Acetate → HCID 131710772, compound

HRID 2398155Notes

Reaction equation

HRID 2398155 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[C@H:16]([NH:17][C:18](=[O:27])[C:19](=[N:25][OH:26])[C:20]3[S:21][CH:22]=[CH:23][CH:24]=3)[C:15](=[O:28])[N:10]2[C:11]=1[C:12]([O-:14])=[O:13])(=[O:3])[CH3:2].[Na+].[Cl:30][CH2:31][CH2:32][N:33]=[C:34]=[O:35].Cl.P([O-])([O-])([O-])=O.C([O-])(=O)C>CN(C)C=O.C(N(CC)CC)C>[C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[C@H:16]([NH:17][C:18](=[O:27])[C:19](=[N:25][O:26][C:34](=[O:35])[NH:33][CH2:32][CH2:31][Cl:30])[C:20]3[S:21][CH:22]=[CH:23][CH:24]=3)[C:15](=[O:28])[N:10]2[C:11]=1[C:12]([OH:14])=[O:13])(=[O:3])[CH3:2]

Participants

8

Reactant 5

HCID 175AcetateHCID 313Hydrochloric AcidHCID 1061PhosphateHCID 160352-Chloroethyl isocyanateHCID 131710758HCID 131710758, compound

Product 1

HCID 131710772HCID 131710772, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Procedure

A solution of sodium 3-acetoxymethyl-7β-[2-hydroxyimino-2-(thien-2-yl)acetamido]ceph-3-em-4-carboxylate (syn-isomer; 0.89 g) in dimethylformamide (11 ml.) containing triethylamine (0.22 g) was treated with 2-chloroethylisocyanate (0.25 g). The solution was allowed to stand at room temperature for thirty minutes, then at 5° for a further hour. It was poured into cold (5°) 2N hydrochloric acid, extracted three times with ethyl acetate, and the combined extracts washed with 2N-hydrochloric acid then water then extracted three times with a cold (5°) saturated aqueous sodium bicarbonate solution. The combined aqueous extracts were washed with ethyl acetate, acidified (2N-hydrochloric acid) and apidly extracted with ethyl acetate. The combined extracts were dried, concentrated to ca. 5 ml., and the concentrate added dropwise to petroleum (b.p. 40°-60° 250 ml.) The precipitated solid was filtered and dried to give the title acid (0.8 g; 76%), [α]D +33° (c 0.7 DMSO) λmax. (pH 6 phosphate buffer) 264 nm. (ε 17,200), νmax. (Nujol), 1786 (β-lactam), 1734 (acetate), 1682 and 1508 cm.-1 (CONH), τ (DMSO-d6) values include 0.12 (doublet J 9 Hz; NH), 2.12, 2.56, 2.74 (three guartets; thienyl protons), 7.97 (s; OCOCH3).

Workup

  1. waitto stand at room temperature for thirty minutes
  2. waitat 5° for a further hour
  3. extractionextracted three times with ethyl acetate
  4. washthe combined extracts washed with 2N-hydrochloric acid
  5. extractionwater then extracted three times with a cold (5°) saturated aqueous sodium bicarbonate solution
  6. washThe combined aqueous extracts were washed with ethyl acetate
  7. extractionapidly extracted with ethyl acetate
  8. customThe combined extracts were dried
  9. concentrationconcentrated to ca. 5 ml
  10. addition, and the concentrate added dropwise to petroleum (b.p. 40°-60° 250 ml.) The precipitated solid
  11. filtrationwas filtered
  12. customdried
  13. customto give the title acid (0.8 g; 76%), [α]D +33° (c 0.7 DMSO) λmax

Sources & evidence

ORD record
ord-c50347bde9d943fdb296c79c96996b76
Source dataset
uspto-grants-1977_05
Patent number
US04024134

Reaction notes

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