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Ethyl bromoacetate → 3-cyano-3-(pyrid-3-yl)pentanedioic Acid Diethyl Ester

HRID 323332
Notes
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Reaction equation

HRID 323332 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH2:7][C:8]#[N:9])[CH:2]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Na+].Br[CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23].[C:27]([O:30][CH2:31][CH3:32])(=[O:29])[CH3:28].CCCCCC>O1CCCC1>[CH2:25]([O:24][C:22](=[O:23])[CH2:21][C:7]([C:8]#[N:9])([C:3]1[CH:2]=[N:1][CH:6]=[CH:5][CH:4]=1)[CH2:28][C:27]([O:30][CH2:31][CH3:32])=[O:29])[CH3:26]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 4

HCID 7748Ethyl bromoacetateHCID 809233-PyridineacetonitrileHCID 2724254Sodium bis(trimethylsilyl)amideHCID 21226206Ethyl acetate hexane

Product 1

HCID 541828903-cyano-3-(pyrid-3-yl)pentanedioic Acid Diethyl Ester

Reagents, catalysts & solvents 1

HCID 8028
Tetrahydrofuran
Solvent
2×

Conditions

Temperature
-70 °C

Procedure

Combine 3-pyridineacetonitrile (25 g, 212 mmol) and tetrahydrofuran (200 mL). Cool to about −70° C . using a dry-ice/acetone bath. Add dropwise, a solution of sodium bis(trimethylsilyl)amide (435 mL, 1 M in tetrahydrofuran, 435 mmol) while maintaining the reaction temperature below about −68° C. When the addition is complete, warm the reaction mixture to ambient temperature and allow to stir for 1 hour. Transfer the above solution via cannula into a cooled (−5° C.) solution of ethyl bromoacetate (84.5 mL, 762 mmol) in tetrahydrofuran (500 mL) at such a rate that the temperature of the reaction mixture does not rise above about 15° C. Allow to stir at ambient temperature. After 18 hours, quench with saturated aqueous solution of ammonium chloride and evaporate in vacuo to remove most of the tetrahydrofuran. Extract the evaporated reaction mixture twice with diethyl ether. Dry the organic layer over MgSO4, filter, and concentrate in vacuo to obtain a residue. Chromatograph the residue on silica gel eluting with 1/1 ethyl acetate/hexane to give the title compound.

Workup

  1. additionAdd dropwise
  2. additionWhen the addition
  3. temperaturewarm the reaction mixture to ambient temperature
  4. customdoes not rise above about 15° C
  5. stirringto stir at ambient temperature
  6. waitAfter 18 hours
  7. customquench with saturated aqueous solution of ammonium chloride
  8. customevaporate in vacuo
  9. customto remove most of the tetrahydrofuran
  10. extractionExtract
  11. customthe evaporated reaction mixture twice with diethyl ether
  12. dry with materialDry the organic layer over MgSO4
  13. filtrationfilter
  14. concentrationconcentrate in vacuo
  15. customto obtain a residue

Sources & evidence

ORD record
ord-06239126d69343b5bae795088977285f
Source dataset
uspto-grants-2001_04
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06211199B1

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes