Propylene → 2-Hydroxymethyl-2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxylic acid diethyl ester

HRID 1175192

Reaction equation

HRID 1175192 reaction equation
[CH2:1]([CH:3]1[O:5][CH2:4]1)Br.C(=O)([O-])[O-].[K+].[K+].[OH:12][C:13]1[C:17]([OH:18])=[C:16]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[S:15][C:14]=1[C:24]([O:26][CH2:27][CH3:28])=[O:25].C=CC>O.C(O)C.CCCCCC.C(OCC)(=O)C>[OH:5][CH2:4][CH:3]1[O:18][C:17]2=[C:16]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[S:15][C:14]([C:24]([O:26][CH2:27][CH3:28])=[O:25])=[C:13]2[O:12][CH2:1]1

Participants

9

Reactant 4

HCID 8252PropyleneHCID 11430Potassium CarbonateHCID 18430Epibromohydrin2×HCID 2455033,4-Dihydroxy-thiophene-2,5-dicarboxylic acid diethyl ester

Product 1

HCID 592947872-Hydroxymethyl-2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxylic acid diethyl esterYield 55%

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 962WaterSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

7.7 mL (0.0902 mol) of epibromohydrin and 1.92 g (0.0139 mol) of potassium carbonate were dissolved in 100 mL water and added to a refluxing mixture of 16.11 g (0.0694 mol) diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate in 350 mL ethanol. After heating to reflux for 1 hour, an additional 5.3 mL (0.0624 mol) epibromohydrin was added and the reaction heated to reflux overnight. Upon cooling to room temperature the reaction was concentrated by evaporation and then poured into 500 ml water. The mixture was acidified and then extracted with methylene chloride until the organic wash no longer indicated product was present. The organic fractions were washed with saturated brine then dried with magnesium sulfate. The solvent was removed under reduced pressure to give a yellow solid. Column chromatography was performed using 60% ethyl acetate in hexane to give a 70:30 mixture of the product and propylene isomer in 55% yield as a white solid. Structure and purity were confirmed by 1H/13C NMR and LC-MS.

Workup

  1. temperatureAfter heating
  2. temperatureto reflux for 1 hour
  3. temperaturethe reaction heated
  4. temperatureto reflux overnight
  5. concentrationwas concentrated by evaporation
  6. additionpoured into 500 ml water
  7. extractionextracted with methylene chloride until the
  8. washorganic wash no longer indicated product
  9. washThe organic fractions were washed with saturated brine
  10. dry with materialthen dried with magnesium sulfate
  11. customThe solvent was removed under reduced pressure
  12. customto give a yellow solid
  13. customto give

Sources & evidence

ORD record
ord-2b22a6db6a2743f1ba3da6325adcd093
Source dataset
uspto-grants-2010_11
Patent number
US07838688B2

Linked notes

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