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

HRID 1110819Notes

Reaction equation

HRID 1110819 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>[Cu].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

5

Reactant 2

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

Product 1

HCID 117781083-Methylthio-4-hydroxy-5-benzyloxybenzaldehydeYield 76%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 1049PyridineSolvent

Conditions

Temperature
95 °C

Procedure

In an alternative procedure a 50-L flask equipped with a mechanical stirrer was charged with 3-bromo-4-hydroxy-5-benzyloxybenzaldehyde (1.332 kg, 4.34 mol), Copper powder (1.068 kg, 16.82 mol), dimethyldisulfide (1.068 kg, 11.36 mol) and pyridine (23 L). The mixture was heated at 95° C. overnight with gentle stirring, filtered, and the filtered cake was washed with dichloromethane (30 L). The pyridine filtrate was distilled off to leave a black residue, from which the product was extracted with the dichloromethane washes. The combined organic extracts were washed with 2N HCl until it became light brown and the acidic aqueous layer was clear. The organic layer was dried (MgSO4), filtered, and the filtrate was evaporated to dryness. Crystallization from dichloromethane-hexane gave the title compound (900 g, 76%): mp 117°-119° C.; NMR (CDCl3) δ 2.50 (s, SCH3), 5.20 (s, OCH2Ar), 6.72 (s, OH), 7.34-7.46 (m, ArH), 9.78 (s, ArCHO)

Workup

  1. customIn an alternative procedure a 50-L flask equipped with a mechanical stirrer
  2. filtrationfiltered
  3. washthe filtered cake was washed with dichloromethane (30 L)
  4. distillationThe pyridine filtrate was distilled off
  5. customto leave a black residue
  6. extractionfrom which the product was extracted with the dichloromethane
  7. washThe combined organic extracts were washed with 2N HCl until it
  8. dry with materialThe organic layer was dried (MgSO4)
  9. filtrationfiltered
  10. customthe filtrate was evaporated to dryness
  11. customCrystallization from dichloromethane-hexane

Sources & evidence

ORD record
ord-d55cb4eadbec4f4ca34f934e2b6b3dd5
Source dataset
uspto-grants-1990_12
Patent number
US04977146

Reaction notes

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