Dimethylformamide → HCID 19773375, compound

HRID 1614261Notes

Reaction equation

HRID 1614261 reaction equation
[H-].[Na+].[O:3]1CC[CH2:5][CH2:4]1.C([C:11]1[CH:20]=[CH:19][CH:18]=[C:17]2[C:12]=1[CH2:13][CH2:14][CH:15]([N:21]([CH2:25][CH2:26][CH3:27])[CH2:22][CH2:23][CH3:24])[CH2:16]2)(=O)C.[CH3:28][N:29](C)C=O>>[C:4]([N:29]([C:11]1[CH:20]=[CH:19][CH:18]=[C:17]2[C:12]=1[CH2:13][CH2:14][CH:15]([N:21]([CH2:22][CH2:23][CH3:24])[CH2:25][CH2:26][CH3:27])[CH2:16]2)[CH3:28])(=[O:3])[CH3:5]

Participants

5

Reactant 4

HCID 6228Dimethylformamide2×HCID 8028TetrahydrofuranHCID 24758Sodium hydrideHCID 19773366HCID 19773366, compound

Product 1

HCID 19773375HCID 19773375, compound

Procedure

0.38 g of a 75% suspension of sodium hydride in paraffin oil (0.012 mol) are added to a mixture of 40 ml of absolute dimethylformamide and 5 ml of absolute tetrahydrofuran. Then 2.88 g (0.010 mol) of 5-acetyl-2-di-n-propylamino-tetraline (Example 4.3.4) dissolved in 10 ml of absolute dimethylformamide are added with stirring and cooling with ice. Then the mixture is stirred at ambient temperature until the reaction is complete (several hours; monitored by DC). After concentration by rotary evaporation, finally at 95° C. under a complete water-jet vacuum, the residue is shaken with 50 ml of water and 50 ml of methylene chloride. The aqueous phase separated off is extracted twice more with 15 ml of methylene chloride. The combined extracts are washed with 20 ml of water, dried with sodium sulphate and, after the drying agent has been filtered off, concentrated by rotary evaporation, finally at 80° C. under a complete water-jet vacuum. The residue cannot be crystallised either as a base or as a salt. Therefore it is purified by column chromatography on 150 g of silica gel with methylene chloride/methanol/conc. ammonia 90:10:0.5. The substance purified in this way (2.8 g, 92.6% of theory) does not crystallise either, even though it is pure according to thin layer chromatography (silica gel, above-mentioned mixture of solvents, Rf =0.64) and by NMR spectroscopy.

Workup

  1. additionare added
  2. temperaturecooling with ice
  3. stirringThen the mixture is stirred at ambient temperature until the reaction
  4. custom(several hours; monitored by DC)
  5. concentrationAfter concentration
  6. customby rotary evaporation
  7. stirringfinally at 95° C. under a complete water-jet vacuum, the residue is shaken with 50 ml of water and 50 ml of methylene chloride
  8. customThe aqueous phase separated off
  9. extractionis extracted twice more with 15 ml of methylene chloride
  10. washThe combined extracts are washed with 20 ml of water
  11. dry with materialdried with sodium sulphate
  12. filtrationafter the drying agent has been filtered off
  13. concentrationconcentrated by rotary evaporation, finally at 80° C. under a complete water-jet vacuum
  14. customThe residue cannot be crystallised either as a base or as a salt
  15. customTherefore it is purified by column chromatography on 150 g of silica gel with methylene chloride/methanol/conc
  16. customThe substance purified in this way (2.8 g, 92.6% of theory)
  17. customdoes not crystallise either, even though it
  18. additionis pure according to thin layer chromatography (silica gel, above-mentioned mixture of solvents, Rf =0.64) and by NMR spectroscopy

Sources & evidence

ORD record
ord-65edd55e84184fd3bc6f3a45fbfb9937
Source dataset
uspto-grants-1993_03
Patent number
US05196454

Reaction notes

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