Pyridine-2-carbonitrile → HCID 23568413, compound

HRID 1822698Notes

Reaction equation

HRID 1822698 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][N:4]=1)#[N:2].Cl.[CH3:10][NH:11][OH:12].C(=O)([O-])[O-].[Na+].[Na+].[C:19]([C:26]([O:28][CH2:29]C)=[O:27])#[C:20][C:21]([O:23][CH2:24][CH3:25])=[O:22]>C(OCC)(=O)C.O.C(O)C>[CH2:24]([O:23][C:21]([C:20]1([CH2:19][C:26]([O:28][CH3:29])=[O:27])[O:12][N:11]([CH3:10])[C:1]([C:3]2[CH:8]=[CH:7][CH:6]=[CH:5][N:4]=2)=[N:2]1)=[O:22])[CH3:25]

Participants

7

Reactant 4

HCID 7522Pyridine-2-carbonitrileHCID 10340Sodium CarbonateHCID 69803Diethyl acetylenedicarboxylateHCID 77906N-methylhydroxylamine hydrochloride

Product 1

HCID 23568413HCID 23568413, compoundYield 111.8%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 19096565Water ethanolSolvent

Procedure

To a stirred solution of 2-cyanopyridine (2.08 g, 20 mmol) and N-methylhydroxylamine hydrochloride (1.66 g, 20 mmol) in 1:1 water/ethanol (30 mL) was added sodium carbonate (1.04 g, 10 mmol) in small portions. LCMS analysis after 5 min indicated that the reaction was complete. To this was added diethyl acetylenedicarboxylate (3.2 mL, 20 mmol) and the reaction mixture stirred for additional 20 min at room temperature. LCMS analysis of the resulting dark-green reaction showed that the reaction was complete. The reaction mixture was taken up into ethyl acetate (200 mL) and washed successively with water (2×25 mL) and brine (25 mL), and the organic layer dried (Na2SO4), filtered and concentrated to give brown oil which was passed through a plug of silica gel (1:1 hexanes/ethyl acetate). The filtrate was concentrated to give the title compound as a yellow oil (6.87 g). LCMS calcd for C15H20N3O5 (M+H): 322.14; found: 322.08.

Workup

  1. customLCMS analysis of the resulting dark-green reaction
  2. washwashed successively with water (2×25 mL) and brine (25 mL)
  3. dry with materialthe organic layer dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give brown oil which
  7. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-61b66a09efd2400f8424db7b48229d8b
Source dataset
uspto-grants-2006_05
Patent number
US07037908B2

Reaction notes

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