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

HRID 1896597Notes

Reaction equation

HRID 1896597 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-7fc966ce4e814311aa3be1d5600b23c5
Source dataset
uspto-grants-2013_08
Patent number
US08518970B2

Reaction notes

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