Dimethyl Disulfide → HCID 70247106, compound

HRID 1741509Notes

Reaction equation

HRID 1741509 reaction equation
[F:1][CH:2]1[C:7]([Si:8]([CH3:11])([CH3:10])[CH3:9])=[C:6]([F:12])[CH:5]=[CH:4][C:3]1([CH2:14][O:15][CH3:16])[OH:13].[Li]CCCC.[CH3:22][S:23]SC>C1COCC1>[F:1][CH:2]1[C:7]([Si:8]([CH3:9])([CH3:10])[CH3:11])=[C:6]([F:12])[CH:5]=[C:4]([S:23][CH3:22])[C:3]1([CH2:14][O:15][CH3:16])[OH:13]

Participants

5

Reactant 3

HCID 12232Dimethyl DisulfideHCID 21707576HCID 21707576, compoundHCID 178418339Butyllithium

Product 1

HCID 70247106HCID 70247106, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
78 °C

Procedure

A flame-dried 3-necked flask was charged with 2,4-difluoro-3-trimethylsilyl-1-methoxymethylphenol (27, 0.63 g, 2.56 mmol) in 15 mL of freshly distilled THF under argon and this mixture was cooled to δ 78° C. (FIG. 2E). nBuLi (2.5 M solution in hexane, 1.16 mL, 2.9 mmol) was added to this reaction mixture which was allowed to stir at -78° C. for 2.5 h under argon. Methyldisulfide (0.27 g, 2.9 mmol) was then added to the mixture at -78° C. and then the acetone/dry ice bath was removed and the reaction was allowed to proceed at room temperature for 14 hours. Sat. NH4Cl (~10 mL) was added to the mixture which was then stirred for an additional 10 min and then extracted with ethyl ether (3×10 mL). The combined organic solution was washed with brine, water and then dried (MgSO4) and filtered. The solvent was removed under vacuo to afford the crude product which was purified by flash chromatography on silica gel (EtOAc:hexanes; 5:95) to yield a yellow oil (0.51 g, 68%). 1H NMR (CDCl3) δ 6.55-6.58 (dd, 1H, ArH), 5.09 (s, 2H, CH2), 3.63 (s, 3H, CH3), 2.41 (s, 3H, CH3), 0.34-0.35 (t, 9 H, Si(CH3)3); FAB-MS 293 (MH+, 24), 292 (M+, 70), 262 (66), 261 (100).

Workup

  1. customthe acetone/dry ice bath was removed
  2. waitto proceed at room temperature for 14 hours
  3. additionSat. NH4Cl (~10 mL) was added to the mixture which
  4. stirringwas then stirred for an additional 10 min
  5. extractionextracted with ethyl ether (3×10 mL)
  6. washThe combined organic solution was washed with brine, water
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customThe solvent was removed under vacuo
  10. customto afford the crude product which
  11. customwas purified by flash chromatography on silica gel (EtOAc:hexanes; 5:95)

Sources & evidence

ORD record
ord-0705956d448940e0ad9a2f805e05aa9f
Source dataset
uspto-grants-1999_10
Patent number
US05973191

Reaction notes

Loading…