Phosphorus trichloride → Diethyl 5-nitropyridine-2,3-dicarboxylate

HRID 1898788Notes

Reaction equation

HRID 1898788 reaction equation
P(Cl)(Cl)Cl.[N+:5]([C:8]1[CH:9]=[C:10]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:11]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[N+:12]([O-])[CH:13]=1)([O-:7])=[O:6]>ClCCCl>[N+:5]([C:8]1[CH:9]=[C:10]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:11]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[N:12][CH:13]=1)([O-:7])=[O:6]

Participants

4

Reactant 2

HCID 24387Phosphorus trichlorideHCID 15451775diethyl 5-nitropyridine-2,3-dicarboxylate-N-oxide

Product 1

HCID 15451770Diethyl 5-nitropyridine-2,3-dicarboxylate

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
25 °C

Procedure

88.8 g (0.648 mol) of phosphorus trichloride were added in the course of 30 minutes while stirring at 25° C. to a mixture of 92 g (0.324 mol) of the above N-oxide and 300 ml of 1,2-dichloroethane. After stirring at 25° C. for 12 hours, the reaction mixture was concentrated in vacuo, the residue was taken up again in methylene chloride and the solution was poured into 2.5 l of ice-water. After phase separation, the aqueous phase was extracted with methylene chloride. The organic extract was washed with water, saturated sodium hydrogencarbonate and sodium chloride solution, dried over magnesium sulfate and filtered off with suction through neutral alumina and silica gel. After concentrating, 58.2 g (67% of theory) of the title compound were obtained as a yellowish syrup. 1H-NMR, 400 MHz (CDCl3) δ: Ar 9.0 (d/1H), 9.55 (d, 1H)

Workup

  1. concentrationthe reaction mixture was concentrated in vacuo
  2. additionthe solution was poured into 2.5 l of ice-water
  3. customAfter phase separation
  4. extractionthe aqueous phase was extracted with methylene chloride
  5. extractionThe organic extract
  6. washwas washed with water, saturated sodium hydrogencarbonate and sodium chloride solution
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered off with suction through neutral alumina and silica gel
  9. concentrationAfter concentrating

Sources & evidence

ORD record
ord-2314b4763b3a4dda81956b33cfb18778
Source dataset
uspto-grants-1996_11
Patent number
US05571774

Reaction notes

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