2-Bromoethanol → 2,2'-(2,7-Dibromo-9H-fluorene-9,9-diyl)di(ethan-1-ol)

HRID 1593717Notes

Reaction equation

HRID 1593717 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)C[C:4]=2[CH:3]=1.[OH-].[Na+].O1CCCCC1[O:24][CH:25]1[CH2:30][CH2:29][CH2:28][CH2:27][O:26]1.BrCCO>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.CS(C)=O.CCCCCC.C(OCC)(=O)C.O>[Br:1][C:2]1[CH:3]=[CH:4][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[C:29]([CH2:30][CH2:25][OH:24])([CH2:28][CH2:27][OH:26])[C:13]=2[CH:14]=1

Participants

10

Reactant 4

HCID 108982-BromoethanolHCID 14798Sodium HydroxideHCID 1400732,7-DibromofluoreneHCID 263182Tetrahydropyranyl ether

Product 1

HCID 692389472,2'-(2,7-Dibromo-9H-fluorene-9,9-diyl)di(ethan-1-ol)Yield 70.8%

Reagents, catalysts & solvents 5

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 679Dimethyl SulfoxideSolventHCID 962WaterSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
35 °C

Procedure

A mixture containing 5.0 grams of 2,7-dibromofluorene, 3.1 grams of sodium hydroxide and 0.35 grams of Benzyltriethylammonium chloride in 50 ml of dimethylsulfoxide was stirred and to it was added 9.7 grams of the tetrahydropyranyl ether of 2-bromoethanol. The temperature rose slowly to 50° C. The temperature was maintained at 35° C. for 1 hr after which the mixture was added to 100 ml of water and 50 ml of ethyl acetate and 50 ml hexane. The organic layer was removed washed 2× with 100 ml of water and dried over sodium sulfate. The solvent was removed and 150 ml of ethanol added followed by 0.5 grams p-toluene sulfonic acid. The mixture was stirred at 70° C. for 30 min. The mixture was cooled and treated with aqueous potassium carbonate to ˜pH8. The solvent was removed and the residue treated with 50 ml of 1;1 ethyl acetate:hexane and 25 ml of water the solid was filtered and washed with water. Recrystallization from 1:1 ethyl acetate hexane to give 4.5 grams of 2-[2,7-dibromo-9-(2-hydroxy-ethyl)-9H-fluoren-9-yl]-ethanol which was esterified by the process described in example 1 to give 3.8 grams of Acrylic acid 2-[9-(2-acryloyloxy-ethyl)-2,7-dibromo-9H-fluoren-9-yl]-ethyl ester(4). This product was verified by NMR analysis to be present and pure.

Workup

  1. customrose slowly to 50° C
  2. customThe organic layer was removed
  3. washwashed 2× with 100 ml of water
  4. dry with materialdried over sodium sulfate
  5. customThe solvent was removed
  6. addition150 ml of ethanol added
  7. stirringThe mixture was stirred at 70° C. for 30 min
  8. temperatureThe mixture was cooled
  9. additiontreated with aqueous potassium carbonate
  10. customThe solvent was removed
  11. additionthe residue treated with 50 ml of 1;1 ethyl acetate
  12. filtrationhexane and 25 ml of water the solid was filtered
  13. washwashed with water
  14. customRecrystallization from 1:1 ethyl acetate hexane

Sources & evidence

ORD record
ord-b8b7a00e2c3e433bac8460d5f0a28f6e
Source dataset
uspto-grants-2007_11
Patent number
US07297810B2

Reaction notes

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