Ethylenediamine → cis-Cinnamic acid

HRID 1840892Notes

Reaction equation

HRID 1840892 reaction equation
[BH4-].[Na+].C(N)CN.[C:7]1([C:13]#[C:14][C:15]([OH:17])=[O:16])[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[H][H]>C(O)C.O.O.O.O.C([O-])(=O)C.[Ni+2].C([O-])(=O)C>[C:7]1(/[CH:13]=[CH:14]\[C:15]([OH:17])=[O:16])[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

7

Reactant 4

HCID 3301EthylenediamineHCID 69475Phenylpropiolic AcidHCID 4311764Sodium borohydrideHCID 178418361HCID 178418361, compound

Product 1

HCID 5372954cis-Cinnamic acidYield 68.8%

Reagents, catalysts & solvents 2

HCID 62601Nickel acetate tetrahydrateCatalystHCID 702EthanolSolvent2×

Procedure

Nickel (II) acetate tetrahydrate (0.16 g, 0.00063 moles) was dissolved in ethanol (6.3 mL) and placed under hydrogen atmosphere. The green solution was stirred rapidly while sodium borohydride (0.024 g, 0.00063 moles) in ethanol (0.63 mL) was added. The deep purple solution was then treated with ethylene diamine (0.42 mL, 0.0063 moles) followed by 3-phenylpropynoic acid (0.73 g, 0.005 moles). The reaction was stirred under hydrogen for 5 hours. The hydrogen was displaced with nitrogen and the suspension was filtered through diatomaceous earth to remove the catalyst. The filtrate was concentrated in vacuo. The residue was taken up in chloroform and water, and concentrated hydrochloric acid was added to acidify the aqueous layer. The layers were separated and the acidic layer was extracted three times more with chloroform. The organic layers were combined and concentrated. The material was purified by reverse phase HPLC on a Waters Bondapak® C18 column using a gradient of 10-40% acetonitrile and 0.25% aqueous trifluoroacetic acid as the eluent to give a white solid (0.51 g).

Workup

  1. additionwas added
  2. filtrationthe suspension was filtered through diatomaceous earth
  3. customto remove the catalyst
  4. concentrationThe filtrate was concentrated in vacuo
  5. additionwater, and concentrated hydrochloric acid was added
  6. customThe layers were separated
  7. extractionthe acidic layer was extracted three times more with chloroform
  8. concentrationconcentrated
  9. customThe material was purified by reverse phase HPLC on a Waters Bondapak® C18 column

Sources & evidence

ORD record
ord-b63a881f6e0a49a69b175d4585c8f5b6
Source dataset
uspto-grants-2004_01
Patent number
US06683090B1

Reaction notes

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