(2,7-BIS(4,4,5,5-TETRAMETHYL-1,3,2-DIOXABOROLAN-2-YL)-9,9-DIOCTYLFLUORENE)

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 80percent yield.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: 78percent)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 77percent.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, 74percent). 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.(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 70percent yield.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 70percent 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 follows2, 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 70percent yield.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 70percent yield.1H NMR, 13CNMR, MS and elementsThe results show that the obtained compound is the target product.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 70percent yield.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, 70percent).(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 70percent.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 -78°C 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 -78°C 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 70percent.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 NAnhydrous 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 -78°C, 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 -78°C, the temperature was raised to 20°C, 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 65percent. GC-MS (EI-m/z) : 642 (M+).(4) Synthesis of Intermediate 1c (2, 7- bis(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolyl)-9, 9-dioctylfluorene) The compound synthesized in the previous step (2.23 g, 4.08 mmol) was added to a 250 mL three-necked flask equipped with a spherical condenser.Bispinol ester boron ester (3.20g, 12.56mmol), Anhydrous potassium acetate (3.20 g, 32.00 mmol)160mL anhydrous 1, 4 dioxane, Vacuum the system and replace the argonPd(dppf)Cl2 (0.28 g, 0.40 mmol) was added under an argon atmosphere.Stir at 80 ° C overnight. After the system is cooled to room temperature, Add 100 mL of distilled water to the reaction solution for dilution.Then extracted with CH2Cl2 (200 mL×6), Washed with saturated brine (200 mL×6), dried over anhydrous magnesium sulfate and filtered.Rotate the solvent, The residue was subjected to silica gel column chromatography [eluent, V ( petroleum ether): V (ethyl acetate) = 20:1]Purified white solid intermediate2 (1.89g), The yield was 72percent.2, 7-dibromo-9, 9-dioctylfluorene (32.85 g, 60 mmol) was placed under argon atmosphere.Bis-pinacol boronate (45 · 7g, 0 · 18mol), potassium acetate (17 · 67g, 0 · 18mol), 1, 1'-bis (diphenylphosphino) ferrocene palladium chloride (PdCl2 (dppf)) (4.90 g, 6 mmol) and 300 ml of solvent dioxane were added into the reaction flask and heated to a temperature of 90° C. for 6 hours. After termination of the reaction, potassium acetate was filtered off, and the organic phase was concentrated and purified by silica gel column chromatography. Petroleum ether and methylene chloride combined solvent (4/1, v/v) was eluted to give a beige solid. Yield: 63

Molecular Weight:642.6
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:16
Exact Mass:642.4990709
Monoisotopic Mass:642.4990709
Topological Polar Surface Area:36.9
Heavy Atom Count:47
Complexity:884
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes