CN116836107B - Carbazol eight-membered ring large conjugated structure OLED material and preparation method thereof - Google Patents
Carbazol eight-membered ring large conjugated structure OLED material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title claims description 12
- GZSUIHUAFPHZSU-UHFFFAOYSA-N 9-ethyl-2,3-dihydro-1h-carbazol-4-one Chemical compound C12=CC=CC=C2N(CC)C2=C1C(=O)CCC2 GZSUIHUAFPHZSU-UHFFFAOYSA-N 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims description 40
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 24
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 24
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 229940093956 potassium carbonate Drugs 0.000 claims description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 15
- 235000011181 potassium carbonates Nutrition 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- -1 2-biphenyl iodonium salt Chemical class 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000012544 monitoring process Methods 0.000 claims description 9
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 9
- 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 9
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000002274 desiccant Substances 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 229940083608 sodium hydroxide Drugs 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229930014626 natural product Natural products 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001716 carbazoles Polymers 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
-
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Indole Compounds (AREA)
Abstract
theinventiondisclosesacarbazoleight-memberedringlargeconjugatedstructureOLEDmaterialandapreparationmethodthereof,wherein2,3-dichloronitrobenzeneisusedasarawmaterial,andissubjectedtocouplingreactionwith2-methylformate-phenylboronicacidpinacolestertoprepareM-A,thentheM-AishydrolyzedunderalkalineconditiontopreparecarboxylicacidM-B,thenthecarboxylicacidM-Bisreactedwith2-biphenyliodoniumsalttoformanitroeight-memberedringM-C,andthenthenitroeight-memberedringisclosedtoprepareatargetproductcarbazoleight-memberedaromaticringstructureM.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a carbazolo eight-membered ring large conjugated structure OLED material and a preparation method thereof.
Background
The multi-element nitrogen-containing heterocyclic skeleton exists in a plurality of active natural products, is an important organic compound, and the synthesis of the intermediate (8-12 membered ring) heterocyclic compound is one of the difficulties in organic synthesis. The current research shows that the natural compounds of 8-12 membered rings containing a plurality of heteroatoms such as N, O have very good biological activity and potential medicinal value, especially the cyclic nitrogen compounds in the natural compounds are more concerned by pharmaceutical chemists, so that the development of a novel method for constructing the cyclic heterocyclic compounds is very significant.
The eight-membered ring is used as a parent nucleus to be derived and prepared into a series of compounds, the eight-membered ring can improve the planeness of molecules, reduce the transmission barrier of carriers, and is matched with aryl or heteroaryl, thereby being beneficial to improving the luminous efficiency of an OLED device using the compound and reducing the driving voltage.
The main patents of the existing synthetic eight-membered ring are: patent CN 111140794A and patent CN 112979548a, the synthesis method is as follows:
the two methods are similar, mainly leading leaving groups into 4 and 5 positions of carbazole, and then carrying out coupling reaction to close the ring to prepare the target eight-membered ring structure.
The method reported in CN 114773353A for synthesizing an eight membered ring is as follows:
this report still requires the introduction of polyhalogenated carbazole, is difficult to prepare, and is prone to side reactions of coupling of self-products and halogen removal during ring closure.
The main defects of the existing synthesis method are as follows:
1. leaving groups are introduced into the 4 and 5 positions of carbazole, so that the intermediate is difficult to synthesize and high in cost.
2. The steric hindrance is large in the ring closing process, the ring closing is difficult, the yield is low, and the halogen is lost.
3. The ring closure technology has a plurality of defects in the preparation process at present, for example, the ring closure is difficult to be successfully realized by introducing other halogen into the benzene ring.
Therefore, the research and development of a novel method for synthesizing the eight-membered ring has a great market prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a carbazolo eight-membered ring large conjugated structure OLED material and a preparation method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows: a preparation method of a carbazolo eight-membered ring large conjugated structure OLED material comprises the following steps:
step 1: taking2,3-dichloronitrobenzeneasarawmaterial,andcarryingoutcouplingreactionwith2-methylformate-phenylpinacolboratetoprepareM-A,whereinthemolarratioofthe2,3-dichloronitrobenzenetothe2-methylformate-phenylpinacolborateis1: 1 to 1.2;
step 2: hydrolyzingM-AunderalkalineconditiontoobtainM-B;
step 3: the M-B reacts with 2-biphenyl iodonium salt to form a ring closure, and the molar ratio of the M-C, the M-B and the 2-biphenyl iodonium salt is 1:1 to 1.5;
step 4: and (3) performing nitro ring closure on M-C by using 1,2, 4-trichlorobenzene to prepare the target product carbazolo eight-membered ring large conjugated structure M.
Preferably, the step 1 specifically includes: undertheprotectionofN2,adding2,3-dichloronitrobenzene,2-methylformate-phenylpinacolborate,potassiumcarbonate,tetrakis(triphenylphosphine)palladium,dioxaneandwaterintoareactionbottle,heatingandrefluxingforreactionfor6-8h,andmonitoringthereactioncompletelybyTLCtoobtainanM-Asolution,whereinthemolarratioofthe2,3-dichloronitrobenzenetothepotassiumcarbonatetothetetrakis(triphenylphosphine)palladiumis1: 1.2 to 1.6: the dosage ratio of 0.01 to 0.02,2,3 of dichloronitrobenzene to dioxane to water is 0.01mol: 21-25 ml: 4-8 ml.
preferably,thepost-treatmentoftheM-asolutionis: ethylacetateandwaterareaddedforextraction,waterisusedforwashingtobeneutral,anintermediateisobtainedaftertheorganicphaseisconcentrated,M-Aisobtainedbyrecrystallizationwithnormalhexane,andthedosageratioofthe2,3-dichloronitrobenzenetotheethylacetatetothewateris0.01mol: 15-20 ml: 10-15 ml.
Preferably, the step 2 specifically includes: addingM-A,sodiumhydroxide,ethanolandwaterintoareactionbottle,heatingtorefluxreaction,andmonitoringthereactiontobecompletebyTLCtoobtainM-Bsolution,whereinthemolarratiooftheM-Atothesodiumhydroxideis1: 2.5to3.5,thedosageratioofM-Atoethanolandwateris0.01mol: 20-25 ml: 5-10 ml.
Preferably, the post-treatment of the M-B solution is: concentrating 70% ethanol, acidifying with hydrochloric acid to pH 3-4, filtering, washing the filter cake with water to neutrality, and drying to obtain M-B.
Preferably, the step 3 specifically includes: adding M-B, biphenyl-2 iodonium salt, palladium acetate, potassium carbonate and NMP into a reaction bottle, heating to 130-140 ℃, stirring and reacting for 16-18 hours, and monitoring the reaction by TLC to obtain an M-C solution, wherein the molar ratio of the M-B to the palladium acetate to the potassium carbonate is 1:0.02 to 0.03:2 to 3, the dosage ratio of M-B to NMP is 0.01mol: 62-70 ml.
Preferably, the post-treatment of the M-C solution is: cooling to room temperature, extracting with ethyl acetate, washing with sodium chloride water solution, drying the organic phase with anhydrous magnesium sulfate, filtering to remove desiccant, removing solvent, and passing the crude product through silica gel column with n-heptane/dichloroethane to obtain M-C.
Preferably, the step 4 specifically includes: under the protection of N2, adding M-C, 1,2, 4-trichlorobenzene and triphenylphosphine into a reaction bottle, heating to 200 ℃ for reaction, and monitoring the reaction by TLC to obtain an M solution, wherein the molar ratio of the M-C to the triphenylphosphine is 1:3-4, and the dosage ratio of the M-C to the 1,2, 4-trichlorobenzene is 0.01mol: 11-15 ml.
Preferably, the post-treatment of the M solution is: concentrating under reduced pressure to remove solvent, extracting with toluene at 60deg.C, filtering to remove insoluble substances, filtering to obtain filtrate, purifying with silica gel column, eluting with toluene, concentrating to obtain crude product, refluxing with ethanol, boiling, cooling to room temperature, filtering, and drying to obtain carbazole octamembered ring large conjugated structure M.
Preferably, the carbazolo-eight-membered ring large conjugated structure OLED material is prepared by the preparation method of the carbazolo-eight-membered ring large conjugated structure OLED material, and the structural formula of the carbazolo-eight-membered ring large conjugated structure M is as followsThe carbazolo eight-membered ring large conjugated structure M is used for preparing an OLED device.
Compared with the prior art, the invention has the advantages that:
(1) theinventiondisclosesapreparationmethodofacarbazoloeight-memberedringlargeconjugatedstructureOLEDmaterial,whichtakes2,3-dichloronitrobenzeneasarawmaterial,carriesoutcouplingreactionwith2-methylformate-phenylboronicacidpinacolestertoprepareM-A,thenhydrolyzesunderalkalineconditiontopreparecarboxylicacidM-B,thenreactswith2-biphenyliodoniumsalttoformanitroeight-memberedringM-C,andthencarriesoutnitroringclosuretoprepareatargetproductcarbazoloeight-memberedaromaticringstructureM,andthepreparationmethodhastheadvantagesofsingle-stepreaction,noisomerism,nopolysubstitutedproduct,singleproductcategoryandeasyseparationandpurification;
(2) The preparation method has short route design, easier synthesis of the intermediate, low cost, the intermediate M-B reacts with 2-biphenyl iodonium salt to form a nitro eight-membered ring M-C, and then the nitro eight-membered ring M-C is subjected to nitroclosing to prepare the target product, and the ring closing process has smaller resistance, simple ring closing, high yield and no halogen loss phenomenon;
(3) The carbazole eight-membered ring large conjugated structure is prepared by using a simple and easily available raw material, a series of compounds can be prepared by taking the structure as a parent nucleus, and the molecular rigidity of the compound is enhanced by increasing the eight-membered ring conjugation, so that the structure is more stable.
Drawings
FIG. 1 shows a nuclear magnetic spectrum of a carbazolo eight-membered ring large conjugated structure M.
Detailed Description
The invention will now be described with reference to the following examples, which are given by way of illustration of the invention, but are not intended to limit the scope of the invention, using conventional commercial products as raw materials, solvents and catalysts.
The invention discloses a preparation method of a carbazolo eight-membered ring large conjugated structure OLED material, which comprises the following steps:
step 1: taking2,3-dichloronitrobenzeneasarawmaterial,andcarryingoutcouplingreactionwith2-methylformate-phenylpinacolboratetoprepareM-A,whereinthemolarratioofthe2,3-dichloronitrobenzenetothe2-methylformate-phenylpinacolborateis1: 1 to 1.2;
step 2: hydrolyzingM-AunderalkalineconditiontoobtainM-B;
step 3: the M-B reacts with 2-biphenyl iodonium salt to form a ring closure, and the molar ratio of the M-C, the M-B and the 2-biphenyl iodonium salt is 1:1 to 1.5;
step 4: and (3) performing nitro ring closure on M-C by using 1,2, 4-trichlorobenzene to prepare the target product carbazolo eight-membered ring large conjugated structure M.
Preferably, the step 1 specifically includes: undertheprotectionofN2,adding2,3-dichloronitrobenzene,2-methylformate-phenylpinacolborate,potassiumcarbonate,tetrakis(triphenylphosphine)palladium,dioxaneandwaterintoareactionbottle,heatingandrefluxingforreactionfor6-8h,andmonitoringthereactioncompletelybyTLCtoobtainanM-Asolution,whereinthemolarratioofthe2,3-dichloronitrobenzenetothepotassiumcarbonatetothetetrakis(triphenylphosphine)palladiumis1: 1.2 to 1.6: the dosage ratio of 0.01 to 0.02,2,3 of dichloronitrobenzene to dioxane to water is 0.01mol: 21-25 ml: 4-8 ml.
preferably,thepost-treatmentoftheM-asolutionis: ethylacetateandwaterareaddedforextraction,waterisusedforwashingtobeneutral,anintermediateisobtainedaftertheorganicphaseisconcentrated,M-Aisobtainedbyrecrystallizationwithnormalhexane,andthedosageratioofthe2,3-dichloronitrobenzenetotheethylacetatetothewateris0.01mol: 15-20 ml: 10-15 ml.
Preferably, the step 2 specifically includes: addingM-A,sodiumhydroxide,ethanolandwaterintoareactionbottle,heatingtorefluxreaction,andmonitoringthereactiontobecompletebyTLCtoobtainM-Bsolution. themolarratioofM-Atosodiumhydroxideis1: 2.5to3.5,thedosageratioofM-Atoethanolandwateris0.01mol: 20-25 ml: 5-10 ml.
Preferably, the post-treatment of the M-B solution is: concentrating 70% ethanol, acidifying with hydrochloric acid to pH 3-4, filtering, washing the filter cake with water to neutrality, and drying to obtain M-B.
Preferably, the step 3 specifically includes: adding M-B, biphenyl-2 iodonium salt, palladium acetate, potassium carbonate and NMP into a reaction bottle, heating to 130-140 ℃, stirring and reacting for 16-18 hours, and monitoring the reaction by TLC to obtain an M-C solution, wherein the molar ratio of the M-B to the palladium acetate to the potassium carbonate is 1:0.02 to 0.03:2 to 3, the dosage ratio of M-B to NMP is 0.01mol: 62-70 ml.
Preferably, the post-treatment of the M-C solution is: cooling to room temperature, extracting with ethyl acetate, washing with sodium chloride water solution, drying the organic phase with anhydrous magnesium sulfate, filtering to remove desiccant, removing solvent, and passing the crude product through silica gel column with n-heptane/dichloroethane to obtain M-C.
Preferably, the step 4 specifically includes: under the protection of N2, adding M-C, 1,2, 4-trichlorobenzene and triphenylphosphine into a reaction bottle, heating to 200 ℃ for reaction, and monitoring the reaction by TLC to obtain an M solution, wherein the molar ratio of the M-C to the triphenylphosphine is 1:3-4, and the dosage ratio of the M-C to the 1,2, 4-trichlorobenzene is 0.01mol: 11-15 ml.
Preferably, the post-treatment of the M solution is: concentrating under reduced pressure to remove solvent, extracting with toluene at 60deg.C, filtering to remove insoluble substances, filtering to obtain filtrate, purifying with silica gel column, eluting with toluene, concentrating to obtain crude product, refluxing with ethanol, boiling, cooling to room temperature, filtering, and drying to obtain carbazole octamembered ring large conjugated structure M.
Preferably, the carbazolo-eight-membered ring large conjugated structure OLED material is prepared by the preparation method of the carbazolo-eight-membered ring large conjugated structure OLED material, and the structural formula of the carbazolo-eight-membered ring large conjugated structure M is as followsThe carbazolo eight-membered ring large conjugated structure M is used for preparing an OLED device.
Example 1
Step 1
At N 2 Under protection, 8.8g (0.046 mol) of 2, 3-dichloronitrobenzene, 12.1g (0.046 mol) of 2-methyl formate-phenylboronic acid pinacol ester, 9.5g (0.068 mol) of potassium carbonate, 0.53g (0.00046 mol) of tetrakis (triphenylphosphine) palladium, 100ml of dioxane and 20ml of water are added into a reaction bottle, the reaction is heated and refluxed for 6 hours, TLC monitors the reaction completion, ethyl acetate and water are added for extraction, water is used for washing until neutrality, an intermediate is obtained after the organic phase is concentrated, and the M-A9.9g is recrystallized by normal hexane, the HPLC purity is 94.5%, and the yield is 73.8%.
Step 2
9.9g(0.034mol)ofM-A,70mlofethanol,4g(0.1mol)ofsodiumhydroxideand20mlofwaterpreparedaboveareaddedintoareactionbottle,themixtureisheatedtorefluxreaction,TLCmonitorsthereactioncompletion,50mlofethanolisconcentrated,hydrochloricacidisusedforacidificationuntilthepHvalueisbetween3and4,filtrationandfiltercakewaterwashingarecarriedoutuntilthepHvalueisneutral,8.7gofM-Bisobtainedafterdrying,theHPLCpurityis96.9%,andtheyieldis92.2%.
Step 3
To the flask were added 8.7g (0.031 mol) of the above M-B, 14.6g (0.04 mol) of biphenyl-2 iodonium salt, 0.17g (0.000775 mol) of palladium acetate, 9.4g (0.068 mol) of potassium carbonate and 200ml of NMP, which were heated to 130℃and stirred for 17 hours, TLC was monitored to complete the reaction, cooled to room temperature, extracted with ethyl acetate, washed with aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, the drying agent was filtered off, the solvent was removed, and the crude product was purified by passing through a silica gel column using n-heptane/dichloroethane to give 7.5g of M-C, HPLC purity was 98.4%, and yield was 67.7%.
Step 4
At N 2 Under protection, adding M-C7.5g (0.021 Mol), 1,2, 4-trichlorobenzene 23ml and triphenylphosphine 16.8g (0.064 Mol) into a reaction bottle, heating to 200 ℃ for reaction, monitoring the reaction by TLC, concentrating under reduced pressure to remove solvent, adding toluene at 60 ℃ for extraction, filtering insoluble substances, filtering the filtrate to obtain a silica gel column, eluting the column bed with toluene, concentrating and drying the column liquid to obtain a crude product, refluxing and boiling with ethanol for washing, cooling to room temperature for filtration, drying to obtain 5.3gM, and obtaining the HPLC with 99.1 percent of purity and 79.5 percent of yield.
As shown in FIG. 1, the nuclear magnetic spectrum of the carbazol eight-membered ring large conjugated structure M is 1H NMR (500 MHz, chloroform) delta 8.42 (s, 4H), 8.10 (s, 4H), 7.66 (s, 1H), 7.40 (s, 2H), 7.18 (s, 2H), 7.08 (s, 2H).
Example 2
At N 2 Under protection, 8.8g (0.046 mol) of 2, 3-dichloronitrobenzene, 14.4g (0.055 mol) of 2-methyl formate-phenylboronic acid pinacol ester, 10.3g (0.074 mol) of potassium carbonate, 1.05g (0.00092 mol) of tetra (triphenylphosphine) palladium, 115ml of dioxane and 36ml of water are added into a reaction bottle, the reaction is heated and refluxed for 7h, TLC monitors the reaction to be complete, ethyl acetate and water are added for extraction, water is used for washing until the reaction is neutral, the organic phase is concentrated to obtain an intermediate, and the intermediate is recrystallized by normal hexane to obtain 10.5g of M-A with the HPLC purity of 93.8 percent, and the yield is 78.3 percent.
Step 2
10.5g(0.036mol)ofM-A,90mlofethanol,5.1g(0.13mol)ofsodiumhydroxideand35mlofwaterpreparedaboveareaddedintoareactionbottle,themixtureisheatedtorefluxreaction,TLCmonitorsthereactioncompletion,80mlofethanolisconcentratedunderreducedpressure,hydrochloricacidisusedforacidificationuntilthepHvalueisbetween3and4,filtrationiscarriedout,afiltercakeiswashedwithwatertobeneutral,8.6gofM-Bisobtainedafterdrying,theHPLCpurityis95.8%,andtheyieldis86.5%.
Step 3
To the reaction flask were added 8.6g (0.03 mol) of the above M-B, 19.2g (0.045 mol) of biphenyl-2 iodonium salt, 0.2g (0.0009 mol) of palladium acetate, 12.4g (0.09 mol) of potassium carbonate and 210ml of NMP, heated to 130℃and stirred for 17 hours, TLC was monitored to complete the reaction, cooled to room temperature, extracted with ethyl acetate, washed with aqueous sodium chloride, dried over anhydrous magnesium sulfate, the drying agent was filtered off, the solvent was removed, and the crude product was purified by passing through a silica gel column with n-heptane/dichloroethane to give 6.8g of M-C, HPLC purity 97.9%, yield 65.1%.
Step 4
At N 2 Under protection, adding M-C6.8g (0.019 Mol), 1,2, 4-trichlorobenzene 28ml and triphenylphosphine 20.0g (0.076 Mol) into a reaction bottle, heating to temperature up to 200 ℃ for reaction, monitoring the reaction completely by TLC, concentrating under reduced pressure to remove solvent, adding toluene for extraction at 60 ℃, filtering insoluble substances, filtering the filtrate to pass through a silica gel column, eluting the column bed by toluene, concentrating and drying the column liquid to obtain a crude product, refluxing and boiling by ethanol, cooling to room temperature, filtering, drying to obtain 4.5gM, and obtaining the HPLC with the purity of 99.0 percent and the yield of 74.5 percent.
Example 3
At N 2 Under the protection, 13.1g (0.068 mol) of 2, 3-dichloronitrobenzene, 20.4g (0.078 mol) of 2-methyl formate-phenylboronic acid pinacol ester, 13.1g (0.095 mol) of potassium carbonate, 1.15g (0.001 mol) of tetra (triphenylphosphine) palladium, 150ml of dioxane and 35ml of water are added into a reaction bottle, the reaction is heated and refluxed for 8 hours, TLC monitors the reaction to be complete, ethyl acetate and water are added for extraction, water is used for washing until the reaction is neutral, the organic phase is concentrated to obtain an intermediate, and the intermediate is recrystallized by normal hexane to obtain M-A16.5g, the HPLC purity is 92.1 percent, and the yield is 82 percent.
Step 2
16.5g(0.057mol)ofM-Apreparedabove,130mlofethanol,6.8g(0.171mol)ofsodiumhydroxideand40mlofwaterareaddedintoareactionbottle,themixtureisheatedtorefluxreaction,TLCmonitorsthereactioncompletion,110mlofethanolisconcentrated,hydrochloricacidisusedforacidificationuntilthePHisbetween3and4,filtrationiscarriedout,afiltercakeiswashedtobeneutral,and13.9gofM-Bisobtainedafterdrying,theHPLCpurityis96.5%,andtheyieldis88%.
Step 3
To the flask were added 13.9g (0.05 mol) of the above M-B, 27.8g (0.065 mol) of biphenyl-2 iodonium salt, 0.29g (0.0013 mol) of palladium acetate, 17.9g (0.13 mol) of potassium carbonate and 325ml of NMP, which were heated to 130℃and stirred for 17 hours, TLC was monitored to complete the reaction, cooled to room temperature, extracted with ethyl acetate, washed with aqueous sodium chloride, dried over anhydrous magnesium sulfate, the drying agent was filtered off, the solvent was removed, and the crude product was purified by passing through a silica gel column using n-heptane/dichloroethane to give 11.2g of M-C, HPLC purity was 98.3%, and yield was 63%.
Step 4
N 2 Under protection, adding M-C11.2g (0.032 Mol), 1,2, 4-trichlorobenzene 45ml and triphenylphosphine 28.8g (0.11 Mol) into a reaction bottle, heating to 200 ℃ for reaction, monitoring the reaction completely by TLC, concentrating under reduced pressure to remove solvent, adding toluene for extraction at 60 ℃, filtering insoluble substances, filtering the filtrate, passing the filtrate through a silica gel column, eluting the column bed by toluene, concentrating and drying the column liquid to obtain a crude product, refluxing and boiling and washing by ethanol, cooling to room temperature, filtering, drying to obtain 7.2gM, and obtaining the HPLC with the purity of 99.2 percent and the yield of 71 percent.
The reaction principle of the invention is as follows:
theinventiontakes2,3-dichloronitrobenzeneasrawmaterial,andcarriesoutcouplingreactionwith2-methylformate-phenylpinacolboratetoprepareM-A,thentheM-AishydrolyzedunderalkalineconditiontopreparecarboxylicacidM-B,thenthecarboxylicacidM-Breactswith2-biphenyliodoniumsalttoclosetheringtopreparenitroeight-memberedringM-C,andthenthenitroclosingringiscarriedouttopreparethecarbazoleeight-memberedaromaticringstructureMofthetargetproduct.
The preparation method has short route design, easier synthesis of the intermediate, low cost, and the intermediate M-B reacts with 2-biphenyl iodonium salt to form a nitro eight-membered ring M-C, and then the nitro eight-membered ring M-C is subjected to nitroclosing to prepare the target product.
According to the invention, the carbazole eight-membered ring large conjugated structure is prepared by using a simple and easily available raw material, a series of compounds can be prepared by taking the structure as a parent nucleus, the molecular rigidity of the compounds is enhanced by increasing the eight-membered ring conjugation, the structure is more stable, and the OLED device using the parent nucleus also has a better service life.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Many other changes and modifications may be made without departing from the spirit and scope of the invention. It is to be understood that the invention is not to be limited to the specific embodiments, but only by the scope of the appended claims.
Claims (9)
1. The preparation method of the carbazole eight-membered ring large conjugated structure OLED material is characterized by comprising the following steps of:
step 1: taking2,3-dichloronitrobenzeneasarawmaterial,andcarryingoutcouplingreactionwith2-methylformate-phenylpinacolboratetoprepareM-A,whereinthemolarratioofthe2,3-dichloronitrobenzenetothe2-methylformate-phenylpinacolborateis1: 1 to 1.2; thestructuralformulaofM-Ais:
step 2: hydrolyzingM-AunderalkalineconditiontoobtainM-B; the structural formula of M-B is:
step 3: the M-B reacts with 2-biphenyl iodonium salt to form a ring closure, and the molar ratio of the M-C, the M-B and the 2-biphenyl iodonium salt is 1:1 to 1.5; the structural formula of M-C is:
step 4: the structural formula of the carbazolo eight-membered ring large conjugated structure M, M is prepared by using 1,2, 4-trichlorobenzene to carry out nitrocyclization on M-C, and the structural formula of the M is as follows:
2. the method for preparing the carbazolo eight-membered ring large conjugated structure OLED material according to claim 1, wherein the step 1 is specifically as follows: at N 2 undertheprotection,adding2,3-dichloronitrobenzene,2-methylformate-phenylpinacolborate,potassiumcarbonate,tetra(triphenylphosphine)palladium,dioxaneandwaterintoareactionbottle,heatingandrefluxingforreactionfor6-8h,andmonitoringthereactionbyTLCtoobtainanM-Asolution,whereinthemolarratioofthe2,3-dichloronitrobenzenetothepotassiumcarbonatetothetetra(triphenylphosphine)palladiumis1: 1.2 to 1.6: the dosage ratio of 0.01 to 0.02,2,3 of dichloronitrobenzene to dioxane to water is 0.01mol: 21-25 ml: 4-8 ml.
3. themethodforpreparingthecarbazoleeight-memberedringlargeconjugatedstructureOLEDmaterialaccordingtoclaim2,whereinthepost-treatmentoftheM-Asolutionisasfollows: ethylacetateandwaterareaddedforextraction,waterisusedforwashingtobeneutral,anintermediateisobtainedaftertheorganicphaseisconcentrated,M-Aisobtainedbyrecrystallizationwithnormalhexane,andthedosageratioofthe2,3-dichloronitrobenzenetotheethylacetatetothewateris0.01mol: 15-20 ml: 10-15 ml.
4. The method for preparing the carbazolo eight-membered ring large conjugated structure OLED material according to claim 1, wherein the step 2 is specifically: addingM-A,sodiumhydroxide,ethanolandwaterintoareactionbottle,heatingtorefluxreaction,andmonitoringthereactiontobecompletebyTLCtoobtainM-Bsolution,whereinthemolarratiooftheM-Atothesodiumhydroxideis1: 2.5to3.5,thedosageratioofM-Atoethanolandwateris0.01mol: 20-25 ml: 5-10 ml.
5. The method for preparing the carbazole eight-membered ring large conjugated structure OLED material according to claim 4, wherein the post-treatment of the M-B solution is as follows: concentrating 70% ethanol, acidifying with hydrochloric acid to pH 3-4, filtering, washing the filter cake with water to neutrality, and drying to obtain M-B.
6. The method for preparing the carbazolo eight-membered ring large conjugated structure OLED material according to claim 1, wherein the step 3 is specifically: adding M-B, biphenyl-2 iodonium salt, palladium acetate, potassium carbonate and NMP into a reaction bottle, heating to 130-140 ℃, stirring and reacting for 16-18 hours, and monitoring the reaction by TLC to obtain an M-C solution, wherein the molar ratio of the M-B to the palladium acetate to the potassium carbonate is 1:0.02 to 0.03:2 to 3, the dosage ratio of M-B to NMP is 0.01mol: 62-70 ml.
7. The method for preparing the carbazole eight-membered ring large conjugated structure OLED material according to claim 6, wherein the post-treatment of the M-C solution is as follows: cooling to room temperature, extracting with ethyl acetate, washing with sodium chloride water solution, drying the organic phase with anhydrous magnesium sulfate, filtering to remove desiccant, removing solvent, and passing the crude product through silica gel column with n-heptane/dichloroethane to obtain M-C.
8. The method for preparing the carbazolo eight-membered ring large conjugated structure OLED material according to claim 1, wherein the step 4 is specifically: at N 2 Under the protection, adding M-C, 1,2, 4-trichlorobenzene and triphenylphosphine into a reaction bottle, heating to 200 ℃ for reaction, and monitoring the reaction by TLC to obtain an M solution, wherein the molar ratio of the M-C to the triphenylphosphine is 1:3-4, and the dosage ratio of the M-C to the 1,2, 4-trichlorobenzene is 0.01mol: 11-15 ml.
9. The method for preparing the carbazole eight-membered ring large conjugated structure OLED material according to claim 8, wherein the post-treatment of the M solution is as follows: concentrating under reduced pressure to remove solvent, extracting with toluene at 60deg.C, filtering to remove insoluble substances, filtering to obtain filtrate, purifying with silica gel column, eluting with toluene, concentrating to obtain crude product, refluxing with ethanol, boiling, cooling to room temperature, filtering, and drying to obtain carbazole octamembered ring large conjugated structure M.
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