3-(3,4-Dichlorophenyl)-2-propynal → 1-(3,4-Dichlorophenyl)hex-5-en-1-yn-3-ol

HRID 1096711Notes

Reaction equation

HRID 1096711 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:9]#[C:10][CH:11]=[O:12])[CH:5]=[CH:6][C:7]=1[Cl:8].[CH2:13]([Mg]Br)[CH:14]=[CH2:15]>C1COCC1>[Cl:1][C:2]1[CH:3]=[C:4]([C:9]#[C:10][CH:11]([OH:12])[CH2:15][CH:14]=[CH2:13])[CH:5]=[CH:6][C:7]=1[Cl:8]

Participants

4

Reactant 2

HCID 592560003-(3,4-Dichlorophenyl)-2-propynalHCID 178455850HCID 178455850, compound

Product 1

HCID 597791521-(3,4-Dichlorophenyl)hex-5-en-1-yn-3-olYield 75%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 3-(3,4-dichlorophenyl)prop-2-yn-1-al (6.46 g; 32.4 mmol; 1 eq) in THF was added to a solution of allylmagnesium bromide (48.5 mL; 1M in Et20, 1.5 eq) at 0° C. over 25 minutes. Stirring was continued for an additional 2 h, and the reaction was carefully quenched with water (50 mL) at 0° C. MTBE (100 mL) was added, and the layers were stirred and allowed to separate. The aqueous phase was re-extracted with MTBE (50 mL) and the combined organic layers were dried over sodium sulfate and filtered. The filtrate was concentrated using a rotary evaporator, and purification of the residue by flash chromatography (4:1→1:1 heptane/EtOAc) afforded the desired homoallylic alcohol (5.86 g; 24.3 mmol; 75%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 2.56 (t, 2 H) 4.63 (t, 1H) 5.21-5.29 (m, 2H) 5.85-5.97 (m, 1H) 7.21 (d, 1H) 7.37 (d, 1H) 7.51 (s, 1H).

Workup

  1. customthe reaction was carefully quenched with water (50 mL) at 0° C
  2. additionMTBE (100 mL) was added
  3. stirringthe layers were stirred
  4. customto separate
  5. extractionThe aqueous phase was re-extracted with MTBE (50 mL)
  6. dry with materialthe combined organic layers were dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated
  9. customa rotary evaporator, and purification of the residue by flash chromatography (4:1→1:1 heptane/EtOAc)

Sources & evidence

ORD record
ord-9eaac413ac814959988b8d031e055406
Source dataset
uspto-grants-2012_03
Patent number
US08138377B2

Reaction notes

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