Sodium hydride → HCID 13663146, compound

HRID 1589648Notes

Reaction equation

HRID 1589648 reaction equation
[H-].[Na+].[CH2:3]([N:10]([CH2:12][CH2:13][OH:14])[CH3:11])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.Cl[CH2:16][C:17](=[O:24])[CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20]>O1CCCC1>[CH2:3]([N:10]([CH2:12][CH2:13][O:14][CH2:16][C:17](=[O:24])[CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH3:11])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 66876N-Benzyl-N-methylethanolamineHCID 69484Ethyl 4-chloroacetoacetate

Product 1

HCID 13663146HCID 13663146, compoundYield 102%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Sodium hydride (60% (by weight) in oil, 8 g) was stirred in dry tetrahydrofuran (THF) (100 ml) under nitrogen while 2-(N-benzyl-N-methylamino)ethanol (17 g) was added slowly. The warm mixture was stirred for 1 hour, then kept cool on a water bath at room temperature (20°) while a solution of ethyl 4-chloroacetoacetate (16.5 g) in dry THF (100 ml) was added dropwise over 3.5 hours. The mixture was stirred overnight at room temperature under nitrogen, then quenched with a little ethanol and poured onto ice (100 g) and concentrated hydrochloric acid (30 ml). The THF was removed by evaporation, and the residue washed with light petroleum (b.p. 60°-80°) to remove mineral oil. The residue was basified with solid sodium carbonate and extracted with ethyl acetate (200 ml and 100 ml). The combined extracts were dried (Na2CO3), filtered and evaporated to give the title compound as an oil (30 g), sufficiently pure for further use. N.m.r. spectrum in CDCl 3, δ values: 7.27 (5H,s); 4.12 (2H,q); 4.06 (2H,s); 3.45-3.70 (6H,m); 2.61 (2H,t); 2.25 (3H,s); 1.23 (3H,t).

Workup

  1. additionwas added slowly
  2. additionwas added dropwise over 3.5 hours
  3. stirringThe mixture was stirred overnight at room temperature under nitrogen
  4. customquenched with a little ethanol
  5. additionpoured onto ice (100 g) and concentrated hydrochloric acid (30 ml)
  6. customThe THF was removed by evaporation
  7. washthe residue washed with light petroleum (b.p. 60°-80°)
  8. customto remove mineral oil
  9. extractionextracted with ethyl acetate (200 ml and 100 ml)
  10. dry with materialThe combined extracts were dried (Na2CO3)
  11. filtrationfiltered
  12. customevaporated

Sources & evidence

ORD record
ord-878e0651ab884705ab5a3b3709b12a9b
Source dataset
uspto-grants-1986_02
Patent number
US04572909

Reaction notes

Loading…