CN116323591A - Pyrimidine derivative and organic electroluminescent element comprising same - Google Patents
Pyrimidine derivative and organic electroluminescent element comprising same Download PDFInfo
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- CN116323591A CN116323591A CN202180070243.0A CN202180070243A CN116323591A CN 116323591 A CN116323591 A CN 116323591A CN 202180070243 A CN202180070243 A CN 202180070243A CN 116323591 A CN116323591 A CN 116323591A
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- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- PFWWZGINJSDVGU-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1.C1CCNCC1 PFWWZGINJSDVGU-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- ARHNUYMDZQZNFI-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound N1=CC(=CC=C1)B(O)O.N1=CC(=CC=C1)B(O)O ARHNUYMDZQZNFI-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000004620 quinolinyl-N-oxide group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
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Abstract
Provided is a pyrimidine derivative which contributes to substantially improving the driving voltage, efficiency and lifetime of an organic electroluminescent element. The organic electroluminescent element of the present invention comprises: an anode; a cathode; more than one organic layer: and an electron transport layer disposed between the anode and the cathode, wherein the organic layer or the electron transport layer contains a pyrimidine derivative represented by chemical formula 1 of the present invention.
Description
Technical Field
The present invention relates to a specific pyrimidine derivative and an organic electroluminescent device including the same, and more particularly, to an organic electroluminescent device having high luminous efficiency and a pyrimidine derivative used for the same.
Background
In the display industry, OLEDs (organic light emitting diodes ) are attracting attention as displays utilizing the phenomenon of self-luminescence.
Regarding the OLED, in 1963, research on carrier injection type Electroluminescence (EL) using a single crystal of Anthracene (Anthracene) arene was initially started by Pope et al. From this study, fundamental mechanisms such as charge injection, recombination, exciton generation, light emission and the like in organic substances, electroluminescent characteristics and the like have been understood and studied.
In particular, various attempts such as structural changes of elements and material development have been made to improve luminous efficiency [ Sun, s., forrest, S.R., appl.Phys.Lett.91, 263503 (2007)/Ken-Tsung Wong, org.
The basic structure of an OLED display is generally composed of a multi-Layer structure of an Anode (Anode), a hole injection Layer (Hole Injection Layer, HIL), a hole transport Layer (Hole Transporting Layer, HTL), an Emission Layer (EML), an electron transport Layer (Electron Transporting Layer, ETL), and a Cathode (Cathode), with an electron organic multi-Layer film formed in a sandwich structure between two electrodes.
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting element utilizing an organic light emitting phenomenon generally has a structure including an anode and a cathode with an organic layer therebetween. In order to improve efficiency and stability of the organic light emitting device, the organic layer may have a multi-layered structure formed of different materials, and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
In such a structure of an organic light emitting element, when a voltage is applied between two electrodes, holes and electrons are injected into an organic layer by an anode and a cathode, respectively, and when the injected holes meet the electrons, excitons (exiton) are formed, and light is emitted when the excitons are de-excited to a ground state. Such an organic light emitting element is known to have characteristics of self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, rapid response, and the like.
In the organic light emitting element, materials used as the organic layer may be functionally classified into a light emitting material and a charge transporting material, for example, a hole injecting material, a hole transporting material, an electron injecting material, and the like.
The luminescent materials are classified into blue, green, and red luminescent materials according to the luminescent colors, and yellow and orange luminescent materials required to display better natural colors. In addition, in order to improve color purity and luminous efficiency based on energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a dopant having a smaller band gap and more excellent light emission efficiency than a host mainly constituting the light emitting layer is mixed in a small amount into the light emitting layer, excitons generated by the host are transferred to the dopant, thereby emitting light efficiently. At this time, the wavelength of the host shifts to the wavelength band of the dopant, and thus light of a desired wavelength can be obtained according to the type of dopant used.
In order to sufficiently express various excellent characteristics of the organic light-emitting element described above, materials constituting the organic layer in the element, for example, a hole injecting material, a hole transporting material, a light-emitting material, an electron transporting material, an electron injecting material, and the like should be supported by a stable and efficient material.
However, since a stable and efficient organic layer material for an organic light emitting element has not been sufficiently developed so far, development of a novel material has been continued.
Disclosure of Invention
Technical problem
The inventors of the present invention, by repeating intensive studies, found a specific pyrimidine derivative compound, and confirmed that when it is used as a material for forming an organic layer of an organic electronic element, effects such as an increase in efficiency, a decrease in driving voltage, and an increase in stability of the element can be achieved.
The present invention is directed to providing the above specific pyrimidine derivative compound and an organic electronic device using the same.
Technical proposal
According to an embodiment of the present invention, there is provided a pyrimidine derivative represented by chemical formula 1.
Chemical formula 1:
in the chemical formula 1 described above, a compound having the formula,
Ar 1 、Ar 2 ar, ar 3 Each independently is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms,
l is a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms,
Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms,
P is an integer of 0 or 2,
when P is 2, a plurality of Ar 4 The same or different.
According to another embodiment of the present invention, there is provided an organic electroluminescent element comprising the above-specified pyrimidine derivative.
According to another embodiment of the present invention, there is provided an organic electroluminescent element including: a first electrode, a second electrode, and one or more organic layers disposed between the plurality of electrodes, wherein the organic layers comprise the specific pyrimidine derivative.
According to another embodiment of the present invention, there is provided an organic electroluminescent element, wherein the pyrimidine derivative is contained in any one layer selected from an electron blocking layer, an electron transporting layer, an electron injecting layer, a functional layer having both an electron transporting function and an electron injecting function, and a light emitting layer constituting the organic layer.
Advantageous effects
The pyrimidine derivative compound of the present invention is useful as a material for an organic layer of an organic light-emitting element.
In addition, according to the present invention, an organic light-emitting element using a pyrimidine derivative compound obtained by introducing a specific heteroarylene group into pyrimidine as a material of an organic layer exhibits excellent characteristics such as high efficiency, low voltage, and long lifetime.
The specific compound described in the present invention can improve efficiency in an organic light-emitting element and improve low driving voltage and/or lifetime characteristics by introducing a cyano group.
Drawings
Fig. 1 is a schematic cross-sectional view of an organic electroluminescent element according to an embodiment of the present invention.
Detailed Description
In this specification, unless otherwise defined, the term "aryl" means a polyunsaturated, aromatic, hydrocarbon substituent which may be a single ring or multiple rings (one to three rings) that are fused together or covalently bonded.
The term "heteroaryl" (in each of the different rings when polycyclic) denotes an aryl group (or ring) containing 1 to 4 heteroatoms selected from N, O and S, the nitrogen and sulfur atoms being optionally oxidized and the nitrogen atom (S) being optionally quaternized. Heteroaryl groups may be bonded to other moieties in the molecule through carbon or heteroatoms.
The aryl groups include suitably 4 to 7, preferably 4 in each ringA monocyclic or fused ring class of 5 or 6 ring atoms. In addition, the structure in which one or more aryl groups are bonded by chemical bonds is also included. As specific examples of the aryl group, there may be mentioned phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, 
Radical, tetracenyl, pyrenyl, fluoranthenyl, and the like, but is not limited thereto.
The heteroaryl group comprises 5-6 membered monocyclic heteroaryl groups and polycyclic heteroaryl groups fused with more than one benzene ring, and can also be partially saturated. In addition, structures in which more than one heteroaryl group is bonded through a chemical bond are also included. The heteroaryl groups include divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized to form, for example, an N-oxide or a quaternary ammonium salt.
Specific examples of the heteroaryl group include, but are not limited to, monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazine, etc., benzofuryl, benzothienyl, isobenzofuryl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, etc., and N-oxides (e.g., pyridyl N-oxide, quinolinyl N-oxide) corresponding thereto, quaternary ammonium salts thereof, etc.
The term "substituted" in the expression of "substituted or unsubstituted" as used in the present specification means that one or more hydrogen atoms in a hydrocarbon are replaced with the same or different substituents independently of each other. Useful substituents are as follows, but are not limited thereto.
Such substituents may be selected from-F; -Cl; -Br; -CN; -NO 2 The method comprises the steps of carrying out a first treatment on the surface of the -OH; is composed of-F, -Cl, -Br,-CN、-NO 2 or-OH is a substituted or unsubstituted C1-C20 alkyl group; is formed by-F, -Cl, -Br, -CN, -NO 2 or-OH is a C1-C20 alkoxy group which is substituted or unsubstituted; is composed of C1-C20 alkyl, C1-C20 alkoxy, -F, -Cl, -Br, -CN, -NO 2 or-OH is a C6-C30 aryl group which is substituted or unsubstituted; is composed of C1-C20 alkyl, C1-C20 alkoxy, -F, -Cl, -Br, -CN, -NO 2 or-OH substituted or unsubstituted C6-C30 heteroaryl; is composed of C1-C20 alkyl, C1-C20 alkoxy, -F, -Cl, -Br, -CN, -NO 2 or-OH substituted or unsubstituted C5-C20 cycloalkyl; is composed of C1-C20 alkyl, C1-C20 alkoxy, -F, -Cl, -Br, -CN, -NO 2 or-OH substituted or unsubstituted C5-C30 heterocycloalkyl; and one or more of groups represented by-N (G1) (G2). At this time, G1 and G2 may be hydrogen independently of each other; alkyl of C1-C10; or C6-C30 aryl substituted or unsubstituted by C1-C10 alkyl.
The present invention will be described in detail below.
The pyrimidine derivative of an embodiment of the present invention may be represented by chemical formula 1.
Chemical formula 1:
in the chemical formula 1 described above, a compound having the formula,
Ar 1 、Ar 2 ar, ar 3 Each independently is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms,
l is a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms,
Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms,
p is an integer of 0 or 2,
when P is 2, a plurality of Ar 4 The same or different.
According to an embodiment of the present invention, the chemical formula 1 may be represented by chemical formula 2.
Chemical formula 2:
in the chemical formula 2 described above, the chemical formula,
l is any one of a substituted or unsubstituted pyridyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted quinolinyl group and a substituted or unsubstituted isoquinolinyl group,
Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted carbazolyl group,
Ar 3 And p is the same as defined in the chemical formula 1.
According to an embodiment of the present invention, in the chemical formula 1,
Ar 3 is any one selected from phenyl, phenyl and pyridyl substituted by cyano.
The pyrimidine derivative of chemical formula 1 of the present invention is a pyrimidine derivative represented by chemical formula 3. However, the compound represented by chemical formula 1 of the present invention is not limited to the plurality of compounds of chemical formula 3.
Chemical formula 3:
the pyrimidine derivative represented by the chemical formula 1 may be synthesized by a known organic synthesis method. The synthetic method of the pyrimidine derivative can be easily understood by those skilled in the art with reference to the preparation examples described later.
In addition, according to the present invention, there is provided an organic electroluminescent element comprising the pyrimidine derivative represented by the chemical formula 1.
The pyrimidine derivative of chemical formula 1 can be used as any one of organic layers constituting an organic electroluminescent element, and in particular, can be used as an electron transport layer material.
The organic electroluminescent element of the present invention includes an anode, a cathode, and one or more organic layers disposed between the electrodes. The organic layer may include one or more pyrimidine derivatives represented by the chemical formula 1.
The organic layer may include at least one layer selected from a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a functional layer having both an electron transport function and an electron injection function.
For example, the pyrimidine derivative may be included in at least one selected from the group consisting of a light emitting layer, an organic layer disposed between an anode and a light emitting layer, and an organic layer disposed between a light emitting layer and a cathode. Preferably, the pyrimidine derivative may be contained in at least one layer selected from the group consisting of a light-emitting layer, a hole injection layer, a hole transport layer, and a functional layer having both a hole injection function and a hole transport function. The pyrimidine derivative may be contained in the organic layer in the form of a single material or a combination of materials different from each other. Alternatively, the pyrimidine derivative may be used in a light-emitting layer, a hole-transporting layer, a hole-injecting layer, or the like in a form of being mixed with a conventionally known compound.
The organic electroluminescent element of the present invention may have a structure of anode/light emitting layer/cathode, anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode or anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode. Alternatively, the organic electroluminescent element may have a structure of anode/functional layer/light emitting layer/electron transporting layer/cathode having both hole injecting function and hole transporting function or anode/functional layer/light emitting layer/electron transporting layer/electron injecting layer/cathode having both hole injecting function and hole transporting function, but is not limited thereto.
Fig. 1 is a schematic cross-sectional view of an organic electroluminescent element according to an embodiment of the present invention.
The organic electroluminescent element may be manufactured using a physical vapor deposition (physical vapor deposition; PVD) method such as sputtering (sputtering) or electron beam evaporation (e-beam evaporation). For example, a metal or a metal oxide having conductivity or an alloy thereof may be deposited on the substrate to form an anode, and after forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer on an upper portion thereof, a material usable as a cathode is deposited on an upper portion thereof. In addition to this method, an organic layer and an anode material may be deposited on a substrate in this order from a cathode material to produce an organic electroluminescent element.
On the other hand, the organic layer may be manufactured using various polymer materials and by a solution process (solution process), for example, spin coating, dip coating, knife coating, screen printing, inkjet printing, or thermal transfer printing, etc., instead of the deposition method.
The organic electroluminescent element of the present invention may be of a top emission type, a bottom emission type or a double-sided emission type depending on the materials used.
Description of the embodiments
The present specification will be described in detail with reference to a plurality of examples. However, the embodiments of the present specification may be modified into other various forms, and the scope of the present application is not limited to the embodiments described below. The various embodiments of the present application are intended to more fully describe the present specification to those skilled in the art.
Preparation example
Intermediate synthesis example 1: synthesis of intermediate 2
(Synthesis of intermediate 1)
In a 2L single-necked flask, 40.0g (203.8 mmol) of 1, 2-diphenylethanone (1, 2-diphenylethan-1-one) and 37.9g (203.8 mmol) of 5-bromonicotinaldehyde (5-bromonicotinaldehyde) were mixed with 750mL of toluene and stirred at 120℃for 2 days. After the reaction, water is added at normal temperature, ethyl acetate is used for extraction, and NaHCO is used 3 The organic layer was washed with an aqueous solution, and then distilled under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex: EA) to obtain 61.0g (yield: 81.2%) of a yellow solid compound (intermediate 1).
(Synthesis of intermediate 2)
In a 2L single-necked flask, 61.0g (167.5 mmol) of intermediate 1, 27.0g (172.5 mmol) of benzamidine hydrochloride (Benzamidine hydrochloride) and 840mL of ethanol were mixed, and then 20.1g (502.4 mmol) of NaOH was added thereto, followed by stirring under reflux for 3 days. After the reaction, cooling to normal temperature, and adding water to stir. After the solids were filtered, they were washed with water and ethanol and dried. After dissolving the dried solid in chloroform, a silica pad (CHCl) 3 : EA) and then solidified with ethanol to obtain 26.6g (yield: 34.2%) of a white solid compound (intermediate 2).
Intermediate synthesis example 2: synthesis of intermediate 4
(Synthesis of intermediate 3)
In a 1L single-necked flask, 28.4g (152.9 mmol) of 6-bromopyridine-2-carbaldehyde (6-bromopyridine), 30.0g (152.9 mmol) of 1,2-diphenylethanone (1, 2-diphenylethane), 2.6g (30.6 mmol) of Piperidine (Pieridine), 9.2g (152.9 mmol) of AcOH and 382mL of toluene were mixed, and then stirred under reflux for 1 day. After the reaction, the mixture was cooled to room temperature, and saturated aqueous sodium hydrogencarbonate and ethyl acetate were added thereto to extract the mixture. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The resulting reaction product was solidified with a mixed solution (EtOH: etOAc) to obtain 39.4g (yield: 70.9%) of an ivory-colored solid compound (intermediate 3).
(Synthesis of intermediate 4)
In a 1L single-necked flask, 34.0g (93.3 mmol) of intermediate 3, 17.5g (112.0 mmol) of benzamidine hydrochloride (benzimidamide hydrochloride), 11.2g (279.9 mmol) of NaOH and 311mL of ethanol were mixed and stirred under reflux for 1 day. After completion of the reaction, the reaction mixture was cooled to room temperature, and the resultant solid was filtered and washed with ethanol to obtain 19.1g (yield: 44.1%) of a white solid compound (intermediate 4).
Intermediate synthesis example 3: synthesis of intermediate 6
(Synthesis of intermediate 5)
In a 500mL two-necked flask, 20g (101.9 mmol) of 1,2-diphenylethanone (1, 2-diphenylethane), 18.9g (101.9 mmol) of 5-bromopyridine-2-carbaldehyde (5-bromopyridine), 2mL (20.3 mmol) of Piperidine (Piperidine), 5.9mL (101.9 mmol) of AcOH and 240mL of toluene were mixed, and then a one-day reaction was performed at 110 ℃. After the reaction, cooling to normal temperature, adding purified water, extracting with ethyl acetate, and removing the solvent under reduced pressure. The resulting reaction mixture was dissolved in chloroform and filtered through silica gel, and the solvent was concentrated under reduced pressure. The resulting reaction mixture was solidified with methanol/hexane to obtain 15.7g (yield: 42.4%) of a white solid compound (intermediate 5).
(Synthesis of intermediate 6)
In a 250mL two-necked flask, 10g (27.4 mmol) of intermediate 5, 8.6g (54.9 mmol) of benzamidine hydrochloride (benzimidamide hydrochloride), 7.6g (54.9 mmol) of K were introduced 2 CO 3 And 160mL of 1,4-After mixing the dioxane, the reaction was carried out at 100℃for 3 days. After the reaction, cooling to normal temperature, adding purified water, extracting with ethyl acetate, and removing the solvent under reduced pressure. The resulting reaction mixture was dissolved in chloroform and filtered through silica gel, and the solvent was concentrated under reduced pressure. The resulting reaction mixture was solidified with methylene chloride/methanol to obtain 5.3g (yield: 41.6%) of a white solid compound (intermediate 6).
Intermediate synthesis example 4: synthesis of intermediate 8
(Synthesis of intermediate 7)
In a 1L single-necked flask, 50.0g (319.3 mmol) of benzamidine hydrochloride (benzimidamide hydrochloride) was mixed with 128mL of distilled water (water), and then 12.8g (319.3 mmol) of NaOH was dissolved in 30mL of distilled water and added dropwise. After 64.4g (335.3 mmol) of ethyl 3-oxo-3-phenylpropionate and 140mL of ethanol were added dropwise, the mixture was stirred at room temperature for 18 hours. After completion of the reaction, the resultant solid was filtered, washed with diethyl ether and ethanol, and dried to obtain 45.9g (yield: 57.9%) of an ivory solid compound (intermediate 7).
(Synthesis of intermediate 8)
In a 2L single-necked flask, 45.9g (184.9 mmol) of intermediate 7 and 1.2L of Acetic acid (acrylic acid) were mixed, and then 49.4g (277.4 mmol) of NBS was added dropwise. After stirring the reaction product at normal temperature for 18 hours, distilled water was added. After extraction with methylene chloride, the separated organic layer was dried over anhydrous sodium sulfate, and then distilled under reduced pressure. The obtained compound was crystallized from ethanol, and then filtered and dried to obtain 51.8g (yield: 85.6%) of a white solid compound (intermediate 8).
Intermediate synthesis example 5: synthesis of intermediate 10
(Synthesis of intermediate 9)
41.8g (127.8 mmol) of intermediate 8, 20.3g (166.1 mmol) of phenylboronic acid (phenylboronic acid), 14.8g (12.8 mmol) of Pd (PPh) are placed in a 2L single-necked flask 3 ) 4 40.6g (383.4 mmol) of Na 2 CO 3 After mixing 1L of dioxane and 213mL of distilled water, reflux stirring was performed. After the completion of the reaction, the reaction mixture was cooled to room temperature, and after distilled water was added thereto, the reaction mixture was stirred at room temperature for 3 hours. After the resulting solid was filtered, it was washed with distilled water. The obtained solid was dried to obtain 33.3g (yield: 80.4%) of a yellow solid compound (intermediate 9).
(Synthesis of intermediate 10)
In a 2L single-necked flask, 33.3g (102.7 mmol) of intermediate 9 was mixed with 514mL of Dioxane (Dioxane), and then 95.9mL (1.0 mol) of POCl was slowly added dropwise at room temperature 3 Then, stirring and refluxing were performed for 3 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was slowly dropped into ice water. Slowly drop Na 2 CO 3 After saturated aqueous solution until pH 6 was reached, extraction was performed with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate, and then distilled under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hexanes: DCM) and solidified with methanol to obtain 27.1g (yield: 77.0%) of a white solid compound (intermediate 10).
Intermediate synthesis example 6: synthesis of intermediate 12
(Synthesis of intermediate 11)
In a 2L single-necked flask,40.0g (122.3 mmol) of intermediate 8, 23.4g (158.9 mmol) of 4-cyanophenylboronic acid, 14.1g (12.2 mmol) of Pd (PPh) 3 ) 4 38.9g (366.8 mmol) of Na 2 CO 3 After mixing 1L of dioxane and 210mL of distilled water, reflux stirring was performed. After the completion of the reaction, the reaction mixture was cooled to room temperature, and after distilled water was added thereto, the reaction mixture was stirred at room temperature for 3 hours. After the resulting solid was filtered, it was washed with distilled water. The obtained solid was dried to obtain 29.7g (yield: 69.5%) of a yellow solid compound (intermediate 11).
(Synthesis of intermediate 12)
In a 2L single-necked flask, 29.7g (85.0 mmol) of intermediate 11 was mixed with 437mL of Dioxane (Dioxane), and then 81.5mL (0.8 mol) of POCl was slowly added dropwise at room temperature 3 Then, stirring and refluxing were performed for 3 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was slowly dropped into ice water. Slowly drop Na 2 CO 3 After saturated aqueous solution until pH 6 was reached, extraction was performed with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate, and then distilled under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hexanes: DCM) and solidified with methanol to obtain 21.3g (yield: 68.1%) of a white solid compound (intermediate 12).
Intermediate synthesis example 7: synthesis of intermediate 14
(Synthesis of intermediate 13)
In a 2L single-necked flask, 40.0g (122.3 mmol) of intermediate 8, 19.5g (158.9 mmol) of 3-pyridineboronic acid (3-Pyridinylboronic acid), 14.1g (12.2 mmol) of Pd (PPh) 3 ) 4 38.9g (366.8 mmol) of Na 2 CO 3 After mixing 1L of dioxane and 210mL of distilled water, reflux stirring was performed. Reaction completionAfter that, the mixture was cooled to room temperature, distilled water was added thereto, and then stirred at room temperature for 3 hours. After the resulting solid was filtered, it was washed with distilled water. The obtained solid was dried to obtain 21.4g (yield: 53.8%) of a yellow solid compound (intermediate 13).
(Synthesis of intermediate 14)
In a 2L single-necked flask, 21.4g (65.8 mmol) of intermediate 13 was mixed with 339mL of Dioxane (Dioxane), and 62.3mL (0.6 mol) of POCl was slowly added dropwise at room temperature 3 Then, stirring and refluxing were performed for 3 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was slowly dropped into ice water. Slowly drop Na 2 CO 3 After saturated aqueous solution until pH 6 was reached, extraction was performed with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate, and then distilled under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hexanes: DCM) and solidified with methanol to obtain 13.2g (yield: 58.4%) of a white solid compound (intermediate 14).
Intermediate synthesis example 8: synthesis of intermediate 17
(Synthesis of intermediate 15)
In a 3L three-necked flask, 1.5L of THF was mixed with 70.0g (214.7 mmol) of 2, 8-dibromodibenzofuran (2, 8-dibromoibzo [ b, d ] furan), followed by stirring for 1 hour. After cooling the mixture to-65 ℃, 94.4mL (235.8 mmol, 2.5M in hexane (hexane)) of n-butyllithium (n-BuLi) was added dropwise for 1 hour. 49.5mL (641.6 mmol) of DMF was slowly added dropwise to the resulting mixture at-65℃and stirred at room temperature for 15 hours. After the reaction was completed, 1.5L of 6N HCl was added, followed by washing with Toluene (tolutene) and water. After the obtained compound was purified by silica gel column chromatography (n-Hex: tolene), it was solidified with MeOH to obtain 28.2g (yield: 47.6%) of a white solid compound (intermediate 15).
(Synthesis of intermediate 16)
In a 1L single-necked flask, 28.2g (102.3 mmol) of intermediate 15, 19.0g (102.3 mmol) of 1,2-diphenylethanone (1, 2-diphenylethanone), 2.0mL (20.4 mmol) of Piperidine (Piperidine), 5.8mL (102.3 mmol) of AcOH and 500mL of toluene were stirred under reflux for 48 hours. After the reaction was completed, the mixture was cooled to room temperature, and a silica pad (CHCl) 3 ) Filtration was performed to remove the solution, and 44.6g (yield: 96.2%) of a brown liquid compound (intermediate 16).
(Synthesis of intermediate 17)
In a 1L single-necked flask, 20.0g (44.1 mmol) of intermediate 16, 7.2g (45.9 mmol) of benzamidine hydrochloride (benzimidamide hydrochloride), 3.5g (88.2 mmol) of NaOH and 250mL of ethanol were mixed and stirred under reflux for 24 hours. After the reaction, cooling to normal temperature, and removing ethanol. After 300mL of 2-Methoxyethanol (2-methoxythanol) was mixed with the obtained compound, reflux stirring was performed for 20 hours. After completion of the reaction, the mixture was cooled to room temperature, washed with ethanol and water, and filtered to obtain 11.0g (yield: 45.1%) of a yellow solid compound (intermediate 17).
Intermediate synthesis example 9: synthesis of intermediate 21
(Synthesis of intermediate 18)
90.0g (343.4 mmol) of 1-bromodibenzo [ b, d ] are placed in a 4L four-necked flask]Furan-4-amine (1-bromoibzo [ b, d ]]Furan-4-amine), 143.1mL (1.4 mol) of 35.0% hydrochloric acid and 400mL of distilled water were mixed at 0 ℃. The internal temperature was kept below 4℃and at a temperature of 30.8g (446.4 mmol) NaNO 2 After dissolution in 125mL of distilled water and slow dropwise addition, the mixture was kept for 1 hour. Kept below 5 ℃ and 114g (686.8 mmol) of KI is dissolved in125mL of distilled water was slowly added dropwise thereto, followed by stirring for 1 hour. After the temperature was raised to normal temperature, a reaction was performed for one day. After the reaction, naS is added into the reaction product 2 O 3 The aqueous solution was neutralized, and then extracted with ethyl acetate. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and the obtained solid mixture was purified by silica gel column chromatography (Hex) to obtain 65.9g (yield: 51.4%) of a white solid compound (intermediate 18).
(Synthesis of intermediate 19)
In a 2L two-necked flask, 56.6g (151.7 mmol) of intermediate 18 was dissolved in 760mL of tetrahydrofuran, and 63.7mL (159.3 mmol) of n-BuLi was added dropwise at-78℃and then stirred for 1 hour. After 23.5mL (303.5 mmol) of DMF was added dropwise, the temperature was raised to room temperature and the reaction was further carried out for 2 hours. Distilled water was added to the reaction product, followed by extraction with ethyl acetate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and the obtained solid mixture was purified by silica gel column chromatography (Hex: DCM) and solidified by a mixed solution (Hex/EA) to obtain 69.0g (yield: 76.4%) of a white solid compound (intermediate 19).
(Synthesis of intermediate 20)
In a 3L two-necked flask, 69.0g (250.8 mmol) of intermediate 19, 49.7g (253.3 mmol) of 1,2-diphenylethanone (1, 2-diphenylethanone), 4.9mL (50.2 mmol) of piperidine, 14034mL (250.8 mmol) of acetic acid and 1L of toluene were mixed, and then stirred at 140℃for 16 hours. After the reaction, cooling to normal temperature, adding purified water, and extracting with ethyl acetate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed under reduced pressure. By silica gel column chromatography (CHCl) 3 ) The obtained reaction mixture was purified and solidified with a mixed solution (Hex/EA) to obtain 77.9g (yield: 68.5%) of a white solid compound (intermediate 20)
(Synthesis of intermediate 21)
In a 2L two-necked flask, 77.9g (171.8 mmol) of intermediate 20, 53.8g (353.7 mmol) of benzamidine hydrochloride (Benzamidine hydrochloride), 95.0g (687.4 mmol) of K were introduced 2 CO 3 And 760mL of 1, 4-dioxane were mixed and stirred at 110℃for 4 days. After the reaction, cooling to normal temperature, adding purified water, and extracting with ethyl acetate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed under reduced pressure. By silica gel column chromatography (CHCl) 3 ) The obtained reaction mixture was purified and solidified with a mixed solution (Hex/EA) to obtain 35.5g (yield: 37.3%, purity: 99.4%) of a white solid compound (intermediate 21).
Intermediate synthesis example 10: synthesis of intermediate 24
(Synthesis of intermediate 22)
In a 2L two-necked flask, 50.0g (202.4 mmol) of 2-bromodibenzofuran (2-bromodibenzo [ b, d ]]Furan) was dissolved in 500mL of THF, 101.0mL (2.0M, 202.4 mmol) of LDA was added dropwise at-78deg.C, and then stirred for 2 hours. After 23.4mL (303.5 mmol) of DMF was added dropwise, the temperature was raised to room temperature, and then the reaction was carried out for 12 hours. After acidification with 2N aqueous HCl, extraction with ethyl acetate was performed. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and purified by silica gel column chromatography (CHCl) 3 ) The resulting solid mixture was purified and solidified using a mixed solution (DCM/Hex) to yield 27.5g (yield: 49.4%) of a white solid compound (intermediate 22).
(Synthesis of intermediate 23)
In a 1L single-necked flask, 19.6g (100.0 mmol) of 1, 2-diphenylethanone (1, 2-diphenylethan-1-one) and 27.5g (100.0 mmol) of intermediate 22 were mixed with 360mL of toluene, and then 5.7mL (100.0 mmol) of AcOH and 4.0 were added mL (40.0 mL) of Piperidine (Piperidine) was reacted at 120℃for 1 day. After the reaction, water is added at normal temperature, ethyl acetate is used for extraction, and NaHCO is used 3 The organic layer was washed with an aqueous solution, and then distilled under reduced pressure. By silica gel column chromatography (CHCl) 3 ) The resulting reaction mixture was purified and the mixed solution (CHCl) 3 Curing with/EtOH) provided 14.4g (yield: 31.8%) of a white solid compound (intermediate 23).
(Synthesis of intermediate 24)
In a 500mL single-necked flask, 10.0g (22.1 mmol) of intermediate 23, 4.2g (26.5 mmol) of benzamidine hydrochloride (Benzamidine hydrochloride) and 110mL of dioxane were mixed, and then 25.2g (77.2 mmol) of Cs was added 2 CO 3 Reflux stirring was performed for 3 days. After adding 6.1g (44.1 mmol) of K 2 CO 3 And after 2 days of reflux stirring, cooling to normal temperature, and then adding water and stirring. After the solid was filtered, washed with water and ethanol, dried, and after the dried solid was dissolved in chloroform, purified by silica gel column chromatography (Hex: CHCl) 3 ) Purification and solidification using a mixed solution (DCM/EtOH) gave 4.3g (yield: 35.2%) of a white solid compound (intermediate 24).
Intermediate synthesis example 11: synthesis of intermediate 25
(Synthesis of intermediate 25)
In a 2L single-necked flask, 50.0g (193.7 mmol) of 4-bromo-4-cyanobiphenyl (4 '-bromo- [1,1' -biphenyl)]-4-carbonifile), 73.8g (290.6 mmol) of bis (pinacolato) diboron (Bis (pinacolato) diboron), 3.2g (3.9 mmol) of Pd (dppf) Cl 2 ·CH 2 Cl 2 After mixing 57.0g (581.1 mmol) of KOAc and 650mL of 1, 4-dioxane, the mixture was stirred at 100deg.C for 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction product was then reactedAfter passing through the celite pad, concentration under reduced pressure was performed. By silica gel column chromatography (CHCl) 3 ) The reaction mixture was purified, solidified with a mixed solution (DCM/MeOH), and filtered to obtain 51.1g (yield: 86.4%) of a white solid compound (intermediate 25).
Intermediate synthesis example 12: synthesis of intermediate 27
(Synthesis of intermediate 26)
In a 2L single-necked flask, 28.5g (168.5 mmol) of 6-Cyano-2-naphthol (6-Cyano-2-naphthol) was dissolved in 800mL of methylene chloride, 68.0mL (842.3 mmol) of pyridine was further added dropwise, and then the temperature was lowered to 0 ℃. After slowly adding dropwise 56.0mL (336.9 mmol) of Tf 2 After O, the temperature was raised to normal temperature, and then the reaction was performed for 12 hours. After washing the reaction product with distilled water, the separated organic layer was dried with anhydrous sodium sulfate, filtered and concentrated, and then purified by column chromatography (CHCl 3 ) Purification and solidification with ethanol gave 24.6g (yield: 48.5%) of a white liquid compound (intermediate 26).
(Synthesis of intermediate 27)
In a 1L single neck flask, 20.0g (66.4 mmol) of intermediate 26, 25.3g (99.6 mmol) of bis (pinacolato) diboron (Bis (pinacolato) diboron), 1.1g (1.3 mmol) Pd (dppf) Cl 2 ·CH 2 Cl 2 After mixing 19.6g (199.2 mmol) of KOAc and 220mL of 1, 4-dioxane, stirring was carried out at 100℃for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and after passing the reaction product through a celite pad, the reaction product was concentrated under reduced pressure. By silica gel column chromatography (CHCl) 3 ) The reaction mixture was purified and solidified with ethanol to obtain 14.6g (yield: 78.8%) of a white liquid compound (intermediate 27).
Intermediate synthesis example 13: synthesis of intermediate 29
(Synthesis of intermediate 28)
In a 250mL single-necked flask, 4.5g (14.9 mmol) of intermediate 26, 2.3g (14.9 mmol) of 4-chlorobenzeneboronic acid ((4-chlorophenyl) boronic acid), 863.0mg (746.9. Mu. Mol) of Pd (PPh) 3 ) 4 9.5g (44.8 mmol) of K 3 PO 4 After 50mL of toluene and 20mL of water were mixed, reflux stirring was performed for 12 hours. After the completion of the reaction, the mixture was cooled to room temperature, water was then added thereto, extraction was performed with chloroform, and the reaction mixture was concentrated. By column chromatography (CHCl) 3 ) The reaction mixture was purified and solidified with ethanol to obtain 3.0g (yield: 76.2%) of a white solid compound (intermediate 28).
(Synthesis of intermediate 29)
In a 1L single neck flask, 3.0g (11.4 mmol) of intermediate 28, 4.3g (17.1 mmol) of bis (pinacolato) diboron (Bis (pinacolato) diboron), 654mg (1.1 mmol) of Pd (dba) 2 After mixing 1.1g (12.3 mmol) of X-phos, 3.3g (34.1 mmol) of KOAc and 55mL of toluene, the mixture was stirred at 110℃for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and after passing the reaction product through a celite pad, the reaction product was concentrated under reduced pressure. By silica gel column chromatography (CHCl) 3 ) The reaction mixture was purified and solidified with ethanol to obtain 2.9g (yield: 72.5%) of a white liquid compound (intermediate 29).
Intermediate synthesis example 14: synthesis of intermediate 30
(Synthesis of intermediate 30)
In a 2L single-necked flask, 40.0g (193.2 mmol) of 5-bromoisophthalonitrile (5-bromoisophthalonitrile), 73.6g (290.0 mmol) of Bis (pinacolato) diboron (Bis)(pinacolato) diboron), 7.9g (9.7 mmol) Pd (dppf) Cl 2 ·CH 2 Cl 2 After mixing 56.9g (579.6 mmol) of KOAc and 700mL of 1, 4-dioxane, the mixture was stirred at 100℃for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and after passing the reaction product through a celite pad, the reaction product was concentrated under reduced pressure. By silica gel column chromatography (CHCl) 3 : EA) the reaction mixture was purified, solidified with hexane, and filtered to obtain 35.1g (yield: 71.5%) of a yellow solid compound (intermediate 30).
Intermediate synthesis example 15: synthesis of intermediate 31
(Synthesis of intermediate 31)
In a 2L two-necked flask, 30.0g (129.3 mmol) of 4-bromo-1-naphthalenecarbonitrile (4-bromoo-1-naphthalonitrile), 39.4g (155.1 mmol) of bis (pinacolato) diboron (Bis (pinacolato) diboron), 5.3g (6.5 mmol) of Pd (dppf) Cl 2 ·CH 2 Cl 2 After mixing 38.1g (387.8 mmol) of KOAc and 650mL of 1, 4-dioxane, one day reflux stirring was performed. After the reaction, cooling to normal temperature, adding purified water, extracting with ethyl acetate, and removing the solvent under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Toluene) and solidified by using a mixed solution (Hex/EA), whereby 23.4g (yield: 64.9%) of a white solid compound (intermediate 31) was obtained.
Intermediate synthesis example 16: synthesis of intermediate 33
(Synthesis of intermediate 32)
In a 2000mL two-necked flask, 75.6g (374.3 mmol) of 1-bromo-2-nitrobenzene (1-bromoo-2-nitrobenzene), 50.0g (340.2 mmol)) 4-cyanophenylboronic acid ((4-cyanophenyl) carboxylic acid), 19.7g (17-0 mmol) of Pd (PPh) 3 ) 4 141.1g (1020.8 mmol) of K 2 CO 3 After 500mL of toluene, 250mL of purified water and 200mL of ethanol were mixed, a one-day reaction was performed at 100 ℃. After the reaction was completed, it was cooled to room temperature, purified water was then added thereto and extraction was performed with ethyl acetate, and then, the solvent was removed under reduced pressure. The resulting reaction mixture was dissolved in chloroform and filtered through silica gel, and the solvent was concentrated under reduced pressure. The resulting reaction mixture was solidified with hexane to obtain 76.0g (yield: 99.6%) of a white solid compound (intermediate 32).
(Synthesis of intermediate 33)
In a 1000mL two-necked flask, 76.3g (340.3 mmol) of intermediate 32, 162.7g (408.4 mmol) of DPPE and 210mL of xylene were mixed, and then a one-day reaction was performed at 135 ℃. After the reaction was completed, it was cooled to 100℃and then 500mL of methylene chloride was added thereto with stirring. The resulting solid was filtered, washed with dichloromethane, and the solvent was concentrated under reduced pressure. By silica gel column Chromatography (CH) 2 C1 2 ) The resulting reaction mixture was purified to obtain 17.2g (yield: 26.3%) of a white solid compound (intermediate 33).
Intermediate synthesis example 17: synthesis of intermediate 34
(Synthesis of intermediate 34)
In a 1L single-necked flask, 30.0g (121.9 mmol) of 3-bromocarbazole (3-bromocarbazole), 16.3g (182.2 mmol) of CuCN and 488mL of NMP were mixed, and then refluxed and stirred for 1 day. After the reaction was completed, the mixture was cooled to room temperature, and distilled water and ethyl acetate were added thereto and stirred. The mixture was filtered through celite, and washed with ethyl acetate. To the filtrate, a mixed aqueous solution (aqueous ammonia: aqueous sodium hydrogencarbonate) was added and extraction was performed. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The obtained reaction product was solidified with toluene to obtain 11.5g (yield: 49.1%) of a brown solid compound (intermediate 34).
Intermediate synthesis example 18: synthesis of intermediate 35
(Synthesis of intermediate 35)
In a 1L single-necked flask, 40.0g (123.0 mmol) of 3,6-Dibromocarbazole (3, 6-Dibromocarbazole), 27.6g (307.5 mmol) of CuCN and 320mL of Dimethylformamide (DMF) were mixed, and then refluxed and stirred for 1 day. After the reaction was completed, the mixture was cooled to room temperature, and ammonia water and ethyl acetate were added thereto and stirred for 30 minutes. The aqueous layer was extracted with ethyl acetate and chloroform. After extraction, the organic layer was directly filtered and concentrated. The resultant reaction product was refluxed in dimethylformamide to be dissolved, silica, diatomaceous earth and magnesium sulfate were laminated in this order, and then filtration and concentration were performed. The obtained reaction product was solidified with dimethylformamide to obtain 8.8g (yield: 32.9%) of a gray solid compound (intermediate 35).
Intermediate synthesis example 19: synthesis of intermediate 37
(Synthesis of intermediate 36)
In a 1L single-necked flask, 15.0g (63.3 mmol) of 2,5-dibromopyridine (2, 5-dibromopyridine), 9.8g (66.5 mmol) of 4-cyanobenzeneboronic acid (4-cyanophenylboronic acid), 3.7g (3.2 mmol) of Pd (PPh) 3 ) 4 64mL (126.6 mmol) of 2M K 2 CO 3 After mixing the aqueous solution, 211.3mL of toluene and 105.7mL of ethanol (EtOH), the mixture was refluxed and stirred for 3 hours. After the reaction, cooling to normal temperature. At the time of addingAfter adding distilled water and methanol and stirring, the resultant solid was obtained by filtration. The resultant reaction product was refluxed into toluene and dissolved, followed by filtration through celite, and the solvent was removed under reduced pressure to obtain 7.8g (yield: 47.3%) of a white solid compound (intermediate 36).
(Synthesis of intermediate 37)
7.8g (29.9 mmol) of intermediate 36, 11.4g (44.9 mmol) of PIN are placed in a 500mL single-necked flask 2 B 2 1.2g (1.5 mmol) Pd (dppf) Cl 2 ·CH 2 Cl 2 After mixing 5.9g (59.8 mmol) of KOAc and 150mL of Dioxane (Dioxane), the mixture was refluxed and stirred for 3 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and then the solvent was removed under reduced pressure. The reaction product was dissolved with ethyl acetate, distilled water was added thereto, and extraction was performed. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. Purification of the resulting reaction product by silica gel column chromatography (Hexanes: etOAc) gave 7.4g (yield: 80.8%) of compound as a brown solid (intermediate 37).
Intermediate synthesis example 20: synthesis of intermediate 39
(Synthesis of intermediate 38)
In a 1L single-necked flask, 15.0g (63.3 mmol) of 3,5-dibromopyridine (3, 5-dibromopyridine), 9.8g (66.5 mmol) of 4-cyanobenzeneboronic acid (4-cyanophenylboronic acid), 3.7g (3.2 mmol) of Pd (PPh) 3 ) 4 64mL (126.6 mmol) of 2M K 2 CO 3 After mixing the aqueous solution, 211.3mL of toluene and 105.7mL of ethanol (EtOH), the mixture was refluxed and stirred for 3 hours. After the reaction, cooling to normal temperature. After adding distilled water and methanol and stirring, the resultant solid was obtained by filtration. The resulting reaction product was refluxed into toluene and dissolved, followed by filtration through celite, and the solvent was removed under reduced pressure to obtain 6.2g (yield: 37.6%) of a white solidCompound (intermediate 38).
(Synthesis of intermediate 39)
6.2g (23.9 mmol) of intermediate 38, 9.1g (35.9 mmol) of PIN are placed in a 500mL single-necked flask 2 B 2 1.0g (1.2 mmol) Pd (dppf) Cl 2 ·CH 2 Cl 2 After 4.7g (47.9 mmol) of KOAc and 120mL of Dioxane (Dioxane) were mixed, the mixture was refluxed and stirred for 3 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and then the solvent was removed under reduced pressure. The reaction product was dissolved in ethyl acetate, distilled water was added thereto, and extraction was performed. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. Purification of the resulting reaction product by silica gel column chromatography (Hexanes: etOAc) gave 5.2g (yield: 71.0%) of compound as a brown solid (intermediate 39).
Intermediate synthesis example 21: synthesis of intermediate 41
(Synthesis of intermediate 40)
In a 250mL single-necked flask, 10.0g (26.8 mmol) of intermediate 18, 4.7g (32.2 mmol) of 4-cyanophenylboronic acid, 1.6g (1.3 mmol) of Pd (PPh 3 ) 4 9.3g (67.0 mmol) of K 2 4CO 3 80mL of 1, 4-dioxane and 20mL of water were mixed, and then stirred under reflux for one day. After the reaction, the mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and ethanol, and then dried. By column chromatography (Hex: CHCl) 3 ) Purification and curing with mixed solvent (DCM/EtOH) gave 6.8g (yield: 73.0%) of a white solid compound (intermediate 40).
(Synthesis of intermediate 41)
In a 250mL single neck flask, 4.0g (11.5 mmol) of intermediate 40, 4.4g (17.2 mmol) of bis (pinacolato) diboron (Bis (pinacolato) diboron), 660.0mg (1.2 mmol) Pd (dba) 2 After mixing 1.1g (2.3 mmol) of X-phos, 2.8g (28.7 mmol) of KOAc and 60mL of toluene, the mixture was stirred at 110℃for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and after passing the reaction product through a celite pad, the reaction product was concentrated under reduced pressure. Column chromatography on silica gel (Hex: CHCl) 3 ) Purification of the reaction mixture gave 2.0g (yield: 43.4%) of a white solid compound (intermediate 41).
Intermediate synthesis example 22: synthesis of intermediate 43
(Synthesis of intermediate 42)
In a 1L single neck flask, 20.0g (58.5 mmol) of 2,8-dibromodibenzo [ b, d]Thiophene (2, 8-Dibromoibizo [ b, d ]]thiophene), 12.8g (70.2 mmol) of 4-cyanophenylboronic acid (4-cyanophenylboronic acid), 3.4g (2.9 mmol) of Pd (PPh) 3 ) 4 24.3g (175.5 mmol) of K 2 CO 3 After mixing 233mL of Tetrahydrofuran (THF) and 59mL of distilled water, the mixture was stirred at 60℃for 18 hours. After the completion of the reaction, distillation under reduced pressure was performed to remove tetrahydrofuran. The obtained reaction product was extracted with methylene chloride, and the separated organic layer was dried over anhydrous sodium sulfate and then distilled under reduced pressure. Column chromatography on silica gel (Hexanes: CHCl) 3 ) Purification of the obtained compound gave 7.0g (yield: 32.8%) of a white solid compound (intermediate 42).
(Synthesis of intermediate 43)
7.0g (19.5 mmol) of intermediate 42, 7.3g (28.8 mmol) of PIN are placed in a 250mL single-necked flask 2 B 2 After 0.8g (1.0 mmol) of Pd (dppf) C1.DCM, 5.6g (57.6 mmol) of KOAc and 96mL of Dioxane (Dioxane) were mixed, the mixture was refluxed and stirred for 18 hours. After the reaction, cooling to normal temperature, removing the solvent under reduced pressure, and then adding distilled water dropwise. The reaction product was extracted with dichloromethane and the separated organic layer was separated with anhydrous sodium sulfate After drying, the solvent was removed under reduced pressure. The resultant reaction product was purified by silica gel column chromatography (Hexanes: DCM) to give 4.0g (yield: 50.6%) of the compound as a white solid (intermediate 43).
Intermediate synthesis example 23: synthesis of intermediate 45
(Synthesis of intermediate 44)
In a 1L single neck flask, 12.2g (35.8 mmol) of 2,8-dibromodibenzo [ b, d]Thiophene (2, 8-Dibromoibizo [ b, d ]]thiophene), 10.0g (35.8 mmol) of intermediate 27, 2.0g (1.8 mmol) of Pd (PPh) 3 ) 4 35.8mL (71.6 mmol) of 2M K 2 CO 3 After mixing the aqueous solution with 239mL of toluene and 119mL of ethanol, stirring and refluxing were performed for 2 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the resultant solid was filtered. The mixture was washed with toluene, distilled water and methanol, and dried. Purification of the resulting solid by column chromatography (Hexanes: DCM) gave 4.5g (yield: 30.6%) of the compound as a white solid (intermediate 44).
(Synthesis of intermediate 45)
In a 250mL single-necked flask, 4.5g (10.9 mmol) of intermediate 44 and 3.3g (13.1 mmol) of PIN were introduced 2 B 2 After mixing 0.4g (0.5 mmol) of Pd (dppf) Cl DCM, 3.2g (32.7 mmol) of KOAc and 54mL of Dioxane (Dioxane), the mixture was refluxed and stirred for 2 hours. After the reaction, cooling to normal temperature, removing the solvent under reduced pressure, and then adding distilled water dropwise. The reaction product was extracted with methylene chloride, and after the separated organic layer was dried with anhydrous sodium sulfate, the solvent was removed under reduced pressure. The resultant reaction product was purified by silica gel column chromatography (Hexanes: DCM) to give 3.4g (yield: 68.0%) of the compound as a white solid (intermediate 45).
Intermediate synthesis example 24: synthesis of intermediate 48
(Synthesis of intermediate 46)
In a 250mL one-necked flask, 10.0g (31.0 mmol) of 3-bromo-9-phenyl-9H-carbazole, 5.0g (34.1 mmol) of 4-cyanobenzeneboronic acid, 1.8g (1.6 mmol) of Pd (PPh) 3 ) 4 16.5g (77.6 mmol) of K 3 PO 4 100mL of toluene, 25mL of ethanol and 25mL of water were mixed, and then one day of reflux stirring was performed. After the completion of the reaction, the mixture was cooled to room temperature, extracted with chloroform, and the solvent was concentrated under reduced pressure. By column chromatography (Hex: CHCl) 3 ) The reaction mixture was purified and cured with a mixed solvent (DCM/EtOH) to yield 6.9g (yield: 64.9%) of a white solid compound (intermediate 46).
(Synthesis of intermediate 47)
In a 500mL single-necked flask, 5.0g (14.5 mmol) of intermediate 46 was dissolved in 70mL of DMF. After 2.6g (14.5 mmol) of NBS was slowly added, the reaction was performed at normal temperature for 3 hours. After the reaction was completed, distilled water was added to the reaction product and stirred. After the resulting solid was filtered, it was washed with distilled water and ethanol, and then dried, whereby 6.1g (yield: 98.8%) of a white solid compound (intermediate 47) was obtained.
(Synthesis of intermediate 48)
In a 500mL single neck flask, 6.0g (14.2 mmol) of intermediate 47, 5.4g (21.3 mmol) of bis (pinacolato) diboron (Bis (pinacolato) diboron), 579mg (708.7. Mu. Mol) Pd (dppf) Cl 2 ·CH 2 Cl 2 After mixing 4.2g (42.5 mmol) of KOAc and 70mL of 1, 4-dioxane, the mixture was stirred at 100deg.C for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and after passing the reaction product through a celite pad, the reaction product was concentrated under reduced pressure. Solidifying with mixed solvent (DCM/MeOH) and filtering gave 5.9g (yield: 87.7%) of a white solidCompound (intermediate 48).
A variety of organic compounds were synthesized in the following manner using the above synthesized intermediate compounds.
Synthesis example 1: synthesis of Compound 3-1 (LT 20-30-183)
In a 250mL single-necked flask, 4.0g (8.6 mmol) of intermediate 2, 1.6g (12.9 mmol) of phenylboronic acid (phenylboronic acid), 498.0mg (430.7. Mu. Mol) of Pd (PPh) 3 ) 4 5.5g (25.8 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and ethanol, and then dried. After dissolving the dried solid in chloroform, column chromatography (CHCl) 3 : EA) and ethyl acetate was used for curing to obtain 2.0g (yield: 50.1%) of a white solid compound 3-1 (LT 20-30-183).
Synthesis example 2: synthesis of Compound 3-2 (LT 20-30-150)
In a 250mL single-necked flask, 3.5g (7.5 mmol) of intermediate 2, 1.2g (8.3 mmol) of 4-cyanophenylboronic acid, 435.5mg (376.9. Mu. Mol) of Pd (PPh) 3 ) 4 4.8g (22.6 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and methanol, and then dried. After dissolving the dried solid in chloroform, a silica pad (CHCl) 3 : EA) and then filtered using a mixed solution (DCM/MeOH)Curing gave 1.8g (yield: 49.9%) of compound 3-2 (LT 20-30-150) as a white solid.
Synthesis example 3: synthesis of Compound 3-3 (LT 20-35-197)
6.0g (16.3 mmol) of intermediate 12, 6.5g (21.2 mmol) of intermediate 39, 0.9g (0.8 mmol) of Pd (PPh) are placed in a 250mL single-necked flask 3 ) 4 25mL (48.9 mmol) of 2M K 2 CO 3 After mixing the aqueous solution with 60mL of toluene and 30mL of ethanol, reflux stirring was performed for 1 day. After the completion of the reaction, the resulting solid was filtered at the reaction temperature. After the obtained solid compound was purified by silica gel column chromatography (hexane): chloroform (chlorform)), it was solidified with methanol to obtain 2.5g (yield: 30.0%) of compound 3-3 (LT 20-35-197) as a white solid.
Synthesis example 4: synthesis of Compound 3-5 (LT 20-30-207)
In a 250mL single-necked flask, 4.0g (8.6 mmol) of intermediate 2, 2.6g (10.3 mmol) of intermediate 30, 497.7mg (430.7. Mu. Mol) of Pd (PPh) 3 ) 4 5.5g (25.8 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and methanol, and then dried. After dissolving the dried solid in chloroform, a silica pad (CHCl) 3 : EA) was filtered and solidified with chloroform to obtain 3.1g (yield: 69.7%) of white solid compound 3-5 (LT 20-30-207).
Synthesis example 5: synthesis of Compound 3-8 (LT 20-30-169)
In a 250mL single-necked flask, 3.5g (7.5 mmol) of intermediate 2, 2.5g (8.3 mmol) of intermediate 25, 435.5mg (376.9. Mu. Mol) of Pd (PPh) 3 ) 4 4.8g (22.6 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and methanol, and then dried. After dissolving the dried solid in chloroform, a silica pad (CHCl) 3 : EA) and then solidified with a mixed solution (DCM/Acetone (acetate)) to obtain 2.2g (yield: 50.7%) of white solid compound 3-8 (LT 20-30-169).
Synthesis example 6: synthesis of Compound 3-12 (LT 20-30-243)
In a 250mL single-necked flask, 3.5g (7.5 mmol) of intermediate 2, 2.5g (9.0 mmol) of intermediate 31, 435.5mg (376.9. Mu. Mol) of Pd (PPh) 3 ) 4 4.8g (22.6 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and methanol, and then dried. By column chromatography (CHCl) 3 : EA) the dried solid was purified and solidified using a mixed solution (DCM/EtOH) to yield 1.1g (yield: 27.0%) of white solid compound 3-12 (LT 20-30-243).
Synthesis example 7: synthesis of Compound 3-13 (LT 20-30-185)
In a 250mL single-necked flask, 3.5g (7.5 mmol) of intermediate 2, 2.5g (9.0 mmol) of intermediate 27, 435.5mg (376.9. Mu. Mol) of Pd (PPh) 3 ) 4 4.8g (22.6 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and ethanol, and then dried. By column chromatography (CHCl) 3 : EA) the dried solid was purified and solidified with ethyl acetate to obtain 2.2g (yield: 55.1%) of white solid compound 3-13 (LT 20-30-185).
Synthesis example 8: synthesis of Compound 3-16 (LT 20-30-201)
In a 250mL single-necked flask, 3.0g (6.5 mmol) of intermediate 2, 2.7g (7.8 mmol) of intermediate 29, 373.3mg (323.0. Mu. Mol) of Pd (PPh) 3 ) 4 4.1g (19.4 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and ethanol, and then dried. By column chromatography (CHCl) 3 : EA) the dried solid was purified and solidified with ethyl acetate to obtain 2.7g (yield: 68.5%) of white solid compound 3-16 (LT 20-30-201).
Synthesis example 9: synthesis of Compound 3-19 (LT 20-30-167)
In a 250mL single-necked flask, 4.0g (8.6 mmol) ofIntermediate 2, 1.7g (10.3 mmol) carbazole (9H-carbazole), 495.0mg (861.4. Mu. Mol) Pd (dba) 2 707.0mg (1.7 mmol) of S-phos, 2.5g (25.8 mmol) of NaOtBu and 40mL of xylene were mixed and stirred under reflux for 12 hours. After the completion of the reaction, the mixture was cooled to room temperature, water was then added thereto, extraction was performed with chloroform, and distillation was performed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex: EA) to obtain 1.9g (yield: 40.5%) of yellow solid compound 3-19 (LT 20-30-167).
Synthesis example 10: synthesis of Compound 3-20 (LT 20-30-195)
In a 250mL single-necked flask, 4.0g (8.6 mmol) of intermediate 2, 2.0g (10.3 mmol) of intermediate 33, 788.8mg (861.4. Mu. Mol) of Pd were introduced 2 (dba) 3 707.0mg (1.7 mmol) of S-phos, 2.5g (25.8 mmol) of NaOtBu and 45mL of xylene were mixed and stirred under reflux for 2 days. After the completion of the reaction, the mixture was cooled to room temperature, water was then added thereto, extraction was performed with chloroform, and distillation was performed under reduced pressure. Column chromatography on silica gel (in DCM, CHCl 3 : EA) the resulting reaction mixture was purified to obtain 1.1g (yield: 21.4%) of white solid compound 3-20 (LT 20-30-195).
Synthesis example 11: synthesis of Compound 3-28 (LT 20-30-262)
In a 250mL single-necked flask, 6.2g (18.1 mmol) of intermediate 10, 7.4g (24.2 mmol) of intermediate 37, 1.1g (0.9 mmol) of Pd (PPh) 3 ) 4 27mL (54.3 mmol) of 2M K 2 Co 3 After mixing the aqueous solution with 60mL of toluene and 30mL of ethanol, reflux stirring was performed for 1 day. After the completion of the reaction, the resulting solid was filtered at the reaction temperature. In the use of siliconAfter purifying the obtained solid compound by column chromatography (Hexanes: chlorform), it was solidified with methanol to obtain 3.5g (yield: 39.8%) of white solid compound 3-28 (LT 20-30-262).
Synthesis example 12: synthesis of Compound 3-29 (LT 20-35-210)
In a 250mL single-necked flask, 6.0g (17.5 mmol) of intermediate 14, 7.0g (22.7 mmol) of intermediate 37, 1.0g (0.9 mmol) of Pd (PPh) 3 ) 4 26mL (52.4 mmol) of 2M K 2 CO 3 After mixing the aqueous solution with 60mL of toluene and 30mL of ethanol, reflux stirring was performed for 1 day. After the completion of the reaction, the resulting solid was filtered at the reaction temperature. After the obtained solid compound was purified by silica gel column chromatography (Hexanes: chloroform), it was solidified with methanol to obtain 2.1g (yield: 24.7%) of white solid compound 3-29 (LT 20-35-210).
Synthesis example 13: synthesis of Compound 3-47 (LT 20-30-168)
In a 100mL single-necked flask, 4.3g (9.3 mmol) of intermediate 4, 2.1g (14 mmol) of 4-cyanobenzeneboronic acid, 0.5g (0.5 mmol) of Pd (PPh) 3 ) 4 5.9g (27.9 mmol) of K 3 PO 4 50mL of dioxane and 10mL of distilled water were mixed, and then refluxed and stirred for 1 hour. After the reaction, cooling to normal temperature. The resulting solid was refluxed to monochlorobenzene and dissolved, followed by filtration through celite and washing with monochlorobenzene. Cooling to room temperature, stirring, filtering the resulting solid, and drying to obtain 3.4g (yield: 74.6%) of white solid compound 3-47 (LT 20-30-168).
Synthesis example 14: synthesis of Compound 3-51 (LT 20-30-193)
In a 250mL two-necked flask, 10.0g (21.5 mmol) of intermediate 4, 6.84g (23.6 mmol) of intermediate 25, 1.24g (1.0 mmol) of Pd (PPh) 3 ) 4 13.6g (64.5 mmol) of K 3 PO 4 100mL of toluene, 50mL of ethanol, and 50mL of distilled water were mixed, and then stirred under reflux for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, and after 30mL of distilled water was further added, the resulting solid was filtered under reduced pressure, washed with distilled water and methanol, and dried. After the obtained solid was dissolved in chloroform, purification was performed by column chromatography (Hexane: EA). After concentration, crystallization was performed using 100mL of ethyl acetate. Reduced pressure filtration and drying were performed. After drying, 4.6g (yield: 83.3%) of compound 3-51 (LT 20-30-193) was obtained as a white solid.
Synthesis example 15: synthesis of Compound 3-53 (LT 20-30-216)
In a 500mL two-necked flask, 10.0g (21.5 mmol) of intermediate 4, 7.2g (25.8 mmol) of intermediate 31, 1.1g (1.0 mmol) of Pd (PPh) 3 ) 4 8.9g (64.5 mmol) of K 2 CO 3 100mL of toluene, 50mL of ethanol (EtOH) and 50mL of distilled water were mixed, and then stirred under reflux for 3 hours. After the completion of the reaction, the mixture was cooled to room temperature, and after 50mL of ethyl acetate and 50mL of distilled water were further added, the layers were separated, and the aqueous layer was removed. 20g of MgSO was charged into the organic layer 4 And after stirring, celite filtration was performed. The filtrate was concentrated under reduced pressure. After the concentrated residue was dissolved in ethyl acetate, silica gel filtration was performed. At the position ofAfter the filtrate was concentrated, it was completely dissolved under reflux using 30ml of ethyl acetate. After cooling to room temperature, hexane was added dropwise, and the resultant solid was filtered under reduced pressure. After drying, 2.0g (yield: 17.4%) of compound 3-53 (LT 20-30-216) as a white solid was obtained.
Synthesis example 16: synthesis of Compound 3-58 (LT 20-30-253)
In a 100mL single-necked flask, 5.0g (10.8 mmol) of intermediate 4, 1.4g (8.3 mmol) of Carbazole, 0.3g (34.5 mmol) of Cu and 1.5g (10.8 mmol) of K were placed 2 CO 3 And 54mL of Dimethylformamide (DMF) were mixed, followed by 1-day refluxing and stirring. After the reaction, cooling to normal temperature. Distilled water was added to the reaction solution and stirred. The resulting solid was purified by silica gel column chromatography (Hexanes: etOAc). The obtained solid was solidified with toluene to obtain 0.6g (yield: 12.3%) of compound 3-58 (LT 20-30-253) as a white solid.
Synthesis example 17: synthesis of Compound 3-59 (LT 20-30-198)
In a 250mL single-necked flask, 4.0g (8.6 mmol) of intermediate 4, 1.3g (6.6 mmol) of intermediate 33, 0.2g (3.6 mmol) of Cu, 1.2g (8.6 mmol) of K 2 CO 3 And 43mL of Dimethylformamide (DMF) were mixed, followed by 1-day refluxing and stirring. After the reaction, cooling to normal temperature. Distilled water was added to the reaction solution and stirred. After solidification of the resulting solid with methanol, purification was performed using silica gel column chromatography (Hexanes: etOAc). The obtained solid was solidified with methanol to obtain 2.9g (yield: 38.2%) of compound 3-59 (LT 20-30-198) as a white solid.
Synthesis example 18: synthesis of Compound 3-60 (LT 20-30-179)
In a 100mL single-necked flask, 4.0g (8.6 mmol) of intermediate 4, 1.3g (6.6 mmol) of intermediate 34, 0.2g (3.6 mmol) of Cu, 1.2g (8.6 mmol) of K 2 CO 3 And 43mL of Dimethylformamide (Dimethylformamide) were mixed, followed by 1-day refluxing and stirring. After the reaction, cooling to normal temperature. Distilled water was added to the reaction solution and stirred. The resulting solid was refluxed to monochlorobenzene and dissolved, then subjected to celite filtration, and after washing with monochlorobenzene, the solvent was removed under reduced pressure. The reaction solution was solidified with acetone to obtain 1.6g (yield: 43.2%) of compound 3-60 (LT 20-30-179) as a white solid.
Synthesis example 19: synthesis of Compound 3-62 (LT 20-30-244)
In a 250mL single-necked flask, 8.9g (19.2 mmol) of intermediate 4, 3.2g (14.8 mmol) of intermediate 35, 0.5g (8.0 mmol) of Cu, 2.7g (19.2 mmol) of K 2 CO 3 And 94mL of Dimethylformamide (DMF) were mixed, followed by 1-day refluxing and stirring. After the reaction, cooling to normal temperature. Distilled water was added to the reaction solution and stirred. The obtained reaction product was dissolved in a mixed solution of chloroform and ethyl acetate, and then subjected to silica filtration, and the solvent was removed under reduced pressure. The resulting concentrate was refluxed into methylene chloride and dissolved, and then cooled to room temperature, and the resulting solid was filtered. The reaction product was purified by silica gel column chromatography (Hexanes: etOAc). The resulting solid was solidified in a mixed solution (Hexanes: chloride) to obtain 2.3g (yield: 26.0%) of compound 3-62 (LT 20-30-244) as a brown solid.
Synthesis example 20: synthesis of Compound 3-65 (LT 20-30-147)
In a 250mL two-necked flask, 5.0g (10.7 mmol) of intermediate 6, 1.6g (10.7 mmol) of 4-cyanophenylboronic acid, 0.6g (0.5 mmol) of Pd (PPh 3 ) 4 2.9g (21.5 mmol) of K 2 CO 3 After 60mL of toluene, 30mL of purified water and 20mL of ethanol were mixed, the reaction was performed at 100℃for 4 hours. After the completion of the reaction, the reaction mixture obtained by filtration was cooled to room temperature, and then dissolved in chloroform and filtered with silica gel. The obtained reaction mixture was solidified with chloroform/methanol to obtain 3.8g (yield: 73.2%) of compound 3-65 (LT 20-30-147) as a white solid.
Synthesis example 21: synthesis of Compound 3-71 (LT 20-30-285)
In a 250mL two-necked flask, 4.0g (8.6 mmol) of intermediate 6, 2.7g (8.7 mmol) of intermediate 25, 0.5g (0.4 mmol) of Pd (PPh) 3 ) 4 2.4g (17.2 mmol) of K 2 CO 3 After mixing 40mL of toluene, 20mL of purified water and 12mL of ethanol, a one-day reaction was performed at 92 ℃. After the reaction, the mixture was cooled to room temperature, purified water was added thereto, and the resulting solid was filtered. After the obtained reaction mixture was dissolved in chloroform and filtered with silica gel to remove the solvent, solidification was performed with hot chloroform, to obtain 1.3g (yield: 27.2%) of compound 3-71 (LT 20-30-285) as a white solid.
Synthesis example 22: synthesis of Compound 3-75 (LT 20-30-263)
In a 100mL two-necked flask, 3.5g (7.5 mmol) of intermediate 6, 2.5g (9.0 mmol) of intermediate 31, 261.3mg (226.1. Mu. Mol) of Pd (PPh) 3 ) 4 3.1g (22.6 mmol) of K 2 CO 3 After 40mL of toluene, 10mL of ethanol and 10mL of distilled water were mixed, a one-day reaction was performed at 90 ℃. After the completion of the reaction, the reaction mixture was cooled to room temperature, 50mL of distilled water was added to the reaction product, and then the mixture was filtered and washed with distilled water, methanol and ethyl acetate. The obtained solid mixture was dissolved in toluene and subjected to silica-mat filtration, followed by solidification with toluene, to obtain 2.08g (yield: 51.4%) of white solid compound 3-75 (LT 20-30-263).
Synthesis example 23: synthesis of Compound 3-76 (LT 20-30-218)
In a 250mL two-necked flask, 3.1g (6.6 mmol) of intermediate 6, 1.8g (6.6 mmol) of intermediate 27, 0.4g (0.3 mmol) of Pd (PPh) 3 ) 4 1.8g (13.4 mmol) of K 2 CO 3 After mixing 37mL of toluene, 15mL of purified water and 10mL of ethanol, a one-day reaction was performed at 90 ℃. After completion of the reaction, the reaction mixture obtained by filtration was cooled to room temperature, then dissolved in chloroform, filtered with silica gel, concentrated under reduced pressure, and then solidified with chloroform/methanol to obtain 2.3g (yield: 65.4%) of compound 3-76 (LT 20-30-218) as a white solid.
Synthesis example 24: synthesis of Compound 3-79 (LT 20-30-217)
Double at 250mL3.1g (6.7 mmol) of intermediate 6, 2.4g (6.7 mmol) of intermediate 29, 0.4g (0.3 mmol) of Pd (PPh) are placed in an open flask 3 ) 4 1.8g (13.4 mmol) of K 2 CO 3 After mixing 37mL of toluene, 15mL of purified water and 10mL of ethanol, a one-day reaction was performed at 90 ℃. After completion of the reaction, the reaction mixture obtained by filtration was cooled to room temperature, was dissolved in chloroform, was filtered using silica gel, was concentrated under reduced pressure, and was solidified using chloroform/methanol to obtain 1.5g (yield: 36.7%) of compound 3-79 (LT 20-30-217) as a white solid.
Synthesis example 25: synthesis of Compound 3-82 (LT 20-30-169)
In a 100mL two-necked flask, 3.0g (6.5 mmol) of intermediate 6, 1.3g (7.8 mmol) of 9H-carbazole, and 1.2g (1.3 mmol) of Pd were introduced 2 (dba) 3 After mixing 1.1mg (2.6 mmol) of S-Phos, 931.3mg (9.7 mmol) of NaOtBu and 60mL of xylene, the mixture was stirred at 130℃for one day. After the completion of the reaction, the reaction mixture was cooled to room temperature, 50mL of distilled water was added to the reaction product, and then the reaction mixture was filtered and washed with distilled water, methanol and hexane. The obtained solid mixture was dissolved in hot toluene, filtered through a celite pad, and recrystallized and purified by using a mixed solvent (Tol/IPA), 2.39g (yield: 67.2%) of white solid compound 3-82 (LT 20-30-169) was obtained.
Synthesis example 26: synthesis of Compound 3-83 (LT 20-30-204)
In a 250mL two-necked flask, 4.1g (9.0 mmol) of intermediate 6, 1.8g (9.4 mmol) of intermediate 33, 1.0g (0.2 mmol) of Pd (dba) were placed 2 1.5g (0.4 mmol) of S-Phos, 2.6g (27.0 mmol)After mixing NaOtBu and 50mL of xylene, the reaction was carried out at 120℃for 18 hours. After the completion of the reaction, the mixture was cooled to room temperature, and purified by silica gel column chromatography (Hex: CH 2 Cl 2 ) The reaction mixture obtained by filtration was purified and solidified with methanol/hexane to obtain 2.7g (yield: 87.3%) of white solid compound 3-83 (LT 20-30-204).
Synthesis example 27: synthesis of Compound 3-142 (LT 20-30-293)
In a 250mL two-necked flask, 5.0g (14.6 mmol) of intermediate 10, 3.2g (15.3 mmol) of dibenzofuran-2-boronic acid, 0.8g (0.7 mmol) of Pd (PPh) 3 ) 4 4.1g (29.2 mmol) of K 2 CO 3 After 50mL of 1, 4-dioxane, 25mL of purified water and 15mL of ethanol were mixed, the reaction was performed at 90℃for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, the resultant solid was filtered with purified water, and the resultant reaction mixture was dissolved in methylene chloride, filtered with silica gel, and solidified with chloroform/methanol to obtain 2.4g (yield: 34.6%) of compound 3-142 (LT 20-30-293) as a white solid.
Synthesis example 28: synthesis of Compound 3-146 (LT 20-30-199)
In a 250mL single-necked flask, 4.3g (7.8 mmol) of intermediate 17, 1.4g (9.4 mmol) of 4-cyanophenylboronic acid, 0.3g (0.2 mmol) of Pd (PPh 3 ) 4 4.2g (19.6 mmol) of K 3 PO 4 After 40mL of toluene, 20mL of ethanol and 20mL of water were mixed, reflux stirring was performed for 72 hours. After the reaction, cooling to normal temperature, filtering the solid, and using water And methanol, and drying. After dissolving the dried solid in chloroform, filtration was performed using a pad of silica, and solidification was performed using a mixed solution (DCM/MeOH), yielding 3.5g (yield: 77.4%) of compound 3-146 (LT 20-30-199) as a white solid.
Synthesis example 29: synthesis of Compound 3-162 (LT 20-30-287)
In a 250mL single-necked flask, 5.8g (10.4 mmol) of intermediate 17, 2.4g (12.5 mmol) of intermediate 33, 0.5g (0.5 mmol) of Pd 2 (dba) 3 After mixing 0.4g (1.0 mmol) of S-phos, 3.0g (31.2 mmol) of NaOtBu and 90mL of xylene, reflux stirring was carried out for 48 hours. After the reaction is finished, cooling to normal temperature, and then utilizing water and CHCl 3 And (5) cleaning. After using silica gel column chromatography (n-hex: CHCl 3 ) After purification of the resulting mixture, recrystallization from toluene (tolene)/MeOH gave 1.7g (yield: 24.3%) of white solid compound 3-162 (LT 20-30-287).
Synthesis example 30: synthesis of Compound 3-169 (LT 20-30-289)
In a 250mL single-necked flask, 3.5g (10.2 mmol) of intermediate 10, 2.2g (10.2 mmol) of dibenzofuran-4-boronic acid (dibenzo [ b, d)]Furan-4-ylboronic acid), 590.0mg (510.5. Mu. Mol) Pd (PPh) 3 ) 4 6.5g (30.6 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and ethanol, and then dried. After dissolving the dried solid in chloroform, a silica pad (CHCl) 3 ) Feeding inFiltration and solidification with methylene chloride gave 3.4g (yield: 70.4%) of compound 3-169 (LT 20-30-289) as a white solid.
Synthesis example 31: synthesis of Compound 3-170 (LT 20-30-305)
In a 100mL two-necked flask, 4.0g (7.2 mmol) of intermediate 21, 1.1g (8.7 mmol) of phenylboronic acid (phenylboronic acid), 250.6mg (216.8. Mu. Mol) of Pd (PPh) 3 ) 4 3.0g (21.7 mmol) of K 2 CO 3 After 36mL of toluene, 9mL of ethanol and 9mL of distilled water were mixed, a one-day reaction was performed at 90 ℃. After the completion of the reaction, the reaction mixture was cooled to room temperature, 50mL of distilled water was added to the reaction product, and then the reaction mixture was filtered and washed with distilled water, methanol and hexane. The obtained solid mixture was dissolved in toluene, and subjected to silica-mat filtration and solidification with ethyl acetate, to obtain 1.6g (yield: 40.7%) of compound 3-170 (LT 20-30-305) as a white solid.
Synthesis example 32: synthesis of Compound 3-171 (LT 20-30-215)
In a 100mL two-necked flask, 3.0g (5.4 mmol) of intermediate 21, 955.8mg (6.5 mmol) of 4-cyanobenzeneboronic acid, 187.9mg (162.6. Mu. Mol) of Pd (PPh) 3 ) 4 2.2g (16.3 mmol) of K 2 CO 3 After mixing 27mL of toluene, 7mL of ethanol and 7mL of distilled water, a one-day reaction was performed at 90 ℃. After the reaction, cooling to room temperature, adding purified water into the reaction product, and extracting by using ethyl acetate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed under reduced pressure. Will beThe resulting solid mixture was dissolved in toluene, and subjected to silica-pad filtration, followed by solidification using a mixed solution (MC/MeOH), to give 2.8g (yield: 89.7%) of compound 3-171 (LT 20-30-215) as a white solid.
Synthesis example 33: synthesis of Compound 3-173 (LT 20-30-304)
In a 100mL two-necked flask, 3.0g (5.4 mmol) of intermediate 21, 1.7g (6.5 mmol) of intermediate 30, 187.9mg (162.6. Mu. Mol) of Pd (PPh) 3 ) 4 2.2g (16.3 mmol) of K 2 CO 3 After mixing 27mL of toluene, 7mL of ethanol and 7mL of distilled water, the reaction was performed at 90℃for 2 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, 50mL of distilled water was added to the reaction product, followed by extraction with ethyl acetate, drying with anhydrous magnesium sulfate, filtration, and concentration. The obtained solid mixture was dissolved in toluene, and subjected to silica-pad filtration, followed by solidification with a mixed solution (Tol/IPA/Hex), to obtain 2.13g (yield: 65.4%) of white solid compound 3-173 (LT 20-30-304).
Synthesis example 34: synthesis of Compound 3-175 (LT 20-30-298)
In a 100mL two-necked flask, 3.0g (5.4 mmol) of intermediate 21, 2.0g (6.5 mmol) of intermediate 25, 187.9mg (162.6. Mu. Mol) of Pd (PPh) 3 ) 4 2.2g (16.3 mmol) of K 2 CO 3 After mixing 27mL of toluene, 7mL of ethanol and 7mL of distilled water, a one-day reaction was performed at 90 ℃. After the completion of the reaction, the reaction mixture was cooled to room temperature, 50mL of distilled water was added to the reaction product, and then the mixture was filtered and purified by using distilled water, methanol and hexaneAnd (5) cleaning. The obtained solid mixture was dissolved in toluene, and subjected to silica-pad filtration, and recrystallized from ethyl acetate, whereby 2.2g (yield: 62.6%) of compound 3-175 (LT 20-30-298) as a white solid was obtained.
Synthesis example 35: synthesis of Compound 3-179 (LT 20-30-309)
In a 100mL two-necked flask, 3.5g (6.3 mmol) of intermediate 21, 2.12g (7.6 mmol) of intermediate 27, 219.2mg (189.7. Mu. Mol) of Pd (PPh) 3 ) 4 2.6g (19.0 mmol) of K 2 CO 3 After mixing 32mL of toluene, 8mL of ethanol and 7mL of distilled water, a one-day reaction was performed at 90 ℃. After the completion of the reaction, the reaction mixture was cooled to room temperature, 50mL of distilled water was added to the reaction product, and then the reaction mixture was filtered and washed with distilled water, methanol and hexane. The obtained solid mixture was dissolved in toluene, and subjected to silica-pad filtration, recrystallization from ethyl acetate and filtration with acetone, to obtain 1.53g (yield: 38.7%) of compound 3-179 (LT 20-30-309) as a white solid.
Synthesis example 36: synthesis of Compound 3-184 (LT 20-30-303)
In a 100mL two-necked flask, 3.0g (5.4 mmol) of intermediate 21, 1.3g (6.5 mmol) of intermediate 33, 496.4mg (542.1. Mu. Mol) of Pd were introduced 2 (dba) 3 890.1mg (2.2 mmol) of S-Phos, 3.5g (16.3 mmol) of K 3 PO 4 And 27mL of xylene were mixed, and the reaction was performed at 130℃for one day. After the completion of the reaction, the reaction mixture was cooled to room temperature, 50mL of distilled water was added to the reaction product, and then the reaction mixture was filtered and washed with distilled water, methanol and hexane. To be obtainedThe solid mixture was dissolved in toluene, and subjected to silica-pad filtration, followed by solidification with a mixed solvent (Hex/EA) to obtain 2.4g (yield: 65.5%) of compound 3-184 (LT 20-30-303) as a white solid.
Synthesis example 37: synthesis of Compound 3-193 (LT 20-30-290)
In a 250mL single-necked flask, 1.7g (5.0 mmol) of intermediate 10, 2.0g (5.0 mmol) of intermediate 41, 288.0mg (249.2. Mu. Mol) of Pd (PPh) 3 ) 4 2.3g (11.0 mmol) of K 3 PO 4 After 20mL of dioxane and 5mL of water were mixed, reflux stirring was performed for 12 hours. After the completion of the reaction, the mixture was cooled to room temperature, extracted with chloroform, and the solvent was concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (Hex: EA) and solidified by ethyl acetate to obtain 1.6g (yield: 56.5%) of compound 3-193 (LT 20-30-290) as a white solid.
Synthesis example 38: synthesis of Compound 3-255 (LT 20-30-258)
In a 250mL single-necked flask, 4.0g (7.2 mmol) of intermediate 24, 1.3g (8.7 mmol) of 4-cyanophenylboronic acid, 417.0mg (361.4. Mu. Mol) of Pd (PPh 3 ) 4 4.6g (21.7 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and ethanol, and then dried. After dissolving the dried solid in chloroform, a silica pad (CHCl) 3 ) Filtration and solidification using a mixed solution (EA/EtOH) gave 1.1g (yield: 26.4 Of the components of the system) is providedWhite solid compound 3-255 (LT 20-30-258).
Synthesis example 39: synthesis of Compound 3-269 (LT 20-30-200)
In a 250mL single-necked flask, 3.0g (8.7 mmol) of intermediate 10, 3.9g (9.6 mmol) of intermediate 43, 0.5g (0.4 mmol) of Pd (PPh) 3 ) 4 13.0mL (26.1 mmol) of 2M K 2 CO 3 After mixing the aqueous solution with 29mL of toluene and 15mL of ethanol, the mixture was refluxed and stirred for 2 hours. After the completion of the reaction, the resulting solid was filtered, and then washed with toluene, distilled water and methanol. The resulting solid was refluxed into monochlorobenzene and then filtered through celite. Washing with monochlorobenzene and filtering the resulting solid and drying gave 3.8g (yield: 73.1%) of compound 3-269 as a white solid (LT 20-30-200).
Synthesis example 40: synthesis of Compound 3-277 (LT 20-30-286)
In a 250mL single-necked flask, 2.5g (7.4 mmol) of intermediate 10, 3.4g (7.4 mmol) of intermediate 45, 0.4g (0.4 mmol) of Pd (PPh) 3 ) 4 11.1mL (22.2 mmol) of 2M K 2 CO 3 After mixing the aqueous solution, 24mL of toluene and 12mL of ethanol, the mixture was refluxed and stirred for 3 hours. After the completion of the reaction, the resulting solid was filtered, and then washed with toluene, distilled water and methanol. The resulting solid was refluxed in dichlorobenzene and filtered through celite. The resultant solid was filtered and dried after washing with dichlorobenzene and cooling to room temperature, whereby 2.0g (yield: 42.6%) of white solid compound 3-277 (LT 20-30-286) was obtained.
SynthesisExample 41: synthesis of Compound 3-278 (LT 20-35-283)
In a 250mL single-necked flask, 6.0g (16.3 mmol) of intermediate 12, 9.8g (21.2 mmol) of intermediate 45, 0.9g (0.8 mmol) of Pd (PPh) 3 ) 4 24mL (48.9 mmol) of 2M K 2 CO 3 After mixing the aqueous solution with 60mL of toluene and 30mL of ethanol, reflux stirring was performed for 1 day. After the completion of the reaction, the resulting solid was filtered at the reaction temperature. After purification of the obtained solid compound by silica gel column chromatography (Hexanes: chloroform), solidification with methanol gave 2.3g (yield: 21.2%) of white solid compound 3-278 (LT 20-35-283)
Synthesis example 42: synthesis of Compound 3-292 (LT 20-30-296)
In a 250mL single-necked flask, 3.0g (8.8 mmol) of intermediate 10, 2.0g (8.8 mmol) of dibenzothiophene-4-boronic acid (dibenzo [ b, d)]thiophen-4-ylboronic acid), 505.0mg (437.5. Mu. Mol) Pd (PPh) 3 ) 4 5.6g (26.3 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and ethanol, and then dried. After dissolving the dried solid in chloroform, a silica pad (CHCl) 3 ) Filtration and curing with methylene chloride gave 2.3g (yield: 52.4%) of white solid compound 3-292 (LT 20-30-296).
Synthesis example 43: synthesis of Compound 3-376 (LT 20-30-288)
In a 250mL single-necked flask, 3.0g (8.8 mmol) of intermediate 10, 2.5g (8.8 mmol) of 9-phenyl-9-carbazole-boronic acid ((9-phenyl-9H-carbazol-3-y 1) carboxylic acid), 505.0mg (437.5. Mu. Mol) of Pd (PPh) 3 ) 4 5.6g (26.3 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and ethanol, and then dried. After dissolving the dried solid in chloroform, a silica pad (CHCl) 3 ) Filtration and solidification with a mixed solvent (DCM/EA) gave 2.3g (yield: 48.0%) of white solid compound 3-376 (LT 20-30-288).
Synthesis example 44: synthesis of Compound 3-380 (LT 20-30-306)
In a 250mL single-necked flask, 3.0g (8.8 mmol) of intermediate 10, 4.1g (8.8 mmol) of intermediate 48, 505.6mg (437.5. Mu. Mol) of Pd (PPh) 3 ) 4 4.6g (21.9 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and ethanol, and then dried. After dissolving the dried solid in chloroform, the solid was purified by silica gel column chromatography (Hex: CHCl) 3 ) Purification and curing with methylene chloride gave 1.8g (yield: 32.0%) of white solid compound 3-380 (LT 20-30-306).
Synthesis example 45: synthesis of Compound 3-381 (LT 20-35-313)
In a 250mL single-necked flask, 3.0g (8.7 mmol) of intermediate 14, 5.3g (10.5 mmol) of intermediate 48, 504.2mg (436.3. Mu. Mol) of Pd (PPh) 3 ) 4 3.6g (26.2 mmol) of K 3 PO 4 After 30mL of toluene, 10mL of ethanol and 10mL of water were mixed, reflux stirring was performed for 12 hours. After the reaction, the mixture was cooled to room temperature, and after the solid was filtered, the solid was washed with water and ethanol, and then dried. After dissolving the dried solid in chloroform, the solid was purified by silica gel column chromatography (Hex: CHCl) 3 ) Purification and curing with methylene chloride gave 1.2g (yield: 21.1%) of white solid compound 3-381 (LT 20-35-313).
Manufacturing element
For manufacturing the element, a transparent electrode ITO was used as an anode layer, 2-TNATA was used as a hole injection layer, NPB was used as a hole transport layer, αβ -ADN was used as a host of a light emitting layer, pyene-CN was used as a blue fluorescent dopant, liq was used as an electron injection layer, and Al was used as a cathode. The structures of these compounds are shown in the following chemical formulas.
Comparative example 1: ITO/2-TNATA (60 nm)/NPB (20 nm)/alpha beta-ADN: 10% pyrene-CN (30 nm)/Alq 3 (30nm)/Liq(2nm)/Al(100nm)
Comparative example 2: ITO/2-TNATA (60 nm)/NPB (20 nm)/alpha beta-ADN: 10% pyrene-CN (30 nm)/REF 02 (30 nm)/Liq (2 nm)/Al (100 nm)
The blue fluorescent organic light emitting element is prepared by ITO (180 nm)/2-TNATA (60 nm)/NPB (20 nm)/alpha beta-ADN: pyrene-CN 10% (30 nm)/electron transport layer (30 nm)/Liq (2 nm)/Al (100 nm) were sequentially deposited to fabricate a device.
Before depositing the organic matter, the ITO electrode is arranged at a ratio of 2×10 -2 Oxygen plasma treatment was performed at 125W for 2 minutes under Torr. At 9X 10 -7 Depositing organic matters under the vacuum degree of Torr, and mixing Liq and alpha beta-ADN, pyrene-CN respectively
Simultaneously depositing the rest of the various organic matters >
Is deposited at a rate of (a).
After the element was manufactured, encapsulation was performed in a glove box filled with nitrogen gas to prevent the element from being exposed to air and moisture. After forming a separator using 3M company adhesive tape, barium Oxide (Barium Oxide) as a moisture absorbent capable of removing moisture and the like is added, and a glass plate is attached.
< example 1 to example 45>
Except for the comparative example 1, each of the compounds shown in table 1 was used instead of REF01 (Alq 3 ) Except for this, the element was manufactured in the same manner as in the comparative example.
The electroluminescent characteristics of the organic light emitting elements manufactured in comparative example 1, comparative example 2, and examples 1 to 45 are shown in table 1.
Table 1:
from the above table 1, it was confirmed that when comparative example 2 (REF 02) was compared with example 21 (compounds 3 to 71), the compound of example 21 exhibited characteristics of low voltage (3.32 (V) compared with 5.11), high efficiency (8.87 (cd/a) compared with 6.18) and long life (101.68 (%) compared with 94.15) because heteroarylene (pyridine) and cyano were introduced into pyrimidine to improve electron injection and electron mobility, and hole and electron were balanced (Balance).
It is confirmed that the heteroarylene-substituted pyrimidine derivative compound of the present invention can be used as a material of an organic material layer of an organic electronic device including an organic light emitting device as a whole, and that the organic electronic device including an organic light emitting device using the same exhibits excellent characteristics in efficiency, driving voltage, stability, and the like. In particular, the compound of the present invention is excellent in hole-electron balance performance and electron transfer performance, and exhibits high efficiency characteristics.
Industrial applicability
The pyrimidine derivative compound of the invention can be used for an organic layer of an organic electroluminescent element to improve the quality of the organic electroluminescent element.
When the compound is used for the organic layer, the organic electroluminescent element can improve the lifetime by the characteristics of the compound while exhibiting the original characteristics.
Claims (6)
1. A pyrimidine derivative for use in an organic electroluminescent element, characterized in that,
the chemical formula (1) is represented by the formula (1),
chemical formula 1:
in the chemical formula 1 described above, a compound having the formula,
Ar 1 、Ar 2 ar, ar 3 Each independently is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms,
L is a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms,
Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or is takenSubstituted or unsubstituted heteroaryl groups having 5 to 20 carbon atoms,
p is an integer of 0 or 2,
when P is 2, a plurality of Ar 4 The same or different.
2. The pyrimidine derivative for organic electroluminescent element as claimed in claim 1, wherein,
the chemical formula 1 is represented by chemical formula 2,
chemical formula 2:
in the chemical formula 2 described above, the chemical formula,
l is any one of a substituted or unsubstituted pyridyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted quinolinyl group and a substituted or unsubstituted isoquinolinyl group,
Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted carbazolyl group,
Ar 3 and p is the same as defined in the chemical formula 1.
3. The pyrimidine derivative for organic electroluminescent element as claimed in claim 1, wherein,
Ar 3 is any one selected from phenyl, phenyl and pyridyl substituted by cyano.
4. The pyrimidine derivative for organic electroluminescent element as claimed in claim 1, wherein,
wherein the chemical formula 1 is selected from the compounds of chemical formula 3,
chemical formula 3:
5. an organic electroluminescent element, comprising:
an anode;
an organic layer disposed on the anode and formed in a plurality of layers; and
a cathode disposed on the organic layer,
the organic layer comprises the pyrimidine derivative according to any one of claims 1 to 4.
6. The organic electroluminescent element as claimed in claim 5, wherein,
the pyrimidine derivative is used as an electron transport layer material of the organic layer.
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