Water → 5-[(2E)-3-(dimethylamino)prop-2-enoyl]-2-methoxybenzyl pivalate

HRID 218346Notes

Reaction equation

HRID 218346 reaction equation
[C:1]([O:7][CH2:8][C:9]1[CH:14]=[C:13]([C:15](=[O:17])[CH3:16])[CH:12]=[CH:11][C:10]=1[O:18][CH3:19])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].CC(O[CH:25](N(C)C)[N:26]([CH3:28])[CH3:27])(C)C.O.CCCC(C)C>C(OC)(C)(C)C>[C:1]([O:7][CH2:8][C:9]1[CH:14]=[C:13]([C:15](=[O:17])/[CH:16]=[CH:25]/[N:26]([CH3:28])[CH3:27])[CH:12]=[CH:11][C:10]=1[O:18][CH3:19])(=[O:6])[C:2]([CH3:4])([CH3:3])[CH3:5]

Participants

6

Reactant 4

HCID 962WaterHCID 78922-MethylpentaneHCID 79885tert-Butoxy bis(dimethylamino)methaneHCID 580154765-Acetyl-2-methoxybenzyl pivalate

Product 1

HCID 580154715-[(2E)-3-(dimethylamino)prop-2-enoyl]-2-methoxybenzyl pivalateYield 79.6%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
54 °C

Procedure

5-acetyl-2-methoxybenzyl pivalate (66.24 g, 251.7 mmol) was added to Bredereck's reagent (175.5 g, 1000.7 mmol) held under a nitrogen atmosphere. The resulting solution was heated at 54° C. for 240 minutes. Water (600 mL) was then added and the mixture allowed to stir for an hour. Methyl tert-butyl ether was then added (500 ml) and the mixture stirred and allowed to settle. The upper organic layer was separated off and retained. Further methyl-tert-butyl ether was then added (500 ml) and the mixture stirred and allowed to settle. The upper organic layer was separated off and combined with the original upper organic layer. The combined organic layers were washed twice with water (2×300 mL), discarding the two lower aqueous washes. Solvent (850 mL) is removed from the reaction by atmospheric distillation and iso-hexane (100 mL) added. The clear solution was allowed to cool to 20° C. whereby a white, crystalline solid was obtained. Further iso-hexane (50 mL) was added and the solid filtered off at around 20° C. The solid was washed twice with fresh iso-hexane (2×100 mL) and dried to constant weight to afford 64 g of the desired 5-[(2E)-3-(dimethylamino)prop-2-enoyl]-2-methoxybenzyl pivalate (2).

Workup

  1. stirringthe mixture stirred
  2. customThe upper organic layer was separated off
  3. additionFurther methyl-tert-butyl ether was then added (500 ml)
  4. stirringthe mixture stirred
  5. customThe upper organic layer was separated off
  6. washThe combined organic layers were washed twice with water (2×300 mL)
  7. customSolvent (850 mL) is removed from the reaction by atmospheric distillation and iso-hexane (100 mL)
  8. additionadded
  9. temperatureto cool to 20° C. whereby a white, crystalline solid
  10. customwas obtained
  11. filtrationthe solid filtered off at around 20° C
  12. washThe solid was washed twice with fresh iso-hexane (2×100 mL)
  13. customdried to constant weight

Sources & evidence

ORD record
ord-7c025e1bf40d43febbac60aea2d1b026
Source dataset
uspto-grants-2012_06
Patent number
US08198441B2

Reaction notes

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