Sodium Hydroxide → Iodomethyl Benzoate

HRID 77352Notes

Reaction equation

HRID 77352 reaction equation
[OH-].[Na+].F[C:4]1[CH:14]=[CH:13][C:7]([C:8]([O:10][CH2:11][I:12])=[O:9])=[CH:6][CH:5]=1>O.[N+]([O-])([O-])=O.[Ag+]>[C:8]([O:10][CH2:11][I:12])(=[O:9])[C:7]1[CH:13]=[CH:14][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 2

HCID 14798Sodium HydroxideHCID 46919443Iodomethyl 4-fluorobenzoate

Product 1

HCID 10015543Iodomethyl Benzoate

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent2×

Procedure

Synthesis of pentachlorophenyl (E)-3-[4-[bis(4-fluorobenzoyloxymethoxyphosphinyl)difluoromethyl]phenyl]-but-2-enoate (6b1 R1=4-Fluorobenzoyloxymethyl) NaOH (80 mg, 2.0 mmol) in 2 mL of H2O was added dropwise to a stirred suspension of pentachlorophenyl (E)-3-(4-phosphonyldifluoromethyphenyl) but-2-enoate (500 mg, 0.92 mmol) in 5 mL of H2O. When the mixture became clear (pH˜9), AgNO3 (510 mg, 3.0 mmol) was added. After 2 h at 4° C. the gray precipitate was collected by filtration, dried over P2O5 in vacuo, and pulverized in a mortar and pestle. The powder (400 mg) was suspended in dry toluene (10 mL) and iodomethyl 4-fluorobenzoate (290 mg, 1.03 mmol) was added and stirred for 48 h at room temperature. After filtration the solvent was removed in vacuo and the crude product was purified by silica gel column chromatography eluting with 30% EtOAc-hexanes to give colorless oil. Yield 290 mg, (61%). 1H NMR (300 MHz, CDCl3): δ 2.49 (s, 3H), 5.87 (m, 4H), 6.3 (s, 1H), 7.01 (m, 4H), 7.45 (d, J=8.4 Hz, 2H), 7.54 (d, J=8.4 Hz, 2H), 7.94 (m, 4H). 13C NMR (75 MHz, CDCl3): δ 18.3, 82.5, 82.8, 115.0, 115.7, 116.1, 124.5, 126.7, 127.9, 131.4, 132.0, 132.7, 132.9, 144.2, 161.6, 163.6, 164.7, 168.1. HRMS (M+H) calc, 844.9272; found, 844.9278.

Workup

  1. additionwas added
  2. filtrationAfter 2 h at 4° C. the gray precipitate was collected by filtration
  3. dry with materialdried over P2O5 in vacuo
  4. filtrationAfter filtration the solvent
  5. customwas removed in vacuo
  6. customthe crude product was purified by silica gel column chromatography
  7. washeluting with 30% EtOAc-hexanes
  8. customto give colorless oil

Sources & evidence

ORD record
ord-fd156a574097450aba199246a0a5a7e6
Source dataset
uspto-grants-2014_09
Patent number
US08841257B2

Reaction notes

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