Hydrochloric Acid → HCID 23050504, compound

HRID 1651842Notes

Reaction equation

HRID 1651842 reaction equation
C([Li])CCC.[CH3:6][O:7][C:8]1[CH:9]=[C:10]([CH:18]([OH:21])[C:19]#[CH:20])[CH:11]=[C:12]([O:16][CH3:17])[C:13]=1[O:14][CH3:15].C[Si](Cl)(C)C.Cl[C:28]([O:30][CH2:31][CH2:32][CH2:33][CH3:34])=[O:29].Cl>CCOCC.C(Cl)Cl.[O-2].[O-2].[Mn+4].C(OCC)(=O)C>[CH3:17][O:16][C:12]1[CH:11]=[C:10]([CH:9]=[C:8]([O:7][CH3:6])[C:13]=1[O:14][CH3:15])[C:18]([C:19]#[C:20][C:28]([O:30][CH2:31][CH2:32][CH2:33][CH3:34])=[O:29])=[O:21]

Participants

10

Reactant 5

HCID 313Hydrochloric Acid2×HCID 6397ChlorotrimethylsilaneHCID 61140Butyl chloroformateHCID 161103271-(3,4,5-Trimethoxyphenyl)-2-propyn-1-olHCID 178418339Butyllithium2×

Product 1

HCID 23050504HCID 23050504, compound

Reagents, catalysts & solvents 4

HCID 178418406HCID 178418406, compoundCatalystHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

8.7 ml of n-butyllithium solution (1.6M in hexane) were added at -78° to a solution of 3.0 g (13.5 mmol) of 1-(3,4,5-trimethoxyphenyl)-2-propyn-1-ol in 40 ml of ether. The reaction mixture was brought to -30°, whereupon 1.8 ml (14.2 mmol) of freshly distilled trimethylsilyl chloride were added at -30°. Thereafter, the mixture was warmed to 0°. stirred and cooled to -78° for 1 hour, whereupon 7.8 ml of n-butyllithium solution (1.6M in hexane) were added. The reaction mixture was stirred at -30° for 1 hour and then treated at -30° with 2.77 ml (20.25 mmol) of butyl chloroformate, whereupon the mixture was stirred at -30° for 30 minutes and at 0° for 1 hour and 150 ml of 1N hydrochloric acid and 150 ml of ethyl acetate were added. Subsequently. 30 ml of 25% hydrochloric acid were added, the mixture was shaken vigorously for 10 minutes in a separating funnel, the aqueous phase was extracted twice with ethyl acetate, the combined organic phases were dried over magnesium sulphate and the solvent was distilled off. The crude product which remained behind as the residue was taken up in 10 ml of methylene chloride and added dropwise at 0° to a suspension 35.2 g (0.405 mol) of manganese dioxide in 50 ml of methylene chloride The reaction mixture was stirred at 0° for 1.5 hours, filtered over magnesium sulphate and evaporated. After chromatography of the residue on silica gel with ethyl acetate/hexane (1:4) there was obtained butyl 3-(3,4,5-trimethoxybenzoyl)propiolate as a pale yellowish oil.

Workup

  1. additionwere added at -30°
  2. temperatureThereafter, the mixture was warmed to 0°
  3. additionwere added
  4. stirringThe reaction mixture was stirred at -30° for 1 hour
  5. stirringwas stirred at -30° for 30 minutes and at 0° for 1 hour
  6. stirringthe mixture was shaken vigorously for 10 minutes in a separating funnel
  7. extractionthe aqueous phase was extracted twice with ethyl acetate
  8. dry with materialthe combined organic phases were dried over magnesium sulphate
  9. distillationthe solvent was distilled off
  10. stirringwas stirred at 0° for 1.5 hours
  11. filtrationfiltered over magnesium sulphate
  12. customevaporated

Sources & evidence

ORD record
ord-d59a5604d51b49b099d9a50f6f9fbb06
Source dataset
uspto-grants-1990_05
Patent number
US04929741

Reaction notes

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