Water → Metabolite 10 of Picoxystrobin

HRID 850154

Reaction equation

HRID 850154 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([C:8]([F:11])([F:10])[F:9])[N:3]=1.[OH-].[Na+].Cl[CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[CH2:22][C:23]([O:25][CH3:26])=[O:24].O>C1OCCOCCOCCOCCOC1.C1(C)C=CC=CC=1.CN(C=O)C.[I-].[Na+]>[F:10][C:8]([F:9])([F:11])[C:4]1[N:3]=[C:2]([O:1][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2[CH2:22][C:23]([O:25][CH3:26])=[O:24])[CH:7]=[CH:6][CH:5]=1

Participants

9

Reactant 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 9855748Methyl 2-[2-(chloromethyl)phenyl]acetateHCID 178516021HCID 178516021, compound

Product 1

HCID 10860344Metabolite 10 of PicoxystrobinYield 83%

Reagents, catalysts & solvents 4

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

Procedure

A mixture of 2-hydroxy-6-trifluoromethylpyridine (2.0 g, 12.3 mmol), sodium hydroxide (0.52 g, 12.9 mmol) and 15-crown-5 (1 drop) in dry toluene (25 ml) were stirred at reflux for 2 hours. The toluene was removed under reduced pressure and the white salt residue was dissolved in dry DMF (15 ml). Methyl 2-chloromethylphenylacetate (2.44 g, 12.3 mmol) in dry DMF (15 ml) was added dropwise along with sodium iodide (10 mg). The mixture was stirred at 75° 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 oil which was purified by column chromatography (silica eluted with 10% ethyl acetate in hexane) to give methyl 2-(6-tri-fluoromethylpyrid-2-yloxymethyl)phenylacetate (3.3 g, 83%) (Compound No.5 in Table 1) as a yellow oil; 1H NMR (270 MHz)δ: 3.68(3H,s), 3.84(2H,s), 5.46(2H,s), 6.89(1H,d), 7,20-7.70(6H,m) ppm.

Workup

  1. temperatureat reflux for 2 hours
  2. customThe toluene was removed under reduced pressure
  3. dissolutionthe white salt residue was dissolved in dry DMF (15 ml)
  4. stirringThe mixture was stirred at 75° 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 oil which
  10. customwas purified by column chromatography (silica eluted with 10% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-fc309df0347749e08d10bf07191036b3
Source dataset
uspto-grants-2000_01
Patent number
US06015905

Linked notes

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