Dimethyl Sulfate → HCID 9889324, compound

HRID 1976352Notes

Reaction equation

HRID 1976352 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([C:7](=[O:21])[CH:8]=[C:9]([C:13]3[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][CH:14]=3)[O:10]2)=[C:5]([OH:22])[C:4]=1[I:23].[C:24]([O-])([O-])=O.[K+].[K+].COS(OC)(=O)=O.CO.C(Cl)Cl>C1COCC1>[I:23][C:4]1[C:5]([O:22][CH3:24])=[C:6]2[C:11](=[CH:12][C:3]=1[O:2][CH3:1])[O:10][C:9]([C:13]1[CH:14]=[CH:15][C:16]([O:19][CH3:20])=[CH:17][CH:18]=1)=[CH:8][C:7]2=[O:21]

Participants

6

Reactant 4

HCID 6497Dimethyl SulfateHCID 11430Potassium CarbonateHCID 11112679HCID 11112679, compoundHCID 21226129Dichloromethane methanol

Product 1

HCID 9889324HCID 9889324, compoundYield 71.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 7 (3.00 g, 7.08 mmol) and K2CO3 (1.47 g, 10.6 mmol) in 150 mL THF was added dimethylsulfate (1.07 g, 8.49 mmol) and the solution heated at reflux overnight. The solvent was evaporated and the residue partitioned between 50 mL each of CHCl3 and H2O. The organic phase was separated and washed with saturated brine, dried over magnesium sulfate, filtered and evaporated to provide a yellow solid. Recrystallization from CHCl3/EtOH (1:2, 150 mL) afforded pale-yellow needles. Column chromatography of the evaporated mother liquor (100 g silica gel, 2% MeOH/CH2Cl2) afforded an additional 720 mg of desired product (total yield 2.21 g, 71.3%); mp 204° C. (lit.13 mp 191-194° C.); 1H NMR (CDCl3) δ 3.89 (s, 3 H), 3.94 (s, 3 H), 4.01 (s, 3 H), 6.62 (s, 1 H), 6.78 (s, 1 H), 7.01 (d, 2 H, J=9.1 Hz), 7.83 (d, 2 H, J=9.1 Hz); EI-MS in/z 438 (M+, 65), 311 (100). Anal. calcd for C18H15IO5: C, 49.34; H, 3.45. Found: C, 48.58; H, 3.21.

Workup

  1. temperaturethe solution heated
  2. temperatureat reflux overnight
  3. customThe solvent was evaporated
  4. customthe residue partitioned between 50 mL each of CHCl3 and H2O
  5. customThe organic phase was separated
  6. washwashed with saturated brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated
  10. customto provide a yellow solid
  11. customRecrystallization from CHCl3/EtOH (1:2, 150 mL)
  12. customafforded pale-yellow needles

Sources & evidence

ORD record
ord-b9c9bb2ffb9d438a85dd811bef1fbe1e
Source dataset
uspto-grants-2001_05
Patent number
US06225481B1

Reaction notes

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