Ammonia → HCID 19711373, compound

HRID 725037Notes

Reaction equation

HRID 725037 reaction equation
[BH4-].[Na+].[C:3]([CH:5]=[CH:6][C:7]1[CH:8]=[C:9]([CH:17]=[C:18]([CH2:20][C:21]2[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=2)[CH:19]=1)[CH:10]=[CH:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])#[N:4].Cl.N>C(O)C.O.O.O.O.O.O.[Co](Cl)Cl>[NH2:4][CH2:3][CH2:5][CH2:6][C:7]1[CH:8]=[C:9]([CH2:10][CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:17]=[C:18]([CH2:20][C:21]2[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=2)[CH:19]=1

Participants

7

Reactant 4

HCID 222AmmoniaHCID 313Hydrochloric AcidHCID 4311764Sodium borohydrideHCID 53820694HCID 53820694, compound

Product 1

HCID 19711373HCID 19711373, compoundYield 40.2%

Reagents, catalysts & solvents 2

HCID 517166Dichlorocobalt hexahydrateCatalystHCID 702EthanolSolvent

Procedure

Sodium borohydride (2.30 g) was added portionwise with vigorous stirring to a solution of ethyl 3-(2-cyanoethenyl)-5-(3-pyridylmethyl)cinnamate (Preparation 19; 2.0 g) and cobalt(II) chloride hexahydrate (4.48 g) in ethanol (150 ml) at 0° C. The mixture was stirred for 2 hours, carefully acidified to pH 2 with concentrated hydrochloric acid, stirred for a further 10 minutes, basified with concentrated aqueous ammonia solution (SG 0.880) and then filtered. The filtered material was washed with ethyl acetate, the combined filtrate and washings washed with water, and the combined aqueous washings then extracted three times with dichloromethane. The organic extracts were combined, dried (MgSO4) and evaporated under vacuum to give a gum, which was chromatographed on silica gel. The column was eluted with a methanol in dichloromethane elution gradient (1% to 5% methanol), followed by a dichloromethane: methanol:aqueous ammonia (SG 0.880) elution gradient (94:5:1 to 90:9:1). The product fractions were combined and evaporated under vacuum to give the title compound as a gum (0.825 g); Rf 0.25 (SS 2); δ (CDCl3): 1.20(3H,t,J=7.1 Hz), 1.70-1.77(4H,m), 2.54-2.60(4H,m), 2.70(2H,t,J=7.0 Hz), 2.87(2H,t,J=7.8 Hz), 3.90(2H,s), 4.09(2H,q,J=7.1 Hz), 6.83(2H,s), 6.88(1H,s), 7.18-7.22(1H,m), 7.43-7.46(1H,m), 8.43-8.48(2H,m).

Workup

  1. stirringstirred for a further 10 minutes
  2. filtrationfiltered
  3. washThe filtered material was washed with ethyl acetate
  4. washthe combined filtrate and washings washed with water
  5. extractionthe combined aqueous washings then extracted three times with dichloromethane
  6. dry with materialdried (MgSO4)
  7. customevaporated under vacuum
  8. customto give a gum, which
  9. customwas chromatographed on silica gel
  10. washThe column was eluted with a methanol in dichloromethane elution gradient (1% to 5% methanol)
  11. washmethanol:aqueous ammonia (SG 0.880) elution gradient (94:5:1 to 90:9:1)
  12. customevaporated under vacuum

Sources & evidence

ORD record
ord-228f85a9d4044991913f497fd0a99d39
Source dataset
uspto-grants-1998_01
Patent number
US05705523

Reaction notes

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