* 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.
Stage #1: With hydrogenchloride; sodium nitrite In water at 0℃; for 0.666667 h; Stage #2: With potassium iodide In water at 20℃; for 2 h;
2,5-Dibromoaniline 10 g was dispersed in diluted hydrochloric acid (concentrated hydrochloric acid 40 ml + water 30 ml), and an aqueous solution of NaNO2 3 g was dropwise added thereto at 0°C. The reaction solution was stirred for 40 minutes and then dropwise added at room temperature to an aqueous solution of potassium iodide 60 g which was separately prepared. After stirring at room temperature for 2 hours, methylene chloride and a small amount of sodium hydrogensulfite were added thereto, and the organic layer was extracted. The organic layer was washed with a 10 percent sodium hydrogensulfite aqueous solution and saturated brine and dried on anhydrous sodium sulfate, and then the solvent was distilled off. The product was refined by silica gel chromatography, whereby targeted 2,5-dibromoiodobenzene 10.5 g (yield: 73 percent) was obtained in the form of white crystal.
70%
Stage #1: With sulfuric acid; acetic acid; sodium nitrite In water at 0℃; for 1 h; Stage #2: With potassium iodide In water for 1 h;
(1) Dissolve 7.8 g (31.2 mmol) of 2,5-dibromoaniline in 16 ml of glacial acetic acid,And 6 ml of 96percent sulfuric acid was added dropwise. 16 ml of an aqueous solution containing 6.42 g of NaNO2 was added dropwise. Stir at 0°C for 1 hour,Then 12 ml of an aqueous solution containing 3.6 g of urea was added dropwise.Excess NaNO2 is completely reacted.Then, an aqueous solution of 15.48 g (93.4 mmol) of KI is added dropwise,After 1 hour of reaction, the product was extracted with dichloromethane.After drying, the column was chromatographed with petroleum ether to give 7.92 g of a white solid.Yield 70percent.
70%
Stage #1: With sulfuric acid; acetic acid; sodium nitrite In water at 0℃; for 1 h; Stage #2: With urea; potassium iodide In water for 1 h;
(1) Dissolve 3.9 g (15.6 mmol) of 2,5-dibromoaniline in 8 ml of glacial acetic acid,3 ml of 96percent sulfuric acid was added dropwise. 8 ml of an aqueous solution containing 3.21 g of NaNO2 was added dropwise.After stirring at 0°C for 1 hour, 6 ml of an aqueous solution containing 1.8 g of urea was added dropwise.Excess NaNO2 is completely reacted. Then an aqueous solution of 7.74 g (46.7 mmol) of KI was added dropwise,After 1 hour reaction, the product was extracted with methylene chloride, dried and then columned with petroleum ether.3.96 g of a white solid are obtained with a yield of 70percent.
47%
With sulfuric acid; potassium iodide; sodium nitrite In water at 0 - 65℃;
Intermediate 42: 5-Bromo-methyl-benzofuran-3-carboxylic acid 41.1 : l ,4-Dibromo-2-iodo-benzene To a stirred mixture of 2.50 g (9.96 mmol) 2,5-dibromoaniline in 7 mL cone, sulfuric acid and 20 mL water, was added a solution of 1.00 g (14.5 mmol) sodium nitrite in 10 mL water dropwise at 0 °C and the mixture was stirred at this temperature for 1.25 h. A solution of 2.15 g (13.0 mmol) potassium iodide in 20 mL water was added dropwise under ice cooling. The ice bath was removed and the reaction mixture was heated to 65 °C for 30 min. After cooling to RT, the mixture was worked up by adding aqueous sodium thiosulfate solution, followed by extraction with PE/EtOAc. The combined organic phases were washed with aqueous sodium thiosulfate solution and saturated aqueous sodium bicarbonate solution, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by flash chromatography (PE/EtOAc = 100 -> 96/4). yield: 1.8 g (47 percent); ESI-MS: m/z = 360 (M+); Rt(HPLC): 1.69 min (method 1)
47%
Stage #1: With sulfuric acid; sodium nitrite In water at 0℃; for 1.25 h; Stage #2: With potassium iodide In water at 65℃; for 0.5 h;
41.1: 1,4-Dibromo-2-iodo-benzene To a stirred mixture of 2.50 g (9.96 mmol) 2,5-dibromoaniline in 7 mL conc. sulfuric acid and 20 mL water, was added a solution of 1.00 g (14.5 mmol) sodium nitrite in 10 mL water dropwise at 0° C. and the mixture was stirred at this temperature for 1.25 h. A solution of 2.15 g (13.0 mmol) potassium iodide in 20 mL water was added dropwise under ice cooling. The ice bath was removed and the reaction mixture was heated to 65° C. for 30 min. After cooling to RT, the mixture was worked up by adding aqueous sodium thiosulfate solution, followed by extraction with PE/EtOAc. The combined organic phases were washed with aqueous sodium thiosulfate solution and saturated aqueous sodium bicarbonate solution, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by flash chromatography (PE/EtOAc=100→96/4). yield: 1.8 g (47percent); ESI-MS: m/z=360 (M+); Rt(HPLC): 1.69 min (method 1)
Reference：
[1] Patent: EP1707550, 2006, A1, . Location in patent: Page/Page column 36
[2] Patent: CN107523089, 2017, A, . Location in patent: Paragraph 0024; 0025; 0026; 0035; 0044
[3] Patent: CN107739529, 2018, A, . Location in patent: Paragraph 0020; 0039; 0040; 0041
[4] Macromolecules, 2004, vol. 37, # 21, p. 7867 - 7878
[5] New Journal of Chemistry, 2018, vol. 42, # 8, p. 5767 - 5773
[6] Tetrahedron Letters, 2001, vol. 42, # 42, p. 7435 - 7438
[7] Angewandte Chemie - International Edition, 2008, vol. 47, # 5, p. 888 - 890
[8] Patent: WO2013/87805, 2013, A1, . Location in patent: Page/Page column 81
[9] Patent: US2013/158042, 2013, A1, . Location in patent: Paragraph 0554; 0555; 0556
[10] Reactive and Functional Polymers, 2016, vol. 105, p. 114 - 121
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[ 106-37-6 ]
[ 89284-52-6 ]
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[1] Journal of the American Chemical Society, 2008, vol. 130, # 2, p. 472 - 480
[2] European Journal of Organic Chemistry, 2008, # 10, p. 1797 - 1801
[3] Bulet., vol. 1, p. 205
[4] Journal of the Indian Chemical Society, 1936, vol. 13, p. 31
[5] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[6] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[7] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[8] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[9] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[10] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[11] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[12] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[13] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
[14] Tetrahedron Letters, 1985, vol. 26, # 1, p. 29 - 32
3
[ 3315-91-1 ]
[ 63262-06-6 ]
[ 3073-05-0 ]
[ 89284-52-6 ]
Reference：
[1] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
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[ 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
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[ 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
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[ 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
7
[ 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
8
[ 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
9
[ 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
10
[ 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
11
[ 3460-18-2 ]
[ 89284-52-6 ]
Reference：
[1] New Journal of Chemistry, 2018, vol. 42, # 8, p. 5767 - 5773
12
[ 932-31-0 ]
[ 63262-06-6 ]
[ 53092-64-1 ]
[ 89284-52-6 ]
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[1] Journal of Organic Chemistry, 1985, vol. 50, # 17, p. 3104 - 3110
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[ 108-86-1 ]
[ 89284-52-6 ]
Reference：
[1] Journal of the Indian Chemical Society, 1936, vol. 13, p. 31
Stage #1: 1.4-dibromobenzene In tetrahydrofuran; hexane; pentane at -30℃; for 24h;
Stage #2: With iodine In tetrahydrofuran; hexane; pentane at 20℃; for 1h; Further stages.;
70%
Stage #1: 1.4-dibromobenzene With 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran at -80℃; Inert atmosphere;
Stage #2: With iodine In tetrahydrofuran at -80℃;
With sulfuric acid; iodine at 220℃;
With sulfur dioxide; iodine; nitric acid; acetic acid at 200℃;
Multi-step reaction with 2 steps
1: 70 percent / iodine, concentrated sulfuric acid / 6 h / 125 - 135 °C
2: tetrahydrofuran / 2.5 h / Ambient temperature
Multi-step reaction with 2 steps
1: 70 percent / iodine, concentrated sulfuric acid / 6 h / 125 - 135 °C
2: 18 percent / tetrahydrofuran / 3.5 h / Ambient temperature
Multi-step reaction with 2 steps
1: 70 percent / iodine, concentrated sulfuric acid / 6 h / 125 - 135 °C
2: 39 percent / tetrahydrofuran / 0.5 h / Ambient temperature
Multi-step reaction with 2 steps
1: 70 percent / iodine, concentrated sulfuric acid / 6 h / 125 - 135 °C
2: 42 percent / tetrahydrofuran / 2 h / Ambient temperature; other dihaloarene, other reaction partners, other times, other temperatures
Multi-step reaction with 2 steps
1: 70 percent / iodine, concentrated sulfuric acid / 6 h / 125 - 135 °C
2: 43 percent / tetrahydrofuran / 3.5 h / Ambient temperature
Multi-step reaction with 2 steps
1: 70 percent / iodine, concentrated sulfuric acid / 6 h / 125 - 135 °C
2: 42 percent / tetrahydrofuran / 2.5 h / Ambient temperature
Multi-step reaction with 2 steps
1: 70 percent / iodine, concentrated sulfuric acid / 6 h / 125 - 135 °C
2: 41 percent / tetrahydrofuran / 2.5 h / Ambient temperature
Multi-step reaction with 2 steps
1: 70 percent / iodine, concentrated sulfuric acid / 6 h / 125 - 135 °C
2: 21 percent / tetrahydrofuran / 2 h / Ambient temperature
Multi-step reaction with 2 steps
1: 70 percent / iodine, concentrated sulfuric acid / 6 h / 125 - 135 °C
2: 35 percent / tetrahydrofuran / 5.5 h / Ambient temperature
Multi-step reaction with 2 steps
1: 70 percent / iodine / H2SO4 / 6 h / 125 - 135 °C
2: 43 percent / 2.) water / tetrahydrofuran / Ambient temperature; examination with further bromo-iodo-benzenes, and Grignard reagents; addition of lithium 2,2,6,6-tetramethylpiperidide or potassium t-butoxide; other reagent: iodine
<strong>[3638-73-1]2,5-Dibromoaniline</strong> 10 g was dispersed in diluted hydrochloric acid (concentrated hydrochloric acid 40 ml + water 30 ml), and an aqueous solution of NaNO2 3 g was dropwise added thereto at 0C. The reaction solution was stirred for 40 minutes and then dropwise added at room temperature to an aqueous solution of potassium iodide 60 g which was separately prepared. After stirring at room temperature for 2 hours, methylene chloride and a small amount of sodium hydrogensulfite were added thereto, and the organic layer was extracted. The organic layer was washed with a 10 % sodium hydrogensulfite aqueous solution and saturated brine and dried on anhydrous sodium sulfate, and then the solvent was distilled off. The product was refined by silica gel chromatography, whereby targeted 2,5-dibromoiodobenzene 10.5 g (yield: 73 %) was obtained in the form of white crystal.
70%
(1) Dissolve 7.8 g (31.2 mmol) of <strong>[3638-73-1]2,5-dibromoaniline</strong> in 16 ml of glacial acetic acid,And 6 ml of 96% sulfuric acid was added dropwise. 16 ml of an aqueous solution containing 6.42 g of NaNO2 was added dropwise. Stir at 0C for 1 hour,Then 12 ml of an aqueous solution containing 3.6 g of urea was added dropwise.Excess NaNO2 is completely reacted.Then, an aqueous solution of 15.48 g (93.4 mmol) of KI is added dropwise,After 1 hour of reaction, the product was extracted with dichloromethane.After drying, the column was chromatographed with petroleum ether to give 7.92 g of a white solid.Yield 70%.
70%
(1) Dissolve 3.9 g (15.6 mmol) of <strong>[3638-73-1]2,5-dibromoaniline</strong> in 8 ml of glacial acetic acid,3 ml of 96% sulfuric acid was added dropwise. 8 ml of an aqueous solution containing 3.21 g of NaNO2 was added dropwise.After stirring at 0C for 1 hour, 6 ml of an aqueous solution containing 1.8 g of urea was added dropwise.Excess NaNO2 is completely reacted. Then an aqueous solution of 7.74 g (46.7 mmol) of KI was added dropwise,After 1 hour reaction, the product was extracted with methylene chloride, dried and then columned with petroleum ether.3.96 g of a white solid are obtained with a yield of 70%.
47%
With sulfuric acid; potassium iodide; sodium nitrite; In water; at 0 - 65℃;
Intermediate 42: 5-Bromo-methyl-benzofuran-3-carboxylic acid 41.1 : l ,4-Dibromo-2-iodo-benzene To a stirred mixture of 2.50 g (9.96 mmol) <strong>[3638-73-1]2,5-dibromoaniline</strong> in 7 mL cone, sulfuric acid and 20 mL water, was added a solution of 1.00 g (14.5 mmol) sodium nitrite in 10 mL water dropwise at 0 C and the mixture was stirred at this temperature for 1.25 h. A solution of 2.15 g (13.0 mmol) potassium iodide in 20 mL water was added dropwise under ice cooling. The ice bath was removed and the reaction mixture was heated to 65 C for 30 min. After cooling to RT, the mixture was worked up by adding aqueous sodium thiosulfate solution, followed by extraction with PE/EtOAc. The combined organic phases were washed with aqueous sodium thiosulfate solution and saturated aqueous sodium bicarbonate solution, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by flash chromatography (PE/EtOAc = 100 -> 96/4). yield: 1.8 g (47 %); ESI-MS: m/z = 360 (M+); Rt(HPLC): 1.69 min (method 1)
47%
41.1: 1,4-Dibromo-2-iodo-benzene To a stirred mixture of 2.50 g (9.96 mmol) <strong>[3638-73-1]2,5-dibromoaniline</strong> in 7 mL conc. sulfuric acid and 20 mL water, was added a solution of 1.00 g (14.5 mmol) sodium nitrite in 10 mL water dropwise at 0 C. and the mixture was stirred at this temperature for 1.25 h. A solution of 2.15 g (13.0 mmol) potassium iodide in 20 mL water was added dropwise under ice cooling. The ice bath was removed and the reaction mixture was heated to 65 C. for 30 min. After cooling to RT, the mixture was worked up by adding aqueous sodium thiosulfate solution, followed by extraction with PE/EtOAc. The combined organic phases were washed with aqueous sodium thiosulfate solution and saturated aqueous sodium bicarbonate solution, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by flash chromatography (PE/EtOAc=100?96/4). yield: 1.8 g (47%); ESI-MS: m/z=360 (M+); Rt(HPLC): 1.69 min (method 1)
Stage #1: 1,4-dibromo-2-iodo-benzene; 1-ethynyl-4-(pentyloxy)benzene With triethylamine In tetrahydrofuran for 0.75h; Inert atmosphere;
Stage #2: With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide In tetrahydrofuran at 30℃; for 10h;
Stage #3: 1-ethynyl-4-(pentyloxy)benzene; hydroquinone Further stages;
3.2; 3.3; 3.4; 3.5 Example 3In this example, a dye molecule of the general formula (1) was prepared.Where R1 is R2, the reaction steps are as follows:
(2) 3.62 g (10.0 mmol) of 2,5-dibromobenzene iodine and 2.26 g (12.0 mmol)PentoxyphenylacetyleneDissolved in a mixture of 120 ml of tetrahydrofuran and triethylamine in a volume ratio of 1:1 and stirred with argon for 45 minutes. 102 mg of triphenylphosphine palladium dichloride, 50 mg of copper iodide was added, and the reaction was carried out at 30°C for 10 hours. Rotary evaporation,Chromatography gave 3.1 g of a white solid with a yield of 73.5%.(3) Dissolve 2.53 g (6.0 mmol) of the product of step (2) in 60 mlIn 1,4-dioxane, sonication was carried out in a 125 ml single-mouth round bottom flask with argon for 1 hour, then 1.32 g (12.0 mmol) of hydroquinone, 3.91 g (12.0 mmol) was added.Cs2CO3, 2.0 g (13.2 mmol) CsF, 19 mg tri-tert-butylphosphine,0.33 g of tris(dibenzylideneacetone)dipalladium was warmed up to 135°C and the reaction was stirred for 48 hours. The solvent was distilled off under reduced pressure, purified by column chromatography to give 1.73 g of a white solid.The yield is 84.5%.(4) 1.37 g (2.0 mmol) of the product of step (3) and 0.45 g (2.4 mmol)The pentyloxyacetylene was dissolved in 70 ml by volume of a 1:1 mixture of tetrahydrofuran and triethylamine, and the mixture was stirred under argon for 55 minutes. 70 mg of triphenylphosphine palladium dichloride, 35 mg of copper iodide was added and the reaction was carried out at 80° C. for 10 hours. Rotary evaporation,Chromatography of the column gave 1.16 g of a pale yellow solid with a yield of 73.2%.(5) 0.79 g (1.0 mmol) of the product of step (4) and 0.22 g (1.2 mmol)The ethynylbenzene sulfonic acid was dissolved in 40 ml of a 1:1 mixture of tetrahydrofuran and triethylamine in a volume ratio of 1:1 and stirred for 55 minutes under argon. 38 mg of triphenylphosphine palladium dichloride, 20 mg of copper iodide was added and the reaction was carried out at 80° C. for 10 hours. Spin-evaporated and chromatographed to give 0.66 g of a pale yellow solid with a yield of 74%.
Stage #1: 1,4-dibromo-2-iodo-benzene; 1-ethynyl-4-(pentyloxy)benzene With triethylamine In tetrahydrofuran for 0.75h; Inert atmosphere;
Stage #2: With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide In tetrahydrofuran at 30℃; for 10h;
2.2
(2) Dissolve 3.62 g (10.0 mmol) of 2,5-dibromobenzene iodide and 2.26 g (12.0 mmol) of p-pentyloxyphenylacetylene100 ml volume ratio of 1:1 in a mixture of tetrahydrofuran and triethylamine,The mixture was stirred with argon for 45 minutes. Added 102 mg of triphenylphosphine dichloride, 50 mg of copper iodide,The reaction was performed at 30°C for 10 hours. Spin-evaporated and chromatographed to give 3.1 g of white solid.The yield was 73.5%.
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