S-Methyl methanethiosulfonate → (5-((2-Methyl-2-(methyldisulfanyl)propylthio)methyl)-1,3-phenylene)dimethanol

HRID 58008Notes

Reaction equation

HRID 58008 reaction equation
[SH:1][C:2]([CH3:17])([CH3:16])[CH2:3][S:4][CH2:5][C:6]1[CH:7]=[C:8]([CH2:14][OH:15])[CH:9]=[C:10]([CH2:12][OH:13])[CH:11]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[CH3:26][S:27](=O)(SC)=O>C(O)C.ClCCl>[CH3:16][C:2]([S:1][S:27][CH3:26])([CH3:17])[CH2:3][S:4][CH2:5][C:6]1[CH:11]=[C:10]([CH2:12][OH:13])[CH:9]=[C:8]([CH2:14][OH:15])[CH:7]=1

Participants

6

Reactant 3

HCID 18064S-Methyl methanethiosulfonateHCID 62657Potassium Phosphate, TribasicHCID 86671281(5-((2-Mercapto-2-methylpropylthio)methyl)-1,3-phenylene)dimethanol

Product 1

HCID 86671282(5-((2-Methyl-2-(methyldisulfanyl)propylthio)methyl)-1,3-phenylene)dimethanolYield 65%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

(5-((2-mercapto-2-methylpropylthio)methyl)-1,3-phenylene)dimethanol (0.120 g, 0.440 mmol) was dissolved in ethanol (5 mL) and 1.0 M potassium phosphate buffer (pH 7) (5.00 mL) and cooled in an ice bath (a ppt formed but it was ignored). S-methyl methanesulfonothioate (0.083 mL, 0.881 mmol) was added and the mixture stirred overnight with gradual (over 30 minutes) warming to room temperature. The reaction was diluted with dichloromethane and the organic layer was removed, washed with water, dried over anhydrous sodium sulfate, and concentrated in vacuo. The residue was dissolved in dichloromethane and loaded onto a 500 micron ptlc plate and developed with 66% ethyl acetate in hexane. The band corresponding to the product was scraped, filtered using ethyl acetate, and concentrated to give (5-((2-methyl-2-(methyldisulfanyl)propylthio)methyl)-1,3-phenylene)dimethanol (0.091 g, 0.286 mmol, 64.9% yield). 1H NMR (400 Hz, CDCl3): δ 7.27 (s, 3H), 4.71 (s, 4H), 3.78 (s, 2H), 2.77 (s, 2H), 2.41 (s, 3H), 1.94 (br s, 2H), 1.38 (s, 6H); 13C NMR (400 Hz, CDCl3): δ 141.6, 139.0, 126.7, 124.2, 65.0, 51.8, 44.0, 38.2, 26.7, 25.3; MS (m/z), expected: 341.5. found 341.1 (M+Na). See FIG. 30.

Workup

  1. customformed
  2. customthe organic layer was removed
  3. washwashed with water
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated in vacuo
  6. dissolutionThe residue was dissolved in dichloromethane
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-d815bf4454004efa9631af60367267ec
Source dataset
uspto-grants-2016_09
Patent number
US09434748B2

Reaction notes

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