Hydrochloric Acid → 2-Carboxy-3-methyl-8-oxo-7-tritylamino-5-thia-1-aza-bicyclo[4.2.0]oct-2-ene

HRID 1902792Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1902792
C(N(CC)CC)C.[NH2:8][CH:9]1[C:16](=[O:17])[N:15]2[CH:10]1[S:11][CH2:12][C:13]([CH3:21])=[C:14]2[C:18]([OH:20])=[O:19].Cl[C:23]([C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)([C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.Cl>CN(C)C=O.C(Cl)(Cl)Cl>[C:18]([C:14]1[N:15]2[CH:10]([S:11][CH2:12][C:13]=1[CH3:21])[CH:9]([NH:8][C:23]([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)([C:36]1[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=1)[C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1)[C:16]2=[O:17])([OH:20])=[O:19]

Komponenten

7

Edukt 4

HCID 313Hydrochloric AcidHCID 18837-Amino-3-methyl-8-oxo-5-thia-1-azabicyclo(4.2.0)oct-2-ene-2-carboxylic acidHCID 6456Trityl chlorideHCID 8471Triethylamine

Produkt 1

HCID 205148112-Carboxy-3-methyl-8-oxo-7-tritylamino-5-thia-1-aza-bicyclo[4.2.0]oct-2-eneAusbeute 40 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6212ChloroformLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
25 °C

Versuchsvorschrift

Triethylamine (55.6 cc) is added to a suspension of 7-amino-2-carboxy-3-methyl-8-oxo-5-thia-1-aza-bicyclo[4.2.0]oct-2-ene (42.8 g) in dry N,N-dimethylformamide (250 cc), and after cooling the mixture to -20° C. a solution of chlorotriphenylmethane (55.8 g) in chloroform (250 cc) is added in the course of 2 hours. The reaction mixture is stirred for 24 hours at 25° C. and then poured into normal hydrochloric acid (400 cc). After filtration, the organic phase is separated off, concentrated to half its volume under reduced pressure (40 mm Hg) at 40° C., and taken up in ethyl acetate (400 cc). The aqueous phase is extracted with ethyl acetate (400 cc), and the combined organic phases are washed with normal hydrochloric acid (2×250 cc) and then extracted with a half-saturated sodium bicarbonate solution (4×500 cc). These combined aqueous phases are washed with ethyl acetate (300 cc), then acidified to pH 3 with 12 N hydrochloric acid and extracted with ethyl acetate (2×500 cc). The combined organic solutions are washed with a saturated sodium chloride solution (250 cc), dried over sodium sulphate and concentrated to dryness under reduced pressure (40 mm Hg) at 40° C. The residue is caused to solidify by adding isopropyl ether (250 cc). The solid is filtered off, washed with isopropyl ether (100 cc) and dried. A mixture (22.2 g) of 2-carboxy-3-methyl-8-oxo-7-tritylamino-5-thia-1-aza-bicyclo[4.2.0]oct-2-ene (40%) and its oct-3-ene isomer (60%) is obtained in the form of a cream-coloured solid.

Aufarbeitung

  1. additionis added in the course of 2 hours
  2. filtrationAfter filtration
  3. customthe organic phase is separated off
  4. concentrationconcentrated to half its volume under reduced pressure (40 mm Hg) at 40° C.
  5. extractionThe aqueous phase is extracted with ethyl acetate (400 cc)
  6. washthe combined organic phases are washed with normal hydrochloric acid (2×250 cc)
  7. extractionextracted with a half-saturated sodium bicarbonate solution (4×500 cc)
  8. washThese combined aqueous phases are washed with ethyl acetate (300 cc)
  9. extractionextracted with ethyl acetate (2×500 cc)
  10. washThe combined organic solutions are washed with a saturated sodium chloride solution (250 cc)
  11. dry with materialdried over sodium sulphate
  12. concentrationconcentrated to dryness under reduced pressure (40 mm Hg) at 40° C
  13. additionby adding isopropyl ether (250 cc)
  14. filtrationThe solid is filtered off
  15. washwashed with isopropyl ether (100 cc)
  16. customdried

Quellen und Nachweise

ORD-Eintrag
ord-767d5bd8019b4aea9fd3af38b015e43c
Quelldatensatz
uspto-grants-1982_12
Patentnummer
US04365062

Notizen zur Reaktion

Wird geladen…