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CAS No. : | 1193092-32-8 | MDL No. : | N/A |
Formula : | C20H22BrNO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | BCCJBKCZGVYYHQ-UHFFFAOYSA-N |
M.W : | 388.30 | Pubchem ID : | 68480420 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313 | UN#: | |
Hazard Statements: | H315-H319 | Packing Group: | |
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 |
---|---|---|
98% | In ethanol for 24h; Reflux; | |
95.01% | In ethanol at 110℃; Inert atmosphere; | 1 A mixture of 9H-Carbazole(5 g, 0.03 mol), and sodium hydroxide (1.2 g, 0.03 mol) in drydimethylformamide (DMF) was heated with stirring. Then 4-fluorobenzaldehyde (3.72 g, 0.03 mol) was added, and the reactionmixture was stirred at 130 C for 6 h. After cooling to roomtemperature, the mixture was poured into distilled water andextracted with ethyl acetate. The organic layer was dried withanhydrous magnesium sulfate and concentrated by vacuum evaporation.The crude product was purified by column chromatographyusing the mixture of petroleum and dichloromethane (vol.ratio 3:1) as an eluent to get the desired compound as a yellow solid(6.43 g) with a yield of 79.08%. |
91.1% | In N,N-dimethyl-formamide at 150℃; for 12h; |
85% | In ethanol for 4h; Reflux; | |
85% | In N,N-dimethyl-formamide at 153℃; for 2h; Inert atmosphere; | |
85% | With ethanol for 6h; | |
82.6% | In ethanol at 60℃; for 6h; Reflux; | |
81% | In ethanol at 78℃; for 24h; Inert atmosphere; | |
80% | In ethanol for 8h; Reflux; | |
62% | In N,N-dimethyl-formamide at 110℃; for 1.5h; Inert atmosphere; | |
30% | In ethanol for 24h; Reflux; | 6-Bromo-2-(2-ethylhexyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione (2) 4-Bromo-1,8-naphthalic anhydride (2.76 g, 10 mmol) and 2-ethylhexan-1-amine (1.93 g, 15 mmol) were dissolved in ethanol (100 mL). The reaction mixture was stirred and refluxed for 24 h. The resulting mixture was filtered and the resulting solid (2.32 g, 6.0 mmol, 60%) was crystallised from ethanol.1H NMR (400 MHz, DMSO-d6) δ 8.53 (dd, J = 7.3, 0.8 Hz, 1H), 8.49 (dd, J = 8.5, 0.9 Hz, 1H), 8.29 (d, J = 7.9 Hz, 1H), 8.18 (d, J = 7.9 Hz, 1H), 7.96 (dd, J = 8.4, 7.4 Hz, 1H), 4.03 - 3.88 (m, 2H), 1.83 (dd, J = 12.2, 6.1 Hz, 1H), 1.28 (tt, J = 13.8, 5.4 Hz, 8H), 0.89 - 0.78 (m, 6H). |
In ethanol for 6h; Reflux; | ||
In N,N-dimethyl-formamide at 120℃; | ||
In N,N-dimethyl-formamide at 110℃; for 1.5h; | ||
With potassium carbonate In N,N-dimethyl-formamide at 30℃; | ||
In ethanol at 90℃; for 8h; Inert atmosphere; | ||
In ethanol Reflux; | ||
In ethanol at 80℃; for 12h; | 1 Synthesis Example 1 Synthesis of naphthalimide dye (Compound D) for blocking blue light 4-Bromo-1,8-Naphthalic anhydride (A)Was mixed with 5 g of 2-ethylhexylamine and 100 g of ethanol, and the mixture was heated to 80 DEG CStir for 12 hours. The reaction product was cooled to room temperature, and crystals were precipitated using water. The product was filtered and dried to obtain a compound B having a molecular weight of 388.30.3 g of allyl alcohol and 3 g of KOH were mixed with 18 g of Compound B and reacted at 90 DEG C for 3 hours to obtain a compound C. The compound C was refluxed with N, N-dimethylaniline for 12 hours to obtain a compound D as a blue light blocking dye | |
In ethanol Reflux; Inert atmosphere; | ||
In ethanol at 80℃; for 12h; | 1; 2 Synthesis Example 1 Synthesis of Ultraviolet Absorption Naphthalimide Dye (Compound C) 10 g of 4-bromo-1,8-naphthalene anhydride (Compound A) was mixed with 5 g of 2-ethylhexylamine and 100 g of ethanol, and then heated to 80 ° C. and stirred for 12 hours. After the reaction was cooled to room temperature, crystals were precipitated using water, which was filtered and dried to obtain Compound B having a molecular weight of 388.30. 10 g of the dried powder was mixed with 100 ml methanol and 10 g K2CO3, and then heated to 80 ° C. and stirred for 12 hours. After the reaction was cooled to room temperature, crystals were precipitated using water, which was filtered and dried to obtain Compound C. | |
In ethanol; isopropanol Reflux; | ||
In ethanol at 78℃; for 2h; | 1 Example 1 Synthesis of compound NAP 1 g of 4-bromo-1,8-naphthalenedicarboxylic acid anhydride, 2-ethylhexylamine and ethanol were added to the flask, stirred, heated, condensed and refluxed for 2 h. After the reaction is completed, cool to room temperature, stop stirring, add water to produce a yellow precipitate, collect the precipitate by suction filtration, wash the filter cake with ethanol, and dry the obtained product to obtain compound NAP. Three groups of experiments were carried out, and different material ratios and temperature conditions were shown in Table 1 below. | |
In ethanol at 80℃; for 10h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With hydrazine hydrate In 2-methoxy-ethanol for 4h; Reflux; | 2-(2-Ethylhexyl)-6-hydrazinyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (3) 6-Bromo-2-(2-ethylhexyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione (3.87 g, 10 mmol) and 85% hydrazine hydrate (2.0 mL) were dissolved in 2-methoxyethanol (20 mL). The reaction mixture was stirred and refluxed for 4 h. Then, the powder (2.54 g, 7.5 mmol, 75%) was collected by filtration and washed with chloroform.1H NMR (400 MHz, DMSO-d6) δ 9.09 (s, 1H), 8.59 (d, J = 7.9 Hz, 1H), 8.40 (d, J = 7.2 Hz, 1H), 8.27 (d, J = 8.6 Hz, 1H), 7.68 - 7.55 (m, 1H), 7.23 (d, J = 8.6 Hz, 1H), 4.66 (s, 2H), 4.05 - 3.80 (m, 2H), 1.91 - 1.73 (m, 1H), 1.40 - 1.07 (m, 8H), 0.83 (dt, J = 15.1, 7.2 Hz, 6H). |
52% | With hydrazine hydrate In ethyl methyl ether at 20℃; for 1.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: hydrazine hydrate / ethyl methyl ether / 1.5 h / 20 °C / Inert atmosphere 2.1: methanol / 60 °C 2.2: 1.5 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: hydrazine hydrate / ethyl methyl ether / 1.5 h / 20 °C / Inert atmosphere 2.1: methanol / 60 °C 2.2: 1.5 h / Reflux 3.1: tetrabutylammomium bromide; potassium hydroxide / acetone / 0.67 h / 50 - 60 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72.8% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine In ethanol for 8h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71.9% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine In ethanol for 8h; Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; Schlenk technique; Inert atmosphere; | 2.2. General procedure for Suzuki-Miyaura reactions General procedure: 4-bromo-N-(2-ethylhexyl)-1,8-naphthalimide or 4-bromo-N-octyl-1,8-naphthalimide (300 mg, 0.77 mmol) and 9,9-dialkyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9H-fluorene (0.85 mmol) or 9,9-dialkyl-2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9H-fluorene (0.38 mmol) were taken in a 100 mL Schlenk flask. A solvent mixture of 20 mL of tetrahydrofuran (THF) and 2 mL of water and powdered potassium carbonate (2.7 mmol) was added. The reaction mixture was purged with nitrogen for 5 min. The reaction flask was degassed and then again purged with nitrogen for 2 min. Bis(triphenylphosphine)palladium(II) dichloride (0.04 mmol) was added into it and stirred for 12-16 h at 80 °C under nitrogen. The reaction mixture was allowed to cool down to the room temperature, diluted with water and extracted using ethyl acetate. The organic layers were dried over sodium sulfate and evaporated at reduced pressure. The crude products were purified by silica gel column chromatography (the details are given below). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; Schlenk technique; Inert atmosphere; | 2.2. General procedure for Suzuki-Miyaura reactions General procedure: 4-bromo-N-(2-ethylhexyl)-1,8-naphthalimide or 4-bromo-N-octyl-1,8-naphthalimide (300 mg, 0.77 mmol) and 9,9-dialkyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9H-fluorene (0.85 mmol) or 9,9-dialkyl-2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9H-fluorene (0.38 mmol) were taken in a 100 mL Schlenk flask. A solvent mixture of 20 mL of tetrahydrofuran (THF) and 2 mL of water and powdered potassium carbonate (2.7 mmol) was added. The reaction mixture was purged with nitrogen for 5 min. The reaction flask was degassed and then again purged with nitrogen for 2 min. Bis(triphenylphosphine)palladium(II) dichloride (0.04 mmol) was added into it and stirred for 12-16 h at 80 °C under nitrogen. The reaction mixture was allowed to cool down to the room temperature, diluted with water and extracted using ethyl acetate. The organic layers were dried over sodium sulfate and evaporated at reduced pressure. The crude products were purified by silica gel column chromatography (the details are given below). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; Schlenk technique; Inert atmosphere; | 2.2. General procedure for Suzuki-Miyaura reactions General procedure: 4-bromo-N-(2-ethylhexyl)-1,8-naphthalimide or 4-bromo-N-octyl-1,8-naphthalimide (300 mg, 0.77 mmol) and 9,9-dialkyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9H-fluorene (0.85 mmol) or 9,9-dialkyl-2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9H-fluorene (0.38 mmol) were taken in a 100 mL Schlenk flask. A solvent mixture of 20 mL of tetrahydrofuran (THF) and 2 mL of water and powdered potassium carbonate (2.7 mmol) was added. The reaction mixture was purged with nitrogen for 5 min. The reaction flask was degassed and then again purged with nitrogen for 2 min. Bis(triphenylphosphine)palladium(II) dichloride (0.04 mmol) was added into it and stirred for 12-16 h at 80 °C under nitrogen. The reaction mixture was allowed to cool down to the room temperature, diluted with water and extracted using ethyl acetate. The organic layers were dried over sodium sulfate and evaporated at reduced pressure. The crude products were purified by silica gel column chromatography (the details are given below). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; Schlenk technique; Inert atmosphere; | 2.2. General procedure for Suzuki-Miyaura reactions General procedure: 4-bromo-N-(2-ethylhexyl)-1,8-naphthalimide or 4-bromo-N-octyl-1,8-naphthalimide (300 mg, 0.77 mmol) and 9,9-dialkyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9H-fluorene (0.85 mmol) or 9,9-dialkyl-2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9H-fluorene (0.38 mmol) were taken in a 100 mL Schlenk flask. A solvent mixture of 20 mL of tetrahydrofuran (THF) and 2 mL of water and powdered potassium carbonate (2.7 mmol) was added. The reaction mixture was purged with nitrogen for 5 min. The reaction flask was degassed and then again purged with nitrogen for 2 min. Bis(triphenylphosphine)palladium(II) dichloride (0.04 mmol) was added into it and stirred for 12-16 h at 80 °C under nitrogen. The reaction mixture was allowed to cool down to the room temperature, diluted with water and extracted using ethyl acetate. The organic layers were dried over sodium sulfate and evaporated at reduced pressure. The crude products were purified by silica gel column chromatography (the details are given below). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; | 2.1.1 4-(4′-Diphenylaminophenyl)-N-ethylhexyl-1,8-naphthalimide (4) The solution of 4-bromo-1,8-naphthalimide (1) (0.5 g, 1.29 mmol) and Pd(PPh3)2Cl2 (0.03 g, 0.04 mmol) in THF (15 mL) was purged with nitrogen, and the solution of 4-(diphenylamino)phenylboronic acid (0.37 g, 1.28 mmol) in THF (3 mL) and aqueous K2CO3 solution (1.70 g, 12.32 mmol) in H2O (2 mL) were added with a syringe. The reaction mixture was stirred at 80 °C for 24 h. After cooling down, the product was extracted with CH2Cl2, washed with water and dried over MgSO4. The solvent was evaporated to afford a crude product. After column chromatography on silica gel with the eluent mixture of ethyl acetate and hexane (1:8, V:V), compound 4 was obtained as yellow powder with the yield of 0.55 g (78%). M.p. 127-128 °C; Rf = 0.54; 1H NMR (300 MHz, CDCl3): δ 8.67 (d, 1H, J = 7.32 Hz, HNaphthalene), 8.66 (d, 1H, J = 8.52 Hz, HNaphthalene), 8.46 (d, 1H, J = 1.16 Hz, HNaphthalene), 8.43 (d, 1H, J = 1.15 Hz, HNaphthalene), 7.75 (t, 1H, J = 7.56 Hz, HNaphthalene), 7.44-7.31 (m, 6H, -Ar), 7.27-7.09 (m, 8H, -Ar), 4.26-4.11 (m, 2H, -CH2, -Haliphatic), 2.06-1.95 (m, 1H, -CH, -Haliphatic), 1.48-1.31 (m, 8H, 4 × CH2, -Haliphatic), 1.01-0.89 (m, 6H, 2 × CH3, -Haliphatic). 13C NMR (75.4 MHz, CDCl3): δ 167.43, 147.76, 146.75, 146.14, 132.85, 131.90, 131.48, 131.29, 130.31, 130.05, 129.31, 128.42, 127.93, 126.73, 125.78, 124.77, 123.83, 121.64, 43.87, 38.14, 31.73, 28.88, 24.59, 23.47, 14.44, 10.82. IR (KBr, υ cm-1): 3060 (CHar), 2954, 2925, 2858 (CHaliphatic), 1697 (C=Oanhydride), 1656, 1584, 1505, 1486 (C=Car), 1350, 1279 (C-N), 784, 759, 695 (CHar); Anal. Calcd. for C38H36N2O2: C, 82.58; H, 6.57; N, 5.07; O, 5.79. Found: C, 82.63; H, 6.60; N, 5.08. MS (APCI+, 20 V), m/z: 553 ([M + H]+) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; | 2.1.1 4-(4-Diphenylaminophenyl)-N-ethylhexyl-1,8-naphthalimide (4) General procedure: The solution of 4-bromo-1,8-naphthalimide (1) (0.5 g, 1.29 mmol) and Pd(PPh3)2Cl2 (0.03 g, 0.04 mmol) in THF (15 mL) was purged with nitrogen, and the solution of 4-(diphenylamino)phenylboronic acid (0.37 g, 1.28 mmol) in THF (3 mL) and aqueous K2CO3 solution (1.70 g, 12.32 mmol) in H2O (2 mL) were added with a syringe. The reaction mixture was stirred at 80 °C for 24 h. After cooling down, the product was extracted with CH2Cl2, washed with water and dried over MgSO4. The solvent was evaporated to afford a crude product. After column chromatography on silica gel with the eluent mixture of ethyl acetate and hexane (1:8, V:V), compound 4 was obtained as yellow powder with the yield of 0.55 g (78%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; | 2.1.1 4-(4-Diphenylaminophenyl)-N-ethylhexyl-1,8-naphthalimide (4) General procedure: The solution of 4-bromo-1,8-naphthalimide (1) (0.5 g, 1.29 mmol) and Pd(PPh3)2Cl2 (0.03 g, 0.04 mmol) in THF (15 mL) was purged with nitrogen, and the solution of 4-(diphenylamino)phenylboronic acid (0.37 g, 1.28 mmol) in THF (3 mL) and aqueous K2CO3 solution (1.70 g, 12.32 mmol) in H2O (2 mL) were added with a syringe. The reaction mixture was stirred at 80 °C for 24 h. After cooling down, the product was extracted with CH2Cl2, washed with water and dried over MgSO4. The solvent was evaporated to afford a crude product. After column chromatography on silica gel with the eluent mixture of ethyl acetate and hexane (1:8, V:V), compound 4 was obtained as yellow powder with the yield of 0.55 g (78%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; | 2.1.1 4-(4-Diphenylaminophenyl)-N-ethylhexyl-1,8-naphthalimide (4) General procedure: The solution of 4-bromo-1,8-naphthalimide (1) (0.5 g, 1.29 mmol) and Pd(PPh3)2Cl2 (0.03 g, 0.04 mmol) in THF (15 mL) was purged with nitrogen, and the solution of 4-(diphenylamino)phenylboronic acid (0.37 g, 1.28 mmol) in THF (3 mL) and aqueous K2CO3 solution (1.70 g, 12.32 mmol) in H2O (2 mL) were added with a syringe. The reaction mixture was stirred at 80 °C for 24 h. After cooling down, the product was extracted with CH2Cl2, washed with water and dried over MgSO4. The solvent was evaporated to afford a crude product. After column chromatography on silica gel with the eluent mixture of ethyl acetate and hexane (1:8, V:V), compound 4 was obtained as yellow powder with the yield of 0.55 g (78%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 2-methoxy-ethanol / 8 h / Reflux 2: dichloromethane / 12 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 2-methoxy-ethanol / 8 h / Reflux 2: dichloromethane / 12 h / 20 °C 3: bis-triphenylphosphine-palladium(II) chloride; triphenylphosphine; copper(l) iodide; triethylamine / tetrahydrofuran / 6 h / 75 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 2-methoxy-ethanol / 8 h / Reflux 2: dichloromethane / 12 h / 20 °C 3: bis-triphenylphosphine-palladium(II) chloride; triphenylphosphine; copper(l) iodide; triethylamine / tetrahydrofuran / 6 h / 75 °C / Inert atmosphere 4: potassium carbonate / dichloromethane; methanol / 0.5 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1.1: 2-methoxy-ethanol / 8 h / Reflux 2.1: dichloromethane / 12 h / 20 °C 3.1: bis-triphenylphosphine-palladium(II) chloride; triphenylphosphine; copper(l) iodide; triethylamine / tetrahydrofuran / 6 h / 75 °C / Inert atmosphere 4.1: potassium carbonate / dichloromethane; methanol / 0.5 h / 20 °C 5.1: copper(l) iodide; diisopropylamine / dichloromethane / 0.17 h 5.2: 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40.2% | In 2-methoxy-ethanol for 8h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine at 90℃; for 24h; Inert atmosphere; | NI-TPA NI-TPA was prepared by the same procedureas compound NI-Cz using 1 (0.50 g, 1.29 mmol), 5 (0.42 g,1.55 mmol), Pd(OAc)2 (5 mg, 0.016 mmol), P(o-tolyl)3 (16 mg,0.071 mmol), DMF (10 mL), and triethylamine (3 mL). The crudeproduct was purified by column chromatography using the mixtureof petroleum and dichloromethane (vol. ratio 2:1) as an eluent toget the desired compound as a red solid (0.39 g) with a yield of 52%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61.33% | With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine at 90℃; for 24h; Inert atmosphere; | NI-Cz A flask was charged with a mixture of 1(0.50 g, 1.29 mmol), 3 (0.42 g, 1.55 mmol), Pd(OAc)2 (5 mg,0.016 mmol), P(o-tolyl)3 (16 mg, 0.071 mmol), DMF (10 mL), andtriethylamine (3 mL). The flask was degassed and purged with N2.The mixture was heated at 90 C for 24 h under N2. Then, it wasfiltered, and the filtrate was poured into distilled water andextracted with ethyl acetate. The organic layer was dried withanhydrous magnesium sulfate and concentrated by vacuum evaporation.The crude product was purified by column chromatographyusing the mixture of petroleum and dichloromethane (vol.ratio 2:1) as an eluent to get the desired compound as a orangeyellowsolid (0.46 g) with a yield of 61.33%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: bis-triphenylphosphine-palladium(II) chloride; triphenylphosphine; copper(l) iodide; triethylamine / 8 h / 90 °C / Inert atmosphere 1.2: 1.5 h / 20 °C 2.1: diisopropylamine; copper(l) iodide / dichloromethane / 24 h / 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: bis-triphenylphosphine-palladium(II) chloride; triphenylphosphine; copper(l) iodide; triethylamine / 8 h / 90 °C / Inert atmosphere 1.2: 1.5 h / 20 °C 2.1: diisopropylamine; copper(l) iodide / dichloromethane / 24 h / 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | Stage #1: 6-bromo-2-(2-ethylhexyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione; trimethylsilylacetylene With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine at 90℃; for 8h; Inert atmosphere; Stage #2: With potassium carbonate In methanol; dichloromethane at 20℃; for 1.5h; | |
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine at 20℃; Inert atmosphere; | 3.5 (5)To a three-necked flask was added 4-bromo-1,8-naphthalenedicarboxamide(4.85 g, 17.6 mmol), N, N-dimethylformamide(200 mL), (2.8 g, 26.4 mmol) of sodium carbonateStirring at 40 ° C for 1 h,2-ethyl bromohexane was added dropwise with magnetic stirring(4 mL, 21.1 mmol) and heated to 50 & lt; 0 & gt; CReaction 12 ~ 14h,After the reaction, add water,Extracted with dichloromethane,Take dichloromethane,The solvent was removed to give pureN- (2-ethylhexyl) -4-bromo-1,8-naphthalenedicarboxamide,Under the protection of argon, N- (2-ethylhexyl) -4-bromo-1,8-naphthalenedicarboxamide was added(5.94 g, 15.3 mmol)Triethylamine (50 mL),Cuprous iodide (0.15 g, 0.763 mmol)(Triphenylphosphine) palladium (0.88 g, 0.763 mmol) was added dropwise to a solution of trimethylsilylacetylene (4 m, 30.6 mmol), followed by reaction at room temperature for 20 to 22 h,After the reaction, triethylamine was removed, methanol and excess sodium carbonate were added to the crude product, followed by stirring at room temperature for 24 to 26 hours. After completion of the reaction, methanol was removed, and petroleum ether and ethyl acetate (the volume ratio of the two was 4: 1) as a eluent, and isolated by chromatography on a columnN- (2-ethylhexyl) -4-ethynyl-1,8-naphthalenedicarboxamide; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; | 2.3.1 3,6-((Di(N-(2-ethylhexyl)-1,8-naphthalimide)-4-yl)-9-metyl-9H-carbazole (5) General procedure: 4-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide (4) (0.5 g, 1.29 mmol) and 15 mL of dry THF and aqueous K2CO3 solution (0.81 g, 5.85 mmol) in 2 mL H2O were added via a syringe under nitrogen to a three-necked round-bottomed flask (50 mL) equipped with a magnetic stirrer, a reflux condenser and a nitrogen input tube. 9-Methyl-3,6-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)-9H-carbazole (3a) (0.25 g, 0.59 mmol) and Pd(PPh3)2Cl2 (0.02 g, 0.02 mmol) were successively added and the reaction mixture was refluxed at 80 °C for 24 h under nitrogen atmosphere. After cooling down to the room temperature methylene chloride (200 mL) was added to the reaction mixture. Then it was washed three times with distilled water, and dried with anhydrous magnesium sulfate. The solution was filtered and concentrated. The crude product was purified by column chromatography on silica gel with ethyl acetate and hexane (1:9, V:V) as eluent and crystallized from the eluent mixture of solvents to give 5 as yellow crystals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; | 2.3.1 3,6-((Di(N-(2-ethylhexyl)-1,8-naphthalimide)-4-yl)-9-metyl-9H-carbazole (5) General procedure: 4-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide (4) (0.5 g, 1.29 mmol) and 15 mL of dry THF and aqueous K2CO3 solution (0.81 g, 5.85 mmol) in 2 mL H2O were added via a syringe under nitrogen to a three-necked round-bottomed flask (50 mL) equipped with a magnetic stirrer, a reflux condenser and a nitrogen input tube. 9-Methyl-3,6-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)-9H-carbazole (3a) (0.25 g, 0.59 mmol) and Pd(PPh3)2Cl2 (0.02 g, 0.02 mmol) were successively added and the reaction mixture was refluxed at 80 °C for 24 h under nitrogen atmosphere. After cooling down to the room temperature methylene chloride (200 mL) was added to the reaction mixture. Then it was washed three times with distilled water, and dried with anhydrous magnesium sulfate. The solution was filtered and concentrated. The crude product was purified by column chromatography on silica gel with ethyl acetate and hexane (1:9, V:V) as eluent and crystallized from the eluent mixture of solvents to give 5 as yellow crystals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; | 2.3.1 3,6-((Di(N-(2-ethylhexyl)-1,8-naphthalimide)-4-yl)-9-metyl-9H-carbazole (5) General procedure: 4-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide (4) (0.5 g, 1.29 mmol) and 15 mL of dry THF and aqueous K2CO3 solution (0.81 g, 5.85 mmol) in 2 mL H2O were added via a syringe under nitrogen to a three-necked round-bottomed flask (50 mL) equipped with a magnetic stirrer, a reflux condenser and a nitrogen input tube. 9-Methyl-3,6-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)-9H-carbazole (3a) (0.25 g, 0.59 mmol) and Pd(PPh3)2Cl2 (0.02 g, 0.02 mmol) were successively added and the reaction mixture was refluxed at 80 °C for 24 h under nitrogen atmosphere. After cooling down to the room temperature methylene chloride (200 mL) was added to the reaction mixture. Then it was washed three times with distilled water, and dried with anhydrous magnesium sulfate. The solution was filtered and concentrated. The crude product was purified by column chromatography on silica gel with ethyl acetate and hexane (1:9, V:V) as eluent and crystallized from the eluent mixture of solvents to give 5 as yellow crystals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; | 2.3.1 3,6-((Di(N-(2-ethylhexyl)-1,8-naphthalimide)-4-yl)-9-metyl-9H-carbazole (5) General procedure: 4-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide (4) (0.5 g, 1.29 mmol) and 15 mL of dry THF and aqueous K2CO3 solution (0.81 g, 5.85 mmol) in 2 mL H2O were added via a syringe under nitrogen to a three-necked round-bottomed flask (50 mL) equipped with a magnetic stirrer, a reflux condenser and a nitrogen input tube. 9-Methyl-3,6-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)-9H-carbazole (3a) (0.25 g, 0.59 mmol) and Pd(PPh3)2Cl2 (0.02 g, 0.02 mmol) were successively added and the reaction mixture was refluxed at 80 °C for 24 h under nitrogen atmosphere. After cooling down to the room temperature methylene chloride (200 mL) was added to the reaction mixture. Then it was washed three times with distilled water, and dried with anhydrous magnesium sulfate. The solution was filtered and concentrated. The crude product was purified by column chromatography on silica gel with ethyl acetate and hexane (1:9, V:V) as eluent and crystallized from the eluent mixture of solvents to give 5 as yellow crystals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; | 2.3.1 3,6-((Di(N-(2-ethylhexyl)-1,8-naphthalimide)-4-yl)-9-metyl-9H-carbazole (5) General procedure: 4-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide (4) (0.5 g, 1.29 mmol) and 15 mL of dry THF and aqueous K2CO3 solution (0.81 g, 5.85 mmol) in 2 mL H2O were added via a syringe under nitrogen to a three-necked round-bottomed flask (50 mL) equipped with a magnetic stirrer, a reflux condenser and a nitrogen input tube. 9-Methyl-3,6-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)-9H-carbazole (3a) (0.25 g, 0.59 mmol) and Pd(PPh3)2Cl2 (0.02 g, 0.02 mmol) were successively added and the reaction mixture was refluxed at 80 °C for 24 h under nitrogen atmosphere. After cooling down to the room temperature methylene chloride (200 mL) was added to the reaction mixture. Then it was washed three times with distilled water, and dried with anhydrous magnesium sulfate. The solution was filtered and concentrated. The crude product was purified by column chromatography on silica gel with ethyl acetate and hexane (1:9, V:V) as eluent and crystallized from the eluent mixture of solvents to give 5 as yellow crystals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h; Inert atmosphere; | 2.3.7 9-((N-(2-ethylhexyl)-1,8-naphthalimide)-4-yl)-9H-carbazole (11) 4-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide (4) (0.5 g, 1.29 mmol), copper powder (0.32 g, 5.15 mmol), 18-crown-6 (0.06 g, 0.26 mmol), K2CO3 (1.42 g, 10.31 mmol), 9H-carbazole (0.94 g, 5.14 mmol) and o-dichlorobenzene (15 mL) were placed into a round-bottom flask and vigorously stirred at 180 °C for 24 h under nitrogen. When the reaction was finished, the inorganic components were removed by filtration. The solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography using the mixture of ethyl acetate and hexane (1:9, V:V) as an eluent and crystallized from the eluent mixture of solvents to obtain 11 as yellow crystals. Yield: 58% (0.36 g), m.p. 110-111 °C; 1H NMR spectrum (300 MHz, CDCl3, δ, ppm): 8.83 (d, 1H, J = 7.7 Hz, -HNaphthalene), 8.72 (d, 1H, J = 1.2 Hz, -HNaphthalene), 8.69 (d, 1H, J = 1.2 Hz, -HNaphthalene), 8.25 (d, 2H, J = 2.6 Hz, -HCarbazole), 7.95 (d, 1H, J = 7.8 Hz, -HNaphthalene), 7.83 (dd, 2H, J1 = 1.2 Hz, J2 = 8.5 Hz, -HCarbazole), 7.66 (t, 1H, -HNaphthalene), 7.45-7.35 (m, 4H, -HCarbazole), 4.31-4.15 (m, 2H, -CH2, -Haliphatic), 2.09-1.99 (m, 1H, -CH, -Haliphatic), 1.56-1.24 (m, 8H, 4 × CH2, -Haliphatic), 1.09-0.82 (m, 6H, 2 × CH3, -Haliphatic). 13C NMR spectrum (75.4 MHz, CDCl3, δ, ppm): 164.6, 164.2, 142.0, 140.4, 132.3, 131.9, 130.3, 129.2, 127.9, 127.6, 126.6, 124.0, 123.0, 120.9, 120.8, 110.2, 44.5, 38.2, 31.0, 28.9, 24.3, 23.4, 14.4, 10.9. IR, (in KBr), cm-1: 3055 ν (CHar); 2958, 2923, 2878, 2856 ν (CHaliphatic); 1699 ν (C=Oanhydride); 1634, 1652, 1587 ν (C=Car); 1457; 1333, 1235 ν (C-N); 782,789, 753, 746 γ (CHar). MS (APCI+, 20 V), m/z: 490 ([M+H]+). Anal. Calcd. for C33H34N2O2: C, 80.78; H, 6.98, N, 5.71; O, 6.52%; found C 80.86, H 6.76, N 5.84%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h; Inert atmosphere; | 2.3.7 9-((N-(2-ethylhexyl)-1,8-naphthalimide)-4-yl)-9H-carbazole (11) General procedure: 4-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide (4) (0.5 g, 1.29 mmol), copper powder (0.32 g, 5.15 mmol), 18-crown-6 (0.06 g, 0.26 mmol), K2CO3 (1.42 g, 10.31 mmol), 9H-carbazole (0.94 g, 5.14 mmol) and o-dichlorobenzene (15 mL) were placed into a round-bottom flask and vigorously stirred at 180 °C for 24 h under nitrogen. When the reaction was finished, the inorganic components were removed by filtration. The solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography using the mixture of ethyl acetate and hexane (1:9, V:V) as an eluent and crystallized from the eluent mixture of solvents to obtain 11 as yellow crystals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine; In N,N-dimethyl-formamide; at 90℃; for 24h;Inert atmosphere; | A round bottom flask was charged with a mixture of 4-bromo-N-(2-ethylhexyl)-1,8-naphthalimide (4) (0.5 g, 1.29 mmol), <strong>[1484-13-5]N-vinylcarbazole</strong> (0.40 g, 1.93 mmol), Pd(OAc)2 (0.005 g, 0.016 mmol), P(o-tolyl)3 (0.016 g, 0.071 mmol), DMF (8 mL) and triethylamine (2 mL). The flask was degassed and purged with N2. The reaction mixture was heated at 90 C for 24 h under nitrogen. Then, it was filtered and the filtrate was poured into methanol. The yellow precipitate was filtered, washed with methanol and dissolved in methylene chloride. After evaporation of the solvent, the crude product was purified by silica gel column chromatography using the mixture of ethylacetate and n-hexane (1:9, V:V) as an eluent and crystallized from the eluent mixture of solvents to give 13 as yellow crystals. Yield 32% (0.21 g), m.p. = 214-215 C. 1H NMR spectrum (300 MHz, CDCl3, delta, ppm):8.71 (d, 1H, J = 1.1 Hz, -HNaphthalene), 8.69 (d, 1H, J = 1.1 Hz, -HNaphthalene), 8.57 (d, 1H, J = 1.1 Hz, -HNaphthalene), 8.55 (d, 1H, J = 1.1 Hz, -HNaphthalene), 8.17 (d, 2H, J = 7.7 Hz, -HCarbazole), 8.06 (d, 1H, J = 2.5 Hz, -HNaphthalene), 7.90-7.83 (m, 4H, -HCarbazole, -vinylic), 7.62-7.55 (m, 2H, -HCarbazole), 7.46-7.39 (m, 2H, -HCarbazole), 4.23-4.14 (m, 2H, -CH2, -Haliphatic), 1.91-1.86 (m, 1H, -CH, -Haliphatic), 1.49-1.33 (m, 8H, 4 × CH2, -Haliphatic), 1.03-0.88 (m, 6H, 2 × CH3, -Haliphatic). 13C NMR spectrum (75.4 MHz, CDCl3, delta, ppm): 164.6, 164.1, 141.7, 140.6, 139.8, 132.3, 131.9, 130.3, 129.4, 129.2, 127.9, 127.6, 126.6, 124.1, 123.0, 120.9, 120.4, 110.3, 45.5, 37.8, 32.1, 28.8, 25.4, 23.5, 14.3, 10.9. IR, (in KBr), cm-1: 3052 nu (CHar); 2956, 2924, 2878, 2856 nu (CHaliphatic); 1700 nu (C=Oanhydride); 1634, 1652, 1587 nu (C=Car); 1457; 1333, 1235 nu (C-N); 955 gamma (trans, CH=CH); 782,789, 753, 746 gamma (CHar). MS (APCI+, 20 V), m/z: 500 ([M+H]+). Anal. Calcd. for C34H32N2O2: C, 81.57; H, 6.44; N, 5.60; O, 6.39%; found C 81.76, H 6.58, N 5.48%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; | 2.3.1 3,6-((Di(N-(2-ethylhexyl)-1,8-naphthalimide)-4-yl)-9-metyl-9H-carbazole (5) 4-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide (4) (0.5 g, 1.29 mmol) and 15 mL of dry THF and aqueous K2CO3 solution (0.81 g, 5.85 mmol) in 2 mL H2O were added via a syringe under nitrogen to a three-necked round-bottomed flask (50 mL) equipped with a magnetic stirrer, a reflux condenser and a nitrogen input tube. 9-Methyl-3,6-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)-9H-carbazole (3a) (0.25 g, 0.59 mmol) and Pd(PPh3)2Cl2 (0.02 g, 0.02 mmol) were successively added and the reaction mixture was refluxed at 80 °C for 24 h under nitrogen atmosphere. After cooling down to the room temperature methylene chloride (200 mL) was added to the reaction mixture. Then it was washed three times with distilled water, and dried with anhydrous magnesium sulfate. The solution was filtered and concentrated. The crude product was purified by column chromatography on silica gel with ethyl acetate and hexane (1:9, V:V) as eluent and crystallized from the eluent mixture of solvents to give 5 as yellow crystals. Yield: 66% (0.31 g), m.p. 147-148 °C; 1H NMR spectrum (300 MHz, CDCl3, δ, ppm): 8.71 (s, 1H, -HNaphthalene), 8.69 (s, 1H, -HNaphthalene), 8.68 (d, 1H, J = 1.1 Hz, -HNaphthalene), 8.65 (d, 1H, J = 1.1 Hz, -HNaphthalene), 8.42 (d, 1H, J = 1.1 Hz, -HNaphthalene), 8.39 (d, 1H, J = 1.1 Hz, -HNaphthalene), 8.33-8.28 (m, 2H, -HNaphthalene), 7.85 (d, 2H, J = 7.6 Hz, -HNaphthalene), 7.75 (s, 2H, -HNaphthalene, -HCarbazole), 7.72 (t, 3H, J = 1.6 Hz, -HCarbazole), 7.70 (s, 2H, -HCarbazole), 4.22-4.16 (m, 4H, -N(CH2)2, -Haliphatic), 4.10 (s, 3H, -NCH2CH2CH2CH3), 2.05-1.97 (m, 2H, 2 × CH, -Haliphatic), 1.47-1.32 (m, 16H, 8 × CH2, -Haliphatic), 1.00-0.90 (m, 12H, 4 × CH3, -Haliphatic). 13C NMR spectrum (75.4 MHz, CDCl3, δ, ppm): 164.9, 164.8, 147.8, 141.6, 133.1, 131.4, 131.1, 130.7, 130.3, 129.1, 128.5, 127.0, 123.2, 123.1, 122.2, 121.6, 109.2, 44.4, 38.2, 31.0, 29.8, 29.0, 24.3, 23.3, 14.4, 10.9. IR, (in KBr), cm-1: 3070 ν (CHar); 2955, 2924, 2856 ν (CHaliphatic); 1700 ν (C=Oanhydride); 1654, 1586, 1510 ν (C=Car); 1352, 1279 ν (C-N); 782, 754, 621 γ (CHar). MS (APCI+, 20 V), m/z: 812 ([M+H]+). Anal. Calcd. for C54H57N3O4: C, 79.87; H, 7.08, N, 5.17; O, 7.88%; found C 79.92, H 7.03, N 5.15%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 16h; Schlenk technique; Inert atmosphere; | 4 2,7-Di((N-(2-ethylhexyl)-1,8-naphthalimide)-4-yl)-9-(2-ethylhexyl)-9H-carbazole (DENC) 4-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide (1a) (0.47 g, 1.21 mmol) and 9-(2-ethylhexyl)-2,7-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-diyl)-9H-carbazole (2a) (0.30 g, 0.55 mmol) were taken in a 100 mL Schlenk flask to which a solvent mixture of 20 mL of tetrahydrofuran (THF) and 2 mL of water was added. Powdered potassium carbonate (1.13 g, 8.19 mmol) was added and the reaction mixture was purged with nitrogen for 5 min. The reaction flask was degassed and then, again purged with nitrogen for 2 min. Bis(triphenylphosphine) palladium(II) dichloride (Pd(Ph3)2Cl2) (0.02 g, 0.03 mmol) was added into it and stirred for 16 h at 80 °C under nitrogen. The reaction mixture was allowed to cool down to the room temperature, diluted with water and extracted with ethyl acetate. The organic layers were dried over sodium sulphate and evaporated at reduced pressure. The product was purified by silica gel column chromatography using using an eluent mixture of hexane and ethyl acetate in a volume ratio of 10:1 to obtain DENC as yellow crystals. Yield = 62% (0.12 g); (FW = 910.26 g/mol); M.p. = 124-125 °C. 1H NMR spectrum (300 MHz, CDCl3, δ, ppm): 8.75 (d, 2H, J = 7.5 Hz, -HNaphthalimide), 8.71 (dd, 2H, J1 = 7.5 Hz, J2 = 1.2 Hz, -HNaphthalimide), 8.65 (dd, 1H, J1 = 1.2 Hz, J2 = 7.2 Hz, -HNaphthalimide), 8.46 (d, 1H, J = 1.2 Hz, -HNaphthalimide), 8.43 (d, 1H, J = 1.1 Hz, -HNaphthalimide), 8.36 (d, 2H, J = 7.9 Hz, -HNaphthalimide), 8.26 (dd, 1H, J1 = 1.1 Hz, J2 = 8.28 Hz, -HNaphthalimide) 7.90 (d, 1H, J = 7.9 Hz, -HCarbazole), 7.80-7.73 (q, 3H, -HCarbazole), 7.60 (s, 1H, -HCarbazole), 7.48 (dd, 1H, J1 = 1.2 Hz, J2 = 7.9 Hz, -HCarbazole), 4.28-4.18 (m, 4H, -NCH2Naphthalimide), 2.06-1.99 (m, 3H, -CHNaphthalimide, -CHCarbazole), 1.45-1.19 (m, 24H, -CH2Naphthalimide, -CH2Carbazole), 1.02-0.89 (m, 18H, -CH3Naphthalimide, CH3Carbazole). 13C NMR spectrum (75.4 MHz, CDCl3, δ, ppm): 162.6, 160.7, 148.6, 143.5, 142.4, 141.9, 138.6, 136.4, 135.4, 134.3, 133.2, 132.5, 131.2, 130.7, 130.2, 129.6, 128.2, 127.4, 126.6, 125.3, 124.6, 123.2, 122.5, 122.1, 121.5, 120.7, 118.4, 116.6, 115.1, 109.6, 106.8, 103.2, 64.4, 45.3, 38.4, 37.7, 36.3, 33.2, 28.3, 26.1, 25.2, 23.2, 18.3, 13.3, 10.7. IR, (in KBr), cm-1: (arene C-H) 3055; (aliphatic C-H) 2942, 2914; (imide C=Osymmetric) 1698; (imide C=Oasymmetric) 1664; (Ar C=C) 1577, 1518; (imide C-N) 1353, 1268; (Ar C-H) 786, 753, 612. MS (APCI+, 20 V), m/z: 911 ([M + H]+). Anal. Calcd. for C61H71N3O4: C, 80.49; H, 7.86, N, 4.62; O, 7.03%; found C 80.52, H 7.81, N 4.67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide at 90℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide at 90℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: 6-bromo-2-(2-ethylhexyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione; 2,5-bis(tributylstannyl)thiophene In toluene for 0.25h; Inert atmosphere; Stage #2: With tetrakis(triphenylphosphine) palladium(0) In toluene at 110℃; for 48h; Inert atmosphere; | 2.5.2. Compound 2 Compound 5 (178 mg, 0.27 mmol) and NMI-Br (200 mg, 0.52 mmol) were dissolved in toluene (30 ml). The mixture was deoxygenated with argon for 15 min. Pd(PPh3)4 (35 mg, 0.03 mmol) was added under argon. The mixturewas refluxed for 48 h and then cooled down to room temperature. Water (30 ml) was added and the mixturewas extracted with chloroform (2 x 40 ml). The organic phase was dried over anhydrous MgSO4 and filtered. After the solvent was removed from the filtrate, the residue was purified by column chromatography on silica gel using petroleum ether/chloroform (1:1, v/v) as eluent, yielding a yellow solid (165 mg, 92%). 1H NMR (300 MHz, CD2Cl2): δ 8.77 (d, J = 8.4 Hz, 2H), 8.64 (d, J = 8.1 Hz, 2H), 8.61 (d, J = 7.8 Hz, 2H), 7.94 (d, J = 7.5 Hz, 2H), 7.84 (t, J = 8.1 Hz, 2H), 7.52 (s, 2H), 4.10 (m, 4H), 1.93 (m, 2H), 1.51 (m, 4H), 1.32 (m, 10H), 0.89 (m, 12H). 13C NMR (75 MHz, CDCl3): δ 164.51, 154.26, 142.18, 138.12, 131.67, 130.81, 129.89, 129.02, 128.84, 127.60, 123.27, 122.56, 44.38, 38.09, 30.93, 28.87, 24.24, 23.24,14.27,10.84. MS (EI): m/z 698.0 (M). Anal. calc. for C44H46N2O4S: C, 75.61; H, 6.63; N, 4.01. Found: C, 75.49; H, 6.71; N, 3.86%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | Stage #1: 6-bromo-2-(2-ethylhexyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione; 1,1'-[4,4,9,9-tetrakis(4-hexylphenyl)-4,9-dihydro-s-indaceno[1,2-b:5,6-b’]dithiophene-2,7-diyl]bis[1,1,1-trimehtylstannyl] In toluene for 0.25h; Inert atmosphere; Enzymatic reaction; Stage #2: With tetrakis(triphenylphosphine) palladium(0) In toluene at 110℃; for 72h; Inert atmosphere; | 2.5.3. Compound 3 Compound 6 (246.6 mg, 0.2 mmol) and NMI-Br (155.3 mg, 0.4 mol) were dissolved in toluene (30 ml). The mixture was deoxygenated with argon for 15 min. Pd(PPh3)4 (23.1 mg, 0.02 mmol) was added under argon. The mixture was refluxed for 72 h and then cooled down to room temperature. Water (30 ml) was added and the mixture was extracted with chloroform (2 x 30 ml). The organic phase was dried over anhydrous MgSO4 and filtered. After the solvent was removed from the filtrate, the residue was purified by column chromatography on silica gel using petroleum ether/chloroform (3:1, v/v) as eluent, yielding an orange-pink solid (210 mg, 70%). 1H NMR (400 MHz, CDCl3): δ 8.69 (d, J = 8.4 Hz, 2H), 8.65 (d, J = 7.6 Hz, 2H), 8.59 (d, J = 7.6 Hz, 2H), 7.85 (d, J = 7.6 Hz, 2H), 7.75 (t, J = 7.6 Hz, 2H), 7.56 (s, 2H), 7.33 (s, 2H), 7.27 (d, J = 7.2 Hz, 8H), 7.12 (d, J = 8.0 Hz, 8H), 4.15 (m, 4H), 2.60 (t, J 7.6 Hz, 8H), 1.97 (m, 2H), 1.64-1.31 (m, 72H). 13C NMR (100 MHz, CDCl3): δ 164.78, 164.48, 157.20, 153.67, 143.71, 142.59, 142.07, 141.75, 139.49, 135.58, 132.31, 131.63, 130.98, 129.79, 129.23, 128.74, 128.47, 128.07, 127.44, 125.36, 123.27, 121.96, 118.19, 63.52, 44.44, 38.15, 35.79, 31.94, 31.58, 30.99, 29.35, 28.95, 24.32, 23.30, 22.82, 14.32, 10.91. MS (MALDI): m/z 1521.0 (M). Anal. calc. for C104H116N2O4S2: C, 81.94; H, 7.85; N, 2.09. Found: C, 82.06; H, 7.68; N, 1.84%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | Stage #1: 6-bromo-2-(2-ethylhexyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione With bis(tri-n-butyltin) In toluene for 0.25h; Inert atmosphere; Stage #2: With tetrakis(triphenylphosphine) palladium(0) In toluene at 110℃; for 48h; Inert atmosphere; | 2.5.1. Compound 1 Compound 4 (312 mg, 0.54 mmol) and NMI-Br (400 mg, 1.04 mmol) were dissolved in toluene (30 ml). The mixture was deoxygenated with argon for 15 min. Pd(PPh3)4 (58 mg, 0.05 mmol) was added under argon. The mixturewas refluxed for 48 h and then cooled down to room temperature. Water (30 ml) was added and the mixturewas extracted with chloroform (2 x 40 ml). The organic phase was dried over anhydrous MgSO4 and filtered. After the solvent was removed from the filtrate, the residue was purified by column chromatography on silica gel using petroleum ether/ dichloromethane (1:1, v/v) as eluent, yielding a pale-yellow solid (61 mg, 20%). 1H NMR (300 MHz, CDCl3): δ 8.73 (d, J = 7.5 Hz, 2H), 8.63 (d, J = 7.2 Hz, 2H), 7.78 (d, J = 7.5 Hz, 2H), 7.70 (d, J = 8.4 Hz, 2H), 7.61 (t, J = 7.8 Hz, 2H), 4.16 (m, 4H), 1.99 (t, J = 6.0 Hz, 2H), 1.66 (m, 4H), 1.39 (m, 10H), 0.89 (m, 12H). 13C NMR (75 MHz, CDCl3): δ 164.53, 164.37, 142.96, 132.12, 131.77, 130.98, 130.72, 128.99, 128.61,127.67,123.41,123.33, 44.47, 38.17, 30.96, 28.88, 24.26, 23.27, 14.28, 10.85. MS (MALDI): m/z 616.7 (M). Anal. calc. for C40H44N2O4: C, 77.89; H, 7.19; N, 4.54. Found: C, 77.88; H, 7.25; N, 4.52%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: copper(l) iodide; triphenylphosphine; triethylamine; bis-triphenylphosphine-palladium(II) chloride / 24 h / 20 °C / Inert atmosphere 2: potassium fluoride; tetrabutylammomium bromide; methanol / dichloromethane / 0.5 h / 60 °C | ||
Multi-step reaction with 2 steps 1: triethylamine; triphenylphosphine; copper(l) iodide / 1,4-dioxane / 12 h / 100 °C / Inert atmosphere 2: sodium hydroxide / toluene / 4 h / 110 °C / Inert atmosphere | ||
Multi-step reaction with 2 steps 1: bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine 2: potassium carbonate / methanol / 0.5 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: copper(l) iodide; triphenylphosphine; triethylamine; bis-triphenylphosphine-palladium(II) chloride / 24 h / 20 °C / Inert atmosphere 2: potassium fluoride; tetrabutylammomium bromide; methanol / dichloromethane / 0.5 h / 60 °C 3: copper(l) iodide; triethylamine / 12 h / 20 °C / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: copper(l) iodide; triphenylphosphine; triethylamine; bis-triphenylphosphine-palladium(II) chloride / 24 h / 20 °C / Inert atmosphere 2: potassium fluoride; tetrabutylammomium bromide; methanol / dichloromethane / 0.5 h / 60 °C 3: copper(l) iodide; triphenylphosphine; triethylamine; bis-triphenylphosphine-palladium(II) chloride / 100 °C / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: copper(l) iodide; triphenylphosphine; triethylamine; bis-triphenylphosphine-palladium(II) chloride / 24 h / 20 °C / Inert atmosphere 2: potassium fluoride; tetrabutylammomium bromide; methanol / dichloromethane / 0.5 h / 60 °C 3: copper(l) iodide; triphenylphosphine; triethylamine; bis-triphenylphosphine-palladium(II) chloride / 100 °C / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: copper(l) iodide; triphenylphosphine; triethylamine; bis-triphenylphosphine-palladium(II) chloride / 24 h / 20 °C / Inert atmosphere 2: potassium fluoride; tetrabutylammomium bromide; methanol / dichloromethane / 0.5 h / 60 °C 3: copper(l) iodide; triphenylphosphine; triethylamine; bis-triphenylphosphine-palladium(II) chloride / 100 °C / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine at 20℃; for 24h; Inert atmosphere; | |
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With tetrakis(triphenylphosphine) palladium(0); In toluene; at 110℃; for 12h;Inert atmosphere; | Tetrakis (triphenylphosphine)palladium (0) [Pd(PPh3)4] (10 mg)was added under nitrogen to a solution of 6-bromo-2-octyl-benzo[de]isoquinoline-1,3-dione (1) (109 mg, 0.28 mmol) and 4,7-bis-(5-trimethylstannanyl-thiophen-2-yl)-benzo [1,2,5] thiadiazole (2)(80 mg, 0.13 mmol) in toluene (40 mL) and stirred at 110 C 12 hlater, the mixturewas quenched withwater (100 mL) and extractedwith dichloromethane (DCM) three times (3 x 100 mL). The obtainedorganic layers was then dried over anhydrous magnesiumsulfate (MgSO4). After that the solvent was removed and the residueswas purified with column chromatography using a mixture ofhexane and DCM (V:V = 1:1) as eluent to obtained NI-BT as red solidwith a yield of 62%. 1H NMR (400 MHz, CDCl3, TMS, delta ppm): 8.76 (d,J = 8.0 Hz, 2H), 8.68 (d, J = 8.0 Hz, 2H), 8.65 (d, J = 8.0 Hz, 2H), 8.27(d, J = 4.0 Hz, 2H), 8.01 (s, 2H), 7.85 (d, J = 4.0 Hz, 2H), 7.83-7.79 (m,2H), 7.48 (d, J = 4.0 Hz, 2H), 4.20-4.10 (m, 4H), 1.99-1.95 (m, 2H), 1.43-1.25 (m, 16H), 0.96-0.93 (m, 12H). 13C NMR (100 MHz, CDCl3) delta 164.57,164.31,152.55,141.50,141.43,138.60,132.15,131.54,130.75,129.87, 128.99, 128.55, 128.32, 127.37, 125.89, 125.79, 123.13, 122.23,44.28, 37.98, 30.80, 29.71, 28.75, 24.12, 23.10, 14.12, 10.70, 1.02.MALDI-MS (MSD, m/z) for [M+] C54H50N4O4S3, 915.190; Found,915.137. Found melting point: 218-220 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With tetrakis(triphenylphosphine) palladium(0); In toluene; at 110℃; for 12h;Inert atmosphere; | General procedure: Tetrakis (triphenylphosphine)palladium (0) [Pd(PPh3)4] (10 mg)was added under nitrogen to a solution of 6-bromo-2-octyl-benzo[de]isoquinoline-1,3-dione (1) (109 mg, 0.28 mmol) and 4,7-bis-(5-trimethylstannanyl-thiophen-2-yl)-benzo [1,2,5] thiadiazole (2)(80 mg, 0.13 mmol) in toluene (40 mL) and stirred at 110 C 12 hlater, the mixturewas quenched withwater (100 mL) and extractedwith dichloromethane (DCM) three times (3 x 100 mL). The obtainedorganic layers was then dried over anhydrous magnesiumsulfate (MgSO4). After that the solvent was removed and the residueswas purified with column chromatography using a mixture ofhexane and DCM (V:V = 1:1) as eluent to obtained NI-BT as red solidwith a yield of 62%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / toluene / Inert atmosphere; Reflux 2: aluminum (III) chloride / chlorobenzene / 6 h / Reflux 3: benzeneseleninic anhydride / chlorobenzene / 130 °C / Reflux 4: toluene-4-sulfonic acid / chloroform / 50 °C / Inert atmosphere | ||
Multi-step reaction with 4 steps 1: tetrakis(triphenylphosphine) palladium(0); copper(l) iodide; cesium fluoride / N,N-dimethyl-formamide / 55 °C / Inert atmosphere 2: aluminum (III) chloride / chlorobenzene / 6 h / Reflux 3: benzeneseleninic anhydride / chlorobenzene / 130 °C / Reflux 4: toluene-4-sulfonic acid / chloroform / 50 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / toluene / Inert atmosphere; Reflux 2: aluminum (III) chloride / chlorobenzene / 6 h / Reflux 3: benzeneseleninic anhydride / chlorobenzene / 130 °C / Reflux 4: toluene-4-sulfonic acid / chloroform / 50 °C / Inert atmosphere | ||
Multi-step reaction with 4 steps 1: tetrakis(triphenylphosphine) palladium(0); copper(l) iodide; cesium fluoride / N,N-dimethyl-formamide / 55 °C / Inert atmosphere 2: aluminum (III) chloride / chlorobenzene / 6 h / Reflux 3: benzeneseleninic anhydride / chlorobenzene / 130 °C / Reflux 4: toluene-4-sulfonic acid / chloroform / 50 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / toluene / Inert atmosphere; Reflux 2: aluminum (III) chloride / chlorobenzene / 6 h / Reflux | ||
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); copper(l) iodide; cesium fluoride / N,N-dimethyl-formamide / 55 °C / Inert atmosphere 2: aluminum (III) chloride / chlorobenzene / 6 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / toluene / Inert atmosphere; Reflux 2: aluminum (III) chloride / chlorobenzene / 6 h / Reflux 3: benzeneseleninic anhydride / chlorobenzene / 130 °C / Reflux | ||
Multi-step reaction with 3 steps 1: tetrakis(triphenylphosphine) palladium(0); copper(l) iodide; cesium fluoride / N,N-dimethyl-formamide / 55 °C / Inert atmosphere 2: aluminum (III) chloride / chlorobenzene / 6 h / Reflux 3: benzeneseleninic anhydride / chlorobenzene / 130 °C / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In toluene Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); cesium fluoride In N,N-dimethyl-formamide at 55℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate / 1,4-dioxane / 24 h / 100 °C / Schlenk technique; Inert atmosphere 2: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / toluene; water / 12 h / 100 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate / 1,4-dioxane / 24 h / 100 °C / Schlenk technique; Inert atmosphere 2: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / toluene; water / 12 h / 100 °C / Inert atmosphere 3: potassium carbonate / 24 h / 130 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate / 1,4-dioxane / 24 h / 100 °C / Schlenk technique; Inert atmosphere 2: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / toluene; water / 12 h / 100 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate / 1,4-dioxane / 24 h / 100 °C / Schlenk technique; Inert atmosphere 2: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / toluene; water / 12 h / 100 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate / 1,4-dioxane / 24 h / 100 °C / Schlenk technique; Inert atmosphere 2: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / toluene; water / 12 h / 100 °C / Inert atmosphere 3: potassium carbonate / 24 h / 130 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 70℃; for 16h; Inert atmosphere; | |
81% | With potassium acetate In toluene for 17h; Reflux; | 1.5-2 Synthesis of Intermediate 5-2 5.6 g of Intermediate 5-1 was diluted in toluene, and 5 g of KOAc, 4.6 g of bis(pinacolato)diboron, and 0.5 g of Pd(dppf)2Cl2 were added thereto and stirred under reflux. After 17 hours, the mixture was cooled to room temperature, and the reaction was terminated by water. An extraction process was performed thereon three times utilizing ethyl acetate, a drying process was performed thereon utilizing anhydrous magnesium sulfate, and a filtering process was performed thereon under reduced pressure. Then, the residue obtained therefrom was separated and purified by column chromatography to obtain 5.1g (81%) of Intermediate 5-2. |
81.1% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamide at 150℃; for 12h; |
80% | With bis-triphenylphosphine-palladium(II) chloride; potassium acetate In toluene at 110℃; for 72h; Inert atmosphere; | |
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 100℃; for 24h; Schlenk technique; Inert atmosphere; | ||
In toluene at 110℃; | ||
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In toluene at 120℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium carbonate In N,N-dimethyl-formamide at 50℃; for 24h; | 1.5-1 Synthesis of Intermediate 5-1 5 g of Intermediate A (6-bromo-1H-benzo[de]isoquinoline-1,3(2H)-dione) was dissolved in dimethylformamide (DMF), and 5 g of K2CO3 and 4 g of 3-(bromomethyl)hexane were added thereto. The mixture was stirred at a temperature of 50° C. for 24 hours, and the reaction was terminated by water. An extraction process was performed thereon three times utilizing ethyl acetate, a drying process was performed thereon utilizing anhydrous magnesium sulfate, and a filtering process was performed thereon under reduced pressure. Then, the residue obtained therefrom was separated and purified by column chromatography to obtain 5.6 g (80%) of Intermediate 5-1. |
Stage #1: 4-bromonaphthalene-1,8-dicarboximide With sodium carbonate In N,N-dimethyl-formamide at 40℃; for 1h; Stage #2: 3-bromomethylheptane at 50℃; | 3.5 To a three-necked flask was added 4-bromo-1,8-naphthalenedicarboxamide(4.85 g, 17.6 mmol), N, N-dimethylformamide(200 mL), (2.8 g, 26.4 mmol) of sodium carbonateStirring at 40 ° C for 1 h,2-ethyl bromohexane was added dropwise with magnetic stirring(4 mL, 21.1 mmol) and heated to 50 & lt; 0 & gt; CReaction 12 ~ 14h,After the reaction, add water,Extracted with dichloromethane,Take dichloromethane,The solvent was removed to give pureN- (2-ethylhexyl) -4-bromo-1,8-naphthalenedicarboxamide,Under the protection of argon, N- (2-ethylhexyl) -4-bromo-1,8-naphthalenedicarboxamide was added(5.94 g, 15.3 mmol)Triethylamine (50 mL),Cuprous iodide (0.15 g, 0.763 mmol)(Triphenylphosphine) palladium (0.88 g, 0.763 mmol) was added dropwise to a solution of trimethylsilylacetylene (4 m, 30.6 mmol), followed by reaction at room temperature for 20 to 22 h,After the reaction, triethylamine was removed, methanol and excess sodium carbonate were added to the crude product, followed by stirring at room temperature for 24 to 26 hours. After completion of the reaction, methanol was removed, and petroleum ether and ethyl acetate (the volume ratio of the two was 4: (2-ethylhexyl) -4-ethynyl-1,8-naphthalenedicarboxamide was isolated by chromatography on a column using a mixed solvent of 1) as an eluent; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); triethylamine; copper(l) iodide / 20 °C / Inert atmosphere 2: tetrakis(triphenylphosphine) palladium(0); triethylamine; copper(l) iodide / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.496 g | With tetrakis(triphenylphosphine) palladium(0) In toluene at 110℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: toluene / 110 °C 2: tetrakis(triphenylphosphine) palladium(0); cesium fluoride / water; toluene / 100 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: toluene / 110 °C 2: tetrakis(triphenylphosphine) palladium(0); cesium fluoride / water; toluene / 100 °C 3: 12 h / 80 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 90℃; for 8h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 90℃; for 8h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 24h; Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.2% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 24h; Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 24h; Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide at 90℃; for 3h; | 1 Synthesis Example 1 Synthesis of naphthalimide dye (Compound D) for blocking blue light 4-Bromo-1,8-Naphthalic anhydride (A)Was mixed with 5 g of 2-ethylhexylamine and 100 g of ethanol, and the mixture was heated to 80 DEG CStir for 12 hours. The reaction product was cooled to room temperature, and crystals were precipitated using water. The product was filtered and dried to obtain a compound B having a molecular weight of 388.30.3 g of allyl alcohol and 3 g of KOH were mixed with 18 g of Compound B and reacted at 90 DEG C for 3 hours to obtain a compound C. The compound C was refluxed with N, N-dimethylaniline for 12 hours to obtain a compound D as a blue light blocking dye | |
With potassium hydroxide at 90℃; for 3h; | 2 Synthesis Example 2 Synthesis of Blue Light Absorption Naphthalimide Dye (Compound E) 10 g of 4-bromo-1,8-naphthalene anhydride (Compound A) was mixed with 5 g of 2-ethylhexylamine and 100 g of ethanol, and then heated up to 80 ° C. and stirred for 12 hours. After the reaction was cooled to room temperature, crystals were precipitated using water, which was filtered and dried to obtain Compound B having a molecular weight of 388.30. 18 g of Compound B was mixed with 3 g of allyl alcohol and 3 g of KOH was added and reacted at 90 ° C. for 3 hours to obtain compound D. The resulting mixture was refluxed for 12 hours using N,N-dimethylaniline, and compound E, a blue light blocking dye was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate at 80℃; for 12h; | 2 Synthesis Example 2 Synthesis of Other Naphthalimide Dyes (Compounds E, F and G) 10 g of 4-bromo-1,8-naphthalic anhydride (A) was dissolved in 5 g of 2-ethylhexylamine and 5 g of ethanolAnd the mixture was heated to 80 DEG C and stirred for 12 hours.After the reaction was cooled to room temperature, crystals were precipitated with water,This was filtered and dried to obtain a compound B having a molecular weight of 388.30.10 g of the dried powder was mixed with 100 g of methanol together with 10 g of K2CO3, and the mixture was heated to 80 DEG C and stirred for 12 hours. The reaction product was cooled to room temperature, and crystals were precipitated by using water. The crystals were collected by filtration and dried to obtain Compound E. | |
With potassium carbonate at 80℃; for 12h; | 1 Synthesis Example 1 Synthesis of Ultraviolet Absorption Naphthalimide Dye (Compound C) 10 g of 4-bromo-1,8-naphthalene anhydride (Compound A) was mixed with 5 g of 2-ethylhexylamine and 100 g of ethanol, and then heated to 80 ° C. and stirred for 12 hours. After the reaction was cooled to room temperature, crystals were precipitated using water, which was filtered and dried to obtain Compound B having a molecular weight of 388.30. 10 g of the dried powder was mixed with 100 ml methanol and 10 g K2CO3, and then heated to 80 ° C. and stirred for 12 hours. After the reaction was cooled to room temperature, crystals were precipitated using water, which was filtered and dried to obtain Compound C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate at 80℃; for 12h; | 2 Synthesis Example 2 Synthesis of Other Naphthalimide Dyes (Compounds E, F and G) General procedure: 10 g of 4-bromo-1,8-naphthalic anhydride (A) was dissolved in 5 g of 2-ethylhexylamine and 5 g of ethanolAnd the mixture was heated to 80 DEG C and stirred for 12 hours.After the reaction was cooled to room temperature, crystals were precipitated with water,This was filtered and dried to obtain a compound B having a molecular weight of 388.30.10 g of the dried powder was mixed with 100 g of methanol together with 10 g of K2CO3, and the mixture was heated to 80 DEG C and stirred for 12 hours. The reaction product was cooled to room temperature, and crystals were precipitated by using water. The crystals were collected by filtration and dried to obtain Compound E. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: triethylamine; triphenylphosphine; copper(l) iodide / 1,4-dioxane / 12 h / 100 °C / Inert atmosphere 2: sodium hydroxide / toluene / 4 h / 110 °C / Inert atmosphere 3: triethylamine; triphenylphosphine; copper(l) iodide / 1,4-dioxane / 12 h / 100 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: triethylamine; triphenylphosphine; copper(l) iodide / 1,4-dioxane / 12 h / 100 °C / Inert atmosphere 2: sodium hydroxide / toluene / 4 h / 110 °C / Inert atmosphere 3: triethylamine; triphenylphosphine; copper(l) iodide / 1,4-dioxane / 12 h / 100 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With copper(l) iodide; triethylamine; triphenylphosphine In 1,4-dioxane at 100℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium acetate In toluene for 17h; Reflux; | 7 Synthesis Example 7: Synthesis of Compound 111 1.6 g (80%) of Compound 111 was synthesized in the same (e.g., substantially the same) manner as in Synthesis of Compound 61, except that 1.8 g of Intermediate 5-1 and 1 g of naphthalen-2-yl boronic acid were utilized. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With potassium acetate In toluene for 17h; Reflux; | 8 Synthesis Example 8: Synthesis of Compound 120 1.1 g (42%) of Compound 120 was synthesized in the same (e.g., substantially the same) manner as in Synthesis of Compound 61, except that 2 g of Intermediate 5-1 and 1.7 g of (4-(pyridin-2-yl)naphthalen-1-yl)boronic acid were utilized. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With N-Bromosuccinimide In dichloromethane for 15h; | 2.7-1 Synthesis of Intermediate 7-1 1.8 g of Intermediate 5-1 was diluted in methylene chloride (MC) and 900 mg of NBS was added dropwise thereto. The mixture was stirred for 15 hours, and the reaction was terminated by water. An extraction process was performed thereon three times, a drying process was performed thereon utilizing anhydrous magnesium sulfate, and a filtering process was performed thereon under reduced pressure. Then, the residue obtained therefrom was separated and purified by column chromatography to obtain 2 g (93%) of Intermediate 7-1. The obtained compound was confirmed by LC-MS. C20H21Br2NO2:M+ 465.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: N-Bromosuccinimide / dichloromethane / 15 h 2: dimethyl sulfoxide / 6 h / 60 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine 2: potassium carbonate / methanol / 0.5 h 3: triethylamine / methanol; tetrahydrofuran / 18 h / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: hydrazine hydrate / 2-methoxy-ethanol / 4 h / Reflux 2: 2-methoxy-ethanol / 24 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: hydrazine hydrate / 2-methoxy-ethanol / 4 h / Reflux 2: 2-methoxy-ethanol / 24 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | In ethanol at 87℃; for 12h; Inert atmosphere; | 1; 5 Example 1: General Procedure for Synthesis of Compounds of Formulae 1a-1d General procedure: A mixture of 1, alkylamine and ethanol was taken in an RB flask and heated at 87° C. under argon atmosphere for 12 hr. After cooling to 30° C., the solid that precipitated was filtered and washed with ethanol. Solvent was removed by vacuum to get pure compound. |
[ 52559-36-1 ]
6-Bromo-1H-benzo[de]isoquinoline-1,3(2H)-dione
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[ 52559-37-2 ]
6-Bromo-2-(2-hydroxyethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione
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