Potassium Carbonate → HCID 102326582, compound

HRID 2090552Notes

Reaction equation

HRID 2090552 reaction equation
C1(C)C=CC(S(O[CH2:11][CH2:12][O:13][CH2:14][CH2:15][O:16][CH2:17][CH2:18][O:19][CH2:20][CH2:21][O:22][CH2:23][CH2:24][O:25][CH2:26][CH2:27]OS(C2C=CC(C)=CC=2)(=O)=O)(=O)=O)=CC=1.[Br:40][C:41]1[CH:42]=[C:43]([OH:47])[CH:44]=[CH:45][CH:46]=1.[C:48]([O-:51])([O-])=O.[K+].[K+]>CN(C=O)C>[Br:40][C:41]1[CH:42]=[C:43]([O:47][CH2:27][CH2:26][O:25][CH2:24][CH2:23][O:22][CH2:21][CH2:20][O:19][CH2:18][CH2:17][O:16][CH2:15][CH2:14][O:13][CH2:12][CH2:11][O:51][C:48]2[CH:44]=[CH:45][CH:46]=[C:41]([Br:40])[CH:42]=2)[CH:44]=[CH:45][CH:46]=1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 115633-BromophenolHCID 428918Hexaethylene Glycol Di-p-toluenesulfonate

Product 1

HCID 102326582HCID 102326582, compoundYield 69%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

A synthesis of was published in Hargadon, M. T.; Davey, E. A.; McIntyre, T. B.; Gnanamgari, D.; Wynne, C. M.; Swift, R. C.; Zimbalist, J. R.; Fredericks, B. L.; Nicastro, A. J.; Goodson, F. E. Macromolecules 2008, 41, 741-750. A 250 mL round-bottomed flask was charged with 5.41 g (9.14 mmol) of hexaethylene glycol di(p-toluenesulfonate), 4.67 g (27.0 mmol) of 3-bromophenol, 12.8 g of K2CO3 (92.6 mmol), and 50 mL of DMF. The reaction was then left to stir overnight in a 60° C. oil bath, after which the solvent was removed via vacuum distillation. Dichloromethane was then added to the residue, and the resulting suspension was filtered to remove excess carbonate and salt byproducts. Afterwards, the solvent was removed with a rotary evaporator, and the residue was heated in a kugelrohr oven under a dynamic 5 mtorr vacuum to remove excess 3-bromophenol. The crude product was then chromatographed on silica with an eluent of hexanes/EtOAc adjusted to give an Rf for the product of 0.2-0.3. Hexaethylene glycol di(3-bromophenyl)ether (3.70 g, 6.26 mmol, 69% yield), was then isolated as a pale yellow oil after distillation at 200° C. (<1 mtorr): 1H NMR (300 MHz, CDCl3) δ 7.05-7.15 (multiple resonances, 6H); 6.84 (dm, Jd=8.1 Hz, 2H); 4.09 (t, J=4.5 Hz, 4H); 3.83 (t, J=4.8 Hz, 4H); 3.64-3.74 (multiple resonances, 8H); 3.65 (s, 8H); 13C NMR (75 MHz, CDCl3) δ 159.7, 130.4, 124.0, 122.7, 118.3, 113.8, 70.9, 70.7, 70.6, 69.6, 67.9, (one signal not resolved). Anal. Calcd. for C24H32Br2O7: C, 48.67; H, 5.44; Found: C, 48.83; H, 5.59.

Workup

  1. customA synthesis
  2. waitThe reaction was then left
  3. customafter which the solvent was removed via vacuum distillation
  4. additionDichloromethane was then added to the residue
  5. filtrationthe resulting suspension was filtered
  6. customto remove excess carbonate and salt byproducts
  7. customAfterwards, the solvent was removed with a rotary evaporator
  8. temperaturethe residue was heated in a kugelrohr oven under a dynamic 5 mtorr vacuum
  9. customto remove excess 3-bromophenol
  10. customThe crude product was then chromatographed on silica with an eluent of hexanes/EtOAc
  11. customto give an Rf for the product of 0.2-0.3

Sources & evidence

ORD record
ord-c02a78e536dd45c188458147be8dfdd5
Source dataset
uspto-grants-2013_05
Patent number
US08436197B2

Reaction notes

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