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CAS No. : | 128-63-2 | MDL No. : | MFCD00428682 |
Formula : | C16H6Br4 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ZKBKRTZIYOKNRG-UHFFFAOYSA-N |
M.W : | 517.84 | Pubchem ID : | 67188 |
Synonyms : |
|
Num. heavy atoms : | 20 |
Num. arom. heavy atoms : | 16 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 100.95 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | Yes |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -3.92 cm/s |
Log Po/w (iLOGP) : | 3.85 |
Log Po/w (XLOGP3) : | 7.8 |
Log Po/w (WLOGP) : | 7.63 |
Log Po/w (MLOGP) : | 7.1 |
Log Po/w (SILICOS-IT) : | 7.38 |
Consensus Log Po/w : | 6.75 |
Lipinski : | 2.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 1.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.17 |
Log S (ESOL) : | -8.56 |
Solubility : | 0.00000144 mg/ml ; 0.0000000028 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -7.65 |
Solubility : | 0.0000117 mg/ml ; 0.0000000226 mol/l |
Class : | Poorly soluble |
Log S (SILICOS-IT) : | -9.79 |
Solubility : | 0.0000000836 mg/ml ; 0.0000000002 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 1.98 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With bromine In nitrobenzene at 80 - 120℃; for 12 h; | Bromine (8.75 g, 0.055 mol) was added dropwise, with vigorous stirring to a solution of pyrene (2.5 g, 12.3 mmol) in nitrobenzene (50 mL) at 80 °C [24]. Then the mixture was heated to 120 °C and kept for 12 h. After cooled to room temperature, the mixture was filtered, washed with ethanol (100 mL), and dried under vacuum to afford 5 (6.04 g, 96percent) as a pale-green solid; m.p. >300 °C (m.p. >300 °C) [21]. (Found C, 36.85; H, 1.23. C16H6Br4 (517.84) requires C, 37.11; H, 1.17percent). This compound was quite insoluble in all common organic solvents. The 1H NMR spectrum was not obtained in CDCl3 due to the limited solubility of this compound. |
92% | With bromine In nitrobenzene at 80℃; for 12 h; | To a stirred nitrobenzene (120 mL) solution of pyrene (1, 4.048 g, 20 mmol) was slowly added nitrobenzene (40 mL) solution of Br2 (4.7 mL, 92 mmol). The solution was stirred at 80°C for 12 h. The solution was cooled to room temperature. Conc. NaOH aq (10 mL) was added to remove remaining Br2. The solid was collected by suction filtration with CHCl3 (100 mL) to give 1,3,6,8-tetrabromopyrene (11, light green solid, 9.6 g, 92percent yield). A stirred mixture of 1,3,6,8-tetrabromopyrene (11, 5.172 g, 10 mmol), trimethylsilylacetylene (6.7 mL, 48 mmol), (PPh3)2PdCl2 (353 mg), CuI (107 mg), PPh3 (263 mg), i-Pr2NH (50 mL), and THF (50 mL) was stirred at 80°C for 12 h. The solution was concentrated in vacuo. Purification by silica gel column chromatography (eluent; hexane) gave 1,3,6,8-tetrakis(trimethylsilylethynyl)pyrene (3, 4.936 g, 84percent yield). |
76% | With bromine In chloroform at 0 - 20℃; for 8 h; | Synthesis of Intermediate 2-h [0156] Intermediate 2-h was synthesized according to Reaction Scheme 12 below: [0157] 50 g (0.247 mol) of pyrene was dissolved in 500 ml of chloroform in a 2 L round-bottom flask, and the temperature was decreased to 0° C. Then, a solution of 158 g (0.989 mol) of bromine dissolved in 150 ml of chloroform was slowly added to the flask, the temperature was slowly raised to room temperature, and the resultant mixture was reacted for 8 hours. After the reaction was complete, 100 ml of water was added and the bromine was removed using sodium thiosulfate, and the crystals formed therefrom were filtered and recrystallized. As a result, 97.5 g of Intermediate 2-h was obtained (76percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sodium chlorate; bromine In water | (a) 220 parts of technical-grade pyrene of 90percent purity are added to a solution of 84 parts of sodium chlorate and 350 parts of water. 370 parts of bromine are then added dropwise at 60°-65° C. in 2 hours. This is followed by stirring at 60°-65° C. for 1 hour. The temperature is then raised to 85° C., and 85°-95° C. is maintained with reflux cooling for 10 hours. The tetrabromopyrene is worked up as described in Example 1a. The 1,3,6,8-tetrabromopyrene (bromine content 61.8percent) is obtained in an amount of 557 parts and a purity of about 83percent, which corresponds to a yield of about 91percent of theory, based on 100percent pure pyrene, and on further processing 253 parts of napthalene-1,4,5,8-tetracarboxylic acid 1,4-monoanhydride are obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sodium chlorate; ammonium hydroxide; bromine In water | (a) 220 parts of technical-grade pyrene of 93percent purity (brazan content 4percent) are added to a solution of 84 parts of sodium chlorate in 340 parts of water. 375 parts of bromine are then added dropwise at 40°-50° C., with slight cooling, in 2 hours. This is followed by stirring at 40°-50° C. for 1-2 hours. The temperature is then gradually raised with reflux cooling to 85° C., which is followed by stirring at 85°-95° C. for 5 hours. The suspension is then diluted with 200 parts of water, and the excess bromine is eliminated by gradual addition of 40percent strength aqueous sodium bisulfite solution. This is followed by cooling down to 50°-60° C. and the dropwise addition of 25percent strength aqueous ammonia solution until a pH value of 9.5 is reached. This is followed by stirring at 50°-60° C. for 4 hours and, finally, by filtration with suction, washing with water until salt-free and drying at 100° C. The 1,3,6,8-tetrabromopyrene is obtained in an amount of 561 parts and purity of about 84percent, which corresponds to a yield of about 90percent of theory, based on 100percent pure pyrene, and on further processing to naphthalene-1,4,5,8-tetracarboxylic acid in accordance with the instructions of Example 1a 263 parts of naphthalene-1,4,5,8-tetracarboxylic acid 1,4-monoanhydride are obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2% | With sodium chlorate; bromine In water | (a) 220 parts of technical-grade pyrene of 90percent purity are added to a solution of 84 parts of sodium chlorate in 280 parts of water. 380 parts of bromine are then added dropwise at 40°-50° C. with slight cooling in 2 hours. This is followed by stirring at 40°-50° C. for 1 hour. The temperature is then gradually raised with reflux cooling to 85° C. and stirring at 85°-95° C. for 10 hours. The suspension is worked up as described in Example 1a. The 1,3,6,8-tetrabromopyrene is obtained in an amount of 564 parts and a purity of about 83percent, which corresponds to a yield of about 2percent of theory, based on 100percent pure pyrene, which on further processing to naphthalene-1,4,5,8-tetracarboxylic acid gives 258 parts of naphthalene-1,4,5,8-tetracarboxylic 1,4-monoanhydride. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With bromine; In nitrobenzene; at 80 - 120℃; for 12h; | Bromine (8.75 g, 0.055 mol) was added dropwise, with vigorous stirring to a solution of pyrene (2.5 g, 12.3 mmol) in nitrobenzene (50 mL) at 80 C [24]. Then the mixture was heated to 120 C and kept for 12 h. After cooled to room temperature, the mixture was filtered, washed with ethanol (100 mL), and dried under vacuum to afford 5 (6.04 g, 96%) as a pale-green solid; m.p. >300 C (m.p. >300 C) [21]. (Found C, 36.85; H, 1.23. C16H6Br4 (517.84) requires C, 37.11; H, 1.17%). This compound was quite insoluble in all common organic solvents. The 1H NMR spectrum was not obtained in CDCl3 due to the limited solubility of this compound. |
92% | With bromine; In nitrobenzene; at 80℃; for 12h; | To a stirred nitrobenzene (120 mL) solution of pyrene (1, 4.048 g, 20 mmol) was slowly added nitrobenzene (40 mL) solution of Br2 (4.7 mL, 92 mmol). The solution was stirred at 80C for 12 h. The solution was cooled to room temperature. Conc. NaOH aq (10 mL) was added to remove remaining Br2. The solid was collected by suction filtration with CHCl3 (100 mL) to give 1,3,6,8-tetrabromopyrene (11, light green solid, 9.6 g, 92% yield). A stirred mixture of 1,3,6,8-tetrabromopyrene (11, 5.172 g, 10 mmol), trimethylsilylacetylene (6.7 mL, 48 mmol), (PPh3)2PdCl2 (353 mg), CuI (107 mg), PPh3 (263 mg), i-Pr2NH (50 mL), and THF (50 mL) was stirred at 80C for 12 h. The solution was concentrated in vacuo. Purification by silica gel column chromatography (eluent; hexane) gave 1,3,6,8-tetrakis(trimethylsilylethynyl)pyrene (3, 4.936 g, 84% yield). |
79% | (b) Using in the bromination described in Example 1a instead of 371 parts of bromine a bromine quantity of only 340 parts gives only 540 parts of 1,3,6,8-tetrabromopyrene having a purity of only about 74%. This corresponds, based on 100% pure pyrene, to a yield of about 79% of theory. |
76% | With bromine; In chloroform; at 0 - 20℃; for 8h; | Synthesis of Intermediate 2-h [0156] Intermediate 2-h was synthesized according to Reaction Scheme 12 below: [0157] 50 g (0.247 mol) of pyrene was dissolved in 500 ml of chloroform in a 2 L round-bottom flask, and the temperature was decreased to 0 C. Then, a solution of 158 g (0.989 mol) of bromine dissolved in 150 ml of chloroform was slowly added to the flask, the temperature was slowly raised to room temperature, and the resultant mixture was reacted for 8 hours. After the reaction was complete, 100 ml of water was added and the bromine was removed using sodium thiosulfate, and the crystals formed therefrom were filtered and recrystallized. As a result, 97.5 g of Intermediate 2-h was obtained (76%). |
With bromine; In nitrobenzene; | 1,3,6,8-tetrabromopyrene was obtained by the reaction of one equivalent of pyrene and 4 times as much as bromine in equivalent in a nitrobenzene, according to the method described in Annalen der Chemie, vol. 531, p.81. Next, 4.4 equivalents of 4-phenoxyphenylboronic acid, 10 equivalents of sodium carbonate in a 2 mol/L aqueous solution, and 0.12 equivalents of tetrakis(triphenylphosphine) palladium (0) were added to one equivalent of 1,3,6,8-tetrabromopyrene, and the mixture was subjected to heating under refluxing to allow reaction for three hours, using benzene as a solvent. After cooling the reaction product, the deposit formed by adding methanol to the reaction product was washed with water, and recrystallized from THF-methanol to obtain a crude product. The crude product was purified by sublimation in vacuo, to form a compound for the purpose. An o-xylene solution of the compound showed a strong blue fluorescence, by irradiating with ultraviolet rays having a wavelength of 365 nm. The molecular weight of the compound by the mass spectrum was 850, coinciding with the expected value for the molecular formula (C62H42O4). | |
With sodium chlorate; bromine; In water; | EXAMPLE 6 220 parts of technical-grade pyrene of 90% purity are added to a solution of 84 parts of sodium chlorate in 440 parts of water. 380 parts of bromine are then added dropwise at 40-50 in 2 hours. This is followed by stirring at 40-50 C. for 1 hour. The reaction vessel is then sealed and the temperature is gradually raised under pressure to 120 C. This is followed by stirring under pressure at 120-130 C. for 8 hours, cooling down to 60-70 C. and working up of the tetrabromopyrene as described in Example 1a. The 1,3,6,8-tetrabromopyrene is obtained in an amount of 556 parts and a purity of about 83%, which corresponds to a yield of about 91% of theory, based on 100% pure pyrene. | |
With hydrogenchloride; potassium bromide; In methanol; sodium bromate; water; | (Production Example 1) Production of tetrakis(2-thienyl)pyrene [Synthesis of raw material] (Production of 1,3,6,8-tetrabromopyrene) To 195 ml of water, 27 g of pyrene (reagent made by Tokyo Kasei Kogyo Co., Ltd., purity: 95%) and 7 ml of tetraglyme (reagent made by Tokyo Kasei Kogyo Co., Ltd.) were added, and 70 ml of hydrochloric acid was further added thereto. The mixture was stirred at 90C for 2 hours to prepare an aqueous dispersion of pyrene. Next, 47 g of potassium bromide (reagent made by Tokyo Kasei Kogyo Co., Ltd.) was added thereto at 40C. While the temperature was kept, a solution of sodium bromate in which 30 g of sodium bromate (reagent made by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 110 ml of water was dropwise added to the dispersion for 3 hours. Thereafter, the resultant was filtered, washed sufficiently with about 300 g of methanol, and dried at 85 to 95C to yield 70 g of 1,3,6,8-tetrabromopyrene. | |
With bromine; In water; nitrobenzene; | (1) Fabrication of 1,3,6,8-tetrabromopyrene Pyrene (10 g, 50 mmol) and 100 ml of nitrobenzene were put into a 2-neck round bottom flask and stirred, and bromine (35.6 g, 200 mmol) was slowly dropped therein for 30 minutes. The mixture was then refluxed at a temperature of 130 for 12 hours. After lowering the temperature down to room temperature, 200 ml of distilled water was poured into the refluxed mixture and then stirred, thus generating solid. | |
With bromine; In nitrobenzene; at 140℃; for 10h; | Pyrene (2.00 g, 9.89 mmol)was dissolved in nitrobenzene (60 mL). Under vigorous stirring, bromine (9.48g, 59.33 mmol) was added. After complete addition, the temperature was increasedto 140 C and maintained for 10h. The cooled reaction suspension was poured into acetone and the precipitatefiltered off. Further drying of the precipitate in high vacuum gave the crudeproduct (4.51 g, 8.70 mmol, 88%), which was used without further purificationfor its poor solubility.1 | |
(Example 1) - Synthesis of 1,3,6,8-tetra(4-biphenyl)pyrene - By reaction of one equivalent of pyrene and four equivalents of bromine, 1,3,6,8-tetrabromopyrene was synthesized in nitrobenzene solvent substantially in accordance with the descriptions in ''. | ||
With bromine; In nitrobenzene; at 80 - 120℃; for 12h; | In a one-necked flask, Pyrene (2.50 g), nitrobenzene (80 mL) was added, and the mixture was heated to (80 C), liquid bromine (8.75 g) was added, and the mixture was heated to 120 C to continue the reaction for 12 hours. After cooling to room temperature, ethanol was added, suction filtered and washed with acetone to give a yellow solid. this solid was insoluble in common organic solvents and was used directly in the next reaction without purification. | |
With bromine; acetic acid; | Ligand pyrene-l,3,6,8-tetracarboxylic acid (FLptca) was synthesized in a total of 3 steps (FIG. 25). The first step was the bromination of pyrene to produce tetrabromopyrene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With copper(l) iodide; diisopropylamine; triphenylphosphine In tetrahydrofuran at 70℃; for 16h; | |
92% | With copper(l) iodide; triphenylphosphine In triethylamine; toluene at 60 - 80℃; | |
76% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triphenylphosphine In tetrahydrofuran; diethylamine at 80℃; for 19h; Inert atmosphere; |
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In tetrahydrofuran | ||
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine In toluene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine; In toluene; at 80℃; for 24h;Inert atmosphere; | The (517mg, 1mmol) 1,3,6,8- tetrabromo pyrene,(588 mg, 6 mmol) trimethylsilylacetylene compound (140 mg, 0.2 mmol) of bis(triphenylphosphine)palladium dichloride,(52mg, 0.2mmol) triphenylphosphine, an appropriate amount of cuprous iodide, mixed into 50mL of toluene solution, heated to 80 C under N2 protection for 24 hours;It was cooled to room temperature, extracted with CH2Cl2 and water.The solvent was spin-dried; finally, column chromatography was performed using petroleum ether as the eluent.An orange-yellow solid was obtained as intermediate compound a in a yield of 90%. |
84% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; triphenylphosphine; In tetrahydrofuran; at 80℃; for 12h; | To a stirred nitrobenzene (120 mL) solution of pyrene (1, 4.048 g, 20 mmol) was slowly added nitrobenzene (40 mL) solution of Br2 (4.7 mL, 92 mmol). The solution was stirred at 80C for 12 h. The solution was cooled to room temperature. Conc. NaOH aq (10 mL) was added to remove remaining Br2. The solid was collected by suction filtration with CHCl3 (100 mL) to give <strong>[128-63-2]1,3,6,8-tetrabromopyrene</strong> (11, light green solid, 9.6 g, 92% yield). A stirred mixture of <strong>[128-63-2]1,3,6,8-tetrabromopyrene</strong> (11, 5.172 g, 10 mmol), trimethylsilylacetylene (6.7 mL, 48 mmol), (PPh3)2PdCl2 (353 mg), CuI (107 mg), PPh3 (263 mg), i-Pr2NH (50 mL), and THF (50 mL) was stirred at 80C for 12 h. The solution was concentrated in vacuo. Purification by silica gel column chromatography (eluent; hexane) gave 1,3,6,8-tetrakis(trimethylsilylethynyl)pyrene (3, 4.936 g, 84% yield). Reddish orange solid; 29Si NMR (100 MHz, CDCl3) delta -17.4 ppm. |
78% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; triphenylphosphine; In tetrahydrofuran; at 80℃; for 12h;Inert atmosphere; | A mixture of <strong>[128-63-2]1,3,6,8-tetrabromopyrene</strong> [98] (1.04 g, 2.0 mmol),trimethylsilylacetylene (0.971 g, 9.9 mmol), PdCl2(PPh3)2 (0.082 g,0.12 mmol), CuI (0.038 g, 0.20 mmol), and PPh3 (0.078 g, 0.30 mmol)in THF (30 mL) and i-Pr2NH (25 mL) was stirred at 80 C for 12 h underan argon atmosphere. The resulting mixture was concentrated in vacuo,giving a residue that was subjected to silica gel column chromatography(eluent: hexane) followed by recycling preparative HPLC (GPC, eluent:CHCl3) to give 1,3,6,8-tetrakis(trimethylsilylethynyl)pyrene (6, 0.91 g,78 % yield, red solid). Lit [60]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With C42H54Cl2N6Pd; triphenylphosphine; sodium hydroxide In 1,4-dioxane at 105 - 110℃; for 8h; Inert atmosphere; | |
89% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate at 160℃; for 48h; Inert atmosphere; Schlenk technique; Darkness; | General Procedure for the Suzuki Coupling: General procedure: Compound8 (0.52g, 1mmol),boronic acid (5mmol),K2CO3 (2.8g, 20mmol) andPd(PPh3)4 (185mg) was added todimethylformamide (20mL) taken in a Schlenk flask. The flask was repeatedly degassed by evacuation and purging with argon. The mixture was heated at 160°C under argon atmosphere under complete exclusion of light for the time mentioned for individual cases after which it was quenched by addingwater. The organic layer was extracted with dichloromethane, washed consecutively with water and brine before being dried over MgSO4. After having removed the solvent under reduced pressure, the crude product was purified by column chromatography (silica gel, hexane/ethyl acetate). |
84% | With water; palladium diacetate; cesium fluoride; cyclo-octa-1,5-diene; DavePhos In neat (no solvent) for 1.65h; Milling; Green chemistry; |
74% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide In toluene at 90℃; for 20h; Inert atmosphere; | |
63% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide In water; toluene at 90℃; for 24h; Inert atmosphere; | 2.2. Synthesis of 1,3,6,8-tetraphenylpyrene (TPPy) TPPy was synthesized as described in a previous publication [44]. 1,3,6,8-Tetrabromopyrene (200 mg, 0.386 mmol), phenylboronic acid(254 mg, 2.08 mmol), Pd(PPh3)4 (50 mg, 0.04 mmol) and 2.0 M NaOHaqueous solution (2 mL) were mixed in a flask containing nitrogensaturated toluene (10 mL). The reaction mixture was stirred at 90 C for24 h. After cooling to room temperature, the reaction mixture wasextracted with dichloromethane (2 × 40 mL). The combined organicextracts were dried with anhydrous magnesium sulfate and evaporated.The crude product was purified by column chromatography using a 1:5petroleum ether/ethyl acetate mixture as the eluent to provide alight-colored powder and recrystallized from hexane to obtain 1,3,6,8-tetraphenylpyrene (TPPy) as a light yellow powder (125 mg, 63%):IR νmax (KBr) 2960, 1600, 1513, 1494, 1459, 1286, 1245, 1176, 1106,1035, 835, 549, 476 cm 1;1H NMR (400 MHz, CD2Cl2) δ 7.36-7.40 (m,4H), 7.47 (t, J = 7.6 Hz, 8H), 7.61 (d, J = 8.0 Hz, 8H), 7.98 (s, 2H), 8.12(s, 4H); 13C NMR (125 MHz, CDCl3) δ 141.10, 137.28, 130.68, 129.57,128.37, 128.15, 127.32, 125.97, 125.35; m/z 506.1948(M+).)TPPy was synthesized as described in a previous publication [44]. 1,3,6,8-Tetrabromopyrene (200 mg, 0.386 mmol), phenylboronic acid(254 mg, 2.08 mmol), Pd(PPh3)4 (50 mg, 0.04 mmol) and 2.0 M NaOHaqueous solution (2 mL) were mixed in a flask containing nitrogensaturated toluene (10 mL). The reaction mixture was stirred at 90 C for24 h. After cooling to room temperature, the reaction mixture wasextracted with dichloromethane (2 × 40 mL). The combined organicextracts were dried with anhydrous magnesium sulfate and evaporated.The crude product was purified by column chromatography using a 1:5petroleum ether/ethyl acetate mixture as the eluent to provide alight-colored powder and recrystallized from hexane to obtain 1,3,6,8-tetraphenylpyrene (TPPy) as a light yellow powder (125 mg, 63%):IR νmax (KBr) 2960, 1600, 1513, 1494, 1459, 1286, 1245, 1176, 1106,1035, 835, 549, 476 cm 1;1H NMR (400 MHz, CD2Cl2) δ 7.36-7.40 (m,4H), 7.47 (t, J = 7.6 Hz, 8H), 7.61 (d, J = 8.0 Hz, 8H), 7.98 (s, 2H), 8.12(s, 4H); 13C NMR (125 MHz, CDCl3) δ 141.10, 137.28, 130.68, 129.57,128.37, 128.15, 127.32, 125.97, 125.35; m/z 506.1948(M+). |
With tetrakis(triphenylphosphine) palladium(0) In toluene for 9h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With piperidine; bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide for 5h; Heating; | |
78% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; triphenylphosphine In tetrahydrofuran at 80℃; for 12h; Inert atmosphere; | 4.10. Preparation of 10 A mixture of 1,3,6,8-tetrabromopyrene [98] (1.04 g, 2.0 mmol), 3,3-dimethyl-1-butyne (0.756 g, 9.2 mmol), 2(PdPhC3l)2 (0.071 g,0.10 mmol), CuI (0.033 g, 0.17 mmol), and PPh3 (0.068 g, 0.26 mmol)in THF (30 mL) and i-Pr2NH (25 mL) was stirred at 80 °C for 12 h underan argon atmosphere. The resulting mixture was concentrated in vacuo,giving a residue that was subjected to silica gel column chromatography(eluent: hexane) followed by recycling preparative HPLC (GPC, eluent:CHCl3) to give 1,3,6,8-tetrakis(3,3-dimethylbut-1-yn-1-yl)pyrene (10,0.81 g, 78 % yield). Lit [60]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium carbonate; triphenylphosphine;palladium diacetate; In 1,3,6,8-tetrakis(2-naphthyl)pyrene; water; | Example 1b Synthesis of 1,3,6,8-tetra(9-phenanthryl)pyrene 1,3,6,8-tetrabromopyrene (4.7 g, 9.1 mmol), 9-phenanthreneboronic acid (11.7 g, 45.4 mmol), triphenylphosphine (1.0 g, 3.6 mmol), palladium(II) acetate (0.2 g, 0.9 mmol), and potassium carbonate (8.8 g, 63.5 mmol) were in 300 mL of xylenes and 50 mL of water. The mixture was purged with nitrogen for ten minutes and slowly brought to reflux under nitrogen. The mixture was refluxed for forty-eight hours. After cooling, the solid was filtered, washed with water and ethanol, and dried. The crude yield was ~95%. Based on the purification of 1,3,6,8-tetra(2-naphthyl)pyrene, sublimation was the most effective means of purifying this crude material; however, 1,3,6,8-tetra(9-phenanthryl)pyrene decomposed under similar sublimation conditions as in 1,3,6,8-tetra(2-naphthyl)pyrene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With C42H54Cl2N6Pd; triphenylphosphine; sodium hydroxide In 1,4-dioxane at 105 - 110℃; for 6h; Inert atmosphere; | |
75% | With potassium carbonate In 1,4-dioxane at 85℃; for 24h; | |
74% | Stage #1: 1,3,6,8-tetrabromopyrene; 4-(trifluoromethyl)benzene boronic acid With potassium carbonate In ethanol; lithium hydroxide monohydrate; toluene for 0.0833333h; Inert atmosphere; Stage #2: With tetrakis-(triphenylphosphine)-palladium In ethanol; lithium hydroxide monohydrate; toluene at 90℃; for 24h; Inert atmosphere; |
27% | With anhydrous sodium carbonate In ethanol; lithium hydroxide monohydrate; toluene at 80℃; for 12h; Heating / reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 2-ethoxy-ethanol; diethylene glycol dimethyl ether; water Reflux; | |
77% | With potassium carbonate In 1,4-dioxane at 85℃; for 24h; | |
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; N,N-dimethyl-formamide for 12h; Reflux; Inert atmosphere; | 1 Synthesis of intermediate (1) 517 mg of 1,3,6,8-tetrabromopyrene, 640 mg of 2-thiopheneboronic acid, 58 mg of tetrakis(triphenylphosphine) palladium, and 828 mg of potassium carbonate were put in 20 mL of DMF and 5 mL of water, and heated to reflux for 12 hours under the protection of nitrogen. After cooling, it was filtered and washed with cyclohexane to obtain intermediate (1) with a yield of 72%. |
66% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 85℃; for 72h; Inert atmosphere; | |
17% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 83 percent / copper(I) iodide; triphenylphosphine / bis(triphenylphosphine)palladium(II)dichloride / triethylamine; toluene / 60 - 80 °C 2: 95 percent / K2CO3 / methanol | ||
Multi-step reaction with 2 steps 1: 33 percent / CuI; PPh3; diisopropylamine / [PdCl2(PPh3)2] / tetrahydrofuran / 12 h / 65 °C 2: 93 percent / nBu4NF / tetrahydrofuran / 1 h / 35 °C | ||
Multi-step reaction with 2 steps 1: copper(l) iodide; bis-triphenylphosphine-palladium(II) chloride; diisopropylamine; triphenylphosphine / tetrahydrofuran / 12 h / 80 °C 2: water; potassium hydroxide / methanol; dichloromethane / 12 h |
Multi-step reaction with 2 steps 1: copper(l) iodide; bis-triphenylphosphine-palladium(II) chloride; diisopropylamine; triphenylphosphine / tetrahydrofuran / 20 h / 50 °C / Inert atmosphere 2: water; potassium hydroxide / tetrahydrofuran / 12 h / 20 °C | ||
Multi-step reaction with 2 steps 1: copper(l) iodide; tetrakis(triphenylphosphine) palladium(0) / tetrahydrofuran; diethylamine / 39 h / 65 °C / Inert atmosphere 2: potassium carbonate / tetrahydrofuran; methanol / 1 h / 20 °C / Inert atmosphere | ||
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); copper(l) iodide; triethylamine / toluene / 60 - 80 °C / Inert atmosphere 2: potassium carbonate / methanol | ||
Multi-step reaction with 2 steps 1: bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triphenylphosphine; diisopropylamine / tetrahydrofuran / 12 h / 80 °C 2: potassium hydroxide; methanol / water; 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran / 1 h / 20 °C | ||
Multi-step reaction with 2 steps 1: triethylamine; bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triphenylphosphine / toluene / 16 h / 80 °C 2: potassium carbonate / methanol / 16 h / 20 °C | ||
Multi-step reaction with 2 steps 1: copper(l) iodide; triphenylphosphine; bis-triphenylphosphine-palladium(II) chloride; diisopropylamine / tetrahydrofuran / Reflux 2: potassium hydroxide / tetrahydrofuran; methanol / 1 h / 20 °C | ||
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); triphenylphosphine; copper(l) iodide; triethylamine / toluene / 48 h / 50 - 90 °C / Inert atmosphere 2: potassium carbonate; methanol / 48 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate at 160℃; for 48h; Inert atmosphere; Schlenk technique; Darkness; | General Procedure for the Suzuki Coupling: General procedure: Compound8 (0.52g, 1mmol),boronic acid (5mmol),K2CO3 (2.8g, 20mmol) andPd(PPh3)4 (185mg) was added todimethylformamide (20mL) taken in a Schlenk flask. The flask was repeatedly degassed by evacuation and purging with argon. The mixture was heated at 160°C under argon atmosphere under complete exclusion of light for the time mentioned for individual cases after which it was quenched by addingwater. The organic layer was extracted with dichloromethane, washed consecutively with water and brine before being dried over MgSO4. After having removed the solvent under reduced pressure, the crude product was purified by column chromatography (silica gel, hexane/ethyl acetate). |
With caesium carbonate In ethanol; water; toluene for 7h; Heating / reflux; | ||
With caesium carbonate In ethanol; water; toluene | (Production Example 9) Production of 1,3,6,8-tetrakis(4-tolyl)pyrene (Production Example 9) Production of 1,3,6,8-tetrakis(4-tolyl)pyrene To 8.0 g of 4-tolylboronic acid (reagent made by Tokyo Kasei Kogyo Co., Ltd.), 5.0 g of 1,3,6,8-tetrabromopyrene, and 31 g of cesium carbonate (reagent made by Kishida Chemical Co., Ltd.), 200 ml of toluene (reagent made by Junsei Chemical Co., Ltd.), 100 ml of ethanol (reagent made by Junsei Chemical Co., Ltd.) and 40 ml of pure water were added, and then the system was purged with nitrogen. Thereafter, 0.6 g of tetrakistriphenylphosphine palladium (0) (reagent made by Tokyo Kasei Kogyo Co., Ltd.) was added thereto. The resultant was heated and refluxed for 7 hours. The reaction solution was concentrated under reduced pressure, and 100 ml of water was added thereto. The resultant was extracted with chloroform, and sodium sulfate was added to the extracted liquid so as to dehydrate the liquid. The liquid was filtered and concentrated, and then the resultant residue was purified by GPC, so as to yield 0.8 g of a yellow solid. From FAB mass spectrometry thereof, it was understood that this component was 1,3,6,8-tetrakis(4-tolyl)pyrene. ·MS:m/z=69,109,145,180,207,256,281,307,424,456,472,523,561,562 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With sodium hydroxide In water; toluene at 110℃; for 16h; | |
77% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide In water; toluene for 16h; Inert atmosphere; Reflux; | |
With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide In 1,4-dioxane; water at 90℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide In 1,4-dioxane at 90℃; for 12h; | |
80% | With sodium hydroxide In water; toluene at 110℃; | |
With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide In 1,4-dioxane; water at 90℃; for 12h; Inert atmosphere; |
With tetrakis(triphenylphosphine) palladium(0) | ||
With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide In 1,4-dioxane at 90℃; for 12h; | ||
With tetrakis(triphenylphosphine) palladium(0) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium carbonate In 1,4-dioxane for 96h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water at 90℃; for 48h; Inert atmosphere; | 1,3,6,8-Tetrabromopyrene 4 (200 mg, 0.39 mmol), 7-tert-butyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene 5 (891 mg,2.32 mmol), and Pd(PPh3)4 (243 mg, 0.156 mmol) and aqueous2.0 M K2CO3 (2 mL) were mixed in a flask containing argon saturatedtoluene (50 mL). The reaction mixture was stirred at 90 Cfor 48 h. After it was cooled to room temperature, the reactionmixture was quenched with saturated sodium bicarbonate solutionand extracted with dichloromethane (100 mL 2). The combinedorganic extracts were dried with anhydrous MgSO4 andevaporated. The crude product was purified by column chromatographyusing hexane/dichloromethane (5:1) as eluent to provide8 (318 mg, 66%) as pale green prisms. mp > 300 C; 1HNMR (CDCl3, 300 MHz): δH = 1.55 (s, 36H, tBu), 7.70-8.25 (m,32H, Ar-H), 8.27 (s, 2H, Py-Ha), 8.38 (s, 4H, Py-Hb) ppm; MS m/z: 1227 [M+]; Anal. calcd. for C96H74 (1227.61) C, 93.90, H, 6.10.Found C, 93.92, H, 6.08. |
42% | With tetrakis(triphenylphosphine) palladium(0); Aliquat 336; potassium carbonate In water; toluene at 80℃; for 48h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; at 130℃; for 72h;Inert atmosphere; Microwave irradiation; | A mixture of (4-(methoxycarbonyl)phenyl)boronic acid (1.040 g, 5.80 mmol), <strong>[128-63-2]1,3,6,8-tetrabromopyrene</strong> (0.500 g, 0.97 mmol), tetrakis(triphenylphosphine) palladium(0) (0.030 g 0.026 mmol), and potassium tribasic phosphate (1.100 g, 5.30 mmol) in dry dioxane (20 mL) was loaded (in a glovebox) into a 20 mL microwave vial (Biotage) and capped. This mixture was stirred under argon for 72 h at 130 C. in an oil bath. The reaction mixture was evaporated to dryness and the solid residue was washed with water to remove inorganic salts. The insoluble material was extracted with chloroform (three times by 50 mL), the extract was dried over magnesium sulfate, and the solvent volume was reduced under vacuum. The residue was boiled in tetrahydrofuran for 2 h and filtered; the resulting filtrate contained mainly impurities. This procedure gave 0.58 g of 1,3,6,8-tetrakis(4-(methoxycarbonyl)phenyl)pyrene (82% yield). 1H NMR (CDCl3-d): delta 3.99 (s, 12H), 7.75 (d, 8H), 8.01 (s, 2H), 8.15 (s, 4H), 8.23 (d, 8H). |
82% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); at 130℃; for 72h;Inert atmosphere; Glovebox; | The present embodiment relates to a method for preparing 4,4',4",4"'-(indol-1,3,6,8-tetraphenyl)tetrabenzoic acid, which comprises the following steps: (4-(methoxycarbonyl)phenyl)boronic acid (1.040 g, 5.80 mmol), <strong>[128-63-2]1,3,6,8-tetrabromopyrene</strong> (0.500 g, 0.97 mmol), tetrakis(triphenylphosphine)palladium(0) (0.030 g) 0.026 mmol) and anhydrous tripotassium phosphate (1.100 g,5.30 mmol) was placed (in a glove box) in a 20 mL microwave vial and capped. The mixture was stirred under an argon atmosphere at 130 C for 72 hours in an oil bath. The reaction mixture was evaporated to dryness and the solid residue was washed with water to remove inorganic salts. The insoluble material (50 mL three times) was extracted with chloroform, and the extract was dried over magnesium sulfate, and the solvent volume was reduced under vacuum. The residue was boiled in tetrahydrofuran for 2 hours and filtered; the filtrate obtained mainly contained impurities. This procedure gave 0.58 g of 1,3,6,8-tetrakis(4-(methoxycarbonyl)phenyl)pyrene 0.58 g (yield 82%).Then, into a 250 mL round bottom flask containing 0.58 g (0.78 mmol) of solid 1,3,6,8-tetrakis(4-(methoxycarbonyl)phenyl)pyrene, add a mixture of 100 mL of tetrahydrofuran/water (ratio 1:1) containing NaOH 1.5 g (37.5 mmol). The resulting suspension was stirred vigorously under reflux overnight.The solvent was removed under vacuum and water was added to a residue that formed a clear yellow solution. The clear yellow solution was stirred at room temperature for 2 hours and the pH was adjusted to 1 using concentrated HCl. The resulting yellow solid was collected by filtration and washed several times with water.The crude product was recrystallized from DMF and filtered.Wash with chloroform and dry in vacuo. This gave 0.49 g (91%) of pure product H4TBAPy, abbreviated as H4L. |
82% | With tetrakis(triphenylphosphine) palladium(0); at 130℃; for 72h;Glovebox; Microwave irradiation; Inert atmosphere; | (4-(Methoxycarbonyl)phenyl)boronic acid (1.040 g, 5.80 mmol), 1,3,6,8-tetrabromoindole (0.500 g, 0.97 mmol), tetrakis(triphenylphosphine)palladium ( 0) (0.030g 0.026mmol) and anhydrous potassium phosphate (1.100g,5.30 mmol) was placed (in a glove box) in a 20 mL microwave vial and capped.The mixture was stirred under an argon atmosphere at 130 C for 72 hours in an oil bath. The reaction mixture was evaporated to dryness and the solid residue was washed with water to remove inorganic salts. ChlorineThe insoluble material (50 mL three times) was extracted, and the extract was dried over magnesium sulfate, and the solvent volume was reduced under vacuum. The residue was boiled in tetrahydrofuran for 2 hours and filtered; the filtrate obtained mainly contained impurities.This procedure gave 1,8,6,8-tetrakis(4-(methoxycarbonyl)phenyl)indole 0.58 g (yield 82%). Then, to a 250 mL round bottom flask containing 0.58 g (0.78 mmol) of solid 1,3,6,8-tetrakis(4-(methoxycarbonyl)phenyl)anthracene, 100 mL of 1.5 g (37.5 mmol) NaOH was added. A mixture of tetrahydrofuran/water (ratio 1:1) was added and the resulting suspension was stirred vigorously under reflux overnight. The solvent was removed under vacuum and water was added to a residue that formed a clear yellow solution. The clear yellow solution was stirred at room temperature for 2 hours and the pH was adjusted to 1 using concentrated HCl. The resulting yellow solid was collected by filtration and washed several times with water. The crude product was recrystallized from DMF, filtered, washed with EtOAc. This gave 0.49 g (91%) of pure product H4TBAPy, abbreviated as H4L. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene for 24h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water at 90℃; for 48h; Inert atmosphere; | 1,3,6,8-Tetrabromopyrene 4 (200mg, 0.39 mmol), 2-[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]-4,4,5,5-tetramethyl[1,3,2]dioxaboro lane9 (1003 mg, 2.32 mmol), and Pd(PPh3)4 (243 mg, 0.156 mmol) andaqueous 2.0M K2CO3 (2 mL) were mixed in a flask containing argon saturatedtoluene (50mL). The reaction mixturewas stirred at 90 Cfor48 h. After it was cooled to room temperature, the reaction mixturewas quenched with saturated sodium bicarbonate solution and extractedwithdichloromethane (100 mL 2). The combinedorganic extractswere dried with anhydrous MgSO4 and evaporated. The crudeproduct was purified by column chromatography using hexane/dichloromethane (9:1) as eluent to provide 8 (452 mg, 70%) as a palegreen solid and recrystallization from CHCl3/EtOH (3:1 v/v) to afford8 as pale yellow prisms. mp 276-278 C; 1H NMR (CDCl3, 300MHz):dH = 0.66-0.69 (m, 48H, Me), 1.23-1.35 (m, 16H, CH2), 2.01-2.06 (m,24H, CH2 and CH), 7.31-7.41 (m, 12H, Ar-H), 7.66-7.88 (m, 16H, Ar-H), 8.16 (s, 2H, Py-Ha), 8.19 (s, 4H, Py-Hb) ppm; MS m/z: 1420 [M+];Anal. calcd. for C108H122 (1420.12) C, 91.33, H, 8.67. Found C, 91.35,H, 8.66. |
50% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 90℃; for 48h; Inert atmosphere; | 1,3,6,8-Tetrakis[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]pyrene (3c) General procedure: A mixture of 1-bromopyrene (0.5 g, 1.79 mmol), K2CO3 (0.3 mg, 2.19 mmol), and 2 (1.16 g, 2.69 mmol) was dissolved in toluene (15 mL) and water (2 mL) was added. The solution was stirred in an ice water bath for 15 min. Then Pd(PPh4)3 (122 mg, 0.08 mmol) was added to the solution, following which the reaction mixture was stirred at 90 °C for 48 h. The reaction mixture was extracted with dichloromethane (50 mL * 2) after which it was cooled to room temperature, and the organic layer was combined and washed with H2O and brine, then dried with anhydrous MgSO4 and evaporated. The crude product was purified by column chromatography using dichloromethane/hexane (1:1) as eluent to afford 1-[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]pyrene (3a) as a white powder (585 mg, 73%) |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 90℃; for 48h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With copper In α,α,α-trifluorotoluene; dimethyl sulfoxide at 130 - 135℃; for 5h; Inert atmosphere; | 1 Perfluorooctyl iodide (CsFi7I, 1.10 ml, 4.13 mmol) was added into a mixture of 1,3,6,8-Tetrabromopyrene (0.146g, 0.25mmol) and copper powder (0.525g, 8.26mmol) in α,α, α -trifluorotoluene and anhydrous DMSO under nitrogen protection at 13O-135°C. 1,3,6,8-Tetrabromopyrene was prepared from pyrene through direct bromonation. The reaction was monitored by TLC and quenched after 5 hours with acidic ice water. The mixture was suction filtered and the precipitate was washed at least three times with hydrochloric acid and D.I. water , then the solid crude product (ash gray) was further extracted with HFE-7200 to yield white crystalline 1,3,6,8-tetrakis-perfluorooctyl- pyrene (0.363 g, 75%) with bright blue fluorescence. Characterization data: IH-NMR: 8.65 ppm (IH) and 8.82 ppm (2H). |
Stage #1: 1,3,6,8-tetrabromopyrene With copper In dimethyl sulfoxide at 135℃; for 0.416667h; Inert atmosphere; Stage #2: 1-iodoheptadecafluorooctane In dimethyl sulfoxide at 135℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.6% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In tetrahydrofuran at 70℃; Inert atmosphere; | 1,3,6,8-Tetrakis[4-(2,2-diphenylvinyl)phenyl]pyrene (TPVPP) General procedure: A two-necked flask was charged with 1-bromopyrene (0.13 g, 0.45 mmol), 4-(2,2-diphenylvinyl)phenylboronic acid (0.30 g, 1.00 mmol), Pd(PPh3)4, and well-degassed THF (30 mL) under N2 atmosphere. After the mixture was stirred for 10 min, sodium carbonate (4 mL, 2 M) was added to the flask. The mixture was then allowed to increase to 70 oC and maintained for 24 h. The solution was extracted with dichloromethane. The organic layer was washed with brine, and dried over Na2SO4. The solvent was evaporated under reduced pressure, and the crude product was purified by flash column chromatography using petroleum/dichloromethane (v/v = 16:1) as eluent to afford a white solid (0.15 g, yield 73.2%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; diisopropylamine In tetrahydrofuran at 80℃; for 16h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene;Inert atmosphere; | General procedure: G3-B(OH)2 (1.04 g, 0.6 mmol), 1,3,6,8-tetrabromo-1,3-dihydropyrene (0.05 g, 0.1 mmol), and tetrakis(triphenylphosphine) palladium (0.012 g, 0.01 mmol) were added to an air-free two-phase system composed of toluene (30 mL) and 2 M K2CO3 aqueous solution (10 mL). The resulting mixture was intensively stirred under an argon atmosphere at 80 C for 24 h. The organic layer was separated and the aqueous phase was extracted with diethyl ether. The organic layers were combined and washed with brine and dried over anhydrous MgSO4. The solvent was evaporated and the residue went through silica-gel column. |
22% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 72h;Inert atmosphere; | In a 250mL three-necked round-bottomed flask, 1,3,6,8-tetrabromo-pyrene (1.0356g, 2mmol) and 4-(9H-carbozol-9yl)phenylboronic acid (2.8712g, 10mmol) were dissolved in dioxane (100mL) and then an aqueous solution of potassium carbonate (3.15g, 23mmol) in water (10mL) and Pd(PPh3)4 catalyst (0.6g, 0.50mmol) were added to the reaction mixture and it was stirred under N2 at 100C for 3days. After cooling to room temperature, the yellow reaction mixture was transferred to dilute hydrochloric acid solution (100mL). The precipitate was collected by filtration and then washed with water (3×40mL). The solid was transferred to a Soxhlet and continuously extracted with CHCl3 for 48h. The CHCl3 extract was evaporated under reduced pressure. The crude product L was further purified by silica-gel column chromatography using CHCl2 as mobile phase to afford a bright yellow solid (0.5g, 22%). 1H NMR (400MHz, CDCl3): delta(ppm) 8.51(4H), 8.32(2H), 8.22(8H), 8.03(8H), 7.84 (8H), 7.61(8H), 7.51(8H), 7.35(8H). FT-IR (ATR4000-400cm-1) 3418, 3047, 2910, 1600, 1514, 1493, 1451, 1359, 1338, 1312, 1223, 1164, 1004, 839, 746, 717, 628, 561, 533. MS(ESI): m/z for C88H54N4 cacld 1166, M+, 1166.02. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In N,N-dimethyl-formamide at 145℃; for 48h; Inert atmosphere; Schlenk technique; | |
62% | With tetrakis-(triphenylphosphine)-palladium; tri-n-octylmethylammonium chloride; potassium carbonate In tetrahydrofuran; lithium hydroxide monohydrate; toluene at 110℃; for 9h; Schlenk technique; Glovebox; Inert atmosphere; Microwave irradiation; | 2.3 Synthesis of 1,3,6,8-tetrakis(N-methylpyridinium-4-yl)pyrene[1]: To a solid mixture of 1,3,6,8-tetrabromopyrene (1.04 g, 2 mmol), 4-pyridinyl boronic acid ( 1.48 mg, 12 mmol) and (Pd(Ph3)4) (138 mg, 0.12mmol) were added a solution of 7 mL tetrahydrofuran (THF) and 1 ml toluene. After 6 mL of 2 M aqueous potassium carbonate (K2CO3) was added to the mixture, it was degassed by bubbling nitrogen for 30 min. . The reaction mixture was stirred for 9 h at 110 °C in Microwave reactor. The reaction mixture was then cooled to room temperature, then the precipitate was collected via vacuum filtration and washed by water, MeOH, and CHCl3. The yellow-green solid powder was obtained (633.1 mg, 62%). |
59% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In tetrahydrofuran; lithium hydroxide monohydrate; toluene for 96h; Inert atmosphere; Reflux; | 3.5 mL of tetrahydrofuran, 0.5 mL of toluene, and 3.0 mL of 2 M aqueous potassium carbonate were added to a solid mixture of 1,3,6,8-tetrabromopyrene and 4-pyridinyl boronic acid (375.8 mg, 3.0 mmol) under N2 atmosphere. Finally, tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (3.25 mg, 0.0028 mmol) was added to the mixture. The mixture was refluxed under nitrogen for 4 days.10 The crude product poured into 10 mL of methanol was filtered with the PTFE membrane filter (Φ = 0.1 μm) and washed by water. The yellow powder was obtained (150.6 mg, 59%). Identity of the product was confirmed using 1H NMR. Synthesized 1,3,6,8-tetrakis(pyridine-4-yl)-pyrene (150.6 mg, 0.29 mmol) was added to a solution of 3.6 mL of iodomethane and 90 mL of acetonitrile. The mixture was refluxed under nitrogen for 6 days. After the reaction mixture was evaporated and dried, 76 mL of water was added and the formed precipitates were removed by filtration. Ammonium hexafluorophosphate (219.4 mg) was added to the filtrate under vigorous stirring. The precipitated yellow solid was collected by filtration with the PTFE membrane filter (Φ = 0.1 μm) (75.9 mg, 48%). |
42% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In N,N-dimethyl-formamide at 145℃; for 48h; | 1,3,6,8-Tetrabromopyrene (520 mg, 1.00 mmol), 4-pyridinylboronic acid (500 mg, 4.00 mmol),DMF (150 mL) and K2CO3 (25.0 mg, 0.183 mmol) were added to a flask and degassed by Arbubbling for 30 minutes. Pd(PPh3)4 (20.0 mg, 0.0173 mmol) was added and the solution wasdegassed for a further 10 minutes before heating to 145 °C for 48 hours. After cooling the mixturewas poured into water (500 mL) and stirred for 30 minutes. The precipitate was collected byfiltration and washed with, water (100 mL), methanol (100 mL) and dichloromethane (100 mL).After drying under reduced pressure, tetra(pyridin-4-yl)pyrene was obtained as a pale green solid in217 mg, Yield: 42 % S2. 1H NMR (600 MHz, DMSO-d6, 298 K) δ (ppm) = 9.09 (d, J = 6.0 Hz, 8H),8.38 (d, J = 6.0 Hz, 8H), 8.35 (s, 2H), 8.29 (s, 4H). |
With tetrakis-(triphenylphosphine)-palladium; potassium carbonate; palladium (II) chloride In 1,4-dioxane; lithium hydroxide monohydrate at 90℃; for 96h; Inert atmosphere; | 1-3 Synthesis of 1,3,6,8-tetrapyridine: Put 30mL of dioxane and 10mL of water in a three-necked flask. After degassing by bubbling with argon for half an hour, add 4-pyridineboronic acid, 1,3,6,8-tetrabromopyrene and potassium carbonate to 6mmol :1mmol:4mmol was added to the mixed solvent successively, and the catalyst palladium chloride and tetrakis(triphenylphosphine)palladium were added to the above suspension in an equivalent ratio of 0.07:0.15. The mixed solution was heated at 90°C. Reflux and stir under argon atmosphere under the conditions of, and react for 4 days. The resulting yellow powder crude product was washed with a large amount of methanol solution and suction filtered, and dried at 100°C for 6 hours.The dried yellow powder crude product and N,N-dimethylformamide are mixed uniformly in the ratio of 10mg:3mL and placed in a hydrothermal reaction kettle for heating at a temperature of 100°C. The heating reaction time is 16 hours, and the temperature is reduced to room temperature. After filtration, a large number of yellow crystals were obtained, namely the product 1,3,6,8-tetrapyrene (Figure 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In N,N-dimethyl-formamide at 120℃; Inert atmosphere; | |
60% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine at 70℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With tri-tert-butyl phosphine; Palladium(0) bis(dibenzylideneacetone); sodium tertiary butoxide In toluene for 24h; Inert atmosphere; Schlenk technique; Reflux; | Octaphenylpyrene-1,3,6,8-tetraamine (1) To a flask containing a mixture of 1,3,6,8-tetrabromopyrene (0.52 g, 1.0 mmol), diphenylamine (0.74 g, 4.4 mmol), sodium tert-butoxide (0.51 g, 5.28 mmol) and Pd(dba)2 (0.040 mmol) was added dry toluene (30 mL). After 30 min. P(tBu)3 (1.2 mol%) was added and the solution mixture was heated to reflux and stirred for 24 h. After cooling, the solution was pumped dry and the residue was extracted with CH2Cl2/brine. The organic layer was dried over magnesium sulfate, then filtered and dried. After recrystallization from dichloromethane and hexane, the crude product was further purified by column chromatography using CH2Cl2/hexane (1:10 by v/v) as eluent to give 1 as a yellow powder (0.82 g, 92%). 1H NMR (400 MHz, acetone-d6): δ (ppm) 7.96 (s, 4 H, pyrene), 7.67 (s, 2 H, pyrene), 7.15 (t, J = 8.64 Hz, 16 H, meta-C6H5), 6.99 (d, J = 8.67 Hz, 16 H, ortho-C6H5), 6.89 (t, J = 8.66 Hz, 8 H, para-C6H5); MS (FAB): m/z 870.1 (M+). Anal. Calcd for C64H46N4: C, 88.25; H, 5.32; N, 6.43. Found: C, 87.97; H, 5.45; N, 6.41. |
72% | With tri-tert-butyl phosphine; palladium diacetate; Cs2CO3 In o-dimethylbenzene at 160℃; for 48h; | 1.8 2.1.8 Synthesis of 1,3,6,8-tetrakis-(N,N-diphenylamino)pyrene (10a) General procedure: The corresponding tetrabromopyrene ( 5) (300 mg, 0.58 mmol), secondary amines ( 6a) (588 mg, 3.48 mmol, 6.0 mol of amine per halogen atom of tetrabromopyrene), Pd(OAc)2 (4 mol% of Pd per halogen atom of bromopyrene), (t-Bu)3P (12 mol% of P per halogen atom of tetrabromopyrene), Cs2CO3 (10 mol of Cs per halogen atom of tetrabromopyrene), and o-xylene (10 mL) were mixed together and heated at 160 °C for 48 h. The reaction was quenched with water (100 mL) and the organic layer taken into 100 mL of CH2Cl2, washed with brine solution, and dried over MgSO4. Evaporated of the solvent under vacuum resulted in a solid residue. The residue was adsorbed in silica gel (Wako gel, C-300) and purified by column chromatography using hexane/CHCl3 (6:1) as eluent and recrystallization from ethyl acetate to afford the corresponding desired compound 10a as pale-yellow powder (378 mg, 72%); m.p. >300 °C; δH (CDCl3) 6.89-7.17 (40H, m, Ar-H), 7.66 (2H, s, Py-Ha) and 7.97 (4H, s, Py-Hb); δC (CDCl3) 117.80, 121.82, 123.33, 127.37, 129.09, 129.31, 130.53, 141.91 and 148.12; m/z 871 (M+) (Found: C, 88.23; H, 5.34; N, 6.45%. C64H46N4 (871.08) requires C, 88.25; H, 5.32; N, 6.43%). |
67.39% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 110℃; for 24h; Inert atmosphere; | 1 Preparation Example 1: In a 250ml three-necked flask, under the protection of nitrogen, add 0.01mol of raw material C1, 0.048mol of raw material B1, 150ml of toluene, stir and mix, then add 0.1mol of sodium tert-butoxide, 4.0×10-4mol Pd2(dba)3, 4.0× 10-4mol tri-tert-butylphosphine, heated to 110°C, refluxed for 24h, sampling point plate, showed that no raw material C1 remained, the reaction was complete; naturally cooled to room temperature, filtered, the filtrate was evaporated under reduced pressure, and purified on a neutral silica gel column to obtain the target product intermediate D1, with a HPLC purity of 99.21% and a yield of 67.39%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In o-xylene; at 160℃; for 48h; | The corresponding tetrabromopyrene ( 5) (300 mg, 0.58 mmol), secondary amines ( 6a) (588 mg, 3.48 mmol, 6.0 mol of amine per halogen atom of tetrabromopyrene), Pd(OAc)2 (4 mol% of Pd per halogen atom of bromopyrene), (t-Bu)3P (12 mol% of P per halogen atom of tetrabromopyrene), Cs2CO3 (10 mol of Cs per halogen atom of tetrabromopyrene), and o-xylene (10 mL) were mixed together and heated at 160 C for 48 h. The reaction was quenched with water (100 mL) and the organic layer taken into 100 mL of CH2Cl2, washed with brine solution, and dried over MgSO4. Evaporated of the solvent under vacuum resulted in a solid residue. The residue was adsorbed in silica gel (Wako gel, C-300) and purified by column chromatography using hexane/CHCl3 (6:1) as eluent and recrystallization from ethyl acetate to afford the corresponding desired compound 10a as pale-yellow powder (378 mg, 72%); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water at 90℃; for 48h; Inert atmosphere; | 1,3,6,8-Tetrabromopyrene 4 (200 mg, 0.386 mmol), 4-methoxyphenylboronicacid 11 (468 mg, 3.8 mmol), and Pd(PPh3)4(243 mg, 0.156 mmol) and aqueous 2.0 M K2CO3 (2 mL) weremixed in a flask containing argon saturated toluene (8 mL). Thereaction mixture was stirred at 90 C for 48 h. After it was cooledto room temperature, the reaction mixture was extracted withdichloromethane (50 mL 2). The combined organic extracts weredried with anhydrous MgSO4 and evaporated. The crude productwas purified by column chromatography using hexane/dichloromethane(1:1.5) as eluents to provide a pale powder and recrystallizationfrom hexane afforded 12 (145 mg, 80%) as a yellow prisms.mp 271-273 C; 1H NMR (CDCl3, 300 MHz): dH = 3.92 (s, 12H,OMe), 7.08 (d, J = 8.8 Hz, 4H, Ar-H), 7.59 (d, J = 8.8 Hz, 4H, Ar-H), 7.96 (s, 2H, Py-H), 8.15 (s, 2H, Py-H); 13C NMR (CDCl3, 75 MHz):dC = 159.1, 136.8, 133.7, 131.8, 129.7, 128.1, 126.2, 125.2, 113.9,55.5 ppm; MS m/z: 626 [M+]; Anal. calcd. for C44H34O4 (626.74)C, 84.32, H, 5.47. Found C, 84.30, H, 5.48. |
77% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate at 160℃; for 48h; Inert atmosphere; Schlenk technique; Darkness; | General Procedure for the Suzuki Coupling: General procedure: Compound8 (0.52g, 1mmol),boronic acid (5mmol),K2CO3 (2.8g, 20mmol) andPd(PPh3)4 (185mg) was added todimethylformamide (20mL) taken in a Schlenk flask. The flask was repeatedly degassed by evacuation and purging with argon. The mixture was heated at 160°C under argon atmosphere under complete exclusion of light for the time mentioned for individual cases after which it was quenched by addingwater. The organic layer was extracted with dichloromethane, washed consecutively with water and brine before being dried over MgSO4. After having removed the solvent under reduced pressure, the crude product was purified by column chromatography (silica gel, hexane/ethyl acetate). |
21% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide In water; toluene at 90℃; for 20h; Inert atmosphere; |
80 % | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 95℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 80℃; Inert atmosphere; | 4,4',4'',4'''-(Pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetrakis(N,N-didodecylaniline) (PT) 4,4',4'',4'''-(Pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetrakis(N,N-didodecylaniline) (PT) To a degassed solution of dry Et3N/THF (1:1, 15 mL), 1,3,6,8-tetrabromopyrene (as compound 1 in supporting information, 0.50 g, 0.97 mmol) and N,N-didodecyl-4-ethynylaniline (2.64 g, 5.82 mmol) were added and the mixture degassed under Ar. Catalytic agents Pd(PPh3)2Cl2 (13.62 mg, 0.019 mmol) and CuI (7.39 mg, 0.039 mmol) were then added, and the reaction mixture was stirred overnight at 80 °C under Ar. The solvent was then removed under reduced pressure, and the crude product was purified by column chromatography (silica gel, petroleum ether/dichloromethane 6:1) to afford PT as an orange solid (1.33 g, 0.66 mmol, 68%). 1H NMR (400 MHz, CDCl3): δ = 8.68 (4H, s), 8.31 (2H, s), 7.53 (d, J = 8.4 Hz, 8H), 6.63 (d, J = 8.4 Hz, 8H), 3.29 (16H, m), 1.60 (16H, s), 1.28 (144H, m), 0.89 (24H, m) ppm. 13C NMR (100 MHz, CDCl3): δ = 147.7, 132.6, 132.2, 130.5, 125.9, 124.0, 119.0, 110.9, 108.5, 96.9, 85.6, 50.5, 31.3, 29.0, 28.8, 26.6, 22.1, 13.6 ppm. FT-IR (KBr): 2923, 2853, 2192, 1607, 1592, 1519, 1459, 1375, 1261, 1184, 1066, 809 cm-1. MALDI-TOF-MS (dithranol): m/z: calcd for C144H222N4: 2007.75 g mol-1, found: 2009.5 g mol-1 [MH]+. Elemental analysis calcd (%) for C144H222N4 (2007.75): C 86.08, H 11.14, N 2.79; found: C 86.03, H 11.19, N 2.78 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine In toluene at 80℃; Inert atmosphere; | 2.2.2. Synthesis of 1,3,6,8-tetrakis(4-triphenylsilylphenyl ethynyl)pyrene (5) 1,3,6,8-Tetrabromopyrene (0.5 g, 0.96 mmol) was suspended in triethylamine (30 mL) and toluene (10 mL), and bis(triphenylphosphine)palladium(II) dichloride (136 mg, 0.2 mmol), copper(I) iodide (72 mg, 0.38 mmol) and triphenylphosphine (100 mg, 0.38 mmol), 4-triphenylsilylphenylethyne (2.08 g, 5.76 mmol) were then added under an argon atmosphere. The reaction mixture was heated to 80 ∘C and stirred overnight. The cooled mixture was diluted with CH2Cl2, washed with water, and dried over Na2SO4. The solvent was removed under reduced pressure. The crude product was purified by silica-gel column chromatography (n-hexane: CH2Cl2 10:1) to afford 5 as an orange solid (1.27 g) in 81% yield. 1H NMR (400 MHz, CDCl3): δ 8.76 (s, 4 H), 8.46 (s, 2 H), 7.72 (d, J = 8.0 Hz, 8 H), 7.65-7.60 (m, 32 H), 7.49-7.39 (m, 36 H). MALDI-TOF MS: m/z calcd for [C120H82Si4]+ m/z = 1634.5, found m/z = 1634.6 [M]+. Anal. Calcd for C120H82Si4; C, 88.08; H, 5.05; found C, 87.87; H, 5.01%; Td 511 ∘C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; | 2.2.1. Synthesis of 1,3,6,8-tetrakis(4-triphenylsilylphenyl) pyrene (4) 1,3,6,8-Tetrabromopyrene (0.19 g, 0.38 mmol), boronic acid terminated tetraphenylsilane (0.71 g, 1.86 mmol), tetrakis(triphenylphosphine)palladium(0) (0.17 g, 0.15 mmol) and THF (30 mL) were added to a round-bottomed flask equipped with a reflux condenser. 7.5mL of aqueous 2M sodium carbonate solution was added and there action mixture was then heated at 80 ∘C for 24 h. The mixture was poured into water, extracted with CH2Cl2, and dried over anhydrous magnesium sulfate. The crude product was purified by silica-gel column chromatography (n-hexane: CH2Cl2 5:1) to obtain 4 as a white solid (0.45 g) in 77% yield. 1H NMR (400 MHz, CDCl3): δ 8.24 (s,4 H), 8.06 (s, 2H), 7.73 (d, J = 8.0 Hz, 8 H), 7.69-7.64 (m, 32 H), 7.48-7.39 (m, 36 H). MALDI-TOF MS: m/z calcd for [C112H82Si4]+ m/z = 1538.5, found m/z = 1538.5 [M]+. Anal. Calcd for C112H82Si4; C,87.34; H, 5.37; found C, 87.16; H, 5.28%; Td = 578 ∘C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With tetrakis(triphenylphosphine) palladium(0) In toluene at 110℃; for 96h; Inert atmosphere; | 2.2 General procedure for the preparation of furyl derivatives of pyrene (7-11) 2-(tributylstannyl)furan (2-2.0mmol, 5-6.0mmol, 6-8mmol, 3 and 4-4mmol, respectively) and Pd(PPh3)4 (0.46g, 0.4mmol) were added under nitrogen to compound 2 or 5 or 6 or to a mixture of non-separated 3 and 4 (2.0mmol) dissolved in 150mL of anhydrous toluene in a 250mL round two-bottom flask. The resulting mixture was stirred for 4 days at 110°C. Subsequently, the mixture was cooled down to room temperature. Water (100mL) was added and the resulting solution was extracted three times with 50mL of CHCl3. The combined organic layers were washed with 50mL brine, dried over MgSO4 and evaporated until brown oil appeared. The crude product (7-11) was purified by column chromatography (hexane/AcOEt, 10:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 90℃; for 16h;Schlenk technique; Inert atmosphere; | Trad. Conditions10101] In a flame-dried Schlenk tube under argon atmosphere, 1 ,3,6,8-tetrabromopyrene (500 mg, 0.97 mmol) and B2Pin (1.47 g, 5.79 mmol) were dissolved in 20 ml 1,4- dioxane. Flame dried KOAc (952 mg, 9.7 mmol) was added quickly to the mixture followed by PdC12 (dppf) (24 mg, 0.029 mmol). The mixture was heated at 90 C. overnight. At the 16 hr mark, 10 mg catalyst was added to complete the reaction. Once complete, the mixture was cooled to room temperature and 20-3 0 ml ethyl acetate was added to quench the reaction. 30 ml DI water was added to extract the aqueous phase, 30 ml brine (2x) was used to wash the organic phase, and it was dried over anhydrous Mg504 and filtered. After concentrating down the filtrate, silica column chromatography with hexanes:ethyl acetate (8:2) mixture as eluent gave a yellow powder (592 mg, 87%). MALDI TOF MS: mlz 707 (M+), 581 (M-Bpin)+, 454(M-2Bpin)+, 227 (M-3Bpin). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / water; toluene / 48 h / Inert atmosphere; Reflux; Schlenk technique 2: boron tribromide / dichloromethane / 3 h / -78 - 20 °C / Schlenk technique; Inert atmosphere | ||
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / 48 h / 160 °C / Inert atmosphere; Schlenk technique; Darkness 2: boron tribromide / dichloromethane / 14 h / 0 - 22 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate at 115℃; Inert atmosphere; | |
94% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate for 72h; Schlenk technique; Inert atmosphere; Reflux; | |
90% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate at 115℃; for 72h; Inert atmosphere; |
90% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate at 115℃; for 72h; Inert atmosphere; Schlenk technique; | |
90% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate at 115℃; for 72h; Inert atmosphere; Schlenk technique; Glovebox; | |
86% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate at 110℃; for 72h; Inert atmosphere; | |
86% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate at 115℃; for 72h; | |
84% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate at 115℃; for 72h; Inert atmosphere; | |
84% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate at 115℃; for 72h; Inert atmosphere; | |
81% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane at 115℃; for 72h; Inert atmosphere; | |
75% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane for 72h; Reflux; Inert atmosphere; | |
75% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate at 115℃; for 72h; | |
70% | With tetrakis-(triphenylphosphine)-palladium; anhydrous potassium carbamate In 1,4-dioxane; lithium hydroxide monohydrate for 72h; Inert atmosphere; Reflux; | |
64% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate for 72h; Inert atmosphere; Reflux; | |
61% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane for 72h; Reflux; Inert atmosphere; | |
58% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane for 72h; Inert atmosphere; Reflux; | |
54% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane Inert atmosphere; Reflux; | |
With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate | ||
With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; lithium hydroxide monohydrate for 72h; Inert atmosphere; Reflux; | 1,3,6,8-tetrakis(4-aminophenyl)pyrene (2) : 1,3,6,8- tetrabromopyrene (2.96 g, 5.72 mmol), 4- aminophenylboronic acid pinacol ester (6.0 g, 27.4 mmol), K2CO3 (4.4 g, 31.6 mmol), and Pd(PPh3)4 (0.66 g, 0.589 mmol) were introduced into a mixture of 1,4- dioxane (100 mL) and H2O (20 mL). The resulting mixture was refluxed under N2 atmosphere for 3 d. After cooling to room temperature, the solution was poured into water. The formed precipitate was filtered off, and washed with water and methanol, which was further purified by flash chromatography with acetone as eluent to afford the title compound as a yellow-brown solid. 1H NMR (400 MHz, d6-DMSO, 298K, TMS): d 8.13 (s, 4H), 7.79 (s, 2H), 7.35 (d, 8H, J=8.4 Hz), 6.77 (d, 8H, J=8.0 Hz), 5.32 (s, 8H) ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine In N,N-dimethyl-formamide at 90℃; for 18h; Schlenk technique; Inert atmosphere; | 1,3,6,8-Tetrakis[(2,6-dimethylpyridin-4-yl)ethynyl]pyrene (18) 1,3,6,8-Tetrakis[(2,6-dimethylpyridin-4-yl)ethynyl]pyrene (18)Dry DMF (2.0 mL) was transferred to a Schlenk flask charged with4-ethynyl-2,6-dimethylpyridine (14a; 75 mg, 0.57 mmol),[PdCl2(PPh3)2] (28 mg, 39 μmol), CuI (8 mg, 0.04 mmol), i-Pr2NH(0.9 mL) and 1,3,6,8-tetrabromopyrene (17;17 49 mg, 0.095 mmol)under argon atmosphere. The mixture was stirred at 90 °C for 18 h.After cooling to r.t., the mixture was diluted with water (10 mL) andthe resulting suspension extracted with EtOAc (1 × 10 mL, discarded).The remaining water phase was extracted with CH2Cl2 (ca. 40 × 30mL) until no green extract was observed. The combined CH2Cl2phases were dried with Na2SO4, filtered and evaporated under reducedpressure. The obtained crude product was washed successivelywith benzene, hexanes and EtOAc (3.0 mL each). As residue,compound 18 (61 mg, 89%) was obtained as an orange solid; mp<300 °C.IR (ATR): 3000-2920 (=C-H, C-H), 2110 (C≡C), 1600 (C=C),1540 (C=N), 1440 cm-1.1H NMR (CDCl3, 700 MHz): δ = 2.64 (s, 24 H, CH3), 7.27 (s, 8 H,3-H, 5-H), 8.43 (s, 2 H, 2-H′, 7-H′), 8.70 (s, 4 H, 4-H′, 5-H′, 9-H′,10-H′).Due to the very poor solubility, the recording of a 13C NMR spectrumwas not possible.HRMS (ESI-TOF): m/z calcd for C52H39N4 [M + H]+: 719.3169;found: 719.3190. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With 1,3-bis[(diphenylphosphino)propane]dichloronickel(II); triethylamine In toluene for 48h; Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 90℃; for 48h;Schlenk technique; Inert atmosphere; Darkness; | M2 (1.60g, 5.24mmol), 1,3,6,8-tetrabromopyrene (M3) (0.30g, 0.87mmol) and Pd(PPh3)4(0) (0.35g, 0.30mmol), were placed in a Schlenk tube, purged with three nitrogen/vacuum cycles, and under nitrogen atmosphere added 2M degassed aqueous K2CO3 (15mL) and dry 1,4-dioxane(30mL). The mixture was heated to 90C and stirred in the dark for 48h. After reaction quenching, the mixture was poured into 50mL water and extracted with CHCl3 (100mL). The combined organic layers were washed with brine and dried over anhydrous MgSO4. The solvent was removed by rotary evaporation, and the final product was obtained after drying in vacuum. Off-white solid. (0.25g, yield: 31.5%) 1H NMR (400MHz; CDCl3; Me4Si): delta=8.15 (s, 1H), 7.94 (s, 4H), 7.57 (d, 8H, J=8.8Hz), 7.07 (d, 8H, J=8.8Hz), 4.12 (t, 8H, J=6.4Hz), 2.51 (t, 8H, J=6.8Hz), 2.29 (s, 24H), 2.02 (m, 8H, J=6.8Hz). 13C NMR (100MHz; CDCl3; Me4Si): 158.66; 136.97; 133.69; 132.27; 131.89; 129.83; 128.21; 126.35; 125.31; 114.63; 66.61; 56.70; 45.80; 27.88. Anal. Calcd for: C60H70N4O4: C, 79.09; H, 7.74; N, 6.15. Found: C, 76.94; H, 7.42; N, 4.90. IR (KBr, cm-1): 2944, 2857, 2814, 2762, 1513, 1494, 1458, 1285, 1244. Melting point: 192C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With bis-triphenylphosphine-palladium(II) chloride In N,N-dimethyl-formamide at 80℃; for 48h; Inert atmosphere; Schlenk technique; | 5-(5-(1,3,6-Tris(5-(3,5-bis(diphenylamino)phenyl)thiophen-2-yl)pyren-8-yl)thio-phen-2-yl)-1,1,3,3-tetraphenylbenzene-1,3-diamine (4) To the flask containing a mixture of 1,3,6,8-tetrabromopyrene (0.52 g, 1.0 mmol), 5-(5-(tributylstannyl)thiophen-2-yl)-1,1,3,3-tetraphenylbenzene-1,3-diamine (3.45 g, 4.4 mmol) and PdCl2(PPh3)2 (22 mg, 0.030 mmol) was added DMF (5 mL), and the mixture was heated at 80 °C for 48 h. After cooling, MeOH was added and the precipitate formed was collected by filtration. the crude product was further purified by column chromatography using CH2Cl2/hexane (2:5 by v/v) as eluent to give the 4 as a pale yellow powder (1.76 g, 61%). 1H NMR (400 MHz, acetone-d6): δ (ppm) 8.41 (s, 4 H, pyrene), 8.07 (s, 2 H, pyrene), 7.23-7.17 (m, 40 H, meta-C6H5 and C4SH2), 7.11 (d, J = 7.47 Hz, 32 H, ortho-C6H5), 6.98-6.95 (m, 24 H, para-C6H5, C6H3), 6.75 (s, 4 H, C6H3); MS (FAB): m/z 2173.6 (M+). Anal. Calcd for C80H78N4: C, 84.02; H, 4.92; N, 5.16. Found: C, 83.63; H, 5.01; N, 5.05. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; for 24h;Inert atmosphere; Schlenk technique; Reflux; | General procedure: To a flask containing a mixture of 1,3,6,8-tetrabromopyrene (0.52 g, 1.0 mmol), diphenylamine (0.74 g, 4.4 mmol), sodium tert-butoxide (0.51 g, 5.28 mmol) and Pd(dba)2 (0.040 mmol) was added dry toluene (30 mL). After 30 min. P(tBu)3 (1.2 mol%) was added and the solution mixture was heated to reflux and stirred for 24 h. After cooling, the solution was pumped dry and the residue was extracted with CH2Cl2/brine. The organic layer was dried over magnesium sulfate, then filtered and dried. After recrystallization from dichloromethane and hexane, the crude product was further purified by column chromatography using CH2Cl2/hexane (1:10 by v/v) as eluent to give 1 as a yellow powder (0.82 g, 92%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; toluene for 24h; Inert atmosphere; Schlenk technique; Reflux; | 1,3,6,8-Tetrakis(9,9-dihexyl-9H-fluoren-2-yl)pyrene (5) General procedure: To the flask containing a mixture of 9,9-dihexyl-9H-fluoren-2-ylboronic acid (7.93 g, 21.0 mmol), 1,3,6,8-tetrabromopyrene (2.11 g, 4.04 mmol), Na2CO3 (2 M in H2O, 9.0 mL, 8.9 mmol), and Pd(PPh3)4 (0.49 g, 0.42 mmol) was added 70 mL of dry toluene. After the reaction mixture was refluxed for 24 h, the solvent was removed and the residue was extracted with CH2Cl2/brine. The organic layer was dried over magnesium sulfate, then filtered and dried. The crude product was further purified by column chromatography using CH2Cl2/hexane (1:5 v/v) as eluent to give the 5 as a pale yellow powder (3.5 g, 57%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In tetrahydrofuran; water for 24h; Inert atmosphere; Reflux; | |
55% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 85℃; for 72h; Inert atmosphere; | PyTTBA.S2e 1,3,6,8-Tetrabromopyrene (500 mg, 0.96 mmol), 4-formylphenylboronic acid (0.87g, 5.80 mmol), palladium tetrakis(triphenylphosphine) (0.06 g, 0.052 mmol), potassium carbonate (1.05 g, 7.60 mmol) and anhydrous dioxane (15 mL) were stirred at 85 °C under argon atmosphere for 3 days. After cooling, the reaction mixture was poured into ice-water containing concd. HCl. The filtrate was washed with 2 M HCl three times, and the solid was extracted with CHCl3 3 times. The organic layer was dried over MgSO4, evaporated. The crude product was purified by recrystallization from hot CHCl3 to afford a light yellow solid in 55% yield. 1H NMR(CDCl3, 400 MHz): δ (ppm) 10.15 (s, 4H), 8.17 (s, 4H), 8.09-8.07 (d, 8H), 8.03 (s, 2H), 7.86-7.84 (d, 8H). MALDI-TOF MS for C44H26O4 (Calc. 618.18), found m/z = 619.53 ([M]+). |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 85℃; |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 110℃; | ||
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 110℃; | ||
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 85℃; | ||
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane for 72h; Inert atmosphere; Reflux; | 4,4',4",4"'-(pyrene-1,3,6,8-tetrayl)tetrabenzaldehyde. 1,3,6,8-tetrabromopyrene (2.96 g, 5.72 mmol), 4-formylphenylboronic acid (4.12 g, 27.4 mmol), K2CO3 (4.4 g, 31.6 mmol), and Pd(PPh3)4 (0.66 g, 0.58 mmol) were introduced into 1,4-dioxane (100 mL). The resulting mixture was refluxed under N2 atmosphere for 3 d. After cooling to room temperature, the solution was poured into water. The formed precipitate was filtered off, and washed with water and acetone. After dying, the resulting solid was Soxhlet extracted with chloroform for one weak. The title product was obtained as a yellow solid after evaporating CHCI3. 1H NMR (400 MHz, CDCI3, 298K, TMS): δ 10.17 (s, 4H), 8.18 (s, 4H), 8.10 (d, 8H, J=8.0 Hz), 8.05 (d, 2H), 7.86 (d, 8H, J=8.0 Hz) ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | In tetrahydrofuran; 1,4-dioxane; | A) Synthesis of 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy) A mixture of (4-(methoxycarbonyl)phenyl)boronic acid (1.040 g, 5.80 mmol), 1,3,6,8-tetrabromopyrene (0.500 g, 0.97 mmol), tetrakis(triphenylphosphine) palladium(O) (0.030 g 0.026 mmol), and potassium tribasic phosphate (1.100 g, 5.30 mmol) in dry dioxane (20 mL) is loaded (in a glovebox) into a 20 mL microwave vial (Biotage) and capped. This mixture is stirred under argon for 72 hours at 130 C. in an oil bath. The reaction mixture is evaporated to dryness and the solid residue is washed with water to remove inorganic salts. The insoluble material is extracted with chloroform (three times by 50 mL), the extract is dried over magnesium sulfate, and the solvent volume is reduced under vacuum. The residue is boiled in tetrahydrofuran for 2 hours and filtered, the resulting filtrate containing mainly impurities. This procedure gives 0.58 g of 1,3,6,8-tetrakis(4-(methoxycarbonyl)phenyl)pyrene (82% yield). 1H NMR (CDCb-d): delta 3.99(s, 12H), 7.75 (d, 8H), 8.01 (s, 2H), 8.15 (s, 4H), 8.23 (d, 8H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: 1,3,6,8-tetrabromopyrene; butan-1-ol With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; N-ethyl-N,N-diisopropylamine In 5,5-dimethyl-1,3-cyclohexadiene at 20℃; for 1h; Inert atmosphere; Glovebox; Stage #2: carbon monoxide In 5,5-dimethyl-1,3-cyclohexadiene at 120 - 140℃; for 48h; Autoclave; | Carboxylic Esters 1a-8a on a Gram Scale: Typical Procedure C General procedure: hetero)arene (5 mmol), Pd(OAc)2 (0.12 g, 0.75 mmol), and rac-BINAP (0.46 g, 0.75 mmol). Next, a N2 saturated mixture of xylenes(55 mL), nBuOH (45 mL), and DIPEA (6.5 mL) was added to the reactionbottle and the mixture was stirred for 1.0 h at r.t. to give a yellowgreento red-brown solution. The resulting solution was transferredto an autoclave, which was then charged with 30 atm of CO, heated to120 °C and then held at 140 °C for 48 h. The mixture was allowed tocool to r.t., the CO gas was released slowly in a well-ventilated hoodand the solution was concentrated. Purification by column chromatography(PE/EtOAc 10:1 to 2:1) gave carboxylic esters 1a-8a (95->99% conversion, 65-92% yield) |
89% | Stage #1: 1,3,6,8-tetrabromopyrene; butan-1-ol With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; N-ethyl-N,N-diisopropylamine In 5,5-dimethyl-1,3-cyclohexadiene for 0.25h; Autoclave; Inert atmosphere; Stage #2: carbon monoxide In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 4h; Autoclave; Inert atmosphere; | |
80 % | With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; N-ethyl-N,N-diisopropylamine In 5,5-dimethyl-1,3-cyclohexadiene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With copper; caesium carbonate In dimethyl sulfoxide at 130℃; for 24h; Inert atmosphere; | 4.2.1. 1,3,6,8-Tetrakis(phenoxy)pyrene (1, TPhOP) In an 100 mL flask, 1.6 g Cs2CO3 and copper (I) (10 mol%) wereadded into a solution of 1,3,6,8-tetrabromopyrene (518 mg,1.0 mmol) in 20 mL DMSO. After degassed and purged with nitrogen,phenol (565 mg, 6.0 mmol) were added and then stirred for24 h at 130°C. The reaction mixture was cooled to room temperatureand quenched by the addition of ethyl acetate (10 mL). Crudeproduct was purified by silica gel column chromatography with theethyl acetate as eluent. Then the main product was furtherrecrystallized from ethyl acetate to give compound 1 (388 mg, 68%).MS (MALDI-TOF): 569.9. 1H NMR (400 MHz, CDCl3): δ 8.24 (s, 4H),7.36 (s, 2H), 7.34e7.32 (d, 8H), 7.12-7.09 (t, 4H), 7.05-7.03 (d, 8H).Anal.calcd for C40H26O4: C, 84.19; H, 4.59; O, 11.22. Found: C, 83.30;H, 4.65; O, 11.56. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With caesium carbonate In ethanol at 80℃; for 24h; | 4.2.2. 1,3,6,8-Tetrakis(phenylthio)pyrene (TPhSP) Diphenyl disulfide (1.3 g, 6.0 mmol) was added to a solution of1,3,6,8-tetrabromopyrene (518 mg, 1.0 mmol) in ethanol. Then 1.6 gCs2CO3 was added and resulted reaction mixture was stirred at80° C. After reacted for 24 h, the mixture was cooled to roomtemperature and poured into water and filtered. The residue wasrecrystallized from toluene to give pure compound 2 (310 mg, 49%).MS (MALDI-TOF): 633.7. 1H NMR (400 MHz, CDCl3): δ 8.6 (s, 4H),8.01 (s, 2H), 7.17-7.09 (m, 20H). Anal.calcd for C40H26S4: C, 75.67; H,4.13; S, 20.20. Found: C, 74.56; H, 4.22; S, 19.89. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60.3% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium hydroxide In tetrahydrofuran at 150℃; for 0.5h; Darkness; Inert atmosphere; | 5 1,3,6,8-Tetrabromopyrene (50 mg, 0.097 mmol), 3a (363.7 mg, 0.58 mmol), KOH (54 mg, 0.97 mmol) (ΒΒΑΒ) (93.8mg, 0.29mmol) was added into a 10mL microwave reaction tube. After N2 (2-3 times) exchange, the catalyst was protected from light and Pd (PPh3) 4 catalyst (9.2 mg, 0.008 mmol). Then, 3 mL of anhydrous tetrahydrofuran (THF) was added into the reaction tube. The reaction was carried out with a CEM microwave reactor at a controlled temperature of 150 ° C. for 30 min. Purification by column chromatography after completion of the reaction gave compound PiF (128.7 mg) in a yield of 60.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With potassium phosphate; palladium diacetate In N,N-dimethyl-formamide at 140℃; for 24h; Inert atmosphere; | 1 Dissolve 1,3,6,8-tetrabromoanthraquinone (100 mg, 0.20 mmol) and diarylamine derivative (484 mg, 1.5 mmol) in 10 mL DMF to obtain 1,3,6,8-tetrabromoanthraquinone and two Aromatic amine derivative mixtures wherein the molar ratio of 1,3,6,8-tetrabromoanthraquinone to the diarylamine derivative is 1:7.5; potassium phosphate (212 mg, 1.0 mmol) and nitrogen are added to 1,3, Deoxygenation of a mixture of 6,8-tetrabromoanthraquinone and diarylamine derivatives,A deoxygenated mixture of 1,3,6,8-tetrabromoanthraquinone and a diarylamine derivative is obtained, wherein the molar ratio of 1,3,6,8-tetrabromoanthraquinone to potassium phosphate is 1:5;Palladium acetate (2 mg, 0.01 mmol) was added to the deoxygenated mixture of 1,3,6,8-tetrabromoanthraquinone and the diarylamine derivative. Under nitrogen protection, 1,3,6,8-tetrabromoanthraquinone was added. The diarylamine derivative was refluxed at 140° C. for 24 hours, and the reaction product was isolated and purified to obtain a triphasic tetraamine quinone in which the molar ratio of 1,3,6,8-tetrabromoanthraquinone to palladium acetate was 1:0.01. Extract three times with dichloromethane, dry the organic phase with anhydrous magnesium sulfate, remove the organic solvent by rotary evaporation, and purify by column chromatography (eluent: petroleum ether/ethyl acetate 1/3, v/v) to obtain The tetramethylguanidine represented by the structure represented by II has a yield of 47%. |
47 % | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 120℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With methanesulfonic acid In chloroform at 0 - 20℃; for 1h; Inert atmosphere; | 1.5 (5) cyclization reaction 500 ml three bottle, nitrogen protection,6.66 g (0.01 mol) of the compound represented by formula A-1 are added, 100 ml twoChloroform,Cool down to 0-10°C,Add 5.8 g (0.06 mol) of methanesulfonic acid dropwise at 0 to -10°C.After adding slowly, the temperature rises to 20°C.Stay for 1 hour,To give the formula (1) The reaction solution of 1,3,6,8-tetrabromopyrene shown,The reaction mixture containing the formula (1) 1,3,6,8-tetrabromopyrene filter,To give crude 1,3,6,8-tetrabromopyrene,Wash the crude product,Methanol washing,To give 3.99 g 1,3,6,8-tetrabromopyrene,Yield 77.0%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.1% | With methanesulfonic acid In dichloromethane at 0 - 20℃; for 1h; Inert atmosphere; | 2.6 (6) cyclization reaction 500ml three bottle,Nitrogen protection,5.82 g (0.01 mol) of the compound of formula A-2 are added,100 ml dichloromethane,Cool down to 0-10°C,Add 5.8 g (0.06 mol) of methanesulfonic acid dropwise at 0 to -10°C.After adding slowly, the temperature rises to 20°C.Stay for 1 hour,To give the formula (1) The reaction solution of 1,3,6,8-tetrabromopyrene shown,The reaction mixture containing the formula (1) 1,3,6,8-tetrabromopyrene filter,To give crude 1,3,6,8-tetrabromopyrene,Wash the crude product,Methanol washing,3.89 g of 1,3,6,8-tetrabromoanthraquinone was obtained.Yield 75.1%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27% | With palladium diacetate; potassium carbonate In toluene for 24h; Inert atmosphere; Reflux; | 2 Synthesis of a hole transporting material having the structure of formula II: 250 mg (0.40 mmol) of tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine, 70 mg (0.44 mmol) 1,3,6,8-tetrabromo, 6 mg (0 • 026 mmol) cesium acetate and 150 mg (1·08 mmol) of potassium carbonate were dissolved in 15 mL of toluene and heated to reflux under nitrogen for 24 hours. After extracting three times with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, and then evaporated, evaporated, evaporated, and then purified by column chromatography (eluent: petroleum ether/ethyl acetate 2/1, v/v) The yield was 27%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With copper(l) iodide; caesium carbonate In N,N-dimethyl-formamide at 120℃; for 40h; Inert atmosphere; | |
92% | With copper(l) iodide; caesium carbonate In N,N-dimethyl-formamide at 120℃; for 40h; Schlenk technique; Inert atmosphere; | Procedure for synthesis 1-3: General procedure: In 25 mL Schlenk flask, di- ortetrabromopyrene (1.0 mmol), pyrazole (2.8/5.6 mmol), cesiumcarbonate (4.0/8.0 mmol), copper(I) iodide (0.4/0.8 mmol) wereplaced. The flaskwas three times evacuated and refilled with argon,subsequently dry DMF (6 mL) was added by syringe. The mixturewas stirring and heating for 24 h/40 h at 120° C. After the reactionwas completed, the mixture was cooled to room temperature andfiltrated by G3 fritted funnel and washed with hexane and diethylether. The products were obtained as grey solids.1 (0.314 g, 94% yield) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With water; sodium hydroxide; In tetrahydrofuran; at 130℃; for 72h;Reflux; | (4-(Methoxycarbonyl)phenyl)boronic acid (1.040 g, 5.80 mmol), 1,3,6,8-tetrabromoindole (0.500 g, 0.97 mmol), tetrakis(triphenylphosphine)palladium ( 0) (0.030g 0.026mmol) and anhydrous potassium phosphate (1.100g,5.30 mmol) was placed (in a glove box) in a 20 mL microwave vial and capped.The mixture was stirred under an argon atmosphere at 130 C for 72 hours in an oil bath. The reaction mixture was evaporated to dryness and the solid residue was washed with water to remove inorganic salts. ChlorineThe insoluble material (50 mL three times) was extracted, and the extract was dried over magnesium sulfate, and the solvent volume was reduced under vacuum. The residue was boiled in tetrahydrofuran for 2 hours and filtered; the filtrate obtained mainly contained impurities.This procedure gave 1,8,6,8-tetrakis(4-(methoxycarbonyl)phenyl)indole 0.58 g (yield 82%). Then, to a 250 mL round bottom flask containing 0.58 g (0.78 mmol) of solid 1,3,6,8-tetrakis(4-(methoxycarbonyl)phenyl)anthracene, 100 mL of 1.5 g (37.5 mmol) NaOH was added. A mixture of tetrahydrofuran/water (ratio 1:1) was added and the resulting suspension was stirred vigorously under reflux overnight. The solvent was removed under vacuum and water was added to a residue that formed a clear yellow solution. The clear yellow solution was stirred at room temperature for 2 hours and the pH was adjusted to 1 using concentrated HCl. The resulting yellow solid was collected by filtration and washed several times with water. The crude product was recrystallized from DMF, filtered, washed with EtOAc. This gave 0.49 g (91%) of pure product H4TBAPy, abbreviated as H4L. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 90℃; for 18h; Inert atmosphere; Schlenk technique; | 2 Py-4Br (258.9 mg, 0.5 mmol), under a nitrogen atmosphere,4-borate-4',4'-dimethoxytriphenylamine (1.08g, 2.5mmol), Pd(PPh3)4 (57.8mg, 0.05mmol), K2CO3 (148.0mg, 2.0mmol) was added to dry In a Schlenk reaction flask, 20 mL of THF and 2.0 mL of water were added, and nitrogen gas was bubbled for 10 min, and heated to 90 ° C for 18 hours under a nitrogen atmosphere; cooled to room temperature, and the mixture was extracted with dichloromethane (20 mL × 3) to obtain organic The layer is dried with anhydrous MgSO4Drying; removing the solvent by rotary distillation to give a crude product, which was recrystallized (50 mL of dichloromethane, and 50 mL of methanol to precipitate a solid).Filtration afforded the desired product as a bright yellow solid (0.63 g, yield: 89%). |
75% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; toluene for 12h; Schlenk technique; Inert atmosphere; Reflux; | |
70.46% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; toluene at 110℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; triphenylphosphine In tetrahydrofuran Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate In water; toluene at 90℃; for 24h; Inert atmosphere; Darkness; Sealed tube; | 6 Example 6 Example 6Under N2 protection and protection from light, a boronic ester compound of a large hindered group (936.0 mg, 1.6 mmol), 1,3,6,8-tetrabromoindole (100 mg, 0.2 mmol),The catalyst Pd(PPh3)4 (57.8 mg, 0.05 mmol) was quickly added, and the phase transfer catalyst TBAB (70.2 mg, 0.2 mmol) was placed in a two-necked flask.Seal the reaction device, replace N2 three times, and insert a balloon.The toluene and K2CO3 aqueous solution were deoxygenated with a nitrogen balloon for half an hour, and then a solution of toluene (40 mL) and a solution of aq.K2CO3 (20 mL, 2M) was stirred at 90 ° C for 24 h. The organic phase was extracted with dichloromethane, after two or three times with deionized water, dried over anhydrous sodium sulfate, filtered off with suction. The crude product was concentrated under reduced pressure in vacuo and purified by column chromatography eluting with DCM/PE = 1:4.The white solid compound (120 mg) was obtained in a yield of 58.0% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With sodium (meta)periodate; ruthenium(III) trichloride hydrate In lithium hydroxide monohydrate; acetonitrile at 120℃; for 15h; | 1.1-22.1 (1) Synthesis of intermediates with chemical structural formula a: Put 1,3,6,8-tetrabromopyrene (3.376g, 6.526 mmol) and magnetic stirred rotor into the reaction bottle, then addNaIO4(13.25 g, 62 mmol) and RuCl3.xH2 O (135mg) to the reaction bottle, stir for a few minutes tomake it mix well, and then injectCH3CN ( 150 mL) andH2O(33.76 mL). React at 120 °C for 15 h. Rotational evaporation after the end of the reaction removes the organic solvent. Extraction filtration was carried out, and the intermediate a was obtained by washing with distilled water, methanol and ether, which was a gray solid with a yield of 59%. |
56% | With sodium (meta)periodate; ruthenium(III) trichloride hydrate In lithium hydroxide monohydrate; acetonitrile at 120℃; for 20h; Sealed tube; Inert atmosphere; | 1.1 Preparation of the above-mentioned n-type organic semiconductor materials based on boron-nitrogen coordination bonds: Weigh 1,3,6,8-tetrabromophosphonium (Compound 1) (1.00 g, 1.93 mmol), sodium periodate (3.93 g, 18.4 mmol) and ruthenium trichloride into the sealed tube accurately. (40mg), then the system was evacuated, the system was evacuated with argon for several times, 45mL of purified acetonitrile and 10mL of water were added. The system was heated at 120 ° C and reacted at high temperature and pressure for 20h. The reaction system was cooled to room temperature, and the solvent was distilled off under reduced pressure to obtain a solid product. The solid product was sequentially washed with water, methanol, and chloroform, followed by suction filtration, to finally obtain 629 mg of an off-white solid (Compound 2) with a yield of 56%. |
38% | With sodium (meta)periodate; ruthenium(III) trichloride hydrate; lithium hydroxide monohydrate In acetonitrile at 120℃; for 15h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 90℃; for 48h; Inert atmosphere; Schlenk technique; | 2.A A. Synthesis of 1.3.6.8-tetrakis(2-methoxyphenyl)pyrene (6a) To a Schlenk tube charged with 1,3,6,8-tetrabromopyrene (5) (500 mg, 0.966 mmol), 2-methoxybenzeneboronic acid (1.18 g, 7.76 mmol) and tetrakis- (triphenylphosphine)palladium(O) (224 mg, 0.194 mmol) under argon was added THF (45 mL, degassed) and a solution of potassium carbonate in water (8 mL, 2 M). The resulting mixture was stirred at 90 °C for 48 h. After cooling to room temperature, the reaction mixture was filtered off and washed with water, methanol and CH2CI2 consecutively. The residue was then dissolved in hot 1,1,2,2-tetrachloroethane and filtered through a PTFE membrane into a filter flask containing methanol. Precipitates were thus obtained and collected by filtration to give compound 6a as a white solid (496 mg, 82% yield). M.p.: 337.5 - 338.9 °C. 1H NMR (500 MHz, C2D2CI4, 403 K, ppm) <5 7.96 (s, 2H), 7.87 (s, 4H), 7.50 (dd, J = 18.1, 8.5 Hz, 8H), 7.20 - 7.14 (m, 8H), 3.76 (s, 12H); 13C NMR (125 MHz, C2D2CI4, 403 K, ppm) d 157.79, 133.58, 132.40, 130.79, 130.30, 128.71, 128.63, 125.10, 120.67, 112.53, 55.99; HRMS (MALDI) m/z Calcd for C44H34O4: 626.2457; Found: 626.2480 [M]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 90℃; for 48h; Inert atmosphere; Schlenk technique; | 3.A A. Synthesis of 1.3.6.8-tetrakis(4-dodecyl-2-methoxyphenyl)pyrene (6b) To a Schlenk tube charged with 1,3,6,8-tetrabromopyrene (5) (200 mg, 0.386 mmol), (4-dodecyl-2-methoxyphenyl)boronic acid (618 mg, 1.93 mmol) and tetrakis(triphenylphosphine)palladium(0) (89 mg, 0.077 mmol) under argon was added THF (20 mL, degassed) and a solution of potassium carbonate in water (2 mL, 2 M). The reaction mixture was stirred at 90 °C for 48 h. After cooling to room temperature, the mixture was extracted with Et20 and washed with water. Then the organic phase was dried over MgS04. After removal of the solvent under reduced pressure, the residue was purified by column chromatography over silica gel (eluent: hexane/ CH2CI2 = 2 : 1) to afford compound 6b as colorless oil (397 mg, 79% yield). 1H NMR (500 MHz, C2D2CU, 403 K, ppm) d 7.93 (s, 2H), 7.87 (s, 4H), 7.39 (d, J = 7.5 Hz, 4H), 7.02 - 6.97 (m, 8H), 3.74 (s, 12H), 2.80 (t, J = 7.7 Hz, 8H), 1.84 (p, J = 7.3 Hz, 8H), 1.39 (s, 72H), 0.98 (t, J = 6.7 Hz, 12H); 13C NMR (125 MHz, C2D2CI4, 403 K, ppm) d 157.64, 143.75, 133.60, 132.14, 130.52, 128.70, 128.11, 125.03, 120.68, 112.84, 55.06, 35.88, 31.57, 30.85, 29.32, 29.29, 22.25, 13.52; HRMS (MALDI) m/z: Calcd for C92H130O4: 1298.9969; Found: 1298.9901 [M]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With potassium fluoride; palladium diacetate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In N,N-dimethyl-formamide Glovebox; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 90℃; for 24h; Inert atmosphere; | 1.3; 1-3; 2.3 (3) Preparation of star-shaped tetraamine pyrene compound; Add (4'-(bis(4-methoxyphenyl)amino)-(1,1'-biphenyl)-4-yl)boronic acid (757mg/1.78mmol),1,3,6,8-Tetrabromopyrene (192mg/0.37mmol), Tetratriphenylphosphine Palladium (32mg/0.028mmol), 2mol/L potassium carbonate aqueous solution 7mL,18 mL of tetrahydrofuran was mixed in the reaction flask, and under the protection of nitrogen, it was heated and stirred to 90° C. and refluxed for 24 h.After the reaction was completed, it was cooled to room temperature, the organic phase was extracted with dichloromethane and dried with anhydrous sodium sulfate,The solvent was removed by rotary evaporation under reduced pressure, and the column chromatography was separated and purified (eluent: petroleum ether/dichloromethane 1/1, v/v) to obtain 555 mg of yellow-green star-shaped tetraamine pyrene compound solid, and the prepared star-shaped four The molecular formula of the amine pyrene compound is C120H94N4O8. Yield: 87%. |
86% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 90℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine In toluene at 80℃; for 24h; | (v) 1,3,6,8-Tetra(4-((S)-citronellyloxy)phenylethynyl)pyrene (1) To a round-bottomed flask were added 1,3,6,8-tetrabromopyrene (231 mg, 0.4 mmol), PdCl2(PPh3)2 (58 mg, 0.08 mmol), CuI (30 mg, 0.16 mmol), Ph3P (15 mg, 0.16 mmol), 1-((S)-citronellyloxy)-4-ethynylbenzene (513 mg, 2.0 mmol), and triethylamine (8 mL, 57 mmol), and toluene (4 mL), and the mixture was stirred at 80 °C for 24 h. To the mixture was added saturated aqueous NH4Cl (5 mL), and the organic and aqueous layers were separated. The aqueous layer was extracted with EtOAc, and combined organic layer was washed with water and brine. The organic layer was dried over MgSO4 and evaporated. The crude product was subjected to flash chromatography (hexane/CH2Cl2, 7:3) to afford the desired substituted pyrene 1 in a 70 % yield (342 mg, an orange solid). Mp: 106-107 °C. 1H NMR (CDCl3, 400 MHz): δ 0.98-1.00 (m, 12H), 1.21-1.30 (m, 4H), 1.39-1.47 (m, 4H), 1.59-1.79 (m, 32H), 1.84-1.93 (m, 4H), 1.98-2.10 (m, 8H), 4.02- 4.09 (m, 8H), 5.11-5.15 (m, 4H), 6.96 (d, 8H, J = 8.6 Hz), 7.65 (d, 8H, J = 8.6 Hz), 8.40 (s, 2H), 8.73 (s, 4H); 13C NMR (CDCl3, 101 MHz): δ 17.8, 19.7, 25.6, 25.9, 29.7, 36.2, 37.3, 66.5, 86.9, 96.2, 114.8, 115.4, 119.0, 123.9, 124.8, 126.5, 131.3, 131.5, 133.2, 133.4, 159.5. HRMS (MALDI-TOF): m/z Calcd for C88H98O4 1218.7465; Found: 1218.7421. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; N-ethyl-N,N-diisopropylamine / 5,5-dimethyl-1,3-cyclohexadiene / 1 h / 20 °C / Inert atmosphere; Glovebox 1.2: 48 h / 120 - 140 °C / 22801.5 Torr / Autoclave 2.1: potassium hydroxide / tetrahydrofuran; water / Reflux | ||
Multi-step reaction with 2 steps 1: 1-methyl-pyrrolidin-2-one 2: sodium hydroxide / ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 60℃; for 24h; Inert atmosphere; | Synthesis of compound C An Airfree flask was charged with 1,3,6,8-tetrabromopyrene P4 (518 mg, 1.00 mmol), 1-phenyl-2-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl]-1H-benzimidazole P2 (1605 mg, 4.05 mmol), andtetrakis(triphenylphosphine)palladium(0) catalyst (180 mg, 0.15 mmol) in a nitrogen atmosphere. Next, 1,4-dioxane (degassed, 80 mL) and an aqueous potassium carbonate solution (degassed, 0.2 M, 25 mL) were addedto the same flask. The reaction mixture was stirred at 60 °C for 24 h under argon atmosphere in a sealed flask.Crude product precipitated inside the flask as a yellow solid upon the completion of the reaction. The crudeproduct was isolated using vacuum filtration, followed by air-drying at an ambient temperature. The crudeproduct was dissolved in chloroform and washed several times with brine solution and DI water, and then driedusing anhydrous magnesium sulfate. The solvent was removed in vacuo, and the crude product was purifiedusing flash column chromatography on silica gel (eluent hexanes: ethyl acetate, 2.5:3 v/v) three times. Aftersolvent evaporation, compound C was obtained as a light brown powder (yield 65%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73.32% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In tetrahydrofuran at 70℃; for 24h; Inert atmosphere; | 1 Preparation Example 1: Synthesis of Compound 1 Under nitrogen atmosphere, in a three-necked flask, add 1mmol of raw material A1, 5mmol of raw material B1 is dissolved in 50ml of tetrahydrofuran, add 15mmol of potassium carbonate and 0.25mmol of Pd(PPh3)4, the reaction mixture is heated to 70 °C, refluxed for 24 hours, sampling point plate, showed that no raw material A1 remained, the reaction was complete, and it was naturally cooled to room temperature; then washed with dichloromethane, and the obtained material was purified by silica gel column to obtain the target product Intermediate C1, HPLC purity 99.16%, yield 73.32%; |
Tags: 128-63-2 synthesis path| 128-63-2 SDS| 128-63-2 COA| 128-63-2 purity| 128-63-2 application| 128-63-2 NMR| 128-63-2 COA| 128-63-2 structure
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