Purity | Size | Price | VIP Price | USA Stock *0-1 Day | Global Stock *5-7 Days | Quantity | |||||
{[ item.p_purity ]} | {[ item.pr_size ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} | Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]} | {[ item.pr_usastock ]} | Inquiry - | {[ item.pr_chinastock ]} | Inquiry - |
* Storage: {[proInfo.prStorage]}
CAS No. : | 68572-87-2 | MDL No. : | MFCD00143524 |
Formula : | C14H11BO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | JCDAUYWOHOLVMH-UHFFFAOYSA-N |
M.W : | 222.05 | Pubchem ID : | 11775704 |
Synonyms : |
|
Num. heavy atoms : | 17 |
Num. arom. heavy atoms : | 14 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 71.28 |
TPSA : | 40.46 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | Yes |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.29 cm/s |
Log Po/w (iLOGP) : | 0.0 |
Log Po/w (XLOGP3) : | 3.33 |
Log Po/w (WLOGP) : | 1.67 |
Log Po/w (MLOGP) : | 2.26 |
Log Po/w (SILICOS-IT) : | 1.39 |
Consensus Log Po/w : | 1.73 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.86 |
Solubility : | 0.0308 mg/ml ; 0.000139 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.86 |
Solubility : | 0.0309 mg/ml ; 0.000139 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -4.65 |
Solubility : | 0.00501 mg/ml ; 0.0000225 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 2.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.98 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
82% | Stage #1: With n-butyllithium In tetrahydrofuran at -78 - 0℃; for 1 h; Inert atmosphere Stage #2: at -78 - 20℃; for 12 h; Inert atmosphere Stage #3: With hydrogenchloride In tetrahydrofuran; water for 0.5 h; Inert atmosphere |
Under nitrogen, 2.57 g (10 mmol) of 9-bromophenanthrene was dissolved in 40 ml of anhydrous THF, the temperature of the reaction was lowered to -78 ° C,After slowly adding 4 ml of 2.5 M n-BuLi dropwise, the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reactionAfter lowering to -78 deg. C, 12.47 g (12 mmol) of trimethylborate was added dropwise, and the mixture was stirred at room temperature for 12 hours. The reactionAfter completion of the reaction, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether.Water in the organic layer was removed with anhydrous MgSO 4, filtered under reduced pressure, and then the organic solvent was concentrated to obtain a compound, Hex: EA = 4:1 to obtain 1.82 g (82percent) of Intermediate-3. |
81% | With n-butyllithium In tetrahydrofuran at -78 - 20℃; for 13.5 h; Inert atmosphere | After tetra-hydro furan gave 500ml put the 9-bromo-phenanthrene 50g (194mmol) in a round bottom flask containing a nitrogen atmosphere the temperature was adjusted to -78 . Slowly added dropwise to 146ml of n-butyllithium (233mmol) in 30 minutes, which was then slowly added dropwise trimethyl borate 28.3g (274mmol) After 1 hour, the temperature was raised to room temperature. After stirring for about 12 hours at room temperature, and then, extraction was collected by distillation under reduced pressure and the organic layer was added dropwise to the reaction solution until the acid is a hydrochloric acid solution 2N (n). After the nucleic acid has a normal filter to dry the recrystallized result, to obtain an intermediate a-20 (35g, yield 81percent) as a white solid. |
81.1% | Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1 h; Inert atmosphere Stage #2: at 20℃; for 12 h; Inert atmosphere Stage #3: With hydrogenchloride; water In tetrahydrofuran at 0℃; Inert atmosphere |
In a three-necked 1.0 L flask 30.0 g (116.7 mmol) of 9-bromophenanthrene are added and dissolved in 292 mL of THF under a nitrogen atmosphere. After cooling the reaction temperature to -78°C, 56.0 mL (140.0 mmol) of 2.5 M n-BuLi solution was slowly added dropwise and stirred.After the dropwise addition was completed, the mixture was stirred at -78 °C for 1 hour, 18.3 mL (163.3 mmol) of trimethylborate was slowly added dropwise.After the temperature was raised to room temperature, the mixture was stirred for 12 hours. After the temperature was lowered to 0 °C, 20 mL of 2 N HCl was added. After adding 500 mL of dichloromethane and 300 mL of H2O,The organic layer was separated and washed with water and brine. Dried over MgSO4, filtered, and the filtrate was concentrated under reduced pressure. The resulting concentrate was solidified and purified by using a solvent to obtain 21.0 g (yield: 81.1percent) of a white solid compound (intermediate (5)). |
42% | Stage #1: With n-butyllithium In tetrahydrofuran at -76℃; for 0.166667 h; Inert atmosphere Stage #2: With hydrogenchloride In tetrahydrofuran; water at 20℃; for 1 h; Inert atmosphere |
In a 500 ml round-bottom flask, 10 g of 9-bromophenanthrene (38.89 mmol) was added and dissolved in150 ml of anhydrous tetrahydrofuran (THF) before stirring.The reaction temperature was maintained at −76° C,and 25.28 ml of 2.0 M n-butyllithium (50.59 mmol) was slowly added to the reaction vessel. After about 10 minutes, 6.07 ml of trimethyl borate (54.45 mmol) was added to the reaction vessel. Once the reaction temperature increased to room temperature after about 1 hour, 7.12 ml of 12 M HCl (85.56 mmol) was added. After the reaction,the mixture was extracted using ethyl acetate (EA)and distilled water. Water remaining in the organic layer was dried with MgSO4. The mixture was concentrated byreduced pressure and re-precipitated with THF and hexane to obtain white solid. The yield was 42percent. 1H-NMR (300 MHz, Chloroform) (ppm): 8.75–8.71(t, 2H), 8.56–8.53 (d, 1H), 8.04 (s , 1H), 7.88–7.85(d, 1H), 7.61–7.52 (m, 6H), 5.79 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: With n-butyllithium In tetrahydrofuran; hexanes at -78℃; for 1 h; Stage #2: With hydrogenchloride; water In tetrahydrofuran; hexanes at -20 - 18℃; for 1 h; |
Compound 42e.; Step a: Preparation of 9-phenanthrene boronic acid; A solution of 9-bromophenanthrene (1 g, 3.9 mmol) and triisopropylborate (1.35 ml, 1.1 g, 5.85 mmol) in absolute THF (30 ml) was cooled down to -78°C and stirred under argon. Then n-BuLi (1.6 M in hexanes, 2.9 ml, 4.68 mmol) was added dropwise to the solution over a period of 1 hour and it was stirred at -78°C for 1 hour. The solution was then warmed to -200C and 2 M HCl (20 ml) was added, then the mixture was warmed to 18 "C and stirred at that temperature for 1 hour. Diethyl ether (300 ml) was then added and it was washed with H2O (2 x 100 ml). The organic phase was dried over MgSO4, filtered and the solvent was removed under reduced pressure to give 9-phenanthrene boronic acid (770 mg, 89percent) as a white solid which was used without further purification. |
70% | With n-butyllithium In tetrahydrofuran at -100℃; for 2 h; Inert atmosphere | In the nitrogen,Clean and dry 1000ml three-mouth bottle,Add 9-bromophenanthrene,Triisopropyl borate,THF, cool down to -100°C,Lithium butyl lithium was added dropwise, and the insulation was kept for 2 hours.Hydrochloric acid, washed,Desiccant solvent, toluene beating, 9-phenanthrene boric acid;HPLC: 99.9percent, yield: 70percent; |
55% | Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1 h; Inert atmosphere Stage #2: for 1 h; |
9-bromophenanthrene (13.26 g, 38.74 mmol) was added to a three-necked flask,Added THF200mL, nitrogen protection,-78 ° C for 30 minutes,N-Butyllithium (2.5 M / 21 mL) was added and reacted for 1 hour.Triisopropyl borate (14 g) was further added,Low temperature reaction for 1 hour, gradually return to room temperature.After the treatment process, add 2M hydrochloric acid to make the solution PH value of 4-5,Quiescent liquid,The aqueous layer was extracted once more with ethyl acetate, the combined organic layers were spin-dried,6-A (6.55 g, y = 55percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81.1% | Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1 h; Inert atmosphere Stage #2: at -78 - 20℃; for 12 h; Inert atmosphere Stage #3: With hydrogenchloride In tetrahydrofuran; dichloromethane at 0℃; Inert atmosphere |
Add 30.0 g (116.7 mmol) of 9-bromophenanthrene to a three-necked 1.0 L flask and dissolve in 292 mL of THF under a nitrogen atmosphere. After cooling the reaction temperature to -78 ° C, 56.0 mL (140.0 mmol) of 2.5 M n-BuLi solution was slowly added dropwise and stirred.After the dropwise addition was completed, the mixture was stirred at -78 ° C for 1 hour, and 18.3 mL (163.3 mmol) of trimethylborate was slowly added dropwise. After the temperature was raised to room temperature, the mixture was stirred for 12 hours. After the temperature was lowered to 0 ° C, 20 mL of 2 N HCl was added.After adding 500 mL of dichloromethane and 300 mL of H2O, the organic layer was separated and washed with water and brine. Dried over MgSO4, filtered, and the filtrate was concentrated under reduced pressure.The resulting concentrate was solidified and purified by using a solvent to obtain 21.0 g (yield: 81.1percent) of a white solid compound (intermediate (5) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With sodium carbonate; triphenylphosphine;palladium diacetate; In propan-1-ol; water; at 20℃; for 5.5h;Heating / reflux; | To n-propanol solution (25 ml) containing 2.0 g (6.73 mmole) of (+/-)-1-methoxy-5-(4-bromophenyl)bicyclo [3.3.0] -2-oxaoctane and 1.9 g (8.49 mmole) of 9-phenanthrylboronic acid, 0.015 g (0.065 mmole) of palladium(II) acetate and 0.052 g (0.198 mmole) of triphenylphosphine were added successively, and the resultant mixture was stirred at the room temperature for 30 minutes. To the obtained reaction mixture, 8 ml of a 2 moles/liter aqueous solution of sodium carbonate was added, and the resultant mixture was heated under the refluxing condition for 5 hours. To the obtained reaction mixture, water was added, and the resultant mixture was treated by extraction 3 times each with 50 ml of ether. The organic layers were combined, washed with water and a saturated aqueous solution of sodium chloride, dried over sodium sulfate and concentrated under a reduced pressure, and a light brown solid substance was obtained. The obtained solid substance was purified in accordance with the silica gel column chromatography using a hexane/ethyl acetate mixed solvent (the ratio of the amounts by volume: 9/1) as the elution solvent, and 2.0 g (4.96 mmole) of (+/-)-1-methoxy-5-{4-(9-phenanthryl)-phenyl}bicyclo [3.3.0] -2-oxaoctane was obtained as a colorless solid substance. The yield was 76%. The analytical data of the obtained compound are shown in the following. The melting point: 144-145C (the solvent of recrystallization: ethyl acetate/hexane) FTIR (CHCl3): 2950, 2881, 2828, 2244, 1610, 1510, 1492, 1450, 1317 1H-NMR (400 MHz): 8.76 (d, J=8.0 Hz, 1H), 8.70 (d, J=8.0 Hz, 1H), 8.00 (d, J=8.0 Hz, 1H), 7.87 (d, J=8.0 Hz, 1H), 7.68-7.57 (m, 4H), 7.54-7.47 (m, 5H), 4.16-4.07 (m, 2H), 3.29 (s, 3H), 2.64-2.57 (m, 1H), 2.39-2.28 (m, 2H), 2.15-2.00 (m, 3H), 1.92-1.82 (m, 2H) 13C-NMR (100 MHz): 143.5 (C), 138.6 (C), 138.1 (C), 131.6 (C), 131.1 (C), 130.6 (C), 129.8 (C), 129.5 (CHx2), 128.6 (CH), 127.5 (CH), 127.2 (CHx2), 127.0 (CH), 126.7 (CH), 126.43 (CH), 126.36 (CHx2), 122.8 (CH), 122.5 (CH), 118.4 (C), 66.3 (CH2), 58.9 (C), 51.0 (CH3), 40.7 (CH2), 38.2 (CH2), 34.4 (CH2), 21.5 (CH2) Anal. Calcd. for C26H26O2: C 85.25, H, 6.64; Found: C 85.60, H 6.85 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium carbonate; triphenylphosphine;palladium diacetate; In 1,3,6,8-tetrakis(2-naphthyl)pyrene; water; | Example 1b Synthesis of 1,3,6,8-tetra(9-phenanthryl)pyrene 1,3,6,8-tetrabromopyrene (4.7 g, 9.1 mmol), 9-phenanthreneboronic acid (11.7 g, 45.4 mmol), triphenylphosphine (1.0 g, 3.6 mmol), palladium(II) acetate (0.2 g, 0.9 mmol), and potassium carbonate (8.8 g, 63.5 mmol) were in 300 mL of xylenes and 50 mL of water. The mixture was purged with nitrogen for ten minutes and slowly brought to reflux under nitrogen. The mixture was refluxed for forty-eight hours. After cooling, the solid was filtered, washed with water and ethanol, and dried. The crude yield was ~95%. Based on the purification of 1,3,6,8-tetra(2-naphthyl)pyrene, sublimation was the most effective means of purifying this crude material; however, 1,3,6,8-tetra(9-phenanthryl)pyrene decomposed under similar sublimation conditions as in 1,3,6,8-tetra(2-naphthyl)pyrene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 10h;Heating / reflux; | EXAMPLE 3: SYNTHESIS OF 6,12-bis(9-phenathryl)chrysene (CH3) Under an argon atmosphere, 3 g of 6,12-dibromochrysene, 5 g of 9-phenathreneboric acid available from Tokyo Kasei Co., Ltd., and 0.36 g of tetrakis(triphenylphosphine)palladium (0) available from Hiroshima Wako Co., Ltd., were dissolved in 100 mL of toluene. The resultant solution was mixed with a solution prepared by dissolving 5 g of sodium carbonate in 24 mL of water, and the resultant mixed solution was refluxed for 10 h and allowed to stand over one night. The obtained reaction mixture was filtered and then successively washed with water, methanol and acetone, thereby obtaining 4.2 g of a light-yellow solid. As a result of the measurement for FD-MS of the obtained compound, it was confirmed that m/z = 580 was obtained relative to C46H28 = 580, and, therefore, the compound was identified to be 6,12-bis(9-phenathryl)chrysene (CH3) (yield: 93%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Compound 42e.; Step a: Preparation of 9-phenanthrene boronic acid; A solution of 9-bromophenanthrene (1 g, 3.9 mmol) and triisopropylborate (1.35 ml, 1.1 g, 5.85 mmol) in absolute THF (30 ml) was cooled down to -78C and stirred under argon. Then n-BuLi (1.6 M in hexanes, 2.9 ml, 4.68 mmol) was added dropwise to the solution over a period of 1 hour and it was stirred at -78C for 1 hour. The solution was then warmed to -200C and 2 M HCl (20 ml) was added, then the mixture was warmed to 18 "C and stirred at that temperature for 1 hour. Diethyl ether (300 ml) was then added and it was washed with H2O (2 x 100 ml). The organic phase was dried over MgSO4, filtered and the solvent was removed under reduced pressure to give 9-phenanthrene boronic acid (770 mg, 89%) as a white solid which was used without further purification. | |
70% | With n-butyllithium; In tetrahydrofuran; at -100℃; for 2h;Inert atmosphere; | In the nitrogen,Clean and dry 1000ml three-mouth bottle,Add 9-bromophenanthrene,Triisopropyl borate,THF, cool down to -100C,Lithium butyl lithium was added dropwise, and the insulation was kept for 2 hours.Hydrochloric acid, washed,Desiccant solvent, toluene beating, 9-phenanthrene boric acid;HPLC: 99.9%, yield: 70%; |
55% | 9-bromophenanthrene (13.26 g, 38.74 mmol) was added to a three-necked flask,Added THF200mL, nitrogen protection,-78 C for 30 minutes,N-Butyllithium (2.5 M / 21 mL) was added and reacted for 1 hour.Triisopropyl borate (14 g) was further added,Low temperature reaction for 1 hour, gradually return to room temperature.After the treatment process, add 2M hydrochloric acid to make the solution PH value of 4-5,Quiescent liquid,The aqueous layer was extracted once more with ethyl acetate, the combined organic layers were spin-dried,6-A (6.55 g, y = 55%). |
36 g | 9 g of bromophenanthrene (117.19 mmol, 1 eq) was added to a 1000 mL three-necked flask equipped with magnetic stirring at room temperature.Tetrahydrofuran 300mL,Turn on the agitation,Nitrogen purge for 15 min,Use ethanol and liquid nitrogen to reduce the unit temperature to -78 C,Add 50 mL (125 mmol, 1.05 eq) of n-butyllithium to the dropping tube.Slowly added dropwise to the reaction solution,Keep -78C2 hours,Under -78C,93.6 mL (234.38 mmol, 2 eq) of triisopropyl borate was added to the dropping tube.And gradually added dropwise to the reaction solution,After the addition is completed,Gradually warm to room temperature,Reaction for 1 hour,Then, 6 mL of dilute hydrochloric acid was added to stop the reaction.After the reaction,Add ethanol,The reaction solution was sprinkled,Obtaining a crude product;The crude product was washed with n-hexane.Obtained 36g of white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In 1,2-dimethoxyethane; water; at 90℃; for 8h; | A 100 mL three-neck flask was charged with 0.80 g (2.37 mmol) of 4,4'-dibromostilbene synthesized in Step 2, 1.2 g (5.40 mmol) of 9-phenanthrene boronic acid, 0.0053 g (0.024 mmol) of palladium acetate, and 0.050 g (0.163 mmol) of tris(o-tolyl)phosphine, and the air in the flask was replaced by nitrogen. Then, 15 mL of ethylene glycol dimethyl ether and 3.5 mL (2.0 mol/L) of potassium carbonate aqueous solution were added thereto and stirred for 8 hours at 90 C. to cause a reaction. After the reaction, precipitate in the reaction mixture was collected by suction filtration. After the filtration, the obtained material was recrystallized from chloroform and hexane to obtain 0.86 g of white solid in a yield of 68%. The obtained white solid was identified as DPNS2 by a nuclear magnetic resonance method (NMR). 1H-NMR of the obtained DPNS2 is shown below. In addition, a 1H-NMR chart is shown in FIG. 15. 1H-NMR (300 MHz, CDCl3); delta=8.81-8.73 (m, 4H), 8.02-7.91 (m, 4H), 7.74-7.57 (m, 18H), 7.34 (s, 2H) A synthesis scheme of DPNS2 is shown below.; Further, when a decomposition temperature Td of DPNS2 was measured by a thermo-gravimetric/differential thermal analyzer (TG/DTA 320, manufactured by Seiko Instruments Inc.), the Td was 416.6 C . Therefore, it was understood that DPNS2 has a high Td. An absorption spectrum of DPNS2 in a state of being dissolved in a toluene solvent is shown in FIG. 16 and that in a thin film state is shown in FIG. 18. An emission spectrum of DPNS2 in the toluene solution is shown in FIG. 17 and that in the thin film state is shown in FIG. 19. In each of FIGS. 16 and 18, the vertical axis indicates absorption intensity (arbitrary unit) and the horizontal axis indicates wavelength (nm). Also, in each of FIGS. 17 and 19, the vertical axis indicates emission intensity (arbitrary unit) and the horizontal axis indicates wavelength (nm). A light emission from DPNS2 had a peak at 420 nm (an excited wavelength: 348 nm) in the state of DPNS2 being dissolved in the toluene solution and had a peak at 437 nm (an excited wavelength: 344 nm) in a thin film state, therefore, it is understood that blue light emission was obtained. Using absorption spectrum data in FIG. 18, an absorption edge was obtained from a Tauc plot. Then, the energy at the absorption edge is used as an energy gap and an energy gap of DPNS2 was found to be 3.2 eV. Since 9,10-diphenylanthracene, which exhibits representative blue emission, has an energy gap of 2.9 eV, it is understood that DPNS2 has a very large energy gap. Further, the HOMO level in the thin film state was measured by an ambient photoelectron spectroscopy with a spectrometer (AC-2, manufactured by Riken Keiki Co., Ltd.), and was found to be -5.9 eV. Using the HOMO level and the energy gap, the LUMO level was found to be -2.7 eV. An optimal molecular structure of DPNS2 in a ground state was calculated by the same method as Synthesis Example 1. From this calculation result, a HOMO level value of the obtained DPNS2 was found to be -5.59 eV. Singlet excitation energy (energy gap) of DPNS2 was calculated by the same method as Synthesis Example 1. The singlet excitation energy was calculated to be 3.34 eV. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In 1,2-dimethoxyethane; water; at 90℃; for 6h; | A 100 mL three-neck flask was charged with 1.75 g (5.19 mmol) of 3,3'-dibromostilbene synthesized in Step 2, 2.63 g (11.8 mmol) of 9-phenanthrene boronic acid, 0.023 g (0.103 mmol) of palladium acetate, and 0.221 g (0.727 mmol) of tris(o-tolyl)phosphine, and the air in the flask was replaced by nitrogen. Then, 40 mL of ethylene glycol dimethyl ether and 8 mL (2.0 mol/L) of potassium carbonate aqueous solution were added thereto and stirred for 6 hours at 90 C. to cause a reaction. After the reaction, precipitate in the reaction mixture was collected by suction filtration. After the filtration, the obtained material was recrystallized from chloroform and hexane to obtain 2.11 g of white solid in a yield of 76%. The obtained white solid was identified as DPNS by a nuclear magnetic resonance method (NMR). 1H-NMR of the obtained DPNS is shown below. In addition, a 1H-NMR chart is shown in FIG. 10. 1H-NMR (300 MHz, CDCl3); delta=8.80-8.72 (m, 4H), 7.96-7.89 (m, 4H), 7.72-7.43 (m, 18H), 7.28 (s, 2H) A synthesis scheme of DPNS is shown below.; Further, when a decomposition temperature Td of DPNS was measured by a thermo-gravimetric/differential thermal analyzer (TG/DTA 320, manufactured by Seiko Instruments Inc.), the Td was 396.4 C. Therefore, it was understood that DPNS has a high Td. An absorption spectrum of DPNS in a state of being dissolved in a toluene solvent is shown in FIG. 11 and that in a thin film state is shown in FIG. 13. An emission spectrum of DPNS in the toluene solution is shown in FIG. 12 and that in the thin film state is shown in FIG. 14. In each of FIGS. 11 and 13, the vertical axis indicates absorption intensity (arbitrary unit) and the horizontal axis indicates wavelength (nm). Also, in each of FIGS. 12 and 14, the vertical axis indicates emission intensity (arbitrary unit) and the horizontal axis indicates wavelength (nm). A light emission from DPNS had peaks at 355 nm and 375 nm (an excited wavelength: 320 nm) in the state of DPNS being dissolved in the toluene solution and had a peak at 410 nm (an excited wavelength: 308 nm) in the state of thin film; therefore, it is understood that blue light emission was obtained. Using absorption spectrum data in FIG. 13, an absorption edge was obtained from a Tauc plot. Then, the energy at the absorption edge is used as an energy gap and an energy gap of DPNS was found to be 3.5 eV. Since 9,10-diphenylanthracene, which exhibits representative blue emission, has an energy gap of 2.9 eV, it is understood that DPNS has a very large energy gap. Further, the HOMO level in the thin film state was measured by an ambient photoelectron spectroscopy with a spectrometer (AC-2, manufactured by Riken Keiki Co., Ltd.), and was found to be -5.9 eV. Using the HOMO level and the energy gap, the LUMO level was found to be -2.4 eV. An optimal molecular structure of DPNS in a ground state was calculated using a density functional theory (DFT) at the B3LYP/6-311 (d, p) level. The accuracy of calculation of the DFT is higher than that of a Hartree-Fock (HF) method which neglects electron correlation. In addition, a calculation cost of the DFT is lower than that of a method of perturbation (MP) which has the same level of accuracy of calculation as the DFT. Therefore, the DFT was employed in this calculation. The calculation was performed using a high performance computer (HPC) (Altix3700 DX, manufactured by SGI Japan, Ltd.). From this calculation result, a HOMO level value of DPNS was found to be -5.85 eV. In addition, singlet excitation energy (energy gap) of DPNS was calculated using a time-dependent density functional theory (TDDFT) at the B3LYP/6-311 (d, p) level of for the molecular structure by the DFT. The singlet excitation energy was calculated to be 3.54 eV. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 12.5h;Heating / reflux; | EXAMPLE 3; (Synthesis of 3-(2,2'-bipyridine-6-yl)-4-phenyl-5-[6-(phenanthrene-9-yl)pyridine-2-yl]-1,2,4-triazole (Compound 11)); To a reaction vessel substituted with argon, 1.35 g of 3-(2,2'-bipyridine-6-yl)-4-phenyl-5-(6-bromopyridine-2-yl)-1,2,4-triazole, 1.0 g of 9-phenanthreneboronic acid, 50 ml of a degassed solution of toluene/ethanol (4/1, v/v), and 8.9 ml of a 1 M-potassium carbonate solution were added, followed by adding thereto 0.17 g of tetrakis(triphenylphosphine)palladium (0) under the argon atmosphere. A reaction was allowed to proceed for 9 hours under reflux, and then 0.09 g of tetrakis(triphenylphosphine)palladium (0) was added to allow the reaction to proceed for 3.5 hours more under reflux. After completion of the reaction, the reaction solution was cooled to a room temperature, and a precipitated crude product was collected by filtration. To the thus-obtained crude product, 100 ml of chloroform was added, followed by elimination of the catalyst by filtration. After concentrating the filtrate, crystallization purification was performed by adding methanol. The thus-obtained white solid was dried at 50C overnight under a reduced pressure, thereby obtaining 1.36 g of 3-(2,2'-bipyridine-6-yl)-4-phenyl-5-[6-(phenanthrene-9-yl)pyridine-2-yl]-1,2,4-triazole (Compound 11) (yield: 83%). A structure of the thus-obtained white solid was identified by using NMR. 1H-NMR measurement results are shown in Fig. 3. The following 24 hydrogen signals were detected by 1H-NMR (CDCl3). delta(ppm) = 8.758-8.697 ppm (2H), 8.552 ppm (1H) 8.390-8.357 ppm (2H), 8.286 ppm (1H), 7.963-7.899 ppm (2H), 7.859-7.809 ppm (2H), 7.712-7.579 ppm (4H), 7.517-7.166 ppm (9H), 6.995 ppm (1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 85 - 110℃; for 21h;Inert atmosphere; | Example 21In this example, an example of producing 9-phenyl-9H-3-{4-[3,5-di(phenanthren-9-yl)phenyl]phenyl}carbazole (abbreviation: Pn2BPPC) that is a carbazole compound of one embodiment of the present invention, in which R1 is a phenyl group, R2 is hydrogen, alpha3 is a biphenyldiyl group having a phenanthrenyl group as a substituent, and Ar3 is a phenanthrenyl group in General Formula (G1) will be described. Step 1: Synthesis Method of 9-[3-chloro-5-(phenanthren-9-yl)phenyl]phenanthrene (abbreviation: Cl-PPn2)In a 200-mL three-neck flask, a mixture of 2.90 g (10.7 mmol) of 1,3-dibromo-5-chlorobenzene, 5.0 g (22.5 mmol) of 9-phenanthrene boronic acid, 50.6 mg (0.23 mmol) of palladium(II) acetate, 207 mg (0.68 mmol) of tri(o-tolyl)phosphine, 70 mL of toluene, 7 mL of ethanol, and 20 mL of a potassium carbonate aqueous solution (2 mol/L) was deaerated while being stirred under reduced pressure and was heated and stirred in a nitrogen atmosphere at 85 C. for 6 hours to be reacted. In addition, 50.6 mg (0.23 mmol) of palladium(II) acetate and 207 mg (0.68 mmol) of tri(o-tolyl)phosphine were added to the mixture, and the mixture was heated and stirred in a nitrogen atmosphere at 85 C. for 7.5 hours, and then heated and stirred at 110 C. for 7.5 hours to be reacted.After reaction, 300 mL of toluene was added to the reaction mixture solution, and an organic layer of the mixture solution was filtrated through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), alumina (neutral, produced by Merck Ltd), and Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855). The obtained filtrate was washed with water, and magnesium sulfate was added thereto so that moisture was adsorbed. This suspension was filtrated to obtain a filtrate. The obtained filtrate was concentrated and purified by silica gel column chromatography. At this time, a mixed solvent of toluene and hexane (toluene:hexane=1:5) was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and toluene and hexane were added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 3.11 g of white powder that was an objective substance in a yield of 63%. The reaction scheme of the synthesis method is shown in (F8-1). The Rf value of the objective substance was 0.25, which was obtained by silica gel thin layer chromatography (TLC) (with a developing solvent containing ethyl acetate and hexane in a 1:10 ratio).The compound obtained in Step 1 was examined by a nuclear magnetic resonance (NMR) method. The measurement data are shown below.1H NMR (CDCl3, 300 MHz): delta (ppm)=7.59-7.73 (m, 11H), 7.79 (s, 2H), 7.92 (d, J=7.81 Hz, 2H), 8.06 (d, J=8.30 Hz, 2H), 8.73 (d, J=8.30 Hz, 2H), 8.79 (d, J=8.30 Hz, 2H).FIGS. 82A and 82B are 1H NMR charts. Note that FIG. 82B is a chart showing an enlarged part of FIG. 82A in the range of 7.00 ppm to 9.00 ppm. The measurement results confirmed that 9-[3-chloro-5-(phenanthren-9-yl)phenyl]phenanthrene (abbreviation: Cl-PPn2) that was the objective substance was able to be obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 100℃; for 5h;Inert atmosphere; | Step 2: Synthesis Method of 3-[3-(9-phenanthryl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: mPCPPn)In a 200-mL three-neck flask, a mixture of 3.0 g (7.5 mmol) of 3-(3-bromophenyl)-9-phenyl-9H-carbazole, 1.8 g (8.29 mmol) of phenanthrene-9-boronic acid, 19 mg (0.1 mmol) of palladium(II) acetate, 76 mg (0.2 mmol) of tris(2-methylphenyl)phosphine, 70 mL of toluene, 7 mL of ethanol, and 20 mL of a potassium carbonate aqueous solution (2 mol/L) was deaerated while being stirred under reduced pressure, and then heated and stirred in a nitrogen atmosphere at 100 C. for 5 hours to be reacted.After the reaction, 500 mL of toluene was added to the reaction mixture solution, and an organic layer of the mixture solution was filtrated through Florisil, alumina, and Celite. The obtained filtrate was washed with water, and magnesium sulfate was added thereto to adsorb moisture. This suspension was filtrated to obtain a filtrate. The obtained filtrate was concentrated and purified by silica gel column chromatography. At this time, a mixed solvent of toluene and hexane (toluene:hexane=2:3) was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and hexane was added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 2.76 g of white powder that was an objective substance in a yield of 74%. The reaction scheme of Step 2 is shown in (F4-2). The Rf values of the objective substance and 3-(3-bromophenyl)-9-phenyl-9H-carbazole were respectively 0.25 and 0.58, which were obtained by silica gel thin layer chromatography (TLC) (with a developing solvent containing ethyl acetate and hexane in a 1:10 ratio).The obtained compound was examined by a nuclear magnetic resonance (NMR) method. The measurement data are shown below.1H NMR (CDCl3, 300 MHz): delta (ppm)=7.28-7.32 (m, 1H), 7.42-7.76 (m, 15H), 7.81-7.84 (m, 2H), 7.92-7.95 (m, 2H), 8.06 (d, J=8.1 Hz, 1H), 8.18 (d, J=7.8 Hz, 1H), 8.44 (d, J=1.5 Hz, 1H), 8.76 (d, J=8.1 Hz, 1H), 8.81 (d, J=8.7 Hz, 1H).FIGS. 17A and 17B are 1H NMR charts. Note that FIG. 17B is a chart showing an enlarged part of FIG. 17A in the range of 6.5 ppm to 9.0 ppm. The measurement results confirmed that mPCPPn that was the objective substance was able to be obtained.FIG. 18A shows an absorption spectrum of mPCPPn, in a toluene solution of mPCPPn, and FIG. 18B shows an emission spectrum thereof. FIG. 19A shows an absorption spectrum of a thin film of mPCPPn, and FIG. 19B shows an emission spectrum thereof. The absorption spectrum was measured with an ultraviolet-visible spectrophotometer (V550, produced by JASCO Corporation). The emission spectrum was measured with a fluorescence spectrophotometer (FS920, produced by Hamamatsu Photonics 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. FIG. 18A show the absorption spectrum of mPCPPn in the solution of mPCPPn which was obtained by subtracting the absorption spectra of the quartz cell and toluene put therein, and FIG. 19A shows the absorption spectrum of the thin film which was obtained by subtracting the absorption spectrum of the quartz substrate. In FIGS. 18A and 18B and FIGS. 19A and 19B, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). In the case of the toluene solution, the absorption peak was observed at around 298 nm, and the maximum emission wavelength was 363 nm (excitation wavelength: 311 nm). In the case of the thin film, the absorption peak was observed at around 350 nm, and the maximum emission wavelength was 389 nm (excitation wavelength: 353 nm). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide; In tetrahydrofuran; water; at 70℃; for 24h;Inert atmosphere; | Under an argon atmosphere, 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (70.0g, 0.166mol), 9- phenanthrene boronic acid (38.6g, 0 .174mol), tetrakis (triphenylphosphine) palladium (3.83 g, 3.31 mmol) was suspended in tetrahydrofuran (1000mL), 4.0M- was added dropwise aqueous sodium hydroxide (124mL, 0.497mol) here. The resulting mixture was stirred for 24 hours at 70 C.. Then, after cooling, water (550 mL) was added, and the precipitated solid was filtered off and washed with water, methanol, a solid with hexane. By recrystallizing (toluene), a reaction intermediate 2- [3-chloro-5- (9-phenanthryl) phenyl] -4,6-diphenyl-1,3,5-triazine as a white solid (yield 78 .9g, 92% yield). |
92% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide; In tetrahydrofuran; for 24h;Inert atmosphere; Reflux; | Under an argon atmosphere, 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (70.0g, 0.166mol), 9- phenanthrene boronic acid (38.6g, 0 .174mol), and tetrakis (triphenylphosphine) palladium (3.83g, weighed 3.31mmol), suspended in 4.0M over sodium hydroxide solution (124mL, 0.497mol) and tetrahydrofuran (1.0L) did. The mixture was heated to reflux for 24 hours. After cooling, water (550 mL) was added, and the precipitated solid was filtered off and washed with water, methanol, a solid with hexane. By recrystallizing (toluene), a reaction intermediate 2- [3-chloro-5- (9-phenanthryl) phenyl] -4,6-diphenyl-1,3,5-triazine as a white solid (yield 78 .9g, 92% yield). |
92% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide; In tetrahydrofuran; water; at 70℃; for 4h;Inert atmosphere; | Under argon stream, a solution of 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (70.0 g, 0.166 mol), 9- phenanthrene boronic acid (38.6 g, 0 , 174 mol) and tetrakis (triphenylphosphine) palladium (3.83 g, 3.31 mmol) were suspended in tetrahydrofuran (1000 mL), and 4.0 M sodium hydroxide aqueous solution (124 mL, 497 mol) was added dropwise. The resulting mixture was stirred at 70 C. for 24 hours. After standing to cool, water (550 mL) was added, the precipitated solid was filtered off, and the solid was washed with water, methanol and hexane. Recrystallization (toluene) gave a white solid of the reaction intermediate 2- [3-chloro-5- (9-phenanthryl) phenyl] -4,6-diphenyl- 1,3,5-triazine (yield 78 .9 g, yield 92%). |
92% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide; In tetrahydrofuran; water; at 70℃; for 24h;Inert atmosphere; | Under argon stream, a solution of 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (70.0 g, 0.166 mol), 9- phenanthrene boronic acid (38.6 g, 0 , 174 mol) and tetrakis (triphenylphosphine) palladium (3.83 g, 3.31 mmol) were suspended in tetrahydrofuran (1000 mL), and 4.0 M aqueous sodium hydroxide solution (124 mL, 497 mol) was added dropwise. The resulting mixture was stirred at 70 C. for 24 hours. After standing to cool, water (550 mL) was added, the precipitated solid was filtered off, and the solid was washed with water, methanol and hexane. Recrystallization (toluene) gave a white solid of the reaction intermediate 2- [3-chloro-5- (9-phenanthryl) phenyl] -4,6-diphenyl- 1,3,5-triazine (yield 78 .9 g, yield 92%) |
92% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide; In tetrahydrofuran; water; at 70℃; for 24h;Inert atmosphere; | Under argon stream, a solution of 2- (3-bromo-5-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (70.0 g, 0.166 mol), 9- phenanthrene boronic acid (38.6 g, 0 , 174 mol), tetrakis (triphenylphosphine) palladium (3.83 g, 3.31 mmol) was suspended in tetrahydrofuran (1000 mL) and added dropwise to a 4.0 M aqueous sodium hydroxide solution (124 mL, 0.497 mol). The resulting mixture was stirred at 70 C. for 24 hours. After standing to cool, water (550 mL) was added, the precipitated solid was filtered off, and the solid was washed with water, methanol and hexane. Recrystallization (toluene) gave a white solid of the reaction intermediate 2- [3-chloro-5- (9-phenanthryl) phenyl] -4,6-diphenyl- 1,3,5-triazine (yield 78 .9 g, yield 92%). |
92% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide; In tetrahydrofuran; water; at 70℃; for 24h;Inert atmosphere; | Under argon flow,2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (70.0 g, 0.166 mol),9-phenanthreneboronic acid (38.6 g, 0.174 mol) and tetrakis (triphenylphosphine) palladium(3.83 g, 3.31 mmol) in tetrahydrofuran(1000 mL) and 4.0 M aqueous sodium hydroxide solution was added to the resulting suspension.(124 mL, 0.497 mol) was added dropwise.The resulting mixture was stirred at 70 C. for 24 hours. After standing to coolWater (550 mL) was added, the precipitated solid was filtered off,The solid was washed with methanol and hexane. It is a reaction intermediate by recrystallization (toluene)2- [3-Chloro-5- (9-phenanthryl) phenyl]White solid of -4,6-diphenyl-1,3,5-triazine(Yield 78.9 g, 92% yield) was obtained. |
91% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; for 18h;Inert atmosphere; Reflux; | In a stream of argon, 0.52 g (2.36 mmol) of 9-phenanthreneboronic acid, 0.91 g (2.15 mmol) of 2-(3-bromo-5-chlorophenyl)-4,6-diphenyl-1,3,5-triazine and 24.8 mg (0.022 mmol) of tetrakis (triphenylphosphine) palladium were suspended in a mixed solvent comprised of 80 mL of toluene and 10 mL of ethanol, and the temperature of the obtained suspension was elevated to 60C. 6.45 mL (6.45 mmol) of an aqueous 1M K2CO3 solution was gradually added dropwise to the suspension, and the obtained mixture was distilled under reflux for 18 hours. The resultant reaction mixture was cooled to room temperature, and then distilled under a reduced pressure to remove all volatile material. Methanol was added-to-the concentrate, and the thus-deposited solid was collected by filtration. The thus-obtained crude product was dissolved in chloroform and the obtained solution was filtered by celite. The filtrate was distilled to remove all volatile materials to give 1.02 g of an intermediate 2-[3-chloro-5-(9-phenanthiyl)phenyl]-4,6-diphenyl-1,3,5-triazine as grayish white solid (yield: 91%). |
90% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 20℃; for 4h;Inert atmosphere; Reflux; | Compound 3-1 (42.1 g, 0.1 mol),9-Phenanthroboric acid (24.4g, 0.11mol) and potassium carbonate (41.4g, 0.3mol) were dissolved in a flask containing toluene / ethanol / water (300mL / 50mL / 50mL),After replacing nitrogen under stirring at room temperature, Pd (PPh3) 4 (1.15 g, 0.001 mol) was added. After the addition, the reaction was stirred and refluxed for 4 hours.TLC monitors the endpoint of the reaction. After filtering down to room temperature,The solid was rinsed with toluene, water, and ethanol, and dried.Purification by column chromatography (eluent is petroleum ether: dichloromethane = 10: 1 to 5: 1),Compound 3-2 was obtained (46.7 g, yield 90%). |
85% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; at 85℃; for 14h;Inert atmosphere; | 24.40 g (57.6 mmol) of 2-(3-bromo-5-chlorophenyl)-4,6-diphenyl-1 ,3,5-triazine (synthesized according to known procedures), 12.80 g (57.6 mmol) of 9-phenanthrylboronic acid and 86 ml (173 mmol) of a 2M sodium carbonate solution were suspended in 450 ml of DME and evacuated and purged with argon 4 times. Then argon was bubbled through for 30 minutes. 1.33 g (1.15 mmol) of tetrakis(triphenylphospin)-palladium(0) were added under argon and argon was bubbled through for another 5 minutes. Then the reaction mixture was heated to 85C. After stirring under argon for 14 hours at this temperature, the reaction mixture was cooled to room temperature and filtered. The residue was washed with hot toluene to give 25.7g (85%) of 3-1.1 H-NMR (400 MHz, CDCI3-0) delta 8.89 - 8.71 (m, 8H), 7.96 (dd, J= 7.8, 1.5 Hz, 1H), 7.91 (dd, J= 8.3, 1.3 Hz, 1 H), 7.83 - 7.63 (m, 5H), 7.64 - 7.52 (m, 7H). |
85% | With tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 85℃; for 14h;Inert atmosphere; | c)24.40 g (57.6 mmol) of 2-(3-bromo-5-chloro-phenyl)-4,6-diphenyl-1,3,5-triazin (synthesized according to known procedures), 12.80 g (57.6 mmol) :of 9-phenanthi^Jboronic .acid and'i86;ml (173 mmol) of a 2M sodium carbonate solution are susp^ud?d ^5.0%Mh.dfDME^nd evacuated and purged with argon 4 times. Then argon is bubbled through for ' 30 minutes, 3 ?g (1.1 Smmol) of tetrakis(triphenylphospin)-palladium(0) are added, under argo and -argon js bub- bled through for another 5 minutes. Then the reaction mixture ?is heated .to*85CA&fterstirrirng under argon for 14 hours at this temperature, the reaction mixture is cooled tO oom temperature and filtered. The residue is washed with hot toluene to give 25.7g (85%) of 2-'[3-chloro-5-(9- phenanthryl)phenyl]-4,6-diphenyl-1 ,3,5-triazine. 1H NMR (400 MHz, Chloroform-o) delta 8.89 - 8.71 (m, 8H), 7.96 (dd, J= 7.8, 1.5 Hz, 1 H), 7:91 (dd, J= 8.3, 1.3 Hz, 1 H), 7.83 - 7.63 (m, 5H), 7.64 - 7.52 (m, 7H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With sodium hydroxide;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; at 70℃; for 5h;Inert atmosphere; Reflux; | In a stream of argon, 1.37 g (6.16 mmol) of 9-phenanthreneboronic acid, 1.20 g (2.57 mmol) of <strong>[1073062-59-5]2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine</strong> and 72.1 mg (0.103 mmol) of dichlorobis(triphenylphosphine)palladium were suspended in 75 mL of tetrahydrofuran, and the temperature of the obtained suspension was elevated to 70C. 4.81 mL (19.3 mmol) of an aqueous 4N NaOH solution was gradually added dropwise to the suspension, and the obtained mixture was distilled under reflux for 5 hours . The resultant reaction mixture was left to stand to room temperature, and then distilled under a reduced pressure to remove all volatile materials. Methanol was added to the concentrate, and the thus-deposited solid was collected by filtration. The thus-obtained crude product was recrystallized from o-xylene to give 1.13 g of the target 2-[3,5-di(9-phenanthryl)phenyl]-4,6-diphenyl-1,3,5triazine as grayish white solid (yield: 66%). 1H-NMR(CDCl3):delta.7.56(t,J=7.1Hz,4H),7.61(t,J=7.3Hz,2H),7.66 (t,J=8.2Hz,2H),7.70(t,J=8.0Hz,2H),7.75(t,J=8.4Hz,2H),7.76(t,J=8.3 Hz,2H),7.97(s,2H),8.02(d,J=8.0Hz,2H),8.03(s,1H),8.18(d,J=8.1Hz, 2H),8.79(d,J=8.3Hz,4H),8.81(d,J=8.4Hz,2H),8.87(d,J=8.4Hz,2H),9.09 (s,2H). The melting point and Tg of the obtained compound are shown in Table 1, below |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 5h;Reflux; | <strong>[1073062-59-5]2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine</strong> (16.5g, 35mmol) and phenanthren-9-ylboronic acid (5g, 24mmol), Tetrakis(triphenylphosphine)palladium (0) (1.4 g, 1.1 mmol) and Potassium carbonate (9.8 g, 71 mmol) were added to 150 mL of toluene, 150 mL of ethanol and 150 mL of water, and the mixture was refluxed with stirring for about 5 hours. After the obtained filter the resulting solid, followed by drying and then to the one-washed twice washed with water and methanol.Separation column (eluent dichloromethane 100%) after the removal of impurities from the 2-(3-bromo-5-(phenanthren-9-yl)phenyl)-4,6-diphenyl-1,3,5-triazine to obtain a 4g (yield 30%). Here Bis (pinacolato) diboron (2.2g, 8.6mmol), [1,1'-Bis (diphenylphosphino)ferrocene]dichloropalladium (II) (0.26g, 0.36mmol), Potassium acetate (2.1g, 22mmol) was added to 100m Dioxane. After reflux stirring for 17 hours, the mixture was cooled to room temperature. The reaction solution was filtered through silica gel and Celite under reduced pressure to obtain a filtrate.2-bromo-1,10-phenanthroline (1.5g, 5.8mmol) in a filtrate, Tetrakis(triphenylphosphine)palladium(0) (0.3g, 0.26mmol), Potassium carbonate (2.4g, 52mmol) about 14 hours while the mixture was stirred under reflux. After gave after cooling to room temperature using a dichloromethane and water and the organic layer was neutralized to remove the water layer, the remaining water layer was removed using a Magnesium sulfate.The organic layer was filtered under reduced pressure on silica gel and celite and silica gel adsorption column to wash the proceeds to the obtained crude with dichloromethane and hexane (eluent hexane: dichloromethane = 9:1?dichloromethane 100%) the compound 1-1 to give a 2g |
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; at 60℃; for 4h;Inert atmosphere;Product distribution / selectivity; | In a stream of argon, 1.91 g (8.56 mmol) of 9-phenanthreneboronic acid, 4.00 g (8.56 mmol) of <strong>[1073062-59-5]2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine</strong> and 98.9 mg (0.086 mmol) of tetrakis (triphenylphosphine) palladium were suspended in a mixed solvent composed of 320 mL of toluene and 40 mL of ethanol, and the resultant suspension was heated to 60C. To the suspension, 25.7 mL (25.7 mmol) of an aqueous 1M K2CO3 solution was gradually added dropwise, and the mixture was stirred for 4 hours. Then the mixture was cooled to room temperature, and 2.56 g (12.8 mmol) of 4- (2-pyridyl)phenylboronic acid and 25.7 mL (25.7 mmol) of an aqueous 1M K2CO3 solution were added. Then the mixture was heated to 70C and maintained at that temperature for 12 hours while being stirred. Then the reaction mixture was cooled to room temperature, and was then distilled under a reduced pressure to remove all volatile materials. Methanol was added to the concentrate, and the thus-deposited solid was collected by filtration. The obtained crude product was purified by silica gel chromatography using a hexane/chloroform (1:2) mixed solvent as an eluent to give 3.91 g of the target 4,6-diphenyl-2-[5-(9-phenanthryl)-4'-(2-pyridyl) biphenyl-3-yl]-1,3,5-triazine as a white solid (yield: 64%) . 1H-NMR(CDCl3):delta.7.31(d,J=7.00Hz,1H),7.58-7.65(m,8H),7.70(t, J=7.0Hz,1H),7.76(t,J=7.0Hz,2H),7.82-7.87(m,2H),7.93(s,1H),7.99(d, J=8.5Hz,2H),8.02(d,J=8.2Hz,1H),8.06(d,J=8.0Hz,1H),8.12(s,1H),8.23 (d,J=8.4Hz,2H),8.78(d,J=8.2Hz,1H),8.82(d,J=8.1Hz,4H),8.89(d,J=8.2 Hz,1H),8.98(s,1H),9.21(s,1H). The obtained triazine compound exhibited a Tg of 133C. | |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 60℃; for 5h;Inert atmosphere; | In a stream of argon, 2.00 g (4.28 mmol) of <strong>[1073062-59-5]2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine</strong>, 1.14 g (5.14 mmol) of 9-phenanthreneboronic acid and 250 mg (0.214 mmol) of tetrakis(triphenylphosphine)palladium were suspended in a toluene (88 mL)/ethanol (88 mL) mixed solvent, and the suspension was heated to 60C. 3.5 mL (3.53 mmol) of an aqueous 1.0 M potassium carbonate solution was gradually dropwise added to the mixture, and the mixture was stirred at that temperature for 5 hours. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With sodium hydroxide;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; at 70℃; for 2h;Inert atmosphere; Reflux; | In a stream of argon, 1.29 g (5.81 mmol) of 9-phenanthreneboronic acid, 1.20 g (2.42 mmol) of 2-(3,5-dibromophenyl)-4,6-di-p-tolyl-1,3,5-triazine and 67.9 mg (0.097 mmol) of dichlorobis(triphenylphosphine)palladium were suspended in 108 mL of tetrahydrofuran, and the temperature of the obtained suspension was elevated to 70C. 4.53 mL (18.2 mmol) of an aqueous 4N NaOH solution was gradually added dropwise to the suspension, and the obtained mixture was distilled under reflux for 2 hours. Further, 0.11 g (0.50 mmol) of 9-phenanthreneboronic acid was added, and the obtained mixture was distilled under reflux for 2 hours. The resultant reaction mixture was left to stand to room temperature, and then distilled under a reduced pressure to remove all volatile materials. Methanol was added to the concentrate, and the thus-deposited solid was collected by filtration. The thus-obtained crude product was recrystallized from o-xylene to give 0.74 g of the target 2-[3,5-di(9-phenanthryl)-phenyl]-4,6-di-p-tolyl-1,3,5-triazine as grayish white solid (yield: 44%). 1H-NMR(CDCl3):delta.2.47(s,6H),7.34(d,J=8.0Hz,4H),7.65(t,J=7.6 Hz,2H),7.69(t,J=7.4Hz,2H),7.75(t,J=6.9Hz,4H),7.97(s,2H),8.01(s, 1H),8.02(d,J=7.4Hz,2H),8.18(d,J=8.1Hz,2H),8.66(d,J=8.2Hz,4H),8.81 (d,J=8.3Hz,2H),8.87(d,J=8.2Hz,2H),9.07(s,2H). The melting point and Tg of the obtained compound are shown in Table 1, below |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With C84H78Cl2O12P2Pd; caesium carbonate; In tetrahydrofuran; water; at 100℃; for 1h;Inert atmosphere; Microwave irradiation; | General procedure: In a microwave glass tube were charged 3 (100 mg, 0.17 mmol), arylboronic acid (0.68 mmol, 4 equiv.), [PdCl2(SPhos)2] (8.5 mg, 0.0085 mmol, 5 mol%) and cesium carbonate (276 mg, 0.85 mmol, 5 equiv.). The tube was purged with argon, THF (1 mL) and water (0.1 mL) were added. The mixture was subjected to microwave irradiation (SEM Discover apparatus) for 1 h at 100 C. The crude mixture was filtered through a pad of Celite, using ethyl acetate as the eluent. Column chromatography of the filtrate (alumina; heptane/EtOAc 9:1) gave 5a-d. (70%, orange oil); Rf 0.2 (30% EtOAc/heptanes); 1H NMR (CDCl3, 500 MHz) delta (ppm) 8.69 (d, J = 8.1 Hz, 2H, HAr), 8.67 (d, J = 8.4 Hz, 2H, HAr), 8.33 (s, 2H, HAr), 7.79 (d, J = 8.4 Hz, 2H, HAr), 7.75 (d, J = 7.8 Hz, 2H, HAr), 7.70-7.50 (m, 6H, HAr), 7.44 (t, J = 7.2 Hz, 2H, HAr), 5.04 (d, J = 12.3 Hz, 2H, Cp-CH2), 4.80 (d, J = 12.3 Hz, 2H, Cp-CH2), 4.8-4.7 (4H, HCp), 4.67 (t, J = 2.4 Hz, 2H, HCp), 1.56 (s, 6H, CH3); 13C NMR (CDCl3, 75 MHz) delta (ppm) 170.8 (MeCO), 144.2 (C), 132.7 (C), 131.4 (C), 131.0 (CH), 130.3 (C), 130.2 (C), 128.7 (CH), 127.0 (CH), 126.9 (CH), 126.5 (CH), 126.2 (CH), 122.8 (CH), 122.6 (CH), 91.8 (CCp), 83.2 (CCp), 75.2 (CHCp), 70.8 (CHCp), 70.4 (CHCp), 61.1 (Cp-CH2), 20.7 (CH3); IR: numax (cm-1) 3058, 2925, 2852, 1730, 1448, 1370, 1223, 1018, 749; MS (ESI), m/z 705.2 [M + Na]+; [alpha]D24 = +104 (c = 0.5, CHCl3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; at 85℃; for 12h; | 25.0 g (112.6 mmol) of 1-amino-4-bromonaphthalene, 30.0 g (135.1 mmol) of 9-phenanthrene boronic acid, and 3.3 g (2.8 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] were dissolved in 750 mL of a toluene solvent. A solution in which 31.1 g (225.1 mmol) of potassium carbonate (K2CO3) was dissolved in 250 ml of water was added thereto, and then reacted at 85 C. for 12 hours. The aqueous layer of the reaction was removed, the solvent was removed under reduced pressure, and the reaction product was rinsed with water and methanol. The obtained solid mixture was separated by a column and dried to provide a yellow solid of an intermediate product (A) in 31.0 g (yield: 86%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; for 12h; | 14.0 g (33.0 mmol) of intermediate product (B), 8.1 g (36.3 mmol) of 9-phenanthrene boronic acid, and 1.2 g (1.0 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] were dissolved in 280 mL of a tetrahydrofuran (THF) solvent. A solution in which 9.1 g (66.0 mmol) of potassium carbonate (K2CO3) was dissolved in 140 ml of water was added thereto, and then they were reacted at 80 C. for 12 hours. The solvent was removed under a reduced pressure, and the reaction product was rinsed with water and methanol. The residue was recrystallized with toluene, and the precipitated crystal was separated by a filter and rinsed with toluene and dried to provide a white solid of an intermediate compound (C) in 14.9 g (yield: 51%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 90℃; for 12h; | 5.0 g (8.4 mmol) of intermediate product (D), 2.3 g (10.1 mmol) of 9-phenanthrene boroic acid, and 0.3 g (0.3 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] were dissolved in 100 mL of a tetrahydrofuran (THF) solvent. A solution in which 2.3 g (16.9 mmol) of potassium carbonate (K2CO3) was dissolved in 50 ml of water was added thereto, and then they were reacted at 90 C. for 12 hours. The solvent was removed under a reduced pressure, and the reaction product was rinsed with water and methanol. The residue was recrystallized with toluene, and the precipitated crystal was separated by a filter and rinsed with toluene and dried to provide a white solid of a compound in 4.2 g (yield: 68%). (calculation value: 734.88, measurement value: MS[M+1] 735.18) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 90℃; for 12h; | 2.2 g (4.9 mmol) of intermediate product (F), 2.4 g (10.7 mmol) of 9-phenanthrene boronic acid, and 0.3 g (0.2 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] were dissolved in 60 mL of a tetrahydrofuran (THF) solvent. A solution in which 2.7 g (19.5 mmol) of potassium carbonate (K2CO3) was dissolved in 20 ml of water was added thereto, and then they were reacted at 90 C. for 12 hours. The solvent was removed under reduced pressure, and the reaction product was rinsed with water and methanol. The residue was recrystallized with toluene, and the precipitated crystal was separated by a filter and rinsed with toluene and dried to provide a white solid of a compound in 2.8 g (yield: 78%). (calculation value: 734.88, measurement value: MS[M+1] 735.18) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 90℃; for 12h; | 13.0 g (20.2 mmol) of intermediate product (G), 5.4 g (24.3 mmol) of 9-phenanthrene boronic acid, and 0.7 g (0.6 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] were dissolved with a solvent of 390 mL of toluene and 260 mL of tetrahydrofuran (THF). A solution in which 5.6 g (40.4 mmol) of potassium carbonate (K2CO3) was dissolved in 20 mL of water was added thereto, and then they were reacted at 90 C. for 12 hours. The solvent was removed under reduced pressure, and the reaction product was rinsed with water and methanol. The residue was recrystallized with toluene, and the precipitated crystal was separated by a filter and rinsed with toluene and dried to provide a white solid of a compound in 13.1 g (yield: 83%). (calculation value: 784.94, measurement value: MS[M+1] 785.29) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 90℃; for 12h; | 8.0 g (24.5 mmol) of intermediate product (H), 19.6 g (88.1 mmol) of 9-phenanthrene boronic acid, and 2.1 g (1.8 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] were dissolved in 240 mL of tetrahydrofuran (THF). A solution in which 20.3 g (146.8 mmol) of potassium carbonate (K2CO3) was dissolved in 120 ml of water was added thereto, and then they were reacted at 90 C. for 12 hours. The solvent was removed under reduced pressure, and the reaction product was rinsed with water and methanol. The residue was recrystallized with toluene, and the precipitated crystal was separated by a filter and rinsed with toluene and dried to provide a white solid of a compound in 12.0 g (yield: 69%). (calculation value: 707.86, measurement value: MS[M+1] 708.26) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 90℃; for 12h; | 5.5 g (13.7 mmol) of intermediate product (J), 6.7 g (30.2 mmol) of 9-phenanthrene boronic acid, and 0.8 g (0.1 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] were dissolved in 110 mL of a tetrahydrofuran (THF) solvent. A solution in which 7.6 g (54.8 mmol) of potassium carbonate (K2CO3) was dissolved in 55 ml of water was added thereto, and then they were reacted at 90 C. for 12 hours. The solvent was removed under reduced pressure, and the reaction product was rinsed with water and methanol. The residue was recrystallized with toluene, and the precipitated crystal was separated by a filter and rinsed with toluene and dried to provide a white solid of a compound in 6.0 g (yield: 64%). (calculation value: 684.82, measurement value: MS[M+1] 685.25) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 90℃; for 12h; | 9.7 g (17.8 mmol) of intermediate product (K), 5.4 g (21.4 mmol) of 9-phenanthrene boronic acid, and 0.6 g (0.5 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] were dissolved in 380 mL of a tetrahydrofuran (THF) solvent. A solution in which 4.9 g (35.6 mmol) of potassium carbonate (K2CO3) was dissolved in 95 mL of water was added thereto, and then they were reacted at 90 C. for 12 hours. The solvent was removed under reduced pressure, and the reaction product was rinsed with water and methanol. The residue was recrystallized with toluene, and the precipitated crystal was separated by a filter and rinsed with toluene and dried to provide a white solid of a compound in 10.0 g (yield: 82%). (calculation value: 684.82, measurement value: MS[M+1] 685.25) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 70℃; for 12h; | 50.0 g (133.6 mmol) of the intermediate product (M), 29.7 g (133.6 mmol) of 9-phenanthreneboroic acid, and 4.6 g (4.0 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] were dissolved in 1000 ml of a tetrahydrofuran (THF) solvent. A solution in which 36.9 g (267.2 mmol) of potassium carbonate (K2CO3) was dissolved in 500 ml of water was added thereto, and then they were reacted at 70 C. for 12 hours. The solvent was removed under a reduced pressure, and the reaction product was rinsed with water and methanol. The residues were recrystallized with monochlorobenzene, precipitated crystals were separated by a filter, rinsed with monochlorobenzene, and dried to provide a white solid of an intermediate product (U) in 55.8 g (yield: 81%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With chloro(1-naphthyl)bis(triphenylphosphine)nickel(II); potassium carbonate; triphenylphosphine; In toluene; at 100℃; for 18h;Inert atmosphere; | General procedure: In a flamed Schlenk tube under nitrogen atmosphere, K2CO3 (2.4 mmol), [NiCl(1-naph)(PPh3)2] (5 mol %), PPh3 (10 mol %), aryl boronic acid 3 (0.9 mmol), and 1,2-bis(n-bromophenyl)ethane 2 (0.3 mmol) were introduced in dry and degassed toluene (3 mL). The reaction mixture was heated at 100 C under nitrogen atmosphere for 18 h. After being quenched with water (3 mL), the reaction mixture was extracted with ethyl acetate (3×5 mL). Combined organic layers were washed with brine and dried over MgSO4. After filtration, solvent was removed under vacuum. The pure product 4 was purified by column chromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; for 24h;Inert atmosphere; Reflux; | 2.22 g (10 mmol) of Intermediate-3 and 2.83 g (10 mmol) of 1-bromo-4-iodobenzene were introduced under nitrogen and dissolved in 40 ml of toluene0.58 g (0.5 mmol) of Pd (PPh3) 4 and 15 ml (30 mmol) of 2M K2CO3 were added, respectively, and refluxed for 24 hours. After the completion of the reaction, the temperature of the reaction mixture was cooled to room temperature, 150 ml of MC and 150 ml of H2O were added to extract the MC layer,Dried over MgSO4, concentrated, and then subjected to column chromatography with Hex: MC = 4: 1 to obtain Intermediate-13 2.60 (78%). |
69% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane;Reflux; | In a round bottom flask,30.0g of phenanthren-9-ylboronic acid,42.0g of 1-bromo-4-iodobenzene is dissolved in 1000mlIn 1,4-dioxan,After putting 200ml (2M) of K2CO3 and 4.7g of Pd (PPh3) 4,Stir at reflux.After confirming the reaction by thin layer chromatography (TLC), after adding water, the reaction was completed.Using methyl cellulose (MC) to extract the organic layer,And filtered under reduced pressure, and then recrystallized,Thus, 31.1 g (yield: 69%) of Intermediate IM1 was obtained. |
66% | With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 9h;Inert atmosphere; | A synthesis scheme of Step 1 is illustrated in (E-1). In a 200 mL three-neck flask, a mixture of 7.7 g (27 mmol) of 1-bromo-4-iodobenzene, 5.0 g (23 mmol) of 9-phenanthrene boronic acid, 61 mg (0.3 mmol) of palladium acetate, 247 mg (0.8 mmol) of tri(ortho-tolyl)phosphine, 100 mL of toluene, 10 mL of ethanol, and 35 mL of an aqueous solution of potassium carbonate (2 mol/L) was degassed while being stirred under reduced pressure, and reacted while being heated and stirred under a nitrogen atmosphere at 80 C. for 9 hours. After the reaction, 500 mL of toluene was added to this reaction mixture solution, and an organic layer of the mixture solution was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., catalog No. 540-00135), alumina (produced by Merck & Co., Inc., neutral), and Celite (produced by Wako Pure Chemical Industries, Ltd., catalog No. 531-16855). The obtained filtrate was washed with water, and magnesium sulfate was added thereto so that moisture was adsorbed. This suspension was filtered to obtain a filtrate. The obtained filtrate was concentrated and purified by silica gel column chromatography. At this time, a mixed solvent of toluene and hexane in a ratio of 1:5 was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and then recrystallized with toluene and hexane, so that the objective substance was obtained as 5.0 g of white powder in a yield of 66%. A nuclear magnetic resonance (NMR) method identified this compound as 9-(4-bromophenyl)phenanthrene (abbreviation: PnPBr). 1H NMR data of the obtained substance are as follows: 1H NMR (CDCl3, 300 MHz): delta (ppm)=7.42 (d, J=8.3 Hz, 2H), 7.49-7.71 (m, 7H), 7.84-7.91 (m, 2H), 8.73 (d, J=7.8 Hz, 1H), 8.78 (d, J=8.3 Hz, 1H). |
53% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water;Reflux; | In a 3 L round flask, 50 g (225.17 mmol, 1eq) of compound 9-Phenanthracenylboronic acid and 127.4 g (450.35 mmol, 2eq) of 1-Bromo-4-iodobenzene, 13 g (11.26) of Pd(PPh3)4 mmol, 0.05eq) and 93.4g (675.52mmol, 3eq) of K2CO3 were added, and 2000ml/400ml of THF/H2O were added under reflux and stirred. After the reaction was completed, the mixture was extracted with CH2Cl2/H2O and CH2Cl2 layer was dried with MgSO4. Silica-gel column purification gave 39.5 g of compound C-11 in 53% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With iron(III) oxide; copper(l) iodide; 1,10-Phenanthroline; di-tert-butyl peroxide; lithium tert-butoxide; In toluene; at 110℃; for 12h;Schlenk technique; Sealed tube; Green chemistry; | General procedure: CuI (0.1 mmol), Fe2O3(0.1 mmol), 1,10-phenanthroline(0.1mmol) ,LiOBu-t(1.0 mmol), t-BuOOBu-t(1.0 mmol), benzooxazole(0.5 mmol) and phenylboronic acid(1.0 mmol)were weighed into an oven-dried Schlenk tube which was sealed with a plug. Then toluene(3.0 mL) was added.The reaction mixture was stirred at 110 oC for 12 h. The resulting mixture was then cooled to room temperatureand diluted with ethyl acetate. The organic layer was collected, washed with water and brine, and dried overNa2SO4. After removal of the solvent in vacuo, the residue was purified by silica gel chromatography to give thedesired 2-phenylbenzo[d]oxazole. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With iron(III) oxide; copper(l) iodide; 1,10-Phenanthroline; di-tert-butyl peroxide; lithium tert-butoxide; In toluene; at 110℃; for 12h;Schlenk technique; Sealed tube; Green chemistry; | General procedure: CuI (0.1 mmol), Fe2O3(0.1 mmol), 1,10-phenanthroline(0.1mmol) ,LiOBu-t(1.0 mmol), t-BuOOBu-t(1.0 mmol), benzooxazole(0.5 mmol) and phenylboronic acid(1.0 mmol)were weighed into an oven-dried Schlenk tube which was sealed with a plug. Then toluene(3.0 mL) was added.The reaction mixture was stirred at 110 oC for 12 h. The resulting mixture was then cooled to room temperatureand diluted with ethyl acetate. The organic layer was collected, washed with water and brine, and dried overNa2SO4. After removal of the solvent in vacuo, the residue was purified by silica gel chromatography to give thedesired 2-phenylbenzo[d]oxazole. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99.1% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 24h;Inert atmosphere; | General procedure: A mixture of phenanthren-9-ylboronic acid (1.00 g, 4.503 mmol), 2-bromo-4-methylpyridine (0.85 g, 4.954 mmol),tetrakis(triphenylphosphine)palladium (0.05 g, 0.045 mol, 1 mol%), potassium carbonate(15 ml, 2M aqueous solution), and tetrahydrofuran (30 mL) was headed under a nitrogenatmosphere at 80C for 24 h. This reaction is the Suzuki coupling reaction. After the reaction,the mixture was cooled to room temperature for 1 h. The compound was extracted byliquid-liquid separation (water and dichloromethane). The compound was purified by acelite-silica gel filtration (solvent: toluene) and column chromatography on silica gel (eluent:hexane/ethyl acetate, 15:1). |
99.1% | The PT-P ligand was synthesized from phenanthren-9-ylboronic acid (1.00 g, 4.503 mmol) and 2-bromopyridine (0.78 g, 4.954 mmol) by Suzuki coupling. Yield: 99.1%(1.14 g); 1H NMR (500 MHz, CDCl3, delta (ppm): 8.93(d, J = 7.3 Hz, 2H), 8.50 (d, J = 7.8 Hz, 1H), 8.44(s, 1H), 8.12 (d, J = 7.1 Hz, 2H), 7.88 (dd, J = 18.2 Hz,2H), 7.82 (dd, J = 19.1 Hz, 2H), 7.51 (dd, J = 14.7 Hz,1H), 7.26 (d, J =4.8 Hz, 1H), 7.00 (dd, J =17.1 Hz, 1H). | |
99% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; at 80℃; for 24h;Inert atmosphere; | Phenanthren-9-ylboronic acid (1.00 g, 4.503 mmol) and2-bromopyridin (0.78 g, 4.954 mmol) were mixed with tetrakis(triphenylphosphine)palladium (0.05, 0.045 mmol,1 mol%), potassium carbonate (15 ml, 2 M aqueous solution),and tetrahydrofuran (30 mL) on heating under anitrogen atmosphere at 80 C for 24 h. After the reaction,the mixture was cooled to room temperature for 1 h.The mixture extracted by liquid-liquid separation (waterand dichloromethane) and dried over anhydrous Na2SO4,filtered concentrated under reduced pressure.2 3 The compoundwas purified by a celite-silica gel filtration (solvent:toluene) and column chromatography on silica gel (eluent:hexane/ethyl acetate, 15:1). Yield: 99% (1.14 g); 1H NMR(500 MHz, CDCl3, delta), delta (ppm): 8.93 (d, J = 7.3 Hz, 2H),8.50 (d, J =7.8 Hz, 1H), 8.44 (s, 1H), 8.12 (d, J =7.1 Hz,2H), 7.88 (dd, J = 18.2 Hz, 2H), 7.82 (dd, J = 19.1 Hz,2H), 7.51 (dd, J =14.7 Hz, 1H), 7.26 (d, J =4.8 Hz, 1H),7.00 (dd, J = 17.1 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.4% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 105℃; for 12h; | phenanthren-9-ylboronic acid (0.555g, 2.5mmol), 4?-(1-(4-bromophenyl)-1H-phenanthro[9,10-d]imidazol-2-yl)- N,N-diphenyl-[1,1?- biphenyl]-4-amine (1.384g, 2mmol) and Pd(PPh3)4 (20mg, 0.04mmol) were suspended in toluene (20mL), 4mL ethanol and 8mL 2M K2CO3. The reaction was stirred at 105C for 12h and cooled to room temperature. The mixture solution was added 15mL brine and then extracted with CH2Cl2 (30mL), washed with water (2×15mL), dried (MgSO4) and evaporated to dryness. After drying under vacuum, then, it was purified by dichloromethane/petroleum ether (3:1) as an eluent to afford white solid, Yield: 1.327g, 82.4%. FTIR (KBr, cm-1): 3053, 3041, 2956, 2911, 1597, 1499, 1422, 1392, 725; 1H NMR (400MHz, CDCl3): delta 8.98 (br, 1H), 8.83 (t, 2H, J=7.27Hz), 8.76 (t, 2H, J=9.29Hz), 8.80-7.95 (m, 2H), 7.88 (s, 1H), 7.82-7.56 (m, 15H), 7.52 (d, 2H, J=8.57Hz), 7.48 (d, 1H, J=8.00Hz), 7.41 (d, 1H, J=6.86Hz), 7.30-7.25 (m, 4H), 7.14 (d, 6H, J=6.29Hz), 7.05 (t, 2H, J=6.86Hz); 13C NMR (100MHz, CDCl3): delta 147.8, 147.5, 123.0, 121.3, 130.6, 130.2, 129.4, 129.1, 128.8, 128.5, 128.1, 127.7, 127.2, 126.8, 126.5, 126.2, 124.6, 124.3, 123.6, 123.3, 122.7, 121.0; EI-MS (m/z): 789.1 (M+); Anal. Calcd for C59H39N3: C, 89.70; H, 4.98; N, 5.32; Found: C, 89.48; H, 5.01; N, 5.51. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.6% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 105℃; for 12h; | 5-bromo-4?-(diphenylamino)-[1,1?-biphenyl]-3-carbaldehyde (1.071g, 2.5mmol), phenanthren-9-ylboronic acid (0.666g, 3mmol) and Pd(PPh3)4 (25mg, 0.05mmol) were suspended in toluene (20mL), 5mL ethanol and 5mL 2M K2CO3. The reaction was stirred at 105C for 12h and cooled to room temperature. The mixture solution was added 10mL brine and then extracted with CH2Cl2 (20mL), washed with water (2×10mL), dried (MgSO4) and evaporated to dryness. After drying under vacuum, then, it was purified by dichloromethane/petroleum ether (1:1) as an eluent to afford light yellow solid, Yield: 1.084g, 82.6%. FTIR (KBr, cm-1): 3098, 3083, 3068, 2933, 2908, 2877, 2833, 1689, 1501, 1403, 1392, 1322, 732; 1H NMR(CDCl3, 400MHz, ppm) delta:10.19 (s, 1H), 8.84 (d, 1H, J=7.99Hz), 8.78 (d, 1H, J=8.17Hz), 8.22 (s, 1H), 8.04 (d, 2H, J=15.25Hz), 7.94 (d, 2H, J=8.29Hz), 7.78 (s, 1H), 7.73 (t, 2H, J=8.30Hz), 7.67 (t, 1H, J=7.32Hz), 7.61 (t, 3H, J=8.43Hz), 7.31 (t. 4H, J=7.92Hz), 7.19 (t, 6H, J=7.42Hz), 7.09 (t, 2H, J=7.71Hz); EI-MS (m/z): 525.3 (M+); Anal. Calcd for C39H27rNO: C, 89.11; H, 5.18; N, 2.66; Found: C, 89.20; H, 5.19; N, 2.65. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 24h;Inert atmosphere; | General procedure: A mixture of phenanthren-9-ylboronic acid (1.00 g, 4.503 mmol), 2-bromo-4-methylpyridine (0.85 g, 4.954 mmol),tetrakis(triphenylphosphine)palladium (0.05 g, 0.045 mol, 1 molpercent), potassium carbonate(15 ml, 2M aqueous solution), and tetrahydrofuran (30 mL) was headed under a nitrogenatmosphere at 80°C for 24 h. This reaction is the Suzuki coupling reaction. After the reaction,the mixture was cooled to room temperature for 1 h. The compound was extracted byliquid-liquid separation (water and dichloromethane). The compound was purified by acelite-silica gel filtration (solvent: toluene) and column chromatography on silica gel (eluent:hexane/ethyl acetate, 15:1). |
97.5% | In 2-ethoxy-ethanol; at 130℃;Inert atmosphere; | The PT-TFP ligand was synthesized as follows:phenanthren-9-ylboronic acid (1.00 g, 4.503 mmol) and<strong>[175205-81-9]2-bromo-4-(trifluoromethyl)pyridine</strong> (1.12 g, 4.954 mmol)were dissolved in 2-ethoxyethanol (67.20 ml) and refluxedovernight at 130 °C under nitrogen. After cooling to roomtemperature (?23 °C ) for 2 h, the compound was extractedby liquid?liquid separation (water-dichloromethane). Theafforded compound was purified, using toluene, by celitesilicagel filtration and column chromatography on silicagel, with a methanol/DMC mixture (1:20) as eluent. Theproduct was further purified by recrystallization. Yield:97.5percent (1.42 g); 1H NMR (500 MHz, CDCl3, delta (ppm):8.93 (d, J = 7.3 Hz, 2H), 8.44 (s, 1H), 8.38 (d, J =6.9 Hz, 1H), 8.12 (d, J = 7.1 Hz, 2H), 8.06 (s, 1H), 7.88(dd, J = 18.2 Hz, 2H), 7.82 (dd, J = 19.1 Hz, 2H), 7.15(d, J = 5.9 Hz, 1H). |
89.3% | Inert atmosphere; | A PT-TFP ligand wasobtained from the reaction of <strong>[175205-81-9]2-bromo-4-(trifluoromethyl)pyridine</strong> (1.12 g, 4.95 mmol)and 9-phenanthrylboronic acid (1.00 g, 4.5 mmol) by Suzuki coupling. The abstraction and purification processes are the same as described above. Yield: 89.3percent (1.30 g); 1H NMR(CDCl3, 500 MHz): deltaH(ppm) 8.93(s, 2H), 8.44(s, 1H), 8.38(s, 1H), 8.12(s, 2H), 8.06(s,1H), 7.88(s, 2H), 7.82(s, 2H), 7.25(s, 1H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Under nitrogen, 2.57 g (10 mmol) of 9-bromophenanthrene was dissolved in 40 ml of anhydrous THF, the temperature of the reaction was lowered to -78 C,After slowly adding 4 ml of 2.5 M n-BuLi dropwise, the reaction was stirred at 0 C for 1 hour. Then, the temperature of the reactionAfter lowering to -78 deg. C, 12.47 g (12 mmol) of trimethylborate was added dropwise, and the mixture was stirred at room temperature for 12 hours. The reactionAfter completion of the reaction, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether.Water in the organic layer was removed with anhydrous MgSO 4, filtered under reduced pressure, and then the organic solvent was concentrated to obtain a compound, Hex: EA = 4:1 to obtain 1.82 g (82%) of Intermediate-3. | |
81% | With n-butyllithium; In tetrahydrofuran; at -78 - 20℃; for 13.5h;Inert atmosphere; | After tetra-hydro furan gave 500ml put the 9-bromo-phenanthrene 50g (194mmol) in a round bottom flask containing a nitrogen atmosphere the temperature was adjusted to -78 . Slowly added dropwise to 146ml of n-butyllithium (233mmol) in 30 minutes, which was then slowly added dropwise trimethyl borate 28.3g (274mmol) After 1 hour, the temperature was raised to room temperature. After stirring for about 12 hours at room temperature, and then, extraction was collected by distillation under reduced pressure and the organic layer was added dropwise to the reaction solution until the acid is a hydrochloric acid solution 2N (n). After the nucleic acid has a normal filter to dry the recrystallized result, to obtain an intermediate a-20 (35g, yield 81%) as a white solid. |
81.1% | In a three-necked 1.0 L flask 30.0 g (116.7 mmol) of 9-bromophenanthrene are added and dissolved in 292 mL of THF under a nitrogen atmosphere. After cooling the reaction temperature to -78C, 56.0 mL (140.0 mmol) of 2.5 M n-BuLi solution was slowly added dropwise and stirred.After the dropwise addition was completed, the mixture was stirred at -78 C for 1 hour, 18.3 mL (163.3 mmol) of trimethylborate was slowly added dropwise.After the temperature was raised to room temperature, the mixture was stirred for 12 hours. After the temperature was lowered to 0 C, 20 mL of 2 N HCl was added. After adding 500 mL of dichloromethane and 300 mL of H2O,The organic layer was separated and washed with water and brine. Dried over MgSO4, filtered, and the filtrate was concentrated under reduced pressure. The resulting concentrate was solidified and purified by using a solvent to obtain 21.0 g (yield: 81.1%) of a white solid compound (intermediate (5)). |
81% | After adding 50 g (194 mmol) of 9-bromo phenanthrene to a round bottom flask containing 500 ml of tetrahydrofuran, the temperature was adjusted to -78 C under a nitrogen atmosphere.After 30 minutes, 146 ml (233 mmol) of normal butyl lithium was slowly added dropwise, and then after 1 hour, 28.3 g (274 mmol) of trimethylborate was slowly added dropwise, and the temperature was raised to room temperature. After stirring at room temperature for about 12 hours, a 2N (normal) hydrochloric acid aqueous solution was added dropwise to the reaction solution until it became an acid, followed by extraction, and the organic layers were collected and distilled under reduced pressure. After recrystallization with the normal nucleic acid and filtered to obtain 35 g (yield 81%) of white solid intermediate 1-a. | |
42% | In a 500 ml round-bottom flask, 10 g of 9-bromophenanthrene (38.89 mmol) was added and dissolved in150 ml of anhydrous tetrahydrofuran (THF) before stirring.The reaction temperature was maintained at -76 C,and 25.28 ml of 2.0 M n-butyllithium (50.59 mmol) was slowly added to the reaction vessel. After about 10 minutes, 6.07 ml of trimethyl borate (54.45 mmol) was added to the reaction vessel. Once the reaction temperature increased to room temperature after about 1 hour, 7.12 ml of 12 M HCl (85.56 mmol) was added. After the reaction,the mixture was extracted using ethyl acetate (EA)and distilled water. Water remaining in the organic layer was dried with MgSO4. The mixture was concentrated byreduced pressure and re-precipitated with THF and hexane to obtain white solid. The yield was 42%. 1H-NMR (300 MHz, Chloroform) (ppm): 8.75-8.71(t, 2H), 8.56-8.53 (d, 1H), 8.04 (s , 1H), 7.88-7.85(d, 1H), 7.61-7.52 (m, 6H), 5.79 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | General procedure: Under a nitrogen atmosphere 0.075 g (0.2 mmol) of2,5-dibromo-3,4-dinitrothiophene were dissolved in 8 mLof anhydrous toluene and treated with 10 mol% of the catalyst(catalysts I-IV). The mixture was then subjected toultrasound irradiation for 5 min and then stirred at roomtemperature for additional 25 min. Then, 0.5 mmol of theboronic acid, 1.6 mmol of potassium phosphate, and 2 mLof water were added, and the mixture was heated underreflux at 100C for 48 h. After cooling to room temperature,the mixture was dried over magnesium sulfate andchromatographed (petroleum ether/dichloromethane 1:3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | General procedure: A sample of 0.075 g (0.2 mmol) of 1-chloro-2,4-dinitrobenzene(22) was dissolved in 8 mL of anhydrous dioxaneunder an atmosphere of nitrogen. Then, 0.010 g (5 mol%)of the cis/trans-bromo-(N-phenylsydnone)palladiumcomplex 9 (catalyst III) was added, the mixture was subjectedto ultrasound irradiation for 5 min and then stirredat room temperature over a period of 25 min. Then, thecorresponding boronic acid, 1.13 g (10.6 mmol) of sodiumcarbonate, and 2 mL of water were added, and the resultingmixture was heated at a temperature of 70C for30 min. After cooling to room temperature, the mixturewas dried over magnesium sulfate and chromatographedon silica gel (petroleum ether/dichloromethane 1:3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium phosphate; C20H25O3P; palladium diacetate; In toluene; at 30℃; for 8h;Inert atmosphere; | General procedure: To a mixture of 1-bromonaphthalen-2-yl triflate (0.1 mmol),arylboronic acid (0.15 mmol, 1.5 equiv), potassium phosphate (0.3 mmol, 3 equiv), palladium acetate (1 mol %) and ligand(1.2 mol %, Pd/L1/1.2) was charged toluene 1.2 ml. The mixture was stirred at 30 C under nitrogen for 8 h. Ethyl acetate (4 ml) andwater (4 ml) was added and the organic layer was separated, washed sequentially with water and brine (5 ml3), dried over sodium sulfate, concentrated and purified by silica gel column chromatography to provide biaryl products. The ee?s were determined by chiral HPLC on a chiralcel OD-H column. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; for 12h;Reflux; | Methyl 2-bromo-benzoate To a round bottom flask, 24g (112mmol), intermediate 20-a 34.7g (0.156mmol), tetrakis triphenylphosphine palladium {Pd (PPh3) 4} 2.6g (2mmol), potassium carbonate 30.9 In the g (223mmol), water 50 mL, 125 ml of toluene and 125 mL of tetrahydrofuran and refluxed for 12 hours. After the reaction was partitioned and the organic layer was concentrated under reduced pressure after the reaction was completed, the dried result by column separation, thereby obtaining a white solid of intermediate 20-b (25 g, 72% yield). |
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; for 12h;Reflux; | The methyl 2-bromobenzoates(24 g, 112 mmol),9-phenantrylboronic acids (34.6 g, 156 mmol), tetrakistriphenylphosphine palladiums (2.6 g, 2 mmol), potassium carbonates (30.9 g, 223 mmol), water 50 mL, toluene 125 mL and tetrahydrofuran 125mL were injected and it refluxed for 12 hours. It separated according to the column chromatography after concentration under reduced pressure is performed to the organic layer [intermediate 1a]and 25 g (yield 72%) was obtained. |
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; for 12h;Reflux; | The reactor was added 9- phenanthrene boronic acid (3.11g, 14mmol),Methyl 2-bromobenzoate (2.15 g, 10 mmol), Pd(PPh3)4 (0.21 g, 0.18 mmol), K2CO3 solution (2.76 g, 20 mmol),5 mL of deionized water, 13 mL of toluene, 130 mL of tetrahydrofuran,The mixture was stirred and refluxed for 12 h, and after the reaction was terminated, the organic layer was separated.Distilled under reduced pressure, purified by silica gel column,Drying gave intermediate 2-1 (2.25 g, 72%). |
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; for 12h;Reflux; | 24 g (112 mmol) of methyl 2-bromobenzoate, 34.7 g (0.156 mmol) of intermediate 20-a, 2.6 g (2 mmol) of tetrakistriphenylphosphinepalladium {Pd (PPh3) 4} g (223 mmol), water (50 mL), toluene (125 mL) and tetrahydrofuran (125 mL), and the mixture was refluxed for 12 hours. After the completion of the reaction, the reaction product was separated, and the organic layer was concentrated under reduced pressure, and then separated and dried to obtain Intermediate 20-b (25 g, yield 72%) as a white solid. |
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; for 12h;Reflux; | In a round bottom flask, 24 g (112 mmol) of methyl 2-bromobenzoate, 34.7 g (0.156 mmol) of intermediate 1-a, tetrakistriphenylphosphinepalladium {Pd(PPh3)4} 2.6g (2mmol), potassium carbonate 30.9 g (223 mmol), water 50 mL, toluene 125 ml and tetrahydrofuran 125 mL were added and refluxed for 12 hours. After completion of the reaction, the reaction material was separated by layer, the organic layer was concentrated under reduced pressure, and then separated by column to dryness to obtain 25 g (yield 72%) of white solid intermediate 1-b. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.3% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 75 - 80℃; for 24h;Inert atmosphere; | Under nitrogen protection,The intermediate a (20.05 g, 0.139 mol) and 9-phenanthreneboronic acid (34.1 g, 0.153 mol) were placed in a mixed solvent of 282.4 g of toluene and 68 g of ethanol and then an aqueous potassium carbonate solution (350 mL, , And Pd (PPh3) 4 (1.6 g, 2.78 mmol) was added as a catalyst. The reaction system was heated to 75-80 and stirred for 24 hours. The reaction was carried out under the catalysis of the catalyst. The reaction formula was as follows. After adding 100 mL of water to the reaction system, the reaction was quenched and the insoluble matter was filtered off to obtain a filtrate , Washed with deionized water, concentrated under reduced pressure, and the crude material was crystallized from ethyl acetate / petroleum ether to give a white solid,Intermediate b, yield 85.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Under a nitrogen atmosphere,During 500mL4 four-necked flask equipped with a stirring device,p- bromochlorobenzene 10.0g (52.2mmol),9-phenanthrene boronic acid 12.2g (54.9mmol),Tetrahydrofuran 130mL,20% aqueous solution of sodium carbonate 83g In addition,And the mixture was stirred for 5 minutes at room temperature. To this solution,Tetrakistriphenylphosphinepalladium 900mg a (0.779mmol) was added,And the mixture was stirred for 10 hours at 65 . After completion of the reaction,The reaction mixture was cooled to room temperature,Tetrahydrofuran was added 50mL,Pure water,Then washed with saturated brine. The resulting organic layer was dried over anhydrous magnesium sulfate,It was concentrated.The resulting concentrated residue was recrystallized from toluene / hexane mixed solvent,White crystals 13.1g (87% yield, 99.5% purity). From 1H-NMR and 13C-NMR analysis,The resulting white crystals desired compound (B-1)It was confirmed |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With oxygen; In 1-methyl-pyrrolidin-2-one; at 20℃; for 1h; | General procedure: Arylboronic acid 2 (0.12 mmol) and (bpy)Cu(SCF3) 1 (0.1 mmol) were added to a Schlenk flask fitted with magnetic stir bar and O2 balloon. The flask was evacuated and back filled with O2. The solvent NMP (2.0 mL) was added by syringe at room temperature and the solution was stirred for 1 h. For the products reported with isolated yields (3a, 3k, 3l, 3m, 3n, 3o, 3p, 3q, 3r, 3s, 3t, 3u and 3w), the reaction mixture was diluted with EtOAc, then washed with water and brine. The organic phase was dried over anhydrous Na2SO4 and filtered. The filtrate was concentrated under reduced pressure and the residue was purified by flash chromatography on silica gel (n-hexane/ethyl acetate gradient) to afford the desired compounds. Gram-scale synthesis of compound 5 was prepared following the similar procedure. The relatively volatile products (3b, 3c, 3d, 3e, 3f, 3g, 3h, 3i, 3j and 3v) were not isolated and their yields were determined by 19F NMR measurement in CDCl3 of the reaction mixture. For the products reported with 19F NMR yields, PhOCF3 (1.0 equiv) was added to the reaction mixture as internal standard added after the reaction completed. The reaction mixture was purified by flash chromatography on silica gel (pentane/diethyl ether gradient) to afford the desired compounds. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81.1% | Add 30.0 g (116.7 mmol) of 9-bromophenanthrene to a three-necked 1.0 L flask and dissolve in 292 mL of THF under a nitrogen atmosphere. After cooling the reaction temperature to -78 C, 56.0 mL (140.0 mmol) of 2.5 M n-BuLi solution was slowly added dropwise and stirred.After the dropwise addition was completed, the mixture was stirred at -78 C for 1 hour, and 18.3 mL (163.3 mmol) of trimethylborate was slowly added dropwise. After the temperature was raised to room temperature, the mixture was stirred for 12 hours. After the temperature was lowered to 0 C, 20 mL of 2 N HCl was added.After adding 500 mL of dichloromethane and 300 mL of H2O, the organic layer was separated and washed with water and brine. Dried over MgSO4, filtered, and the filtrate was concentrated under reduced pressure.The resulting concentrate was solidified and purified by using a solvent to obtain 21.0 g (yield: 81.1%) of a white solid compound (intermediate (5) | |
81% | 50 g (194 mmol) of 9-bromophenanthrene was added to a round bottom flask containing 500 ml of tetrahydrofuran,The temperature was adjusted to -78 DEG C under a small atmosphere. After 30 minutes, 146 ml (233 mmol) of n-butyllithium was slowly added dropwiseThen, after 1 hour, 28.3 g (274 mmol) of trimethylborate was slowly added dropwise, and the temperature was raised to room temperature. About 12After stirring for about an hour, 2N (normal) hydrochloric acid aqueous solution was added dropwise to the reaction solution until it became an acid,The residue was distilled under reduced pressure. After recrystallization with normal nucleic acid, it was filtered and dried to obtain white solid intermediate 20-a(35 g, yield 81%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 80℃; for 12h; | The intermediate compound (7) 10.0 g (19.5 mmol) and intermediate compound (5) 4.75 g (21.4 mmol) were melted in the toluene 150 mL and ethanol 45 mL and the tetrakistriphenylphosphine palladium (Pd(PPh(sub)3(/sub))(sub)4(/sub)) 449 mg (389 mumol) and 2M potassium carbonate aqueous solution 29.2 mL (58.4 mmol) were together put and it was stirred in 80 for 12 hours. The reaction mixture was filtered after doing the cooling in a room temperature and it wiped off with water and methanol and it was refined and the intermediate compound (10) 10.2 g (yield : 93.5%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.9% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 24h;Inert atmosphere; | A mixture of phenanthren-9-ylboronic acid (1.00 g, 4.503 mmol), 2-bromo-4-methylpyridine (0.85 g, 4.954 mmol),tetrakis(triphenylphosphine)palladium (0.05 g, 0.045 mol, 1 mol%), potassium carbonate(15 ml, 2M aqueous solution), and tetrahydrofuran (30 mL) was headed under a nitrogenatmosphere at 80C for 24 h. This reaction is the Suzuki coupling reaction. After the reaction,the mixture was cooled to room temperature for 1 h. The compound was extracted byliquid-liquid separation (water and dichloromethane). The compound was purified by acelite-silica gel filtration (solvent: toluene) and column chromatography on silica gel (eluent:hexane/ethyl acetate, 15:1). Yield: 98.9% (1.20 g); 1HNMR500MHz,CDCl3, delta), delta(ppm): 8.93(d, J = 7.3 Hz, 2H), 8.44(s, 1H), 8.39(d, J = 6.7 Hz, 1H), 8.12 (d, J = 7.1 Hz, 2H), 7.96(s, 1H),7.88(dd, J = 18.2 Hz, 2H), 7.82(dd, J = 19.1 Hz, 2H), 7.05(d, J = 5.3 Hz, 1H), 2.36(s, 3H). |
98.9% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; at 80℃; for 24h;Inert atmosphere; | General procedure: Phenanthren-9-ylboronic acid (1.00 g, 4.503 mmol) and2-bromopyridin (0.78 g, 4.954 mmol) were mixed with tetrakis(triphenylphosphine)palladium (0.05, 0.045 mmol,1 mol%), potassium carbonate (15 ml, 2 M aqueous solution),and tetrahydrofuran (30 mL) on heating under anitrogen atmosphere at 80 C for 24 h. After the reaction,the mixture was cooled to room temperature for 1 h.The mixture extracted by liquid-liquid separation (waterand dichloromethane) and dried over anhydrous Na2SO4,filtered concentrated under reduced pressure.2 3 The compoundwas purified by a celite-silica gel filtration (solvent:toluene) and column chromatography on silica gel (eluent:hexane/ethyl acetate, 15:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With tris-(dibenzylideneacetone)dipalladium(0); potassium carbonate; hydroquinone; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In 1,4-dioxane; at 110℃; for 48h;Inert atmosphere; Sealed tube; | General procedure: To a 25 ml sealed tube were added anhydrous K2CO3 (powder, 4.0 equiv.), hydroquinone (2.0 equiv.), Pd2(dba)3 (2.5 mol%), Xantphos (7.5 mol%) and ArB(OH)2 (0.3 or 0.5 mmol) or Ar-Beg (0.3 or 0.5 mmol) under argon. A solution of ClCF2H in 1,4-dioxane (2.0 M, 1.5 ml for 0.3 mmol scale or 2.5 ml for 0.5 mmol scale, 10 equiv.) and fresh distilled 1,4-dioxane (1.0 ml for 0.3 mmol scale or 2.5 ml for 0.5 mmol scale) were added subsequently. The sealed tube was screw capped and heated to 110 C (oil bath). After stirring for 48 h, the reaction was cooled to room temperature and fluorobenzene (1.0 equiv.) was added. The yield was determined by 19F NMR before working up. The reaction mixture was then diluted with ethyl acetate, filtered through a pad of Celite and concentrated. The residue was purified with silica gel chromatography to provide the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 120℃; for 3h; | The reaction container Riga C - 28 - 1 (2.5 g, 8.4 mmol), philippine boric acid (3.79 g, 17 . 07 mmol), four-triphenylphosphine palladium (0.7 g, 1 . 08 mmol), potassium carbonate (5.3 g, 38.3 mmol), toluene 60 ml, ethanol 20 ml and distilled water 20 ml after 120 C is stirred under the condition 3 h. After the end of the reaction the distilled water to stop reaction, extracted with ethyl acetate. The organic layer using MgSO4Drying. For removing the solvent is distilled under reduced pressure after silica gel column purification to obtain compound C - 28 - 2 (3.1 g, 75%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With bis-triphenylphosphine-palladium(II) chloride; tetrakis(triphenylphosphine) palladium(0); bis(acetylacetonato)palladium(II); palladium(II) bromide; In toluene; at 30℃; for 1h;Inert atmosphere; | At 30 C,Diphenylcyclopropenone (0.1 mmol), 0.001 mmol Pd (PPh3) 4, 0.001 mmolPdBr2, 0.001 mmol PdCl2 (PPh3) 2, 0.001 mmol Pd (acac) 2, and 0.15 mmol 9-phenanthroline were added to a reaction tube, And then pumping nitrogen gas three times, under a nitrogen atmosphere, adding 1 ml of toluene and stirring at 30 C for 1 hour to obtain alpha, beta-bisPhenyl-1-aryl propenone compound;Then, 10 ml of ethyl acetate was added, and further silica gel powder was added to obtain the product by column chromatography (eluent: petroleumEther: ethyl acetate = 20: 1) as a colorless liquid in 94% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 110℃;Inert atmosphere; | 31.2 g 2,4-dibromo bibenzene and 24.4 g 9-phenanthrenyl boric acid were added into a 2 L three-neck flask, followed by adding 600 mL toluene and 150 mL ethanol to dissolve. The reaction mixture was aerated with nitrogen gas for 15 minutes, then 150 mL aqueous K2CO3 solution (3.0 eq., 2M) and 2.3 g Pd(PPh3)4 (2 mol %) were sequentially added. The reaction mixture was heated up to 110 C. and reacted overnight. After the reaction was completed, the residual was absorbed by the added activated carbon, filtered by suction filtration and removed with solvent by rotary evaporation, followed by drying and recrystallization with a mixture of toluene and ethanol, to produce 37.2 g Intermediate (33) at a yield of 91%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.2% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80 - 100℃; for 24h;Inert atmosphere; Schlenk technique; | 3,7-Dibromo 2-Naphthalene-10-phenoxazine (0.350 g, 0.749 mmol, 1.00 equiv.) and <strong>[68572-87-2]9-phenanthracenyl boronic acid</strong> (0.569 g, 3.00 mmol, 4.00 equiv.) were added to a 250 mL storage tube flask and cycled between vacuum and nitrogen three times before 30.0 mL of dried and degassed THF was added. Once all of the reagents were dissolved, 10.0 mL of a 2.00 M aqueous solution of K2CO3, which had been sparged with nitrogen, was added and the biphasic system was heated to 80 C. In a separate Schlenk flask, palladiumtetrakis(triphenyl phosphine) (0.130 g, 0.112 mmol, 0.150 equiv.) was dissolved in 30.0 mL of THF under inert atmosphere. The solution of Pd(PPh3)4 was then added to the reaction mixture and the reaction was heated at 100 C. for 24 h before it was allowed to cool to room temperature and exposed to oxygen. The reaction mixture was concentrated under reduced pressure, diluted with DCM, and passed through a short plug of silica gel. The solution was then moved to a separatory funnel, washed with de-ionized water three times and brine one time. The solution was dried over magnesium sulfate, concentrated under vacuum, and recrystallized using DCM/methanol at -25 C. The product was collected via vacuum filtration as a yellow solid (0.408 g, 0.616 mmol, 82.2% yield). 1H NMR (C6D6, 500 MHz) delta 8.55 (d, J=8.13 Hz, 2H), 8.49 (d, J=8.03 Hz, 2H), 8.26 (d, J=8.18 Hz, 2H), 7.64 (m, 8H), 7.41 (m, 8H), 7.28 (m, 3H), 7.15 (d, J=1.82 Hz, 2H), 6.79 (dd, J=8.18, 1.86 Hz, 2H), 6.14 (d, J=8.19 Hz, 2H). 13C NMR (C6D6, 300 MHz) delta 144.15, 137.99, 136.31, 134.93, 134.59, 133.84, 133.09, 131.88, 131.46, 131.40, 130.98, 130.16, 130.00, 128.67, 127.82, 127.77, 127.27, 126.88, 126.80, 126.62, 126.44, 126.36, 126.34, 126.33, 125.25, 123.02, 122.54, 117.70, 113.52. HRMS (ESI): calculated for M+ C50H31NO, 661.2405; observed 661.2413. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; ethanol; water; at 90℃; for 6h; | General procedure: The synthesisof S2e is shown as representative: To a solution of 1-bromo-2-naphthaldehyde (S3, 541 mg, 2.30mmol), 1-pyrenylboronic acid (S4e, 850 mg, 3.45 mmol), and Pd(PPh3)4 (133 mg, 0.115 mmol) inDME (23 mL) and EtOH (8.6 mL) was added a solution of Na2CO3 (1.95 g, 18.4 mmol) in H2O (9.2mL). The mixture was stirred at reflux (bath temperature at 90 ) for 6 h. The solvents wereremoved under reduced pressure, and then water and EtOAc were added. The organic layer wasseparated, and the aqueous layer was extracted with EtOAc. The combined organic layer waswashed with water and brine, dried over MgSO4, filtered through a pad of Celite, and thenevaporated under reduced pressure. The residual dark-brown solid was chromatographed on silicagel with hexane/CHCl3 = 1/1 (Rf = 0.38) to give 1-(1-pyreneyl)-2-naphthaldehyde (S2e) as pale-yellow solid (581 mg, 1.63 mmol, 71%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide; In tetrahydrofuran; water; at 80℃; for 24h; | Phenanthracene-9-boronic acid (76.61 g, 345 mmol) in a 2L round bottom flask, THF (700 mL), After adding H2O (350 mL) and dissolving <strong>[51686-78-3]2,4-dibromo-1-nitrobenzene</strong> (146 g, 518 mmol), NaOH (42 g, 1035 mmol), Pd(PPh3)4 (20 g, 17.3 mmol) was added in order and reacted at 80C for about 24 hours. When the reaction is complete, methylene chloride and water, Extracted with brine and dried the organic layer with MgSO4. The obtained organic layer was silicagel column to give 80.4 g (62%) of product. |
With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide; In tetrahydrofuran; water; at 70℃; for 12h; | General procedure: To the round flask was added phenanthren-9-ylboronic acid (1 eq.),Sub 5-1(1 eq)(PPh3) 4 (0.05 eq.) And NaOH aqueous solution were added to the mixture, and the mixture was refluxed at 70 C for 12 hours. After the mixture was extracted with MC and water, the organic layer was dried over MgSO4, The resulting organics are purified by silicagel column and recrystallized to obtain the product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 80℃; for 19h;Inert atmosphere; | Under an argon stream, 16.28 g (61.4 mmol) of methyl 1-bromonaphthalene-2-carboxylate, 15.00 g (67.5 mmol) of 9-phenanthreneboronic acid and 1.42 g (1.23 mmol) of tetrakis(triphenylphosphine) palladium (0) were dissolved in 110 ml of toluene and 40 ml of ethanol. Then, 92 ml of an aqueous solution containing 184.0 mmol of sodium carbonate was added, and the mixture was stirred under reflux for 19 hours. After cooling to room temperature, water was added to the reaction solution, and extracted with toluene. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by column chromatography to obtain white solid (yield 22.03 g, yield 99%) of the objective compound (1-1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium carbonate; In ethanol; toluene; at 90℃; for 12h; | Intermediate C (8 g, 19.4 mmol) and <strong>[68572-87-2]9-phenanthracenyl boronic acid</strong> (5.2 g, 23.2 mmol) were dissolved in toluene and the mixture was refluxed with ethanol and 4M K2CO3 for 12 hours at 90 C. After completion of the reaction, the reaction product was precipitated with distilled water and methanol. Dried and then subjected to column purification (MC) and recrystallization with Hx yielded 7.8 g (yield 80%). |
80% | With potassium carbonate; In ethanol; toluene; at 90℃; for 12h; | To a round bottom flask was added intermediate C (8 g, 19.4 mmol),<strong>[68572-87-2]9-phenanthracenyl boronic acid</strong> (5.2 g, 23.2 mmol)Dissolved in toluene, and then refluxed with ethanol and 4M K2CO3 at 90 C for 12 hours.After completion of the reaction, the reaction product was precipitated with distilled water and methanol.After drying, column purification (MC) was performed and Hx and recrystallized to obtain 7.8 g (yield 80%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.3% | With [2,2]bipyridinyl; palladium diacetate; toluene-4-sulfonic acid; In toluene; at 75℃; for 25h; | S2: at room temperature,Add 100mmol to the appropriate amount of organic solvent toluenea compound of the above formula (3),175 mmol of the compound of the above formula (4),8mmol palladium acetate,7.5 mmol of organic ligand L1 and 1100 mmol of p-toluenesulfonic acid monohydrate,Then, the temperature was stirred to 75 C and the reaction was stirred at this temperature for 25 hours;After the reaction is completed, the reaction system is naturally cooled to room temperature.Wash with a saturated aqueous solution of potassium carbonate,Add ethyl acetate three times,Combine the organic phase,Dry with anhydrous Na2SO4,Distillation under reduced pressure, and the residue was purified by silica gel flash column chromatography (eluent eluting with a mixture of petroleum ether and ethyl acetate at a ratio of 16:1 as eluent), and the eluent was collected and evaporated to remove the eluent. The compound of the above formula (5) was yellow solid, which was named K4, and the yield was 86.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; ethanol; water; toluene; at 50℃; for 5.5h;Inert atmosphere; Reflux; | General procedure: ((5-bromopyridin-2-yl)methylene)oxonium (0.76g, 4.08mmol), Pd(PPh3)4 (0.38g, 0.33mmol) were added to a 20ml/20ml anhydrous toluene/THF solution. Then, anhydrous ethanol 10ml and 2MK2CO3 solution (15ml) dissolved in H2O were added to the reaction mixture at 50C. Naphthalen-1-ylboronic acid (1.05g, 6.12mmol) was added after half an hour and the mixture was refluxed for 5h under nitrogen. After the reaction had finished, the mixture was filtered. The product was isolated using silica gel column chromatography with PE and EtAc (5:1) as the solvent. The solvent was removed by evaporation. Recrystallization of the residue from EtOH afforded a beige compound (0.94g, 4.03mmol, 99% yield). 2.2.2 5-(phenanthren-9-yl)picolinaldehyde (3) This compound was prepared via a similar procedure for Compound 2 from ((5-bromopyridin-2-yl)methylene)oxonium (0.75?g, 4.02?mmol) and phenanthren-9-ylboronic acid (1.33?g, 6.03?mmol). The product was obtained as a pale yellow solid (1.06?g, 3.74?mmol, 93% yield). 1H NMR (400?MHz, DMSO) delta 10.17 (s, 1H), 9.09-8.99 (m, 2H), 8.96 (d, J?=?8.1?Hz, 1H), 8.31 (d, J?=?7.8?Hz, 1H), 8.18 (d, J?=?7.8?Hz, 1H), 8.11 (t, J?=?10.7?Hz, 1H), 7.99 (s, 1H), 7.87-7.77 (m, 4H), 7.73-7.65 (m, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | With potassium carbonate; XPhos; In tetrahydrofuran; water; at 75℃; for 15h;Inert atmosphere; Schlenk technique; | In a nitrogen stream, in a 50 mL Schlenk tube,3.52 g (11.43 mmol) of <strong>[1000577-94-5]3-bromo-4-iodobenzonitrile</strong>, 6.35 g (28.58 mmol) of 9-phenanthreneboronic acid,51 mg (0.23 mmol),218 mg (0.46 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (Xphos), 15 mL of tetrahydrofuran,And 15 mL of 2 M potassium carbonate aqueous solution were added, and the mixture was stirred at 75 C. for 15 hours. After cooling to room temperature, methanol 100 mL was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol.By recrystallizing (chloroform / methanol) the residue,1.62 g (3.56 mmol) of a colorless powder of 9- [4-cyano-2- (9-phenanthryl) -phenyl] - phenanthrene was isolated (yield 31%, HPLC purity 98.4%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 70℃; for 24h;Inert atmosphere; | Under a nitrogen gas flow, 12.0 g (37.8 mmol) of 2-bromo-4-chloro-iodobenzene, 8.81 g of 9-phenanthrene boronic acid (39.7mmol), tetrakis (triphenylphosphine) palladium (0) 437 mg (0. 04 mmol), tetrahydrofuran 100 mL, and 2 M potassium carbonate aqueous solutionAnd the mixture was stirred at 70 C. for 24 hours. After cooling to room temperature, 100 mL of pure water,100 mL of chloroform was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was absentAfter drying with magnesium sulfate, it was concentrated under reduced pressure. Recrystallization (methanol) of the residue6.54 g (17.8 mmol) of a colorless powder of 9- [2-bromo- (4-chloro) -phenyl] - phenanthrene was isolated (yield 47%, HPLC purity 99.8%). |
20 g | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 50℃; for 36h; | To a round bottom flask was added phenanthren-9-ylboronic acid (15.39 g, 69.3 mmol), <strong>[31928-44-6]2-bromo-4-chloro-1-iodobenzene</strong> (20 g, 63 mmol), tetrakis (triphenylphosphine) palladium 3.6 g, 3.1 mmol), potassium carbonate (30 g), toluene 100 mL, ethanol 50 mL, and water 100 mL were addedand stirred at50C for36 hours.After completion of the reaction, the reaction solution is concentrated to obtain a crude product.Crude was dissolved by heating in MC, filtered under reduced pressure on silica gel, and concentrated.20 g of 9- (2-bromophenyl) phenanthrene was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With palladium diacetate; potassium carbonate; XPhos; In tetrahydrofuran; water; at 75℃; for 24h;Inert atmosphere; | In a nitrogen stream, into a 300 mL two-neck eggplant flask,2-Bromo-4-chloro-1-iodobenzene22.21 g (70.00 mmol),35.75 g (161.0 mmol) of 9-phenanthrene boronic acid, 157 mg (0.70 mmol) of palladium acetate,667 mg (1.40 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (Xphos), 80 mL of tetrahydrofuran and 70 mL of a 2 M potassium carbonate aqueous solution were added and the mixture was stirred at 75 C. for 24 hours. After cooling to room temperature, 200 mL of methanol was added and stirred, the precipitated solid was collected by filtration and washed with pure water and methanol,27.23 g (58.56 mmol) of a colorless powder of 9- [4-chloro-2- (9-phenanthryl) -phenyl] - phenanthrene was isolated (yield 84%, HPLC purity 94.7%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 75℃; for 48h;Inert atmosphere; | In a nitrogen stream, into a 300 mL two-neck eggplant flask,1,1 ': 4', 1 "-terphenyl, 2-bromo-4-chloro12.8 g (37.2 mmol), 9-phenanthrene boronic acid 9.26 g(41.7 mmol), tetrakis (triphenylphosphine) palladium (0) 430 mg (0.37 mmol), tetrahydrofuran 70 mL, and 2 M potassium carbonate aqueous solution 25 mL were added and stirred at 75 C. for 2 days.After cooling to room temperature, 100 mL of pure water and 100 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated,The obtained organic layer was dried over anhydrous sodium sulfate,And concentrated under reduced pressure. By recrystallizing (chloroform / methanol) the residue,Phenanthrene,9- (1,1 ': 4', 1 "-terphenyl) -4-chloro-2-yl(Yield: 91%, HPLC purity: 98.4%) of 15.00 g (34.0 mmol) of a colorless powder. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate; In toluene; at 50 - 100℃;Inert atmosphere; | (1) In a 500mL three-necked bottle,5-Bromo-3-chloro-1,2,4-thiadiazole (19.94 g, 100 mmol),Phenanthrene-9-ylboronic acid (22.20 g, 100 mmol), cesium carbonate (48.87 g, 150 mmol),Add 200 mL of toluene under a nitrogen atmosphere,[1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (1.46 g, 2 mmol) was added.The temperature is raised to 50-100 C for 4 to 48 hours, the liquid phase monitoring reaction is completed, and cooled to room temperature.Washed, filtered, concentrated, separated by column chromatography,To give 5-bromo-3- (phenanthrene-9-yl) -1,2,4-thiadiazole 25.25g, yield 74% |
74% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate; In toluene; at 50 - 100℃;Inert atmosphere; | (1) In a 500 mL three-necked flask, 5-bromo-3-chloro-1,2,4-thiadiazole (19.94 g, 100 mmol) and phenanthrene-9-ylboronic acid (22.20 g, 100 mmol) were charged., cesium carbonate (48.87g, 150mmol), added 200mL of toluene, under nitrogen atmosphere,[1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (1.46 g, 2 mmol) was added.The temperature is raised to 50-100 C for 4 to 48 hours, the liquid phase monitoring reaction is completed, and cooled to room temperature.Washed, filtered, concentrated, separated by column chromatography,25,25 g of 5-bromo-3-(phenanthr-9-yl)-1,2,4-thiadiazole is obtained in a yield of 74%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With XPhos; In tetrahydrofuran; water; at 70℃; for 10h;Inert atmosphere; | 2- [2 ', 5'-dichlorobiphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine (1.50 g, 3.30 mmol) obtained in Synthesis Example 1 under nitrogen stream ), 9-phenanthreneboronic acid (2.20 g, 9.90 mmol), palladium acetate (14.8 mg, 0.066 mmol), and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (62). .9 mg, 0.132 mmol) was dissolved in tetrahydrofuran (50 mL). To this, 2 M aqueous potassium phosphate solution (9.90 mL, 19.8 mmol) was added and stirred at 70 C. for 10 hours. After cooling to room temperature, water (30 mL) and methanol (30 mL) were added. The precipitated solid was separated by filtration and washed with water (50 mL) and acetone (50 mL). The resulting precipitate is purified by silica gel chromatography (developing solvent: toluene) to give the desired 2- [2 ', 5'-bis (9-phenanthryl) -biphenyl-3-yl] -4,6-diphenyl- A white solid (2.10 g, 86% yield) of 1,3,5-triazine (compound A-7) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate; In toluene; at 110℃; for 0.75h;Microwave irradiation; | 3-Iodolevoglucosenone [13b] (1.5?g, 5.95?mmol), 9-phenanthrylboronic acid (1.98?g, 8.92?mmol), K3PO4 (2.53?g, 11.92?mmol), SPhos (49?mg, 0.12?mmol) and Pd(OAc)2 (14?mg, 0.06?mmol) were combined in toluene (15?mL) and refluxed at 110? C for 45?min in a microwave reactor. The mixture was diluted with H2O (20?mL), extracted with DCM (30?mL x 3) and the organic phase concentrated. The organic residue was isolated via flash chromatography (1:1 EtOAc:hexanes) then recrystallized from EtOH to afford the product as colorless crystals (1.39?g, 77%); Rf (1:1 EtOAc:hexanes) 0.89; mp 163-172?C; [alpha]D25 -168 (c 0.6, CHCl3); 1H NMR (500?MHz, CDCl3) delta 8.74-8.63 (m, 2H, ArH), 7.88-7.83 (m, 1H, ArH), 7.70-7.53 (m, 6H, ArH), 7.30 (d, J?=?4.8?Hz, 1H, H-2), 5.61 (s, 1H, H-5), 5.20 (dd, J?=?4.8, 4.8?Hz, 1H, H-1), 4.10-3.98 (m, 2H, H-7); 13C NMR (125?MHz, CDCl3) delta 188.2 (C-4), 146.1 (C-2), 138.6 (C-3), 131.2 (ArC), 130.7 (ArC), 130.62 (ArC), 130.58 (ArC), 130.4 (ArC), 128.9 (ArC), 128.2 (ArC), 127.3 (ArC), 127.0 (ArC), 126.91 (ArC), 126.89 (ArC), 126.0 (ArC), 123.1 (ArC), 122.7 (ArC), 101.9 (C-5), 72.6 (C-1), 67.0 (C-7); FT-IR (neat) 3062, 2963, 2899, 1699, 1492, 1449, 1351, 1292, 1239, 1106, 1069, 1041, 1003, 748?cm-1; MS (ESI) m/z 325.0 [M+Na]+; HRMS (ESI) calc. for C20H14O3Na [M + H]+, 325.0841; found 325.0839. |
77% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate; In toluene; at 110℃; for 0.75h;Microwave irradiation; Inert atmosphere; Sealed tube; | A solution of LGO (6) (1.5 g, 1.0 equiv, 5.95 mmol), 9-phenanthrylboronic acid (1.98 g, 1.5 equiv, 8.92 mmol), K3PO4 (2.53 g, 2.0 equiv, 11.92 mmol), SPhos (49 mg, 0.02 equiv, 0.12 mmol) and Pd(OAc)2 (14 mg, 0.01 equiv, 0.06 mmol) in toluene (15 mL) was heated to 110 C for 45 min in a sealed tube in a microwave reactor. The mixture was diluted with H2O (20 mL), extracted with CH2Cl2 (3 × 30 mL) and the organic phase concentrated under reduced pressure. The residue was purified by flash chromatography (1:1 EtOAc:hexanes) and the product recrystallized from EtOH to afford S3 as colorless crystals (1.39 g, 77%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium hydroxide; In water; toluene; at 80℃; for 12h;Inert atmosphere; | Comp 5 synthetic: under the environment of nitrogen, will (11.5 g, 20 mmol) of compound 17 and (44.4 g, 20 mmol) of the compound 20, (0.7 g, 0.6 mmol) four (triphenyl phosphate) palladium, (3.2 g, 10 mmol) tetrabutyl ammonium bromide, (1.6 g, 40 mmol) sodium hydroxide, (10 ml) and water (80 ml) toluene by adding 250 ml of bottle in three, heating 80 C stirring for 12 hours, the end of the reaction, the reaction liquid rotary evaporate most of the solvent, dichloromethane is used for dissolving water washing 3 times, to collect organic the fluid mixes silica gel column purification, yield 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79.2% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 5h;Reflux; | 20 g (80.2 mmol) of <strong>[46258-62-2]1-acetyl-4-bromonaphthalene</strong> and 19.6 g (88.26 mmol) of 9-phenanthreneboronic acid were added to a 500 ml three-necked flask. After adding 33.3 g (240.87 mmol) of potassium carbonate and 2.78 g (2.4 mmol) of Pd (PPh3) 4, 150 ml of toluene, 75 ml of H2O,Ethanol (75 ml), and the mixture was refluxed for 5 hours while stirring.After completion of the reaction, the reaction mixture was extracted with MC. The organic layer was dried over MgSO4, purified by column chromatography, and crystallized with MeOH to obtain 22 g (79.2%) of Intermediate E. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.7% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 3h;Reflux; | A 500 ml three-necked flask was charged with 10 g (50 mmol) of <strong>[59278-65-8]2-amino-4-bromobenzaldehyde</strong> and 14.4 g (65 mmol) of 9-phenanthrenorbornic acidmmol). After adding 20.73 g (150 mmol) of potassium carbonate and 1.73 g (1.5 mmol) of Pd (PPh3) 4, 100 ml of toluene,50 ml of H2O and 50 ml of ethanol, and the mixture was refluxed for 3 hours while stirring. When the reaction is completeThe organic layer was dried over MgSO4, purified by column chromatography and crystallized with Hex to give intermediate C12g (80.7%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene;Reflux; | A 5 L round-bottom flask was charged with 94.3 g (450.35 mmol, 1 eq) of <strong>[33863-76-2]1-bromo-3-chloro-5-fluorobenzene</strong> 9-phenanthrenyl boronic acid 100 g (450.35 mmol, 1 eq), 26.0 g (22.52 mmol, 0.05 eq) of Pd(PPh3)4, 186.7 g (1351.05 mmol, 3 eq) of K2CO 3 was added and 2 L / 400 ml / 400 ml of Toluene / EtOH / H2O was added, followed by stirring under reflux. After the reaction was completed, the reaction mixture was extracted with CH2Cl2 / H2O and the CH2Cl2 layer was dried over MgSO4. Thereafter, the silica-gel column was purified to obtain 103.1 g of Compound 2-1 in a yield of 75%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); tetrabutyl-ammonium chloride; potassium carbonate; In ethanol; water; toluene; at 75 - 80℃; for 4h;Inert atmosphere; | 9-phenanthrene boronic acid (30g, 135.12mmol),4-bromoaniline (28.57g, 166.12mmol),Tetrakis (triphenylphosphine) palladium (9.59g, 8.30mmol),Potassium carbonate (45.92g, 332.24mmol),Tetrabutylammonium chloride (1.89g, 8.31mmol),Toluene (240ml),Ethanol (120ml) and deionized water (36ml) were added to a three-necked flask.Under nitrogen protection, the temperature was raised to 75 C to 80 C, and the mixture was heated under reflux and stirred for 4h.After the reaction was completed, the solution was cooled to room temperature, and dichloromethane and water were added to extract the reaction solution.The organic phases were combined, dried over anhydrous magnesium sulfate, filtered to obtain a filtrate, and concentrated;The crude product was purified by silica gel column chromatography.Intermediate-B-2 (27.29 g, yield 75%) was obtained. |
59% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; for 15h;Inert atmosphere; Reflux; | In the argon atmosphere, in 4 - bromophenyl (4 - bromoaniline) 172.03 g (1 muM), Philippine -9 - borate (phenanthren - 9 - ylboronic acid) 266.46 g (1.2 muM), four (triphenylphosphine) palladium (tetrakis (triphenylphosphine) palladium) (0) 23.5 g (20 mm) in toluene (toluene) into 2 L, 2 M concentration of Na2CO3Aqueous solution 1 L, reflux 15 hours of heating at the same time. After the reaction, methylene chloride (dichlorome thane) extraction, is put into the MgSO4, Filtering. Removing the organic layer after the filtering of the solvent, purification by column chromatography, to obtain intermediate I - 1 (4 - (Philippine -9 - yl) aniline) (4 - (p henanthren - 9 - yl) aniline) 158.92 g. (Yield 59%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; 1,4-dioxane; water; at 65℃; for 48h;Inert atmosphere; | Potassium carbonate (as 2 M aqueous solution, 2 eq.) was degassed with nitrogen for 30 min. Dioxane (976 ml) was also degassed with nitrogen for 30 min. The THF flask was then charged with corresponding 9-phenanthreneboronic add (10 mmol, 1.32 eq.), previously synthesized formula 6 intermediate (78 g, 1 eq.) and tetrakis(triphenylphosphin)palladium(o) (0.035 eq.) under a positive nitrogen pressure. The degassed potassium carbonate solution was added, nitrogen purged reflux condenser was attached to the flask and a reaction mixture heated to 65 C with stirring for 48 h. The mixture was allowed to cool down to the room temperature, dioxane was evaporated. Extraction with 1.75 L chloroform was performed. After washing the organic layer with 5 x 250 mL water, it was dried over MgSOq and filtered over silicagel layer. Evaporation almost to dryness followed by hexane addition provided a precipitate that was still colored. Further washing with Na2S20s sat. aqueous solution afforded 49.2g (54%) product, m/z 366, 368 [M]+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 20℃; for 4h;Inert atmosphere; Reflux; | Compound 4-2 (22.2 g, 0.05 mol),9-phenanthroboric acid (12.2g, 0.055mol),Potassium carbonate (20.7g, 0.15mol) was dissolved in a flask containing toluene / ethanol / water (250mL / 50mL / 50mL).After replacing nitrogen under stirring at room temperature, Pd (PPh3) 4 (578 mg, 0.5 mmol) was added.After the addition, the reaction was stirred and refluxed for 4 hours.TLC monitors the endpoint of the reaction. After cooling to room temperature, suction filtration was performed, and the solid was rinsed with toluene, water, and ethanol, respectively, and dried. Purification by column chromatography (eluent: petroleum ether: dichloromethane = 10: 1 to 3: 1),Compound 4-3 was obtained (25.2 g, yield 93%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 12h;Inert atmosphere; Reflux; | Compound <strong>[188813-05-0]3-bromo-5-chlorobenzaldehyde</strong> (21.8 g, 100 mmol),9- phenanthrene boronic acid (22.2g, 100mmol) and potassium carbonate (41.4g, 300mmol)Add to a flask containing tetrahydrofuran: water (250mL: 50mL),After replacing nitrogen under stirring at room temperature, Pd (PPh3) 4 (1155 mg, 1 mmol) was added.After the addition was completed, the reaction was heated under reflux under a nitrogen atmosphere for 12 hours.TLC showed the reaction was complete. The precipitated white solid was filtered. Dissolve in dichloromethane,Dried over anhydrous sodium sulfate,Column chromatography (eluent dichloromethane) to give a pale yellow oily compound 3-1 (28.4g,Yield: 90%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane;Reflux; | In a round bottom flask,20.0g of phenanthren-9-ylboronic acid,32.4 g of bis (4-bromophenyl) amine is dissolved in 800 ml of 1,4-dioxan,And put in 150ml (2M) of K2CO3After 3.1 g of Pd (PPh3) 4, the mixture was stirred under reflux.After confirming the reaction by thin layer chromatography (TLC), after adding water, the reaction was completed.The organic layer was extracted with methyl cellulose (MC) and filtered under reduced pressure before recrystallization.Thus, 21.6 g (yield: 72%) of Intermediate IM4 was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium hydroxide; In water; toluene; at 80℃; for 12h;Inert atmosphere; | Under a nitrogen atmosphere, (11.5 g, 20 mmol) of compound 23 and (44.4 g, 20 mmol) of compound 25, (0.7 g, 0.6 mmol) tetrakis(triphenylphosphonium)palladium,(3.2g, 10mmol) tetrabutylammonium bromide, (1.6g, 40mmol) sodium hydroxide, (10mL) water and (80mL) toluene were added to a 250mL three-necked flask, and the reaction was stirred with heating at 80 C for 12 hours to end the reaction. Rotate the reaction solution to evaporate most of the solvent, and wash it with methylene chloride for 3 times. the organic liquid was collected and purified by column chromatography on silica gel. The yield was 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89.7% | With bis-triphenylphosphine-palladium(II) chloride; tetrabutylammomium bromide; potassium carbonate; In water; toluene; at 70 - 110℃; | In a 5000ml reaction bottle, 569.3g (2.973mol) of o-chlorobromobenzene, 616g (4.46mol) of potassium carbonate, 95.7g (0.297mol) of tetrabutylammonium bromide, 570ml of toluene,2280ml of water, heated to 70 ,Add 2.08g (2.973mmol) of Pd (PPh3) 2Cl2, and then add 660g (2.973mol) of phenanthrene-9-boronic acid in batches. After the addition, the temperature is raised to 90-110 C, and the reaction is held. The temperature was reduced to 5 C, suction filtration, and the cake were dried to obtain 830 g of crude product, which was then dissolved in toluene, passed through a silica gel column, and concentrated to dryness under reduced pressure to obtain 9- (2-chlorobenzene) phenanthrene: 770 g, gas phase purity: 99.2%, yield. 89.7% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.7% | With bis-triphenylphosphine-palladium(II) chloride; tetrabutylammomium bromide; potassium carbonate; In water; toluene; at 70 - 110℃; | In a 5000 ml reaction bottle, 535 g (2.0 mol) of 4-bromo-3-chloro-1,1'biphenyl, 414.6 g (3.0 mol) of potassium carbonate, 64.4 g (0.2 mol) of tetrabutylammonium bromide, 535 ml of toluene, 2240 ml of water, heated to 70 C, added 1.4 g (2.0 mmol) of Pd (PPh3) 2Cl2, and then added 444 g (2.0 mol) of phenanthrene-9-boric acid in portions, and the temperature was raised to 90 to 110 C.Incubate the reaction and monitor the complete reaction of the raw materials by gas chromatography.The temperature was lowered to 5 C, suction filtration, and the cake were dried to obtain 726 g of crude product, which was then dissolved in toluene, passed through a silica gel column, and concentrated to dryness under reduced pressure to obtain 9- (3-chloro- [1,1'-biphenyl] -4- ) Phenanthrene: 670 g, gas phase purity: 98.7%, yield 91.7%, |
Tags: 68572-87-2 synthesis path| 68572-87-2 SDS| 68572-87-2 COA| 68572-87-2 purity| 68572-87-2 application| 68572-87-2 NMR| 68572-87-2 COA| 68572-87-2 structure
[ 251659-87-7 ]
Anthracene-9,10-diyldiboronic acid
Similarity: 1.00
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
Home
* Country/Region
* Quantity Required :
* Cat. No.:
* CAS No :
* Product Name :
* Additional Information :