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[ CAS No. 2620-76-0 ] {[proInfo.proName]}

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Chemical Structure| 2620-76-0
Chemical Structure| 2620-76-0
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Product Details of [ 2620-76-0 ]

CAS No. :2620-76-0 MDL No. :MFCD09261342
Formula : C19H13BrN2 Boiling Point : No data available
Linear Structure Formula :- InChI Key :DXRLALXPCIOIDK-UHFFFAOYSA-N
M.W : 349.22 Pubchem ID :23094070
Synonyms :

Calculated chemistry of [ 2620-76-0 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 22
Num. arom. heavy atoms : 21
Fraction Csp3 : 0.0
Num. rotatable bonds : 2
Num. H-bond acceptors : 1.0
Num. H-bond donors : 0.0
Molar Refractivity : 94.21
TPSA : 17.82 ?2

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : Yes
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : Yes
Log Kp (skin permeation) : -4.56 cm/s

Lipophilicity

Log Po/w (iLOGP) : 3.36
Log Po/w (XLOGP3) : 5.45
Log Po/w (WLOGP) : 5.46
Log Po/w (MLOGP) : 4.95
Log Po/w (SILICOS-IT) : 4.7
Consensus Log Po/w : 4.78

Druglikeness

Lipinski : 1.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -6.01
Solubility : 0.000339 mg/ml ; 0.00000097 mol/l
Class : Poorly soluble
Log S (Ali) : -5.58
Solubility : 0.000917 mg/ml ; 0.00000262 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -7.93
Solubility : 0.00000408 mg/ml ; 0.0000000117 mol/l
Class : Poorly soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 2.32

Safety of [ 2620-76-0 ]

Signal Word:Warning Class:
Precautionary Statements:P261-P305+P351+P338 UN#:
Hazard Statements:H315-H319-H335 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 2620-76-0 ]

* 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.

  • Downstream synthetic route of [ 2620-76-0 ]

[ 2620-76-0 ] Synthesis Path-Downstream   1~19

  • 1
  • [ 597554-03-5 ]
  • [ 2620-76-0 ]
  • 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-1-phenyl-1H-benzimidazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 7h;Heating / reflux; (2) Synthesis of 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-1-phenyl-1H-benzimidazole (Compound (1-7)) Dissolving 4.0 g (11 mmol) of <strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzimidazole</strong>, 4.0 g (11 mmol) of 10-naphthalene-2-yl-anthracene-9-boronic acid and 0.27 g of tetrakis (triphenylphosphine) palladium into 40 milliliter of 1,2-dimethoxyethane, adding 18 milliliter of 2.0M sodium carbonate aqueous solution, the resultant suspension was refluxed with heating for 7 hours. After completion of the reaction, separation with filtration was carried out and resultant crystals were washed with water and methanol, thereby obtaining 5.1 g of yellowish white solids (yield: 78 %). As a result of mass spectrum (MS) analysis, it was recognized that the yellowish white solids were identified as the aimed substance and that m/e= 572 for molecular weight of 572.23.
  • 2
  • [ 359427-13-7 ]
  • [ 2620-76-0 ]
YieldReaction ConditionsOperation in experiment
93% With acetic acid; at 100℃; for 12h; Intermediate 1-1 (31.4 g, 85.5 mmol) in a 500 mL three neck flask was dissolved in acetic acid (120 mL) and refluxed at 100C for 12 hours. After completion of the reaction, distillation under reduced pressure removed acetic acid, and the mixture was washed with water (100 mL x 4). The resulting solid compound was dried under reduced pressure to obtain Intermediate 1-2.This was confirmed by 1H NMR Yield: 27.9 g, 93%
90% With trichlorophosphate; In 1,4-dioxane; at 100℃; Example 1.3.2; 9; [0086] 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 (POCl3) (9.2 mL, 100 mmol) slowly. The whole was then heated at 100C overnight. After cooling to r.t, the mixture was poured into ice (20Og) with stirring. Filtration, followed by recrystallization in DCM/hexanes gave a pale grey solid (Compound 9) (8.2 g, in 90% yield).
90% 0075] 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 POCl3 (9.2 mL, 100 mmol) slowly. The whole was then heated at about 100 C overnight. After cooling to room temperature, the mixture was poured into ice (200g) with stirring. Filtration, followed by recrystallization in DCM/hexanes gave a pale grey solid (8.2 g, in 90% yield).
90% With trichlorophosphate; In 1,4-dioxane; 2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazole (2): To a suspension of amide (1) (9.6 g, 26 mmol) in anhydrous 1,4-dioxane (100 mL) was added POCl3 (9.2 mL, 100 mmol) slowly. The whole was then heated at about 100 C. overnight. After cooling to room temperature, the mixture was poured into ice (200 g) with stirring. Filtration, followed by recrystallization in DCM/hexanes gave a pale grey solid (8.2 g, in 90% yield).
90% With trichlorophosphate; In 1,4-dioxane; at 100℃; Example 1.3.2 2-(4-bromophenyl)-1-phenyl-1H-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 (POCl3) (9.2 mL, 100 mmol) slowly. The whole was then heated at 100 C. overnight. After cooling to r.t., the mixture was poured into ice (200 g) with stirring. Filtration, followed by recrystallization in DCM/hexanes gave a pale grey solid (Compound 9) (8.2 g, in 90% yield).
90% With trichlorophosphate; In 1,4-dioxane; at 100℃; [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 (POCI3) (9.2 mL, 100 mmol) slowly. The whole was then heated at 100 C overnight. After cooling to RT, the mixture was poured into ice (200 g) with stirring. Filtration, followed by recrystallization in DCM/hexanes gave a pale grey solid 4 (8.2 g, in 90% yield).
90% With trichlorophosphate; In 1,4-dioxane; at 100℃; Example 1.1.2 2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazole (Compound 2) To a suspension of amide 1 (9.6 g, 26 mmol) in anhydrous 1,4-dioxane (100 mL) was added phosphorus oxychloride (POCl3) (9.2 mL, 100 mmol) slowly. The whole was then heated at about 100 C. overnight. After cooling to RT, the mixture was poured into ice (200 g) with stirring. Filtration, followed by recrystallization in DCM/hexanes gave a pale grey solid 2 (8.2 g, in 90% yield).
85% With acetic acid; at 100℃; for 16h;Inert atmosphere; Compound 1 (5.3g, 14.43mmol) was dissolved in glacial acetic acid (80ml), and the reaction was stirred at 100C for 16 hours under N2 atmosphere. After the reaction is over, glacial acetic acid is distilled off under reduced pressure, dissolved in dichloromethane, distilled water is added and extracted with dichloromethane, the organic layer is dried over anhydrous magnesium sulfate and filtered, and dichloromethane is removed by distillation under reduced pressure to obtain the crude product It was separated by column chromatography, and the eluent was a mixed solvent of petroleum ether and dichloromethane (1:1 v/v) to obtain a white solid (compound 2) with a yield of 85% (4.2 g).
84% With acetic acid; at 100℃; for 12h; 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 95% 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, 84% yield) of the desired compound 12 at -98% purity by LC-MS and NMR. *H NMR (500 MHz, CDC13) δ 7.89 (d, / = 8.0 Hz, 1H), 7.56 - 7.48 (m, 3H), 7.48 - 7.41 (m, 4H), 7.38 - 7.33 (m, 1H), 7.33 - 7.27 (m, 3H), 7.27 - 7.22 (m, 1H); 13C NMR (126 MHz, CDC13) δ 151.17, 142.90, 137.24, 136.74, 131.51, 130.80, 129.96, 128.89, 128.73, 127.33, 124.00, 123.54, 123.11, 119.88, 110.43.
78.9% With acetic acid;Reflux; In a 100 mL round-bottom flask, 20 g (54 mmol) of [Formula 38-b] obtained from [Scheme 32] was diluted in 60 mL of acetic acid, refluxed overnight (12 hours), stirred, cooled to room temperature, and filtered. 15 g (78.9% yield) of a compound represented by Chemical Formula 38-c] was obtained.
77% With acetic acid; at 115℃; for 0.5h; a four-neck 1 L round bottom flask equipped with an overhead stirrer, thermocouple, heating pack, and water condenser plus nitrogen inlet, charged with 4-bromo-indole-(2-(anilino)phenyl)benzene Formamide (9.0 g, 24.51 mmol) and glacial acetic acid (350 mL). The reaction was heated to an internal temperature of 115 C during 30 min, at which time the solid was completely dissolved and the reaction was completed as indicated by HPLC analysis. The reaction was allowed to cool to room temperature and acetic acid was removed via rotary evaporation to afford a pink solid. The solid residue was dissolved in CH2C12R and concentrated on EtOAc (~ 60 g). The ruthenium gel mixture was then loaded into a silica gel plug (~0.5" high, 30 g vermiculite) and eluted with CH2C12 (~5 L). The solvent was removed via rotary evaporation. The title compound (26.18 g, 75.0 mmol, 77%) was obtained from EtOAc (EtOAc).
67% With acetic acid; for 12h;Reflux; [Chemical Formula 70-f] 33.6g (0.091mol) obtained from [Scheme 25] and 100 mL of acetic acid were added to a 500 mL round-bottom flask and stirred under reflux for 12 hours. When the reaction was completed, 100 mL of water was added to the reaction mixture, stirred for 1 hour, filtered, washed twice with methanol and hexane, and dried to obtain 21.5g (yield 67%) of the compound represented by [Chemical Formula 70-g].
at 300℃; under 20.0 Torr; for 0.5h; (1) Synthesis of 2-(4-bromop;henyl)-1-phenyl-1H-benzimidazole Suspending 3.0 g (15 mmol) of 4-bromobenzoic acid into 30 milliliter of 1,2-dichloroethane, adding 2.7 g (23 mmol) of thionyl chloride and 3 drops of N,N-dimethylformamide, the resultant solution was stirred with heating at the temperature of about 50 C for 1 hour and 30 minutes until benzoic acid as the material disappeared. After completion of the reaction, removing the solvent and excess thionyl chloride by distillation, dissolving the resultant acid chloride into 30 milliliter of N-methylpyrrolidone, adding 2.8 g (15 mmol) of N-phenyl-1,2-phenylenediamine, the resultant solution was stirred at room temperature for a night. After completion of the reaction, adding water and filtering the precipitated solid, further washing with water and by drying under reduced pressure, 5.2 g of 4-bromo-N-(2-phenylamino-phenyl)-benzamide was obtained. The benzamide was stirred with heating under reduced pressure (about 20 mmHg) and at the temperature of about 300 C for 30 minutes. After completion of the reaction, the resultant solution was further dissolved in dichloro-methane, and by refining with the use of silicagel column chromatography, 3.5 g of 2-(4-bromophenyl-1-phenyl-1H) -benzimidazole was obtained (yield: 80 %).
12 g With acetic acid; for 12h;Reflux; Synthesis 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 to reflux for 12 hours, the reaction end, reduced pressure to remove the solvent, by adding methanol (50 ml), filtered, get 12g white solid (compound 15-4), yield of 69%
12 g With acetic acid; for 12h;Reflux; 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 69%
8.1 g With toluene-4-sulfonic acid; In toluene; at 130℃; for 5h;Inert atmosphere; Next, 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).

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  • 3
  • [ 1122-91-4 ]
  • [ 534-85-0 ]
  • [ 2620-76-0 ]
YieldReaction ConditionsOperation in experiment
92% With sodium hydrogensulfite; In N,N-dimethyl-formamide; for 1h; 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, 92%.
89% With sodium hydrogensulfite; In N,N-dimethyl-formamide; for 1h;Reflux; 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, 89%.
80% With sodium metabisulfite; In N,N-dimethyl-formamide; at 90℃; for 5h;Inert atmosphere; Amixture of 1-N-phenylbenzene-1,2-diamine (3.29 g, 17.86 mmol), pbromobenzaldehyde(3.30 g, 17.84 mmol) and Na2S2O5 (7.21 g, 37.93mmol) was dissolved in DMF (50 mL), and heated at 90 C under a nitrogenatmosphere for 5 h. After cooling to room temperature, themixture was poured into the distilled water (200 mL) and then extractedwith dichloromethane (3 × 100 mL). The organic phase was dried overanhydrous Na2SO4 and concentrated in vacuum. The crude product waspurified by silica gel column chromatography with dichloromethane toobtain a white solid (5.0 g, 80%). 1H NMR (500 MHz, DMSO-d6, , ppm):7.80 (d, J = 7.9 Hz, 1H), 7.60-7.54 (m, 5H), 7.46-7.42 (m, 4H),7.34-7.26 (m, 2H), 7.19 (d, J = 8.0 Hz, 1H). 13C NMR (126 MHz, CDCl3,, ppm): 151.2, 142.9, 137.3, 136.8, 131.6, 130.9, 130.1, 128.9, 128.8,127.4, 124.1, 123.6, 123.2, 119.9, 110.5
60% In benzene; at 180℃; for 6h; 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.
57.71% With toluene-4-sulfonic acid; In toluene; for 16h;Heating / reflux; 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=57.71%).
49% In acetic acid; for 12h;Reflux; 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). After the mixture was refluxed for 12 h, distilled water was added and the organic layer was extracted with dichloromethane. The organic layer was washed with sodium bicarbonate and brine and dried using anhydrous sodium sulfate. The filtrate was concentrated in vacuo to give a crude mixture, which was then subjected to column chromatography on silica gel using ethyl acetate and hexane (v/v 1:20) as the eluent. Analytically pure 2-(4-bromophenyl)-1-phenyl-1H-benz[d]imidazole was isolated as a white solid (1.39 g, 49%). 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 8.4 Hz, 1H), 7.53-7.42 (m, 7 H), 7.35-7.21 (m, 5H). 13C NMR (CDCl3, 100 MHz) δ 151.21, 142.90, 137.25, 136.75, 131.55, 130.84, 130.01, 128.90, 128.77, 127.37, 124.04, 123.58, 123.15, 119.90, 110.48. MALDI-TOF MS: calcd for C19H13BrN2 348.03, found 349.20.
35% With Oxone; In N,N-dimethyl-formamide; at 20 - 40℃;Inert atmosphere; 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, and 4-bromobenzaldehyde (45.5 g, 0.25 mol) is added dropwise. The reaction mixture is warmed to 40 C., and Oxone (potassium hydrogen monopersulfate, 98.1 g, 0.16 mol) is added in portions. After the mixture has been stirred at room temperature for 120 min., 1 l of water is added. The precipitated product is filtered off, washed with water and dried in vacuo. Recrystallisation from acetonitrile gives a cream-coloured solid (31 g, 35%).
23.6% With acetic acid; at 140℃;Inert atmosphere; 2.1Weigh 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 23.6%, HPLC 99.7%;
With Oxone; In N,N-dimethyl-formamide; for 12h;Heating / reflux; [Exemplary embodiment 2] Synthesis of compound 3 Compound 3 <n="67"/>[Reaction formula 2]OxoneDMF, reflux 12hr 4-bromobenzaldehyde (5g, 27mmol), Nl-phenylbenzene- 1,2-diamine (5.47g, 29.7mmol) and oxone (18.25g,29.7mmol) were put into a reactor, melted by DMF of 80ml and agitated for 10 hours at 120C to thereby synthesize2- (4-bromophenyl) -1-phenyl-lH-benzo [d] imidazole. The synthesized 2- (4-bromophenyl) -1-phenyl-lH- benzo [d] imidazole (β.98g, 20mmol) was melted by THF of50ml, gradually added with 2Mn-BuLi (11ml, 22mmol) at -78 C and agitated for one hour at low temperatures. The mixture was added with (Z) -3- (5-bromothiophene-2-yl) -2- cyanoacrylic acid (5.1βg, 20mmol) at -78C, agitated for one hour at low temperatures and then additionally agitated for 30 minutes at 0C to complete the reaction. <n="68"/>After extracting an organic layer from the mixture with dichloromethane and distilled water, the solvent was removed through a distiller, the organic layer was recrystallized by n-hexane, and dried and purified after filtering sediment (yield 48%) .1H NMR(CDCl3) : 11.0 (s, IH), 8.16 (s, IH), 7.70 (m, 3H), 7.54 (dd, 3JHH = 8Hz, 4H), 7.3 (s, IH), 7.26 (m, 7H) .

  • 4
  • [ 894073-37-1 ]
  • [ 2620-76-0 ]
  • [ 1072346-20-3 ]
YieldReaction ConditionsOperation in experiment
47.12% Synthesis of 2,4,7-triphenyl-9-(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-1,10-phenanthrolineTo a three-necked flask of 250 ml, 3.84 g (11 mmol) of <strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazole</strong> and 70 ml of THF were charged, then 6.9 ml (11 mmol) n-butyllithium (1.6M in Hexane solution) was dropped under stirring at -78 C. in a nitrogen atmosphere. The mixture was stirred for one hour at -78 C., and a solution of 2.29 g (5.6 mmol) 2,4,7-triphenyl-1,10-phenanthroline in 30 ml THF was dropped. Then the mixture was stirred at room temperature for overnight and was added with water. The organic layer was extracted with Dichloromethane and dried with anhydrous magnesium sulfate, the solvent was removed by rotary evaporation. The product was purified by column chromatography on alumina using Dichloromethane/Hexane as eluent and dried in vacuo, obtaining white powder compound 1.78 g (yield of 47.12%). MS (m/z, FAB+) 676.8(100%).
  • 5
  • [ 2620-76-0 ]
  • [ 73183-34-3 ]
  • [ 1146340-38-6 ]
YieldReaction ConditionsOperation in experiment
98% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃;Inert atmosphere; The compound BMBr1 (1.75 g, 5.0 mmol), boronic acid pinacol ester (1.91 g, 7.5 mmol) and KOAc (1.47 g, 15.0) were dissolved in anhydrous 1,4-dioxane (40 mL) After replacing with nitrogen, Pd(dppf)Cl2 (0.18 g,0.25 mmol) was added and the mixture was refluxed for 3 h. After the reaction was cooled to room temperature, the mixture was poured into water and extracted with methylene chloride, the organic layer was dried over anhydrous MgSO4, and the solvent was removed by rotary evaporation. Finally the crude product was purified using hexane/ethyl acetate (V / V =. 1: 2) of SiO2 column injection line to afford a white powdery solid. Yield: 1.94 g, 98%.
97% With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; for 6h;Reflux; d) 1-Phenyl-244-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1H-benzimidazole A mixture of <strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzimidazole</strong> (20.0 g, 57 mmol), bis(pinacolato)diboron (16.0 g, 63 mmol), potassium acetate (18.6 g, 0.19 mol), PdCl2(dppf)×CH2Cl2 (0.75 g, 1 mmol) and dioxane (360 ml) is degassed for 30 min. The reaction mixture is heated under reflux for 6 h. After cooling to room temperature, the mixture is poured into ice-water (80 ml) and extracted with toluene. The combined organic phases are dried over sodium sulfate, and the solvent is distilled off under reduced pressure, leaving a brown liquid. The end product is isolated as pale-brown solid (22.8 g, 97%).
95% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; for 3h;Inert atmosphere; Reflux; A mixture of compound 1a (1.745 g, 5.0 mmol),(1.91 g, 7.5 mmol) and KOAc (1.47 g, 15.0)Was dissolved in anhydrous 1,4-dioxane (40 mL)After nitrogen replacement,Pd (dppf) Cl2 (0.18 g, 0.25 mmol) was added,Heated to reflux for 3h.After completion of the reaction, the mixture was cooled to room temperature, the mixture was poured into water and extracted with dichloromethane. The organic layer was dried over anhydrous MgSO4 and the solvent was removed by steaming.The final crude product was purified using n-hexane / ethyl acetate (v / v = 1: 3) SiO2 column,A white powdery solid was obtained.Yield: 1.88 g, 95%.
90% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 40 - 80℃;Inert atmosphere; A procedure from the literature [Ge, Z.; Hayakawa, T.; Ando, S.; Ueda, M.; Akiike, T.; Miyamoto, H.; Kajita, T.; Kakimoto, M. Chem. Mater. 2008, 20(7), 2532-2537] was modified as follows: a mixture of Compound 1 (36.00 g, 103.1 mmol), bis(pinacolato)diboron (28.80 g, 113.4 mmol), [1,1′-bis(diphenylphosphino)-ferrocene]dichloropalladium(II) (3.771 g, 5.154 mmol), potassium acetate (30.35 g, 309.3 mmol) and 1,4-dioxane (480 mL) was degassed with argon for about 1 h at about 40 C. while stirring. The reaction mixture was then maintained under argon at about 80 C. while stirring. Upon confirming consumption of the starting material by TLC (SiO2, 9:1 hexanes-ethyl acetate), the reaction was cooled to RT and poured over ethyl acetate (EtOAc) (ca. 1.6 L). The mixture was then filtered through a short silica gel plug (ca. inch) and the filtrant washed copiously with EtOAc (ca. 200 mL). The combined organics were then washed with sat. NaHCO3, water and brine, dried over MgSO4, filtered and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 4:1 to 1:1-hexanes:ethyl acetate) afforded Compound 2 (36.8 g, 90%) as an off-white powder: confirmed by LCMS (APCI): calculated for C25H26BN2O2 (M+H+): 397; Found: 397.
84.1% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 120 - 150℃; for 10h;Inert atmosphere; In a 500 mL three-necked flask,Access to nitrogen,0.05 Intermediate N1 was added to 300 ml of N, N-dimethylformamide (DMF)Then 0.06 mol bis (pinacolato) diboron,0.0005 mol of (1,1'-bis (diphenylphosphino) ferrocene) dichloropalladium (II) and0.125 mol of potassium acetate was added,Stirring the mixture,The mixed solution of the above reactants was reacted at a reaction temperature of 120-150 CUnder reflux for 10 hours;After the reaction,Cool and add 200 ml of water,And the mixture was filtered and dried in a vacuum oven.The obtained residue was separated and purified on a silica gel column,To give the compound intermediate C1;HPLC purity 99.5%, yield 84.1%.
84.1% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 120 - 150℃; for 10h;Inert atmosphere; (3) in 500mL three-necked flask,Purged with nitrogen,0.05 was added as an intermediate N1 to 300 ml of N, N-dimethylformamide (DMF)0.06 mol of bis (pinacolato) diboron,0.0001 mol (1,1'-bis (diphenylphosphino) ferrocene) dichloropalladium (II) and 0.125 mol of potassium acetate were added,The mixture was stirred,The mixed solution of the above reactants was heated to reflux for 10 hours at a reaction temperature of 120-150 C;After the reaction was over, 200 ml of water was cooled and added, and the mixture was filtered and dried in a vacuum oven.The obtained residue was separated and purified on a silica gel column to obtain Compound Intermediate B1;HPLC purity 99.5%, yield 84.1%.
84.1% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetylacetonate; In N,N-dimethyl-formamide; for 10h;Inert atmosphere; Reflux; (3) In a 500mL three-necked flask, purged with nitrogen, 0.05N intermediate N1 was dissolved in 300mlN, N- dimethylformamide (DMF), then 0.06mol bis (pinacolato) diboron,0.0001 mol (1,1'-bis (diphenylphosphino) ferrocene) dichloropalladium (II) and 0.125 mol of potassium acetate were added and the mixture was stirred. The mixed solution of the above reactants was stirred at a reaction temperature of 120 to 150 C Heated to reflux for 10 hours;After the reaction was over, 200 ml of water was cooled and added, and the mixture was filtered and dried in a vacuum oven.The obtained residue was separated and purified on a silica gel column to obtain Compound Intermediate B1; HPLC purity 99.5%, yield 84.1%.
84% With tris-(dibenzylideneacetone)dipalladium(0); potassium acetate; tricyclohexylphosphine; In 1,4-dioxane; at 100℃;Inert atmosphere; Reaction process: tris(dibenzylideneacetone)dipalladium (1.05 g, 1.145 mmol)Tricyclohexylphosphine (0.8 g, 2.86 mmol) was added to a dry 1,4-dioxane solvent, and the air was replaced with nitrogen three times and activated at room temperature for 30 minutes.E-1 (20.0 g, 57.27 mmol) was added to the reaction mixture.Pinacol borate (17.45 g, 68.724 mmol) and potassium acetate (22.45 g, 229.08 mmol). Replace the air three times with nitrogen,The reaction solution was heated to 100 C.Treatment: TLC monitors the reaction. After the reaction is over,Cool to room temperature under nitrogen. Using diatomaceous earth to remove the catalyst,The filter cake was rinsed with dichloromethane until no product. Concentrate the filtrate to a little,The concentrated droplets were added to petroleum ether with stirring. When the solids are completely precipitated,Filtering and drying to obtain intermediate G-1(19.06 g, yield 84%).
82% With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 80℃; for 18h; Preparation of Compound F[186] Compound F-2 (38.6g, 110mmol), potassium acetate (32.4g, 330mmol), bis(pinacolato)diboron (36.5g, 143mmol), 1,4-dioxane (390mL), and PdCl2(dppf) (1.8g, 2mmol) were mixed and stirred at 80 for 18 hours, and then cooled at room temperature. Water (400mL) was added to the reactant and stirred. After stirring, an organic layer was extracted by adding saturated sodium chloride aqueous solution and ethyl acetate, dried over magnesium sulfate, and treated with activated charcoal, followed by filtering with celite. A solid prepared by concentrating the filtrate under reduced pressure was re-crystallized, thereby obtaining Compound F (36g, 82%).[187] 1H NMR (CDCl3) d 7.92(d, 1H), 7.76(d, 2H), 7.59(d, 2H), 7.56-7.45(m, 3H), 7.41-7.29(m, 4H), 7.27(s, 1H), 1.35(s, 12H)
81% With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃;Inert atmosphere; Example 1.3.3; 10; [0087] l-phenyl-2-(4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl)- lH-benzo[d] imidazole (10): A mixture of Compound 9 (0.70 g, 2 mmol), bis(pinacolate)diborane (0.533 g, 2.1 mmol), l,l'-Bis(diphenylphosphino)ferrocene] dichloropalladium (Pd(dppf)Cl2) (0.060 g, 0.08 mmol) and anhydrous potassium acetate (0.393 g, 4mmol) in 1,4-dioxane (20 mL) was heated at 800C under argon overnight. After cooling to r.t., the whole mixture was diluted with ethyl acetate (80 mL) then filtered. The solution was absorbed on silica gel, then purified by column chromatography (hexanes/ethyl acetate 5:1 to 3:1) to give a white solid (Compound 10) (0.64 g, in 81% yield).
81% With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃;Inert atmosphere; Example 1.1.3 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole (3): A mixture of Compound 2 (0.70 g, 2 mmol), bis(pinacolate)diborane (0.533 g, 2.1 mmol), bis(diphenylphosphino)ferrocene]dichloropalladium (Pd(dppf)Cl2) (0.060 g, 0.08 mmol) and anhydrous potassium acetate (KOAc) (0.393 g, 4 mmol) in 1,4-dioxane (20 ml) was heated at 80 C. under argon overnight. After cooling to RT, the whole was diluted with ethyl acetate (80 ml) then filtered. The solution was absorbed on silica gel, then purified by column chromatography (hexanes/ethyl acetate 5:1 to 3:1) to give a white solid 3 (0.64 g, in 81% yield).
81% With potassium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃;Inert atmosphere; Example 1.3.3 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole (10): A mixture of Compound 9 (0.70 g, 2 mmol), bis(pinacolate)diborane (0.533 g, 2.1 mmol), 1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium (Pd(dppf)Cl2) (0.060 g, 0.08 mmol) and anhydrous potassium acetate (0.393 g, 4 mmol) in 1,4-dioxane (20 mL) was heated at 80 C. under argon overnight. After cooling to r.t., the whole mixture was diluted with ethyl acetate (80 mL) then filtered. The solution was absorbed on silica gel, then purified by column chromatography (hexanes/ethyl acetate 5:1 to 3:1) to give a white solid (Compound 10) (0.64 g, in 81% yield).
81% With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃;Inert atmosphere; Example 1.1.3bis(pinacolate)diborane81%[0044] l-phenyl-2-(4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl)-lH- benzo[d]imidazole (3): A mixture of Compound 2 (0.70 g, 2 mmol), bis(pinacolate)diborane (0.533g, 2.1 mmol), bis(diphenylphosphino)ferrocene]dichloropalladium (Pd(dppf)Ci2) (0.060 g, 0.08 mmol) and anhydrous potassium acetate (KOAc) (0.393 g, 4mmol) in 1,4-dioxane (20 ml) was heated at 80 C under argon overnight. After cooling to RT, the whole was diluted with ethyl acetate (80 ml) then filtered. The solution was absorbed on silica gel, then purified by column chromatography (hexanes/ethyl acetate 5:1 to 3:1) to give a white solid 3 (0.64 g, in 81% yield)
81% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃; for 12h;Inert atmosphere; Schlenk technique; A mixture of 1a (0.70 g , 2.0 mmol), bis(pinacolate)diborane (0.53 g, 2.1 mmol), l,l'-bis(diphenylphosphino)ferrocene]dichloropalladium (Pd(dppf)Cl2) (0.060g,0.08mmol), andanhydrous potassium acetate (0.393 g, 4.0 mmol) in 1,4-dioxane(20 mL) was heated at 80C under nitrogen for 12 h. After cooling to room temperature, the mixture was extracted with ethyl acetate (30 mL*3). The organic extracts were washed with water, brine, and then dried with anhydrous MgSO4. After filtration, the filtrate was pumped dry in vacuo. The crude residue was subjected to column chromatography by eluting with hexanes/EA (8:1) as the eluent to give a white solid (yield: 81%). 1H NMR (400 MHz, acetone-d6): d (ppm ) 7.79 (d, J 7.6 Hz, 1H), 7.71 (d, J=7.6 Hz, 2H), 7.62-7.56 (m,5H), 7.45 (d, J=7.6 Hz, 2H), 7.37-7.23 (m, 3H) and 1.34 (s, 12H); 13C NMR (125 MHz, acetone-d6): d (ppm) 152.9, 144.3, 138.6, 138.2, 135.2, 134.0, 131.0, 129.7, 129.6, 128.6, 124.3, 123.7, 120.7, 111.4, 84.9, 25.3; Mass (FAB ): m/z: 397.1 [M+H]+.
81% With palladium bis[bis(diphenylphosphino)ferrocene] dichloride; potassium acetate; In 1,4-dioxane; at 80℃;Inert atmosphere; [122] 1 -phenyl-2-(4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl)phenyl)-1 H-benzo[d]imidazole (5): A mixture of Compound 4 (0.70 g, 2 mmol), bis(pinacolate)diborane (0.533g, 2.1 mmol), bis(diphenylphosphino)ferrocene]dichloropalladium (Pd(dppf)CI2) (0.060 g, 0.08 mmol) and anhydrous potassium acetate (KOAc) (0.393 g, 4mmol) in 1 ,4-dioxane (20 ml) was heated at about 80 C under argon overnight. After cooling to RT, the whole was diluted with ethyl acetate (80 ml) then filtered. The solution was absorbed on silica gel, then purified by column chromatography (hexanes/ethyl acetate 5:1 to 3: 1 ) to give a white solid 5 (0.64 g, in 81 % yield).
81% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃;Inert atmosphere; A mixture of Compound 2 (0.70 g, 2 mmol), bis(pinacolate)diborane (0.533 g, 2.1 mmol), bis(diphenylphosphino)ferrocene]dichloropalladium (Pd(dppf)C12) (0.060 g,0.08 mmol) and anhydrous potassium acetate (KOAc) (0.3 93g, 4 mmol) in 1 ,4-dioxane (20 ml) was heated at 80 C. under argon overnight. Afier cooling to RT, the whole was diluted with ethyl acetate (80 ml) then filtered. The solution wasabsorbed on silica gel, then purified by column chromatog-raphy (hexanes/ethyl acetate 5:1 to 3:1) to give a white solid3 (0.64 g, in 81% yield).
81% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃;Inert atmosphere; Example 1.1.3 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole (Compound 3) A mixture of Compound 2 (0.70 g, 2 mmol), bis(pinacolate)diborane (0.533 g, 2.1 mmol), bis(diphenylphosphino)ferrocene]dichloropalladium (Pd(dppf)Cl2) (0.060 g, 0.08 mmol) and anhydrous potassium acetate (KOAc) (0.393 g, 4 mmol) in 1,4-dioxane (20 ml) was heated at about 80 C. under argon overnight. After cooling to RT, the whole was diluted with ethyl acetate (80 mL) then filtered. The solution was absorbed on silica gel, then purified by column chromatography (hexanes/ethyl acetate 5:1 to 3:1) to give a white solid 3 (0.64 g, in 81% yield).
81.2% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 120 - 150℃; for 10h; (3) In a 500 mL three-necked flask, nitrogen gas was introduced, and 0.05 mol of the intermediate Y1 was added and dissolved in 300 ml of N,N-dimethylformamide (DMF).Further, 0.06 mol of bis(pinacolyl)diboron, 0.0005 mol of (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium (II), and 0.125 mol of potassium acetate were added, and the mixture was stirred.Mixing the above reactants at the reaction temperatureHeating under reflux at 120-150 C for 10 hours;After the reaction was completed, it was cooled and 200 ml of water was added, and the mixture was filtered and dried in a vacuum oven.The obtained residue was separated and purified through silica gel column to give Compound Intermediate B1; HPLC purity 99.2%, yield: 81.2%.
79% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 85℃; for 20h;Inert atmosphere; General procedure: In a 250 mLreaction flask, the intermediate IV (2.00 g, 3.78 mmol), bis(pinacolato)diboron (1.44 g, 5.67 mmol), potassium acetate (1.49 g, 15.18 mmol)and Pd (dppf)Cl2 (0.17 g, 0.23 mmol) were dissolved in dry 1,4-dioxane(80 mL) and refluxed for 20 h under a nitrogen atmosphere. Aftercooling to room temperature, the mixture was poured into the distilledwater and then extracted with dichloromethane. The organic phase wasdried over anhydrous Na2SO4 and concentrated in vacuum. The crudeproduct was purified by silica gel column chromatography using petroleum ether/dichloromethane (2:1, v/v) as eluent to obtain a whitesolid (1.52 g, 69.8
78% With bis-triphenylphosphine-palladium(II) chloride; potassium acetate; In tetrahydrofuran; at 80℃; for 3h;Inert atmosphere; Compound 2 (2.8g, 8.02mmol), diboron pinacol ester (3.1g, 12.03mmol) and potassium acetate (2.36g, 24.06mmol) were added to a certain amount of tetrahydrofuran (80ml), In the N2 atmosphere, Add bistriphenylphosphorus palladium dichloride (168mg, 0.24mmol), The reaction was stirred at 80C for 3 hours. After the reaction is over, Distill under reduced pressure to remove tetrahydrofuran, Dissolve with dichloromethane, Add distilled water and extract with dichloromethane. The obtained organic layer was dried with anhydrous magnesium sulfate and filtered, Distilled under reduced pressure to remove dichloromethane, The crude product obtained is separated by column chromatography, The eluent is a mixed solvent of dichloromethane and ethyl acetate (3:1v/v), A white solid (Compound 3) was obtained with a yield of 78% (2.5 g).
With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃;Inert atmosphere; [0076] l-phenyl-2-(4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl)- lH-benzo[d]imidazole (3): A mixture of compound (2) (0.70 g, 2 mmol), bis(pinacolate)diborane (0.533g, 2.1 mmol), Pd(dppf)Cl2 (0.060 g, 0.08 mmol) and anhydrous potassium acetate (0.393 g, 4mmol) in 1,4-dioxane (20 mL) was heated at about 80 C under argon overnight. After cooling to room temperature, the whole was diluted with ethyl acetate (~80 mL) then filtered. The solution was absorbed on silica gel, then purified by column chromatography (hexanes/ethyl acetate 5: 1 to 3:1) to give a white solid (0.64 g, in 81% yield).
Under N2 gas purification system, Compound A, 1.5 equivalents of Bu-Li into diethyl ether, and the mixture was stirred at a temperature of -78 deg. C. After 2 hours the reaction was complete, added 1.2 equivalents of compound B, and the mixture was stirred at a temperature of -78 deg. C for 30 minutes. The dry ice bath was removed and the reaction temperature was raised to room temperature. After 8 hours the reaction was complete, deionized water, dilute HCl (30ml) to remove the organic solvent. After complete removal of the organic solvent, water and the precipitated white solid was filtered off to obtain a compound C.
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃;Glovebox; In a glovebox, three oven-dried reaction jars were each charged with 2-(4- bromophenyl)-l -phenyl- lH-benzimidazole 12 (4.20 g, 12.0 mmol), bis(pinacolato)- diboron (Bpin) (3.05 g, 12 mmol, 1 eq.), potassium acetate (2.95 g, 30 mmol, 2.5 eq.), and Pd(dppf)Cl2 (300 mg, 0.36 mmol, 3 mol%). The solvent (1,4-dio-xane, 80 mL) was added to each jar and the reactions were stirred at 80 C overnight. After complete conversion (-95%) as determined by LC-MS, the contents of the reaction jars were mixed and the solvent removed under reduced pressure. Water (200 mL) was added the product was extracted into chloroform (3x200 mL), the product was passed through a silica plug and recrystallized from acetonitrile. The reaction was successfully scaled up to 12 g in 90% yield after recrystallization to give the desired boronic ester 8 at -98% purity as judged by LC-MS and NMR. *H NMR (500 MHz, cdcl3) δ 7.90 (dt, J = 8.1, 0.9 Hz, 1H), 7.76 - 7.71 (m, 2H), 7.60 - 7.55 (m, 2H), 7.49 - 7.41 (m, 3H), 7.35 - 7.21 (m, 6H), 1.32 (s, 12H); 13C NMR (126 MHz, CDC13) δ 172.37, 157.10, 152.56, 135.25,133.58, 133.11, 131.25, 130.46, 128.49, 128.13, 128.03, 127.96, 127.73, 127.11, 126.47, 125.24, 124.99, 123.30

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  • 6
  • 1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium (Pd(dppf)Cl2) [ No CAS ]
  • [ 2620-76-0 ]
  • [ 73183-34-3 ]
  • [ 1146340-38-6 ]
YieldReaction ConditionsOperation in experiment
81% With potassium acetate; In 1,4-dioxane; Example 1.3.3 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole (10): A mixture of Compound 9 (0.70 g, 2 mmol), bis(pinacolate)diborane (0.533 g, 2.1 mmol), 1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium (Pd(dppf)Cl2) (0.060 g, 0.08 mmol) and anhydrous potassium acetate (0.393 g, 4 mmol) in 1,4-dioxane (20 mL) was heated at 80 C. under argon overnight. After cooling to r.t., the whole mixture was diluted with ethyl acetate (80 mL) then filtered. The solution was absorbed on silica gel, then purified by column chromatography (hexanes/ethyl acetate 5:1 to 3:1) to give a white solid (Compound 10) (0.64 g, in 81% yield).
  • 7
  • [ 2620-76-0 ]
  • [ 201802-67-7 ]
  • [ 1259883-01-6 ]
YieldReaction ConditionsOperation in experiment
76% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In tetrahydrofuran; methanol; water; for 24h;Inert atmosphere; Reflux; General procedure: A mixture of compound B1 (0.70 g, 2.00 mmol), 4-(diphenylamino)phenylboronic acid (0.70 g, 2.40 mmol), tetrakis(triphenylphosphine)palladium (0.12 g, 0.10 mmol), and aqueous sodium carbonate (2 M, 10 mL) in tetrahydrofuran (40 mL) and methanol (10 mL) was heated to reflux in a nitrogen atmosphere for 24 h. After the reaction mixture was concentrated in vacuo, the resulting mixture was extracted with dichloromethane. The organic layer was washed with water and brine and dried using anhydrous sodium sulfate. The filtrate was concentrated in vacuo to give a crude mixture, which was then subjected to column chromatography on silica gel using dichloromethane and hexane (v/v 1:1) as the eluent to afford analytically pure N,N-diphenyl-4'-(1-phenyl-1H-benzo[d]imidazol-2-yl)biphenyl-4-amine as a yellow solid (0.78 g, 76%). 1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8 Hz, 1H), 7.61 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 8 Hz, 4H), 7.45 (d, J = 8.8 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H), 7.27-7.23 (m, 8H), 7.10 (dd, J = 8.8, 2 Hz, 6H), 7.02 (t, J = 7.2 Hz, 2H). 13C NMR (CDCl3, 100 MHz) δ 152.18, 147.65, 147.51, 141.39, 137.29, 137.09, 133.66, 129.89, 129.79, 129.28, 128.57, 127.62, 127.47, 127.24, 124.53, 123.62, 123.28, 123.09, 122.98, 119.75, 110.38. MALDI-TOF MS: calcd for C37H27N3 513.22 g/mol, found 513.26 g/mol. HRMS (FAB+) [M + H: C37H28N3]: calcd for 514.2283, found 514.2283. Anal. Calcd. For C37H27N3: C, 86.52; H, 5.30; N, 8.18. Found: C, 86.05; H, 5.18; N, 8.11.
62% With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 100℃;Inert atmosphere; [0104] Compound 26: A mixture of Compound 25 (4- (diphenylamino)phenyl)boronic acid (900 mg, 3.1 mmol), Compound 9 (1.09 g, 3.1 mmol), Pd(PPh3)4 (180 mg, 0.16 mmol) and K2CO3 (1.38 g, 10 mmol) in 1,4- dioxane/H2O (25 mL/5 mL) was degassed and the resulting mixture was heated at about 100 0C overnight under an argon atmosphere. After cooling to room temperature, the resulting mixture was poured into water, extracted with ethyl acetate (100 mL x 2). The organic phase was dried over Na2SO4 and filtered. After addition of hexanes (100 mL), a yellow precipitate formed after about one hour. Filtration gave a yellow solid (760 mg) and the filtrate was absorbed on silica gel and purified by flash chromatography to give a yellow solid (200 mg). The total amount of product (Compound 26) was 960 mg in 62% yield.
  • 8
  • [ 586-75-4 ]
  • [ 534-85-0 ]
  • [ 2620-76-0 ]
YieldReaction ConditionsOperation in experiment
94% 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 (CH2Cl2) (575 mL) was added 4-bromobenzoyl chloride (25.00 g, 113.9 mmol) portion-wise, followed by dropwise addition of triethylamine (Et3N) (31.8 mL). The reaction was allowed to warm to room temperature and stirring continued until TLC (SiO2, 4:1 hexanes-ethyl acetate) indicated consumption of the starting material. Upon completion, the reaction was washed with water and brine, dried over MgSO4, filtered and concentrated in vacuo. The resulting crude was then dissolved in anhydrous 1,4-dioxane (500 mL) and heated to about 80 C. Upon completely dissolving, phosphorus oxychloride (31.2 mL, 335 mmol) was added to the solution slowly via syringe and the reaction then maintained at about 115 C. Upon completion (ca. 1 h), the solution was cooled to room temperature (RT) and poured over CH2Cl2 (ca. 3 L) and washed with brine. The organics were then dried over MgSO4, filtered and concentrated in vacuo. Purification of the crude product by recrystallization from CH2Cl2 and hexanes provided Compound 1 (37.5 g, 94%) as an off-white solid: confirmed by LCMS (APCI): calculated for C19H13BrN2 (M+): 349; Found: 349.
81.6% In 1-methyl-pyrrolidin-2-one; at 160℃;Inert atmosphere; Weigh 10.95g p-bromobenzoyl chloride,9.15g o-aminodiphenylamine dissolved in 200ML of NMP,After filling and releasing nitrogen 3 times,Set the temperature to 160,Start the reaction; after the reaction,Cool down to room temperature,A large amount of gray solid precipitated after being poured into water,filter,The filter cake was slurried with methanol to obtain 14.2g of brown-gray solid powder,The yield was 81.6% and HPLC was 98.9%.
  • 9
  • [ 2620-76-0 ]
  • [ 618442-57-2 ]
  • [ 1258780-50-5 ]
  • 10
  • [ 100124-06-9 ]
  • [ 2620-76-0 ]
  • [ 1312212-67-1 ]
YieldReaction ConditionsOperation in experiment
92% With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 90℃; for 4.5h;Inert atmosphere; [Example 5] This example will give descriptions of a method of synthesizing 2-[4-(dibenzofuran-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBFBIm-II) represented by the following Structural formula (130). [Show Image] [Synthesis of 2-[4-(dibenzofuran-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBFBIm-II)] The synthesis scheme of 2-[4-(dibenzofuran-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBFBIm-II) is illustrated in (B-5). [Show Image] In a 100-mL three-neck flask, a mixture of 1.7 g (5.0 mmol) of <strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzimidazole</strong>, 1.0 g (5.0 mmol) of dibenzofuran-4-boronic acid, 22 mg (0.1 mmol) of palladium(II) acetate, 60 mg (0.2 mmol) of tri(ortho-tolyl)phosphine, 30 mL of toluene, 3 mL of ethanol, and 7.5 mL of a 2 mol/L aqueous solution of potassium carbonate was stirred to be degassed under reduced pressure. Then, the mixture was heated and stirred at 90 C for 4.5 hours under a nitrogen stream. After a predetermined time, 50 mL of toluene was added to this mixture solution, and the organic layer of the resulting suspension was suction filtered through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855). The resulting filtrate was concentrated, followed by purification using silica gel column chromatography. The chromatography was carried out using a mixed solvent of toluene and ethyl acetate in a ratio of 19 to 1 as a developing solvent. The obtained fractions were concentrated, and hexane was added to the mixture, followed by irradiation with ultrasonic waves. The precipitated solid was collected by suction filtration. Thus, 2.0 g of a white powder was obtained in 92% yield, which was the substance to be produced. The Rf values of the produced substance and <strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzimidazole</strong> were respectively 0.10 and 0.22, which were found by silica gel thin layer chromatography (TLC) (with a developing solvent containing ethyl acetate to hexane in a ratio of 1 to 10). A nuclear magnetic resonance (NMR) method identified this compound as 2-[4-(dibenzofuran-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBFBIm-II), which was the substance to be produced. 1H NMR data of the obtained substance are as follows: 1H NMR (CDCl3, 300 MHz): δ (ppm) = 7.27-7.63 (m, 13H), 7.74-7.78 (m, 2H), 7.89-8.00 (m, 5H). FIGS. 21A and 21B illustrate the 1H NMR charts. Note that FIG. 21B is a chart showing an enlarged part of FIG. 21 A in the range of 7.0 ppm to 8.5 ppm. Further, FIG. 22A shows an absorption spectrum of a toluene solution of DBFBIm-II, and FIG. 22B shows an emission spectrum thereof. FIG. 23A shows an absorption spectrum of a thin film of DBFBIm-II, and FIG. 23B shows an emission spectrum thereof. The absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V-550, produced by JASCO Corporation). The measurements were performed with samples prepared in such a manner that the solution was put in a quartz cell while the thin film was obtained by evaporation onto a quartz substrate. The absorption spectrum of the solution was obtained by subtracting the absorption spectra of quartz and toluene from those of quartz and the solution, and the absorption spectrum of the thin film was obtained by subtracting the absorption spectrum of a quartz substrate from those of the quartz substrate and the thin film. In FIGS. 22A and 22B and FIGS. 23A and 23B, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). In the case of the toluene solution, an absorption peak was observed at around 323 nm, and emission wavelength peaks were 365 nm, 385 nm and 405 nm (excitation wavelength: 329 nm). In the case of the thin film, absorption peaks were observed at around 300 nm and 324 nm, and an emission wavelength peak was 405 nm (excitation wavelength: 330 nm).
  • 11
  • [ 108847-20-7 ]
  • [ 2620-76-0 ]
  • [ 1297270-55-3 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 6h;Inert atmosphere; [Example 1] This example will give descriptions of a method of synthesizing 2-[4-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-II) represented by the following Structural formula (108). [Show Image] [Synthesis of 2-[4-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-II)] The synthesis scheme of 2-[4-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-II) is illustrated in (B-1). [Show Image] In a 500-mL three-neck flask were put 5.1 g (15 mmol) of <strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzimidazole</strong>, 3.7 g (16 mmol) of dibenzothiophen-4-boronic acid, and 0.2 g (0.7 mmol) of tri(ortho-tolyl)phosphine. The air in the flask was replaced with nitrogen. To this mixture were added 16 mL of a 2.0 mmol/L aqueous solution of potassium carbonate, 55 mL of toluene, and 18 mL of ethanol. Under reduced pressure, this mixture was stirred to be degassed. Then, 33 mg (0.2 mmol) of palladium(II) acetate was added to this mixture, and the mixture was stirred at 80 C for 6 hours under a nitrogen stream. After a predetermined time, water was added to the obtained mixture, and the aqueous layer was extracted with chloroform. The extracted solution and the organic layer were combined and washed with saturated brine, followed by drying with magnesium sulfate. This mixture was gravity filtered. The resulting filtrate was concentrated to give an oily substance. This oily substance was purified by silica gel column chromatography. The silica gel column chromatography was carried out using toluene as a developing solvent. The obtained fractions were concentrated to give a solid. Hexane was added to this solid, followed by irradiation with ultrasonic waves. Suction filtration was carried out, whereby 5.8 g of a white powder was obtained in 88% yield, which was the substance to be produced. By a train sublimation method, 2.8 g of the obtained white powder was purified. In the purification, the white powder was heated at 235 C under a pressure of 2.4 Pa with a flow rate of argon gas of 5 mL/min. After the purification, 2.2 g of a pale yellow glassy solid was obtained in a yield of 79%, which was the substance to be produced. A nuclear magnetic resonance (NMR) method identified this compound as 2-[4-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-II), which was the substance to be produced. 1H NMR data of the obtained substance are as follows: 1H NMR (CDCl3, 300 MHz): δ (ppm) = 7.27-7.30 (m, 2H), 7.32-7.60 (m, 10H), 7.67-7.75 (m, 4H), 7.82-7.85 (m, 1H), 7.83 (dd, J = 8.4Hz, 1.5 Hz, 1H), 8.13-8.19 (m, 2H). FIGS. 9A and 9B illustrate the 1H NMR charts. Note that FIG. 9B is a chart showing an enlarged part of FIG. 9A in the range of 7.0 ppm to 8.5 ppm. Further, FIG. 10A shows an absorption spectrum of a toluene solution of DBTBIm-II, and FIG. 10B shows an emission spectrum thereof. FIG. 11A shows an absorption spectrum of a thin film of DBTBIm-II, and FIG. 11B shows an emission spectrum thereof. The absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V-550, produced by JASCO Corporation). The measurements were performed with samples prepared in such a manner that the solution was put in a quartz cell while the thin film was obtained by evaporation onto a quartz substrate. The absorption spectrum of the solution was obtained by subtracting the absorption spectra of quartz and toluene from those of quartz and the solution, and the absorption spectrum of the thin film was obtained by subtracting the absorption spectrum of a quartz substrate from those of the quartz substrate and the thin film. In FIGS. 10A and 10B and FIGS. 11A and 11B, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). In the case of the toluene solution, absorption peaks were observed at around 294 nm, 315 nm, and 337 nm, and emission wavelength peaks were 371 nm and 386 nm (excitation wavelength: 315 nm). In the case of the thin film, absorption peaks were observed at around 234 nm, 298 nm, 319 nm, and 338 nm, and an emission wavelength peak was 401 nm (excitation wavelength: 316 nm).
  • 12
  • [ 949925-61-5 ]
  • [ 2620-76-0 ]
  • [ 1312212-65-9 ]
YieldReaction ConditionsOperation in experiment
80% With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 4h;Inert atmosphere; [Example 3] This example will give descriptions of a method of synthesizing 2-[4-(2,8-diphenyldibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-III) represented by the following Structural formula (189). [Show Image] [Synthesis of 2-[4-(2,8-diphenyldibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-III)] The synthesis scheme of 2-[4-(2,8-diphenyldibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-III) is illustrated in (B-3). [Show Image] In a 50-mL three-neck flask were put 1.8 g (5.0 mmol) of <strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzimidazole</strong>, 2.2 g (5.8 mmol) of 2,8-diphenyldibenzothiophen-4-boronic acid, and 76 mg (0.2 mmol) of tri(ortho-tolyl)phosphine. The air in the flask was replaced with nitrogen. To this mixture were added 5.8 mL of a 2.0 mmol/L aqueous solution of potassium carbonate, 19 mL of toluene, and 6 mL of ethanol. Under reduced pressure, this mixture was stirred to be degassed. Then, 11 mg (50 μmol) of palladium(II) acetate was added to this mixture, and the mixture was stirred at 80 C for 4 hours under a nitrogen stream. After a predetermined time, the aqueous layer of the obtained mixture was extracted with chloroform. The extracted solution and the organic layer were combined and washed with saturated brine, followed by drying with magnesium sulfate. This mixture was separated by gravity filtration, and the filtrate was concentrated to give an oily substance. This oily substance was purified by silica gel column chromatography. The chromatography was carried out using toluene as a developing solvent. The obtained fractions were concentrated to give an oily substance. Recrystallization of this oily substance from a mixed solvent of toluene and hexane gave 1.9 g of a pale yellow powder in 63% yield, which was the substance to be produced. By a train sublimation method, 1.9 g of the obtained yellow powder was purified. In the purification, the yellow powder was heated at 310 C under a pressure of 2.0 Pa with a flow rate of argon gas of 5 mL/min. After the purification, 1.5 g of a white glassy solid was obtained in a yield of 80%, which was the substance to be produced. The nuclear magnetic resonance (NMR) measurement identified this compound as 2-[4-(2,8-diphenyldibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-III). 1H NMR data of the obtained compound are as follows: 1H NMR (CDCl3, 300 MHz): δ (ppm) = 7.27-7.31 (m, 2H), 7.33-7.61 (m, 12H), 7.70-7.77 (m, 10H), 7.88-7.95 (m, 2H), 8.42 (dd, J = 6.6 Hz, 1.5 Hz, 2H). FIGS. 15A and 15B illustrate the 1H NMR charts. Note that FIG. 15B is a chart showing an enlarged part of FIG. 15A in the range of 7.0 ppm to 8.5 ppm. Further, FIG. 16A shows an absorption spectrum of a toluene solution of DBTBIm-III, and FIG. 16B shows an emission spectrum thereof. FIG. 17A shows an absorption spectrum of a thin film of DBTBIm-III, and FIG. 17B shows an emission spectrum thereof. The absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V-550, produced by JASCO Corporation). The measurements were performed with samples prepared in such a manner that the solution was put in a quartz cell while the thin film was obtained by evaporation onto a quartz substrate. The absorption spectrum of the solution was obtained by subtracting the absorption spectra of quartz and toluene from those of quartz and the solution, and the absorption spectrum of the thin film was obtained by subtracting the absorption spectrum of a quartz substrate from those of the quartz substrate and the thin film. In FIGS. 16A and 16B and FIGS. 17A and 17B, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). In the case of the toluene solution, absorption peaks were observed at around 284 nm, 301 nm, and 351 nm, and an emission wavelength peak was 381 nm (excitation wavelength: 307 nm). In the case of the thin film, absorption peaks were observed at around 265 nm, 306 nm, and 357 nm, and an emission wavelength peak was 407 nm (excitation wavelength: 335 nm). Further, the glass transition temperature of DBTBIm-III was examined with a differential scanning calorimeter (DSC). The measurement results show that the glass transition temperature of DBTBIm-III is 136 C. Thus, DBTBIm-III has a high glass transition temperature and good heat resistance. In addition, a peak indicating crystallization was not observed; thus, it is found that DBTBIm-III is a substance which is difficult to crystallize.
  • 13
  • [ 1115640-18-0 ]
  • [ 2620-76-0 ]
  • [ 1312212-66-0 ]
YieldReaction ConditionsOperation in experiment
83% With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 90℃; for 2.5h;Inert atmosphere; [Example 4] This example will give descriptions of a method of synthesizing 2-[4-(6-phenyldibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-IV) represented by the following Structural formula (188). [Show Image] [Synthesis of 2-[4-(6-phenyldibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-IV)] The synthesis scheme of 2-[4-(6-phenyldibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-IV) is illustrated in (B-4). [Show Image] In a 100-mL three-neck flask, a mixture of 1.7 g (5.0 mmol) of <strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzimidazole</strong>, 1.5 g (5.0 mmol) of 6-phenyldibenzothiophen-4-boronic acid, 22 mg (0.1 mmol) of palladium(II) acetate, 60 mg (0.2 mmol) of tri(ortho-tolyl)phosphine, 20 mL of toluene, 2 mL of ethanol, and 7.5 mL of a 2 mol/L aqueous solution of potassium carbonate was stirred to be degassed under reduced pressure. Then, the mixture was heated and stirred at 90 C for 2.5 hours under a nitrogen stream. After a predetermined time, 150 mL of toluene was added to this mixture solution, and the organic layer of the resulting suspension was suction filtered through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855). The resulting filtrate was concentrated, followed by purification using silica gel column chromatography. The silica gel column chromatography was carried out using a mixed solvent of toluene and ethyl acetate in a ratio of 19 to 1 as a developing solvent. The obtained fractions were concentrated, and acetone and methanol were added to the mixture, followed by irradiation with ultrasonic waves. The precipitated solid was collected by suction filtration. Thus, 2.2 g of a white powder was obtained in 83% yield, which was the substance to be produced. The Rf values of the produced substance and <strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzimidazole</strong> were respectively 0.21 and 0.36, which were found by silica gel thin layer chromatography (TLC) (with a developing solvent containing ethyl acetate and hexane in a ratio of 1 to 5). The nuclear magnetic resonance (NMR) measurement identified this compound as 2-[4-(6-phenyldibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-IV). 1H NMR data of the obtained compound are as follows: 1H NMR (CDCl3, 300 MHz): δ (ppm) = 7.26-7.59 (m, 15H), 7.64-7.71 (m, 6H), 7.90-7.93 (d, J = 7.8 Hz, 1H), 8.15-8.19 (m, 2H). FIGS. 18A and 18B illustrate the 1H NMR charts. Note that FIG. 18B is a chart showing an enlarged part of FIG. 18A in the range of 7.0 ppm to 8.5 ppm. Further, FIG. 19A shows an absorption spectrum of a toluene solution of DBTBIm-IV, and FIG. 19B shows an emission spectrum thereof. FIG. 20A shows an absorption spectrum of a thin film of DBTBIm-IV, and FIG. 20B shows an emission spectrum thereof. The absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V-550, produced by JASCO Corporation). The measurements were performed with samples prepared in such a manner that the solution was put in a quartz cell while the thin film was obtained by evaporation onto a quartz substrate. The absorption spectrum of the solution was obtained by subtracting the absorption spectra of quartz and toluene from those of quartz and the solution, and the absorption spectrum of the thin film was obtained by subtracting the absorption spectrum of a quartz substrate from those of the quartz substrate and the thin film. In FIGS. 19A and 19B and FIGS. 20A and 20B, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). In the case of the toluene solution, an absorption peak was observed at around 316 nm and emission wavelength peaks were 371 nm and 387 nm (excitation wavelength: 320 nm). In the case of the thin film, absorption peaks were observed at around 242 nm, 304 nm, and 319 nm, and an emission wavelength peak was 402 nm (excitation wavelength: 349 nm).
  • 14
  • [ 2620-76-0 ]
  • [ 952514-79-3 ]
  • 15
  • [ 100622-34-2 ]
  • [ 2620-76-0 ]
  • [ 944801-79-0 ]
YieldReaction ConditionsOperation in experiment
73% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 5h;Reflux; Inert atmosphere; In the flask, 9-indoleboronic acid (5 g, 22 mmol) was added.<strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzimidazole</strong> (7.9 g, 22 mmol),Potassium carbonate (6g, 44mmol),Tetrahydrofuran (100mL),Water (50mL),Tetrakistriphenylphosphine palladium (0.5g),Heated under nitrogen for 5 hours,cool down,The crude product was purified by column chromatography to give 7.1 g,The yield was 73%.
  • 16
  • [ 1311407-94-9 ]
  • [ 2620-76-0 ]
YieldReaction ConditionsOperation in experiment
90% With trichlorophosphate; In 1,4-dioxane; at 100℃; Example 1.1.2 2-(4-bromophenyl)-1-phenyl-1H-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 (POCl3) (9.2 mL, 100 mmol) slowly. The whole was then heated at 100 C. overnight. After cooling to RT, the mixture was poured into ice (200 g) with stirring. Filtration, followed by recrystallization in DCM/hexanes gave a pale grey solid 2 (8.2 g, in 90% yield).
90% With trichlorophosphate; In 1,4-dioxane; at 100℃; Exam 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 (POCl3) (9.2 mL, 100 mmol) slowly. The whole was then heated at 100 C overnight. After cooling to RT, the mixture was poured into ice (200g) with stirring. Filtration, followed by recrystallization in DCM/hexanes gave a pale grey solid 2 (8.2 g, in 90% yield).
90% With trichlorophosphate; In 1,4-dioxane; at 100℃; To 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 90% yield).
  • 17
  • [ 924895-30-7 ]
  • [ 2620-76-0 ]
  • [ 924895-26-1 ]
YieldReaction ConditionsOperation in experiment
80% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 8h;Reflux; Inert atmosphere; (1-7) Synthesis of Compound (1); Into a 300 ml three-necked flask, 2.0 g (5.0 mmole) of Intermediate 6, 3.9 g (11 mmole) of <strong>[2620-76-0]2-(4-bromophenyl)-1-phenylbenzimidazole</strong>, 0.23 g (0.20 mmole) of tetrakis(triphenylphosphine)palladium(0), 50 ml of 1,2-dimethoxyethane and 15 ml (30 mmole) of a 2 M aqueous solution of sodium carbonate were placed under the stream of argon, and the resultant mixture was heated under the refluxing condition for 8 hours. After the reaction was completed, the organic layer was washed with water and dried with magnesium sulfate, and the solvent was removed by distillation using a rotary evaporator. The obtained crude crystals were washed with 50 ml of toluene and 100 ml of methanol, and 3.4 g of a light yellow powder substance was obtained. The obtained substance was identified to be Compound (1) by the measurement of the field desorption mass spectrum (FD-MS) (the yield: 80%).
  • 18
  • [ 924895-31-8 ]
  • [ 2620-76-0 ]
  • [ 924895-29-4 ]
YieldReaction ConditionsOperation in experiment
78% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 8h;Reflux; Inert atmosphere; (4-7) Synthesis of Compound (4); Into a 300 ml three-necked flask, 1.1 g (2.1 mmole) of Intermediate 14, 1.6 g (4.6 mmole) of <strong>[2620-76-0]2-(4-bromophenyl)-1-phenylbenzimidazole</strong>, 0.10 g (0.09 mmole) of tetrakis(triphenylphosphine)palladium(0), 20 ml of 1,2-dimethoxyethane and 6.5 ml (13 mmole) of a 2 M aqueous solution of sodium carbonate were placed under the stream of argon, and the resultant mixture was heated under the refluxing condition for 8 hours. When the reaction was completed, the organic layer was washed with water and dried with magnesium sulfate, and the solvent was removed by distillation using a rotary evaporator. The obtained crude crystals were washed with 50 ml of toluene and 100 ml of methanol, and 1.6 g of a light yellow powder substance was obtained. The obtained substance was identified to be Compound (4) by the measurement of the field desorption mass spectrum (FD-MS) (the yield: 78%).
  • 19
  • [ 1155912-13-2 ]
  • [ 2620-76-0 ]
  • [ 1236211-21-4 ]
YieldReaction ConditionsOperation in experiment
67.8% With potassium phosphate;palladium diacetate; tris-(o-tolyl)phosphine; In 1,4-dioxane; water; toluene; for 16h;Reflux; Example 5 Synthesis of 1-phenyl-2-(5-benzo[c]phenanthren-4-ylphenyl)benzimidazole 913 mg (3 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added to a vigorously stirred suspension of 17.5 g (50 mmol) of 1-phenyl-2-(4-bromophenyl)benzimidazole, 14.9 g (55 mmol) of benzo[c]phenanthrene-5-boronic acid and 25.5 g (120 mmol) of tripotassium phosphate in a mixture of 300 ml of toluene, 100 ml of dioxane and 400 ml of water, and the mixture is subsequently heated under reflux for 16 h. After the mixture has been cooled, the precipitated solid is filtered off with suction, washed three times with 50 ml of toluene, three times with 50 ml of ethanol:water (1:1, v:v) and three times with 100 ml of ethanol and recrystallised three times from DMF (about 7 ml/g). Yield: 16.8 g (34 mmol), 67.8%, purity 99.9% (HPLC).
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