Diisopropylamine → HCID 86629994, compound

HRID 656464Notes

Reaction equation

HRID 656464 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH2:13]([N:20]1[CH:25]([C:26]#[N:27])[CH2:24][CH2:23][CH2:22][CH:21]1[C:28]#[N:29])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.CN(C)P(=O)(N(C)C)N(C)C.Br[CH2:42][C:43]([O:45][C:46]([CH3:49])([CH3:48])[CH3:47])=[O:44]>O1CCCC1>[CH2:13]([N:20]1[CH:25]([C:26]#[N:27])[CH2:24][CH2:23][CH2:22][C:21]1([CH2:42][C:43]([O:45][C:46]([CH3:49])([CH3:48])[CH3:47])=[O:44])[C:28]#[N:29])[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 12679HexamethylphosphoramideHCID 79177tert-Butyl bromoacetateHCID 1767161-Benzylpiperidine-2,6-dicarbonitrileHCID 178418339Butyllithium

Product 1

HCID 86629994HCID 86629994, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-20 °C

Procedure

A solution of 378.000 mmol of diisopropylamine in 180 ml of tetrahydrofuran is admixed dropwise at −78° C. with 179.000 mmol of n-butyllithium (1.6M in hexane). The yellowish solution is stirred at −20° C. for 30 minutes then cooled again to −78° C. This solution is admixed dropwise at −78° C. with a solution of 126.000 mmol of 1-benzylpiperidine-2,6-dicarbonitrile [98195-08-5] and 138.600 mmol of hexamethylphosphorictriamide in 50 ml of tetrahydrofuran. The mixture is subsequently stirred at this temperature for 30 minutes. Then a solution of 130.000 mmol of tert-butyl bromoacetate in 50 ml of tetrahydrofuran is added dropwise. The mixture is subsequently stirred at −78° C. for an hour, the cold bath is removed, and the temperature is allowed to increase slowly overnight to room temperature. The reaction mixture is admixed with aqueous saturated ammonium chloride solution, the organic phase is separated off and the aqueous phase is extracted repeatedly with diethyl ether. The combined organic phases are washed with water and brine, dried with sodium sulphate and evaporated. From the residue the title compound is obtained by means of flash chromatography (SiO2 60 F) and identified on the basis of the Rf value.

Workup

  1. temperaturethen cooled again to −78° C
  2. stirringThe mixture is subsequently stirred at this temperature for 30 minutes
  3. stirringThe mixture is subsequently stirred at −78° C. for an hour
  4. customthe cold bath is removed
  5. temperatureto increase slowly overnight to room temperature
  6. customthe organic phase is separated off
  7. extractionthe aqueous phase is extracted repeatedly with diethyl ether
  8. washThe combined organic phases are washed with water and brine
  9. dry with materialdried with sodium sulphate
  10. customevaporated

Sources & evidence

ORD record
ord-017280aeed7640c4a73a189a8b1998d5
Source dataset
uspto-grants-2011_12
Patent number
US08071773B2

Reaction notes

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