Phenoxyethanol → Methyl 6-bromo-3-(2-phenoxyethoxy)picolinate

HRID 1641083Notes

Reaction equation

HRID 1641083 reaction equation
[Br:1][C:2]1[N:7]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[C:5]([OH:12])=[CH:4][CH:3]=1.[O:13]([CH2:20][CH2:21]O)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C(Cl)Cl>[Br:1][C:2]1[N:7]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[C:5]([O:12][CH2:21][CH2:20][O:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 31236PhenoxyethanolHCID 5363146Diisopropyl azodicarboxylateHCID 22175135Methyl 6-bromo-3-hydroxypicolinate

Product 1

HCID 59418733Methyl 6-bromo-3-(2-phenoxyethoxy)picolinateYield 72%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of methyl 6-bromo-3-hydroxypicolinate (26B) (308 mg, 1.33 mmol) and 2-phenoxyethanol (183 mg, 1.33 mmol) were stirred in dry DCM (10 mL). PPh3-polystyrene bound (665 mg, 2.0 mmol) was added, followed by the drop-wise addition of DIAD (0.387 mL, 2.0 mmol). The mixture was stirred for 48 hours, then filtered through Celite and concentrated under reduced pressure. The crude material was purified by flash column chromatography on silica gel eluting with a gradient of PE/EtOAc 9:1-7:3 to provide 334 mg (72%) of the desired compound methyl 6-bromo-3-(2-phenoxyethoxy)picolinate (27A): 1H NMR (300 MHz, CDCl3) δ7.58-6.90 (7H, m), 4.43 (2H, m), 4.34 (2H, m), 3.91 (3H, s).

Workup

  1. additionwas added
  2. filtrationfiltered through Celite
  3. concentrationconcentrated under reduced pressure
  4. customThe crude material was purified by flash column chromatography on silica gel eluting with a gradient of PE/EtOAc 9:1-7:3

Sources & evidence

ORD record
ord-17b54dcebd7f44eca27a07cbd2af5d28
Source dataset
uspto-grants-2012_02
Patent number
US08114893B2

Reaction notes

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