KR102427160B1 - Method for preparation of High-purity amine-based compound - Google Patents

Abstract

The present invention relates to a method capable of preparing an amine-based compound having high purity.

Description

Method for preparing a high-purity amine-based compound {Method for preparation of High-purity amine-based compound}

The present invention relates to a production method capable of producing an amine-based compound having high purity.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, it may be made of an electron injection layer, etc. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons It lights up when it falls back to the ground state.

Meanwhile, in order to reduce process costs, an organic light emitting device using a solution process, particularly an inkjet process, is being developed instead of a conventional deposition process. In the early days, all organic light emitting device layers were coated with a solution process to develop an organic light emitting device, but the current technology has limitations, so only HIL, HTL, and EML are processed as a solution process, and the subsequent process utilizes the existing deposition process. (hybrid) process is being studied.

Accordingly, the development of novel compounds that can be used in an organic light emitting device and can be used in a solution process at the same time are continuously being developed.

In particular, in order for the organic light emitting device to exhibit low driving voltage and improved light efficiency and lifetime characteristics, the purity of the compound used in each layer of the organic light emitting device must be high.

Accordingly, there is a demand for a method capable of manufacturing a compound used in an organic light emitting device with high purity, and as a result of intensive research on this method, when using the manufacturing method to be described later, commercial mass production is possible, and further, the overall The present invention was completed by confirming a manufacturing method in which impurities were reduced while the yield was improved.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a production method capable of producing an amine-based compound having high purity.

In order to solve the above problems, the present invention provides a method for preparing a compound represented by the following formula (1) comprising the following steps.

reacting the compound represented by the following Chemical Formula 1-1 with the compound represented by the following Chemical Formula 1-2 in the presence of a palladium catalyst and a base (step 1);

dissolving the reaction product prepared in step 1 in an organic solvent containing dichloromethane and hexane in a volume ratio of 1:0.5 to 1:2 (step 2); and

A step of drying after removing impurities using at least one adsorbent selected from the group consisting of silica gel, activated carbon, and activated alumina (step 3):

[Formula 1]

[Formula 1-1]

[Formula 1-2]

In Formula 1, Formula 1-1 and Formula 1-2,

X is halogen,

L ₁ is C _6-20 arylene; or (C _6-20 arylene)-(C _6-20 arylene),

Here, the C _6-20 arylene is unsubstituted or substituted with C _1-10 alkyl,

L ₂ is a single bond; Or a substituted or unsubstituted C _1-10 alkylene,

Ar ₁ and Ar ₂ are each independently C _6-60 aryl, substituted or unsubstituted, or C _2- containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S ₆₀ heteroaryl;

R ₁ and R ₂ are each independently hydrogen; substituted or unsubstituted C _6-60 aryl; or R';

R and R' are each independently any one selected from the group consisting of

above,

L is substituted or unsubstituted C _1-10 alkylene.

The above-described method for preparing the compound represented by Chemical Formula 1 has an advantage in that a high-purity amine-based compound having a reduced impurity content can be prepared in high yield.

Hereinafter, it will be described in more detail to help the understanding of the present invention.

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

and

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an aryl phosphine group; or N, O, and S atoms, which is substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing one or more . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably from 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, in the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

In the present 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 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group 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 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

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 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. 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, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 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, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenylyl group, or a terphenylyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrylenyl group, a fluorenyl group, a benzofluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다. 또한, 벤조플루오레닐기도 상기 플루오레닐기와 마찬가지로 치환되거나, 2개가 서로 결합하여 스피로 구조를 형성할 수 있다. In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. can be However, the present invention is not limited thereto. In addition, the benzofluorenyl group may be substituted in the same manner as the fluorenyl group, or two may be bonded to each other to form a spiro structure.

In the present specification, heteroaryl is a heteroaryl containing at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but is preferably from 2 to 60 carbon atoms. Examples of heteroaryl include xanthene, thioxanthen, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, Pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyridopyrazinyl group, pyrazino Pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group ( phenanthroline), an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, the arylamine group, and the arylsilyl group is the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group. In the present specification, as for heteroaryl among heteroarylamines, the description regarding heteroaryl described above may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the above-described alkenyl groups. In the present specification, the description of the above-described aryl group may be applied except that arylene is a divalent group. In the present specification, the description of the aforementioned heteroaryl may be applied, except that heteroarylene is a divalent group.

On the other hand, the present invention provides a preparation method comprising the following steps in order to prepare a compound represented by Formula 1 with high purity:

(Step 1) reacting the compound represented by Formula 1-1 with the compound represented by Formula 1-2 in the presence of a palladium catalyst and a base;

(Step 2) dissolving the reaction product prepared in Step 1 in an organic solvent containing dichloromethane and hexane in a volume ratio of 1:0.5 to 1:2; and

(Step 3) Drying after removing impurities using at least one adsorbent selected from the group consisting of silica gel, activated carbon, and activated alumina.

Conventionally, in order to increase the purity of the amine compound as in Formula 1, the crude product prepared by the Buchwald-Hartwig amination reaction is subjected to column purification such as medium pressure liquid chromatography (MPLC). did. However, such column purification requires the use of a large amount of solvent, so the raw material cost is high, and it is not environmentally friendly, and it is difficult to apply to mass production, and there is a problem that the process takes a long time.

However, the prepared crude product is completely dissolved in an organic solvent containing dichloromethane and hexane at the same time as in step 2 without column purification, and then purified by the impurity removal process using silica gel in step 3, Not only is it easy to apply to mass production of compounds, but it is also suitable for obtaining high-purity compounds in high yield by effectively removing by-products and residual catalysts generated in the Buchwald-Hartwig amination reaction with a small solvent and shortened process time.

Hereinafter, the present invention will be described in detail for each step.

(Step 1)

In step 1, the compound represented by Formula 1-1 as a starting material and the compound represented by Formula 1-2 are reacted in the presence of a palladium catalyst and a base to form a crude product of the compound represented by Formula 1 ) as a step of preparing, specifically, it is prepared through the following Reaction Scheme 1.

[Scheme 1]

In Scheme 1, the description of each substituent is as described above, and the reaction is a Buchwald-Hartwig amination reaction, which is a reaction for introducing a substituent into an amine in the presence of a palladium catalyst and a base.

In this case, the compound represented by Formula 1-1 and the compound represented by Formula 1-2 may be used in a molar ratio of 1: 1 to 1: 1.1.

In addition, the palladium catalyst may be a palladium (0) catalyst having a valency of 0 of palladium (Pd) in the compound, or a palladium (II) catalyst having a valency of +2. For example, as the palladium catalyst, bis(tri-tert-butylphosphine)palladium(0), tris(dibenzylideneacetone)dipalladium(0), tetrakis(triphenylphosphine)palladium(0), bis At least one selected from the group consisting of [tris(2-methylphenyl)phosphine]palladium and palladium(II) acetate and dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) may be used can

In addition, the base used in the reaction of step 1 may be at least one selected from the group consisting of cesium carbonate, potassium carbonate, sodium carbonate, sodium tert-butoxide and potassium tert-butoxide. Among them, sodium tert-butoxide is preferably used in terms of reaction rate and yield.

In addition, as a solvent for the reaction, a solvent exhibiting inertness to the Buchwald-Hartwig amination reaction may be used. For example, a solvent such as toluene, dioxane, dimethylformamide (DMF), or butyl alcohol may be used, but toluene is preferred in terms of reaction rate and yield.

In addition, the reaction may be performed at a temperature of 70° C. to 85° C. for 60 minutes to 120 minutes. When the reaction is carried out under a lower temperature condition and/or a shorter reaction time than the above-mentioned range, the reaction may not proceed sufficiently, and thus the production yield may be lowered. In addition, even if the reaction is performed under a temperature condition higher than the above-mentioned range and/or a long reaction time, the production yield does not substantially increase, which is not preferable in terms of process cost.

(Step 2)

In step 2, the reaction product prepared in step 1, that is, the crude product of the compound represented by Formula 1, is dissolved in an organic solvent containing dichloromethane and hexane in a volume ratio of 1:0.5 to 1:2 to prepare a solution. In the preparation step, impurities such as by-products and residual platinum catalyst remaining in the crude product may remain in the solution to increase the purity of the compound. Specifically, due to the purification process according to the organic solvent containing dichloromethane and hexane, impurities such as a platinum catalyst, a residual base, and a starting material can be effectively removed. In addition, compared to a method of purifying a compound using a chromatography column, it has an advantage of being advantageously applied to mass production.

At this time, the reason for including dichloromethane and hexane as the organic solvent at the same time is because of the mixing effect of the solvent/antisolvent, and in this case, dichloromethane is a solvent for dissolving the crude reaction product prepared in step 1, hexane It serves as an antisolvent for the reaction product. Therefore, when only one of the solvent and the anti-solvent is used, there may be a problem in that a desired product cannot be obtained or impurities are excessively precipitated together with the crystal of the product.

In addition, in the organic solvent, the dichloromethane and hexane are included in a volume ratio of 1:0.5 to 1:2. If the hexane is used too little out of the above ratio compared to the dichloromethane, crystallization according to the role of the anti-solvent of hexane in the subsequent step 3 process may not be effectively performed, so that there may be excessive loss of the reaction product, and the yield is lowered, Impurities may not be effectively purified, and if the hexane is used in excess of the ratio relative to the dichloromethane, it may be difficult to sufficiently dissolve the crude reaction product prepared in step 1 above.

More specifically, the organic solvent may include only dichloromethane and hexane in a volume ratio of 1:0.7 to 1:1.5, 1:0.9 to 1:1.2, or 1:1.

In the above step, the organic solvent may be used in an amount (ml/g) of 20 to 80 times the weight of the reaction product prepared in step 1. In this case, if the organic solvent is used too little relative to the weight of the reaction product prepared in step 1, there may be a problem of excessive precipitation of impurities along with the crystals of the product, and the organic solvent is used too much relative to the weight of the reaction product If used, there may be a loss of reaction products, which is not preferred.

In particular, when the reaction product prepared in step 1 is purified by column purification such as medium pressure liquid chromatography (MPLC), the organic solvent used as the eluent is about 300 times to about 300 times the weight of the reaction product prepared in step 1 Considering that it is used about 1,000 times, the above-described manufacturing method according to an embodiment uses a much smaller amount of an organic solvent, which is eco-friendly and can reduce the cost of raw materials.

In this case, when the reaction product prepared in step 1 is dissolved in an organic solvent including dichloromethane and hexane, the temperature may be 20°C to 70°C.

(Step 3)

In step 3, impurities of the solution prepared in step 2 are removed using one or more adsorbents selected from the group consisting of silica gel, activated carbon, and activated alumina, and then the solution from which impurities are removed is dried to obtain high purity of Chemical Formula 1 As a step of preparing a compound represented by , polar impurities such as a platinum catalyst, a base, and a residual starting material remaining in the solution after the reaction of step 1 may be adsorbed and removed by the adsorbent.

Meanwhile, in the above step, the removal of impurities using the adsorbent may be performed by introducing the adsorbent into the solution prepared in step 2 or passing the solution prepared in step 2 through a filter filled with the adsorbent. The purification method using a filter filled with the adsorbent or pre-injection/stirring of the adsorbent has the advantage that a smaller amount of filler and solvent can be used than the MPLC column purification method, and the process time is also greatly shortened.

More specifically, when the removal of impurities using the adsorbent is performed by adding the adsorbent to the solution prepared in step 2, the following steps may be performed:

adding an adsorbent to the solution prepared in step 2, wherein the adsorbent is used in an amount of 15 to 30 weight (g) based on 100 ml of the solution volume;

stirring the solution in which the adsorbent is added at 500 to 1500 rpm for 60 minutes to 2 hours; and

Filtering the adsorbent to obtain a solution from which impurities are removed, wherein the filtration is performed under vacuum using a Buchner filter funnel covered with filter paper.

In addition, when the solution prepared in step 2 is passed through a filter filled with an adsorbent, it proceeds to the following steps to obtain a solution from which impurities are removed. In this case, a filter paper is covered as a filter, and a Buchner filter funnel in which an adsorbent of 15 to 30 weight (g) is pre-filled with respect to 100 ml of the volume of the solution prepared in step 2 may be used.

Meanwhile, among the adsorbents, silica gel having a plurality of silanol (Si-OH) end groups on the surface thereof is more preferable as the adsorbent. Specifically, impurities exhibiting strong polarity present on the surface of the silica gel without being dissolved in the organic solvent including dichloromethane and hexane used in step 2 can be effectively adsorbed.

In addition, the silica gel preferably has a porous spherical particle shape so that the above-mentioned impurities can be effectively adsorbed. Specifically, the silica gel may have a porous structure having an average particle diameter (D50) of 40 to 200 μm, a pore size of 40 to 80 Å, and a BET specific surface area of 150 to 550 m ² /g. For example, the average particle diameter (D50) is 55 to 65 μm, the average pore diameter is 40 to 63 μm, the BET specific surface area is 480 to 540 m ² /g, and the pore volume (N ₂ -isotherm) is 0.74 to 0.74 μm Silica gel 60 (230-400 mesh ASTM) with 0.84 ml/g is suitable for use.

In this case, "particle diameter (D50)" means the particle diameter at the n% point of the cumulative distribution of the number of particles according to the particle diameter. That is, D50 is the particle size at 50% of the cumulative distribution of the number of particles according to the particle size, D90 is the particle size at 90% of the cumulative distribution of the number of particles according to the particle size, and D10 is 10% of the cumulative distribution of the number of particles according to the particle size It is the particle diameter at the point. The Dn may be measured using a laser diffraction method. Specifically, after dispersing the powder to be measured in the dispersion medium, it is introduced into a commercially available laser diffraction particle size measuring device (eg Microtrac S3500) to measure the diffraction pattern difference according to the particle size when the particles pass through the laser beam to measure the particle size distribution to calculate D10, D50, and D90 can be measured by calculating the particle diameter at the point used as 10%, 50%, and 90% of the particle number cumulative distribution according to the particle diameter in a measuring apparatus.

In addition, "specific surface area" is measured by the BET method, and specifically, it can be calculated from the amount of nitrogen gas adsorbed under liquid nitrogen temperature (77 K) using BELSORP-mino II manufactured by BEL Japan.

In addition, "pore size" can be analyzed as the amount of adsorption/desorption of nitrogen according to partial pressure (0.11<p/po<1) using the ASAP 2010 instrument of Micrometrics.

Next, a high-purity compound from which the organic solvent is removed may be prepared by drying the solution obtained by the above method from which impurities are removed. It may be carried out for 5 hours to 18 hours at a temperature of 40 ℃ to 80 ℃. However, in order to effectively remove the organic solvent, the organic solvent in the solution may be removed with a vacuum rotary concentrator and then a drying process may be performed.

(additional purification step)

On the other hand, in order to further increase the purity of the compound prepared in step 3, an additional purification step may be further included after step 3 above. Specifically, it is preferable in terms of securing the purity of the final material and obtaining uniform crystals to include an additional purification step by recrystallization.

For example, the compound prepared in step 3 is dissolved in one selected from the group consisting of methyl ethyl ketone, 1,4-dioxane, 3-butanone and ethyl acetate, followed by ethanol, isopropyl alcohol and hexane It may further comprise the step of crystallizing by one selected from the group.

From the viewpoint of effectively removing impurities that may remain in step 3 among the solvents and obtaining high-purity recrystallization, it is preferable to dissolve the compound prepared in step 3 in methylethoneketone and then crystallize it with hexane. do.

At this time, one selected from the group consisting of methyl ethyl ketone, 1,4-dioxane, 3-butanone and ethyl acetate is used in an amount (ml) of 8 to 15 times the weight of the compound prepared in step 3. /g), and the process of dissolving the compound in methyl ethyl ketone may be performed by stirring at a temperature of about 25° C. to 50° C. for 30 minutes to 1 hour.

In addition, one selected from the group consisting of ethanol, isopropyl alcohol and hexane may be used in an amount (ml/g) of 8 to 15 times the volume of the compound prepared in step 3 (ml/g), and in hexane The crystallization process can be performed by slowly adding the hexane dropwise to a solution in which the compound is completely dissolved in methyl ethyl ketone while lowering the temperature to room temperature. In this case, the time for recrystallization may be 5 to 30 hours.

When crystals are formed under the above conditions, the crystals are filtered and dried to obtain a compound.

In addition, the method may further include dissolving the compound prepared in step 3 in tetrahydrofuran and then crystallizing the compound with ethanol.

In this case, tetrahydrofuran may be used in an amount (ml/g) of 12 to 15 times the weight of the compound prepared in step 3, and the process of dissolving the compound in tetrahydrofuran is about 25° C. to 50° C. It may be carried out by stirring at a temperature of ℃ for 30 minutes to 1 hour.

In addition, ethanol may be used in an amount (ml/g) of 25 to 30 times the weight of the compound prepared in step 3 above, and the crystallization process by ethanol is a solution in which the compound is completely dissolved in tetrahydrofuran. The ethanol may be slowly added dropwise to the ethanol while lowering the temperature to room temperature, or ethanol may be added to a solution completely dissolved in tetrahydrofuran at room temperature to precipitate immediately. In this case, the time for recrystallization may be 0.5 hours to 18 hours.

When crystals are formed under the above conditions, the crystals are filtered and dried to obtain a compound.

Alternatively, after step 3, both of the above-described two crystallization steps may be performed.

Specifically, the step of dissolving the dried product prepared in step 3 in methyl ethyl ketone, and then primary crystallization with hexane; and

The method may further include dissolving the crystal obtained by the crystallization in tetrahydrofuran and then performing secondary crystallization with ethanol.

At this time, it is preferable to perform crystallization with hexane before crystallization with ethanol from the viewpoint of preparing a high-purity compound.

(compound)

Meanwhile, the compound represented by Formula 1 prepared by the above-described manufacturing method may be a high-purity compound with reduced impurity content. Specifically, the prepared high-purity compound may exhibit a purity of 98.5% or more, 99% or more, or 99.2% or more. In addition, according to the preparation method, the compound can be obtained in a yield of 44% or more, 50% or more, 60% or more, or 65% or more.

In this case, in Formula 1,

L ₁ is phenylene, biphenyldiyl, naphthylene, 9,9-diphenylfluorenylene, or (naphthylene)-(phenylene),

Here, L ₁ may be unsubstituted or substituted with one or more C _1-4 alkyl.

For example, L ₁ may be phenylene, more specifically 1,4-phenylene.

In addition, L ₂ is a single bond, or methylene, ethylene, propylene, butylene, pentylene, hexylene, or heptylene,

Here, when L ₂ is methylene, ethylene, propylene, butylene, pentylene, hexylene and heptylene, L ₂ may be unsubstituted or substituted with C _1-4 alkyl.

For example, L ₂ may be a single bond.

In addition, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, phenanthryl, fluorenyl, or dibenzofuranyl,

Here, Ar ₁ and Ar ₂ may be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, halogen, C _1-10 alkyl, C _1-10 haloalkyl and phenyl.

For example, Ar ₁ is phenyl, biphenylyl, biphenylyl substituted with C _1-10 alkyl, naphthyl, or dibenzofuranyl;

Ar ₂ may be any one selected from the group consisting of:

.

.

Further, R ₁ is phenyl unsubstituted or substituted with deuterium, halogen, C _1-10 alkyl, or C _1-10 haloalkyl; Or it may be R' which is a heat or photocurable group.

In addition, R ₂ is hydrogen; phenyl unsubstituted or substituted with halogen; Or it may be R' which is a heat or photocurable group.

이고,For example, R ₁ is phenyl, phenyl substituted with CF ₃ , or a thermally or photocurable group.

ego,

일 수 있다.R ₂ is phenyl, or a thermally or photocurable group

can be

More specifically, the compound represented by Chemical Formula 1 prepared by the above-described preparation method may be represented by the following Chemical Formula 1-1:

[Formula 1-1]

In Formula 1-1,

Ar ₁ and Ar ₂ are as defined in Formula 1 above,

이고,R ₁ is phenyl, phenyl substituted with CF ₃ , or a thermally or photocurable group

ego,

이다.R ₂ is phenyl, or a thermally or photocurable group

to be.

For example, the compound represented by Formula 1, which can be prepared by the above preparation method, is any one selected from the group consisting of the following compounds:

.

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto. In addition, the equivalent (eq) in the following may be understood to mean the number of moles relative to the starting material in the reaction proceeding in each step.

Example 1

(Step 1)

Compound 1-1 (8.05 g, 13.7 mol), compound 1-2 (6.48 g, 14.4 mol), bis(tri-tert-butylphosphine)palladium(0) (BTP, 0.21 g, 0.41 mol), sodium tert -Butoxide (NaOtBu, 2.63 g, 27.3 mol) was added to a 1-neck RBF and dissolved in toluene (205 g). Then, the jacket temperature was raised to 80 degrees and stirred for 1 hour. After lowering the temperature of the reaction solution with ice water, it was worked up using diethyl ether. Next, the collected organic solution was dried using MgSO ₄ to obtain Compound 1 as a solid reaction product.

MS: [M+H] ⁺ = 959

¹ H NMR: δ 8.44 (dd, J = 13.8, 1.8 Hz, 2H), 7.81 - 7.09 (m, 37H), 6.95 (s, 2H), 6.89 (s, 1H), 6.80 (dd, J = 17.6, 10.9 Hz, 1H), 6.70 (dd, J = 17.7, 10.9 Hz, 1H), 5.83 (d, J = 17.6 Hz, 1H), 5.72 (d, J = 17.6 Hz, 1H), 5.28 (d,J = 10.9 Hz, 1H), 5.21 (d, J = 10.9 Hz, 1H), 2.16 (s, 3H), 1.60 (s, 3H).

(Step 2)

2 g of the reaction product prepared in step 1 was dissolved in 80 ml of an organic solvent (a volume of 40 times the weight of the reaction product) in which dichloromethane and hexane were mixed in a volume ratio of 1:1. The temperature at this time was 25 degreeC.

(Step 3)

Silica gel 60 (manufactured by Merck, Inc., average particle diameter (D50): 55 to 65 μm, average pore diameter: 40 to 63 μm, BET specific surface area: 480 to 540 m ² /g, pores Volume (N ₂ -isotherm): 0.74 to 0.84 ml/g, 230-400 mesh ASTM) is passed through a packed filter, and then the same organic solvent as used in step 2 is passed through the filter once again to remove impurities solution was obtained.

Next, using a rotary evaporator (product name: R-300, manufactured by Buchi), the organic solvent was removed from the solution, and then dried at a temperature of 60° C. for 12 hours to obtain purified compound 1 (yield: 87.2). %).

Example 2

(Steps 1 to 3)

Purified compound 1 was obtained in the same manner as in steps 1 to 3 of Example 1.

(additional purification step)

3 g of the purified compound 1 was completely dissolved in 30 ml of methyl ethyl ketone (an amount of 10 times the volume relative to 1 weight of compound) at a temperature of 50° C. for 30 minutes, and then 30 ml of hexane (10 times the volume of 1 weight of compound) of the solution) was slowly added dropwise while cooling the temperature of the solution to room temperature so that crystals were formed. After 24 hours, the mixture was dried at a temperature of 50° C. for 12 hours to obtain a purified compound 1 of ivory color (yield 65.9%).

Example 3

(Steps 1 and 2)

A solution in which the compound was dissolved in dichloromethane and hexane was prepared in the same manner as in steps 1 and 2 of Example 1.

(Step 3)

In the solution prepared in step 2, silica gel (manufactured by Merck, 230-400 mesh ASTM) was added in an amount of 20 weight (g) based on 100 ml of the solution volume.

Next, the silica gel-infused solution was stirred at 1000 rpm for 1 hour, and a hot plate stirrer (product name: C-MAG HS 7, manufactured by IKA) was used as a stirring device. Thereafter, the silica gel was filtered, and the filtered silica gel was washed with the same organic solvent used in step 2 to obtain a solution from which impurities were removed.

Next, using a rotary evaporator (product name: R-300, manufactured by Buchi), the organic solvent was removed from the solution, and then dried at a temperature of 50° C. for 12 hours.

(additional purification step)

3 g of the dried compound 1 was completely dissolved in 30 ml of methyl ethyl ketone (an amount of 10 times the volume of the dried compound 1 weight) for 30 minutes at a temperature of 50° C., and then 30 ml of hexane (relative to the 1 weight of the dried compound 1 weight) 10 times the volume) was slowly added dropwise while cooling the temperature of the solution to room temperature so that crystals were formed. After 24 hours, the resulting crystals were filtered and dried at a temperature of 50° C. for 12 hours.

Thereafter, 2 g of the dried compound 1 was completely dissolved in 24 ml of tetrahydrofuran (amount of volume 12 times the weight of compound 1) at a temperature of 30° C. for 30 minutes, and then 50 ml of ethanol (25 based on 1 weight of compound) The volume of the pear) was slowly added dropwise while cooling to room temperature so that crystals were formed. After 3 hours, the resulting crystals were filtered and dried at a temperature of 50° C. for 12 hours to obtain ivory colored purified compound 1 (yield: 44.6%).

Comparative Example 1

A reaction product, Compound 1, was obtained by using the same method as in Step 1 of Example 1.

Next, the reaction product was precipitated in ethanol to dissolve the impurities in the ethanol, and then the ethanol in which the impurities were dissolved was removed through a filter. Next, MPLC column purification with silica gel adsorbed (filler: silica gel, eluent: dichloromethane: hexane = 2:5 (v/v), used in an amount of 100 to 500 times the weight of the reaction product) Compound 1 was obtained (yield 43%).

Comparative Example 2

In Example 1, Compound 1 was obtained in the same manner as in Example 1, except that the organic solvent of step 2 was used as an organic solvent in which dichloromethane and hexane were mixed in a volume ratio of 1:0.3 (yield 61%). .

Comparison of Examples and Comparative Examples

In order to confirm the purity of the final compounds prepared in Examples and Comparative Examples, impurities were separated according to relative retention time (RRT) under the conditions shown in Table 1 below using high performance liquid chromatography (HPLC). and the results are shown in Table 2 below together with the yield.

column Capcell Pak C18, 250 x 4.6 mm, 5 m Mobile phase A THF/acetonitrile = 50% Mobile phase B H20 = 100% UV 280 nm column temp. 40℃ Flaw rate 1 ml/min sample preparation Compound 10mg / THF 2ml gradient

transference number water impurities
RRT=1.71 impurities
RRT=4.69 impurities
RRT=5.97 Example 1 87.2% 99.99% 0.31 0.13 0.01 Example 2 65.9% 99.71% 0.05 0.06 0.02 Example 3 44.9% 99.61% - - - Comparative Example 1 43% 93.1% - - - Comparative Example 2 61% 91.5% - - -

(In Table 2 above, “-” means no measurement.)

As shown in Table 2, it can be seen that when the compound is prepared by the process of the Example, a high-purity compound with reduced impurities can be prepared in a high yield compared to the process of the Comparative Example described above.

Claims (13)

reacting the compound represented by the following Chemical Formula 1-1 with the compound represented by the following Chemical Formula 1-2 in the presence of a palladium catalyst and a base (step 1);
dissolving the reaction product prepared in step 1 in an organic solvent containing dichloromethane and hexane in a volume ratio of 1:0.5 to 1:2 (step 2); and
Including; and drying after removing impurities using one or more adsorbents selected from the group consisting of silica gel, activated carbon and activated alumina (step 3);
In step 2, the organic solvent is used in an amount (ml/g) of 20 to 80 times the weight of the reaction product prepared in step 1 by volume,
A method for preparing a compound represented by the following formula (1):
[Formula 1]

[Formula 1-1]

[Formula 1-2]

In Formula 1, Formula 1-1 and Formula 1-2,
X is halogen,
L ₁ is C _6-20 arylene; or (C _6-20 arylene)-(C _6-20 arylene),
Here, the C _6-20 arylene is unsubstituted or substituted with C _1-10 alkyl,
L ₂ is a single bond; Or a substituted or unsubstituted C _1-10 alkylene,
Ar ₁ and Ar ₂ are each independently C _6-60 aryl, substituted or unsubstituted, or C _2- containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S ₆₀ heteroaryl;
R ₁ and R ₂ are each independently hydrogen; substituted or unsubstituted C _6-60 aryl; or R';
R and R' are each independently any one selected from the group consisting of

above,
L is substituted or unsubstituted C _1-10 alkylene.
According to claim 1,
In step 1, the compound represented by Formula 1-1 and the compound represented by Formula 1-2 are used in a molar ratio of 1: 1 to 1: 1.1,
manufacturing method.
According to claim 1,
In step 1, the palladium catalyst is bis(tri-tert-butylphosphine)palladium(0), tris(dibenzylideneacetone)dipalladium(0), tetrakis(triphenylphosphine)palladium(0), At least one selected from the group consisting of bis [tris (2-methylphenyl) phosphine] palladium and palladium (II) acetate and dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium (II),
manufacturing method.
According to claim 1,
In step 1, the base is at least one selected from the group consisting of cesium carbonate, potassium carbonate, sodium carbonate, sodium tert-butoxide and potassium tert-butoxide,
manufacturing method.
According to claim 1,
In step 1, the reaction is carried out at a temperature of 70 ° C. to 85 ° C. for a time of 60 minutes to 120 minutes,
manufacturing method.
delete According to claim 1,
In step 3, the removal of impurities using the adsorbent is performed by introducing an adsorbent to the solution prepared in step 2, or passing the solution prepared in step 2 through a filter filled with an adsorbent,
manufacturing method.
According to claim 1,
In step 3, silica gel having a porous structure having an average particle diameter (d50) of 40 to 200 μm and a BET specific surface area of 150 to 550 m ² /g is used as the adsorbent,
manufacturing method.
According to claim 1,
In step 3, the drying is carried out at a temperature of 40 ° C to 80 ° C for 5 hours to 18 hours,
manufacturing method.
According to claim 1,
After dissolving the compound prepared in step 3 in one selected from the group consisting of methyl ethyl ketone, 1,4-dioxane, 3-butanone and ethyl acetate, in the group consisting of ethanol, isopropyl alcohol and hexane Further comprising the step of crystallizing by one selected,
manufacturing method.
According to claim 1,
After dissolving the compound prepared in step 3 in tetrahydrofuran, further comprising the step of crystallizing with ethanol,
manufacturing method.
According to claim 1,
After dissolving the dried product prepared in step 3 in one selected from the group consisting of methyl ethyl ketone, 1,4-dioxane, 3-butanone and ethyl acetate, in the group consisting of ethanol, isopropyl alcohol and hexane Primary crystallization by one selected type; and
Further comprising the step of secondary crystallization with ethanol after dissolving the crystal in tetrahydrofuran,
manufacturing method.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of the following compounds,
Manufacturing method:

.