ml of dichloromethane and, under stirring, 1.37 ml of the above acid bromide solution were added at a temperature not exceeding -40° C. Following this dropwise addition, the mixture was stirred at room temperature for one hour. Then, a solution of 0.085 g of pyridine in 2 ml of dichloromethane was added and the mixture was further stirred for 30 minutes. A saturated aqueous solution of sodium chloride was added to the reaction mixture, which was then extracted with ethyl acetate. The ethyl acetate layer was washed with a saturated aqueous solution of sodium chloride and dried over magnesium sulfate. The solvent was evaporated off under reduced pressure and the residue was loosened up with the addition of ether. The resultant powder was recovered by filtration and dried. By the above procedure 0.383 g of benzhydryl 7-(4-bromo-3-oxobutyrylamino)-3-(5-acetylamino-1,3,4-thiadiazol-2-yl)-3-cephem-4-carboxylate was obtained.

Workup

  1. customexceeding -20° C
  2. additionAfter the dropwise addition
  3. stirringunder stirring
  4. customexceeding -40° C
  5. additionthis dropwise addition
  6. stirringthe mixture was stirred at room temperature for one hour
  7. stirringthe mixture was further stirred for 30 minutes
  8. extractionwas then extracted with ethyl acetate
  9. washThe ethyl acetate layer was washed with a saturated aqueous solution of sodium chloride
  10. dry with materialdried over magnesium sulfate
  11. customThe solvent was evaporated off under reduced pressure
  12. additionthe residue was loosened up with the addition of ether
  13. filtrationThe resultant powder was recovered by filtration
  14. customdried

Sources & evidence

ORD record
ord-f4ce3d12c9ba4bcba11477c7b39a3aba
Source dataset
uspto-grants-1979_12
Patent number
US04179502

Reaction notes

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