Sodium Iodide → 4-Allyloxymandelic acid

HRID 22575

Reaction equation

HRID 22575 reaction equation
O.[Na+].[OH:3][C:4]1[CH:14]=[CH:13][C:7]([CH:8]([OH:12])[C:9]([O-:11])=[O:10])=[CH:6][CH:5]=1.[OH-].[K+].[I-].[Na+].[CH2:19](Br)[CH:20]=[CH2:21].[CH2:23](Cl)[C:24](=[CH2:26])[CH3:25]>CO>[CH2:21]([O:3][C:4]1[CH:14]=[CH:13][C:7]([CH:8]([OH:12])[C:9]([OH:11])=[O:10])=[CH:6][CH:5]=1)[CH:20]=[CH2:19].[CH2:25]([O:3][C:4]1[CH:14]=[CH:13][C:7]([CH:8]([OH:12])[C:9]([OH:11])=[O:10])=[CH:6][CH:5]=1)[C:24](=[CH2:23])[CH3:26]

Participants

8

Reactant 5

HCID 5238Sodium IodideHCID 7841Allyl bromideHCID 112413-Chloro-2-methyl-1-propeneHCID 14797Potassium HydroxideHCID 236981332-Hydroxy-2-(4-hydroxyphenyl)acetic acid, sodium salt hydrate

Product 2

HCID 199305644-Allyloxymandelic acidYield 70%HCID 199305664-Methallyloxymandelic acid

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

20.8 g (0.10 mol) of 4-hydroxymandelic acid sodium salt monohydrate and 6.6 g (0.10 mol) of potassium hydroxide are dissolved with 1.0 g (6.7 mmol) of sodium iodide in 75 ml of methanol. Then 0.12 mol of allyl bromide (methallyl chloride in the case of methallyl) is added and the reaction mixture is refluxed for 16 hours under nitrogen. The reaction mixture is concentrated on a vacuum rotary evaporator and the residue is acidified with concentrated hydrochloric acid. The product is extracted 3 times with butyl acetate. The organic phases are washed with water, combined, dried over sodium sulfate and concentrated on a vacuum rotary evaporator. Crystallisation of the residue from toluene/petroleum ether give 4-allyloxymandelic acids such as 4-allyloxymandelic acid as an amorphous powder (70%) and 4-methallyloxymandelic acid, m.p. 121°-126° (65%).

Workup

  1. temperaturethe reaction mixture is refluxed for 16 hours under nitrogen
  2. concentrationThe reaction mixture is concentrated on a vacuum rotary evaporator
  3. extractionThe product is extracted 3 times with butyl acetate
  4. washThe organic phases are washed with water
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated on a vacuum rotary evaporator
  7. customCrystallisation of the residue from toluene/petroleum ether

Sources & evidence

ORD record
ord-c5f188d297c44361a81bdec3606b483a
Source dataset
uspto-grants-1995_06
Patent number
US05428177

Linked notes

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