Dimethyl Disulfide → 3-Methylthio-4-hydroxy-5-benzyloxybenzaldehyde

HRID 1196691Notes

Reaction equation

HRID 1196691 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:9]=1[OH:10])[CH:5]=[O:6].[CH3:19][S:20]SC>N1C=CC=CC=1>[CH3:19][S:20][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:9]=1[OH:10])[CH:5]=[O:6]

Participants

4

Reactant 2

HCID 12232Dimethyl DisulfideHCID 150782813-Bromo-4-hydroxy-5-benzyloxybenzaldehyde

Product 1

HCID 117781083-Methylthio-4-hydroxy-5-benzyloxybenzaldehyde

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
90 °C

Procedure

A five liter flask equipped with a mechanical stirrer was charged with 100 g of 3-bromo-4-hydroxy-5-benzyloxybenzaldehyde, 80 g Cu powder, 80 mL methyldisulfide and 1.7 L pyridine, and the mixture was heated at 90° C. overnight with gentle stirring. The following day, the reaction mixture was filtered and most of the pyridine (1.3 L) was distilled off. The remaining solid residue was washed with about 2 L of methylene chloride and combined with the residue left after pyridine evaporation. The combined organic fraction was washed with 1.5N HCl until the dark methylene chloride layer turned light brown and the aqueous layer was clear. The resulting light brown methylene chloride layer was dried over MgSO4 and filtered through a bed of silica gel. Evaporation and crystallization from methylene chloride-hexane gave the title compound: NMR (200 MHz, CDCl3) 2.50 (s, SCH3), 5.20 (s, OCH2Ar), 6.72 (s, OH), 7.34-7.46 (m, ArH), 9.78 (s, ArCHO).

Workup

  1. customA five liter flask equipped with a mechanical stirrer
  2. filtrationThe following day, the reaction mixture was filtered and most of the pyridine (1.3 L)
  3. distillationwas distilled off
  4. washThe remaining solid residue was washed with about 2 L of methylene chloride
  5. waitleft
  6. customafter pyridine evaporation
  7. washThe combined organic fraction was washed with 1.5N HCl until the dark methylene chloride layer
  8. dry with materialThe resulting light brown methylene chloride layer was dried over MgSO4
  9. filtrationfiltered through a bed of silica gel
  10. customEvaporation and crystallization from methylene chloride-hexane

Sources & evidence

ORD record
ord-3cc2fc685318463bbca81bfe0ab63419
Source dataset
uspto-grants-1992_05
Patent number
US05114961

Reaction notes

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