反応 #451693

反応方程式

p-nitrobenzyl 7-amino-3-cephem-4-carboxylate hydrochloride

trimethylsilylacetamide

Vilsmeier reagent

phosphorus oxychloride

2-(2-formamido-4-thiazolyl)-2-methoxyimino acetic acid

→

p-nitrobenzyl 7-{2-(2-formamido-4-thiazolyl)-2-methoxyimino-acetamido}-3-cephem-4-carboxylate

収率 49.4%

溶媒

ethyl acetate

ethyl acetate

Water

ethyl acetate

dimethylformamide

反応条件

後処理

1. 1
   温度cooling
2. 2
   workup.STIRRINGthe mixture was stirred at the same temperature for 30 minutes
3. 3
   その他to prepared the activated acid solution
4. 4
   workup.ADDITIONTo the solution was added the activated acid solution at -20° C. all at once, and the mixture
5. 5
   workup.STIRRINGwas stirred at the same temperature for 2.5 hours
6. 6
   その他the ethyl acetate layer was separated
7. 7
   洗浄washed with 10% hydrochloric acid (60 ml.)
8. 8
   乾燥a saturated aqueous solution of sodium bicarbonate (60 ml.) and an aqueous solution of sodium chloride (50 ml.) in turn, dried over magnesium sulfate
9. 9
   workup.ADDITIONtreated with activated charcoal
10. 10
    その他evaporated under reduced pressure
11. 11
    workup.ADDITIONDiethyl ether was added to the residue
12. 12
    ろ過the precipitates were collected by filtration

実験手順

Vilsmeier reagent prepared from dimethylformamide (0.43 g.) and phosphorus oxychloride (0.92 g.) was suspended in dry ethyl acetate (10 ml.). To the suspension was added 2-(2-formamido-4-thiazolyl)-2-methoxyimino acetic acid (syn isomer, 1.15 g.) under ice-cooling with stirring, and the mixture was stirred at the same temperature for 30 minutes to prepared the activated acid solution. On the other hand, p-nitrobenzyl 7-amino-3-cephem-4-carboxylate hydrochloride (1.79 g.) and trimethylsilylacetamide (5.0 g.) were dissolved in ethyl acetate (40 ml.). To the solution was added the activated acid solution at -20° C. all at once, and the mixture was stirred at the same temperature for 2.5 hours. Water (60 ml.) and ethyl acetate (200 ml.) were added to the resultant solution, and the ethyl acetate layer was separated, washed with 10% hydrochloric acid (60 ml.), a saturated aqueous solution of sodium bicarbonate (60 ml.) and an aqueous solution of sodium chloride (50 ml.) in turn, dried over magnesium sulfate, treated with activated charcoal, and then evaporated under reduced pressure. Diethyl ether was added to the residue, and the precipitates were collected by filtration to give p-nitrobenzyl 7-{2-(2-formamido-4-thiazolyl)-2-methoxyimino-acetamido}-3-cephem-4-carboxylate (syn isomer, 1.30 g.), m.p. 210° to 212° C. (dec.).

出典