Hydrochloric Acid → 2,7-Bis(acryloyloxy)-9-methylfluorene

HRID 1943537Notes

Reaction equation

HRID 1943537 reaction equation
[C:1](Cl)(=[O:4])[CH:2]=[CH2:3].[OH:6][C:7]1[CH:19]=[CH:18][C:17]2[C:16]3[C:11](=[CH:12][C:13]([OH:20])=[CH:14][CH:15]=3)[CH:10]([CH3:21])[C:9]=2[CH:8]=1.C(N([CH2:27][CH3:28])CC)C.Cl.[OH-:30].[Na+].Cl[CH2:33]Cl>C(C1C(O)=C(C(C)(C)C)C=C(C)C=1)(C)(C)C.O>[C:33]([O:6][C:7]1[CH:19]=[CH:18][C:17]2[C:16]3[C:11](=[CH:12][C:13]([O:20][C:1](=[O:4])[CH:2]=[CH2:3])=[CH:14][CH:15]=3)[CH:10]([CH3:21])[C:9]=2[CH:8]=1)(=[O:30])[CH:27]=[CH2:28]

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 6344DichloromethaneHCID 8471TriethylamineHCID 13140Acryloyl chlorideHCID 14798Sodium HydroxideHCID 219606279-methyl-9H-fluorene-2,7-diol

Product 1

HCID 672843372,7-Bis(acryloyloxy)-9-methylfluorene

Reagents, catalysts & solvents 2

HCID 314042,6-Di-tert-butyl-4-methylphenolCatalystHCID 962WaterSolvent2×

Procedure

Acryloyl chloride (55.4 g, 612.1 mmol) was added dropwise to a mixture of dichloromethane (500 mL), 2,7-dihydroxy-9-methylfluorene (T-11) (50.0 g, 235.6 mmol), triethylamine (61.7 g, 609.7 mmol) and 2,6-di-tert-butyl-p-cresol (52.0 mg, 0.24 mmol) in an ice bath under an atmosphere of nitrogen, and then the mixture was warmed slowly to room temperature. The stirring was continued at room temperature for 16 hours, and the reaction mixture was poured into water. The organic layer was wished with 1M-hydrochloric acid, aqueous 1M-sodium hydroxide solution and water. After the organic layer had been dried over anhydrous magnesium sulfate, the organic solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (eluent: toluene), and then by recrystallization from a mixed solvent of dichloromethane and ethanol to give colorless crystals (34.2 g) of 2,7-bis(acryloyloxy)-9-methylfluorene (1-3-4).

Workup

  1. dry with materialAfter the organic layer had been dried over anhydrous magnesium sulfate
  2. distillationthe organic solvent was distilled off under reduced pressure
  3. customThe residue was purified by silica gel chromatography (eluent: toluene)
  4. customby recrystallization from a mixed solvent of dichloromethane and ethanol

Sources & evidence

ORD record
ord-3cc25621b2f84187a5d806add8184e5f
Source dataset
uspto-grants-2013_03
Patent number
US08394468B2

Reaction notes

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