N,N,N',N'-Tetramethylethylenediamine → HCID 178503126, compound

HRID 1249553Notes

Reaction equation

HRID 1249553 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][C:12]([S:15][CH3:16])=[CH:11][CH:10]=1)[CH3:3].CN(C)CCN(C)C.C([Li])CCC.[F:35][C:36]([F:48])([F:47])[C:37](=[N:42][Si](C)(C)C)[C:38]([F:41])([F:40])[F:39].C(=O)(O)[O-].[Na+]>O1CCCC1.CCCCCC>[CH3:3][CH:2]([C:4]1[N:5]=[C:6]([C:37]([C:38]([F:41])([F:40])[F:39])([C:36]([F:48])([F:47])[F:35])[NH2:42])[NH:7][C:8]=1[C:9]1[CH:10]=[CH:11][C:12]([S:15][CH3:16])=[CH:13][CH:14]=1)[CH3:1]

Participants

8

Reactant 5

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 516892Sodium BicarbonateHCID 13274636[1,1-Di(trifluoromethyl)methyleneamino]trimethylsilaneHCID 137544744-(1-Methylethyl)-5-(4-methylthiophenyl)-1-(alpha-ethoxyethyl)imidazoleHCID 178418339Butyllithium

Product 1

HCID 178503126HCID 178503126, compoundYield 16.8%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a stirred solution of 4-(1-methylethyl)-5-(4-methylthiophenyl)-1-(α-ethoxyethyl)imidazole (12.0 g, 0.04 mole) in 150 ml of dry tetrahydrofuran was added 6.85 ml of tetramethylethylenediamine (0.045 moles). The reaction was cooled to -78° C. and 39.47 ml of 1.6M n-butyl lithium in hexane was added dropwise. After stirring the mixture for 20 minutes, 15.45 g of [1,1-di(trifluoromethyl)methyleneamino]-trimethylsilane was added dropwise. The reaction mixture was stirred an additional hour, warmed to 0° C. and 140 ml of saturated aqueous sodium bicarbonate solution was added dropwise. The reaction was warmed to room temperature and the layers were separated. The aqueous layer was extracted with ethyl acetate. The organic layers were combined and concentrated and the residue was stirred overnight in 260 ml of ethanol and 260 ml of 2N aqueous hydrochloric acid. The ethanol was evaporated and the aqueous was extracted with ether (3×), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The product was purified by flash chromatography on silica gel (92:8 hexane/ethyl acetate) to afford 2.67 g of a white crystalline solid, m.p. 105°-107° C.

Workup

  1. stirringThe reaction mixture was stirred an additional hour
  2. temperaturewarmed to 0° C.
  3. temperatureThe reaction was warmed to room temperature
  4. customthe layers were separated
  5. extractionThe aqueous layer was extracted with ethyl acetate
  6. concentrationconcentrated
  7. stirringthe residue was stirred overnight in 260 ml of ethanol
  8. customThe ethanol was evaporated
  9. extractionthe aqueous was extracted with ether (3×)
  10. dry with materialdried over anhydrous magnesium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. customThe product was purified by flash chromatography on silica gel (92:8 hexane/ethyl acetate)

Sources & evidence

ORD record
ord-6b07a24f42d94e67ace34e2148129832
Source dataset
uspto-grants-1986_12
Patent number
US04632930

Reaction notes

Loading…