Benzene → HCID 178494283, Verbindung

HRID 1111717

Reaktionsgleichung

Reaktionsgleichung von HRID 1111717
[C:1]([O:5][C:6]([C:8]1[N:13]2[C:14](=[O:17])[CH:15]([NH2:16])[C@H:12]2[S:11][CH2:10][C:9]=1[CH:18]([S:25][C:26]1[NH:30][N:29]=[N:28][N:27]=1)[CH2:19][CH2:20][S:21](=[O:24])(=[O:23])[NH2:22])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(C1C=C(C=C(C(C)(C)C)C=1O)[CH:38]=[O:39])(C)(C)C.C1C=CC=CC=1.[Pb](=O)=O>ClCCCl.O>[C:1]([O:5][C:6]([C:8]1[N:13]2[C:14](=[O:17])[C@:15]([NH2:16])([O:39][CH3:38])[C@H:12]2[S:11][CH2:10][C:9]=1[CH:18]([S:25][C:26]1[NH:30][N:29]=[N:28][N:27]=1)[CH2:19][CH2:20][S:21](=[O:24])(=[O:23])[NH2:22])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Komponenten

7

Edukt 4

HCID 241BenzeneHCID 14793Lead dioxideHCID 732193,5-Di-tert-butyl-4-hydroxybenzaldehydeHCID 178450703HCID 178450703, Verbindung

Produkt 1

HCID 178494283HCID 178494283, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 111,2-DichloroethaneLösungsmittelHCID 962WaterLösungsmittel

Versuchsvorschrift

A solution of 1.91 g. (4 mmol.) of 7-amino-3-[1-(2-sulfamoylethyl)tetrazol-5-ylthiomethyl]-3-cephem-4-carboxylic acid t-butyl ester and 0.94 g. (4 mmol.) of 3,5-di-t-butyl-4-hydroxybenzaldehyde in 150 ml. of dry benzene is refluxed for ca. 4 hours under a Dean-Stark trap until no more water separates. The solution is evoporated under reduced pressure to give a residue which is dissolved in 150 ml. of 1,2-dichloroethane and cooled to 0°-5° in an ice bath. Freshly prepared lead dioxide (5 g.) is added in 1 g. portions over 30 minutes and the reaction is stirred in the cold until complete consumption of the starting material is indicated by thin layer chromatography. The mixture is then filtered through Celite and the filter cake is washed with two 30 ml. portions of cold 1,2-dichloroethane. The filtrate is treated with 30 ml. of dry methanol (distilled from magnesium) and the reaction is stirred at ambient temperature for 3 hours until complete consumption of the intermediate and formation of a new product is shown by thin layer chromatography. The reaction mixture is evaporated to dryness and the residue is taken up in 50 ml. of methanol and treated with 4.0 g. of Girard reagent T (trimethylaminoacetohydrazide chloride). This solution is stirred at ambient temperature for 3 hours and evaporated under vacuum to give a solid residue which is partitioned between 150 ml. of ethyl acetate and 100 ml. of 20% aqueous sodium chloride solution. The organic phase is washed with three 100 ml. portions of 10% aqueous sodium chloride, two 100 ml. portions of water and 100 ml. of a saturated sodium chloride solution. The organic phase is dried (MgSO4), filtered and evaporated to dryness to give 7β-amino-7α-methoxy-3-[1-(2-sulfamoylethyl)tetrazol-5-ylthiomethyl]-3-cephem-4-carboxylic acid t-butyl ester.

Aufarbeitung

  1. customto give a residue which
  2. dissolutionis dissolved in 150 ml
  3. customcold until complete consumption of the starting material
  4. filtrationThe mixture is then filtered through Celite
  5. washthe filter cake is washed with two 30 ml
  6. additionThe filtrate is treated with 30 ml
  7. stirringof dry methanol (distilled from magnesium) and the reaction is stirred at ambient temperature for 3 hours until complete consumption of the intermediate and formation of a new product
  8. customThe reaction mixture is evaporated to dryness
  9. additionof methanol and treated with 4.0 g
  10. stirringThis solution is stirred at ambient temperature for 3 hours
  11. customevaporated under vacuum
  12. customto give a solid residue which
  13. customis partitioned between 150 ml
  14. washThe organic phase is washed with three 100 ml
  15. dry with materialThe organic phase is dried (MgSO4)
  16. filtrationfiltered
  17. customevaporated to dryness

Quellen und Nachweise

ORD-Eintrag
ord-9f37cc97b3164a3988399e02c1b271ad
Quelldatensatz
uspto-grants-1978_10
Patentnummer
US04118490

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