KR20200031358A - Manufacturing method of organic compound - Google Patents

Abstract

A specification of the present invention provides a method for manufacturing an organic compound. The method comprising: a first step of making a compound represented by chemical formula 1 react with phenylmagnesium bromide; and a second step of making phenol react with a first product obtained through the first step. The present specification is intended to provide the method of manufacturing an organic compound capable of mass production without including a cryogenic process.

Description

Manufacturing method of organic compounds {MANUFACTURING METHOD OF ORGANIC COMPOUND}

The present specification relates to a method for preparing an organic compound.

Conventionally, a deposition process has been mainly used to manufacture an organic light emitting device. However, when manufacturing an organic light emitting device by a deposition process, there is a problem that a lot of material loss occurs, and in order to solve this, a technology for manufacturing a device through a solution process that can increase production efficiency by reducing material loss and Materials used in organic light emitting devices for solution processing are being developed.

However, it is difficult to deal with the manufacturing process for synthesizing the material for the solution processing because the cryogenic process is performed in the process of synthesizing the material for the solution processing, or benzene corresponding to the special management material is used, and the scale-up of the factory for mass production ( There is a problem that scale up) is difficult.

Therefore, a new manufacturing method for solving such a problem is required.

Korean Patent Publication No. 10-2015-0066429

This specification does not include a cryogenic process, and is intended to provide a method of manufacturing an organic compound capable of mass production.

The present specification is a first step of reacting the compound represented by the formula (1) and phenyl magnesium bromide; And a second step of reacting phenol and the first product obtained through the first step.

[Formula 1]

X is a halogen group.

In addition, it provides a method for producing an organic compound further comprising a third step of reacting the second product obtained through the second step and trifluoromethanesulfonic acid.

Finally, the third product obtained through the third step; And a fourth step of reacting vinyl magnesium bromide or vinyl borate.

The method for preparing the organic compound of the present invention uses phenyl magnesium bromide instead of n-butyllithium (n-BuLi), which was used in the conventional synthesis process in the process for synthesizing the compound represented by Formula 5, which is the final product of the present invention. By doing so, a cryogenic process (about -78 ° C) can be avoided, and scale-up of a factory for mass production is possible by using phenol instead of benzene, which is difficult to handle.

1 is a diagram showing a graph for measuring the mass of Compound 1.

Hereinafter, the present invention will be described in detail.

According to an exemplary embodiment of the present specification, the first step of reacting the compound represented by the formula (1) and phenyl magnesium bromide; And a second step of reacting phenol and the first product obtained through the first step.

[Formula 1]

X is a halogen group.

According to another exemplary embodiment, the first step of reacting the compound represented by Formula 1 and phenyl magnesium bromide in a solvent; And a second step of reacting the phenol and the first product obtained through the first step in a solvent.

According to an exemplary embodiment of the present specification, X is F (fluorine), Cl (chlorine), Br (bromine) or I (iodine).

According to another exemplary embodiment, X is Br (bromine).

[Step 1]

According to an exemplary embodiment of the present specification, the first step is to react the compound represented by the formula (1) and phenyl magnesium bromide (Phenyl Magnesium Bromide) in a solvent.

The solvent used in the first step may be tetrahydrofuran (THF), but is not limited thereto.

According to an exemplary embodiment of the present specification, the first step is performed at -30 ° C to 10 ° C, preferably at -10 ° C to 5 ° C. When the first step is performed in the temperature range, it has an advantage that it has an appropriate reaction rate and does not require additional process equipment. Specifically, when the reaction temperature of the first step proceeds in excess of 10 ° C, the reaction is not likely to proceed in a desired direction and impurities are likely to be generated, and when the reaction temperature is performed at a temperature lower than the temperature range, the reaction is slow. As it progresses, additional equipment is needed to lower the reaction temperature. In particular, the process of synthesizing the compound represented by Chemical Formula 5 to be described later using butyl lithium (n-BuLi) as in the conventional synthesis process requires additional process equipment to lower the reaction temperature to a cryogenic temperature (about -78 ° C). There is a problem.

In an exemplary embodiment of the present invention, in the first step, the molar ratio of the compound represented by Chemical Formula 1 and phenyl magnesium bromide (Chemical Formula 1: phenyl magnesium bromide) may be 1: 1 to 1: 2, preferably It may be 1: 1.5 to 1: 2. When the content of the compound represented by Chemical Formula 1 and the phenyl magnesium bromide satisfies the above range, when the content of the compound represented by Chemical Formula 1 is high, it is possible to prevent the problem of lowering the overall yield, and the phenyl magnesium bromide In the case of high content of phenyl magnesium bromide, which does not participate in the reaction, it has the advantage of preventing the economic loss caused by unnecessary raw materials.

According to an exemplary embodiment of the present specification, the first step may be performed through the following process.

In one embodiment of the present specification, the first step may be performed for 10 hours to 72 hours, and more preferably 15 hours to 24 hours. When the reaction time in the first step satisfies the above range, there is an advantage that the highest yield can be obtained within a range in which additional addition reaction does not proceed.

[Step 2]

The method for preparing an organic compound of the present invention includes a first step obtained through the first step and a second step of reacting phenol.

According to another exemplary embodiment, the first product obtained through the first step and a second step of reacting phenol in a solvent are included.

According to another exemplary embodiment, the first product is represented by Chemical Formula 2 below.

[Formula 2]

X is a halogen group.

The solvent used in the second step may be dichloromethane, but is not limited thereto.

According to another exemplary embodiment, the second step may further include additional compounds such as methane sulfonic acid, sulfuric acid, and p-toluenesulfonic acid, but is not limited thereto.

In one embodiment of the present specification, in the second step, the molar ratio (chemical formula 2: phenol: additional compound) of additional compounds such as the compound represented by Chemical Formula 2, phenol, and methane sulfonic acid may be 1: 5: 1 have.

According to the exemplary embodiment of the present specification, the second step may be performed through the following process.

According to another exemplary embodiment, the second step is performed at 15 ° C to 40 ° C, preferably at 17 ° C to 25 ° C. If the second step is out of the temperature range, there is a problem that additional equipment is required or the boiling point of the solvent is exceeded to maintain reflux.

In one embodiment of the present specification, the second step may be performed for 5 hours to 24 hours, and more preferably 15 hours to 18 hours. If it is out of the reaction time range, there is a problem that the yield falls or no further reaction proceeds.

[Step 3]

According to an exemplary embodiment of the present specification, the method for preparing an organic compound of the present invention further includes a third step of reacting the second product and trifluoromethanesulfonic acid obtained through the second step.

According to another exemplary embodiment, the method for producing an organic compound of the present invention further includes a third step of reacting the second product and trifluoromethanesulfonic acid obtained through the second step in a solvent.

In another exemplary embodiment, the second product is represented by Chemical Formula 3 below.

[Formula 3]

X is a halogen group.

The solvent used in the third step may be dichloromethane, but is not limited thereto.

According to another exemplary embodiment, in the third step, pyridine or triethylamine; And trifluoromethanesulfonic acid.

In one embodiment of the present specification, the compound represented by Chemical Formula 3 in the third step; The molar ratio of pyridine or triethylamine; and trifluoromethanesulfonic acid (Formula 3: Pyridine or triethylamine: trifluoromethanesulfonic acid) may be 1: 2: 1.2.

According to the exemplary embodiment of the present specification, the third step may be performed through the following process.

In one embodiment of the present specification, the third step is performed at -20 ° C to 10 ° C, preferably at -5 ° C to 0 ° C. When the third step is performed in the temperature range, there is an advantage that it is possible to reduce the generation of impurities and does not require additional equipment and energy consumption to lower the reaction temperature to a very low temperature.

In one embodiment of the present specification, the third step may be performed for 30 minutes to 10 hours, and more preferably 2 hours to 5 hours. If it is out of the reaction time range, there is a problem that the yield falls or no further reaction proceeds.

[Step 4]

According to an exemplary embodiment of the present specification, the method for producing an organic compound of the present invention comprises a third product obtained through the third step; And a fourth step of reacting vinyl magnesium bromide or vinyl borate.

According to another exemplary embodiment, the method for preparing an organic compound of the present invention includes a third product obtained through the third step; And a fourth step of reacting vinyl magnesium bromide or vinyl borate in a solvent.

In another exemplary embodiment, the third product is represented by Chemical Formula 4 below.

[Formula 4]

X is a halogen group.

The solvent used in the fourth step may be tetrahydrofuran (THF), but is not limited thereto.

In another exemplary embodiment, the fourth step may further include additional compounds of zinc chloride, sodium potassium, or lithium bromide.

In one embodiment of the present specification, the compound represented by Chemical Formula 4 in the fourth step; The molar ratio of vinyl magnesium bromide or vinyl borate and the additional compound (Formula 4: Vinyl magnesium bromide or vinyl borate: additional compound) may be 1: 1.2: 1.2.

According to the exemplary embodiment of the present specification, the fourth step may be performed through a Negishi reaction, a Suzuki reaction, or a Kumada reaction. Specifically, in the fourth step, when the compound represented by Chemical Formula 4, vinyl magnesium bromide, and zinc chloride are included, a Negishi reaction proceeds, and the compound represented by Chemical Formula 4, vinyl borate, and sodium potassium When included, the Suzuki reaction proceeds, and when the compound represented by Chemical Formula 4, vinyl magnesium bromide, and lithium bromide is included, the Kumada reaction proceeds.

[Negishi Reaction Scheme]

In the above reaction formula,

X ₁ is Br, R ₁ is a vinyl group (vinyl group), X is OTf (trifluoromethylsulfonyl group), R means the following structure.

In addition, in the above reaction formula, the catalyst may be included in 0.02 to 0.15 equivalents, preferably 0.03 to 0.1 equivalent, and the catalyst means a palladium catalyst, and specifically Pd (P (t-Bu) ₃ ) ₂ Or Pd (dppp) Cl ₂ .

In one embodiment of the present specification, the fourth step is performed at 15 ° C to 100 ° C, and preferably 60 ° C to 85 ° C. When the fourth step is performed in the temperature range, there is an advantage that the product can be obtained with a high yield.

In one embodiment of the present specification, the fourth step may be performed for 1 hour to 24 hours, and more preferably 18 hours to 20 hours. When the reaction time is satisfied, there is an advantage in that the yield and synthetic purity of the product are high.

According to an exemplary embodiment of the present specification, the organic compound prepared in the method for producing the organic compound is a compound represented by the formula (5).

[Formula 5]

X is a halogen group.

In one embodiment of the present specification, the compound represented by Chemical Formula 5 may be Compound 1 below.

[Compound 1]

According to an exemplary embodiment of the present specification, in order to obtain the product of each step, stopping the reaction; Extracting; Drying and filtering; And one or more steps selected from the group consisting of removing the organic solvent may be performed.

In the step of stopping the reaction, saturated NH ₄ Cl (aq), saturated NaHCO ₃ (aq), water, and the like may be used, but are not limited thereto.

In the extraction step, dichloromethane, ethyl acetate (EA), or the like may be used, but is not limited thereto.

The step of drying and filtering may be performed using MgSO ₄ (magnesium sulfate), but is not limited thereto.

The step of removing the organic solvent may be performed using a vacuum rotary concentrator.

According to an exemplary embodiment of the present invention, a compound for solution processing may be prepared by using the compound represented by Chemical Formula 5 as an intermediate through the method for preparing the organic compound.

According to another exemplary embodiment, the organic material layer of the organic light emitting device may be formed using a coating composition including the solution process compound and a solvent.

In one embodiment of the present specification, the coating composition may be liquid. The term "liquid phase" means a liquid state at normal temperature and pressure.

Examples of the solvent included in the coating composition include chlorine-based solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene; Ether-based solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene and mesitylene; Aliphatic hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, isosophone, tetralone, decalone and acetylacetone; Ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalent values of ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. Alcohols and derivatives thereof; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide-based solvents such as dimethyl sulfoxide; And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; A solvent such as tetralin is exemplified, but a solvent capable of dissolving or dispersing the fluorene derivative according to an exemplary embodiment of the present invention is sufficient, and is not limited thereto.

In another exemplary embodiment, the solvent included in the coating composition may be used alone or as a mixture of two or more solvents.

In one embodiment of the present specification, the coating composition may further include one or two types of compounds selected from the group consisting of a compound having a thermosetting group or a photocurable group introduced into a molecule and a polymer compound.

In one embodiment of the present specification, the coating composition may further include a compound having a thermosetting group or a photocurable group introduced into the molecule. When the coating composition further includes a compound in which a thermosetting group or a photocurable group is introduced into the molecule, the degree of curing of the coating composition may be further increased.

In one embodiment of the present specification, the molecular weight of the compound in which a thermosetting group or photocurable group is introduced into the molecule is 1,000 g / mol to 3,000 g / mol.

In one embodiment of the present specification, the coating composition may further include a polymer compound. When the coating composition further includes a polymer compound, ink characteristics of the coating composition may be improved. That is, the coating composition further comprising the polymer compound may provide a suitable viscosity for coating or inkjet.

In one embodiment of the present specification, the coating composition may further include one or more additives selected from the group consisting of a thermal polymerization initiator and a photo polymerization initiator.

As the thermal polymerization initiator, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl per Oxide, bis-3,5,5-trimethyl hexanoyl peroxide, lauryl peroxide, benzoyl peroxide, p-crol benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- (t- Butyl oxy) -hexane, 1,3-bis (t-butyl peroxy-isopropyl) benzene, t-butyl cumyl peroxide, di-tbutyl peroxide, 2,5-dimethyl-2,5- (Dit-butyl peroxy) hexane-3, tris- (t-butyl peroxy) triazine, 1,1-dit-butyl peroxy-3,3,5-trimethyl cyclohexane, 1,1-di t-butyl peroxy cyclohexane, 2,2-di (t-butyl peroxy) butane, 4,4-di-t-butyroxycybareric acid n-butyl ester, 2,2-bis (4 , 4-t-butyl perox Cycyclohexyl) propane, t-butylperoxyisobutylate, dit-butyl peroxy hexahydro terephthalate, t-butyl peroxy-3,5,5-trimethylhexaate, t-butylperoxybenzoate, Peroxides such as dit-butyl peroxytrimethyl adipate, or azo systems such as azobis isobutylnitrile, azobisdimethylvaleronitrile, and azobis cyclohexyl nitrile, but are not limited thereto.

As the photopolymerization initiator, diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy ) Phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1- Phenyl propan-1-one, 2-methyl-2-morpholino (4-methyl thiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) Acetophenone-based or ketal-based photopolymerization initiators such as oxime, benzoin, benzoin methyl ether, benzoin ether ether, benzoin isobutyl ether, benzoin isopropierate, benzoin, etc. Ether-based photopolymerization initiators, benzophenone-based photopolymerization initiators such as benzophenone, 4-hydroxybenzophenone, 2-benzoyl naphthalene, 4-benzoyl biphenyl, 4-benzoyl phenyl ether, acrylate benzophenone, 1,4-benzoyl benzene, and the like. , 2-isopropyl thioxanthone, 2-chloro Thioxanthone-based photopolymerization initiators such as thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, and other photopolymerization initiators include ethyl anthraquinone, 2 , 4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, bis (2,4 -Dimethoxy benzoyl) -2,4,4-trimethyl pentylphosphine oxide, methyl phenyl glyciokistelyl, 9,10-phenanthrene, acridine compounds, triazine compounds, imidazole compounds have. Moreover, what has a photopolymerization promoting effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyl diethanol amine, ethyl 4-dimethylamino benzoate, isoamyl 4-dimethylamino benzoate, ethyl benzoate (2-dimethylamino), 4,4'-dimethylaminobenzophenone, and the like, It is not limited.

In one embodiment of the present specification, the coating composition does not further include a p-doped material.

In one embodiment of the present specification, the coating composition further includes a p-doped material.

In the present specification, the p-doped material means a material that makes the host material have p-semiconductor properties. The p-semiconductor property means a property in which holes are injected or transported at a HOMO (highest occupied molecular orbital) energy level, that is, a property of a material having high hole conductivity.

In one embodiment of the present specification, the p-doped material may be F4TCNQ or a Farylborate-based compound as in the following Chemical Formulas 6-1 to 6-3, but is not limited thereto.

[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

In the present specification, the p-doped material is sufficient as long as it is a material having p-semiconductor properties, and one or two or more types may be used, and the type of the p-doped material is not limited.

In one embodiment of the present specification, the content of the p-doped material is 0% to 50% by weight based on the fluorene-based compound of Chemical Formula 1 above.

In one embodiment of the present specification, the content of the p-doped material includes 0 to 30% by weight based on the total solid content of the coating composition. In one embodiment of the present specification, the content of the p-doped material preferably includes 1 to 30% by weight based on the total solid content of the coating composition, and in another embodiment, the p-doped material It is more preferable that the content of 10 to 30% by weight based on the total solids content of the coating composition.

In another embodiment, the coating composition is a single molecule comprising a thermosetting group or a photocurable group; Or it may further include a single molecule containing a terminal group capable of forming a polymer by heat. Single molecule containing a thermosetting group or a photocurable group as described above; Alternatively, the molecular weight of a single molecule containing a terminal group capable of forming a polymer by heat may be 2,000 g / mol or less.

In one embodiment of the present specification, the coating composition has a molecular weight of 2,000 g / mol or less, a single molecule comprising a thermosetting group or a photocurable group; Or it further includes a single molecule containing a terminal group capable of forming a polymer by heat.

A single molecule comprising the thermosetting group or photocurable group; Or a single molecule containing a terminal group capable of forming a polymer by heat includes aryl of phenyl, biphenyl, fluorene, and naphthalene; Arylamine; Or it may mean a single molecule in which fluorene is substituted with a thermosetting group or a photocurable group or a terminal group capable of forming a polymer by heat.

In another exemplary embodiment, the viscosity of the coating composition is 2 cP to 15 cP.

The present specification also provides an organic light emitting device formed using the coating composition.

In one embodiment of the present specification, the first electrode; A second electrode; And at least one layer of an organic material provided between the first electrode and the second electrode, and at least one layer of the organic material layer is formed using the coating composition or a cured product thereof. The cured product of the coating composition means a state in which the coating composition is cured by heat treatment or light treatment.

In one embodiment of the present specification, the organic material layer including the coating composition or a cured product thereof is a hole transport layer, a hole injection layer, or a layer simultaneously performing hole transport and hole injection.

In another exemplary embodiment, the organic layer containing the coating composition or a cured product thereof is a light emitting layer.

In one embodiment of the present specification, the organic light emitting device is a hole injection layer, a hole transport layer. It further includes at least one layer or two or more layers selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer.

In one embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.

According to another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

In another exemplary embodiment, the organic light emitting device may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

In another exemplary embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

The organic material layer of the organic light emitting device of the present specification may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention is a hole injection layer, a hole transport layer, a layer simultaneously performing hole injection and hole transport as an organic material layer, a light emitting layer, an electron blocking layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron injection and electron transport It may have a structure including a layer and the like at the same time. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light emitting device of the present specification is known in the art except that at least one layer of the organic material layer is formed using a coating composition containing a compound for solution processing prepared by using the compound represented by Chemical Formula 5 as an intermediate. It can be made from materials and methods.

For example, the organic light emitting device of the present specification can be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate. At this time, an anode is formed by depositing a metal or conductive metal oxide or alloys thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection and electron transport layer at the same time is formed through a deposition or solution process, and then produced by depositing a material that can be used as a cathode thereon. You can. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The present specification also provides a method for manufacturing an organic light emitting device formed using the coating composition.

Specifically, in one embodiment of the present specification, preparing a substrate; Forming a first electrode on the substrate; Forming one or more organic material layers on the first electrode; And forming a second electrode on the organic material layer, wherein at least one layer of the organic material layer is formed using the coating composition.

According to one embodiment of the present specification, the organic material layer formed using the coating composition is formed using a solution process.

In one embodiment of the present specification, the organic material layer formed using the coating composition is formed using spin coating.

In another embodiment, the organic layer formed using the coating composition is formed by a printing method.

In the state of the present specification, the printing method includes, for example, inkjet printing, nozzle printing, offset printing, transfer printing or screen printing, but is not limited thereto.

Since the coating composition according to one embodiment of the present specification has a structural property and a solution process is suitable, it can be formed by a printing method, and thus has an economical effect in time and cost when manufacturing the device.

In one embodiment of the present specification, forming an organic material layer formed using the coating composition may include coating the coating composition on the cathode or anode; And heat-treating or photo-treating the coated coating composition.

In one embodiment of the present specification, the heat treatment temperature in the heat treatment step is 85 ° C to 250 ° C.

In another exemplary embodiment, the heat treatment time in the heat treatment step may be 1 minute to 1 hour.

As the anode material, a material having a large work function is preferably used to facilitate hole injection into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO ₂ : Combination of metal and oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the cathode material include metals such as barium, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; There is a multilayer structure material such as LiF / Al or LiO ₂ / Al, but is not limited thereto.

The hole injection layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated in the light emitting layer. A compound which prevents migration of the excitons to the electron injection layer or the electron injection material, and which has excellent thin film formation ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances. Organic materials, anthraquinones, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer. As a hole transport material, the hole is transported to the light emitting layer by transporting holes from the anode or the hole injection layer, and the mobility of holes is large. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

As the light emitting material, a material capable of emitting light in the visible region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly (p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes arylamino groups such as pyrene, anthracene, chrysene, periplanten, and the substituted or unsubstituted styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer, a material having high mobility for electrons is suitable Do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

The hole blocking layer is a layer that prevents the cathode from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but are not limited thereto.

The organic light emitting device according to the present specification may be a front emission type, a back emission type, or a double-sided emission type, depending on the material used.

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

< Experimental example >

Example  One.

One)

                                             [Compound A]

2)

     [Compound A] [Compound B]

3)

     [Compound B] [Compound C]

4)

     [Compound C] [Compound 1]

1) 2-Bromo-9H-fluorene-9-one [2-Bromo-9H-fluoren-9-one] (30 g, 115 mmol) was dissolved in 250 ml of tetrahydrofuran and lowered to 0 ° C. Phenyl Magnesium Bromide (1M in THF, 208 ml, 208 mmol) was added and stirred overnight at 0 ° C. The reaction was terminated with saturated NH ₄ Cl (aq), extracted with dichloromethane, and the collected organic solution was dried and filtered using MgSO ₄ (magnesium sulfate), and then the organic solvent was removed with a vacuum rotary concentrator to remove the compound without further purification. A was obtained.

2) 250 ml dichloromethane was added to the concentrated Crude compound A, phenol (54 ml, 579 mmol) and methane sulfonic acid (7.5 ml, 115 mmol) were added and stirred overnight at room temperature. After neutralizing the acid with saturated NaHCO ₃ (aq), column purification gave 30.1 g of compound B (yield 63%).

3) Compound B (30.1 g, 55.3 mmol) was dissolved in dichloromethane, pyridine (8.9 ml, 111 mmol) and trifluromethanesulfonic acid (11.2 ml, 66.3 mmol) were added and stirred for 2 hours. The reaction was stopped with saturated NaHCO ₃ (aq), dried using MgSO ₄ (magnesium sulfate) and filtered, and then the organic solvent was removed with a vacuum rotary concentrator. The residue was purified by column to obtain 15.1 g of compound C (yield 50%).

4) Compound C (15.1 g, 35.6 mmol), zinc chloride (3.6 g, 77.4 mmol) and vinylmagnesium bromide (1M in THF, 77.4 ml, 77.4 mmol), and Pd (dppp) Cl ₂ tetra It was put in hydrofuran [tetrahydrofuran] and stirred at 75 ° C overnight. The reaction was stopped with water and extracted with ethyl acetate (EA). MgSO ₄ (magnesium sulfate) was added to the collected organic solution, dried and filtered, and then the organic solvent was removed with a vacuum rotary concentrator. The residue was purified by column to obtain 6.78 g (45% yield) of Compound 1.

The mass measurement graph of Compound 1 is shown in FIG. 1, the vertical axis in FIG. 1 refers to intensity, and the horizontal axis refers to m / z value.

In the LC mass analysis of FIG. 1, an LTQ mass spectrometer (Thermo, USA) instrument was used, and a solvent A was a volume ratio of Capcellpak C18 (4.6 mm id x 50 mm L, 3 um) column, and acetonitrile and tetrahydrofuran in a volume ratio. (THF) has a composition of 50%, 50%, and solvent B uses H ₂ O, acetonitrile 100%, and 1% composition in a volume ratio to detect compound 1 having a molecular weight of 422 at 266 nm. Did.

Comparative example  One.

                                               [Compound T-1]

 [Compound T-2] [Compound T-3] [Compound 1]

1-bromo-4- (diethoxymethyl) benzene [1-bromo-4- (diethyoxymethyl) benzene] (30 g, 115 mmol) was dissolved in 250 ml of tetrahydrofuran and lowered to -78 ° C. n-BuLi (2.5M in hexane, 42ml, 105mol) was added and stirred at -78 ° C for 30 minutes. 2-Bromo-9H-fluorene-9-one [2-Bromo-9Hfluoren-9-one] (18.9 g, 73 mmol) was added at once and stirred overnight to obtain compound T-1. The reaction was added with 1N HCl (aq), extracted with ethyl acetate, and the collected organic solution was dried and filtered using MgSO ₄ (magnesium sulfate), and then the organic solvent was removed with a vacuum rotary concentrator. After the column was purified, the residue was recrystallized (toluene / hexane) to obtain 23 g of compound T-2 (yield 87%).

Compound T-2 (11.5 g, 31.4 mmol) was added with 400 ml of benzene [methane sulfonic acid] (2.1 ml, 31.4 mmol), and refluxed using a dean-stark mechanism. . After neutralizing the acid with saturated NaHCO ₃ (aq), column purification gave 6.5 g (49% yield) of compound T-3.

Compound T-3 (5.3 g, 12.3 mmol) and CH ₃ BrPPh ₃ (8.8 g, 24.7 mmol) were added to tetrahydrofuran [THF] and potassium tert-butoxide (2.77 g, 24.7 mmol) Was added at 0 ° C and stirred for 1 hour. The reaction was stopped with water and extracted with ethyl acetate (EA). MgSO ₄ (magnesium sulfate) was added to the collected organic solution, dried and filtered, and then the organic solvent was removed with a vacuum rotary concentrator. The residue was purified by column to obtain 4.67 g (yield 89%) of Compound 1.

The compound represented by Chemical Formula 5 (Compound 1) may be prepared through the production methods of Example 1 and Comparative Example 1, but the production method of Comparative Example 1 uses n-butyl lithium (n-BuLi). Therefore, the reaction should be carried out at cryogenic conditions (-78 ° C), and it is difficult to apply to mass production as benzene, a special management material, is used, but the preparation method of Example 1 is phenyl magnesium instead of n-butyllithium (n-BuLi). Cryogenic reaction can be avoided by using bromide, and phenol may be used instead of benzene to be applicable to mass production.

Claims (8)

A first step of reacting the compound represented by the formula (1) and phenyl magnesium bromide; And
Method of producing an organic compound comprising a second step of reacting the phenol and the first product obtained through the first step.
[Formula 1]

X is a halogen group. The method according to claim 1,
The first step is a method for producing an organic compound that is performed at -30 ℃ to 10 ℃. The method according to claim 1,
The first product is a method for producing an organic compound that is a compound represented by the following formula (2).
[Formula 2]

X is a halogen group. The method according to claim 1,
Method for producing an organic compound further comprising a third step of reacting the second product obtained through the second step and trifluoromethanesulfonic acid. The method according to claim 4,
The second product is a method for producing an organic compound that is a compound represented by the following formula (3).
[Formula 3]

X is a halogen group. The method according to claim 4,
A third product obtained through the third step; And a fourth step of reacting vinyl magnesium bromide or vinyl borate. The method according to claim 6,
The third product is a method for producing an organic compound that is a compound represented by the following formula (4).
[Formula 4]

X is a halogen group. The method according to claim 1,
The organic compound is a method for producing an organic compound that is a compound represented by the formula (5).
[Formula 5]

X is a halogen group.

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