Ammonium Chloride → Methyl 2-azido-3-(2-methoxy-3-methylphenyl)acrylate

HRID 1505656Notes

Reaction equation

HRID 1505656 reaction equation
[CH3:1][O:2][C:3]1[C:10]([CH3:11])=[C:9](OC)[CH:8]=[CH:7][C:4]=1[CH:5]=O.[N:14]([CH2:17][C:18]([O:20][CH3:21])=[O:19])=[N+:15]=[N-:16].CO[Na].[Cl-].[NH4+]>CO>[N:14]([C:17](=[CH:5][C:4]1[CH:7]=[CH:8][CH:9]=[C:10]([CH3:11])[C:3]=1[O:2][CH3:1])[C:18]([O:20][CH3:21])=[O:19])=[N+:15]=[N-:16]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 2516932,4-Dimethoxy-3-methylbenzaldehydeHCID 4020482Methyl 2-azidoacetateHCID 178418582HCID 178418582, compound

Product 1

HCID 90405544Methyl 2-azido-3-(2-methoxy-3-methylphenyl)acrylateYield 88.5%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To the mixture of 2.46 g of 2-methoxy-3-methylanisaldehyde (16 mmol) and 4.72 g of methyl azidoacetate (41 mmol) in 20 mL of MeOH is added 7.6 mL of 5.4M MeONa over 30 minute at −10 degrees. After addition the mixture was stirred for additional hour at the same temperature and then transferred in cold room (4 degrees) and stirred overnight. On the morning reaction mixture was poured in 0.5 L mixture of ice and conc. ammonium chloride solution, stirred for 10 minutes and filtered off. The solid was washed with plenty of ice cold water and then moved at ambient temperature. After air drying for 1 hr the solid was dissolved in 50 mL of DCM, dried over magnesium sulfate and passed through short silica gel plug. Evaporation of solvent produced 3.5 g of methyl 2-azido-3-(2-methoxy-3-methylphenyl)acrylate, that was used in the next step without further purification.

Workup

  1. additionAfter addition the mixture
  2. customtransferred in cold room (4 degrees)
  3. stirringstirred overnight
  4. customOn the morning reaction mixture
  5. stirringstirred for 10 minutes
  6. filtrationfiltered off
  7. washThe solid was washed with plenty of ice cold water
  8. custommoved at ambient temperature
  9. customAfter air drying for 1 hr the solid
  10. dissolutionwas dissolved in 50 mL of DCM
  11. dry with materialdried over magnesium sulfate
  12. customEvaporation of solvent

Sources & evidence

ORD record
ord-d0ee719e5025401f921542c170ec674e
Source dataset
uspto-grants-2015_12
Patent number
US09216993B2

Reaction notes

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