tert-Butanol → tert-Butyl 4-chloropicolinate

HRID 450427Notes

Reaction equation

HRID 450427 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([C:8](Cl)=[O:9])[CH:3]=1.[CH3:11][C:12]([OH:15])([CH3:14])[CH3:13]>C(Cl)Cl.CN(C1C=CN=CC=1)C.N1C=CC=CC=1>[C:12]([O:15][C:8]([C:4]1[CH:3]=[C:2]([Cl:1])[CH:7]=[CH:6][N:5]=1)=[O:9])([CH3:14])([CH3:13])[CH3:11]

Participants

6

Reactant 2

HCID 6386tert-ButanolHCID 110951464-chloropyridine-2-carbonyl Chloride

Product 1

HCID 11806045tert-Butyl 4-chloropicolinateYield 49.2%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of 4-chloro-pyridine-2-carbonyl chloride (150 g, 0.857 mol) in DCM (750 ml) was slowly added to a solution of 2-methyl-propan-2-ol (158.8 g, 2.14 mol) and DMAP (21 g, 0.171 mol) in DCM (750 mL) and pyridine (750 mL). The resultant mixture was stirred at 30° C. overnight. The reaction mixture was concentrated in vacuo and the residue was purified by chromatography to give 4-chloro-pyridine-2-carboxylic acid t-butyl ester (90 g, 49% yield) as a yellow solid. 1H NMR (CDCl3): δ 8.63 (d, J=8.0 Hz, 1H), 8.03 (s, 1H), 7.44 (d, J=8.0 Hz 1H), 1.63 (s, 9H); MS (ESI) m/z: 214 (M+H+).

Workup

  1. concentrationThe reaction mixture was concentrated in vacuo
  2. customthe residue was purified by chromatography

Sources & evidence

ORD record
ord-62da110a9a724a0aa705de470b02cac5
Source dataset
uspto-grants-2013_07
Patent number
US08486951B2

Reaction notes

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