Pyridine → 2-Tert-butyl 5-methyl pyridine-2,5-dicarboxylate

HRID 2047001Notes

Reaction equation

HRID 2047001 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:6]=[CH:7][C:8]([C:11]([OH:13])=[O:12])=[N:9][CH:10]=1)=[O:4].N1C=CC=CC=1.[C:20]1([CH3:30])[CH:25]=CC(S(Cl)(=O)=O)=C[CH:21]=1.C(=O)(O)[O-].[Na+]>C(O)(C)(C)C.C(OCC)C>[CH3:1][O:2][C:3]([C:5]1[CH:6]=[CH:7][C:8]([C:11]([O:13][C:20]([CH3:30])([CH3:25])[CH3:21])=[O:12])=[N:9][CH:10]=1)=[O:4]

Participants

7

Reactant 4

HCID 1049PyridineHCID 73974-Toluenesulfonyl chlorideHCID 3149925-(Methoxycarbonyl)pyridine-2-carboxylic acidHCID 516892Sodium Bicarbonate

Product 1

HCID 543263102-Tert-butyl 5-methyl pyridine-2,5-dicarboxylateYield 57.3%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6386tert-ButanolSolvent

Procedure

5-(Methoxycarbonyl)pyridine-2-carboxylic acid (7.72 g, 42.65 mmol) was suspended in tert-butanol (70 mL) and pyridine (25 mL) and cooled in an ice-water bath. 4-Toluenesulfonyl chloride (19.4 g, 102 mmol) was added in one portion and the mixture was stirred 30 minutes in the ice-water bath. The reaction mixture was warmed to room temperature and stirred for 16 h. The reaction mixture was then slowly poured into a stirring mixture of saturated aqueous sodium bicarbonate (300 mL) and ethyl ether (150 mL). The resulting two-phase mixture was then extracted with ethyl ether (3×150 mL). The extracts were combined, washed with brine, dried with anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product (5.8 g, 51% yield) was used in the next step without further purification.

Workup

  1. extractionThe resulting two-phase mixture was then extracted with ethyl ether (3×150 mL)
  2. washwashed with brine
  3. dry with materialdried with anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-47c5594a138b45298dde1006584a09e4
Source dataset
uspto-grants-2013_11
Patent number
US08591943B2

Reaction notes

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