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Malononitrile → 1,1-Dicyanocyclopentane

HRID 12478
Notes
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Reaction equation

HRID 12478 reaction equation
[C:1](#[N:5])[CH2:2][C:3]#[N:4].[CH2:6]1[CH2:16]CN2C(=NCCC2)[CH2:8][CH2:7]1.BrCCCCBr>CN(C=O)C>[C:2]1([C:1]#[N:5])([C:3]#[N:4])[CH2:8][CH2:7][CH2:6][CH2:16]1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 8010MalononitrileHCID 80561,4-DibromobutaneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene

Product 1

HCID 151720351,1-Dicyanocyclopentane

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

Malononitrile (15.0 g) was dissolved in dry DMF (200 mL) and cooled in an ice bath. Subsequently, DBU (75 mL, 2.2. equiv.) and 1,4-dibromobutane (29.6 mL, 1.1 equiv.) were added dropwise. The ice bath was removed, an extra 100 mL of dry DMF was added, and the mixture was stirred at 80° C. for 2 h. After cooling to ambient temperature, DCM was added and the mixture was washed 5 times with 5% aqueous NaHCO3. The organic phase was dried over Na2SO4 and evaporated under reduced pressure to give 40 g of a black oily substance. This was purified by flash chromatography eluting with PA:EA 9:1 (Rf=0.35, visualized with 12) to give 23.4 g of a colorless liquid. 1H NMR (400 MHz, CDCl3) δ 1.94-2.03 (m, 4H), 2.41 (t, J=7 Hz, 4H).

Workup

  1. temperaturecooled in an ice bath
  2. customThe ice bath was removed
  3. additionan extra 100 mL of dry DMF was added
  4. temperatureAfter cooling to ambient temperature
  5. additionDCM was added
  6. washthe mixture was washed 5 times with 5% aqueous NaHCO3
  7. dry with materialThe organic phase was dried over Na2SO4
  8. customevaporated under reduced pressure
  9. customto give 40 g of a black oily substance
  10. customThis was purified by flash chromatography
  11. washeluting with PA

Sources & evidence

ORD record
ord-00f2e267ad9c482b927013f0e68e637b
Source dataset
uspto-grants-2010_06
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07728018B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes