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

HRID 58008

反応式

HRID 58008 の反応式
[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

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 6344Dichloromethane溶媒

実験手順

(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.

後処理

  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

出典と根拠

ORDレコード
ord-d815bf4454004efa9631af60367267ec
出典データセット
uspto-grants-2016_09
特許番号
US09434748B2

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