Perchloric Acid → tert-Butyl 2,6-dichloro-4,5-dimethylnicotinate

HRID 1482060Notes

Reaction equation

HRID 1482060 reaction equation
[Cl:1][C:2]1[N:10]=[C:9]([Cl:11])[C:8]([CH3:12])=[C:7]([CH3:13])[C:3]=1[C:4]([OH:6])=[O:5].Cl(O)(=O)(=O)=O>C(OC(C)(C)C)(=O)C.CCOC(C)=O>[Cl:1][C:2]1[N:10]=[C:9]([Cl:11])[C:8]([CH3:12])=[C:7]([CH3:13])[C:3]=1[C:4]([O:6][C:3]([CH3:7])([CH3:4])[CH3:2])=[O:5]

Participants

5

Reactant 2

HCID 24247Perchloric AcidHCID 713829042,6-Dichloro-4,5-dimethylpyridine-3-carboxylic acid

Product 1

HCID 118316314tert-Butyl 2,6-dichloro-4,5-dimethylnicotinateYield 144.8%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 10908tert-Butyl acetateSolvent

Procedure

To a solution of 2,6-dichloro-4,5-dimethylnicotinic acid (2.75 g, 12.5 mmol, 1 equiv) in tertbutyl acetate (83 mL) was added concentrated perchloric acid (3.2 mL, 37.5 mmol, 3 equiv). The reaction was stirred 1 h and then diluted with EtOAc. The organic solution was then washed with 10% potassium carbonate, dried (Na2SO4), and concentrated in vacuo. The crude product was purified by silica gel flash column chromatography (0-100% DCM/hexane) to provide the product (2.50 g, 72%) as a waxy white solid. 1H NMR (400 MHz, CDCl3) δ 2.35 (s, 3H), 2.32 (s, 3H), 1.62 (s, 9H); LCMS (ESI, M+1): 276.00.

Workup

  1. washThe organic solution was then washed with 10% potassium carbonate
  2. dry with materialdried (Na2SO4)
  3. concentrationconcentrated in vacuo
  4. customThe crude product was purified by silica gel flash column chromatography (0-100% DCM/hexane)

Sources & evidence

ORD record
ord-cddb99acc1df466085df405259a0d45b
Source dataset
uspto-grants-2016_08
Patent number
US09409922B2

Reaction notes

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