反应详情

A 500 ml. Morton flask equipped with a condenser, stirrer, and dropping funnel was flame dried and charged with NaH (11.9 g - 61% dispersion in mineral oil; 0.3 mole) and 150 ml. of 10% DMF in benzene. Triethyl 1,1,2-ethanetricarboxylate (73.9 g; 0.3 mole) was then added with vigorous stirring over a one hour period. After stirring at room temperature for 0.5 hour, there was then added as rapidly as possible o-nitrobenzyl chloride (51.5 g; 0.3 mole). The resulting reaction mixture was heated at reflux for 23 hours. After cooling, insoluble material was removed by filtration (supercel). Water was added to the filtrate followed by aqueous HCl to acidify the aqueous layer. Extraction with ether followed. The combined ethereal extracts were then washed twice with water, once with brine, dried over Na2SO4, filtered and rendered free of solvent in vacuo. The viscous oil so obtained was dissolved in acetonitrile and washed with n-pentane to remove the mineral oil. Removal of the acetonitrile afforded the crude product. The IR (infrared) and NMR (nuclear magnetic resonance) spectra were consistent with the structure and this material was used directly in the next step without further purification.

1. customMorton flask equipped with a condenser, stirrer
2. temperaturewas flame
3. customdried
4. stirringAfter stirring at room temperature for 0.5 hour
5. customThe resulting reaction mixture
6. temperaturewas heated
7. temperatureat reflux for 23 hours
8. temperatureAfter cooling
9. custominsoluble material was removed by filtration (supercel)
10. additionWater was added to the filtrate
11. extractionExtraction with ether
12. washThe combined ethereal extracts were then washed twice with water, once with brine
13. dry with materialdried over Na2SO4
14. filtrationfiltered
15. customThe viscous oil so obtained
16. washwashed with n-pentane
17. customto remove the mineral oil
18. customRemoval of the acetonitrile