Sulfuric Acid → t-Butyl 7beta-amino-3-methyl-3-cephem-4-carboxylate

HRID 1763806Notes

Reaction equation

HRID 1763806 reaction equation
[NH2:1][C@@H:2]1[C:13](=[O:14])[N:4]2[C:5]([C:10]([OH:12])=[O:11])=[C:6]([CH3:9])[CH2:7][S:8][C@H:3]12.S(=O)(=O)(O)O.[CH3:20][C:21](=[CH2:23])[CH3:22].C(=O)(O)[O-].[Na+]>C(OCC)(=O)C.O1CCOCC1>[NH2:1][C@@H:2]1[C:13](=[O:14])[N:4]2[C:5]([C:10]([O:12][C:21]([CH3:23])([CH3:22])[CH3:20])=[O:11])=[C:6]([CH3:9])[CH2:7][S:8][C@H:3]12

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 8255IsobutyleneHCID 334987-Aminodeacetoxycephalosporanic acidHCID 516892Sodium Bicarbonate

Product 1

HCID 10869362t-Butyl 7beta-amino-3-methyl-3-cephem-4-carboxylate

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 7β-amino-3-methylceph-3-em-4-carboxylic acid (16.09 g., 75.2 m.moles), dioxan (100 ml.), sulphuric acid (10 ml.) and isobutylene (90 ml.) was shaken in a pressure bottle until a clear solution resulted (21/2 hours). The solution was cooled and poured into a mixture of aqueous sodium bicarbonate (600 ml.), ice (100 g.), and ethyl acetate (150 ml.). The aqueous layer was twice more extracted with ethyl acetate and the extracts were washed with brine and dried. Evaporation left a gum which was triturated with petrol (b.p. 40° - 60°) to give off-white crystals (11.17 g., 55%). A sample was recrystallised from ether to give the pure ester, m.p. 126°, [α]D + 107° (EtOH), λmax. 271 nm. (E1cm.1% 239) (Found: C, 53.1; H, 6.5; N, 10.1; S, 11.5 C12H18N2O3S requires: C, 53.3; H, 6.7; N, 10.35; S, 11.85%).

Workup

  1. customresulted (21/2 hours)
  2. temperatureThe solution was cooled
  3. extractionThe aqueous layer was twice more extracted with ethyl acetate
  4. washthe extracts were washed with brine
  5. customdried
  6. customEvaporation
  7. waitleft a gum which
  8. customwas triturated with petrol (b.p. 40° - 60°)
  9. customto give off-white crystals (11.17 g., 55%)
  10. customA sample was recrystallised from ether

Sources & evidence

ORD record
ord-5d6e8d039fb449e4b694137e40f39f38
Source dataset
uspto-grants-1978_09
Patent number
US04113591

Reaction notes

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