KR20170120767A - Compound for organic electric element, organic electric element comprising the same and electronic device thereof - Google Patents

Abstract

The present invention provides a compound represented by chemical formula 1, an organic electric device using the same, and an electronic device comprising the organic electric device. According to the present invention, the compound has a nitrogen atom incorporated in a six membered ring heterocyclic core backbone, and may be used as a material for an organic electric device to lower driving voltage of the organic electric device, and drastically improve luminous efficiency and lifetime of the device.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for organic electroluminescent devices, an organic electroluminescent device using the same, and an electronic device using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent (EL)

  TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

In the case of a polycyclic ring compound containing a hetero atom, the difference in characteristics depending on the material structure is very large and is applied to various layers as a material of an organic electric device. Especially, it has a feature that the bandgap (HOMO, LUMO), electrical characteristic, chemical property and physical property are different according to the number of rings and fused position, kind and arrangement of heteroatoms, Has progressed.

For example, U.S. Patent Application Publication No. 2008/0145708 A1 (2008.06.19) discloses an embodiment in which a polycyclic ring compound is applied to a hole transporting layer or a phosphorescent host of an organic electronic device, and Korean Patent Laid-Open Publication No. 10-2007-0012218 (Jan. 25, 2007) discloses an embodiment in which a polycyclic ring compound is applied to an electron transport layer of an organic electronic device. At present, development of materials for organic electronic devices with respect to kinds, number and position of heteroatoms of polycyclic ring compounds is actively under way.

Disclosure of the Invention An object of the present invention is to provide a compound capable of improving the luminous efficiency and lifetime of a device while lowering the driving voltage of the device using the characteristics of the polycyclic ring compound, an organic electric device using the organic compound, and an electronic device thereof.

In one aspect, the invention provides compounds of the formula:

The present invention also provides an organic electronic device using the compound having the above formula and a terminal including the organic electronic device.

According to the present invention, by using a specific compound in which N is introduced into a six-ring heterocyclic core backbone as a material for an organic electric device, a HOMO, LUMO energy level and a high T1 value The driving voltage of the organic electronic device can be lowered, and the luminous efficiency and lifetime of the device can be greatly improved.

1 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference numerals whenever possible, even if they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:

The term " halo "or" halogen ", as used herein, unless otherwise indicated, is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I).

As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Alkyl " means a radical of a saturated aliphatic group, including alkyl, cycloalkyl-substituted alkyl groups.

The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise stated.

The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group is replaced by a heteroatom.

The term "alkenyl group" or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups, It is not.

The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

The term "alkoxyl group "," alkoxy group ", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached and, unless otherwise stated, has a carbon number of 1 to 60, It is not.

The term "alkenoyl group "," alkenoyl group ", "alkenyloxy group ", or" alkenyloxy group "as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.

As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group attached to an oxygen radical and, unless otherwise stated, has a carbon number of 6 to 60, but is not limited thereto.

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a fluorene group, a spirobifluorene group, or a spirobifluorene group.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.

Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, the arylalkoxy group means an alkoxy group substituted with an aryl group, the alkoxycarbonyl group means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group means Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.

The term "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings and includes a heteroaliphatic ring and hetero Aromatic rings. Adjacent functional groups may be combined and formed.

As used herein, the term "heteroatom " refers to N, O, S, P or Si unless otherwise stated.

The "heterocyclic group" may also include a ring containing SO ₂ in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.

Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms and an "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

Unless otherwise specified, the term "carbonyl" as used herein refers to -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, A cycloalkyl group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group of 1-20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C of ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group.

Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.

When a is an integer of 0, substituent R ¹ is absent. When a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R ¹ may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.

1 is an illustration of an organic electroluminescent device according to an embodiment of the present invention.

1, an organic electroluminescent device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110, ) Comprising an organic compound layer comprising a compound according to the present invention. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. (Not shown), a buffer layer 141, and the like. The electron transport layer 160 and the like may further serve as a hole blocking layer (not shown). The electron transport layer 160 may include a hole blocking layer, an electron blocking layer, It might be.

Also, although not shown, the organic electroluminescent device according to the present invention may further include a protective layer or a light-efficiency-improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer includes a hole injecting layer 130, a hole transporting layer 140, an electron transporting layer 160, an electron injecting layer 170, an emission auxiliary layer 151, The host of the light emitting layer 150, or the material of the dopant or the light efficiency improving layer. Preferably, the compound of the present invention may be used as the light emitting layer 150.

On the other hand, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at any position even in the same core, the selection of the core and the combination of the sub- In particular, when the optimal combination of the energy level and T1 value and the intrinsic properties (mobility, interfacial characteristics, etc.) between the organic layers is achieved, it is possible to achieve long life and high efficiency at the same time.

Accordingly, in the present invention, by forming the light emitting layer using the compound represented by the general formula (1), it is possible to optimize the energy level and the Tl value between the respective organic layers, the mobility of the material, And efficiency can be improved at the same time.

The organic light emitting device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, and an electron transporting layer 160 and an electron injection layer 170, and then depositing a material usable as the cathode 180 on the organic layer. An emission auxiliary layer 151 may be further formed between the hole transport layer 140 and the emission layer 150 and an electron transport auxiliary layer may be additionally provided between the emission layer 150 and the electron transport layer 160 As shown in FIG.

In addition, the organic material layer may be formed using a variety of polymer materials, not a vapor deposition method, or a solution process or a solvent process such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, It is possible to produce a smaller number of layers by a method such as a dipping process, a screen printing process, or a thermal transfer process. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

The organic electroluminescent device according to the present invention may be of a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.

The organic electroluminescent device according to the present invention may be one of an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), or a monochrome or white illumination device.

Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. The electronic device may be a current or future wired or wireless communication terminal and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound according to one aspect of the present invention will be described. A compound according to one aspect of the present invention is represented by the following formula (1).

1) A and B are each independently any one of NL ¹ -Ar ¹ , S, O, C (R ^a ) (R ^b )

2) m and n are integers of 0 or 1, m + n is 1 or more,

(Where A is a single bond when m is 0 and B is a single bond when n is 0)

3) X is any one of NL ² -Ar ² , S, O, C (R ^c ) (R ^d )

4) Z ¹ to Z ¹² are each independently CR ¹ or N, and at least one of Z ¹ to Z ¹² is N, and when at least two of Z ¹ to Z ¹² are CR ¹ , each CR ¹ is independently Are the same or different,

5) Ar ¹ and Ar ² are each independently a C ₆ -C ₆₀ aryl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fluorenyl group; A fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; A C ₆ -C ₃₀ aryloxy group, and -L ^a -N (R ^e ) (R ^f )

6) R ¹ is hydrogen; heavy hydrogen; Tritium; halogen; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; -L ^a -N (R ^e ) (R ^f ); A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group, or adjacent R ^{1 s} may be bonded to each other to form a ring, R ¹ , which does not form a ring, is the same as defined above,

7) R ^a to R ^f independently of one another are hydrogen; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group, or R ^a and R ^b or R ^c and R ^d may combine with each other to form a spiro compound together with C to which they are bonded, or R ^e and R ^f may combine with each other to form a ring,

8) L ¹ , L ² and L ^a independently of one another are a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And an aliphatic hydrocarbon group,

Here, each of the aryl group, the arylene group, the fluorenyl group, the fluorenylene group, the heterocyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxy group and the aryloxy group may be deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; -N (R ^g ) (R ^h ); And aryl alkenyl group of C ₈ -C _20; may be substituted with one or more substituents selected from the group consisting of and (wherein R ^g and R ^h are each independently an aryl group of C ₆ -C _60; fluorene group And a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si, and P; when these substituents are adjacent to each other, To form a ring.

The aryl group may be an aryl group having 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and the heterocyclic group may have 2 to 60 carbon atoms, preferably 2 carbon atoms More preferably 1 to 30 carbon atoms, more preferably 2 to 24 carbon atoms, and in the case of the alkyl group, the number of carbon atoms is 1 to 50, preferably 1 to 30, more preferably 1 to 20, May be an alkyl group of 1 to 10 carbon atoms.

Specifically, when the aryl group or the arylene group is the aryl group or the arylene group, the aryl group or the arylene group may be independently selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a triphenylene group, a pyrene group, a benzochrysene group, Or a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group or a phenanthrylene group.

Specifically, the formula (1) may be represented by one of the following formulas (2) and (3). Herein, the formula (2) is a case where n in the formula (1) is '0', and the formula (3) is a case where m is '0'.

In Formulas 2 and 3, A, B, X and Z ¹ to Z ¹² are the same as A, B, X and Z ¹ to Z ¹² defined in Formula 1 above.

The formula (1) may be represented by one of the following formulas (4) to (11).

In the above Chemical Formulas 4 to 11, A, B, Z ¹ to Z ¹² , L ² , Ar ² , R ^c and R ^d represent A, B, Z ¹ to Z ¹² , L ² , Ar ² , R ^c and R ^d .

The formula 1 may be represented by one of the following formulas (12) to (19).

In the above Chemical Formulas 12 to 19,

1) A, B, X and Z ¹ to Z ¹² are the same as A, B, X and Z ¹ to Z ¹² defined in the above formula (1)

2) Y is the same as defined in X of claim 1,

3) Z ¹³ to Z ²⁴ are independently of each other CR ² or N,

4) R ² is hydrogen; heavy hydrogen; Tritium; halogen; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ aryloxy groups, or adjacent R ² groups may be bonded to each other to form a ring, and R ² which does not form a ring is the same as defined above.

More specifically, the compound represented by Formula 1 may be any one of the following compounds, but is not limited to the following compounds.

In another embodiment, the present invention provides a compound for an organic electroluminescent device represented by the general formula (1).

In another embodiment, the present invention provides an organic electronic device containing the compound represented by the above formula (1).

The organic electroluminescent device includes a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Formula 1, and the compound represented by Formula 1 may include a hole injecting layer, a hole transporting layer, , The light emitting auxiliary layer, the light emitting layer, the electron transporting auxiliary layer, the electron transporting layer and the electron injecting layer.

That is, the compound represented by the general formula (1) can be used as a material for the hole injecting layer, the hole transporting layer, the light emitting auxiliary layer, the light emitting layer, the electron transporting auxiliary layer, the electron transporting layer or the electron injecting layer. In particular, the compound represented by the general formula (1) can be used as a phosphorescent host material of the light emitting layer. Specifically, the organic electroluminescent device includes one of the compounds represented by the formula (1), and more specifically, And an organic material layer containing a compound represented by the above-mentioned individual formulas (P1-1 to P2-85).

In another embodiment, at least one of the hole injecting layer, the hole transporting layer, the light emitting auxiliary layer, the light emitting layer, the electron transporting auxiliary layer, the electron transporting layer, and the electron injecting layer of the organic material layer contains Or an organic electroluminescent device characterized in that the compound is contained in combination of two or more different compounds, or the compound is contained in combination with two or more kinds of other compounds. In other words, each of the layers may contain a compound corresponding to the formula (I) alone or a mixture of two or more compounds of the formula (I), and the compound of the formula (I) Mixtures may be included. Herein, the compound not corresponding to the present invention may be a single compound or may be two or more compounds. When the compound is contained in combination with two or more kinds of other compounds, the other compound may be a known compound of each organic layer or a compound to be developed in the future. At this time, the compound contained in the organic material layer may be composed of the same kind of compound, but it may be a mixture of two or more different kinds of compounds represented by the general formula (1).

In another embodiment of the present invention, the light efficiency improving layer is formed on at least one side of the one side of the first electrode opposite to the organic layer, or one side of the one side of the second electrode opposite to the organic layer, And an organic electroluminescent device.

Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.

[ Synthetic example ]

The compounds represented by formula (1) according to the present invention are synthesized by the reaction path of the following reaction formula (1) and (2), but are not limited thereto.

A, B, X, Z ¹ to Z ¹² , m and n are the same as defined in formula (1), and Hal ⁵ is Br or Cl.

I. Synthesis of Sub 1A, Sub 1B

Sub 1A of Reaction Scheme 1 and Sub 1B of Reaction Scheme 2 may be synthesized by the reaction path of Reaction Scheme 3 and Reaction Scheme 4, but the present invention is not limited thereto.

Hal ¹ and Hal ⁴ are I, Br or Cl, Hal ² is I or Br, and Hal ³ is Br or Cl.

M < 1 > in the above Reaction Scheme 3 can be synthesized by the reaction path of the following Reaction Schemes 5 to 7.

When A or B is NL ¹ -Ar ¹ , Sub 1A of Scheme 1 can also be synthesized by the reaction path of Reaction Scheme 8 below.

Examples of the synthesis of specific compounds belonging to Sub 1 are as follows.

1. Sub 1A-1 Synthetic example

(1) Synthesis of M 1-I-1

2-bromo-3-nitropyridine (CAS Registry Number: 19755-53-4) (82.34 g, 405.62 mmol) was dissolved in DMF (2030 ml) into a round bottom flask and then bis (pinacolato) diboron 446.18 mmol), Pd (dppf) Cl 2 (9.94 g, 12.17 mmol), KOAc (119.42 g, 1216.85 mmol) was added and stirred at 90 ° C. When the reaction was complete, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 54.77 g (yield: 54%) of the product.

(2) Synthesis of M 1-II-1

M-I-1 (54.77 g, 219.03 mmol) obtained in the above synthesis was dissolved in THF (760 ml) in a round bottom flask and then 1-bromo-3-iodobenzene (CAS Registry Number: 591-18-4) g, 240.93 mmol), Pd ( PPh 3) 4 (10.12 g, 8.76 mmol), NaOH (26.28 g, 657.08 mmol), water (380ml) was added and the mixture was stirred at 80 DEG C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 44.62 g (yield: 73%) of the product.

(3) Synthesis of M 1 -III-1

M 1-II-1 (44.62 g, 159.88 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (1340 ml) in a round bottom flask, and then triphenylphosphine (104.84 g, 399.69 mmol) was added and stirred at 200 ° C. When the reaction was complete, o- dichlorobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 16.59 g (yield: 42%) of the product.

(4) Synthesis of M 1-1 Synthesis

(16.59 g, 67.14 mmol) obtained in the above synthesis was dissolved in toluene (670 ml) in a round-bottomed flask and Sub 2-1 (CAS Registry Number: 591-50-4) (13.70 g, 67.14 was added _{mmol), Pd 2 (dba)} 3 (1.84 g, 2.01 mmol), 50% P (t -Bu) 3 (2.0ml, 4.03 mmol), NaO t -Bu (19.36 g, 201.42 mmol) and 100 DEG C < / RTI > After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 14.32 g of the product (yield: 66%).

(5) Sub 1A-I'-1 synthesis

The starting material, 8-iodonaphthalen-1-yl) methyl sulfane (CAS Registry Number: 1705595-89-6) (155.16 g, 516.92 mmol) and vanadium (V) oxide (9.40 g, 51.69 mmol) After dissolving in a flask with acetonitrile (2070 ml), the temperature was lowered to 0 ° C using an ice bath, and 35% H ₂ O ₂ (70.7 ml, 775.39 mmol) was added and stirred at 10 ° C. After the reaction was completed, water was added to the reaction mixture, the temperature was slowly raised to room temperature, and the mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO ₄ and concentrated to obtain 130.74 g of the product (yield: 80%).

(6) Sub 1A-I-1 synthesis

After the Sub 1A-I'-1 (130.74 g, 413.52 mmol) obtained in the above synthesis in a round bottom flask was dissolved in DMF (1650ml), Bis (pinacolato ) diboron (115.51 g, 454.88 mmol), Pd (dppf) Cl 2 (10.13 g, 12.41 mmol), KOAc (121.75 g, 1240.57 mmol) was added and stirred at 90 ° C. When the reaction was complete, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 91.54 g (yield: 70%) of the product.

(7) Sub 1A-1 synthesis

Sub-1A-I-1 (13.29 g, 42.03 mmol) obtained in the above synthesis was dissolved in THF (140 ml) in a round bottom flask and then M 1-1 (13.58 g, 42.03 mmol), Pd (PPh ₃ ) ₄ g, 1.68 mmol), NaOH (5.04 g, 126.08 mmol) and water (70 ml), and the mixture was stirred at 80 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 13.63 g (yield: 75%) of the product.

2. Sub 1A-6, Sub 1A-18 Synthetic example

(1) Sub 1A-I'-6 synthesis

Vanadium (V) oxide (3.97 g, 21.80 mmol) and 35% H ₂ O were added to the starting material, 4-chloro-5- (methylthio) quinolone (CAS Registry Number: 1824098-83-0) (45.72 g, 218.04 mmol) ₂ (29.8 ml, 327.05 mmol) and acetonitrile (1090 ml) were added, and 34.94 g (yield: 71%) of the product was obtained using the Sub 1A-I'-1 synthesis method.

(2) Sub 1A-I-6 synthesis

Bis (pinacolato) diboron (43.24 g, 170.30 mmol), Pd (dppf) Cl ₂ (34.94 g, (3.79 g, 4.64 mmol), KOAc (45.58 g, 464.44 mmol) and DMF (775 ml) were added, and 33.39 g (Yield: 68%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(3) Sub 1A-II-6 synthesis

(CAS Registry Number: 16807-11-7) (25.91 g, 105.26 mmol) and Pd (PPh ₃ ) ₄ (33.39 g, 105.26 mmol) were added to Sub 1A-I- 28.89 g (Yield: 77%) of the product was obtained using the Sub 1A-1 synthesis method by adding 4.87 g, 4.21 mmol), NaOH (12.63 g, 315.78 mmol), THF (350 ml) and water (175 ml).

(4) Sub 1A-6 synthesis

Sub 1A-II-6 (13.61 g, 38.18 mmol) obtained in the above synthesis was dissolved in toluene (380 ml) in a round bottom flask and Sub 2-51 (CAS Registry Number: 80984-79-8) (11.92 g, 38.18 was added _{mmol), Pd 2 (dba)} 3 (1.05 g, 1.15 mmol), 50% P (t -Bu) 3 (1.1ml, 2.29 mmol), NaO t -Bu (11.01 g, 114.55 mmol) and 100 DEG C < / RTI > After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 17.95 g (yield: 80%) of the product.

(5) Sub 1A-18 synthesis

Obtained in the above Synthesis Sub 1A-II-6 (14.97 g, 42.00 mmol) in Sub 2-81 (12.21 g, 42.00 mmol ), Pd 2 (dba) 3 (1.15 g, 1.26 mmol) 50% P (t -Bu _{) 3 (1.2ml, 2.52 mmol)} , NaO t -Bu (12.11 g, 126.00 mmol), was added to toluene (420ml) and the Sub 1A-6 synthesis using the product 18.72 g (yield: 73% was obtained).

3. Sub 1A-22 Synthetic example

(1) Synthesis of M 1-II-22

4-bromo-2-iodopyridine (CAS Registry Number: 100523-83-9) (47.22 g, 166.32 mmol) was added to M-I-22 (CAS Registry Number: 100523-83-9) (37.66 g, 151.20 mmol) _{, Pd (PPh 3) 4 (} 6.99 g, 6.05 mmol), NaOH (18.14 g, 453.61 mmol), THF (530ml), was added to water (265ml) using the M 1-II-1 synthesis product 27.43 g (Yield: 65%).

(2) Synthesis of M 1 -III-22 Synthesis

Triphenylphosphine (64.45 g, 245.71 mmol) and o- dichlorobenzene (860 ml) were added to M 1 -II-22 (27.43 g, 98.28 mmol) obtained in the above synthesis and 14.09 g (Yield: 58%).

(3) Sub 1A-II-22 synthesis

(14.04 g, 56.83 mmol), Pd (PPh ₃ ) ₄ (2.63 g, 2.27 mmol) and NaOH (6.82 g, 56.83 mmol) were added to Sub 1A-I- , 170.48 mmol), THF (190 ml) and water (95 ml) were added, and 14.58 g (Yield: 72%) of the product was obtained using the Sub 1A-1 synthesis method.

(4) Sub 1A-22 synthesis

Obtained in the above Synthesis Sub 1A-II-22 (14.58 g, 40.90 mmol) in Sub 2-93 (14.19 g, 40.90 mmol ), Pd 2 (dba) 3 (1.12 g, 1.23 mmol) 50% P (t -Bu _{) 3 (1.2ml, 2.45 mmol)} , NaO t -Bu (11.79 g, 122.71 mmol), was added to toluene (410ml) and the Sub using a 1A-6 synthesis product was 20.73 g (yield: yield 76%).

4. Sub 1A-37 Synthetic example

(1) Sub 1A-I-37 synthesis

Bis (pinacolato) diboron (27.66 g, 108.94 mmol) and Pd (dppf) Cl ₂ (2.43 g, 99.04 mmol) were added to the starting material, 5-bromoisoquinolin-4-ol (CAS Registry Number: 1779748-39-8) g, 2.97 mmol), KOAc (29.16 g, 297.11 mmol) and DMF (395 ml), and 19.33 g of the product (yield: 72%) was obtained using the Sub 1A-I-1 synthesis method.

(2) Sub 1A-II-37 synthesis

(CAS Registry Number: 16807-11-7) (17.55 g, 71.30 mmol) and Pd (PPh ₃ ) ₄ (19.33 g, 71.30 mmol) were added to Sub 1A- (Yield: 81%) of the product was obtained by adding Sub-1A-1 synthesis method by adding NaOH (8.56 g, 213.89 mmol), THF (240 ml) and water (120 ml).

(3) Sub 1A-37 synthesis

Obtained in the above Synthesis Sub 1A-II-37 (17.92 g, 57.74 mmol) in Sub 2-95 (22.34 g, 57.74 mmol ), Pd 2 (dba) 3 (1.59 g, 1.73 mmol) 50% P (t -Bu _{) 3 (1.7ml, 3.46 mmol)} , NaO t -Bu (16.65 g, 173.22 mmol), was added to toluene (575ml) and the Sub 1A-6 synthesis using the product 28.23 g (yield: 74% was obtained).

5. Sub 1A-48 Synthetic example

(1) M 1 -I'-48 synthesis

(91.57 g, 262.97 mmol), which is the starting material, was dissolved in THF (920 ml) in a round-bottomed flask and then (2 , 6-dibromophenyl) (methyl) sulfane (CAS Registry Number: 301151-74-6) (81.57 g, 289.27 mmol), Pd (PPh 3) 4 (12.16 g, 10.52 mmol), NaOH (31.56 g, 788.92 mmol) , Water (460 ml) was added, and the mixture was stirred at 80 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 115.64 g (yield: 87%) of the product.

(2) Synthesis of M 1 -I "-48

After dissolving M 1 -I'-48 (115.64 g, 228.78 mmol) and vanadium (V) oxide (4.16 g, 22.88 mmol) obtained in the above synthesis in a round bottom flask with acetonitrile (915 ml) The temperature was lowered to 0 ° C and 35% H ₂ O ₂ (31.3 ml, 343.17 mmol) was added and stirred at 10 ° C. After the reaction was completed, water was added to the reaction mixture, the temperature was slowly raised to room temperature, and the mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO ₄ and concentrated to obtain 88.28 g of the product (yield: 74%).

(3) Synthesis of M 1-I-48

Bis (pinacolato) diboron (47.29 g, 186.22 mmol), Pd (dppf) CI ₂ (88.28 g, 169.29 mmol) (4.15 g, 5.08 mmol), KOAc (49.84 g, 507.87 mmol) and DMF (675 ml) were added, and 77.00 g (Yield: 80%) of the product was obtained using the M 1 -I-1 synthesis method.

(4) Synthesis of M 1-II-48

4-bromo-2-iodopyridine (CAS Registry Number: 100523-83-9) (42.29 g, 148.98 mmol) and Pd (PPh ₃ ) ₄ (77.00 g, 135.43 mmol) (Yield: 63%) of the product was obtained using the above M 1-II-1 synthesis method by the addition of triethylamine (6.26 g, 5.42 mmol), NaOH (16.25 g, 406.30 mmol), THF (470 ml) .

(5) M 1-48 Synthesis

(51.07 g, 85.32 mmol) obtained in the above synthesis was added to a round bottom flask together with triflic acid (113.3 ml, 1279.82 mmol), stirred at room temperature for 24 hours, and then pyridine aqueous solution (ml, H ₂ O = 1: 5) was slowly added dropwise and the mixture was refluxed with stirring for 30 minutes. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 22.23 g of the product (yield: 46%).

(6) Sub 1A-48 synthesis

Obtained in the above Synthesis Sub 1A-I-1 (12.41 g, 39.24 mmol) in M 1-48 (22.23 g, 39.24 mmol ), Pd (PPh 3) 4 (1.81 g, 1.57 mmol), NaOH (4.71 g, 117.73 mmol), THF (130 ml) and water (65 ml) were added, and 18.57 g (yield: 70%) of the product was obtained using the Sub 1A-1 synthesis method.

6. Sub 1A-53 Synthetic example

(1) Sub 1A-I'-53 Synthesis

The starting material, 2,4-dichloroquinazolin-5-ol ( CAS Registry Number: 1379310-92-5) was dissolved the (21.72 g, 101.01 mmol) in THF (350ml) in a round bottom flask, 2- (dibenzo [b, d] thiophen-4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS Registry Number: 912824-84-1) (34.47 g, 111.11 mmol), Pd (PPh 3) ₄ (4.67 g, 4.04 mmol), NaOH (12.12 g, 303.03 mmol) and water (175 ml) were added and stirred at 80 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column and recrystallization to obtain 20.52 g (yield: 56%) of the product.

(2) Sub 1A-53 synthesis

Sub 1A-I'-53 (20.52 g, 56.56 mmol) obtained in the above synthesis was dissolved in toluene (565 ml) in a round bottom flask and 14H-benzo [ c ] benzo [4,5] thieno [2,3- a ] carbazole (CAS Registry Number: 1313395-18-4 ) (18.29 g, 56.56 mmol), Pd 2 (dba) 3 (1.55 g, 1.70 mmol), 50% P (t -Bu) 3 (1.7ml, 3.39 mmol ) And NaO t- Bu (16.31 g, 169.67 mmol) were added, and the mixture was stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 26.83 g (yield: 73%) of the product.

7. Sub 1A-70 Synthetic example

(1) Sub 1A-II-70 synthesis

(CAS Registry Number: 1627580-05-5) (20.78 g, 84.09 mmol) and Pd (PPh ₃ ) ₄ (26.59 g, 84.09 mmol) were added to Sub 1A-I- 3.89 g, 3.36 mmol), NaOH (10.09 g, 252.26 mmol), THF (280 ml) and water (140 ml) were added and 21.88 g of the product (yield: 73%) was obtained using the Sub 1A-1 synthesis method.

(4) Sub 1A-70 synthesis

Obtained in the above Synthesis Sub 1A-II-70 (21.88 g, 61.38 mmol) in Sub 2-39 (17.94 g, 61.38 mmol ), Pd 2 (dba) 3 (1.69 g, 1.84 mmol) 50% P (t -Bu _{) 3 (1.8ml, 3.68 mmol)} , NaO t -Bu (17.70 g, 184.15 mmol), was added to toluene (615ml) and the Sub using a 1A-6 synthesis product was 20.21 g (yield: 58% was obtained).

8. Sub 1A-75 Synthetic example

(1) Synthesis of M 1-I-75

Bis (pinacolato) diboron (236.70 g, 932.13 mmol) and Pd (dppf) Cl ₂ (20.76 g, 847.39 mmol) were added to the starting material, 4-bromo-3- nitropyridine (CAS Registry Number: 23056-44-2) g, 25.42 mmol), KOAc (249.49 g, 2542.17 mmol) and DMF (2120 ml) were added, and 118.66 g of the product (yield: 56%) was obtained using the above M 1 -I-1 synthesis method.

(2) Synthesis of M 1-II-75

1-bromo-2-iodobenzene (CAS Registry Number: 583-55-1) (147.67 g, 521.98 mmol) and Pd (PPh ₃ ) ₄ (21.93 g, 474.53 mmol) were added to M 1 -I- 18.98 mmol), NaOH (56.94 g, 1423.58 mmol), THF (1660 ml) and water (830 ml) were added and 95.35 g of the product (yield: 72%) was obtained using the M 1 -II-1 synthesis method.

(3) Synthesis of M 1 -III-75

Triphenylphosphine (224.03 g, 854.12 mmol) and o- dichlorobenzene (2990 ml) were added to M 1 -II-75 obtained in the above synthesis (95.35 g, 341.65 mmol) and 32.92 g (Yield: 39%).

(4) Sub 1A-II-75 Synthesis

To the Sub 1A-I-1 (19.91 g, 62.96 mmol) obtained in the above synthesis, M 1 -III-75 (15.56 g, 62.96 mmol), Pd (PPh ₃ ) ₄ (2.91 g, 2.52 mmol) , 188.89 mmol), THF (210 ml) and water (105 ml) were added, and 17.06 g (Yield: 76%) of the product was obtained using the Sub 1A-1 synthesis method.

(4) Sub 1A-75 synthesis

Obtained in the above Synthesis Sub 1A-II-75 (17.06 g, 47.86 mmol) in Sub 2-70 (15.83 g, 47.86 mmol ), Pd 2 (dba) 3 (1.31 g, 1.44 mmol) 50% P (t -Bu _{) 3 (1.4ml, 2.87 mmol)} , NaO t -Bu (13.80 g, 143.59 mmol), was added to toluene (480ml) and the Sub 1A-6 by using the synthetic product was 18.69 g (yield: 60% was obtained).

9. Sub 1A-95 Synthetic example

(1) Sub 1A-I-95 synthesis

Bis (pinacolato) diboron (32.77 g, 129.05 mmol) and Pd (dppf) Cl ₂ (2.87 g, 117.32 mmol) were added to the starting material, 8-bromonaphthalen-1-ol (CAS Registry Number: 62456-32-0) g, 3.52 mmol), KOAc (34.54 g, 351.95 mmol) and DMF (470 ml) were added, and 27.57 g (Yield: 87%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(2) Sub 1A-II-95 synthesis

M 1 -III-70 (CAS Registry Number: 1627580-05-5) (25.22 g, 102.06 mmol), Pd (PPh ₃ ) ₄ (27.57 g, 102.06 mmol) was added to Sub 1A- 4.72 g, 4.08 mmol), NaOH (12.25 g, 306.17 mmol), THF (340 ml) and water (170 ml) were added and 25.02 g of the product (yield: 79%) was obtained using the Sub 1A-1 synthesis method.

(3) Sub 1A-95 synthesis

Obtained in the above Synthesis Sub 1A-II-95 (25.02 g, 80.62 mmol) in Sub 2-70 (27.96 g, 80.62 mmol ), Pd 2 (dba) 3 (2.21 g, 2.42 mmol) 50% P (t -Bu _{) 3 (2.4ml, 4.84 mmol)} , NaO t -Bu (23.24 g, 241.85 mmol), was added to toluene (805ml) and the Sub 1A-6 synthesis using the product 31.03 g (yield: 62% was obtained).

10. Sub 1A-99 Synthetic example

(1) Sub 1A-I-99 synthesis

Bis (pinacolato) diboron (54.38 g, 214.14 mmol) and Pd (dppf) Cl ₂ (51.88 g, 194.67 mmol) were added to the starting material methyl 1-bromoisoquinoline-8- carboxylate (CAS Registry Number: 1369181-72-5) (4.77 g, 5.84 mmol), KOAc (57.32 g, 584.01 mmol) and DMF (780 ml) were added, and 31.09 g (yield: 51%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(2) Sub 1A-II-99 synthesis

(CAS Registry Number: 3652-89-9) (24.43 g, 99.28 mmol) and Pd (PPh ₃ ) ₄ (31.09 g, 99.28 mmol) were added to Sub 1A- 4.59 g, 3.97 mmol), NaOH (11.91 g, 297.83 mmol), THF (330 ml) and water (165 ml) were added and 27.99 g (Yield: 80%) of the product was obtained using the Sub 1A-1 synthesis method.

(3) Sub 1A-99 synthesis

Obtained in the above Synthesis Sub 1A-II-99 (27.99 g, 79.43 mmol) in Sub 2-102 (33.59 g, 79.43 mmol ), Pd 2 (dba) 3 (2.18 g, 2.38 mmol) 50% P (t -Bu _{) 3 (2.3ml, 4.77 mmol)} , NaO t -Bu (22.90 g, 238.29 mmol), was added to toluene (795ml) and the Sub 1A-6 synthesis using the product 46.36 g (yield: 79% was obtained).

11. Sub 1A-112 Synthetic example

(1) Synthesis of M 1-II-112

1-bromo-2-iodobenzene (CAS Registry Number: 583-55-1) (54.68 g, 193.27 mmol) was added to M 1-I-112 (CAS Registry Number: 1244772-69-7) (38.84 g, 175.70 mmol) _{, Pd (PPh 3) 4 (} 8.12 g, 7.03 mmol), NaOH (21.08 g, 527.10 mmol), THF (610ml), was added to water (305ml) using the M 1-II-1 synthesis product 32.52 g (Yield: 74%).

(2) M 1-112 Synthesis

Put together with _{Pd (OAc) 2 (2.92 g} , 13.00 mmol), 3-nitropyridine (1.61 g, 13.00 mmol) in a round bottom flask for M 1-II-112 (32.52 g, 130.03 mmol) obtained in the above Synthesis C ₆ F ₆ (195 ml) and DMI (130 ml), tert- butyl peroxybenzoate (50.51 g, 260.06 mmol) was added thereto and stirred at 90 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 12.90 g of the product (yield: 40%).

(3) Sub 1A-I'-112 Synthesis

Bis (pinacolato) diboron (24.90 g, 98.04 mmol) and Pd (dppf) were added to the starting material 3-amino-8-bromonaphthalen-1-ol (CAS Registry Number: 1785511-40-1) (21.22 g, 89.13 mmol) Cl ₂ (2.18 g, 2.67 mmol), KOAc (26.24 g, 267.39 mmol) and DMF (445 ml) were added, and 22.87 g (yield: 90%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(4) Sub 1A-I "-112 synthesis

2-bromonaphthalene (CAS Registry Number: 580-13-2) (16.61 g, 80.20 mmol) was dissolved in toluene (800 ml) in a round bottom flask. Sub 1A-I'- was added _{mmol), Pd 2 (dba)} 3 (2.20 g, 2.41 mmol), 50% P (t -Bu) 3 (2.3ml, 4.81 mmol), NaO t -Bu (23.13 g, 240.61 mmol) and 100 DEG C < / RTI > After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 23.75 g (yield: 72%) of the product.

(5) Sub 1A-I-112 synthesis

Sub-1A-I "-112 (23.75 g, 57.74 mmol) obtained in the above synthesis was dissolved in toluene (575 ml) in a round bottom flask and then 3-bromo-1,1'-biphenyl (CAS Registry Number: 2113-57- 7) (13.46 g, 57.74 mmol ), Pd 2 (dba) 3 (1.59 g, 1.73 mmol), 50% P (t -Bu) 3 (1.7ml, 3.46 mmol), NaO t -Bu (16.65 g, 173.23 After the reaction was complete, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 27.33 g of the product (yield: 84 %).

(6) Sub 1A-112 synthesis

The Sub 1A-I-112 (27.33 g, 48.50 mmol) obtained in the above Synthesis M 1-III-112 (12.03 g, 48.50 mmol), Pd (PPh 3) 4 (2.24 g, 1.94 mmol), NaOH (5.82 g , 145.50 mmol), THF (160 ml) and water (80 ml) were added, and 24.05 g (Yield: 82%) of the product was obtained using the Sub 1A-1 synthesis method.

12. Sub 1A-118 Synthetic example

(1) Synthesis of M 1-II-118

3-bromo-4-iodopyridine (CAS Registry Number: 89167-19-1) (83.35 g, 293.60 mmol) was added to M-I-118 (CAS Registry Number: 653589-95-8) (69.96 g, 266.91 mmol) _{, Pd (PPh 3) 4 (} 12.34 g, 10.68 mmol), NaOH (32.03 g, 800.73 mmol), THF (930ml), was added to water (465ml) using the M 1-II-1 synthesis product 54.58 g (Yield: 70%).

(2) M 1-118 Synthesis

Ml-II-118 (54.58 g, 186.83 mmol) obtained in the above synthesis was dissolved in THF (935 ml) in a round bottom flask, and then methylmagnesium bromide 1.0 M in THF (747.3 ml, 747.34 mmol) Lt; / RTI > After the reaction was completed, the reaction mixture was extracted with diethyl ether and water. The organic layer was dried over MgSO ₄ and concentrated to obtain an intermediate product. This intermediate was dissolved in acetic acid (750 ml), HCl (15 ml) was added, and the mixture was refluxed. After the reaction was completed, water was added, and the resulting solid was filtered off under reduced pressure and then washed with water and methanol to obtain 18.95 g (yield: 37% over two steps) of the product as a white powder.

(3) Sub 1A-I-118 synthesis

Bis (pinacolato) diboron (23.55 g, 92.73 mmol), Pd (dppf) Cl ₂ (26.57 g, 84.30 mmol) was added to the starting material, methyl 8-bromophenanthrene-9-carboxylate (CAS Registry Number: 4648-67-3) (2.07 g, 2.53 mmol), KOAc (24.82 g, 252.91 mmol) and DMF (420 ml) were added, and 25.04 g (yield: 82%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(4) Sub 1A-118 synthesis

To a Sub 1A-118 (25.04 g, 69.13 mmol) obtained in the above synthesis, M 1 -III-118 (18.95 g, 69.13 mmol), Pd (PPh ₃ ) ₄ (3.20 g, 2.77 mmol) and NaOH , 207.38 mmol), THF (230 ml) and water (115 ml) were added, and 26.43 g of the product (yield: 89%) was obtained using the Sub 1A-1 synthesis method.

13. Sub 1B-11 Synthetic example

(1) Sub 1B-I-11 synthesis

Bis (pinacolato) diboron (22.54 g, 88.76 mmol) and Pd (dppf) Cl ₂ (1.98 g, 80.69 mmol) were added to the starting material 4-bromo-5-nitroquinoline (CAS Registry Number: 933486-44-3) g, 2.42 mmol), KOAc (23.76 g, 242.08 mmol) and DMF (400 ml) were added, and 17.92 g (yield: 74%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(2) Sub 1B-II-11 Synthesis

(CAS Registry Number: 16807-11-7) (14.70 g, 59.71 mmol) and Pd (PPh ₃ ) ₄ (17.92 g, 59.71 mmol) were added to Sub 1B-I- 1.95 g (Yield: 59%) of the product was obtained by using Sub 1A-1 synthesis method by adding 2.76 g, 2.39 mmol), NaOH (7.17 g, 179.13 mmol), THF (200 ml) and water (100 ml).

(3) Sub 1B-III-11 Synthesis

Obtained in the above Synthesis Sub 1B-II-11 (11.95 g, 35.21 mmol) in Sub 2-81 (10.24 g, 35.21 mmol ), Pd 2 (dba) 3 (0.97 g, 1.06 mmol) 50% P (t -Bu ) ₃ (1.0 ml, 2.11 mmol), NaO t- Bu (10.15 g, 105.64 mmol) and toluene (350 ml) were added and 16.51 g (yield: 79%) of the product was obtained using the Sub 1A-6 synthesis method.

(4) Sub 1B-11 synthesis

Sub 1B-III-11 (16.51 g, 27.81 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (485 ml) in a round bottom flask and then triphenylphosphine (18.24 g, 69.53 mmol) was added and stirred at 200 ° C. When the reaction was complete, o- dichlorobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 10.78 g (yield: 69%) of the product.

14. Sub 1B-24 Synthetic example

(1) Sub 1B-I-24 synthesis

Bis (pinacolato) diboron (15.24 g, 60.01 mmol) and Pd (dppf) Cl ₂ (1.34 g, 54.56 mmol) were added to the starting material, 5-iodo-4-nitroquinoline (CAS Registry Number: 40107-04-8) g, 1.64 mmol), KOAc (16.06 g, 163.67 mmol) and DMF (270 ml) were added, and 11.63 g (Yield: 71%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(2) Sub 1B-II-24 Synthesis

M-1-24 (CAS Registry Number: 97511-05-2) (10.20 g, 38.75 mmol) and Pd (PPh ₃ ) ₄ (1.79 g, 38.75 mmol) were added to Sub 1B-I- (Yield: 78%) was obtained using the above Sub 1A-1 synthesis method by adding NaOH (4.65 g, 116.25 mmol), THF (130 ml) and water (65 ml).

(3) Sub 1B-24 synthesis

Triphenylphosphine (19.82 g, 75.55 mmol) and o- dichlorobenzene (530 ml) were added to Sub 1B-II-24 (10.77 g, 30.22 mmol) obtained in the above synthesis and 7.74 g : 79%).

15. Sub 1B-37 Synthetic example

(1) Sub 1B-I-37 synthesis

Bis (pinacolato) diboron (21.53 g, 84.79 mmol) and Pd (dppf) Cl ₂ (1.89 g) were added to 1-bromo-8-nitronaphthalene (CAS Registry Number: 13658-56-5) g, 2.31 mmol), KOAc (22.69 g, 231.25 mmol) and DMF (385 ml) were added, and 20.52 g (Yield: 89%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(2) Sub 1B-II-37 Synthesis

Obtained in the above Synthesis Sub 1B-I-37 (20.52 g, 68.60 mmol) in M 1-III-75 (16.95 g, 68.60 mmol), Pd (PPh 3) 4 (3.17 g, 2.74 mmol), NaOH (8.23 g , 205.80 mmol), THF (230 ml) and water (115 ml) were added, and 14.90 g (Yield: 64%) of the product was obtained using the Sub 1A-1 synthesis method.

(3) Sub 1B-III-37 Synthesis

Sub 2-1 (CAS Registry Number: 591-50-4) (8.96 g, 43.91 mmol) and Pd ₂ (dba) ₃ (1.21 g, 43.91 mmol) were added to Sub 1B-II- , 1.32 mmol) was added 50% P ( t- Bu) ₃ (1.3 ml, 2.63 mmol), NaO t- Bu (12.66 g, 131.72 mmol) and toluene (440 ml) 14.05 g (Yield: 77%) was obtained.

(4) Sub 1B-37 synthesis

Triphenylphosphine (22.18 g, 84.55 mmol) and o- dichlorobenzene (590 ml) were added to Sub 1B-III-37 (14.05 g, 33.82 mmol) obtained in the above synthesis and 9.34 g : 72%).

16. Sub 1B-58 Synthetic example

(1) Sub 1B-II-58 Synthesis

Obtained in the above Synthesis Sub 1B-I-24 (13.59 g, 45.28 mmol) in M 1-58 (CAS Registry Number: 65642-94-6 ) (11.92 g, 45.28 mmol), Pd (PPh 3) 4 (2.09 g , 1.81 mmol), NaOH (5.43 g, 135.85 mmol), THF (150 ml) and water (75 ml) were added and 11.78 g (Yield: 73%) of the product was obtained using the Sub 1A-1 synthesis method.

(2) Sub 1B-58 Synthesis

Triphenylphosphine (21.67 g, 82.63 mmol) and o- dichlorobenzene (580 ml) were added to Sub 1B-II-58 obtained in the above synthesis (11.78 g, 33.05 mmol) and 8.04 g : 75%).

The compounds belonging to Sub 1A and Sub 1B may be, but not limited to, the following compounds, and Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 1A and Sub 1B.

]

]

II. Synthesis of Sub 2

Sub 2 of Reaction Scheme 2 may be synthesized by the reaction route of Reaction Scheme 25, but is not limited thereto. Ar ^A = Ar ¹ and Ar ² , L ^A = L ¹ and L ² , and Hal ^A is Hal ³ and Hal ⁵ . Hal ³ and Hal ⁵ are Br or Cl and Hal ⁶ is I or Br.

Examples of the synthesis of specific compounds belonging to Sub 2 are as follows.

1. Sub 2-39 Synthetic example

The starting material 2,4-dibromopyrimidine (CAS Registry Number: 3921-01-5) (24.46 g, 102.82 mmol) was dissolved in THF (360 ml) in a round bottom flask and 4,4,5,5-tetramethyl- - (naphthalen-1-yl- d7) -1,3,2-dioxaborolane (CAS Registry Number: 1280709-91-2) (29.54 g, 113.11 mmol), Pd (PPh 3) 4 (4.75 g, 4.11 mmol), K ₂ CO ₃ (42.63 g, 308.47 mmol) and water (180 ml) were added and stirred at 90 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 18.03 g of the product (yield: 60%).

2. Sub 2-70 Synthetic example

(Dibenzo [ b , d ] furan-4-yl) -4,4,5,5-hexafluorophosphate was added to the starting material 2,4- dichloroquinazoline (CAS Registry Number: 607-68-1) (18.95 g, -tetramethyl-1,3,2-dioxaborolane (CAS Registry Number: 912824-85-2) (30.81 g, 104.73 mmol), Pd (PPh 3) 4 (4.40 g, 3.81 mmol), K 2 CO 3 (39.48 g , 285.64 mmol), THF (330 ml) and water (165 ml) were added, and 17.01 g (yield: 54%) of the product was obtained using the Sub 2-39 synthesis method described above.

3. Sub 2-81 Synthetic example

(1) Sub 2-I-81 Synthesis

The starting material, 1-amino-2-naphthoic acid (CAS Registry Number: 4919-43-1) (75.11 g, 401.25 mmol) was added to a round bottom flask with urea (CAS Registry Number: 57-13-6) 2808.75 mmol) and stirred at 160 ° C. After confirming the reaction by TLC, the reaction mixture was cooled to 100 ° C, water (200 ml) was added, and the mixture was stirred for 1 hour. After completion of the reaction, the resulting solid was filtered under reduced pressure, washed with water, and dried to obtain 63.86 g (yield: 75%) of the product.

(2) Sub 2-II-81 Synthesis

After the dropwise addition was dissolved to ₃ (200ml) POCl in the Sub 2-I-81 (63.86 g, 300.94 mmol) obtained in the above Synthesis round bottom flask at room temperature, N, N -Diisopropylethylamine (97.23 g , 752.36 mmol) slowly , And stirred at 90 ° C. After completion of the reaction, the reaction mixture was concentrated, and then ice water (500 ml) was added thereto, followed by stirring at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 67.47 g (yield: 90%) of the product.

(3) Sub 2-81 Synthesis

4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (CAS Registry Number: 24388-23-6) was added to Sub 2-II-81 (67.47 g, 270.86 mmol) (60.80 g, 297.94 mmol), Pd (PPh 3) 4 (Yield: 57%) was obtained by using the sub 2-39 synthesis method, to which 12.52 g, 10.83 mmol), K ₂ CO ₃ (112.30 g, 812.57 mmol), THF (950 ml) and water (475 ml) .

4. Sub 2-93 Synthetic example

The starting material, 2,4-dichlorobenzo [4,5] thieno [3,2- d ] pyrimidine (CAS Registry Number: 160199-05-3) (32.01 g, 125.47 mmol) -2- (naphthalen-2-yl) -1,3,2-dioxaborolane (CAS Registry Number: 256652-04-7) (35.07 g, 138.02 mmol), Pd (PPh 3) 4 (5.80 g, 5.02 mmol), K 2 CO 3 (52.02 g, 376.41 mmol), THF (440ml), was added to water (220ml) and use the Sub 2-39 synthesis product was 19.58 g (yield: 45%) .

5. Sub 2-95 Synthetic example

(Dibenzo [b, d] pyrimidin-2-one) was added to the starting material 2,4-dichlorobenzo [4,5] thieno [3,2- d ] pyrimidine (CAS Registry Number: 160199-05-3) (35.15 g, 137.78 mmol) (CAS Registry furan-2-yl ) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Number: 947770-80-1) (44.58 g, 151.56 mmol), Pd (PPh 3) 4 (6.37 g, 5.51 mmol), K 2 CO 3 (57.13 g, 413.33 mmol), THF (480ml), water (240ml) was added and the product was 22.92 g with the Sub 2-39 Synthesis (yield: 43%) .

6. Sub 2-102 Synthetic example

(24.89 g, 97.56 mmol) was added to the starting material, 2,4-dichlorobenzo [4,5] thieno [2,3-d] pyrimidine (CAS Registry Number: 76872-40-7) -2- (3- (naphthalen-1- yl) phenyl) -1,3,2-dioxaborolane (CAS Registry Number: 1263272-83-8) (35.44 g, 107.32 mmol), Pd (PPh 3) 4 19.81 g (yield: 48%) of the product was obtained using the Sub-2-39 synthesis method by adding the compound (4.51 g, 3.90 mmol), K ₂ CO ₃ (40.45 g, 292.69 mmol), THF (170 ml) .

The compound belonging to Sub 2 may be, but not limited to, the following compounds, and Table 2 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 2.

III. Product synthesis

1. P 1-1 Synthetic example

Then put together and Sub 1A-1 (13.34 g, 30.84 mmol) a triflic acid (40.9ml, 462.62 mmol) in a round bottom flask was obtained in the above synthesis was stirred at room temperature for 24 hours, pyridine aqueous solution (540ml, pyridine: H ₂ O = 1: 5) was slowly added dropwise and the mixture was refluxed for 30 minutes. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 8.40 g (yield: 68%) of the product.

2. P 1-6 Synthetic example

Triflic acid (40.2 ml, 453.80 mmol) and pyridine aqueous solution (530 ml, pyridine: H ₂ O = 1: 5) were added to Sub 1A-6 (17.78 g, 30.25 mmol) 10.09 g (Yield: 60%) of the product was obtained.

3. P 1-18 Synthetic example

Triflic acid (40.1 ml, 453.38 mmol) and pyridine aqueous solution (530 ml, pyridine: H ₂ O = 1: 5) were added to Sub 1A-18 (18.46 g, 30.23 mmol) 10.32 g (Yield: 59%) of the product was obtained.

4. P 1-22 Synthetic example

Triflic acid (39.4 ml, 445.17 mmol) and pyridine aqueous solution (520 ml, pyridine: H ₂ O = 1: 5) were added to Sub 1A-22 (19.79 g, 29.68 mmol) 10.17 g (Yield: 54%) of the product was obtained.

5. P 1-37 Synthetic example

Insert with a Sub 1A-37 (26.64 g, 40.32 mmol) of _{Pd (OAc) 2 (0.91 g} , 4.03 mmol), 3-nitropyridine (0.50 g, 4.03 mmol) in a round bottom flask was obtained in the above Synthesis C ₆ F ₆ (60 ml) and DMI (40 ml), tert- butyl peroxybenzoate (15.66 g, 80.64 mmol) was added, and the mixture was stirred at 90 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 10.89 g (yield: 41%) of the product.

6. P 1-52 Synthetic example

Sub 1-B-11 (CAS Registry Number: 2113-57-7) (4.20 g, 18.04 mmol) was dissolved in toluene (180 ml) in a round bottom flask, was _{added, Pd 2 (dba) 3 (} 0.50 g, 0.54 mmol) 50% P (t -Bu) 3 (0.5ml, 1.08 mmol), NaO t -Bu (5.20 g, 54.11 mmol) and stirred at 100 DEG C Respectively. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 9.91 g (yield: 77%) of the product.

7. P 1-64 Synthetic example

Obtained in the above Synthesis Sub 1B-24 (7.29 g, 22.47 mmol) in Sub 2-81 (6.53 g, 22.47 mmol ), Pd 2 (dba) 3 (0.62 g, 0.67 mmol) 50% P (t -Bu) 3 (0.7ml, 1.35 mmol), NaO t -Bu (6.48 g, 67.42 mmol), was added to toluene (225ml) and the product was 9.62 using the P 1-52 synthesis g (yield: 74%) was obtained.

8. P 1-83 Synthetic example

Triflic acid (34.8 ml, 393.72 mmol) and pyridine aqueous solution (460 ml, pyridine: H ₂ O = 1: 5) were added to Sub 1A-48 (17.74 g, 26.25 mmol) 9.46 g (Yield: 56%) of the product was obtained.

9. P 1-87 Synthetic example

Pd (OAc) ₂ (0.90 g, 4.02 mmol), 3-nitropyridine (0.50 g, 4.02 mmol) and tert- butyl peroxybenzoate (15.61 g, 80.36 mmol) were added to Sub 1A-53 (26.11 g, 40.18 mmol) ), C ₆ F ₆ (60 ml) and DMI (40 ml) were added, and 9.89 g of the product (yield: 38%) was obtained using the above P 1-37 synthesis method.

10. P 2-7 Synthetic example

Triflic acid (45.4 ml, 513.37 mmol) and pyridine aqueous solution (600 ml, pyridine: H ₂ O = 1: 5) were added to Sub 1A-70 (19.43 g, 34.22 mmol) 9.53 g (yield: 52%) of the product was obtained.

11. P 2-10 Synthetic example

Triflic acid (37.9 ml, 427.81 mmol) and pyridine aqueous solution (500 ml, pyridine: H ₂ O = 1: 5) were added to Sub 1A-75 (18.56 g, 28.52 mmol) Was used to obtain 11.29 g of the product (yield: 64%).

12. P 2-29 Synthetic example

Pd (OAc) ₂ (1.12 g, 4.97 mmol), 3-nitropyridine (0.62 g, 4.97 mmol) and tert- butyl peroxybenzoate (19.31 g, 99.40 mmol) were added to Sub 1A-95 (30.85 g, 49.70 mmol) ), C ₆ F ₆ (75 ml) and DMI (50 ml) were added, and 10.15 g (yield: 33%) of the product was obtained using the above P 1-37 synthesis method.

13. P 2-34 Synthetic example

Sub 1A-99 (44.72 g, 60.52 mmol) obtained in the above synthesis was dissolved in THF (300 ml) in a round bottom flask, and then methylmagnesium bromide 1.0M in THF (242.1 ml, 242.10 mmol) was slowly added dropwise. Respectively. After the reaction was completed, the reaction mixture was extracted with diethyl ether and water. The organic layer was dried over MgSO ₄ and concentrated to obtain an intermediate product. The intermediate product was dissolved in acetic acid solution (250 ml), and HCl (5 ml) was added thereto, followed by refluxing. After completion of the reaction, water was added, and the resulting solid was filtered off under reduced pressure, and then washed with water and methanol to obtain 14.83 g (yield: 34% over two steps) of the product as a white powder.

14. P 2-45 Synthetic example

Sub 2.35 (CAS Registry Number: 861339-06-2) (5.87 g, 23.03 mmol) and Pd ₂ (dba) ₃ (0.63 g, 0.69 mmol) were added to Sub 1B-37 (8.83 g, 23.03 mmol) mmol) was added 50% P ( t- Bu) ₃ (0.7 ml, 1.38 mmol), NaO t- Bu (6.64 g, 69.08 mmol) and toluene (230 ml) (Yield: 70%).

15. P 2-54 Synthetic example

The Sub 1B-58 (7.79 g, 24.01 mmol) obtained in the above Synthesis Sub 2-81 (6.98 g, 24.01 mmol ), Pd 2 (dba) 3 (0.66 g, 0.72 mmol) 50% P (t -Bu) 3 (7.0 ml, 1.44 mmol), NaO t- Bu (6.92 g, 72.04 mmol) and toluene (240 ml) were added and the product P.152 was used to obtain 10.14 g of the product (yield: 73%).

16. P 2-80 Synthetic example

Sub 1A-118 (26.33 g, 61.30 mmol) obtained in the above synthesis was dissolved in THF (305 ml) in a round bottom flask, and methylmagnesium bromide 1.0 M in THF (245.2 ml, 245.20 mmol) was slowly added dropwise. Respectively. After the reaction was completed, the reaction mixture was extracted with diethyl ether and water. The organic layer was dried over MgSO ₄ and concentrated to obtain an intermediate product. Acetic acid solution (250 ml) and HCl (5 ml) were added to the intermediate product, and 10.09 g (yield: 40% over two steps) of the product was obtained using the P 2-34 synthesis method.

17. P 2-82 Synthetic example

Pd (OAc) ₂ (0.89 g, 3.97 mmol), 3-nitropyridine (0.49 g, 3.97 mmol) and tert- butyl peroxybenzoate (15.44 g, 79.48 mmol) were added to Sub 1A-112 (24.03 g, 39.74 mmol) ), C ₆ F ₆ (60 ml) and DMI (40 ml) were added, and 10.06 g (Yield: 42%) of the product was obtained using the above P 1-37 synthesis method.

The FD-MS values of some compounds of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

In the meantime, although an exemplary synthesis example of the present invention represented by the formula (1) has been described above, all of them have been described by Intramolecular acid-induced cyclization reaction (J.Mat.Chem . 1999, 9 , 2095.), Pd cyclization reaction (Org. Lett. 2011, 13 , 5504), Grignard reaction, Cyclic Dehydration reaction, Buchwald-Hartwig cross coupling reaction, Miyaura boration reaction, Suzuki cross-coupling reaction, and PPh ₃ -mediated reductive cyclization reaction (J. Org. Chem. 2005, 70, 5014.) the other substituent in addition to the substituents specifically set forth in synthetic example as defined in formula (I), based or the like (a, B, X, Z 1 to Z _12, a substituent, such as m and n) are coupled to the even It will be understood by those skilled in the art that the reaction proceeds. For example, reaction schemes from 1 Sub 1A -> Final Product reaction (when X is S), in Scheme 6 M 1-II -> M 1 reaction (A, if B is S) is Intramolecular acid-induced cyclization reaction (J ... mater Chem 1999, 9 , would, based on 2095.), Sub 1A in Scheme 1 -> Final Product reaction (when X is O), M 1-II in scheme 6 -> M 1 reaction (a, B If the O) is Pd (.. II) -catalyzed oxidative cyclization reaction (Org Lett 2011, 13, is based on 5504), in Scheme 1 Sub 1A -> Final Product reaction (X is c (R ^c) (R ^d ), the M 1-II -> M 1 reaction (where A and B are C (R ^a ) (R ^b )) in scheme 6 is based on the Grignard reaction and the cyclic dehydration reaction, 1B -> Final Product reaction (when X is NL ² -Ar ² ), M 1-III -> M 1 reaction in Scheme 7, Sub 1-II -> Sub 1A (or Sub 1-III) reaction in Scheme 8 Are all based on the Buchwald-Hartwig cross coupling reaction. Sub 1-I -> Sub 1-I reaction in Scheme 3, starting material -> M 1-I reaction in Scheme 5 is based on the Miyaura boration reaction, Sub 1-III reaction), M 1 -I -> M 1 -II reaction in Scheme 5, M 1 -III and Sub 1 -I -> Sub 1 -II reaction in Scheme 8, 2 reaction is based on the Suzuki cross-coupling reaction, the Sub 1-III -> Sub 1B reaction in Scheme 4, and the M 1-II -> M 1 -III reaction in Scheme 7 are PPh ₃ -mediated reductive cyclization reactions ( J. Org . Chem . 2005, 70 , 5014.). The reactions will proceed until a substituent that is not specifically specified is attached.

Sub 1A-I'-112 -> Sub 1A-I "-112 reaction and Sub 1A-I" -112 - Reaction in the reaction of Sub 1A-I'- > Sub 1A-112 reaction is both Buchwald-Hartwig cross coupling that is based on the reaction of carbon (C) bond with R ¹ of Z ¹ to Z ¹² in the CR ¹ of Z ¹ to Z ¹² is a carbon (C) - nitrogen (N ), It can be confirmed that it is generally synthesized by the Buchwald-Hartwig cross coupling reaction. Reactants such as 14H-benzo [ c ] benzo [4,5] thieno [2,3- a ] carbazole, which is used when R ¹ is bonded as a CN type to a polycyclic ring compound (invention compound P 1-87) When the synthesis method disclosed in Korean Patent Nos. 10-1561566, 10-151555, 10-1497124, and 10-1355562 of the present applicant is used and R ¹ is bonded to an amine compound in CN type Reactants such as N-phenyl- [1,1'-biphenyl] -3-amine used in the compound P 2-35 of the present invention are disclosed in Korean Patent Nos. 10-1298489 and 10-1298483 10-1251451. ≪ / RTI >

Evaluation of manufacturing of organic electric device

[ Example  One] Red organic electroluminescent device  (Phosphorescent host)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting host material of a light emitting layer. First, a 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as 2-TNATA) film was vacuum deposited on the ITO layer (anode) A hole transporting layer was formed on the hole injection layer by vacuum evaporation of a NPD film as a hole transporting compound to a thickness of 60 nm. The above compound P 1-9 of the present invention was used as a host on the hole transporting layer and bis (1-phenylisoquinoline) iridium (III) acetylacetonate (hereinafter referred to as "(piq) ₂ Ir (acac)" ) Was doped at a weight ratio of 95: 5 to deposit a light emitting layer with a thickness of 30 nm. Subsequently, aluminum (1,1'-biphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited as a hole blocking layer to a thickness of 10 nm, Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm as a transport layer. Then, LiF, an alkali metal halide serving as an electron injecting layer, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm as an anode to produce an organic electroluminescent device.

[ Example  2] to [ Example  65] Red organic electroluminescent device

An organic electroluminescent device was prepared in the same manner as in Example 1 except that the compound of the present invention described in Table 4 was used instead of the compound P 1-9 according to Example 1 of the present invention as a host material of the light emitting layer .

[ Comparative Example  1] to [ Comparative Example  6] Red organic electroluminescent device

Except that the compound P 1-9 according to Example 1 of the present invention was used as a host material in the light emitting layer, one of the comparative compounds 1 to 6 described in the following Table 4 was used, Thereby preparing a light emitting device.

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 1 to 65 and Comparative Examples 1 to 6 of the present invention And the T95 lifetime was measured by a life measuring apparatus manufactured by Mac Science Inc. at a reference brightness of 2500 cd / m ^2. The measurement results are shown in Table 4 below.

As can be seen from the measurement results in Table 4, it was confirmed that the device using the compound according to one embodiment of the present invention as a phosphorescent red host material in the light emitting layer had significantly improved luminescence efficiency and lifetime compared with Comparative Compounds 1 to 6 .

As a result of the above, it can be confirmed that even if the same skeleton is present, at least one more N is introduced into the 6-ring heterocyclic core backbone, resulting in different results.

The compounds of the present invention in which at least one N is introduced into the six-ring heterocyclic core backbone than the Comparative Compounds 2 to 6 in which N is not introduced into the six-ring heterocyclic core backbone has a relatively higher T1 value . This shows that the electron blocking ability is improved and the charge transfer from the host to the dopant is facilitated. As a result, it can be confirmed that the device result is the best in luminous efficiency and lifetime.

Among the compounds of the present invention, the results show different results depending on the positions where N is introduced into the six-ring heterocyclic core backbone. This can be confirmed by comparing the compounds P1-9, P1-11 and P1-12 of the present invention, and has a higher T1 value in the order of P1-12> P1-9> P1-11. As a result, the pentacyclic heterocycle (P1-9) in the case where N is introduced into the aromatic ring part fused between the pentagonal heterocyclic ring and the hexagonal heterocyclic ring (P1-9) when N is introduced into the aromatic ring part (terminal) And life span. In addition, when N is introduced (P 1-12) in the aromatic ring portion (terminal) fused with the hexagonal heterocycle, it can be confirmed that the light emitting efficiency and lifetime are better than those in the above two cases.

[ Example  66] Green organic electroluminescent device  (Phosphorescent host)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting host material of a light emitting layer. First, a 2-TNATA film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm. Then, an NPD film as a hole transporting compound was vacuum- To form a transport layer. The above compound P1-6 of the present invention was used as a host on the hole transport layer and tris (2-phenylpyridine) -iridium (hereinafter abbreviated as "Ir (ppy) ₃ " Doped to form a light emitting layer with a thickness of 30 nm. Subsequently, BAlq was vacuum deposited as a hole blocking layer to a thickness of 10 nm, and Alq ₃ was formed to a thickness of 40 nm as an electron transporting layer. Then, LiF, an alkali metal halide serving as an electron injecting layer, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm as an anode to produce an organic electroluminescent device.

[ Example  67] to [ Example  70] Green organic electroluminescent device

An organic electroluminescent device was prepared in the same manner as in Example 66 except that the compound of the present invention described in Table 5 was used instead of the compound P1-6 according to Example 1 of the present invention as a host material of the light emitting layer.

[ Example  71] Green organic electroluminescent device

Except that the compound P1-55 of the present invention described in Table 5 below and P1-83 were mixed in a ratio of 1: 1 in place of the compound P1-6 according to Example 1 of the present invention as a host material of the light emitting layer, An organic electroluminescent device was prepared in the same manner as in Example 66. [

[ Example  72] Green organic electroluminescent device

Except that the compound P2-7 and P1-77 of the present invention described in the following Table 5 were mixed in a ratio of 1: 1 in place of the compound P1-6 according to Example 1 of the present invention as a host material of the light emitting layer, An organic electroluminescent device was prepared in the same manner as in Example 66. [

[ Comparative Example  7] to [ Comparative Example  9] Green organic electroluminescent device  (Phosphorescent host)

The same method as in Example 66, except that one of the comparative compound 1, the comparative compound 7 and the comparative compound 8 described in the following Table 5 was used in place of the compound P1-6 according to Example 1 of the present invention as the host material of the light emitting layer To prepare an organic electroluminescent device.

Electruminescence (EL) characteristics of the organic electroluminescent devices manufactured in Examples 66 to 72 and Comparative Examples 7 to 9 of the present invention were evaluated by PR bias of photoresearch by applying a forward bias DC voltage And the T95 lifetime was measured through a life measuring apparatus manufactured by Mac Science Inc. at a reference luminance of 5000 cd / m ^2. The measurement results are shown in Table 5 below.

As can be seen from the measurement results in Table 5, the device using the compound according to one embodiment of the present invention as the phosphorescent green host material of the light emitting layer has significantly improved luminescence efficiency and lifetime than the comparative compound 1, the comparative compound 7 and the comparative compound 8 . This is because the structure in which at least one N is further introduced into the six-ring heterocyclic core backbone is used not only as a light emitting layer (used as a host) of a red organic electroluminescence device but also as a light emitting layer It can be confirmed that it acts as a main factor of performance improvement.

The compound of the present invention which is used as a host material in the light emitting layer has the most appropriate T1 value and energy band gap so that the charge transfer from the host to the dopant can be smoothly performed and thus exhibits remarkably high luminous efficiency and high lifetime Can be confirmed.

In addition, in the case of a phosphorescent host, it is necessary to grasp the correlation with the hole transporting layer and the dopant, so that it is very difficult to use the similar cores to infer the excellent electrical characteristics of the compound of the present invention.

The foregoing description is merely illustrative of the present invention, and various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are for the purpose of limiting the present invention and are not to be construed as limiting the spirit and scope of the present invention. The scope of protection of the present invention should be construed according to the claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

Claims (11)

A compound represented by the following formula (1):

1) A and B are each independently any one of NL ¹ -Ar ¹ , S, O, C (R ^a ) (R ^b )
2) m and n are integers of 0 or 1, m + n is 1 or more,
(Where A is a single bond when m is 0 and B is a single bond when n is 0)
3) X is any one of NL ² -Ar ² , S, O, C (R ^c ) (R ^d )
4) Z ¹ to Z ¹² are each independently CR ¹ or N, and at least one of Z ¹ to Z ¹² is N, and when at least two of Z ¹ to Z ¹² are CR ¹ , each CR ¹ is independently Are the same or different,
5) Ar ¹ and Ar ² are each independently a C ₆ -C ₆₀ aryl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fluorenyl group; A fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; A C ₆ -C ₃₀ aryloxy group, and -L ^a -N (R ^e ) (R ^f )
6) R ¹ is hydrogen; heavy hydrogen; Tritium; halogen; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; -L ^a -N (R ^e ) (R ^f ); A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group, or adjacent R ^{1 s} may be bonded to each other to form a ring, R ¹ , which does not form a ring, is the same as defined above,
7) R ^a to R ^f independently of one another are hydrogen; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group, or R ^a and R ^b or R ^c and R ^d may combine with each other to form a spiro compound together with C to which they are bonded, or R ^e and R ^f may combine with each other to form a ring,
8) L ¹ , L ² and L ^a independently of one another are a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And an aliphatic hydrocarbon group,
Here, each of the aryl group, the arylene group, the fluorenyl group, the fluorenylene group, the heterocyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxy group and the aryloxy group may be deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; -N (R ^g ) (R ^h ); And aryl alkenyl group of C ₈ -C _20; may be substituted with one or more substituents selected from the group consisting of and (wherein R ^g and R ^h are each independently an aryl group of C ₆ -C _60; fluorene group And a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si, and P; when these substituents are adjacent to each other, To form a ring. The method according to claim 1,
(1) is represented by one of the following formulas (2) and (3): < EMI ID =

In the general formulas (2) and (3)
A, B, X and Z ¹ to Z ¹² are the same as A, B, X and Z ¹ to Z ¹² defined in the above formula (1). The method according to claim 1,
(1) is represented by one of the following formulas (4) to (11):

In the above Chemical Formulas 4 to 11,
A, B, Z ¹ to ^{Z 12, L 2, Ar 2} , R c and R ^d are as defined in Formula ¹ A, B, Z 1 to ^{Z 12, L 2, Ar 2} , R c and R ^d and same. The compound of formula (I) is represented by one of the following formulas (12) to (19):

In the above Chemical Formulas 12 to 19,
1) A, B, X and Z ¹ to Z ¹² are the same as A, B, X and Z ¹ to Z ¹² defined in the above formula (1)
2) Y is the same as defined in X of claim 1,
3) Z ¹³ to Z ²⁴ are independently of each other CR ² or N,
4) R ² is hydrogen; heavy hydrogen; Tritium; halogen; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ aryloxy groups, or adjacent R ² groups may be bonded to each other to form a ring, and R ² which does not form a ring is the same as defined above. The method according to claim 1,
Wherein the compound represented by formula (1) is one of the following compounds.

A first electrode;
A second electrode; And
And one or more organic layers including a light-emitting layer disposed between the first electrode and the second electrode, wherein one of the organic layers is formed of the compound of any one of claims 1 to 5 And an organic electroluminescent device. The method according to claim 6,
The compound is contained in at least one of the hole injection layer, the hole transport layer, the light emission assisting layer, the light emitting layer, the electron transport assisting layer, the electron transport layer and the electron injection layer of the organic material layer, Characterized in that the compound is contained as a component of the mixture. The method according to claim 6,
Wherein the compound is used as a phosphorescent host material of the light emitting layer. The method according to claim 6,
Wherein the organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device including the organic electroluminescent device of claim 6; And a control unit for driving the display device. 11. The method of claim 10,
Wherein the organic electroluminescent device is one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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