CN116903650A - Boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon and synthesis method thereof - Google Patents
Boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon and synthesis method thereof Download PDFInfo
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 32
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 8
- 238000005893 bromination reaction Methods 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 238000003786 synthesis reaction Methods 0.000 claims description 33
- 230000015572 biosynthetic process Effects 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 26
- 239000012043 crude product Substances 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 26
- 229940125782 compound 2 Drugs 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 18
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- 241000209094 Oryza Species 0.000 claims description 10
- 235000007164 Oryza sativa Nutrition 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 235000009566 rice Nutrition 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 9
- 238000005885 boration reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- HVQSEKGARNNWON-UHFFFAOYSA-N boric acid pyrene Chemical class OB(O)O.c1cc2ccc3cccc4ccc(c1)c2c34 HVQSEKGARNNWON-UHFFFAOYSA-N 0.000 claims description 3
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000004440 column chromatography Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 2
- -1 boron nitride compound Chemical class 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- NCQDQONETMHUMY-UHFFFAOYSA-N dichloro(phenyl)borane Chemical compound ClB(Cl)C1=CC=CC=C1 NCQDQONETMHUMY-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- QHADMMAFBAZFTE-UHFFFAOYSA-N naphtho[2,1,8-def]quinoline Chemical compound C1=CN=C2C=CC3=CC=CC4=CC=C1C2=C43 QHADMMAFBAZFTE-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- MWEKPLLMFXIZOC-UHFFFAOYSA-N pyren-1-ylboronic acid Chemical compound C1=C2C(B(O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 MWEKPLLMFXIZOC-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/658—Organoboranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides conjugated polycyclic aromatic hydrocarbon related to boron-nitrogen doped naphthalene fused pyrene and a synthesis method thereof, and tests the photoelectric physical properties of the compounds. The structural formula of the compounds isThe invention takes commercially available 2-naphthylamine as a starting material, and synthesizes a target product through a series of reactions such as bromination, suzuki coupling, electrophilic boronation and the like. The synthesis method has the characteristics of simple operation, short reaction route, mild reaction conditions and the like.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and in particular relates to boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon and a synthesis method thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Pyrene is a planar aromatic condensed ring formed by four condensed benzene rings, and is widely applied to the research of fluorescence and organic semiconductor materials as a flexible chemical synthon, wherein the condensed ring is a chemical active site for simultaneously giving electrons and withdrawing electrons, has good molecular planarity, is conjugated in a molecule, is stacked in a pi-pi manner between molecules and has high fluorescence quantum efficiency.
With the intensive research in the field of boron nitride chemistry, researchers find that introducing boron nitride units into the molecular skeleton of polycyclic aromatic hydrocarbon can not only effectively improve the photoelectric properties of molecules, but also provide additional intermolecular interaction force, so that the boron nitride compound has a unique solid-state stacking structure, and further excellent charge transport capacity is obtained. In recent years, precise synthesis with functions as guiding is gradually developed in the field of boron nitride chemistry, and the boron aza-polycyclic aromatic hydrocarbon has good photoelectric characteristics and huge application prospect in the aspect of organic electronic devices.
In 1960, dewar et al used a bis-amino-site electrophilic boration reaction starting from a raw material of biphenyldiamine, and used phenyl boron chloride as a boron source to undergo electrophilic boration under the catalytic action of aluminum trichloride, to successfully obtain bis-borazine pyrene.
In 2007, piers et al succeeded in synthesizing boron-nitrogen embedded boron-nitrogen heteropyrene based on boron-nitrogen embedded boron-nitrogen heterophenanthrene. They first reacted with an orthoalkynyl pyridine using borandihexenes to form an intermediate containing a borazine bond that can be rapidly converted to a homolog of borazine by cycloisomerisation of the alkyne, and finally a second cyclisation to form borazine-embedded borazine via platinum dichloride catalysis.
In 2015, wang et al successfully synthesized diboron azapyrene using photothermal elimination. They first activated the nitrogen on pyridine with n-butyllithium to make it positively charged, then added with dimidiate boron fluoride to form four coordinated boron nitrogen compound, finally irradiated with light of 300nm wavelength, and the boron is stripped of one rice group to obtain the final product.
With the intensive research of borazine polycyclic aromatic hydrocarbon, the application thereof starts to show an expanding trend. In 2016, liu et al developed a series of polymeric electron acceptors containing boron and nitrogen units that exhibited higher electron mobility and greatly improved the performance of organic photovoltaic cell devices. Zhang et al successfully designed and synthesized polycyclic aromatic hydrocarbons with single boron nitrogen saw tooth edges, had excellent optical properties, and fluorescence quantum yields of up to 0.49, and demonstrated a strong potential for application in the OLED field.
However, in the industry, there is no conjugated polycyclic aromatic hydrocarbon of boron-nitrogen doped naphthalene fused pyrene with better absorption and emission capability for specific wave bands.
Disclosure of Invention
In order to solve the problems, the invention provides conjugated polycyclic aromatic hydrocarbon of boron-nitrogen doped naphthalene fused pyrene and researches the photoelectric property of the conjugated polycyclic aromatic hydrocarbon. The boron-nitrogen doped polycyclic aromatic hydrocarbon synthesized by the method has excellent photoelectric properties, and provides more schemes for obtaining more efficient organic photoelectric materials.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect of the invention, there is provided a boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon, which is one of the following compounds:
。
researches show that the introduction of boron nitrogen units into the conjugated framework is a feasible strategy for obtaining a stable functional material with excellent photoelectric properties, and the electron body replacement strategy can be widely applied to the research and development of other novel materials, and the related properties of organic electronic devices are greatly improved.
Therefore, due to the excellent photoelectric property and application potential of the boron-nitrogen doped polycyclic aromatic hydrocarbon, the invention synthesizes the conjugated polycyclic aromatic hydrocarbon of the boron-nitrogen doped naphthalene fused pyrene and discovers that the conjugated polycyclic aromatic hydrocarbon has the excellent photoelectric property.
The invention also provides a method for synthesizing the boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon, which comprises the following steps:
synthesis of compounds of formula 1: 2-naphthylamine is subjected to bromination reaction to generate a compound 2; carrying out Suzuki coupling reaction on the compound 2 and 1-pyrene boric acid to generate a compound 3-1; performing electrophilic boration reaction on the compound 3-1 to generate a compound shown in the formula 1, thus obtaining the compound;
the synthetic route for the compounds of formula 1 is as follows:
；
synthesis of compounds of formula 2: 2-naphthylamine is subjected to bromination reaction to generate a compound 2, the compound 2 and 2-pyrene boric acid ester are subjected to Suzuki coupling reaction to generate a compound 3-2, and the compound 3-2 is subjected to electrophilic boration reaction to generate a compound of formula 2, so that the compound is obtained;
the synthetic route for the compounds of formula 2 is as follows:
；
synthesis of compounds of formula 3: 2-naphthylamine is subjected to bromination reaction to generate a compound 2, the compound 2 is subjected to alkylation reaction to generate a compound 3-3, the compound 3-3 is subjected to Suzuki coupling reaction to generate a compound 4-3, and the compound 4-3 is subjected to electrophilic boration reaction to generate a compound of formula 3;
the synthetic route for the compounds of formula 3 is as follows:
。
in some embodiments, the synthesis of compound 2 specifically comprises: 2-naphthylamine and N-bromosuccinimide are added into DMF for dissolution, reaction is carried out at room temperature, after the reaction is finished, the reaction is quenched by sodium hydroxide solution, dichloromethane extraction is carried out, anhydrous magnesium sulfate is dried, and the organic solvent is removed by filtration and spin drying, thus obtaining the crude product.
In some embodiments, the synthesis of compound 3-1 specifically includes: adding the weighed compound 2 and 1-pyrene boric acid into the dried Schlenk, adding toluene for dissolution, adding catalyst tetra-triphenylphosphine palladium and potassium carbonate solution, and reacting for 16h at 120 ℃ under the protection of nitrogen; after the reaction, the mixture is quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and dried to remove the organic solvent, thus obtaining a crude product.
In some embodiments, the synthesis of the compound of formula 1 specifically comprises: adding a compound 3-1 into the dried Schlenk, dissolving with o-dichlorobenzene, adding boron tribromide, and reacting for 24 hours at 180 ℃ under the protection of nitrogen; after the reaction is finished, cooling to room temperature, adding a rice-based format reagent, and reacting for 6 hours at room temperature; after the reaction, saturated brine, dichloromethane extraction, anhydrous magnesium sulfate drying, and filtration and spin-drying are carried out to remove the organic solvent, thus obtaining a crude product.
In some embodiments, the synthesis of compound 3-2 specifically includes: adding the weighed compound 2 and 2-pyrene borate into the dried Schlenk, adding toluene for dissolution, adding catalyst tetra-triphenylphosphine palladium and potassium carbonate solution, and reacting for 16h at 120 ℃ under the protection of nitrogen; after the reaction, the mixture is quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and dried to remove the organic solvent, thus obtaining a crude product.
In some embodiments, the synthesis of the compound of formula 2 specifically includes: adding a compound 3-2 into the dried Schlenk, dissolving with o-dichlorobenzene, adding boron tribromide, and reacting for 24 hours at 180 ℃ under the protection of nitrogen; after the reaction is finished, cooling to room temperature, adding a rice-based format reagent, and reacting for 6 hours at room temperature; after the reaction, saturated brine, dichloromethane extraction, anhydrous magnesium sulfate drying, and filtration and spin-drying are carried out to remove the organic solvent, thus obtaining a crude product.
In some embodiments, the synthesis of compound 3-3 specifically includes: dissolving the compound 2 and iodobutane in DMF, adding potassium hydroxide, and stirring at room temperature for 24 hours; after the reaction, the mixture is quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and dried to remove the organic solvent, thus obtaining a crude product.
In some embodiments, the synthesis of compound 4-3 specifically includes: adding a compound 3-3 and disubstituted pyrene borate into dry Schlenk, dissolving with toluene, adding a catalyst of tetraphenylphosphine palladium and potassium carbonate solution, and reacting for 16h at 120 ℃ under the protection of nitrogen; after the reaction, the mixture is quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and dried to remove the organic solvent, thus obtaining a crude product.
In some embodiments, the synthesis of the compound of formula 3 specifically includes: adding a compound 4-3 into the dried Schlenk, dissolving with o-dichlorobenzene, adding boron tribromide, and reacting for 48 hours at 180 ℃ under the protection of nitrogen; after the reaction is finished, cooling to room temperature, adding a rice-based format reagent, and reacting at room temperature for 12 hours; after the reaction, saturated brine, dichloromethane extraction, anhydrous magnesium sulfate drying, and filtration and spin-drying are carried out to remove the organic solvent, thus obtaining a crude product.
The beneficial effects of the invention are that
(1) The invention synthesizes the conjugated polycyclic aromatic hydrocarbon of the boron-nitrogen doped naphthalene fused pyrene and explores the photoelectric property of the conjugated polycyclic aromatic hydrocarbon. The results show that: the boron-nitrogen doped polycyclic aromatic hydrocarbon synthesized by the method has excellent photoelectric properties and has application potential in serving as an organic photoelectric material.
(2) The invention takes commercially available 2-naphthylamine as a starting material, and synthesizes a target product through a series of reactions such as bromination, suzuki coupling, electrophilic boronation and the like. The synthesis method has the characteristics of simple operation, short reaction route, mild reaction conditions and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is an absorption spectrum of a compound of formula 1 of the present invention.
FIG. 2 is an emission spectrum of the compound of formula 1 of the present invention.
FIG. 3 shows 1H-NMR of a compound of formula 1 according to the present invention.
FIG. 4 is 1H-NMR of a compound of formula 2 according to the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
Example 1
The overall synthesis method, synthesis route and specific synthesis method of conjugated polycyclic aromatic hydrocarbon (formula 1) of boron-nitrogen doped naphthalene fused pyrene:
the above compounds are exemplified by the following:
1) Synthesis of Compound 2: in a dry 100ml round bottom flask, 2-naphthylamine (7195 mg,5mmol,1.00 eq) and N-bromosuccinimide (934 mg,5.25mmol,1.05 eq) were added, dissolved in 10ml DMF and stirred at room temperature for three hours. After the reaction, the reaction was quenched with sodium hydroxide solution, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the organic solvent was removed by filtration and spin-drying. The crude product was separated by column chromatography to give compound 2.
2) Synthesis of Compound 3-1: to 100ml of Schlenk, which was dried, weighed amounts of compound 2 (200 mg,0.9mmol,1.00 eq) and 1-pyrenylboronic acid (332 mg,1.35mmol,1.50 eq), 3ml of toluene were dissolved, and catalyst tetra triphenylphosphine palladium (52 mg,0.045mmol,0.05 and,) and 2ml of potassium carbonate solution (5M) were added and reacted at 120℃for 16h under nitrogen. After the reaction, the reaction was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the organic solvent was removed by filtration and spin-drying. The crude product is separated by column chromatography to obtain the compound 3-1.
3) Synthesis of compounds of formula 1: in dry Schlenk, weighed amount of Compound 3 (345 mg,1.0mmol,1.00 eq), 5ml of o-dichlorobenzene was dissolved, and boron tribromide (375 mg,1.5mmol,1.5 eq) was added and reacted at 180℃for 24h under nitrogen. After the reaction was completed, the reaction mixture was cooled to room temperature, 4.5ml of a rice-based format reagent (1M) was added, and the reaction mixture was reacted at room temperature for 6 hours. After the completion of the reaction, saturated brine was added, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the organic solvent was removed by spin-drying. The crude product is separated by column chromatography to obtain the compound of formula 1.
The compound of the formula 1 is characterized and tested for photoelectric performance, the absorption spectrum is shown in figure 1, the emission spectrum is shown in figure 2, the compound has good absorption performance for light in the 300-500 nm range, and the emission wavelength is 500-700 nm. The 1H-NMR is shown in FIG. 3.
Example 2
The synthesis method of the conjugated polycyclic aromatic hydrocarbon (formula 2) of the boron-nitrogen doped naphthalene fused pyrene comprises the following synthesis route:
1) Synthesis of Compound 2: in a dry round bottom flask, weighed 2-naphthylamine and N-bromosuccinimide were added, dissolved in a suitable amount of DMF and stirred at room temperature for three hours. After the reaction, the reaction was quenched with sodium hydroxide solution, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the organic solvent was removed by filtration and spin-drying. The crude product was separated by column chromatography to give compound 2.
2) Synthesis of Compound 3-2: in the dried Schlenk, the weighed compound 2 and 2-pyrene borate are added, a proper amount of toluene is dissolved, a catalyst of tetra-triphenylphosphine palladium and a proper amount of potassium carbonate solution are added, and the mixture is reacted for 16 hours at 120 ℃ under the protection of nitrogen. After the reaction, the reaction was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the organic solvent was removed by filtration and spin-drying. The crude product is separated by column chromatography to obtain the compound 3-2.
3) Synthesis of compounds of formula 2: in the dried Schlenk, adding the weighed compound 3-2, dissolving a proper amount of o-dichlorobenzene, adding boron trichloride, and reacting for 24 hours at 180 ℃ under the protection of nitrogen. After the reaction is finished, cooling to room temperature, adding a proper amount of rice-based format reagent, and reacting for 6 hours at room temperature. After the completion of the reaction, saturated brine was added, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the organic solvent was removed by spin-drying. The crude product was isolated by column chromatography to give the compound of formula 2, 1H-NMR as shown in FIG. 4.
Example 3
The synthesis method of the conjugated polycyclic aromatic hydrocarbon (formula 3) of the boron-nitrogen doped naphthalene fused pyrene comprises the following synthesis route:
1) Synthesis of Compound 2: in a dry round bottom flask, weighed 2-naphthylamine and N-bromosuccinimide were added, dissolved in a suitable amount of DMF and stirred at room temperature for three hours. After the reaction, the reaction was quenched with sodium hydroxide solution, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the organic solvent was removed by filtration and spin-drying. The crude product was separated by column chromatography to give compound 2.
2) Synthesis of Compound 3-3: in a dry round bottom flask, weighed amounts of compound 2 and iodobutane were added, an appropriate amount of DMF was dissolved, an appropriate amount of potassium hydroxide was added, and stirring was performed at room temperature for 24h. After the reaction, the reaction was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the organic solvent was removed by filtration and spin-drying. The crude product is separated by column chromatography to obtain the compound 3-3.
3) Synthesis of Compound 4-3: in the dried Schlenk, the weighed compound 3 and the disubstituted pyrene borate are added, a proper amount of toluene is dissolved, a catalyst of tetra-triphenylphosphine palladium and a proper amount of potassium carbonate solution are added, and the mixture is reacted for 16 hours at 120 ℃ under the protection of nitrogen. After the reaction, the reaction was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the organic solvent was removed by filtration and spin-drying. The crude product is separated by column chromatography to obtain the compound 4-3.
4) Synthesis of compounds of formula 3: in the dried Schlenk, the weighed compound 4-3 and a proper amount of o-dichlorobenzene are added for dissolution, boron tribromide is added for reaction at 180 ℃ for 48 hours under the protection of nitrogen. After the reaction is finished, cooling to room temperature, adding a proper amount of rice-based format reagent, and reacting for 12 hours at room temperature. After the completion of the reaction, saturated brine was added, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the organic solvent was removed by spin-drying. The crude product is separated by column chromatography to obtain the compound of formula 3.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon is characterized in that the conjugated polycyclic aromatic hydrocarbon is one of the following compounds:
。
2. a method for synthesizing the boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon according to claim 1, which comprises the following steps:
synthesis of compounds of formula 1: 2-naphthylamine is subjected to bromination reaction to generate a compound 2; carrying out Suzuki coupling reaction on the compound 2 and 1-pyrene boric acid to generate a compound 3-1; performing electrophilic boration reaction on the compound 3-1 to generate a compound shown in the formula 1, thus obtaining the compound;
the synthetic route for the compounds of formula 1 is as follows:
；
synthesis of compounds of formula 2: 2-naphthylamine is subjected to bromination reaction to generate a compound 2, the compound 2 and 2-pyrene boric acid ester are subjected to Suzuki coupling reaction to generate a compound 3-2, and the compound 3-2 is subjected to electrophilic boration reaction to generate a compound of formula 2, so that the compound is obtained;
the synthetic route for the compounds of formula 2 is as follows:
；
synthesis of compounds of formula 3: 2-naphthylamine is subjected to bromination reaction to generate a compound 2, the compound 2 is subjected to alkylation reaction to generate a compound 3-3, the compound 3-3 is subjected to Suzuki coupling reaction to generate a compound 4-3, and the compound 4-3 is subjected to electrophilic boration reaction to generate a compound of formula 3;
the synthetic route for the compounds of formula 3 is as follows:
。
3. the method for synthesizing the boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon according to claim 2, wherein the synthesis of the compound 2 specifically comprises: 2-naphthylamine and N-bromosuccinimide are added into DMF for dissolution, reaction is carried out at room temperature, after the reaction is finished, the reaction is quenched by sodium hydroxide solution, dichloromethane extraction is carried out, anhydrous magnesium sulfate is dried, and the organic solvent is removed by filtration and spin drying, thus obtaining the crude product.
4. The method for synthesizing the boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon according to claim 2, wherein the synthesis of the compound 3-1 specifically comprises: adding the weighed compound 2 and 1-pyrene boric acid into the dried Schlenk, adding toluene for dissolution, adding catalyst tetra-triphenylphosphine palladium and potassium carbonate solution, and reacting for 16h at 120 ℃ under the protection of nitrogen; after the reaction, the mixture is quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and dried to remove the organic solvent, thus obtaining a crude product.
5. The method for synthesizing the boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon according to claim 2, wherein the synthesis of the compound of formula 1 specifically comprises: adding a compound 3-1 into the dried Schlenk, dissolving with o-dichlorobenzene, adding boron tribromide, and reacting for 24 hours at 180 ℃ under the protection of nitrogen; after the reaction is finished, cooling to room temperature, adding a rice-based format reagent, and reacting for 6 hours at room temperature; after the reaction, saturated brine, dichloromethane extraction, anhydrous magnesium sulfate drying, and filtration and spin-drying are carried out to remove the organic solvent, thus obtaining a crude product.
6. The method for synthesizing the boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon according to claim 2, wherein the synthesis of the compound 3-2 specifically comprises: adding the weighed compound 2 and 2-pyrene borate into the dried Schlenk, adding toluene for dissolution, adding catalyst tetra-triphenylphosphine palladium and potassium carbonate solution, and reacting for 16h at 120 ℃ under the protection of nitrogen; after the reaction, the mixture is quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and dried to remove the organic solvent, thus obtaining a crude product.
7. The method for synthesizing the boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon according to claim 2, wherein the synthesis of the compound of formula 2 specifically comprises: adding a compound 3-2 into the dried Schlenk, dissolving with o-dichlorobenzene, adding boron tribromide, and reacting for 24 hours at 180 ℃ under the protection of nitrogen; after the reaction is finished, cooling to room temperature, adding a rice-based format reagent, and reacting for 6 hours at room temperature; after the reaction, saturated brine, dichloromethane extraction, anhydrous magnesium sulfate drying, and filtration and spin-drying are carried out to remove the organic solvent, thus obtaining a crude product.
8. The method for synthesizing the boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon according to claim 2, wherein the synthesis of the compound 3-3 specifically comprises: dissolving the compound 2 and iodobutane in DMF, adding potassium hydroxide, and stirring at room temperature for 24 hours; after the reaction, the mixture is quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and dried to remove the organic solvent, thus obtaining a crude product.
9. The method for synthesizing the boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon according to claim 2, wherein the synthesis of the compound 4-3 specifically comprises: adding a compound 3-3 and disubstituted pyrene borate into dry Schlenk, dissolving with toluene, adding a catalyst of tetraphenylphosphine palladium and potassium carbonate solution, and reacting for 16h at 120 ℃ under the protection of nitrogen; after the reaction, the mixture is quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and dried to remove the organic solvent, thus obtaining a crude product.
10. The method for synthesizing the boron-nitrogen doped naphthalene fused pyrene conjugated polycyclic aromatic hydrocarbon according to claim 2, wherein the synthesis of the compound of formula 3 specifically comprises: adding a compound 4-3 into the dried Schlenk, dissolving with o-dichlorobenzene, adding boron tribromide, and reacting for 48 hours at 180 ℃ under the protection of nitrogen; after the reaction is finished, cooling to room temperature, adding a rice-based format reagent, and reacting at room temperature for 12 hours; after the reaction, saturated brine, dichloromethane extraction, anhydrous magnesium sulfate drying, and filtration and spin-drying are carried out to remove the organic solvent, thus obtaining a crude product.
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