Name: 198964-46-4|9,9-Dioctyl-2,7-dibromofluorene|97%
Brand: Ambeed
SKU: A307700
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1
[ 123863-99-0 ]
[ 198964-46-4 ]

Yield	Reaction Conditions	Operation in experiment
99%	With bromine; iron(III) chloride In chloroform at 0 - 25℃; for 24h;
99%	With bromine; iron(III) chloride In chloroform for 3h; Ambient temperature;
98%	With benzyltrimethylazanium tribroman-2-uide; zinc(II) chloride In dichloromethane at 40℃; for 24h; Inert atmosphere;

92%	With bromine In N,N-dimethyl-formamide Ambient temperature;
90%	With bromine; iron(III) chloride In chloroform at 0 - 20℃; for 3h;
79%	With bromine; iron(III) chloride In chloroform at 0 - 20℃;
74%	With bromine; iodine In dichloromethane at 0 - 20℃; for 3h;
	With bromine; iron(III) chloride
	With bromine; iodine In dichloromethane at 20℃; for 20h;
	With bromine; iodine In dichloromethane at 20℃;
	With bromine; iron(III) chloride In chloroform at 20℃; for 3h;
	With bromine In chloroform at 0℃;
	With bromine In N,N-dimethyl-formamide

Reference： [1]Ranger, Maxime; Leclerc, Mario [Chemical Communications, 1997, # 17, p. 1597 - 1598]
[2]Ranger, Maxime; Leclerc, Mario [Canadian Journal of Chemistry, 1998, vol. 76, # 11, p. 1571 - 1577]
[3]Saito, Hitoshi; Kuwabara, Junpei; Kanbara, Takaki [Journal of Polymer Science, Part A: Polymer Chemistry, 2015, vol. 53, # 19, p. 2198 - 2201]
[4]Kay, Kwang-Yol; Oh, In Chul [Tetrahedron Letters, 1999, vol. 40, # 9, p. 1709 - 1712]
[5]Aubert, Pierre-Henri; Knipper, Martin; Groenendaal, Lambertus; Lutsen, Laurence; Manca, Jean; Vanderzande, Dirk [Macromolecules, 2004, vol. 37, # 11, p. 4087 - 4098]
[6]Qiang, Liang-Liang; Fan, Qu-Li; Ma, Zhun; Zheng, Zhe; Wang, Yun-Yun; Zhang, Guang-Wei; Huang, Wei [Chemistry Letters, 2005, vol. 34, # 8, p. 1164 - 1165]
[7]Sung, Yong Cho; Grimsdale, Andrew C.; Jones, David J.; Watkins, Scott E.; Holmes, Andrew B. [Journal of the American Chemical Society, 2007, vol. 129, # 39, p. 11910 - 11911]
[8]Leclerc, Mario; Ranger, Maxime; Belanger-Gariepy, Francine [Acta Crystallographica, Section C: Crystal Structure Communications, 1998, vol. 54, # 6, p. 799 - 801]
[9]Ding, Jianfu; Day, Michael; Robertson, Gilles; Roovers, Jacques [Macromolecules, 2002, vol. 35, # 9, p. 3474 - 3483]
[10]Park, Taiho; Haque, Saif A.; Potter, Robert J.; Holmes, Andrew B.; Durrant, James R. [Chemical Communications, 2003, # 23, p. 2878 - 2879]
[11]Liu, Shu-Juan; Zhao, Qiang; Chen, Run-Feng; Deng, Yun; Fan, Qu-Li; Li, Fu-You; Wang, Lian-Hui; Huang, Chun-Hui; Huang, Wei [Chemistry - A European Journal, 2006, vol. 12, # 16, p. 4351 - 4361]
[12]Chen, Run-Feng; Zhu, Rui; Fan, Qu-Li; Huang, Wei [Organic Letters, 2008, vol. 10, # 13, p. 2913 - 2916]
[13]Location in patent: scheme or table Pei, Jianing; Wen, Shanpeng; Zhou, Yinhua; Dong, Qingfeng; Liu, Zhaoyang; Zhang, Jibo; Tian, Wenjing [New Journal of Chemistry, 2011, vol. 35, # 2, p. 385 - 393]

2
[ 111-83-1 ]
[ 16433-88-8 ]
[ 198964-46-4 ]

Yield	Reaction Conditions	Operation in experiment
96%	With [benzene-1,3,5-triyltris(methylene)]tris(triphenylphosphonium) tribromide; sodium hydroxide In water; dimethyl sulfoxide at 30℃; for 1h; Inert atmosphere;	Synthesis of 2,7-dibromo-9,9-dioctyl-9H-fluorene (6c) To a stirred solution of 2,7-dibromofluorene 4c (1 g, 3.0 mmol) in DMSO, 25 % aq. sodium hydroxide solution added dropwise over a period of 10 min under nitrogen gas purging, then the catalyst 3 (10 mol %) was added followed by 1-bromooctane 5a (1.19 g, 6.1 mmol). Reaction completion was confirmed by TLC, then extracted with ethyl acetate, washed with water, dried over sodium sulfate and evaporated under reduced pressure, to obtain a white solid with 96 % yield. 1H NMR(300 MHz, CDCl3) d: 7.53-7.43 (m, 6H), 1.92-1.88 (m, 4H), 1.20-1.05 (m, 20H),0.85 (t, J = 6 Hz, 6H), 0.59 (d, J = 6 Hz, 4H); 13C NMR (75 MHz, DMSO) d:152.54, 139.05, 130.14, 126.16, 121.47, 121.09, 55.67, 40.14, 31.75, 29.85, 29.16,29.14, 23.61, 22.59, 14.07.
91.2%	With sodium hydroxide In dimethyl sulfoxide at 20℃; for 3h;
91%	With tetrabutylammomium bromide; sodium hydroxide In toluene at 90℃; for 24h;	5 Preparation of 2,7-dibromo-9,9-dioctyl-9H-fluorene (Compound e-2) Into the 2,7-dibromo-9H-fluorene (compound 1-e) (5g, 15.42mmol) in a round flask equipped with a condenser, it binds the toluene (Toluene) in 200mL solvent. And to put the NaOH solution in the flask after the quasi put TBAB (Tetra-butylammoniumbromide), raise the temperature to 90 °C. Then after a slow gave put octyl bromide (2.2eq), and the mixture was stirred for 24 hours. After the reaction with ethyl acetate (EA) and the organic layer was extracted with brine to remove the remaining water over anhydrous magnesium sulfate and, after evaporation of the solvent was recrystallized from methanol and the MC of the white solid 2,7-dibromo-9,9- to give a dioctyl-9H-fluorene (compound e-2) (yield: 91%).

91%	With tetrabutylammomium bromide; sodium hydroxide In dimethyl sulfoxide at 20℃; for 8h;	2.4.2. Synthesis of compound 5 According to the literature [58], to a mixture of 2,7-dibromo-9Hfluorene(3.24 g, 10 mmol), bromooctane (4 mL, 23 mmol) andtetrabutylammonium bromide (TBAB, catalytic amount) in DMSO(100 mL) was added sodium hydroxide solution (25 mL, 50 wt%).The resulting mixture was stirred at room temperature for 8 h. Theprogress of the reactionwas monitored by TLC using hexane:CH2Cl2as the eluent. After completion of the reaction, the reaction mixturewas poured into water and extracted with CH2Cl2. The organiclayers were separated, dried over anhydrous MgSO4, and filtered.Solvents were removed under reduced pressure and the cruderesiduewas further purified by column chromatography (hexane aseluent) to afford the compound 5 as a white solid (4.95 g, yield:91%). 1H NMR (400 MHz, CDCl3): δ 7.51 (d, J = 8.5 Hz, 2H), 7.47-7.41(m, 4H), 1.97-1.85 (m, 4H), 1.29-0.97 (m, 20H), 0.83 (t, J = 7.1 Hz,6H), 0.58 (s, 4H). 13C NMR (101 MHz, CDCl3): δ 152.44, 139.19,130.14, 126.16, 121.46, 121.12, 55.64, 40.25,31.76, 29.86, 29.18, 29.16,23.62, 22.60, 14.09.
90%	With tetrabutylammomium bromide; sodium hydroxide In toluene at 60℃; for 16h; Inert atmosphere;
90.2%	With sodium hydroxide In water; toluene
90%	With tetrabutylammomium bromide; sodium hydroxide In dimethyl sulfoxide at 20℃; for 10h;	4 Into a 250mL single-necked flask, added the compound 2, 7-dibromofluorene (3.24 g, 10mmol), DMSO (100mL), the amount of TBAB and sodium hydroxide solution (25mL, 50wt %), after stirring at room temperature for a few minutes, added the drops of bromo-n-octane (4mL, 23mmol) with a syringe, and carry on reaction at room temperature for 10h. Stop the reaction, by using hydrochloric acid adjust the pH-= 7, extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous magnesium sulfate. Filter, the filtrate is evaporated to remove the solvent, the crude product is purified by silica gel (200-300 mesh) column chromatography [eluent, petroleum ether] and obtained 4.91 g white solid 2,7-dibromo-9,9-dioctylfluorene, yield 90%.
90%	Stage #1: 2,7-dibromo-9H-fluorene With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water; dimethyl sulfoxide at 20℃; Stage #2: 1-bromo-octane With 3-chloro-benzenecarboperoxoic acid In water; dimethyl sulfoxide at 20℃; for 3h;	1.2 2) Preparation of 2,7-dibromo-9,9-di-n-octylfluorene (2) Dibromofluorene (9.7 g, 30 mmol) and benzyltriethylammonium chloride (0.07 g, 0.3 mmol) were dissolved in 90 mL of dimethyl sulfoxide,And add 45mL mass fraction of 50% aqueous sodium hydroxide solution. Stirred at room temperature to form a suspension. Bromo-n-octane (12.5 g, 65 mmol) was slowly added dropwise and stirring was continued for 3 hours, followed by extraction with ethyl acetate. The organic phase was washed with saturated aqueous sodium chloride and dried over anhydrous magnesium sulfate. The solvent was evaporated and the product was purified by column chromatography using petroleum ether as eluent to give white crystals (14.8 g, 90%).
90%	Stage #1: 2,7-dibromo-9H-fluorene With tetrabutylammomium bromide In dimethyl sulfoxide at 20℃; Stage #2: With sodium hydroxide In dimethyl sulfoxide at 20℃; for 0.166667h; Stage #3: 1-bromo-octane In dimethyl sulfoxide	2 Synthesis of intermediate 2 Add 2,7-dibromoindole (6.48 g, 20 mmol), DMSO (200 mL), and appropriate amount of TBAB to a 500 mL three-necked flask.After stirring for a few minutes at room temperature,Sodium hydroxide solution (50 mL, 50% by weight) was slowly added to the reaction system.Continue magnetic stirring at room temperature, after 10 minutes,Inject brominated n-octane (8 mL, 46 mmol) with a syringe.Stir overnight. Stop the reaction,The reaction solution was adjusted to neutral with HCl solution.Then extracted with CH2Cl2 (200 mL×6),Saturated saline (200 mL × 6),Dry over anhydrous magnesium sulfate,Rotate the solvent,The residue was subjected to silica gel column chromatography [eluent, petroleum ether]Purified white solid2,7-dibromo-9,9-dioctylfluorene 9.82 g,The yield was 90%.
90%	Stage #1: 2,7-dibromo-9H-fluorene With tetrabutylammomium bromide; sodium hydroxide In water; dimethyl sulfoxide at 20℃; for 1h; Inert atmosphere; Stage #2: 1-bromo-octane In water; dimethyl sulfoxide	1.2 2) Synthesis of 2,7-dibromo-9,9-di-n-octylfluorene (2): 2,7-dibromofluorene (20 g, 61.7 mmol),Tetrabutylammonium bromide (1.9 g, 6 mmol) was dissolved in 250 mL of dimethyl sulfoxide.Stir at room temperature under a nitrogen atmosphere. 12 mL of a 50% by mass aqueous sodium hydroxide solution was slowly added dropwise to the reaction solution.Immediately after 1 hour, 1-bromooctane (29.8 g,154.2 mmol), overnight reaction. After stopping the reaction,The reaction solution was poured into water and quenched and extracted with ethyl acetate.Dry over anhydrous magnesium sulfate and purify by column chromatography.200-300 mesh silica gel as the stationary phase and petroleum ether as the eluent.Then, it was recrystallized from acetone to obtain white needle crystals (30.4 g, 90%).
89%	With sodium hydroxide; tetrabutylammomium bromide In toluene at 70℃; for 24h;
89%	With tetrabutylammomium bromide; sodium hydroxide In water; dimethyl sulfoxide at 20℃; for 3h;
88.6%	Stage #1: 2,7-dibromo-9H-fluorene With tetrabutylammomium bromide; potassium hydroxide In dimethyl sulfoxide at 20℃; for 0.5h; Stage #2: 1-bromo-octane In dimethyl sulfoxide at 20℃; for 24h;	1.1; 2.1; 3.1 Preparation of 2,7-dibromo-9,9'-dioctylfluorene take2,7-dibromofluorene (30 g, 92.59 mmol) in a 500 ml round bottom three-necked flask,And successively adding 300 ml of dimethyl sulfoxide,29ml aqueous solution of 50% potassium hydroxide,Tetrabutylammonium bromide (0.17 g, 0.53 mmol)Stir for 30 minutes at room temperature.ThenFollowed by addition of bromoctane (42.89 g, 222.22 mmol)Stir for 24 hours at room temperature.After the reaction is over,The reaction solution was poured into 300 ml of water,Add hydrochloric acid until the solution is neutral.Extracted with dichloromethane several times,The organic phases were combined and dried over anhydrous magnesium sulfate,The resulting filtrate was dried with a rotary evaporator to dry most of the solvent,Get the initial concentration of the initial product.The initial product was purified by column chromatography,With petroleum ether as detergent,Purification gave 45 g of a white powdery solid (yield: 88.6%)
86%	With tetrabutylammomium bromide; potassium hydroxide In acetone at 57℃; for 4h; Reflux;
85%	With sodium hydroxide In dimethyl sulfoxide
85%		IV Synthesis of 2,7-dibromo-9,9-di-n-octylfluorene: Example IV Synthesis of 2,7-dibromo-9,9-di-n-octylfluorene: This compound was prepared from 2,7-dibromofluorene and n-octyl bromide, using a similar procedure as described in Example III. The product was obtained in an 85% yield as colorless crystals.
85%	With tetrabutylammomium bromide; sodium hydroxide In water; toluene at 70℃; for 24h;
84.1%	Stage #1: 2,7-dibromo-9H-fluorene With potassium iodide; potassium hydroxide In dimethyl sulfoxide for 0.166667h; Cooling with ice; Inert atmosphere; Stage #2: 1-bromo-octane In dimethyl sulfoxide at 20℃; Inert atmosphere;
84.1%	Stage #1: 2,7-dibromo-9H-fluorene With potassium iodide; potassium hydroxide In dimethyl sulfoxide for 0.166667h; Stage #2: 1-bromo-octane In dimethyl sulfoxide for 0.5h;
83%	With tetrabutylammomium bromide; water; sodium hydroxide In dimethyl sulfoxide at 100℃; for 10h;
83%	With tetrabutylammomium bromide; sodium hydroxide In water; dimethyl sulfoxide at 20℃; for 3h;
83%	With tetrabutylammomium bromide; sodium hydroxide In water; dimethyl sulfoxide at 100℃; for 10h;	2,7-Dibromo-9,9-dioctyl-9H-fluorene To mixture of2,7-dibromofluorene (1 g, 3.09 mol), 1-bromooctane(1.1 mL, 6.48 mol) and catalyst amounts of tetrabutylammoniumbromide in DMSO and 3mL of 50% aqueousNaOH was added a solution of in DMSO. The reactionmixture was stirred and heated at 100 C for 10 h andthen poured into dilute hydrochloric acid. The aqueouslayer was extracted by dichloromethane. The combinedextracts were washed with water and NaHCO3 solutionand then dried over MgSO4. The mixture was purified byflash chromate-graphy with an eluent of hexane to give awhite solid (1.4 g, 83%). mp 45-47 C (from hexane); 1HNMR (CDCl3, 300 MHz) [ppm]: 7.52 (d, 2 H), 7.44(d, 2 H), 7.43 (s, 2 H), 1.90 (m, 4 H), 1.27-1.02 (m, 20 H),0.82 (t, 6 H), 0.57 (m, 4 H); 13C NMR (CDCl3, 75 MHz)[ppm]: 152.5, 139.0, 130.2, 126.1, 121.3, 121.1, 55.5,40.2, 31.8, 29.7, 29.1, 23.5, 22.7, 14.2.
83%	Stage #1: 2,7-dibromo-9H-fluorene With tetrabutylammomium bromide In dimethyl sulfoxide for 0.25h; Inert atmosphere; Stage #2: 1-bromo-octane With sodium hydroxide In dimethyl sulfoxide at 20℃; Inert atmosphere;	14 2,7-dibromo-9,9-dioctylfluorene Under argon atmosphere, 2,7-dibromoanthraquinone (32.48, 100% dirty), 300 ml of dimethyl sulfoxide, and tetrabutylammonium bromide (0.32 g, 1.0 mmol) were added to a 500 ml three-necked flask. Stir for 15 minutes. A 50 wt% aqueous NaOH solution (40 g, 1.0 mol) was slowly added. Afterwards, bromooctane (42.5 g, 220 mmol) was added. After reacting at room temperature for several hours, an appropriate amount of dilute hydrochloric acid was added, extracted with dichloromethane, dried over anhydrous magnesium sulfate, purified by silica gel column chromatography, and petroleum ether was eluted to give a pale yellow viscous liquid. Yield: 83%
81%	With tert-butylammonium hexafluorophosphate(V); sodium hydroxide Inert atmosphere;
80%	Stage #1: 2,7-dibromo-9H-fluorene With tetrabutylammomium bromide; potassium hydroxide In dimethyl sulfoxide for 0.5h; Inert atmosphere; Stage #2: 1-bromo-octane In dimethyl sulfoxide at 80℃; for 24h; Inert atmosphere;
80%	With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water; dimethyl sulfoxide at 20℃; for 10.5h;	(3) Synthesis of Intermediate 1b (2,7-dibromo-9,9-dioctylfluorene) In 250ml single-neck flask was sequentially added 2,7-dibromofluorene compound (3g, 9.3mmol), DMSO (85mL), TEBA (0.2g, 0.84mmol) and aqueous sodium hydroxide (25mL, 50wt%), then was added dropwise under magnetic stirring over 0.5h 1-bromo-n-octane (4g, 20.46mmol), reacted at room temperature then stopped after 10h, the reaction mixture was cooled to room temperature and poured into 300mL water and extracted three times with dichloromethane (60mL × 3), then several times with saturated brine, and the combined organic phase was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, the residue was treated with petroleum ether: ethyl acetate = 15: 1 as eluent on silica gel (200-300 mesh) column chromatography, the final product was 2,7-dibromo-9,9-dioctylfluorene 4g, 80% yield.
80%	Stage #1: 2,7-dibromo-9H-fluorene With tetrabutylammomium bromide; sodium hydroxide In water; dimethyl sulfoxide for 2h; Inert atmosphere; Stage #2: 1-bromo-octane In water; dimethyl sulfoxide for 10h;	2 Preparation of 2,7-dibromo-9,9-dioctylfluorene Under argon protection, in a 500 mL three-necked flask,Was added 2,7-dibromofluorene (32.4 g, lOO mmol) and dimethylsulfoxide (250 mL)In the strong stirring (stirring speed of 800rpm)Tetrabutylammonium bromide (1.61 g, 5 mmol) was added,Then, sodium hydroxide (40 g, 1 mol) of a 50 wt% aqueous solution was slowly added dropwise,Plus finished,Reaction for 2 hours,1-bromooctane (57.9 g, 0.3 mol) was injected again.After 10 hours of continuous reaction,Stop the reaction,The reaction solution was poured into water,Adding hydrochloric acid aqueous solution for neutralization,Extracted with dichloromethane,Washed with saturated salt water 7 times,dry,After drying the solvent,The crude product was purified by column chromatography,The product was purified with petroleum ether as eluent,To give 43.8 g of a white solid,The yield is about 80%.
80%	Stage #1: 2,7-dibromo-9H-fluorene With tetrabutylammomium bromide; sodium hydroxide In water; dimethyl sulfoxide for 2h; Inert atmosphere; Stage #2: 1-bromo-octane In water; dimethyl sulfoxide for 10h; Inert atmosphere;	2 Example 2 2,7-dibromo-9,9-dioctylfluorene (M-1) Under argon protection,In a 500 mL three-necked flask,Was added 2,7-dibromofluorene (32.4 g, 100 mmol)And dimethyl sulfoxide (250 mL),Strong stirring,Tetrabutylammonium bromide (1.61 g, 5 mmol) was added,Then, 50% by weight aqueous solution of sodium hydroxide (40 g, 1000 mmol) was slowly added dropwise,Plus,Reaction for 2 hours,1-bromooctane (57.9 g, 300 mmol) was injected again.After 10 hours of continuous reaction,The reaction solution was stopped, the reaction solution was poured into water, neutralized by adding an aqueous hydrochloric acid solution, extracted with methylene chloride, washed with saturated brine seven times, dried and the solvent was dried. The crude product was purified by column chromatography, As a stationary phase, using petroleum ether as the mobile phase, and purified to give 43.8 g of a white solid in 80% yield.
80%	With tetra-(n-butyl)ammonium iodide; sodium hydroxide In water; toluene at 60℃; for 10h; Inert atmosphere;
77%	With sodium t-butanolate In tetrahydrofuran at 0 - 20℃; for 24h;
76%	Stage #1: 2,7-dibromo-9H-fluorene With potassium hydroxide In dimethyl sulfoxide at 20℃; for 0.166667h; Stage #2: 1-bromo-octane In dimethyl sulfoxide at 60℃; for 120h;	3.2. Experimental procedure for 2,7-dibromo-9,9-dioctyl-9H-fluorene(III) 972 mg of 2,7-dibromofluorene (0.0030 mmol, 1.0 eq.) and 1.6831 gof potassium hydroxide (0.0300 mmol, 10.0 eq.) in dimethyl sulphoxide(10 mL) was stirred at room temperature for 10 min. Then, 1.4484 g of 1-bromooctane was added and continued the reaction at 60 C for 5 days.The reaction mixture was transferred to water (100 mL) and thenextracted with ethyl acetate (3 × 20 mL). The organic portion was driedover anhydrous Na2SO4 and concentrated under reduced pressure. Theobtained crude product was chromatographed on a silica columnafforded compound III as colourless semisolid (1.6453 g, 76%). Rf =0.70 (5% EA/PE); FT-IR (KBr): 3735, 2925, 2855, 2354, 1878, 1745,1573, 1455, 1254, 1124, 1061, 1061, 1004, 879, 808, 735 cm 1; 1HNMR (500 MHz, CDCl3, in ppm): 0.86 (t, 6H, J = 5.0 Hz), 1.08-1.31(m, 24H), 1.92-1.95 (m, 4H), 7.47 (d, 4H, J = 5.0 Hz), 7.53 (d, 2H, J =10.0 Hz); 13C NMR (125 MHz, CDCl3, in ppm): 14.0, 22.6, 23.6, 29.15,29.17, 29.8, 31.7, 40.1, 55.7, 121.1, 121.4, 126.2, 130.1, 139.0, 152.5.
75%	With sodium hydroxide; tetrabutylammomium bromide; water In toluene for 4h;
75.3%	Stage #1: 2,7-dibromo-9H-fluorene With sodium hydride In tetrahydrofuran at 60℃; Stage #2: 1-bromo-octane In tetrahydrofuran Heating; Further stages.;
75%	With tetrabutylammomium bromide; sodium hydroxide In water; toluene at 60℃; for 4h; Inert atmosphere;
75%	Stage #1: 2,7-dibromo-9H-fluorene With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 1-bromo-octane In N,N-dimethyl-formamide at 20℃;	13.1 (1) 2,7-Dibromofluorene (10 g, 30.86 mmol),KOH (8.66 g, 154.32 mmol) was added to a 250 ml two-necked flask,Further, 100 ml of N, N-dimethylformamide was added thereto to completely dissolve,After stirring at room temperature for one hour, then bromooctane (17.88 g, 92.59 mmol) was added in one portion,The mixture was stirred overnight at room temperature.The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and extracted with ethyl acetate. The solution was concentrated and purified by silica gel column chromatography (petroleum ether selected as the eluent). The resulting product was recrystallized from acetone to give a white solid. Yield 75%.
75%	With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 25h;	9.1 Preparation of 2,7-dibromo-9,9-dioctylfluorene A solution of 2,7-dibromofluorene (10 g, 30.86 mmol), KOH (8.66 g, 154.32 mmol) was added to a 250 mL two-necked flask and 100 mL of N, N-dimethylformamide was added to complete dissolution, After stirring for 1 hour, bromooctane (17.88 g, 92.59 mmol) was added at room temperature and stirred at room temperature for 24 hours. After extraction with ethyl acetate, the organic layer was washed thoroughly with brine and dried over anhydrous magnesium sulfate. And purified by silica gel column chromatography (eluent selection of petroleum ether). The resulting product was recrystallized from acetone to give a white solid. Yield 75%. 1H NMR, 13CNMR, MS and elemental analysis showed that the obtained compound was the target product and the preparation process chemical reaction
75%	Stage #1: 2,7-dibromo-9H-fluorene With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 1-bromo-octane In N,N-dimethyl-formamide at 20℃; for 24h;	5.1 Example 5 2,7-dibromo-9,9-dioctyl fluorene (1) 2,7-dibromofluorene (10 g, 30 · 86 mmol), KOH (8 · 66 g, 154 · 32 mmol) was added to a 250 mL two-mouth bottle, Add 100 mL of N,N-dimethylformamide for complete dissolution.After stirring for 1 hour at room temperature, bromooctane (17.88 g, 92.59 mmol) was added in one portion and the mixture was stirred at room temperature for 24 hours. The mixture was extracted with ethyl acetate, and the organic layer was completely washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated and purified by silica gel column chromatography (eluent selected for petroleum ether). The resulting product was recrystallized from acetone to give a white solid. The yield was 75%.
75%	Stage #1: 2,7-dibromo-9H-fluorene With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 1-bromo-octane In N,N-dimethyl-formamide at 20℃; for 24h;	9.1 (1) 2,7-dibromofluorene (10g, 30.86mmol), KOH (8.66g, 154.32mmol) was added to 250mL of two bottles,Further, 100 mL of N,N-dimethylformamide was added to completely dissolve, and after stirring at room temperature for 1 hour,Bromooctane (17.88 g, 92.59 mmol) was added in one portion and stirred at room temperature for 24 hours;After extracting with ethyl acetate, the organic layer was washed with brine and dried over anhydrous magnesium sulfate.Purification by silica gel column chromatography (eluent eluting petroleum ether), and the obtained product was recrystallized from acetone to give a white solid.The yield was 75%.
75%	Stage #1: 2,7-dibromo-9H-fluorene With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 1-bromo-octane In N,N-dimethyl-formamide at 20℃; for 24h;	15.1 Add 2,7-dibromofluorene (10g, 30.86mmol) and KOH (8.66g, 154.32mmol) to a 250ml two-necked bottle, then add 100ml N, N-dimethylformamide to completely dissolve, After stirring at room temperature for 1 hour,Bromooctane (17.88g, 92.59mmol) was added in one portion and stirred at room temperature for 24 hours; extracted with ethyl acetate, the organic layer was washed with brine and dried over anhydrous magnesium sulfate; after the solution was concentrated, a silica gel column layer was used Separation and purification (selection of petroleum ether as the eluent), the obtained product was recrystallized with acetone, and finally a white solid was obtained. The yield is 75%
74%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 5.5h;	General procedure A: Synthesis of 2,7-dibromo-9,9-dialkylfluorene (4 B, 4 O) ^{58, 60} General procedure: To a mixture of 2,7-dibromofluorene (3) (1 eq) and 1-bromoalkane (4 eq) in tetrahydrofuran (8 mL per gram), a solution of potassium tert-butoxide (2.25 eq) in dry tetrahydrofuran (200 mL) was added dropwise at 0°C - +5°C over 1.5 h with vigorous stirring. The reaction was then stirred at room temperature for 4 h and the mixture was filtered through a silica plug to remove the KBr precipitate, and was washed with dichloromethane. After evaporation of the solvent, the crude residue was treated with activated carbon in hot n-hexane and filtered through a silica plug to remove coloured by-products. After evaporation of the solvent, the crude product was treated with activated carbon in methanol, filtered by gravity and allowed to crystallize, obtaining the product that was recrystallized from hexane to remove traces of methanol.
71%	Stage #1: 2,7-dibromo-9H-fluorene With potassium iodide; potassium hydroxide In dimethyl sulfoxide for 0.5h; Stage #2: 1-bromo-octane In dimethyl sulfoxide at 20℃;
65%	With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In dimethyl sulfoxide at 20℃; for 2h;
	With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In dimethyl sulfoxide
	With sodium hydroxide; tetrabutylammomium bromide In toluene at 60℃;
	With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In dimethyl sulfoxide at 20℃; for 3h;
	Stage #1: 2,7-dibromo-9H-fluorene With sodium hydroxide In water; dimethyl sulfoxide Stage #2: 1-bromo-octane With N-benzyl-N,N,N-triethylammonium chloride In water; dimethyl sulfoxide
	With sodium hydroxide In dimethyl sulfoxide
	With tetraethylammonium bromide In dimethyl sulfoxide
	With tetraethylammonium bromide In dimethyl sulfoxide
	With tetrabutylammomium bromide; sodium hydroxide In toluene
	With tetrabutylammomium bromide; sodium hydroxide In water; dimethyl sulfoxide at 100℃; for 12h;
	With tetrabutylammomium bromide; sodium hydroxide In water Inert atmosphere;
	With sodium hydroxide In dimethyl sulfoxide
	With sodium hydroxide In dimethyl sulfoxide Inert atmosphere;
	With potassium iodide; potassium hydroxide In dimethyl sulfoxide at 20℃;
	With sodium hydroxide In dimethyl sulfoxide
	With sodium hydroxide In dimethyl sulfoxide at 20℃;
	Stage #1: 2,7-dibromo-9H-fluorene With potassium hydroxide In dimethyl sulfoxide for 1h; Inert atmosphere; Stage #2: 1-bromo-octane In dimethyl sulfoxide at 90℃; for 24h; Inert atmosphere;	1.ii (ii) Synthesis of 2,7-dibromo-9,9-dioctyl-9H-fluorene (Compound (3)) (ii) Synthesis of 2,7-dibromo-9,9-dioctyl-9H-fluorene (Compound (3)) 2,7-dibromo-9H-fluorene and KOH is stirred with dimethyl sulfoxide under an inert gas (argon, Ar) for 1 hour, 1-bromoctane is slowly added thereto, and the mixture is refluxed at 90° C. for one day. Then, water is used to stop the reaction, diethylether is used to perform an extraction, and hexane in a mobile phase is used to purify an extract therefrom through column chromatography. Finally, ethanol (100 mL) and chloroform (10 mL) are used to perform recrystallization, obtaining the Compound (3).
	Stage #1: 2,7-dibromo-9H-fluorene With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water; dimethyl sulfoxide at 20℃; Stage #2: 1-bromo-octane In water; dimethyl sulfoxide for 3h;	2 Example 2 Preparation of 2,7-dibromo-9,9-dioctylfluorene To a three-necked flask was added 2,7-dibromofluorene (9.7 g, 0.03 mol)Benzyltriethylammonium chloride (0.07 g,0.3 mmol), dimethylsulfoxide (90 mL) and 45 mL aqueous sodium hydroxide (50 wt%) were added and stirred at room temperature to form a suspension.1-bromoisoctane (12.5 g, 65 mmol) was added, stirring was continued for 3 hours, then extracted with ether; washed with saturated aqueous sodium chlorideEther phase, dried over anhydrous magnesium sulfate; the solvent was evaporated and the product was purified by petroleum ether as eluent column chromatography to give a white solid
	Stage #1: 2,7-dibromo-9H-fluorene With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water; dimethyl sulfoxide at 20℃; Stage #2: 1-bromo-octane In water; dimethyl sulfoxide for 3h;	3 Example 3Preparation of 2,7-dibromo-9,9-dioctylfluoreneThe chemical reaction equation is as follows: To the three-necked flask was added 2,7-dibromofluorene (9.7 g, 0.03 mol)Benzyltriethylammonium chloride (0.07 g, 0.3 mmol),Dimethyl sulfoxide 90 mL and 45 mL aqueous sodium hydroxide solution (50 wt%),Stirring at room temperature to form a suspension;Join1-bromoN-octane(12.5 g, 65 mmol), Stirring was continued for 3 hours, followed by extraction with diethyl ether,The ether phase was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate,The solvent was distilled off and the product was purified by petroleum ether as eluant column chromatography, A white solid. 1H NMR, 13CNMR, MS and elemental analysis showed that the resulting compound was the target product.
	With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water; dimethyl sulfoxide at 20℃; for 3h;	3 Preparation of 2,7-dibromo-9,9-dioctylfluorene To the three-necked flask was added 2,7-dibromofluorene (9.7 g, 0.03 mol), Benzyltriethylammonium chloride (0.07 g, 0.3 mmol), Dimethyl sulfoxide 90 mL and 45 mL aqueous sodium hydroxide solution (50 wt%), stirring at room temperature to form a suspension; 1-bromoctane octane (12.5 g, 65 mmol) was added, After stirring for 3 hours, extracted with ether, the ether phase was washed with saturated aqueous sodium chloride solution, Dried over anhydrous magnesium sulfate, The solvent is distilled off, The product was purified by column eluting with petroleum ether as eluent to give a white solid.
	With tetraethylammonium bromide; sodium hydroxide In dimethyl sulfoxide at 20℃; for 24h; Inert atmosphere; Darkness;	1.2 2)Synthesis of 9,9-dioctyl-2,7-dibromoanthraquinone In a 100 mL three-necked flask, 2 g of 2,7-dibromoanthracene, 2.66 g of bromooctane, and 0.0704 g were successively added.Tetraethylammonium bromide, 2.4 g sodium hydroxide, and solvent dimethylsulfoxide 20 mL. Filled with nitrogen protection. The mixture was stirred for 24 h at room temperature under the condition of darkness, and the color of the solution was observed to be stopped from colorless change to dark green. After the reaction was completed, excess water and methylene chloride were added and extracted and separated. The methylene chloride layer was separately pickled, washed with water, and dried. After filtration, dichloromethane was distilled off under reduced pressure and recrystallized from ethanol to give light yellow needles,
	With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water; dimethyl sulfoxide at 20℃;	3 The chemical reaction equation is as follows: To a three-necked flask were added 2,7-dibromoanthraquinone (9.7 g, 0.03 mol), benzyltriethylammonium chloride (0.07 g, 0.3 mmol), dimethyl sulfoxide (90 mL), and 45 mL of aqueous sodium hydroxide solution (50 wt %), stirring at room temperature to form a suspension;Add 1-bromo-n-octane (12.5 g, 65 mmol), continue stirring for 3 hours, and extract with ether. Wash the ether phase with saturated aqueous sodium chloride, dry over anhydrous magnesium sulfate, and evaporate the solvent. The product is washed with petroleum ether. The derivatization column chromatography was used to obtain a white solid.
	With tetrabutylammomium bromide; sodium hydroxide In dimethyl sulfoxide at 20℃; for 12h;
	With tetra(n-butyl)ammonium hydroxide at 80℃;
	With tetrabutylammomium bromide; potassium hydroxide In water; dimethyl sulfoxide
	With potassium hydroxide In dimethyl sulfoxide
	With tetrabutylammomium bromide; sodium hydroxide In toluene
	With tetrabutylammomium bromide In N,N-dimethyl-formamide at 60℃; for 10h;
	With sodium hydroxide In toluene at 60℃;

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3
[ 61676-62-8 ]
[ 198964-46-4 ]
[ 196207-58-6 ]

Yield	Reaction Conditions	Operation in experiment
80%		Under argon protection,In a 500 mL long three-necked flask,Was added 2,7-dibromo-9,9-dioctylfluorene (21.9 g, 40 mmol)And 250 mL of anhydrous tetrahydrofuran,The reaction solution was cooled to -78 C with liquid nitrogen,A n-hexane solution of n-butyllithium (48 mL, 2.5 M, 120 mmol) was slowly added dropwise,After stirring at -78 C for 2 hours,2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (26 g, 140 mmol) was injected in one portion,Let it naturally rise to room temperature,Continue to react for 20 h.The reaction mixture was poured into water and extracted with methylene chloride. The mixture was washed five times. The organic phase was separated, dried, filtered and the solvent was dried. The residue was purified by column chromatography. The crude product was purified by silica gel as a stationary phase and petroleum ether / dichloromethane as the mobile phase. After purification, 43.8 g of a white solid was obtained in 80% yield.
80%		2,7-Dibromo-9,9-di-n-octyl fluorene (5.6 g, 10.2 mmol) was dissolved in 130 mL of anhydrous tetrahydrofuran, and 1.6 M n-butyllithium was added dropwise at -78 C in an argon atmosphere. N-hexane solution (20 mL, 32 mmol). The reaction was carried out at -78 C for 2 hours.Then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethanedioxyborate (25 mL, 123 mmol) was added rapidly, and the reaction was continued at -78 C for 1 hour. .The reaction was then allowed to warm to room temperature overnight. After the reaction is completed, the reaction solution is poured into water and quenched, extracted with dichloromethane, and washed with a sodium chloride aqueous solution.Dry over anhydrous magnesium sulfate. After concentration, it was recrystallized from tetrahydrofuran/methanol.Further purification by silica gel column chromatography (petroleum ether:Ethyl acetate = 9:1 as eluent) gave a white solid (5.1 g, 80%).
78%		2,7-dibromo-9,9-dioctyl-9H-fluorene (Compound e-2) after a round bottom flask containing a 1g and a tetrahydrofuran (Tetrahydrofuran) 200mL. at -78 was added a n-BuLi (2.0M in Hexane), and the mixture was stirred for 2 hours. Again at -78 2--4,4,5,5,--1,3,2-(2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) And then slowly added, after stirring for 2 hours and was stirred at room temperature for 48 hours, to complete the reaction. After completion of the reaction (quenching) with methanol and extracted with MC and the organic layer and aqueous NaCl (brine), remove the remaining water over anhydrous magnesium sulfate (MgSO4) and the solvent was evaporated, recrystallized from methanol and the MC 2,2 (9,9-dioctyl-9Hfluorene-2,7-diyl) a bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (compound E) was obtained. (Yield: 78%)

77%		argon protection, in the 500mL long three bottles,Was added 2,7-dibromo-9,9-dioctylfluorene (21.9 g, 40 mmol) and anhydrous tetrahydrofuran (250 mL)The reaction solution was cooled to -78 C with liquid nitrogen,A n-hexane solution of n-butyllithium (48 mL, 2.5 M, 120 mmo 1) was slowly added dropwise,After stirring at -78 C for 2 hours,2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (26 g, 140 mmol) was injected in one portion,Let it naturally rise to room temperature,Continue to react for 20 h.Adding ammonium chloride aqueous solution quenching reaction,Rotate to evaporate most of the solvent,The reaction mixture was poured into water,And extracted with dichloromethane,Washed 5 times,Separation of organic phase,dry,After filtering the dry solvent,The crude product was purified by column chromatography (eluent: petroleum ether)Purification gave 19.8 g of a white solid,Yield about 77%.
74%		n-BuLi (2.5 M in hexane;2.4 mL, 6.0 mmol) was added slowly over 30 min to astirred solution of 2,7-dibromo-9,9-dioctylfluorene (1.5 g,2.7 mmol) in dry tetrahydrofuran (70 mL) at -78 C. Themixture was stirred for 1 h at the same temperature andthen 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.7 mL, 8.2 mmol) was added slowly. The mixturewas allowed to warm up slowly to room temperatureand stirred vigorously for overnight. The reaction wasquenched with water and the residue was extracted withdichloromethane. The combined organic phase was driedover MgSO4 and evaporated under reduced pressure. Thecrude product was purified by flash chromatography onsilica gel and recrystallized from acetone to give the titlecompound as colourless crystals (1.3 g, 74%). 1H NMR(CDCl3, 300 MHz) [ppm]: 7.83 (d, 2 H), 7.74-7.72(m, 4 H), 1.96 (m, 4 H), 1.42 (s, 24 H), 1.26-1.05(m, 20 H), 0.81 (t, 6 H), 0.62 (m, 4 H); 13C NMR (CDCl3,75 MHz) [ppm]: 150.5, 143.5, 133.3, 128.6, 119.4,119.3, 83.7, 55.5, 40.1, 31.8, 29.8, 29.1, 29.0, 24.9, 23.7,22.7, 14.1.
70%		(2) Under an argon atmosphere,2,7-dibromo-9,9-dioctylfluorene (5 g, 10.65 mmol) was dissolvedIn 180 mL of purified THF, 28 mL of 1.6 mol of L-1 n-butyllithium was gradually added dropwise at -78 C,The reaction was carried out for 2 hours,Then, 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added, and the reaction was continued at -78 C for 1 hour. The reaction was allowed to proceed to room temperature for 24 hours . The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed thoroughly with brine and dried over anhydrous magnesium sulfate. After concentrating, the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 20/1, v / v)The product was left in the freezer for a long time to give a white solid in 70% yield.
70%		2,7-dibromo-9,9-dioctylfluorene (5 g, 10.65 mmol) was dissolved in 180 mL of purified THF under argon atmosphere and 1.6 mol of L-1 was gradually added dropwise at -78 C N-butyllithium 28 mL, Reaction for 2 hours, Then, 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborane was added and the reaction was continued at -78 C for 1 hour. The temperature was raised to room temperature for 24 hours The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed thoroughly with brine and dried over anhydrous magnesium sulfate. After the solution was concentrated, a crude product was obtained as a pale yellow viscous solid which was purified by silica gel column chromatography The product was placed in a refrigerator to give a white solid in 70% yield. & Lt; / RTI & gt; 1H NMR, 13CNMR, MS and elemental analysis showed that the resulting compound was the target product, The reaction equation is as follows
70%		2,7-dibromo-9,9-dioctylfluorene (5 g, 9.12 mmol) was dissolved in 180 mL of purified THF under an argon atmosphere,A dropwise addition of 1.6 mol at -78 & lt; 0 & gt; C.L-1Of n-butyllithium (28 mL) was reacted for 2 hours and then 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborane was added at -78 C The reaction was continued for 1 hour,And then heated to room temperature for 24 hours; the reaction mixture was poured into water,Extracted with ethyl acetate, and the organic layer was completely washed with brine,Add anhydrous magnesium sulfate dry; solution concentrated,Get light yellow viscous thick,Purification by silica gel column chromatography (eluent selection of petroleum ether / ethyl acetate Ester = 15/1, v / v), the product was left in a refrigerator for a long time to give a white solid in 70% yield.
70%		Under argon atmosphere, 2,7-dibromo-9,9-dioctylfluorene (5 g, 9.12 mmol)Was dissolved in 180 mL of purified THF,A solution of 1.6 mol of L-1 of n-butyllithium (28 mL) was gradually added dropwise at -78 C,The reaction was carried out for 2 hours and then added2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, the reaction was continued at -78 C for 1 hour,And then heated to room temperature for 24 hours; the reaction mixture was poured into water,Extracted with ethyl acetate, and the organic layer was completely washed with brine,Add anhydrous magnesium sulfate dry; solution concentrated, get light yellow viscous thick,Purification by silica gel column chromatography (eluent selection of petroleum ether / ethyl acetate = 15/1, v / v) gave the product a long time in a refrigerator to give a white solid in 70% yield.1H NMR, 13CNMR, MS and elementsThe results show that the obtained compound is the target product.
70%		Under an argon atmosphere, 2,7-dibromo-9,9-dioctylfluorene (5 g, 9.12 mmol) was dissolved in 180 mL of purified tetrahydrofuran (THF), A solution of 1.6 mol of L-1 of n-butyllithium (28 mL) was gradually added dropwise at -78 C, reaction for 2 hours, then, 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborane was added, the reaction was continued at -78 C for 1 hour and then allowed to warm to room temperature for 24 hours; The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed thoroughly with brine and dried over anhydrous magnesium sulfate. After the solution was concentrated, a crude product was obtained as a pale yellow viscous and purified by silica gel column chromatography The product was allowed to stand for a long time in a refrigerator to give a white solid in 70% yield.
70%		2,7-Dibromo-9,9-di-n-octylfluorene (5.6 g, 10.22 mmol) was dissolved in 130 mL of dry tetrahydrofuran. Under argon atmosphere, a 1.6 M n-butyllithium solution (20 mL, 32 mmol) was added dropwise at -78 C, and the mixture was reacted at -78 C for 2 hours. Then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethanedioxyborate (25 mL, 123 mmol) was quickly added and the reaction was continued for an additional 40 minutes. The reaction was gradually warmed to room temperature for 36 hours. After the reaction was completed, the reaction mixture was poured into water, extracted with dichloromethane, washed with brine, driedDry over magnesium sulfate. The solvent was evaporated and the residue was recrystallized from tetrahydrofuran / methanol. Further purification by silica gel column chromatography (petroleum ether: ethyl acetate = 9: 1) gave a white solid powder (4.59 g, 70%).
70%		(2) 2,7-dibromo-9,9-dioctylfluorene (5 g, 10.65 mmol) was dissolved in 180 mL of purified tetrahydrofuran (THF) under an argon atmosphere. 1.0 mL of n-butyllithium 28 mL was gradually added dropwise at -78 C. Reaction for 2 hours,Then add 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The reaction was continued at -78 C for 1 hour and warmed to room temperature for 24 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was completely washed with brine and dried over anhydrous magnesium sulfate; the solution was concentrated. Obtained as a pale yellow viscous crude product, which was purified by silica gel column chromatography (eluent selected petroleum ether/ethyl acetate=20/1, v/v) and the product was placed in a refrigerator to obtain a white solid with a yield of 70%.
70%		Under an argon atmosphere, 2,7-dibromo-9,9-dioctylfluorene (5 g, 9.12 mmol) was dissolved in 180 mL of purified tetrahydrofuran (THF).A 28 mL portion of n-butyllithium 1.6 mol.L-1 was gradually added dropwise at -78C and reacted for 2 hours.Then 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added, the reaction was continued at -78C for 1 hour, and then the temperature was raised to room temperature. hour;The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was completely washed with brine and dried over anhydrous magnesium sulfate. After the solution was concentrated, a pale yellow viscous crude product was obtained and purified by silica gel column chromatography (eluting The agent was selected from petroleum ether/ethyl acetate = 15/1, v/v) and the product was left in the refrigerator for a long time to obtain a white solid with a yield of 70%.
70%		(2) 2,7-dibromo-9,9-dioctylfluorene (5 g, 10.65 mmol) was dissolved in 180 mL of purified THF under an argon atmosphere.1.6 mL of L-1 n-butyllithium 28 mL was gradually added dropwise at -78 C for 2 hours.Then 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolanewas added, and the reaction was continued at -78 C for 1 hour.Raising to room temperature for 24 hours;The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate.After concentrating the solution, a pale yellow viscous crude was obtained, which was purified by silica gel column chromatography (eluent petroleum ether / ethyl acetate = 20/1, v/v)The product was placed in a refrigerator to give a white solid, yield 70%.
70%		Under argon atmosphere, dissolve 2,7-dibromo-9,9-dioctylfluorene (5g, 10.65mmol) in 180mL of purified THF, and gradually add 1.6mol L dropwise at -78 -1 n-butyl lithium 28mL, after 2 hours of reaction, add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 25mL, at -78 The reaction was continued for 1 hour at , and the temperature was raised to room temperature for 24 hours; the reaction mixture was poured into water, extracted with ethyl acetate, the organic layer was washed with brine, dried over anhydrous magnesium sulfate; after the solution was concentrated, a pale yellow The viscous crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 20/1, v / v), and allowed to stand for refrigeration to obtain a white solid with a yield of 70%
65%		Example 1, this Example discloses the organic semiconductor material polymer P1, P2 with the following formula: [0048] The preparation method of P1, P2 is described as follows: [0049] Step one, preparation of 2,7 - bis (4,4,5,5 - tetramethyl-1 ,3,2 - dioxaborolan -yl) -9,9 - dioctylfluorene: [0050] Anhydrous anaerobic reactor was assembled, under a continuing stirring and N2 protection, white 9.0mmol of 2,7 - dibromo-9 ,9 - dioctylfluorene were added into a three-necked flask, 150mL of refined tetrahydrofuran solvent was added by a syringe, 27.0 mmol of n-BuLi was added by a syringe under a temperature of -78C, the mixture was stirred for 2 hours. Then, 30.6mmol of 2 - isopropoxy-4, 4, 5, 5 - tetramethyl-1, 3, 2 - two hetero oxygen pentaborane was added by a syringe under a temperature of -78C, the temperature was raised to 20C, and the reaction was carried out for 14 hours. [0051] After the reaction was finished, a saturated aqueous NaCl solution was added, extracted with chloroform, dried by anhydrous sodium sulfate, suction filtered, and the filtrate was collected and solvent was rotary evaporated. The raw product was finally refined by a silica gel column chromatography using petroleum ether: ethyl acetate (v/v=15:1) as eluent to obtain powdered solid 2, 7 - bis (4,4,5,5 - tetramethyl-1 ,3,2-dioxaborolan -yl) -9,9 - dioctylfluorene in a yield of 65%. GC-MS (EI-m/z): 642 (M+).
65%		Anhydrous anaerobic reactor was assembled, under a continuing stirring and N2 protection, white 9.0mmol of2, 7- dibromo-9 , 9- dioctylfluorene were added into a three-necked flask, 150mL of refined tetrahydrofuran solvent wasadded by a syringe, 27.0 mmol of n-BuLi was added by a syringe under a temperature of -78C, the mixture was stirredfor 2 hours. Then, 30.6mmol of 2- isopropoxy-4, 4, 5, 5-tetramethyl-1, 3, 2- dioxaborolane was added by a syringe undera temperature of -78C, the temperature was raised to 20C, and the reaction was carried out for 14 hours.[0051] After the reaction was finished, a saturated aqueous NaCl solution was added, extracted with chloroform, driedby anhydrous sodium sulfate, suction filtered, and the filtrate was collected and solvent was rotary evaporated. The rawproduct was finally refined by a silica gel column chromatography using petroleum ether: ethyl acetate (v/v=15:1) aseluent to obtain powdered solid 2, 7- bis (4, 4, 5, 5-tetramethyl-1,3,2- the dioxaborolan- yl) -9, 9- dioctylfluorene in ayield of 65%. GC-MS (EI-m/z) : 642 (M+).
		Specific preparation process is described as follows: in the presence ofnitrogen and at the temperature of -78 C., adding 23.00 mE (2.00 M) n-butyl lithium solution with injector into2-neck flask containing 11.00 g 2,7-dibromo-9,9-dioctylfluo-rene and 100 mE tetrahydrofuran, afier a two-hour stirring, dripping 9.80 mE 2-isopropoxy-4,4,5,5-tetramethyl- 1,3,2- dioxaborolane slowly, stirring for 25 hours when it returns to room temperature. After the reaction, pouring reacting solution into water, extracting with diethyl ether, drying with anhydrous magnesium sulfate, rotary evaporating, separating by colunm chromatography to obtain solid products. The test result is: MAEDI-TOF-MS (mlz): 642.6 (Mj.

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4
[ 198964-46-4 ]
[ 1066-54-2 ]
[ 380600-92-0 ]

Yield	Reaction Conditions	Operation in experiment
94.05%	With copper(l) iodide; triethylamine; triphenylphosphine for 12h; Reflux;
76%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20 - 80℃; for 25h; Inert atmosphere;	4 Into a 100mL three-necked flask, added the compound 2, 7-dibromo-9, 9-dioctylfluorene (3.0g, 5.5mmol), CuI (0.217g, 1.14mmol), PdCl2 (PPh3)2 (0.53g, 0.55mmol) and triethylamine (50mL), evacuated, pass through the argon protection, slowly added the drops of Trimethyl silylacetylene (3.1mL, 22mmol) at room temperature. Stir for 1 h at room temperature, and then temperature is raised at 80 ° C and carries on reaction for 24 h. The reaction stopped, extracted with dichloromethane, washed with saturated brine, and dried over anhydrous magnesium sulfate. Filtration, the filtrate rotary evaporation to remove the solvent, the crude product is purified by silica gel (200-300 mesh) column chromatography [eluent, petroleum ether] and then obtained white solid 2.44g, yield 76%.
76%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 80℃; for 24h; Inert atmosphere;	2.4.3. Synthesis of compound 6 According to the modified literature [57], to the mixture ofcompound 5 (3.0 g, 5.5 mmol), Pd (PPh3)2Cl2 (0.53 g, 0.55 mmol)and CuI (0.217 g, 1.1 mmol) in Et3N (50 mL) was added trimethylsilylacetylene(3.1 mL, 22 mmol). The resulting suspension wasstirred at 80 °C for 24 h under argon atmosphere. The progress ofthe reaction was monitored by TLC using hexane:CH2Cl2 as theeluent. After cooled to room temperature, the reaction mixture wasfiltered and the filtrate was evaporated to dryness. The solid obtainedwas dissolved in CH2Cl2, washed with brine, dried withanhydrous MgSO4 and filtered. Solvents were removed underreduced pressure and the crude residue was further purified bycolumn chromatography (hexane as eluent) to afford the compound6 as a white solid (2.44 g, yield: 76%). 1H NMR (400 MHz,CDCl3): δ 7.59 (d, J = 7.8 Hz, 2H), 7.45 (d, J = 7.9 Hz, 2H), 7.41 (s, 2H),1.96-1.89 (m, 4H), 1.24-1.00 (m, 20H), 0.82 (t, J = 7.1 Hz, 6H), 0.51(s, 4H), 0.28 (s, 18H). 13C NMR (101 MHz, CDCl3): δ 150.94, 140.87,131.24, 126.22, 121.73, 119.86, 106.09, 94.26, 55.24, 40.36, 31.81, 29.99, 29.26, 23.60, 22.62, 14.12, 0.07.

72%	With copper(l) iodide; Pd(PPh₃)(OAc)2 In tetrahydrofuran for 16h; Heating;
70%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine In toluene Inert atmosphere; Stage #2: trimethylsilylacetylene With diisopropylamine at 70℃; for 6h; Inert atmosphere;
61%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 70℃; for 24h; Reflux;
44%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 80℃; for 5h; Inert atmosphere; Stage #2: trimethylsilylacetylene for 5h; Heating;
44%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 80℃; for 5h; Inert atmosphere; Stage #2: trimethylsilylacetylene for 5h; Reflux;	Bis(trimethylsilylethynyl)-9,9-dioctyl-9H-fluorene.- 2,7-Dibromo-9,9-dioctyl-9H-fluorene (TCI, Japan) (5 mmol, 2.74 g),bis(triphenylphosphino)palladium(II) dichloride ((Sigma Aldrich))(6 mol %, 0.210 g), copper iodide (TCI, Japan) (6 mol %, 0.057 g)were taken in round bottom flask under nitrogen atmosphere. To this, dehydrated triethylamine (TCI, Japan) (125 ml) was added and theresulting solution was heated at 80C for 5 hrs. With continuousstirring of the above reaction mixture, trimethylsilylacetylene (TCI,Japan) (1.77 ml, 12.7 mmol) was added dropwise and the reactionmixture was refluxed for 5 hrs. After the reaction mixture wascooled down to room temperature, the product was extracted withdiethylether (3 × 20 ml) and washed with water (3 × 20 ml). Thecombined organic layer was dried with magnesium sulfate andthe product was concentrated by evaporating the solvent on rotaryevaporator. The concentrate was dissolved in n-hexane and thedesired compound was separated by column chromatography afteradsorbing it on silica gel using pure n-hexane as an eluent. Theproduct obtained after separation was viscous yellow liquid whichwas solidified after keeping it overnight for cooling in the refrigerator.(Yield-1.283 g, 2.19 mmol, 44%).
	With copper(l) iodide; tetrakis(triphenylphosphine) palladium⁽⁰⁾; diisopropylamine
	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine at 50℃; for 20.3333h; Inert atmosphere; Glovebox; Sealed tube;
	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide at 70℃;

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[2]Current Patent Assignee: DONGGUAN UNIVERSITY OF TECHNOLOGY - CN106632438, 2017, A Location in patent: Paragraph 0068
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5
[ 198964-46-4 ]
[ 258865-48-4 ]
poly(9,9-dioctylfluorene), M_n: 7.9, M_w: 13.7, PDI: 1.73, DP: 20.3; T_g: 51 deg C; monomer(s): 2,7-dibromo-9,9-dioctylfluorene; 9,9-dioctylfluorene-2,7-diboronic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate In toluene Heating; Suzuki coupling;

Reference： [1]Ding, Jianfu; Day, Michael; Robertson, Gilles; Roovers, Jacques [Macromolecules, 2002, vol. 35, # 9, p. 3474 - 3483]

6
[ 198964-46-4 ]
[ 258865-48-4 ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 4.5h; Inert atmosphere; Stage #2: With Triisopropyl borate In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere;
65%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In diethyl ether at -78 - 20℃; Stage #2: With Triisopropyl borate In diethyl ether at 20℃; for 20h; Stage #3: With hydrogenchloride In diethyl ether at 20℃; for 1h;
31%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With iodine; magnesium In tetrahydrofuran Heating; Stage #2: With triethyl borate In tetrahydrofuran at 20℃; for 48h; Further stages.;

	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Stage #2: With Triisopropyl borate In tetrahydrofuran; hexane at -78 - 20℃; Stage #3: With hydrogenchloride In tetrahydrofuran; hexane; water
	Multi-step reaction with 2 steps 1.1: Mg; iodine / tetrahydrofuran 1.2: tetrahydrofuran / -78 - 20 °C 2.1: 4.3 g / aq. H₂SO₄ / cooling
	Multi-step reaction with 2 steps 1.1: n-butyllithium / tetrahydrofuran; hexane / 0.5 h / -78 °C / Inert atmosphere 1.2: 1 h / -78 °C 2.1: hydrogenchloride / tetrahydrofuran; hexane

Reference： [1]Location in patent: experimental part Zhu, Haifeng; Tong, Hui; Gong, Yongyang; Shao, Shiyang; Deng, Chunmei; Yuan, Wang Zhang; Zhang, Yongming [Journal of Polymer Science, Part A: Polymer Chemistry, 2012, vol. 50, # 11, p. 2172 - 2181]
[2]Ding, Jianfu; Day, Michael; Robertson, Gilles; Roovers, Jacques [Macromolecules, 2002, vol. 35, # 9, p. 3474 - 3483]
[3]Chen, Xiwen; Liao, Jin-Long; Liang, Yongmin; Ahmed; Tseng, Hao-En; Chen, Show-An [Journal of the American Chemical Society, 2003, vol. 125, # 3, p. 636 - 637]
[4]Xin, Yu; Wen, Gui-An; Zeng, Wen-Jing; Zhao, Lei; Zhu, Xing-Rong; Fan, Qu-Li; Feng, Jia-Chun; Wang, Lian-Hui; Wei, Wei; Peng, Bo; Cao, Yong; Huang, Wei [Macromolecules, 2005, vol. 38, # 16, p. 6755 - 6758]
[5]Liu, Shu-Juan; Zhao, Qiang; Chen, Run-Feng; Deng, Yun; Fan, Qu-Li; Li, Fu-You; Wang, Lian-Hui; Huang, Chun-Hui; Huang, Wei [Chemistry - A European Journal, 2006, vol. 12, # 16, p. 4351 - 4361]
[6]Yang, Chao; Zheng, Meng; Li, Yiping; Zhang, Deteng; Xue, Shanfeng; Yang, Wenjun [Journal of Polymer Science, Part A: Polymer Chemistry, 2014, vol. 52, # 7, p. 944 - 951]

7
[ 75-77-4 ]
[ 198964-46-4 ]
[ 620624-94-4 ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In diethyl ether; hexane at -10℃; for 3h; Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at 20℃; Further stages.;
94%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In diethyl ether; hexane at -70 - 20℃; for 1h; Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at -70 - 20℃;
94%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1.5h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at 20℃;

71%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.333333h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at 20℃;
	With n-butyllithium

Reference： [1]Jeeva, Shezhad; Moratti, Stephen C. [Synthesis, 2007, # 21, p. 3323 - 3328]
[2]Li, Binsong; Li, Jing; Fu, Yaqin; Bo, Zhishan [Journal of the American Chemical Society, 2004, vol. 126, # 11, p. 3430 - 3431]
[3]Location in patent: experimental part Ren, Shijie; Zeng, Danli; Zhong, Hongliang; Wang, Yaochuan; Qian, Shixiong; Fang, Qiang [Journal of Physical Chemistry B, 2010, vol. 114, # 32, p. 10374 - 10383]
[4]Jacob, Josemon; Sax, Stefan; Piok, Thomas; List, Emil J. W.; Grimsdale, Andrew C.; Mullen, Klaus [Journal of the American Chemical Society, 2004, vol. 126, # 22, p. 6987 - 6995]
[5]Sandee, Albertus J.; Williams, Charlotte K.; Evans, Nicholas R.; Davies, John E.; Boothby, Clare E.; Koehler, Anna; Friend, Richard H.; Holmes, Andrew B. [Journal of the American Chemical Society, 2004, vol. 126, # 22, p. 7041 - 7048]

8
[ 33513-42-7 ]
[ 198964-46-4 ]
[ 534600-14-1 ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In tetrahydrofuran at -78 - 20℃; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -78 - 20℃;
61%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In diethyl ether; hexane at -78 - 20℃; for 1h; Stage #2: N,N-dimethyl-formamide In hexane; acetone at -78 - 20℃;
58%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In tetrahydrofuran at -78℃; for 1.5h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -78 - 20℃; Inert atmosphere; Stage #3: With hydrogenchloride In tetrahydrofuran; water at 0℃; for 0.5h;

33%

Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 1h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; hexane at 20℃; Inert atmosphere;

Reference： [1]Location in patent: scheme or table Zhou, Huipeng; Zhao, Xin; Huang, Tianhao; Lu, Ran; Zhang, Hanzhuang; Qi, Xiaohui; Xue, Pengchong; Liu, Xingliang; Zhang, Xiaofei [Organic and Biomolecular Chemistry, 2011, vol. 9, # 5, p. 1600 - 1607]
[2]Li, Binsong; Li, Jing; Fu, Yaqin; Bo, Zhishan [Journal of the American Chemical Society, 2004, vol. 126, # 11, p. 3430 - 3431]
[3]Location in patent: experimental part Barik, Satyananda; Friedland, Sayuri; Skene [Canadian Journal of Chemistry, 2010, vol. 88, # 9, p. 945 - 953]
[4]Location in patent: experimental part Firstenberg, Michal; Shivananda, Kammasandra Nanjunda; Cohen, Irit; Solomeshch, Olga; Medvedev, Vladislav; Tessler, Nir; Eichen, Yoav [Advanced Functional Materials, 2011, vol. 21, # 4, p. 634 - 643]

9
[ 61676-62-8 ]
[ 198964-46-4 ]
[ 620624-96-6 ]

Yield	Reaction Conditions	Operation in experiment
63%	With n-butyllithium In tetrahydrofuran for 20h; Inert atmosphere;
51%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In diethyl ether; hexane at -78 - 0℃; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In diethyl ether; hexane at -78 - 20℃; for 19h;
49%	Stage #1: 2,7-dibromo-9,9-dioctylfluorene With n-butyllithium In diethyl ether at -78℃; for 1h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In diethyl ether at -78℃; for 1h; Inert atmosphere;

Reference： [1]Li, Zhongjing; Sun, Wenfang [Dalton Transactions, 2013, vol. 42, # 38, p. 14021 - 14029]
[2]Sandee, Albertus J.; Williams, Charlotte K.; Evans, Nicholas R.; Davies, John E.; Boothby, Clare E.; Koehler, Anna; Friend, Richard H.; Holmes, Andrew B. [Journal of the American Chemical Society, 2004, vol. 126, # 22, p. 7041 - 7048]
[3]Location in patent: experimental part Gutacker, Andrea; Lin, Chi-Yen; Ying, Lei; Nguyen, Thuc-Quyen; Scherf, Ullrich; Bazan, Guillermo C. [Macromolecules, 2012, vol. 45, # 11, p. 4441 - 4446]

10
[ 106-49-0 ]
[ 198964-46-4 ]
poly(iminoarylene), M_n = 12 300, M_w = 29 100; monomer(s): 2,7-dibromo-9,9-di-n-octylfluorene; p-toluidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃; for 36h;

Reference： [1]Jung, Byung-Jun; Lee, Jeong-Ik; Chu, Hye Yong; Do, Lee-Mi; Shim, Hong-Ku [Macromolecules, 2002, vol. 35, # 6, p. 2282 - 2287]

11
[ 198964-46-4 ]
[ 196207-58-6 ]
[ 444579-39-9 ]
polymer, M_n 16 kg/mol, M_w/M_n 2.7 by GPC; monomer(s): 2,7-dibromo-9,9-dioctylfluorene; 4,7-bis(5-bromo-4-hexyl-2-thienyl)-2,1,3-benzothiadiazole; 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene [ No CAS ]