Thionyl Chloride → 2-Chloro-4-methyl-5-nitropyridine

HRID 728770

Reaction equation

HRID 728770 reaction equation
[CH3:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][NH:5][C:4](=O)[CH:3]=1.S(Cl)([Cl:14])=O>CN(C)C=O>[Cl:14][C:4]1[CH:3]=[C:2]([CH3:1])[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]=1

Participants

4

Reactant 2

HCID 24386Thionyl ChlorideHCID 3453714-Methyl-5-nitro-1,2-dihydropyridin-2-one

Product 1

HCID 3453642-Chloro-4-methyl-5-nitropyridineYield 95%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideCatalyst

Procedure

A mixture of 4-methyl-5-nitro-1H-pyridine-2-one (5.00 g, 32.44 mmol), thionyl chloride (20 ml), and two drops of dimethylformamide was heated atreflux under nitrogen for 52 hours. The resultant orange colored solution was evaporated under reduced pressure, and a small amount of anhydrous toluene was added and then removed via evaporation under reduced pressure to remove traces of thionyl chloride. The residual oil then passed througha silica gel filter (dried at 150° C. under vacuum overnight, approximately 100 g) followed by methylene chloride (1 1). This filtrate was evaporated under reduced pressure to afford 2-chloro-4-methyl-5-nitropyridine (5.30 g, 30.71 mmol, 95%) as an orange oil, which crystallized below 0° C.; IR (CHCl3) 1605, 1550, 1520, 1450, 1360, 1345 cm-1 ; 1H NMR (CDCl3) δ 9.03 (s, 1H), 7.83 (s, 1H), 2.60 (s, 3H); LRMS (m/z, relative intensity) 174 (25), 173 (19), 172 (M+, 68), 157 (74), 155 (100), 128 (27), 101 (47), 100(55], 99 (74), 90 (43), 75 (36).

Workup

  1. temperaturewas heated atreflux under nitrogen for 52 hours
  2. customThe resultant orange colored solution was evaporated under reduced pressure
  3. additiona small amount of anhydrous toluene was added
  4. customremoved via evaporation under reduced pressure
  5. customto remove traces of thionyl chloride
  6. filtrationfilter
  7. custom(dried at 150° C. under vacuum overnight, approximately 100 g)
  8. customThis filtrate was evaporated under reduced pressure

Sources & evidence

ORD record
ord-b16f6c0d450342a2ba5c77bfdc929048
Source dataset
uspto-grants-1991_09
Patent number
US05051412

Linked notes

Loading…