Tetrahydrofuran → (E)-N-ethyl-N-(6,6-dimethyl-2-hepten-4-ynyl)-6-hydroxy-4-oxo-6-[3-(3-thienyl)phenyl] hexenylamine

HRID 1756152Notes

Reaction equation

HRID 1756152 reaction equation
O1CCCC1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH2:16]([N:18]([CH2:28][CH2:29][CH2:30][C:31](=[O:33])[CH3:32])[CH2:19]/[CH:20]=[CH:21]/[C:22]#[C:23][C:24]([CH3:27])([CH3:26])[CH3:25])[CH3:17].[S:34]1[CH:38]=[CH:37][C:36]([C:39]2[CH:40]=[C:41]([CH:44]=[CH:45][CH:46]=2)[CH:42]=[O:43])=[CH:35]1>O.C(OCC)(=O)C.C(O)(=O)C>[CH2:16]([N:18](/[CH:28]=[CH:29]/[CH2:30][C:31](=[O:33])[CH2:32][CH:42]([OH:43])[C:41]1[CH:44]=[CH:45][CH:46]=[C:39]([C:36]2[CH:37]=[CH:38][S:34][CH:35]=2)[CH:40]=1)[CH2:19][CH:20]=[CH:21][C:22]#[C:23][C:24]([CH3:25])([CH3:26])[CH3:27])[CH3:17]

Participants

8

Reactant 4

HCID 8028Tetrahydrofuran4×HCID 2733832Lithium HexamethyldisilazideHCID 45475263-(Thiophen-3-yl)benzaldehydeHCID 19917081HCID 19917081, compound

Product 1

HCID 86747786(E)-N-ethyl-N-(6,6-dimethyl-2-hepten-4-ynyl)-6-hydroxy-4-oxo-6-[3-(3-thienyl)phenyl] hexenylamineYield 40%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

A 1M tetrahydrofuran solution (0.6 ml) of lithium bis-(trimethylsilyl)amide was added to 1 ml of tetrahydrofuran under an argon atmosphere, and the mixture was cooled to -78° C. To this solution were added, dropwise with stirring, a tetrahydrofuran solution (2 ml) of 125 mg of (E)-N-ethyl-N-(6,6-dimethyl-2-hepten-4-ynyl)-4-oxo-pentylamine, followed by a tetrahydrofuran solution (2 ml) of 94 mg of 3-(3-thienyl)-benzaldehyde. The mixture was stirred at -78° C. for 1 hour, and then at 0° C. for 1 hour. The reaction mixture was neutralized with acetic acid, and ethyl acetate and water were added to extract it. The organic layer was separated, washed with a saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate. The desiccant was separated by filtration, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography [ethyl acetate→ethyl acetate/methanol=20/1] to give 78 mg (yield 40%) of (E)-N-ethyl-N-(6,6-dimethyl-2-hepten-4-ynyl)-6-hydroxy-4-oxo-6-[3-(3-thienyl)phenyl] hexenylamine.

Workup

  1. additionTo this solution were added
  2. stirringThe mixture was stirred at -78° C. for 1 hour
  3. additionwere added
  4. extractionto extract it
  5. customThe organic layer was separated
  6. washwashed with a saturated aqueous solution of sodium chloride
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customThe desiccant was separated by filtration
  9. customthe solvent was evaporated under reduced pressure
  10. customThe residue was purified by silica gel column chromatography [ethyl acetate→ethyl acetate/methanol=20/1]

Sources & evidence

ORD record
ord-f3cb65862ac044e6ad8e8144e91f4eda
Source dataset
uspto-grants-1995_08
Patent number
US05439932

Reaction notes

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