Dimethylformamide → 2,3,6,7,10,1-Hexakis[6-(perfluoro)hexyloxy]-triphenylene

HRID 2297327Notes

Reaction equation

HRID 2297327 reaction equation
O[C:2]1[C:19]([OH:20])=[CH:18][C:17]2[C:16]3[C:11](=[CH:12][C:13]([OH:22])=[C:14]([OH:21])[CH:15]=3)[C:10]3[C:5](=[CH:6][C:7]([OH:24])=[C:8]([OH:23])[CH:9]=3)[C:4]=2[CH:3]=1.[H-].[Na+].C1(C)C=CC(S(OCC[CH2:39][CH2:40][CH2:41][CH2:42][C:43](F)(F)[C:44]([F:47])(F)F)(=O)=O)=CC=1.CN(C)[CH:53]=[O:54]>C(Cl)(Cl)Cl.O>[F:47][CH2:44][CH2:43][CH2:42][CH2:41][CH2:40][CH2:39][O:24][C:7]1[C:8]([O:23][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][F:47])=[CH:9][C:10]2[C:11]3[C:16](=[CH:15][C:14]([O:21][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][F:47])=[C:13]([O:22][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][F:47])[CH:12]=3)[C:17]3[C:4](=[CH:3][CH:2]=[C:19]([O:20][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][F:47])[CH:18]=3)[C:5]=2[C:6]=1[O:54][CH2:53][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][F:47]

Participants

7

Reactant 4

HCID 6228Dimethylformamide2×HCID 24758Sodium hydrideHCID 110886102,3,6,7,10,11-HexahydroxytriphenyleneHCID 130082316-(Perfluoroethyl)hexyl p-toluenesulfonate

Product 1

HCID 183809352,3,6,7,10,1-Hexakis[6-(perfluoro)hexyloxy]-triphenyleneYield 36.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6212ChloroformSolvent2×

Procedure

0.30 g (0.925 mmol) of 2,3,6,7,10,11-hexa-hydroxytriphenylene (3) was dissolved with 3 ml of DMF (dimethylformamide) in a 30 ml round-bottomed flask, and under stirring at room temperature, 0.27 g (6.75 mmol) of sodium hydride (60% in oil) was added little by little thereto. After the addition, the system was stirred for 10 minutes at room temperature and heated to ca. 80° C. on an oil bath, and 2.56 g (6.84 mmol) of 6-(perfluoroethyl)hexyl p-toluenesulfonate (2) dissolved in 2 ml of DMF was gradually added dropwise thereto. After the dropwise addition, the system was stirred for 5 hours under heating at the same temperature. After the reaction, the system was cooled to room temperature and stirred while adding chloroform and water thereto. The chloroform layer was condensed and purified by silica gel column chromatography with a chloroform eluent. After distilling off the chloroform, the resultant crystal was further purified by silica gel column chromatography with a toluene eluent and recrystallized from an acetone-methanol mixture solvent to obtain 0.52 g (yield=36.6%) of 2,3,6,7,10,1-hexakis[6-(perfluoro)hexyloxy]-triphenylene (1-5). The compound exhibited the following phase transition series.

Workup

  1. additionAfter the addition
  2. stirringthe system was stirred for 10 minutes at room temperature
  3. temperatureheated to ca. 80° C. on an oil bath
  4. additionwas gradually added dropwise
  5. additionAfter the dropwise addition
  6. stirringthe system was stirred for 5 hours
  7. temperatureunder heating at the same temperature
  8. customAfter the reaction
  9. temperaturethe system was cooled to room temperature
  10. stirringstirred
  11. customcondensed
  12. custompurified by silica gel column chromatography with a chloroform eluent
  13. distillationAfter distilling off the chloroform
  14. customthe resultant crystal was further purified by silica gel column chromatography with a toluene eluent
  15. customrecrystallized from an acetone-methanol mixture solvent

Sources & evidence

ORD record
ord-0b1573c5158b4ab68d9ebaa934eb53fc
Source dataset
uspto-grants-2002_12
Patent number
US06491847B1

Reaction notes

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