Bisphenoxyethanolfluorene

White powder

A reaction was carried out by (a) adding 80.0 g (0.444 mol) of fluorenone, 613.5 g (4.44 mol) of 2-phenoxyethanol, and 2.0 g of tungstophosphoric acid [(HA thermometer, a stirrer, 2 - neck flask equipped with condenser 4 544.7 g phenoxyethanol (3.94mol) as raw materials, the reaction vessel was replaced with nitrogen after, at 40 °C 840.7 g was added methanesulfonic acid (8.75mol). Then, 3.8 g of β - mercaptopropionic acid were added at 50 °C, 2 - phenoxyethanol is 9 - fluorenone (1.93mol) dissolved therein (3.78mol) 521.9 g 347.9 g was added dropwise over 1 hour at 50 °C solution after the reaction. After the completion of the dropping, stirring was carried out at 50 °C 17 hours. By using high-performance liquid chromatography analysis of the reaction solution as a result of calibration curve, 9, 9 - bis (4 - (2 - hydroxyethoxy) phenyl) fluorene in the reaction liquid is present in the yield of 85.4percent. After completion of the reaction, stirring 1287.2 g toluene, 50 °C 890.9 g water was added followed by order, standing water layer 1664 g being pulled. In 48percent aqueous methanesulfonic acid concentrations, the recovery rate was 95percent. Thereafter heated to 80 °C, 16percent sodium hydroxide aqueous solution was added 3 hours 1042.4 g. After stirring, the aqueous layer was extracted after standing, 75percent phosphoric acid aqueous solution was added to the neutralizing aqueous 347.9 g and 14.3 g. After that, the water layer to settle out, water is added after stirring at 80 °C 347.9 g oil, water washing operation was performed twice to remove isolation layer 2. Oil obtained from toluene, 2 - phenoxyethanol was removed by vacuum distillation of the excess. After distillation of the residual liquid is added to the homogeneous solution after toluene 2435.3 g, 2 hours to precipitate out at 65 °C, 25 °C gradually cooled filtrate the deposited crystal, drying the crude crystal 630.4 g was obtained. The 97.6percent purity by analytical high-performance liquid chromatography was. 60.0 g of crude crystals were obtained with a thermometer, a stirrer, a cooling pipe 4 neck flask equipped with a charge and, after nitrogen substitution, addition of 1 - butanol 120.0 g, 78 °C temperature raised to dissolve. Thereafter, 9, 9 - bis [4 - (2 - hydroxyethoxy) phenyl] fluorene is 75 °C at high melting point crystalline seed crystal was added, 1 hour at 55 °C crystalline precipitate. After heated up to 65 °C, gradually cooling the precipitated crystal was filtered off 25 °C. The resulting crystals under vacuum, dried and heated to 80 °C, 9, 9 - bis [4 - (2 - hydroxyethoxy) phenyl] fluorene 52.8 g was obtained. 88percent yield for crude crystals which, 98.7percent purity by analytical high-performance liquid chromatography was. Fig. 1 shows the data obtained from DSC crystal. An endothermic maximum temperature: (differential scanning calorimetry) 121.1 °CProduction of crude product Into a glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer and a water separator with cooling tube was added 86.4 g (0.48 mol) of fluorenone, 397.9 g (2.88 mol) of phenoxyethanol, 350 g of toluene and 4.3 g of phosphotungstic acid [(H500 ml stainless steel reactor was added fluorenone 50 g (0.277), ethylene glycol monophenyl ether, 172.5 g, 0.6 g 3-mercaptopropionic acid, sealed reactor, pressure tested with nitrogen, the reactor sealed after confirmation, system was purged twice with nitrogen, the autoclave was cooled to -40 ~ -50 ° C , slow flow of anhydrous hydrogen fluoride gas is condensed to a liquid hydrogen fluoride in a reactor, to the reactor 150 g weight gain, hydrogen fluoride was stopped.The reaction vessel was heated to 70 ~ 80 ° Creaction for 17 hours.The reaction system was cooled to 40 ~ 50 ° C, slowly open the exhaust valve, exhaust gas is hydrogen fluoride, hydrogen fluoride gas recovery after a condenser to condense the hydrogen fluoride until the basic system is discharged to the reaction vessel purged with nitrogen, the remaining hydrogen fluoride rush out, stop nitrogen.Was slowly added to the kettle 6percent potassium bicarbonate 150 g, was heated to 70 ~ 80 ° C, stirred for 15 minutes, 150 g of toluene was added, stirred for 20 minutes, allowed to stand, the organic phase was separated, the aqueous phase with 60 g of toluene extracted once, and the combined organic phase was washed with pure water twice the amount of 60 grams.The organic phase cooling crystallization, filtration, washing, drying dryness to give 9, 9-bis [(4-hydroxy) phenyl]fluorene 104.5 g, 99.2percent purity.A 500 mL pressure reaction vessel was added 35 g of bisphenol fluorene, 200 ml of isopropanol, 1.5 g of potassium hydroxide dissolved in 1.5 ml of an aqueous solution, installed reactor, stirred into the cooling water, stirred open, open heating, temperature was raised to 30 , start of passing 10.5 g of ethylene oxide (pass once every 5 minutes), which leads to 50 minutes, then pass into the finished, temperature was raised to 65 , for 6 hours. After the reaction, the reaction solution was poured into 500 ml beaker, allowed to stand for cooling the precipitate is then filtered off with suction, the liquid ethanol recovered for reuse next, the solid was recrystallized from 154 ml of toluene after which the solid was dried 2, dissolved by heating to 85 , standing to cool to precipitate, filtration and drying, to obtain 40.0 g bis-fluorenyl ether as a white solid, yield 91.5percent, LC purity of 98.5percent obtained characterization, platinum cobalt color 15 Hazen around.100 g (285.3 mmol) of bis (4-hydroxyphenyl) fluorene (1-1) obtained in the step 1 of Example 1, 500 ml of DMF, 52.7 g (599.0 mmol) of ethylene carbonate, 1 g of KF was added and the mixture was subjected to a reflux reaction for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and 1 L of purified water was added thereto, followed by stirring for 20 minutes. After 1 L of methylene chloride was added, the mixture was stirred for 30 minutes, and the organic layer was separated.(Yield: 75percent), Under a nitrogen atmosphere, 100.0 g (285.3 mmol) of bis (4-hydroxyphenyl) fluorene (4-1) obtained in the step 1 of Example 4, DMF (500 ml), ethylene carbonate52.7 g (599.0 mmol), KF 1gAnd the mixture was refluxed for 4 hours.After completion of the reaction, the reaction mixture was cooled to room temperature and 1 L of purified water was added thereto, followed by stirring for 20 minutes. After 1 L of methylene chloride was added, the mixture was stirred for 30 minutes, and the organic layer was separated. Washed with 1 L of purified water four times, and the organic layer was concentrated to obtain the target [yield 75[0152] Reaction of adding EO to bisphenol fluorene (BPF) was carried out in the similar manner as in except for the following. Specifically, into an autoclave, charged were 100 g of BPF, 200 g of ethyleneglycol monomethyl ether (δ=11.4), and 10.0 g of anion exchange resin A (Cl-type dried material), with addition of 31 g of EO. Next, the mixture was reacted in the autoclave at 100° C. for 12 hours. After the reaction, the anion exchange resin A was separated from the reaction solution. [0153] A result of GC analysis on the composition of the reaction solution reveals that the content of BPF-2EO was 97.1percent, and the content of BPF-3EO was 2.7percent, respectively. No BPF and BPF-1EO were detected. [0154] After letting the reaction solution obtained in Example 10 stand at 25° C., a white solid was precipitated. The solid was recovered and dried. A result of GC analysis on the composition of the reaction solution reveals that the content of BPF-2EO was 98.0percent, and the content of BPF-3EO was 2.0percent, respectively. The yield of BPF-2EO was 60percent.mixer, Nitrogen blowing tube, 23.5 g (0.17 mol) of 2-phenoxyethanol was charged in a glass reactor equipped with a thermometer and a cooling tube, After replacing the reaction vessel with nitrogen, A mixed solution of 10.0 g (0.0425 mol) of 9, 9-dichloro-9H-fluorene and 11.7 g (0.08 mol) of 2-phenoxyethanol was added dropwise at 70 ° C. over 1 hour with stirring.After completion of the dropwise addition, After stirring at 70 ° C. for 2 hours, 4.1 g (0.04 mol) of methanesulfonic acid was added and stirred at 110 ° C. for 9 hours. As a result of analyzing the obtained reaction solution by high performance liquid chromatography, The composition value of 9, 9-bis [4- (2-hydroxyethoxy) phenyl] fluorene was 72.5percent (area percentage / 2-phenoxyethanol excluded). From the composition value, formation of 13.5 g of 9, 9-bis [4- (2-hydroxyethoxy) phenyl] fluorene was confirmed.

Molecular Weight:438.5
XLogP3:5.2
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:8
Exact Mass:438.18310931
Monoisotopic Mass:438.18310931
Topological Polar Surface Area:58.9
Heavy Atom Count:33
Complexity:540
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes