1,2-Dimethoxyethane → HCID 13637989, compound

HRID 1372142Notes

Reaction equation

HRID 1372142 reaction equation
[S:1]1[C:5]2[CH:6]=[CH:7][CH2:8][CH:9](OS(C(F)(F)F)(=O)=O)[C:4]=2[CH:3]=[CH:2]1.C([O-])([O-])=O.[Na+].[Na+].CO[CH2:26][CH2:27][O:28][CH3:29]>CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:29][O:28][C:27]1[CH:5]=[CH:4][C:3]([C:9]2[C:4]3[CH:3]=[CH:2][S:1][C:5]=3[CH:6]=[CH:7][CH:8]=2)=[CH:2][CH:26]=1

Participants

6

Reactant 3

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 86011561HCID 86011561, compound

Product 1

HCID 13637989HCID 13637989, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of trifluoromethanesulfonic acid 4,5-dihydro-1-benzothiophene-4-yl ester (9.0 g, 31.7 mmol), Na2CO3 (39.6 ml 2 N aqueous, 79.2 mmol), Pd(PPh3)4 (1.83 g, 1.6 mmol), 4-methoxyboronic acid (5.78 mg, 38.03 mmol), and ethylene glycol dimethyl ether (350 ml) was heated to reflux for 6 h. The reaction was cooled, diluted with EtOAc and the layers separated. The organic layer was dried over anhydrous Na2SO4, passed through a silica plug and concentrated to 5.0 g solid (1.44:1 ratio of desired to [6,7,6′,7′-tetrahydro-[4,4′]bi[benzo[b]thiophenyl]). This material was dissolved in toluene (50 ml) and activated MnO2 (4.5 g) was added. The mixture was refluxed overnight, cooled, filtered, and concentrated to afford a 5 g solid (1.4:1 ratio of [4,4′]bi[benzo[b]thiophenyl] to desired). Column chromatography (3:97 EtOAc/hexanes) managed to isolate 880 mg of pure product: 1H NMR (300 MHz, DMSO-d6): δ 3.83 (3H, s), 7.09 (2H, d, J=8.6 Hz), 7.33 (1H, d, J=7.2 Hz), 7.40–7.45 (2H, m), 7.51 (2H, d, J=8.7 Hz), 7.79 (1H, d, J=5.5 Hz), 7.99 (1H, d, J=8.0 Hz).

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 6 h
  3. temperatureThe reaction was cooled
  4. customthe layers separated
  5. dry with materialThe organic layer was dried over anhydrous Na2SO4
  6. concentrationconcentrated to 5.0 g solid (1.44:1 ratio
  7. dissolutionThis material was dissolved in toluene (50 ml)
  8. additionactivated MnO2 (4.5 g) was added
  9. temperatureThe mixture was refluxed overnight
  10. temperaturecooled
  11. filtrationfiltered
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-8162fe4eee03456d90aff6bbe91501f1
Source dataset
uspto-grants-2007_01
Patent number
US07157491B2

Reaction notes

Loading…