Triethyl phosphite → Methyl 2-{[tert-butyl(dimethyl)silyl]oxy}-4-[(diethoxyphosphoryl)methyl]benzoate

HRID 217461Notes

Reaction equation

HRID 217461 reaction equation
Br[CH2:2][C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15])[CH:4]=1.[CH2:21]([O:23][P:24]([O:28]CC)[O:25][CH2:26][CH3:27])[CH3:22]>>[Si:14]([O:13][C:5]1[CH:4]=[C:3]([CH2:2][P:24]([O:25][CH2:26][CH3:27])([O:23][CH2:21][CH3:22])=[O:28])[CH:12]=[CH:11][C:6]=1[C:7]([O:9][CH3:10])=[O:8])([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15]

Participants

3

Reactant 2

HCID 31215Triethyl phosphiteHCID 58438927Methyl 4-(Bromomethyl)-2-[(tert-butyldimethylsilyl)oxy]benzoate

Product 1

HCID 58439044Methyl 2-{[tert-butyl(dimethyl)silyl]oxy}-4-[(diethoxyphosphoryl)methyl]benzoateYield 66.1%

Conditions

Temperature
130 °C

Procedure

A mixture of methyl 4-(bromomethyl)-2-{[tert-butyl(dimethyl)silyl]oxy}benzoate (0.30 g) and triethylphosphite (0.17 g) was mixed at 25° C. and then stirred at 130° C. for 24 hours. The reaction liquid was concentrated under reduced pressure and azeotroped with toluene twice (30 mL×2). The residue was purified by silica gel column chromatography (automatic purification device, hexane:EtOAc=40:60 to 10:90) to obtain methyl 2-{[tert-butyl(dimethyl)silyl]oxy}-4-[(diethoxyphosphoryl)methyl]benzoate (0.23 g) as a colorless liquid

Workup

  1. additionwas mixed at 25° C.
  2. customThe reaction liquid
  3. concentrationwas concentrated under reduced pressure
  4. customazeotroped with toluene twice (30 mL×2)
  5. customThe residue was purified by silica gel column chromatography (automatic purification device, hexane:EtOAc=40:60 to 10:90)

Sources & evidence

ORD record
ord-6a898880ec514d74b320b9fbadf44aee
Source dataset
uspto-grants-2012_06
Patent number
US08193378B2

Reaction notes

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