3-(p-Tolyl)propiolaldehyde → 1-p-Tolyl-hex-5-en-1-yn-3-ol

HRID 1096697Notes

Reaction equation

HRID 1096697 reaction equation
[C:1]1([CH3:11])[CH:6]=[CH:5][C:4]([C:7]#[C:8][CH:9]=[O:10])=[CH:3][CH:2]=1.[CH2:12]([Mg]Br)[CH:13]=[CH2:14]>C1COCC1>[C:1]1([CH3:11])[CH:2]=[CH:3][C:4]([C:7]#[C:8][CH:9]([OH:10])[CH2:14][CH:13]=[CH2:12])=[CH:5][CH:6]=1

Participants

4

Reactant 2

HCID 113848723-(p-Tolyl)propiolaldehydeHCID 178455850HCID 178455850, compound

Product 1

HCID 597791321-p-Tolyl-hex-5-en-1-yn-3-olYield 81%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 3-p-tolylprop-2-yn-1-al (4.69 g; 32.5 mmol; 1 eq) in THF (40 mL) was added to a solution of allylmagnesium bromide (49 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, the layers were stirred, and then 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→2:1 heptane/EtOAc) afforded the desired homoallylic alcohol (4.9 g; 26.3 mmol; 81%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 2.34 ((s, 3 H)) 2.56 (t, 2 H) 4.64 (t, 1H) 5.19-5.26 (m, 2H) 5.88-5.99 (m, 1H) 7.10 (d, 2H) 7.31 (d, 2H).

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→2:1 heptane/EtOAc)

Sources & evidence

ORD record
ord-6e49c683611740829563970e3c2d0f74
Source dataset
uspto-grants-2012_03
Patent number
US08138377B2

Reaction notes

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