Phosphorus oxychloride → 2-Chloro-3-methyl-5-nitropyridine

HRID 2088505Notes

Reaction equation

HRID 2088505 reaction equation
[CH3:1][C:2]1[C:3](O)=[N:4][CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.O=P(Cl)(Cl)[Cl:14]>>[Cl:14][C:3]1[C:2]([CH3:1])=[CH:7][C:6]([N+:8]([O-:10])=[O:9])=[CH:5][N:4]=1

Participants

3

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 178428770HCID 178428770, compound

Product 1

HCID 896482-Chloro-3-methyl-5-nitropyridineYield 89%

Conditions

Temperature
85 °C

Procedure

POCl3 (410 ml) was added slowly, with stirring, to 3-methyl-5-nitropyridin-2-ol (75.0 g, 0.487 mol) [J. Org. Chem. 14, 328-32 (1949)] from Part H in a 4 neck, 3 L round bottom flask (temperature rose to 30° C.) and the reaction mixture was heated at 85° C. for 16 h. The solution was cooled and the excess POCl3 was removed in vacuo. The residue was poured onto wet ice (4 L beaker) with stirring and the precipitate were collected by filtration and air dried, followed by drying in the vacuum oven to give 2-chloro-3-methyl-5-nitropyridine (75.0 g, 89% yield) as an off-white solid which was used in the next step without further purification: 1H NMR (300 MHz, CDCl3) δ 9.04 (d, J=2.5 Hz, 1H), 8.33 (d, J=2.2 Hz, 1H), 2.50 (s, 3H).

Workup

  1. temperatureThe solution was cooled
  2. customthe excess POCl3 was removed in vacuo
  3. additionThe residue was poured onto wet ice (4 L beaker)
  4. filtrationthe precipitate were collected by filtration and air
  5. customdried
  6. customby drying in the vacuum oven

Sources & evidence

ORD record
ord-13ab8a6bbade41b7bde50e8674f4fdb1
Source dataset
uspto-grants-2013_05
Patent number
US08436000B2

Reaction notes

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