Azobisisobutyronitrile → (E)-3-[2-Bromomethyl-6-(3-ethoxycarbonylpropoxy)phenyl]acrylic acid ethyl ester

HRID 418057Notes

Reaction equation

HRID 418057 reaction equation
[CH2:1]([O:3][C:4](=[O:23])[CH2:5][CH2:6][CH2:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH3:15])[C:10]=1/[CH:16]=[CH:17]/[C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH3:2].[Br:24]N1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>ClC1C=CC=CC=1.O>[CH2:1]([O:3][C:4](=[O:23])[CH2:5][CH2:6][CH2:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH2:15][Br:24])[C:10]=1/[CH:16]=[CH:17]/[C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH3:2]

Participants

6

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 575864834-[2-((E)-2-ethoxycarbonyl-vinyl)-3-methyl-phenoxy]-butyric acid ethyl ester

Product 1

HCID 57586460(E)-3-[2-Bromomethyl-6-(3-ethoxycarbonylpropoxy)phenyl]acrylic acid ethyl esterYield 71.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 7964ChlorobenzeneSolvent

Conditions

Temperature
85 °C

Procedure

To a solution of 4-[2-((E)-2-ethoxycarbonyl-vinyl)-3-methyl-phenoxy]-butyric acid ethyl ester (8.0 g, 25.0 mmol) in chlorobenzene (190 mL) were added N-bromosuccinimide (6.67 g, 37.5 mmol) and 2,2′-azobisisobutyronitrile (AIBN) (591 mg, 3.6 mmol) at room temperature. Then, the solution was heated to 85° C. and stirred for 1 h. Then, the reaction mixture was cooled to room temperature and diluted with water (100 mL). Then, the organic compound was extracted into hexanes (3×100 mL). The combined organic extracts were washed with brine solution (150 mL) and the organic solution was dried over anhydrous magnesium sulfate. Filtration of the drying agent and the removal of the solvent gave a crude oil. The crude oil was purified by using a Biotage (40 L) column eluting with 15-25% ethyl acetate in hexanes to isolate 4-[3-bromomethyl-2-((E)-2-ethoxycarbonyl-vinyl)-phenoxy]-butyric acid ethyl ester (7.11 g, 71%) as a low melting solid: ES(+)-HRMS m/e calculated for C18H23BrO5 (M+Na)+ 421.0621, found 421.0621.

Workup

  1. temperatureThen, the reaction mixture was cooled to room temperature
  2. extractionThen, the organic compound was extracted into hexanes (3×100 mL)
  3. washThe combined organic extracts were washed with brine solution (150 mL)
  4. dry with materialthe organic solution was dried over anhydrous magnesium sulfate
  5. filtrationFiltration of the drying agent
  6. customthe removal of the solvent
  7. customgave a crude oil
  8. customThe crude oil was purified
  9. washeluting with 15-25% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-3e01fdbf72e04b8f9fa3e3ab96b16763
Source dataset
uspto-grants-2012_01
Patent number
US08093253B2

Reaction notes

Loading…