Method for manufacturing fluorene-based diamine compound

Abstract

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

Description

Technology Field

[0001] This specification relates to a method for manufacturing fluorene-based diamine compounds. Background Technology

[0002] Organic light emission is one example in which electric current is converted into visible light through internal processes of specific organic molecules. In particular, instead of conventional deposition processes that involve significant material loss, technology for manufacturing devices through solution processes that can increase production efficiency with less material loss is being developed, and there is a need for the development of materials that can be used in solution processes.

[0003] However, the materials that can be used in the above solution process have disadvantages such as being difficult to handle because the synthesis step for preparing the material or the reactant to produce it is complex, or because the manufacturing process requires volatile or toxic substances.

[0004] Accordingly, there is a need for a method that can simplify steps such as synthesis and purification required to manufacture materials for organic light-emitting diodes that can be used in solution processes or reactants for producing them, or to resolve safety drawbacks. Prior art literature

[0005] International Patent Application Publication No. 1998-006773 The problem to be solved

[0006] This specification aims to provide a method for manufacturing a fluorene-based diamine compound. means of solving the problem

[0007] One embodiment of the present specification includes (s1) a step of adding a diamine compound, a halogenated compound, and an organometallic catalyst and substituting nitrogen; and

[0008] (s2) A method for preparing a fluorene-based diamine compound is provided, comprising the step of adding a first organic solvent to the product of step (s1) above and stirring. Effects of the invention

[0009] According to the method for manufacturing a fluorene-based diamine compound according to one embodiment of the present specification, a fluorene-based diamine compound of high purity can be manufactured.

[0010] According to the method for producing a fluorene-based diamine compound according to one embodiment of the present specification, a high yield of fluorene-based diamine compound can be produced. Specific details for implementing the invention

[0011] The present specification will be described in more detail below.

[0012] One embodiment of the present specification provides a method for preparing a fluorene-based diamine compound as follows.

[0013] (s1) a step of replacing nitrogen after introducing a diamine compound, a halogen compound, and an organometallic catalyst; and

[0014] (s2) A method for preparing a fluorene-based diamine compound is provided, comprising the step of adding a first organic solvent to the product of step (s1) and stirring.

[0015] According to conventional technology, only an organometallic catalyst (Comparative Example 1-1 below) is included in step (s1) above. Conventional methods result in many side reactions, which lowers the yield and purity of the target compound. However, the manufacturing method according to one embodiment of the present invention promotes the reaction and minimizes side reactions, so the fluorene-based diamine compound produced has the advantage of having higher purity and yield than compounds produced by conventional methods.

[0016] According to one embodiment of the present invention, a method for preparing a fluorene-based diamine compound is provided, which further comprises the step (s3) of filtering the product of step (s2) using a second organic solvent and an alkane as eluents after step (s2).

[0017] According to a method for manufacturing a fluorene-based diamine compound according to one embodiment of the present specification, a fluorene-based diamine compound can be manufactured without undergoing column purification, which is a conventional process.

[0018] When fluorene-based diamine compounds are manufactured using conventional technology, the process becomes complex due to column purification, making scale-up difficult and reducing efficiency in terms of economy due to the complex process. In addition, the purity and yield of the compounds decrease as a result of the complex process.

[0019] However, when the fluorene-based diamine compound is manufactured according to the method for manufacturing the fluorene-based diamine compound according to the present specification, the process can be simplified by undergoing filter purification instead of column purification, thereby ensuring manufacturing efficiency and economic viability, and facilitating scale-up for mass production. In addition, the purity and yield of the compound can be increased by avoiding multiple processes through a simple manufacturing method using a filter process.

[0020] In this specification, when a part is described as "comprising" a certain component, it means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0021] In this specification, the step of "adding A to B" or the step of "adding B to A" means a step of adding A to B or adding B to A, and the method of addition may be, for example, a dropwise method, but is not limited thereto.

[0022] In this specification, the term "mixing" does not specifically limit the mixing process; for example, it may involve mixing by stirring, and stirring may involve rotating using a magnetic bar or a mechanical mixer, but is not limited to the above examples.

[0023] Unless otherwise defined in the present invention, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those skilled in the art to which the present invention pertains. Methods and materials similar or equivalent to those described in the present invention may be used in the practice or testing of embodiments of the present invention, but suitable methods and materials are described below.

[0024] All publications, patent applications, patents, and other references mentioned in this invention are incorporated by reference in their entirety, and in the event of a conflict, this invention, including its definitions, shall prevail unless a specific passage is mentioned otherwise. Furthermore, materials, methods, and embodiments are merely illustrative and are not intended to be limiting.

[0025] According to one embodiment of the present specification, the organometallic catalyst comprises a palladium-based metal catalyst.

[0026] According to one embodiment of the present specification, the organometallic catalyst is a palladium-based metal catalyst.

[0027] According to one embodiment of the present specification, the organometallic catalyst is preferably Pd2(dba)3(Tris(dibenzylideneacetone)dipalladium(0)) or BTP(Bis(tri-tert-butylphosphine)palladium(0)), but is not limited thereto.

[0028] According to one embodiment of the present specification, the organometallic catalyst comprises one type of palladium-based metal catalyst.

[0029] According to one embodiment of the present specification, the organometallic catalyst is Pd2(dba)3(Tris(dibenzylideneacetone)dipalladium(0)).

[0030] According to one embodiment of the present specification, the organometallic catalyst is BTP (Bis(tri-tert-butylphosphine)palladium(0)).

[0031] According to one embodiment of the present specification, the organometallic catalyst is included in an amount of 0.01 to 0.1 equivalents relative to 1 equivalent of the diamine compound.

[0032] According to one embodiment of the present specification, the organometallic catalyst is included in an amount of 0.01 to 0.09 equivalents relative to 1 equivalent of the diamine compound.

[0033] According to one embodiment of the present specification, the organometallic catalyst is included in an amount of 0.01 to 0.06 equivalents relative to 1 equivalent of the diamine compound.

[0034] According to one embodiment of the present specification, the organometallic catalyst is included in an amount of 0.01 to 0.03 equivalents relative to 1 equivalent of the diamine compound.

[0035] According to one embodiment of the present specification, the organometallic catalyst is included in an amount of 0.03 equivalents relative to 1 equivalent of the diamine compound.

[0036] When an organometallic catalyst is included in the above amount, the reaction is promoted, and the reaction can proceed with almost no side reactions.

[0037] According to one 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.

[0038] When the above halogenated compound is included in an equivalent amount relative to 1 equivalent of the above diamine compound, side reactions can be suppressed, and the purity and yield are increased.

[0039] If the above halogenated compound is used in an amount exceeding 2.1 equivalents relative to 1 equivalent of the above diamine compound, side reactions occur, and the purity and yield of the compound are lowered, and if it is used in an amount less than 2 equivalents, it does not react sufficiently with the above diamine compound, resulting in a lower yield.

[0040] According to one embodiment of the present specification, step (s1) further comprises adding a basic compound.

[0041] According to one embodiment of the present specification, the basic compound is sodium tert-butoxide.

[0042] According to one embodiment of the present specification, the basic compound is included in an amount of 4 to 10 equivalents relative to 1 equivalent of the diamine compound, preferably in an amount of 4 to 8 equivalents, and more preferably in an amount of 5 equivalents.

[0043] According to one embodiment of the present specification, the ligand in step (s1) is a phosphine-based ligand.

[0044] According to one 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.

[0045] According to one embodiment of the present specification, the phosphine-based ligand is included in an equivalent amount of 0.01 to 0.1 relative to 1 equivalent of the diamine compound.

[0046] According to one embodiment of the present specification, the phosphine-based ligand is included in an amount of 0.01 to 0.09 equivalents relative to 1 equivalent of the diamine compound.

[0047] According to one embodiment of the present specification, the phosphine-based ligand is included in an amount of 0.01 to 0.06 equivalents relative to 1 equivalent of the diamine compound.

[0048] According to one embodiment of the present specification, the phosphine-based ligand is included in an amount of 0.06 equivalents relative to 1 equivalent of the diamine compound.

[0049] When a phosphine-based ligand is included in the above amount, the reaction is promoted, and the reaction can proceed with almost no side reactions.

[0050] According to one embodiment of the present specification, the first organic solvent of step (s2) is an aromatic hydrocarbon organic solvent. The aromatic hydrocarbon organic solvent may be benzene, fluorobenzene, bromobenzene, chlorobenzene, toluene, xylene, mesitylene, etc., and may be used alone or in combination.

[0051] According to one embodiment of the present specification, the first organic solvent of step (s2) is toluene.

[0052] According to one embodiment of the present specification, the first organic solvent is added in an amount of 0.1 M to 0.3 M, and preferably in an amount of 0.1 M to 0.26 M. When the first organic solvent is added in the above amount, the solute added to the reaction is sufficiently dissolved so that the forward reaction can proceed with almost no side reactions. When the amount exceeds the above amount, the reaction rate decreases and side reactions may occur, resulting in a lower yield and economic losses due to the replacement of the reactor with a large capacity and the excessive use of solvent. When the amount is added in less than the above amount, the solute added to the reaction is not sufficiently dissolved, resulting in a lower yield.

[0053] According to one embodiment of the present specification, step (s2) is carried out in a temperature range of 60°C to 80°C. Preferably, step (s2) is carried out in a temperature range of 65°C to 75°C. When such a temperature range is satisfied, the reaction efficiency increases. Specifically, by maintaining a temperature about 35°C to 55°C higher than room temperature, the reaction between the halogenated compound and the diamine compound can proceed effectively. Furthermore, since unintended side reactions may occur if the temperature range is exceeded, satisfying the aforementioned temperature range allows the forward reaction to proceed consistently, thereby offering the advantage of expecting a high yield of the product.

[0054] According to one embodiment of the present specification, the purity at 260 nm of a fluorene-based diamine compound prepared by a method for preparing a fluorene-based diamine compound comprising steps (s1) and (s2) is 93% to 96%.

[0055] The above purity can be measured by conventional methods, and preferably by using HPLC.

[0056] The purity of a fluorene-based diamine compound according to one embodiment of the present specification is measured without undergoing a purification process after step (s2).

[0057] According to one embodiment of the present specification, an intermediate purification step for purifying an intermediate product may be included. The intermediate purification step

[0058] (s21) A step of cooling the product of step (s2) above;

[0059] (s22) Quench and layer separation step;

[0060] (s23) Drying step;

[0061] (s24) Filtration step; and

[0062] (s25) Includes a concentration step.

[0063] According to one embodiment of the present specification, the step (s21) is performed by reducing the temperature to a range of 30°C to 50°C. Preferably, the step (s21) may be performed by reducing the temperature to a range of 45°C to 50°C, but is not limited thereto. When such a temperature range is satisfied, the progress of the reaction can be terminated and the exothermic reaction can be prevented.

[0064] According to one embodiment of the present specification, the cooling rate may be such that the temperature of the reaction system is gradually lowered, thereby forming a temperature gradient over the entire reaction system rather than just a part of the reaction system. Specifically, it may be performed under a temperature reduction condition of 4 ℃ / min to 7 ℃ / min, but is not limited thereto.

[0065] According to one embodiment of the present specification, the step (s22) (quench and layer separation step) is a step of adding a reaction termination substance to terminate the reaction and separate the layers.

[0066] According to one embodiment of the present specification, the reaction termination material of step (s22) may be distilled water, an aqueous ammonium chloride solution, an aqueous sodium bicarbonate solution, an aqueous HCl solution, an aqueous NaCl solution, ethyl acetate, etc., but is not limited thereto. Preferably, the reaction termination material is an aqueous ammonium chloride solution, an aqueous sodium bicarbonate solution, an aqueous NaCl solution, or ethyl acetate.

[0067] The order in which the reaction termination and phase separation proceed in the above step (s22) is not limited to a specific order. In one embodiment, the reaction termination and phase separation may proceed simultaneously, and in another example, the reaction may be terminated by adding a reaction termination substance, and then phase separation may proceed. However, the order of proceeding is not limited to the examples described above.

[0068] According to one embodiment of the present specification, the step (s23) (drying step) is carried out by adding a drying agent to one of the layers of the material separated in the step (s102). For example, if the ethyl acetate exemplified above is used as the reaction termination material, the drying agent is added to the upper layer, the ethyl acetate layer, i.e., the organic layer. Examples of the drying agents include magnesium sulfate, sodium magnesium, etc., but are not limited thereto. According to a preferred embodiment, the drying agent is magnesium sulfate.

[0069] In this specification, a sufficient amount of desiccant is added for drying as is customarily required in the industry.

[0070] According to one embodiment of the present specification, the step (s24) (filtration step) may be performed using methods known in the art. Representative examples may include a method of drawing in air using an aspirator and filtering out impurities, such as desiccant separated from the target product, through a filter, or a method of removing other impurities using a solvent in which the target product is not dissolved but other impurities are dissolved by utilizing a difference in solubility for a specific solvent.

[0071] According to one embodiment of the present specification, the step (s25) (concentration step) may be carried out using methods known in the art. A typical example is that it may be carried out by evaporating the solvent using a vacuum rotary evaporator, but is not limited thereto. Through the above (s25), the product of the above step (s2) is concentrated until the amount of solvent is at least 5 times the theoretical yield (mass) of the fluorene-based diamine compound.

[0072] According to one embodiment of the present specification, after step (s25), additional filtration and drying steps may be added.

[0073] According to one embodiment of the present specification, an intermediate purification step for purifying an intermediate product may be included. The intermediate purification step

[0074] (s21) A step of cooling the product of step (s2) above;

[0075] (s22) Quench and layer separation step;

[0076] (s23-1) First drying step;

[0077] (s24-1) First filtration step;

[0078] (s25) Concentration step;

[0079] (s26) Second filtration step; and

[0080] (s27) Includes a second drying step.

[0081] According to one embodiment of the present specification, the description of step (s23-1) applies to step (s23), and the description of step (s24-1) applies to step (s24).

[0082] According to one embodiment of the present specification, the second filtration step (s26) can be performed using a method known in the art. An alcohol-based solvent, preferably isopropyl alcohol, can be added to the product of step (s25) to precipitate it, and then stirred and filtered in the same manner as step (s24). At this time, only impurities are dissolved in the alcohol-based solvent, and through filtration, only impurities pass through the filter paper.

[0083] According to one embodiment of the present specification, the second drying step (s27) is a step of drying the product of the step (s26), i.e., the filter cake. The second drying step may be carried out by methods known in the art, such as vacuum oven drying, spray drying, flash drying, etc., and preferably, drying may be performed by vacuum oven drying.

[0084] According to one embodiment of the present specification, step (s3) includes a preprocessing step. The preprocessing step may be performed after step (s2) and before step (s3).

[0085] According to one embodiment of the present specification, the pretreatment step includes the step of dissolving the product of step (s2) in a second organic solvent and an alkane.

[0086] In the above pretreatment step, the second organic solvent: the alkane is 2:0.1 (v / v) to 1:5 (v / v), preferably 1.5:1 (v / v). With such a ratio, the product of step (s2) can be sufficiently dissolved, and by-products and impurities are not dissolved.

[0087] According to one embodiment of the present specification, the second organic solvent in step (s3) is an aromatic hydrocarbon organic solvent. The aromatic hydrocarbon organic solvent may be benzene, fluorobenzene, bromobenzene, chlorobenzene, toluene, xylene, mesitylene, etc., and may be used alone or in combination.

[0088] According to one embodiment of the present specification, the second organic solvent of step (s3) is toluene.

[0089] According to one embodiment of the present specification, the alkane in step (s3) may be n-phenane, 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., and these may be used alone or in combination.

[0090] According to one embodiment of the present specification, the alkane of step (s3) is n-heptane.

[0091] According to one embodiment of the present specification, the second organic solvent: the alkane is in a ratio of 1:0.1 (v / v) to 1:10 (v / v), preferably 1:0.5 (v / v) to 1:5 (v / v), and more preferably 1:1 (v / v). When the eluent is in such a ratio, by-products and impurities are not dissolved in the eluent, and only the desired substance, namely the fluorene-based diamine compound, is dissolved, thereby increasing the yield and purity. However, if the ratio exceeds the above range, there is a disadvantage that the desired substance is not sufficiently dissolved or by-products are dissolved.

[0092] According to one embodiment of the present specification, the filtering step in step (s3) uses a filter containing alumina.

[0093] According to one embodiment of the present specification, the filtering step in step (s3) uses a filter comprising alumina and silica.

[0094] According to one embodiment of the present specification, the filtering step in step (s3) uses a filter made of alumina and silica.

[0095] According to one embodiment of the present specification, the alumina:silica of the filtering step (s3) is in a ratio of 1:0.1 (v / v) to 1:0.5 (v / v). Preferably, it is 1:0.2 (v / v). When the alumina and silica of the filtering step are included in the above ratio, there is an advantage that only the desired substance, namely the fluorene-based diamine compound, passes through the filter, and byproducts and impurities do not pass through the filter.

[0096] According to one embodiment of the present specification, the step (s3) further comprises the step of obtaining the fluorene-based diamine compound.

[0097] The step of obtaining the above according to one embodiment of the present specification

[0098] (s31) Concentration step;

[0099] (s32) Filtration step;

[0100] (s33) Drying step; and

[0101] (s34) Includes the obtaining step.

[0102] According to one embodiment of the present specification, the step (s31) (concentration step) may be performed using methods known in the art. A typical example is that it may be performed by evaporating the solvent using a vacuum rotary evaporator, but is not limited thereto.

[0103] According to one embodiment of the present specification, the step (s32) (filtration step) is a step of removing other impurities from the substance concentrated in the step (s31). The step (s32) may be carried out by methods known in the art, and as a representative example, a method of drawing in air using an aspirator and filtering it through a filter may be used, but is not limited thereto. The step of removing other impurities may be carried out by utilizing differences in solubility for a specific solvent. As a specific example, other impurities may be removed by using a solvent in which the fluorene-based diamine compound to be obtained is insoluble but other impurities are soluble. The solvent may be toluene, ethyl alcohol, or isopropyl alcohol, but is not limited thereto.

[0104] According to one embodiment of the present specification, the step (s33) (drying step) is a step of drying the product of the step (s32), i.e., the filter cake of the fluorene-based diamine compound. The drying step may be carried out by methods known in the art, such as vacuum oven drying, spray drying, flash drying, etc., and preferably, drying may be performed by vacuum oven drying.

[0105] According to one embodiment of the present specification, the step (s34) (obtaining step) is a step of obtaining the fluorene-based diamine compound dried in the step (s33).

[0106] According to one embodiment of the present specification, in the obtaining step, (s31) and (s32) may be performed three or more times as needed.

[0107] According to one embodiment of the present specification, the fluorene-based diamine compound of step (s3) is represented by the following chemical formula 1.

[0108] [Chemical Formula 1]

[0109]

[0110] In the above chemical formula 1,

[0111] L is a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group, and

[0112] L1 and L11 are the same or different from each other, and each is independently a single bond; a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group, and

[0113] Ar1 and Ar11 are the same or different from each other, and each is independently a photocurable group; or a thermocurable group, and

[0114] At least one of G1 to G5 is a halogen group, and the remainder is hydrogen; deuterium; or a substituted or unsubstituted alkyl group,

[0115] At least one of G11 to G15 is a halogen group, and the remainder is hydrogen; deuterium; or a substituted or unsubstituted alkyl group, and

[0116] R1 to R3 and R11 to R13 are the same or different from each other, and each is independently hydrogen; deuterium; 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, and

[0117] r1 is an integer from 1 to 5, and if r1 is 2 or more, the 2 or more R1s are the same or different from each other, and

[0118] r2 is an integer from 1 to 4, and if r2 is 2 or more, the 2 or more R2s are the same or different from each other,

[0119] r3 is an integer from 1 to 3, and if r3 is 2 or more, the 2 or more R3s are the same or different from each other, and

[0120] r11 is an integer from 1 to 5, and if r11 is 2 or more, the 2 or more R11s are the same or different from each other, and

[0121] r12 is an integer from 1 to 4, and if r12 is 2 or more, the 2 or more R12s are the same or different from each other,

[0122] r13 is an integer from 1 to 3, and if r13 is 2 or more, the 2 or more R13s are the same or different from each other.

[0123] Examples of substituents in this specification are described below, but are not limited thereto.

[0124] In this specification, refers to the connected part.

[0125] Throughout this specification, the term “combination thereof” included in the Markush-type expression means one or more mixtures or combinations selected from the group consisting of the components described in the Markush-type expression, and means including one or more selected from the group consisting of said components.

[0126] The term "substitution" above means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the substitution site is not limited to the site where the hydrogen atom is substituted, that is, any site where a substituent can be substituted, and in the case of two or more substitutions, the two or more substituents may be the same or different from each other.

[0127] In this specification, the term “substituted or unsubstituted” means that it is substituted with one or more substituents selected from the group consisting of deuterium; halogen group; hydroxyl group; cyano group; nitro group; alkyl group; cycloalkyl group; alkoxy group; alkenyl group; haloalkyl group; aryl group; and heteroaryl group, or is substituted with a substituent in which two or more of the exemplified substituents are connected, or has no substituents.

[0128] In this specification, the connection of two or more substituents means that a hydrogen of one substituent is connected to another substituent. For example, the connection of two substituents means that a phenyl group and a naphthyl group are connected or It can be a substituent. In addition, the connection of three substituents includes not only the consecutive connection of (substituent 1)-(substituent 2)-(substituent 3), but also the connection of (substituent 2) and (substituent 3) to (substituent 1). For example, a phenyl group, a naphthyl group, and an isopropyl group are connected, , or It can be a substituent. The aforementioned definition applies equally to the connection of 4 or more substituents.

[0129] In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

[0130] In the present specification, the alkyl group may be a straight chain or a branched chain, 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-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, Examples include 4-methylhexyl, 5-methylhexyl, etc., but are not limited to these.

[0131] In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 30 carbon atoms. Specifically, it includes 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, etc., but is not limited thereto.

[0132] In the present specification, the alkoxy group may be a straight chain, a branched chain, or a cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but it is preferred to have 1 to 30 carbon atoms. Specifically, it may be 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., but is not limited thereto.

[0133] In the present specification, the alkenyl group may be a straight chain or a branched chain, 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.

[0134] In this 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.

[0135] In the present specification, the aryl group is not particularly limited, but is preferably 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

[0136] When the above aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferable that the number of carbon atoms be 6 to 30. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

[0137] When the above aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferable that the number of carbon atoms be 10 to 30. Specifically, the polycyclic aryl group may be a naphthyl group, anthracene group, phenanthrene group, triphenylene group, pyrene group, phenalene group, perylene group, chrysene group, fluorene group, etc., but is not limited thereto.

[0138] In the present specification, the fluorene group may be substituted, and adjacent groups may combine with each other to form a ring.

[0139] When the above fluorene group is substituted, , , , , , , and There are, but are not limited to, the following.

[0140] In this specification, "adjacent" groups may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located closest to the atom on which the substituent is substituted, or another substituent substituted on the atom on which the substituent is substituted. For example, two substituents substituted at the ortho position in a benzene ring and two substituents substituted on the same carbon in an aliphatic ring may be interpreted as "adjacent" groups to each other.

[0141] In the present specification, the heteroaryl group comprises one or more non-carbon atoms or heteroatoms, and specifically, the heteroatoms may comprise one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but it is preferable that the number of carbon atoms be 2 to 30, and the heteroaryl group may be monocyclic or polycyclic. Examples of heteroaryl groups include thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, pyridine, bipyridine, pyrimidine, triazine, triazole, acridine, pyridazine, pyrazine, quinoline, quinazolin, quinoxaline, phthalazine, pyridopyrimidine, pyridopyrazine, pyrazinopyrazine, isoquinoline, indole, carbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiophen, dibenzothiophen, benzofuran, phenanthridine, phenanthroline, isooxazole, and thiadiazole. Dibenzofuran group, dibenzosilol group, phenoxanthine group (phenoxathiine), phenoxazine group, phenothiazine group, dihydroindenocarbazole group, spiroflurenxanthen group, and spiroflurentioxanthen group are included, but are not limited to these.

[0142] In this specification, an arylene group refers to a group having two binding sites to an aryl group, i.e., a divalent group. Except for the fact that each of these is a divalent group, the description of the aryl group described above may apply.

[0143] In this specification, a heteroarylene group refers to a heteroaryl group having two binding sites, i.e., a divalent group. Except for the fact that each of these is a divalent group, the description of the heteroaryl group described above may apply.

[0144] According to one embodiment of the present specification, L is a substituted or unsubstituted arylene group.

[0145] According to one embodiment of the present specification, L is a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

[0146] According to one embodiment of the present specification, the L is selected as any one of the following structures.

[0147]

[0148] According to one embodiment of the present specification, L1 and L11 are the same or different from each other and are each independently directly bonded; or are a single or polycyclic arylene group having 6 to 30 carbon atoms.

[0149] According to one embodiment of the present specification, L1 and L11 are the same or different from each other and are each independently directly bonded; or are phenylene groups.

[0150] According to one embodiment of the present specification, at least one of G1 to G5 is a halogen group, and the remainder is hydrogen; deuterium; or a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms.

[0151] According to one embodiment of the present specification, at least one of G1 to G5 is a fluoro group, and the remainder is hydrogen; deuterium; or a methyl group.

[0152] According to one embodiment of the present specification, at least one of G11 to G15 is a halogen group, and the remainder is hydrogen; deuterium; or a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms.

[0153] According to one embodiment of the present specification, at least one of G11 to G15 is a fluoro group, and the remainder is hydrogen; deuterium; or a methyl group.

[0154] According to one embodiment of the present specification, of the formula 1 and They are the same or different from each other, and each is independently selected from the following structures.

[0155]

[0156] According to one embodiment of the present specification, of the formula 1 and They are identical to each other.

[0157] According to one embodiment of the present specification, of the formula 1 and They are different from each other.

[0158] According to one embodiment of the present specification, Ar1 and Ar11 are the same or different from each other, and each is independently L'-R', where L' is a direct bond, -O-, -S-, -CH2-, -C H2 O-, -OCH2-, or -CH2OCH2-, and R' is any one of the structures selected from the following.

[0159]

[0160] According to one embodiment of the present specification, R1 and R11 are the same or different from each other and are each independently hydrogen; or a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms that is substituted or unsubstituted.

[0161] According to one embodiment of the present specification, R1 and R11 are the same or different from each other and are each independently hydrogen; or a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms.

[0162] According to one embodiment of the present specification, R1 and R11 are the same or different from each other and are each independently hydrogen; or a methyl group.

[0163] According to one embodiment of the present specification, R2, R3, R12 and R13 are hydrogen.

[0164] According to one embodiment of the present specification, the fluorene-based diamine compound of step (s3) is any one selected from the following compounds.

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171] .

[0172] According to one embodiment of the present specification, the cured product of the fluorene-based diamine compound is for organic light-emitting devices.

[0173] According to one embodiment of the present specification, the cured product of the fluorene-based diamine compound is included in the hole injection layer or hole transport layer of an organic light-emitting diode.

[0174] According to one embodiment of the present specification, the method for producing the fluorene-based diamine compound includes only a filtering step without column purification, and has the advantage of being simple and not having any loss of product yield due to the product remaining in the column during conventional column purification.

[0175] Hereinafter, to specifically explain this specification, examples will be described in detail. However, the embodiments according to this specification may be modified in various different forms, and the scope of this specification is not to be interpreted as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain this specification to those with average knowledge in the art.

[0176] Example 1-1

[0177]

[0178] 1) A1 (1eq), B1 (2.05eq), NaOtBu (5eq), Pd2(dba)3 (0.03eq), and XPhos (0.06eq) were placed in a 2-neck round-bottom flask and nitrogen was applied.

[0179] 2) Toluene (0.1M) was added to 1) in a round-bottom flask and stirred at 70°C for 1 hour.

[0180] Example 2-1, and Comparative Example 1-1

[0181] The above Example 1 was carried out in the same manner, except that the organometallic catalyst and ligand of Table 1 below were used instead of Pd2(dba)3 and XPhos in 1).

[0182] The purity values ​​of Example 1-1, Example 2-1, and Comparative Example 1-1 according to one embodiment of the present specification, measured by HPLC, are shown in Table 1 below.

[0183] 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 Pd2(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 Pd2(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

[0184] - Pd2(dba)3: Tris(dibenzylideneacetone)dipalladium(0)

[0185] - BTP: Bis(tri-tert-butylphosphine)palladium(0)

[0186] - P(tBu)3: Tri-tert-butylphosphine

[0187] - XPhos: 2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl

[0188] In Table 1 above, it can be seen that the fluorene-based diamine compound prepared by Example 1-1 or Example 2-1, which is a manufacturing method according to one embodiment of the present specification, has a higher purity than the compound prepared by Comparative Example 1-1, which is a conventional method.

[0189] This indicates that the manufacturing method of Examples 1-1 and 2-1, which includes both an organometallic catalyst and a ligand, promotes the reaction of the starting material and causes almost no side reactions compared to Comparative Example 1-1, which includes only an organometallic catalyst, and thus the fluorene-based diamine compound produced by the above method has a higher purity than the compound produced by the method of Comparative Example 1-1.

[0190] Examples 1-2

[0191] 1) After cooling 2) of Example 1-1 above to 50°C, the reaction was terminated with an aqueous NH4Cl solution, and then ethyl acetate was added to work up, followed by working up with an aqueous NaHCO3 solution and water in sequence.

[0192] 2) After work-up, the product was dehydrated by treatment with MgSO4 and concentrated until the amount of solvent was five times the theoretical yield (mass).

[0193] 3) Isopropyl alcohol (25V) was added dropwise to the solution concentrated in 4) to precipitate it, and then the mixture was stirred for about three hours and filtered.

[0194] After drying the filter cake in a vacuum oven, it was dissolved in toluene (1.5V) and heptane (1V).

[0195] The solution of 4) 6) was filtered onto an alumina (neutral) (15V) / silica (3V) pad using a Toluene:heptane=1:1 (v / v) eluent.

[0196] 5) The process of concentrating the eluent from 7) under reduced pressure, dissolving it in toluene (5V), precipitating it in IPA (25V), and filtering it was repeated two more times.

[0197] 6) After filtering, the filter cake was spread thinly on a tray and dried in a vacuum oven.

[0198] 7) P1 was obtained as a white solid with 99.55% purity at 260 nm, 99.67% purity at 364 nm, and a yield of 65%.

[0199] According to one embodiment of the present specification, the purity was measured using HPLC.

[0200] Comparative Example 1-2

[0201] 1) After cooling 2) of Example 1-1 above to room temperature, ethyl acetate, brine, and water were added to extract with ethyl acetate / brine, and then treated with MgSO4 and filtered with celite.

[0202] 2) After removing all the solvent from the solution of 1), it was dissolved again in dichloromethane and placed in a 2L round-bottom flask. Then, silica (190 g) was added in an amount equal to twice the theoretical yield weight of P1 (95 g in the above case) for adsorption. (60 o C, 0 torr)

[0203] 3) The adsorbate from 2) was divided into a loading cartridge and purified by primary MPLC (Medium pressure liquid chromatography) under 0→20→25→30% dichloromethane conditions to obtain P1 (260 nm purity 97.1%).

[0204] 4) Dissolve the purified product of 3) in dichloromethane, adsorb it onto 190 g of silica, and divide the adsorbed product into loading cartridges.

[0205] 5) Secondary purification was performed using MPLC (Medium Pressure Liquid Chromatography) under 0→10→20% ethyl acetate conditions. (260 nm purity 97.1%)

[0206] 6) The solid obtained in 5) was dissolved in dichloromethane and filtered using a Florisil filter.

[0207] 7) After evaporating the solvent from the solution of 6), the solution was dissolved in dichloromethane, 500 mL of a dichloromethane:ethanol (DCM:EtOH)=1:1 (v / v) solvent was added, and only the dichloromethane was evaporated and crystallized at 280 torr and 40 ℃, and stirred for 2 hours.

[0208] 8) 7) was washed with ethanol after filtering.

[0209] 9) 8) was spread thinly on a tray and dried in a vacuum oven to obtain P1 as a white solid with 99.5% purity at 260 nm, 99.6% purity at 364 nm, and a yield of 55%.

[0211] When comparing Example 1-2, in which the fluorene-based diamine compound of Example 1-1 was filter-purified according to one embodiment of this specification, with Comparative Example 1-2, in which the fluorene-based diamine compound of Example 1-1 was conventionally column-purified, it can be seen that Example 1-2 makes it easier to produce the target compound compared to the compound produced by Comparative Example 1-2, which is a conventional method; the process is simplified compared to Comparative Example 1-2, making the cost of the process more economical compared to Comparative Example 1-2; and unnecessary processes are reduced, resulting in a higher yield of the produced compound.

[0212] In the case of Comparative Example 1-2, which is a conventional method, the process becomes complex due to column purification, and thus efficiency is reduced in terms of economy due to the complex process. In addition, the yield of the compound is lowered due to the loss of product resulting from the product remaining in the reactor and column while undergoing the complex process.

[0213] However, since the method for manufacturing a fluorene-based diamine compound according to the present specification, Example 1-2, can simplify the process by undergoing filter purification without undergoing a column purification process, it is possible to secure manufacturing efficiency and economic feasibility, scale up for mass production of the target compound is easy, and the yield of the compound is high because it is a simple manufacturing method through a filter process that does not involve multiple processes.

Claims

Claim 1 (s1) a step of adding a diamine compound containing an arylamine group, a fluorene bromide compound, an organometallic catalyst, and a ligand to each of the two ends of a spirofluorene ring and substituting nitrogen; (s2) a step of adding a first organic solvent to the product of step (s1) and stirring; A method for preparing a fluorene-based diamine compound comprising the step of (s3) filtering the product of step (s2) using a second organic solvent and an alkane as eluent, wherein the organometallic catalyst is Pd2(dba)3(Tris(dibenzylideneacetone)dipalladium(0)), the ligand is P(tert-Bu)3(Tri-tert-butylphosphine) or XPhos(2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl), the first organic solvent is toluene, the second organic solvent is toluene, and the alkane is n-heptane. Claim 2 delete Claim 3 A method for preparing a fluorene-based diamine compound according to claim 1, wherein in step (s1), the fluorene bromide compound is included in an amount of 2 to 2.1 equivalents relative to 1 equivalent of the diamine compound. Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 A method for preparing a fluorene-based diamine compound according to claim 1, wherein in step (s3), the ratio of the second organic solvent to the alkane is 1:0.1 (v / v) to 1:10 (v / v). Claim 9 A method for producing a fluorene-based diamine compound according to claim 1, wherein the filtering step in step (s3) uses a filter comprising alumina. Claim 10 A method for producing a fluorene-based diamine compound according to claim 1, wherein the filtering step in step (s3) uses a filter comprising alumina and silica. Claim 11 A method for preparing a fluorene-based diamine compound according to claim 1, wherein the fluorene-based diamine compound is represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, L is And, L1 and L11 are the same or different from each other and are each independently a single bond; a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group; Ar1 ​​and Ar11 are the same or different from each other and are each independently a photocurable group; or a thermocurable group; at least one of G1 to G5 is a halogen group, and the remainder is hydrogen; deuterium; or a substituted or unsubstituted alkyl group; at least one of G11 to G15 is a halogen group, and the remainder is hydrogen; deuterium; or a substituted or unsubstituted alkyl group; R1 to R3 and R11 to R13 are the same or different from each other and are each independently hydrogen; deuterium; 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 is a substituted or unsubstituted heteroaryl group, r1 is an integer from 1 to 5, and if r1 is 2 or more, the 2 or more R1s are the same or different from each other, r2 is an integer from 1 to 4, and if r2 is 2 or more, the 2 or more R2s are the same or different from each other, r3 is an integer from 1 to 3, and if r3 is 2 or more, the 2 or more R3s are the same or different from each other, r11 is an integer from 1 to 5, and if r11 is 2 or more, the 2 or more R11s are the same or different from each other, r12 is an integer from 1 to 4, and if r12 is 2 or more, the 2 or more R12s are the same or different from each other, r13 is an integer from 1 to 3, and if r13 is 2 or more, the 2 or more R13s are the same or different from each other. Claim 12 A 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: . Claim 13 A method for manufacturing a fluorene-based diamine compound according to claim 1, wherein the cured product of the fluorene-based diamine compound is for organic light-emitting diodes. Claim 14 A method for manufacturing a fluorene-based diamine compound according to claim 1, wherein the cured product of the fluorene-based diamine compound is included in the hole injection layer or hole transport layer of an organic light-emitting diode.

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