Dimethyl Sulfate → 4-(3-Methoxycarbonylpropyl)-1-methoxypyridinium methyl sulfate salt

HRID 326138Notes

Reaction equation

HRID 326138 reaction equation
[C:1](OO)(=[O:3])C.[CH3:6][O:7][C:8]([CH2:10][CH2:11][CH2:12][C:13]1[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=1)=[O:9].COC(CCCC1C=C[N+]([O-])=CC=1)=O.[CH3:33][O:34][S:35]([O:38]C)(=[O:37])=[O:36]>C1(C)C=CC=CC=1>[CH3:33][O:34][S:35]([O-:38])(=[O:37])=[O:36].[CH3:6][O:7][C:8]([CH2:10][CH2:11][CH2:12][C:13]1[CH:18]=[CH:17][N+:16]([O:3][CH3:1])=[CH:15][CH:14]=1)=[O:9]

Participants

6

Reactant 4

HCID 6497Dimethyl SulfateHCID 6585Peracetic AcidHCID 12114953Methyl 4-(Pyridin-4-yl)butanoateHCID 204466714-(3-methoxycarbonylpropyl)pyridine-N-oxide

Product 1

HCID 204466694-(3-Methoxycarbonylpropyl)-1-methoxypyridinium methyl sulfate salt

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Peracetic acid (40%, 2.9 ml) is added to 4-(3-methoxycarbonylpropyl)pyridine (3.20 g) at room temperature. The mixture is heated at 80° for 1 hour and the acetic acid is evaporated after a test for peroxide is negative. The residue is taken up in methylene chloride (50 ml), filtered, and the solvent evaporated. The resulting 4-(3-methoxycarbonylpropyl)pyridine-N-oxide is treated with dimethylsulfate (2.8 g, 22.2 mmol) in 12 ml of toluene at 80° C. for 1 hour. The solvent is evaporated to yield 5.45 g of the 4-(3-methoxycarbonylpropyl)-1-methoxypyridinium methyl sulfate salt which is added at 0° to a solution of 89.75 g potassium cyanide in 20 ml of water. The reaction is stirred at 0° for l hour and 25° for 3 hours and then extracted with methylene chloride (1×30 ml). The aqueous phase is reextracted, after standing for 24 hours, with methylene chloride (1×30 ml), and the combined extracts are dried over sodium sulfate and evaporated to yield a red oil. Chromatography on 70 g of silica gel with ether as the eluent yields 2-cyano-4-(3-methoxycarbonylpropyl)pyridine as an oil; NMR (CDCl3) 3.67 (s, 3 H), 7.42 (d, 1 H), 7.60 (s, 1 H), 8.60 (d, 1 H); IR (CH2Cl2) 1725 cm-1.

Workup

  1. temperatureThe mixture is heated at 80° for 1 hour
  2. customthe acetic acid is evaporated after a test for peroxide
  3. filtrationfiltered
  4. customthe solvent evaporated
  5. customThe solvent is evaporated

Sources & evidence

ORD record
ord-80510f81bd6646b7b4716fc7e83bdd8c
Source dataset
uspto-grants-1984_04
Patent number
US04444775

Reaction notes

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