CN115677775A - Preparation method of dibenzophospholane pentadiene compound with electroluminescence function - Google Patents
Preparation method of dibenzophospholane pentadiene compound with electroluminescence function Download PDFInfo
- Publication number
- CN115677775A CN115677775A CN202110864825.8A CN202110864825A CN115677775A CN 115677775 A CN115677775 A CN 115677775A CN 202110864825 A CN202110864825 A CN 202110864825A CN 115677775 A CN115677775 A CN 115677775A
- Authority
- CN
- China
- Prior art keywords
- dibenzophospholane
- compound
- reaction
- compound according
- preparation
- 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
- -1 pentadiene compound Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000005401 electroluminescence Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- IQZPDFORWZTSKT-UHFFFAOYSA-N nitrosulphonic acid Chemical group OS(=O)(=O)[N+]([O-])=O IQZPDFORWZTSKT-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 231100000171 higher toxicity Toxicity 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000003208 petroleum Substances 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- RYFWKKPOIPDSBC-UHFFFAOYSA-N O=[PH2]C1=CC=CC=C1C1=CC=CC=C1 Chemical compound O=[PH2]C1=CC=CC=C1C1=CC=CC=C1 RYFWKKPOIPDSBC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- IGDNJMOBPOHHRN-UHFFFAOYSA-N 5h-benzo[b]phosphindole Chemical class C1=CC=C2C3=CC=CC=C3PC2=C1 IGDNJMOBPOHHRN-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- HCWMKUFIKIQADR-UHFFFAOYSA-N 1,4-dibromo-2-diphenylphosphorylbenzene Chemical compound BrC1=C(C=C(C=C1)Br)P(C1=CC=CC=C1)(C1=CC=CC=C1)=O HCWMKUFIKIQADR-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DJMUYABFXCIYSC-UHFFFAOYSA-N 1H-phosphole Chemical compound C=1C=CPC=1 DJMUYABFXCIYSC-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- NMHIDRUWAYHZMY-UHFFFAOYSA-N 9H-fluoren-1-yl-oxido-oxophosphanium Chemical compound P(=O)(=O)C1=CC=CC=2C3=CC=CC=C3CC1=2 NMHIDRUWAYHZMY-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- YYQLNLDMILHCQP-UHFFFAOYSA-N [PH3]=O.C1=CC=CC=C1C1=CC=CC=C1 Chemical compound [PH3]=O.C1=CC=CC=C1C1=CC=CC=C1 YYQLNLDMILHCQP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
Abstract
The preparation method of the dibenzophospholane compound is characterized in that the dibenzophospholane compound is prepared by taking a biphenyl phosphine oxide compound as an initial raw material and silver nitrate as a catalyst in an organic solvent through reaction. The method adopts alcohol solvent with lower toxicity, particularly ethanol, as the solvent, and the yield of the prepared product is higher compared with the solvent with higher toxicity used by other methods.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a phosphorus-containing compound with an electroluminescent function, and more particularly relates to a preparation method of a dibenzophospholane pentadiene compound.
Background
Phenylphosphene, a phospha compound similar to indole, is an important compound containing a phosphorus heterocyclic skeleton. The organic photoelectric material has unique optical and electrochemical properties, so that the organic photoelectric material has wide application in the field of organic photoelectric material science. The Dibenzophosphole derivative (also called as phosphofluorene) has a core of phosphole and a fused ring structure formed by two benzene rings, and the 9-position carbon atom of fluorene is replaced by phosphorus atom in the molecular structure. The phosphorus atom can change the electronic structure of the material through the interaction between the d orbit and the pi-conjugated system, and has good modifiability, such as oxidation, vulcanization or coordination with metal, so that the photoelectric property of the material can be effectively adjusted. Therefore, the dibenzophosphole derivatives have attracted extensive attention as a novel phosphorus-containing optoelectronic functional unit with electroluminescent properties
The synthesis method of the diphenyl propane phospholane pentadiene compound mainly comprises the following steps:
(1) The dibenzophosphole is obtained by taking biphenyl phosphine oxide as a starting material and palladium acetate as a catalyst in a way of removing H. THF is used as a solvent in the reaction, and the target product can be obtained by the reaction for three hours at the temperature of 65 ℃ through the breakage of P-H and C-H bonds. And can achieve 94% yield. Because the steps are less, the treatment steps are reduced in the post-treatment process, higher yield is obtained, and the method is one of better methods for synthesizing the target product. However, the method uses a Pd catalyst, so that the method is expensive and has high toxicity, and the catalyst is easy to deactivate.
(2) The diphenyl propane phosphorus heterocyclic pentadiene compound is synthesized by taking a mixture consisting of 2, 5-dibromo phenyl diphenyl phosphine oxide and aryl boric acid or a heteroaryl compound as a raw material, taking palladium salt or a palladium complex as a catalytic precursor, using inorganic base and taking trimethyl acetic acid as an auxiliary agent, and reacting in an organic solvent at 100-120 ℃ for 10-24h under the protection of inert gas. The invention adopts 2, 5-dibromo phenyl diphenyl phosphine oxide as a raw material for preparation, and provides a brand new method for preparing the diphenylphosphine phospholane pentadiene compound, but the method has extremely complex reaction conditions, long reaction time and low overall efficiency.
(3) The diphenylphosphine oxide is used as an initial raw material, manganese acetate is used as an accelerator, and the diphenylphosphine heterocyclic pentadiene compound is prepared by reacting at 20-120 ℃ in an organic solvent.
(4) Also starting from terphenyl phosphine oxide, the reaction is triggered not by catalytic methods but by means of free-radical initiators (e.g. AIBN, BPO, et3B, etc.), the conversion being effected in methanol solution at room temperature. However, this method has a long reaction time (17 hours or more) and the yield of the reaction is low.
However, these methods have problems such as complicated steps, severe reaction conditions, complicated reaction system, low yield, and poor universality, and thus there is an urgent need for a simple and efficient method for synthesizing dibenzophospholane compounds.
However, no report is found on the method for preparing the dibenzophospholane compound by using simple and easily available silver nitrate as a catalyst.
Disclosure of Invention
The invention aims to overcome the defects existing in the preparation of dibenzophospholane compounds in the prior art, and provides a preparation method of the dibenzophospholane compounds, which is characterized in that the dibenzophospholane compounds are prepared by taking a biphenyl phosphine oxide compound as a starting material and silver nitrate as a catalyst through reaction in an organic solvent, wherein the structural formula of the biphenyl phosphine oxide compound is shown in the specification
The structural formula of the dibenzophospholane compound is shown as the specification, wherein R is 1 Is a substituted or unsubstituted aryl radical, R 2 -R 9 Optionally hydrogen, C1-C10 alkyl, C1-C10 alkoxy, substituted or unsubstituted aryl, halogen, nitro, sulfonic acid group, cyano, N, N-dimethylamino or hydroxy.
According to the preparation method of the dibenzophospholane compound, the substituent group is alkyl with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms, halogen or nitro.
According to the preparation method of the dibenzophospholane compound, the aryl is phenyl, naphthyl or anthryl.
According to the preparation method of the dibenzophospholane compound, preferably, the aryl is phenyl.
According to the preparation method of the dibenzophospholane pentadiene compound, the organic solvent is selected from alcohol solvents.
According to the preparation method of the dibenzophospholane compound, the organic solvent is selected from ethanol, methanol or propanol.
According to the preparation method of the dibenzophospholane pentadiene compound, the organic solvent is preferably ethanol.
The method for preparing a dibenzophospholane compound according to the invention is characterized in that the reaction is carried out at a temperature of 20 to 100 ℃.
The preparation method of the dibenzophospholane compound is characterized in that the reaction is carried out at the temperature of 20-78 ℃.
The preparation method of the dibenzophospholane compound is characterized in that the reaction is preferably carried out at the temperature of 30-78 ℃.
The preparation method of the dibenzophospholane compound is characterized by comprising the following steps: the feeding molar ratio of the biphenyl phosphine oxide compound to the silver nitrate is 1.
The preparation method of the dibenzophospholane compound is characterized by comprising the following steps: preferably, the feeding molar ratio of the biphenyl phosphine oxide compound to the silver nitrate is 1.
The method for preparing a dibenzophospholane compound according to the invention comprises the following steps: the reaction time is 0.5-5h.
The method for preparing a dibenzophospholane compound according to the invention comprises the following steps: preferably, the reaction time is 1 to 3 hours.
The main contributions of the invention relative to the prior art are mainly:
compared with the prior art, the method for preparing the dibenzophospholane pentadiene compound by using the biphenyl phosphine oxide compound as the starting material and silver nitrate as the catalyst has the advantages of simple and easily obtained catalyst, low price and more efficient reaction method. The method adopts alcohol solvent with lower toxicity, particularly ethanol, as the solvent, and the yield of the prepared product is higher compared with the solvent with higher toxicity used by other methods. Overall, by adopting the technical scheme of the invention, the overall reaction is simpler, economic and environment-friendly, and is suitable for large-scale production.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure are clearly and completely described. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without any inventive step, are within the scope of protection of the disclosure.
The preparation method of the dibenzophospholane compound is characterized in that the dibenzophospholane compound is prepared by taking a biphenyl phosphine oxide compound as an initial raw material and silver nitrate as a catalyst through reaction in an organic solvent, wherein the structural formula of the biphenyl phosphine oxide compound is shown in the specification
The structural formula of the dibenzophospholane pentadiene compound is shown in the specification
Wherein R is 1 Is substituted or unsubstituted aryl, R 2 -R 9 Optionally hydrogen, C1-C10 alkyl, C1-C10 alkoxy, substituted or unsubstituted aryl, halogen, nitro, sulfonic acid group, cyano, N, N-dimethylamino or hydroxy.
According to the preparation method of the dibenzophospholane compound, the substituent group is alkyl with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms, halogen or nitro.
According to the preparation method of the dibenzophospholane compound, the aryl is phenyl, naphthyl or anthryl.
According to the preparation method of the dibenzophospholane compound, preferably, the aryl is phenyl.
According to the preparation method of the dibenzophospholane compound, the organic solvent is selected from alcohol solvents.
According to the preparation method of the dibenzophospholane compound, the organic solvent is selected from ethanol, methanol or propanol.
According to the preparation method of the dibenzophospholane compound, the organic solvent is preferably ethanol.
The method for preparing a dibenzophospholane compound according to the invention is characterized in that the reaction is carried out at a temperature of 20 to 100 ℃.
The preparation method of the dibenzophospholane compound is characterized in that the reaction is carried out at the temperature of 20-78 ℃.
The preparation method of the dibenzophospholane compound is characterized in that the reaction is preferably carried out at the temperature of 30-78 ℃.
The preparation method of the dibenzophospholane compound is characterized by comprising the following steps: the feeding molar ratio of the biphenyl phosphine oxide compound to the silver nitrate is 1.
The preparation method of the dibenzophospholane compound is characterized by comprising the following steps: preferably, the feeding molar ratio of the biphenyl phosphine oxide compound to the silver nitrate is 1.
The method for preparing a dibenzophospholane compound according to any one of the claims of the present invention, wherein: the reaction time is 0.5-5h.
The method for preparing a dibenzophospholane compound according to the invention comprises the following steps: preferably, the reaction time is 1 to 3 hours.
Example 1
100mmol of biphenyl phosphine oxide compound (R) 1 = phenyl, R 2-9 H) and 50mmol of silver nitrate are placed in a reaction vessel, 100mL of ethanol is added, the system is stirred to be uniform, the reaction is carried out at the temperature of 50 ℃, the temperature is kept for reaction for 1H, after the reaction is finished, the system is naturally cooled to the room temperature, the reduced pressure concentration is carried out, and the system is subjected to column chromatography separation (V) Ethyl acetate :V Petroleum ether = 3:2) to obtain the corresponding dibenzophospholane compound in a yield of 92%.
Example 2
100mmol of biphenyl phosphine oxide compound (R) 1 = phenyl, R 2-9 H) and 50mmol of silver nitrate are placed in a reaction vessel, 100mL of acetonitrile is added, the system is stirred to be uniform, the reaction is carried out at the temperature of 50 ℃, the temperature is kept for reaction for 1H, after the reaction is finished, the system is naturally cooled to the room temperature, the reduced pressure concentration is carried out, and the system is subjected to column chromatography separation (V) Acetic acid ethyl ester :V Petroleum ether = 3:2) to yield the corresponding dibenzophosphopentadiene compound in a yield of 75%.
Example 3
100mmol of biphenylyl phosphine oxide (R) 1 = phenyl, R 2-9 H) and 50mmol of silver nitrate are placed in a reaction vessel, 100mL of THF is added, the system is stirred to be uniform, the reaction is carried out at the temperature of 50 ℃, the temperature is kept for reaction for 1H, after the reaction is finished, the system is naturally cooled to the room temperature, the decompression and the concentration are carried out, and the system is subjected to column chromatography separation (V) Acetic acid ethyl ester :V Petroleum ether = 3:2) to obtain the corresponding dibenzophospholane compound in a yield of 78%.
Example 4
100mmol of biphenyl phosphine oxide compound (R) 1 = phenyl, R 2-9 All H) and 50mmol of silver nitrate are placed in a reaction vessel, 100mL of DMF is added, the system is stirred to be uniform, the reaction is carried out at the temperature of 50 ℃, the temperature is kept for reaction for 1H, after the reaction is finished, the system is naturally cooled to the room temperature, the reduced pressure concentration is carried out, and the system is subjected to column chromatography separation (V) Ethyl acetate :V Petroleum ether = 3:2) to obtain the corresponding dibenzophospholane pentadiene compound with a yield of 69%.
Example 5
100mmol of biphenylyl phosphine oxide (R) 1 = phenyl, R 2-9 H) and 50mmol of silver nitrate are placed in a reaction vessel, 100mL of methanol is added, the system is stirred to be uniform, the reaction is carried out at the temperature of 50 ℃, the temperature is kept for reaction for 1H, after the reaction is finished, the system is naturally cooled to the room temperature, the reduced pressure concentration is carried out, and the system is subjected to column chromatography separation (V) Ethyl acetate :V Petroleum ether = 3:2) to obtain the corresponding dibenzophosphole pentadiene compound with a yield of 88%.
Example 6
100mmol of biphenylyl phosphine oxide (R) 1 = phenyl, R 2-9 H) and 100mmol of silver nitrate are placed in a reaction vessel, 100mL of ethanol is added, the system is stirred to be uniform, the reaction is carried out at the temperature of 78 ℃, the temperature is kept for reaction for 1H, after the reaction is finished, the system is naturally cooled to the room temperature, the reduced pressure concentration is carried out, and the system is subjected to column chromatography separation (V) Ethyl acetate :V Petroleum ether = 3:2) to obtain the corresponding dibenzophosphole pentadiene compound with a yield of 95%.
Example 7
100mmol of biphenyl phosphine oxide compound (R) 1 = phenyl, R 2-9 H) and 100mmol of silver nitrate are placed in a reaction vessel, 100mL of ethanol is added, the system is stirred to be uniform, the reaction is carried out at the temperature of 30 ℃, the temperature is kept for reaction for 3 hours, after the reaction is finished, the system is naturally cooled to the room temperature, the reduced pressure concentration is carried out, and the system is subjected to column layerSeparation and analysis (V) Acetic acid ethyl ester :V Petroleum ether = 3:2) to obtain the corresponding dibenzophosphole diene compound with a yield of 90%.
Example 8
100mmol of biphenyl phosphine oxide compound (R) 1 = phenyl, R 2-9 All H) and 10mmol of silver nitrate are placed in a reaction vessel, 100mL of ethanol is added, the system is stirred to be uniform, the reaction is carried out at the temperature of 30 ℃, the temperature is kept for reaction for 3 hours, after the reaction is finished, the system is naturally cooled to the room temperature, the reduced pressure concentration is carried out, and the system is subjected to column chromatography separation (V) Ethyl acetate :V Petroleum ether = 3:2) to obtain the corresponding dibenzophosphole pentadiene compound with a yield of 80%.
Example 9
100mmol of biphenylyl phosphine oxide (R) 1 = phenyl, R 2-8 Are all H, R 9 = methyl) and 50mmol silver nitrate in a reaction vessel, adding 100mL ethanol, stirring the system to be uniform, reacting at 50 ℃, keeping the temperature for reaction for 1h, after the reaction is finished, naturally cooling the system to room temperature, concentrating under reduced pressure, and performing column chromatography separation (V) on the system Ethyl acetate :V Petroleum ether = 3:2) to obtain the corresponding dibenzophosphole diene compound with a yield of 90%.
Example 10
100mmol of biphenylyl phosphine oxide (R) 1 = phenyl, R 2-8 Are all H, R 9 Putting the mixture in a reaction vessel, adding 100mL ethanol, stirring the system to be uniform, reacting at 78 ℃, keeping the temperature for reacting for 1h, naturally cooling the system to room temperature after the reaction is finished, concentrating under reduced pressure, and performing column chromatography separation (V) on the system Acetic acid ethyl ester :V Petroleum ether = 3:2) to obtain the corresponding dibenzophospholane compound in a yield of 92%.
Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A preparation method of a dibenzophospholane compound is characterized in that a dibenzophospholane compound is prepared by taking a biphenyl phosphine oxide compound as an initial raw material and silver nitrate as a catalyst through reaction in an organic solvent, wherein the structural formula of the biphenyl phosphine oxide compound is shown in the specification
The structural formula of the dibenzophospholane compound is shown as
Wherein R is 1 Is substituted or unsubstituted aryl, R 2 -R 9 Optionally hydrogen, C1-C10 alkyl, C1-C10 alkoxy, substituted or unsubstituted aryl, halogen, nitro, sulfonic acid group, cyano, N, N-dimethylamino or hydroxy.
2. The method for preparing a dibenzophospholane compound according to claim 1, wherein said substituent group is an alkyl group having 1-6 carbon atoms, an alkoxy group having 1-6 carbon atoms, a halogen or a nitro group.
3. The process for preparing a dibenzophospholane compound according to any one of claims 1-2, wherein said aryl group is phenyl, naphthyl or anthryl.
4. The process for producing a dibenzophospholane compound according to any one of claims 1 to 3, wherein said aryl group is a phenyl group.
5. The process for producing a dibenzophospholane compound according to any one of claims 1 to 4, wherein said organic solvent is selected from alcoholic solvents.
6. The process for producing a dibenzophospholane compound according to any one of claims 1 to 5, wherein the organic solvent is selected from ethanol, methanol and propanol, preferably ethanol.
7. The process for producing a dibenzophospholane compound according to any one of claims 1 to 6, wherein the reaction is carried out at a temperature of 20 to 100 ℃.
8. The process for producing a dibenzophospholane compound according to any one of claims 1 to 7, wherein the reaction is carried out at a temperature of from 20 to 78 ℃.
9. The process for producing a dibenzophospholane compound according to any one of claims 1 to 8, wherein: the feeding molar ratio of the biphenyl phosphine oxide compound to the silver nitrate is 1.
10. The process for producing a dibenzophospholane compound according to any one of claims 1 to 9, wherein: the reaction time is 0.5-5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110864825.8A CN115677775A (en) | 2021-07-29 | 2021-07-29 | Preparation method of dibenzophospholane pentadiene compound with electroluminescence function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110864825.8A CN115677775A (en) | 2021-07-29 | 2021-07-29 | Preparation method of dibenzophospholane pentadiene compound with electroluminescence function |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115677775A true CN115677775A (en) | 2023-02-03 |
Family
ID=85058683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110864825.8A Pending CN115677775A (en) | 2021-07-29 | 2021-07-29 | Preparation method of dibenzophospholane pentadiene compound with electroluminescence function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115677775A (en) |
-
2021
- 2021-07-29 CN CN202110864825.8A patent/CN115677775A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114031542A (en) | Novel preparation method of azabicyclo medical intermediate | |
| CN108017613B (en) | Method for preparing polyaryl substituted naphthalene derivative by ruthenium-catalyzed reaction of heterocyclic aromatic ketone and tolane | |
| CN112920145B (en) | Method for synthesizing 2, 5-furandicarboxylic acid by visible light catalysis | |
| CN112321527B (en) | Lipid drop targeted fluorescent probe and synthetic method and application thereof | |
| CN113105357B (en) | Synthesis method and application of novel p-aryl azophenol derivative | |
| CN111471046B (en) | Carbazole indole quinone derivative and preparation method and application thereof | |
| CN115677775A (en) | Preparation method of dibenzophospholane pentadiene compound with electroluminescence function | |
| CN115677766A (en) | Preparation method of phosphorus-containing photoelectric functional material | |
| CN107382910B (en) | Difluoromethyl aldehyde hydrazone compound and preparation method thereof | |
| CN113582940B (en) | Lipid drop specific fluorescent probe and synthetic method thereof | |
| CN113444041B (en) | Method for synthesizing polysubstituted quinoline compound by photocatalysis | |
| CN113896675A (en) | Organic luminescent material based on carbazole-triphenylamine derivative and preparation method thereof | |
| CN113201014B (en) | Preparation method of organophosphorus compound containing unsaturated bonds | |
| CN111732516A (en) | A kind ofNProcess for preparing (E) -aryl-substituted heterocyclic compounds | |
| CN113201015B (en) | Preparation method of allyl organophosphorus compound | |
| KR102292794B1 (en) | Preparation method of 2-substituted 1,2,3,4-tetrahydroquinoline compound | |
| CN113735799B (en) | Synthesis method of dyclonine hydrochloride | |
| CN115322200B (en) | Preparation method of spiro pyrroloquinoxaline derivative | |
| CN114031507B (en) | Synthesis method of o-aminobenzyl alcohol compound | |
| CN113234083B (en) | Tetrahydroquinoline pyran compound and preparation method and application thereof | |
| CN113735867B (en) | Chiral indolo oxa seven-membered ring compound and synthesis method thereof | |
| CN110194734B (en) | Chiral fluorescent compound based on cyclophane alkyl skeleton and preparation method and application thereof | |
| CN116573983A (en) | 1,3, 5-triarylbenzene compound and preparation method thereof | |
| CN115703810A (en) | Preparation method of organic luminescent material | |
| CN116574072A (en) | Method for preparing 2, 5-diaryl substituted furan |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20230203 |