2-(4-Bromophenyl)-1-phenyl-1H-benzoimidazole

White to yellow Crystal

2-(4-bromophenyl)-l-phenyI-lH-benzo[d]imidazole (9): To a suspension of amide 1 (9.6 g, 26 mmol) in anhydrous 1, 4-dioxane (100 mL) was added phosphorous oxychloride (POCl0075] 2-(4-bromophenyl)-l-phenyl-lH-benzo[d]imidazole (2): To a suspension of amide (1) (9.6 g, 26 mmol) in anhydrous 1, 4-dioxane (100 mL) was added POCl2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazole (2):Example 1.3.2[121 ] 2-(4-bromophenyl)-1 -phenyl-1 H-benzo[d]imidazole (4): To a suspension of amide 3 (9.6 g, 26 mmol) in anhydrous 1 , 4-dioxane (100 mL) was added phosphorus oxychloride (POCIExample 1.1.2 A 1-L three-neck round bottom flask was charged with 4-bromo-N-(2-(phenylamino)- phenyl)benzamide 11 (30.0 g, 82.0 mmol) followed by glacial acetic acid (300 mL). The mixture was refluxed (100 °C) with stirring for 12 h, after which LC-MS of an ahquot showed 95percent conversion. Acetic acid was removed under reduced pressure and the residue was triturated with hot hexanes to give a purple solid (34.0 g) after removing solvent under reduced pressure. The crude solids were dissolved in a minimal amount of chloroform and separated into two equal portions. Each portion was passed through slurry of silica gel topped with sea sand. The plug was washed with chloroform enough times to elute the desired compound. The solvent was removed under reduced pressure and the product recrystallized from chloroform/hexanes to give a white solid (24.0 g, 84percent yield) of the desired compound 12 at -98percent purity by LC-MS and NMR. *H NMR (500 MHz, CDC1Synthesis of Compound 15-3 and 15-4 Adding in the flask N-phenyl -1, 2-phenylenediamine (9.2g, 50mmol) and NMP (80 ml, N-methyl pyrrolidone), then adding 4-bromophenylacetic formyl chloride (10.9g, 50mmol) stirring the reaction overnight at room temperature. Reaction end, in the reaction solution is poured into the water, a large number of solid precipitation, filtration, because (tetrahydrofuran) and methanol THF recrystallization, the get white solid (compound 15-3) by adding acetic acid (100 ml) heating reflux for 12 hours, the reaction end, reduced pressure to remove the solvent, by adding methanol (50 ml), filtered, get 12g white solid (compound 17-1), yield of 69percentNext, under a nitrogen atmosphere, xylene (100 ml) was added to the compound represented by the formula (3) (9.9 g, 27.0 mmol) and p-toluene sulfonic acid (1.5 g), and the reaction solution was heated to 130° C. and refluxed to be dehydrated for 5 hours. Thereafter, the reaction solution was cooled to room temperature, and was filtrated to obtain the solid product. This solid product was dissolved again in chloroform (200 ml), and the chloroform solution was washed with a saturated sodium bicarbonate aqueous solution and water. On the other hand, ethyl acetate (50 ml) was added to the xylene-soluble part which was the filtrate obtained by the filtration, and then, this mixed solution was washed with a saturated sodium bicarbonate aqueous solution and water in the same manner as described above. Thereafter, the organic layers were mixed, and the mixed solution was dried over anhydrous sodium sulfate. Thereafter, the mixed solution was concentrated under a reduced pressure, to thereby obtain a crude product. This crude product was purified through column purification, to thereby obtain the compound represented by the aforementioned formula (4) (8.1 g, 23.2 mmol).Compound 1 (Ge, Z.; Hayakawa, T.; Ando, S.; Ueda, M.; Akiike, T.; Miyamoto, H.; Kajita, T.; Kakimoto, M. Chem. Mater. 2008, 20(7), 2532-2537) was prepared as follows: to a chilled (ca. 0° C.), stirring solution of N-phenyl-o-phenylene-1, 2-diamine (21.41 g, 116.2 mmol) in anhydrous dichloromethane (CHExample 1.1.2Exam le 1.1.21 2[0043] 2-(4-bromophenyl)-l-phenyl-lH-benzo[d]imidazole (2): To a suspension of amide 1 (9.6 g, 26 mmol) in anhydrous 1, 4-dioxane (100 mL) was added phosphorus oxychloride (POClTo a suspension of amide 1 (9.6 g, 26 mmol) in anhydrous 1 , 4-dioxane (100 mE) was added phosphorus oxychloride (POC13) (9.2 mE, 100 mmol) slowly. The whole wasthen heated at 1000 C. overnight. Afier cooling to RT, themixture was poured into ice (200 g) with stirring. Filtration, followed by recrystallization in DCMlhexanes gave a palegrey solid 2 (8.2 g, in 90percent yield).In a 250 mL three-necked flask, Access to nitrogen, 0.04 mol of intermediate M1 was added, 100mlTHF, 0.05 mol of phenylboronic acid, 0.0004 mol of tetrakis (triphenylphosphine) palladium, Stir, Then, 0.06 mol of K2CO3 aqueous solution (2 M) was added, Heated to 80 ° C, Reflux reaction for 10 hours, Sampling point plate, The reaction is complete.Natural cooling, Extracted with 200 ml of dichloromethane, The extract was dried over anhydrous sodium sulfate, filtered, the filtrate was steamed and purified on a silica gel column, Intermediate N1 was obtained, HPLC purity 99.6percent yield 84.9percent.(2) In a 250 mL three-necked flask, Purged with nitrogen, 0.04 mol of intermediate M1 was added, 100mlTHF, 0.05mol phenylboronic acid, 0.0004 mol of tetrakis (triphenylphosphine) palladium, Stirring, Then 0.06 mol K2CO3 aqueous solution (2M) was added, Heated to 80 ° C, The reaction was refluxed for 10 hours, Sample board, the reaction was complete.The mixture was naturally cooled and extracted with 200 ml of dichloromethane. The layers were separated, the extract was dried over anhydrous sodium sulfate, filtered, and the filtrate was rotary evaporated and purified over a silica gel column to give the intermediate N1, HPLC purity 99.6percent, yield 84.9percent.(2) In a 250 mL three-necked flask, purged with nitrogen, 0.04 mol of intermediate M1, 100 ml of THF, 0.05 mol of phenylboronic acid, 0.0004mol tetrakis (triphenylphosphine) palladium, stirred, then add 0.06mol K2CO3 aqueous solution (2M), heated to 80 ° C, the reaction was refluxed for 10 hours, the sample point plate, the reaction was complete.The mixture was naturally cooled and extracted with 200 ml of dichloromethane. The layers were separated and the extract was dried over anhydrous sodium sulfate and filtered. The filtrate was rotary evaporated and purified on a silica gel column to give the intermediate N1 with an HPLC purity of 99.6percent and a yield of 84.9percent.A solution of Ν-(4-phenyl)benzene-1, 2-diamine (3.68 g, 20 mmol), 4-bromobenzaldehyde (3.70 g, 20 mmol) and sodium bisulfite (2.04 g, 10mmol) was dissolved in DMF (80 mL) and stirred in air for 1 h. After the completion of the reaction, the reaction solution was poured into water to precipitate the product. After standing for some time, the product was filtered and washed with a small amount of methanol. Finally, the crude product was purified by silica gel column chromatography using a mixture of n-hexane and ethyl acetate (1: 5) as eluent to give a white powdery solid product. Yield: 6.40 g, 92percent.willN- (4-phenyl) benzene-1, 2-diamine(3.68 g, 20 mmol), 4-bromobenzaldehyde (3.70 g, 20 mmol) and sodium bisulfite (2.04 g, 10 mmol)Of the mixture was dissolved in DMF (80 mL)Mix in air for 1 h.Point plate test After the end of the reaction cooled to room temperature, The reaction solution was poured into water, Precipitation products.After standing for some time, Filter out the product, Wash with a small amount of methanol.At last, The crude product was mixed with n-hexane and ethyl acetate (1: 3)As a eluent by silica gel column chromatography to obtain a white powder solid product.Yield: 6.18 g, 89percent.4-bromo-benzaldehyde (8.3g, 45mmol) was dispersed in the benzene in 10ml of N-phenyl-1, 2-phenylenediamine (N-phenyl-1, 2-phenylenediamine, 8.3g, 45mmol ), which was heated at 180 °C for 6 hours. After cooling to room temperature, and then removed by distillation under reduced pressure to nitrobenzene, the resulting solid was filtered and dried in vacuo, washed with ethyl ether to obtain a compound A.Synthesis of 2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazoleN-Phenyl-o-phenylenediamine 13.27 g (72 mmole), 4-bromobenzaldehyde 16 g (87 mmole), and 2.8 g of PTSA (14 mmole) was stirred in 150 ml of Toluene, the reaction mixture was then heated to reflux for 16 hours, after cooling, the reaction mixture was extracted with water, and then the organic layer was evaporated to dry, the residue was then recrystallized with acetone to get 14.51 g of product (yield=57.71percent).Acetic acid (20 mL) was added to a flask containing N-phenyl-o-phenylenediamine (1.50 g, 8.14 mmol) and 4-bromobenzaldehyde (1.66 g, 8.96 mmol). c) 2-(4-Bromophenyl)-1-phenyl-1H-benzimidazole N-Phenyl-o-phenylenediamine (50 g, 0.27 mol) is dissolved in anhydrous DMF (400 ml) under N2.1Weigh 7.36 g of 4-bromobenzaldehyde and 7.3 g of o-aminodiphenylamine in 200 mL of acetic acid.After charging and discharging nitrogen for 3 times, the temperature was set to 140 ° C to start the reaction;2.2After the reaction, the temperature was lowered to room temperature, and a large amount of gray solid was precipitated after pouring into water, and filtered.After the filter cake was added with 5 g of silica gel, the column was passed to obtain 3.2 g of a white solid powder, the yield was 23.6percent, HPLC 99.7percent;Preparation of Compound F-2[183] Compound F-1 (50g, 136mmol), p-toluene sulfonic acid (PTSA, 46.9g, 272mmol), and toluene (500mL) were mixed and stirred under reflux with a Dean-stark trap under nitrogen atmosphere. After 2 hours, the reactant was cooled to room temperature, and an organic layer was extracted by adding saturated sodium chloride aqueous solution and ethyl acetate, dried over magnesium sulfate, and then treated with activated charcoal, followed by filtering with celite. A solid obtained by concentrating the filtrate under reduced pressure was re-crystallized, thereby obtaining Compound F-2 (39g, 81percent).[184]

Molecular Weight:349.2
XLogP3:5.5
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:2
Exact Mass:348.02621
Monoisotopic Mass:348.02621
Topological Polar Surface Area:17.8
Heavy Atom Count:22
Complexity:360
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes