Acetic Acid → HCID 18937643, compound

HRID 357645Notes

Reaction equation

HRID 357645 reaction equation
C([Li])CCC.C(NC(C)C)(C)C.[C:13]([O:17][CH2:18][CH3:19])(=[O:16])[C:14]#[CH:15].[CH3:20][O:21][CH2:22][O:23][C:24]1[CH:31]=[CH:30][C:27]([CH:28]=[O:29])=[C:26]([N+:32]([O-:34])=[O:33])[CH:25]=1.C(O)(=O)C>O1CCCC1.O>[OH:29][CH:28]([C:27]1[CH:30]=[CH:31][C:24]([O:23][CH2:22][O:21][CH3:20])=[CH:25][C:26]=1[N+:32]([O-:34])=[O:33])[C:15]#[C:14][C:13]([O:17][CH2:18][CH3:19])=[O:16]

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 7912DiisopropylamineHCID 12182Ethyl propiolateHCID 18937665HCID 18937665, compoundHCID 178418339Butyllithium

Product 1

HCID 18937643HCID 18937643, compoundYield 105.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

1.5N butyllithium (19.3 ml, 29.0 mmole) was added under the argon atmosphere to a solution of diisopropylamine (4.3 ml, 30.6 mmole) in tetrahydrofuran (50 ml) at -78° C., and the mixture was stirred for 1 hour. Next, ethyl propiolate (2.4 ml, 23.7 mmole) and a solution of 4-methoxymethoxy-2-nitrobenzaldehyde (3.6 g, 17.0 mmole) in tetrahydrofuran (35 ml) were added in this sequence, and the reaction mixture was stirred at -78° C. for further 2 hours. After a solution of acetic acid (5.0 ml, 87.5 mmole) in tetrahydrofuran (20 ml) and water were sequentially added, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, water, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous saline in this sequence. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure to give ethyl 4-hydroxy-4-(4-methoxymethoxy-2-nitrophenyl)-2-butynoate as an oil (5.53 g).

Workup

  1. stirringthe reaction mixture was stirred at -78° C. for further 2 hours
  2. extractionthe reaction mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with dilute hydrochloric acid, water
  4. dry with materialAfter the organic layer was dried over anhydrous magnesium sulfate
  5. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-3ee7054bc303455da529fcbfcf2b4dea
Source dataset
uspto-grants-1998_11
Patent number
US05840895

Reaction notes

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