Oxygen → 1-(Ethoxycarbonyloxy)ethyl 5-(2,4-difluorophenyl)salicylate

HRID 1719728Notes

Reaction equation

HRID 1719728 reaction equation
[Cl-].[Na+].C([O-])(=O)C.[Na+].C1(=O)OCCO1.[C:14]([O:23][CH:24]([O:26][C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH3:25])(=[O:22])[C:15]1[C:16](=[CH:18][CH:19]=[CH:20][CH:21]=1)[OH:17].[F:32][C:33]1[CH:38]=[CH:37][CH:36]=[C:35]([F:39])[CH:34]=1.O=O.[OH-].[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(O)(=O)C>[F:32][C:33]1[CH:34]=[C:35]([F:39])[CH:36]=[CH:37][C:38]=1[C:20]1[CH:21]=[C:15]([C:14]([O:23][CH:24]([O:26][C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH3:25])=[O:22])[C:16]([OH:17])=[CH:18][CH:19]=1

Participants

10

Reactant 7

HCID 977OxygenHCID 5234Sodium ChlorideHCID 7303Ethylene carbonateHCID 97411,3-DifluorobenzeneHCID 14798Sodium HydroxideHCID 517045Sodium AcetateHCID 538260801-(Ethoxycarbonyloxy)ethyl salicylate

Product 1

HCID 134913951-(Ethoxycarbonyloxy)ethyl 5-(2,4-difluorophenyl)salicylate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
25 °C

Procedure

A glass-lined autoclave is charged with 1 mmole of palladium acetate, 5 mmole of sodium chloride, 1.6 mmole of sodium acetate, 2 mmole of phosphomolybdenovanadic acid, 10 g of ethylene carbonate, 5.0 ml of acetic acid, 465 mmole of 1-(ethoxycarbonyloxy)ethyl salicylate, and 510 mmole of m-difluorobenzene. The mixture is stirred for 48 hours at 90° C. and under 200 psi oxygen pressure. The solution is cooled to 25° C. and excess m-difluorobenzene is removed by distillation. Fifty ml of water and 150 ml of toluene are then added to the residue. The pH is adjusted to 7-8 with aqueous sodium hydroxide (80 mmoles). The layers are separated and the aqueous solution is extracted with 150 ml of toluene. The toluene and then the excess starting materials are removed by distillation. The resulting residue is recrystallized from methanol to obtain pure 1-(ethoxycarbonyloxy)ethyl 5-(2,4-difluorophenyl)salicylate.

Workup

  1. customexcess m-difluorobenzene is removed by distillation
  2. additionFifty ml of water and 150 ml of toluene are then added to the residue
  3. customThe layers are separated
  4. extractionthe aqueous solution is extracted with 150 ml of toluene
  5. customare removed by distillation
  6. customThe resulting residue is recrystallized from methanol

Sources & evidence

ORD record
ord-ea78099213ba4e3993de00f16675cdd1
Source dataset
uspto-grants-1985_09
Patent number
US04542158

Reaction notes

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