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. : | 870774-25-7 | MDL No. : | MFCD08669639 |
Formula : | C16H13BO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | BQHVXFQXTOIMQM-UHFFFAOYSA-N |
M.W : | 248.08 | Pubchem ID : | 44119399 |
Synonyms : |
|
Num. heavy atoms : | 19 |
Num. arom. heavy atoms : | 16 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 79.21 |
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) : | -5.19 cm/s |
Log Po/w (iLOGP) : | 0.0 |
Log Po/w (XLOGP3) : | 3.7 |
Log Po/w (WLOGP) : | 2.19 |
Log Po/w (MLOGP) : | 2.72 |
Log Po/w (SILICOS-IT) : | 1.93 |
Consensus Log Po/w : | 2.11 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -4.2 |
Solubility : | 0.0156 mg/ml ; 0.0000631 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -4.24 |
Solubility : | 0.0143 mg/ml ; 0.0000575 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -5.49 |
Solubility : | 0.00081 mg/ml ; 0.00000327 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 2.16 |
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 |
---|---|---|
67% | Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -60℃; for 2 h; Inert atmosphere Stage #2: With Triisopropyl borate In tetrahydrofuran; hexane at -60 - 20℃; for 17 h; Inert atmosphere Stage #3: With hydrogenchloride In tetrahydrofuran; hexane; water at 20℃; for 1 h; |
Under an argon gas atmosphere, a mixture of 208.8 g (737.4 mmol) of 1-(4-bromophenyl)naphthalene and 2.1 L of dehydrated TI-IF was cooled down to minus 60 degree C. Then, 567 ml (884.9 mmol) of hexane solution of 1.56M n-butyllithium was dropped into the mixture while the mixture was being stirred. The reaction mixture was further stirred at minus 60 degrees for 2 hours. 416 g (2.21 mol) of triisopropylborate was dropped into the reaction mixture at minus 60 degrees C. The reaction mixture was then stirred at room temperature for 17 hours. The reaction mixture was added with aqueous solution of hydrochloric acid and stirred at room temperature for 1 hour. After the reaction, the reaction mixture was added with toluene, and aqueous phase thereof was eliminated. Then, organic phase thereof was dried with magnesium sulfate, and the solvent was distilled away under reduced pressure. By recrystallizing the obtained solid by toluene, 126 g of 4-(1-naphthyl)phenylboronic acid was obtained at an yield of 67percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With hydrogenchloride; n-butyllithium In tetrahydrofuran; hexane; toluene | (8) Synthesis of Compound 2-8 Under an argon gas atmosphere, a mixture of 208.8 g (737.4 mmol) of 1-(4-bromophenyl) naphthalene and 2.1 L of dehydrated THF was cooled down to -60 degrees C., and added with 567 mL (884.9 mmol) of hexane solution of 1.56M n-butyllithium in drops while being stirred. Then, the reaction mixture was stirred for two hours at -60 degree C. 416 g (2.21 mol) of triisopropyl borate was dropped into the reaction solution at -60 degrees C. Subsequently, the reaction mixture was stirred for 17 hours at room temperature. The reaction mixture was further added with solution of hydrochloric acid to be stirred for one hour at room temperature. After the reaction, the reaction mixture was further added with toluene, so that aqueous phase thereof was eliminated. After organic phase thereof was dried with magnesium sulfate, the solvent was distilled away under reduced pressure. By recrystallizing the obtained solid by toluene, 126 g of 4-(1-naphthyl) phenylboronic acid was obtained at an yield of 67percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 8h;Heating / reflux; | (Synthesis of Compound (AN-2)) (1) Synthesis of Intermediate [1-bromo-6-(4-naphthalene-1-yl-phenyl) pyrene] 7.4 g of 4-(naphthalene-1-yl) phenyl boronic acid prepared by a well known method and 7.0 g of conventional 1-bromopyrene were dissolved in 80 ml of dimethoxyethane (DME). Subsequently, 0.58 g of tetrakistriphenylphosphine palladium and 40 ml of 2M-sodium carbonate aqueous solution were added therein, followed by argon displacement. After heating and refluxing over 8 hours, it was stood to cool and then an organic layer was extracted therefrom by toluene. The organic layer was washed by saturated salt water, followed by drying through anhydrous sodium sulfate, and then the organic solvent was removed by an evaporator. The residue was refined through a silica gel chromatography (a developing solvent: toluene) and then 10.0 g of 1-(4-naphthalene-1-yl-phenyl) pyrene was obtained. (yield: 99 %) 10.0 g of 1-(4-naphthalene-1-yl-phenyl)pyrene obtained was dispersed into 100 ml of dimethyl formaldehyde (DMF), and 5.3 g N-bromosuccinamide (NBS) in DMF solution was dropped therein at room temperature. After stirred over 5 hours, it was left around overnight. After the overnight, 150 ml of water was added to it and the deposited crystal was filtrated, followed by water and ethanol washing of the crystal. The crystal obtained was refined through a silica gel chromatography (a developing solvent: hexane / toluene = 2 / 1) and then 4.5 g of 1-bromo-6-(4-naphthalene-1-yl-phenyl)pyrene (the yield: 38%) and 3.8 g of 1-bromo-8-(4-naphthalene-1-yl-phenyl)pyrene were obtained (the yield: 32%) as the intermediates. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With hydrogenchloride; n-butyllithium; In tetrahydrofuran; hexane; toluene; | (8) Synthesis of Compound 2-8 Under an argon gas atmosphere, a mixture of 208.8 g (737.4 mmol) of 1-(4-bromophenyl) naphthalene and 2.1 L of dehydrated THF was cooled down to -60 degrees C., and added with 567 mL (884.9 mmol) of hexane solution of 1.56M n-butyllithium in drops while being stirred. Then, the reaction mixture was stirred for two hours at -60 degree C. 416 g (2.21 mol) of triisopropyl borate was dropped into the reaction solution at -60 degrees C. Subsequently, the reaction mixture was stirred for 17 hours at room temperature. The reaction mixture was further added with solution of hydrochloric acid to be stirred for one hour at room temperature. After the reaction, the reaction mixture was further added with toluene, so that aqueous phase thereof was eliminated. After organic phase thereof was dried with magnesium sulfate, the solvent was distilled away under reduced pressure. By recrystallizing the obtained solid by toluene, 126 g of 4-(1-naphthyl) phenylboronic acid was obtained at an yield of 67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 100℃; for 18h;Inert atmosphere; | Example 7; In Example 7, a synthesis method of 2-(4-{10-[4-(1-naphthyl)phenyl]-9-anthryl}phenyl)benzoxazole (abbrev.: NPhABOx) represented by Structural Formula (131) will be described. [Step 1: Synthesis of 2-(4-{10-[4-(1-naphthyl)phenyl]-9-anthryl}phenyl)benzoxazole] A synthesis scheme of 2-(4-{10-[4-(1-naphthyl)phenyl]-9-anthryl}phenyl)benzoxazole is shown in (F-1). In a 50 mL three-neck flask, 0.97 g (2.2 mmol) of 2-[4-(10-bromo-9-anthryl)phenyl]benzoxazole, 0.57 g (2.3 mmol) of 4-(1-naphthyl)phenylboronic acid, 0.46 g (4.3 mmol) of sodium carbonate, 15 mL of toluene, 3 mL of ethanol, and 3 mL of water were placed. The mixture was degassed by being stirred under reduced pressure, and the air in the flask was replaced with nitrogen. To the mixture, 35 mg (0.030 mmol) of tetrakis(triphenylphosphine)palladium(0) was added, and the mixture was stirred under nitrogen stream at 100 C. for 18 hours. After a certain period, water was added to the mixture, and an aqueous layer was extracted with toluene. The obtained extracted solution and the organic layer were combined and washed with a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, and the organic layer was dried with magnesium sulfate. The mixture was gravity filtered, and the obtained filtrate was condensed to give a solid. The solid was purified by silica gel column chromatograghy (toluene:hexane=2:1) and recrystallized with toluene/hexane, giving 1.2 g of the target white powder in a yield of 94%. Then, 1.2 g of the target substance was subjected to sublimation purification at 385 C. under argon stream (flow rate: 3.0 mL/min) and a pressure of 10 Pa for 15 hours; thus, 1.1 g of the target substance was recovered in a yield of 91%. This compound was measured by nuclear magnetic resonance (NMR) spectrometry and identified as 2-(4-{10-[4-(1-naphthyl)phenyl]-9-anthryl}phenyl)benzoxazole (abbrev.: NPhABOx). The 1H NMR data is shown below. 1H NMR (300 MHz, CDCl3): delta (ppm)=7.38-7.47 (m, 6H), 7.55-7.78 (m, 13H), 7.84-7.99 (m, 5H), 8.17-8.20 (m, 1H), 8.53 (d, J=8.1 Hz, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium carbonate; tris-(o-tolyl)phosphine;palladium diacetate; In ethanol; water; toluene; at 80℃; for 5h;Inert atmosphere; | In a 200 mL three neck flask were put 2.5 g (4.4 mmol) of 3-bromo-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole, 1.1 g (4.4 mmol) of 4-(1-naphthyl)phenylboronic acid, and 0.33 g (1.1 mmol) of tri(ortho-tolyl)phosphine. The atmosphere in the flask was replaced with nitrogen. To this mixture were added 5.0 mL of an aqueous potassium carbonate solution (2.0 mol/L), 60 mL of toluene, and 20 mL of ethanol. This mixture was stirred to be degassed while the pressure was reduced. To this mixture was added 49 mg (0.22 mmol) of palladium(II) acetate. This mixture was stirred under a nitrogen stream at 80 C. for 5 hours.After being stirred, the mixture was separated into an aqueous layer and an organic layer. The aqueous layer was extracted with toluene. The extract and the organic layer were combined and washed with saturated brine. Then, the organic layer was dried with magnesium sulfate, followed by gravity filtration of this mixture. An oily substance obtained by concentration of the resulting filtrate was dissolved in about 10 mL of toluene. This solution was suction filtered through Celite (manufactured by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), alumina, and Florisil (manufactured by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135). An oily substance obtained by concentration of the resulting filtrate was purified by silica gel column chromatography (the developing solvent was a mixed solvent of a 5:1 ratio of hexane to toluene) to give a light yellow oily substance.This oily substance was recrystallized with a mixed solvent of toluene and hexane to give the desired substance as 2.4 g of a light yellow powder in a yield of 79%. Sublimation purification of 2.3 g of the light yellow powder obtained was performed by a train sublimation method. The light yellow powder was heated at 340 C. with an argon flow rate of 4.0 mL/min under reduced pressure. After the sublimation purification, 2.2 g of a light yellow solid which was the desired substance was obtained in a yield of 95%. By a nuclear magnetic resonance (NMR) method, this compound was confirmed to be 3-[4-(1-naphthyl)phenyl]-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPAalphaNP) which was the desired compound.The following are data of the 1H NMR measurement of the compound obtained: 1H NMR (CDCl3, 300 MHz):delta=7.37-7.67 (m, 17H), 7.70-7.80 (m, 6H), 7.85-7.96 (m, 9H), 8.06 (d, J=8.1 Hz, 1H), 8.29 (d, J=7.8 Hz, 1H), 8.52 (d, J=0.90 Hz, 1H)In addition, FIGS. 18A and 18B show 1H NMR charts. Note that FIG. 18B is a chart showing an enlarged part in the range of 7.2 ppm to 8.4 ppm in FIG. 18A. |
With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 5h;Inert atmosphere; | Into a 200 mL three-neck flask were put 2.5 g (4.4 mmol) of 3-bromo-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole, 1.1 g (4.4 mmol) of 4-(l-naphthyl)phenylboronic acid, and 0.33 g (1.1 mmol) of tri(ortho-tolyl)phosphine , and the air in the flask was replaced with nitrogen. To this mixture were added 5.0 mL (2.0 mol/L) of a potassium carbonate aqueous solution, 60 mL of toluene, and 20 mL of ethanol. This mixture was stirred to be degassed while the pressure was reduced. To the mixture was added 49 mg (0.22 mmol) of palladium(II) acetate, and the mixture was stirred at 80 0C under a nitrogen stream for 5 hours. After the stir, the aqueous layer of the mixture was extracted with toluene and the extracted solution and the organic layer were washed together with saturated saline. After that, the organic layer was dried with magnesium sulfate, and this mixture was subjected to gravity filtration. The obtained filtrate was concentrated to give an oily substance. The obtained oily substance was dissolved in about 10 mL of toluene. This solution was subjected to suction filtration through Celite (Catalog No. 531-16855, manufactured by Wako Pure Chemical Industries, Ltd.), alumina, and Florisil (Catalog No. 540-00135, manufactured by Wako Pure Chemical Industries, Ltd.). The obtained filtrate was concentrated to give an oily substance. The obtained oily substance was purified by silica gel column chromatography (a developing solvent was a mixed solvent of hexane and toluene (hexane: toluene= 5: I)) to give a light yellow oily substance. The oily substance was recrystallized with a mixed solvent of toluene and hexane to give 2.4 g of light yellow powder, which was the object, at a yield of 79%[0476]Sublimation purification by train sublimation was performed on 2.3 g of the obtained light yellow powder. The sublimation purification was performed under such conditions that the light yellow powder was heated at 340 0C with an argon gas applied at a flow rate of 4.0 mL/min under reduced pressure. After the sublimation purification, 2.2 g of a light yellow solid, which was the objective compound, was obtained at a yield of 95%. [0477]This compound was identified as3-[4-(l-naphthyl)phenyl]-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (CzPAaNP) which was the object by nuclear magnetic resonance (NMR). 1H NMR data of the obtained compound is shown below. 1H NMR(CDCl3, 300 MHz): d= 7.37-7.67(m, 17H), 7.70-7.80(m, 6H), 7.85-7.96(m, 9H), 8.06(d, J= 8.1 Hz, IH), 8.29(d, J= 7.8 Hz,IH), 8.52(d, J= 0.90 Hz, IH)[0478]Further, the 1H NMR chart is illustrated in FIGS. 52A and 52B. Note that FIG.52B is a chart showing an enlarged portion of FIG. 52A in the range of from 7.2 ppm to 8.4 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; | (2-3) Synthesis of Compound 35; 4 g of Intermediate 11, 2.3 g of 4-(l~naphthalene)-l-phenylboronic acid, 40 ml of tetrahydrofuran, 2.5 g of potassium carbonate and 20 ml of water were mixed in a 100 ml round-bottom flask with stirring. 0.53 g of tetrakis(triphenylphosphine)palladium(0) was added to the mixture, which was heated to 80 C . The reaction solution was cooled and filtered, and the precipitated crystals were washed with acetone and subjected to recrystalization with methylene chloride, to obtain 2 g of the title compound. 1H-NMR(CDCl3, 500MHz) (IH, d, 8.48532, 8.46735), (IH, d, 8.41562, 8.40007), (IH, d, 8.07572, 8.05957), (2H, d, 7.99909, 7.98380), (3H, m, 7.94149-7.88387), (IH, d, 7.83335, 7.81698), (6H, m,7.71184-7.61582), (4H, m5 7.56625 -7.48845), (2H, t, 7.4.551 -7.37579), (IH, t, 7.19805 -7.16625), (IH, t, 7.15543 -7.12234), (3H, t, 7.10562, 7.07492), (2H, d, 7.02127 -7.00615), (IH, t, 6.84303 -6.81196), (IH, d, 6.62948, 6.61470) EI-MS : m/z 618(M+) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; for 0.5h; | General procedure: A solution of 3-bromo-10-phenylspiro[benzo[ij]tetraphene-7,9'-fluorene] (5.71 g, 10 mmol), tetrakis(triphenylphosphine)palladium(0) (0.59 g, 0.51 mmol), and naphthalene-1-boronic acid (1.72 g, 10 mmol) dissolved in THF (150 mL) was stirred in a double-necked flask for 30 min. Potassium carbonate (2 M, 150 mL) was added dropwise over 20 min. The resulting reaction mixture was refluxed overnight at 80C and then extracted with ethyl acetate and water. After the organic layer was evaporated with a rotary evaporator, the resulting powdery product was purified by column chromatography from dichloromethane/n-hexane (1/1) to give the yellow 1N-PSBTF crystalline product. 2N-PSBTF and NP-PSBTF were prepared using similar procedures described above. |
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; | (3-5) Synthesis of Compound 110; 1.6 g of Intermediate 12, 0.86 g of 4-(l -naphthalene)- 1-phenylboronic acid, 20 ml of tetrahydrofuran, 1 g of potassium carbonate and 10 ml of water were mixed in a 100 ml round-bottom flask with stirring. 0.2 g of tetrakis(triphenylphosphine)palladium(0) was added to the mixture, which was heated to 80 C . The reaction solution was cooled and filtered, and the precipitated crystals were washed with acetone and subjected to recrystalization with methylene chloride, to obtain 1.5 g of the title compound. 1H-NMR(CDCl3, 500MHz) (IH, d, 8.50970-8.49168), (IH, d, 8.42353, 8.4.794), (IH, d, 8.07996, 8.06194), (2H, d, 8.01643, 8.00113), (IH, d, 7.98321, 7.96542), (3H, m, 7.94593-7.89355), (IH, d, 7.84365, 7.82718), (5H, m, 7.69204-7.61719), (6H, d, 7.58142-7.47368), (4H, m, 7.41957-7.35884), (IH, t, 7.30467-7.27303), (5H, m, 7.16011-7.09383), (2H, d, 7.05529, 7.04019), (IH, d, 6.64619, 6.63128) EI-MS : m/z 695(M+) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; | (5-6) Synthesis of Compound 260; 1O g of Intermediate 16, 4.7 g of 4-(l -naphthalene)- 1-phenylboronic acid, 100 ml of tetrahydrofuran, 3.9 g of potassium carbonate and 40 ml of water were mixed in a 100 ml round-bottom flask with stirring. 1.1 g of tetrakis(triphenylphosphine)palladium(0) was added to the mixture, which was heated to 80 C . The reaction solution was cooled and filtered, and the precipitated crystals were washed with acetone and subjected to recrystalization with methylene chloride, to obtain 12 g of the title compound. 1H-NMR(CDCl3, 500MHz) lH(d, 8.48257-8.46562), lH(d, 8.40254-8.38596), lH(d, 8.05832-8.04220), 2H(d, 8.00324-7.98666), lH(d, 7.97954-7.96394), 3H(m, 94291-7.88471), lH(d, 7.86588-7.84936), 5H(m, 7.60124-7.61055), 6H(m, 7.56555-7.48242), 4H(m, 7.44577-7.38305), lH(t, 7.31357-7.29255), 4H(7.18356-7.12363), lH(d, 7.09144-7.07529), lH(d, 6.65264-6.63775), 3H(s, 2.68341) EI-MS : m/z 709(M+) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 60 - 80℃; for 1.5h;Inert atmosphere; | Step 1: Synthesis of 4'-(1-naphthyl)biphenyl-4-amine To a 50 mL three-neck flask were added 0.70 g (4 mmol) of 4-bromoaniline, 1.0 g (4 mmol) of 4-(1-naphthyl)phenylboronic acid, and 61.8 mg (0.2 mmol) of tris(o-tolyl)phosphine, and nitrogen substitution in the flask was carried out. To the mixture were added 14 mL of toluene, 6 mL of ethanol, and 4 mL of an aqueous solution of potassium carbonate (2 mol/L). The mixture was stirred to be degassed under a reduced pressure, and then the mixture was heated at 60 C., which was followed by addition of 11.9 mg (0.05 mmol) of palladium(II) acetate. This mixture was stirred at 80 C. for 1.5 hours. After the reaction, toluene and water were added to the mixture, the organic layer and the aqueous layer were separated from each other, and the aqueous layer was extracted twice with toluene. The obtained extract and the organic layer were combined, washed with brine, and dried with magnesium sulfate. The mixture was subjected to gravity filtration to remove magnesium sulfate, and the filtrate was concentrated to obtain an oily product. The oily product was subjected to suction filtration through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina, resulting in a filtrate. The filtrate obtained was concentrated to give 1.1 g of an oily substance which was a target substance in 95% yield. The synthetic scheme of 4'-(1-naphthyl)biphenyl-4-amine is shown in (B-1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In toluene; for 12h;Inert atmosphere; Reflux; | d. Preparation of Intermediate IInto a RBF (5000 mL) was added 9-bromoanthracene (100 g, 0.389 mol), 4-(Naphthalene-1-yl) Phenyl boronic acid (116 g, 0.469 mol), followed by the addition of toluene (3000 mL). The mixture was purged with N2 for 10 min. Then Na2CO3 (124 g, 1.167 mole) dissolved in the water (600 mL) was added. The mixture was continued to be purged with N2 for 10 min. A catalytic amount of Pd(PPh3)4 (2.3 g, 1.95 mmole) was added. The mixture was refluxed under N2 for 12 h. Cooled down the reaction mixture to 40 C., filtered, separated off water layer, and concentrate the organic phase to a final volume (150 ml) to obtain the solid of intermediate I (131 g, yield: 92%). C30H2O: El, MS m/z (%): 380 (100, M+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | Under an argon gas atmosphere, a mixture of 208.8 g (737.4 mmol) of 1-(4-bromophenyl)naphthalene and 2.1 L of dehydrated TI-IF was cooled down to minus 60 degree C. Then, 567 ml (884.9 mmol) of hexane solution of 1.56M n-butyllithium was dropped into the mixture while the mixture was being stirred. The reaction mixture was further stirred at minus 60 degrees for 2 hours. 416 g (2.21 mol) of triisopropylborate was dropped into the reaction mixture at minus 60 degrees C. The reaction mixture was then stirred at room temperature for 17 hours. The reaction mixture was added with aqueous solution of hydrochloric acid and stirred at room temperature for 1 hour. After the reaction, the reaction mixture was added with toluene, and aqueous phase thereof was eliminated. Then, organic phase thereof was dried with magnesium sulfate, and the solvent was distilled away under reduced pressure. By recrystallizing the obtained solid by toluene, 126 g of 4-(1-naphthyl)phenylboronic acid was obtained at an yield of 67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;tetrakis(triphenylphosphine)palladium (0); In tetrahydrofuran; water; toluene; | 3-a. Synthesis of 1-methoxy-4-{4-(naphthalen-1-yl)phenyl}naphthalene 1-Methoxy-4-{4-(naphthalen-1-yl)phenyl} was synthesized as follows. 1-Bromo-4-methoxynaphthalene (25 g, 0.105 mol), 4-(naphthalen-1-yl)phenylboronic acid (30.4 g, 0.137 mol), potassium carbonate (21.9 g, 0.16 mol), tetrakis(triphenylphosphine)palladium(0) (2.4 g, 0.01 mol), water (25 mL), tetrahydrofuran (75 mL) and toluene (75 mL) were stirred in a 250 mL round-bottom flask for 12 hours under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with ethyl acetate (300 mL) and water (1000 mL). The organic layer was dried with magnesium sulfate and concentrated under reduced pressure to obtain a solid. The solid was dissolved in hot toluene (400 mL) and then filtered. The filtrate was recrystallized in methanol (800 mL). The resultant solid was filtered and washed with hexane (300 mL) to obtain a product (20 g, 0.055 mol, 52.6%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With sodium carbonate;bis-triphenylphosphine-palladium(II) chloride; In water; acetonitrile; at 50℃;Inert atmosphere; Microwave irradiation; | Step 1: Synthesis of 3,5-Dimethyl-2-(4-naphthalen-1-yl-phenyl)pyrazine (abbreviation: Hdm1nppr)First, into a recovery flask equipped with a reflux pipe were placed 0.74 g of 2-chloro-3,5-dimethylpyrazine, 1.29 g of 4-(1-naphthyl)phenylboronic acid, 0.55 g of sodium carbonate, 0.024 g of bis(triphenylphosphine)palladium(II) dichloride (abbreviation: Pd(PPh3)2Cl2), 10 mL of water, and 10 mL of acetonitrile, and the air in the flask was replaced with argon. This reaction container was irradiated with microwaves (2.45 GHz, 100 W) for 15 minutes, so that heating was performed. Then, the reaction container was cooled to 50 C. or less. Water was added to the reaction solution, and the organic layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried with magnesium sulfate. The solution which had been dried was filtered. The solvent of this solution was distilled, and recrystallized using ethyl acetate, whereby Hdm1nppr, which is the pyrazine derivative to be produced, was obtained (as a white powder in 50% yield). Note that the microwave irradiation was performed using a microwave synthesis system (Discover, manufactured by CEM Corporation). The synthesis scheme of Step 1 is illustrated in the following (a-1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | Synthesis Example 1 This example illustrates the preparation of compound A1 .To a 500 ml_ round bottle flask were added 4,4'-dibromo-2,2'-dimethyl-1 ,1 '- binaphthyl (4.40 g, 10 mmol), 4-(naphthalen-1 -yl)phenylboronic acid (5.21 g, mmol), sodium carbonate (2 M, 30 ml_, 60 mmol), toluene (120 ml_) and Aliquat 336 (0.5 g). The mixture was system was stirred under nitrogen for 20 min. After which Tetrakis(triphenylphosphine) (462 mg, 0.4 mmol) was added and the mixture was stirred under nitrogen for another 15 min. The reaction was then heated in an oil bath at 95 C for 18 hour. After cooling, the mixture was filtered through a Celite pad to remove the insoluble materials. The solution was washed with diluted HCI (10%, 80 ml_), water (80 ml_) and saturated brine (50 ml_). The solvent was removed by rotary evaporation. The crude product was passed through a Silica gel column eluted with toluene. The product containing fractions were combined and the solvent was removed by rotary evaporation.Recrystallization from methylene chloride and acetonitrile gave the product as a white crystalline material. Yield, 2.6 g (38%). NMR spectra was consistent with the structure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; water;Reflux; | Example 14; This example illustrates the preparation of phenanthroline derivative Compound 19.To 4,7-dichlorophenanthroline (1.245 g, 0.0050 mol) and the 3-boronate ester of triphenylamine (4.1 g, 0.0111 mol), Pd2/DBA3 (0.3 g) and tricyclohexyl phosphine (0.21 g) in 30 ml 1,4-dioxane was added followed by 4.75 g K3PO4 in 15 ml of water and refluxed overnight. Cooled and performed water/Chloroform extraction of mixture. recrystallized from DCM/hexanes, then silica chromatography using CHCl3/MeOH concentrated heart cuts almost all the way and filtered for 1.6 grams Yield is 89%. The structure was confirmed by NMR analysis to be Compound 19: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; water; at 80 - 100℃;Inert atmosphere; | Example 2; Example 2 illustrates the preparation of phenanthroline derivative Compound 3, using Suzuki coupling of 2,9-dichloro-4,7-diphenyl-1,10-phenanthroline from Example 1 with 4-(1-naphthyl)-phenylboronic acid; To 2.0 g of dichlorobathophenanthroline (5 mM) from Example 1 was added 2.6 g (11 mM) boronic acid in a glove box. To this was added 0.15 g tris(dibenzylideneacetone)dipalladium (0) (?Pd2 DBA3?) (0.15 mM), 0.1 g tricyclohexylphosphine (0.35 mM), and 3.75 g potassium phosphate (17 mM), and all were dissolved into 30 mL dioxane and 15 mL water. This was mixed and heated in a glove box at 100 C. for 1 hr, then warmed gently (minimum rheostat setting) under nitrogen overnight. On reaching about 80 C. the mixture was a tan brown slurry which slowly became clear brown with a dense precipitate. As the solution refluxed (air condensor) a white fibrous precipitate formed. This was cooled and the white fibers were filtered from the dioxane after adding additional water. The fibers were dissolved into chloroform and then evaporated and precipitated in toluene by adding methanol, as off white powder. This was collected by filtration and washed well with methanol to isolate 2.75 g of Compound 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 85℃; for 13h;Inert atmosphere; | Example 7; In this example, an example in which 3,6-bis-[4-(1-naphthyl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: NP2PC) represented by Structural Formula (112) in Embodiment 1 is manufactured will be described. In a 200-mL three-neck flask, a mixture of 2.0 g (5.0 mmol) of 3,6-dibromo-9-phenyl-9H-carbazole, 2.7 g (11 mmol) of 4-(1-naphthyl)phenylboronic acid, 100 mg (0.5 mmol) of palladium(II) acetate, 41 mg (0.1 mmol) of tri(o-tolyl)phosphine, 20 mL of toluene, 2 mL of ethanol, and 30 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 85° C. for 13 hours to be reacted.After the reaction, 150 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=1:4) was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and acetone and methanol were added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 2.2 g of white powder that was an objective substance in a yield of 69percent. The reaction scheme of the synthesis method is shown in (F7-1). The Rf values of the objective substance and 3,6-dibromo-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)=7.45-7.68 (m, 19H), 8.02 (dd, J=2.1 Hz, 9.0 Hz, 2H), 7.87-7.95 (m, 8H), 8.05 (d, J=7.8 Hz, 2H), 8.55 (d, J=1.5 Hz, 2H).FIGS. 26A and 26B are 1H NMR charts. Note that FIG. 26B is a chart showing an enlarged part of FIG. 26A in the range of 7.0 ppm to 9.0 ppm. The measurement results confirmed that NP2PC that was the objective substance was able to be obtained.FIG. 27A shows an absorption spectrum of NP2PC in a toluene solution of NP2PC, and FIG. 27B shows an emission spectrum thereof. FIG. 28A shows an absorption spectrum of a thin film of NP2PC, and FIG. 28B shows an emission spectrum thereof. The absorption spectrum was measured with a UV-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. 27A show the absorption spectrum of NP2PC in the solution of NP2PC which was obtained by subtracting the absorption spectra of the quartz cell and toluene put therein, and FIG. 28A shows the absorption spectrum of the thin film which was obtained by subtracting the absorption spectrum of the quartz substrate. In FIGS. 27A and 27B and FIGS. 28A and 28B, 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 314 nm, and the maximum emission wavelength was 392 nm (excitation wavelength: 310 nm). In the case of the thin film, the absorption peak was observed at around 314 nm, and the maximum emission wavelength was 404 nm (excitation wavelength: 315 nm).The absorption spectrum showed that NP2PC described in this example is a material having weak absorption of light in the visible region. In addition, the emission spectrum shows that NP2PC exhibits blue-violet emission.Further, the thermophysical property was examined with a differential scanning calorimeter (DSC). The measurement result showed that the melting point is 269° C. In addition, glass transition and a crystallization peak were not observed; thus, it was found that NP2PC is a substance which is difficult to be crystallized. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 85℃; for 9h;Inert atmosphere; | Synthesis Example 1; In a 200-mL three-neck flask, a mixture of 5.0 g (15.5 mmol) of 3-bromo-9-phenyl-9H-carbazole, 4.2 g (17.1 mmol) of 4-(1-naphthyl)-phenylboronic acid, 38.4 mg (0.2 mmol) of palladium(II) acetate, 104 mg (0.3 mmol) of tris(2-methylphenyl)phosphine, 50 mL of toluene, 5 mL of ethanol, and 30 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 85 C. for 9 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 (Catalog No. 540-00135, produced by Wako Pure Chemical Industries, Ltd.), alumina (neutral, produced by Merck Ltd), and Celite (Catalog No. 531-16855, produced by Wako Pure Chemical Industries, Ltd.). 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=1:4) was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and methanol was added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 6.24 g of white powder that was an objective substance in a yield of 90%. The reaction scheme of Synthesis Example 1 above is shown in (F1-1). The Rf values of the objective substance and 3-bromo-9-phenyl-9H-carbazole were respectively 0.42 and 0.58, which were obtained by silica gel thin layer chromatography (TLC) (with a developing solvent of ethyl acetate and hexane in a 1:10 ratio).The compound obtained in Synthesis Example 1 was examined by a nuclear magnetic resonance (NMR) method. The measurement data are shown below.1H NMR (CDCl3, 300 MHz): delta (ppm)=7.30-7.35 (m, 1H), 7.44-7.67 (m, 14H), 7.76 (dd, J=8.7 Hz, 1.8 Hz, 1H), 7.84-7.95 (m, 4H), 8.04 (d, J=7.8, 1H), 8.23 (d, J=7.8, 1H), 8.46 (d, J=1.5, 1H).FIGS. 7A and 7B are 1H NMR charts. Note that FIG. 7B is a chart showing an enlarged part of FIG. 7A in the range of 7.0 ppm to 9.0 ppm. The measurement results confirmed that 3-[4-(1-naphthyl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: PCPN) that was the objective substance was able to be obtained. |
90% | With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 85℃; for 9h;Inert atmosphere; | In a 200 mL three-neck flask, a mixture of 5.0 g (15.5 mmol) of 3-bromo-9-phenyl-9H-carbazole, 4.2 g (17.1 mmol) of 4-(1-naphthyl)-phenylboronic acid, 38.4 mg (0.2 mmol) of palladium(II) acetate, 104 mg (0.3 mmol) of tri(ortho-tolyl)phosphine, 50 mL of toluene, 5 mL of ethanol, and 30 mL of a 2 mol/L aqueous potassium carbonate solution was degassed while being stirred under reduced pressure, and reacted by being stirred and heated at 85 C. for 9 hours under a nitrogen atmosphere. (0523) After the reaction, 500 mL of toluene was added to this reaction mixture solution, and the organic layer of this mixture solution was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), alumina, 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 (toluene:hexane=1:4) was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and methanol was added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 6.24 g of a white powder in a yield of 90%, which was the object of the synthesis. (0524) This compound was identified as 3-[4-(1-naphthyl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: PCPN), which was the object of the synthesis, by nuclear magnetic resonance (1H-NMR) spectroscopy. (0525) 1H NMR data of the obtained substance are as follows: 1H NMR (CDCl3, 300 MHz): delta (ppm)=7.30-7.35 (m, 1H), 7.44-7.67 (m, 14H), 7.76 (dd, J=8.7 Hz, 1.8 Hz, 1H), 7.84-7.95 (m, 4H), 8.04 (d, J=7.8, 1H), 8.23 (d, J=7.8, 1H), 8.46 (d, J=1.5, 1H). |
90% | With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 85℃; for 9h;Inert atmosphere; | In a 200 mL three-necked flask3-bromo-9-phenyl-9H-carbazole(11.5 mmol) of 4- (1-naphthalene) phenylboronic acid, 38.4 mg (0.2 mmol) of palladium (II) acetate, 104 mg (0.3 mmol) of tris (o-tolyl) , 50 mL of toluene, 5 mL of ethanol and 2 ml of a 20 mol / L aqueous solution of potassium carbonate were degassed with stirring under reduced pressure, and then stirred at 85 C for 9 hours under nitrogen atmosphere to cause reaction.After the reaction, 500 mL of toluene was added to the reaction mixture, and the organic layer of the mixed solution was treated with magnesium silicate (Japan Wako Pure Chemical Industries, Ltd., catalog number: 540-00135), alumina and diatomaceous earth (Manufactured by Wako Pure Chemical Industries, Ltd., catalog number: 531-16855). The resulting filtrate was washed with water and magnesium sulfate was added to adsorb moisture. The suspension was filtered to obtain a filtrate. The resulting filtrate was concentrated and then purified by silica gel column chromatography. In this case, as a developing solvent for silica gel column chromatography, a mixed solvent of toluene and hexane (toluene: hexane = 1: 4) was used. The resulting rinsing was concentrated, and methanol was added and ultrasonic waves were applied, followed by recrystallization, and a white powder of the desired product was obtained at a yield of 6.24 g and a yield of 90%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 100℃; for 7h;Inert atmosphere; | Step 2: Synthesis Method of 9-(1-naphthyl)-3-[4-(1-naphthyl)-phenyl]-9H-carbazole (abbreviation: NCPN)In a 200-mL three-neck flask, a mixture of 5.0 g (13 mmol) of 3-bromo-9-(1-naphthyl)-9H-carbazole, 3.7 g (15 mmol) of 4-(1-naphthyl)phenylboronic acid, 34 mg (0.2 mmol) of palladium(II) acetate, 91 mg (0.3 mmol) of tris(2-methylphenyl)phosphine, 50 mL of toluene, 5 mL of ethanol, and 30 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 1 hour to be reacted. Furthermore, 334 mg (1.35 mmol) of 4-(1-naphthyl)phenylboronic acid, 15.0 mg (0.07 mmol) of palladium(II) acetate, and 45 mg (0.15 mmol) of tris(2-methylphenyl)phosphine were added, and the mixture was heated and stirred in a nitrogen atmosphere at 100 C. for 6 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=1:4) 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 5.4 g of white powder that was an objective substance in a yield of 82%. The reaction scheme of Step 2 is shown in (F6-2). The Rf values of the objective substance and 3-bromo-9-(1-naphthyl)-9H-carbazole were respectively 0.25 and 0.53 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)=7.04 (dd, J=6.3 Hz, 1.5 Hz, 1H), 7.11 (d, J=8.4 Hz, 1H), 7.30-7.70 (m, 14H), 7.83-7.94 (m, 4H), 8.02-8.07 (m, 3H), 8.28 (dd, J=6.3 Hz, 2.4 Hz, 1H), 8.52 (d, J=1.5 Hz, 1H).FIGS. 23A and 23B are 1H NMR charts. Note that FIG. 23B is a chart showing an enlarged part of FIG. 23A in the range of 6.0 ppm to 9.0 ppm. The measurement results confirmed that NCPN that was the objective substance was able to be obtained.FIG. 24A shows an absorption spectrum of NCPN in a toluene solution of NCPN, and FIG. 24B shows an emission spectrum thereof. FIG. 25A shows an absorption spectrum of a thin film of NCPN, and FIG. 25B shows an emission spectrum thereof. The absorption spectrum was measured with a UV-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. 24A show the absorption spectrum of NCPN in the solution of NCPN which was obtained by subtracting the absorption spectra of the quartz cell and toluene put therein, and FIG. 25A shows the absorption spectrum of the thin film which was obtained by subtracting the absorption spectrum of the quartz substrate. In FIGS. 24A and 24B and FIGS. 25A and 25B, 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 300 nm, and the maximum emission wavelength was 388 nm (excitation wavelength: 300 nm). In the case of the thin film, the absorption peak was observed at around 322 nm, and the maximum emission wavelength was 397 nm (excitation wavelength: 328 nm).The absorption spectrum showed that NCPN described in this example is a material having weak absorption of light in the visible region. In addition, the emission spectrum shows that NCPN exhibits blue-violet emission. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.5% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 1.5h;Inert atmosphere; Reflux; | In a 1000ml three-necked flask, with mechanical stirring, Ar gas protection, 11.7g of 9,10-dibromoanthracene (molecular weight(0.35, 0.035 mol), 8.7 g of 4- (1-naphthyl) benzeneboronic acid (molecular weight: 248,0.035 mol), and Pd (PPh3)1.8 g (molecular weight 1154, 0.001556 mol), 120 ml (2M) of sodium carbonate aqueous solution, 250 ml of toluene and 150 ml of ethanol. The mixture was stirred and refluxed, and the reaction was monitored by TLC. The reaction was complete after 1.5 hrs of reaction. Cooled, separated, evaporated to dryness, the product was isolated by column chromatography, drenchedLotion with 1: 5 ethyl acetate: petroleum ether gave 15.8 g of a white solid9- (4- (1-naphthyl) phenyl) -10-bromoanthracene (AN1), product molecular weight 458, purity 98.7%, yield: 97.5%. |
9,10-Dibromoanthracene (10 g, 0.03 mol), tetrakis(triphenylphosphine)palladium(0) (1.72 g, 1.49 mmol) and <strong>[870774-25-7]4-(naphthalene-1-yl)phenylboronic acid</strong> (7.4 g, 0.03 mol) were dissolved in THF (350 mL) in a double-necked flask and stirred for 30 min. Then, potassium carbonate (2 M, 200 mL) was added dropwise over 20 min. The mixture was degassed and refluxed overnight at 80 C under a nitrogen atmosphere. After being cooled, the solvent was evaporated under vacuum, and the product was extracted with ethyl acetate and water. The ethyl acetate solution was washed with water and dried with MgSO4. Evaporation of the solvent, followed by column chromatography using n-hexane on a silica gel, yielded a white yellow product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With acetylacetonato(1,5-cyclooctadiene)rhodium(I); In 1,4-dioxane; water; at 100℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: Zerumbone (1) (1 equiv), boronic acid 2a (2 equiv) and [Rh(acac)(cod)] (10 mol %) were added to a Schlenk tube and the contents degassed. The mixture was dissolved in 1,4-dioxane-H2O (3:1, 2 mL) and stirred at 100 C for 12-24 h under an Ar atm. After completion of the reaction (as indicated by TLC analysis), the solvent was evaporated in vacuo. The residue was purified by silica gel column chromatography (EtOAc-hexane) to afford the product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 12h;Inert atmosphere; | This example shows a method of synthesizing 2-[4-(naphthalen-1-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: NPDBq) represented by the following structural formula (101). In a 200 mL three-neck flask, a mixture of 2.7 g (10 mmol) of 2-chlorodibenzo[f,h]quinoxaline, 2.7 g (11 mmol) of 4-(1-naphthyl)phenylboronic acid, 23 mg (0.1 mmol) of palladium(II) acetate, 91 mg (0.3 mmol) of tri(ortho-tolyl)phosphine, 43 mL of toluene, 4 mL of ethanol, and 14 mL of an aqueous solution of potassium carbonate (2 mol/L) was degassed while being stirred under reduced pressure, and was then reacted by being heated and stirred under a nitrogen atmosphere at 80 C. for 12 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 resulting filtrate was concentrated, followed by purification using 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 methanol was added thereto. The mixture was irradiated with supersonic and then recrystallized, so that the objective substance was obtained as 3.0 g of yellow powder in a yield of 69%. The Rf values of the objective substance and 2-chlorodibenzo[f,h]quinoxaline were respectively 0.33 and 0.55, which were found by silica gel thin layer chromatography (TLC) (with a developing solvent of ethyl acetate and hexane in a ratio of 1:10). A nuclear magnetic resonance (NMR) method identified this compound as 2-[4-(naphthalen-1-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: NPDBq), which was the objective substance. 1H NMR data of the obtained substance are as follows: 1H NMR (CDCl3, 300 MHz): delta (ppm)=7.47-7.62 (m, 4H), 7.75-8.03 (m, 9H), 8.50 (d, J=8.3 Hz, 2H), 8.68 (d, J=7.3 Hz, 2H), 9.27 (d, J=7.8 Hz, 1H), 9.46-9.50 (m, 2H). The 1H NMR chart is shown in FIGS. 10A and 10B. Note that FIG. 10B is a chart showing an enlarged part of FIG. 10A in the range of 7.00 ppm to 9.60 ppm. Further, FIG. 11A shows an absorption spectrum of a toluene solution of NPDBq, and FIG. 11B shows an emission spectrum thereof. In addition, FIG. 12A shows the absorption spectrum of a thin film of NPDBq, and FIG. 12B shows the emission spectrum thereof. The measurement of the absorption spectrum was conducted by using a UV-visible spectrophotometer (V-550, produced by JASCO Corporation). The measurements were performed with samples prepared in such a manner that the solution was put in a quartz cell and the thin film was obtained by evaporation onto a quartz substrate. The absorption spectrum of the solution was obtained by subtracting the absorption spectra of quartz and toluene from the spectrum of the solution, and the absorption spectrum of the thin film was obtained by subtracting the absorption spectrum of a quartz substrate from the spectrum of the thin film. In FIGS. 11A and 11B and FIGS. 12A and 12B, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). In the case of the toluene solution, an absorption peak was observed at around 377 nm, and an emission wavelength peak was 398 nm. In the case of the thin film, an absorption peak was observed at around 385 nm, and emission wavelength peaks were 429 nm, 445 nm, and 488 nm (at an excitation wavelength of 378 nm). Electrochemical characteristics of a thin film of NPDBq were measured (the measuring instrument was AC-2 produced by Riken Keiki, Co., Ltd.). Note that the measurement of electrochemical characteristics of the thin film was carried out as follows. The value of the HOMO level was obtained by conversion of the value of the ionization potential measured with a photoelectron spectrometer (AC-2, produced by Riken Keiki Co., Ltd.) in the air into a negative value. The value of the LUMO level was obtained in such a manner that the absorption edge, which was obtained from Tauc plot with an assumption of direct transition using data on the absorption spectrum of the thin film, was regarded as an optical energy gap and was added to the value of the HOMO level. From the results of the measurement of electrochemical characteristics of the thin film, the HOMO level, the LUMO level, and the band gap (Bg) were found to be -5.84 eV, -2.78 eV, and 3.06 eV, respectively. The above results reveal that NPDBq has a relatively deep HOMO level, a relatively shallow LUMO level, and a relatively wide Bg. Electrochemical characteristics of an NPDBq solution were also measured. As a measuring... |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2.6g | With potassium phosphate; bis(dibenzylideneacetone)-palladium(0); tricyclohexylphosphine; In ethanol; water; toluene; for 6.5h;Inert atmosphere; Reflux; | Under the nitrogen atmosphere, 7-(10-(naphthalen-1-yl)anthracen-9-yl)naphthalen-2-yl trifluoromethane sulfonate (3.0 g) as the fifth intermediate compound, <strong>[870774-25-7](4-(naphthalen-1-yl)phenyl)boronic acid</strong> (1.9 g), bis(dibenzylideneacetone)palladium (0) (Pd(dba)2) (0.03 g), tricyclohexyl phosphine (0.03 g), potassium phosphate (2.2 g) and a mixture solvent (22 ml) of toluene, ethanol, and water (toluene/ethanol/water = 9/1/1 (volume ratio)) were added to a flask and refluxed for 6.5 hours. Once the heating is completed, the reaction solution was cooled to room temperature and added with methanol. The precipitates were collected by suction filtration. The obtained solid was washed with water followed by methanol, and washed further with ethyl acetate. The obtained crude product was dissolved in toluene, and colored components were removed by passing through a silica gel short column. The solvent was distilled off under reduced pressure. The obtained oily phase substance was added with ethyl acetate and the precipitated products were collected by suction filtration to give 9-(naphthalen-1-yl)-10-(7-(naphthalen-1-yl)phenyl)naphthalen-2-yl)anthracene (2.6 g) as the target compound represented by Formula (1-21). The scheme is illustrated in the following 'Reaction 9'. According to NMR measurement, structure of the target compound (1-21) was determined. 1H-NMR (CDCl3) : delta = 8.24 (d, 1H), 8.12-8.19 (m, 3H), 8.09 (d, 1H), 8.03 (m, 2H), 7.99 (dd, 1H), 7.88-7.96 (m, 4H), 7.83 (d, 2H), 7.64-7.76 (m, 4H), 7.62 (d, 1H), 7.46-7.59 (m, 7H), 7.31-7.35 (m, 2H), 7.20-7.28 (m, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With potassium phosphate; [5-(3-butylbenzimidazol-2-yliden-1-yl)-25,26,27,28-tetrapropyloxy calix[4]arene] (pyridine) palladium(II) dibromide; In 1,4-dioxane; at 100℃; for 24h;Inert atmosphere; | General procedure: In air, potassium phosphate (3mmol, 0.636g), catalyst 1 (0.08mol%, 0.0009g) and arylboronic acid (2mmol) were weighed into a 50mL glass vial that was sealed with a septum and purged with N2 (3×). Dioxane (1mL) was then injected via syringe followed by the aryl bromide (1mmol) (if liquid). If the aryl bromide was a solid, it was introduced into the vial prior to purging with N2. At this time, the reaction stirred for 24h at 100C. The reaction mixture was concentrated in vacuo and directly purified via silica gel flash chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.2% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 4.5h;Inert atmosphere; Reflux; | The 4,6-dibromo-2-{4-(pyridin-3-yl)phenyl}-2H-benzotriazole synthesized in Example 7 1,5 g, 4-(Naphthalen-1-yl)phenylboronic acid 2.2 g, 2M Potassium carbonate aqueous solution 5.3 ml, Toluene 30 ml, Ethanol 6 ml, and Tetrakistriphenylphosphine palladium (0) 0.1 g, were put into the reaction vessel purged with nitrogen, and were heated and refluxed for 4.5 hours with stirring. [0143] The organic layer was picked up by the separating operation, concentrated under a reduced pressure and was refined by the column chromatography to obtain 2.0 g of a yellow powder of 4,6-bis{4-(naphthalen-1-yl)phenyl}-2-{4-(pyridin-3-yl)phenyl}-2H-benzotriazole (compound 66) (yield, 84.2%). [0144] The obtained yellow powder was identified for its structure by the NMR. Fig. 12 shows the results of the 1H-NMR measurement. [0145] The following 32 signals of hydrogen were detected by the 1H-NMR (CDCl3). delta (ppm) = 8.62 (1H) 8.61 (1H) 8.36 (2H) 8.22 (1H) 8.11 (1H) 8.08 (1H) 8.02 (1H) 7.96 - 7.83 (8H) 7.81 (2H) 7.75 (2H) 7.68 (2H) 7.59 - 7.49 (10H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With potassium carbonate; triphenylphosphine; palladium dichloride; at 70℃; for 24h;Sealed tube; | General procedure: A mixture of dihaloarene (0.4 mmol), arylboronicacid (0.4 mmol), K2CO3 (0.8 mmol), PdCl2 (7 mol %),PPh3 (15 mol %), and PEG-400 (2 mL) in a sealed tubewas stirred in air at 70C for the desired time until completeconsumption of starting material as monitored byTLC. After that the mixture was poured into ethyl acetate,then washed with water, extracted with ethyl acetate, driedby anhydrous Na2SO4, then fi ltered and evaporated undervacuum, the residue was purifi ed by fl ash column chromatography(petroleum ether or petroleum ether/ethylacetate) to afford the corresponding coupling products |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In methanol; water; toluene; for 12h;Inert atmosphere; Reflux; | Under the protection of nitrogen to 100 ml to three-opening bottle 4.78g (0.01mol) adding compound D, 2.48g (0.01mol) 4 - (1-naphthyl) phenylboronic acid, 0.23g (2×10-4mol) Pd (PPh3)4, 4.14g (0.03mol) anhydrous potassium carbonate, 30 ml toluene, 30 ml methanol, 10 ml water, reflux reaction 12h, is dropped to the room temperature by adding 50 ml ethyl acetate, 50 ml water, extracting the liquid, washing the organic phase, the organic phase after turns on lathe does, through the column chromatography separation to obtain the solid 5.12g intermediate, yield 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In methanol; water; toluene; for 12h;Reflux; | The 4.26g (0.008mol) in intermediate by adding three-mouth bottle, then adding 1.98g (0.008mol) 4-1-naphthyl) phenylboronic acid, 0.23g (2×10-4mol) Pd (PPh3)4, 4.14g (0.03mol) anhydrous potassium carbonate, 30 ml toluene, 30 ml methanol, 10 ml water, reflux reaction 12h, directly to the room temperature filtration, the filter cake after filtering for respectively 50 ml ethanol and 50 ml water, water is pumped into the filter cake after the flask with 500 ml dichloromethane dissolved, by silica-gel column, eluant turns on lathe does, to obtain white solid A1 4.66g, yield 84%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 4.083h;Inert atmosphere; Reflux; | Under a nitrogen atmosphere, the reaction trifluoromethanesulfonic acid 13 is obtained as in the first intermediate compound 9 7- (10-phenyl anthracene-9-yl) naphthalene-2-yl ester 7.0g, (4 - (naphthalen-1-yl) phenyl) boronic acid 3.94g, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh3)4) 0.31 g, potassium phosphate was 5.62 g, and a mixed solvent of toluene and 53ml of ethanol (toluene / ethanol = 4/1 (volume ratio)) was added to the flask and stirred for 5 minutes.Thereafter, 5ml water was added and refluxed for 4 hours.After heating the reaction solution was cooled, add methanol 50ml, and filtered the precipitate.Furthermore, the use of methanol and water washing of the precipitate to obtain a crude product as a target by the formula (1-21) a compound represented by the.The crude products were purified by silica gel short column chromatography (solvent: toluene), the use of a mixed solvent of methanol and ethyl acetate (toluene / ethyl acetate = 1/5 (volume ratio)) was recrystallized, and then purified by sublimation, i.e., to obtain the objective compound 9- (7- (4- (naphthalen-1-yl) phenyl) naphthalen-2-yl) -10-phenylanthracene 5.95 g of the (yield: 77%).Which processes are shown in "Reaction 17." |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 120℃; for 8h; | General procedure: 8-Bromo- [1,2,4] triazolo [1,5-a] pyridin-2-amine 10 g (46.9 mmol) and 9-phenyl-3- (4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl) to -9H-carbazole 19.1 g (51.6 mmol) was added to 200 mL toluene, 50 mL EtOH, 50 mL H2O. Pd(PPh3)4 2.7 g (2.3 mmol), Na2CO3 14.9 g (141 mmol) was added at 8 hours after 120 was heated to reflux. It was cooled to room temperature and stop the reaction with 300 mL of purified water to the reaction solution. Extract the mixture with E.A 500 mL, and washed with distilled water. The resulting organic layer was dried over anhydrous MgSO4, was evaporated under reduced pressure, and purified by silica gel column chromatography to give the title compound 13.0 g (yield 74%).Reaction with Preparation Example 1 and 4 - (naphthalen-1-yl) phenylboronic acid with the exception of that, the Preparation Example 2 and the same procedure carried out by the desired compound 12.8 g (yield 81%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2.16 g | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene;Inert atmosphere; Reflux; | This example illustrates the preparation of a compound having Formula I, N3,N9-bis(3-(9H-carbazol-9-yl)phenyl)-7,7-dimethyl-N3,N9- diphen -7H-benzo[de]anthracene-3,9-diamine, which is Compound 1-1 . Pd(PPh3)4, Aliquat 336 Na2C03 H20-Toluene Compound 1-1 To a 250 mL mL three-necked round bottom flask were added 3,9- dibromo-7,7-dimethyl-7H-benzo[de]anthracene (2.85 g, 7.08 mmol), (4- (naphthalen-1 -yl)phenyl)boronic acid (3.69 g, 14.88 mmol), toluene (100 ml), aqueous sodium carbonate (2 M, 22 ml_) and Aliquat 336 (1.00g). With stirring, the system was purged with nitrogen for 20 min. Pd(PPh3)4 (245mg, 0.21 mmol), was added and the system was purged for another 10 min. The reaction was stirred and refluxed under nitrogen overnight. During the time, some solid was formed. After cooling to ambient temperature, the solid was filtered off, dried in air and washed with DCM to give 3.5 g of crude product in 99.32% purity by UPLC analysis. The material was dissolved in chloroform (200 ml_) and adsorbed onto Celite (22g) and dried in the vacuum oven overnight. This was separated on preparative chromatography (CombiFlash) eluted with chloroform/hexanes gradient. Fractions were identified by UPLC analysis and the solvent was evaporated. The product was recrystallized from toluene /ethanol under heating, collected, rinsed with toluene/ethanol (3/2), and dried in the vacuum oven at 50 C for 5 hours. The desired product was obtained as a white powder, 1 .15g in >99.9% purity by UPLC analysis, and 1.01 g was recovered in 99.85% purity, The structure of the product was confirmed by NMR analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50.4% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In N,N-dimethyl-formamide; at 90℃; for 9h;Inert atmosphere; | (S)-Ethyl 2-(tert-butoxy)-2-(4-(4, 4-dimethylpiperidin-l-yl)-2, 6-dimethyl-5-(4- (naphthalen-l-yl)phenyl)pyridin-3-yl)acetate: A mixture of (S)-ethyl 2-(5-bromo-4-(4,4- dimethylpiperidin-l-yl)-2,6-dimethylpyridin-3-yl)-2-(tert-butoxy)acetate (0.02 g, 0.044 mmol), (4-(naphthalen-l-yl)phenyl)boronic acid (0.022 g, 0.088 mmol) and 2M Na2C03 (0.055 ml, 0.110 mmol) in DMF (1 mL) was degassed for 3 min. Then, Pd(Ph3P)4 (5.07 mg, 4.39 mupiiotaomicron) was degassed for 1 min and placed in a pre-heated oil bath at 90 C. After 9 h, cooled and purified by prep-HPLC to afford (S)-ethyl 2-(tert-butoxy)-2-(4-(4,4- dimethylpiperidin-l-yl)-2,6-dimethyl-5-(4-(naphthalen-l-yl)phenyl)pyridin-3-yl)acetate (0.0128 g, 0.022 mmol, 50.4 % yield) as brown paste. LCMS(M+H) = 579.4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.3% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; for 4h;Inert atmosphere; Reflux; | A mixture of 2-bromo-12- (4-bromopyridin-2-yl) benzo [b] acridine (molecular weight 464, 0.02 mol), 4- (naphthalene-1- Yl) phenylboronic acid (11.0 g) (Molecular weight: 248, 0.044 mol), Pd (PPh3) 4 using 2.31 g (molecular weight 1154, 0.002 mol), sodium carbonate 150 ml (2M), toluene 150 ml, ethanol 150 ml. After the addition of argon, reflux was carried out and the reaction was monitored by TLC. After 4 hours, the reaction was complete, the organic layer was separated, evaporated to dryness, separated by column chromatography and eluted with ethyl acetate / petroleum ether to give 12.6 g of the formula (31) Compound, molecular weight 710, yield 88.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; for 12h;Reflux; Inert atmosphere; | Under nitrogen protection,A mixture of intermediate c (4.76 g, 0.01 mol) and 4- (1-naphthyl) phenylboronic acid (2.98 g, 0.012 mmol) was added to 100 mL of toluene,The catalyst was then charged with tetraphenylphenylphosphine palladium (0.12 g, 0.1 mmol) and potassium carbonate(4.14 g, 0.03 mol) in water.The system was heated to reflux for 12 hours,Natural cooling to room temperature after liquid separation, steaming to get crude.The crude product was chromatographed on a neutral alumina column,The eluent was separated by purification with V dichloromethane: V ethyl acetate = 1: 3,Get white powder,The obtained powder was further sublimed and purified by a chemical vapor deposition system,Sublimation temperature 360 ,To obtain a compoundC03, yield 56%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62.7% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 12h;Inert atmosphere; Reflux; | 250 ml of a four-necked flask under nitrogen, O. Olmol intermediate I, 0.0105 mol 4-alpha-naphthyl) benzene boronAcid, 0.05 g pd (pph3) 4 (tetraphenylphenylphosphine palladium), 025piomicron1 sodium carbonate, toluene, ethanol, water 60ml, heated reflux12 hours, the reaction is complete; natural cooling, filtration, the filtrate steamed, silica gel column, with toluene: ethanol = 1: 2 (volume ratio)The solvent was beaten and recrystallized to give a white solid with a purity of 97.8% and a yield of 62.7%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
11 g | With palladium diacetate; potassium carbonate; lithium bromide; tri tert-butylphosphoniumtetrafluoroborate; In water; toluene; at 85 - 88℃; for 5h;Inert atmosphere; | The compound 8-j (14.2 g, 25.0 mmol) obtained in step (10) (4- (naphthalen-1-yl) phenyl) boronic acid (7.4 g, 30 mmol) Potassium carbonate (6.9 g, 50 mmol), Water 50g, Lithium bromide (2.2 g, 25 mmol) And 150 g of toluene, Under nitrogen protection, To the system was added palladium acetate (113 mg, 0.5 mmol) And p (t-Bu) 3 · HBF4 (290 mg, 1.0 mmol) Reaction at 85-88 C for 5.0 hours while TLC tracks the progress of the reaction. After completion of the reaction, the system was triturated, washed with water, removed from the organic phase under reduced pressure to no fractions, and then the residue was recrystallized with a toluene ethanol mixture to obtain 14.2 g of compound 8, further crude product in a chemical vapor deposition system In 360 C sublimation to give 11.0 g of a white solid powder in a yield of 58.20% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; at 110℃; for 6h;Inert atmosphere; | Under N2 protection,To a 50 mL three-necked flask was added 0.50 g of the reduced product 3,5-diamino-4'-bromobenzophenone (1.72 mmol) obtained in Step II, 0.51 g of 4- (alpha-naphthyl) phenylboronic acid (2.06 mmol), 0.0198 g Pd (PPh3) 4 (0.017 mmol), 0.73 g Na2CO3 (6.87 mmol), 15 mL of toluene and 7.5 mL of distilled water, and the temperature was raised to 110C.6h, the reaction process a large number of bubbles produced, and TLC point board to track the reaction, until the reaction is completely cooled to room temperature, decompression pumpingFilter cake and filtrate, filter cake washed with toluene 2 times, the filtrate separated with a separatory funnel, take the liquid layer with toluene extraction 2 times,The organic layers were extracted twice, washed overnight with anhydrous MgSO4, filtered under reduced pressure and the filter cake was rinsed twice with toluene and the tolueneThe green solid was obtained and combined with the filter cake to give a crude product which was purified under N2 under a volume ratio of ethanol: water = 9: 1 as solvent.The resulting dark green solid was 3,5-diamino-4 '- (alpha-naphthyl) phenylbenzophenone in a yield of 86% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.4% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 1.5h;Inert atmosphere; Reflux; | In a 1000ml three bottles, with mechanical mixing,Ar gas protection,And 13.5 g (molecular weight: 384, 0.035 mol) of 6,12-dibromo Chrysene,4- (1-naphthyl) benzene boronic acid 8.7 g (molecular weight 248, 0.035 mol)Catalyst Pd (PPh3) 4 dosage1.8 g (molecular weight 1154, 0.001556 mol),Aqueous sodium carbonate solution 120 ml (2M)Toluene 250ml, ethanol 150ml.Stirring reflux, monitoring reaction with TLC,After reaction for 1.5 hs, the reaction was complete.Cooling, separating, drying, separating the product by column chromatography, eluting with 1: 5 ethyl acetate: petroleum ether,To give 17.5 g of a pale yellow solid 6- (4- (1-naphthyl) phenyl) -12-bromo Chrysene having a molecular weight of 508,Purity 97.2%, yield: 95.4%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 3.5h;Inert atmosphere; Reflux; | The synthesis process is divided into three steps,The first step is the same as in the first step of Example 1,Except that the starting material 3-bromo-6-chloroimidazo [1,2-A] pyrimidine was used3-bromo-8-chlorimidazo [1,2-A] pyrazine instead,The remaining reagents unchanged,To give 8-chloroimidazo [1,2-A] pyrazine-3-boronic acid pinacol ester;The second step is the same as the second step of the first embodiment,Except that one of the starting materials, 6-chloroimidazo [1,2-A] pyrimidine-3-borate,8-chloroimidazo [1,2-A] pyrazine-3-boronic acid pinacol ester instead of starting material,To obtain the corresponding dichloro intermediate;The third step is the same as the second step of Example 1,Except that one of the raw materials, 6,12-dibromo Chrysene, was replaced with the dichloro intermediate synthesized in the second step,6-chloroimidazo [1,2-A] pyrimidine-3-borate4- (1-naphthyl) benzene boronic acid instead of starting materials,The remaining reagents unchanged,To give the yellow solid compound 9.The second step,In a 1000ml three bottles,With mechanical mixing, Ar gas protection,5,76 g of 6,12-dibromo Chrysene (molecular weight: 384, 0.015 mol) was added,The first step of the synthesis of 6-chloroimidazo [1,2-A] pyrimidine-3-boronic acid cleanyl ester 9.21g(Molecular weight: 279, 0.033 mol),The catalyst Pd (PPh3) 4 was used in an amount of 1.8 g (molecular weight 1154, 0.001556 mol)Aqueous sodium carbonate solution 120 ml (2M)Toluene 300ml, ethanol 150ml.Stirring reflux, with TLC monitoring reaction, a total reaction after 3.5hs complete reaction.Cooled, separated, evaporated to dryness, separated by column chromatography, eluent with 1: 1 ethyl acetate: petroleum ether,To give 6.7 g of a yellow solid compound having a purity of 97.0% and a yield of 81.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 3.5h;Inert atmosphere; Reflux; | The synthesis process is divided into three steps,The first step is the same as in Example 7,Except that the starting material 4- (1-naphthyl) phenylboronic acid was replaced with 2-naphthaleneboronic acid,The remaining reagents unchanged,To give 6- (2-naphthyl) -12-bromo Chrysene;The second step is the same as the second step of the first embodiment,Except that one of the starting materials, 6-chloroimidazo [1,2-A] pyrimidine-3-borate,8-chloroimidazo [1,2-A] pyrazine-3-boronic acid pinacol ester instead,6,12-dibromo Chrysene synthesized here in the first step6- (2-naphthyl) -12-bromo Chrysene instead of starting material,To obtain the corresponding monochloro intermediate;The third step is the same as the second step of Example 1,Except that one of the raw materials, 6,12-dibromo Chrysene, was replaced by a chlorine-containing intermediate synthesized in the second step,6-chloroimidazo [1,2-A] pyrimidine-3-borate4- (1-naphthyl) benzene boronic acid instead of starting materials,The remaining reagents did not change to give the yellow solid compound 10.The second step,In a 1000ml three bottles,With mechanical mixing, Ar gas protection,5,76 g of 6,12-dibromo Chrysene (molecular weight: 384, 0.015 mol) was added,The first step of the synthesis of 6-chloroimidazo [1,2-A] pyrimidine-3-boronic acid cleanyl ester 9.21g(Molecular weight: 279, 0.033 mol),The catalyst Pd (PPh3) 4 was used in an amount of 1.8 g (molecular weight 1154, 0.001556 mol)Aqueous sodium carbonate solution 120 ml (2M)Toluene 300ml, ethanol 150ml.Stirring reflux, with TLC monitoring reaction, a total reaction after 3.5hs complete reaction.Cooled, separated, evaporated to dryness, separated by column chromatography, eluent with 1: 1 ethyl acetate: petroleum ether,To give 6.7 g of a yellow solid compound having a purity of 97.0% and a yield of 81.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 3.5h;Inert atmosphere; Reflux; | The synthesis process is divided into two steps,The first step is the same as in the second step of the first embodiment,Except that the starting material 6-chloroimidazo [1,2-A] pyrimidine-3-borate is used8-chloroimidazo [1,2-A] pyrazine-3-boronic acid pinacol ester instead of starting material,6,12-dibromo Chrysene1,6-dibromopyrene instead,To obtain the corresponding dichloro intermediate;In a second step with the second step of Example 1,Except that one of the raw materials, 6,12-dibromo Chrysene, was replaced with the dichloro intermediate synthesized therefrom,6-chloroimidazo [1,2-A] pyrimidine-3-borate4- (1-naphthyl) benzene boronic acid instead of starting materials,The remaining reagents unchanged,To give the yellowish solid compound 11.The second step,In a 1000ml three bottles,With mechanical mixing, Ar gas protection,5,76 g of 6,12-dibromo Chrysene (molecular weight: 384, 0.015 mol) was added,The first step of the synthesis of 6-chloroimidazo [1,2-A] pyrimidine-3-boronic acid cleanyl ester 9.21g(Molecular weight: 279, 0.033 mol),The catalyst Pd (PPh3) 4 was used in an amount of 1.8 g (molecular weight 1154, 0.001556 mol)Aqueous sodium carbonate solution 120 ml (2M)Toluene 300ml, ethanol 150ml.Stirring reflux, with TLC monitoring reaction, a total reaction after 3.5hs complete reaction.Cooled, separated, evaporated to dryness, separated by column chromatography, eluent with 1: 1 ethyl acetate: petroleum ether,To give 6.7 g of a yellow solid compound having a purity of 97.0% and a yield of 81.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 3.5h;Inert atmosphere; Reflux; | The synthesis process is divided into two steps, the first step is the same as in the second step of Example 1 except that the starting material 6-chloroimidazole[1,2-A] pyrimidine-3-boronic acid lauryl ester was replaced with 8-chloroimidazo [1,2-A] pyrazine-3-borate, 6,12-bisBromine Chrysene was replaced with 3,9-dibromo perylene as the starting material to give the dichloro intermediate;In a second step with the second step of Example 1,Wherein the feedstock just 6-chloro-imidazo [1,2-A] pyrimidine-3-boronic acid esters with it knit the brows4- (1-naphthyl) phenylboronic acid,6,12-dibromo Chrysene was obtained first hereDichloro intermediate instead of raw materials,The remaining reagents unchanged,To give the pale yellow solid compound 27The second step,In a 1000ml three bottles,With mechanical mixing, Ar gas protection,5,76 g of 6,12-dibromo Chrysene (molecular weight: 384, 0.015 mol) was added,The first step of the synthesis of 6-chloroimidazo [1,2-A] pyrimidine-3-boronic acid cleanyl ester 9.21g(Molecular weight: 279, 0.033 mol),The catalyst Pd (PPh3) 4 was used in an amount of 1.8 g (molecular weight 1154, 0.001556 mol)Aqueous sodium carbonate solution 120 ml (2M)Toluene 300ml, ethanol 150ml.Stirring reflux, with TLC monitoring reaction, a total reaction after 3.5hs complete reaction.Cooled, separated, evaporated to dryness, separated by column chromatography, eluent with 1: 1 ethyl acetate: petroleum ether,To give 6.7 g of a yellow solid compound having a purity of 97.0% and a yield of 81.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; at 110℃; for 6h;Inert atmosphere; | Under N2 protection, 0.43 g of the step (III) was added to a 50 mL three-necked flask5,5'-dibromo-3,3'-diamino-4,4'-dimethoxybenzophenone (1.00 mmol), 0.54 g4- (alpha-naphthyl) phenylboronic acid (2.20 mmol)0.0347 g Pd (PPh3) 4 (0.02 mmol),0.424 g Na2CO3 (4.00 mmol), 10 mL of toluene and 5 mL of distilled water,Heated to 110 reflux reaction 6h, the reaction process a large number of bubbles produced,And the TLC point board to track, until the reaction is completely cooled to room temperature, filter to remove insoluble matter, take the filtrate separated with a separatory funnel, take the liquid layer of extraction with toluene extraction 3 times, the organic layer after extraction,Dried overnight with anhydrous MgSO4, filtered under reduced pressure, the filter cake rinsed twice with toluene,Followed by spin drying and distilling off the toluene to give the pale yellow crude product 0.62g,Recrystallization from N2 with ethanol: water = 9: 1 as solvent gave 0.56 g of a pale yellow solid which was(4 '' - alpha-naphthyl) phenyl-3,3'-diamino-4,4'-dimethoxybenzophenone,The yield was 84%, and the gray solid was characterized. The results were as follows: Mp .: 214-216oC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 12h;Inert atmosphere; Reflux; | To a flask was added 3,5-dibromobenzonitrile (3 g, 11.6 mmol), 4-(1-naphthyl)-benzenesulfonic acid (2.9 g, 11.6 mmol), potassium carbonate (4.1 g, 30 mmol)tetraphenyllphosphine palladium (0.1 g),tetrahydrofuran (30 mL) and water (15 mL)heated to reflux under nitrogen for 12 hours, cooled, extracted with dichloromethane, dried and concentrated. The crude product was purified by column chromatography to give 2.5 g of product in 57% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 80 - 85℃; for 12h;Inert atmosphere; | Under nitrogen protection,The intermediate (4.01 g, 0.01 mol)And 4- (1-naphthyl) benzeneboronic acid (2.98 g, 0.012 mmol)Was added to 100mL of toluene,Then catalyst Pd (PPh3) 4 (0.12 g, 0.1 mmol)And potassium carbonate (4.14 g, 0.03 mol) in water,The system was warmed to 80-85 , refluxed for 12h,Natural cooling to room temperature, liquid separation, rotary to obtain the crude product.The crude product was purified by neutral alumina column chromatography,The eluent was purified with V dichloromethane: V ethyl acetate = 1: 3,Get white-like powder,The resulting powder using chemical vapor deposition system further sublimation purification, sublimation temperature of 350 C,Compound C-03 was obtained in a yield of 58% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76.7% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; for 4h;Inert atmosphere; | 1000 ml bottle, with magnetic stirring,9-Bromo-7- (4-bromopyridin-2-yl) benzo [c] acridine was added9.3 g (molecular weight 464, 0.02 mol)4- (naphthalen-1-yl) benzeneboronic acid(Molecular weight: 248,0.044 mol), 2.31 g (molecular weight: 1154, .002 mol) of Pd (PPh3) 4, 150 ml (2M) of sodium carbonate, 150 ml of toluene and 150 ml of ethanol. After the argon was replaced, the reaction mixture was refluxed and the reaction was monitored by TLC. After 4 hours, the reaction was complete. The mixture was cooled and the organic layer was separated. The organic layer was separated, evaporated to dryness, chromatographed on a column and eluted with ethyl acetate / petroleum ether to give 10.9 g of Compound, molecular weight 710, yield 76.7%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.4% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; for 4h;Inert atmosphere; Reflux; | In a 1000 ml bottle with magnetic stirrer, 8.30 g (molecular weight 414, 0.02 mol) of the parent 2,7-dibromo-9-(pyridin-2-yl)acridine shown in the formula (16) was added.4-(naphthalen-1-yl)phenylboronic acid 11.0 g (molecular weight 248, 0.044 mol), Pd(PPh3)4 usage 2.31 g (molecular weight 1154, 0.002 mol), sodium carbonate 150 ml (2M), toluene 150 ml, ethanol 150 ml .After replacing with argon, refluxing, the reaction was monitored by TLC, the reaction was complete after 4 hours, and the temperature was lowered.The organic layer was separated, evaporated to dryness, and purified by column chromatography and eluted with ethyl acetate/petroleum ether to give 11.7 g of a compound represented by the formula (21), a molecular weight of 660, and a yield of 88.4%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; for 8h;Reflux; Inert atmosphere; | Intermediate C (3.9 g, 0.01 mol) and 4-naphthyl-1phenylboronic acid (2.98 g, 0.012 mol) were added to 100 mL of toluene under a nitrogen atmosphere, and then the catalyst tetratriphenylphosphine palladium (0.12) was charged. g, 0.1 mmol) and potassium carbonate (4.14 g, 0.03 mol) in water. The system was heated to reflux for 8 hours, and the mixture was naturally cooled to room temperature, then separated and then evaporated to give a crude product.The crude product was subjected to silica gel column chromatography, and the eluent was purified by V-hexane:V chloroform = 1:5 to obtain a pale yellow powder. The obtained powder was further purified by a chemical vapor deposition system, and the sublimation temperature was 360 C to obtain a compound C01. The yield was 52%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 65℃; for 18h; | (4) 5-Bromo-3,9,-dimethyl-10-(naphthalen-1-yl)benzo[G]quinoline of step (3)(MW: 412.33) 32.16g (0.078mol),(4-(1-naphthalene)phenyl)boronic acid (MW: 248.1) 21.3 g (0.086 mol),Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium) (MW: 1155.58) 0.9 g,Sodium carbonate (MW: 106) 9.92g,Toluene 250mL,50mL of ethanol,50 mL of water was placed in a 500 mL reaction flask and inserted into a condenser tube.thermometer,Stir the reaction and warm to 65 C.The reaction was carried out for 18 hours, and the temperature was lowered after the reaction was completed.Add 150mL of ethanol, then filter,Washed,drying,3,9,-Dimethyl-10-(naphthalen-1-yl)5-(4(naphthalen-1-yl)benzene)benzo[G]quinoline (MW: 535.69) 36.76 g (0.06864 mol) was obtained.Is the compound (1),The yield was 88%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 65℃; for 18h; | (4) 5-bromo-10-(naphthalen-1-yl)benzo[G]quinoline (MW: 383.29) of step (3) 29.89 g(0.078mol),(4-(1-naphthalene)phenyl)boronic acid (MW: 248.1) 21.3 g (0.086 mol), Pd(PPh3) 4 (tetrakis(triphenylphosphine)palladium) (MW: 1155.58) 0.9 g,Sodium carbonate (MW: 106) 9.92g,Toluene 250mL,50mL of ethanol,50 mL of water was placed in a 500 mL reaction flask and inserted into a condenser tube.thermometer,The reaction was stirred, the temperature was raised to 65 C, and the reaction was carried out for 18 h. After the reaction was completed, the temperature was lowered, 150 mL of ethanol was added, and then filtered.Washed,Dry, get10-(naphthalen-1-yl)5-(4(naphthalen-1-yl)benzene)benzo[G]quinoline(MW: 507.6) 34.84 g (0.06864 mol), which is the compound (1a), yield 88%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; for 6h;Reflux; Inert atmosphere; | General procedure: The reaction mixture containing intermediate 3 (289 mg,1 mmol), the corresponding Phenylboronic Acid forA1, [4-(diphenylamino)phenyl]-boronic acid for A2, 4-(1-naphthyl)phenylboronic acid for A3, and [4-(9H-carbazol-9-yl)phenyl]boronic acid for A4 (1.1 mmol), toluene(10 mL), H2O(5 mL), K2CO3(2.5 mL, 5 mmol), and tetrakis-(triphenylphosphino)palladium(0) (28 mg, 0.02 mmol)was refluxed under nitrogen atmosphere for 6 h. After thereaction finished, the reaction mixture was cooled to roomtemperature and diluted by water (20 mL). The reactionmixture was separated into organic layer and aqueous layer,and the layer of which was extracted with dichloromethane(3 × 20 mL). After the combined organic layers were washedwith brine (50 mL), dried over anhydrous magnesium sulfate,and filtered, the solvent was removed under reducedpressure. Then, the residue was isolated by column chromatographyover silica using petroleum ether/ethyl acetate(10:1, v/v) as eluent and further purified by recrystallizationin methanol/chloroform to give pure products as white solids. 9-([1,1?-biphenyl]-2-ylmethyl)-3,6-diphenyl-9H-carbazole(C1) Yield: 73%. Mp: 168-170 C. 1H NMR (400 MHz, DMSOd6,delta, ppm): 8.60 (s, 2H), 7.81 (d, J = 7.2 Hz, 4H), 7.72 (d,J = 7.5 Hz, 2H), 7.59 (t, J = 7.3 Hz, 2H), 7.49 (t, J = 2.0 Hz,5H), 7.47 (d, J = 7.3 Hz, 2H), 7.42 (t, 4H), 7.34 (t, J = 7.5 Hz,1H), 6.54 (d, J = 7.8 Hz, 1H), 5.64 (s, 2H, -CH2-). 13C NMR(101 MHz, DMSO-d6, delta, ppm): 141.4, 141.1, 140.6, 140.5,134.9, 132.1, 130.5, 129.7, 129.3, 129.1, 128.2, 128.0,127.7, 127.1, 127.0, 126.0, 125.5, 123.5, 119.4, 110.1, 44.6.Anal. calcd for C37H27N:C, 91.51; H, 5.60; N, 2.88. Found:C, 91.48; H, 5.59; N, 2.85. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With sodium phosphate; In toluene; for 24h;Reflux; Inert atmosphere; | 0.1 mol of the compound (3), 0.1 mol of the compound (4), 0.3 mol of sodium phosphate, 0.025 mol of a palladium catalyst and toluene (1000 mL) were added to the reaction flask, and the mixture was heated under reflux for 24 hours under nitrogen atmosphere.After cooling, the toluene was removed, dichloromethane was added, washed with water, dried, and the crude product was passed through a column, and then purified by recrystallization from dichloromethane and ethanol to give a product, compound 5, yield 53%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; at 110℃; for 7h; | General procedure: A solution of bis(3-bromo-4-methoxyphenyl)-methanone (2) (2.00 g, 0.005 mol), phenylboronic acid (1.34 g, 0.01 mol) or [4-(naphthalen-1-yl)phenyl]boronicacid (2.73 g, 0.01 mol), Pd[P(C6H5)3]4 (0.17 g, 0.015 mmol), and Na2CO3 (2.12 g, 0.02 mol) in water (10 ml) and toluene (20 ml) was stirred at 110 C for 7 h. After TLC examination indicated that no starting material remained, the aqueous phase was extracted with EtOAc (3×35 ml). The organic phase was dried over anhydrous Na2SO4, concentrated under reduced pressure, the product was recrystallized from appropriate solvent mixture |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49.2% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 70℃; for 12h;Inert atmosphere; | The charged contents were heated, and stirred for 12 hours at 70 C. to obtain a reaction liquid. The reaction liquid was cooled to room temperature, and an organic stratum was collected by a liquid separating operation. The collected organic stratum was concentrated under reduced pressure to obtain a crude product. The crude product was purified by colunm chromatography (carrier: silica gel, eluting solution:ethyl acetate/heptane), and then purified by recrystallization using a toluene/acetone mixed solvent. As a result, 3.0 g (yield 49.2%) of Compound 2-16 was obtained as a whitepowdet.For the resulting white powder, its structure was identified using NMR. In ?H-NMR (CDC13), the following signals of 31 hydrogens were detected.oe (ppm)=9.00-8.81 (2H)8.65 (1H)8.51-8.28 (2H)8.20-7.35 (26H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With tetrakis(triphenylphosphine) palladium(0); 18-crown-6 ether; potassium carbonate; In water; toluene; for 8h;Inert atmosphere; Reflux; | Under the protection of nitrogen,6-Chlorobenzo[4',5']thieno[2',3':4,5]pyrrolo[1,2-f]phenanthridine(3.58 g, 0.01 mol) and 4-(1-naphthyl)benzeneboronic acid (2.98 g, 0.012 mol)Adding to 100 g of toluene, then adding potassium carbonate (2.76 g, 0.02 mol) aqueous solution, 18-crown-6 (0.13 g, 0.5 mmol), catalyst tetratriphenylphosphine palladium (0.12 g, 0.1 mmol); After stirring for 8 hours under reflux, the mixture was naturally cooled to room temperature, and then the mixture was separated and evaporated to give a crude product. The crude product was subjected to silica gel column chromatography to give an off-white powder, and the obtained powder was further purified by a chemical vapor deposition system to obtain Compound C01 in a yield of 46%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77.3% | With palladium diacetate; sodium carbonate; XPhos; In ethanol; water; toluene; at 85 - 90℃;Inert atmosphere; | Under the protection of nitrogen,45 g of intermediate I (127.7 mmol), 31.6 g of starting material D (127.7 mmol), 33.8 g of sodium carbonate (319 mmol), ethanol 62 g, water 78.8 g (78.8 ml), 143.4 mg of Pd(OAC) 2 (0.638 mmol) were weighed in order. 608 mg X-phos (1.28 mmol), stirred and mixed with toluene, heated to 85-90 C, and refluxed for 5-10 hours.The sampling plate shows that there is no intermediate 1 remaining, the reaction is complete; it is naturally cooled to room temperature, filtered, and the filtrate is passed through a silica gel column, and the column liquid is steamed to a non-fraction, and the crude gray solid is refined with toluene.Drying to give 47 g of compound 1,Yield: 77.3%, HPLC: 99.9%,HPLC-MS: The theoretical molecular weight of Compound 1 was 475.5, and the molecular weight of the actual test was 475.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; for 12h;Inert atmosphere; Reflux; | Intermediate c (4.58 g, 0.01 mol) and 4-(1-naphthyl)benzeneboronic acid (2.98 g, 0.012 mol) were added to 100 mL of toluene under a nitrogen atmosphere, and then the catalyst tetratriphenylphosphine palladium ( 0.12g, 0.1mmol) and potassium carbonate(4.14 g, 0.03 mol) aqueous solution. The system was heated to reflux and stirred for 12 hours, and then naturally cooled to room temperature, and then separated and then evaporated to give a crude product.The crude product was chromatographed on a neutral alumina column, and the eluent was purified by V-dichloromethane: V ethyl acetate = 1:3 to obtain an off-white powder, and the obtained powder was further purified by a chemical vapor deposition system to obtain a sublimation temperature. At 360 C, compound C03 was obtained in a yield of 56%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; for 12h;Reflux; | The compound material (2.34 g, 11.9 mmol),Compound p-(4-indolyl)benzeneboronic acid (2.95 g, 11.9 mmol), Pd(PPh3)4(0.7 g, 0.59 mmol) and Na2CO3 (3.8 g, 35.7 mmol)After dissolving in a mixture of dioxane (55 mL) and distilled water (14 mL),The reaction was refluxed for 12 h. Then use PE/EA to pass the column,Get compound 3-5(3.14g, 8.57mmol, 72.0%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.2 g | With tetrakis(triphenylphosphine) palladium(0); 1,2,4-Trimethylbenzene; In water; tert-butyl alcohol; for 6h;Reflux; Inert atmosphere; | 5- (3- (10-bromoanthracen-9-yl) phenyl) -3,4'-bipyridine (2.0 g),(4- (naphthalen-1-yl) phenyl) boronic acid (1.2 g), Pd (PPh 3) 4 (0.14 g),Potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (12 ml), t-butyl alcohol (1 ml) and waterThe flask containing (1 ml) was stirred at reflux temperature for 6 hours.The reaction solution was cooled to room temperature, and water and toluene were added for liquid separation.The solvent was distilled off under reduced pressure, and the resulting solid was purified by amino group-modified silica gel (NH DM1020: manufactured by Fuji Silysia) column chromatography (developing solution: toluene). After distilling off the solvent under reduced pressure,Reprecipitate with toluene / heptane mixed solvent,Compound represented by formula (1-2-74):5- (3- (10- (4- (Naphthalen-1-yl) phenyl) anthracen-9-yl) phenyl) -3,4'-bipyridine (1.2 g) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 110℃; for 6h;Inert atmosphere; | The same approach for synthesizing P1 was followed. P2 was prepared from intermediate 3 (0.30 g, 0.645 mmol)and <strong>[870774-25-7][4-(naphthalene-1-yl)phenyl]boronic acid</strong> (0.32 g,1.29 mmol). The crude product was purified through silica gel chromatography using petroleum ether/dichloromethane(5:1, v/v) as eluent to obtain desire product as white solid 0.28 g. Yield: 61%. Mp: 203-205 C. 1H NMR (400 MHz,DMSO-d6, delta, ppm): 8.54 (d, J = 8.0 Hz, 4H), 8.34 (s, 2H),8.13 (d, J = 7.2 Hz, 2H), 7.99-8.03 (m, 12H), 7.93 (d,J = 8.4 Hz, 2H), 7.53-7.66 (m, 15H). 13C NMR (101 MHz,DMSO-d6, delta, ppm): 156.0, 149.6, 140.3, 139.3, 138.9, 138.5,137.9, 137.6, 133.4, 130.7, 130.4, 129.3, 129.0, 128.3,127.7, 127.6, 127.3, 126.9, 129.8, 126.7, 126.4, 125.9,125.5, 125.2, 116.6. Anal. calcd. For C55H37N:C, 92.57; H,5.24; N, 1.97. Found C, 92.70; H, 5.19; N, 1.97. |
Tags: 870774-25-7 synthesis path| 870774-25-7 SDS| 870774-25-7 COA| 870774-25-7 purity| 870774-25-7 application| 870774-25-7 NMR| 870774-25-7 COA| 870774-25-7 structure
[ 867044-35-7 ]
(9,10-di(Naphthalen-1-yl)anthracen-2-yl)boronic acid
Similarity: 1.00
[ 872050-52-7 ]
(4-(Pyren-1-yl)phenyl)boronic acid
Similarity: 1.00
[ 597553-98-5 ]
(9,10-Diphenylanthracen-2-yl)boronic acid
Similarity: 1.00
[ 597553-98-5 ]
(9,10-Diphenylanthracen-2-yl)boronic acid
Similarity: 1.00
[ 911390-81-3 ]
(4-(10-(Naphthalen-2-yl)anthracen-9-yl)phenyl)boronic 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 :