Ethyl Acetate → HCID 131715002, compound

HRID 1249426Notes

Reaction equation

HRID 1249426 reaction equation
BrCC(=O)CC(NC1C(=O)[N:10]2C(C(OC(C3C=CC=CC=3)C3C=CC=CC=3)=O)=C(/C=C/Cl)C[S:14][C@H:9]12)=O.[N:37]([O-])=O.[Na+].Br[CH2:42][C:43](=O)[C:44](=[N:76][OH:77])[C:45]([NH:47][CH:48]1[C:74](=[O:75])[N:50]2[C:51]([C:58]([O:60][CH:61]([C:68]3[CH:73]=[CH:72][CH:71]=[CH:70][CH:69]=3)[C:62]3[CH:67]=[CH:66][CH:65]=[CH:64][CH:63]=3)=[O:59])=[C:52](/[CH:55]=[CH:56]/[Cl:57])[CH2:53][S:54][C@H:49]12)=[O:46].C(OCC)(=O)C>C(Cl)Cl.C(O)(=O)C>[OH:77][N:76]=[C:44]([C:43]1[N:10]=[C:9]([NH2:37])[S:14][CH:42]=1)[C:45]([NH:47][CH:48]1[C:74](=[O:75])[N:50]2[C:51]([C:58]([O:60][CH:61]([C:68]3[CH:69]=[CH:70][CH:71]=[CH:72][CH:73]=3)[C:62]3[CH:67]=[CH:66][CH:65]=[CH:64][CH:63]=3)=[O:59])=[C:52](/[CH:55]=[CH:56]/[Cl:57])[CH2:53][S:54][C@H:49]12)=[O:46]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 23668193Sodium NitriteHCID 131714995HCID 131714995, compoundHCID 178520133HCID 178520133, compound

Product 1

HCID 131715002HCID 131715002, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of benzhydryl 7-(4-bromo-3-oxobutyramido)-3-[(E)-2-chlorovinyl]-3-cephem-4-carboxylate (3.5 g) in a mixture of methylene chloride (32 ml) and acetic acid (12 ml) was dropwise added an aqueous solution (3 ml) of sodium nitrite (0.61 g) at -22° C. and the mixture was stirred for 6 minutes at the same temperature to give a reaction mixture containing benzhydryl 7-(4-bromo-2-hydroxyimino-3-oxobutyramido)-3-[(E)-2-chlorovinyl]-3-cephem-4-carboxylate. To the reaction mixture was added ethyl acetate (0.77 g). The mixture was stirred for 5 minutes at -20° C. and washed with water and 10% aqueous solution of sodium chloride successively, and a mixture of thiourea (0.54 g) and N,N-dimethylacetamide (7.0 ml) was added thereto at 36° C. The mixture was evaporated to remove methylene chloride. The residue was dissolved in ethyl acetate, washed with water and dried over magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was triturated with diisopropyl ether and collected by filtration to give benzhydryl 7-[2-hydroxyimino-2-(2-aminothiazol-4-yl)acetamido]-3-[(E)-2-chlorovinyl]-3-cephem-4-carboxylate (syn isomer) (2.65 g).

Workup

  1. customto give a reaction mixture
  2. stirringThe mixture was stirred for 5 minutes at -20° C.
  3. washwashed with water and 10% aqueous solution of sodium chloride successively
  4. additiona mixture of thiourea (0.54 g) and N,N-dimethylacetamide (7.0 ml)
  5. additionwas added
  6. customat 36° C
  7. customThe mixture was evaporated
  8. customto remove methylene chloride
  9. dissolutionThe residue was dissolved in ethyl acetate
  10. washwashed with water
  11. dry with materialdried over magnesium sulfate
  12. customThe solvent was evaporated under reduced pressure
  13. customthe residue was triturated with diisopropyl ether
  14. filtrationcollected by filtration

Sources & evidence

ORD record
ord-df7bb8d6c22849178996c05d6c80b90c
Source dataset
uspto-grants-1986_12
Patent number
US04631274

Reaction notes

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