Sodium Chloride → HCID 178459334, compound

HRID 358267Notes

Reaction equation

HRID 358267 reaction equation
CC(OCC1CS[C@@H]2[C@H](N)C(=O)N2C=1C(O)=O)=O.CC1(C)OC(=O)C(C(=O)CC)C(=O)O1.O=C(CCC)C(N[C@@H]1C(=O)N2C(C(O)=O)=C(COC(=O)C)CS[C@H]12)=O.[O:58]=[C:59]([CH2:81][CH3:82])[CH2:60][C:61]([NH:63][C@@H:64]1[C:79](=[O:80])[N:66]2[C:67]([C:76]([OH:78])=[O:77])=[C:68]([CH2:71][O:72][C:73](=[O:75])[CH3:74])[CH2:69][S:70][C@H:65]12)=[O:62].[N:83]([O-])=[O:84].[Na+].[Cl-].[Na+]>C(O)(=O)C.O1CCCC1.O.C(OCC)(=O)C.O.O1CCCC1>[OH:84][N:83]=[C:60]([C:59](=[O:58])[CH2:81][CH3:82])[C:61]([NH:63][C@@H:64]1[C:79](=[O:80])[N:66]2[C:67]([C:76]([OH:78])=[O:77])=[C:68]([CH2:71][O:72][C:73](=[O:75])[CH3:74])[CH2:69][S:70][C@H:65]12)=[O:62]

Participants

12

Reactant 6

HCID 5234Sodium ChlorideHCID 4413287-Aminocephalosporanic acidHCID 108218792,2 dimethyl-5-propionyl-[1,3]dioxane-4,6 dioneHCID 23668193Sodium NitriteHCID 131713659HCID 131713659, compoundHCID 131713660HCID 131713660, compound

Product 1

HCID 178459334HCID 178459334, compound

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 21881883Oxolane--water (1/1)Solvent

Procedure

A suspension of 8.2 g. 7β-aminocephalosporanic acid in 100 ml. of tetrahydrofuran and 24 ml. of N,O-bistrimethylsilylacetamide is heated to reflux and stirred for two hours to yield a limpid solution. 6 grams of 2,2-dimethyl-4,6-dioxo-5-propanoyl-1,3-dioxane are added and the mixture is stirred for 3 hours at reflux and then cooled to room temperature and evaporated to dryness. The residue is dissolved in 300 ml. of ethyl acetate and 200 ml. of water. The insoluble phase is filtered off and separated. The organic phase is washed with 100 ml. of water, dried, decolourised over charcoal and evaporated to dryness. The residue is taken up with diisopropyl ether and a gummy product is obtained, which is triturated with diethyl ether to give 2 g. of 7β-(2-oxovaleramido)-3-acetoxymethylceph-3-em-4carboxylic acid melting at 127°-134° C. (with decomposition). To a solution of 1.6 g. of 7β-(3-oxovaleramido)-3-acetoxymethylceph-3-em-4-carboxylic acid in 25 ml of glacial acetic acid are added dropwise 0.6 g of sodium nitrite dissolved in 6 ml. of water. The mixture is stirred for one hour and a half, then 100 ml. of ethyl acetate and 100 ml. of a saturated solution of sodium chloride are added thereto. The organic phase is separated, washed twice with 50 ml. of water, made anhydrous and concentrated to small volume. The precipitate is filtered off and gives 0.9 g. of 7β-(2-hydroxyimido-3-oxovaleramido)-3-acetoxymethylceph-3-em-4-carboxylic acid melting at 190°-204° C. (with decomposition); [α]D =+97° C. (c=0.2 in tetrahydrofuran/water 1:1).

Workup

  1. additionA suspension of 8.2 g
  2. temperatureto reflux
  3. customto yield a limpid solution
  4. stirringthe mixture is stirred for 3 hours
  5. temperatureat reflux
  6. customevaporated to dryness
  7. dissolutionThe residue is dissolved in 300 ml
  8. filtrationThe insoluble phase is filtered off
  9. customseparated
  10. washThe organic phase is washed with 100 ml
  11. dry with materialof water, dried
  12. customevaporated to dryness
  13. customa gummy product is obtained
  14. customwhich is triturated with diethyl ether
  15. customto give 2 g
  16. dissolutiondissolved in 6 ml
  17. stirringThe mixture is stirred for one hour
  18. customThe organic phase is separated
  19. washwashed twice with 50 ml
  20. concentrationconcentrated to small volume
  21. filtrationThe precipitate is filtered off
  22. customgives 0.9 g

Sources & evidence

ORD record
ord-4189517c76764c4bb28df6987602f2f1
Source dataset
uspto-grants-1984_08
Patent number
US04465831

Reaction notes

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