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CAS No. : | 164461-18-1 | MDL No. : | MFCD04974062 |
Formula : | C16H11BO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MWEKPLLMFXIZOC-UHFFFAOYSA-N |
M.W : | 246.07 | Pubchem ID : | 5084102 |
Synonyms : |
|
Num. heavy atoms : | 19 |
Num. arom. heavy atoms : | 16 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 79.97 |
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) : | -5.0 cm/s |
Log Po/w (iLOGP) : | 0.0 |
Log Po/w (XLOGP3) : | 3.94 |
Log Po/w (WLOGP) : | 2.26 |
Log Po/w (MLOGP) : | 2.65 |
Log Po/w (SILICOS-IT) : | 2.11 |
Consensus Log Po/w : | 2.19 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -4.4 |
Solubility : | 0.00968 mg/ml ; 0.0000394 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -4.49 |
Solubility : | 0.00797 mg/ml ; 0.0000324 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -5.48 |
Solubility : | 0.000815 mg/ml ; 0.00000331 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 2.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 2.05 |
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 |
---|---|---|
74% | Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1 h; Stage #2: at -78 - 20℃; for 2 h; |
To a round bottom flask1-Bromo-pyrene (30g, 107 mmol) was dissolved in 240 mL THF. In the cooling state up to -78 n-BuLi in n-hexane (1.6M) was put in a slow (80 mL). At the end of the addition and then stirred for about 1 hour at -78 was put trimethyl borate (15.5 g, 149 mmol). After 1 hour stirring at -78 stirred at room temperature for about two hours and put in a 2N HCl was adjusted to acidic. While the removal of the solvent after extraction with EA obtained with hexane to give the 1-pyreneboronic acid 19.5 g (yield 74 percent). |
74% | With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 3 h; | 30 g (107 mmol) of 1-bromopyrene was dissolved in 240 mL of THF in a round bottom flask. The n-BuLi in n-hexane (1.6M) (80 mL) was slowly added to the solution while cooling to -78 ° C. After the addition, trimethylborate (15.5 g, 149 mmol) was added thereto at -78 ° C for about 1 hour. After stirring at -78 ° C for 1 hour, the mixture was stirred at room temperature for 2 hours and 2N HCl was added to adjust the acidity. The solvent was removed by extraction with EA, and crystals were obtained with hexane to obtain 19.5 g (yield: 74percent) of 1-pyrene boronic acid. |
70% | Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 1 h; Inert atmosphere Stage #2: at -78 - 20℃; for 24 h; Stage #3: With hydrogenchloride In tetrahydrofuran; hexane for 1 h; |
Synthesis of Pyren-1-ylboronic acid An excess of 1.6 M n-BuLi in hexane (50 mL, 80 mmol) was added to a solution of 1-bromopyrene (20.4 g, 72.6 mmol) in 500 ml dry tetrahydrofuran at -78° C. under N2. The reaction mixture was then maintained at 0° C. for 1 h before cooling to -78° C. Trimethyl borate (10.4 g, 100 mmol) was added dropwise; the solution was then warmed slowly to room temperature and stirred for 24 h. 2N HCl (150 ml) was added and then the mixture was stirred for a further 1 h. The reaction mixture was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuo, and the residue was crystallized (n-hexane) to give the pyren-1-ylboronic acid 12.5 g as a yellow solid (70percent) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 0.5 h; |
1-Bromopyrene (1.0g, 3.56 mmol) was dissolved in anhydrousTHF solution (20 mL) and stirred at−78C. Then, 1.6Mn-BuLi (2.1 mL) was added.Triisopropyl borate (1.2 mL) was added to the reaction after 30 min. After the reactionwas finished, the solution was acidified with 2 N HCl solution at room temperature andextracted with ethyl acetate and water. The organic layer was dried with anhydrous MgSO4and filtered. The solution was evaporated. The residue was redissolved in hexane and addedto ethyl acetate. The precipitate was filtered and washed with hexane to obtain a beigecompound (0.63 g, 72percent). 1H-NMR (300 MHz, DMSO): δ(ppm) = 8.72-8.69 (d, 1H) 8.60 (s, 2H) 8.30-8.15 (m,7H) 8.06-8.04 (t, 1H). |
68% | Stage #1: With n-butyllithium In tetrahydrofuran at -100℃; for 2 h; Inert atmosphere Stage #2: for 4 h; Inert atmosphere |
In the nitrogen,Clean and dry 1000ml three-mouth bottle,Add 1-bromoindole, THF,Cool down to -100°C,Butyllithium, plus complete, insulation 2h,Triisopropyl borate was added dropwise, incubated for 4 h, acidified with hydrochloric acid, washed with water, dehydrated with solvent, and beaten with toluene.Get 1 - deuterated boric acid;HPLC: 99.3percent, yield: 68percent; |
60% | With hydrogenchloride In tetrahydrofuran | <Step 9> Synthesis of pyrene-1-boronic acid (Compound 1-13) 1-Bromopyrene (compound 1-12, 30 g) was dissolved in tetrahydrofuran (500 ml). The reaction mixture was cooled to -78° C. and stirred for one hour while gradually adding an n-butyllithium solution (1.6N, 80 ml) thereto, and triisopropylborate (30 ml) was added thereto. The reaction solution was gradually raised to room temperature and stirred at that temperature for 15 hours. 1N HCl (250 ml) was gradually added and an aqueous layer was removed. The resultant organic layer was washed with a saturated ammonium chloride solution and a saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated. The crude product was recrystallized from n-hexane to give a titled compound (15.7 g, yield 60.0percent) as a pale yellow solid. |
51% | With n-butyllithium In tetrahydrofuran at -78 - 20℃; Inert atmosphere | 1-Bromo-pyrene 10 g was added to 500 mL round floorflask, melted in anhydrous tetrahydrofuran (THF) 120 mL, and agitated. After reaction temperature was set to −78 C,2.0 M n-Butyllithium 23.4 mL (50.59 mmol) was addedinto reaction mixture slowly. In 10 minutes, triisopropylborate 10 mL was added to reaction mixture. When reactiontemperature increased to room temperature in an hour,12 M HCl 7.2 mL was added. The reaction was completed,compound was extracted with ethyl acetate (EA)and water, and the organic layer was dried with anhydrousMgSO4 and filtered. After the compound was concentratedunder reduced pressure, white solid was obtained in 51percent.1H-NMR (300 MHz, THF-d8) (ppm): 8.89–8.85(m, 1H), 8.32–8.28 (m, 1H), 8.21–8.15 (m, 3H), 8.14–8.03(m, 3H), 8.01–7.94 (m, 1H), 7.10 (s, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With n-butyllithium; Triisopropyl borate | |
82% | Stage #1: 1-bromopyrene With n-butyllithium In tetrahydrofuran at -78 - -10℃; for 0.833333h; Stage #2: With Triisopropyl borate In tetrahydrofuran at 20℃; for 36h; | |
73% | Stage #1: 1-bromopyrene With n-butyllithium In diethyl ether at 0℃; for 0.5h; Stage #2: With Trimethyl borate In diethyl ether at -78 - 20℃; for 26h; Stage #3: In diethyl ether at 20℃; for 3h; Acid hydrolysis; |
Multi-step reaction with 2 steps 1.1: nBuLi / hexane / 0.5 h / 20 °C 1.2: hexane; diethyl ether / 26 h / -78 - 20 °C 2.1: 0.64 g / 3 h / 20 °C / Acid hydrolysis | ||
Multi-step reaction with 2 steps 1.1: n-BuLi / diethyl ether / 0.5 h / 0 °C 1.2: diethyl ether / 26 h / -78 - -20 °C 2.1: H3O(+) / 3 h / 20 °C | ||
Multi-step reaction with 2 steps 1.1: n-BuLi / tetrahydrofuran; hexane / -78 - 0 °C 1.2: tetrahydrofuran; hexane / 0.33 h / 0 °C 2.1: HCl; H2O / tetrahydrofuran; hexane | ||
Stage #1: 1-bromopyrene With n-butyllithium In tetrahydrofuran at -78℃; for 1.5h; Stage #2: With Trimethyl borate In tetrahydrofuran at -78 - 20℃; Stage #3: With hydrogenchloride; water In tetrahydrofuran | ||
Stage #1: 1-bromopyrene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: With Trimethyl borate In tetrahydrofuran; pentane at -78 - 20℃; for 3h; | ||
Stage #1: 1-bromopyrene With n-butyllithium In tetrahydrofuran at -78℃; for 3h; Stage #2: With Trimethyl borate In tetrahydrofuran at -78 - 20℃; Stage #3: With hydrogenchloride In tetrahydrofuran; water for 1h; | ||
Multi-step reaction with 2 steps 1: n-butyllithium / tetrahydrofuran / -78 °C 2: hydrogenchloride / water / 20 °C | ||
Multi-step reaction with 2 steps 1.1: potassium acetate; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / 1,4-dioxane / 90 °C / Inert atmosphere; Schlenk technique 2.1: sodium periodate / tetrahydrofuran; water / 20 °C 2.2: 24 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With sodium carbonate In ethanol; water; toluene at 20 - 77℃; for 5.5h; | 1 <Synthesis Example 1>; [Synthesis of Exemplified Compound No. 1] [7-DIBROMO-9,] 9-dimethylfluorene [[1],] 4.2 g (17.0 mmol) of [PYRENE-1-BORONIC] acid [2], 120 ml of toluene, and 60 ml of ethanol were added. Then, an aqueous solution of 24 g of sodium carbonate/120 ml of water was dropped thereinto with stirring in a nitrogen atmosphere at a room temperature, followed by the addition of 0.33 g (0.28 mmol) of tetrakis (triphenylphosphine) palladium (0). After stirring the mixture for 30 minutes at a room temperature, the temperature was allowed to rise to [77°C,] followed by stirring for 5 hours. After the reaction, an organic . layer was extracted with chloroform and was then dried with anhydrous sodium sulfate, followed by purification with a silica gel column (hexane + toluene mixture developing solvent). Consequently, 3.0 g [(89%] yield) of an exemplified compound No. 1 (white crystal) was obtained. |
73% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 4h; Reflux; | 2.1.1. General Procedure for the SuzukiCross-Coupling Reaction General procedure: 1-pyrenyl boronic acid 1.0 g (2.78 mmol) and the correspondingaryl bromide (1.00 mmol), Pd(PPh34 128 mg(0.11 mmol), aqueous 2.0 M Na2CO3 14 ml (27.8 mmol),Ethanol(14 ml) and toluene (28 ml) were mixed in a flask.The mixture was refluxed for 4 h. After the reaction hadfinished, the reaction mixture was extracted with ethylacetate and washed with water. After cooling, the crudeproducts were purified through column chromatographyand recrystallization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With sodium carbonate In ethanol; water; toluene at 20 - 77℃; for 5.5h; | 2 <Synthesis Example 2>; [Synthesis of Exemplified Compound No. 6] To a 500-ml three-neck flask, 3.0 g (5.49 mmol) of dibromofluorene compound [3], 4.0 g (16.5 mmol) of [PYRENE-1-BORONIC] acid [2], 100 ml of toluene, and 50 ml of ethanol were added. Then, an aqueous solution of 20 g of sodium carbonate/100 ml of water was dropped thereinto with stirring in a nitrogen atmosphere at a room temperature, followed by the addition of 0.33 g (0.28 mmol) of tetrakis (triphenylphosphine) palladium (0). After stirring the mixture for 30 minutes at a room temperature, the temperature was allowed to rise to [77°C,] followed by stirring for 5 hours. After the reaction, an organic layer was extracted with chloroform and was then dried with anhydrous sodium sulfate, followed by purification with a silica gel column (hexane + toluene mixture developing solvent). Consequently, 3.4 g [(79%] yield) of an exemplified compound No. 6 (white crystal) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With sodium carbonate In ethanol; water; toluene at 20 - 77℃; for 5.5h; | 3 <Synthesis Example 3>; [Synthesis of Exemplified Compound No. 7] To a 500-ml three-neck flask, 3.0 g (4.07 mmol) of dibromofluorene compound [[4],] 3.0 g (12.2 mmol) of [PYRENE-1-BORONIC] acid [2], 100 ml of toluene, and 50 ml of ethanol were added. Then, an aqueous solution of 16 g of sodium carbonate/80 ml of water was dropped thereinto with stirring in a nitrogen atmosphere at a room temperature, followed by the addition of 0.23 g (0.20 mmol) of tetrakis (triphenylphosphine) palladium (0). After stirring the mixture for 30 minutes at a room temperature, the temperature was allowed to rise to [77°C,] followed by stirring for 5 hours. After the reaction, an organic layer was extracted with chloroform and was then dried with anhydrous sodium sulfate, followed by purification with a silica gel column (hexane + toluene mixture developing solvent). Consequently, 2.7 g [(68%] yield) of an exemplified compound No. 7 (white crystal) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 20 - 77℃; for 8.5h; | In a 500-ml three-neck flask, 2.0 g (3.16 mmol) of 2, [2'-7,] [7'-TETRABROMO-9,] 9'-spirobifluorene [[1],] 4.7 g (19.0 mmol) of [PYRENE-1-BORONIC] acid [[2],] 140 ml of toluene, and 70 ml of ethanol were added, and an aqueous solution of 25 g of sodium carbonate/130 ml of water was dropped with stirring in a nitrogen atmosphere at room temperature, followed by the addition of 0.7 g (0.63 mmol) of tetrakis (triphenylphosphine) palladium (0). After stirring the mixture for 30 minutes at room temperature, the temperature is allowed to rise to [77C,] followed by stirring for 8 hours. After the reaction, an organic layer was extracted with chloroform and was then dried with anhydrous sodium sulfate, followed by purification with a silica gel column (hexane + toluene mixture developing solvent). Consequently, 2.3 g [(65%] yield) of the exemplified compound No. 7 (white crystal) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With sodium carbonate In water; toluene at 80℃; for 8h; | 4.3 Under an argon atmosphere, 4-bromoiodobenzene (2. 8 g, 10 mmol), pyrene-1-boronic acid (3.0 g, 12 mmol), tetrakis (triphenylphosphine)palladium (0.35 g, 0.3 mmol), toluene (20 mL), and a 2-M aqueous solution of sodium carbonate (15 mL, 30 mmol) were added to a 200-mL three-necked flask, and the whole was heated at 80°C for 8 hours. Water (100 mL) was added to the reaction liquid in such a manner that a solid would be precipitated. Then, the solid was filtered. The resultant was purified by means of silica gel column chromatography, whereby Intermediate 4-3 was obtained (amount 2.8 g, yield 79 %). |
76% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 110℃; | 1 [Reaction formula4] 24.6g(100mmol, 1.0eq.) 1-decaneboronic acidAnd 31.1g (110mmol, 1.1eq.) p-bromoiodobenzene was added to a 2L three-necked flask, dissolved in 1100ml of toluene and 110ml of ethanol, nitrogen was passed for 15 minutes, and 150ml of 2M containing 41.5g (300mmol, 3.0eq.) was added. An aqueous solution of K2CO3 was finally added with 2.3 g of Pd(PPh3)4 (2 mol %).The temperature was raised to 110°C and the reaction was completed overnight. Activated carbon adsorption, suction filtration, solvent removal, drying, recrystallization with toluene and ethanol, to obtain 27.2g of Intermediate-4, a yield of 76%. |
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran for 4h; Reflux; | 5 Synthesis of compound d1 Tetrakistriphenylphosphine palladium (2.1 g, 1.83 mmol) and potassium carbonate(75.7 g, 549 mmol) added to 1-indole boric acid(46.0 g, 187 mmol) and p-bromoiodobenzene (51.6 g, 183 mmol)a solution in degassed tetrahydrofuran (500 mL),And the mixture was heated under reflux for 4 hours.Hot filtration, a large amount of solid is obtained, and the solid is dissolved in a solvent.After concentration,Compound d1 was obtained by silica gel column chromatography(39.2 g, yield 60%). |
50% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; toluene at 110℃; for 12h; | |
43% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 90℃; for 12h; Inert atmosphere; | 2.2 (2) Synthesis of intermediate M3: Prepared by Suzuki coupling. In a 100mL round bottom flask, p-bromoiodobenzene (5mmol, 1.42g), 1-pyreneboronic acid (5mmol, 1.23g) and tetratriphenylphosphine palladium (0.1mmol, 115mg) were dissolved in 40mL of toluene and 20mL of potassium carbonate In an aqueous solution (2.0molL-1), stir and reflux at 90°C for 12 hours under nitrogen protection. After the reaction, it was extracted with dichloromethane, and the extract was concentrated by rotary evaporation, and separated by column chromatography (petroleum ether: dichloromethane=4:1, volume ratio) to obtain a light yellow-green solid (768 mg, yield: 43%). |
With tetrakis(triphenylphosphine)palladium (0) | n 1st step: 1st step: 1-(4-bromophenyl)pyrene 1-bromo-4-iodobenzene (21.9 g, 77.41 mmol, 1.0 eq), pyren-1-ylboronic acid (20.0 g, 81.3 mmol, 1.05 eq), tetrakis(triphenylphosphine)palladium(0) (1.79 g, 1.55 mmol, 2.0 mol. %) were dissolved in degassed DME (300 mL). A degassed solution of potassium carbonate (22.1 g, 232.2 mmol, 3.0 eq) in water (120 mL) was added, and the mixture was stirred at 95° C. for 17 h, after which the mixture was filtered hot. The mother liquors were left to recrystallize, and the solid was filtered off. It was then dissolved in chloroform and extracted with water. The organic layer was decanted, dried over magnesium sulfate, and evaporated to dryness. HPLC purity: 97.75% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With sodium carbonate In water; toluene at 80℃; for 8h; | 5.1 Under an argon atmosphere, Intermediate 4-1 (4.0 g, 12. 4 mmol), 1-pyrenylboronic acid (3.0 g, 12 mmol), tetrakis(triphenylphosphine)palladium (0.4 g, 0.4 mmol), toluene (40 mL), and a 2-M aqueous solution of sodium carbonate (18 mL, 36 mmol) were added to a 200-mL three-necked flask, and the whole was heated at 80°C for 8 hours. Water (100 mL) was added to the reaction liquid in such a manner that a solid would be precipitated. Then, the solid was filtered. The resultant was purified by means of silica gel column chromatography, whereby Intermediate 5-1 was obtained (amount 4.2 g, yield 73 %). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With sodium carbonate In water; toluene at 80℃; for 9h; | 1 Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples without departing from its gist. Synthesis Example 1 (synthesis of spiro[cyclohexane-1,9'-fluorene-2',7'-bis(1-pyrenyl)] (Compound 1)) Compound 1 was synthesized as described below. [Show Image] Under an argon atmosphere, spiro[cyclohexane-1,9'-fluorene-2',7'-dibromide] (2.0 g, 5.1 mmol), pyrene-1-boronic acid (3.0 g, 12 mmol), tetrakis(triphenylphosphine)palladium (0.35 g, 0.3 mmol), toluene (20 mL), and a 2-M aqueous solution of sodium carbonate (15 mL, 30 mmol) were added to a 200-mL three-necked flask, and the whole was heated at 80°C for 9 hours. Water (100 mL) was added to the reaction liquid in such a manner that a solid would be precipitated. Then, the solid was filtered. The resultant was purified by means of silica gel column chromatography (amount 1.75 g, yield 54 %). The purified product was identified as Compound 1 on the basis of 1H-NMR and a field desorption mass spectrum (FD-MS). The measured value of the FD-MS was 634. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With potassium carbonate In water; N,N-dimethyl-formamide at 80℃; for 9h; | 7 Intermediate (8-1) was synthesized in an amount of 3.54 g and a yield of 69 % by performing the same operation as that of Example 1 (3) except that Intermediate 5-1 described above (3.92 g, 10.0 mmol), 1-pyreneboronic acid (2.46 g, 10.0 mmol), tetrakis (triphenylphosphine) palladium (0.2.3 g, 0.20 mmol), N,N-dimethylformamide (20 mL), and 15 mL of an aqueous solution of potassium carbonate (4.15 g, 30. 0 mmol) were used under an argon atmosphere. Subsequently, Compound 8 was synthesized in an amount of 3.70 g and a yield of 80 % by performing the same operation as that of Example 1 (3) except that a reaction liquid containing Intermediate (8-1) (3.33 g, 6.5 mmol), 4-pyrenylbenzeneboronic acid (2.30 g, 7.15 mmol), tetrakis(triphenylphosphine)palladium (0.15 g, 0.13 mmol), N,N-dimethylformamide (20mL), and 10 mL of an aqueous solution of potassium carbonate (2.70 g, 19.5 mmol) with one another was used. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With sodium carbonate In water; toluene at 80℃; for 9h; | 2.5 Under an argon atmosphere, Intermediate 2-4 (1.3 g, 2.4 mmol), pyrene-1-boronic acid (0.74 g, 3.0 mmol), tetrakis(triphenylphosphine)palladium (0.1 g, 0.1 mmol), toluene (20 mL), and a 2-M aqueous solution of sodium carbonate (3.6 mL, 7.2 mmol) were added to a 200-mL three-necked flask, and the whole was heated at 80°C for 9 hours. Water (100 mL) was added to the reaction liquid in such a manner that a solid would be precipitated. Then, the solid was filtered. The resultant was purified by means of silica gel column chromatography (amount 1.3 g, yield 81 %). The purified product was identified as Compound 2 on the basis of 1H-NMR and FD-MS. The measured value of the FD-MS was 668. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; at 80℃; for 9h; | Under an argon atmosphere, <strong>[86-90-8]4-bromophthalic anhydride</strong> (3.3 g, 12 mmol), pyrene-1-boronic acid (3.0 g, 12 mmol), tetrakis(triphenylphosphine)palladium (0.35 g, 0.3 mmol), toluene (20 mL), and a 2-M aqueous solution of sodium carbonate (18 mL, 36 mmol) were added to a 200-mL three-necked flask, and the whole was heated at 80C for 9 hours. Water (100 mL) was added to the reaction liquid in such a manner that a solid would be precipitated. Then, the solid was filtered. The resultant was purified by means of silica gel column chromatography, whereby Intermediate 2-1 was obtained (amount 2.5 g, yield 61 %). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | Stage #1: 1-bromopyrene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: Trimethyl borate In tetrahydrofuran; hexane at -78 - 20℃; for 2h; | 8-1 Synthesis Example 8-1. 1-pyreneboronic acid synthesis To a round bottom flask1-Bromo-pyrene (30g, 107 mmol) was dissolved in 240 mL THF. In the cooling state up to -78 n-BuLi in n-hexane (1.6M) was put in a slow (80 mL). At the end of the addition and then stirred for about 1 hour at -78 was put trimethyl borate (15.5 g, 149 mmol). After 1 hour stirring at -78 stirred at room temperature for about two hours and put in a 2N HCl was adjusted to acidic. While the removal of the solvent after extraction with EA obtained with hexane to give the 1-pyreneboronic acid 19.5 g (yield 74 %). |
74% | With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 3h; | 1-2-a The composition of the synthesis example 1-2-a)1- boron acid pyrene 30 g (107 mmol) of 1-bromopyrene was dissolved in 240 mL of THF in a round bottom flask. The n-BuLi in n-hexane (1.6M) (80 mL) was slowly added to the solution while cooling to -78 ° C. After the addition, trimethylborate (15.5 g, 149 mmol) was added thereto at -78 ° C for about 1 hour. After stirring at -78 ° C for 1 hour, the mixture was stirred at room temperature for 2 hours and 2N HCl was added to adjust the acidity. The solvent was removed by extraction with EA, and crystals were obtained with hexane to obtain 19.5 g (yield: 74%) of 1-pyrene boronic acid. |
70% | Stage #1: 1-bromopyrene With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; hexane at -78 - 20℃; for 24h; Stage #3: With hydrogenchloride In tetrahydrofuran; hexane for 1h; | 1 Synthesis of Pyren-1-ylboronic acid Synthesis of Pyren-1-ylboronic acid An excess of 1.6 M n-BuLi in hexane (50 mL, 80 mmol) was added to a solution of 1-bromopyrene (20.4 g, 72.6 mmol) in 500 ml dry tetrahydrofuran at -78° C. under N2. The reaction mixture was then maintained at 0° C. for 1 h before cooling to -78° C. Trimethyl borate (10.4 g, 100 mmol) was added dropwise; the solution was then warmed slowly to room temperature and stirred for 24 h. 2N HCl (150 ml) was added and then the mixture was stirred for a further 1 h. The reaction mixture was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuo, and the residue was crystallized (n-hexane) to give the pyren-1-ylboronic acid 12.5 g as a yellow solid (70%) |
61% | With hydrogenchloride; n-butyllithium In diethyl ether; hexane BuLi soln. (hexane) addn. to org. compd. soln. (Et2O) at 0°C, mixt. addn. to B-compd. soln. (Et2O) at -78°C over 30 min, stirring 3 h at -50 to -70°C and 60 h at room temp., 2 M HCl addn., stirring 2 h, org. phase sepn.; org. phase washing (water), drying (MgSO4), treating with charcoal, ethereal soln. concn. to dryness, residue vac. drying at 50°C; | |
Stage #1: 1-bromopyrene With n-butyllithium In diethyl ether Stage #2: Trimethyl borate | ||
Stage #1: 1-bromopyrene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; hexane at 20℃; for 18h; Inert atmosphere; | 2.2.4 BPN-Ph General procedure: To a 50mL round flask was added dry THF (20mL) as solvent under nitrogen. The solvent was cooled to -78°C and injected bromobenzene (3mL). Then, a solution of n-butyllithium (1.6M in hexane, 6.5mL) was injected slowly and stirred for 1h. Trimethyl borate (1.17mL) was injected into the mixture and stirred at room temperature for 18h. The mixture was quenched by HClaq (2N) and extracted with DCM. The organic phase was collected and dried over MgSO4. The boronic acid crude product was collected. Then, a mixture of the crude compound (1.120g, 9.20mmol), BPN-Br (3.012g, 8.36mmol), Pd(PPh3)4 (0.193g, 0.167mmol), K2CO3 (2M) (12.5mL) and toluene (20mL) was reacted at 95°C for 12h. After the solvent was removed in vacuo, the residue was extracted with DCM. The organic phase was collected and dried over MgSO4. Finally, the crude product was further purified through silica chromatography using n-Hexane/DCM (5/2 by vol.) as eluent. The yellow powder was obtained (0.81g, 33%). | |
Stage #1: 1-bromopyrene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; hexane at 20℃; for 18h; Inert atmosphere; | 2.2.4 BPN-Ph General procedure: To a 50mL round flask was added dry THF (20mL) as solvent under nitrogen. The solvent was cooled to -78°C and injected bromobenzene (3mL). Then, a solution of n-butyllithium (1.6M in hexane, 6.5mL) was injected slowly and stirred for 1h. Trimethyl borate (1.17mL) was injected into the mixture and stirred at room temperature for 18h. The mixture was quenched by HClaq (2N) and extracted with DCM. The organic phase was collected and dried over MgSO4. The boronic acid crude product was collected. Then, a mixture of the crude compound (1.120g, 9.20mmol), BPN-Br (3.012g, 8.36mmol), Pd(PPh3)4 (0.193g, 0.167mmol), K2CO3 (2M) (12.5mL) and toluene (20mL) was reacted at 95°C for 12h. After the solvent was removed in vacuo, the residue was extracted with DCM. The organic phase was collected and dried over MgSO4. Finally, the crude product was further purified through silica chromatography using n-Hexane/DCM (5/2 by vol.) as eluent. The yellow powder was obtained (0.81g, 33%). |
Yield | Reaction Conditions | Operation in experiment |
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Pd(PPh3)4; In ethanol; toluene; | Synthesis of 2-pyrenyl-9.10-di(naphthalen-2-yl)anthracene <strong>[474688-76-1]2-bromo-9,10-di(naphthalen-2-yl)anthracene</strong> (2.5 g 4.9 mmole) was placed into a 100 ml round bottom flask along with pyrene-1-boronic acid (1.33 g, 5.4 mmole), toluene (30 ml), EtOH 910 ml), and 2.0M aqueous sodium carbonate (9.8 ml). The reaction mixture was purged with nitrogen for 30 minutes and then Pd(PPh3)4(0.01 g), 2-dicyclohexylphosphinobiphenyl (0.01 g) was added. The reaction was heated at reflux for 18 hours and then cooled down to room temperature. A yellow-green product was collected by filtration. The solid was wash with MeOH/H2O and dry in vacuum to get crude product. Further purification was achieved by sublimation (2.0 g, 64.5%). The product was identified through EI-MS measurement, m/s=631 |
Yield | Reaction Conditions | Operation in experiment |
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Pd(PPh3)4; In ethanol; toluene; | Synthesis of 2-pyrenyl-9.10-di(9,9-dimethylfluoren-2-yl)anthracene 2-bromo-9,10-di(9.9-dimethylfluoren-2-yl)anthracene (1.68 g 2.6 mmole) was placed into a 100 ml round bottom flask along with pyrene-1-boronic acid (0.8 g 3.3 mmole), toluene (30 ml), EtOH (10 ml), and 2.0M aqueous sodium carbonate (5 ml). The reaction mixture was purged with nitrogen for 30 minutes and then Pd(PPh3)4(0.02 g), 2-dicyclohexylphosphinobiphenyl (0.01 g) was added. The reaction was heated at reflux for 18 hours and then cool down to room temperature. A yellow-green product was collected by filtration. The solid was wash with MeOH/H2O and dry in vacuum to get crude product. Further purification was achieved by sublimation (0.96 g, 48.5%). The product was identified through FAB-MS measurement, m/s=762 |
Yield | Reaction Conditions | Operation in experiment |
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Pd(PPh3)4; In ethanol; toluene; | Synthesis of 2-pyrenyl-9,10-di(naphthalen-1-yl)anthracene 2-bromo-9,10-di(naphthalen-1-yl)anthracene (2.2 g 4.3 mmole) was placed into a 100 ml round bottom flask along with pyrene-1-boronic acid (1.16 g 4.73 mmole), toluene (30 ml), EtOH (10 ml), and 2.0M aqueous sodium carbonate (8.6 ml). The reaction mixture was purged with nitrogen for 30 minutes and then Pd(PPh3)4 (0.01 g), 2-dicyclohexylphosphinobiphenyl (0.01 g) was added. The reaction was heated at reflux for 18 hours and then cooled down to room temperature. A yellow-green product was collected by filtration. The solid was wash with MeOH/H2O and dry in vacuum to get crude product. Further purification was achieved by sublimation (1.45 g, 53.5%). The product was identified through FAB-MS measurement, m/s=630 |
Yield | Reaction Conditions | Operation in experiment |
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87% | Stage #1: 1-Bromo-2-iodobenzene With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine In 1,2-dimethoxyethane for 0.25h; Inert atmosphere; Schlenk technique; Stage #2: 1-pyrenylboronic acid With sodium carbonate In water at 95℃; for 12h; Inert atmosphere; Schlenk technique; | |
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene for 10h; Inert atmosphere; Reflux; | 1 Synthesis of Compound II Under the protection of argon, 1-boronic acid (24.6 g), o-bromoiodobenzene (31.0 g), toluene (300 mL), water (30 mL) were sequentially added to the flask.Tetrakis(triphenylphosphine)palladium (200 mg) and potassium carbonate (27.6 g) were heated under reflux for 10 h.The reaction was stopped, extracted three times with ethyl acetate, and the organic phases were combined and washed with water to neutral;The organic phase was separated, dried over anhydrous magnesium sulfate, suction filtered and dried.Silica gel column chromatography gave white solidCompound II 30.3 g, yield 85%. |
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene for 10h; Inert atmosphere; Reflux; | 1 Synthesis of Compound II Under the protection of argon, 1-pyreneboronic acid (24.6g) was added to the flask in sequence,O-Bromoiodobenzene (28.2g), toluene (300mL), water (30mL),Tetrakis (triphenylphosphine) palladium (200mg), potassium carbonate (27.6g), heated to reflux for 10h.Stop the reaction, extract three times with ethyl acetate, combine the organic phases,Wash with water until neutral; separate the organic phase, dry with anhydrous magnesium sulfate, filter with suction,Spin dry; silica gel column chromatography to obtain 30.3g of white solid compound II, yield 85%. |
75% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 90℃; for 9h; Inert atmosphere; | 2 Under an argon atmosphere, 2.99 g (12.1 mmol) of 1-pyreneboronic acid, 3.76 g (13.3 mmol) of 2-bromoiodobenzene, 0.70 g (0.61 mmol) of tetrakis(triphenylphosphine) palladium, toluene 20 mL, ethanol 15 mL, and 15 mL of 2M sodium carbonate aqueous solution were added. Heated to 90 °C and the mixture was stirred for 9 hours. After cooling the reaction vessel to room temperature, the solvent was distilled off, the residue was purified using silica gel column chromatography (hexane) 3.20 g of 1- (2-bromophenyl)pyrene (white solid, 9.0 mmol, Yield 75%). |
75% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 90℃; for 9h; Inert atmosphere; | |
75% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 90℃; for 9h; Inert atmosphere; | 1 Reference Example 1 In an argon atmosphere, in a reaction vessel, 2.99 g (12.1 mmol) of 1-pyreneboronic acid, 3.76 g (13.3 mmol) of 2-bromoiodobenzene, 700 mg (0.61 mmol) of tetrakis(triphenylphosphine)palladium; 15 mL (7.5 mmol) of 0 M aqueous sodium carbonate solution, 20 mL of toluene and 15 mL of ethanol were added.The reaction mixture was heated to 90 ° C. and stirred for 9 hours.After cooling to room temperature, the solvent was distilled off under reduced pressure.The obtained residue was purified by silica gel column chromatography (eluent hexane) to obtain 1-(2-bromophenyl)pyrene (white solid, 3.20 g, 9.0 mmol, yield 75%). |
47% | With tetrakis(triphenylphosphine) palladium(0); 1,2-dimethoxyethane; potassium carbonate In water at 20 - 120℃; Inert atmosphere; | |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran at 120℃; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane; water at 70℃; for 120h; Inert atmosphere; | |
33% | With sodium carbonate In 1,4-dioxane; water at 75℃; for 72h; | 4'-iodo-2',6'-dipyrazolyl-pyridine (0.674g, 2 mmol), pyreneboronicacid (0.492 g, 2 mmol) and Pd(PPh3)4 (0.231 g, 0.2 mmol, 10%) were suspended in a N2 gas bubbled solution of 1, 4-dioxane (150 mL) and 2M Na2CO3 (5 mL) and heated to 75°C for 3 days under nitrogen atmosphere. The 1,4-dioxane was removed using a rotary evaporator and the remaining residue was treated with water and extracted with CH2Cl2 solvent. The separated organic layer was dried over MgSO4 and the solvent was removed by evaporation. The solid yellow residue was washed with methanol to remove the soluble impurities and to afford a white coloured powder. The solid residue was column chromatographed on silica with dichloromethane eluent and the second colourless fraction was collected and the resultant combined solution upon evaporation yielded bluish white powder of VI (0.270 g, yield 33%). 1H NMR (300 MHz, CDCl3, 25 °C): δ = 8.73 (dd, 2H), {8.28, 8.27, 8.25, 8.26, 8.24, 8.23, 8.22 (m, 4H pyrene)}, 8.18 (s, 2H), {8.17, 8.14, 8.13, 8.11, 8.09, 8.08, 8.07, 8.05, 8.02 (m, 5H, pyrene)}, 7.78 (d, 2H), 6.55 (m, 2H) ppm. |
Yield | Reaction Conditions | Operation in experiment |
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67% | With sodium hydrogencarbonate In 2-ethoxy-ethanol; water at 90℃; for 18h; Inert atmosphere; | a 6-Bromo-2-methylquinoline (4.5; 20mmole) was dissolved in 2-ethoxy ethanol (30 ml) and to the magnetically stirred solution under nitrogen was added tetrakis(triphenyl phosphine) palladium (1 g; 0.9 mmole). After 5 minutes stirring at room temperature, 1-pyreneboronic acid (5.0 g; 20mmole) was added followed by 2- ethoxyethanol (10 ml). Sodium hydrogencarbonate (10 g; 94 mmole) in water (60 ml) was added all at once and the reaction mixture was stirred and heated under nitrogen atmosphere at 90 0C for 18 h. The reaction mixture was allowed to cool, dichloromethane (100 ml) was added and the reaction mixture was filtered through a layer of silica gel. To the filtrate further dichloromethane (50 ml) was added and extracted with de-ionised water (2 x 100 ml). The organic phase was dried over anhydrous magnesium sulphate and the solvent removed to give the required product. The product was dried under vacuum at 80 0C, Yield 4.5 g (67 %). Mp 133 0C (DSC, onset). Elemental analysis: Found C 90.80, H 5.09, N 4.32; C26H17N requires C 90.93, H 4.99 and N 4.08 %. |
67% | Stage #1: 6-Bromo-2-methyl-quinoline With tetrakis(triphenylphosphine) palladium(0) In 2-ethoxy-ethanol at 20℃; for 0.0833333h; Inert atmosphere; Stage #2: 1-pyrenylboronic acid With sodium hydrogencarbonate In 2-ethoxy-ethanol; water at 90℃; for 18h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With sodium carbonate In methanol; toluene at 80℃; for 120h; Inert atmosphere; Darkness; | 22 Synthesis of 5-[(1-pyrenyl)-3-pyridyl]-10,15,20-tris-(4-pyridyl)-21H,23H-porphyrin ('TPy3PyPyr1P') Example 22 Synthesis of 5-[(1-pyrenyl)-3-pyridyl]-10,15,20-tris-(4-pyridyl)-21H,23H-porphyrin ("TPy3PyPyr1P") 16.99 µmol TPy3PyBr1P and 33.97 µmol pyrene-1-boronic acid are dissolved in 40 ml toluene and 10 ml methanol. Then the mixture is degassed and saturated with argon. After that 0.9 µmol tetrakis(triphenylphosphine)palladium(0) and 1 ml 2 M Na2CO3 solution are added under argon atmosphere. Then the reaction mixture is protected from light, heavily stirred and heated up to 80 °C for 120 h. After that, the reaction mixture is filtered, extracted with deionized water, dried over Na2SO4 and evaporated to dryness. For the purification of the crude product, intensive column chromatography is needed. Silica gel is used as stationary phase and the product is eluted using a mixture of CHCl3 :MeOH 49:1 (v/v). The second band is the desired product, which is evaporated to dryness after the separation process. Yield: 94 % 1H-NMR (500 MHz, CDCl3, 303.57 K, δ): 9.59 (s, 1H, pyridyl-4-H-a), 9.38 (s, 1H, pyridyl-6-H-a), 9.11 (d, J = 4.19, 2H, β-pyrrole-H), 9.08 (m, 4H, pyridyl-3,5-H-b), 9.08 (m, 2H, pyridyl-3,5-H-c), 8.95 (d, J = 4.19, 2H, β-pyrrole-H), 8.88 (s, 4H, β-pyrrole-H), 8.88 (m, 1H, pyrenyl-H), 8.83 (bs, 1H, Pyridyl-2-H-a), 8.52 (d, J = 9.24, 1H, pyrenyl-H), 8.35 (d, J = 7.91, 1H, pyrenyl-H), 8.30 (d, J = 7.91, 1H, pyrenyl-H), 8.25 (d, J = 8.54, 1H, pyrenyl-H), 8.22 (d, J = 9.29, 2H, pyrenyl-H), 8.18 (M, 4H, pyridyl-2,6-H-b), 8.18 (m, 2H, pyridyl-2,6-H-c), 8.05 (t, J = 7.61, 1H, pyrenyl-H), 7.72 (d, J = 4.56, 1H, pyrenyl-H), -2.84 (s, 2H, pyrrole-NH) 13C-NMR (125 MHz, CDCl3, 303.57 K, δ): 152.3 (d, 1C, pyridyl-4-a-CH), 150.8 (d, 1C, pyridyl-6-a-CH), 150.8 (d, 1C, pyrenyl-CH), 150.1 (s, 4C, quart. ipso pyridyl-l-C), 148.5 (d, 4C, pyridyl-3,5-b-CH); 148.5 (d, 2C, pyridyl-3,5-c-CH), 142.9 (d, 1C, pyridyl-2-a-CH), 137.4 (s, 1C, quart. pyrenyl-C), 135.6 (s, 1C, quart pyrenyl-C), 133.8 (s, 8C, quart. α-pyrrole-C), 132.9 (s, 1C, quart. pyridyl-5-C), 131.7 (s, 2C, quart. pyrenyl), 131.4 (d, 8C, β-pyrrole-CH), 131.0 (s, 1C, quart. pyrenyl-C), 129.2 (s, 1C, quart. pyrenyl-C), 128.1 (d, 1C, pyrenyl-CH), 126.5 (d, 1C, pyrenyl-CH), 125.9 (d, 1C, pyrenyl-CH), 125.5 (d, 2C, pyrenyl-CH), 125.1 (d, 1C, pyrenyl-CH), 125.0 (s, 1C, quart. pyrene-1-C), 124.3 (d, 1C, pyrenyl-CH), 122.3 (d, 1C, pyrenyl-CH), 118.0 (s, 2C, quart. meso pyridyl-1-b-C), 117.8 (s, 1C, quart. meso pyridyl-c-C), 117.0 (s, 1C, meso pyridyl-1-a-C) ESI-MS (Chloroform/Methanol 1:1, positive ion mode): m/z = 819.67 ([M+H]+). C56H34N8 theoretical mass = 818.29 |
Yield | Reaction Conditions | Operation in experiment |
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72% | Stage #1: 1-bromopyrene With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Stage #2: Triisopropyl borate In tetrahydrofuran | Synthesis of 1-boropyrene (7) 1-Bromopyrene (1.0g, 3.56 mmol) was dissolved in anhydrousTHF solution (20 mL) and stirred at-78C. Then, 1.6Mn-BuLi (2.1 mL) was added.Triisopropyl borate (1.2 mL) was added to the reaction after 30 min. After the reactionwas finished, the solution was acidified with 2 N HCl solution at room temperature andextracted with ethyl acetate and water. The organic layer was dried with anhydrous MgSO4and filtered. The solution was evaporated. The residue was redissolved in hexane and addedto ethyl acetate. The precipitate was filtered and washed with hexane to obtain a beigecompound (0.63 g, 72%). 1H-NMR (300 MHz, DMSO): δ(ppm) = 8.72-8.69 (d, 1H) 8.60 (s, 2H) 8.30-8.15 (m,7H) 8.06-8.04 (t, 1H). |
68% | Stage #1: 1-bromopyrene With n-butyllithium In tetrahydrofuran at -100℃; for 2h; Inert atmosphere; Stage #2: Triisopropyl borate In tetrahydrofuran for 4h; Inert atmosphere; | 3.3 (3) Synthesis of 1-pyrene boronic acid In the nitrogen,Clean and dry 1000ml three-mouth bottle,Add 1-bromoindole, THF,Cool down to -100°C,Butyllithium, plus complete, insulation 2h,Triisopropyl borate was added dropwise, incubated for 4 h, acidified with hydrochloric acid, washed with water, dehydrated with solvent, and beaten with toluene.Get 1 - deuterated boric acid;HPLC: 99.3%, yield: 68%; |
60% | With hydrogenchloride In tetrahydrofuran | S.6.1 <Step 9> Synthesis of pyrene-1-boronic acid (Compound 1-13) Synthesis of pyrene-1-boronic acid (Compound 1-13) 1-Bromopyrene (compound 1-12, 30 g) was dissolved in tetrahydrofuran (500 ml). The reaction mixture was cooled to -78° C. and stirred for one hour while gradually adding an n-butyllithium solution (1.6N, 80 ml) thereto, and triisopropylborate (30 ml) was added thereto. The reaction solution was gradually raised to room temperature and stirred at that temperature for 15 hours. 1N HCl (250 ml) was gradually added and an aqueous layer was removed. The resultant organic layer was washed with a saturated ammonium chloride solution and a saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated. The crude product was recrystallized from n-hexane to give a titled compound (15.7 g, yield 60.0%) as a pale yellow solid. |
51% | With n-butyllithium In tetrahydrofuran at -78 - 20℃; Inert atmosphere; | Synthesis of Compound 1 1-Bromo-pyrene 10 g was added to 500 mL round floorflask, melted in anhydrous tetrahydrofuran (THF) 120 mL, and agitated. After reaction temperature was set to -78 C,2.0 M n-Butyllithium 23.4 mL (50.59 mmol) was addedinto reaction mixture slowly. In 10 minutes, triisopropylborate 10 mL was added to reaction mixture. When reactiontemperature increased to room temperature in an hour,12 M HCl 7.2 mL was added. The reaction was completed,compound was extracted with ethyl acetate (EA)and water, and the organic layer was dried with anhydrousMgSO4 and filtered. After the compound was concentratedunder reduced pressure, white solid was obtained in 51%.1H-NMR (300 MHz, THF-d8) (ppm): 8.89-8.85(m, 1H), 8.32-8.28 (m, 1H), 8.21-8.15 (m, 3H), 8.14-8.03(m, 3H), 8.01-7.94 (m, 1H), 7.10 (s, 2H). |
With n-butyllithium In tetrahydrofuran; hexane; water at -78 - 20℃; for 24h; | ||
With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
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63% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; for 10h;Inert atmosphere; Reflux; | Synthesis of Intermediate A2; Intermediate A1 (2.5 g, 6.9 mmoles), 1-pyreneboronic acid (1.7 g, 6.9 mmoles) and tetrakis(triphenylphosphine)palladium(0) (0.24 g, 0.21 mmoles, 3% Pd) were suspended in 1,2-dimethoxyethane (20 mL) under a nitrogen atmosphere, to which was then added a 2M sodium carbonate aqueous solution (2.2 g, 21 mmoles, 3 eq./10 mL), and the mixture was refluxed for 10 hours. Toluene (150 mL) and water (50 mL) were added to the reaction mixture, an organic layer was aliquoted, washed with saturated salt water (50 mL) and then dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a pale yellow solid. This was purified by means of column chromatography (silica gel/hexane and 17% dichloromethane) to obtain a white solid (1.9 g, 63%). 1H-NMR (400 MHz, CDCl3, TMS): delta7.32 (1H, d, J = 8 Hz), 7.60 (1H, dd, J = 8 Hz, 2 Hz), 7.68 (1H, d, J = 9 Hz), 7.83 (1H, d, J = 8 Hz), 7.96 to 8.02 (3H, m), 8. 10 (2H, s), 8.16 (1H, d, J = 8 Hz), 8.20 (1H, d, J = 8 Hz), 8.21 (1H, d, J = 8 Hz) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 10h;Inert atmosphere; Reflux; | Synthesis of Intermediate D2; Intermediate D1 (12.4 g, 39 mmoles), 1-pyreneboronic acid (9.6 g, 39 mmoles) and tetrakis(triphenylphosphine)palladium(0) (1.4 g, 1.2 mmoles, 3% Pd) were suspended in 1,2-dimethoxyethane (120 mL) under a nitrogen atmosphere, to which was then added a 2M sodium carbonate aqueous solution (12.4 g, 0.12 moles, 3 eq./60 mL), and the mixture was refluxed for 10 hours. Toluene (200 mL) and water (50 mL) were added to the reaction mixture, an organic layer was aliquoted, washed with saturated salt water (50 mL) and then dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a brown solid. This was purified by means of column chromatography (silica gel/hexane and 10% dichloromethane) to obtain a white solid (11. 7g, 77%). 1H-NMR (400 MHz, CDCl3, TMS): delta7.38 (1H, d, J = 8 Hz), 7.45 (1H, dd, J = 8 Hz, 2 Hz), 7.68 (1H, d, J = 9 Hz), 7.81 (1H, d, J = 2 Hz), 7.83 (1H, d, J = 8 Hz), 7.99 (1H, d, J = 7 Hz), 8.00 (1H, d, J = 9 Hz), 8.09 (2H, s), 8.16 (1H, d, J = 7Hz), 8.19 (1H, d, J = 7 Hz), 8.21 (1H, d, J = 8 Hz) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In N,N-dimethyl-formamide at 105℃; for 10h; Inert atmosphere; | The typical procedure of cross-coupling reactions (Table 2, entry 1): General procedure: K2CO3 (83 mg, 0.6 mmol) and p-(methoxycarbonyl)phenylboronic acid (81 mg, 0.45 mmol) were dried in vacuo in a Schelenk tube with heating, then bromide 16 (149 mg, 0.3 mmol), and Pd(PPh3)4 (69 mg, 0.06 mmol) were added. The whole system was evacuated and backfilled with argon three times, and 1.2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 min, and then conducted at 105 °C for 21 h. After the reaction, the mixture was diluted with 15 mL EtOAc, and filtered through a pad of Celite and florisil. Purification by silica gel column chromatography gave 17 (134 mg, 81%) as pale yellow solid materials. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.1% | With potassium phosphate In N,N-dimethyl-formamide at 70℃; for 8h; Inert atmosphere; | 9 (Example 9) According to the following reaction formula (scheme), Ex. 9 compound was synthesized.Pd(PPi¾)4, K3PO4 13 DM FEx. 9- 1 compoundA 200 mL three-neck flask was charged with Compound 13 (1.6 g, 1.0 mmol), potassium phosphate (0.5 g) and DMF (30 mL). The resultant mixture was bubbled with argon for 30 min. Thereafter, 1 -pyrenylboronic acid (0.62 g, 2.5 mmol) andtetrakis(triphenylphosphine)palladium(0) (104 mg, 0.18 mM) were added to the mixture, followed by stirring under heating at 70°C for 8 hours. The mixture was cooled to room temperature. The precipitate of interest was recovered through filtration, washed with hexane, and recrystallized from toluene, to thereby obtain Ex. 9 1 compound (yield amount: 500 mg, yield rate :84.1%). The analysis results of Ex. 9 compound are shown below. Mass spectrometry: GC-MS m/z = 594(M+) From the above analysis results, it was confirmed that a structure of the synthesized product did not contradict that of Ex. 9- 1 compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With Fe2O3-SiO2 nanoparticles; air; In water; at 50℃; for 5h;Green chemistry; | General procedure: In a round bottomed flask 1 mmol phenyl boronic acid, and4mg of Fe2O3SiO2 in 4 ml of the H2O were taken and stirred atroom temperature for appropriate time. Progress of the reactionwas monitored by TLC. After completion of the reaction mixturewas extracted with Ethyl acetate. Further, the organic layer wasseparated and dried with sodium sulfate. The mixture was concentratedin rotary evaporator and product was purified by column chromatography. The product was analyzed by taking 1H and 13CNMR spectroscopy. |
71% | With oxygen; triethylamine; In 2-methyltetrahydrofuran; at 20℃; under 760.051 Torr; for 48h;UV-irradiation; | General procedure: [1,1'-Biphenyl] -4-phenylboronic acid (59.4mg, 0.3mmol, 1.0equiv) was added to a dried 20mL quartz test tube,Vacuum the quartz test tube while backfilling with oxygen three times.Under oxygen conditions, Et3N (62.5 L, 0.45 mmol, 1.5 equiv) and 2-methyltetrahydrofuran (4 ml) were sequentially added through a syringe.The resulting mixture was stirred for 5 minutes, then the quartz test tube was transferred to a photoreactor.The test tube was placed about 2 cm from the 15W UV lamp.The reaction mixture was stirred and illuminated for 24 h,After the specified time, the crude product was diluted with ethyl acetate, filtered through a pad of silica gel, and concentrated under reduced pressure.Flash chromatography on silica gel was then performed directly on silica gel (EtOAc / PE = 1/10) to give the desired product 1b (92% yield, white solid). |
45% | With 2,2-dimethoxy-2-phenylacetophenone; N-ethyl-N,N-diisopropylamine; In water; at 20℃; for 72h;Irradiation; Green chemistry; | General procedure: Substituted boronic acid (0.60 mmol) was placed in a glass vial and dissolved in water(1.0 mL), followed by 2,2-dimethoxy-2-phenylacetophenone (30.0 mg, 0.12 mmol).DIPEA (580 mg, 4.50 mmol) was added consecutively. The reaction mixture was leftopen stirring at room temperature under household bulb irradiation (2 x 80W householdlamps, see photos below) under open air (in the present of O2) for 72 hours. The reactionmixture was quenched by aqueous solution of HCl (1N, 20 ml). The reaction mixturewas extracted with Et2O (20 mL). The organic layer was washed with brine (20 mL)and dried over Na2SO4. After removal of the solvent in vacuum, the crude product waspurified using flash column chromatography (10% EtOAc in Pet. Ether) to afford thedesired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium carbonate In tetrahydrofuran; water at 70℃; for 5h; | 1 4.93 g (20.0 mmol) of pyren-1-yl-1-boronic acid, 4.04 g (20.0 mmol) of 2-bromonitrobenzene, 1.15 g (1.0 mmol) of Pd(PPh3)4, and 8.29 g (60.0 mmol) of K2CO3 were dissolved in 60 mL of a mixed tetrahydrofuran (THF) and H2O (2:1) solution to obtain a solution, which was then stirred at about 70°C for about 5 hours. The reaction solution was cooled to room temperature, and 100 mL of water was added thereto, followed by three times of extraction with 50 mL of ethylether. The organic phase was collected, and was dried using magnesium sulfate to evaporate the solvent. The residue was separated and purified using silica gel column chromatography to obtain 5.95 g of Intermediate I-1 (Yield: 92 %). This compound was identified using liquid chromatography-mass spectroscopy (LC-MS) and nuclear magnetic resonance (NMR). C22H13NO2 : M+ 323.1 1H NMR (CDCl3, 400MHz) δ (ppm) 8.22-8.20 (d, 2H), 8.17-8.10 (m, 4H), 8.03-8.01 (d, 1H), 8.01-7.98 (d, 1H), 7.88-7.85 (d, 1H), 7.69-7.67 (m, 2H), 7.66-7.56 (m, 2H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With sodium hydroxide;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; at 70℃; for 3h;Inert atmosphere; Reflux; | In a stream of argon, 1.26 g (5.13 mmol) of 1-pyreneboronic acid, 1.00 g (2.14 mmol) of <strong>[1073062-59-5]2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine</strong> and 60.1 mg (0.081 mmol) of dichlorobis(triphnylphosphine)palladium were suspended in 75 mL of tetrahydrofuran, and the temperature of the obtained suspension was elevated to 70C. 4.01 mL (16.1 mmol) of an aqueous 4N NaOH solution was gradually added dropwise to the suspension, and the obtained mixture was distilled under reflux for 3 hours. The resultant reaction mixture was left to stand to room temperature, and then distilled under a reduced pressure to remove all volatile materials. Methanol was added to the concentrate, and the thus-deposited solid was collected by filtration. The thus-obtained crude product was recrystallized from o-xylene to give 1.23 g of the target 2-[3,5-di(1-pyrenyl)-phenyl]-4,6-diphenyl-1,3,5-triazine as grayish white solid (yield: 81%). 1H-NMR(CDCl3):delta.7.55(t,J=7.0Hz,4H),7.60(t,J=7.1Hz,2H),8.08 (t,J=7.6,2H),8.11-8.21(m,7H),8.24(d,J=7.5Hz,2H),8.27(d,J=8.7Hz, 2H),8.31(d,J=8.1Hz,2H),8.38(d,J=7.8Hz,2H),8.48(d,J=9.3Hz,2H),8.80 (d,J=7.2Hz,4H),9.20(s,2H). The melting point and Tg of the obtained compound are shown in Table 1, below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; at 60℃; for 3h;Inert atmosphere; | In a stream of argon, 0.53 g (2.14 mmol) of 1-pyreneboronic acid, 1.00 g (2.14 mmol) of <strong>[1073062-59-5]2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine</strong> and 24.7 mg (0.0214 mmol) of tetrakis(triphenylphosphine)palladium were-suspended in a mixed solvent composed of 80 mL of toluene and 10 mL of ethanol, and the resultant suspension was heated to 60C. To the suspension, 8.56 mL (8.56 mmol) of an aqueous 1M K2CO3 solution was gradually added dropwise, and the mixture was stirred for 3 hours. Then the mixture was cooled to room temperature, and 0.64 g (3.21 mmol) of 4-(2-pyridyl)phenylboronic acid wad added. Then the mixture was heated to 70C and maintained at that temperature for 3 hours while being stirred. Then the reaction mixture was cooled to room temperature, and was then distilled under a reduced pressure to remove all volatile materials. Methanol was added to the concentrate, and the thus-deposited solid was collected by filtration. The obtained crude product was purified by silica gel chromatography using a hexane/chloroform (1:2) mixed solvent as an eluent to give 0.37 g of the target 4,6-diphenyl-2-[5-(1-pyrenyl)-4'-(2-pyridyl)biphenyl-3-yl]-1,3,5-triazine as a white solid (yield: 26%). 1H-NMR(CDCl3):delta.7.35(brs,1H),7.57-7.65(m,6H),7.86-7.91(m, 2H),8.03(d,J=8.4Hz,2H),8.08(t,J=7.6Hz,1H),8.13(d,J=9.3Hz,1H),8.18 -8.29(m,8H),8.33(d,J=9.3Hz,1H),8.37(d,J=7.8Hz,1H),8.80(d,J=4.8Hz, 1H),8.83(d,J=7.9Hz,4H),9.07(s,1H),9.23(s,1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With sodium hydroxide In tetrahydrofuran at 70℃; for 6h; Inert atmosphere; Reflux; | 59 In a stream of argon, 1.20 g (4.87 mmol) of 1-pyreneboronic acid, 1.50 g (3.03 mmol) of 2-(3,5-dibromophenyl)-4,6-di-p-tolyl--1,3,5-triazine and 57 mg (0.081 mmol) of dichlorobis-(triphenylphosphine)palladium were suspended in 135 mL of tetrahydrofuran, and the temperature of the obtained suspension was elevated to 70°C. 3.81 mL (15.2 mmol) of an aqueous 4N NaOH solution was gradually added dropwise to the suspension, and the obtained mixture was distilled under reflux for 2 hours. Then, 29 mg (0.041 mmol) of dichlorobis(triphenylphosphine)palladium was added, followed by distillation under reflux for 2 hours. Further, 0.20 g (0.81 mmol) of 1-pyreneboronic acid was added, followed by distillation under reflux for 2 hours. The resultant reaction mixture was left to stand to room temperature, and then distilled under a reduced pressure to remove all volatile materials. Methanol was added to the concentrate, and the thus-deposited solid was collected by filtration. The thus-obtained crude product was recrystallized from o-xylene. The recrystallization by o-xylene was repeated three times in total to give 1.14 g of the target 2-[3,5-di(1-pyrenyl)phenyl]--4,6-di-p-tolyl-1,3,5-triazine as grayish white solid (yield: 51%). 1H-NMR(CDCl3):δ.2.46(s,6H),7.33(d,J=8.0Hz,4H),8.08(t,J=7.6 Hz,2H),8.16(d,J=9.3Hz,2H),8.19(d,J=3.7Hz,4H),8.21(s,1H),8.24(d,J= 7.4Hz,2H),8.27(d,J=9.0Hz,2H),8.29(d,J=8.0Hz,2H),8.37(d,J=7.9Hz, 2H),8.48(d,J=9.3Hz,2H),8.67(d,J=8.2Hz,4H),9.18(s,2H). The melting point and Tg of the obtained compound are shown in Table 1, below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 90℃; for 24h;Inert atmosphere; | Synthesis of 1-(6-bromonaphthalen-2-yl)pyrene A mixture of 12 g (42.4 mmol) of <strong>[13720-06-4]2,6-dibromonaphthalene</strong>, 10.43 g (42.4 mmol) of Pyren-1-ylboronic acid, 0.5 g (0.424 mmol) of Tetrakis(triphenylphosphine)palladium, 32 ml of 2M Na2CO3, 80 ml of EtOH and 160 ml toluene was degassed and placed under nitrogen, and then heated at 90 C. for 24 h. After the reaction finish, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica (hexane-dichloromethane) to give product 8.3 g (48%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; toluene at 85℃; for 4h; Inert atmosphere; Schlenk technique; | |
89.8% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran; water at 85℃; Inert atmosphere; | |
45% | With potassium phosphate; palladium diacetate; tricyclohexylphosphine In water; toluene at 150℃; for 0.0166667h; Microwave irradiation; | Synthesis of 4-arylstyrenes (3a-e) (general procedure) General procedure: The corresponding arylboronic acid (2a-e) (1.5 mmol) and K3PO4 (531 mg, 2.5 mmol) were added to a solution of 1-bromo-4-vinylbenzene (1) (182 mg, 1.0 mmol) in a mixture of toluene (5 mL) and H2O (0.25 mL). The resulting reaction mixture was microwave irradiated at 150 °C (250 W) for 1 min, and the solvent was distilled off in vacuo. The obtained residue was separated by chromatography using hexane as the eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With palladium diacetate; caesium carbonate In ethanol; water at 100℃; for 1.5h; Inert atmosphere; Microwave irradiation; Sealed tube; | 1 General procedure for the Suzuki-Miyaura couplings giving 7-aryl-9,9,9a-trimethyl-9,9a-dihydro-1H-imidazo[1,2-a]indol-2(3H)-ones (7a-e) General procedure: A sealed vessel containing a mixture of compound 4 (295mg, 1mmol), an appropriate boronic acid (1.20-1.50mmol), Cs2CO3 (652mg, 2mmol), ethanol (2mL), water (2mL) and Pd(OAc)2 (29mg, 0.13mmol) was irradiated (50W) under Ar atmosphere at 100°C for the indicated time. After cooling to rt the reaction mixture was filtered over Celite, the filter cake was washed with tetrahydrofuran (5mL). The filtrate was concentrated under reduced pressure and the residue was dissolved in dichloromethane (10mL). The solution was washed with brine (5mL), organic layer was separated, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel [hexane/dichloromethane 1:1→dichloromethane→dichloromethane/methanol 100:1 (v/v)] and the obtained target product was recrystallized from acetone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With potassium phosphate; C20H25O3P; palladium diacetate In toluene at 30℃; for 8h; Inert atmosphere; enantioselective reaction; | 4.4. General procedure of asymmetric Suzuki-Miyaura cross-coupling General procedure: To a mixture of 1-bromonaphthalen-2-yl triflate (0.1 mmol),arylboronic acid (0.15 mmol, 1.5 equiv), potassium phosphate (0.3 mmol, 3 equiv), palladium acetate (1 mol %) and ligand(1.2 mol %, Pd/L1/1.2) was charged toluene 1.2 ml. The mixture was stirred at 30 C under nitrogen for 8 h. Ethyl acetate (4 ml) andwater (4 ml) was added and the organic layer was separated, washed sequentially with water and brine (5 ml3), dried over sodium sulfate, concentrated and purified by silica gel column chromatography to provide biaryl products. The ee’s were determined by chiral HPLC on a chiralcel OD-H column. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With potassium carbonate; In 1,2-dimethoxyethane; water; at 85℃; for 18h;Inert atmosphere; | General procedure: The halogen compound, the boronic acid, Pd(P93u3)4 and the solvent were mixed togethet A degassed 2M aqueous K2C03 solution was added. The mixture was stirred at 85 C. (oil bath temperature) for 18 h and cooled afierwards. In case that a solid precipitated, the solid was filtered off and purified by column chromatography directly. Otherwise, the organic phase was washed with water, dried over Na2504, reduced to dryness and purified by column chromatography afierwards. According to general procedure B (0141) <strong>[5525-40-6](4-bromophenyl)diphenylphosphine oxide</strong>: 4.8 g (13.4 mmol, 1.0 eq) (0142) 1-pyreneboronic acid: 3.97 g (16.1 mmol, 1.2 eq) (0143) Pd(PPh3)4: 466 mg (0.40 mmol, 3 mol. %) (0144) K2CO3, 2M: 20 mL (0145) 1,2-dimethoxyethane (DME): 60 mL (0146) Column chromatography: SiO2, ethyl acetate (0147) Yield: 4.45 g (69%) pale yellow solid (0148) mp: 208 C. (0149) EI-MS: m/z=478 |
41% | With potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; In 1,4-dioxane; at 100℃; for 7h;Inert atmosphere; | Under the argon atmosphere, in 1-Pyren boric acid (2.21g, 9 . 00mmol), (4-bromophenyl) phosphine oxide (3.21g, 9 . 00mmol), tris(dibenzylideneacetone)dipalladium(0) (124 mg, 0 . 135mmol), triphenylphosphine (283 mg, 1 . 08mmol), potassium phosphate (11.5g, 54 . 0mmol) is added in 1,4-dioxane (100 ml), the 100 C stirring 7 hours. After the reaction, the mixture is diluted with water, extraction with chloroform. Furthermore, the mixture is saturated salt water for washing, by using magnesium sulphate concentration is carried out after drying. Furthermore, the mixture after the purification by the silica gel column chromatography, in re-crystallization from ethyl acetate, to obtain compound (1.77g, 3 . 69mmol) (yield 41%). The compound is the quality of the result of the analysis m/e=478, identified as the above-mentioned compound (6) (Exact mass: 478.15). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium phosphate; palladium diacetate; XPhos In water; toluene; butan-1-ol at 100℃; for 19h; Inert atmosphere; | 3 Under a stream of argon, 4,6-diphenyl-2-[3-chloro-5-(2-pyridyl)phenyl]pyrimidine (1.0g), 1-pyreneboronic acid (645mg), palladium acetate (10.7mg), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (68 mg), 3M potassium phosphate aqueous solution (1.6 mL), were suspended in a mixed solvent of toluene (9.5 mL) and 1-butanol (2.4 mL) and stirred for 19 h at 100 . After cooling the reaction, water was added and methanol. The precipitated solid was filtered off, washing with water and methanol afforded the target compound 4,6-diphenyl-2-[5-(1-pyrenyl)-3-(2-pyridyl)phenyl]pyrimidine (A-2) as yellow powder (1.35 g, 97% yield).; Purification Example - 2 Heating yellow powder Compound A-2 (7.70g) to 330 C under 1.0×10-3 Pa vacuum to purify by sublimation afforded yellow powder Compound A-2 (5.90 g, 77% yield, 99% purity). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 80℃; for 12h; | 10 Synthesis Example 10: Synthesis of Compound 1-4-4 Put 4-bromobenzaldehyde (10.0g, 54.1mmol) and 1-pyrene-1-ylboronic acid (15.0g, 61.0mmol) into the reaction flask, toluene (100 ml) was added. Dissolve potassium carbonate (18.7g, 135.3mmol) in 60ml deionized water and add it to the reaction tank. Add tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (3.1g, 2.7mmole) and ethanol (20ml) to open Heat and stir. The reaction was heated to 80 ° C for 12 hours. After the reaction was completed, 80 ml of deionized water was added and stirred for 30 minutes to perform extraction. The filtrate after extraction was filled with silica gel for chromatography purification, concentrated to a thick, 150 mL of hexane (Hexanes) was added to precipitate, and the solid was filtered after precipitation the white solid intermediate compound 1-4-4-A1 was obtained(10.3 g, 62% yield). |
62% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 80℃; for 12h; | 10 Put 4-bromobenzaldehyde (10.0 g, 54.1 mmol) and pyrene-1-ylboronic acid (15.0 g, 61.0 mmol) in the reaction flask, and add toluene (100 ml). Dissolve potassium carbonate (18.7 g, 135.3 mmol) in 60 ml of deionized water and add it to the reaction tank. Add tetrakis(triphenylphosphine)palladium (Pd(PPh3 )4) (3.1 g, 2.7 mmole) and ethanol (20 ml) Turn on heating and stirring. Heated to 80 for 12 hours. After the reaction, 80ml of deionized water was added and stirred for 30 minutes for extraction. The extracted filtrate was filled with silica gel and purified by chromatography, concentrated to a thick, 150mL of Hexanes was added for precipitation, and the solid was filtered after precipitation to obtain White solid intermediate compound 1-4-4-A1 (10.3 g, yield 62%). |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene;Inert atmosphere; Reflux; | Compound 2586 synthesis: with intermediate 1 - 1 synthesis, to obtain 27.4g compound 256 (yield 69percent)._: The 9 - anthracene boric acid (10mmol), 1 - bromo -4 iodine naphthalene (10mmol), potassium carbonate (30mmol), four-triphenylphosphine palladium (0.1mmol) are sequentially added to the toluene, ethanol, water in the mixed solution in the reaction temperature under the protection of nitrogen to reflux the reaction overnight. The reaction cooling to room temperature a large number of solid is separated out filtering for products obtained toluene baggy air dissolved completely after-filtration, filtrate cooling crystallization product is obtained 219 - 1 (yield 65percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66.7% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene;Inert atmosphere; Reflux; | Compound 269 synthesis of: With intermediate 1 - 1 synthesis, to obtain 24g compound 269 (yield 66.7%).The 9 - anthracene boric acid (10mmol), 1 - bromo -4 iodine naphthalene (10mmol), potassium carbonate (30mmol), four-triphenylphosphine palladium (0.1mmol) are sequentially added to the toluene, ethanol, water in the mixed solution in the reaction temperature under the protection of nitrogen to reflux the reaction overnight. The reaction cooling to room temperature a large number of solid is separated out filtering for products obtained toluene baggy air dissolved completely after-filtration, filtrate cooling crystallization product is obtained 219 - 1 (yield 65%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 110℃; for 24h; Inert atmosphere; | 12 Synthesis of Compound PCzSP The intermediate product I-4 (0.85 g, 2 mmol), 1-pyrene boronic acid (0.59 g, 2.4 mmol), tetrakis (triphenylphosphine) palladium (Pd (PPh3) 4) (10 mg, 0.01 mmol) Potassium carbonate aqueous solution (2.0 M, 3.5 mL), ethanol (3.5 mL) and toluene (10.5 mL) were placed in a two-necked flask. The oxygen was removed and nitrogen was added and the reaction was warmed to 110 ° C and stirred for 24 hours. The metal was removed by filtration, extracted with ethyl acetate (EA), the organic layer was collected, the water was removed with magnesium sulfate (MgSO4), filtered and the solvent was removed by concentration under reduced pressure and separated by column chromatography (dichloromethane: Hexane = 1: 5) to collect the solid. (E) -9-phenyl-3- (4- (pyren-1-yl) styryl) -9H-carbazole) was obtained by sublimation at 275 ° C to obtain the yellow compound PCzSP (0.73 g, yield 67%). |
67% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 110℃; for 24h; Inert atmosphere; | 12 Synthesis of Compound PCzSP The intermediate product I-4 (0.85 g, 2 mmol), 1-pyreneboronic acid (0.59 g, 2.4 mmol), Tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (10 mg, 0.01 mmol), potassium carbonate aqueous solution (2.0 M, 3.5 mL), Ethanol (3.5 mL) and toluene (10.5 mL) were placed in a two-necked flask. The oxygen was removed and nitrogen was added, and the reaction was warmed to 110 °C and stirred for 24 hours. The metal was removed by filtration, extracted with ethyl acetate (EA), the organic layer was collected, water was removed with magnesium sulfate (MgSO4). The solvent was filtered and the solvent was removed by concentration under reduced pressure and purified by column chromatography (dichloromethane: hexane = 1: 5) to collect the solid and sublimated at 275 °C to obtain a yellow compound PCZSP ((E)-9-phenyl-3-(4-(pyren-1-yl)styryl)-9H-carbazole) (0.73 g, yield 67%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 110℃; for 24h; Inert atmosphere; | 11 Synthesis of Compound NASP The intermediate product I-3 (0.95 g, 2 mmol), 1-pyrene boronic acid (0.59 g, 2.4 mmol), tetrakis (triphenylphosphine) palladium (Pd (PPh3) 4) (10 mg, 0.01 mmol) Potassium carbonate aqueous solution (2.0 M, 3.5 mL), Ethanol (3.5 mL) And toluene (10.5 mL) Placed in a two-necked flask. Remove the oxygen and add nitrogen, The reaction was warmed to 110 ° C and stirred for 24 hours. The metal was removed by filtration, extracted with ethyl acetate (EA), the organic layer was collected, the water was removed with magnesium sulfate (MgSO4), filtered and the solvent was removed by concentration under reduced pressure and separated by column chromatography (dichloromethane: Hexane = 1: 5) to collect the solid. (N) -N-phenyl-N- (4- (pyren-1-yl) styryl) phenyl) naphthalen-1-amine was obtained by sublimation at 295 ° C to obtain the yellow compound (0.85 g, 71% yield). |
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 110℃; for 24h; Inert atmosphere; | 11 Synthesis of Compound NASP The intermediate product I-3 (0.95 g, 2 mmol), 1-pyreneboronic acid (0.59 g, 2.4 mmol) Tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (10 mg, 0.01 mmol) Potassium carbonate aqueous solution (2.0 M, 3.5 mL), ethanol (3.5 mL) and toluene (10.5 mL) were placed in a two-necked flask. The oxygen was removed and nitrogen was added and the reaction was warmed to 110 °C and stirred for 24 hours. The metal was removed by filtration, extracted with ethyl acetate (EA), the organic layer was collected, water was removed with magnesium sulfate (MgSO4). The solvent was filtered and the solvent was removed by concentration under reduced pressure and purified by column chromatography (dichloromethane: hexane = 1: 5) to collect the solid. Sublimation was carried out at 295 °C to obtain a yellow compound NASP ((E)-N-phenyl-N-(4-(4-(pyren-1-yl)styryl)phenyl)naphthalen-1-amine (0.85 g, 71% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87.68% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 8h;Inert atmosphere; Reflux; | In the 1L three bottles, 1-pyrene boronic acid (49.2 g, 0.20 mol) was added, <strong>[57381-43-8]2,5-dibromobenzoic acid methyl ester</strong> (61.7 g, 0.21 mol) potassium carbonate (55.2 g, 0.40 mol) 165.6 g of water, Pd (PPh3) 4 (1.156 g, 1.0 mmol) Toluene (400 mL), Anhydrous ethanol (100mL), N2 protection, heating to reflux, incubation reaction 8 hours, Stop the reaction, cool to 25 ° C, liquid separation, collecting organic phase, washed to neutral, The organic phase was depressurized to remove the solvent, purified by pure toluene column chromatography, toluene, Anhydrous ethanol recrystallization, To give intermediate 1-1 (yield 87.68percent) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In 1,4-dioxane; water at 60℃; for 7.5h; Inert atmosphere; | |
69% | Stage #1: 3-chloro-8-phenyl-8-(4-(piperidin-1-yl)phenyl)-1-(4-((tetrahydro-2H-pyran-2-yl)oxy)butoxy)-8H-pyrano[3,2-f]quinazoline; 1-pyrenylboronic acid With caesium carbonate In 1,4-dioxane; water at 60℃; Inert atmosphere; Stage #2: With tetrakis(triphenylphosphine) palladium(0) In 1,4-dioxane; water at 60℃; for 7.5h; Inert atmosphere; | 6 Synthesis of 8-Phenyl-8-(4-(piperidin-1-yl)phenyl)-3-(pyren-1-yl)-1-(4-((tetrahydro-2H-pyran-2-yl)oxy) butoxy)-8H-pyrano[3,2-f]quinazoline 3-chloro-8-phenyl-8-(4-(piperidin-1-yl)phenyl)-1-(4-((tetrahydro-2H-pyran-2-yl)oxy)butoxy)-8H-pyrano[3,2-f]quinazoline (300 mg, 0.48 mmol) and 1-pyreneboronic acid (202 mg, 0.82 mmol) are dissolved in 1,4-dioxane (10 mL) and 1M aqueous cesium carbonate solution (1.4 mL, 1.4 mmol) and degassed by blowing nitrogen gas for 1 hour. Tetrakis (triphenylphosphine) palladium (0) (163 mg, 0.14 mmol) is added thereto and the mixture is stirred at 60° C. for 7.5 hours. After filtration through celite, the filtrate is extracted with ethyl acetate and washed with ion-exchanged water. The organic layer is dried, the solvent is distilled off under reduced pressure, the residue is purified by silica gel column chromatography (ethyl acetate:dichloromethane:hexane=3:50:15) and yellow solid of 261 mg is obtained in 69% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 120℃; for 3h; | 21 Synthesis of compound 21-1 General procedure: Using the synthesis method of Intermediate 2-1 of Reaction Example 2, using dibromide (11.7 g, 32 mmol)Compound w (8.9 g, 32 mmol), tetrakis (triphenylphosphine) palladium (0.7 g, 1.08 mmol)Potassium carbonate (11.1 g, 76 mmol) synthesized 13.7 g of compound 21-1 in a yield of 88% Dibromo (6.2 g, 16.9 mmol), compound b (4.1 g, 18.4 mmol), tetrakis(Triphenylphosphine) palladium (0.7 g, 1.08 mmol), potassium carbonate (5.3 g, 38.3 mmol), toluene (100 mL), 30 mL of ethanol and 30 mL of distilled water were added and the mixture was stirred at 120 ° C for 3 hours. After completion of the reaction, the mixture was washed with distilled water, and the organic layer was extracted with ethyl acetate. The resulting organic layer was dried over anhydrous magnesium sulfate and the solvent was spin-dried using a rotary evaporator. The column was separated and purified to give 7.6 g of compound 2-1 in 80% yield |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In ethanol; water monomer; toluene at 110℃; Inert atmosphere; | Preparation of 2-arylpyridines General procedure: 2-Bromopyridine (2.0 mmol, 1.0 equiv) was added to a solution of arylboronic acid (1.3 equiv), Na2CO3(7.4 equiv), and Pd(PPh3)4(3.0 mol %) in toluene (7.0 mL), ethanol (1.5 mL), and H2O (7.0 mL) in 50 mL two-necked flask underargonatmosphere. After being refluxed at 110oC for overnight, the reaction mixture was cooled to room temperature. The reaction mixture was quenched by aqueous NH4Cl, extracted by EtOAc (3 x 20 mL, 60 mL), dried over Na2SO4, and evaporated invacuoto afford the crude product, which was further purified by flash chromatography on silica gel with EtOAc and hexane to give the corresponding 2-arylpyridineS1-S8in good yield.[2] |
With tetrakis-(triphenylphosphine)-palladium In ethanol; toluene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; at 100℃; for 12h;Inert atmosphere; | <strong>[1257220-44-2]2-bromo-7,7-dimethyl-5-phenyl-5,7-dihydroindeno[2,1-b]carbazole</strong>(0.9 g, 2.0 mmol), 1.5 equivalent of arylboronic acid, 2M K2CO3(10 mL), and Pd(PPh3)4 (0.023 g, 0.02 mmol) were added to 1,4-dioxane(80 mL), and stirred at 100 C for 12 h under nitrogen atmosphere.The organic layer was concentrated and purified by silica gelcolumn chromatography using an eluent mixture of dichloromethaneand petroleum ether in the volume ratio of 1:3, which give a whitepowder with 0.96 g (yields: 77%) and 0.84 g (yields: 73%), respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With tetraamminepalladium(II) chloride; tetra(n-butyl)ammonium hydroxide In water at 45℃; for 1h; Green chemistry; | |
92% | With potassium carbonate In ethanol; water at 50℃; for 4h; Inert atmosphere; | 2.3 General Procedure for Suzuki Cross-Coupling Between Aryl Boronic Acid and Aryl Halide General procedure: A 15 mL round bottom flask (back-filled with N2) was loaded with HAPd/Fe3O4 (50 mg). Aryl halide (1 equiv.),aryl boronic acid (1.1 equiv.) and potassium carbonate (2.0equiv.) were added to the flask followed by 1:1 mixture of ethanol and water (4 mL). The resultant mixture was stirred at 50 °C for 4 h under nitrogen atmosphere. With the aid of an external magnet, the catalyst was recovered and the product was extracted using ethyl acetate (5 mL × 3). The organic layer was separated and dried over Na2SO4 followedby evaporation under reduced pressure and the mixture was purified using column chromatography on silica gel (Petroleumether/Ethyl acetate). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With tetraamminepalladium(II) chloride; tetra(n-butyl)ammonium hydroxide In water at 45℃; for 2h; Green chemistry; | |
88% | With potassium carbonate In ethanol; water at 50℃; for 4h; Inert atmosphere; | 2.3 General Procedure for Suzuki Cross-Coupling Between Aryl Boronic Acid and Aryl Halide General procedure: A 15 mL round bottom flask (back-filled with N2) was loaded with HAPd/Fe3O4 (50 mg). Aryl halide (1 equiv.),aryl boronic acid (1.1 equiv.) and potassium carbonate (2.0equiv.) were added to the flask followed by 1:1 mixture of ethanol and water (4 mL). The resultant mixture was stirred at 50 °C for 4 h under nitrogen atmosphere. With the aid of an external magnet, the catalyst was recovered and the product was extracted using ethyl acetate (5 mL × 3). The organic layer was separated and dried over Na2SO4 followedby evaporation under reduced pressure and the mixture was purified using column chromatography on silica gel (Petroleumether/Ethyl acetate). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; N,N-dimethyl-formamide at 80℃; for 18h; | |
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; N,N-dimethyl-formamide at 80℃; for 17h; Inert atmosphere; | Synthesis of [3]rotaxane 7 K2CO3 aq. (0.22 g, 1.6 mmol, H2O 0.4 mL) was added to a solution of 1-pyreneboronic acid (0.39 g, 1.6 mmol) and[3]rotaxane S4 (0.26 g, 0.10 mmol) in DMF (2.0 mL), then the system was freeze degassed. Pd(PPh3)4 (12 mg, 0.010mmol) was added to a solution quickly, and the mixture was stirred for 17 hours at 80 °C. The heterogeneous mixturewas poured into H2O and filtered to collect the precipitate. It was washed with water and acetone dried in vacuo togive the [3]rotaxane 7 (0.25 g, 88%) as a gray solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With copper(I) oxide; tert.-butylhydroperoxide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; In toluene; at 130℃; for 8h;Schlenk technique; | Under a one-pressure oxygen atmosphere, 2-propionylthiophene 1d (70.1 mg, 0.50 mmol), 1-pyreneboronic acid 2d (61.1 mg, 0.50 mmol), and cuprous oxide (7.0 mg, 0.05) were sequentially added to a 15 mL Schlenk reaction tube. mmol), tert-butyl hydroperoxide (182.2 mg, 2.0 mmol), 2,2,6,6-tetramethylpiperidine oxide (1.6 mg, 0.01 mmol) and toluene (toluene, 3.0 mL) at 130 The reaction was performed at 8 C for 8 hours. After the reaction, the reaction mixture was cooled to room temperature, filtered through celite, and concentrated to obtain a crude product. The crude product was separated by chromatography using a prepared silica gel plate. The developing agent or eluent was petroleum ether and ethyl acetate, and the volume ratio of petroleum ether and ethyl acetate was 50: 1. The product (E) -3- ( 3A, 3A-1-fluoren-1-yl) -1- (thien-2-yl) prop-2-en-1-one (3d), the product was a pale yellow solid, and the product yield was 50% (84.5mg ). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In tetrahydrofuran at 80℃; for 12h; Reflux; Inert atmosphere; | 3.2.1. Synthesis of Py-NBN-Ph 1-pyrenylboronic acid (0.246 g, 1 mmol) and 1,2-phenylenediamine (0.108 g, 1 mmol)were dissolved in THF (10 mL), and the reaction solution was heated from room temperatureto 80 C to reflux and continued for 12 h under nitrogen protection. The reactionwas stopped and cooled, then the solution was concentrated by a rotary evaporator underreduced pressure and the crude product was purified by column chromatography onsilica gel (petroleum ether: ethyl acetate = 10:1) to yield Py-NBN-Ph. 1H NMR (600 MHz,DMSO-d6) (ppm) 6.89 (dd, J = 4.8, 4.92 Hz, 2H, -C6H4), 7.20 (dd, J = 4.86, 4.92 Hz, 2H,-C6H4), 9.37 (s, 2H, -NH). 11B NMR (600MHz, DMSO-d6) (ppm) 28.21. |
82% | In tetrahydrofuran at 50℃; for 6h; | 2.2. Synthesis General procedure: Compound 1: The mixture of Pyren-1-ylboronic acid (123 mg, 0.5mmol) and o-phenylenediamine (54 mg, 0.5 mmol) in THF (20 mL) washeated to 50 for 6 h. After evaporation of volatile material underreduced pressure, the crude product was purified by flash columnchromatography on silica gel (petroleum ether: EtOAc = 10:1) to affordpure 1 (130 mg, 82 %). 1H NMR (400 MHz, CDCl3): δ/ppm 8.53 (d, J =9.2 Hz, 1 H), 8.29 (d, J =7.6 Hz, 1 H), 8.21 (d, J=7.77 Hz, 3 H),8.14 8.08 (m, 3 H), 8.03 (t, J = 7.6, 7.6 Hz, 1 H), 7.26 7.24 (m, 2 H),7.08 7.06 (m, 2 H), 7.02 (brs, 2 H). 13C NMR (100 MHz, CDCl3): δ/ppm136.4, 134.6, 132.1, 132.1, 131.5, 131.0, 128.1, 127.9, 127.8, 127.6,126.0, 125.3, 125.2, 125.0, 124.7, 124.5, 119.7, 111.5. HR-MS: m/zcalcd for C22H16BN2: 319.1405; found: 319.1388 [M]+. 11B NMR (128MHz, CDCl3): δ/ppm 29.41. Anal. Calcd for C22H16BN2: C, 83.05; H,4.75; N, 8.80. Found: C, 83.00; H, 4.83; N, 8.77. |
In tetrahydrofuran at 80℃; for 12h; Inert atmosphere; | 1 Preparation ofC22H15BN2 molecule Weigh 1 mmol of 1-indoleboric acid, 1 mmol of 1,2-phenylenediamine, add 10 ml of tetrahydrofuran, raise the temperature from room temperature to 80 °C, and reflux under nitrogen for 12 h, cool After obtaining a solution of the crude product, a silica gel powder of 200-300 mesh is used for separation of a solution of the crude product by using a mixture of 10:1 (v/v) petroleum ether and ethyl acetate as an eluent to obtain a dark yellow powder. C22H15BN2 crude product, yield 163.9 mg, yield 51.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In methanol; water; toluene; at 110℃; for 4h;Schlenk technique; Inert atmosphere; | General procedure: A dried Schlenk tube flask was charged with [Pd(PPh3)4] (3 mol %), Na2CO3 (2equiv/mmol), <strong>[5467-58-3]1-bromo-4-methoxynaphthalene</strong> (1-2 mmol), and the corresponding boronic acid (1.2 equiv). After three vacuum-argon cycles, toluene (1 mL/mmol substrate), methanol (0.2 mL/mmol substrate), and water (0.25 mL/mmol substrate) were added with the aid of a syringe. The reaction mixture was heated to 110 C for 4 hours, then cooled to room temperature, diluted with CH2Cl2 and finally filtered through celite. The organic phase was concentrated to dryness and the crude products were purified by column chromatography (n-hexane/EtOAc mixtures). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; potassium carbonate In 1,4-dioxane; water at 80℃; for 3h; Inert atmosphere; | 5-(10-Hexyl-8-(pyren-1-yl)-10H-phenothiazin-3-yl)thiophene-2-carbaldehyde (6) Compound 3 (151 mg, 0.35 mmol), pyren-1-ylboronic acid (104 mg, 0.423 mmol), SPhos (5.7 mg,14 μmol), Pd(OAc)2 (1.5 mg, 6.7 μmol), and K2CO3 (198 mg, 1.44 mmol) were added to degassed 1,4-dioxane (2 mL) and deionized water (2 mL) under nitrogen atmosphere. The reaction mixturewas stirred for 3 hours at 80 °C. The reaction was quenched with water (10 mL) and extractedwith ethyl acetate (3 × 20 mL). The combined organic phases were washed with brine (50 mL) anddried over anhydrous Na2SO4, and the solvent removed in vacuo. The crude product was purifiedusing silica-gel column chromatography (n-pentane/ethyl acetate, 10:1) to give compound 6 asorange crystals (160 mg, 0.27 mmol, 76%), |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; for 12h;Reflux; Inert atmosphere; | <strong>[4592-94-3]3-(4-bromophenyl)-3-oxopropanenitrile</strong> (1.1 g, 5 mmol), 1-pyrenylboronic acid(1.35 g, 5.5 mmol) were mixed in 70 ml of THF, K2CO3 (2.0 M, 35 mL) was added, and the mixture was stirred with magnetic stirring. Then tetrakis (triphenylphsosphine)palladium (25 mg, 0.025 mmol) was added to the mixture. The reaction solution was heated under reflux for 12 h under the atmosphere of nitrogen. After the mixture cooled, the solvent was evaporated and the product was extracted with dichloromethane. The organic product was washed with water and brine, and then dried by anhydrous Na2SO4. The solvent was evaporated, and the residue was purifiedby flash column chromatography on silica gel using dichloromethane/petroleum etheras eluent to afford compound 1n. Yellow solid (47%, 800 mg), m.p.: 187 - 188 C ;1H NMR (400 MHz, CDCl3) delta 8.27 - 8.22 (m, 2H, ArH), 8.20 (d, J = 7.4 Hz, 1H,ArH), 8.16 - 8.02 (m, 7H, ArH), 7.95 (d, J = 7.9 Hz, 1H, ArH), 7.78 (d, J = 8.3 Hz,2H, ArH), 4.15 (s, 2H, CH2); 13C NMR (100 MHz, CDCl3) delta 186.7, 148.0, 135.5,132.9, 131.4, 131.3, 130.8, 128.6, 128.3, 128.2, 128.1, 127.3, 127.2, 126.3, 125.6,125.2, 124.9, 124.7, 124.3, 113.8, 29.4. MS (ESI-): m/z: 344 ([M-H]-), HRMS-ESIm/z ([M-H]-) calcd for C25H14NO: 344.1075, found 344.1081. IR (KBr): 3378, 3118,3036, 2936, 2260, 1697, 1688, 1601, 1560, 1513, 1486, 1405, 1390, 1322 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; at 70℃; for 2h;Inert atmosphere; | 1-Pyreneboronic acid (0.22 g, 0.90 mmol), <strong>[18179-39-0]methyl 4-iodosalicylate</strong>(0.20 g, 0.72 mmol), and K2CO3 (1.12 g, 8.10 mmol) were first dissolvedin THF (25 mL) and water (9 mL). The solution was then degassedunder a N2 atmosphere for 20 min. Pd(PPh3)4 (0.05 g, 0.04 mmol) wasthen added, and the mixture was stirred at 70 C for 2 h under a N2atmosphere. Once the reaction mixture had cooled, it was diluted withwater (20 mL) and washed with DCM (3×30 mL). The organic extractswere combined, MgSO4 was added to dry the mixture, and the mixturewas filtered. The solvent was evaporated from the filtrate, and the crudeproduct was purified using silica gel column chromatography withgradient elution; the mobile phase was changed from pure hexane tohexane/DCM 4:1 (v/v), affording Compound 1 as a yellow solid(0.2176 g, 85% yield, mp: 156-158 C). 1H-NMR (400 MHz, CDCl3): delta(ppm) 10.93 (s, 1 H), 8.23-8.17 (m, 4 H), 8.11 (s, 1 H), 8.10 (s, 1 H),8.06-8.00 (m, 3 H), 7.97 (d, J =7.6 Hz, 1 H), 7.29 (d, J =1.6 Hz, 1 H),7.18 (dd, J=8 and 1.6 Hz, 1 H), 4.03 (s, 3 H). 13C-NMR (100 MHz,CDCl3): delta (ppm) 170.6, 161.5, 149.1, 136.1, 131.4, 131.1, 130.9, 129.8,128.2, 127.9, 127.8, 127.4, 127.1, 126.2, 125.4, 125.1, 124.9, 124.8,124.8, 124.7, 121.9, 119.5, 111.3, 52.4. HRMS-ESI m/z calcd forC24H16NaO3: 375.0992 [M+Na]+, found: 375.0991. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With palladium diacetate; potassium carbonate; catacxium A In 1,2-dimethoxyethane; water at 90℃; for 24h; Inert atmosphere; | |
99% | With palladium diacetate; potassium carbonate; catacxium A In 1,2-dimethoxyethane; water at 90℃; for 24h; Inert atmosphere; | 4 Example 4 Synthesis of Chiral Spiro Compound 1d Under nitrogen atmosphere, add (R)-1b (132mg, 0.22mmol), potassium carbonate (161mg, 1.2mmol), 1-pyreneboronic acid (541mg, 2.2mmol), palladium acetate (1.0mg , 4.4μmol), n-butylbis(1-adamantyl) phosphine (2.1mg, 6.0μmol), water (2.0mL) and ethylene glycol dimethyl ether (2.0mL), the resulting solution is quickly degassed by an oil pump And the double row tube was filled with nitrogen, after 5 times of replacement, stirred at 90°C for 24 hours under a nitrogen atmosphere. The solution was cooled to room temperature, saturated aqueous ammonium chloride solution (20mL) was added to the reaction solution, and then dichloromethane (3x 20mL) was used for extraction. The organic phases were combined and washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated. Coarse matter. Then, the crude material was purified by silica gel column chromatography to obtain 175 mg of the target product (R)-1d as a mixture due to axial chirality, and the calculated yield was 99%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tetrakis-(triphenylphosphine)-palladium In tetrahydrofuran; water monomer at 70℃; for 3h; Inert atmosphere; Alkaline conditions; | 2.5. Synthesis of Compound 2 A combination of Compound 1 (100 mg, 0.14 mmol), Pd(PPh3)4 (18 mg, 0.16 mmol), and 1-pyreneboronic acid (38.0 mg, 0.15 mmol) in THF (5 mL) and water (1 mL) was added to K2CO3 (1.0 g, 7.2 mmol) under an N2 gas and then agitated for 3 h at 70 °C. After the reaction mixture had cooled, it was diluted with 1 M HCl (20 mL) and then extracted with EtOAc (2 ×15 ml). The organic extracts were then mixed, MgSO 4 was added to dry the mixture, and the mixture was filtered. The solvent was removed from the filtrate, and the crude product was purified using silica gel column chromatography with gradient elution; the mobile phase was changed from a pure hexane to hexane/DCM (3:1) as an eluent to afford Compound 2 as a yellow solid (948.2 mg, 83% yield, mp: 168-170 °C). 1 H NMR (400 MHz, CDCl3): δ (ppm) 7.99-8.28 (m, 9H), 7.84 (d, J = 8.0 Hz, 2H), 7.58 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 8.0 Hz, 3H), 7.32 (dd, J = 8.0,4.0 Hz, 3H), 7.20 (d, J = 8.0 Hz, 3H), 7.09 (s, 2H), 7.01 (d, J = 8.0 Hz, 2H), 3.94 (s, 6H). 13 C NMR (100 MHz, CDCl3):δ (ppm) 170.3, 161.3, 148.2, 146.2, 137.1, 136.7, 133.1, 131.7, 131.5, 131.1, 130.8, 129.8, 128.5, 127.6, 127.7, 127.4, 127.3, 126.0, 125.7, 125.2, 125.1, 125.0, 124.8, 124.7, 122.8, 122.3, 120.1, 115.9, 115.8, 111.8, 93.1, 88.1 52.3. HRMS-ESI m/z calcd for C54H35NO6Na: 816.1850 [M + Na] + , found: 816.1850. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60.2% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In tetrahydrofuran; lithium hydroxide monohydrate at 90℃; for 8h; Inert atmosphere; | 2.3. General procedure for the synthesis of the phthalonitrilederivatives General procedure: Corresponding Iodophthalonitrile (0.4 g, 1.57 mmol), pyrene-1-boronic acid (0.387 g, 1.57 mmol) and potassium carbonate(0.65 g,4.71 mmol) were dissolved in a binary solvent mixture oftetrahydrofuran / water (4:1) 5 mL and nitrogen was bubbled for15 min. Then tetrakis(triphenylphosphine)palladium (0)(0.09 g,0.078 mmol) was added and nitrogen bubbling continuedfor another 10 min. The reaction mixture was refluxed under inertatmosphere for 8 h and then, the volatiles evaporated to dryness.The crude product was partitioned using water / ethyl acetate(3 100 mL). Organic layer was collected and dried over anhydroussodium sulphate and evaporated. Column purification usingDCM/hexane (3:7) gave the product, which was reprecipitatedfrom DCM/hexane mixture and dried to obtain the title compounds.Scheme 1 provides the synthetic conditions employedfor the synthesis of 3-PyPN and 4-PyPN. Complete characterisationand purity of the materials were provided in the supporting information(figures S 1 to S 12). |
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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.
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