CN118307471A - Novel azaphenanthrene structural compound and synthesis method thereof - Google Patents
Novel azaphenanthrene structural compound and synthesis method thereofInfo
- Publication number
- CN118307471A CN118307471A CN202410741605.XA CN202410741605A CN118307471A CN 118307471 A CN118307471 A CN 118307471A CN 202410741605 A CN202410741605 A CN 202410741605A CN 118307471 A CN118307471 A CN 118307471A
- Authority
- CN
- China
- Prior art keywords
- novel
- azaphenanthrene
- structural compound
- synthesizing
- compound according
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 42
- HCAUQPZEWLULFJ-UHFFFAOYSA-N benzo[f]quinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=N1 HCAUQPZEWLULFJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title abstract description 12
- -1 aryl borate Chemical compound 0.000 claims abstract description 23
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 12
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Chemical class 0.000 claims description 7
- RSQXKVWKJVUZDG-UHFFFAOYSA-N 9-bromophenanthrene Chemical compound C1=CC=C2C(Br)=CC3=CC=CC=C3C2=C1 RSQXKVWKJVUZDG-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- BNGNNFQSUWVWCW-UHFFFAOYSA-N 3-bromophenanthrene Chemical compound C1=CC=C2C3=CC(Br)=CC=C3C=CC2=C1 BNGNNFQSUWVWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- SQTPFYJEKHTINP-UHFFFAOYSA-N 2-bromophenanthrene Chemical compound C1=CC=C2C3=CC=C(Br)C=C3C=CC2=C1 SQTPFYJEKHTINP-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 9
- 238000010926 purge Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 10
- 238000004896 high resolution mass spectrometry Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000004020 luminiscence type Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XIPFMBOWZXULIA-UHFFFAOYSA-M 2,2-dimethylpropanimidate Chemical compound CC(C)(C)C([O-])=N XIPFMBOWZXULIA-UHFFFAOYSA-M 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PYXBCVWIECUMDW-UHFFFAOYSA-N 2-bromoanthracene Chemical compound C1=CC=CC2=CC3=CC(Br)=CC=C3C=C21 PYXBCVWIECUMDW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a novel aza-phenanthrene structural compound and a synthesis method thereof, which belong to the technical field of organic compound synthesis, wherein aryl borate and bromoarene are coupled through a suzuki coupling reaction to obtain an intermediate; the intermediate is then reacted with POCl 3 and P 2O5 to give the novel azaphenanthrene structural compounds. The invention utilizes the suzuki reaction to obtain a synthetic method with simple operation, and the synthesized compound has the advantages of high yield and strong stability.
Description
Technical Field
The invention belongs to the technical field of organic compound synthesis, and particularly relates to a novel azaphenanthrene structure compound and a synthesis method thereof.
Background
Room temperature phosphorescence (Room Temperature Phosphorescence, RTP) materials are a promising class of luminescent materials with unique physicochemical properties such as large stokes shift, long lifetime luminescence, etc. Compared with inorganic phosphorescent materials, the pure Organic RTP materials have superior advantages in the aspects of Organic Light-Emitting Diodes (OLED), high-sensitivity chemical sensing, information encryption, high-resolution biological imaging, data storage and the like, and have the advantages of low cost, simple preparation process, easy color tuning and the like. In recent years, the new design concept of ultra-long room temperature organic phosphorescent (Ultralong Organic Room Temperature Phosphorescence, UORTP) materials has attracted a lot of attention. In general, the phosphorescent properties of a light emitter are closely related to its surroundings. Rigid environments such as intermolecular interactions and H-aggregation will greatly inhibit the non-radiative decay of triplet excitons, leading to high quantum yields and long lifetime RTP. The flexibility and adjustability of the luminescent color is a significant advantage of UORTP materials.
At present, a more common method for regulating and controlling single-component luminescence is to regulate the energy gap (delta EST) between the lowest singlet state and the triplet state by a molecular engineering means, or change the stacking mode of crystals to regulate the luminescence color, but the preparation process is complicated.
Therefore, there is a need to provide a functional luminescent small molecule compound with simple synthesis method, high yield and strong product stability and a method thereof.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel azaphenanthrene structural compound and a synthesis method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows:
a novel azaphenanthrene structural compound has a structural formula:
、 Or (b) 。
The second technical scheme of the invention is as follows:
The synthesis method of the novel azaphenanthrene structural compound comprises the following steps: performing suzuki coupling reaction on aryl borate and halogenated aromatic hydrocarbon to obtain an intermediate; and then reacting the intermediate with POCl 3 and P 2O5 to prepare the novel azaphenanthrene structural compound.
Preferably, the arylboronic acid ester is N- (2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) pivaloamide;
The halogenated aromatic hydrocarbon is 9-bromophenanthrene, 3-bromophenanthrene or 2-bromophenanthrene.
The beneficial effects are that: since the reaction of chloro (particularly sterically hindered chloro) and some heterocyclic boric acid is difficult to carry out, the invention adopts bromine substituted aromatic hydrocarbon to react with aryl borate, thereby improving the reaction rate.
Preferably, the method comprises the following steps:
S1, dissolving aryl borate, halogenated aromatic hydrocarbon and alkaline solution in an organic solvent to obtain mixed solution, then adjusting the pH value of the mixed solution to be alkaline, adding tetrakis (triphenylphosphine) palladium into the mixed solution, and carrying out suzuki coupling reaction to obtain an intermediate;
S2, mixing the intermediate with POCl 3 and P 2O5, and reacting to prepare the novel azaphenanthrene structural compound.
Still further, the molar volume ratio of the halogenated aromatic hydrocarbon, the arylboronic acid ester and the organic solvent is: 3.55 mmol:4.26 mmol:70 mL;
The molar volume ratio of the intermediate, POCl 3 and P 2O5 is: 0.63 mmol: 10 mL: 6.3mmol.
Further, the synthesis method of the novel azaphenanthrene structural compound 9SF comprises the following steps:
S1: dissolving 9-bromophenanthrene, N- (2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) pivaloyl amide and alkaline solution in an organic solvent to obtain a mixed solution, regulating the pH of the mixed solution to be alkaline, rapidly adding tetrakis (triphenylphosphine) palladium (Pd (PPh 3)4) for suzuki coupling reaction, cooling to room temperature after the reaction is finished, sequentially extracting, drying, filtering, decompressing, evaporating and purifying to obtain an intermediate 9F;
S2: and mixing the intermediate 9F, POCl 3 with P 2O5 under nitrogen atmosphere, reacting, cooling to room temperature after the reaction is finished, pouring the obtained mixture into ice water and ethyl acetate, neutralizing to alkalinity by using sodium hydroxide solution, and then sequentially extracting, drying, filtering, evaporating and purifying to obtain a white solid, namely the novel azaphenanthrene structural compound 9SF.
The synthesis flow of the novel azaphenanthrene structural compound 9SF is as follows:
。
further, the synthesis method of the novel azaphenanthrene structural compound 3SF comprises the following steps:
S1: dissolving 3-bromophenanthrene, N- (2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) pivaloyl amide and an alkaline solution in an organic solvent to obtain a mixed solution, regulating the pH of the mixed solution to be alkaline, rapidly adding tetrakis (triphenylphosphine) palladium (Pd (PPh 3)4) for suzuki coupling reaction, cooling to room temperature after the reaction is finished, sequentially extracting, drying, filtering, decompressing, evaporating and purifying to obtain an intermediate 3F;
S2: and (3) mixing the intermediate 3F, POCl 3 with P 2O5 in a nitrogen atmosphere, reacting, cooling to room temperature after the reaction is finished, pouring the obtained mixture into ice water and ethyl acetate, neutralizing to alkalinity by using sodium hydroxide solution, and then sequentially extracting, drying, filtering, evaporating and purifying to obtain a white solid, namely the novel azaphenanthrene structural compound 3SF.
Further, the synthesis method of the novel azaphenanthrene structural compound 2SE comprises the following steps:
S1: dissolving 2-bromoanthracene, N- (2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) pivaloyl amide and an alkaline solution in an organic solvent to obtain a mixed solution, regulating the pH of the mixed solution to be alkaline, rapidly adding tetrakis (triphenylphosphine) palladium (Pd (PPh 3)4) for suzuki coupling reaction, cooling to room temperature after the reaction is finished, sequentially extracting, drying, filtering, decompressing, evaporating and purifying to obtain an intermediate 2E;
s2: and (3) mixing the intermediate 2E, POCl 3 with P 2O5 under nitrogen atmosphere, reacting, cooling to room temperature after the reaction is finished, pouring the obtained mixture into ice water and ethyl acetate, neutralizing to alkalinity by using sodium hydroxide solution, and then sequentially extracting, drying, filtering, evaporating and purifying to obtain a white solid, namely the novel azaphenanthrene structural compound 2SE.
In the step S1, the reaction temperature of the suzuki coupling reaction is 70-120 ℃ and the reaction time is 48 hours.
Still further, in step S1, the organic solvent includes one or more of methanol, tetrahydrofuran, acetonitrile, N-dimethylformamide, N-dimethylacetamide, or dimethylsulfoxide.
Further, in step S1, the alkaline solution is K 2CO3.
In the step S1, the mixed solution is purged with nitrogen for 30min before adding the tetra (triphenylphosphine) palladium.
The beneficial effects are that: the existing Suzuki reaction is sensitive to oxygen, and a small amount of oxygen dissolved in a solvent can cause the formation of by-products of boric acid self-coupling, so that the mixed solution is purged by nitrogen, the oxygen in the mixed solution is discharged, no oxygen exists in a reaction system, the formation of a polymer is ensured, and the purity of a finally prepared compound is improved.
Further, in the step S2, the conditions in the reaction process are as follows: the reaction temperature is 110 ℃, and the reaction time is 16-24h.
And the third technical scheme is as follows:
A composite film is prepared from the novel azaphenanthrene structural compound.
Preferably, the preparation process of the composite film comprises the following steps: and (3) blending the novel azaphenanthrene structural compound with a polymer, and heating to prepare the doping system with long afterglow.
Further, the mass ratio of the novel azaphenanthrene structural compound to the polymer is 1:200.
Further, the polymer is PMMA.
Preferably, the heating conditions are: heating at 100deg.C for 30min; and then heating at 140 ℃ until the solvent is volatilized, thus obtaining the composite film.
The fourth technical scheme is as follows:
the application of the composite film in information storage and anti-counterfeiting.
Compared with the prior art, the invention has the following advantages and technical effects:
The invention prepares the novel nitrogen-containing hetero-phenanthrene structure light-emitting unit with high yield, strong product stability and certain plane configuration by a simple synthesis method; the fused ring type azaphenanthrene structure is synthesized for the first time, and is blended with a polymer (such as PMMA) to form a doping system with long afterglow, so that the fused ring type azaphenanthrene structure can be applied to information storage and anti-counterfeiting application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a nuclear magnetic resonance image of the 9SF compound prepared in example 1;
FIG. 2 is a carbon spectrum of the 9SF compound prepared in example 1;
FIG. 3 is a chemical structure of the 9SF compound prepared in example 1;
FIG. 4 is an HR MS plot of the 9SF compound prepared in example 1;
FIG. 5 is a nuclear magnetic resonance image of the 3SF compound prepared in example 2;
FIG. 6 is a carbon spectrum of the 3SF compound prepared in example 2;
FIG. 7 is a chemical structure of the 3SF compound prepared in example 2;
FIG. 8 is an HR MS plot of the 3SF compound prepared in example 2;
FIG. 9 is a nuclear magnetic resonance image of the 2SE compound prepared in example 3;
FIG. 10 is a graph of the carbon spectrum of the 2SE compound prepared in example 3;
FIG. 11 is an HR MS plot of the 2SE compound prepared in example 3;
FIG. 12 is a luminescent image of the film prepared in effect examples 1-3 excited under 365nm UV light;
Wherein (a) is effect example 1; (b) is effect example 2; (c) is effect example 3.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the examples of the present invention are all commercially available. The specific raw materials are shown in Table 1 below.
TABLE 1
The technical scheme of the invention is further described by the following examples.
Example 1
A synthesis method of a novel azaphenanthrene structural compound comprises the following steps:
S1: to a round bottom flask was added 9-bromophenanthrene (912.35 mg,3.55 mmol), N- (2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) pivalamide (1.59 g,4.26 mmol), K 2CO3 (5.3 g,38.41 mmol), tetrahydrofuran (THF, 70 mL) and deionized water (10 mL). The mixture was purged with nitrogen for 30 min, then Pd (PPh 3)4 (89 mg,0.077 mmol) was added rapidly, the mixture was stirred at 90 ℃ for 48 h, after cooling to room temperature, extracted 3 times with saturated brine and DCM (50 mL), the organic layers were combined, dried over anhydrous Na 2SO4, filtered and evaporated to dryness under reduced pressure.
S2: a mixture of 9F (222 mg,0.63 mmol), POCl 3 (10 mL) and phosphorus pentoxide (P 2O5, 0.89g,6.3 mmol) was stirred at 110℃for 20 hours under a nitrogen atmosphere. After cooling to room temperature, the resulting mixture was poured into ice water (150 mL) and ethyl acetate (20 mL), slowly neutralized to ph=9 with aqueous sodium hydroxide (8M NaOH), and then extracted 3 times with DCM (50 mL). The combined organic phases were dried over anhydrous Na 2SO4, filtered and evaporated to dryness. The crude product was purified on a silica gel column using PE: ea=20:1 (v/v) as eluent to give 9SF (168 mg, 89.1%) as a white solid. The nuclear magnetic resonance diagram of the compound 9SF is shown in figure 1, the carbon spectrum diagram is shown in figure 2, the single crystal XRD diffraction diagram is shown in figure 3, and the HR MS diagram is shown in figure 4; the relevant characterization data are as follows:
9SF：1H NMR（600 MHz,CDCl3）：δ 8.74（d,J = 5.36 Hz,1H）,8.63（t,J = 5.12 Hz,2H）,8.51（d,J = 5.36 Hz,1H）,8.16（dd,J = 5.36 Hz,2H）,7.76（t,J = 4.76 Hz,1H）,7.71-7.66（m, 2H）,7.60（t,J = 4.76Hz,1H）,7.53（q,J = 4.80 Hz,2H）,1.58（s,9H）.13C NMR（100 MHz,CDCl3）：δ 165.55,144.82,134.94,132.14,130.80,130.49,129.62,129.42,128.58,128.37,128.14,128.07,126.98,126.87,126.52,125.54,125.32,123.69,123.14,121.90,121.81,41.52,32.58,32.58,32.58.HR MS C25H21N m/z： Calculated values: for [ M ] +, precise mass: 335.45, found: 336.06 [ M +H]+ ].
Example 2
The difference from example 1 is that,
In S1, 9-bromophenanthrene is replaced by 3.55 mmol of 3-bromophenanthrene; the intermediate obtained in the step is 3F;
9F was replaced with 0.63mmol 3F in S2;
other conditions were consistent with example 1, the final compound prepared was 3SF in 87% yield.
The nuclear magnetic resonance diagram of the compound 3SF is shown in figure 5, the carbon spectrum diagram is shown in figure 6, the single crystal XRD diffraction diagram is shown in figure 7, and the HR MS diagram is shown in figure 8. The 3SF related characterization data are as follows:
3SF：1H NMR（600 MHz,CDCl3）：δ 9.97（s,1H）,9.12（s, 1H）,9.00（d,J = 5.40 Hz,1H）,8.84（d,J = 5.24 Hz,1H）,8.17（d,J = 3.96 Hz,1H）,7.93（t,J = 5.16 Hz,2H）,7.80 – 7.77（m,2H）,7.75-7.70（m,3H）,1.84（s,9H）.13C NMR（100 MHz,CDCl3）：δ 167.11,132.71,131.60,130.64,130.44,129.97,129.85,129.76,128.85,128.50,127.84,127.70,127.56,127.12,126.72,123.70,123.17,122.74,121.76,119.93,116.49,41.52,32.58,32.58,32.58.HR MS C25H21N m/z： Calculated values: for [ M ] +, precise mass: 335.45, found: 336.09 [ M +H]+ ].
Example 3
The difference from example 1 is that,
In S1, 9-bromophenanthrene is replaced by 3.55 mmol of 2-bromoanthracene; the intermediate obtained in the step is 2E;
In S2, 9F is replaced by 0.63mmol of 2E;
other conditions were consistent with example 1, the final compound prepared was 2SE in 75% yield.
The nuclear magnetic resonance diagram of the compound 2SE is shown in fig. 9, the carbon spectrum diagram is shown in fig. 10, and the HR MS diagram is shown in fig. 11. The 2 SE-related characterization data are as follows:
2SE：1H NMR（600 MHz,CDCl3）：δ 9.04（s,1H）,8.48（d,J = 5.56 Hz,1H）,8.40（t,J = 8.12 Hz,2H）,8.13（t,J = 4.56 Hz,2H）,8.09（t,J = 5.24 Hz,2H）,7.73（t,J = 5.32 Hz,1H）,7.62 – 7.57（m,3H）,1.67（s,9H）.13C NMR（100 MHz,CDCl3）：δ 166.24,143.60,134.07,131.44,130.81,130.06,129.90,128.86,128.48,128.27,127.65,126.12,126.11,125.68,125.19,122.18,122.11,121.84,120.00,41.67,32.56,32.56,32.56,33.37、14.08.HR MS C25H21N m/z： Calculated values: for [ M ] +, precise mass: 335.45, found: 336.08 [ M +H]+ ].
Effect verification
Effect example 1
A film was prepared by compounding the compound 9SF prepared in example 1 with PMMA, denoted 9sf@pmma; the preparation process of the film comprises the following steps:
(1) Dissolving PMMA in an organic reagent dimethyl sulfoxide (DMSO) to form a uniform polymer solution, wherein the concentration of the solution is 200 mg/mL;
(2) 9SF was dissolved in organic reagent N, N-Dimethylformamide (DMF) to form a uniform solution with a concentration of 10mg/mL;
(3) A mixed solution of PMMA: 9 sf=200:1 (mass ratio) was prepared and mixed uniformly.
(4) The mixed solution 200 uL is measured and dripped on a 2.5 x 2.5cm glass sheet at 100 ℃, the temperature is raised to 140 ℃ after heating for 30 min ℃ and the heating is continued until the solvent is completely volatilized, so that a stable and uniform film is formed, which is marked as 9SF@PMMA.
Effect example 2
The difference from effect example 1 is that the compound 3SF prepared in example 2 was used as a raw material, and the other conditions were the same as those in effect example 1. The film produced was designated 3sf@pmma.
Effect example 3
The difference from effect example 1 is that compound 2SE prepared in example 3 was used as a starting material, and the other conditions were the same as effect example 1. The film produced was designated 2SE@PMMA.
The films prepared in effect examples 1-3 were excited under 365 nm UV light, and the corresponding luminescence patterns are shown in FIG. 12. From the graph, the steady-state fluorescence color of the 9SF@PMMA changes from blue green to light purple, the long afterglow luminescence color changes from yellow to green, and the luminescence time is optimal and is 14s; the steady-state fluorescence color of 3SF@PMMA is purple red, the long afterglow luminescence color is orange to green, and the luminescence time is 8s; the steady-state fluorescence color of 2SE@PMMA is blue, the long afterglow color is light yellow-green, and the time is 2s.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (10)
1. A novel azaphenanthrene structural compound is characterized by having the structural formula:
、 Or (b) 。
2. The method for synthesizing the novel azaphenanthrene structural compound according to claim 1, which comprises the following steps: performing suzuki coupling reaction on aryl borate and halogenated aromatic hydrocarbon to obtain an intermediate; and then reacting the intermediate with POCl 3 and P 2O5 to prepare the novel azaphenanthrene structural compound.
3. The method for synthesizing a novel azaphenanthrene structural compound according to claim 2, wherein the arylboronic acid ester is N- (2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) pivalamide;
The halogenated aromatic hydrocarbon is 9-bromophenanthrene, 3-bromophenanthrene or 2-bromophenanthrene.
4. The method for synthesizing the novel azaphenanthrene structural compound according to claim 2, which comprises the following steps:
s1, dissolving aryl borate, halogenated aromatic hydrocarbon and alkaline solution in an organic solvent to obtain mixed solution, adjusting the pH value of the mixed solution to be alkaline, adding tetrakis (triphenylphosphine) palladium into the mixed solution, and performing suzuki coupling reaction to obtain an intermediate;
S2, mixing the intermediate with POCl 3 and P 2O5, and reacting to prepare the novel azaphenanthrene structural compound.
5. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S1, the molar volume ratio of the halogenated aromatic hydrocarbon, the arylboronic acid ester and the organic solvent is as follows: 3.55 mmol:4.26 mmol:70 mL;
The molar volume ratio of the intermediate, POCl 3 and P 2O5 is: 0.63 mmol: 10 mL: 6.3mmol.
6. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S1, the reaction temperature of the suzuki coupling reaction is 70-120 ℃ and the reaction time is 48h.
7. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S1, the organic solvent comprises one or more of methanol, tetrahydrofuran, acetonitrile, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.
8. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S1, the alkaline solution is K 2CO3.
9. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S1, nitrogen purging is performed on the mixed solution for 30min before adding tetrakis (triphenylphosphine) palladium.
10. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S2, the reaction process is performed under the following conditions: the reaction temperature is 110 ℃, and the reaction time is 16-24h.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118307471A true CN118307471A (en) | 2024-07-09 |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Preparation, characterization, and properties of PMMA-doped polymer film materials: a study on the effect of terbium ions on luminescence and lifetime enhancement | |
| CN111205271B (en) | Ligand compound, functionalized metal-organic framework compound prepared from ligand compound, and preparation method and application of functionalized metal-organic framework compound | |
| TWI553003B (en) | Synthesis method of the 2,6 - bis [3 '- (n- carbazolyl) phenyl] pyridine compounds | |
| CN112300793B (en) | Preparation method of pure organic phosphorescent material based on dicarbazole pyridine derivative | |
| KR101113313B1 (en) | Blue-luminous iridium complex, iridium complex monomer, phosphorescent polymer and organic electroluminescent device having the same | |
| CN115819281B (en) | Cyano-substituted p-phenylene ethylene derivative, preparation method and application | |
| CN118307471A (en) | Novel azaphenanthrene structural compound and synthesis method thereof | |
| CN108586438B (en) | Mono-substituted five-membered heterocyclic barbituric acid derivative and preparation method thereof | |
| CN112175607B (en) | Organic room temperature phosphorescent material and preparation method and application thereof | |
| TW200531994A (en) | Color filter for electrical display device | |
| CN113214155B (en) | Long-life pure organic room-temperature phosphorescent material and preparation method and application thereof | |
| CN113004191B (en) | White circular polarization luminescent organic micro-nano crystal material and preparation method thereof | |
| CN115010619A (en) | Organic luminescent material and application thereof | |
| CN105085579B (en) | N hexyl carbazole substituted-phenyl benzothiazole iridium (III) complexs and its preparation | |
| JP2008528754A (en) | ELECTROLUMINESCENT MATERIAL CONTAINING MIXTURE, ITS MANUFACTURING METHOD, AND DISPLAY ELEMENT HAVING THE ELECTROELECTRIC LIGHT EMITTING MATERIAL | |
| KR102050163B1 (en) | New organic light emitting mesogenic copolymers with composition containing iridium complex chromophore, capable of polarized light emission and method for preparing the same | |
| CN113444519A (en) | Organic phosphorescent composition and preparation method and application thereof | |
| CN109320528B (en) | Triheteroaryl free radical capable of stably emitting light at room temperature, and preparation method and application thereof | |
| CN115028653B (en) | Organic room-temperature phosphorescent material and application thereof | |
| CN100432078C (en) | Complexes of rare earth-beta-diketone-naphthisodiazine and synthetic method | |
| CN117924290A (en) | Preparation method and application of long-life organic room-temperature phosphorescent material of filter paper matrix | |
| CN113200909B (en) | Force-induced color-changing material based on isonicotinic acid derivative and preparation method thereof | |
| WO2021036978A1 (en) | Tetradentate ligands, gold(iii) complexes, preparation method and use thereof | |
| CN114853657A (en) | Amide compound and preparation method thereof | |
| CN117903002A (en) | Dicyanoethylene based on tetraphenyl ethylene functionalization, preparation method and application thereof, and ink-free writing material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication |