Potassium Carbonate → (5-((2-Methyl-2-(methyldisulfanyl)propylthio)methyl)-1,3-phenylene)dimethanol

HRID 1615094Notes

Reaction equation

HRID 1615094 reaction equation
CS([O:5][CH2:6][C:7]1[CH:12]=[C:11]([CH2:13][S:14][CH2:15][C:16]([CH3:21])([S:18][S:19][CH3:20])[CH3:17])[CH:10]=[C:9]([CH2:22][O:23]S(C)(=O)=O)[CH:8]=1)(=O)=O.C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O>[CH3:21][C:16]([S:18][S:19][CH3:20])([CH3:17])[CH2:15][S:14][CH2:13][C:11]1[CH:10]=[C:9]([CH2:22][OH:23])[CH:8]=[C:7]([CH2:6][OH:5])[CH:12]=1

Participants

4

Reactant 2

HCID 11430Potassium CarbonateHCID 86671283(5-((2-Methyl-2-(methyldisulfanyl)propylthio)methyl)-1,3-phenylene)bis(methylene) dimethanesulfonate

Product 1

HCID 86671282(5-((2-Methyl-2-(methyldisulfanyl)propylthio)methyl)-1,3-phenylene)dimethanolYield 57.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

IBD monomer (177 mg, 0.602 mmol) in anhydrous N,N-dimethylformamide (1.75 mL) was added to (5-((2-methyl-2-(methyldisulfanyl)propylthio)methyl)-1,3-phenylene)bis(methylene) dimethanesulfonate (119 mg, 0.251 mmol) at ambient temperature. Potassium carbonate (173 mg, 1.253 mmol) was added and the reaction was allowed to stir at ambient temperature for 20 hours. The reaction mixture was quenched with water and extracted with dichloromethane. The extracts were washed with brine and then dried with anhydrous sodium sulfate, filtered and concentrated on high vacuum. The crude product was purified by flash silica gel chromatography (neat DCM→2% MeOH/DCM). Fractions containing product were combined, concentrated and purified by semi-prep RP-HPLC (C18, A=DI water B=ACN, 20 mL/min). Fractions containing desired product were combined, extracted with dichloromethane, dried with anhydrous magnesium sulfate, filtered and concentrated to yield the desired product (46 mg, 21%). 1H NMR (400 Hz, CDCl3): δ 8.19 (d, J=8.0 Hz, 2H), 7.77 (m, d, J=4.4 Hz, 2H), 7.50 (s, 2H), 7.34 (s, 1H), 7.31 (s, 2H), 7.19 (m, 4H), 7.03 (t, J=7.2, 7.6 Hz, 2H), 6.77 (s, 2H), 5.14 (m, 4H), 4.40 (m, 2H), 3.91 (s, 6H), 3.70 (m, 2H), 3.63 (m, 2H), 3.41 (m, 2H), 2.65 (s, 2H), 2.29 (s, 3H), 1.26 (s, 6H). MS (m/z), Calcd. 893.2 (M+Na)+. found 893.2 (M+Na)+, 911.2 (M+H2O+Na)+, 929.2 (M+2H2O+Na)+, 945.1 (M+2H2O+K)+. See FIG. 30.

Workup

  1. customThe reaction mixture was quenched with water
  2. extractionextracted with dichloromethane
  3. washThe extracts were washed with brine
  4. dry with materialdried with anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated on high vacuum
  7. customThe crude product was purified by flash silica gel chromatography (neat DCM→2% MeOH/DCM)
  8. additionFractions containing product
  9. concentrationconcentrated
  10. custompurified by semi-prep RP-HPLC (C18
  11. additionFractions containing desired product
  12. extractionextracted with dichloromethane
  13. dry with materialdried with anhydrous magnesium sulfate
  14. filtrationfiltered
  15. concentrationconcentrated

Sources & evidence

ORD record
ord-271eb3038ea249749d8378d36d9cb163
Source dataset
uspto-grants-2014_07
Patent number
US08765740B2

Reaction notes

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