Water → Methyl 2-(6-bromopyrid-2-yloxymethyl)phenylacetate

HRID 850157

Reaction equation

HRID 850157 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Br:8])[N:3]=1.[OH-].[Na+].Cl[CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[CH2:19][C:20]([O:22][CH3:23])=[O:21].O>C1OCCOCCOCCOCCOC1.C1(C)C=CC=CC=1.CN(C=O)C.[I-].[Na+]>[Br:8][C:4]1[N:3]=[C:2]([O:1][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[CH2:19][C:20]([O:22][CH3:23])=[O:21])[CH:7]=[CH:6][CH:5]=1

Participants

9

Reactant 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 9855748Methyl 2-[2-(chloromethyl)phenyl]acetateHCID 178515930HCID 178515930, compound

Product 1

HCID 19366333Methyl 2-(6-bromopyrid-2-yloxymethyl)phenylacetateYield 51.2%

Reagents, catalysts & solvents 4

HCID 5238Sodium IodideCatalystHCID 3633615-Crown-5CatalystHCID 1140TolueneSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of 2-hydroxy-6-bromopyridine (1.3 g, 7.5 mmol), sodium hydroxide (0.36 g, 9.0 mmol) and 15-crown-5 (1 drop) in dry toluene (20 ml) were stirred at reflux for 1.5 hours. The toluene was removed under reduced pressure and the white salt residue was dissolved in dry DMF (10 ml). Methyl 2-chloromethylphenylacetate (1.0 g, 5 mmol) in dry DMF (10 ml) was added dropwise along with sodium iodide (10 mg). The mixture was stirred at 80° C. for 2 hours, poured into water and extracted with diethyl ether. The ether extracts were washed with water, dried and the ether removed in vacuo leaving an orange oil which was purified by column chromatography (silica eluted with 10% ethyl acetate in hexane) to give methyl 2-(6-bromopyrid-2-yloxymethyl)phenylacetate (0.86 g, 51%) (Compound No. 2 in Table 1) as an orange oil; 1H NMR (270 MHz)δ: 3.68(3H,s), 3.73(2H,s), 5.38(2H,s), 6.68(1H,d), 7.06(1H,d), 7.25-7.50(5H,m) ppm.

Workup

  1. temperatureat reflux for 1.5 hours
  2. customThe toluene was removed under reduced pressure
  3. dissolutionthe white salt residue was dissolved in dry DMF (10 ml)
  4. stirringThe mixture was stirred at 80° C. for 2 hours
  5. extractionextracted with diethyl ether
  6. washThe ether extracts were washed with water
  7. customdried
  8. customthe ether removed in vacuo
  9. customleaving an orange oil which
  10. customwas purified by column chromatography (silica eluted with 10% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-2d2c758f19d640058b0f3b90bd5eaee6
Source dataset
uspto-grants-2000_01
Patent number
US06015905

Linked notes

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