9H-fluoren-9-ol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 250 ml 3 neck round bottom was added 9-Hydroxyfluorene (5 g, 0.027 mole, 1.0 equivalent), 2-methyltetrahydrofuran (50 g), triethylamine (3.3 g, 0.03 mole, 1.2 equivalents) and cooled in an ice bath. The cooled solution was treated with acryloyl chloride (2.7 g, 0.03 mole, 1.1 equivalents) dropwise over 1 hour. Analysis by gas chromatography indicated 60/40 mixture. The reaction was washed two times with sodium chloride brine (25 ml, 20% aqueous solution), concentrated invacuo to recover a solid. The material was dissolved in chloroform (50 ml) and added to a silica gel column containing 500 g silica gel and eluted with hexane/ethyl acetate at varying concentrations of 1-2.5% (ethyl acetate). The product was eluted first and was recovered by concentrating invacuo. Recovered 2.5 g of a pale yellow oil, which quickly solidified, having a melting point of 64-65 C. Polymerizable Resin Composition 1: 40 parts of FA-1 (with a refractive index of 1.613), 50 parts CN120 (epoxy acrylate available from Sartomer Company, Exton, Pa., reported by Sartomer to have a viscosity of 2150 cps at 65° C., a refractive index of 1.5556 and a Tg of 60° C.), 10 parts SR339(2-phenoxyethyl acrylate available form Sartomer), and 0.3 parts Darocur 4265 (available from Ciba Specialty Chemicals, Tarrytown, N.Y.) were mixed together thoroughly in an amber jar. Optical Film Sample Preparation: Brightness enhancing films samples were made using Polymerizable Resin Composition 1. About 3 grams of warm resin was applied to a 2 mil primed PET (polyester) film, available from DuPont under the trade designation “Melinex 623” and placed against a microstructured tool with a 90/24 pattern similar to the commercially available Vikuiti TBEF-90/24. The PET, resin and tool were passed through a heated laminator set at approximately 150° F. to create a uniformly thick sample. The tool containing the film and coated resin sample was passed at 50 fpm through a Fusion UV processor containing two 600 W/in D-bulbs. The PET and cured resin were removed from the tool and cut into samples. Gain Test Method cooled in an ice bath The reaction was washed two times with sodium chloride brine (25 ml, 20% aqueous solution) concentrated invacuo to recover a solid The material was dissolved in chloroform (50 ml) added to a silica gel column containing 500 g silica gel eluted with hexane/ethyl acetate The product was eluted first was recovered by concentrating invacuo Recovered 2.5 g of a pale yellow oil, which at 65° C. a refractive index of 1.5556 and a Tg of 60° C.), 10 parts SR339(2-phenoxyethyl acrylate available form Sartomer), and 0.3 parts Darocur 4265 (available from Ciba Specialty Chemicals, Tarrytown, N.Y.) were mixed together thoroughly in an amber jar Optical Film Sample Preparation set at approximately 150° F. The tool containing the film and coated resin sample containing two 600 W/in D-bulbs were removed from the tool

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using 9-fluorenol and 4-piperidinol, the procedure of Reference Example 23 was otherwise repeated to provide the title compound. Yield 38%.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using 9-fluorenol and 4-piperidinol, the procedure of Reference Example 23 was otherwise repeated to provide the title compound. Yield 38%.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a cold (0° C.) suspension of 9-hydroxyfluorene (49 g) in benzene (650 mL) was added thionylchloride (70 mL). This solution was allowed to stir while warming up to room temperature overnight. The benzene was distilled off and the product was recrystallized from isopropylether to give 41 g of the title compound as a white solid: m.p. 87°-89° C. The benzene was distilled off the product was recrystallized from isopropylether

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a cold (0° C.) suspension of 9-hydroxyfluorene (49 g) in benzene (650 mL) was added thionylchloride (70 mL). This solution was allowed to stir while warming up to room temperature overnight. The benzene was distilled off and the product was recrystallized from isopropylether to give 41 g of the title compound as a white solid: m.p. 87°-89° C. The benzene was distilled off the product was recrystallized from isopropylether

Conditions: temp:8.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 250 mL round-bottomed flask was added 9-hydroxyfluorene (5 g, 27.4 mmol) and triethylamine (3.86 ml, 27.4 mmol) in benzene (150 mL) to give a colorless solution. The solution was cooled to 8° C. with an ice bath. Next, acryloyl chloride (2.229 mL, 27.4 mmol) was dissolved in 25 mL of benzene, placed in a dropping funnel, and added over 1 hour with vigorous stirring. The reaction formed a white precipitate. The ice bath was removed and the viscous sludge was stirred overnight at room temperature. The resulting cloudy white suspension was washed with 50 mL water, followed by 50 mL 5% NaOH solution, and 50 mL water. The benzene layer was collected and dried with MgSO4, filtered, and rotovapped to give the 9-fluorenylacrylate as a viscous beige oil which crystallized on cooling to 4° C. (4.73 g, 20.02 mmol, 73.0% yield). to give a colorless solution placed in a dropping funnel added over 1 hour with vigorous stirring The reaction formed a white precipitate The ice bath was removed The resulting cloudy white suspension was washed with 50 mL water The benzene layer was collected dried with MgSO4 filtered

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: With stirring and ice cooling, 111 g of triethylamine was added to a mixture of 120 g of methacrylic acid chloride, 182 g of 9-hydroxyfluorene, and 1500 g of toluene. The mixture was stirred at room temperature for 16 hours. By standard aqueous work-up and solvent distillation, a crude product was obtained. It was purified by column chromatography, yielding the target compound, 9-fluorenyl methacrylate. The mixture was stirred at room temperature for 16 hours By standard aqueous work-up and solvent distillation a crude product was obtained It was purified by column chromatography

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Quinuclidine-3-carboxylic acid hydrochloride (95 mg, 0.50 mmol), EDC (143 mg, 0.74 mmol), triethylamine (242 μl, 1.73 mmol), and HOBT (114 mg, 0.74 mmol) were dissolved in dry THF (5 ml). 9H-fluoren-9-ol (99 mg, 0.54 mmol) was dissolved in dry THF (2 ml) and then added to the reaction mixture. The resulting suspension was stirred at room temperature overnight. The mixture was evaporated, and the crude taken up with EtOAc and washed sequentially with water and sat. NaHCO3. The organic phase was dried over sodium sulfate, filtered. and evaporated under vacuum. The crude was purified by flash chromatography (DCM/MeOH=9/1) to afford 9H-fluoren-9-yl quinuclidine-3-carboxylate (102 mg, racemic mixture). added to the reaction mixture The mixture was evaporated washed sequentially with water and sat. NaHCO3 The organic phase was dried over sodium sulfate filtered and evaporated under vacuum The crude was purified by flash chromatography (DCM/MeOH=9/1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 0.8 g of sodium hydride (60% dispersion in mineral oil) was added over 5 minutes under ice-cooling to a solution of 3.64 g of 9-fluorenol and 3 ml of ethyl bromoacetate in 40 ml of N,N-dimethylformamide. After stirring for 50 minutes, the reaction mixture was poured into ice-cold 5% HCl and extracted with ether. The organic layer was washed with a saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was purified by a silica gel column chromatography (eluting solution: methylene chloride-hexane) to give 2.28 g of ethyl 9-fluorenyloxyacetate. extracted with ether The organic layer was washed with a saturated saline dried over anhydrous magnesium sulfate concentrated The residue was purified by a silica gel column chromatography (eluting solution: methylene chloride-hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The sodium salt of 9-hydroxyfluorene was made by reacting sodium metal in anhydrous benzene before the etherization with 7-(3-methylisoxazol-5-yl)-heptyl bromide in the same solvent.