CN115703810A - Preparation method of organic luminescent material - Google Patents
Preparation method of organic luminescent material Download PDFInfo
- Publication number
- CN115703810A CN115703810A CN202110912522.9A CN202110912522A CN115703810A CN 115703810 A CN115703810 A CN 115703810A CN 202110912522 A CN202110912522 A CN 202110912522A CN 115703810 A CN115703810 A CN 115703810A
- Authority
- CN
- China
- Prior art keywords
- compound
- reaction
- benzo
- preparation
- pentadiene
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title description 6
- -1 benzo phosphorus heterocycle pentadiene compound Chemical class 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229940125782 compound 2 Drugs 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005605 benzo group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 26
- 238000001816 cooling Methods 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- CSECPSKVMZLOCQ-UHFFFAOYSA-N 1-ethynyl-2,3,4-trimethylbenzene Chemical group CC1=CC=C(C#C)C(C)=C1C CSECPSKVMZLOCQ-UHFFFAOYSA-N 0.000 description 1
- QYZOKWLTSOHTJI-UHFFFAOYSA-N C1=CC=C2P(=O)C=CC2=C1 Chemical compound C1=CC=C2P(=O)C=CC2=C1 QYZOKWLTSOHTJI-UHFFFAOYSA-N 0.000 description 1
- HFBFHSZJGYITHA-UHFFFAOYSA-N O=P(=O)C1=CC=CC1 Chemical compound O=P(=O)C1=CC=CC1 HFBFHSZJGYITHA-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 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
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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 invention provides a preparation method of a benzo phosphorus heterocycle pentadiene compound, which is characterized in that the benzo phosphorus heterocycle pentadiene compound is prepared only by taking a 2-alkynyl phosphine oxide derivative as a substrate and copper acetate as a catalyst, and compared with the prior art, the catalyst is simple and easy to obtain, the price is low, and the reaction method is more efficient. Especially when DMF and toluene are used as solvents, the yield of the obtained product is higher for other solvents. 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.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of an organic luminescent material, and more particularly relates to a preparation method of a benzo phosphorus heterocycle pentadiene compound.
Background
Phenylphosphene, a phospha compound similar to indole, is an important compound containing a phosphorus heterocyclic skeleton. The benzene-propyl-phosphorus heterocyclic cyclopentadiene has unique optical and electrochemical properties and wide application in the field of organic photoelectric material science, and the phosphorus atom at the center of the benzene-propyl-phosphorus heterocyclic cyclopentadiene can be used for generating oxides, sulfides, transition metal complexes, quaternary phosphonium salts and the like by a chemical modification method. In particular oxides and sulphides, exhibit high chemical and thermodynamic stability. Benzophosphocyclopentadiene as a special structure of phosphocyclopentadiene is widely used in organic luminescent materials such as solar cells, organic light emitting diodes, photochromic molecular switches, biological imaging, fluorescent probes, etc. The past few decades have attracted extensive attention in the field of material chemistry.
The synthesis method of the phenylpropyl phospholane compound at present mainly comprises the following steps:
(1) The method is characterized in that tolane is used as a raw material, a dilithium transition state compound is generated under the action of n-BuLi, and then the dilithium transition state compound reacts with phenyl phosphorus dichloride to generate a benzo phospha cyclopentadiene product.
(2) Using trimethylphenylacetylene as a substrate and n-hexane as a solvent, sequentially adding diisobutylaluminum hydride (DIBLA) and NBS to obtain an intermediate brominated compound, then adding 2.0 equiv of n-butyllithium as an organic reagent to obtain a dilithio transition state compound, and finally adding phenylphosphonic dichloride to react with the dilithio transition state compound to obtain the benfopentalene compound. The method has complicated reaction process, uses extremely unstable n-butyllithium, needs to react under the condition of deep cooling, and has harsh reaction conditions.
(3) 2-alkynyl phenyl phosphine oxide is used as a substrate, 20mol percent of potassium tert-butoxide (t-BuOK) is used as alkali, dimethyl sulfoxide (DMSO) is used as a solvent, and 2-phenyl alkynyl phenyl phosphorus oxide raw materials are reacted at 70 ℃ for 24 h to obtain the benzo phosphole oxide. The reaction is characterized by mild reaction conditions and better yield, but the consumption of alkali is a little bit larger than that of other reactions.
(4) 1,2-diphenylacetylene and diaryl phosphorus oxide are used as reaction raw materials, silver oxide is used as a catalyst or zinc nitrate and a small amount of silver oxide are used as catalysts, 8 h is reacted at 100 ℃ to obtain the benzo-phospholane pentadiene compound.
However, the above synthetic methods have some problems such as complicated steps, severe reaction conditions, complex reaction system, low yield, poor universality and the like, and therefore, there is an urgent need to develop a simple and efficient method for synthesizing the benzo phospholane compound.
However, no report is found on the method for preparing the benzo phospholane pentadiene compound by using simple and easily obtained copper acetate as a catalyst.
Disclosure of Invention
The invention aims to overcome the defects existing in the preparation of the benzo phosphorus heterocycle pentadiene compound in the prior art, and provides a preparation method of the benzo phosphorus heterocycle pentadiene compound, which is characterized in that in an organic solvent, 2-alkynyl phosphine oxide derivative 1 is used as a raw material, copper acetate is used as a catalyst, and the benzo phosphorus heterocycle pentadiene compound 2 is prepared by reaction, wherein the structural formula of the 2-alkynyl phosphine oxide derivative 1 is shown in the specification
The structural formula of the benzo phospholane pentadiene compound 2 is shown in the specification
Wherein R is 1 Is alkyl, substituted or unsubstituted aryl, R 2 Is a substituted or unsubstituted aryl group.
According to the preparation method of the benzo phospholane pentadiene compound, the alkyl is an alkyl with 1-10 carbon atoms.
According to the preparation method of the benzo phospholane compound, the alkyl is preferably an alkyl with 1-4 carbon atoms.
According to the preparation method of the benzo phospholane pentadiene compound, the aryl is an aryl with 6-12 carbon atoms.
According to the preparation method of the benzo phospholane compound, the aryl is preferably phenyl.
According to the preparation method of the benzo phospholane compound, the substituent group in the substituted aryl is alkyl with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms, halogen or nitro.
According to the preparation method of the benzo phospholane compound, the substituted group in the substituted aryl is preferably an alkyl group with 1-4 carbon atoms or an alkoxy group with 1-4 carbon atoms.
According to the preparation method of the benzo phospholane pentadiene compound, the halogen is F, cl, br and I.
According to the preparation method of the benzo phospholane compound, the organic solvent is selected from one or more of DMF, toluene, DMSO or DMA.
According to the preparation method of the benzo phospholane compound, the organic solvent is preferably selected from DMF and toluene.
The preparation method of the benzo phosphorus heterocycle pentadiene compound is characterized in that the reaction is carried out at the temperature of 0-200 ℃.
The preparation method of the benzo phosphorus heterocycle pentadiene compound is characterized in that the reaction is carried out at the temperature of 50-200 ℃.
The preparation method of the benzo phosphorus heterocycle pentadiene compound is characterized in that the reaction is carried out at the temperature of 100-200 ℃.
The preparation method of the benzo phospholane compound is characterized in that the reaction is preferably carried out at the temperature of 100-155 ℃.
The preparation method of the benzo phospholane compound is characterized by comprising the following steps: the molar amount of the catalyst is 0.1-10% of that of the 2-alkynyl phosphine oxide derivative.
The preparation method of the benzo phospholane compound is characterized by comprising the following steps: preferably, the molar amount of the catalyst is 0.5-10% of the molar amount of the 2-alkynyl phosphine oxide derivative.
The preparation method of the benzo phospholane compound is characterized by comprising the following steps: preferably, the molar amount of the catalyst is 1-10% of the molar amount of the 2-alkynyl phosphine oxide derivative.
The method for preparing benzo phospholane compound according to the invention comprises the following steps: the reaction time is 10min-60min.
The method for preparing a benzo phospholane compound according to the invention is characterized in that: preferably, the reaction time is 30min to 60min.
The main contributions of the invention relative to the prior art are mainly as follows:
according to the invention, the benzo-phospholane pentadiene compound is prepared by only taking the 2-alkynyl phosphine oxide derivative as a substrate and copper acetate as a catalyst, compared with the prior art, the catalyst is simple and easy to obtain, the price is low, and the reaction method is more efficient. Especially when DMF and toluene are used as solvents, the yield of the obtained product is higher for other solvents. 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 inventive step, are within the scope of protection of the disclosure.
The preparation method of the benzo phosphorus heterocycle pentadiene compound is characterized in that in an organic solvent, 2-alkynyl phosphine oxide derivatives 1 are used as raw materials, copper acetate is used as a catalyst, and the benzo phosphorus heterocycle pentadiene compound 2 is prepared through reaction, wherein the structural formula of the 2-alkynyl phosphine oxide derivatives 1 is shown in the specification
BenzophosphacyclopentadieneThe structural formula of the compound 2 is
Wherein R is 1 Is alkyl, substituted or unsubstituted aryl, R 2 Is a substituted or unsubstituted aryl group.
According to the preparation method of the benzo phospholane compound, the alkyl is the alkyl with 1-10 carbon atoms.
According to the preparation method of the benzo phospholane compound, the alkyl is preferably an alkyl with 1-4 carbon atoms.
According to the preparation method of the benzo phospholane compound, the aryl is an aryl with 6-12 carbon atoms.
According to the preparation method of the benzo phospholane compound, the aryl is preferably phenyl.
According to the preparation method of the benzo phospholane compound, the substituent group in the substituted aryl is alkyl with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms, halogen or nitro.
According to the preparation method of the benzo phospholane compound, the substituted group in the substituted aryl is preferably an alkyl group with 1-4 carbon atoms or an alkoxy group with 1-4 carbon atoms.
According to the preparation method of the benzo phospholane compound, the halogen is F, cl, br and I.
According to the preparation method of the benzo phospholane compound, the organic solvent is selected from one or more of DMF, toluene, DMSO or DMA.
According to the preparation method of the benzo phospholane compound, the organic solvent is preferably selected from DMF and toluene.
The preparation method of the benzo phospholane diene compound is characterized in that the reaction is carried out at the temperature of 0 to 200 ℃.
The preparation method of the benzo phosphorus heterocycle pentadiene compound is characterized in that the reaction is carried out at the temperature of 50-200 ℃.
The preparation method of the benzo phosphorus heterocycle pentadiene compound is characterized in that the reaction is carried out at the temperature of 100-200 ℃.
The preparation method of the benzo phospholane compound is characterized in that the reaction is preferably carried out at the temperature of 100-155 ℃.
The preparation method of the benzo phospholane compound is characterized by comprising the following steps: the molar amount of the catalyst is 0.1-10% of that of the 2-alkynyl phosphine oxide derivative.
The preparation method of the benzo phospholane compound is characterized by comprising the following steps: preferably, the molar amount of the catalyst is 0.5-10% of the molar amount of the 2-alkynyl phosphine oxide derivative.
The preparation method of the benzo phospholane pentadiene compound is characterized by comprising the following steps: preferably, the molar amount of the catalyst is 1-10% of the molar amount of the 2-alkynyl phosphine oxide derivative.
The method for preparing a benzo phospholane compound according to the invention is characterized in that: the reaction time is 10min-60min.
The method for preparing a benzo phospholane compound according to the invention is characterized in that: preferably, the reaction time is 30min to 60min.
Example 1
0.1mol2-alkynyl phosphine oxide derivative (R) 1 = phenyl, R 2 Putting the phenyl group and 10mmol of copper acetate in a reaction vessel, adding 50mL of toluene, stirring the system to be uniform, then slowly heating to 100 ℃, keeping the temperature for reaction for 30min, and naturally cooling the system to the temperature after the reaction is finishedConcentrating under reduced pressure at room temperature, and subjecting the system to column chromatography (V) DCM :V Ethyl acetate = 5:1) to give the corresponding phenylphosphidiene compound in a yield of 88.1%.
Example 2
0.1mol of 2-alkynyl phosphine oxide derivative (R) 1 = phenyl, R 2 Putting the phenyl group and 10mmol copper acetate in a reaction vessel, adding 50mLDMF, stirring the system to be uniform, then slowly heating to 150 ℃, keeping the temperature for reaction for 30min, 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 DCM :V Ethyl acetate = 5:1) to obtain the corresponding benphospha pentadiene compound with yield of 87.5%.
Example 3
0.1mol of 2-alkynyl phosphine oxide derivative (R) 1 = phenyl, R 2 Putting the phenyl and 10mmol of copper acetate in a reaction vessel, adding 50ml of DMA, stirring the system to be uniform, then slowly heating to 160 ℃, keeping the temperature for reaction for 30min, after the reaction is finished, naturally cooling the system to room temperature, concentrating under reduced pressure, and carrying out column chromatography separation (V) on the system DCM :V Ethyl acetate = 5:1) to obtain the corresponding benphospha-pentadiene compound with a yield of 60.8%.
Example 4
0.1mol of 2-alkynyl phosphine oxide derivative (R) 1 = phenyl, R 2 Putting the phenyl group and 10mmol of copper acetate in a reaction vessel, adding 50mLDMSO, stirring the system to be uniform, then slowly heating to 185 ℃, keeping the temperature for reaction for 30min, after the reaction is finished, naturally cooling the system to room temperature, concentrating under reduced pressure, and carrying out column chromatography separation (V) on the system DCM :V Ethyl acetate = 5:1) to obtain the corresponding ben-phospha pentadiene compound with a yield of 65%.
Example 5
0.1mol of 2-alkynyl phosphine oxide derivative (R) 1 = phenyl, R 2 = phenyl) and 10mmol copper acetate are placed in a reaction vessel, 50mL acetonitrile is added, the system is stirred to be uniform,heating to 80 deg.C slowly, maintaining the temperature, reacting for 30min, cooling to room temperature, concentrating under reduced pressure, and separating by column chromatography (V) DCM :V Acetic acid ethyl ester = 5:1) to yield the corresponding benzophospholane compound in a 40% yield.
Example 6
0.1mol of 2-alkynylphosphine oxide derivative (R) 1 = p-methylphenyl, R 2 Putting the phenyl group and 10mmol of copper acetate in a reaction vessel, adding 50mL of toluene, stirring the system to be uniform, then slowly heating to 100 ℃, keeping the temperature for reaction for 60min, after the reaction is finished, naturally cooling the system to room temperature, concentrating under reduced pressure, and carrying out column chromatography separation (V) on the system DCM :V Ethyl acetate = 5:1) to obtain the corresponding benphospha pentadiene compound with a yield of 90.5%.
Example 7
0.1mol of 2-alkynyl phosphine oxide derivative (R) 1 = p-methylphenyl, R 2 Putting the phenyl group and 1mmol of copper acetate in a reaction vessel, adding 50mL of toluene, stirring the system to be uniform, then slowly heating to 100 ℃, keeping the temperature for reaction for 60min, after the reaction is finished, naturally cooling the system to room temperature, concentrating under reduced pressure, and carrying out column chromatography separation (V) on the system DCM :V Ethyl acetate = 5:1) to obtain the corresponding benphospha pentadiene compound with a yield of 83.4%. .
Example 8
0.1mol of 2-alkynylphosphine oxide derivative (R) 1 = p-methylphenyl, R 2 Putting the phenyl group and 10mmol copper acetate in a reaction vessel, adding 50mLDMF, stirring the system to be uniform, then slowly heating to 150 ℃, keeping the temperature for reaction for 60min, 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 DCM :V Ethyl acetate = 5:1) to obtain the corresponding benphospha-heterocyclopeneoxydiene compound with a yield of 88.2%.
Example 9
0.1mol of 2-alkynyl phosphine oxide derivative（R 1 = p-methylphenyl, R 2 Putting phenyl and 5mmol copper acetate in a reaction vessel, adding 50mLDMF, stirring the system to be uniform, slowly heating to 150 ℃, keeping the temperature for reaction for 60min, 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 DCM :V Ethyl acetate = 5:1) to yield 82.7% of the corresponding phenylphospholane compound.
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. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications are intended to be within the scope of the present invention.
Claims (10)
1. A preparation method of a benzo phosphorus heterocycle pentadiene compound is characterized in that a benzo phosphorus heterocycle pentadiene compound 2 is prepared by taking a 2-alkynyl phosphine oxide derivative 1 as a raw material and copper acetate as a catalyst through reaction in an organic solvent, wherein the structural formula of the 2-alkynyl phosphine oxide derivative 1 is shown in the specification
The structural formula of the benzo phospholane pentadiene compound 2 is shown in the specification
Wherein, R1 is alkyl, substituted or unsubstituted aryl, R2 is substituted or unsubstituted aryl.
2. The method for preparing a benphospha-pentadiene compound according to claim 1, wherein the alkyl group is an alkyl group having 1 to 10 carbon atoms.
3. The process for preparing a benphospha-pentadiene compound according to any one of claims 1-2, wherein the aryl group is an aryl group having 6-12 carbon atoms, preferably a phenyl group.
4. The method for preparing a benphospha-pentadiene compound according to any one of claims 1-3, wherein the substituent group in the substituted aryl group is an alkyl group having 1-6 carbon atoms, an alkoxy group having 1-6 carbon atoms, a halogen or a nitro group.
5. A process for the preparation of a ben-phospha-pentadiene according to any one of claims 1 to 4, wherein the organic solvent is one or more selected from DMF, toluene, DMSO or DMA.
6. The process for producing a phenylphosphopentadiene compound according to any one of claims 1 to 5, wherein the reaction is carried out at a temperature of from 0 to 200 ℃.
7. The process for preparing a bendophosphapentadiene compound according to any one of claims 1 to 6, wherein the reaction is carried out at a temperature of 50 to 200 ℃.
8. The process for preparing a bendophosphapentadiene compound according to any one of claims 1 to 7, wherein the reaction is carried out at a temperature of 100 to 200 ℃.
9. The process for preparing a benphosphacyclopentadiene compound according to any one of claims 1 to 8, characterized in that: the molar amount of the catalyst is 0.1-10% of that of the 2-alkynyl phosphine oxide derivative.
10. The process for preparing a benphosphacyclopentadiene compound according to any one of claims 1 to 9, characterized in that: the reaction time is 10min-60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110912522.9A CN115703810A (en) | 2021-08-10 | 2021-08-10 | Preparation method of organic luminescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110912522.9A CN115703810A (en) | 2021-08-10 | 2021-08-10 | Preparation method of organic luminescent material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115703810A true CN115703810A (en) | 2023-02-17 |
Family
ID=85179477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110912522.9A Pending CN115703810A (en) | 2021-08-10 | 2021-08-10 | Preparation method of organic luminescent material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115703810A (en) |
-
2021
- 2021-08-10 CN CN202110912522.9A patent/CN115703810A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1944308B1 (en) | Process for production of ortho-metallized 1:3 complex of iridium with homoligand | |
| CN108558949B (en) | Method for catalytically synthesizing benzo-phospha-cyclopentadiene by using Pd nanoparticles | |
| CN102030770A (en) | Preparation method of aromatic boronic acid ester composite | |
| CN111848675B (en) | Tetrahydroquinoline framework chiral phosphine-nitrogen ligand and preparation method and application thereof | |
| CN111285881B (en) | Thieno [3,4-b ] indole derivative and synthetic method thereof | |
| CN115703810A (en) | Preparation method of organic luminescent material | |
| CN113999196B (en) | Preparation method of 4- (2-nitrophenyl) dibenzo [ b, d ] furan | |
| RU2122001C1 (en) | Method of preparing tetrathiafulvalene precursor | |
| CN112694489B (en) | Preparation method of N-heterocyclic carbene copper catalyst | |
| CN115703809A (en) | Preparation method of photoelectric material compound | |
| CN115703808A (en) | Method for simply preparing organic photoelectric material compound | |
| CN115703807A (en) | Method for preparing organic photoelectric material compound | |
| US6489526B2 (en) | Method for synthesis of hydrocarbyl bridged indenes | |
| CN113201014B (en) | Preparation method of organophosphorus compound containing unsaturated bonds | |
| CN113201015B (en) | Preparation method of allyl organophosphorus compound | |
| CN114805268B (en) | Synthesis method of visible light mediated cyclopenta [ b ] benzofuran derivative | |
| TWI773602B (en) | Triarylcinnolin-2-ium salts and method of manufacturing the same | |
| CN115260103B (en) | Preparation method of 4,5-dihalogen-1- (difluoromethyl) -1H-imidazole | |
| CN112811974B (en) | Novel aryl trifluoroethylene synthesized by arylation reagent and preparation method thereof | |
| CN115960062B (en) | Preparation method of 9-chloronaphtho [2,3-b ] benzofuran | |
| JP6842696B2 (en) | Compounds, compound synthesis methods and organic semiconductor materials | |
| JPS61287964A (en) | Production of t-butyl-substituted phthalocyanine and its intermediate | |
| CN115677766A (en) | Preparation method of phosphorus-containing photoelectric functional material | |
| CN101993318A (en) | Preparation method of aromatic halogenated compound | |
| CN115677745A (en) | Preparation method of 9-anthraceneboronic acid |
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: 20230217 |