3-Methyl-1-pentyn-3-ol → 4-Methyl-1-{4-(methylthio)phenyl}-2-hexyn-1,4-diol

HRID 2298286Notes

Reaction equation

HRID 2298286 reaction equation
[CH3:1][C:2]([OH:7])([CH2:5][CH3:6])[C:3]#[CH:4].[CH2:8]([Li])[CH2:9][CH2:10]C.CC1C=CC([CH:18]=[S:19])=CC=1.[CH2:22]1[CH2:26][O:25][CH2:24][CH2:23]1>CCCCCC>[CH3:1][C:2]([OH:7])([CH2:5][CH3:6])[C:3]#[C:4][CH:24]([C:23]1[CH:22]=[CH:26][C:10]([S:19][CH3:18])=[CH:9][CH:8]=1)[OH:25]

Participants

6

Reactant 4

HCID 64943-Methyl-1-pentyn-3-olHCID 8028TetrahydrofuranHCID 181775354-MethylthiobenzaldehydeHCID 178418339Butyllithium

Product 1

HCID 183860124-Methyl-1-{4-(methylthio)phenyl}-2-hexyn-1,4-diol

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

To a stirred solution of 3-methyl-1-pentyn-3-ol (23.3 g) in 150 ml anhydrous THF at −78° C. under argon, was added 130 ml of 2.5 M butyllithium in hexane dropwise over 20 minutes. The reaction solution was stirred for another 20 minutes, followed by dropwise addition 16 ml of 4-methylthiobenzaldehyde. After stirring for another 2 hours, the reaction was quenched by adding 200 ml of dilute aqueous HCl. The reaction solvent was removed in vacuo, and the resulting aqueous solution was extracted with dichloromethane (100 ml×3). The organic layer was concentrated under reduced pressure and the resulting residue was purified by column chromatography (hexane/ethylacetate=1:1) to yield 30 g of 4-methyl-1-{4-(methylthio)phenyl}-2-hexyn-1,4-diol as an oil. NMR: δ1.05 (t, J=7.5 Hz, 3H), 1.51 (s, 3H), 1.73 (m, 2H), 2.18 (s, 1H), 2.50 (s, 3H), 5.49 (s, 1,H), 7.26 (d, J=8.7 Hz, 2H), 7.45 (d, J=8.7 Hz, 2H). IR (cm−1): 3348, 2974, 2930, 1492, 1092, 983, 795, 523.

Workup

  1. stirringAfter stirring for another 2 hours
  2. customthe reaction was quenched
  3. additionby adding 200 ml of dilute aqueous HCl
  4. customThe reaction solvent was removed in vacuo
  5. extractionthe resulting aqueous solution was extracted with dichloromethane (100 ml×3)
  6. concentrationThe organic layer was concentrated under reduced pressure
  7. customthe resulting residue was purified by column chromatography (hexane/ethylacetate=1:1)

Sources & evidence

ORD record
ord-98df4fab046c4a06b5ebc83659f8fef1
Source dataset
uspto-grants-2002_12
Patent number
US06492416B1

Reaction notes

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