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CAS No. :486-25-9 MDL No. :MFCD00001141
Formula : C13H8O Boiling Point : 341.5°C at 760 mmHg
Linear Structure Formula :- InChI Key :N/A
M.W :180.20 g/mol Pubchem ID :10241
Synonyms :

1. 9-Fluorenone

Safety of [ 486-25-9 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 486-25-9 ]

  • Upstream synthesis route of [ 486-25-9 ]
  • Downstream synthetic route of [ 486-25-9 ]

[ 486-25-9 ] Synthesis Path-Upstream   1~41

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Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2013, vol. 23, # 24, p. 6805 - 6810
[2] European Journal of Medicinal Chemistry, 2014, vol. 74, p. 333 - 339
[3] European Journal of Medicinal Chemistry, 2015, vol. 92, p. 415 - 426
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Reference: [1] Patent: US4780541, 1988, A,
[2] Patent: EP259530, 1988, A1,
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Reference: [1] Patent: US4780541, 1988, A,
[2] Patent: EP259530, 1988, A1,
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Reference: [1] Organic Letters, 2015, vol. 17, # 9, p. 2106 - 2109
[2] Organic Letters, 2015, vol. 17, # 9, p. 2106 - 2109
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  • [ 583-55-1 ]
  • [ 201230-82-2 ]
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Reference: [1] Organic Letters, 2015, vol. 17, # 9, p. 2106 - 2109
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YieldReaction ConditionsOperation in experiment
88%
Stage #1: With magnesium In tetrahydrofuran at 55 - 60℃; for 2.5 h; Inert atmosphere
Stage #2: at 55 - 60℃; for 2.5 h; Inert atmosphere
Bromobenzene (37.7g, 0.24mol) and 200mL THF (tetrahydrofuran) were uniformly mixed into a pressure-equalizing dropping funnel. Under nitrogen, a 1L flask was added three pieces of magnesium (6.1g, 0.25mol) and was heated at 55-60°C. 20mL of the above mixture was added dropwise THF and bromobenzene at 55-60°C for the Grignard reaction initiator for 0.5 hours. The reaction was incubated at 55-60°C and stirred for 2 hours. 9-fluorenone (36.0,0.20mol) mixed with 100mL THF was added dropwise to the homogeneous reaction system for 0.5 hours. . The reaction was incubated at 55-60°C and stirred for 2 hours. Ammonium chloride aqueous solution (200mL, 2.5mol / L) was added to the reaction system after the completion of the reaction. The reaction was quenched and left to stand for liquid separation. It was then washed with deionized water, solvent was removed, and recrystallized from toluene or ethanol to give a pale yellow solid 9-phenyl-9-fluorenol, yield 88percent.
74.7%
Stage #1: With iodine; magnesium In tetrahydrofuran at 40 - 80℃; for 4 h; Inert atmosphere
Stage #2: for 15 h; Inert atmosphere; Reflux
(1) 250mL three-necked flask,In a nitrogen-purged atmosphere,Join 0.05mol raw material U1,0.06molMg powder,Dissolved in 60 ml of dry tetrahydrofuran,Add 0.0004mol elemental I2,Heated to 40 ° C and stirred until the solution changed from yellow to colorless,The above mixed solution was heated to 80 ° C,The reaction was stirred for 4 hours,No magnesium powder left,Reaction is complete,Generate format reagent intermediates V1,Without purification,Go directly to the next step.
(2) 250mL three-necked flask,In a nitrogen-purged atmosphere,0.03 mol of 9-fluorenone was added,Dissolved in 40 ml of dry tetrahydrofuran,Slowly add the above format reagent intermediate V1 solution,Heated to reflux for 15 hours,Generate a lot of white precipitate,Then cooled to room temperature,The addition of saturated NHCl4 converts the salt of form into alcohol;After the reaction is completed,Ether extraction,Drying and steaming,After the silica gel column,A slightly yellow solid tert-alcohol intermediate W1 was obtained,HPLC purity 99.2percentYield 74.7percent.
74.7%
Stage #1: With iodine; magnesium In tetrahydrofuran at 40 - 80℃; for 4 h; Inert atmosphere
Stage #2: for 15 h; Inert atmosphere; Reflux
(1) 250mL three bottle,In a nitrogen atmosphere, 0.05 mol of U1, 0.06 mol of Mg powder was added.Dissolve in 60ml of dry tetrahydrofuran and add 0.0004mol of elemental I2.Heat to 40°C and stir until the solution turns from yellow to colorless,The mixed solution was heated to 80°C and the reaction was stirred for 4 hours.No magnesium powder remained and the reaction was complete. The reagent intermediate V1 was generated in the format without further purification, and the next step was performed directly.(2) A 250 mL three-necked flask, under a nitrogen atmosphere,0.03 mol of 9-fluorenone was added, dissolved in 40 ml of dry tetrahydrofuran, and the solution of the above-mentioned reagent intermediate V1 was slowly added dropwise, and the mixture was heated under reflux for 15 hours.Generate a lot of white precipitate,It is then cooled to room temperature and saturated salt NHCl4 is added to convert the format salt to alcohol;After the reaction is completed, ether is extracted, dried and evaporated.Through a silica gel column, a slightly yellowish solid tertiary alcohol intermediate W1 is obtained.HPLC purity 99.2percent, yield 74.7percent.
Reference: [1] Advanced Synthesis and Catalysis, 2016, vol. 358, # 6, p. 947 - 957
[2] Journal of Organic Chemistry, 2018, vol. 83, # 11, p. 6162 - 6170
[3] Patent: CN105541747, 2016, A, . Location in patent: Paragraph 0041; 0042; 0043
[4] Patent: CN107337680, 2017, A, . Location in patent: Paragraph 0046; 0047; 0048; 0049; 0054
[5] Patent: CN107573356, 2018, A, . Location in patent: Paragraph 0061; 0063; 0064; 0065
[6] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1990, # 12, p. 2167 - 2177
[7] Journal of Organic Chemistry, 1985, vol. 50, # 8, p. 1239 - 1246
[8] Organic Syntheses, 1993, vol. 71, p. 220 - 220
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YieldReaction ConditionsOperation in experiment
76%
Stage #1: at 0 - 20℃; for 16 h; Inert atmosphere
Stage #2: With ammonium chloride In tetrahydrofuran; water
Under nitrogen atmosphere, a solution of 9-fluorenone (18.2 g, 100 mmol) in 150 mL of dry tetrahydrofuran (THF) was dropwise added at 0° C. to 100 mL of a 1M solution of phenylmagnesium bromide solution in THF. At the end of addition, the reaction mixture was stirred at room temperature for 16 hr. The reaction mixture was poured into 100 mL of saturated solution of ammonium chloride. The mixture was extracted twice with diethyl ether. The combined ether solution was dried over MgSO4 and the solvent was removed under reduced pressure to provide 19.5 g (76percent) of intermediate (I1). 1H NMR (CDCl3) δ: 7.72=7.73 (m, 2H), 7.27-7.57 (m, 11H). 13C NMR (CDCl3) δ: 150.74, 143.5, 139.87, 135.02, 129.38, 128.75, 128.53, 127.51, 125.71, 125.12124.69, 120.619, 120.39.
70% at 0 - 20℃; for 24 h; Preparation of compound 3-19-fluorenone (20.0 g, 111.0 mmol) was dissolved in THF (554.0 mL) in a flask and phenylmagnesium bromide (36.9 mL) was slowly added thereto at 0 °C. The mixture was stilTed at room temperature for 24 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. The layer was separated by column chromatography to obtain compound 3-1(20.0 g, 70 percent).
70% at 0 - 20℃; for 24 h; Preparation of compound 3-1[118]After 9-fluorenone (20.0 g, 111.0 mmol) was dissolved in THF (554 mL) in a flask, phenyl magnesium bromide (36.9 mL) was slowly added thereto at 0°C and the mixture was stirred at room temperature for 24 hrs. After completing the reaction, the organic layer was extracted with EA, was dried by removing the remaining moisture with MgSO4, and was separated through column chromatography to obtain compound 3-1 (20.0 g, 70 percent).
Reference: [1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1986, p. 405 - 408
[2] Patent: US2016/16872, 2016, A1, . Location in patent: Paragraph 0037
[3] Patent: WO2015/84021, 2015, A1, . Location in patent: Paragraph 179; 180; 181; 182
[4] Patent: WO2015/167199, 2015, A1, . Location in patent: Paragraph 117; 118
[5] Patent: JP2005/120030, 2005, A, . Location in patent: Page/Page column 44
[6] Journal of Organic Chemistry, 2010, vol. 75, # 12, p. 4124 - 4130
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YieldReaction ConditionsOperation in experiment
100% at 0 - 20℃; for 16 h; Inert atmosphere; Schlenk technique To a stirred solution of 9-fluorenone (540 mg, 3 mmol) in THF (1.5 mL), PhLi in n-Bu2O (2mL, 1.8 M, 3.6 mmol) was added dropwise at 0 °C. The reaction mixture was warmed toroom temperature and stirred over 16 h. The reaction mixture was then cooled to 0 °C,diluted with Et2O (~3 mL) before being quenched with NH4Claq (~3 mL). The product wasextracted with Et2O (3 x ~5 mL). The combined organic layer was sequentially washed withH2O (~5 mL), then brine, dried over Na2SO4 and concentrated under reduced pressure. Theresidual was passed through a short silica plug (hexanes:EtOAc = 20:1) to afford the 9-phenyl-9-fluorenol in quantitative yield as a white solid. To a stirred solution of 9-phenyl-9-fluorenol (258 mg, 1 mmol) in DCM (5 mL) cooled to 0 °C, trifluoroacetic acid (0.3 mL, 4mmol) and then Et3SiH (0.4 mL, 2.5 mmol) were added dropwise. The reaction mixture wasstirred at 0 °C for 10 min. before being quenched with Na2CO3aq (~4 mL). The product wasextracted with DCM (3 x ~10 mL). The combined organic layer was washed with brine,dried over Na2SO4, and passed through a silica plug (hexanes:EtOAc = 20:1) to afford thetitled compound 5a in 82percent yield (197 mg) as a white solid.
Reference: [1] Synlett, 2017, vol. 28, # 20, p. 2936 - 2940
[2] Organic Syntheses, 1993, vol. 71, p. 220 - 220
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Reference: [1] Patent: US6162824, 2000, A,
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Reference: [1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1983, vol. 32, # 11, p. 2351 - 2356[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1983, # 11, p. 2615 - 2620
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Reference: [1] Chemische Berichte, 1904, vol. 37, p. 73
[2] Chemische Berichte, 1905, vol. 38, p. 292
[3] Chemische Berichte, 1904, vol. 37, p. 73
[4] Chemische Berichte, 1905, vol. 38, p. 292
[5] Bulletin de la Societe Chimique de France, 1973, p. 562 - 569
[6] Bulletin de la Societe Chimique de France, 1971, p. 1526 - 1533
[7] Journal of the Chemical Society, 1961, p. 3052 - 3058
[8] Journal of Organic Chemistry, 1963, vol. 28, p. 1479 - 1484
[9] Journal of Organic Chemistry, 1977, vol. 42, # 1, p. 19 - 28
[10] Journal of the Chemical Society [Section] B: Physical Organic, 1971, p. 503 - 507
[11] Journal of the American Chemical Society, 1943, vol. 65, p. 49[12] Journal of the American Chemical Society, 1944, vol. 66, p. 376
[13] Journal of the American Chemical Society, 1984, vol. 106, p. 1432
[14] Canadian Journal of Chemistry, 1975, vol. 53, p. 1635 - 1641
[15] Journal of Medicinal Chemistry, 1994, vol. 37, # 15, p. 2334 - 2342
[16] Angewandte Chemie - International Edition, 2007, vol. 46, # 26, p. 4937 - 4939
[17] Tetrahedron Letters, 2003, vol. 44, # 48, p. 8649 - 8652
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Reference: [1] Journal of Organic Chemistry, 2002, vol. 67, # 14, p. 4924 - 4936
[2] Angewandte Chemie - International Edition, 2018, vol. 57, # 22, p. 6696 - 6700[3] Angew. Chem., 2018, vol. 130, p. 6806 - 6810,5
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Reference: [1] Journal of Organic Chemistry, 2012, vol. 77, # 4, p. 1663 - 1674
[2] Angewandte Chemie - International Edition, 2018, vol. 57, # 22, p. 6696 - 6700[3] Angew. Chem., 2018, vol. 130, p. 6806 - 6810,5
[4] Patent: EP1053578, 2002, B1,
[5] Tetrahedron Letters, 2012, vol. 53, # 41, p. 5544 - 5547
[6] Patent: JP6257340, 2018, B2,
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Reference: [1] Tetrahedron, 2004, vol. 60, # 1, p. 145 - 158
[2] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 3, p. 329 - 336
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[2] Journal of the American Chemical Society, 1930, vol. 52, p. 2881,2887
[3] Heterocycles, 2010, vol. 81, # 5, p. 1157 - 1168
[4] Monatshefte fur Chemie, 2011, vol. 142, # 9, p. 907 - 916
[5] Chemistry - An Asian Journal, 2017, vol. 12, # 2, p. 181 - 189
[6] Patent: KR2016/102949, 2016, A,
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Reference: [1] Patent: CN108863694, 2018, A,
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Reference: [1] Tetrahedron Letters, 1985, vol. 26, # 40, p. 4955 - 4956
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Reference: [1] Chemistry - An Asian Journal, 2016, vol. 11, # 16, p. 2312 - 2315
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Reference: [1] Dyes and Pigments, 2013, vol. 96, # 3, p. 642 - 652
[2] Chemical Biology and Drug Design, 2018, vol. 91, # 6, p. 1078 - 1086
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Reference: [1] Zeitschrift fuer Chemie (Stuttgart, Germany), 1985, vol. 25, # 12, p. 438
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Reference: [1] Zeitschrift fuer Chemie (Stuttgart, Germany), 1985, vol. 25, # 12, p. 438
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Reference: [1] Zeitschrift fuer Chemie (Stuttgart, Germany), 1985, vol. 25, # 12, p. 438
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Reference: [1] Justus Liebigs Annalen der Chemie, 1878, vol. 193, p. 135
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YieldReaction ConditionsOperation in experiment
97% With hydrogenchloride In Zinc chloride; water; isopropyl alcohol EXAMPLE 4
9,9-bis-(4-hydroxyphenyl)-fluorene
20 moles of phenol containing 9percent by weight of water were stirred in an autoclave and then one mole of zinc chloride and 10 moles of fluorenone were dissolved therein.
Then, 5 moles of gaseous hydrogen chloride were added to the stirred mixture and the mixture was reacted at 70° C. for 4 hours.
The reaction mixture was then dissolved in 5 liters of isopropanol at 60° C. and the solution was poured with vigorous stirring into a ten-fold volume of water to precipitate 3.4 kg of 9,9,-bis-(4-hydroxyphenyl)-fluorene (97percent yield in the form of a yellow product.
97% With hydrogenchloride In Zinc chloride; water; isopropyl alcohol EXAMPLE 5
9,9-bis-(4-hydroxyphenyl)-fluorene
40 moles of phenol containing 9percent by weight of water were stirred in an autoclave and 2 moles of zinc chloride and 10 moles of fluorenone were dissolved therein.
Then, 10 moles of gaseous hydrogen chloride were added and the mixture was reacted for 4 days at room temperature.
The reaction mixture was dissolved in 5 liters of isopropanol at 60° C. and the solution was poured with vigorous stirring into 10 fold volume of water to obtain 3,4 kg of 9,9-bis-(4-hydroxyphenyl)-fluorene (97percent yield) in the form of a light-yellow product of greater purity than Examples 3 and 4.
92.5% With sulfuric acid; 3-mercaptopropionic acid In dichloromethane at 20 - 40℃; for 6 h; To the equipped with a mechanical stirring, thermometer, condenser of 100 ml flask, adding 10 g 9 - fluorenone (0.055 µM), 31.5 g phenol (0.33 µM), 16 g dichloroethane, stirring is placed in the water bath, adding 2.5 g of concentrated sulfuric acid, to control the temperature 20 °C the left and the right, slowly adding 0 . 37 g 3 - mercapto propionic acid (0.0035 µM), after adding, in 20 °C reaction 2 hours, slowly raising the temperature to 30 °C continue to reaction 1 hours. System completely turn into a white color after shape fluid, sampling liquid phase analysis, 9 - fluorenone reaction is complete, the liquid phase content of 95percent (deduction of phenol). After adding 30 g of dichloroethane, to cool down to room temperature filtration, the filter cake is washed with a small amount of dichloroethane. Filter cake at the mass ratio of 1:1 of 5percent sodium hydroxide solution in a mashing, filtering, drying to obtain 18.3 g of pure white solid, yield 94.1percent, content is greater than 99.3percent. The combined organic filtrate is recycled.To the above-mentioned filtrate is sequentially added in 10 g 9 - fluorenone (0.055 µM), 11.5 g of phenol (0.12 µM), concentrated sulfuric acid 1.2 g, 0 . 12 g 3 - mercapto propionic acid (0.0013 µM) after 20 °C reaction 2 hours, heating to 40 °C reaction 1 hours. Until the system completely turn into a pure white slurry after the reaction, the sampling liquid phase analysis, 9 - fluorenone reaction is complete, the content 96.1percent (deduction of phenol). Cooling to room temperature filtering, washing, beating, filtering, drying to obtain about 18.0 g pure white solid, yield 92.5percent, the purity is greater than 99percent.
91% at 110℃; for 3 h; Green chemistry Accurately weigh 0.1 mol of anthrone and add it to a 250 mL three-necked flask, followed by0.4 mol of phenol and 0.010 mol of acidic ionic liquid N-(3-sulfopropyl)-2-indenyl The benzothiazole p-toluenesulfonatewas stirred and reacted at 110 ° C for 3 h.A sample was taken for liquid chromatography analysis, the conversion of anthrone was 100percent, andthe selectivity ofbisphenol oxime (9,9-bis(p-hydroxyphenyl)anthracene) was 94percent (as shown in Figure 1).The reaction solution was poured into a beaker while hot, and anappropriate amount of 20 ° C waterwas added to the beaker towash the ionic liquid, and the layer was allowed to stand. The ionic liquid catalyst was distilled off from the aqueous phase under reduced pressure; and90 ° C hot water was addedto the oily viscoussolid. After thorough mixing, the mixture was allowed to stand for separation, and the aqueous phase was separated from the oily viscous solid phase. The above operation was repeateduntil the hot phase was stirred at 90 ° C, and the solid phase was no longer viscous.The solid particles and the filtrate were obtained under reduced pressure, and the solid particleswere dried to obtain a bisphenol hydrazine product.The filtrate which was suction-filtered under reduced pressure was distilled under reduced pressure to obtain phenol, and the phenol recoverywas 80percent.The solid crude product was recrystallized from methylene chloride to give purified bisphenolphthalein in a yield of 91percent, and the purity of the bisphenol oxime wasmore than 99percent.
89% at 90℃; for 6 h; Preparation of bisphenolphthalein:Accurately weighedA certain amount of fluorenone, added to a 50 mL three-necked flask, then add the right amount of phenol,Ionic Liquid [(CH2)3SO3HBth][HSO4],At a temperature of 90°C,heating,Backflow 6h,After the reaction is over,Dip a suitable amount of reaction solution into CH3OH with a glass rod.Analyzed by liquid chromatography. Pour the reaction solution into the beakerAdd an appropriate amount of water at 20°C in the beaker to wash it.Stably layered,The upper layer is water phase,The lower layer is an oily viscous solid.Separating the aqueous phase from the oily viscous solid phase,The aqueous phase contains an ionic liquid catalyst and a small amount of phenol,Pending;Add 90°C hot water to the viscous solidStir with a glass rod,Stably layered,The upper layer is water phase,The lower layer is still an oily viscous solid,Separating the aqueous phase from the oily viscous solid phase,Repeat the above operation,After adding hot water at 90°C, stirThe solid phase is no longer viscous,Solids become granular,Stop the above operation.Decompression,Get solid particles and filtrate,Dry the solid particles,That is,Bisphenol quinone of crude product,The solid yield was 94percent.Recrystallization of bisphenolphthalein,The yield of bisphenolphthalein is 89percent.Product purity is greater than 99percent.
85% With silica-gel-supported sulfuric acid; 3-mercaptopropionic acid In toluene at 30 - 45℃; for 3.5 h; Inert atmosphere A solid acid H2SO4-SiO2 catalytic preparation of bisphenol fluorene process, the method comprises the following steps:
1) In a 1000 ml three-necked flask equipped with a thermometer, 50 g (0.275 mol) of 9-fluorenone was added under nitrogen atmosphere, phenol (157 g, 1.67 mol), toluene 50 ml, 1 g (0.01 mol) of 3-mercaptopropionic acid was added dropwise, after being completely dissolved by heating to 30 ° C, 16.6 g (8percent wt) of solid acid H2SO4-SiO2 was slowly added, after completion of the dropwise addition, the reaction was carried out at 45 ° C for 3.5 hours, after completion of the reaction, the solution A was analyzed for bisphenol fluorene content, 96.50percent (HPLC detection), the test results shown in Figure 2.
2) Solution A was hot filtered at 45 ° C to recover the solid acid, the filtrate was distilled to remove toluene, and then 100 ml of boiling water was added to the reaction flask to make two phases. Poured into 250 ml of ice water while vigorously stirred, the precipitated solid was suction filtered, the solid B and filtrate C were obtained.
3) Solid B was dried at 60 ° C for 2 hours, to obtain 91.5 g of bisphenol fluorene as a white solid powder, yield 98, purity 96.0percent; by toluene and methanol mixture solution (V toluene: V methanol = 10: 1) 275 ml recrystallization, filtered, 80 deg. C drying, a white crystalline bisphenol fluorene 80 grams, yield 85percent, purity 99.7percent;
85% With methanesulfonic acid; 3-mercaptopropionic acid In toluene at 40℃; for 13 h; Inert atmosphere Under a nitrogen atmosphere, 9-fluorene (138.7 mmol, 25.0 g), phenol (332.5 mmol, 31.29 g) was added to a 500 Ml reaction flask,3-Mercaptopropionic acid (13.8 mmol, 1.47 g) was added and toluene (140.5 g) was added. Methanesulfonic acid (276.7 mmol, 26.6 g) was added to the mixture, the temperature was gradually raised to 40 ° C, and the mixture was stirred at the same temperature for 13 hours. The reaction mixture was cooled to room temperature and then concentrated to remove toluene, 155.5 g of tetrahydrofuran was added and dissolved by stirring. After confirming dissolution, 198.7 g of methylene chloride was added, and the mixture was washed twice with 150.0 g of purified water, and concentrated to remove the solvent. 175.0 g of methanol was added, and the mixture was heated to reflux for 30 minutes. After cooling to 10 ° C, the mixture was stirred for 1 hour, filtered and dried to obtain the target compound, 9,9-bis (4-hydroxyphenyl) fluorene (1-1) (yield: 85percent).
85% With methanesulfonic acid; 3-mercaptopropionic acid In toluene at 40℃; for 13 h; Inert atmosphere Under a nitrogen atmosphere, 9-fluorene (138.7 mmol, 25.0 g), phenol (332.5 mmol, 31.29 g)3-mercaptopropionic acid(13.8 mmol, 1.47 g) was added and toluene (140.5 g) was added.To the mixture was added methanesulfonic acid(276.7 mmol, 26.6 g) was added thereto, the temperature was gradually raised to 40 ° C, and the mixture was stirred at the same temperature for 13 hours.The reaction mixture was cooled to room temperature and then concentrated to remove toluene,155.5 g of tetrahydrofuran was added and dissolved by stirring.After confirming dissolution, 198.7 g of methylene chloride was added, and the mixture was washed twice with 150.0 g of purified water and concentrated to remove the solvent.175.0 g of methanol was added, and the mixture was heated to reflux for 30 minutes. After cooling to 10 ° C, the mixture was stirred for 1 hour, filtered, and dried to obtain the target compound, 9,9-bis (4-hydroxyphenyl) fluorene (4-1)

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YieldReaction ConditionsOperation in experiment
97% With hydrogenchloride In Zinc chloride; water; isopropyl alcohol EXAMPLE 3
9,9-bis-(4-hydroxyphenyl)-fluorene
30 moles of phenol containing 9percent by weight of water were stirred in an autoclave and then 2 moles of zinc chloride and 10 moles of fluorenone were dissolved therein.
Then, 10 moles of gaseous hydrogen chloride were added to the stirred mixture and the mixture was reacted at 80° C. for one hour and then at 70° C. for 3 hours.
The reaction mixture was then dissolved in 5 liters of isopropanol at 60° C. and the solution was then poured with vigorous stirring into a ten-fold volume of water whereby the resulting bisphenol precipitated as 3.4 kg (97percent yield) of the product in the form of a yellow product.
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[2] Patent: US4467122, 1984, A,
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YieldReaction ConditionsOperation in experiment
93.4% With sodium hydrogensulfite In toluene at 125 - 150℃; for 6 h; 72 g of 9-fluorenone , 155.4 g of aniline hydrochloride, 10 g of sodium bisulfite, and 72 g of a 9-fluorenone, were added to the reaction apparatus equipped with a water trap.145 g of aniline and 100 g of toluene are heated to 125-130° C. under stirring, and incubated at 125-130° C. for 3 hours, and the generated water passes through. Toluene was brought to the trap. Then, the temperature was raised slowly to 145-150 for 3 hours. After the reaction is over, cool down to 95°C. At this temperature, 10percent sodium hydroxide solution was added dropwise until the pH of the feed solution was approximately , 95° C., and the mixture was neutralized for 3 hours. Thermal stratification was performed at 95° C., the aqueous layer was separated, and the upper oil layer was collected and added to the flask. Under stirring, the temperature was gradually lowered to 20 to 30°C, and the mixture was sufficiently stirred at 20 to 30°C for 1 hour to be sufficiently crystallized. filter,About 185.6g after drying. 185.6 g of 9,9-bis(4-aminophenyl)fluorene and 300 g of xylene were added to the biscuit, 20 to 30Fully beaten at °C, filter,The product had a wet weight of 170 g, 141 g after drying, and a purity of 99.5percent (HPLC normalized content).Obtained above was 141 g of 9,9-bis(4-aminophenyl)fluorene, 2800 g of deionized water, 49.3 g of 33percent hydrochloric acid and 28 g ofActivated carbon was added to the flask, and the temperature was raised to 65-70°C to defocus for 2 hours. Heat filtration at 70°C. Add filtrate to burnIn the bottle, add 10percent ammonia water and feed solution at pH 60 to 65°C to pH 9 to 10. Stir at 60-65°C for 3 hours.Make it fully neutralized. After the end of the neutralization,After cooling down to 20 to 30°C, filtering and drying the 130g product, the yield is 93.4percent, the appearance is pure white solid,The purity is 99.7percent.
Reference: [1] Patent: CN107892649, 2018, A, . Location in patent: Paragraph 0023-0042
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[2] Patent: CN107573356, 2018, A,
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YieldReaction ConditionsOperation in experiment
90.2% at 130℃; for 4 h; Inert atmosphere Example 12 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 [(H3PW12O40).nH2O] serving as a catalyst to a glass reactor vessel equipped with a stirrer, a nitrogen-blowing tube, a thermometer and a T-tube and (b) allowing a mixture to react for 4 hours under a reduced pressure of 2.0.x.103 Pa at 130° C. The content of multimers in a reaction mixture obtained after completion of the reaction was 3.9percent. To the reaction mixture thus obtained, 800.0 g of toluene was added. The reaction mixture was neutralized with a sodium hydroxide aqueous solution and washed with water. Thereafter an organic phase was separated. Toluene and excess 2-phenoxyethanol were removed from an obtained organic phase by concentration under reduced pressure. To an obtained concentrate, 560.0 g of toluene was added, and the mixture was heated and stirred at 80° C. for 1 hour and thereafter directly cooled to 70° C. Thereafter, 0.4 g of crystals of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene serving as seed crystals were added, and a mixture was incubated at 70° C. for 2 hours and thereafter directly cooled to 20° C. Then, precipitated crystals were subjected to filtration and drying to obtain 78.0 g of white crystals of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (yield: 90.2percent, purity: 99.2percent). The 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene thus obtained had a melting point of 163° C.
85.4% at 50℃; for 18 h; Inert atmosphere A 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 °C
75.1% for 12 h; Inert atmosphere; Reflux Example 3: Production 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 [(H3PW12O40)] which had been dried under reduced pressure at 100°C to remove crystal water, and the mixture was stirred for 12 hours while removing generated water out of the system, under toluene reflux. The resultant reaction liquid was analyzed by high performance liquid chromatography to find generation of 197.3 g (0.45 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene. To this reaction liquid was added 300 g of toluene, and water-washed at 80°C using 100 g of water. The resultant organic layer was cooled gradually, to find initiation of deposition of a crystal at 12°C, and the organic layer was cooled down to 10°C without any other procedure, and stirred for 12 hours. The deposited crystal was taken out by filtration, and the crystal was dried to obtain 158.0 g (yield: 75.1percent, LC purity: 99.9percent) of a white crystal of a crude product of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene. The resultant crystal had a melting point (melt endotherm maximum by differential scanning calorimetry) of 109°C, and a bulk density of 0.24 g/cm3.
104.5 g at -40 - 80℃; for 17 h; Autoclave; Inert atmosphere 500 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.

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