Nitric Acid → 3-(4-Nitrophenyl)pyridine

HRID 2413059Notes

Reaction equation

HRID 2413059 reaction equation
[C:1]1([C:7]2[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[N+:13]([O-])([OH:15])=[O:14].S(=O)(=O)(O)O>CC(C)=O.CCCCCC>[N+:13]([C:4]1[CH:3]=[CH:2][C:1]([C:7]2[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=2)=[CH:6][CH:5]=1)([O-:15])=[O:14]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 138863-Phenylpyridine

Product 1

HCID 2315043-(4-Nitrophenyl)pyridine

Reagents, catalysts & solvents 1

HCID 21880519Acetone hexaneSolvent

Conditions

Temperature
70 °C

Procedure

3-Phenylpyridine (25.0 g, 0.161 mole) is added carefully and with cooling (ice-bath) to 70% nitric acid (140 ml). The resulting solution is stirred and, when TLC (1:1 acetone-hexane) shows no reaction after 24 hr, it is heated in a 70° C. oil bath. Some reaction is observed by TLC but it is very slow and so, after 4 days, concentrated sulfuric acid (50 ml) is added. The mixture is stirred over several days at room temperature after which the starting material is entirely consumed. The solution is poured onto ice and the mixture is made alkaline by the cautious addition of 50% aqueous NaOH. The mixture is extracted 3 times with ethyl acetate. (650 ml), the combined organic layers are washed with brine, dried over MgSO4, filtered, and reduced in volume to 400 ml. Crystallization occurred, giving a first crop of 13.139 g of tilted product, melting point of 145°-148° C. and, from the concentrated filtrate, a second crop of 4.16 g (total 17.299 g, 0.0865 mole, 53%) of product, melting point 143°-147° C.

Workup

  1. customno reaction after 24 hr
  2. stirringThe mixture is stirred over several days at room temperature after which the starting material
  3. customis entirely consumed
  4. additionThe solution is poured onto ice
  5. additionby the cautious addition of 50% aqueous NaOH
  6. extractionThe mixture is extracted 3 times with ethyl acetate
  7. wash(650 ml), the combined organic layers are washed with brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customCrystallization

Sources & evidence

ORD record
ord-97711b0179324ef2b6e56056e786684f
Source dataset
uspto-grants-1985_01
Patent number
US04495357

Reaction notes

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