Propionic Acid → 2-Propenoic acid, 3-(4-methoxyphenyl)-, 2-ethylhexyl ester

HRID 327914Notes

Reaction equation

HRID 327914 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6](N)=[CH:5][CH:4]=1.C(O)(=O)CC.S(=O)(=O)(O)O.N([O-])=O.[Na+].[C:24]([O:28][CH2:29][CH:30]([CH2:35][CH3:36])[CH2:31][CH2:32][CH2:33][CH3:34])(=[O:27])[CH:25]=[CH2:26].[OH-].[Na+].C(OC(CC)CCCCC)(=O)C=C>O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].C(N)(C)(C)C>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH:26]=[CH:25][C:24]([O:28][CH2:29][CH:30]([CH2:35][CH3:36])[CH2:31][CH2:32][CH2:33][CH3:34])=[O:27])=[CH:5][CH:4]=1

Participants

11

Reactant 7

HCID 1032Propionic Acid3×HCID 1118Sulfuric AcidHCID 76362-Ethylhexyl acrylateHCID 7732P-AnisidineHCID 14798Sodium HydroxideHCID 15748566Octane-3-yl acrylateHCID 23668193Sodium Nitrite

Product 1

HCID 216302-Propenoic acid, 3-(4-methoxyphenyl)-, 2-ethylhexyl esterYield 94.1%

Reagents, catalysts & solvents 3

HCID 6385Tert-ButylamineCatalystHCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 962WaterSolvent2×

Conditions

Temperature
0 °C

Procedure

p-Anisidine (123 g), propionic acid (200 ml) and water (250 ml) were mixed in a 5 liter reaction flask and cooled to 0° C. Sulfuric acid 98% (202 g) was added gradually with cooling followed by the addition of sodium nitrite (69 g) dissolved in 200 ml water over a 50 minute period. The stirring was continued for a further one hour at 0°-2° C., t-Butylamine (0.5 g) was then added. After an additional 15 minutes of stirring Pd(dba)2 (1.0 g) and propionic acid (250 ml) were added. 2-Ethylhexyl acrylate (276 g) was then added over a period of 10 minutes while maintaining the temperature at 0° C. The reaction was then allowed to warm to room temperature and stirred for 24 hours. Sodium hydroxide (333 g of 30% solution) was added and after 10 minutes the lower aqueous layer was separated and extracted twice with ether (200 ml). The ether layers were combined and evaporated. The residue was combined with the organic layer and distilled to give separate fractions of propionic acid, excess ethylhexyl acrylate and 273 g of 2-ethylhexyl p-methoxycinnamate (94.0% yield).

Workup

  1. temperaturewith cooling
  2. temperaturewhile maintaining the temperature at 0° C
  3. temperatureto warm to room temperature
  4. customwas separated
  5. extractionextracted twice with ether (200 ml)
  6. customevaporated
  7. distillationdistilled
  8. customto give

Sources & evidence

ORD record
ord-ebf9ac92fe7b43f09b8521d638f9f1e8
Source dataset
uspto-grants-1993_12
Patent number
US05274171

Reaction notes

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