Ethyl 2-butynoate → HCID 66893867, compound

HRID 19116Notes

Reaction equation

HRID 19116 reaction equation
[CH2:1]([O:3][C:4]1[C:5]([F:12])=[C:6]([OH:11])[C:7]([F:10])=[CH:8][CH:9]=1)[CH3:2].[CH2:13]([O:15][C:16](=[O:20])[C:17]#[C:18][CH3:19])[CH3:14].N12CCCN=C1CCCCC2>O1CCCC1>[CH2:13]([O:15][C:16](=[O:20])/[CH:17]=[C:18](/[O:11][C:6]1[C:7]([F:10])=[CH:8][CH:9]=[C:4]([O:3][CH2:1][CH3:2])[C:5]=1[F:12])\[CH3:19])[CH3:14]

Participants

5

Reactant 3

HCID 78043Ethyl 2-butynoateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 552757683-Ethoxy-2,6-difluorophenol

Product 1

HCID 66893867HCID 66893867, compoundYield 67.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred mixture of 3-ethoxy-2,6-difluoro-phenol (4.26 g, 0.024 mol) and ethyl-2-butynoate (5.48 g, 0.049 mol) in tetrahydrofuran (30 mL) was added 1,8-diazabicyclo[5.4.0]undec-7-ene (3.73 g, 0.025 mol) slowly. After addition was complete the mixture was stirred at reflux for 6 h. Upon completion of the reaction the tetrahydrofuran was removed in vacuo and the residue was diluted in diethyl ether and washed first with 1N aqueous hydrochloric acid, then 10% aqueous sodium hydroxide solution, a saturated sodium chloride solution and dried over magnesium sulfate. The crude product was purified by ISCO column chromatography (Teledyne Isco RediSep Flash Column 120 g, 0% to 20% ethyl acetate/hexanes) which afforded (E)-3-(3-ethoxy-2,6-difluoro-phenoxy)-but-2-enoic acid ethyl ester (4.63 g, 66%) as a white crystalline solid.

Workup

  1. additionAfter addition
  2. temperatureat reflux for 6 h
  3. customwas removed in vacuo
  4. additionthe residue was diluted in diethyl ether
  5. washwashed first with 1N aqueous hydrochloric acid
  6. dry with material10% aqueous sodium hydroxide solution, a saturated sodium chloride solution and dried over magnesium sulfate
  7. customThe crude product was purified by ISCO column chromatography (Teledyne Isco RediSep Flash Column 120 g, 0% to 20% ethyl acetate/hexanes) which

Sources & evidence

ORD record
ord-d69bc81208024a4dba05f317e3bcac65
Source dataset
uspto-grants-2010_06
Patent number
US07741327B2

Reaction notes

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