Dimethylformamide → Triethyl 3-(2-nitrophenyl)propane-1,2,2-tricarboxylate

HRID 1283115Notes

Reaction equation

HRID 1283115 reaction equation
[H-].[Na+].CN(C=O)C.[CH:8]([C:20]([O:22][CH2:23][CH3:24])=[O:21])([C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11].[N+:25]([C:28]1[CH:35]=[CH:34][CH:33]=[CH:32][C:29]=1[CH2:30]Cl)([O-:27])=[O:26]>C1C=CC=CC=1.C(#N)C>[C:15]([C:8]([C:20]([O:22][CH2:23][CH3:24])=[O:21])([CH2:30][C:29]1[CH:32]=[CH:33][CH:34]=[CH:35][C:28]=1[N+:25]([O-:27])=[O:26])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])([O:17][CH2:18][CH3:19])=[O:16]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 119212-Nitrobenzyl chlorideHCID 24758Sodium hydrideHCID 81961Triethyl ethane-1,1,2-tricarboxylate

Product 1

HCID 21519361Triethyl 3-(2-nitrophenyl)propane-1,2,2-tricarboxylate

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 6342AcetonitrileSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-60404a6bf7f34a93be312d8817019a77
Source dataset
uspto-grants-1976_08
Patent number
US03974165

Reaction notes

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