Structure of 890042-13-4
*Storage: {[sel_prStorage]}
*Shipping: {[sel_prShipping]}
The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
4.5
*For Research Use Only !
Change View
Size | Price | VIP Price | US Stock |
Global Stock |
In Stock | ||
{[ item.pr_size ]} |
Inquiry
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,1,item.pr_is_large_size_no_price, item.discount_usd) ]} {[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]} |
Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]} | Inquiry {[ item.pr_usastock ]} In Stock Inquiry - | {[ item.pr_chinastock ]} {[ item.pr_remark ]} In Stock 1-2 weeks - Inquiry - | Login | - + | Inquiry |
Please Login or Create an Account to: See VIP prices and availability
US Stock: ship in 0-1 business day
Global Stock: ship in 5-7 days
1-2weeks
Inquiry
{[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
{[ getRatePrice(item.pr_usd,1,item.mem_rate,item.pr_is_large_size_no_price, item.pr_usd) ]}
Inquiry
{[ getRatePrice(item.pr_usd,item.pr_rate,1,item.pr_is_large_size_no_price, item.vip_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
In Stock
- +
Please Login or Create an Account to: See VIP prices and availability
US Stock: ship in 0-1 business day
Global Stock: ship in 2 weeks
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
CAS No. : | 890042-13-4 |
Formula : | C24H23BO2 |
M.W : | 354.25 |
SMILES Code : | CC1(C)C(C)(C)OB(C2=CC=C3C4=CC=CC=C4C5=CC=CC=C5C3=C2)O1 |
MDL No. : | MFCD26401844 |
InChI Key : | VXLBBSLCTFTKOE-UHFFFAOYSA-N |
Pubchem ID : | 58769449 |
GHS Pictogram: |
![]() |
Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 5h;Inert atmosphere; | Inthe nitrogen ambient, after 2- bromo triphenylene (2-bromotriphenylene) 100g(326 mmol) was melted in the dimethylformamide (dimethylformamide, DMF) 1L herethe bis (pinacolrato) diboron (bis(pinacolato)diboron) 99.2 g (391 mmol),(1,1'- bis (diphenyl phosphine) dichloropalladium (II)((1,1'-bis(diphenylphosphine)ferrocene) dichloropalladium (II)) 2.66 g (3.26mmol) and potassium acetate (potassium acetate) 80 g (815 mmol) were put and150 heated for 5 hours and itrefluxed. After water was put in into the reaction solution after the reactioncompletion and the mixture was filtered it dried in the vacuum oven. Theresidue obtained in this way was refined to the flash column chromatography afterdividing and the compound I-1 113 g (98 %) was obtained. |
98% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 5h;Inert atmosphere; | It was dissolved 2-bromo-triphenylene (2-bromotriphenylene) 100g (326 mmol) in dimethylformamide (dimethylformamide, DMF) in a nitrogen environment 1L, where the bis (pinacolato) diboron (bis (pinacolato) diboron ) 99.2 g (391 mmol) and (1, 1 '- bis (diphenylphosphine) dichloropalladium (II) ((1, 1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II)) 2.66 g (3.26 mmol) and potassium acetate (potassium acetate) 80 put g (815 mmol) was heated to reflux for 5 hours at 150 . after the reaction was completed. Add water to the reaction mixture, filter the mixture, and dried in a vacuum oven. the obtained residue was flash column chromatography (flash column chromatography) separation and purification to give the compound I-1 113 g (98%) |
98% | With palladium bis[bis(diphenylphosphino)ferrocene] dichloride; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 5h;Inert atmosphere; | In a nitrogen atmosphere, 100 g (326 mmol) of 2-bromotriphenylene was dissolved in dimethylformamide(Pinacolato diboron) 99.2 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 1,000 mL of dimethylformamide (DMF)G (391 mmol) and 1,1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II) (1,1-Bis (diphenylphosphine) ferrocene) dichloropalladium (II)) 2.66 g (3.26 mmol) and potassium acetate 80 g (815 mmol) of potassium acetate were added and the mixture was refluxed by heating at 150 DEG C for 5 hours. After completing the reaction,Water was added to the solution, the mixture was filtered, and then dried in a vacuum oven. The thus obtained residue was purified by flash column chromatographyTo obtain 113 g (98%) of the compound I-1. HRMS (70 eV, EI +): m / z Calcd for C24H23BO2: 354.1791, found |
98% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; for 5h;Inert atmosphere; Reflux; | In a nitrogen environment,100 g (326 mmol) of 2-bromo-trisbenzene (TCI) was dissolved in 1 L of dimethyl formamide (DMF)To this was added 99.2 g (391 mmol)Bis (pinacolato) diboron(Sigma - Aldrich Co., Ltd.),2.66 g (3.26 mmol) of (1,1'-bis (diphenylphosphino) dichloropalladium (II) and 80 g (815 mmol) of potassium acetate,And the mixture was heated and allowed to reflux at 150 C for 5 hours.When the reaction is complete,Water was added to the reaction solution,And the mixture is filtered and dried in a vacuum oven.The residue obtained is purified by column chromatography,113 g (98%) of compound I-1 were obtained. |
98% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 5h;Inert atmosphere; | 100 g (326 mmol) of 2-bromotriphenylene was dissolved in 1 L of dimethylformamide (DMF) under a nitrogen condition, and 99.2 g (391 mmol) of bis(pinacolato)diboron, 2.66 g (3.26 mmol) of (1,1′-bis(diphenylphosphine)ferrocene)dichloropalladium (II), and 80 g (815 mmol) of potassium acetate were added thereto. The mixed solution was refluxed by heating at a temperature of 150 C. for 5 hours. After the reaction was completed, water was added to the reaction solution. The mixture of the resulting reaction solution was then filtered, and dried in a vacuum oven. The residue obtained therefrom was separated and purified by flash column chromatography to obtain 113 g (98%) of Compound 1-1. (0435) HRMS (70 eV, EI+): m/z calcd for C24H23BO2: 354.1791, found: 354. (0436) Elemental Analysis: C, 81%; H, 7% |
91% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 100 - 110℃; for 5h;Inert atmosphere; | Flask for 2-bromo-triphenylene (2-bromotriphenylene) 20 g (65.11 mmol), PIN2B2 19.8g (78.13mmol), Pd (dppf) Cl2 2.66g (3.26mmol), KOAc 11.5g (117.2mmol) and Dioxane put 180 mL steps was refluxed for 5 hours at 100 ~ 110oC under nitrogen. Lower the temperature to room temperature, the solvent was removed by distillation under reduced pressure. Purification of the resulting compound by silica gel column chromatography to give compound (Intermediate 20) as a pale yellow solid 20.9 g (yield: 91.0%) was obtained. |
84% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; for 12h;Reflux; | 2000mL 3-neck round bottom flask was added 2-bromo-triphenylene (70g, 0.283mol), bis (pinacolato) diboron (73.4g, 0.289mol), 1,4- dioxane (1000mL), 1,1 '-bis (diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex a mixture (4.6g, 0.0057mol) and potassium acetate (55.6g, 0.566mol) and heated to reflux for 12 hours. After cooling the precipitated solid was filtered under reduced pressure and then the acid clay treatment, and was filtered through Celite. And by using the resulting filtrate was concentrated under reduced pressure The resulting solid was suspended in hexane, filtered and washed with hexane again, the white solid compound was obtained a (70g, 84% yield). |
80% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; for 24h;Inert atmosphere; Reflux; | 2-bromotriphenylene (10g, 32.6mmol), bis(pinacolato) diborate (9.9g, 39.1mmol), [1,10-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.5g, 0.7mmol), and potassium acetate (16.2g, 162.8mmol) were dissolved in anhydrous 1,4-dioxane (180ml) and refluxed under nitrogen for 24h. After the reaction had finished, the mixture was washed three times with distilled water and extracted with chloroform. The organic layer was separated, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography using n-hexane-tetrahydrofuran (5:1) eluent to afford ( 1) a white solid, yield 80%. 1H NMR (400MHz, CDCl3) 9.15 (s, 1H), 8.84-8.82 (m, 1H), 8.71-8.64 (m, 4H), 8.07-8.05 (d, J=8.0Hz, 1H), 7.70-7.66 (m, 4H), 1.43 (s, 12H) ppm. |
75% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 130℃; for 5h;Inert atmosphere; | Under a nitrogen stream 3,1 g (10.0 mmol) of 2-bromotriphenylene, 3.1 g (12.0 mmol) of 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2' -bis (1,3,2-dioxaborolane) 0.3 g (5 mol%) of Pd (dppf) cl 2, KOAc, 3.0 g (30.0 mmol) and 100 ml of 1,4-dioxane were placed and stirred at 130 C for 5 hours. The solvent of the organic layer was removed, and the residue was purified by column chromatography to obtain the desired compound A13 (2.7 g, 7.5 mmol, yield 75%). |
68.6% | With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; at 100℃; for 4h;Inert atmosphere; | (2) Synthesis of Compound d-4; A nitrogen atmosphere was established in a 300-ml three-necked flask. After that, the following reagents and solvent were loaded into the flask.Compound d-2 : 11.5 g (37.4 mmol)Compound d-3: 11.4 g (44.9 mmol)Potassium acetate: 6.61 g (67.4 mmol)Dioxane: 100 ml[0094] Next, the reaction solution was stirred at roomtemperature under a nitrogen atmosphere, and to the stirred solution were added 1.53 g (1.87 mmol) of a bis (diphenylphosphino) ferrocene palladium ( II )dichloride dichloromethane adduct . The reaction solution was then warmed to a temperature of 100 C and stirred at the same temperature (100C) for 4 hours. After the completion of the reaction, the solvent in the reaction solution was evaporated under reduced pressure to give a crude product. Next, the resultant crude product was purified by silica gel column chromatography (developing solvent: chloroform-heptane mixed solvent) to afford 10.42 g of Compound d-4 as a white solid (yield: 68.6%). |
With potassium acetate;Pd(dppf)2Cl2; In dimethyl sulfoxide; at 20 - 80℃; for 12h; | [0098] 20.0 g of the bromotriphenylene mixture which contains about 70% of 2- bromotriphenylene based on HPLC monitored at 254nm, 18.7 g (73 mmol) of bis(pinacolato)diboron, 1.6 g of Pd(dppf)2Ci2, 20 g (200 mmol) of potassium acetate, and 400 Ml of DMSO was mixed at room temperature under N2. The mixture was degassed then heated up to 8O0C for 12 hours. After cooling to room temperature, the mixture was poured into ice water. The precipitate was then collected by filtration. The solid was dissolved in dichloromethane and dried over magnesium sulfate. The crude product was purified by column using a mixture of hexanes and dichloromethane (from 6:1 to 3:1) as eluent. 10 g of the pure product, 4,4,5,5- tetramethyl-2-(triphenylen-2-yl)-l ,3,2-dioxaborolane, was isolated. | |
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃; for 24h; | General procedure: S-2 (1 eq.) in 1,4-dioxane 300 mL, after it was added 2,2,3,3,7,7,8,8-octamethyl-1,4,6,9-tetraoxaspiro[4.4]nonane (2 eq.), PdCl2(dppf ) (0.05eq.), into the KOAc (3 eq.) was stirred for 24 hours at 80C . After the reaction was completed the mixture was extracted with dichloromethane and H2O. After extraction and purification separated by column chromatography to give the S-1. | |
20.8 g | With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In N,N-dimethyl-formamide; for 5h;Inert atmosphere; Reflux; | 20 g of 2-bromotriphenylene, 20 g of potassium acetate and 22.1 g of pinacoledboron were added to 200 ml of DMF, and the mixture was stirred under a nitrogen atmosphere. To this solution was added 4 g of palladium tetrakis triphenylphosphine and the mixture was slowly heated. Reflux was started and reflux reaction was carried out for 5 hours to confirm that the raw material disappeared by TLC analysis and the reaction was completed.The DMF solvent was distilled under reduced pressure, cooled to room temperature, dissolved in 200 ml of ethyl acetate, and washed three times with 100 ml of water to separate layers. Anhydrous magnesium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration. The organic layer was short-lined with silica gel, washed thoroughly with ethyl acetate, and concentrated under reduced pressure.60 ml of dichloromethane and 120 ml of methanol were added to the concentrate, and the mixture was refluxed for 1 hour. The mixture was cooled to room temperature. The resulting pale cream solid was filtered, washed with methanol, and hot-air dried at 80 to obtain 20.8 g of 2-triphenyleneboronic acid pinacol ester Gas chromatographic analysis was obtained at 98.6% purity. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With potassium acetate;1,1'-bis-(diphenylphosphino)ferrocene; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; for 8h;Inert atmosphere; Reflux; | (B-1) Synthesis of triphenylene-2-boronic acid pinacol ester Under an argon atmosphere, 37.6 g of triphenylenyl trifluoromethanesulfonate, 27.9 g of bis(pinacolato)diboron, 2.45 g of 1,1'-bis(diphenylphosphino)ferrocene palladium (II) dichloride dichloromethane complex, 1.66 g of 1,1'-bis(diphenylphosphino)ferrocene and 29.4 g of potassium acetate were placed in a flask. 600 mL of anhydrous dioxane was added thereto, and the resultant was refluxed with stirring while heating for 8 hours. After cooling to room temperature, 300 mL of water was added to the reaction solution, followed by extraction with toluene. An aqueous phase was removed, and an organic phase was washed with water and saturated brine, and then dried with magnesium sulfate. Magnesium sulfate was removed and the solvent was distilled under reduced pressure. The resulting residue was purified by means of silica gel column chromatography, whereby 14.1 g (yield: 40%) of triphenylene-2-boronic acid piconal ester was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With palladium diacetate; sodium carbonate; triphenylphosphine; In water; toluene; for 7h;Inert atmosphere; Reflux; | 4,4,5,5-tetra-methyl-2-(triphenylene-2-yl) 1,3,2-dioxaborolan 7.08g (20.0mmol), m- bromoiodobenzene16.97g (60.0mmol) , palladium acetate 135 mg (0.60 mmol), triphenylphosphine629 mg (2.40 mmol), sodium carbonate 4.24 g (40.0 mmol), was mixed1,2-dimethoxyethane 100 mL, water 50 mL, under nitrogen atmosphere, 7 It washeated to reflux time. After the reaction, the organic layer was extracted byadding water and ethyl acetate. The organic layer was concentrated underreduced pressure, silica gel column chromatography (developing solvent:toluene) to remove origin ingredients. The solvent was evaporated under reducedpressure, and the resulting solid was dissolved in a small amount of methylenechloride, solid was precipitated with the addition of methanol. The solid wasfiltered, methanol, to give 7.33g of the synthetic intermediate 2 bysequentially washed with hexane (96% yield). |
95% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 8h;Reflux; Inert atmosphere; | (B-2) Synthesis of intermediate B Under an argon atmosphere, 3.54 g of triphenylene-2-boronic acid piconal ester, 2.83 g of 3-bromoiodebenzene, 0.231 g of tetrakis(triphenylphosphine)palladium (0), 40 mL of toluene and 20 mL of a 2M sodium carbonate aqueous solution were placed in a flask, and refluxed with stirring for 8 hours. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous phase was removed, and an organic phase was washed with water and saturated brine sequentially, and then dried with magnesium sulfate. Magnesium sulfate was filtered out, and then the organic phase was concentrated. The resulting residue was purified by means of a silica gel column chromatography to obtain 3.64 g (95%) of an intermediate B. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; for 8h;Inert atmosphere; Reflux; | (1) Synthesis of 2-(2-anthryl)triphenylene Under an argon atmosphere, 7.79 g of triphenylene-2-boronic acid piconal ester, 5.14 g of 2-bromoanthracene, 0.462 g of tetrakis(triphenylphosphine)palladium (0), 30 mL of 1,2-dimethoxyethane and 15 mL of a 2M sodium carbonate aqueous solution were placed in a flask, and refluxed with stirring for 8 hours. After cooling to room temperature, deposited crystals were collected by filtration. The resulting solid was subjected to repeated recrystallization with toluene-hexane and washing to obtain 6.07 g (yield: 75%) of 2-(2-anthryl)triphenylene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | 2- bromo triphenylene 10 g (32.55mmol) was dissolvedin the anhydrous tetrahydrofuran (100mL). The mixturethe n-butyl lithium 30 mL (48.83mmol) was gradually added to -78 after doing the cooling and it was stirred for 10 minutes. 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- dioxaborolane (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 26.57 mL (130.2mmol) was added in the reaction mixture and it reacted for 1 hour. After reaction was completed it dried to the MgSO 4 and 3times repetition extraction, and the extracted organic layer were recrystallized using the mixed solvent (waterchloroform: = 1 1: volume ratio) of chloroform and water after doing the concentration using the n-hexane and the compound 2-1 9.6 g (yield : 83%) was obtained. | |
83% | 2-bromo-triphenylene 10g (32.55mmol) was dissolved in anhydrous THF (200mL). After the mixture was cooled to -78 C , n- butyl lithium was added 30mL (48.83mmol) slowly and stir for 10 minutes 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) to the reaction mixture, dioxaborolane-2) by the addition of 26.57mL (130.2mmol) was allowed to react for one hour. After the reaction was completed, a mixed solvent of water and chloroform (water: chloroform = 1: 1 volume ratio) and then using the extraction repeated three times, and drying the extracted organic layer with MgSO4 and concentrated, re-crystallized using n- hexane 9.6g to give the compound 2-1 (yield: 83%) | |
Preparation of Compound (115)In tetrahydrofuran (100 mL), 1-bromotriphenylene (Compound 114) (5.0 g, 16.2 mmol) was dissolved, and n-BuLi (2.5 M in n-hexane) (9.7 mL, 24.3 mmol) was slowly added dropwise thereto at -78 C. After stirring for 1 hour, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.0 g, 48.6 mmol) was added thereto at -78 C., and the resultant mixture was stirred at 25 C. for 2 hours. The reaction mixture was washed with water (100 mL), extracted with ethyl acetate (100 mL) and dried over anhydrous magnesium sulfate. Evaporation of the organic layer under reduced pressure and recrystallization from methanol (50 mL) gave solid, which was then filtered and dried to obtain Compound (115) (4.7 g, 10.0 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Aliquat 336;tetrakis(triphenylphosphine) palladium(0); calcium carbonate; In water; toluene; at 130℃; for 4h; | Preparation of Compound (116)A reaction vessel was charged with Compound (113) (4.2 g, 30.0 mmol) and the ester compound (Compound 115) (4.7 g, 10.0 mmol), and tetrakispalladiumtriphenylphosphine (Pd(PPh3)4) (1.2 g, 1.0 mmol) was added thereto. The mixture was dissolved in toluene (80 mL). To the solution, added were Aliquat 336 (0.5 g, 1.0 mmol) and aqueous 2M calcium carbonate solution (24 mL). The resultant mixture was stirred at 130 C. under reflux for 4 hours. To the precipitate formed, methanol (200 mL) was poured to form solid, which was then dissolved in chloroform (300 mL). After filtration, the organic layer was evaporated under reduced pressure. Recrystallization from tetrahydrofuran (30 mL) gave the target compound (116) (TPN-1) (2.2 g, overall yield: 38%).1H NMR (200 MHz, CDCl3) δ=7.22-7.32 (m, 8H), 7.48-7.54 (m. 5H), 7.67-7.89 (t, 8H), 8.10-8.12 (m, 3H), 8.34 (d, 1H), 8.93-8.99 (m, 3H)MS/FAB: 556.22 (found), 556.69 (calculated) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Aliquat 336; calcium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; at 130℃; for 5h; | Preparation of Compound (140)A reaction vessel was charged with Compound (139) (8.5 g, 13.3 mmol) and the ester compound (Compound 115) (7.0 g, 19.9 mmol), and tetrakistriphenylphosphinepalladium (Pd(PPh3)4) (1.5 g, 1.3 mmol) was added thereto. The mixture was dissolved in toluene (150 mL). To the solution, added were Aliquat 336 (0.3 g, 1.3 mmol) and aqueous 2M calcium carbonate solution (45 mL). The resultant mixture was stirred at 130 C. under reflux for 5 hours. To the precipitate formed, excess amount of methanol was poured to form solid, which was then dissolved in chloroform (500 mL). After filtration, the solvent was removed under reduced pressure. Recrystallization from tetrahydrofuran (200 mL) gave the target compound (140) (TPN-4) (4.1 g, overall yield: 39%).1H NMR (200 MHz, CDCl3) δ=1.67 (s, 12H), 7.28-7.36 (m, 6H), 7.84 (m, 19H), 8.10-8.12 (m, 3H), 8.34-8.36 (m, 1H), 8.93-8.99 (m, 3H)MS/FAB: 788.34 (found), 789.01 (calculated) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Aliquat 336; calcium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; at 130℃; for 3h; | Preparation of Compound (135)A reaction vessel was charged with Compound (134) (5.0 g, 8.9 mmol) and the ester compound (Compound 115) (4.7 g, 13.4 mmol), and tetrakistriphenylphosphinepalladium (Pd(PPh3)4) (1.0 g, 0.9 mmol) was added thereto. The mixture was dissolved in toluene (80 mL). To the solution, added were Aliquat 336 (0.4 g, 0.9 mmol) and aqueous 2M calcium carbonate solution (24 mL). The resultant mixture was stirred at 130 C. under reflux for 3 hours. To the precipitate formed, excess amount (200 mL) of methanol was poured to form solid, which was then dissolved in chloroform (500 mL). After filtration, the organic solvent was removed under reduced pressure. Recrystallization from tetrahydrofuran (200 mL) gave the target compound (135) (TPN-3) (2.0 g, overall yield: 32%).1H NMR (200 MHz, CDCl3) δ=7.20-7.22 (m, 2H), 7.29-7.32 (m. 6H), 7.48-7.54 (m, 13H), 7.55-7.58 (m, 3H), 7.82-7.88 (m, 5H), 8.10-8.12 (m, 3H), 8.34 (dd, 1H), 8.93-8.99 (m, 3H)MS/FAB: 708.28 (found), 708.89 (calculated) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 80℃; for 5h;Inert atmosphere; | In a 100-ml three-neck flask, 0.530 g (1.50 mmol) of compound a-14, 0.638 g (1.80 mmol) of compound a-15, 6.4 g of sodium carbonate, 30 ml of toluene, 10 ml of ethanol, and 20 ml of water were placed, and in a nitrogen atmosphere, under stirring at room temperature, 86.6 mg oftetrakis (triphenylphosphine) palladium(O) was added thereto. The resulting mixture was heated to 80 C, and stirring was performed for 5 hours. After completion of the reaction, the organic layer was extracted with toluene and dried over anhydrous sodium sulfate, followed by purification by silica gel column chromatography (developing solvent:toluene/heptane mixture) to give 0.554 g (yield 74%) of exemplary compound 1-7 (white solid) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 3h;Inert atmosphere; Reflux; | Example 10; Synthesis of Example Compound B-8; [0143][Chem. 23]F-15[0144] The following reagents and solvents were placed in a 200 mL round-bottomed flask.F-15: 2.6 g (5 mmol)F-7: 4.3 g (12 mmol)Tetrakis (triphenylphosphine) palladium ( 0 ) : 137 mg (0.12 mmol) Toluene: 50 mLEthanol: 20 mL30 wt% Aqueous sodium carbonate solution: 30 mL[0145] The reaction solution was refluxed for 3 hours under heating and stirring in a nitrogen atmosphere. Upon completion of the reaction, water was added to the reaction solution, followed by stirring. The precipitated crystals were separated by filtration and washed with water and ethanol to obtain a crude product. The crude product was dissolved in toluene under heating, subjected to hotfiltration, column-purified with toluene/heptane, and recrystallized twice with toluene/ethanol . The obtained crystals were vacuum dried at 100C. As a result, 2.4 g (yield: 60%) of high-purity Example Compound B-8 wasobtained.[MALDI-TOF- S]Observed value: m/z = 814.46Calculated value: 814.42[0146] The Ti energy of Example Compound B-8 was measured as in Example 1. The Τχ energy was 473 nm on a wavelength basis .[0147] The energy gap of Example Compound B-8 was determined as in Example 1. The energy gap of ExampleCompound B-8 was 3.5 eV. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 3h;Reflux; Inert atmosphere; | Example 6; Synthesis of Example Compound A-13; [0122][Chem. 19][0123] The following reagents and solvents were placed in a 200 mL round-bottomed flask.F-1 : 1.9 g (5 mmol)F-7: 4.3 g (12 mmol)Tetrakis (triphenylphosphine) palladium (0) : 137 mg (0.12 mmol) Toluene: 50 mLEthanol: 20 mL 30 wt% Aqueous sodium carbonate solution: 30 mL[0124] The reaction solution was refluxed for 3 hours under heating and stirring in a nitrogen atmosphere. Upon completion of the reaction, water was added to the reaction solution, followed by stirring. The precipitated crystals were separated by filtration and washed with water, ethanol, and acetone to obtain a crude product. The crude product was dissolved in chlorobenzene under heating, subjected to hot filtration, and recrystallized twice with achlorobenzene solvent. The obtained crystals were vacuum dried at 100C. As a result, 1.4 g (yield: 42%) of high- purity Example Compound A-13 was obtained.[MALDI-TOF-MS]Observed value: m/z = 674.22Calculated value: 674.26[0125] The i energy of Example Compound A-13 was measured as in Example 1. The i energy was 472 nm on a wavelength basis .[0126] The energy gap of Example Compound A-13 was determined as in Example 1. The energy gap of ExampleCompound A-13 was 3.5 eV. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 12h;Inert atmosphere; | (3) Synthesis of Compound d-6; A nitrogen atmosphere was established in a 200-ml three-necked flask. After that, the following reagents and solvents were loaded into the flask.Compound d-4: 7.08 g (20.0 mmol)Compound d-5: 5.46 g (22.0 mmol)Sodium carbonate: 10.6 g (100 mmol)Toluene: 100 mlEthanol: 20 mlWater: 100 ml[0096] Next, the reaction solution was stirred at roomtemperature under a nitrogen atmosphere, and to the stirred solution were added 1.16 g of tetrakis (triphenylphosphine) palladium ( 0 ) . Next, the reaction solution was warmed to a temperature of 80 C and stirred at the same temperature (80C) for 12 hours. After the completion of the reaction, the organic layer was extracted with toluene, and the resultant organic layer was dried over anhydrous sodium sulfate. The organic layer was then concentrated under reduced pressure to give a crude product. Next, the resultant crude product was purified by silica gel columnchromatography (developing solvent: toluene-ethyl acetate mixed solvent) to afford 4.92 g of Compound d-6 as a white solid (yield: 62%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With potassium phosphate;dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; In water; toluene; at 120℃; for 7.5h; | 2) Synthesis of Compound D-5[0089] The following reagents and solvents:Compound D-3 (1.62 g, 4.37 mmol).Compound D-4 (1.78 g, 5.02 mmol),toluene: 50 mL, andwater : 1.5 mLwere put into a reaction vessel.[0090] Subsequently, the following reagents:palladium( II ) acetate: 80 mg (0.4 mmol),2 -dicyclohexylphosphino- 2 ' , 6 ' -dimethoxybiphenyl ( SPhos ) : 420 mg (1.02 mmol), andpotassium phosphate: 2.75 g (13.0 mmol)were added to the reaction vessel.[0091] Subsequently, the reaction solution was heated to 120 C and was stirred at the same temperature (120 C) for 7.5 hours. After cooling of the reaction solution, water and heptane were added to the reaction solution. The resulting precipitate was collected by filtration and was dissolved in toluene. The resulting toluene solution was applied to silica gel, and the eluted toluene solution was concentrated under reduced pressure. The resulting residue was recrystallized from a solvent mixture of toluene and heptane to obtain 1.91 g (yield: 78%) of Compound D-5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; for 12h;Reflux; | The compound (10 g, 28.33 mmol) synthesized in , <strong>[890042-13-4]4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane</strong> (11.04 g, 31.16 mmol), Pd(PPh3)4 (0.65 g, 0.57 mmol) and sodium carbonate (9.01 g, 84.99 mmol) were suspended in a mixed solvent of 300 ml of toluene and 80 ml of ethanol, and then the mixture was stirred while refluxing for 12 hr. [0058] After the completion of the reaction, the reaction product was extracted with dichloromethane and then purified by silica gel column chromatography (Hexane:MC=4:1 (v/v)) to obtain the desired title compound Inv-1 (11.5 g, yield 81%). [0059] 1H NMR: 6.67 (m, 4H), 6.90 (t, 2H), 6.98 (m, 5H), 7.01 (s, 1H), 7.87 (m, 4H), 8.01 (d, 1H), 8.11 (m, 3H), 8.89 (t, 2H), 9.11 (s, 1H). [0060] GC-Mass (theoretical value: 501.16 g/mol, measured value: 502 g/mol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene;Reflux; Inert atmosphere; | A solution of (3,5-dibromophenyl)triphenylsilane (2.20 g, 4.45 mmol), <strong>[890042-13-4]4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane</strong> (3.15 g, 8.90 mmol), Pd(PPh3)4 (0.051 g, 0.045 mmol) and K2CO3 (1.23 g, 8.90 mmol) in toluene (100 mL) and water (20 mL) was refluxed under nitrogen overnight. After cooling to room temperature, the organic phase was isolated, filtered through a short plug of Celite and the solvent was evaporated. The residue was purified by column chromatography on silica gel with hexane/DCM (7/3, v/v) as eluent followed by recrystallization from the same solvent to yield (3-bromo-5-(triphenylen-2-yl)phenyl)triphenylsilane (1.50 g, 52%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In water; toluene;Reflux; Inert atmosphere; | A solution of (6-(3-Chlorophenyl)dibenzo[b,d]furan-4-yl)triphenylsilane (1.63 g, 3.03 mmol), <strong>[890042-13-4]4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane</strong> (1.12 g, 3.16 mmol), Pd2(dba)3 (0.090 g, xx mmol) and SPhos (0.10 g, 0.24 mmol) and K3PO4 (2.03 g, 8.8 mmol) in toluene (100 mL) and water (1 mL) was refluxed under nitrogen overnight. After cooling to room temperature, the solid was filtered of After evaporation off the solvent, the residue was purified by column chromatography on silica gel with hexane/DCM (7/3, v/v) as eluent followed by column chromatography on C18 column with acetonitrile as eluent to yield Compound 13 (1.6 g, 72%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In toluene; at 130℃; for 48h;Inert atmosphere; | <strong>[890042-13-4]4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane</strong> (0.65g, 1.84mmol), 9,9′-(5-bromo-1,3-phenylene)bis(9H-carbazole) (0.91g, 1.87mmol), tetrakis(triphenylphosphine) palladium(0) (0.06g, 0.06mmol), and 1M Na2CO3 (7.3ml) in 40ml of Toluene was stirred at 130C for 48h under nitrogen atmosphere. After the reaction had finished, the mixture was washed three times with distilled water and extracted with chloroform. The organic layer was separated, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography using n-hexane-tetrahydrofuran (5:1). The final product was obtained as a white powder after purification by vacuum sublimation at a synthetic yield of 38%. 1H NMR (400MHz, CDCl3) 8.97 (s, 1H), 8.79-8.77 (d, J=8.8Hz, 1H), 8.71-8.67 (m, 4H), 8.22-8.20 (d, J=7.6Hz, 4H), 8.16 (s, 2H), 8.02-8.00 (d, J=8.8Hz, 1H), 7.88 (s, 1H), 7.72-7.62 (m, 8H), 7.52-7.48 (t, J=8.4Hz, 4H), 7.37-7.33 (t, J=6.8Hz, 4H) ppm; 13C NMR (CDCl3, 400MHz) 142.5, 138.6, 137.8, 135.5, 128.2, 128, 127.9, 127.7, 127.3, 127.2, 127, 126.2, 125.5, 125.3, 124.2, 123.8, 122.5, 122.2, 122, 121.6, 121.4, 121.3, 121.2, 119.8, 118.5, 118.4ppm. ESI-MS [M+H]+: m/z calcd. 635.2487; found 635.2460. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In toluene; at 130℃; for 48h;Inert atmosphere; | 9-(3,5-dibromophenyl)-9H-carbazole (1.8g, 4.49mmol), <strong>[890042-13-4]4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane</strong> (3.34g, 9.42mmol), tetrakis(triphenylphosphine) palladium(0) (0.26g, 0.22mmol), and 1M Na2CO3 (19.1ml) in 140ml of Toluene was stirred at 130C for 48h under nitrogen atmosphere. After the reaction had finished, the mixture was washed three times with distilled water and extracted with chloroform. The organic layer was separated, dried over anhydrous magnesium sulfate, and evaporated under reduce pressure. The crude product was purified by silica gel column chromatography using n-hexane-tetrahydrofuran (5:1). The final product was obtained as a white powder after purification by vacuum sublimation at a synthetic yield of 74%. 1H NMR (400MHz, CDCl3) 9.02 (s, 2H), 8.83-8.81 (d, J=8.8Hz, 2H), 8.78-8.77 (d, J=7.2Hz, 2H), 8.74-8.69 (m, 6H), 8.34 (s, 1H), 8.25-8.23 (d, J=7.6Hz, 2H), 8.10-8.08 (d, J=5.6Hz, 4H), 7.72-7.65 (m, 10H), 7.52-7.48 (t, J=7.2Hz, 2H), 7.38-7.34 (t, J=7.6Hz, 2H) ppm. MALDI-TOF [M+H]+: 695.329. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In toluene; at 90℃; for 48h;Inert atmosphere; | 1-bromo-3-iodobenzene (2.0g, 7.07mmol), <strong>[890042-13-4]4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane</strong> (2.5g, 7.07mmol), tetrakis(triphenylphosphine)palladium(0) (0.25g, 0.21mmol), and 1M Na2CO3 (35.4ml) in 100ml of toluene was stirred at 90C for 48h under nitrogen atmosphere. To the reaction mixture was added a dibenzo[b,d]thiophene-4-ylboronic acid (1.61g, 7.07mmol) and then stirred at 120C for 24h under nitrogen atmosphere. After the reaction had finished, the mixture was washed three times with distilled water and extracted with chloroform. The organic layer was separated, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography using n-hexane-tetrahydrofuran (5:1). The final product was obtained as a white powder after purification by vacuum sublimation at a synthetic yield of 46%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 3h;Reflux; Inert atmosphere; | Example 2<Synthesis of 10-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-2-(triphenylene-2-yl)acridan (Compound 71)>2-bromo-10-(9,9-dimethyl-9H-fluoren-2-yl)- 9,9-dimethylacridan (7.00 g), 4,4,5,5-tetramethyl-2-(triphenylene-2-yl)-[1,3,2]dioxaborolane (5.16 g), tetrakis(triphenylphosphine)palladium (0.34 g), potassium carbonate (4.03 g), toluene (40 ml), ethanol (10 ml), and water (15 ml) were added to a reaction vessel in a nitrogen atmosphere, heated, and stirred for 3 hours under reflux. After the mixture was allowed to cool to room temperature, water and toluene were added to perform liquid separation in order to collect an organic layer. The organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (support: silica gel, eluent: toluene/ hexane=1/1) to obtain a white powder of 10-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-2-(triphenylene-2-yl)acridan (Compound 71; 5.40 g; yield 59%).The structure of the product white powder was identified by NMR. The 1H-NMR measurement result is shown in FIG. 2. 1H-NMR (THF-d8) detected 37 hydrogen signals, as follows. δ (ppm) = 8.93 (1H), 8.85 (1H), 8.80-8.71 (4H), 8.09 (1H), 8.01 (1H), 7.95 (1H), 7.87 (1H), 7.69-7.61 (4H), 7.59-7.46 (4H), 7.42-7.34 (3H), 6.98-6.87 (2H), 6.51 (1H), 6.39 (1H), 1.85 (6H), 1.57(6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; for 12h;Inert atmosphere; Reflux; | 10.00 g (31.04 mmol) of 3-bromo-N-phenylcarbazole, 10.99 g (31.04 mmol) of 2-triphenylene boronic ester, 150 mL of a mixture of tetrahydrofuran (THF) and toluene (1:1), and 75 mL of an aqueous solution of 2 M potassium carbonate were mixed in a 500-mL round-bottom flask equipped with a stirrer in a nitrogen atmosphere, and 1.79 g (1.55 mmol) of tetrakis(triphenylphosphine)palladium(0) was added thereto, and heated under reflux in a nitrogen atmosphere for about 12 hours. After completion of the reaction, the reaction product was added to methanol to obtain a solid by filtering. This solid was thoroughly washed with water and methanol, and then dried. The resulting product was dissolved in 400 mL of chlorobenzene by heating, followed by filtration using silica gel and removing the solvent. The resulting product was dissolved in 300 mL of toluene by heating, followed by recrystallization to obtain Compound A15 (8.74 g, Yield: 60%). calcd. C36H23N: C, 92.08; H, 4.94; N, 2.98; found: C, 92.43; H, 4.63; N, 2.84 |
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; for 12h;Inert atmosphere; Reflux; | A 500 mL round bottom flask equipped with a stirrer in a nitrogen atmosphere 3-Bromo-phenyl carbazole -N- 10.00 g (31.04 mmol), 2-With triphenyl renbo Nick ester 10.99 g (31.04 mmol) and tetrahydrofuran: toluene (1: 1) of potassium carbonate and 150 mL accommodate 2M-After mixing the solution 75mL, put tetrakistriphenylphosphine palladium (0) 1.79 g (1.55mmol) copper 12 hours under a nitrogen gas streamNot heated to reflux. After the end of reaction the reaction was poured in methanol, filtered solids, the solids water obtained therefromAnd it was sufficiently washed with methanol and dried. Is the result obtained therefrom is then dissolved by heating in chlorobenzene in 400mLSilica gel filter that the solution and remove the solvent completely, and then recrystallized by heating to dissolve granulation to 300mL of tolueneCompounds A15 8.74 g (yield: 60%). |
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; toluene; for 12h;Inert atmosphere; Reflux; | Nitrogen atmosphere equipped with a stirrer a 500 mL round bottom flask was charged with 3-bromo-N-phenyl carbazole 10.00 g (31.04 mmol), 2-triphenyleneboronicesters 10.99 g (31.04 mmol) and tetrahydrofuran: toluene (1: 1) 150 mL and 2M- into the aqueous solution of potassium carbonate were mixed 75mL, tetrakistriphenylphosphine palladium (0) 1.79 g (1.55mmol) was heated to reflux for 12 hours under a nitrogen flow. After the end of reaction the reaction was poured in methanol, filtered, the solid was sufficiently washed with a solid obtained therefrom with water and methanol and dried. The results obtained therefrom is then dissolved by heating in chlorobenzene, and then a solution of 400mL silica gel filter, and remove the solvent completely, and then recrystallization is then dissolved by heating in 300mL of toluene to afford A15 8.74 g (yield 60%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; at 80℃; for 23h;Inert atmosphere; | Intermediate 26 (39.5 mmol) was dissolved in 0.2 L of tetrahydrofuran (THF) under a nitrogen environment, Intermediate 27 (39.5 mmol) and tetrakis(triphenylphosphine)palladium (0.46 g, 0.4 mmol) were added thereto, and the mixture was stirred. Potassium carbonate saturated in water (13.6 g, 98.8 mmol) was added thereto, and the obtained mixture was heated and refluxed at 80 C. for 23 hours. When a reaction was complete, water was added to the reaction solution, dichloromethane (DCM) was used for an extraction, anhydrous MgSO4 was used to remove moisture from an extract, and the extract was filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography to obtain Compound A-2 (a yield of 75%). (0188) calcd. C45H29N3: C, 88.35; H, 4.78; N, 6.87. found: C, 88.35; H, 4.78; N, 6.87. |
74% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In monoethylene glycol diethyl ether; water; toluene; for 16h;Reflux; Inert atmosphere; | DME (100 ml), toluene (100 ml), and in water (10 ml), 4,4,5,5-tetramethyl-2-(triphenylene-2-yl) 1,3,2-dioxaborolane (2.53 g, 7.14 mmol), 2,4-di-([1,1'-biphenyl]-3-yl)-6-chloro-1,3,5-triazine (2.50g, 5.95mmol), Pd(PPh3)4 (0.69g, 0.60mmol), and K2CO3 (1.65g, 11.91mmol) was the solution of the reflux for 16 hours under nitrogen. After cooling to room temperature, the reaction mixture was diluted with water. The solid was collected by filtration, washed with water, ethanol, and washed with toluene, then redissolved in boiling toluene and filtered through a short plug of silica gel. Evaporation of the solvent, toluene, was re-crystallized compound 5 as a white solid (2.70g, 74%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In monoethylene glycol diethyl ether; water; toluene; for 16h;Reflux; Inert atmosphere; | DME (54.7ml) and in water (5.47ml), 4,4,5,5- tetra-methyl-2-(triphenylene-2-yl)1,3,2-dioxaborolane (2.345g, 6. 62 mmol), 2-chloro-4- (dibenzo[b, d]thiophen-4-yl)-6-phenyl-1,3,5-triazine (2.25g, 6.02mmol), Pd (PPh3) 4 ( 0.348g, 0.301mmol), and potassium carbonate (2.495g, the solution 18.05mmol) were refluxed for 16 hours under nitrogen. After cooling to room temperature, the reaction mixture was diluted with water and the solid was collected by filtration, THF, washed sequentially with water and ethanol, triturated with boiling ethanol, as a white solid to give Compound 32 (3. 3g, 80%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59.7% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene;Inert atmosphere; Reflux; | Pitching 25 mL flask, the intermediate (9) 500 mg (0.89 mmol), intermediate (20) 379 mg (1.07 mmol) and Pd (PPh3) 4 52 mg (0.045mmol) were placed under nitrogen atmosphere Toluene 6 mL EtOH and 3 was dissolved in mL, 2M Na2CO3 solution was added to 1.34 mL was stirred under reflux. After completion of the reaction, the reaction was cooled to room temperature and added to 5 mL H2O. 2 MC extracted once with 20 mL To a mixtureAfter drying the extract with Na2SO4, filtered and concentrated under a reduced pressure. Recrystallization of the resulting compound with the compound MC green-yellow solid by two times (5-42, KJ-06-25), 422 mg (yield: 59.7%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
33% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene;Inert atmosphere; Reflux; | Pitching 100 mL intermediate (12) was charged to the flask 0.5g (0.892mmol), (4,4,5,5-tetramethyl-2- (triphenylen-2-yl) -1,3,2-dioxaborolane) 0.28 g (0.981 mmol) and Pd (PPh3) 4 was introduced into the 41mg (0.044 mmol) was dissolved in Toluene 5 mL EtOH and 2 mL under a nitrogen atmosphere, was added a 2M K2CO3 solution 0.7 mL was stirred under reflux. After completion of the reaction, the reaction was cooled to room temperature and added to 5 mL H2O. Drying the mixture and then extracted twice with MC 10 mL extract with Na2SO4, filtered and concentrated under a reduced pressure. Purification of the resulting compound was purified by silica gel column chromatography to obtain the compound (5-51, HSB-06-028) 0.21 g (Yield: 33%) of a white solid was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58.7% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene;Inert atmosphere; Reflux; | Pitching 25 mL flask, the intermediate (18) 500 mg (0.89 mmol), intermediate (20) 348 mg (0.98 mmol) and Pd (PPh3) 4 52 mg (0.045mmol) were placed under nitrogen atmosphere Toluene 6 mL EtOH and 3 was dissolved in mL, 2M Na2CO3 solution was added to 1.34 mL was stirred under reflux. After completion of the reaction, the reaction was cooled to room temperature and added to 5 mL H2O. Drying the mixture and then extracted two times with MC 20 mL extract with Na2SO4, filtered and concentrated under a reduced pressure. Purification of the resulting compound was purified by silica gel column chromatography to obtain the compound (5-41, KJ-06-23), 370 mg (yield: 58.7%) of a green-yellow solid was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54.9% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene;Inert atmosphere; Reflux; | Pitching 25 mL flask, the intermediate (28) 300 mg (0.54 mmol), intermediate (20) 228 mg (0.64 mmol) and Pd (PPh3) 4 32 mg (0.027mmol) were placed under nitrogen atmosphere Toluene 6 mL EtOH and 3 was dissolved in mL, 2M Na2CO3 solution was added to 1.34 mL was stirred under reflux. After completion of the reaction, the reaction was cooled to room temperature and added to 5 mL H2O. Drying the mixture and then extracted two times with MC 20 mL extract with Na2SO4, filtered and concentrated under a reduced pressure. Purification of the resulting compound was purified by silica gel column chromatography to obtain the compound (5-76, KJ-07-30), 209 mg (yield: 54.9%) of a yellow solid was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 120℃; for 3h; | D-2 7g (14.02mmol),4,4,5,5--2-(-2-)-1,3,2-(<strong>[890042-13-4]4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane</strong>) 5.96g (16.82mmol), tetrakis (triphenylphosphine) palladium (0) 1.62g (1.4mmol), and 5.81g K2CO3 (42.06mmol) in toluene (Toluene) 140mL, ethanol (EtOH), 28mL, 28mL H2O under 120 C.It was stirred under reflux for 3 hours . After the reaction was extracted with distilled water and dichloromethane (dichloromethane). Purified to remove the solvent by rotary evaporation The organic layer was dried over anhydrous MgSO4 dichloromethane and hexane by column chromatography as a developing solvent to obtain 4.92g of the desired compound 1-119 (54%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; at 80℃; for 53h;Inert atmosphere; | In the nitrogen ambient, after the compound I-1100 g (282 mmol) was melted in the tetrahydrofuran (THF) 1 L here 1- bromo -2-iodobenzene (1-bromo-2-iodobenzene) 95.9 g (339 mmol) and tetrakis(triphenylphosphine) palladium (tetrakis(triphenylphosphine)palladium) 3.26 g(2.82 mmol) were put and it mixed. The saturated potassium carbonate 97.4 g(705 mmol) was put in water and it heated up in 80 for 53 hours and it refluxed. After water was put in into the reaction solutionafter the reaction completion and it extracted in the dichloromethane (DCM)moisture was removed to the anhydrous MgSO4 it filtered and it was concentratedunder reduced pressure. The residue obtained in this way was refined to theflash column chromatography after dividing and the compound I-4 95.1 g (88 %)was obtained |
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 53h;Inert atmosphere; | The compound I-1 100 g (282 mmol) in tetrahydrofuran (THF) in a nitrogen environment, was dissolved in 1 L, where the 1-bromo-2-iodo-benzene (1-bromo-2-iodobenzene) 95.9 g (339 mmol) and was stirred into the tetrakis (triphenylphosphine) palladium (tetrakis (triphenylphosphine) palladium) 3.26 g (2.82 mmol).Into a potassium carbonate 97.4 g (705 mmol) in saturated water it was heated to reflux for 53 hours at 80 .After the reaction was completed, the reaction solution into water, extracted with dichloromethane (DCM) and then water was removed with anhydrous MgSO4, filter and was concentrated under reduced pressure.Thus the resulting residue was separated and purified by flash column chromatography to give the compound I-4 95.1 g (88%). |
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 53h;Inert atmosphere; Reflux; | in a nitrogen environment,100 g (282 mmol) of compound I-1 was dissolved in 1 L of tetrahydrofuran (THF)95.9 g (339 mmol) of 1-bromo-2-iodobenzene (Sigma-Aldrich Co., Ltd.) and 3.26 g (2.82 mmol) of tetrakistriphenylphosphine palladium were added thereto,And the mixture was stirred.To this was added a saturated aqueous solution of potassium carbonate 97.4 g (705 mmol)The mixture was heated and allowed to reflux for 53 hours at 80 C.When the reaction is complete,Water was added to the reaction solution,And the mixture was extracted with dichloromethane (DCM)Followed by removal of water with anhydrous MgSO4 filtered,And concentrated under reduced pressure.The residue obtained is isolated and purified by column chromatography,95.1 g (88%) of compound I-4 was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 20h;Inert atmosphere; | In the nitrogen ambient, after the compound 1-120 g (56.5 mmol) was melted in the tetrahydrofuran (THF) 0.2 L here 2- chloro-4,6- diphenyl -1,3,5- triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) 15.1 g(56.5 mmol) and tetrakis (triphenylphosphine) palladium(tetrakis(triphenylphosphine)palladium) 0.65 g (0.57 mmol) were put and itmixed. The saturated potassium carbonate 19.5 g (141 mmol) was put in water andit heated up in 80 for 20 hours and it refluxed. After water was put ininto the reaction solution after the reaction completion and it extracted inthe dichloromethane (DCM) moisture was removed to the anhydrous MgSO4 it filteredand it was concentrated under reduced pressure. The residue obtained in thisway was refined to the flash column chromatography after dividing and compoundA - 1s (22.1 g, 85 %) were obtained |
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 20h;Inert atmosphere; | Dissolve 20 g of the above mentioned compound 1-1 (56.5 mmol) in tetrahydrofuran (THF) in a nitrogen environment, 0.2 L, here the 2-chloro-4,6-diphenyl-1,3,5-triazine (2 chloro-4-diphenyl-,6-1 ,3,5-triazine) 15.1 g (56.5 mmol) and tetrakis (triphenylphosphine) palladium (tetrakis (triphenylphosphine) palladium) 0.65 g (0.57 mmol) and the mixture was stirred .Into a potassium carbonate 19.5 g (141 mmol) in saturated water it was heated to reflux at 80 for 20 hours.After the reaction was completed, the reaction solution into water, extracted with dichloromethane (DCM) and then water was removed with anhydrous MgSO4, filter and was concentrated under reduced pressure.Thus the resulting residue was separated and purified by flash column chromatography to give the compound A-1 (22.1 g, 85%). |
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 20h;Inert atmosphere; | Under a nitrogen atmosphere, 20 g (56.5 mmol) of Intermediate 1-1 was dissolved in 0.2 liters (L) of tetrahydroffiran (THF), and 15.1 g (56.5 mmol) of 2-chloro-4,6- diphenyl-1,3,5-triazine and 0.65 g (0.57 mmol) of tetrakis (triphenylphosphine)palladium were added thereto and the reaction mixture was agitated. 19.5 g (141 mmol) of potassium carbonate saturated in water was added thereto, and the resultant was heated at a temperature 80 C. for 20 hours under reflux. Afier the reaction was completed, water was added to the reaction solution and the mixture was extracted by using dichloromethane (DCM). Then, an anhydrous magnesium sulfate (MgSO4) was added thereto to perform dehydration. The resultant was filtered and concentrated under reduced pressure. The obtained residual was separated and purified by flash column chromatography to obtain 22.1 g (85%) of Compound A-1 HRMS (70 eV, EI+): m/z calcd for C33H21N3:459.1735, found: 459. Elemental Analysis: C, 86%; H, 5% |
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 20h;Inert atmosphere; | 20 g (56.5 mmol) of Compound 1-1 was dissolved in 0.2 L of tetrahydrofuran (THF) under a nitrogen condition (a nitrogen atmosphere), and 15.1 g (56.5 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 0.65 g (0.57 mmol) of tetrakis(triphenylphosphine)palladium were added thereto. The mixed solution was then stirred. 19.5 g (141 mmol) of potassium carbonate saturated in water was added thereto, and refluxed by a heating process performed thereon at a temperature of 80 C. for 20 hours. After the reaction was completed, water was added to the reaction solution, and an extraction process was performed thereon by using dichloromethane (DCM). Moisture in the extraction was dried by using anhydrous magnesium sulfate (MgSO4), and the resulting mixture was then filtered and concentrated under reduced pressure. The residue obtained therefrom was separated and purified by flash column chromatography to obtain 22.1 g (85%) of Compound A-1. (0439) HRMS (70 eV, EI+): m/z calcd for C33H21N3: 459.1735, found: 459. (0440) Elemental Analysis: C, 86%; H, 5% |
A498711 [N/A]
(7-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyren-2-yl)boronic acid
Similarity: 1.00
A561053 [853377-11-4]
4,4,5,5-Tetramethyl-2-(pyren-2-yl)-1,3,2-dioxaborolane
Similarity: 1.00
A531829 [68716-52-9]
4,4,5,5-Tetramethyl-2-(naphthalen-1-yl)-1,3,2-dioxaborolane
Similarity: 0.98
A219500 [349666-24-6]
4,4,5,5-Tetramethyl-2-(pyren-1-yl)-1,3,2-dioxaborolane
Similarity: 0.98
A306909 [863992-56-7]
9,10-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anthracene
Similarity: 0.98
A498711 [N/A]
(7-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyren-2-yl)boronic acid
Similarity: 1.00
A561053 [853377-11-4]
4,4,5,5-Tetramethyl-2-(pyren-2-yl)-1,3,2-dioxaborolane
Similarity: 1.00
A531829 [68716-52-9]
4,4,5,5-Tetramethyl-2-(naphthalen-1-yl)-1,3,2-dioxaborolane
Similarity: 0.98
A856797 [950761-81-6]
4,4,5,5-Tetramethyl-2-(perylen-3-yl)-1,3,2-dioxaborolane
Similarity: 0.98
A219500 [349666-24-6]
4,4,5,5-Tetramethyl-2-(pyren-1-yl)-1,3,2-dioxaborolane
Similarity: 0.98