Peracetic Acid → 4-(3-Chloropropyl)-2-cyanopyridine

HRID 280236

Reaction equation

HRID 280236 reaction equation
C(OO)(=O)C.[Cl:6][CH2:7][CH2:8][CH2:9][C:10]1[CH:15]=[CH:14][N:13]=[CH:12][CH:11]=1.ClCCCC1C=C[N+:23]([O-])=[CH:22]C=1.COS([O-])(=O)=O.ClCCCC1C=C[N+](OC)=CC=1.[C-]#N.[K+]>S(OC)(OC)(=O)=O.O.[OH-].[Na+]>[Cl:6][CH2:7][CH2:8][CH2:9][C:10]1[CH:15]=[CH:14][N:13]=[C:12]([C:22]#[N:23])[CH:11]=1

Participants

9

Reactant 5

HCID 6585Peracetic AcidHCID 9032Potassium CyanideHCID 2054424-(3-Chloropropyl)pyridineHCID 124817564-(3-chloropropyl)-pyridine-N-oxideHCID 233218824-(3-Chloropropyl)-1-methoxypyridinium methyl sulfate salt

Product 1

HCID 233218694-(3-Chloropropyl)-2-cyanopyridine

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6497Dimethyl SulfateSolventHCID 14798Sodium HydroxideSolvent

Procedure

Peracetic acid (40%, 5.0 ml) is added to 4-(3-chloropropyl)pyridine (5.18 g) at such a rate as to keep the reaction temperature at 80°. The mixture is stirred until the temperature falls to 30°. Excess peracid is destroyed with sodium sulfite solution and the solvent is vacuum distilled. The residue is redissolved in methylene chloride (50 ml), filtered and evaporated to yield and crude 4-(3-chloropropyl)-pyridine-N-oxide which is heated to 80° in dimethyl sulfate (4.66 g) for 2 hours. The resulting 4-(3-chloropropyl)-1-methoxypyridinium methyl sulfate salt is dissolved in 10 ml of water, cooled to 0° and reacted with an ice-cold solution of potassium cyanide (6.7 g, 100 mmol) in 20 ml of 0.25N sodium hydroxide solution for 22 hours. The product is extracted with methylene chloride (3×30 ml) and dried over sodium sulfate. The solvent is evaporated and the residue filtered through 45 g of silica gel with ether to yield 4-(3-chloropropyl)-2-cyanopyridine; NMR (CDCl3) 3.56 (t, 2H), 7.40 (d, 1H), 7.57 (s, 1H), 8.60 (d, 1H).

Workup

  1. customat 80°
  2. customfalls to 30°
  3. customExcess peracid is destroyed with sodium sulfite solution
  4. distillationdistilled
  5. dissolutionThe residue is redissolved in methylene chloride (50 ml)
  6. filtrationfiltered
  7. customevaporated
  8. customto yield
  9. temperaturecooled to 0°
  10. extractionThe product is extracted with methylene chloride (3×30 ml)
  11. dry with materialdried over sodium sulfate
  12. customThe solvent is evaporated
  13. filtrationthe residue filtered through 45 g of silica gel with ether

Sources & evidence

ORD record
ord-f275d66e8ba6472993cbe40207dc5ab0
Source dataset
uspto-grants-1986_05
Patent number
US04588732

Linked notes

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