* 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.
Reference:
[1] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
2
[ 63262-06-6 ]
[ 873-77-8 ]
[ 89284-52-6 ]
[ 21711-52-4 ]
Reference:
[1] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
3
[ 63262-06-6 ]
[ 28987-79-3 ]
[ 4499-84-7 ]
[ 89284-52-6 ]
Reference:
[1] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
4
[ 63262-06-6 ]
[ 4294-57-9 ]
[ 89284-52-6 ]
[ 97295-31-3 ]
Reference:
[1] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
5
[ 63262-06-6 ]
[ 2633-66-1 ]
[ 89284-52-6 ]
[ 97295-32-4 ]
Reference:
[1] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
6
[ 63262-06-6 ]
[ 92-94-4 ]
[ 89284-52-6 ]
Reference:
[1] Tetrahedron Letters, 1985, vol. 26, # 1, p. 29 - 32
[2] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[3] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[4] Tetrahedron Letters, 1985, vol. 26, # 1, p. 29 - 32
[5] Tetrahedron Letters, 1985, vol. 26, # 1, p. 29 - 32
7
[ 21473-01-8 ]
[ 63262-06-6 ]
[ 17096-38-7 ]
[ 89284-52-6 ]
Reference:
[1] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
8
[ 63262-06-6 ]
[ 703-55-9 ]
[ 89284-52-6 ]
[ 64065-97-0 ]
Reference:
[1] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
9
[ 932-31-0 ]
[ 63262-06-6 ]
[ 53092-64-1 ]
[ 89284-52-6 ]
Reference:
[1] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
10
[ 106-37-6 ]
[ 63262-06-6 ]
Yield
Reaction Conditions
Operation in experiment
73%
at 0 - 20℃; for 33 h;
to 250 ml reaction flask add 2.66g (11.7mmol) potassium periodate, lowering the temperature to 0 °C, adding 60 ml concentrated sulfuric acid. Stirring, add 5.82g (35.1mmol) potassium iodide, 15 minutes later, adding 5.52g (23.4mmol) to two bromobenzene and 24 ml concentrated sulfuric acid, 0 °C lower reaction 18 hours. Gradually increasing temperature to room temperature, the reaction 15 hours. The reaction solution is poured into the bottle in the ice, stirring, filtering the obtained filter cake is 1, 4 - dibromo - 2, 5 - diiodide of crude product, dissolving the filters cake Canada, dilute NaOH solution for washing, extraction, the organic phase dried, concentrated, recrystallized, shall 8.326g (yield 73percent) 1, 4 - dibromo - 2, 5 - diiodide, recrystallization using chloroform and tetrahydrofuran as the solvent of the mixed solution, the mixed solution in chloroform: tetrahydrofuran=2:1.
72%
at 125℃; for 72 h;
Add 1,4-dibromobenzene (10.00 g, 42.39 mmol) to a 500 ml one-neck flaskAnd iodine (43.04 g, 169.56 mmol), slowly add 200 ml of concentrated sulfuric acid at room temperature.A spherical condenser was placed above the single-mouth flask, and the flask was placed in an oil bath at 125 ° C to heat.The condensed water was turned on, refluxed, and reacted for 3 days.The color of the solution gradually changed from the initial purple to dark purple to black.The final product is white with black and the solution is black.Take a 1000ml large beaker, add a lot of ice, and pour the solution slowly after the reaction.Stir it to cool it, and filter it with a suction filter.Wash repeatedly with NaHCO3 and Na2S2O3 solution,In order to remove I2, the filter residue is filtered by suction filtration, and the filter residue is heated by DCM.The mixture was filtered and washed with water-free methanol to give a white solid. With DCM:PE=1:1 eluent,The silica gel powder was used as a carrier and purified by column chromatography.A white solid of 14.88 g was obtained in a yield of 72.0percent.
68%
at 130℃; for 24 h;
S1 was synthesized using known methods. Its 1H and 13C NMR spectra were consistent with previously reported data
56%
at 80 - 130℃; for 48 h;
20 g (85 mmol) of 1 ,4-dibromobenzene were dissolved in 250 mL of concentrated sulphuric acid at 80°C. Iodine (47.3 g, 187 mmol) was added to the reaction flask in several portions. After complete addition the reaction temperature was increased to 130°C and the mixture was heated during 2 days. The reaction mixture was cooled to room temperature and carefully poured into ice-water. The black solid was filtered-off and extensively washed with water, before it was dissolved in warm chlorobenzene (300 mL). The organic chlorobenzene layer was washed several times with a concentrated aqueous sodium thiosulfate solution and water. The organic layer was separated and dried over anhydrous magnesium sulphate. The solution was concentrated and then precipitated into well stirred methanol. The formed solid was filtered off and the title compound was recovered as a white solid (23.3 g, 48 mmol, 56percent yield). 1 H NMR (400 MHz, CDCI3): <5 8.04 (s, 2H). 13C NMR (100 MHz, CDCI3): <5 142.44, 129.34, 101.48. MS (El): m/z calcd for Ce^B^ (M+) 488, 486, 490, 489 found 488, 486, 490, 489.
50%
at -30 - -25℃; for 36 h;
To a 1 L three-necked flask fitted with a mechanical stirrer were added 16.7 g (73.0 mmol) of periodic acid and 525 ml of sulfuric acid. After periodic acid was dissolved, 36.4 g (219 mmol) of potassium iodide was added portionwise. The content was cooled to a temperature of -30°C and 34.5 g (146 mmol) of 1,4-dibromobenzene was added over a period of 5 minutes. The resulting mixture was stirred at -25°C for 36 hours. After the reaction mixture was poured into ice (2 kg), the whole was filtrated and a solid was taken out. The solid was dissolved in chloroform, the solution was washed with a 5percent aqueous sodium hydroxide solution and water, and the organic phase was dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was recrystallized from chloroform to obtain white crystals (36.0 g, yield 50percent). 1H-NMR (CDCl3, 21°C) : δ=8.02 (s, 2H).
50%
at -25℃; for 36 h;
Periodic acid 16.7g (73.0mmol) and 525ml sulfuric acid were added to a three-necked flask with a mechanical stirrer with 1l. After periodate was dissolved, it was added potassium iodide 36.4 g (219 mmol) portionwise. The temperature of the contents were cooled to -30 ° C., it was added over 1,4-dibromobenzene 34.5g of (146mmol) 5 min. The resulting mixture was stirred for 36 hours at -25 ° C.. The reaction mixture was poured into ice (2Kg), filtered to remove solids. The solid was dissolved in chloroform, washed with 5percent aqueous solution of sodium hydroxide and water, the organic phase was dried with anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was recrystallized from chloroform to give white crystals 36.0g (50percent yield). 1H NMR (CDCl3,21 ): δ = 8.02 (s, 2H). Than that 1H NMR spectrum was consistent with the literature value, 1,4-dibromo-2,5-diiodobenzen it was confirmed that the obtained.
Reference:
[1] Organic Letters, 2009, vol. 11, # 20, p. 4656 - 4659
[2] Journal of Organic Chemistry, 2003, vol. 68, # 23, p. 8750 - 8766
[3] Journal of the American Chemical Society, 2011, vol. 133, # 10, p. 3284 - 3287
[4] Patent: CN106543216, 2017, A, . Location in patent: Paragraph 0023; 0024; 0036; 0043
[5] Patent: CN108117563, 2018, A, . Location in patent: Paragraph 0028; 0029; 0030
[6] Tetrahedron Letters, 1985, vol. 26, # 1, p. 29 - 32
[7] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[8] Angewandte Chemie - International Edition, 2012, vol. 51, # 48, p. 12051 - 12054[9] Angew. Chem., 2012, vol. 124, # 48, p. 12217 - 12220
[10] Patent: US2014/212668, 2014, A1, . Location in patent: Paragraph 0067; 0068
[11] Patent: WO2017/191468, 2017, A1, . Location in patent: Page/Page column 31
[12] Patent: WO2006/109569, 2006, A1, . Location in patent: Page/Page column 47-48
[13] Patent: EP2067782, 2009, A1, . Location in patent: Page/Page column 23
[14] Patent: JP2015/38044, 2015, A, . Location in patent: Paragraph 0109; 0110
[15] Journal of the American Chemical Society, 1997, vol. 119, # 20, p. 4578 - 4593
[16] Organic and Biomolecular Chemistry, 2012, vol. 10, # 31, p. 6275 - 6278
[17] Journal of Organic Chemistry, 2013, vol. 78, # 2, p. 752 - 756
[18] Chemistry - A European Journal, 2015, vol. 21, # 22, p. 8257 - 8261
[19] Tetrahedron Letters, 2005, vol. 46, # 47, p. 8153 - 8157
[20] Journal of the American Chemical Society, 2002, vol. 124, # 26, p. 7762 - 7769
[21] Organic Letters, 2008, vol. 10, # 19, p. 4323 - 4326
[22] Dalton Transactions, 2010, vol. 39, # 21, p. 5145 - 5151
[23] Macromolecules, 2013, vol. 46, # 5, p. 2032 - 2037
[24] Chemical Science, 2015, vol. 6, # 6, p. 3582 - 3592
With sulfuric acid; periodic acid; potassium iodide; at 0 - 20℃; for 33h;
to 250 ml reaction flask add 2.66g (11.7mmol) potassium periodate, lowering the temperature to 0 C, adding 60 ml concentrated sulfuric acid. Stirring, add 5.82g (35.1mmol) potassium iodide, 15 minutes later, adding 5.52g (23.4mmol) to two bromobenzene and 24 ml concentrated sulfuric acid, 0 C lower reaction 18 hours. Gradually increasing temperature to room temperature, the reaction 15 hours. The reaction solution is poured into the bottle in the ice, stirring, filtering the obtained filter cake is 1, 4 - dibromo - 2, 5 - diiodide of crude product, dissolving the filters cake Canada, dilute NaOH solution for washing, extraction, the organic phase dried, concentrated, recrystallized, shall 8.326g (yield 73%) 1, 4 - dibromo - 2, 5 - diiodide, recrystallization using chloroform and tetrahydrofuran as the solvent of the mixed solution, the mixed solution in chloroform: tetrahydrofuran=2:1.
72%
With sulfuric acid; iodine; at 125℃; for 72h;
Add 1,4-dibromobenzene (10.00 g, 42.39 mmol) to a 500 ml one-neck flaskAnd iodine (43.04 g, 169.56 mmol), slowly add 200 ml of concentrated sulfuric acid at room temperature.A spherical condenser was placed above the single-mouth flask, and the flask was placed in an oil bath at 125 C to heat.The condensed water was turned on, refluxed, and reacted for 3 days.The color of the solution gradually changed from the initial purple to dark purple to black.The final product is white with black and the solution is black.Take a 1000ml large beaker, add a lot of ice, and pour the solution slowly after the reaction.Stir it to cool it, and filter it with a suction filter.Wash repeatedly with NaHCO3 and Na2S2O3 solution,In order to remove I2, the filter residue is filtered by suction filtration, and the filter residue is heated by DCM.The mixture was filtered and washed with water-free methanol to give a white solid. With DCM:PE=1:1 eluent,The silica gel powder was used as a carrier and purified by column chromatography.A white solid of 14.88 g was obtained in a yield of 72.0%.
68%
With sulfuric acid; iodine; at 130℃; for 24h;
S1 was synthesized using known methods. Its 1H and 13C NMR spectra were consistent with previously reported data
56%
With sulfuric acid; iodine; at 80 - 130℃; for 48h;
20 g (85 mmol) of 1 ,4-dibromobenzene were dissolved in 250 mL of concentrated sulphuric acid at 80C. Iodine (47.3 g, 187 mmol) was added to the reaction flask in several portions. After complete addition the reaction temperature was increased to 130C and the mixture was heated during 2 days. The reaction mixture was cooled to room temperature and carefully poured into ice-water. The black solid was filtered-off and extensively washed with water, before it was dissolved in warm chlorobenzene (300 mL). The organic chlorobenzene layer was washed several times with a concentrated aqueous sodium thiosulfate solution and water. The organic layer was separated and dried over anhydrous magnesium sulphate. The solution was concentrated and then precipitated into well stirred methanol. The formed solid was filtered off and the title compound was recovered as a white solid (23.3 g, 48 mmol, 56% yield). 1 H NMR (400 MHz, CDCI3): <5 8.04 (s, 2H). 13C NMR (100 MHz, CDCI3): <5 142.44, 129.34, 101.48. MS (El): m/z calcd for Ce^B^ (M+) 488, 486, 490, 489 found 488, 486, 490, 489.
50%
With sulfuric acid; periodic acid; potassium iodide; at -25℃; for 36h;
Periodic acid 16.7g (73.0mmol) and 525ml sulfuric acid were added to a three-necked flask with a mechanical stirrer with 1l. After periodate was dissolved, it was added potassium iodide 36.4 g (219 mmol) portionwise. The temperature of the contents were cooled to -30 C., it was added over 1,4-dibromobenzene 34.5g of (146mmol) 5 min. The resulting mixture was stirred for 36 hours at -25 C.. The reaction mixture was poured into ice (2Kg), filtered to remove solids. The solid was dissolved in chloroform, washed with 5% aqueous solution of sodium hydroxide and water, the organic phase was dried with anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was recrystallized from chloroform to give white crystals 36.0g (50% yield). 1H NMR (CDCl3,21 ): delta = 8.02 (s, 2H). Than that 1H NMR spectrum was consistent with the literature value, 1,4-dibromo-2,5-diiodobenzen it was confirmed that the obtained.
50%
With sulfuric acid; periodic acid; potassium iodide; at -30 - -25℃; for 36h;
To a 1 L three-necked flask fitted with a mechanical stirrer were added 16.7 g (73.0 mmol) of periodic acid and 525 ml of sulfuric acid. After periodic acid was dissolved, 36.4 g (219 mmol) of potassium iodide was added portionwise. The content was cooled to a temperature of -30C and 34.5 g (146 mmol) of 1,4-dibromobenzene was added over a period of 5 minutes. The resulting mixture was stirred at -25C for 36 hours. After the reaction mixture was poured into ice (2 kg), the whole was filtrated and a solid was taken out. The solid was dissolved in chloroform, the solution was washed with a 5% aqueous sodium hydroxide solution and water, and the organic phase was dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was recrystallized from chloroform to obtain white crystals (36.0 g, yield 50%). 1H-NMR (CDCl3, 21C) : delta=8.02 (s, 2H).
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; In tetrahydrofuran; at 23℃; for 17h;Inert atmosphere;
To a solution of <strong>[63262-06-6]1,4-dibromo-2,5-diiodo-benzene</strong> (15.0 g, 31 mmol) and ethynyl-trimethyl-silane (6.0 g, 62 mmol) in tetrahydrofuran (150 cm3) under nitrogen atmosphere at room temperature is added diisopropylamine (90 cm3, 640 mmol), copper(I)iodide (353 mg, 1.9 mmol) and bis(triphenylphosphine) palladium(II)chloride (60 mg, 0.9 mmol). The resulting mixture is stirred at 23 C for 17 hours, poured into water (100 cm3) and extracted with diethyl ether (5×50 cm3). The combined organic layer is washed with water (50 cm3), brine (50 cm3) and dried over anhydrous magnesium sulfate then filtered. The filtrate is concentrated in vacuo to obtain an oily residue. The crude is purified using silica gel column chromatography (40-60 petroleum) to obtain an oily residue. The resulting oil is triturated with methanol to form a fine cream precipitate, which was filtered and washed well with methanol to give 1,4-dibromo-2,5-bis-trimethylsilanylethynyl-benzene (11 g, 84%) as a cream solid.
80%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; at 20℃;Inert atmosphere;
Under the protection of nitrogen, 4.85 g of compound II, 2.50 g of trimethylsilylacetylene, 50 ml of triethylamine, 100 mg of cuprous iodide and 150 mg of dichlorobis(triphenylphosphine)palladium were added.Block the reaction system, stir at room temperature overnight, gas phase detectionReaction process, after the reaction is over,The triethylamine was distilled off under reduced pressure, and the column was eluted with a solvent of n-hexane to afford a crude product.White solid 3.2 g, yield 80%.
69%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; In toluene; at 20℃; for 20h;Inert atmosphere;
Anhydrous PhMe (30 mL) and freshly distilled diisopropylamine (15 mL) were added to a 100 mL flask and sparged with N2 for 20 min. <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (3.000 g, 6.15 mmol), TMS-acetylene (1.510 g, 15.38 mmol), Pd(PPh3)2Cl2 (216 mg, 0.308 mmol) and CuI (117 mg, 0.615 mmol) were added to the solution, in sequence. The mixture was stirred at rt for 20 h. The crude reaction mixture was filtered through celite and washed with additional CH2Cl2 (400 mL). Evaporation of the solvent provided the crude product as a solid, which was purified by chromatography (SiO2, hexanes) followed by recrystallization from DMSO to give S2 (1.801 g, 69% yield) as white needles. 1H and 13C NMR spectroscopy were consistent with previous reports
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); diisopropylamine; at 90℃; for 24h;Inert atmosphere;
A <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (0.487 g, 1mmol), Trimethylsilylacetylene (0.589 g, 6 mmol), Copper(I) iodide (6 mg, 0.03 Mmol), Tetrakis(triphenylphosphine)palladium (10 mg, 0 mmol) were added to dry reaction flask. In the pipeline carried out Vacuum pumping - maintain nitrogen gas - vacuum pumping, repeat the cycle three times, and finally the use of nitrogen to protect the entire reaction system. The dried diisopropylamine (25 mL) was re-steaned in advance with a syringe and sealed at 90 C for 24 hours. Extraction carried out with water and ethyl acetate, take the organic layer then dry with anhydrous Na2SO4 ,then spin dry and through the column to get the corresponding alkynyl compound 2;
With bis-triphenylphosphine-palladium(II) chloride; In N,N-dimethyl-formamide; at 80℃; for 40h;Inert atmosphere; Schlenk technique;
To a stirred solution of 2-(tributylstannyl)thiophene (20.7 g, 55.3 mmol) and<strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (13.5 g, 27.7 mmol) in dry DMF (100 mL) was addedPd(PPh3)2Cl2 (0.78 g, 1.12 mmol). The mixture was stirred for 40 h at 80 C. Aftercooling to room temperature, the reaction mixture was poured into water and thenextracted with toluene. The combined organic layers were washed with water and driedover anhydrous Na2SO4. After filtration and evaporation, the crude product wasrecrystallized from methanol to provide 8 as a white solid (yield = 10.3 g, 93%).
5.6 g
With bis-triphenylphosphine-palladium(II) chloride; In toluene; at 80℃; for 48h;
9.75 g of compound 3 and 0.562 gBis(triphenylphosphine)palladium dichlorideAnd 2-tributylstannylthiophene was dissolved in 70 mL of toluene.Stirring at 80 C for 2 days,It was then cooled to room temperature.Remove all liquids by rotary evaporator.The residue was recrystallized from methanol to give 5.6 g of Compound 4.
With copper(l) iodide; triethylamine;bis-triphenylphosphine-palladium(II) chloride; In toluene; at 20℃; for 12h;
[Example 2] The following will describe other synthetic examples based on reaction formula (VI) below. First, a method of synthesis from 1,4-bis[(2-bromophenyl)ethynyl]-2,5-dibromobenzene (6) as a raw material will be described. A 3/1 toluene/triethylamine (9 mL) solution of 2-bromo-1-ethynylbenzene (90 mg, 4.98 mmol) was added to a mixed 3/1 toluene/triethylamine (12 mL) solution of <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (1.15 g, 2.35 mmol), dichlorobis(triphenylphosphine) palladium (II) (33 mg, 47 mmol), and copper iodide (18 mg, 95 mmol) at room temperature and stirred for 12 hours at room temperature. A 1N aqueous solution of hydrochloric acid was added to the reaction mixture. The mixture was then subjected to extraction using methylene chloride. The obtained organic layer was washed in a saturated saline solution and dried with anhydrous magnesium sulfate. After removing the drying agent by filtering, the filtered solution was concentrated under reduced pressure. The resultant mixture was recrystallized from benzene, to obtain 1.17 g (1.97 mmol) of the target product 6 in the form of a white solid at a yield of 84%. 1H NMR (CDCl3): delta 7.20-7.35 (m, 4H), 7.59-7.65 (m, 4H), 7.83 (s, 2H). 13C NMR (CDCl3): delta 90.81, 95.00, 123.57, 124.47, 125.59, 126.40, 127.02, 130.15, 132.54, 133.66, 136.34. Anal. Calcd for C22H10Br4: C, 44.49; H, 1.70. Found: C, 44.42; H, 1.54.
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 85℃; for 15h;
To a 100 ml Schlenk reaction vessel were added under a nitrogen atmosphere 4.39 g (9.00 mmol) of <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (compound of the formula (5)) synthesized in Synthetic Example 1, 974 mg (0.84 mmol) of tetrakis(triphenylphosphine)palladium (manufactured by Tokyo Chemical Industry Co. Ltd.) as a catalyst, and 4.16 g (20.7 mmol) of 2-bromophenylboronic acid (manufactured by Sigma-Aldrich) (compound of the formulae (6) and (7)). Further, 72 ml of toluene, 18 ml of ethanol, and an aqueous solution composed of 5.72 g (54.0 mmol) of sodium carbonate and 22 ml of water were added. The whole was immersed in an oil bath at 85C and stirred for 15 hours. After cooling to room temperature, dichloromethane and a saturated aqueous sodium chloride solution were added and phase separation was conducted. The organic phase was concentrated under reduced pressure. The residue was recrystallized from toluene to obtain white needle-like crystals (3.68 g, yield 75%). Melting point: 230-231C. 1H-NMR (CDCl3, 21C): delta=7.70 (d, J=8.0Hz, 2H), 7.55 (d, J=1.5Hz, 2H), 7.45-7.23 (m, 6H). MS m/z: 546 (M+, 92%), 466 (M+-Br, 45), 386 (M+-2Br, 53), 226 (M+-4Br, 100).
74%
With silver (II) carbonate; tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 45℃; for 3h;Reflux; Inert atmosphere;
A nitrogen gas atmosphere was prepared in a reaction vessel equipped with a stirrer, then, a compound 1 (22.0 g), 2-bromophenylboronic acid (19.1 g), tetrakis(triphenylphosphine)palladium(0) (2.43 g) and tetrahydrofuran (440 mL) were added, and the mixture was heated at 45 C. Thereafier, to this was added silver carbonate (47.2 g), and the mixture was refluxed for 3 hours. The resultant reaction liquid was cooled down to room temperature, then, water and toluene were added, and the mixture was stirred at room temperature. Thereafter, the aqueous layer was separated, and the organic layer was washed with a saturated sodium chloride aqueous solution. To the resultant organic layer was added sodium sulfate, then, the layer was filtrated, and concentrated to obtain a coarse product. Thereafier, to this were added toluene and activated carbon, and the mixture was stirred at 70 C. for 1 hour. Thereafter, the mixture was filtrated through a filter pre-coated with Celite. The resultant residue was washed with toluene several times. The resultant washing liquid was concentrated, then, recrystallized using toluene, thereby obtaining 17.9 g of a compound 2 (yield:74%, purity: 98.9%) as a white solid. ?H-NMR (DMSO-d5, 300 MHz): oe (ppm)7.43 (4H, t), 7.49 (2H, t), 7.71 (2H, d), 7.76 (2H, d).
With tris-(dibenzylideneacetone)dipalladium(0); potassium carbonate; tris-(o-tolyl)phosphine; In water; toluene; at 90℃; for 12h;
A flame dried RBF was charged with l,4-dibromo-2,5-diiodobenzene (18.4 g, 37.7 mmol, 1.0 equiv.), (0225) phenylboronic acid (9.7 g, 79.2 mmol, 2.1 equiv.), potassium carbonate (20.8 g, 150.8 mmol, 4.0 equiv.), toluene (100 mL), deionized water (25 mL), and a stir bar. (Pd2dba3) (172.6 mg, 0.189 mmol, 0.5 mol%) and P(o-tolyl)3 (229.5 mg, 0.754 mmol, 2 mol%) were added last to the flask before the reaction mixture was lowered into a bath that was preheated to 90 C and stirred for l2h with a condenser. Upon completion, the reaction was diluted with water, extracted 3 times with DCM, dried on MgS04, and concentrated via rotary evaporation. The solid was then recrystallized in EtOH that provided 14.1 g (36.3 mmol, 96% yield) of white needles. NMR (400 MHz, CDCb): d 7.65 (s, 2H), 7.47-7.42 (m, 10H). 13C NMR (100 MHz, CDCb): d 142.9, 139.4, 135.2, 129.3, 128.2, 128.1, 121.3. HRMS (TOF-EI, m/z) calcd. for CisHiiBn [M]+: 385.9306; found: 385.9306.
63.7%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; at 74℃; for 8h;Inert atmosphere;
100 ml to double-mouth bottle 1,4-dibromo -2,5- phenyl-diiodide 974.5 mg (2mmol), phenylboronic acid 609.5 mg (5mmol), four (triphenylphosphine) palladium 115.6 mg (0.1mmol), vacuum heat nitrogen three times post-injection by adding oxygen-free tetrahydrofuran 20 ml aqueous solution of potassium carbonate and the 10 ml (2mol/L), in 74 C lower reflux 8h, DCM extraction for reaction is ended, and salt water washing three phase after drying with anhydrous sodium sulfate, after filtration turns on lathe does, with pure petroleum ether column separation and purification, to obtain white powder 2,5-dibromo -1,4- diphenyl benzene, the yield is 63.7%, that is, the intermediate product 1. Product characterization data are as follows
7 g
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 100℃; for 8h;Inert atmosphere;
1,4-dibromo-12,5-diiodobenzene (40.0 g, 83.01 mmol), phenylboronic acid (10.12 g in a nitrogen stream, 83.01 mmol), K2CO3 (34.41 g, 249.03 mmol put) in Toluene / H2O in 200 ml / 40 ml After stirring Pd (PPh3) 4 (4.79 g, 4.15 mmol) was stirred in 100 deg for 8 hours. After completion of the reaction under reduced pressure and extracted with methylene chloride Concentrated and to give the a-1 7 g purified by column chromatography.
To a 100 ml Schlenk reaction vessel were added under a nitrogen atmosphere 461 mg (0.640 mmol) of 2-bromo-3-iodo-6,7-didodecylanthracene synthesized in Synthetic Example 4 and 8 ml of THF. The solution was cooled to -40C and 1.0 ml (0.65 mmol) of a THF solution of isopropylmagnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65M) was added dropwise. After 30 minutes of aging, the mixture was cooled to -78C and 0.65 ml (0.65 mmol) of a diethyl ether solution of zinc chloride (manufactured by Sigma-Aldrich, 1.0M) was added dropwise. After the temperature was gradually raised to room temperature, the resulting reaction liquid was concentrated under reduced pressure. To the obtained residue were added 145 mg (0.298 mmol) of <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> synthesized in Synthetic Example 1, 27.5 mg (0.0238 mmol) of tetrakis(triphenylphosphine)-palladium (manufactured by Tokyo Chemical Industry Co. Ltd.), and 8 ml of THF. After the reaction was carried out at 60C for 7 hours, the vessel was cooled with water and the reaction was stopped by adding 3 ml of 3N hydrochloric acid. After toluene was added, phase separation was conducted, and the organic phase was washed with an aqueous sodium chloride solution. The organic phase was concentrated under reduced pressure, the solvent was removed by distillation, and further drying was conducted under vacuum. Toluene was added to the resulting residue and a 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.06 ml) was added, followed by 2 hours of stirring at room temperature. The solution was washed with water and the organic phase was concentrated under reduced pressure to effect precipitation. The residue was filtrated through a column chromatography packed with silica gel (solvent; hexane:chloroform=5:2) and the filtrate was concentrated under reduced pressure. The obtained residue was washed with hexane and then dried under vacuum to obtain 254 mg of a yellow solid (yield 60%). MS m/z: 1419 (M+, 100%), 1339 (M+-Br, 8), 1108 (M+-2C11H23, 15).
With diisopropylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; In benzene; at 20℃; for 14h;Inert atmosphere;
Under nitrogen atmosphere, <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (3.0 g, 6.2 mmol) was dissolved in diisopropylamine (45 ml) and anhydrous benzene (45 ml), followed by stirring for 30 minutes. Copper iodide (235 mg, 0.12 mmol), PdCl2(PPh3)2 (430 mg, 0.61 mmol), and 1-dodecene (1.9 ml, 12.9 mmol) were added to the mixture, followed by stirring at room temperature for 14 hours. The reaction liquid was poured into water and extracted with chloroform, and the obtained organic layer was washed with 200 ml of water three times. The resulting organic layer was dried over anhydrous sodium sulfate and purified by a column chromatography (silica gel and methylene chloride:hexane = 1:3), followed by recrystallization in ethanol, thereby colorless powdery 1,4-dibromo-2,5-bis(octyne-1-yl)benzene was obtained (1.56 g, yield: 56%). 1H-NMR (400 MHz, CDCL3) delta7.59 (s, 2H) 2.45 (t, J=7.2 Hz, 4H) 1.65-1.23 (m, 32H) 0.88 (t, J=6.4 Hz, 6H)
With tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 65℃;
To an oven dried round bottom flask was added 1 (14.5 g, 29.8 mmol) and (0206) tetrakistriphenylphosphinepalladium(O) (1.7 g, 1.5 mmol) before a 0.5 M (3-bromothiophen- 2-yl)zinc(ll) bromide solution in THF (125 ml_, 62.5 mmol) was added. The reaction mixture was stirred and heated at 65 C (oil bath temperature) overnight. The mixture was cooled to room temperature and poured into 150 ml_ of saturated aqueous ammonium chloride solution. The precipitate was filtered off and washed with water, acetone and diethyl ether. Compound 2 was recovered as an off-white solid (1 1.6 g, 20.8 mmol, 70% yield). 1 H NMR (400 MHz, CDCIs): delta 7.74 (s, 2H), 7.44 (d, J = 5.3 Hz, 2H), 7.1 1 (d, J = 5.3 Hz, 2H). 13C NMR (100 MHz, CDCI3): delta 136.63, 136.11 , 135.17, 130.51 , 126.97, 123.53, 1 11.79, 77.16. HRMS (El): m/z calcd for Ci4H6Br4S2 (M+) 557.6603 found 557.6603.
dichlorobis(triphenylphosphine)palladium[II]; In tetrahydrofuran; methanol; isopropyl alcohol;
EXAMPLE 1 Preparation of 2,2'-(2,5-dibromobenzene-1,4-diyl)bis(3-bromothiophene) A oven dried 2000 cm3 flask is charged with <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (61.00 g, 125.1 mmol), dichlorobis(triphenylphosphine)palladium(II) (2.195 g, 3.127 mmol) and anhydrous tetrahydrofuran (300 cm3). Once the starting materials are dissolved, a solution of 0.5 M of 3-bromo-2-thienylzinc bromide in tetrahydrofuran (500 cm3, 250.2 mmol) is transfered using a canula and the reaction heated to 85 C. for 3 hours. The reaction is cooled down overnight and the white precipitate filtered off. This precipitate is washed with water (750 cm3) and methanol (250 cm3) to obtain 25.77 g of the title product. Further product is recovered from the initial filtrate. The filtrate is reduced to ca. 90 cm3 in vacuo and then 500 cm3 of methanol is added. The precipitate is filtered off, washed with water (750 cm3) and methanol (250 cm3) and finally triturated three times in hot propan-2-ol to obtain an additional 12.72 g of the title product. (38.49 g, Yield: 55%). NMR (1H, 300 MHz, CDCl3): delta 7.71 (s, 2H); 7.42 (d, J=5.3 Hz, 2H); 7.09 (d, J=5.3 Hz, 2H). NMR (13C, 75 MHz, CDCl3): delta 136.62; 136.10; 135.16; 130.50; 126.97; 123.52; 111.78.
2,2'-(2,5-dibromobenzene-1,4-diyl)bis(1-benzothiophene)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With sodium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In tetrahydrofuran; water; at 65℃; for 12h;Inert atmosphere;
Example 1 Production of 2,2'-(2,5-dibromobenzene-1,4-diyl)bis(1-benzothiophene) A mixed liquid of <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (1.38 g, 2.83 mmol), benzo[b]thiophen-2-ylboronic acid (1.5 g, 8.43 mmol), a dichloro-[1,1'-bis(diphenylphosphino)ferrocene]palladium dichloromethane complex (0.26 g, 0.23 mmol), tetrahydrofuran (16 mL) and an aqueous sodium carbonate solution (2M, 8 mL) was refluxed under a nitrogen atmosphere at about 65 C. for 12 hours. After the reaction mixed liquid was allowed to cool to room temperature, water was added to the reaction mixed liquid and the reaction mixed liquid was extracted with chloroform. The obtained organic layer was dried over sodium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained mixture was separated and purified by silica gel chromatography to obtain 2,2'-(2,5-dibromobenzene-1,4-diyl)bis(1-benzothiophene) (1.2 g, 2.4 mmol) in a yield of 85%. Physical properties of 2,2'-(2,5-dibromobenzene-1,4-diyl)bis(1-benzothiophene) were as follows. 1H-NMR (CDCl3, deltappm): 7.91 (s, 2H), 7.84-7.90 (m, 4H), 7.59 (s, 2H), 7.35-7.45 (m, 4H)
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; In tetrahydrofuran; at 23℃; for 24h;
To a degassed solution of 1 ,4-dibromo-2,5-diiodo-benzene (60.0 g, 123 mmol) in diisopropylamine (174 cm3, 1230 mmol) and THF (600 cm3) at 23 C is added trimethylsilylacetylene (35 cm3, 250 mmol) and Pd2(PPh3)2Cl2 (433 mg, 0.615 mmol) followed by Cul (234 mg, 1.23 mmol). The reaction mixture is stirred at 23 C for 24 hours before being poured into aqueous citric acid (250 cm3, 10% w/w) and extracted with diethyl ether (3 x 300 cm3). The combined organic layers are washed with water and brine, dried over magnesium sulfate and concentrated in vacuo to give a dark orange oily residue which is purified by column chromatography on silica gel (eluent: petroleum ether 40-60). The resulting pale yellow oil becomes solid at room temperature and is triturated in cooled petroleum ether 40-60 to give a pale yellow solid (38.00 g, 88.72 mmol, 72%).1H NMR (300 MHz, CDCI3): 0.28 (18H, s, CH3), 7.68 (2H, s, ArH).
1,4-dibromo-2,5-bis(4-octyltetradec-1-yn-1-yl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 20℃;Inert atmosphere;
General procedure: In argon atmosphere, Pd(PPh3)2Cl2(115 mg, 0.164mmol) and CuI (156 mg, 0.820 mmol) were added to a stirring solutionof CuI (4.00 g, 8.20 mmol) in anhydrous THF/Et3N (30 ml, 1/1). 4-Ethyloct-1-yne(2.49 g, 18.0 mmol) was then added with a syringe. Theresulting mixture was stirred overnight at room temperature, and then pouredinto a large amount of dilute ammonia water for extraction with petroleum ether.The combined organic extracts were washed with saturated NH4Claqueous solution and brine until to neutral, dried over anhydrous MgSO4and concentrated in vacuum. The residue was purified with column chromatographyon silica gel with petroleum ether as the eluent
1,4-dibromo-2,5-bis(4-ethyloct-1-yn-1-yl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 20℃;Inert atmosphere;
In argon atmosphere, Pd(PPh3)2Cl2(115 mg, 0.164mmol) and CuI (156 mg, 0.820 mmol) were added to a stirring solutionof CuI (4.00 g, 8.20 mmol) in anhydrous THF/Et3N (30 ml, 1/1). 4-Ethyloct-1-yne(2.49 g, 18.0 mmol) was then added with a syringe. Theresulting mixture was stirred overnight at room temperature, and then pouredinto a large amount of dilute ammonia water for extraction with petroleum ether.The combined organic extracts were washed with saturated NH4Claqueous solution and brine until to neutral, dried over anhydrous MgSO4and concentrated in vacuum. The residue was purified with column chromatographyon silica gel with petroleum ether as the eluent. A light yellow oil of 1a (3.54 g, 85%) was obtained. 1HNMR (400 MHz, CDCl3, 298 K, ppm):delta = 7.58 (s, 2H), 2.45 (d, J = 5.6 Hz, 4H), 1.59-1.53 (m, 2H), 1.51-1.40(m, 8H), 1.37-1.24 (m, 8H), 0.94-0.89 (m, 12H). 13C NMR (100 MHz,CDCl3, 298 K, ppm): delta = 136.2, 126.7, 123.7, 97.1, 79.2, 38.9, 33.0,29.2, 26.3, 23.6, 23.1, 14.3, 11.3. EI-HRMS (m/z): calcd for C26H36Br2,506.1184; found, 506.1177 (error = -1.3 ppm).
1,4-dibromo-2,5-bis(4-hexyldodecyl-1-yn-1-yl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 20℃;Inert atmosphere;
General procedure: In argon atmosphere, Pd(PPh3)2Cl2(115 mg, 0.164mmol) and CuI (156 mg, 0.820 mmol) were added to a stirring solutionof CuI (4.00 g, 8.20 mmol) in anhydrous THF/Et3N (30 ml, 1/1). 4-Ethyloct-1-yne(2.49 g, 18.0 mmol) was then added with a syringe. Theresulting mixture was stirred overnight at room temperature, and then pouredinto a large amount of dilute ammonia water for extraction with petroleum ether.The combined organic extracts were washed with saturated NH4Claqueous solution and brine until to neutral, dried over anhydrous MgSO4and concentrated in vacuum. The residue was purified with column chromatographyon silica gel with petroleum ether as the eluent
1,4-dibromo-2,5-di(tetradec-1-yn-1-yl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In N,N-dimethyl-formamide at 20℃; for 72h; Schlenk technique; Inert atmosphere;
1,4-bis[(2-n-hexyl-4-thienyl) sulfanyl]-2,5-dibromobenzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
Under a nitrogen atmosphere, to a 50mL three-necked flask 1,4-dibromo-2,5-di-iodobenzene 219 mg (0.45 mmol) and diethyl ether (5 ml) was added and cooled to -78 C..Thereafter, it was added dropwise n- butyllithium 0.54ml at the same temperature (1.66 M hexane solution, 0.90 mmol), and stirred for 1 hour.At Thereafter the same temperature, it was added dropwise synthesized bis previous step was dissolved in diethyl ether (1ml) (2-n- hexyl-4-thienyl) disulfide 359 mg (0.90 mmol), and stirred at room temperature for 12 hours.The reaction by the addition of water was stopped, after extraction with diethyl ether, and the organic layer was dried over anhydrous sodium sulfate.And concentrated under reduced pressure, the resulting residue was purified by silica gel column chromatography (hexane), 1,4-bis [(2-n-hexyl-4-thienyl) sulfanyl] of 2,5-dibromobenzene yellow solid 228mg was obtained (80% yield).
1,4-di(3-methoxythienyl)-2,5-dibromobenzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
63%
With tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 50℃; for 8h;Inert atmosphere; Schlenk technique;
In a nitrogen atmosphere, 300 ml Schlenk reaction vessel was charged with 2,2,6,6-tetramethylpiperidine (Wako Pure Chemical Industries, Ltd.) 4.70 g (33.2 mmol) and 12 ml of THF (dehydrated grade) were added. At 0 C., a solution of isopropyl magnesium chloride · lithium chloride (Sigma-Aldrich, 1.3 M) in THF (33.0 ml) (43.0 mmol), and the mixture was stirred at room temperature for 2 days. 5.18 g (45.3 mmol) of 3-methoxythiophene (Wako Pure Chemical Industries, Ltd.) was added dropwise to the obtained magnesium chloride 2,2,6,6-tetramethylpiperidide · lithium chloride solution, And aged at room temperature for 8 hours. 20 ml of THF (dewatering grade) was added and the mixture was cooled to -60 C. To this, zinc chloride (Wako Pure Chemical Industries) 6.13 g (45.0 m Mol) and THF (dehydration grade) 40 ml was charged using a Teflon cannula.Further, 10 ml of THF (dehydration grade) was used for washing. After gradually raising the temperature to room temperature, 7.01 g of <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (Tokyo Kasei Kogyo Co., Ltd.) was added to the obtained white slurry solution (3-methoxythienyl-2-zinc chloride) 244 mg (0.214 mmol, 1.49 mol% based on <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong>) of tetrakis (triphenylphosphine) palladium (Tokyo Chemical Industry Co., Ltd.) The resulting mixture was reacted at 50 C. for 8 hours. The mixture was cooled to room temperature and the whole was concentrated under reduced pressure. 100 ml of water and 100 ml of hexane were added to the resulting residue, and the mixture was filtered, and the solid obtained by filtration was purified with a silica gel column chromatograph (Hexane / toluene = 2/1 to 0/1) and further recrystallized from toluene to obtain 4.19 g of a pale yellow solid of 1,4-di(3-methoxythienyl)-2,5-dibromobenzene (Yield: 63%).
4.19 g
With tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 50℃; for 8h;
Under a nitrogen atmosphere,4.00 g (33.2 mmol) of 2,2,6,6-tetramethylpiperidine (Wako Pure Chemical Industries) and 12 ml of THF (dehydrated grade) were added to a 300 ml Schlenk reaction vessel.At 0 C.,Isopropyl magnesium chloride33.0 ml (42.9 mmol) of lithium chloride (Sigma-Aldrich, 1.3 M) in THF solution was added,And the mixture was stirred at room temperature for 2 days.The resulting magnesium chloride 2,2,6,6-tetramethylpiperidide5.18 g (45.3 mmol) of 3-methoxythiophene (Wako Pure Chemical Industries) was added dropwise to the lithium chloride solution,And aged at room temperature for 8 hours.20 ml of THF (dehydration grade) was added,It was cooled to -60 C.Here,A solution consisting of 6.13 g (45.0 mmol) of zinc chloride (Wako Pure Chemical Industries) and 40 ml of THF (dehydration grade) was charged using a Teflon cannula.Further washing was carried out using 10 ml of THF (dewatering grade).After gradually raising the temperature to room temperature,To the obtained white slurry liquid (3-methoxythienyl-2-zinc chloride)7.01 g (14.4 mmol) of <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (Tokyo Chemical Industry Co., Ltd.)244 mg (0.214 mmol, 1.49 mol% based on <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong>) of tetrakis (triphenylphosphine) palladium (Tokyo Chemical Industry)The obtained mixture was reacted at 50 C. for 8 hours.After cooling to room temperature,The whole was concentrated under reduced pressure.To the resulting residue were added 100 ml of water and 100 ml of hexane and filtered.The solid obtained by filtration was purified by silica gel column chromatography (hexane / toluene = 2/1 to 0/1) and recrystallized from toluene to give 1,4-di (3-methoxythienyl) -2, 4.19 g of 5-dibromobenzene as a pale yellow solid (yield 63%).
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran for 8h; Reflux; Inert atmosphere;
18.5 g (0.038 mol) of 1,4-dibromo-2,5-diiodobenzene,17.5 g (0.078 mol) of (3-fluoro-4-trifluoromethoxy) phenylboronic acid,2.2 g of tetrakis (triphenylphosphine) palladium (0)2M potassium carbonate 114ml,Were mixed with 360 ml of tetrahydrofuran,And the mixture was refluxed under nitrogen for 8 hours.After cooling,Extraction with water and dichloromethane,The residue was further purified by silica gel column (developing solvent: ethyl acetate / hexane = 10/1)7.6 g (34.0%) of a white solid was obtained.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; for 12h;Reflux; Inert atmosphere;
18.5 g (0.038 mol) of 1,4-dibromo-2,5-diiodobenzene(0.078 mol) of (2-fluoro-4-trifluoromethoxy) phenylboronic acid,2.2 g of tetrakis (triphenylphosphine) palladium (0)2M potassium carbonate 114ml,Were mixed with 360 ml of tetrahydrofuran,And the mixture was refluxed under nitrogen for 12 hours.After cooling,Extraction with water and dichloromethane,The residue was further purified by silica gel column (developing solvent: ethyl acetate / hexane = 10/1)7.0 g (31.0%) of a white solid was obtained.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; for 12h;Reflux; Inert atmosphere;
18.5 g (0.038 mol) of 1,4-dibromo-2,5-diiodobenzene(0.078 mol) of (4- (2,2,2-trifluoroethoxy) phenyl) boronic acid,2.2 g of tetrakis (triphenylphosphine) palladium (0)2M potassium carbonate 114ml,Was mixed with 380 ml of tetrahydrofuran,And the mixture was refluxed under nitrogen for 12 hours.After cooling,Extraction with water and dichloromethane,The residue was further purified by silica gel column (developing solvent: ethyl acetate / hexane = 10/1)7.4 g (33.3%) of a white solid was obtained.
5,6,7,8-tetra-n-butyl-2-bromo-3-iodonaphthalene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
47%
Stage #1: 5-decyne With n-butyllithium; zirconocene dichloride In tetrahydrofuran at -78 - 20℃; for 3h; Inert atmosphere;
Stage #2: With copper(l) chloride In tetrahydrofuran at 0 - 20℃; for 0.166667h;
Stage #3: 1,4-dibromo-2,5-diiodobenzene With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone In tetrahydrofuran at 50℃; for 2h;
1.2 Step two to prepare nabumetone derivatives
under the protection of nitrogen, to the 200 ml reaction tube adding 5.70g (19.5mmol) two chlorine two luxuriant zirconium and 100 ml tetrahydrofuran, stirring. Lowering the temperature to -78 °C, add 15.6 ml (39.0mmol) n-BUli, reaction 1 hours, adding 4.15g (30.0mmol) 5 - decyne, react at room temperature for 3 hours; cooling to 0 °C, adding 4.45g (45mmol) CuCl, react at room temperature for 10 minutes, added 7.3 ml (60mmol) DMPU (1, 3 - dimethyl - 3, 4, 5, 6 - tetrahydro -2 - pyrimidone), adding 14.63g (30mmol) prepared by the above-mentioned step a 1, 4 - dibromo -2.5 - diiodide, heating to 50 °C, reaction 2 hours. Washing with dilute hydrochloric acid, ethyl acetate extraction, the organic phase dried, concentrated, column chromatography, eluting agent is pure hexane, shall 7.86g (yield 47%) 5, 6, 7, 8 - four-butyl -2 - bromo -3 - iodine naphthalene. The above reaction route is as follows:
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In ethanol; water; toluene; at 80℃; for 12h;Inert atmosphere;
In a 200 ml three-necked flask, in a nitrogen atmosphere, compound e-3, 4.30 g(10.0 mmol), compound e-4, 1.95 g (4.0 mmol),10 g of cesium carbonate, 100 ml of toluene,20 ml of ethanol and 100 ml of water were placed, and under stirring at room temperature in a nitrogen atmosphere,Tetrakis (triphenylphosphine) palladium (0),Was added. The temperature was raised to 80 degrees,And the mixture was stirred for 12 hours. After the reaction, the organic layer was extracted with toluene, dried over anhydrous sodium sulfate, and purified with a silica gel column (toluene, mixed with heptane, developing solvent)6.05 g (yield 72%) of compound e-5 (white solid) was obtained.
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 50℃; for 24h;Inert atmosphere;
Under an argon atmosphere, <strong>[63262-06-6]dibromodiiodobenzene</strong> (4.00 g, 8.20 mmol), compound 1-2 (6.81 g, 16.8 mmol, 1.05 eq.), and Pd(PPh3)4 (474 mg, 0.41 mmol, 5% Pd) were dissolved in 1 ,2-dimethoxyethane (800 mE) and water (200 mE) in which K3P04 (10.4 g, 49.2 mmol) was dissolved was added thereto, and the mixture was stirred with heating at 500 C. for 24 hours. Afier completion of the reaction, extraction with ethyl acetate was conducted, and the solvent was concentrated. The resulting solid was purified by column chromatography, whereby obtaining a white solid (5.0 g, yield: 77%). The obtained solid was compound 1-3, which is an intended product, and by mass spectrum analysis, it was confirmed that it had an mle value of 790 with respect to a molecular weight of 790.
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; dimethyl sulfoxide; toluene; at 90℃; for 24h;Inert atmosphere;
Under an argon atmosphere, <strong>[63262-06-6]dibromodiiodobenzene</strong> (2.5 g, 5.1 mmol), Intermediate 3 (4.97 g, 15.4 mmol), and Pd(PPh3)4 (237 mg, 0.205 mmol) were dissolved in toluene (250 mE) and dimethylsulfoxide (DMSO, 50 mE), 2 MNa2CO3 aqueous solution (13 mE) was added thereto, and the mixture was stirred with heating at 90 C. for 24 hours. Afier completion of the reaction, toluene was removed under reduced pressure, and the precipitated solid was filtered off. This solid was washed with methanol and ethyl acetate,whereby obtaining a white solid (2.5 g, yield: 75%). The obtained solid was Intermediate 4, which is an intended product, and by mass spectrum analysis, it was confirmed that it had an mle value of 626 with respect to a molecular weight of 626.
With potassium dihydrogenphosphate; tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 50℃; for 24h;Inert atmosphere;
Under an argon atmosphere, <strong>[63262-06-6]dibromodiiodobenzene</strong> (400mg, 0.820 mmol), Intermediate 10 (535 mg, 1.68 mmol),Pd(PPh (47 mg, 0.041 mmol) and potassium phosphate(1.05 g, 4.92 mmol) were dissolved in dimethoxyethane (80mE) and water (20 mE), and the mixture was stirred withheating at 50 C. for 24 hours. After completion of thereaction, the precipitate was filtered off. This solid waswashed with water and methanol, whereby obtaining a whitesolid (365 mg, yield: 72%). The obtained solid was Inter15 mediate 11, which is an intended product, and by mass spectrum analysis, it was confirmed that it had an mle valueof 616 with respect to a molecular weight of 616.
With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; potassium carbonate; tri tert-butylphosphoniumtetrafluoroborate; In water; toluene; at 20℃;Inert atmosphere;
Under nitrogen protection, weigh compounds S5 (4.5 mmol), S4 (9.6 mmol),[Pd2 (dba) 3] · CHCl3 (0.18 mmol) and HP (tBu) 3 · BF4 (0.36 mmol),Add to a 250 mL two-necked flask. Inject 80mL of toluene into the two-necked flask (pass N2 for 15min to remove oxygen in advance),Then, 8 mL of a 1M K2CO3 aqueous solution was added dropwise (N215min in advance to remove oxygen), and the mixture was stirred overnight at room temperature.After the reaction was completed, 20 mL of deionized water was added, and a few drops of 2M HCl were added dropwise.Extract with dichloromethane, collect the organic phase, and dry over anhydrous Na2SO4.The dried solution was filtered, and the solvent was removed on a rotary evaporator to obtain a crude product.The crude product was purified by a silica gel chromatography column, and finally purified to obtain solid S6 (3.4 mmol, 75%).
With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; potassium carbonate; tri tert-butylphosphoniumtetrafluoroborate; In water; toluene; at 20℃;Inert atmosphere;
Under nitrogen protection, weigh compounds S5 (3.6 mmol), S16 (7.8 mmol),[Pd2 (dba) 3] · CHCl3 (0.15mmol) and HP (tBu) 3 · BF4 (0.30mmol),Add to a 250 mL two-necked flask.Inject 100mL of toluene into the two-necked flask (pass N2 in advance for 15min to remove oxygen),Then add 6.5 mL of a 1M K2CO3 aqueous solution (pass N2 for 15 min to remove oxygen in advance), and stir overnight at room temperature.After the reaction was completed, 25 mL of deionized water was added, and a few drops of 2M HCl were added dropwise.Extract with dichloromethane, collect the organic phase, and dry over anhydrous Na2SO4.The dried solution was filtered, and the solvent was removed on a rotary evaporator to obtain a crude product.The crude product was purified by a silica gel column, and finally purified to obtain solid S17 (2.5 mmol, 69%).
4) Add 38.9g of 2,5-dibromo-4-iodoaniline to 272ml of acetic acid with stirring,Dissolve by heating to 40-50C ,Add 38.7g of 50% sulfuric acid solution,Cool down to 0-5C, ,Slowly drop in 26.8g of 40% sodium nitrite aqueous solution and keep it for 1 hour.The diazotization reaction solution is ready for use;Add 41.3g of potassium iodide to another reaction bottle,120g of water, start stirring, after dissolving,Slowly add the prepared diazotization reaction solution.2h after the addition is complete,After the reaction was completed, the mixture was filtered, and the reaction solution was extracted with 390 ml of dichloroethane.The organic phase was washed with 58.0 g of a 10% aqueous solution of sodium sulfite,Wash with water until the reaction solution is neutral,The organic phase was concentrated to a residual dichloroethane volume of 85 ml.41.9g of 1,4-dibromo-2,5-diiodobenzene was obtained by recrystallization,Yield: 83.3%, total yield: 67.6%, gas phase detection purity: 99.4460%, and the detection chart is shown in FIG. 4.In this step, Shimadzu GC2014 high-performance gas chromatograph, column: DB-1, detection conditions: 150-10 C / min, 30min, He, and area normalization method were used to analyze product composition.
A 500 mL four-neck flask equipped with a stirrer was charged with copper iodide (22.80 g, 119.7 mmol), potassium fluoride (7.00 g, 120.5 mmol), 1,10-phenanthroline (0.72 g, 4.6 mmol) and N,N-dimethylformamide (275 mL) under nitrogen atmosphere, and with stirring, trifluoromethyl trimethylsilane (14.4 g, 101.3 mmol) was gradually added thereto at 30 to 40 C., and the mixture was stirred at 35 C. for 1 hour. Next, a N,N-dimethylformamide solution (80 mL) in which <strong>[63262-06-6]2,5-dibromo-1,4-diiodobenzene</strong> (19.40 g, 39.8 mmol) was dissolved was added thereto and the mixture was stirred at 60 C. for 3 hours. After cooling, an aqueous hydrochloric acid solution, n-hexene and ethyl acetate were added thereto to perform extraction, and the organic layer was washed with a 20% aqueous ammonium chloride solution (100 mL*3 times). The resulting organic layer was dried over anhydrous magnesium sulfate and then the filtrate was concentrated under reduced pressure. The concentrate obtained was purified by silica gel chromatography to give 13.4 g of white solid 1,4-dibromo-2,5-bis(trifluoromethyl)benzene (purity=99.7 wt %, isolated yield=90%).
Trimethyl(thieno[3,2-b]thiophen-2-yl)silane (2.74 g, 12.9 mmol) was added to a nitrogen-substituted three-neck flask THF (tetrahydrofuran, 200 mL).After putting it in and melting it, the temperature was lowered to -78 C, and 2.5M n-Butyllithium (5.2 mL, 12.9 mmol) was dropped and stirred for 2 hours.Then, after dissolving ZnCl2 (1.76 g, 12.9 mmol) in THF (30 mL), raise the temperature to -40 C,After dropping slowly, the mixture was stirred at 0C for 1 hour. <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (3.0 g, 6.1 mmol) and Pd(PPh3)4 (0.71 g, 0.6 mmol) were added and refluxed for 12 hours.Then, after lowering to room temperature, extracted with MC, the organic layer was washed with water, dried over MgSO 4, and then the solvent was removed using a rotary evaporator.Then, it was purified by recrystallization (MeOH/dichloromethane) to obtain a yellow solid compound C (yield=65%).
With copper(I) oxide; 2,2,6,6-tetramethylheptane-3,5-dione; potassium hydroxide; In N,N-dimethyl-formamide; at 110℃; for 124h;Inert atmosphere;
According to the above reaction formula, under nitrogen protection, the purchased <strong>[63262-06-6]1,4-dibromo-2,5-diiodobenzene</strong> (1.00g/2.05mmol),Carbazole (514.29mg, 3.08mmol), potassium hydroxide (230.1mg, 4.10mmol 2,2,6,6-Tetramethyl-3,5-heptanedione (37.80mg, 0.205mmol) and cuprous oxide (29mg, 0.205mmol) were added to 10mL DMF,After heating to 110C for 124 hours, the reaction was extracted three times with 50 ml of saturated brine and 15 ml of dichloromethane.The organic phase was dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by column chromatography using petroleum etherdichloromethane=3:1 (VV) as eluent.1.02 g of white solid product was obtained with a yield of 87.8%.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene for 12h; Inert atmosphere; Reflux;
38 Synthesis of Intermediate 38-1
Add 3-boronic acid triphenylamine (5.98g, 20mmol) and 1.4 dibromo-2,5-diiodobenzene (4.88g, 10mmol) into a three-necked flask, stir to dissolve with 100ml of toluene,Under nitrogen protection, Pd(PPh3)4 (556mg, 0.5mmol) and K2CO3 (5.6g, 40mmol) aqueous solutions were added. Then the reaction solution was stirred and refluxed for 12 hours, cooled, evaporated to remove the solvent, and DCM dissolved the residue.Then wash the organic phase three times with 100 ml of water, separate the layers, concentrate the organic phase,Purified by column with DCM/PE (1:10) to obtain a pale yellow solid (3.61g, yield 60%)