Ammonium Chloride → Ethyl 2-azido-3-(4-trimethylsilylphenyl)propenoate

HRID 1948775Notes

Reaction equation

HRID 1948775 reaction equation
[Na].[N:2]([CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7])=[N+:3]=[N-:4].[CH3:11][Si:12]([CH3:22])([CH3:21])[C:13]1[CH:20]=[CH:19][C:16]([CH:17]=O)=[CH:15][CH:14]=1.[Cl-].[NH4+]>C(O)C>[N:2]([C:5](=[CH:17][C:16]1[CH:19]=[CH:20][C:13]([Si:12]([CH3:11])([CH3:22])[CH3:21])=[CH:14][CH:15]=1)[C:6]([O:8][CH2:9][CH3:10])=[O:7])=[N+:3]=[N-:4]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 69480Acetic acid, azido-, ethyl esterHCID 6375734-(Trimethylsilyl)benzaldehydeHCID 5360545Sodium

Product 1

HCID 86649677Ethyl 2-azido-3-(4-trimethylsilylphenyl)propenoateYield 62.4%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

1.26 g (54.96 mmol) of sodium and 30 ml of anhydrous ethanol are introduced into a 100 ml round-bottomed flask equipped with a magnetic stirrer and maintained under a nitrogen atmosphere. The reaction mixture is stirred at ambient temperature until a homogeneous solution is obtained. A solution containing 16.83 ml (54.96 mmol) of ethyl azidoacetate (34% in CH2Cl2) and 5 g (27.48 mmol) of 4-trimethylsilylbenzaldehyde in 5 ml of ethanol is added dropwise to this solution, cooled to −10° C. The reaction mixture is subsequently stirred at 0° C. for 4 hours. The reaction medium is hydrolysed by adding 100 ml of an ammonium chloride solution (30% aqueous) with vigorous stirring. The product is extracted with three times 50 ml of ethyl acetate. The combined organic phases are washed with twice 20 ml of water, dried over sodium sulphate and concentrated under reduced pressure. The resulting oil is purified by silica gel column chromatography, elution being carried out with a mixture of heptane and dichloromethane. 4.96 g of the expected product are isolated in the form of a yellow oil.

Workup

  1. customequipped with a magnetic stirrer
  2. temperaturemaintained under a nitrogen atmosphere
  3. customis obtained
  4. additionis added dropwise to this solution
  5. temperaturecooled to −10° C
  6. stirringThe reaction mixture is subsequently stirred at 0° C. for 4 hours
  7. extractionThe product is extracted with three times 50 ml of ethyl acetate
  8. washThe combined organic phases are washed with twice 20 ml of water
  9. dry with materialdried over sodium sulphate
  10. concentrationconcentrated under reduced pressure
  11. customThe resulting oil is purified by silica gel column chromatography, elution
  12. additionbeing carried out with a mixture of heptane and dichloromethane

Sources & evidence

ORD record
ord-c3e71fb7f50245bd827b4fbdadd37f89
Source dataset
uspto-grants-2013_03
Patent number
US08399491B2

Reaction notes

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