CN115521256B - Preparation method of 4-amino-1, 8-naphthalimide derivative - Google Patents

Preparation method of 4-amino-1, 8-naphthalimide derivative Download PDF

Info

Publication number
CN115521256B
CN115521256B CN202211246750.8A CN202211246750A CN115521256B CN 115521256 B CN115521256 B CN 115521256B CN 202211246750 A CN202211246750 A CN 202211246750A CN 115521256 B CN115521256 B CN 115521256B
Authority
CN
China
Prior art keywords
mmol
naphthalimide derivative
follows
structural formula
amino
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211246750.8A
Other languages
Chinese (zh)
Other versions
CN115521256A (en
Inventor
王建勇
韩晨
孙韶彬
冀勋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qilu University of Technology
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN202211246750.8A priority Critical patent/CN115521256B/en
Publication of CN115521256A publication Critical patent/CN115521256A/en
Application granted granted Critical
Publication of CN115521256B publication Critical patent/CN115521256B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Abstract

The invention provides a preparation method of a 4-amino-1, 8-naphthalimide derivative, which comprises a first-stage reaction, redissolution and a second-stage reaction; the first stage reaction method is that 4-bromo-1, 8-naphthalimide derivative, benzophenone imine, BINAP, palladium acetate, metal alkali salt and organic solvent are added into a reaction vessel to react for 8-24 hours at 40-85 ℃; the re-dissolving method comprises the steps of removing the organic solvent, and adding a proper amount of tetrahydrofuran for dissolving; the second stage reaction method is that the 4-amino-1, 8-naphthalimide derivative is obtained by post-treatment separation after adding hydrochloric acid aqueous solution and stirring for 28-32 minutes. The preparation method provided by the invention is used for preparing the 4-amino-1, 8-naphthalimide derivative by a one-pot two-step method, and has the advantages of simple and easily obtained raw materials, wide substrate range, simplicity and safety in operation, environment-friendly production process and high yield.

Description

Preparation method of 4-amino-1, 8-naphthalimide derivative
Technical Field
The invention relates to a preparation method of a 4-amino-1, 8-naphthalimide derivative, belonging to the technical field of chemical synthesis.
Background
1, 8-naphthalimides have been reported and widely used since a long time ago. Because of the bright color and strong fluorescence, the material becomes an important functional material. The compounds have high thermal stability and high light resistance, and are widely used as fluorescent dyes and fluorescent whitening agents in textile, printing and dyeing, printing ink, paint and other industries. In addition, the compound has high quantum efficiency and excellent photochemical stability, and has wide application in the fields of metal fluorescent probes, photoelectric energy sensitive materials, DNA, intercalators, organic photoconductive materials and the like. At present, the research of the dye is very active at home and abroad, the industrial production of the dye is greatly increased each year, and the dye has very wide application prospect.
The 4-amino-1, 8-naphthalimide derivative is used as a typical representative of naphthalimide compounds, has excellent optical characteristics, and has many researches in the fields of fluorescent dyes and fluorescent molecular probes. In recent years, studies on the naphthalene amide-based dye have been reported many times, but there are few reports on the synthesis method thereof. The traditional synthetic route of the 4-amino-1, 8-naphthalimide derivative is to take acenaphthene as raw material and prepare the 4-amino-1, 8-naphthalimide derivative through four steps of reactions of nitration, oxidation, reduction and ammonification, wherein dilute nitric acid, acetic acid nitration, sodium dichromate and acetic acid oxidation are needed in the synthesis, the raw materials have environmental pollution and have stronger corrosiveness to equipment, and in addition, sodium azide is also used for preparing the 4-amino-1, 8-naphthalimide derivative by people, but azide compounds are easy to explode and are unsafe to operate.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of 4-amino-1, 8-naphthalimide derivatives, which avoids using raw materials polluting the environment, reduces corrosion to equipment, is safe to operate and improves the yield.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
technical scheme A:
a preparation method of a 4-amino-1, 8-naphthalimide derivative, which comprises a first-stage reaction, redissolution and a second-stage reaction;
the first stage reaction method is that 4-bromo-1, 8-naphthalimide derivative, benzophenone imine, BINAP, palladium acetate, metal alkali salt and organic solvent are added into a reaction vessel to react for 8-24 hours at 40-85 ℃;
the re-dissolving method comprises the steps of removing the organic solvent, and adding a proper amount of tetrahydrofuran for dissolving;
the second stage reaction method is that the 4-amino-1, 8-naphthalimide derivative is obtained by post-treatment separation after adding hydrochloric acid aqueous solution and stirring for 28-32 minutes.
The post-treatment separation method comprises the steps of adding saturated sodium bicarbonate aqueous solution to neutralize to be neutral after the second-stage reaction is finished, adopting an organic solvent to extract, collecting an organic phase, and obtaining the 4-amino-1, 8-naphthalimide derivative after drying and purifying by a chromatographic column.
The molar ratio of the 4-bromo-1, 8-naphthalimide derivative to the benzophenone imine is 1:1.2;
the molar ratio of the 4-bromo-1, 8-naphthalimide derivative to BINAP is 1:0.2;
the molar ratio of the 4-bromo-1, 8-naphthalimide derivative to palladium acetate is 1:0.2;
the molar ratio of the 4-bromo-1, 8-naphthalimide derivative to the metal base salt is 1:1.5;
the volume ratio of the benzophenone imine to the organic solvent is 1:49-52.
The metal alkali salt is one of cesium carbonate, potassium hydroxide, potassium phosphate and potassium carbonate; the organic solvent is one of dioxane, ethyl acetate, tetrahydrofuran, N-dimethylformamide, dichloromethane and toluene.
In the redissolution step, the volume ratio of tetrahydrofuran to benzophenone imine is 49-52:1.
in the second stage reaction, the concentration of the hydrochloric acid aqueous solution is 1.8-2.2M; the volume ratio of the hydrochloric acid aqueous solution to the benzophenone imine is 49-52:1, a step of; the stirring speed is 750-850r/min.
The structural general formula of the 4-bromo-1, 8-naphthalimide derivative is as follows
；
The 4-bromo-1, 8-naphthalimide derivative is 1a, 1b, 1c, 1d, 1e, 1f, 1g, 1h, 1i, 1j, 1k, 1l, 1m, 1n;
the structural formula of the 1a is as follows:
the structural formula of 1b is as follows:
the structural formula of 1c is as follows:
the structural formula of 1d is as follows:
the structural formula of 1e is as follows:
the structural formula of 1f is as follows:
the structural formula of 1g is as follows:
the structural formula of 1h is as follows:
the structural formula of 1i is as follows:
the structural formula of 1j is as follows:
the structural formula of 1k is as follows:
the structural formula of 1l is as follows:
the structural formula of 1m is as follows:
the structural formula of 1n is as follows:
。
the structural general formula of the 4-amino-1, 8-naphthalimide derivative is as follows
The yield of the 4-amino-1, 8-naphthalimide derivative prepared in the above scheme A is 50-98%.
The preferred technical scheme B is as follows:
on the basis of the technical scheme A, the metal alkali salt is one of cesium carbonate, potassium phosphate and potassium carbonate;
the yield of the 4-amino-1, 8-naphthalimide derivative prepared in the technical scheme B is 65-98%.
The preferred technical scheme C is as follows:
on the basis of the technical scheme A, the change is that: 1b is not included in the 4-bromo-1, 8-naphthalimide derivative; the metal alkali salt is cesium carbonate; the organic solvent is one of dioxane, ethyl acetate and dichloromethane; the reaction temperature of the first-stage reaction is 60-80 ℃;
the yield of the 4-amino-1, 8-naphthalimide derivative prepared in the technical scheme C is 80-98%.
The preferred technical scheme D is as follows:
on the basis of the technical scheme A, the change is that: the metal alkali salt is cesium carbonate; the organic solvent is dioxane; the reaction temperature of the first-stage reaction is 80 ℃; 1b is not contained in the 4-bromo-1, 8-naphthalimide derivative; namely, the 4-bromo-1, 8-naphthalimide derivatives are 1a, 1c, 1d, 1e, 1f, 1g, 1h, 1i, 1j, 1k, 1l, 1m, 1n.
The yield of the 4-amino-1, 8-naphthalimide derivative prepared in the above preferred embodiment D is 89-98%.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method is safe and simple in operation process, green and environment-friendly, high in final yield, cost-saving, wide in substrate application range, and the yield of the prepared 4-amino-1, 8-naphthalimide derivative is 50-98%, and the yield of the most preferable technical scheme can reach 89-98%.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Unless otherwise indicated, reagents, equipment, and methods employed in the present invention are those conventionally commercially available in the art, equipment, and methods conventionally employed.
Embodiment one:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 40 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in 65% yield.
Embodiment two:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 60 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in 87% yield.
Embodiment III:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in 98% yield.
Embodiment four:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), ethyl acetate (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL of dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in 85% yield.
Fifth embodiment:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), and tetrahydrofuran (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer 800 r/min for 30 min. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in 65% yield.
Example six:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), N-dimethylformamide (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in 65% yield.
Embodiment seven:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), and methylene chloride (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in 86% yield.
Example eight:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), toluene (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in 80% yield.
Example nine:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), potassium hydroxide (1.5 mmol,84.2 mg), and dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in 50% yield.
Example ten:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), potassium carbonate (1.5 mmol,207.3 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in 69% yield.
Example eleven:
to the pressure-resistant tube were added 1a (1.0 mmol,318.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), potassium phosphate (1.5 mmol,318.4 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3a in a yield of 72%.
The yellow powders 3a prepared in examples one to eleven were mixed in equal mass ratio, 1HNMR
The data for 13C NMR are as follows:
1HNMR (400 MHz, DMSO) δ 8.61 (d, J = 8.3 Hz, 1H), 8.43 (d, J = 7.2 Hz, 1H), 8.19 (d, J = 8.4 Hz, 1H), 7.65 (t, J = 7.8 Hz, 1H), 7.45 (s, 2H), 6.84 (d, J = 8.4 Hz, 1H), 4.04 – 3.89 (m, 2H), 1.67 – 1.54 (m, 2H), 0.90 (t, J = 7.4 Hz, 3H)；13C NMR (101 MHz, DMSO) δ 164.24 (s), 163.48 (s), 153.13 (s), 134.38 (s), 131.42 (s), 131.26 – 130.41 (m), 129.90 (d, J = 45.6 Hz), 124.40 (s), 122.22 (s), 119.82 (s), 108.60 (s), 108.02 (s), 41.17 (s), 21.44 (s), 11.86 (s)。
embodiment twelve:
to the pressure-resistant tube were added 1b (1.0 mmol,320.1 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the reaction is completed, the mixture is rotatedThe organic solvent was removed at 50deg.C by evaporation, dissolved in tetrahydrofuran (10 mL), and then stirred with aqueous hydrochloric acid (2M, 10 mL) for 30 min using a magnetic stirrer 800 r/min. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3b in 80% yield. 1 H NMR (400 MHz, DMSO) δ 8.61 (d, J = 8.3 Hz, 1H), 8.42 (d, J = 7.1 Hz, 1H), 8.19 (d, J = 8.3 Hz, 1H), 7.76 – 7.57 (m, 1H), 7.44 (s, 2H), 6.84 (d, J = 8.3 Hz, 1H), 4.79 (t, J = 5.7 Hz, 1H), 4.20 – 4.04 (m, 2H), 3.61 – 3.52 (m, 2H)； 13 C NMR (101 MHz, DMSO) δ 164.40 (s), 163.51 (s), 153.12 (s), 134.37 (s), 131.43 (s), 130.21 (s), 129.72 (s), 124.42 (s), 122.36 (s), 119.84 (s), 108.52 (s), 108.13 (s), 58.46 (s), 41.82 (s)。
Embodiment thirteen:
to the pressure-resistant tube were added 1c (1.0 mmol,304.1 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3c in 90% yield. 1 H NMR (400 MHz, DMSO) δ 8.61 (d, J = 8.3 Hz, 1H), 8.43 (d, J = 7.2 Hz, 1H), 8.20 (d, J = 8.4 Hz, 1H), 7.65 (t, J = 7.8 Hz, 1H), 7.45 (s, 2H), 6.84 (d, J = 8.4 Hz, 1H), 4.05 (q, J = 7.0 Hz, 2H), 1.18 (t, J = 7.0 Hz, 3H); 13 C NMR (101 MHz, DMSO) δ 164.02 (s), 163.16 (s), 153.13 (s), 134.34 (s), 131.38 (s), 130.20 (s), 129.62 (s), 124.40 (s), 122.27 (s), 119.81 (s), 108.60 (s), 108.04 (s), 34.75 (s), 13.77 (s)。
Fourteen examples:
to the pressure-resistant tube were added 1d (1.0 mmol,419.3 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain a yellow powder 3d in 98% yield. 1 H NMR (400 MHz, DMSO) δ 8.60 (d, J = 8.3 Hz, 1H), 8.43 (t, J = 10.8 Hz, 1H), 8.18 (d, J = 8.3 Hz, 1H), 7.65 (t, J = 7.8 Hz, 1H), 7.41 (s, 2H), 6.84 (d, J = 8.5 Hz, 2H), 4.09 (t, J = 5.4 Hz, 2H), 3.26 – 3.14 (m, 2H), 1.22 (d, J = 31.2 Hz, 9H).; 13 C NMR (101 MHz, DMSO) δ 164.46 (s), 163.57 (s), 156.18 (s), 153.10 (s), 137.38 – 134.48 (m), 132.77 (d, J = 298.9 Hz), 130.30 (s), 129.60 (s), 126.40 – 125.38 (m), 123.42 (d, J = 183.2 Hz), 119.83 (s), 108.41 (d, J = 18.5 Hz), 77.86 (s), 38.51 (s), 28.59 (s), 24.79 (s)。
Example fifteen:
to the pressure-resistant tube were added 1e (1.0 mmol,332.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3e in 90% yield. 1 H NMR (400 MHz, DMSO) δ 8.61 (d, J = 8.3 Hz, 1H), 8.43 (d, J = 7.2 Hz, 1H), 8.19 (d, J = 8.4 Hz, 1H), 7.65 (t, J = 7.8 Hz, 1H), 7.45 (s, 2H), 6.84 (d, J = 8.4 Hz, 1H), 4.02 (dt, J = 14.5, 7.2 Hz, 2H), 1.68 – 1.45 (m, 1H), 1.33 (dq, J = 14.6, 7.3 Hz, 2H), 0.97 – 0.87 (m, 3H).; 13 C NMR (101 MHz, DMSO) δ 164.12 (s), 163.36 (s), 153.14 (s), 134.38 (s), 131.42 (s), 130.79 – 130.21 (m), 129.93 (d, J = 39.7 Hz), 124.41 (s), 122.25 (s), 119.83 (s), 108.61 (s), 107.98 (s), 39.35 (s), 30.30 (s), 20.30 (s), 14.21 (s)。
Example sixteen:
to the pressure-resistant tube were added 1f (1.0 mmol,332.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, and the organic phase was collected and driedFinally, the mixture solvent of ethyl acetate and petroleum ether 1/2 is used for chromatographic column purification to obtain yellow powder 3f, and the yield is 96%. 1 H NMR (400 MHz, DMSO) δ 8.62 (d, J = 8.3 Hz, 1H), 8.44 (t, J = 6.9 Hz, 1H), 8.20 (d, J = 8.4 Hz, 1H), 7.66 (t, J = 7.8 Hz, 1H), 7.45 (s, 2H), 6.85 (d, J = 8.4 Hz, 1H), 3.87 (d, J = 7.3 Hz, 2H), 2.16 – 2.05 (m, 1H), 0.88 (d, J = 6.7 Hz, 6H); 13 C NMR (101 MHz, DMSO) δ 164.52 (s), 163.65 (s), 153.10 (s), 134.44 (s), 131.49 (s), 130.17 (s), 129.69 (s), 124.40 (s), 122.21 (s), 119.81 (s), 108.61 (s), 108.00 (s), 46.46 (s), 27.32 (s), 20.63 (s)。
Example seventeenth:
to the pressure-resistant tube were added 1g (1.0 mmol,352.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by column chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain 3g of yellow powder in 95% yield. 1 H NMR (400 MHz, DMSO) δ 8.66 (d, J = 8.3 Hz, 1H), 8.43 (d, J = 7.2 Hz, 1H), 8.20 (d, J = 8.4 Hz, 1H), 7.68 (t, J = 7.8 Hz, 1H), 7.53 – 7.40 (m, 5H), 7.30 (d, J = 7.5 Hz, 2H), 6.88 (d, J = 8.4 Hz, 1H); 13 C NMR (101 MHz, DMSO) δ 164.51 (s), 163.64 (s), 153.31 (s), 137.09 (s), 134.46 (s), 131.60 (s), 130.67 (s), 129.95 (s), 129.69 (s), 129.20 (s), 128.28 (s), 124.49 (s), 122.69 (s), 119.97 (s), 108.69 (s), 108.29 (s)。
Example eighteenth:
to the pressure-resistant tube were added 1h (1.0 mmol,366.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain a yellow powder for 3 hours in 96% yield. 1 H NMR (400 MHz, DMSO) δ 8.64 (d, J = 8.2 Hz, 1H), 8.45 (d, J = 7.0 Hz, 1H), 8.22 (d, J = 8.4 Hz, 1H), 7.67 (t, J = 7.8 Hz, 1H), 7.51 (s, 2H), 7.30 (dt, J = 15.0, 7.3 Hz, 4H), 7.22 (t, J = 6.9 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 5.22 (s, 2H); 13 C NMR (101 MHz, DMSO) δ 164.30 (s), 163.36 (s), 153.41 (s), 138.47 (s), 134.66 (s), 131.71 (s), 130.27 (s), 129.99 (s), 128.74 (s), 127.96 (s), 127.32 (s), 124.48 (s), 122.11 (s), 119.86 (s), 108.74 (s), 107.79 (s), 42.91 (s)。
Example nineteenth:
to the pressure-resistant tube were added 1i (1.0 mmol,473.3 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. Removing organic solvent at 50deg.C by rotary evaporator, adding tetrahydrofuran (10 mL) for dissolving, and adding hydrochloric acid for dissolvingThe solution (2M, 10 mL) was stirred with a magnetic stirrer 800 r/min for 30 min. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3i in 98% yield. 1 H NMR (400 MHz, DMSO) δ 8.61 (d, J = 8.3 Hz, 1H), 8.38 (d, J = 7.2 Hz, 1H), 8.15 (d, J = 8.4 Hz, 1H), 7.75 – 7.53 (m, 4H), 7.45 (s, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.83 (d, J = 8.4 Hz, 1H), 4.13 – 3.99 (m, 2H), 3.03 (dd, J = 12.9, 6.4 Hz, 2H), 2.27 (s, 3H); 13 C NMR (101 MHz, DMSO) δ 164.33 (s), 163.39 (s), 153.11 (s), 142.88 (s), 138.01 (s), 134.39 (s), 131.42 (s), 130.26 (s), 129.81 (d, J = 17.5 Hz), 126.82 (s), 124.39 (s), 122.24 (s), 119.77 (s), 108.56 (s), 108.01 (s), 21.32 (s)。
Example twenty:
to the pressure-resistant tube were added 1j (1.0 mmol,389.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3j in 92% yield. 1 H NMR (400 MHz, DMSO) δ 8.62 (d, J = 8.3 Hz, 1H), 8.43 (d, J = 7.2 Hz, 1H), 8.19 (d, J = 8.4 Hz, 1H), 7.66 (t, J = 7.8 Hz, 1H), 7.47 (s, 2H), 6.84 (d, J = 8.4 Hz, 1H), 4.13 (dt, J = 12.3, 6.1 Hz, 2H), 3.60 – 3.49 (m, 4H), 2.57 – 2.52 (m, 2H), 2.45 (s, 4H); 13 C NMR (101 MHz, DMSO) δ 164.23 (s), 163.41 (s), 153.20 (s), 134.48 (s), 131.48 (s), 130.17 (s), 129.79 (s), 124.44 (s), 122.20 (s), 119.82 (s), 108.63 (s), 107.95 (s), 66.59 (s), 56.28 (s), 53.89 (s)。
Example twenty-one:
to the pressure-resistant tube were added 1k (1.0 mmol,348.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3k in 89% yield. 1 H NMR (400 MHz, DMSO) δ 8.61 (d, J = 8.3 Hz, 1H), 8.43 (d, J = 7.2 Hz, 1H), 8.19 (d, J = 8.3 Hz, 1H), 7.65 (t, J = 7.8 Hz, 1H), 7.45 (s, 2H), 6.84 (d, J = 8.3 Hz, 1H), 4.07 (t, J = 7.0 Hz, 2H), 3.40 (t, J = 6.2 Hz, 2H), 3.22 (d, J = 2.6 Hz, 3H), 1.90 – 1.77 (m, 2H); 13 C NMR (101 MHz, DMSO) δ 164.25 (s), 163.37 (s), 153.12 (s), 134.35 (s), 131.39 (s), 130.13 (s), 129.69 (s), 124.38 (s), 122.25 (s), 119.82 (s), 108.60 (s), 108.08 (s), 70.55 (s), 58.28 (s), 37.42 (s), 28.38 (s)。
Example twenty two:
1l (1)0 mmol,360.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain 3l of yellow powder in 90% yield. 1 H NMR (400 MHz, DMSO) δ 8.60 (d, J = 8.2 Hz, 1H), 8.42 (d, J = 7.1 Hz, 1H), 8.19 (d, J = 8.3 Hz, 1H), 7.73 – 7.56 (m, 1H), 7.45 (s, 2H), 6.84 (d, J = 8.3 Hz, 1H), 5.15 (t, J = 11.6 Hz, 1H), 3.97 (d, J = 8.2 Hz, 2H), 3.46 – 3.38 (m, 2H), 2.74 (dt, J = 20.3, 10.0 Hz, 2H), 1.52 (d, J = 11.3 Hz, 2H); 13 C NMR (101 MHz, DMSO) δ 164.68 (s), 163.80 (s), 153.01 (s), 134.50 (s), 131.48 (s), 130.17 (s), 129.64 (s), 124.42 (s), 122.65 (s), 119.64 (s), 108.67 (s), 108.23 (s), 67.79 (s), 49.74 (s), 29.31 (s)。
Example twenty-three:
to the pressure-resistant tube were added 1m (1.0 mmol,353.2 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). 16. 16h were stirred at 80 ℃. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, it was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally extracted with ethyl acetate and petroleum ether 1/2The mixed solvent is purified by a chromatographic column to obtain yellow powder with the yield of 3m and 93 percent. 1 H NMR (400 MHz, DMSO) δ 8.49 (d, J = 8.3 Hz, 1H), 8.35 (d, J = 4.3 Hz, 1H), 8.29 (d, J = 7.2 Hz, 1H), 8.06 (d, J = 8.4 Hz, 1H), 7.61 – 7.49 (m, 2H), 7.33 (s, 2H), 7.16 (d, J = 7.7 Hz, 1H), 7.09 (dd, J = 6.9, 5.3 Hz, 1H), 6.72 (d, J = 8.4 Hz, 1H), 4.24 (dd, J = 16.8, 9.2 Hz, 2H), 2.98 – 2.87 (m, 2H); 13 C NMR (101 MHz, DMSO) δ 164.17 (s), 163.28 (s), 159.34 (s), 153.15 (s), 149.39 (s), 136.98 (s), 134.37 (s), 131.43 (s), 130.12 (s), 129.73 (s), 124.42 (s), 123.58 (s), 122.11 (d, J = 13.0 Hz), 119.80 (s), 108.64 (s), 108.01 (s), 39.55 (s), 36.24 (s)。
Example twenty-four:
to the pressure-resistant tube were added 1n (1.0 mmol,452.3 mg), 2 (1.2 mmol,0.20 mL), palladium acetate (0.2 mmol,45.0 mg), BINAP (0.2 mmol,124.5 mg), cesium carbonate (1.5 mmol,489.7 mg), dioxane (10 mL). Stirred at 80℃for 16h. After the completion of the reaction, the organic solvent was removed by a rotary evaporator at 50℃and dissolved in tetrahydrofuran (10 mL), and then an aqueous hydrochloric acid solution (2M, 10 mL) was added thereto and stirred with a magnetic stirrer at 800 r/min for 30 minutes. After the reaction, the mixture was neutralized to ph=7 with saturated aqueous sodium bicarbonate, extracted with 50mL dichloromethane, the organic phase was collected, dried, and finally purified by chromatography using a mixed solvent of ethyl acetate and petroleum ether 1/2 to obtain yellow powder 3n in 91% yield. 1 H NMR (400 MHz, DMSO) δ 8.72 (d, J = 8.2 Hz, 1H), 8.42 (d, J = 7.2 Hz, 1H), 8.18 (d, J = 8.4 Hz, 1H), 7.64 (d, J = 11.9 Hz, 3H), 6.89 (d, J = 8.4 Hz, 1H), 4.68 (t, J = 5.3 Hz, 1H), 4.21 (t, J = 6.1 Hz, 2H), 3.60 (dd, J = 20.1, 13.9 Hz, 5H), 3.46 (s, 7H), 3.37 (d, J = 5.0 Hz, 2H); 13 C NMR (101 MHz, DMSO) δ 164.32 (s), 163.36 (s), 153.45 (s), 134.46 (s), 131.52 (s), 130.19 (d, J = 8.2 Hz), 124.35 (s), 122.06 (s), 119.83 (s), 108.64 (s), 107.65 (s), 72.73 (s), 70.12 (dd, J = 10.8, 8.5 Hz), 67.59 (s), 60.57 (s), 38.74 (s)。

Claims (6)

1. A preparation method of a 4-amino-1, 8-naphthalimide derivative is characterized by comprising the following steps of: the preparation method comprises a first-stage reaction, redissolution and a second-stage reaction;
the first stage reaction method is that 4-bromo-1, 8-naphthalimide derivative, benzophenone imine, BINAP, palladium acetate, metal alkali salt and organic solvent are added into a reaction vessel to react for 8-24 hours at 40-85 ℃;
the metal alkali salt is one of cesium carbonate, potassium hydroxide, potassium phosphate and potassium carbonate;
the re-dissolving method comprises the steps of removing the organic solvent, and adding a proper amount of tetrahydrofuran for dissolving;
the second stage reaction method is that hydrochloric acid aqueous solution is added and stirred for 28-32 minutes, and then 4-amino-1, 8-naphthalimide derivative is obtained through post-treatment separation;
the 4-bromo-1, 8-naphthalimide derivative is 1a, 1b, 1c, 1d, 1e, 1f, 1g, 1h, 1i, 1j, 1k, 1l, 1m, 1n;
the structural formula of the 1a is as follows:
；
the structural formula of 1b is as follows:
；
the structural formula of 1c is as follows:
；
the structural formula of 1d is as follows:
；
the structural formula of 1e is as follows:
；
the structural formula of 1f is as follows:
；
the structural formula of 1g is as follows:
；
the structural formula of 1h is as follows:
；
the structural formula of 1i is as follows:
；
the structural formula of 1j is as follows:
；
the structural formula of 1k is as follows:
；
the structural formula of 1l is as follows:
；
the structural formula of 1m is as follows:
；
the structural formula of 1n is as follows:
。
2. the method for producing a 4-amino-1, 8-naphthalimide derivative according to claim 1, wherein: the molar ratio of the 4-bromo-1, 8-naphthalimide derivative to the benzophenone imine is 1:1.2; the molar ratio of the 4-bromo-1, 8-naphthalimide derivative to BINAP is 1:0.2; the molar ratio of the 4-bromo-1, 8-naphthalimide derivative to palladium acetate is 1:0.2; the molar ratio of the 4-bromo-1, 8-naphthalimide derivative to the metal base salt is 1:1.5; the volume ratio of the benzophenone imine to the organic solvent is 1:49-52.
3. The method for producing a 4-amino-1, 8-naphthalimide derivative according to claim 1, wherein: the organic solvent is one of dioxane, ethyl acetate, tetrahydrofuran, N-dimethylformamide, dichloromethane and toluene.
4. The method for producing a 4-amino-1, 8-naphthalimide derivative according to claim 1, wherein: in the redissolution step, the volume ratio of tetrahydrofuran to benzophenone imine is 49-52:1.
5. the method for producing a 4-amino-1, 8-naphthalimide derivative according to claim 1, wherein: in the second stage reaction, the concentration of the hydrochloric acid aqueous solution is 1.8-2.2M; the volume ratio of the hydrochloric acid aqueous solution to the benzophenone imine is 49-52:1, a step of; the stirring speed is 750-850r/min.
6. The method for producing a 4-amino-1, 8-naphthalimide derivative according to claim 1, wherein: the post-treatment separation method comprises the steps of adding saturated sodium bicarbonate aqueous solution to neutralize to be neutral after the second-stage reaction is finished, adopting an organic solvent to extract, collecting an organic phase, and obtaining the 4-amino-1, 8-naphthalimide derivative after drying and purifying by a chromatographic column.
CN202211246750.8A 2022-10-12 2022-10-12 Preparation method of 4-amino-1, 8-naphthalimide derivative Active CN115521256B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211246750.8A CN115521256B (en) 2022-10-12 2022-10-12 Preparation method of 4-amino-1, 8-naphthalimide derivative

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211246750.8A CN115521256B (en) 2022-10-12 2022-10-12 Preparation method of 4-amino-1, 8-naphthalimide derivative

Publications (2)

Publication Number Publication Date
CN115521256A CN115521256A (en) 2022-12-27
CN115521256B true CN115521256B (en) 2024-03-08

Family

ID=84701035

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211246750.8A Active CN115521256B (en) 2022-10-12 2022-10-12 Preparation method of 4-amino-1, 8-naphthalimide derivative

Country Status (1)

Country Link
CN (1) CN115521256B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110066246A (en) * 2019-06-05 2019-07-30 哈尔滨工业大学 A method of preparing isoquinoline-1-ketone derivative
CN110183380A (en) * 2019-06-26 2019-08-30 青岛大学 A kind of synthetic method and application of 4- hydroxyl -1,8- naphthalimide derivative
CN110669005A (en) * 2019-07-09 2020-01-10 济南大学 Fluorescent probe for detecting cysteine
CN114456114A (en) * 2021-12-22 2022-05-10 青海师范大学 Naphthalene diimide fluorescent chemical sensor based on ICT and PET dual mechanisms and synthetic method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110066246A (en) * 2019-06-05 2019-07-30 哈尔滨工业大学 A method of preparing isoquinoline-1-ketone derivative
CN110183380A (en) * 2019-06-26 2019-08-30 青岛大学 A kind of synthetic method and application of 4- hydroxyl -1,8- naphthalimide derivative
CN110669005A (en) * 2019-07-09 2020-01-10 济南大学 Fluorescent probe for detecting cysteine
CN114456114A (en) * 2021-12-22 2022-05-10 青海师范大学 Naphthalene diimide fluorescent chemical sensor based on ICT and PET dual mechanisms and synthetic method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Xin Chen,等.Ambipolar charge-transport property for the D–A complex with naphthalene diimide motif.《J. Mater. Chem. C》.2014,第2卷2869–2876. *

Also Published As

Publication number Publication date
CN115521256A (en) 2022-12-27

Similar Documents

Publication Publication Date Title
CN110283586B (en) Near-infrared fluorescent dye and preparation method thereof
CN115521256B (en) Preparation method of 4-amino-1, 8-naphthalimide derivative
CN112920184B (en) Method for preparing moxifloxacin intermediate (S, S) -2, 8-diazabicyclo [4,3,0] nonane
CN112358443B (en) Pyridine compound and preparation method thereof
CN111471046B (en) Carbazole indole quinone derivative and preparation method and application thereof
CN112679498A (en) Sulfonic acid quaternary ammonium salt compound and preparation method and application thereof
CN109320468B (en) Method for mild preparation of benzo [ a ] phenazine compound
CN109020864B (en) Application of metal hydride/palladium compound catalytic reduction system in reduction of alkenyl active methylene compound and reduction method
CN114044767B (en) Fluorescent probe for detecting cyanide ions and preparation method and application thereof
CN113248356B (en) Industrial production method of 4-hydroxy-1-indanone
US3344189A (en) Amino-fluorene-compounds and process for the preparation thereof
CN112047896A (en) Method for synthesizing aromatic ring group or aromatic heterocyclic group tetrazole
CN116332845B (en) Dialkylamine substituted naphthalimide dye in supercritical CO2In (a) synthesis and dyeing method
CN114456141B (en) Synthesis method of aldehyde-substituted chromene derivative
CN116589475B (en) Preparation method of 2',4',5',7' -tetrachloro-5 (6) -carboxyl-4, 7-dichloro fluorescein
CN115745965B (en) Fluorescent molecule and preparation method and application thereof
CN109851567B (en) Pyrazine compound and application thereof
CN113816912B (en) Preparation method of phenazine
CN114621070B (en) Synthesis method of 3, 4-dihydronaphthalene-1 (2H) -one derivative
CN114262293B (en) Preparation method of 2-amino-3-bromopyridine
CN108865113B (en) For detecting Fe3+、Co2+Naphthaldehyde-dipyrrole boron fluorine fluorescent molecular probe and preparation method thereof
CN116606238A (en) N-Boc-3-nitroindole and preparation method thereof
CN116606186A (en) Aromatic nitro compound and preparation method thereof
CN116693517A (en) Metal organic cage compound and preparation method and application thereof
CN108239099A (en) Compound and its preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant