* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
3) Synthesis of a compound 3 The compound 2 (10.6 mmol, 5 g) was dissolved in 150 ml of chloroform and cooled to 0°C, bromine (21.19 mmol, 3.39 g) was slowly dropped thereon, and agitation was conducted for 3 hours. After the reaction, 50 ml of 2 M potassium hydroxide was injected into the reaction vessel to bring about neutralization. The reactants were then washed three times using distilled water. Next, an organic layer was separated and subjected to vacuum distillation, and the resulting solid was recrystallized using a mixed solution of chloroform and ethanol to produce a compound 3 (9.01 mmol, 5.65 g) (Yield 85 percent).
2) Synthesis of a compound 2 After the compound 1 (14.28 mmol, 7 g) was dissolved in 70 ml of acetic acid, three drops of concentrated HCl were added thereto, and refluxing was conducted for 12 hours. After the reaction, the resulting mixture was slowly dropped into 250 ml of water to produce a precipitate. After the precipitate was dried, purification was conducted using a developer having hexane and ethyl acetate in a volume ratio of 10:1 to produce a compound 2 (12.72 mmol, 6 g) (Yield 89 percent).
86%
at 120℃; for 24 h;
Under the protection of argon, add 2,7-dibromofluorenone 10 mmol to the reaction flask.11mmol of 2-fluorobiphenyl and 20ml of tetrahydrofuran solvent, after stirring evenly,22 mmol of lithium metal tablets were added to the reaction solution in batches.Then, the temperature is raised to about 40 ° C, and the reaction is carried out for 24 hours.After the reaction was completed and returned to room temperature, the reaction was quenched with 20 mL of 1N aqueous hydrochloric acid.The organic phase was separated, and the tetrahydrofuran was evaporated to dryness on a rotary evaporator.The crude solid was added to 10 ml of acetic acid.Heating to 120 ° C for 24 hours, after the end of the ring closure reactionFiltration gave crude 2,7-dibromo-9,9'-spirobifluorene.The crude product uses a mixed solvent of dichloromethane and n-hexane as an eluent.Perform column chromatography separation, and the chromatographic silica gel is 200-300 mesh.Finally, the product 2,7-dibromo-9,9'-spirobifluorene 4.08g was obtained.The yield was 86percent.
82%
With hydrogenchloride; acetic acid In water for 1 h; Reflux
2-iodobiphenyl 1mol was dissolved in THF after the dropwise addition of n-BuLi at -78 a stirred for 1 hour After dropwise dissolving 2,7-dibromo-9H-fluoren-9-one 1mol in THF. The temperature was raised to room temperature and then stirred for one hour to confirm the completion of the reaction and extracted with CH2Cl2 and 1N HCl. The organic layer was dried over MgSO4 to give the Intermediate K was purified by column chromatography and recrystallized (yield 71percent). After the K intermediate was dissolved in acetic acid to complete the addition of concentrated hydrochloric acid for 1 hour under reflux reaction. It was extracted using ether and water and the organic layer was washed with mwot Sat NaHCO3. The organic layer was dried over MgSO4 and purified by column chromatography and recrystallization to give the intermediate L (Yield 82percent).
80%
With sulfuric acid In toluene at 20℃; for 2 h;
To 180 g of a toluene solution of 9- (2-biphenyl) -2,7-dibromo-9-fluorene alcohol obtained in Example 3,Concentrated sulfuric acid 18.0 g (0.180 mol, 2.00 M.R.) was charged,The reaction was carried out at room temperature for 2 hours.After caustic water was added to the obtained reaction mixture solution to neutralize it,Toluene was added to crystallize,By filtration and drying,35.9 g of 2,7-dibromo-9,9'-spirobifluorene as white crystals(Yield: 80percent, total yield from Example 3: 72percent, purity: 95percent).
57%
With hydrogenchloride In acetic acid at 50℃; Heating / reflux
22 g (45.0 mmol) of 9-biphenyl-2-yl-2,7-dibromo-9-fluorenol, and 100 mL of glacial acetic acid were placed in a 300 mL three-necked flask, several drops of concentrated hydrochloric acid were added, and the mixture was refluxed. After the reaction, the precipitates were filtered The precipitate was recrystallized with ethanol, and 12.3 g of 2,7-dibromo-spiro-9,9'-bifluorene was obtained as a white solid, in a yield of 57percent. [0359]A synthesis scheme (h-4) of 2,7-dibromo-9,9'-spiro-bifluorene is shown below. [0360]
Reference：
[1] Patent: EP1777227, 2007, A1, . Location in patent: Page/Page column 6-7
[2] Macromolecules, 2010, vol. 43, # 24, p. 10355 - 10365
[3] Patent: CN108863694, 2018, A, . Location in patent: Paragraph 0039; 0040
[4] Patent: KR101555155, 2015, B1, . Location in patent: Paragraph 0119; 0120; 0121; 0122
[5] Patent: JP6257340, 2018, B2, . Location in patent: Paragraph 0050
[6] Patent: WO2007/43354, 2007, A1, . Location in patent: Page/Page column 101
[7] Journal of the American Chemical Society, 2002, vol. 124, # 39, p. 11576 - 11577
[8] Journal of Organic Chemistry, 2002, vol. 67, # 14, p. 4924 - 4936
[9] Patent: US2011/54229, 2011, A1, . Location in patent: Page/Page column 32
[10] Advanced Functional Materials, 2010, vol. 20, # 23, p. 4152 - 4161
[11] Journal of the American Chemical Society, 2017, vol. 139, # 32, p. 11073 - 11080
[12] Chemical Communications, 2018, vol. 54, # 6, p. 642 - 645
3
[ 14348-75-5 ]
[ 100-58-3 ]
[ 583-53-9 ]
[ 171408-84-7 ]
Yield
Reaction Conditions
Operation in experiment
76.2%
Stage #1: at 80℃; for 12 h; Inert atmosphere Stage #2: for 2 h; Reflux Stage #3: With hydrogenchloride; acetic acid In 2-methyltetrahydrofuran; diethyl ether at 75℃; for 4 h;
A solution of 10 mL of o-dibromobenzene (0.1 mmol) in methyl tetrahydrofuran was added dropwise to a solution of 5 mL of phenylmagnesium bromide (0.11 mmol) in methyltetrahydrofuran under argon atmosphere at 80 ° C. Reaction 12 h. The reaction solution was then added dropwise to 10 mL of 2, 7-dibromofluorenone (0.1 mmol) in ether. The mixture was heated to reflux for 2 h, hydrolyzed and filtered. The solid was dissolved in 5 mL of mixed acid (glacial acetic acid and hydrochloric acid) (200-300 mesh silica gel) to give the product 2, 7-dibromo-9, 9 '-spirobifluorene , which was purified by column chromatography on silica gel eluted with a mixed solvent of methylene chloride and n-hexane.36 . 2 mg, yield 76.2percent. The resulting 2, 7-dibromo-9,9-spirobifluorene was reacted with lithium diphenylphosphine (0.15 mmol) in tetrahydrofuran solvent. After refluxing for 12 h, methanol was added to the reaction solution, (200-300 mesh silica gel) to obtain the desired product. 2-Bis (diphenylphosphino) -9, 9-spirobifluorene 35. 9 mg was obtained by the same procedure as that of Example 1, Mg, and the yield was 70.1percent.
Reference：
[1] Synthetic Communications, 2008, vol. 38, # 12, p. 1888 - 1895
[2] Chemistry - An Asian Journal, 2016, vol. 11, # 18, p. 2555 - 2563
[3] Angewandte Chemie - International Edition, 2018, vol. 57, # 22, p. 6696 - 6700[4] Angew. Chem., 2018, vol. 130, p. 6806 - 6810,5
[5] Chemical Communications, 2018, vol. 54, # 6, p. 642 - 645
5
[ 159-66-0 ]
[ 171408-84-7 ]
Reference：
[1] Patent: CN106946750, 2017, A, . Location in patent: Paragraph 0107; 0108; 0109; 0120; 0121; 0123; 0124
6
[ 14348-75-5 ]
[ 171408-84-7 ]
Reference：
[1] Journal of the American Chemical Society, 2002, vol. 124, # 39, p. 11576 - 11577
[2] Journal of Organic Chemistry, 2002, vol. 67, # 14, p. 4924 - 4936
[3] Patent: US2011/54229, 2011, A1,
[4] Macromolecules, 2010, vol. 43, # 24, p. 10355 - 10365
[5] Advanced Functional Materials, 2010, vol. 20, # 23, p. 4152 - 4161
[6] Patent: KR101555155, 2015, B1,
[7] Journal of the American Chemical Society, 2017, vol. 139, # 32, p. 11073 - 11080
7
[ 2052-07-5 ]
[ 6344-61-2 ]
[ 14348-75-5 ]
[ 171408-84-7 ]
Yield
Reaction Conditions
Operation in experiment
77%
With ammonium chloride; magnesium In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; diethyl ether; acetic acid
c 2,7-Dibromo-9,9'-spirobifluorene A Grignard reagent prepared from 0.72 g (30 mmol) of magnesium turnings and 5.1 ml (30 mmol) of 2-bromobiphenyl in 15 ml of diethyl ether was added dropwise while stirring (in an ultrasonic bath) to a boiling suspension of 10.0 g (29.6 mmol) of 2,7-dibromo-9-fluorenone in 100 ml of dry diethyl ether over a period of 2 hours. After addition was complete, the mixture was boiled for a further 3 hours. After cooling overnight, the precipitate formed was filtered off with suction and washed with cold ether. The magnesium complex which had been filtered off with suction was hydrolyzed in a solution of 15 g of ammonium chloride in 250 ml of ice water. After 1 hour, the 9-(2-biphenylyl)-2,7-dibromo-9-fluorenol formed was filtered off with suction, washed with water and sucked dry. For the ring closure reaction, the dried fluorenol was boiled in 100 ml of glacial acetic acid, after addition of 3 drops of 30 concentrated HCl, for 6 hours. The mixture was allowed to crystallize overnight, the product formed was filtered off with suction and washed with glacial acetic acid and water. Yield: 11 g (77percent) of 2,7-dibromo-9,9'-spirobifluorene. This was purified further by recrystallization from THF. 1H-NMR (CDCl3, ppm): 6.73 (d, J=7.63 Hz, 2 H, H-1',8'); 6.84 (d, J=1.83 Hz, 2 H, H-1,8); 7.15 (td, J=7.63, 1.22 Hz, 2 H, H-2',7'); 7.41 (td, J=7.63, 1.22 Hz, 2 H, H-3',6'); 7.48 (dd, J=8.24, 1.83 Hz, 2 H, H-3,6); 7.67 (d, J=8.24; 2 H; H-4,5); 7.85 (d, J=7.63, 2 H, H-4',5').
77%
With hydrogenchloride; ammonium chloride; magnesium In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; diethyl ether; acetic acid
Example 1 Synthesis of 2,7-dibromo-9,9'-spirobifluorene A Grignard reagent prepared from 0.72 g (30 mmol) of magnesium turnings and 5.1 ml (30 mmol) of 2-bromobiphenyl in 15 ml of diethyl ether is added dropwise over the course of 2 hours while stirring (in an ultrasonic bath) to a boiling suspension of 10.0 g (29.6 mmol) of 2,7-dibromo-9-fluorenone in 1 00 ml of dry diethyl ether. After addition is complete, the mixture is boiled for a further 3 hours. After cooling overnight, the precipitate formed is filtered off with suction and washed with cold ether. The magnesium complex filtered off is hydrolyzed in a solution of 15 g of ammonium chloride in 250 ml of ice water. After 1 hour, the 9-(2-biphenylyl)-2,7-dibromo-9-fluorenol formed is filtered off with suction, washed with water and sucked dry. For the ring closure reaction, the dried fluorenol is boiled in 100 ml of glacial acetic acid, after addition of 3 drops of concentrated hydrochloric acid, for 6 hours. The mixture is allowed to crystallize overnight, the product formed is filtered off with suction and washed with glacial acetic acid and water. Yield: 11 g (77percent) of 2,7-dibromo-9,9'-spirobifluorene. It can be further purified by recrystallization from THF. 1 H-NMR (CDCl3, ppm): 6.73 (d, J=7.63 Hz, 2H, H-1',8'); 6.84 (d, J=1.83 Hz, 2H, H-1,8); 7.15 (td, J=7.63, 1.22 Hz, 2H, H-2',7'); 7.41 (td, J=7.63, 1.22 Hz, 2H, H-3',6'); 7.48 (dd, J=8.24, 1.83 Hz, 2H, H-3,6); 7.67 (d, J=8.24; 2H; H-4,5); 7.85 (d, J=7.63, 2H, H-4',5').
77 %
With ammonium chloride; magnesium In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; diethyl ether; acetic acid
l) Synthesis of 2,7-dibromo-9,9'-spirobifluorene The Grignard reagent prepared from 0.72 g (30 mmol of magnesium turnings and 5.1 ml (30 mmol) of 2-bromobiphenyl in 15 ml of diethyl ether is added dropwise over a period of 2 hours, while stirring (in an ultrasonic bath), to a boiling suspension of 10.0 g (29.6 mmol) of 2,7 dibromo-9-fluorenone in 100 ml of dry diethyl ether. After the addition is complete, the mixture is boiled for a further 3 hours. After cooling overnight, the precipitated solid is filtered off with suction and washed with cold ether. The magnesium complex filtered off is hydrolyzed in a solution of 15 g of ammonium chloride in 250 ml of ice water. After 1 hour, the 9-(2-biphenylyl)-2,7-dibromo-9-fluorenol formed is filtered off with suction, washed with water and sucked dry. For the ring-closure reaction, the dried fluorenol is boiled in 100 ml of glacial acetic acid for 6 hours, after addition of 3 drops of concentrated HCI. The mixture is allowed to crystallize overnight, the product formed is filtered off with suction and is washed with glacial acetic acid and water. Yield: 11 g (77 percent) of 2,7-dibromo-9,9'-spirobifluorene. It can be further purified by recrystallization from THF. 1H-NMR (CDCl3, ppm): 6.73 (sd, J = 7.63 Hz, 2 H, H-1',8'); 6.84 (d, J = 1.83 Hz, 2 H, H-1,8); 7.15 (td, J = 7.63, 1.22 Hz, 2 H, h-2',7'); 7.41 (td, J = 7.63, 1.22 Hz, 2H, H-3',6'); 7.48 (dd, J = 8.24, 1.83 Hz, 2H, H-3,6); 7.67 (d, J = 8.24 Hz; 2 H; H-4,5); 7.85 (d, J= 7.63, 2H, H-4',5').
With iodine; bis-[(trifluoroacetoxy)iodo]benzene; In chloroform; at 20℃; for 12h;
92.0 g (194.1 mmol) of 2,7-dibromospirobifluorene were dissolved in 200 ml of CHCl3, after which 100.1 g (233 mmol) of bis(trifluoroacetoxy)iodobenzene and 59.0 g of I2 were added and the mixture was stirred at RT under nitrogen for 12 hours. The suspension was filtered, the residue washed with CHCl3 and recrystallized twice from 1,4-dioxane. The yield of the diiodated spirobifluorene was 121.4 g (86percent) at a purity of >99percent (1H-NMR). 1H NMR (DMSO-d6, 500 MHz)-8.04 (d, 3JHH=7.9 Hz, 2H), 7.88 (d, 3JHH=7.9 Hz, 2H), 7.82 (dd, 3JHH=7.9 Hz, 4JHH=1.5 Hz, 2H), 7.66 (dd, 3JHH=8.3 Hz, 4JHH=1.9 Hz, 2H), 6.98 (d, 4JHH=1.2 Hz, 2H), 6.83 (d, 4JHH=1.5 Hz, 2H).
2,7-bis(phenylethynyl)-9,9'-spyrobifluorene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
59.7%
With piperidine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; at 20 - 110℃; for 12h;
10 g (21.09 mmol) of 2.7-dibromo-9.9'-spyrobifluorene, 0.43 g (0.63 mmol) of bistriphenylphosphine palladium dichloride and 0.12 g (0.63 mmol) of copper iodide were put into a 500 ml three-neck round bottom flask equipped with a stirrer, a thermometer and a reflux condenser under an argon atmosphere, and then 300 ml of piperidine was added thereto so as to dissolve the resultant. 5.38 g (52.61 mmol) of phenylacetylene was gradually dropped thereto at room temperature. After completion of the dropping, the temperature of the reaction mixture was gradually raised to 110° C. and then stirred at 110° C. for 12 hours. When the reaction was completed, the reaction mixture was cooled down to room temperature. Generated salt was filtered off, and then the filtrate was concentrated under a reduced pressure. The residue was dissolved in dichloromethane, washed with water several times and then dried with anhydrous magnesium sulfate, which was then filtered off. The solvent was removed, and the residue was re-crystallized from a mixture of ethyl acetate and hexane to obtain yellow crystal, which was dried sufficiently in a vacuum oven at 40° C. to give 6.52 g (59.7percent yield) of [M-10], of which melting point was 210-212° C. 1H NMR (CDCl3), delta=6.74-6.78(d, 2H, aromatic), 6.90(s, 2H, aromatic), 7.10-7.18(t, 2H, aromatic), 7.24-7.28(m, 6H, aromatic), 7.36-7.42(m, 6H, aromatic), 7.52-7.57(d, 2H, aromatic) 7.79-7.88(t, 4H, aromatic).
With ammonium chloride; magnesium; In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; diethyl ether; acetic acid;
c 2,7-Dibromo-9,9'-spirobifluorene A Grignard reagent prepared from 0.72 g (30 mmol) of magnesium turnings and 5.1 ml (30 mmol) of 2-bromobiphenyl in 15 ml of diethyl ether was added dropwise while stirring (in an ultrasonic bath) to a boiling suspension of 10.0 g (29.6 mmol) of 2,7-dibromo-9-fluorenone in 100 ml of dry diethyl ether over a period of 2 hours. After addition was complete, the mixture was boiled for a further 3 hours. After cooling overnight, the precipitate formed was filtered off with suction and washed with cold ether. The magnesium complex which had been filtered off with suction was hydrolyzed in a solution of 15 g of ammonium chloride in 250 ml of ice water. After 1 hour, the 9-(2-biphenylyl)-2,7-dibromo-9-fluorenol formed was filtered off with suction, washed with water and sucked dry. For the ring closure reaction, the dried fluorenol was boiled in 100 ml of glacial acetic acid, after addition of 3 drops of 30 concentrated HCl, for 6 hours. The mixture was allowed to crystallize overnight, the product formed was filtered off with suction and washed with glacial acetic acid and water. Yield: 11 g (77percent) of 2,7-dibromo-9,9'-spirobifluorene. This was purified further by recrystallization from THF. 1H-NMR (CDCl3, ppm): 6.73 (d, J=7.63 Hz, 2 H, H-1',8'); 6.84 (d, J=1.83 Hz, 2 H, H-1,8); 7.15 (td, J=7.63, 1.22 Hz, 2 H, H-2',7'); 7.41 (td, J=7.63, 1.22 Hz, 2 H, H-3',6'); 7.48 (dd, J=8.24, 1.83 Hz, 2 H, H-3,6); 7.67 (d, J=8.24; 2 H; H-4,5); 7.85 (d, J=7.63, 2 H, H-4',5').
11 g (77%)
With hydrogenchloride; ammonium chloride; magnesium; In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; diethyl ether; acetic acid;
Example 1 Synthesis of 2,7-dibromo-9,9'-spirobifluorene A Grignard reagent prepared from 0.72 g (30 mmol) of magnesium turnings and 5.1 ml (30 mmol) of 2-bromobiphenyl in 15 ml of diethyl ether is added dropwise over the course of 2 hours while stirring (in an ultrasonic bath) to a boiling suspension of 10.0 g (29.6 mmol) of 2,7-dibromo-9-fluorenone in 1 00 ml of dry diethyl ether. After addition is complete, the mixture is boiled for a further 3 hours. After cooling overnight, the precipitate formed is filtered off with suction and washed with cold ether. The magnesium complex filtered off is hydrolyzed in a solution of 15 g of ammonium chloride in 250 ml of ice water. After 1 hour, the 9-(2-biphenylyl)-2,7-dibromo-9-fluorenol formed is filtered off with suction, washed with water and sucked dry. For the ring closure reaction, the dried fluorenol is boiled in 100 ml of glacial acetic acid, after addition of 3 drops of concentrated hydrochloric acid, for 6 hours. The mixture is allowed to crystallize overnight, the product formed is filtered off with suction and washed with glacial acetic acid and water. Yield: 11 g (77percent) of 2,7-dibromo-9,9'-spirobifluorene. It can be further purified by recrystallization from THF. 1 H-NMR (CDCl3, ppm): 6.73 (d, J=7.63 Hz, 2H, H-1',8'); 6.84 (d, J=1.83 Hz, 2H, H-1,8); 7.15 (td, J=7.63, 1.22 Hz, 2H, H-2',7'); 7.41 (td, J=7.63, 1.22 Hz, 2H, H-3',6'); 7.48 (dd, J=8.24, 1.83 Hz, 2H, H-3,6); 7.67 (d, J=8.24; 2H; H-4,5); 7.85 (d, J=7.63, 2H, H-4',5').
11 g (77%)
With ammonium chloride; magnesium; In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; diethyl ether; acetic acid;
l) Synthesis of 2,7-dibromo-9,9'-spirobifluorene The Grignard reagent prepared from 0.72 g (30 mmol of magnesium turnings and 5.1 ml (30 mmol) of 2-bromobiphenyl in 15 ml of diethyl ether is added dropwise over a period of 2 hours, while stirring (in an ultrasonic bath), to a boiling suspension of 10.0 g (29.6 mmol) of 2,7 dibromo-9-fluorenone in 100 ml of dry diethyl ether. After the addition is complete, the mixture is boiled for a further 3 hours. After cooling overnight, the precipitated solid is filtered off with suction and washed with cold ether. The magnesium complex filtered off is hydrolyzed in a solution of 15 g of ammonium chloride in 250 ml of ice water. After 1 hour, the 9-(2-biphenylyl)-2,7-dibromo-9-fluorenol formed is filtered off with suction, washed with water and sucked dry. For the ring-closure reaction, the dried fluorenol is boiled in 100 ml of glacial acetic acid for 6 hours, after addition of 3 drops of concentrated HCI. The mixture is allowed to crystallize overnight, the product formed is filtered off with suction and is washed with glacial acetic acid and water. Yield: 11 g (77 percent) of 2,7-dibromo-9,9'-spirobifluorene. It can be further purified by recrystallization from THF. 1H-NMR (CDCl3, ppm): 6.73 (sd, J = 7.63 Hz, 2 H, H-1',8'); 6.84 (d, J = 1.83 Hz, 2 H, H-1,8); 7.15 (td, J = 7.63, 1.22 Hz, 2 H, h-2',7'); 7.41 (td, J = 7.63, 1.22 Hz, 2H, H-3',6'); 7.48 (dd, J = 8.24, 1.83 Hz, 2H, H-3,6); 7.67 (d, J = 8.24 Hz; 2 H; H-4,5); 7.85 (d, J= 7.63, 2H, H-4',5').
3) Synthesis of a compound 3 The compound 2 (10.6 mmol, 5 g) was dissolved in 150 ml of chloroform and cooled to 0°C, bromine (21.19 mmol, 3.39 g) was slowly dropped thereon, and agitation was conducted for 3 hours. After the reaction, 50 ml of 2 M potassium hydroxide was injected into the reaction vessel to bring about neutralization. The reactants were then washed three times using distilled water. Next, an organic layer was separated and subjected to vacuum distillation, and the resulting solid was recrystallized using a mixed solution of chloroform and ethanol to produce a compound 3 (9.01 mmol, 5.65 g) (Yield 85 percent).
With tri-tert-butyl phosphine; sodium t-butanolate;bis(dibenzylideneacetone)-palladium(0); In hexane; toluene; at 80℃; for 6h;
5.0 g (10.6 mmol) of 2, 7-dibromo-spiro-9,9'-bifluorene, 7.4 g (21.0 mmol) of DPA, 63 mg (0.1 mmol) of bis(dibenzylideneacetone)palladium(0), and 3.6g (37 mmol) of t-butoxysodium were placed in a 300 mL three-necked flask, and nitrogen substitution was conducted. 100 mL of toluene was added to the mixture, and the mixture was degassed at reduced pressure. 0.05 mL of tri(t-butyl)phosphine (10 wtpercent hexane solution) was added, and the mixture was stirred for 6 hours at 8O0C. After the reaction, the mixture was filtered through Celite. The filtrate was washed 3 times with EPO <DP n="103"/>water and once with a saturated saline solution, then dried with magnesium sulfate. The reaction mixture was naturally filtered, and the filtrate was concentrated to obtain an oily product. This oily product was purified by silica gel column chromatography (hexane:ethyl acetate = 7:3), and recrystallized with chloroform and ethanol, giving 6.0 g of a pale yellow powdered solid in a yield of 57percent. It was confirmed that this pale yellow powdered solid was DPA2SF by a nuclear magnetic resonance method (NMR). [0363]1H NMR of the compound obtained is shown below. Also, a 1H NMR chart is shown in FIG. 27.1H NMR (300 MHz, DMSO-d6), delta=7.84 (d, J= 7.21 Hz, 2H), 7.77 (d, J= 7.80 Hz, 2H), 7.32-7 79 (m, 40H), 6.73 (d, J= 7.80 Hz, 2H), 6.16 (d, J= 2.10 Hz, 2H) [0364]A synthesis scheme (i-1) of DPA2SF is shown below. [0366]Sublimation purification was conducted on 2.0 g of the DPA2SF for 24 hours at a pressure of 6.7 Pa and a temperature of 3500C. 1.3 g was recovered, in a yield of 66percent.
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In toluene; for 24h;Reflux; Inert atmosphere;
Example 1 - Synthesis of 4,4'-(2l,7l-dibromo-9,9'-spirobi[fluorene]-2,7-diyl)dibenzonitrile (3); Step 1 - Synthesis of 4,41-(9,9'-spirobi[fluorene]-2,7-diyl)dibenzonitrile (2); To a mixture of <strong>[171408-84-7]2,7-dibromo-9,9'-spirobi[fluorene]</strong> (1 ) (1.76 g, 3.7 mmol) and 4- cyanophenylboronic acid (2.04 g, 13.9 mmol ), (PPh3)4Pd (0.23 g, 0.20 mmol) was added in a glovebox. Toluene (32 ml.) and 2M Na2CO3 (16 mL) was added into the mixture and heated to reflux with stirring in the dark for 24 h under the protection of nitrogen. After cooling to room temperature, the organic layer was separated and the aqueous layer was extracted with ethyl acetate (8OmL) twice. The combined organic layer was washed with water, brine and dried over sodium sulfate. The solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography with n- hexane/ethyl acetate (5:1 ) as eluent to give (2) as a white powder (1.94g, 77.5 percent). 1H NMR (CDCI3, 400 MHz, ppm) delta 7.98(d, 2H, J=8.0 Hz), 7.89 (d, 2H, J= 7.6 Hz ), 7.64 (dd, 2H, J= 1.6, 8.0 Hz), 7.60 (d, 4H, J= 8.4 Hz), 7.52 (d, 4H, J = 8.4Hz), 7.41 (t, 2H), 7.14(t, 2H), 6.94 (s, 2H), 6.80(d, 2H, J= 7.6 Hz).
{2-(2-Bromo-9,9-spirobifluoren-7-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolan}3.5 g of 2,7-dibromo-9,9-spirobifluorene (7.38 mmol) was dissolved in 80 ml of tetrahydrofuran in a flask filled with nitrogen gas, and the temperature of the flask was reduced to -78°C. 5.1 ml of normal-butyllithium (1.6M hexane solution) was added dropwise to the resultant mixture via a syringe.The resultant mixture was stirred at -78°C for 30 minutes, and 1.7 ml of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaboralne (8.33 mmol) was slowly added to the resultant mixture.The reaction temperature was raised to room temperature, and the resultant mixture was then stirred for 8 hours.Water was added to the resulting mixture to complete the reaction.The reaction mixture was extracted with dichloromethane, and the remaining moisture existing in the layer was removed with MgSO4.Then, column chromatography (stationary phase: silica gel, mobile phase:ethylacetate:hexane= 1:10 volume ratio) was performed on the resultant layer to obtain 3.26 g of a desired Compound 3 at a yield of 85percent.Mp: 305 °C1HNMR (300 MHz, CDCl3): delta 7.85 (d, 4H J=7.2Hz),7.73(d,1HJ=7.2Hz),7.48(d,1HJ=7.2Hz),7.38(dd,2HJ=7.2Hz),7.16(s,1H),7.11 (dd,2 HJ=7.2Hz),6.79(s,1H),6.71(d,2HJ=7.2Hz), 1.25(s,12H).13CNMR(300MHz,CDCl3):delta 151.8, 147.8, 147.61, 143.8, 142, 140.4, 135.08, 134.93, 131.01, 130.41, 128.08, 128.04, 127.34, 124.29, 122.11, 121.84, 120.29, 119.51, 83.9, 65.9, 48.2, 24.9.
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; diethylene glycol; at 80℃; for 12h;
Compound (126) (10 g, 21.08 mmol), 4-bromophenylboronic acid (4.23 g, 21.1 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (2.43 g, 21.1 mmol), aqueous 1.0 M potassium carbonate solution (105 mL) and diethyleneglycol (DME) (100 mL) were mixed, and the mixture was stirred at 80° C. under reflux for 12 hours. After cooling to ambient temperature, the organic layer was extracted with dichloromethane (200 mL), and the extract was washed with distilled water (200 mL), dried over magnesium sulfate, and distilled under reduced pressure. Purification via silica gel column chromatography (n-hexane: dichloromethane=7:1) gave Compound (127) (2.4 g, 4.4 mmol).
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; diethylene glycol; at 80℃; for 12h;
Compound (144) (10 g, 21.1 mmol), 4-bromophenylboronic acid (4.2 g, 42.2 mmol), tetrakis(triphenylphosphine)palladium 1.0 (Pd(PPh3)4) (2.4 g, 2.1 mmol), aqueous 2.0 M potassium carbonate solution (105 mL) and diethyleneglycol (100 mL) were suspended, and the suspension was stirred at 80° C. under reflux for 12 hours. After cooling to ambient temperature, the organic layer was extracted with dichloromethane (700 mL), and the extract was washed with distilled water (400 mL), dried over magnesium sulfate, and distilled under reduced pressure. Purification via silica column chromatography (n-hexane:dichloromethane=7:1) gave Compound (146) (2.7 g, 4.4 mmol).
With palladium diacetate; acetic acid; In ethanol; toluene;
Example 1 Synthesis of N,N,N',N'-tetra-p-tolyI-9,9'-spirobifluorene-2,7-diamine (HTM1) 100 g (211 mmol) of 2,7-dibromospirobifluorene (Beijing Aglaia Techn. Dev. Co. Ltd.) and 60.8 g (633 mmol) of NaOtBu in 1.5 l of abs. toluene are initially introduced under N2 into a 4 l four-necked flask with internal thermometer, precision-glass stirrer and reflux condenser and degassed for 30 minutes by passing-through of N2. 1.65 ml (8.7 mmol) of di-t-butyl-chlorophosphine and 1.15 g (1.5 mmol) of palladium acetate are subsequently added. 104.1 g (527 mmol) of di-p-tolylamine are then added, and the mixture is heated under reflux for 12 h. 100 ml of acetic acid are added dropwise to the cooled batch, and 500 ml of ethanol and a further 100 ml of acetic acid are then added. The precipitated solid is filtered off with suction via a frit and dried at 40° C. in vacuo. The resultant solid is recrystallised 5* from dioxane and sublimed in vacuo (10-5 mbar, 340° C.), giving 63 g (89 mmol, 42percent) of N,N,N',N'-tetra-p-tolyl-9,9'-spirobifluorene-2,7-diamine (HTM1) as a colourless solid. Analytical data: Tg (DSC) 123° C., purity >99.98percent.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 12h;Reflux; Inert atmosphere;
General procedure: A mixture of 3 (0.81 g, 2.2 mmol), 4 (0.48 g, 1 mmol), Pd(PPh3)4 (0.11 g, 0.1 mmol), and K2CO3 (1.1 g, 8.0 mmol) in toluene/ethanol/water (100 mL, 8/1/1 v/v/v) was heated to reflux for 12 h under nitrogen. Then the reaction mixture was cooled to room temperature and poured into water. The organic layer was extracted with dichloromethane, and the combined organic layers were washed with a saturated brine solution and water, and dried over anhydrous magnesium sulfate. After filtration and solvent evaporation, the residue was purified by silica-gel column chromatography using hexane/dichloromethane as eluent. White solid of (DMesB)2DPF was obtained in 83percent yield (0.8 g, 0.83 mol).
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 12h;Reflux; Inert atmosphere;
General procedure: A mixture of 2 (0.83 g, 2.2 mmol), 5 (0.48 g, 1 mmol), Pd(PPh3)4 (0.11g, 0.1mmol), and K2CO3 (1.1 g, 8.0 mmol) in toluene/ethanol/water (100 mL, 8/1/1 v/v/v) was heated to reflux for 12 h under nitrogen. Then the reaction mixture was cooled to room temperature and poured into water. The organic layer was extracted with dichloromethane, and the combined organic layers were washed with a saturated brine solution and water, and dried over anhydrous magnesium sulfate. After filtration and solvent evaporation, the residue was purified by silica-gel column chromatography using hexane/dichloromethane as eluent. White solid of (TPE)2PF was obtained in 56percent yield.
With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; copper(l) iodide; 18-crown-6 ether; potassium carbonate; at 180℃; for 48h;
General procedure: 3,3?,6,6?-tetra-tert-butyl-9?-(9,9-diphenyl-9H-fluoren-2-yl)-9?H-9,3?:6?,9?-tercarbazole (2DPF-TCz), 9?-(9,9?-spirobi[fluoren]-2-yl)-3,3?,6,6?-tetra-tert-butyl-9?H-9,3?:6?,9?-tercarbazole (2SBF-TCz), 9?,9-(9,9-diphenyl-9H-fluorene-2,7-diyl)bis(3,3?,6,6?-tetra-tert-butyl-9?H-9,3?:6?,9?-tercarbazole) (27DPF-TCz), and 2,7-bis(3,3?,6,6?-tetra-tert-butyl-9?H-[9,3?:6?,9?-tercarbazol]-9?-yl)-9,9??-spirobi[fluorene] (27SBF-TCz) were synthesized by a similar procedure: A mixture of 2-bromo-9,9-diphenyl-9H-fluorene (2-bromo-9,9?-spirobi[fluorene], 2,7-dibromo-9,9-diphenyl-9H-fluorene, and 2,7-dibromo-9,9?-spirobi[fluorene]) (1.5 mmol), TCz (1.6 mmol or 3.2 mmol), CuI (0.06 mmol), 18-crown-6 (0.06 mmol), K2CO3 (4.5 mmol), and DMPU (5 mL) was heated at 180 °C for 48 h. After cooling, the mixture was treated with water and extracted with diethyl ether. The organic extraction was dried over MgSO4 with removal of the volatiles. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate as an eluent.
General procedure: 1a) Synthesis of 4-bromospiro-9,9'-bifluorene 60 g ( 188.5 mmol) 2,2'-Dibromo-biphenyl (CAS 13029-09-9) is dissolved in 750 mL of dry THF and cooled down to -78°C. 75.4 mL (188.5 mmol) of a 2.5M solution of nBuLi in heptane is added dropwise. After 1h a solution of 34.6 g of fluorenone (188.5 mmol) (CAS 486-25-9) in 250 mL of THF is added dropwise. The reaction mixture is allowed to reach the room temperature overnight, then quenched with saturated NH4CI (100 mL) solution, the mixture is stirred briefly, the organic phase is separated off, and the solvent is removed in vacuum. The residue is suspended in 500 ml of glacial acetic acid at 40°C, 0.5 ml of cone, hydrochloric acid is added to the suspension, and the mixture is subsequently stirred at 100°C for a further 2 h. After cooling, the precipitated solid is filtered off with suction, washed once with 100 ml of glacial acetic acid, three times with 100 ml of ethanol each time and finally recrystallized from dioxane. Yield: 70.1 g (169 mmol), 90percent; purity about 98percent according to 1H-NMR.
Sub 1-2-1 (10) (9.5g, 20mmol) dissolved in anhydrous Ether, a reaction temperatureof -78 ° C to a lower, n-BuLi (2.5M in hexane) (1.4g, 22mmol) was slowly addeddropwise and after I, the reaction is stirred for 30 min. After the dropwise additionTriisopropyl borate (5.64g, 30mmol) lowering the temperature of the reaction back to -78 ° C. Stirring at room temperature, diluted with water and it binds the 2N HCl. Aftercompletion of reaction, ethyl acetate and water, the organic layer was dried overMgSO4, concentrated and extracted by the resulting organic silicagel column andrecrystallized to obtain 6.4g of Sub 1-2-2 (10). (Yield: 73percent)
With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 12h;Inert atmosphere; Reflux;
250mL reaction flask, <strong>[171408-84-7]2,7-dibromo-9,9'-spirobi[fluorene]</strong> 10.0g (21.09mmol), 11-phenyl-11,12-dihydroindolo[2,3-a]carbazole 7.71g (23.19mmol), palladium (II) acetate, 47mg (0.21mmol), tree tert-butylphosphine (50percent) 0.2mL (0.42mmol), sodium tert-butoxy 3.04g (31.63mmol) In a nitrogen stream, and and the mixture was stirred under reflux for 12 hours in 100mL of toluene. After completion of the reaction slowly cooled to room temperature and then the reaction solution was poured into a saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The filtered organic layer is separated, dried over anhydrous magnesium sulfate. The filtrate was concentrated under reduced pressure to give the separated purified by column chromatography intermediate compound as a white solid [1-1] 7.2g (47percent).
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