2-(Bromomethyl)acrylic acid ethyl ester → HCID 10492188, compound

HRID 263967Notes

Reaction equation

HRID 263967 reaction equation
[O:1]=[C:2]([CH3:15])[CH2:3][O:4][C:5]1[CH:6]=[CH:7][CH:8]=[C:9]2[C:14]=1[N:13]=[CH:12][CH:11]=[CH:10]2.Br[CH2:17][C:18](=[CH2:24])[C:19](OCC)=[O:20].C([O-])(O)=O.[Na+]>O1CCCC1.[Zn].C1(C=CC(O)=CC=1)O>[CH3:15][C:2]1([CH2:3][O:4][C:5]2[CH:6]=[CH:7][CH:8]=[C:9]3[C:14]=2[N:13]=[CH:12][CH:11]=[CH:10]3)[CH2:24][C:18](=[CH2:17])[C:19](=[O:20])[O:1]1

Participants

7

Reactant 3

HCID 3106202-(Bromomethyl)acrylic acid ethyl esterHCID 516892Sodium BicarbonateHCID 15269575HCID 15269575, compound

Product 1

HCID 10492188HCID 10492188, compoundYield 82%

Reagents, catalysts & solvents 3

HCID 785HydroquinoneCatalystHCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 7a (0.60 g, 3 mmol) in dry tetrahydrofuran (60 ml) were added activated zinc powder (0.26 g, 3.9 mmol), hydroquinone (6 mg), and ethyl 2-(bromomethyl)acrylate (0.78 g, 4 mmol). The mixture was refluxed under nitrogen atmosphere for 6 h (monitored by TLC). After cooling, it was poured into an ice-cold 5% HCl solution (300 ml), neutralized with 1.0N NaHCO3, and extracted with CH2Cl2 (60 ml×3). The dichloromethane extracts were combined and washed with water, dried over Na2SO4, and then evaporated to give a residual oil which was purified by column chromatography on silica gel using CH2Cl2 as the eluent to afford the title compound (0.66 g, 82%). UV λmax (log ε): 250 (4.69) (0.1N HCl in MeOH), 237 (4.60) (MeOH), 238 (4.64) (0.1N NaOH in MeOH); 1H-NMR (CDCl3): δ1.61 (s, 3H, 2'-CH3), 2.84 (dt, 1H, 3'-H), 3.48 (dt, 1H, 3'-H), 4.25 (d, 1H, OCH), 4.32 (d, 1H, OCH), 5.66 (t 1H, vinylic H), 6.26 (t, 1H, vinylic H), 7.13-8.91 (m, 6H, Ar--H). Anal. Calcd for C16H15NO3.1/8H2O: C, 70.77; H, 5.65; N, 5.16. Found: C, 70.80; H, 5.75; N, 5.08.

Workup

  1. temperatureThe mixture was refluxed under nitrogen atmosphere for 6 h (monitored by TLC)
  2. temperatureAfter cooling
  3. extractionextracted with CH2Cl2 (60 ml×3)
  4. washwashed with water
  5. dry with materialdried over Na2SO4
  6. customevaporated
  7. customto give a residual oil which
  8. customwas purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-e4c9fff77fe64650bcf118a696f70f90
Source dataset
uspto-grants-1997_07
Patent number
US05646164

Reaction notes

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