* 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.
With sulfuric acid; iodine; periodic acid In water; acetic acid at 60℃; for 4.5 h;
[Step 1: Method of Synthesizing 2-Iododibenzofuran]In a 500-mL three-neck flask was put a suspension of 8.4 g (50 mmol) of dibenzofuran, 6.2 g (25 mmol) of iodine, 5.7 g (25 mmol) of orthoperiodic acid, 150 mL of glacial acetic acid, 30 mL of water, and 500 μL of sulfuric acid, and the suspension was heated and stirred at 60° C. for 4.5 hours to cause a reaction.After the reaction, the reaction mixture was further stirred at room temperature for 16 hours. The generated precipitate was collected by filtration, and the resulting matter was dissolved in 150 mL of toluene. Then, the solution was washed with water three times. Magnesium sulfate was added to the toluene solution to adsorb moisture.This solution was filtered, and the resulting filtrate was concentrated. Then, hexane was added thereto, followed by irradiation with ultrasonic waves. The generated solid was collected by filtration and dried, so that the objective substance was obtained as 11.3 g of white powder in 77percent yield. A reaction scheme of this synthesis method is shown in (B-1) below. The compound obtained in Step 1 was subjected to a nuclear magnetic resonance (NMR) measurement. The measurement data are shown below.1H NMR (CDCl3, 300 MHz):δ (ppm)=7.33-7.38 (m, 2H), 7.48 (dt, J=1.5 Hz, 8.4 Hz, 1H), 7.56 (d, J=8.1 Hz, 1H), 7.72 (dd, J=2.1 Hz, 8.4 Hz, 1H), 7.95 (d, J=7.8 Hz, 1H), 8.27 (d, J=1.5 Hz, 1H).The measurement results confirmed that the objective substance, 2-iododibenzofuran, was obtained.
77%
With iodine; periodic acid In water; acetic acid at 60℃; for 4.5 h;
Step 1: Method of Synthesizing 2-Iododibenzofuran In a 500 mL three-neck flask was put a suspension of 8.4 g (50 mmol) of dibenzofuran, 6.2 g (25 mmol) of iodine, 5.7 g (25 mmol) of orthoperiodic acid, 150 mL of glacial acetic acid, 30 mL of water, and 500 μL of sulfuric acid, and the suspension was heated and stirred at 60° C. for 4.5 hours to cause a reaction. After the reaction, the reaction mixture was further stirred at room temperature for 16 hours. The generated precipitate was collected by filtration, and this obtained residue was dissolved in 150 mL of toluene. Then, the solution was washed with water three times. Magnesium sulfate was added to the toluene solution to adsorb moisture. This solution was filtered, and the obtained filtrate was concentrated. Then, hexane was added thereto, and the mixture was irradiated with ultrasonic waves. The generated solid was collected by filtration and dried to give 11.3 g of a white powder in 77percent yield, which was the object of the synthesis. A reaction scheme of the above synthesis method is illustrated in (B-1) below. The compound obtained in Step 1 above was subjected to nuclear magnetic resonance (NMR) spectroscopy. The measurement data are shown below. 1H NMR (CDCl3, 300 MHz): δ (ppm)=7.33-7.38 (m, 2H), 7.48 (dt, J=1.5 Hz, 8.4 Hz, 1H), 7.56 (d, J=8.1 Hz, 1H), 7.72 (dd, J=2.1 Hz, 8.4 Hz, 1H), 7.95 (d, J=7.8 Hz, 1H), 8.27 (d, J=1.5 Hz, 1H).
30.4%
for 2 h;
Exemplified Compound 1-1, 30 g (0.178 mol)340 ml of acetic acid, 60 ml of acetic anhydride and 26.1 g (× 0.455 mol) of iodobenzene diacetate were mixed and dissolved by stirring. To this solution, 20.6 g (× 0.455 mol) of iodine and 0.5 ml of sulfuric acid were alternately added in 10 minutes. And the mixture was further stirred for 2 hours.Precipitated crystals were filtered under reduced pressure. 100 ml of ethanol was added to the obtained crystals, and the suspension was refluxed for 30 minutes. After stirring at room temperature for 1 hour, filtration under reduced pressure gave exemplified compound 3-1, 15.9 g. (Yield 30.4percent)
Reference：
[1] Patent: US2012/157694, 2012, A1, . Location in patent: Page/Page column 25
[2] Patent: US2012/184755, 2012, A1, . Location in patent: Page/Page column 24
[3] Journal of Chemical Research, Miniprint, 1999, # 10, p. 2501 - 2517
[4] Patent: JP5968214, 2016, B2, . Location in patent: Paragraph 0051-0054
[5] Journal of the American Chemical Society, 1934, vol. 56, p. 2473,2476
[6] Dyes and Pigments, 2015, vol. 114, # C, p. 278 - 282
[7] Organometallics, 2015, vol. 34, # 18, p. 4433 - 4440
[8] Chemistry - A European Journal, 2015, vol. 21, # 37, p. 12881 - 12884
[9] Dyes and Pigments, 2016, vol. 128, p. 84 - 88
[10] Angewandte Chemie - International Edition, 2017, vol. 56, # 12, p. 3191 - 3195[11] Angew. Chem., 2017, vol. 129, # 12, p. 3239 - 3243,5
2
[ 132-64-9 ]
[ 10450-60-9 ]
[ 5408-56-0 ]
Yield
Reaction Conditions
Operation in experiment
77%
With sulfuric acid; iodine; magnesium sulfate In hexane; water; acetic acid; toluene
Step 1: Synthesis of 2-Iododibenzofuran In a 500-mL three-neck flask, a suspension of 8.4 g (50 mmol) of dibenzofuran, 6.2 g (25 mmol) of iodine, 5.7 g (25 mmol) of orthoperiodic acid, 150 mL of glacial acetic acid, 30 mL of water, and 500 μL of sulfuric acid was heated and stirred at 60° C. for 4.5 hours. After that, the mixture was stirred at room temperature for 16 hours. The generated precipitate was collected by filtration, and the resulting matter was dissolved in 150 mL of toluene and a toluene solution was made. This toluene solution was washed with water three times. After the washing, magnesium sulfate was added to the toluene solution to adsorb moisture. This mixture was filtered and the given filtrate was concentrated. After that, hexane was added, and the mixture was irradiated with ultrasonic waves to perform recrystallization, so that 11.3 g of white powder, which was the objective substance, was obtained in 77percent yield. A synthetic scheme of Step 1 is shown in (a-1) below.
Reference：
[1] Patent: US2012/104370, 2012, A1,
3
[ 5408-56-0 ]
[ 3693-22-9 ]
Reference：
[1] Journal of the American Chemical Society, 1945, vol. 67, p. 349
With sulfuric acid; iodine; periodic acid; In water; acetic acid; at 60℃; for 4.5h;
[Step 1: Method of Synthesizing 2-Iododibenzofuran]In a 500-mL three-neck flask was put a suspension of 8.4 g (50 mmol) of dibenzofuran, 6.2 g (25 mmol) of iodine, 5.7 g (25 mmol) of orthoperiodic acid, 150 mL of glacial acetic acid, 30 mL of water, and 500 muL of sulfuric acid, and the suspension was heated and stirred at 60 C. for 4.5 hours to cause a reaction.After the reaction, the reaction mixture was further stirred at room temperature for 16 hours. The generated precipitate was collected by filtration, and the resulting matter was dissolved in 150 mL of toluene. Then, the solution was washed with water three times. Magnesium sulfate was added to the toluene solution to adsorb moisture.This solution was filtered, and the resulting filtrate was concentrated. Then, hexane was added thereto, followed by irradiation with ultrasonic waves. The generated solid was collected by filtration and dried, so that the objective substance was obtained as 11.3 g of white powder in 77% yield. A reaction scheme of this synthesis method is shown in (B-1) below. The compound obtained in Step 1 was subjected to a nuclear magnetic resonance (NMR) measurement. The measurement data are shown below.1H NMR (CDCl3, 300 MHz):delta (ppm)=7.33-7.38 (m, 2H), 7.48 (dt, J=1.5 Hz, 8.4 Hz, 1H), 7.56 (d, J=8.1 Hz, 1H), 7.72 (dd, J=2.1 Hz, 8.4 Hz, 1H), 7.95 (d, J=7.8 Hz, 1H), 8.27 (d, J=1.5 Hz, 1H).The measurement results confirmed that the objective substance, 2-iododibenzofuran, was obtained.
77%
With iodine; periodic acid;sulfuric acid; In water; acetic acid; at 60℃; for 4.5h;
Step 1: Method of Synthesizing 2-Iododibenzofuran In a 500 mL three-neck flask was put a suspension of 8.4 g (50 mmol) of dibenzofuran, 6.2 g (25 mmol) of iodine, 5.7 g (25 mmol) of orthoperiodic acid, 150 mL of glacial acetic acid, 30 mL of water, and 500 muL of sulfuric acid, and the suspension was heated and stirred at 60 C. for 4.5 hours to cause a reaction. After the reaction, the reaction mixture was further stirred at room temperature for 16 hours. The generated precipitate was collected by filtration, and this obtained residue was dissolved in 150 mL of toluene. Then, the solution was washed with water three times. Magnesium sulfate was added to the toluene solution to adsorb moisture. This solution was filtered, and the obtained filtrate was concentrated. Then, hexane was added thereto, and the mixture was irradiated with ultrasonic waves. The generated solid was collected by filtration and dried to give 11.3 g of a white powder in 77% yield, which was the object of the synthesis. A reaction scheme of the above synthesis method is illustrated in (B-1) below. The compound obtained in Step 1 above was subjected to nuclear magnetic resonance (NMR) spectroscopy. The measurement data are shown below. 1H NMR (CDCl3, 300 MHz): delta (ppm)=7.33-7.38 (m, 2H), 7.48 (dt, J=1.5 Hz, 8.4 Hz, 1H), 7.56 (d, J=8.1 Hz, 1H), 7.72 (dd, J=2.1 Hz, 8.4 Hz, 1H), 7.95 (d, J=7.8 Hz, 1H), 8.27 (d, J=1.5 Hz, 1H).
30.4%
With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine; acetic anhydride; acetic acid; for 2h;
Exemplified Compound 1-1, 30 g (0.178 mol)340 ml of acetic acid, 60 ml of acetic anhydride and 26.1 g (× 0.455 mol) of iodobenzene diacetate were mixed and dissolved by stirring. To this solution, 20.6 g (× 0.455 mol) of iodine and 0.5 ml of sulfuric acid were alternately added in 10 minutes. And the mixture was further stirred for 2 hours.Precipitated crystals were filtered under reduced pressure. 100 ml of ethanol was added to the obtained crystals, and the suspension was refluxed for 30 minutes. After stirring at room temperature for 1 hour, filtration under reduced pressure gave exemplified compound 3-1, 15.9 g. (Yield 30.4%)
Dibenzofuran (10.0 g, 59.4 mmol) and periodic acid (16.2 g, 71.3 mmol) were dissolved in acetic acid (600 ml) and iodine (9.0 g, 71.3 mmol) was added to the solution. The solution was stirred at 60C for 30 min followed by addition of distilled water (120 ml) and sulfuric acid (1.20 ml). The solution was refluxed for 12 h, cooled to room temperature and poured into distilled water. White powder was filtered off and then the filtrate was extracted using ethyl acetate. The extracted solution was washed with 5% NaOH solution and aqueous sodium sulfate. Ethyl acetate was removed by evaporation and yellowish white powder was obtained (12.0 g, yield: 69%) after drying in vacuum. 2-Iododibenzofuran was included 85% of all powder and it was used in amination without purification.
EXAMPLE 6 A 100 ml three-necked glass container was charged with 4.20 g (25 millimoles) of dibenzofurane, 6.35 g (25 millimoles) of iodine, 50 ml of acetic acid, 25 ml of chloroform, 2 ml of sulfuric acid and 2 ml of water, and the reaction was carried out at 90 C. for 6 hours. Nitrogen as containing NO2 was blown into the reaction mixture at a rate of 30 ml/min. The total amount of NO2 fed was 56.5 millimoles. The reaction product was extracted with chloroform, and analyzed by gas chromatography. There was no unreacted material, and 2,8-diiododibenzofurane and 2-iododibenzofurane were obtained in a yield of 94.6% and 5.4%, respectively. The iodination yield was 97.3%.
With N2;tris-(dibenzylideneacetone)dipalladium(0); Pd2(dba)3; In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene; hexane; dichloromethane; toluene;
A mixture of 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (12 g, 32.5 mmol), 3-bromo-9H-carbazole (6.66 g, 27.1 mmol), and potassium phosphate (34.5 g, 162 mmol) in 500 mL of toluene and 50 mL of H2O was bubbled with N2 for 20 min. Dicyclohexyl(2',6'-dimethoxybiphenyl-2-yl)phosphine (0.445 g, 1.083 mmol) and Pd2(dba)3 (0.248 g, 0.271 mmol) were then added, and the mixture was heated to reflux under N2 for 5 h. TLC indicated the reaction was done. The reaction was extracted with dichloromethane and washed with brine and dried with magnesium sulfate. The solution was heated up to boil. Hexane was added. The dichloromethane was boiled off and hexanes volume reached about 1200 mL. Precipitate formed during boiling off dichloromethane. The solution was cooled to room temperature and stirred overnight. The precipitate was filtered and dissolved in THF and ran a short silica gel plug. After dried under vacuum at 60 C., 9.6 g (87%) of product was obtained. Synthesis of Compound 1. A mixture of <strong>[5408-56-0]2-iododibenzo[b,d]furan</strong> (2.59 g, 8.81 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole (3 g. 7.34 mmol), and sodium t-butoxide (1.764 g, 18.36 mmol) in 200 mL of xylene was bubbled with N2 for 20 min. Dicyclohexyl(2',6'-dimethoxybiphenyl-2-yl)phosphine (0.121 g, 0.294 mmol) and Pd2(dba)3 (0.067 g, 0.073 mmol) were then added, and the mixture was heated to reflux under N2 for 24 h. The mixture was cooled and filtered through Celite. After solvent evaporation, the residue was coated on Celite and purified by column chromatography 3.7 g of product was obtained after column.
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); In xylene; for 24h;Inert atmosphere; Reflux;
Compound 1[0130] Synthesis of Compound 1. A mixture of <strong>[5408-56-0]2-iododibenzo[b,d]furan</strong> (2.59 g, 8.81 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole (3 g, 7.34 mmol), and sodium t-butoxide (1.764 g, 18.36 mmol) in 200 mL of xylene was bubbled with N2 for 20 min. Dicyclohexyl(2',6'- dimethoxybiphenyl-2-yl)phosphine (0.121 g, 0.294 mmol) and Pd2(dba)3 (0.067 g, 0.073 mmol) were then added, and the mixture was heated to reflux under N2 for 24 h. The mixture was cooled and filtered through Celite. After solvent evaporation, the residue was coated on Celite and purified by column chromatography 3.7 g of product was obtained after column.
With sulfuric acid; iodine; magnesium sulfate; In hexane; water; acetic acid; toluene;
Step 1: Synthesis of 2-Iododibenzofuran In a 500-mL three-neck flask, a suspension of 8.4 g (50 mmol) of dibenzofuran, 6.2 g (25 mmol) of iodine, 5.7 g (25 mmol) of orthoperiodic acid, 150 mL of glacial acetic acid, 30 mL of water, and 500 muL of sulfuric acid was heated and stirred at 60 C. for 4.5 hours. After that, the mixture was stirred at room temperature for 16 hours. The generated precipitate was collected by filtration, and the resulting matter was dissolved in 150 mL of toluene and a toluene solution was made. This toluene solution was washed with water three times. After the washing, magnesium sulfate was added to the toluene solution to adsorb moisture. This mixture was filtered and the given filtrate was concentrated. After that, hexane was added, and the mixture was irradiated with ultrasonic waves to perform recrystallization, so that 11.3 g of white powder, which was the objective substance, was obtained in 77% yield. A synthetic scheme of Step 1 is shown in (a-1) below.
[Step 1: Method of Synthesizing Dibenzofuran-2-boronic Acid] In a 500-mL three-neck flask was put 8.8 g (30 mmol) of <strong>[5408-56-0]2-iododibenzofuran</strong>, and the atmosphere in the flask was replaced by nitrogen. Then, 200 mL of dehydrated tetrahydrofuran (abbreviation: THF) was added thereto and the mixture was cooled to -78 C. To this mixture was dripped 22 mL (36 mmol) of an n-butyllithium hexane solution (1.63 mol/L), and the mixture was stirred for 4 hours to cause a reaction. To this reaction mixture was added 4.6 mL (45 mmol) of trimethyl borate, and the mixture was stirred at -78 C. for 2 hours and at room temperature for 20 hours. After the reaction, diluted hydrochloric acid was added to this reaction solution until the mixture was made acid, and then the mixture was stirred for 2 hours. The stirred solution was subjected to extraction with ethyl acetate, and the obtained organic layer was washed with a saturated aqueous solution of sodium chloride. After the washing, magnesium sulfate was added to the organic layer to adsorb moisture. This suspension was filtered, and the resulting filtrate was concentrated to give an objective substance. A reaction scheme of this synthesis method is shown in (C-1) below.
With sodium t-butanolate;tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); In hexane; xylene; at 120℃; for 5h;Inert atmosphere;
[Step 2: Method of Synthesizing N-(Dibenzofuran-2-yl)-phenylamine (Abbreviation: FrA)]In a 100-mL three-neck flask were put 4.5 g (15 mmol) of <strong>[5408-56-0]2-iododibenzofuran</strong>, 2.0 g (20 mmol) of aniline, 45 mg (0.1 mmol) of bis(dibenzylideneacetone)palladium(0), and 3.0 g (30 mmol) of sodium-tert-butoxide (abbreviation: tert-BuONa), and 30 mL of dehydrated xylene was added. Then, deaeration was performed for 3 minutes until no bubbles came out. To this suspension, 0.5 mL (0.3 mmol) of tri-tert-butylphosphine (10 wt % hexane solution) was added, and then the mixture was heated and stirred at 120 C. for 5 hours in a nitrogen atmosphere to cause a reaction.About 200 mL of toluene was added to this reaction suspension, and the mixture was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), alumina, and Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855). The resulting filtrate was washed with water, and magnesium sulfate was added thereto to adsorb moisture.This suspension was further filtered through Florisil, alumina, and Celite, and the resulting filtrate was concentrated. Then, methanol was added thereto, followed by irradiation with ultrasonic waves. The generated solid was collected by filtration and dried, so that the objective substance was obtained as 1.6 g of white powder in 39% yield. A reaction scheme of this synthesis method is shown in (B-2) below. The Rf values of the objective substance, <strong>[5408-56-0]2-iododibenzofuran</strong>, and aniline were respectively 0.28, 0.59, and 0.07, which were found by silica gel thin layer chromatography (TLC) (with a developing solvent of ethyl acetate and hexane in a ratio of 1:10).The compound obtained in Step 2 was subjected to a nuclear magnetic resonance (NMR) measurement. The measurement data are shown below.1NMR (CDCl3, 300 MHz):delta (ppm)=5.80 (s, 1H), 6.94-7.68 (m, 10H), 8.99 (d, J=7.8 Hz, 1H), 8.11 (s, 1H).The measurement results confirmed that the objective substance, N-(dibenzofuran-2-yl)-phenylamine (abbreviation: FrA), was obtained.
39%
With sodium t-butanolate;tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); In hexane; xylene; at 120℃; for 5h;Inert atmosphere;
Step 2: Method of Synthesizing N-(Dibenzofuran-2-yl)-phenylamine (Abbreviation: FrA) Into a 100 mL three-neck flask were placed 4.5 g (15 mmol) of <strong>[5408-56-0]2-iododibenzofuran</strong>, 2.0 g (20 mmol) of aniline, 45 mg (0.1 mmol) of bis(dibenzylideneacetone)palladium(0), and 3.0 g (30 mmol) of sodium-tert-butoxide (abbreviation: tert-BuONa), and 30 mL of dehydrated xylene was added. Then, deaeration was performed for 3 minutes until a bubble ceased to appear. To this suspension, 0.5 mL (0.3 mmol) of tri-tert-butylphosphine (a 10 wt % hexane solution) was added, and the mixture was heated and stirred at 120 C. for 5 hours in a nitrogen atmosphere to cause a reaction. About 200 mL of toluene was added to this reaction suspension, and the mixture was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), alumina, and Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855). The obtained filtrate was washed with water, and magnesium sulfate was added thereto to adsorb moisture. This suspension was further filtered through Florisil, alumina, and Celite, and the obtained filtrate was concentrated. Then, methanol was added thereto, and the mixture was irradiated with ultrasonic waves. The generated solid was collected by filtration and dried to give 1.6 g of a white powder in 39% yield, which was the object of the synthesis. A reaction scheme of the above synthesis method is illustrated in (B-2) below. The Rf values of the object of the synthesis, <strong>[5408-56-0]2-iododibenzofuran</strong>, and aniline were respectively 0.28, 0.59, and 0.07, which were found by silica gel thin layer chromatography (TLC) (ethyl acetate:hexane (1:10) as the developing solvent). The compound obtained in Step 2 above was subjected to nuclear magnetic resonance (NMR) spectroscopy. The measurement data are shown below. 1H NMR (CDCl3, 300 MHz): delta (ppm)-=5.80 (s, 1H), 6.94-7.68 (m, 10H), 8.99 (d, J=7.8 Hz, 1H), 8.11 (s, 1H).
With potassium phosphate; copper(l) iodide; trans cyclohexane-1,2-diamine; In 1,4-dioxane; at 120℃; for 72h;Inert atmosphere;
General procedure: Under a nitrogen atmosphere, a mixture of 2.4 g (5.4 mmol) of Intermediate A-7, 1.4 g (5.9 mmol) of 3-bromobiphenyl, 0.2 g (1.1 mmol) of copper iodide, 3.1 g (26.8 mmol) of tripotassium phosphate, 1.1 g (5.3 mmol) of trans-1,2-cyclohexanediamine, and 30 ml of 1,4-dioxane was prepared and heated at 120C with stirring for 72 hours. The reaction solution was cooled to room temperature, the precipitated crystal was collected by filtration, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography and Compound 1-21 weighing 1.2 g (2.0 mmol, 37% yield) was obtained as a white solid. APCI-TOFMS: m/z 600 [M+H]+. The result of 1H-NMR measurement (solvent: THF-d8) is shown in Fig. 6.
<strong>[5408-56-0]2-Iododibenzofuran</strong> (11.0 g, 37.4 mmol) and carbazole (7.2 g, 43.0 mmol) were dissolved in 1,4-dioxane (250 ml) at room temperature under nitrogen. After 30 min, trans-1,2-diaminocyclohexane (2.0ml, 18.7mmol) was added to the solution and the solution was refluxed overnight. After cooling to room temperature, the solution was extracted using methylene chloride. Methylene chloride was removed by evaporation and obtained product was purified by column chromatography on silica gel using toluene/n-hexane (1: 2) as an eluent. A white powder was obtained as a product (7.9g, yield: 63%). (0007) 1H NMR (400MHZ, CDCl3): delta 8.17 (d, 2H, J=3.8Hz), 8.11 (d, 1H, J=1Hz), 7.94 (d, 1H, J=4Hz), 7.78 (d, 1H, J=4Hz), 7.66-7.59 (m, 2H), 7.54-7.50 (m, 1H), 7.41-7.35 (m, 5H), 7.31-7.25 (m, 2H).
With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine; In 1,4-dioxane; at 120℃;Inert atmosphere;
Under nitrogen environment, by adding intermediate C 6.4 g (0.034 mol), 2-iodo benzofuranacetic 21.5 g (0.073 mol), copper iodide 36.2 g (0.19 mol), potassium phosphate 40.3 g (0.19 mol), trans-1,2-cyclohexane diamine 23.1 ml (0.19 mol), 1,4-dioxan 162 ml rear, 120 C lower stirred for a night. The reaction solution after cooling to room temperature, the precipitated crystalline effect, the distill goes solvent under reduced pressure. Purification by silica gel column chromatography of the residue obtained, the obtaining white solid intermediate D 7.0 g (0.020 mol, yield 58%).
With potassium phosphate; copper(l) iodide; (1R,2R)-1,2-Dimethyl-cyclohexane; In 1,4-dioxane; for 14h;Inert atmosphere; Reflux;
The bottom of argon atmosphere, <strong>[5408-56-0]2-iododibenzofuran</strong> 38g (154mmol), 45.4 g (154mmol) of 3-bromocarbazole, the copper iodide 8.8g (46.3mmol), 17.6 g (154mmol) of trans-1,2-cyclohexanediamines and the tripotassium phosphate 68.8g (324mmol) were added to 700 ml of drying 1,4-dioxane, and heating-at-reflux stirring was carried out for 14 hours. 500 ml of tetrahydrofurans were added and agitated to the residue produced by condensing under decompression of a reaction solution, and the insoluble matter was filtered through silica gel. By dissolving the residue produced by condensing under decompression of filtrate in toluene, and refining with silica gel column chromatography (toluene 100%), the intermediate field G38g (59% of yield) were obtained as a white solid
10 g (0.034 mol) of Exemplified Compound 3-1 and 200 ml of acetic acid were mixed, and 10.9 g (× 2 mol) of bromine was added dropwise in the vicinity of 50 C. over 10 minutes,And the mixture was further stirred for 16 hours. (Internal temperature 65 to 66 C.) After stirring at room temperature for 1 hour, filtration under reduced pressure was carried out.The obtained crystals were added to a THF / methanol mixture and the suspension was refluxed for 30 minutes. After stirring at room temperature for 1 hour, filtration under reduced pressure gave Exemplified Compound 2-1, 7.9 g. (Yield 62.2%) Identification of each compound in the examples was carried out by MASS and NMR spectra, and it was confirmed that they were the target compound. Exemplary compounds according to other general formulas [2] and [5] can also be synthesized according to the above-mentioned method.
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In toluene; for 18h;Reflux; Inert atmosphere;
Toluene (100 mL) was bubbled with nitrogen gas for 15 min., followed by the addition of 2-dicyclohexylphosphino-2?,6?-dimethoxybiphenyl (2.1 g, 5.1 mmol) and Pd2(dba)3 (1.1 g, 1.2 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then <strong>[5408-56-0]2-iododibenzo[b,d]furan</strong> (5.3 g, 18.0 mmol), 9H-tetrabenzo[b,d,f,h]azonine (4.0 g, 12.5 mmol), and sodium tert-butoxide (1.7 g, 17.7 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (22 C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10% DCM in hexane to afford Compound III-a-6 (4.6 g, 76% yield) as a white solid.
Under a nitrogen atmosphere, 53.5 g (0.243 mol) of intermediate A was added,1,2-dimethoxyethane (DME), and the resulting DME solution was cooled to 0 C.A 96.9 mL solution of n-butyllithium in hexane was added dropwise,And the mixture was stirred under ice-cooling for 30 minutes. 67 mL of pyridine was added,After stirring at room temperature for 10 minutes, 75.6 g (0.763 mol) of copper (I) chloride was added,And stirred at 65 C for 30 minutes. Thereafter, 76.4 g (0.260 mol) of <strong>[5408-56-0]2-iododibenzofuran</strong> was added,And stirred at 95 C overnight. After the reaction solution was cooled to room temperature,The precipitated crystals were collected by filtration, and the solvent was evaporated under reduced pressure.The resulting residue was purified by silica gel column chromatography,To give 37.6 g (97.2 mmol, 40% yield) of intermediate B. & lt; / RTI & gt;
With pyridine; cesium fluoride; In dimethyl sulfoxide; at 105℃; for 2h;Inert atmosphere; Schlenk technique;
General procedure: An oven-dried Schlenk tube, containing a Teflon-coated magnetic stir bar was charged with CsF (228 mg, 1.5 mmol, 3 equiv) and bispinacolatodiboron (254 mg, 1 mmol, 2 equiv). Under an argon atmosphere, freshly distilled DMSO (0.4 mL), the appropriate aryl iodide (0.5mmol), and pyridine (0.4 to 1 equiv) were added successively. The reaction mixture was heated to 105 C and stirred for 2 h under argon.
With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 2h;Inert atmosphere; Reflux;
General procedure: A degassed solution of 25 g (155 mmol) bromobenzene and 84 g (150 mmol) of 2,4-diphenyl-6-(9-phenyl-9H-carbazol-3-yl)-9H-pyrimido [4,5-b]indole in 600 ml of toluene is saturated with N2 for 1 h. Then, firstly 2.09 ml (8.6 mmol) of P(tBu)3, then 1 .38 g (6.1 mmol) of palladium(ll) acetate are added to the solution, and 17.7 g (185 mmol) of NaOiBu in the solid state are subsequently added. The reaction mixture is heated under reflux for 1 h. After cooling to room temperature, 500 ml of water are carefully added. The aqueous phase is washed with 3 x 50 ml of toluene, dried over MgS04 and the solvent removed under vacuum. Thereafter, the crude product is purified by chromatography on silica gel with heptane / acetic ester (20/1 ). The residue is recrystallized from toluene, and finally sublimed in a high vacuum (p=5 x 10-6 mbar). The yield is 76 g (120 mmol), corresponding to 80% of theory.
Under a nitrogen atmosphere, 35.0 g (0.243 mol) of m-carborane and 350 mL of DME were added, and the resulting DME solution was cooled to 0C. 96.8 mL of a 2.69 M n-butyllithium hexane solution was added dropwise, and the mixture was stirred under ice-cooling for 30 minutes.After adding 67 mL of pyridine and stirring at room temperature for 10 minutes, 75.6 g (0.763 mol) of copper (I) chloride was added, followed by stirring at 65 C. for 30 minutes. Subsequently, 76.4 g (0.260 mol) of 2-iodobenzofuran was added and stirred at 95C overnight. After the reaction solution was cooled to room temperature, the precipitated crystals were collected by filtration, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 25.0 g (3.22 mmol, yield 33%) of Intermediate C.
With tris-(dibenzylideneacetone)dipalladium(0); bis[2-(diphenylphosphino)phenyl] ether; sodium t-butanolate; In toluene; at 50℃; for 8h;
Under a nitrogen atmosphere, <strong>[5408-56-0]2-iodo-dibenzofuran</strong> (2.94 g, 10 mmol) was added to a 300 ml two-necked flask.4-bromo-1,2-benzenedithiol (2.21 g, 10 mmol), sodium tert-butoxide (4.81 g, 50 mmol),Tris(dibenzylideneacetone)dipalladium(458mg,0.5 mmol) of bis(2-diphenylphosphoryl)ether (269 mg, 0.5 mmol) and 150 ml of toluene were heated to 50C and the reaction was stirred for 8 hours.After the reaction was completed, the product was extracted with methylene chloride. The organic phase was washed with a saturated aqueous solution of sodium chloride, and the solvent was evaporated under reduced pressure. The crude product was eluted with a mixed solvent of petroleum ether:dichloromethane=8:1 (v/v). The residue was purified by column chromatography to give 2.34 g of a white solid with a yield of 60%.
7,9-dihydrobenzo[4,5]furo[2,3-g]benzofurano[2',3':4,5]indolo[2,3-b]carbazole[ No CAS ]
C42H22N2O3[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
50%
With potassium phosphate; copper(l) iodide; ethylenediamine; In toluene; at 120℃; for 4h;
In a 1 L round bottom flask, add the above compound 2 (7,9-dihydrobenzo[4,5]furo[2,3-g]benzofurano[2',3':4,5]indolo[2,3-b]carbazole (35.3 g, 81 mmol), <strong>[5408-56-0]2-iodobenzo[b,d]furan</strong> (24.1 g, 82 mmol), CuI (16.1 g), Ethylenediamine (8.2 mL), K3PO4 (17.3 g) and toluene (400 mL) were stirred at 120 C for 4 hours. The reaction mixture was separated with ethyl acetate (EA)/distilled water, and the water was removed with MgSO4 and distilled under reduced pressure. The product was subjected to column chromatography to give Compound 6 (24.4 g, 50%).
With Cu2O/SBA-15; In N,N-dimethyl-formamide; at 120℃; for 8h;
Synthesis of intermediate 2-61-3:450 ml of DMF and 43.51 g of <strong>[5408-56-0]2-iododibenzofuran</strong> were added to the three-necked flask.193g K4[Fe(CN)6], 400mg Cu2O/SBA-15,The reaction was carried out at 120 C for 8 h, and the basic reaction of the raw materials was determined by HPLC.After cooling to room temperature, the reaction solution was dried under reduced pressure.The residue was subjected to column chromatography to give 26.2 g of Intermediate 2-61-3(yield 77%)
With potassium phosphate; copper(l) iodide; 1,10-Phenanthroline; In dimethyl sulfoxide; at 130℃; for 24h;
To a flask containing synthetic intermediate F (21.6 g), 1,10-phenanthroline (1.8 g), copper iodide (1.0 g), potassium phosphate (21.2 g) and dimethylsulfoxide (DMSO) 2-iodobenzo [b, d] furan (15.0 g) was added,At 130 CFollowed by heating and stirring for 24 hours.After completion of the reaction, the reaction solution was cooled, ammonia water (200 ml) was added, and the mixture was partitioned with toluene. The solvent was distilled off under reduced pressure, and the obtained solid was washed with ethanol to obtain 12.4 g of a synthetic intermediate G as a white solid
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