2-(Bromomethyl)acrylic acid ethyl ester → HCID 381514, compound

HRID 263956Notes

Reaction equation

HRID 263956 reaction equation
[O:1]=[C:2]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[CH2:3][O:4][C:5]1[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=2[O:8][C:7](=[O:15])[CH:6]=1.Br[CH2:23][C:24](=[CH2:30])[C:25](OCC)=[O:26]>O1CCCC1.[Zn].C1(C=CC(O)=CC=1)O>[CH2:23]=[C:24]1[C:25](=[O:26])[O:1][C:2]([CH2:3][O:4][C:5]2[C:10]3[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=3[O:8][C:7](=[O:15])[CH:6]=2)([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH2:30]1

Participants

6

Reactant 2

HCID 3106202-(Bromomethyl)acrylic acid ethyl esterHCID 386272NSC678029

Product 1

HCID 381514HCID 381514, compoundYield 86.4%

Reagents, catalysts & solvents 3

HCID 785HydroquinoneCatalystHCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2a (0.84 g, 3 mmol) in dry tetrahydrofuran (60 ml) were added activated zinc powder (0.255 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 18 h. (monitored by TLC). After cooling it was poured into an ice-cold 5% HCl solution (300 ml) and extracted with CH2Cl2 (75 ml×3). The dichloromethane extracts were combined and washed with saline, dried over Na2SO4, and then evaporated to give a residual solid which was crystallized from ethyl acetate to afford the title compound (0.90 g, 86.4%). mp: 212°-214° C.; IR(KBr) νmax : 1766, 1717, 1620; UV(CHCl3) νmax (log ε): 306 (3.89), 277 (4.10), 266 (4.14); 1H-NMR (CDCl3): δ3.33 (dt, 1H, 4'-H), 3.66 (dt, 1H, 4'-H), 4.26, 4.32 (two d, 2H, OCH2), 5.60 (s, 1H, 3-H), 5.79 (t, 1H, vinylic H), 6.42 (t, 1H, vinylic H), 7.20-7.61 (m, 9H, 5,6,7,8-H, and aromatic H). Anal. Calcd for C21H16O5 0.25H2O: C, 71.48; H, 4.71. Found: C, 71.37; H, 4.67.

Workup

  1. temperatureThe mixture was refluxed under nitrogen atmosphere for 18 h. (monitored by TLC)
  2. temperatureAfter cooling it
  3. extractionextracted with CH2Cl2 (75 ml×3)
  4. washwashed with saline
  5. dry with materialdried over Na2SO4
  6. customevaporated
  7. customto give a residual solid which
  8. customwas crystallized from ethyl acetate

Sources & evidence

ORD record
ord-bde1d9c0f5fb4aaa95c79013b5f04db9
Source dataset
uspto-grants-1997_07
Patent number
US05646164

Reaction notes

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