KR20230018621A - Method for manufacturing fluorene-based diamine compound - Google Patents

Abstract

The present specification relates to a method for producing a fluorene-based diamine compound. The method for producing the fluorene-based diamine compound comprises the following steps of: replacing nitrogen with a diamine compound, a halogenated compound, an organometallic catalyst, and a ligand (s1); and adding a first organic solvent to the product of the step (s1) followed by stirring (s2). Therefore, a high-purity fluorene-based diamine compound can be produced.

Description

Manufacturing method of fluorene-based diamine compound {METHOD FOR MANUFACTURING FLUORENE-BASED DIAMINE COMPOUND}

The present specification relates to a method for preparing a fluorene-based diamine compound.

The organic light emitting phenomenon is one example in which electric current is converted into visible light by an internal process of specific organic molecules. In particular, instead of the conventional deposition process with a lot of material loss, a technology for manufacturing a device through a solution process that can increase production efficiency with low material loss is being developed, and the development of materials that can be used in the solution process is required. It is becoming.

However, the materials that can be used in the solution process have disadvantages such as complicated synthesis steps for preparing the materials or reactants for generating the materials, or difficult handling due to the need for volatile or toxic materials in the manufacturing process. there is.

Accordingly, there is a need for a method for simplifying steps such as synthesis and purification required for preparing a material for an organic light emitting device that can be used in a solution process or a reactant for producing the same, or for solving safety disadvantages.

International Patent Application Publication No. 1998-006773

The present specification is intended to provide a method for preparing a fluorene-based diamine compound.

An exemplary embodiment of the present specification includes (s1) replacing nitrogen with a diamine compound, a halogenated compound, and an organometallic catalyst; and

(s2) providing a method for producing a fluorene-based diamine compound comprising the step of stirring after adding a first organic solvent to the product of step (s1).

According to the method for producing a fluorene-based diamine compound according to an exemplary embodiment of the present specification, a high-purity fluorene-based diamine compound can be prepared.

According to the method for producing a fluorene-based diamine compound according to an exemplary embodiment of the present specification, a high-yield fluorene-based diamine compound can be prepared.

Hereinafter, this specification will be described in more detail.

An exemplary embodiment of the present specification provides a method for preparing a fluorene-based diamine compound as follows.

(s1) replacing nitrogen after adding a diamine compound, a halogenated compound, and an organometallic catalyst; and

(s2) It provides a method for preparing a fluorene-based diamine compound comprising the step of adding a first organic solvent to the product of step (s1) and stirring it.

According to the prior art, only the organometallic catalyst (Comparative Example 1-1 below) is included in the step (s1). In the conventional method, many side reactions occur, resulting in a decrease in yield and purity of the target compound. However, in the production method according to an exemplary embodiment of the present invention, the reaction is accelerated and side reactions hardly occur, so the prepared fluorene-based diamine compound has an advantage of higher purity and yield than the compound prepared by the conventional method.

According to an exemplary embodiment of the present invention, after the step (s2), (s3) further comprising filtering the product of the step (s2) with a second organic solvent and an alkane as an eluent. A method for producing an orene-based diamine compound is provided.

According to the method for producing a fluorene-based diamine compound according to an exemplary embodiment of the present specification, the fluorene-based diamine compound can be prepared without undergoing column purification, which is a conventional process.

When a fluorene-based diamine compound is prepared by the conventional technique, since the process is complicated through column purification, it is difficult to scale up, and efficiency is lowered in terms of economy due to the complicated process. In addition, the purity and yield of the compound are lowered through complicated processes.

However, when the fluorene-based diamine compound is prepared according to the method for preparing the fluorene-based diamine compound according to the present specification, the process can be simplified through filter purification without going through a column purification process, so the efficiency and economic efficiency of the production can be secured, and scale up for mass production becomes easy. In addition, it is possible to increase the purity and yield of the compound without going through various processes by a simple manufacturing method through a filter process.

In the present specification, when a part is said to "include" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

In the present specification, the step of "putting A into B" or the step of "putting B into A" means adding A to B or adding B to A, etc., and the addition method is, for example, , It may be achieved in a dropwise manner, but is not limited thereto.

In the present specification, the process of "mixing" is not particularly limited, and may be, for example, mixing through stirring, and stirring may be rotating using a magnetic bar or a mechanical mixer, It is not limited to the above examples.

Unless defined otherwise in the present invention, all technical and scientific terms used in the present invention have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Although methods and materials similar or equivalent to those described herein may be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below.

All publications, patent applications, patents and other references mentioned herein are hereby incorporated by reference in their entirety, and in case of conflict, the present invention, including definitions, will control unless a specific passage is stated. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

According to one embodiment of the present specification, the organometallic catalyst includes a palladium-based metal catalyst.

According to an exemplary embodiment of the present specification, the organometallic catalyst is a palladium-based metal catalyst.

According to an exemplary embodiment of the present specification, the organometallic catalyst is preferably Pd ₂ (dba) ₃ (Tris (dibenzylideneacetone) dipalladium (0)) or BTP (Bis (tri-tert-butylphosphine) palladium (0)). However, it is not limited thereto.

According to an exemplary embodiment of the present specification, the organometallic catalyst includes one type of palladium-based metal catalyst.

According to an exemplary embodiment of the present specification, the organometallic catalyst is Pd ₂ (dba) ₃ (Tris(dibenzylideneacetone)dipalladium(0)).

According to an exemplary embodiment of the present specification, the organometallic catalyst is BTP (Bis(tri-tert-butylphosphine)palladium(0)).

According to an exemplary embodiment of the present specification, an equivalent of 0.01 to 0.1 of the organometallic catalyst is included relative to 1 equivalent of the diamine compound.

According to an exemplary embodiment of the present specification, an equivalent of 0.01 to 0.09 of the organometallic catalyst is included relative to 1 equivalent of the diamine compound.

According to an exemplary embodiment of the present specification, the organometallic catalyst is included in an equivalent amount of 0.01 to 0.06 based on 1 equivalent of the diamine compound.

According to an exemplary embodiment of the present specification, the organometallic catalyst is included in an equivalent amount of 0.01 to 0.03 based on 1 equivalent of the diamine compound.

According to an exemplary embodiment of the present specification, 0.03 equivalent of the organometallic catalyst is included relative to 1 equivalent of the diamine compound.

When the organometallic catalyst is included in the above amount, the reaction can be accelerated and the reaction can proceed with little side reaction.

According to an exemplary embodiment of the present specification, in step (s1), the halogenated compound is included in an amount of 2 to 2.1 equivalents relative to 1 equivalent of the diamine compound.

When the halogenated compound is included in an equivalent amount compared to 1 equivalent of the diamine compound, side reactions can be suppressed, and purity and yield are increased.

When the halogenated compound is used in excess of 2.1 equivalents relative to 1 equivalent of the diamine compound, a side reaction occurs, resulting in lower purity and yield of the compound, and when used in less than 2 equivalents, it does not sufficiently react with the diamine compound, resulting in yield this lowers

According to one embodiment of the present specification, the step (s1) further includes introducing a basic compound.

According to one embodiment of the present specification, the basic compound is sodium tert-butoxide.

According to one embodiment of the present specification, the basic compound is included in 4 to 10 equivalents, preferably 4 to 8 equivalents, and more preferably 5 equivalents, relative to 1 equivalent of the diamine compound.

According to one embodiment of the present specification, the ligand in step (s1) is a phosphine-based ligand.

According to an exemplary embodiment of the present specification, the phosphine-based ligand is preferably P (tert-Bu) ₃ (Tri-tert-butylphosphine) or XPhos (2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) , but is not limited thereto.

According to an exemplary embodiment of the present specification, an equivalent of 0.01 to 0.1 of the phosphine-based ligand is included relative to 1 equivalent of the diamine compound.

According to an exemplary embodiment of the present specification, an equivalent of 0.01 to 0.09 of the phosphine-based ligand is included relative to 1 equivalent of the diamine compound.

According to an exemplary embodiment of the present specification, the phosphine-based ligand is included in an equivalent amount of 0.01 to 0.06 relative to 1 equivalent of the diamine compound.

According to an exemplary embodiment of the present specification, the phosphine-based ligand is included in an equivalent of 0.06 relative to 1 equivalent of the diamine compound.

When the phosphine-based ligand is included in the above amount, the reaction can be accelerated and the reaction can proceed with almost no side reaction.

According to one embodiment of the present specification, the first organic solvent in step (s2) is an aromatic hydrocarbon-based organic solvent. The aromatic hydrocarbon-based organic solvent may be benzene, fluorobenzene, bromobenzene, chlorobenzene, toluene, xylene, mesitylene, etc., and these may be used alone or in combination.

According to one embodiment of the present specification, the first organic solvent in step (s2) is toluene.

According to an exemplary embodiment of the present specification, the first organic solvent is added at 0.1 M to 0.3 M, preferably at 0.1 M to 0.26 M. When the first organic solvent is added in the above amount, the solute introduced into the reaction is sufficiently dissolved so that the forward reaction can proceed with almost no side reaction. When the amount is exceeded, the reaction rate is reduced and side reactions may occur, resulting in an increase in yield. It is low, and economic loss is followed by replacement of the reactor with a large capacity and excessive use of the solvent.

According to one embodiment of the present specification, the step (s2) is performed in a temperature range of 60 °C to 80 °C. Preferably, the step (s2) is performed in a temperature range of 65 °C to 75 °C. When the above temperature range is satisfied, the reaction efficiency increases. Specifically, by maintaining the temperature at about 35° C. to 55° C. higher than room temperature, the reaction between the halogenated compound and the diamine compound can be effectively progressed. In addition, since unintended side reactions may proceed when the above temperature range is exceeded, there is an advantage in that a high yield of the product can be expected by maintaining a constant forward reaction by satisfying the above-mentioned temperature range.

According to an exemplary embodiment of the present specification, the purity at 260 nm of the fluorene-based diamine compound prepared by the method for producing a fluorene-based diamine compound including the steps (s1) and (s2) is 93% to 96 %am.

The purity can be measured by a conventional method, preferably using HPLC.

The purity of the fluorene-based diamine compound according to an exemplary embodiment of the present specification is measured without going through a purification process after the step (s2).

According to one embodiment of the present specification, an intermediate purification step of purifying an intermediate product may be included. The intermediate purification step is

(s21) cooling the product of step (s2);

(s22) Quench and layer separation step;

(s23) drying step;

(s24) a filtration step; and

(s25) a concentration step.

According to one embodiment of the present specification, the step (s21) is performed by reducing the temperature to a temperature range of 30 °C to 50 °C. Preferably, the step (s21) may be performed by reducing the temperature to a temperature range of 45 °C to 50 °C, but is not limited thereto. When the above temperature range is satisfied, the progress of the reaction may be terminated and exotherm may be prevented.

According to an exemplary embodiment of the present specification, the temperature reduction rate may allow a temperature gradient of the entire reaction system to be formed, rather than a part of the reaction system, while slowly lowering the temperature of the reaction system. Specifically, it may be performed under a temperature lowering condition of 4 °C/min to 7 °C/min, but is not limited thereto.

According to an exemplary embodiment of the present specification, the step (s22) (quenching and layer separation step) is a step of terminating the reaction by adding a reaction terminating material and separating the layers.

According to an exemplary embodiment of the present specification, distilled water, aqueous ammonium chloride solution, aqueous sodium bicarbonate solution, aqueous HCl solution, aqueous NaCl solution, ethyl acetate, etc. may be used as the reaction terminating material in step (s22), but is not limited thereto. . Preferably, an aqueous solution of ammonium chloride, an aqueous solution of sodium hydrogen carbonate, an aqueous solution of NaCl, and ethyl acetate are used as the reaction terminating material.

The order in which the reaction is terminated and the layers are separated in the step (s22) is not limited to a specific order. In one embodiment, the reaction termination and layer separation may proceed simultaneously, and in another example, the reaction may be terminated by adding a reaction termination material, and then layer separation may proceed. However, the proceeding sequence is not limited to the above example.

According to one embodiment of the present specification, the step (s23) (drying step) is performed by adding a drying agent to any one layer of the materials separated in the step (s102). For example, when ethyl acetate exemplified above is used as the reaction terminating material, a drying agent is added to the upper ethyl acetate layer, that is, the organic layer. Examples of the desiccant include magnesium sulfate, sodium magnesium, and the like, but are not limited thereto. According to one preferred embodiment, the desiccant is magnesium sulfate.

In this specification, the desiccant is added in a sufficient amount required for drying conventionally in the art.

According to one embodiment of the present specification, the (s24) step (filtering step) may be performed through a method known in the art. As a representative example, a method of sucking in air using an inhaler and filtering impurities including a desiccant separated from the target product through a filter, or using a difference in solubility in a specific solvent so that the target product is not dissolved but other impurities A method of removing other impurities using a solvent in which they are dissolved may be used.

According to one embodiment of the present specification, the step (s25) (concentration step) may be performed through a method known in the art. A typical example may be achieved by evaporating the solvent using a vaccum rotary evaporator, but is not limited thereto. Through (s25), the product of step (s2) is concentrated until the amount of the solvent compared to the theoretical yield (mass) of the fluorene-based diamine compound is 5 times or more.

According to one embodiment of the present specification, additional filtration and drying steps may be added after the step (s25).

According to one embodiment of the present specification, an intermediate purification step of purifying an intermediate product may be included. The intermediate purification step is

(s21) cooling the product of step (s2);

(s22) Quench and layer separation step;

(s23-1) a first drying step;

(s24-1) a first filtration step;

(s25) a concentration step;

(s26) a second filtration step; and

(s27) A second drying step is included.

According to one embodiment of the present specification, the description of the step (s23) is applied to the step (s23-1), and the description of the step (s24) is applied to the step (s24-1).

According to one embodiment of the present specification, the second filtration step (s26) may be performed through a method known in the art. An alcoholic solvent, preferably isopropyl alcohol, is added to the product of the step (s25), precipitated, stirred, and filtered in the same manner as in the step (s24). At this time, only impurities are dissolved in the alcohol-based solvent. As a result, only the impurities pass through the filter paper.

According to one embodiment of the present specification, the second drying step (s27) is a step of drying the product of the step (s26), that is, the filter cake. The second drying step may be performed through a method known in the art, and representative examples include vacuum oven drying, spray drying, flash drying, and the like, and may be preferably vacuum oven drying.

According to one embodiment of the present specification, the step (s3) includes a preprocessing step. The preprocessing step may be performed after the step (s2) and before the step (s3).

According to one embodiment of the present specification, the pretreatment step includes dissolving the product of step (s2) with a second organic solvent and an alkane.

In the pretreatment step, the ratio of the second organic solvent: the alkane is 2:0.1 (v/v) to 1:5 (v/v), preferably 1.5:1 (v/v). In the case of the above ratio, the product of step (s2) can be sufficiently dissolved, and by-products and impurities are not dissolved.

According to one embodiment of the present specification, the second organic solvent in step (s3) is an aromatic hydrocarbon-based organic solvent. The aromatic hydrocarbon-based organic solvent may be benzene, fluorobenzene, bromobenzene, chlorobenzene, toluene, xylene, mesitylene, etc., and these may be used alone or in combination.

According to one embodiment of the present specification, the second organic solvent in the step (s3) is toluene.

According to an exemplary embodiment of the present specification, the alkane of the step (s3) is n-fenpain, isopentane, neopentane, tert-pentane, n-hexane, 1-methylpentane, 2-methylpentane, 4-methyl-2-pentane, 3,3-dimethylbutane, 2-ethylbutane, n-heptane, 1-methylhexane, cyclopentylmethane, cyclohexylmethane, n-octane, tert-octane, 1-methylheptane, 2-ethylhexane, 2-propylpentane, n-nonane, 2,2-dimethylheptane, etc. may be used, and these may be used alone or in combination. and can be used.

According to an exemplary embodiment of the present specification, the alkane of step (s3) is n-heptane.

According to an exemplary embodiment of the present specification, the second organic solvent: the alkane is 1: 0.1 (v / v) to 1: 10 (v / v), preferably 1: 0.5 (v / v) to 1:5 (v/v), more preferably 1:1 (v/v). When the eluent has the above ratio, by-products and impurities are not dissolved in the eluent, and only the desired material, that is, the fluorene-based diamine compound is dissolved, increasing yield and purity. However, if it exceeds the above range, there is a disadvantage that the desired material is not sufficiently dissolved or by-products are dissolved.

According to one embodiment of the present specification, the filtering in step (s3) uses a filter containing alumina.

According to one embodiment of the present specification, the filtering in step (s3) uses a filter containing alumina and silica.

According to one embodiment of the present specification, the filtering in step (s3) uses a filter made of alumina and silica.

According to one embodiment of the present specification, the alumina: the silica of the filtering step of the step (s3) is 1: 0.1 (v / v) to 1: 0.5 (v / v). Preferably it is 1:0.2 (v/v). When the alumina and silica in the filtering step are included in the above ratio, there is an advantage in that only the desired material, that is, the fluorene-based diamine compound passes through the filter, and by-products and impurities do not pass through the filter.

According to one embodiment of the present specification, the step (s3) further includes obtaining the fluorene-based diamine compound.

The obtaining step according to an exemplary embodiment of the present specification

(s31) a concentration step;

(s32) filtration step;

(s33) drying step; and

(s34) an obtaining step.

According to one embodiment of the present specification, the step (s31) (concentration step) may be performed through a method known in the art. A typical example may be achieved by evaporating the solvent using a vaccum rotary evaporator, but is not limited thereto.

According to one embodiment of the present specification, the step (s32) (filtration step) is a step of removing other impurities from the material concentrated in the step (s31). The step (s32) may be performed through a method known in the art, and as a representative example, a method of sucking in air using an inhaler and filtering it through a filter may be used, but is not limited thereto. The step of removing the other impurities may be performed using a solubility difference for a specific solvent. As a specific example, other impurities may be removed using a solvent in which the fluorene-based diamine compound to be obtained is not dissolved but other impurities are dissolved. Toluene, ethyl alcohol or isopropyl alcohol may be used as the solvent, but is not limited thereto.

According to one embodiment of the present specification, the step (s33) (drying step) is a step of drying the filter cake of the product of the step (s32), that is, the fluorene-based diamine compound. The drying step may be performed through a method known in the art, and representative examples include vacuum oven drying, spray drying, flash drying, and the like, and may be preferably vacuum oven drying.

According to an exemplary embodiment of the present specification, the (s34) step (obtaining step) is a step of obtaining the fluorene-based diamine compound dried in the (s33) step.

According to an exemplary embodiment of the present specification, in the obtaining step, (s31) and (s32) may be performed three or more times as needed.

According to an exemplary embodiment of the present specification, the fluorene-based diamine compound in the step (s3) is represented by Formula 1 below.

[Formula 1]

In Formula 1,

L is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

L1 and L11 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

Ar1 and Ar11 are the same as or different from each other, and each independently a photocurable group; Or a thermosetting group,

At least one of G1 to G5 is a halogen group, and the others are hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group,

At least one of G11 to G15 is a halogen group, and the others are hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group,

R1 to R3 and R11 to R13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

r1 is an integer from 1 to 5, and when r1 is 2 or more, the two or more R1s are the same as or different from each other;

r2 is an integer from 1 to 4, and when r2 is 2 or more, the two or more R2s are the same as or different from each other;

r3 is an integer from 1 to 3, and when r3 is 2 or more, the two or more R3s are the same as or different from each other;

r11 is an integer from 1 to 5, and when r11 is 2 or more, 2 or more R11s are the same as or different from each other;

r12 is an integer from 1 to 4, and when r12 is 2 or more, 2 or more R12s are the same as or different from each other;

r13 is an integer of 1 to 3, and when r13 is 2 or more, 2 or more R13s are the same as or different from each other.

Examples of substituents in the present specification are described below, but are not limited thereto.

는 연결되는 부위를 의미한다.In this specification,

indicates the connecting part.

Throughout the present specification, the term "combination thereof" included in the expression of the Markush form means a mixture or combination of one or more selected from the group consisting of the components described in the expression of the Markush form, and the components It means including one or more selected from the group consisting of.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same as or different from each other.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; hydroxy group; cyano group; nitro group; an alkyl group; cycloalkyl group; alkoxy group; alkenyl group; haloalkyl group; aryl group; And it means that it is substituted with one or more substituents selected from the group consisting of a heteroaryl group, is substituted with a substituent in which two or more substituents among the above exemplified substituents are connected, or does not have any substituents.

또는

의 치환기가 될 수 있다. 또한, 3개의 치환기가 연결되는 것은 (치환기 1)-(치환기 2)-(치환기 3)이 연속하여 연결되는 것뿐만 아니라, (치환기 1)에 (치환기 2) 및 (치환기 3)이 연결되는 것도 포함한다. 예컨대, 페닐기, 나프틸기 및 이소프로필기가 연결되어,

,

또는

의 치환기가 될 수 있다. 4 이상의 치환기가 연결되는 것에도 전술한 정의가 동일하게 적용된다.In the present specification, two or more substituents are linked means that the hydrogen of any one substituent is linked to another substituent. For example, when two substituents are connected, a phenyl group and a naphthyl group are connected.

or

can be a substituent of In addition, the three substituents are connected not only by connecting (substituent 1)-(substituent 2)-(substituent 3) in succession, but also by connecting (substituent 2) and (substituent 3) to (substituent 1). include For example, a phenyl group, a naphthyl group and an isopropyl group are connected,

,

or

can be a substituent of The above definition is equally applied to the case where 4 or more substituents are connected.

In this specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl group, etc. , but is not limited thereto.

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It is not limited.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, etc., but are not limited thereto.

In the present specification, the haloalkyl group means that at least one halogen group is substituted for the hydrogen of the alkyl group in the definition of the alkyl group.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is 10-30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a phenalene group, a perylene group, a chrysene group, a fluorene group, and the like, but is not limited thereto.

In the present specification, the fluorene group may be substituted, and adjacent groups may bond to each other to form a ring.

,

,

,

,

,

,

및

등이 있으나, 이에 한정되지 않는다.When the fluorene group is substituted,

,

,

,

,

,

,

and

etc., but is not limited thereto.

As used herein, "adjacent" refers to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. can For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups.

In the present specification, the heteroaryl group includes at least one atom or heteroatom other than carbon, and specifically, the heteroatom may include at least one atom selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, a triazole group, and an acridine group. , pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyrido pyrimidine group, pyrido pyrazine group, pyrazino pyrazine group, isoquinoline group, indole group, carbazole group, benz Oxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthridine group, phenanthroline group, isoxazole group, thia Diazole group, dibenzofuran group, dibenzosilol group, phenoxanthine group (phenoxathiine), phenoxazine group (phenoxazine), phenothiazine group (phenothiazine group), dihydroindenocarbazole group, spirofluorene xanthene group and spirofluorene Thioxanthene group and the like, but is not limited thereto.

In the present specification, the arylene group means that the aryl group has two binding sites, that is, a divalent group. The description of the aryl group described above can be applied except that each is a divalent group.

In the present specification, the heteroarylene group means a heteroaryl group having two bonding sites, that is, a divalent group. The above description of the heteroaryl group may be applied except that each is a divalent group.

According to an exemplary embodiment of the present specification, L is a substituted or unsubstituted arylene group.

According to an exemplary embodiment of the present specification, L is a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, the L is selected from any one of the following structures.

According to an exemplary embodiment of the present specification, the L1 and L11 are the same as or different from each other, and are each independently a direct bond; or a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, the L1 and L11 are the same as or different from each other, and are each independently a direct bond; or a phenylene group.

According to an exemplary embodiment of the present specification, at least one of G1 to G5 is a halogen group, and the others are hydrogen; heavy hydrogen; or a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, at least one of G1 to G5 is a fluoro group, and the others are hydrogen; heavy hydrogen; or a methyl group.

According to an exemplary embodiment of the present specification, at least one of G11 to G15 is a halogen group, and the others are hydrogen; heavy hydrogen; or a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, at least one of G11 to G15 is a fluoro group, and the others are hydrogen; heavy hydrogen; or a methyl group.

및

는 서로 같거나 상이하고, 각각 독립적으로 하기 구조 중에서 선택된다.According to an exemplary embodiment of the present specification, of Formula 1

and

are the same as or different from each other, and are each independently selected from the following structures.

및

는 서로 동일하다.According to an exemplary embodiment of the present specification, of Formula 1

and

are equal to each other

및

는 서로 상이하다.According to an exemplary embodiment of the present specification, of Formula 1

and

are different from each other

According to an exemplary embodiment of the present specification, Ar1 and Ar11 are the same as or different from each other, each independently represents L'-R', and L' is a direct bond, -O-, -S-, -CH ₂ -, - C _H2 O-, -OCH ₂ -, or -CH ₂ OCH ₂ -, and R' is any one selected from the following structures.

According to an exemplary embodiment of the present specification, R1 and R11 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R1 and R11 are the same as or different from each other, and each independently hydrogen; or a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R1 and R11 are the same as or different from each other, and each independently hydrogen; or a methyl group.

According to an exemplary embodiment of the present specification, R2, R3, R12 and R13 are hydrogen.

According to an exemplary embodiment of the present specification, the fluorene-based diamine compound in the step (s3) is any one selected from the following compounds.

.

.

According to one embodiment of the present specification, the cured product of the fluorene-based diamine compound is for an organic light emitting device.

According to an exemplary embodiment of the present specification, the cured product of the fluorene-based diamine compound is included in the hole injection layer or the hole transport layer of the organic light emitting device.

According to an exemplary embodiment of the present specification, the method for producing the fluorene-based diamine compound includes only a filtering step without column purification, and the process is simple, and the loss of product due to the product remaining in the column during conventional column purification is also There are advantages to not having

Hereinafter, examples will be described in detail in order to specifically describe the present specification. However, embodiments according to the present specification may be modified in many different forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present specification to those skilled in the art.

Example 1-1

1) A1 (1eq), B1 (2.05eq), NaOtBu (5eq), Pd ₂ (dba) ₃ (0.03eq), and XPhos (0.06eq) were placed in a 2neck round bottom flask and purged with nitrogen.

2) Toluene (0.1M) was added to 1) in a round bottom flask and stirred at 70 °C for 1 hour.

Example 2-1 and Comparative Example 1-1

The same procedure as in Example 1 was performed except that the organometallic catalyst and ligands in Table 1 were used instead of Pd ₂ (dba) ₃ and XPhos in 1).

The purity values of Example 1-1, Example 2-1, and Comparative Example 1-1 according to an exemplary embodiment of the present specification measured by HPLC are shown in Table 1 below.

Organometallic catalyst/ligand
(amount used (eq/g)) Toluene
(M) 064 HPLC area (%) @260 nm_70:30, 15 min 1.84 2.19 5.31 7.04 7.63 8.11 9.53 10.80 product Example 1-1 Pd ₂ (dba) ₃ /XPhos
(0.03/0.06) 0.1 0.85 2.19 0.08 0.03 95.32 0.15 0.27 0.16 Example 2-1 Pd ₂ (dba) ₃ //P(tBu)₃
(0.03/0.06) 0.1 0.90 3.52 0.10 0.05 93.86 0.19 0.44 0.12 Comparative Example 1-1 BTP/-(0.03/-) 0.1 1.53 7.79 0.34 0.27 87.05 0.07 0.43 1.11

-Pd ₂ (dba) ₃ : Tris(dibenzylideneacetone)dipalladium(0)

- BTP: Bis(tri-tert-butylphosphine)palladium(0)

- P(tBu) ₃ : Tri-tert-butylphosphine

- XPhos: 2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl

In Table 1, the fluorene-based diamine compound prepared by Example 1-1 or Example 2-1, which is a manufacturing method according to an exemplary embodiment of the present specification, is higher than the compound prepared by Comparative Example 1-1, which is a conventional method. It can be seen that the purity is high.

This is because the preparation methods of Examples 1-1 and 2-1, which include both the organometallic catalyst and the ligand, accelerate the reaction of the starting materials and hardly cause side reactions, compared to Comparative Example 1-1, which includes only the organometallic catalyst. It can be seen that the fluorene-based diamine compound prepared by is higher in purity than the compound prepared by the method of Comparative Example 1-1.

Example 1-2

1) After cooling 2) of Example 1-1 to 50 ° C, the reaction was terminated with aqueous NH ₄ Cl solution, work-up was performed by adding ethyl acetate, and then work-up was performed with aqueous NaHCO ₃ solution and water. -up) was done.

2) After work-up, MgSO ₄ was treated, dehydrated, and concentrated until the amount of solvent was five times greater than the theoretical yield (mass).

3) Isopropyl alcohol (25V) was added dropwise to the concentrated solution in 4) to precipitate, followed by stirring for about 3 hours and filtering.

After drying the filter cake in a vacuum oven, it was dissolved in toluene (1.5V) and heptane (1V).

4) The solution of 6) was filtered on an alumina (neutral) (15V) / silica (3V) pad using Toluene: heptane = 1: 1 (v/v) eluent.

5) After concentrating the eluate of 7) under reduced pressure, dissolving in toluene (5V), precipitating in IPA (25V) and filtering, the process was repeated twice more.

6) After filtering, the filter cake was spread thinly on a tray and dried in a vacuum oven.

7) P1 was obtained as a white solid with a purity of 260 nm of 99.55% and a purity of 364 nm of 99.67% with a yield of 65%.

According to one embodiment of the present specification. The purity was measured through HPLC.

Comparative Example 1-2

1) After cooling 2) of Example 1-1 to room temperature, ethyl acetate, brine and water were added, extracted with ethyl acetate/brine, treated with MgSO ₄ and celite filtered did

2) After removing all the solvent from the solution of 1), dissolve it in dichloromethane again, put it in a 2L round bottom flask, add silica (190 g) twice the theoretical weight of P1 (95 g in the case of the above) and adsorb did (60 ^o C, 0 torr)

3) The adsorbate of 2) was divided into loading cartridges, and P1 (260 nm purity: 97.1%) was obtained by primary purification by MPLC (Medium pressure liquid chromatography) under 0→20→25→30% dichloromethane conditions.

4) After dissolving the purified product of 3) in dichloromethane, it is adsorbed on 190 g of silica, and the adsorbate is divided into loading cartridges.

5) Secondary purification was performed by MPLC (Medium pressure liquid chromatography) under the condition of 0→10→20% ethyl acetate. (260 nm purity 97.1%)

6) The solid obtained in 5) was dissolved in dichloromethane and subjected to a florisil filter.

7) After evaporating the solvent from the solution of 6), dissolve it in dichloromethane, add 500 mL of dichloromethane: ethanol (DCM:EtOH) = 1:1 (v/v) solvent, and evaporate only dichloromethane at 280 torr, 40 ℃ to determine , stirred for 2 hours.

8) 7) was washed with ethanol after filtering.

9) 8) was spread thinly on a tray and dried in a vacuum oven to obtain P1 as a white solid with a purity of 260 nm of 99.5% and a purity of 364 nm of 99.6% with a yield of 55%.

Example 1-2, in which the fluorene-based diamine compound of Example 1-1 was purified by a filter according to an exemplary embodiment of the present specification, is a comparative example in which the fluorene-based diamine compound of Example 1-1 is purified by a conventional column. Compared to 1-2, the preparation of the target compound in Example 1-2 is easier than the compound prepared in Comparative Example 1-2, which is a conventional method, and the process is simplified than Comparative Example 1-2, It can be seen that the cost is more economical than Comparative Example 1-2, and the yield of the compound produced is high because unnecessary processes are reduced.

In the case of Comparative Example 1-2, which is a conventional method, since the process becomes complicated through column purification, efficiency is lowered in terms of economy due to the complicated process. In addition, the yield of the compound is lowered due to the loss of product due to the product remaining in the reactor and column through the complicated process.

However, since Example 1-2, which is a method for producing a fluorene-based diamine compound according to the present specification, can simplify the process through filter purification without going through a column purification process, it is possible to secure efficiency and economic efficiency of production, It is easy to scale-up for mass production of the target compound, and the yield of the compound is high because it does not go through various processes as a simple manufacturing method through a filter process.

Claims (14)

(s1) replacing nitrogen with a diamine compound, a halogenated compound, an organometallic catalyst, and a ligand; and
(s2) a method for producing a fluorene-based diamine compound comprising the step of stirring after adding a first organic solvent to the product of step (s1). The fluorene-based diamine compound according to claim 1, further comprising the step of (s3) filtering the product of step (s2) with a second organic solvent and an alkane as an eluent after step (s2). Manufacturing method of. The method for preparing a fluorene-based diamine compound according to claim 1, wherein the halogenated compound in step (s1) is included in an amount of 2 to 2.1 equivalents relative to 1 equivalent of the diamine compound. The method for preparing a fluorene-based diamine compound according to claim 1, wherein the ligand in step (s1) is a phosphine-based ligand. The method according to claim 1, wherein the first organic solvent in step (s2) is toluene. The method according to claim 2, wherein the second organic solvent in step (s3) is toluene. The method for preparing a fluorene-based diamine compound according to claim 2, wherein the alkane of step (s3) is n-heptane. The method according to claim 2, wherein the second organic solvent: the alkane in step (s3) is 1: 0.1 (v / v) to 1: 10 (v / v) of the fluorene-based diamine compound manufacturing method. The method for preparing a fluorene-based diamine compound according to claim 2, wherein the filtering in step (s3) uses a filter containing alumina. The method for preparing a fluorene-based diamine compound according to claim 2, wherein the filtering in step (s3) uses a filter containing alumina and silica. The method for preparing a fluorene-based diamine compound according to claim 1, wherein the fluorene-based diamine compound is represented by Formula 1 below:
[Formula 1]

In Formula 1,
L is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
L1 and L11 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,
Ar1 and Ar11 are the same as or different from each other, and each independently a photocurable group; Or a thermosetting group,
At least one of G1 to G5 is a halogen group, and the others are hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group,
At least one of G11 to G15 is a halogen group, and the others are hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group,
R1 to R3 and R11 to R13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
r1 is an integer from 1 to 5, and when r1 is 2 or more, the two or more R1s are the same as or different from each other;
r2 is an integer from 1 to 4, and when r2 is 2 or more, the two or more R2s are the same as or different from each other;
r3 is an integer from 1 to 3, and when r3 is 2 or more, the two or more R3s are the same as or different from each other;
r11 is an integer from 1 to 5, and when r11 is 2 or more, 2 or more R11s are the same as or different from each other;
r12 is an integer from 1 to 4, and when r12 is 2 or more, 2 or more R12s are the same as or different from each other;
r13 is an integer of 1 to 3, and when r13 is 2 or more, 2 or more R13s are the same as or different from each other. The method for preparing a fluorene-based diamine compound according to claim 1, wherein the fluorene-based diamine compound is any one selected from the following compounds:

. The method of manufacturing a fluorene-based diamine compound according to claim 1, wherein the cured product of the fluorene-based diamine compound is for use in an organic light emitting device. The method according to claim 1, wherein the cured product of the fluorene-based diamine compound is included in a hole injection layer or a hole transport layer of an organic light emitting device.