Diisopropylamine → HCID 23325187, compound

HRID 1380488Notes

Reaction equation

HRID 1380488 reaction equation
[CH:1](=[N:8][CH2:9][C:10]#[C:11][Si](C)(C)C)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([N-]C(C)C)(C)C.[Li+].C([Li])CCC.C(NC(C)C)(C)C.CN(C)CCN(C)C.Br[CH2:45][C:46]([O:48][C:49]([CH3:52])([CH3:51])[CH3:50])=[O:47].[Cl-].[NH4+]>O1CCCC1.CCCCCC>[CH:1](=[N:8][CH:9]([C:10]#[CH:11])[CH2:45][C:46]([O:48][C:49]([CH3:52])([CH3:51])[CH3:50])=[O:47])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

10

Reactant 7

HCID 7912DiisopropylamineHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 25517Ammonium ChlorideHCID 79177tert-Butyl bromoacetateHCID 2724682Lithium diisopropylamideHCID 12918300HCID 12918300, compoundHCID 178418339Butyllithium

Product 1

HCID 23325187HCID 23325187, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 17.6 g of 1B in 300 ml of dry tetrahydrofuran was added drop-by-drop to a solution of lithium diisopropylamide (prepared by adding 38 ml of a 2.2M solution of n-butyllithium in hexane to a solution of 11 ml of diisopropylamine and 12 ml of tetramethylethylenediamine in 450 ml of tetrahydrofuran) at -78° C. under argon. The resulting solution was held at -78° C. for 40 minutes, then a solution of 13.5 ml of tert-butyl bromoacetate in 50 ml of dry tetrahydrofuran was added. The resulting mixture was stirred at -78° C. for 30 minutes, at 0° C. for 10 minutes, then was poured into 300 ml of ice water containing 4.5 g of ammonium chloride. The resulting mixture was extracted with ether, the extract was washed with water, treated with charcoal and the solvent was evaporated. The residue was stirred in a solution of 7.5 g of sodium methoxide in 700 ml of methanol for 24 hours at room temperature. Then the solvent was evaporated and the residue was mixed with 200 ml of water containing 7.5 g of ammonium chloride. The mixture was extracted with ether, the extract was washed with water, dried (MgSO4) and the solvent was evaporated to give tert-butyl 3-(benzylideneamino)-4-pentynoate (5A), as a brown oil.

Workup

  1. customprepared
  2. extractionThe resulting mixture was extracted with ether
  3. washthe extract was washed with water
  4. additiontreated with charcoal
  5. customthe solvent was evaporated
  6. stirringThe residue was stirred in a solution of 7.5 g of sodium methoxide in 700 ml of methanol for 24 hours at room temperature
  7. customThen the solvent was evaporated
  8. additionthe residue was mixed with 200 ml of water containing 7.5 g of ammonium chloride
  9. extractionThe mixture was extracted with ether
  10. washthe extract was washed with water
  11. dry with materialdried (MgSO4)
  12. customthe solvent was evaporated

Sources & evidence

ORD record
ord-59e729c1beed49e6916390b3a3339b58
Source dataset
uspto-grants-1986_04
Patent number
US04582529

Reaction notes

Loading…