117344-32-8

Usage

Chemical Properties

White powder

Uses

4,4′-(9-Fluorenylidene)bis(2-phenoxyethanol) may be used for the following syntheses:poly-(carbotetramethyldisiloxane)s, containing poly[oxy{4,4′-(9-fluorenylidene)bis(2-phenoxyethylene)}oxytetramethyldisiloxane] (a fluorescent aromatic chromophore group)poly[oxy(arylene)oxy(tetramethyldisilylene)]s, containing fluorescent aromatic chromophore groups in the polymer main chain, via melt copolymerization reaction with 1,2-bis(diethylamino)tetramethyldisilane

General Description

4,4′-(9-Fluorenylidene)bis(2-phenoxyethanol) is an aryldiol.

Synthetic route

2-Phenoxyethanol (122-99-6) + 9-fluorenone (486-25-9) → 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8)

Conditions	Yield
With sulfuric acid; ethanethiol for 12h; Reagent/catalyst; Reflux;	94.5%
With 3-mercaptopropionic acid In chlorobenzene at 115℃; for 2h; Solvent; Temperature; Reagent/catalyst;	92.5%
tungstophosphoric acid In toluene at 130℃; under 15.0015 Torr; for 4h; Product distribution / selectivity; Inert atmosphere;	90.2%

oxirane (75-21-8) + 9,9-bis(4-hydroxyphenyl)fluorene (3236-71-3) → 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8)

Conditions	Yield
With potassium hydroxide In water; isopropyl alcohol at 30 - 65℃; for 6.83333h; Solvent; Temperature; Reagent/catalyst;	91.5%

[1,3]-dioxolan-2-one (96-49-1) + 9,9-bis(4-hydroxyphenyl)fluorene (3236-71-3) → 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8)

Conditions	Yield
With potassium fluoride In N,N-dimethyl-formamide for 4h; Inert atmosphere; Reflux;	75%
With potassium fluoride In N,N-dimethyl-formamide for 4h; Inert atmosphere; Reflux;	75%

oxirane (75-21-8) + 9,9-bis(4-hydroxyphenyl)fluorene (3236-71-3) → BPF + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8)

Conditions	Yield
anion exchange resin A (Cl-type) In 2-methoxy-ethanol at 100℃; for 12h;	A 2.0 %Chromat. B 98.0 %Chromat.

phenoxyethyl alcohol (56101-99-6) + 9-fluorenone (486-25-9) + phenol (108-95-2) → 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8)

9-fluorenone (486-25-9) → 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 3-mercaptopropionic acid; methanesulfonic acid / toluene / 13 h / 40 °C / Inert atmosphere 2: potassium fluoride / N,N-dimethyl-formamide / 4 h / Inert atmosphere; Reflux View Scheme

phenol (108-95-2) → 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 3-mercaptopropionic acid; methanesulfonic acid / toluene / 13 h / 40 °C / Inert atmosphere 2: potassium fluoride / N,N-dimethyl-formamide / 4 h / Inert atmosphere; Reflux View Scheme

2-Phenoxyethanol (122-99-6) + 9,9-dichloro-9H-fluorene (25023-01-2) → 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8)

Conditions	Yield
Stage #1: 2-Phenoxyethanol; 9,9-dichloro-9H-fluorene at 70℃; for 3h; Inert atmosphere; Stage #2: With methanesulfonic acid at 110℃; for 9h; Inert atmosphere;	13.5 g

epichlorohydrin (106-89-8) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → 9,9-bis[4-(2,3-epoxypropoxyethoxy)phenyl]fluorene

Conditions	Yield
With calcium chloride; sodium hydroxide at 65℃; Green chemistry;	98.8%
With N-benzyl-N,N,N-triethylammonium chloride at 60℃; for 1h;
With N-benzyl-N,N,N-triethylammonium chloride at 60℃; for 1h;

3-mercaptobutyric acid (26473-49-4) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → 9,9-bis{4-(3-mercaptobutyloyloxyethoxy)phenyl}fluorene

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 140℃; for 3h;	97.1%

9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → C29H24Cl2O2

Conditions	Yield
With pyridine; thionyl chloride In tetrahydrofuran at 60℃; for 4h; Inert atmosphere;	95%
With pyridine; thionyl chloride In tetrahydrofuran at 60℃; for 4h; Inert atmosphere;	95%
With pyridine; thionyl chloride In tetrahydrofuran at 60℃; for 4h; Inert atmosphere;	95%

p-toluenesulfonyl chloride (98-59-9) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → C43H38O8S2 (1203647-68-0)

Conditions	Yield
With triethylamine In tetrahydrofuran at 0 - 20℃; for 120h;	93%

1,4-diisocyanatobenzene (104-49-4) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) + 2-hydroxyethyl acrylate (818-61-1) → C55H50N4O14

Conditions	Yield
Stage #1: 1,4-diisocyanatobenzene; 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene With dibutyltin(II) dilaurate; 4-methoxy-phenol In toluene at 40 - 95℃; for 3h; Inert atmosphere; Stage #2: 2-hydroxyethyl acrylate In toluene at 40 - 95℃; for 2h; Inert atmosphere;	88%

9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) + 2-mercapto-2-methylpropanoic acid (4695-31-2) → 9,9-bis{4-(2-mercaptoisobutyloyloxyethoxy)phenyl}fluorene

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 140℃; for 4h;	86.8%

acryloyl chloride (814-68-6) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene

Conditions	Yield
With triethylamine In acetone at 0 - 20℃; for 6.5h;	83.6%

D-glucose (50-99-7) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → 9-[4-(2-hydroxyethoxy)phenyl]-9-[4-(2-glucosyloxyethoxy)phenyl]fluorene + 9-[4-(2-hydroxyethoxy)phenyl]-9-{4-[2-(2-formyl-5-furylmethoxy)ethoxy]phenyl}fluorene + 9-[4-(2-hydroxyethoxy)phenyl]-9-{4-[2-(4-oxopentanoyloxy)ethoxy]phenyl}fluorene

Conditions	Yield
With sulfuric acid at 200℃; for 1h; Temperature; Reagent/catalyst;	A 0.7% B n/a C 73.6%

acrylic acid (79-10-7) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene

Conditions	Yield
With methanesulfonic acid In benzene for 12h; Inert atmosphere; Reflux; Dean-Stark;	65%
With methanesulfonic acid In benzene for 12h; Dean-Stark; Inert atmosphere; Reflux;	65%
With toluene-4-sulfonic acid; 4-methoxy-phenol In toluene at 110 - 115℃;	258.8 g

9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) + poly(ethylene terephthalate), Mn 31 kg/mol, Mw 72 kg/mol, PDI 2.3; monomer(s): bis(2-hydroxyethyl) terephthalate → polymer, Mn 29 kg/mol, Mw 68 kg/mol, PDI 2.3, fluorene units content 10 percent; monomer(s): bis(2-hydroxyethyl) terephthalate; 4,4\-(9-fluorenylidene)bis(2-phenoxyethanol)

Conditions	Yield
With antimony(III) trioxide at 20 - 210℃; under 0.045004 Torr; for 25.5h;

9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → C67H50O6 (1203647-70-4)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: triethylamine / tetrahydrofuran / 120 h / 0 - 20 °C 2.1: potassium carbonate / N,N-dimethyl-formamide / 80 °C 3.1: n-butyllithium / tetrahydrofuran; hexane / 1.67 h / -78 °C 3.2: -78 - 20 °C View Scheme

9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → C41H32Br2O4 (1203647-69-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: triethylamine / tetrahydrofuran / 120 h / 0 - 20 °C 2: potassium carbonate / N,N-dimethyl-formamide / 80 °C View Scheme

9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) + acetylene (74-86-2) → 9,9-bis(4-(2-(vinyloxy)ethoxy)phenyl)-9H-fluorene

Conditions	Yield
With potassium hydroxide In dimethyl sulfoxide at 100℃; under 300.03 Torr; for 6h; Inert atmosphere;

acryloyl chloride (814-68-6) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) + Methacryloyl chloride (920-46-7) → C36H32O6

Conditions	Yield
Stage #1: acryloyl chloride; 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene With triethylamine In tetrahydrofuran at 20℃; for 3h; Cooling with ice; Stage #2: Methacryloyl chloride In tetrahydrofuran at 20℃; for 12h;

coniferol (458-35-5) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → C39H36O6 + C49H50O9

Conditions	Yield
In 1,4-dioxane at 180℃; for 0.5h;

2-Isocyanatoethyl methacrylate (30674-80-7) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → (((((((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethane-2,1-diyl))bis(oxy))bis(carbonyl))bis(azanediyl))bis(ethane-2,1-diyl) bis(2-methylacrylate)

Conditions	Yield
With stannous octoate In ethyl acetate at 60℃; for 16h;

acrylic acid 2-isocyanatoethyl ester (13641-96-8) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → (((((((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethane-2,1-diyl))bis(oxy))bis(carbonyl))bis(azanediyl))bis(ethane-2,1-diyl) diacrylate

Conditions	Yield
With stannous octoate In ethyl acetate at 60℃; for 16h;

3-(trimethoxysilyl)propyl isocyanate (15396-00-6) + 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (117344-32-8) → C36H41NO8Si

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane In tetrahydrofuran for 6h; Reflux;

Upstream product

• 122-99-6 2-Phenoxyethanol 
• 486-25-9 9-fluorenone 
• 75-21-8 oxirane 
• 3236-71-3 9,9-bis(4-hydroxyphenyl)fluorene 
• 96-49-1 [1,3]-dioxolan-2-one 
• 108-95-2 phenol 
• 25023-01-2 9,9-dichloro-9H-fluorene 
• 56101-99-6 phenoxyethyl alcohol 

Downstream Products

• 161182-73-6 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene 
• 259881-39-5 9,9-bis[4-(2,3-epoxypropoxyethoxy)phenyl]fluorene 
• 1203647-69-1 C₄₁H₃₂Br₂O₄ 
• 1203647-68-0 C₄₃H₃₈O₈S₂ 

Relevant academic research and scientific papers

Synthesis of fluorenebisphenoxy derivatives by acid-sulfur compound catalyzed condensation reaction

An efficient method for the synthesis of fluorenebisphenoxy derivatives from fluorenone and phenoxy compounds is successfully performed by the combined use of concentrated sulfuric acid as catalyst and 3-mercaptopropionic acid as co-catalyst. Several fluorenebisphenoxy derivatives are obtained in good yields by this one-step reaction.

Efficient microwave-assisted synthesis of 9,9-bis[4-(2-hydroxyethoxy) phenyl]fluorene from 9-fluorenone and 2-phenoxyethanol

9-Fluorenone (1) smoothly reacts with phenoxyethanol (2) in the presence of Al3+-montmorillonite catalyst and 3-mercaptopropionic acid as a cocatalyst under microwave irradiation at 160°C for 10 min to give 9,9-bis[4-(2- hydroxyethoxy)phenyl]fluorene (3) in 81% yield, which was much higher than the yield of 33% obtained by conventional heating using an oil bath. A similar acceleration effect of microwave irradiation was observed in other metal-cation-exchanged montmorillonite catalysts as well. Copyright Taylor & Francis Group, LLC.

Synthesis method of 9, 9-di [4-(2-hydroxyethoxy) phenyl] fluorene

The invention discloses a synthesis method of 9, 9di [4 -(2-hydroxy ethoxy) phenyl] fluorene, and belongs to the technical field of chemical synthesis. 9-fluorenone, phenoxyethanol, a catalyst and a cocatalyst are stirred and heated to reflux in an alkane solvent, generated water is removed from a reaction solution in an azeotropic manner while reaction is performed, water is added for dilution after the reaction is finished, the mixture is stirred uniformly, cooled, crystallized and filtered, a filter cake is rinsed and dried, and a 9, 9-di [4- (2-hydroxy ethoxy) phenyl] fluorene finished product is obtained; standing and layering the crystallized mother liquor obtained by filtering, removing a water phase, distilling an organic phase to recover the alkane solvent, and rectifying a concentrate to recover phenoxyethanol. The method has the advantages of cheap and easily available raw materials, simple operation, good atom economy, high synthesis yield, good product quality, environmental friendliness and the like, and is suitable for industrial application.

A fluorene skeleton fragrant ether class compound preparation method (by machine translation)

A fluorene skeleton fragrant ether class compound preparation method, the difference lies in that, in order to replace the 9 - fluorenylmethylchloroformate ketone derivatives and substituted aryl ethers or substituted aryloxy alcohol compound as a raw material, in the load SO4 2 - Composite solid super strong acid catalyst catalytic reaction under the fragrant ether class containing fluorene skeleton of the compound in the crude product, obtained after purifying the product containing fluorene skeleton fragrant ether class compounds. This invention has used the composite solid super strong acid catalyst, to replace the existing process for use in the catalyst, its advantages that not only the catalyst and reaction recovery solution can be repeatedly used, the production cost is reduced, thereby improving the production efficiency, and reducing the pollution of the environment; and the reaction yield is high, the operation is simple, the product is easy to purify, is more suitable for sustainable industrial production development. (by machine translation)

9,9-BIS(4-(2-HYDROXYETHOXY)PHENYL)FLUORENE CRYSTAL

PROBLEM TO BE SOLVED: To produce 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene crystal which shows a melting peak by a differential scan calorimetry in a temperature region of 115-125°C and has a bulk density of 0.60-0.75 g/cm3. SOLUTION: Fluorenone and phenoxy ethanol are reacted to obtain rough crystal of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, and the rough crystal is purified to prepare purified crystal of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene having the enhanced degree of purity to at least 99%. The purified crystal is dissolved in a mixed solvent of acetonitrile and methanol of which a temperature is controlled to -20°C to 5°C to prepare a solution, and crystal is precipitated in the solution. When the precipitated crystal is separated and dried, the target 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene crystal is obtained. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT

9, 9 - bis (4 - (2 - hydroxyethoxy) phenyl) fluorene in production, and the crystal, and production of the crystal

A method for producing 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, which can be used for obtaining 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene having a high static bulk density and a low melting point, and is characterized in that 9-fluorenone is reacted with 2-phenoxy ethanol in the presence of methanesulfonic acid and the resultant product is purified using butanol.

9, 9 - bis (4 - (2 - hydroxyethoxy) phenyl) fluorene crystal

[Problem] differential scanning calorimetry melting peak is observed in the temperature range of 115 d 125 °C, and, the bulk specific gravity of 0.60-to 0.75 g/cm3 9, 9 - bis (4 - (2 - hydroxyethoxy) phenyl) fluorene in new production method of crystals. 9, 9 - bis [a] (4 - (2 - hydroxyethoxy) phenyl) fluorene in the reaction phenoxyethanol yielded crude fluorene, 9, 9 - bis at least 99% purity of the purified crude crystal (4 - (2 - hydroxyethoxy) phenyl) can be enhanced by preparation of crystals of fluorene. Methanol mixed solvent refined crystal controlled temperature - 20 c 5 °C acetonitrile solution was prepared by dissolving, in this solution to precipitate crystals, separating and drying the deposited crystals, 9, 9 - bis (4 - (2 - hydroxyethoxy) phenyl) fluorene crystal method. Figure 2 [drawing]

9, 9 - Bis (hydroxy alkoxy phenyl) preparation of fluorene

For the purpose of providing a method for producing a 9,9-bis(hydroxyalkoxyphenyl)fluorene, the present invention provides a method for producing a 9,9-bis(hydroxyalkoxyphenyl)fluorene represented by general formula (3), which is characterized by reacting a 9,9-dihalogenated fluorene represented by general formula (1) with a phenoxy alcohol represented by general formula (2). (In general formula (1), each R1 independently represents an alkyl group, an alkoxy group, an aromatic hydrocarbon group or a halogen atom; X represents a halogen atom; and each m independently represents 0 or an integer of 1-4, provided that in cases where m is 2 or more, the R1 moieties may be the same as or different from each other.) (In general formula (2), R2 represents an alkyl group, an alkoxy group, an aromatic hydrocarbon group or a halogen atom; R3 represents a linear or branched alkylene group; and n represents 0 or an integer of 1-4, provided that in cases where n is 2 or more, the R2 moieties may be the same as or different from each other.) (In general formula (3), R1, R2, R3, m and n are as defined above.)

HIGH REFRACTIVE MONOMER, RESIN COMPOSITION FOR PRISM SHEET CONTAINING THE SAME AND PRISM SHEET USING THE SAME

Disclosed are a high refractive monomer having at least one acryl functional group in a terminal and designed to meet a refractive index more than 1.57, a resin composition for forming the prism sheet capable of controlling refraction, viscosity, hardness, and yellowness by containing the high refractive monomer only or a mixture comprising the same, a prism sheet embodying high refraction and low viscosity of a liquid before curing and having excellent clarity and yellowing resistance by using the resin composition for forming the prism sheet which is made of the optimum mix. According to the present invention, the high luminance prism sheet is provided, thereby reducing the number of the sheet applied to embody the same luminance so as to contribute to slimming down the sheet, enhancing the performance, and saving costs. Therefore, the number of LED lamps used for a backlight unit can be reduced, thereby saving energy.

HIGH REFRACTIVE OLIGOMER, RESIN COMPOSITION FOR PRISM SHEET CONTAINING THE SAME AND PRISM SHEET USING THE SAME

The present invention relates to a high refractive oligomer, a resin composition for molding a prism sheet containing the same, and a prism sheet using the same. The present invention provides a low viscosity and low yellowing type highly refractive oligomer, which comprises acryl functional groups on both terminus and contains at least two urethane functional groups in a molecular structure, and meets a refractive index higher than 1.61, and provides a prism sheet embodying a high refractive index and low viscosity of a liquid before curing and having excellent transparence and yellowing resistance, and meeting excellent adhesive strength and pencil hardness after curing through the resin composition for molding the prism sheet containing the highly refractive oligomer or an optimized mixing ratio between the highly refractive oligomer and highly refractive monomer. Accordingly, the prism sheet of the present invention contributes to slimming of the sheet, performance improvement, and reduction of manufacturing costs by reducing the number of the sheets applied to embody equal luminance, thereby reducing the number of LED lamps used for a backlight unit and saving energy.