Pyridine → tert-Butyl 3-methyl-4-nitrobenzoate

HRID 1953759Notes

Reaction equation

HRID 1953759 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[N+:11]([O-:13])=[O:12])[C:5]([OH:7])=[O:6].N1C=CC=CC=1.C1(S(Cl)(=O)=O)C=CC=CC=1.[C:30](O)([CH3:33])([CH3:32])[CH3:31]>CCCCCC.C(OCC)(=O)C>[CH3:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[N+:11]([O-:13])=[O:12])[C:5]([O:7][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:6]

Participants

6

Reactant 4

HCID 1049Pyridine2×HCID 6386tert-ButanolHCID 7369Benzenesulfonyl chlorideHCID 183703-Methyl-4-nitrobenzoic acid

Product 1

HCID 15283350tert-Butyl 3-methyl-4-nitrobenzoateYield 97%

Reagents, catalysts & solvents 1

HCID 21226206Ethyl acetate hexaneSolvent

Procedure

3-Methyl-4-nitrobenzoic acid (500 g, 2.76 mol) was added to pyridine (1.25 L) and stirred until it dissolved. Benzenesulfonyl chloride (609 g, 3.45 mol) was added rapidly while maintaining the internal temperature <30° C. with an ice bath. A precipitate formed towards the end of the addition and pyridine (500 mL) was added to improve stirring. The mixture was stirred for 30 min and t-butanol (523 mL) was added dropwise over 30 min at <30° C. The mixture was stirred for 2 h, dissolved in hexane:ethyl acetate (4:1; 2.5 L) and the resulting mixture was extracted with water. The organic phase was concentrated to give a light yellow oil which crystallized on cooling to give the title compound (635 g, 97%). mp 56-58° C.

Workup

  1. dissolutiondissolved
  2. temperaturewhile maintaining the internal temperature <30° C. with an ice bath
  3. additionwas added
  4. stirringto improve stirring
  5. stirringThe mixture was stirred for 30 min
  6. stirringThe mixture was stirred for 2 h
  7. extractionthe resulting mixture was extracted with water
  8. concentrationThe organic phase was concentrated
  9. customto give a light yellow oil which
  10. customcrystallized
  11. temperatureon cooling

Sources & evidence

ORD record
ord-8a70ec7758594408940a9dc68a2ddbce
Source dataset
uspto-grants-2000_09
Patent number
US06117866

Reaction notes

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