Dimethyl Sulfoxide → 1,1,1-Tris(4-(2-bromotetrafluoroethoxy)phenyl)ethane

HRID 2380002Notes

Reaction equation

HRID 2380002 reaction equation
CS(C)=O.[OH:5][C:6]1[CH:11]=[CH:10][C:9]([C:12]([C:21]2[CH:26]=[CH:25][C:24]([OH:27])=[CH:23][CH:22]=2)([C:14]2[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][CH:15]=2)[CH3:13])=[CH:8][CH:7]=1.[OH-].[K+].Br[C:31]([F:37])([F:36])[C:32]([F:35])([F:34])[Br:33]>O.C1(C)C=CC=CC=1>[Br:33][C:32]([F:35])([F:34])[C:31]([F:37])([F:36])[O:5][C:6]1[CH:11]=[CH:10][C:9]([C:12]([C:14]2[CH:19]=[CH:18][C:17]([O:20][C:31]([F:37])([F:36])[C:32]([F:35])([F:34])[Br:33])=[CH:16][CH:15]=2)([C:21]2[CH:22]=[CH:23][C:24]([O:27][C:31]([F:37])([F:36])[C:32]([F:35])([F:34])[Br:33])=[CH:25][CH:26]=2)[CH3:13])=[CH:8][CH:7]=1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 14797Potassium HydroxideHCID 313011,2-Dibromo-1,1,2,2-tetrafluoroethaneHCID 931181,1,1-Tris(4-hydroxyphenyl)ethane

Product 1

HCID 189564651,1,1-Tris(4-(2-bromotetrafluoroethoxy)phenyl)ethaneYield 12.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
35 °C

Procedure

A 1 liter 5-necked round bottom flask is fitted with a mechanical stirrer, a Dean Stark trap topped with a nitrogen padded reflux condenser, and a thermocouple attached to a temperature controller. A mixture of DMSO (450 ml), toluene (150 ml), and 1,1,1 -tris(4'-hydroxyphenyl)ethane (55.1 g, 0.18 mole) is added to the flask under nitrogen purge. After stirring for 15 minutes under a vigorous nitrogen purge, potassium hydroxide (85 percent pellets, 80.Og, 1.2 mole) is slowly added to the reaction flask. The mixture is then stirred at reflux for 48 hours with azeotropic removal of water. The resulting suspension is cooled to 35° C. in an ice bath and 1,2-dibromotetrafluoroethane (155 g, 0.60 mole) is added at a rate that maintains a temperature of 30°-35° C. When the addition is complete, the mixture is heated to 50° C. with continuous stirring for 3 hours. After filtration, the solvents are removed by heating under vacuum on a rotary evaporator. The brown residue is purified by column chromatography on neutral alumina using hexane as eluent to provide as product 1,1,1-tris(4'-[2"-bromotetrafluoroethoxy]phenyl)ethane (18.3 g, 0.022 mole, 12 percent yield).

Workup

  1. customA 1 liter 5-necked round bottom flask is fitted with a mechanical stirrer
  2. temperaturepadded reflux condenser
  3. additionis added to the flask under nitrogen
  4. custompurge
  5. custompurge
  6. stirringThe mixture is then stirred
  7. customa temperature of 30°-35° C
  8. additionWhen the addition
  9. temperaturethe mixture is heated to 50° C.
  10. stirringwith continuous stirring for 3 hours
  11. filtrationAfter filtration
  12. customthe solvents are removed
  13. temperatureby heating under vacuum on a rotary evaporator
  14. customThe brown residue is purified by column chromatography on neutral alumina

Sources & evidence

ORD record
ord-97024c76b442445cb5db420328934071
Source dataset
uspto-grants-1994_11
Patent number
US05364917

Reaction notes

Loading…