Triethylamine → HCID 131713497, compound

HRID 326167Notes

Reaction equation

HRID 326167 reaction equation
[C:1]([NH:4]/[CH:5]=[CH:6]/[S:7][C:8]1[CH2:14][C@H:13]2[N:10]([C:11](=[O:18])[C@H:12]2[C@@H:15]([OH:17])[CH3:16])[C:9]=1[C:19]([O-:21])=[O:20])(=[O:3])[CH3:2].[Na+:22].[Na].C(N(CC)CC)C.[Br:31]Br>O.CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-].ClCCl.C(Cl)(Cl)(Cl)Cl>[C:1]([NH:4][CH:5]=[C:6]([Br:31])[S:7][C:8]1[CH2:14][C@H:13]2[N:10]([C:11](=[O:18])[C@H:12]2[C@@H:15]([OH:17])[CH3:16])[C:9]=1[C:19]([O-:21])=[O:20])(=[O:3])[CH3:2].[Na+:22]

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 24408BromineHCID 5360545SodiumHCID 131713498HCID 131713498, compound

Product 1

HCID 131713497HCID 131713497, compound

Reagents, catalysts & solvents 4

HCID 21218Trioctylmethylammonium chlorideCatalyst2×HCID 962WaterSolventHCID 5943Carbon TetrachlorideSolventHCID 6344DichloromethaneSolvent3×

Procedure

Sodium (5R,6R)-3-[(E)-2-acetamidoethenylthio]-6-[(S)-1-hydroxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (200 mg; 85% pure) in water (10 ml) was treated with dichloromethane (10 ml) containing Aliquat 336 (600 mg). After shaking and separating the aqueous layer was again treated with dichloromethane (10 ml) containing Aliquat 336 (600 mg). The two dichloromethane extracts were dried (MgSO4) and evaporated to leave a mixture of Aliquat 336 and the quaternary ammonium salt corresponding to the starting sodium salt. This mixture was taken up in dry dichloromethane (10 ml), cooled to -70° and treated with triethylamine in dichloromethane (0.55 ml; 100 mg/ml), followed by bromine in carbon tetrachloride (0.82 ml; 100 mg/ml). After stirring in the cold for 25 minutes the mixture was warmed to room temperature, washed with water (3.5 ml) and extracted with saturated aqueous NaCl (2×5 ml). The NaCl extracts were combined and loaded onto a column of DIAION HP20 (18×1 cm). The column was eluted with saturated aqueous NaCl (25 ml) and then with deionised water. Some fractions containing the title compound (λmax ca 299 and 248 nm) were obtained. The column was then eluted with water containing 10% ethanol to give further fractions containing the title compound. Fractions containing the title compound were combined and evaporated in vacuo to low volume, ethanol was added and evaporated to low volume (4×), and toluene added and evaporated to dryness (3×) to give the title compound (29 mg) of estimated purity of ca 40%:λmax (H2O) 300(6,100), 246 (9,000) nm; λmax(KBr) 1750, 1690, 1620 cm-1.

Workup

  1. customseparating the aqueous layer
  2. additionwas again treated with dichloromethane (10 ml)
  3. additioncontaining Aliquat 336 (600 mg)
  4. dry with materialThe two dichloromethane extracts were dried (MgSO4)
  5. customevaporated
  6. customto leave
  7. temperaturecooled to -70°
  8. stirringAfter stirring in the cold for 25 minutes the mixture
  9. washwashed with water (3.5 ml)
  10. extractionextracted with saturated aqueous NaCl (2×5 ml)
  11. washThe column was eluted with saturated aqueous NaCl (25 ml)
  12. additionSome fractions containing the title compound (λmax ca 299 and 248 nm)
  13. customwere obtained
  14. washThe column was then eluted with water containing 10% ethanol
  15. customto give further fractions

Sources & evidence

ORD record
ord-80e1b2a830c04defa8adfb6901b4faf6
Source dataset
uspto-grants-1984_04
Patent number
US04444783

Reaction notes

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