Preparation method of conjugated compound containing bis(phenylsulfonyl)benzene structure and an organic electroluminescent diode device using the conjugated compound

Patent metadata

Field	Value
Publication number	US-9604941-B2
Application number	US-201514763830-A
Country	US
Kind code	B2
Filing date	May 22, 2015
Priority date	Apr 28, 2015
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

The invention provides a conjugated compound containing a bis(phenylsulfonyl)benzene structure, a preparation method and an application thereof, the compound includes a chemical structure with one of structural general formulas as follows:

the invention obtains a conjugated compound containing a bis(phenylsulfonyl)benzene structure by selecting multiple kinds of conjugated aromatic units to react with halogen-substituted bis(phenylsulfonyl)benzene in the manner of Suzuki coupling reaction, Buchwald-Hartwig coupling reaction or copper-catalyzed halogenated aromatic amination reaction. The novel compound prepared by the invention has the characteristic of fluorescence as well as a certain electrical conductivity, and thus can be applied to fabricate a light-emitting layer or an electron transport layer of an organic electroluminescent diode.

First claim

What is claimed is:

1. A preparation method of a conjugated compound containing a bis(phenylsulfonyl)benzene structure, the conjugated compound comprising a chemical structure with one of structural general formulas as follows:

in the formula A and the formula B, each benzene ring being covalently bonded with adjacent sulfonyl group, Ar unit or N(Ar) 2 unit at an arbitrary position;
wherein the Ar unit has a conjugated structure and is one of aromatic rings constituted by vinylene group, ethynylene group and hydrogen and carbon atoms, aromatic heterocyclic rings constituted by carbon, nitrogen and hydrogen atoms, aromatic heterocyclic rings constituted by carbon , nitrogen, oxygen and hydrogen atoms, aromatic heterocyclic rings constituted by carbon, sulfur and hydrogen atoms, aromatic heterocyclic rings constituted by carbon, silicon and hydrogen atoms, aromatic heterocyclic rings constituted by carbon, nitrogen, sulfur and hydrogen atoms, aromatic heterocyclic rings constituted by carbon, silicon, sulfur and hydrogen atoms, and any combinations thereof;
the preparation method comprising following steps:
step 10, synthesizing a precursor of halogen-substituted bis(phenylsulfonyl)benzene;
step 20, making the synthesized precursor of halogen-substituted bis(phenylsulfonyl)benzene to react with a borate ester compound of a Ar unit in the presence of catalyst in a manner of Suzuki coupling reaction, to thereby prepare the conjugated compound containing a bis(phenylsulfonyl)benzene structure, and a reaction equation is as follows:

or,
step 20′, making the synthesized precursor of halogen-substituted bis(phenylsulfonyl)benzene to react with a NH(Ar) 2 compound containing secondary amine atoms in a manner of Buchwald-Hartwig coupling reaction or copper-catalyzed halogenated aromatic amination reaction to thereby prepare the conjugated compound containing a bis(phenylsulfonyl)benzene structure, and a reaction equation is as follows:

2. The preparation method of a conjugated compound containing a bis(phenylsulfonyl)benzene structure as claimed in claim 1 , wherein the step 10 concretely comprises following steps:
step 11, dissolving a halogenated thiophenol and a dichloro-dicyano-p-benzoquinone (DDQ) in a solvent, heating to react, and thereby obtaining a halogenated diphenyl disulfide;
step 12, dissolving the halogenated diphenyl disulfide, a dihalogeno-benzene, a catalyst and an alkali in a solvent, heating to react and thereby obtaining a halogen-substituted bis(phenylsulfenyl)benzene;
step 13, dissolving the halogen-substituted bis(phenylsulfenyl)benzene in a solvent, adding an oxidizer, heating to react and thereby obtaining the halogen-substituted bis(phenylsulfonyl)benzene.

3. The preparation method of a conjugated compound containing a bis(phenylsulfonyl)benzene structure as claimed in claim 2 , wherein the step 20 concretely is that dissolving the synthesized halogen-substituted bis(phenylsulfonyl)benzene, the borate ester of the Ar unit, the catalyst and the alkali in a solvent, heating to react and thereby obtaining the conjugated compound containing a bis(phenylsulfonyl)benzene structure;
the step 20′ concretely is that dissolving the synthesized halogen-substituted bis(phenylsulfonyl)benzene, the NH(Ar) 2 compound containing secondary amine atoms, the catalyst and the alkali in a solvent, heating to react and thereby obtaining the conjugated compound containing a bis(phenylsulfonyl)benzene structure.

4. The preparation method of a conjugated compound containing a bis(phenylsulfonyl)benzene structure as claimed in claim 3 , wherein:
in the step 11, a molar ratio of the halogenated thiophenol to the dichloro-dicyano-p-benzoquinone is 2:1;
in the step 12, a molar ratio of the halogenated diphenyl disulfide, the dihalogeno-benzene, the catalyst and the alkali is (1˜1.2):1:(0.02˜0.05):(2˜6);
in the step 13, a molar ratio of the halogen-substituted bis(phenylsulfenyl)benzene to the oxidizer is 1:(5˜8);
in the step 20, a molar ratio of the halogen-substituted bis(phenylsulfonyl)benzene, the borate ester of the Ar unit, the catalyst and the alkali is 1:(2.2˜3):(0.02˜0.05):(3˜6);
in the step 20′, a molar ratio of the halogen-substituted bis(phenylsulfonyl)benzene, the NH(Ar) 2 compound containing secondary amine atoms, the catalyst and the alkali is 1: (2.2˜3):(0.05˜0.1):(3˜6).

5. The preparation method of a conjugated compound containing a bis(phenylsulfonyl)benzene structure as claimed in claim 3 , wherein:
in the step 11, the halogenated thiophenol is at least one of ortho-bromobenzenethiol, para-bromobenzenethiol and meta-bromobenzenethiol;
in the step 12, the dihalogeno-benzene is at least one of para-diiodobiphenyl and meta-diiodobiphenyl, the catalyst is at least one of cuprous sulfide, cuprous iodide and cuprous oxide;
in the step 13, the oxidizer is at least one of hydrogen peroxide, potassium permanganate and pyridinium chlorochromate;
in the step 20, the catalyst is at least one of tetrakis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium dichloride, tris(dibenzylideneacetone)dipalladium and phosphorus tricyclohexylphosphine;
in the step 20′, the catalyst is one of palladium acetate, tri-butyl phosphine and 1,1′-bis(diphenylphosphino) ferrocene;
in the steps 12, 20 and 20′, the alkalis are at least one of potassium carbonate, sodium carbonate and potassium phosphate;
in the steps 11, 12, 13, 20 and 20′, the solvents are at least one of toluene, ethanol, 1,4-dioxane, tetrahydrofuran, dimethyl sulfoxide , methylene chloride, N, N-dimethylformamide and 1,3-dimethyl-3 ,4,5,6-tetrahydro-2-pyrimidone.

6. An organic electroluminescent diode device, comprising a substrate, an anode, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and a cathode sequentially arranged in that order from bottom to top, wherein a material of the light-emitting layer is a host material doped with a conjugated compound containing a bis(phenylsulfonyl)benzene structure, the host material is bis(o-phenylene diphenyl phosphorus oxy)ether;
wherein the conjugated compound containing a bis(phenylsulfonyl)benzene structure comprises a chemical structure with one of structural general formulas as follows:

in the formula A and the formula B, each benzene ring being covalently bonded with adjacent sulfonyl group, Ar unit or N(Ar) 2 unit at an arbitrary position;
wherein the Ar unit has a conjugated structure and is one of aromatic rings constituted by vinylene group, ethynylene group and hydrogen and carbon atoms, aromatic heterocyclic rings constituted by carbon, nitrogen and hydrogen atoms, aromatic heterocyclic rings constituted by carbon, nitrogen, oxygen and hydrogen atoms, aromatic heterocyclic rings constituted by carbon, sulfur and hydrogen atoms, aromatic heterocyclic rings constituted by carbon, silicon and hydrogen atoms, aromatic heterocyclic rings constituted by carbon, nitrogen, sulfur and hydrogen atoms, aromatic heterocyclic rings constituted by carbon, silicon, sulfur and hydrogen atoms, and any combinations thereof.

7. The organic electroluminescent diode device as claimed in claim 6 , wherein the substrate is a glass substrate, a material of the anode is indium tin oxide, the cathode is a dou

Assignees

• Shenzhen China Star Optoelect

Inventors

• Li Xianjie
• Wu Yuanchun
• Su Shijian
• Liu Kunkun
• Liu Ming

Classifications

• C07C315/04

  by reactions not involving the formation of sulfone or sulfoxide groups · CPC title

• C07D213/34

  to which a second hetero atom is attached · CPC title

• H01L51/5012

  Electricity · mapped topic

• C09K2211/1029

  containing one nitrogen atom as the heteroatom · CPC title

• C09K2211/1044

  containing two nitrogen atoms as heteroatoms · CPC title