N,N,N',N'-Tetramethylethylenediamine → HCID 178440152, compound

HRID 1249556Notes

Reaction equation

HRID 1249556 reaction equation
[CH3:1][CH:2]([C:4]1[N:5]=[CH:6][N:7](C(OCC)C)[C:8]=1[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[CH3:3].CN(C)CCN(C)C.C([Li])CCC.[F:33][C:34]([F:42])([F:41])[C:35]([C:37]([F:40])([F:39])[F:38])=[O:36].C(=O)(O)[O-].[Na+]>O1CCCC1.CCCCCC>[CH3:3][CH:2]([C:4]1[N:5]=[C:6]([C:35]([C:37]([F:40])([F:39])[F:38])([C:34]([F:42])([F:41])[F:33])[OH:36])[NH:7][C:8]=1[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1)[CH3:1]

Participants

8

Reactant 5

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 12695HexafluoroacetoneHCID 516892Sodium BicarbonateHCID 20223464HCID 20223464, compoundHCID 178418339Butyllithium

Product 1

HCID 178440152HCID 178440152, compoundYield 70%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a stirred solution of 4-(1-methylethyl)-5-phenyl-1-(α-ethoxyethyl)imidazole (13.9 g, 0.054 mole) in 210 ml of dry tetrahydrofuran was added 9.45 ml of tetramethylethylenediamine (0.06 moles). The reaction was cooled to -78° C. and 56.15 ml of 1.66M n-butyl lithium in hexane was added dropwise. After stirring the mixture for 20 minutes, hexafluoroacetone (14.0 ml) was condensed and added dropwise. The reaction was stirred an additional hour at -78° C. and then 275 ml of saturated aqueous sodium bicarbonate solution was added dropwise. After warming to room temperature, the layers were separated and the aqueous was extracted with ethyl acetate. The organic layers were combined and concentrated in vacuo. The residue was stirred overnight in 350 ml of ethanol and 350 ml of 2N aqueous hydrochloric acid. The ethanol was evaporated and the reaction mixture was basified to a pH of 8 with saturated aqueous potassium carbonate. The mixture was extracted with ether, washed with 10% aqueous sodium bicarbonate and dried over anhydrous magnesium sulfate. The residue was purified via flash chromatography on silica gel (98:2 hexane/ethyl acetate) to afford 13.19 g (70%) of the product which was recrystallized from hexane to give a white crystalline solid, m.p. 80°-81° C.

Workup

  1. customcondensed
  2. additionadded dropwise
  3. stirringThe reaction was stirred an additional hour at -78° C.
  4. temperatureAfter warming to room temperature
  5. customthe layers were separated
  6. extractionthe aqueous was extracted with ethyl acetate
  7. concentrationconcentrated in vacuo
  8. stirringThe residue was stirred overnight in 350 ml of ethanol
  9. customThe ethanol was evaporated
  10. extractionThe mixture was extracted with ether
  11. washwashed with 10% aqueous sodium bicarbonate
  12. dry with materialdried over anhydrous magnesium sulfate
  13. customThe residue was purified via flash chromatography on silica gel (98:2 hexane/ethyl acetate)

Sources & evidence

ORD record
ord-9444bcde5c8a40edb84e2d322d09ae13
Source dataset
uspto-grants-1986_12
Patent number
US04632930

Reaction notes

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