Fluorene → 9-(2-Ethylhexyl)-9-(3,6,9-trioxadecyl)-fluorene

HRID 1075374Notes

Reaction equation

HRID 1075374 reaction equation
C([Li])CCC.C1C2CC3C(=CC=CC=3)C=2C=CC=1.C(C(CCCC)CBr)C.[CH2:28]([CH:30]([CH2:45][CH2:46][CH2:47][CH3:48])[CH2:31][CH:32]1[C:44]2[CH:43]=[CH:42][CH:41]=[CH:40][C:39]=2[C:38]2[C:33]1=[CH:34][CH:35]=[CH:36][CH:37]=2)[CH3:29].Cl[CH2:50][CH2:51][O:52][CH2:53][CH2:54][O:55][CH2:56][CH2:57][O:58][CH3:59]>CCCCCC.O1CCCC1.O>[CH2:28]([CH:30]([CH2:45][CH2:46][CH2:47][CH3:48])[CH2:31][C:32]1([CH2:50][CH2:51][O:52][CH2:53][CH2:54][O:55][CH2:56][CH2:57][O:58][CH3:59])[C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][C:38]=2[C:39]2[C:44]1=[CH:43][CH:42]=[CH:41][CH:40]=2)[CH3:29]

Participants

9

Reactant 5

HCID 6853FluoreneHCID 868042-Ethylhexyl bromideHCID 5478521-Chloro-3,6,9-trioxadecaneHCID 225685419-(2-Ethylhexyl)-9H-fluoreneHCID 178418339Butyllithium2×

Product 1

HCID 178943469-(2-Ethylhexyl)-9-(3,6,9-trioxadecyl)-fluorene

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×

Conditions

Temperature
-7.5 °C

Procedure

7.69 g of butyllithium dissolved in 48 ml of hexane was slowly added during 5 minutes into 20.0 g of fluorene dissolved in 150 ml of anhydrous tetrahydrofuran at -50° C. under nitrogen protection. The mixture was stirred at -30 to 15° C. for 1 hour before it was cooled again to -40 to -50° C. Then, 23.17 g of 2-ethylhexyl bromide was added in 5 minutes. The mixture was subsequently stirred for 2 hours while the temperature was gradually increased to 22° C. The main product in the solution was 9-(2-ethylhexyl)-fluorene as detected by GC-MS. This solution was then cooled to -50° C., and 7.7 g of butyllithium dissolved in 48 ml of hexane was slowly added in 5 minutes under nitrogen protection. The mixture was stirred at -30~15° C. for 1 hour before it was cooled again to -40 to -50° C. Then, 23.75 g of 1-(2-chloroethoxy)-2-(2-methoxyethoxy)-ethane was added in 5 minutes. The mixture was subsequently stirred for 15 hours at 22° C., dispersed in water, and extracted with ether. The etheral solution was washed with water and brine, dried with magnesium sulfate, and evaporated. The residue was distilled to collect 45.5 g (89%) of colorless liquid at 190° C./0.12 mm Hg. MS (m/z): 424 (M+), 277, 205, 191, 178, 165, 133, 103, 59.

Workup

  1. temperaturewas cooled again to -40 to -50° C
  2. stirringThe mixture was subsequently stirred for 2 hours while the temperature
  3. temperaturewas gradually increased to 22° C
  4. temperatureThis solution was then cooled to -50° C.
  5. additionwas slowly added in 5 minutes under nitrogen protection
  6. stirringThe mixture was stirred at -30~15° C. for 1 hour before it
  7. temperaturewas cooled again to -40 to -50° C
  8. stirringThe mixture was subsequently stirred for 15 hours at 22° C.
  9. extractionextracted with ether
  10. washThe etheral solution was washed with water and brine
  11. dry with materialdried with magnesium sulfate
  12. customevaporated
  13. distillationThe residue was distilled
  14. customto collect 45.5 g (89%) of colorless liquid at 190° C./0.12 mm Hg

Sources & evidence

ORD record
ord-42694d9a28ab429dbfe84f17d2d0e85a
Source dataset
uspto-grants-1999_05
Patent number
US05900327

Reaction notes

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