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Tetrahydrofuran → Benzyl alpha-[3-phenoxymethyl-7-oxo4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-alpha-(methanesulfonyloxyethylidene)acetate

HRID 1155828
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1155828
C(N(CC)CC)C.[CH3:8][S:9](Cl)(=[O:11])=[O:10].[O:13]([CH2:20][C:21]1[S:27][CH:26]2[CH:23]([C:24](=[O:42])[N:25]2[C:28](=[C:39](O)[CH3:40])[C:29]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)=[O:30])[N:22]=1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.[O:43]1CCCC1>>[O:13]([CH2:20][C:21]1[S:27][CH:26]2[CH:23]([C:24](=[O:42])[N:25]2[C:28](=[CH:39][CH2:40][O:10][S:9]([CH3:8])(=[O:11])=[O:43])[C:29]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)=[O:30])[N:22]=1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1
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Komponenten

5

Edukt 4

HCID 8028TetrahydrofuranHCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 70503985Benzyl alpha-[3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-alpha-(1-hydroxyethylidene)acetate

Produkt 1

HCID 53869939Benzyl alpha-[3-phenoxymethyl-7-oxo4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-alpha-(methanesulfonyloxyethylidene)acetate

Versuchsvorschrift

One adds triethylamine (1.42 ml), and methanesulfonyl chloride (0.41 ml) to a solution of benzyl α-[3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-α-(1-hydroxyethylidene)acetate (2.12 g) in tetrahydrofuran (30 ml) at -30° C., stirs for 70 minutes to give benzyl α-[3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]-hept-2-en-6-yl]-α-(methanesulfonyloxyethylidene)acetate, adds morphline (0.6 ml) and stirs for 4 hours 50 minutes at 0° C. to give benzyl α-[3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-α-(1-morpholinoethylidene)acetate, cools to -50° C., adds pyridine (0.385 ml) and bromine (0.25 ml), and stirs for 30 minutes to give benzyl α-[3-phenoxymethyl-7-oxo-4-thia-2,6-bicyclo[3,2,0]hept-2-en-6-yl]-α-(1-morpholino-2-bromoethylidene)acetate, adds 5% hydrochloric acid (36 ml), methanol (42.5 ml), and tetrahydrofuran (12.5 ml) to give clear solution. The solution is concentrated, the resulting solution being extracted with ethyl acetate, washed with saturated saline, dried over sodium sulfate, and concentrated to give residue (2.31 g). Purification of the residue by chromatography over silica gel containing 10% water gives benzyl 7β-phenoxyacetamido-3-hydroxy-3-cephem-4-carboxylate (1.11 g). m.p. 126°-127° C.

Quellen und Nachweise

ORD-Eintrag
ord-c2bd9fb2a6254edb88aacc4740f5ad40
Quelldatensatz
uspto-grants-1982_06
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US04332722

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