KR102095837B1 - Novel Method for Preparing Carbazole Derivatives, Novel Carbazole Derivatives Made thereby, Composition Comprising the Same, and Material for Organic Light Emitting Diode Comprising the Same - Google Patents

Abstract

The present invention relates to a method for preparing a novel carbazole derivative and to a carbazole derivative prepared therefrom and their use, the production method according to the present invention is an effective multi-element reaction, which is efficiently eco-friendly even under mild reaction conditions. Synthesis can be carried out, and by using commercially available starting materials, it represents an advantage that manufacturing cost can be reduced. In addition, the novel carbazole derivatives according to the present invention show excellent fluorescence sensing ability, and in particular, can be usefully used as a composition or an OLED material for detecting Cu ²⁺ ions.

Description

Novel Method for Preparing Carbazole Derivatives, Novel Carbazole Derivatives Made thereby, Composition Comprising the Same, and Material for Organic Light Emitting Diode Comprising the Same}

The present invention relates to a novel method for manufacturing a carbazole derivative, a novel carbazole derivative prepared therefrom, and a composition for detecting copper ions comprising the same as an active ingredient and an organic light emitting diode material.

Multicomponent reactions (MCRs) can overcome the common challenges of increasing efficiency, with minimal reaction conditions, high convergence and minimal waste to maintain the environment, especially in the field of synthetic chemistry related to atomic and phase economics. That is a very powerful weapon. Recently, this MCR has emerged as a green synthesis tool capable of effectively constructing complex molecular architectures that exhibit high levels of structural diversity through a one-step reaction. In addition, their various applications have been reported in the fields of pharmaceutical chemistry, natural product synthesis, polymer chemistry, agriculture-related chemistry and fusion chemistry.

On the other hand, carbazole and related compounds constitute an important class of alkaloids that exhibit a wide variety of bioactive and pharmaceutical activities, and unique thermal and electrical properties. Specifically, benzo [b] carbazoles exhibit a very wide range of activities including anti-tumor activity, anti-cancer activity, anti-inflammatory activity, anti-fungal activity, anti-estrogen and kinase inhibitor activity. In addition, benzocarbazoles containing high-expansion π-bonds are used as organic light emitting diodes, semiconductors, polymers, and monomers of chemiluminescent and electroluminescent materials. They can also be used in the development of dye-sensitive solar cells and fluorescent reagents.

Because of the very useful properties of carbazole-based systems, many methods for their synthesis have been developed. Among them, Hoye and his co-researchers recently reported a clear intramolecular hexadihydrodiels-alder reaction of diynamides to synthesize carbazole. In addition, the inventors of the present invention, using 2-nitrocinnamaldehyde or 2-nitrochalcon as a starting material, condensation between a base-promoting molecule between 2-nitrocinnamaldehyde or 2-nitrochalcone and β-ketoester The reaction was developed.

For the synthesis of aryl-ringed carbazoles such as benzo [b] carbazole, some methods have been employed. These reactions include intramolecular ring addition reactions of monomers prepared through a multi-step process that produces products of limited substitution patterns. Therefore, there is a need to develop a method for synthesizing an aryl-ringed carbazole derivative capable of exhibiting various substitution patterns from efficient and sustainable, currently available feedstocks.

Korean Registered Patent No. 10-1026171 (registered on March 24, 2011).

It is an object of the present invention to provide novel carbazole derivatives exhibiting various activities.

Another object of the present invention is to provide a composition that can effectively detect ^divalent copper ions (Cu ²⁺ ) and a kit comprising the same.

Another object of the present invention is to provide an organic light emitting diode material having excellent performance and an organic light emitting diode including the same.

Another object of the present invention is to provide a method for preparing the novel carbazole derivative.

In order to achieve the above object, the present invention provides a carbazole derivative represented by Formula 1 or 2, or a pharmaceutically acceptable salt thereof:

[Formula 1]

In Chemical Formula 1, R ¹ and R ² may each be the same or different, and any one substituent selected from the group consisting of hydrogen, (C1 to C3) alkoxy, tri (halogen) (C1 to C4) alkyl, and halogen Or, R ¹ and R ² are connected to each other to form a benzene ring; R ³ and R ⁴ may be the same or different, hydrogen, (C1 to C4) alkyl, (C1 to C3) alkoxy, ethynyl, aryl, tri (halogen) (C1 to C3) alkoxy, halogen, And tri (halogen) (C1 to C4) alkyl, or one substituent selected from the group consisting of, or R ³ and R ⁴ are connected to each other to form a benzene ring;

[Formula 2]

In Formula 2, X is any one of S, N or O, and Y is a 5-membered heteroaryl ring including any one of S, N or O.

In order to achieve the other object, the present invention is a composition for detecting a divalent copper ion (Cu ^{2 +} ) containing the carbazole derivative represented by Formula 1 or 2, or a pharmaceutically acceptable salt thereof as an active ingredient. to provide.

In addition, the present invention provides a kit for detecting a divalent copper ion (Cu ^{2 +} ) containing the composition as an active ingredient.

In order to achieve the above another object, the present invention provides an organic light emitting diode (OLED) material comprising the carbazole derivative represented by Formula 1 or 2, or a pharmaceutically acceptable salt thereof as an active ingredient.

In addition, the present invention provides an organic light emitting diode (OLED) including the organic light emitting diode material.

In order to achieve the above another object, the present invention, in the presence of a copper catalyst and the base Cs ₂ CO ₃ , a) 2-nitrocinnamaldehyde derivatives; And b) one or more compounds selected from the group consisting of substituted or unsubstituted benzyl cyanide derivatives, 5-ring heteroaryl cyanide derivatives, and 1,2-diphenylethan-1-one; It provides a method for producing a sol derivative.

The novel manufacturing method of the present invention is an eco-friendly, simple, mild and inexpensive but effective Cu (I) -catalyzed multi-element [5 + 3 + 1] -ring-forming reaction, thereby commercially available 2-nitro Using a cinnamic aldehyde compound and benzyl cyanide, carbazole derivatives having polysubstituted aryl- and heteroaryl-rings can be prepared with high yield. In addition, the compound thus synthesized exhibits excellent activity in sensing divalent copper ions, and thus may be used as a composition for divalent copper ion fluorescence sensing, and may also be used as an organic light emitting diode material.

1 shows a reaction for obtaining a carbazole derivative when reacting a 2-cinnamaldehyde derivative with a benzyl cyanide derivative in the production method according to the present invention.
Figure 2 shows by identifying the mechanism by which the carbazole derivative according to the present invention is obtained.
Figure 3 shows the results according to the density function theory to demonstrate the mechanism of formation of compounds 12 and 13.
4 is a result of confirming the metal ion sensing activity including divalent copper ions of carbazole derivatives 3f and 5d according to the present invention.
5 is a result confirming the color development characteristics of the divalent copper ion sensing activity of the carbazole derivatives 3f and 5d according to the present invention.
Figure 6 shows the mechanism of divalent copper ion sensing activity of carbazole derivatives 3f and 5d according to the present invention.

The inventors of the present invention, simple and inexpensive, through the addition reaction of a carbazole containing a structurally complex polyaryl-ring, one-pot de novo (5 + 3 + 1) -benzopyrrole However, it was intended to be synthesized by combining multi-elements using commercially available starting materials. Thus, de novo [5 + 3 +] was obtained through a multi-element combination reaction of Cu (I) -catalyst of 2-nitrocinnamaldehyde and benzyl cyanide. The present invention was completed by confirming that a carbazole derivative containing a polyaryl-ring having a complex structure can be prepared through a 1] -cyclization reaction.

Accordingly, the present invention provides a carbazole derivative represented by Formula 1 or 2, or a pharmaceutically acceptable salt thereof:

[Formula 1]

In Chemical Formula 1, R ¹ and R ² may each be the same or different, and any one substituent selected from the group consisting of hydrogen, (C1 to C3) alkoxy, tri (halogen) (C1 to C4) alkyl, and halogen Or, R ¹ and R ² are connected to each other to form a benzene ring; R ³ and R ⁴ may be the same or different, hydrogen, (C1 to C4) alkyl, (C1 to C3) alkoxy, ethynyl, aryl, tri (halogen) (C1 to C3) alkoxy, halogen, And tri (halogen) (C1 to C4) alkyl, or one substituent selected from the group consisting of, or R ³ and R ⁴ are connected to each other to form a benzene ring;

[Formula 2]

In Formula 2, X is any one of S, N or O, and Y is a 5-membered heteroaryl ring including any one of S, N or O.

Specifically, in Formula 1, R ¹ and R ² may each be the same or different, and are any one substituent selected from the group consisting of hydrogen, methoxy, trifluoromethyl, and chloro, or R ¹ And R ² are connected to each other to form a benzene ring; R ³ and R ⁴ may each be the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, methoxy, ethynyl, phenyl, trifluoromethoxy, chloro, and trifluoromethyl Or any one substituent, or R ³ and R ⁴ may be connected to each other to form a benzene ring.

In addition, in Chemical Formula 2, X may be S and Y may be thiazole.

More specifically, the carbazole derivatives are 6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [6-Phenyl-5H-benzo [b] carbazole-11-carbonitrile], 8-methyl-6 -(p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 10-methyl- 6- (o-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [10-Methyl-6- (o-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-ethyl -6- (4-ethylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Ethyl-6- (4-ethylphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8 -Isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11- carbonitrile], 10-methoxy-6- (2-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [10-Methoxy-6- (2-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Methoxy-6- (4-methoxyphenyl) -5H- benzo [b] carbazole-11-carbonitri le], 8-ethynyl-6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Ethynyl-6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 6-([1,1'-biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile [6-([1,1 '-Biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 8- (trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl)- 5H-benzo [b] carbazole-11-carbonitrile [8- (Trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-chloro-6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Chloro-6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8- (tri Fluoromethyl) -6- (4- (trifluoromethyl) phenyl) -5H-benzo [b] carbazole-11-carbonitrile [8- (Trifluoromethyl) -6- (4- (trifluoromethyl) phenyl)- 5H-benzo [b] carbazole-11-carbonitrile], 4-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [4-Methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 4-methoxy- 8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [4-Methoxy-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole- 11-carbonitrile], 6-phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole-11-carbonitrile [6-Phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole- 11-carbonitrile], 3-chloro-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 3- Chloro-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 3-chloro-8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile [7- (Naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 9-methoxy-7- (naphthalen-1-yl) -8H-naphtho [2,1-b ] Carbazole-13-carbonitrile [9-Methoxy-7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carba zole-13-carbonitrile], 11-chloro-7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile [11-Chloro-7- (naphthalen-1 -yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 7- (naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b ] Carbazole-13-carbonitrile [7- (Naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 13- (naphthalen-2-yl ) -12H-naphtho [1,2-b] carbazole-7-carbonitrile [13- (Naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile], 11- Methoxy-13- (naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile [11-Methoxy-13- (naphthalen-2-yl) -12H-naphtho [ 1,2-b] carbazole-7-carbonitrile; 5f], 12-phenyl-13H-dibenzo [a, h] carbazole-7-carbonitrile [12-Phenyl-13H-dibenzo [a, h] carbazole-7-carbonitrile], 10-methyl-12- ( p-tolyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile [10-Methyl-12- (p-tolyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile], 10 -Methoxy-12- (4-methoxyphenyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile [10-Methoxy-12- (4-methoxyphenyl) -13H-dibenzo [a, h ] carbazole-7-carbonitrile], 7- (naphthalen-1-yl) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile [7- (naphthalen-1-yl) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile], 10- (thiophen-3-yl) -9H-thieno [2,3-b] carbazole-4-carbonite Reel [10- (Thiophen-3-yl) -9H-thieno [2,3-b] carbazole-4-carbonitrile], 6-([1,1'-biphenyl] -4-yl) -10-me Methoxy-5H-benzo [b] carbazole-11-carbonitrile [6-([1,1'-Biphenyl] -4-yl) -10-methoxy-5H-benzo [b] carbazole-11-carbonitrile], And 10-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [10-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonit rile] may be selected from the group consisting of.

In addition, the present invention provides a composition for detecting a divalent copper ion (Cu ²⁺ ) comprising a carbazole derivative represented by the following Chemical Formula 1 or 2, or a pharmaceutically acceptable salt thereof as an active ingredient:

[Formula 1]

In Chemical Formula 1, R ¹ and R ² may each be the same or different, and any one substituent selected from the group consisting of hydrogen, (C1 to C3) alkoxy, tri (halogen) (C1 to C4) alkyl, and halogen Or, R ¹ and R ² are connected to each other to form a benzene ring; R ³ and R ⁴ may be the same or different, hydrogen, (C1 to C4) alkyl, (C1 to C3) alkoxy, ethynyl, aryl, tri (halogen) (C1 to C3) alkoxy, halogen and Tri (halogen) (C1 ~ C4) alkyl is any one substituent selected from the group consisting of alkyl, or R ³ and R ⁴ are connected to each other to form a benzene ring;

[Formula 2]

In Formula 2, X is any one of S, N or O, and Y is a 5-membered heteroaryl ring including any one of S, N or O.

Specifically, in Formula 1, R ¹ and R ² may each be the same or different, and are any one substituent selected from the group consisting of hydrogen, methoxy, trifluoromethyl, and chloro, or R ¹ And R ² are connected to each other to form a benzene ring; R ³ and R ⁴ may each be the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, methoxy, ethynyl, phenyl, trifluoromethoxy, chloro, and trifluoromethyl Or any one substituent, or R ³ and R ⁴ may be connected to each other to form a benzene ring.

In addition, in Chemical Formula 2, X may be S and Y may be thiazole.

More specifically, the carbazole derivatives are 6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [6-Phenyl-5H-benzo [b] carbazole-11-carbonitrile], 8-methyl-6 -(p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 10-methyl- 6- (o-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [10-Methyl-6- (o-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-ethyl -6- (4-ethylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Ethyl-6- (4-ethylphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8 -Isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11- carbonitrile], 10-methoxy-6- (2-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [10-Methoxy-6- (2-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Methoxy-6- (4-methoxyphenyl) -5H- benzo [b] carbazole-11-carbonitri le], 8-ethynyl-6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Ethynyl-6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 6-([1,1'-biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile [6-([1,1 '-Biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 8- (trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl)- 5H-benzo [b] carbazole-11-carbonitrile [8- (Trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-chloro-6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Chloro-6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8- (tri Fluoromethyl) -6- (4- (trifluoromethyl) phenyl) -5H-benzo [b] carbazole-11-carbonitrile [8- (Trifluoromethyl) -6- (4- (trifluoromethyl) phenyl)- 5H-benzo [b] carbazole-11-carbonitrile], 4-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [4-Methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 4-methoxy- 8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [4-Methoxy-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole- 11-carbonitrile], 6-phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole-11-carbonitrile [6-Phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole- 11-carbonitrile], 3-chloro-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 3- Chloro-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 3-chloro-8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile [7- (Naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 9-methoxy-7- (naphthalen-1-yl) -8H-naphtho [2,1-b ] Carbazole-13-carbonitrile [9-Methoxy-7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carba zole-13-carbonitrile], 11-chloro-7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile [11-Chloro-7- (naphthalen-1 -yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 7- (naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b ] Carbazole-13-carbonitrile [7- (Naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 13- (naphthalen-2-yl ) -12H-naphtho [1,2-b] carbazole-7-carbonitrile [13- (Naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile], 11- Methoxy-13- (naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile [11-Methoxy-13- (naphthalen-2-yl) -12H-naphtho [ 1,2-b] carbazole-7-carbonitrile; 5f], 12-phenyl-13H-dibenzo [a, h] carbazole-7-carbonitrile [12-Phenyl-13H-dibenzo [a, h] carbazole-7-carbonitrile], 10-methyl-12- ( p-tolyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile [10-Methyl-12- (p-tolyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile], 10 -Methoxy-12- (4-methoxyphenyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile [10-Methoxy-12- (4-methoxyphenyl) -13H-dibenzo [a, h ] carbazole-7-carbonitrile], 7- (naphthalen-1-yl) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile [7- (naphthalen-1-yl) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile], 10- (thiophen-3-yl) -9H-thieno [2,3-b] carbazole-4-carbonite Reel [10- (Thiophen-3-yl) -9H-thieno [2,3-b] carbazole-4-carbonitrile], 6-([1,1'-biphenyl] -4-yl) -10-me Methoxy-5H-benzo [b] carbazole-11-carbonitrile [6-([1,1'-Biphenyl] -4-yl) -10-methoxy-5H-benzo [b] carbazole-11-carbonitrile], And 10-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [10-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonit rile] may be selected from the group consisting of.

In addition, the present invention provides a kit for detecting a divalent copper ion (Cu ^{2 +} ) containing the composition as an active ingredient.

Moreover, the present invention provides an organic light emitting diode (OLED) material comprising a carbazole derivative represented by Formula 1 or 2, or a pharmaceutically acceptable salt thereof as an active ingredient:

[Formula 1]

In Chemical Formula 1, R ¹ and R ² may each be the same or different, and any one substituent selected from the group consisting of hydrogen, (C1 to C3) alkoxy, tri (halogen) (C1 to C4) alkyl, and halogen Or, R ¹ and R ² are connected to each other to form a benzene ring; R ³ and R ⁴ may be the same or different, hydrogen, (C1 to C4) alkyl, (C1 to C3) alkoxy, ethynyl, aryl, tri (halogen) (C1 to C3) alkoxy, halogen and Tri (halogen) (C1 ~ C4) alkyl is any one substituent selected from the group consisting of alkyl, or R ³ and R ⁴ are connected to each other to form a benzene ring;

[Formula 2]

In Formula 2, X is any one of S, N or O, and Y is a 5-membered heteroaryl ring including any one of S, N or O.

Specifically, in Formula 1, R ¹ and R ² may each be the same or different, and are any one substituent selected from the group consisting of hydrogen, methoxy, trifluoromethyl, and chloro, or R ¹ And R ² are connected to each other to form a benzene ring; R ³ and R ⁴ may each be the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, methoxy, ethynyl, phenyl, trifluoromethoxy, chloro, and trifluoromethyl Or any one substituent, or R ³ and R ⁴ may be connected to each other to form a benzene ring.

In addition, in Chemical Formula 2, X may be S and Y may be thiazole.

More specifically, the carbazole derivatives are 6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [6-Phenyl-5H-benzo [b] carbazole-11-carbonitrile], 8-methyl-6 -(p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 10-methyl- 6- (o-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [10-Methyl-6- (o-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-ethyl -6- (4-ethylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Ethyl-6- (4-ethylphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8 -Isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11- carbonitrile], 10-methoxy-6- (2-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [10-Methoxy-6- (2-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Methoxy-6- (4-methoxyphenyl) -5H- benzo [b] carbazole-11-carbonitri le], 8-ethynyl-6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Ethynyl-6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 6-([1,1'-biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile [6-([1,1 '-Biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 8- (trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl)- 5H-benzo [b] carbazole-11-carbonitrile [8- (Trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-chloro-6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Chloro-6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8- (tri Fluoromethyl) -6- (4- (trifluoromethyl) phenyl) -5H-benzo [b] carbazole-11-carbonitrile [8- (Trifluoromethyl) -6- (4- (trifluoromethyl) phenyl)- 5H-benzo [b] carbazole-11-carbonitrile], 4-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [4-Methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 4-methoxy- 8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [4-Methoxy-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole- 11-carbonitrile], 6-phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole-11-carbonitrile [6-Phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole- 11-carbonitrile], 3-chloro-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 3- Chloro-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 3-chloro-8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile [7- (Naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 9-methoxy-7- (naphthalen-1-yl) -8H-naphtho [2,1-b ] Carbazole-13-carbonitrile [9-Methoxy-7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carba zole-13-carbonitrile], 11-chloro-7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile [11-Chloro-7- (naphthalen-1 -yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 7- (naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b ] Carbazole-13-carbonitrile [7- (Naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 13- (naphthalen-2-yl ) -12H-naphtho [1,2-b] carbazole-7-carbonitrile [13- (Naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile], 11- Methoxy-13- (naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile [11-Methoxy-13- (naphthalen-2-yl) -12H-naphtho [ 1,2-b] carbazole-7-carbonitrile; 5f], 12-phenyl-13H-dibenzo [a, h] carbazole-7-carbonitrile [12-Phenyl-13H-dibenzo [a, h] carbazole-7-carbonitrile], 10-methyl-12- ( p-tolyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile [10-Methyl-12- (p-tolyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile], 10 -Methoxy-12- (4-methoxyphenyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile [10-Methoxy-12- (4-methoxyphenyl) -13H-dibenzo [a, h ] carbazole-7-carbonitrile], 7- (naphthalen-1-yl) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile [7- (naphthalen-1-yl) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile], 10- (thiophen-3-yl) -9H-thieno [2,3-b] carbazole-4-carbonite Reel [10- (Thiophen-3-yl) -9H-thieno [2,3-b] carbazole-4-carbonitrile], 6-([1,1'-biphenyl] -4-yl) -10-me Methoxy-5H-benzo [b] carbazole-11-carbonitrile [6-([1,1'-Biphenyl] -4-yl) -10-methoxy-5H-benzo [b] carbazole-11-carbonitrile], And 10-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [10-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonit rile] may be selected from the group consisting of.

Moreover, the present invention provides an organic light emitting diode comprising the organic light emitting diode material.

In addition, the present invention, in the presence of a copper catalyst and the base Cs ₂ CO ₃ , a) 2-nitrocinnamaldehyde derivatives; And b) one or more compounds selected from the group consisting of substituted or unsubstituted benzyl cyanide derivatives, 5-ring heteroaryl cyanide derivatives, and 1,2-diphenylethan-1-one; It provides a method for producing a sol derivative.

As shown in FIG. 1, the ring-forming reaction that is performed during the preparation method is an intramolecular Bayer-Williger oxidation oxidative CC bond cleavage process, Sp2 CH bond activation process, C-CN bond cleavage under mild reaction conditions. Process, 6π-electron cycle process, and oxidative aromatization process. Moreover, the method according to the invention comprises tetracyclic benzo [b] -carbazole derivatives or thieno [2,3-b] carbazole, pentacyclic naphtho [2,1] comprising various polyaryls or heteroaryls -b]-or, naphtho [1,2-b] -carbazole and dibenzo [a, h] carbazole, hexacyclic benzo [a] naphtho [1,2-h] carbazole It can be obtained by starting from an inexpensive and readily available substrate through a pot reaction.

At this time, in the reaction, selected from the group consisting of 1 equivalent of 2-nitrocinnamaldehyde derivative and substituted or unsubstituted benzyl cyanide derivative, 5-ring heteroaryl cyanide derivative, and 1,2-diphenylethan-1-one. Two equivalents of one or more compounds can be reacted.

The reaction may be performed using tetrahydrofuran (THF) as a solvent, and may be performed during reflux for 3 hours to 7 hours. In addition, the copper catalyst may be used by 3 to 8 mol%, and in detail, it may be used by 5 mol%, but is not limited thereto.

Specifically, the copper catalyst may be CuI, but is not limited thereto.

The 2-nitrocinnamaldehyde derivative may be represented by Formula 3 below:

[Formula 3]

In Chemical Formula 3, Z is hydrogen or a phenyl group, and R ⁵ and R ⁶ may be the same or different from each other, and are composed of hydrogen, (C1 to C3) alkoxy, tri (halogen) (C1 to C4) alkyl, and halogen Or any one substituent selected from R ⁵ and R ⁶ are connected to each other to form a benzene ring.

More specifically, in Chemical Formula 3, R ⁵ and R ⁶ may be the same or different from each other, and are any one substituent selected from the group consisting of hydrogen, methoxy, trifluoromethyl, and chloro, or R ⁵ and R ⁶ may be connected to each other to form a benzene ring.

The benzyl cyanide derivative may be represented by Formula 4 below:

[Formula 4]

In Chemical Formula 4, R ⁷ and R ⁸ may be the same or different, and hydrogen, (C1 to C4) alkyl, (C1 to C3) alkoxy, ethynyl, aryl, tri (halogen) (C1 to C3) ) Alkoxy, halogen and tri (halogen) (C1 ~ C4) alkyl is any one substituent selected from the group consisting of, or, R ⁷ and R ⁸ may be connected to each other to form a benzene ring.

More specifically, in Chemical Formula 4, R ⁷ and R ⁸ may be the same or different, respectively, hydrogen, methyl, ethyl, isopropyl, methoxy, ethynyl, phenyl, trifluoromethoxy, chloro and trifluoro It may be any one substituent selected from the group consisting of methyl, or R ⁷ and R ⁸ may be linked to each other to form a benzene ring.

In addition, the 5-cyclic heteroaryl cyanide derivative may be represented by the following Chemical Formula 5.

[Formula 5]

X 'is either S, N, or O.

In more detail, in Chemical Formula 5, X 'may be S.

The carbazole derivatives prepared through the above method may be represented by the following Chemical Formula 1 or 2:

[Formula 1]

In Chemical Formula 1, R ¹ and R ² may each be the same or different, and any one substituent selected from the group consisting of hydrogen, (C1 to C3) alkoxy, tri (halogen) (C1 to C4) alkyl, and halogen Or, R ¹ and R ² are connected to each other to form a benzene ring; R ³ and R ⁴ may be the same or different, hydrogen, (C1 to C4) alkyl, (C1 to C3) alkoxy, ethynyl, aryl, tri (halogen) (C1 to C3) alkoxy, halogen and Tri (halogen) (C1 ~ C4) alkyl is any one substituent selected from the group consisting of alkyl, or R ³ and R ⁴ are connected to each other to form a benzene ring;

[Formula 2]

In Formula 2, X is any one of S, N or O, and Y is a 5-membered heteroaryl ring including any one of S, N or O.

Specifically, in Formula 1, R ¹ and R ² may each be the same or different, and are any one substituent selected from the group consisting of hydrogen, methoxy, trifluoromethyl, and chloro, or R ¹ And R ² are connected to each other to form a benzene ring; R ³ and R ⁴ may each be the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, methoxy, ethynyl, phenyl, trifluoromethoxy, chloro, and trifluoromethyl Or any one substituent, or R ³ and R ⁴ may be connected to each other to form a benzene ring.

In addition, in Chemical Formula 2, X may be S and Y may be thiazole.

More specifically, the carbazole derivatives are 6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [6-Phenyl-5H-benzo [b] carbazole-11-carbonitrile], 8-methyl-6 -(p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 10-methyl- 6- (o-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [10-Methyl-6- (o-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-ethyl -6- (4-ethylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Ethyl-6- (4-ethylphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8 -Isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11- carbonitrile], 10-methoxy-6- (2-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [10-Methoxy-6- (2-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Methoxy-6- (4-methoxyphenyl) -5H- benzo [b] carbazole-11-carbonitri le], 8-ethynyl-6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Ethynyl-6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 6-([1,1'-biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile [6-([1,1 '-Biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 8- (trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl)- 5H-benzo [b] carbazole-11-carbonitrile [8- (Trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-chloro-6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Chloro-6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8- (tri Fluoromethyl) -6- (4- (trifluoromethyl) phenyl) -5H-benzo [b] carbazole-11-carbonitrile [8- (Trifluoromethyl) -6- (4- (trifluoromethyl) phenyl)- 5H-benzo [b] carbazole-11-carbonitrile], 4-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [4-Methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 4-methoxy- 8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [4-Methoxy-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole- 11-carbonitrile], 6-phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole-11-carbonitrile [6-Phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole- 11-carbonitrile], 3-chloro-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 3- Chloro-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 3-chloro-8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile [7- (Naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 9-methoxy-7- (naphthalen-1-yl) -8H-naphtho [2,1-b ] Carbazole-13-carbonitrile [9-Methoxy-7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carba zole-13-carbonitrile], 11-chloro-7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile [11-Chloro-7- (naphthalen-1 -yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 7- (naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b ] Carbazole-13-carbonitrile [7- (Naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 13- (naphthalen-2-yl ) -12H-naphtho [1,2-b] carbazole-7-carbonitrile [13- (Naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile], 11- Methoxy-13- (naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile [11-Methoxy-13- (naphthalen-2-yl) -12H-naphtho [ 1,2-b] carbazole-7-carbonitrile; 5f], 12-phenyl-13H-dibenzo [a, h] carbazole-7-carbonitrile [12-Phenyl-13H-dibenzo [a, h] carbazole-7-carbonitrile], 10-methyl-12- ( p-tolyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile [10-Methyl-12- (p-tolyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile], 10 -Methoxy-12- (4-methoxyphenyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile [10-Methoxy-12- (4-methoxyphenyl) -13H-dibenzo [a, h ] carbazole-7-carbonitrile], 7- (naphthalen-1-yl) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile [7- (naphthalen-1-yl) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile], 10- (thiophen-3-yl) -9H-thieno [2,3-b] carbazole-4-carbonite Reel [10- (Thiophen-3-yl) -9H-thieno [2,3-b] carbazole-4-carbonitrile], 6-([1,1'-biphenyl] -4-yl) -10-me Methoxy-5H-benzo [b] carbazole-11-carbonitrile [6-([1,1'-Biphenyl] -4-yl) -10-methoxy-5H-benzo [b] carbazole-11-carbonitrile], And 10-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [10-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonit rile] may be selected from the group consisting of.

Hereinafter, examples will be described in detail to help understanding of the present invention. However, the following examples are provided to more fully explain the present invention to those having average knowledge in the art, and are merely illustrative of the contents of the present invention, so the scope of the present invention is limited to the following examples. no.

<Preparation Example> Preparation of reagents and compounds

All experiments according to the invention were carried out in contact with air. Various starting materials 2-nitrocinnamaldehyde and benzyl cyanide compounds were purchased from Sigma-Aldrich and used. Al ³⁺ , Ca ²⁺ , Co ²⁺ , Cu ²⁺ , Hg ²⁺ , Ni ²⁺ , Pb ^2+, and Zn ²⁺ were purchased from Sigma-Aldrich.

TLC for analysis was performed using a pre-coated silica gel plate (Art. 5554) with Merck's fluorescence indicator, and the melting point of each compound was measured using a Fisher-Johns melting point device including a micro-cover glass. Measured and not calibrated. ¹ H NMR analysis and ¹³ C NMR analysis was measured by using CDCl _3, DMSO-d ₆ and acetone-VNS Varian spectrometer at -d ₆ or DPX spectrometer (600 MHz and 300 MHz). IR analysis (infrared analysis) was recorded with a JASCO FTIR 5300 spectrophotometer, and high-resolution mass spectra was performed using a JOEL JMS-700 spectrometer (Korea Basic Science Institute).

<Example 1> Optimization of reaction conditions

(1) Optimization of reaction conditions

In order to find the optimum reaction conditions, (E) -3- (2-nitrophenyl) acrylaldehyde (1a) and 2 equivalents of 2-phenylacetonitrile (2a), as shown in <Table 1> below The catalyst was reacted under the conditions of base use and temperature.

(a: reaction conditions (1a and 2a included in the solvent (5 mL)) b: separated yield, c: unreacted 1a is recovered)

First, the reaction for 6 hours of 1 equivalent of triethyl amine (TEA) in THF in reflux was unsuccessful (entry 1). However, when reacted with DBU (1 eq.), The desired compound 3a could be separated with a yield of 7% (entry 2). Based on these results, further experiments were conducted using different bases. That is, when NaOMe (1 eq.) And K ₂ CO ₃ (1 eq.) Were used in THF in reflux, desired compound 3a was obtained with yields of 15% and 27%, respectively (entry 3 and 4). When Cs ₂ CO ₃ (1 equivalent) was used, the yield of 3a was improved to 46% (entry 5).

Next, various transition metal catalysts combined with Cs ₂ CO ₃ were screened to increase the yield of the reaction. First, 1 equivalent of Cs ₂ CO ₃ in THF in reflux, FeCl ₃ , Fe (OTf) _{3 ,} In (OTf) ₃ , InCl ₃ , CuBr ₂ , CuCl ₂ , Cu (OAc) ₂ , and Cu (OTf) _It was confirmed that the yield of the product increases when ₂ is used together (entry 6 to 13). The highest yield of the 3a compound was obtained when CuI (5 mol%) as a catalyst and Cs ₂ CO ₃ (1 equivalent) as a base were reacted in refluxing THF for 6 hours (entry 14). However, the yield was not improved when the loading amount of CuI was increased to 10 mol% (entry 15) or decreased to 2 mol% (entry 16).

On the other hand, when the compounds 1a and 2a were reacted in a ratio of 1: 1, the yield of the product was reduced to 30%, and unreacted 1a appeared (entry 17).

Other solvents such as toluene, 1,4-dioxane, acetonitrile, DMSO showed yields of 21, 45, 53 and 16%, respectively (entry 18 to 21). When the reaction was carried out for 8 hours at 100 ° C. in a solvent-free condition, the yield of compound 3a was 15% (entry 14).

The structure of compound 3a was determined by analyzing its spectral data. The ¹ H NMR spectral data of compound 3a showed a characteristic singlet of NH protons at 7.96 ppm d . ^{The 13} C NMR spectrum showed a characteristic signal of aromatic carbon containing -CN group at d 98.9 ppm. Additional structural identification was identified by X-ray crystallographic analysis of structurally related compound 5d.

Then, in order to optimize the reaction conditions, the substrate range of the above-described tandem cyclization reaction, as shown in <Scheme 1>, (E) -3- (2-nitrophenyl) acrylaldehyde (1a ) And various 2-phenyl acetonitriles 2a to 2l.

[Scheme 1]

The tandem ring addition reaction of compound 1a and 2b-1l containing both an electron donor and a pre-attached substituent was successfully carried out. The reaction of compound 1a with compound 2b-2g, i.e., the reaction of compound 2b-2g with electron donor substituents methyl, ethyl, isopropyl and methoxy substituents in the aromatic ring of 2-phenylacetonitrile, is the desired aryl-ring. The benzo [b] carbazole 3b-3g compound formed was produced with a yield of 55-64%. In addition, 2-phenylacetonitrile compounds 2h and 2i substituted with ethynyl and phenyl produced products 3h and 3i with yields of 64% and 58%, respectively. In addition, in the reaction of 1a with 2j-2l containing the electron donor substituents trifluoromethoxy, chloride and trifluoromethyl group, 3j, 3k and 3l products were obtained at 61, 55 and 63%, respectively.

Next, by using (E) -3- (2-nitroferrin) acrylaldehyde derivative 1b-1d, as shown in <Scheme 2>, it was intended to confirm the range of the continuous ring-substitution reaction.

[Scheme 2]

As a result, when compound 1b and 2-phenylacetonitrile compound 2a or 2b were reacted with an electron-donating substituent methoxy group on the aromatic ring, desired compounds 4a and 4b were obtained at 63% and 60%, respectively. In addition, the reaction of the compound 1c and 1d and the compounds 2a, 2b or 2g containing a trifluoromethyl group or a chloride substituent, which is an electron-withdrawing substituent on the aromatic ring, yields the desired compound 4c-4f with a yield of 55-64%. there was. Therefore, the above-mentioned environmentally sustainable tandem ring formation process enables the rapid production of tetracyclic benzo [b] carbazole derivatives having various substitution patterns with high yield.

(2) generalization of the reaction

Next, in order to confirm the generality of the above-described tandem ring-forming reaction, as shown in <Scheme 3> below, pentacyclic naphtho [1,2-b]-and naphtho [2,1-b]- The versatility of the above synthetic method for the synthesis of carbazole derivatives was confirmed.

[Scheme 3]

For example, as a result of reacting 2- (naphthalen-1-yl) acetonitrile compound 2m with different (E) -3- (2-nitrophenyl) acrylaldehyde derivatives 1a-1e as a substrate, penta Cyclic naphtho [2,1-b] -carbazole derivatives 5a-5d were produced with a yield of 58-65%. In addition, upon reaction of 2- (naphthalen-2-yl) acetonitrile 2n with 1a and 1b, naphto [1,2-b] -carbazole derivatives 5e and 5f were produced with yields of 59% and 61%, respectively. . Obviously, these examples are pentacyclic naphthos formed with aryl-rings that are conjugated with a simple yet commercially available starting material through current one-port multi-element assembly methods [1,2-b]. -And the ability to be converted to naphtho [2,1-b] -carbazole skeleton.

(3) Expansion of reaction

Whether the versatility of the above synthesis method can synthesize pentacyclic dibenzo [a, h] carbazole and hexacyclic benzo [a] naphtho [1,2-h] carbazole derivatives < As shown in Scheme 4>, it was confirmed through the reaction.

[Reaction Scheme 4]

As a result, in the reaction of (E) -3- (1-nitronaphthalen-2-yl) acrylaldehyde 1f with compounds 2a, 2b or 2g, various and complex pentacyclic dibenzo [a, h] carbazole compounds 6a-6c were produced with yields of 40-48%. In addition, the reaction between 1f and 2m produced hexacyclic benzo [a] naphtho [1,2-h] carbazole derivative 6d with a yield of 45%.

Next, an experiment to expand the substrate range of the synthetic method for the production of the heteroaryl-ring-formed carbazole derivative was performed as shown in <Reaction Scheme 5>.

[Scheme 5]

For example, when 2 equivalents of 2- (thiophen-3-yl) acetonitrile (2o) containing compound 1a and heteroatoms are treated together, 10- (thiophen-3-yl) -9H- Thieno [2,3-b] carbazole-3-carbonitrile (7) could be obtained with a yield of 43%. On the basis of these results, it was confirmed that the method according to the present invention exhibits versatility not only in the synthesis of carbazole with an aryl-ring, but also in the synthesis of carbazole with a heteroaryl-ring.

(4) Identification of reaction mechanism

To illustrate the mechanism of the reaction, (E) -3- (2-nitrophenyl) -1-phenylprop-2-en-1-one (1 g), as shown in the following <Scheme 6> Control experiments were performed.

[Scheme 6]

Interestingly, the reaction of compound 1g with 2a or 2b under optimized reaction conditions produced compounds 3a and 3b with yields of 48% and 51%, respectively. These results indicate that the benzoyl groups were cleaved from the 1g substrate compound during product 3a and 3b formation.

Based on the results of the above experiment, as shown in the following <Scheme 7>, it was tested whether the carbazole molecule can be synthesized from compound 1a or 1g using two different benzyl cyanides.

[Scheme 7]

As a result, when the benzyl cyanide compounds 2f and 2i reacted with 1a, while the compounds 3f and 3i were obtained with yields of 5 and 35%, respectively, the expected cross product 8a was also obtained with a yield of 35%. Interestingly, the reaction of compound 1g with 2f and 2i produced the other products 3f and 3i with yields of 5% and 15%, respectively, while the cross product 8a with 40% yield.

The structure of the compound 8a was confirmed by comparison with ¹ H NMR data of 3f and 3g, which are structurally similar compounds. Referring to the ¹ H NMR data of 8a, a characteristic peak of the methoxy group (close to -CN group) was observed at δ 4.16 ppm. This is a result consistent with the chemical shift ( δ = 4.05 ppm) of the methoxy group (close to -CN group), while other methoxy groups of compound 3f appear in the high field ( δ = 3.58 ppm). It is also noteworthy that at 3 g, two methoxy group peaks distant from the -CN group appear in the high field ( δ = 3.93 and 3.77 ppm).

Moreover, as shown in the following <Scheme 8>, by replacing one molecule of the benzyl cyanide compound with an activated methylene substrate, multiples of compounds 1a, 2f and 1,2-diphenylethan-1-one (2p) Urea reactions were performed.

[Scheme 8]

Interestingly, the desired product, 8b, was produced with a yield of 55% along with a 5% yield of the intractable mixture (8c).

To investigate the mechanism of this reaction, the observed product and the results of the control experiment were observed, and the mechanism of formation of the 3a compound is shown in FIG. 2.

Referring to FIG. 2, in a base medium condition, a 1,4-addition reaction occurs by reacting a compound 1a with a ketenimine anion, which is suggested to be derived from compound 2a ', to produce enol compound 9. The intramolecular addition reaction of the enol compound 9 to the nitro group produces the reaction intermediate 10. In the presence of CuI, the removal of water from the intermediate 10 results in reaction intermediate 11 (path a), which is 2,5-dioxa-3-azabi to form the ester reaction intermediate 12 or 13 The formation of cyclo [2.1.0] pentane undergoes the Bayer-Billiger oxidation process. Alternatively, after functional rearrangement of the reaction intermediate 10 from -ON-OH to -NO-OH, the base-induced removal reaction of H ₂ O ₂ results in 15 via compound 14 (path b). The intramolecular Bayer-Billiger oxidation process of compound 15 with H ₂ O ₂ produces compound 12 or 13. Subsequently, the addition of 2 equivalents of ketenimine anion derived from 2a 'produces reaction intermediate 16, which is subsequently subjected to the removal of carboxylic acid to yield compound 17. When the removal reaction of HCN occurs after the tautomerization of the compound 17 occurs, the intermediate 19 is generated through the compound 18, and finally the 6π-electron cycle of the compound 19 occurs to generate the compound 20, and through oxidation in air, the final product 3a Is created.

In order to demonstrate the mechanism in forming the proposed compounds 12 and 13, the density function theory calculation was performed, and the results are shown in FIG. 3.

Referring first to FIG. 3A, each calculation was first performed in an environment without CuI, and then, in a step requiring high energy, in order to confirm the role of CuI, it was calculated in the presence of CuI. The 1,4 addition reaction of compound 2a 'to 1a was calculated as the first step. The ketenimine 2a 'compound was used as a model compound, which had a value of 47.2 kcal / mol (TS1) as an activation barrier for the intramolecular addition reaction with compound 1a. The reaction of the enol compound 9 to the nitro group that has undergone six transition states of TS2 has an activation energy of 21.5 kcal / mol. In TS2, C-N bonds are formed by the simultaneous transfer of hydrogen from -OH of enol to nitro in the presence of a base.

The likelihood of pathways a and b for the conversion of compound 10 to compound 12 was measured, in pathway a, the production of N-oxide intermediate 11 (path a) is TS3 (14.8 kcal /) through removal of H ₂ O in reaction conditions. mol). In addition, the intra-molecular Bayer-Villiger oxidation process of N-oxide intermediate 11 occurring in situ leads to compound 12 through relatively high energy variance (67.9 kcal / mol, TS5) in the absence of CuI. However, this step is aided by the addition of CuI, showing a reduction of 20 kcal / mol in the calculated energy barrier. This is presumed to be due to the joint between Cu ⁺ and the oxygen atom of 2,5-dioxa-3-azabicyclo [2.1.0] pentane, which promotes the dissociation of the NO bond in TS5-CuI.

On the other hand, in route b, the relative energy of compound 14 is only 7 kcal / mol but higher than compound 10. Formation of H ₂ O ₂ from compound 14 is more difficult than formation of compound 11 (TS4, 4.8 kcal / mol) (TS4, 34.1 kcal / mol). Interestingly, these calculation results show that through the removal process of H ₂ O (TS3 ′, 10.8 kcal / mol), compound 14 can be converted to compound 11, where 'path a' is more than 'path b'. It proves that it can happen well.

Referring to FIG. 3B of the present invention, as a result of energy calculation of successive steps, nucleophilic addition of ketenimine to imine / removal of carboxylic acid / totomization / 1,4-HCN removal / 6π-electron cycle and anoxic oxidation It can be seen that it proceeds very smoothly in the presence of CuI.

< Synthetic example > Polyaromatic  Collared Carbazole  Preparation of derivatives

1. Compound analysis

All experiments according to the present invention were performed in contact with air. TLC for analysis was performed using a pre-coated silica gel plate (Art 5554) with Merck's fluorescence indicator, in order to perform flash column chromatography. Silica gel 9385 (Merck) was used. The melting point of each compound was measured and not calibrated using a Fisher-Johns melting point apparatus with micro-cover glass, and ¹ H NMR analysis was performed in CDCl ₃ with a solvent chemical shift of 724 ppm, and 0.00 ppm as reference. The solvent chemical shift of was recorded on a TMS through a Varian-VNS (600 MHz) spectrometer. ^{The 13} C NMR spectrum was measured using a Varian-VNS (150 MHz) spectrometer in CDCl ₃ with 770 ppm as the solvent chemical shift.

Chemical shifts (d) are expressed in ppm, and J values are expressed in Hz.

Multiplicities are abbreviated as follows: s = singlet, d = doublet, t = triplet, q = quartet, br s = broad singlet, dd = double of doublet, td = double of triplet, quint = quintet, sept = septet and m = multiple terms.

IR analysis (infrared analysis) was recorded by FTIR (BIO-RAD), and high-resolution mass spectra was performed using a JOEL JMS-700 spectrometer (Korea Basic Science Institute).

2. Synthesis method

The general procedure for a CuI catalyst-based synthesis method of carbazole derivatives 3 to 8 was as follows: After filling a 50 mL 2-neck round flask dried in an oven with nitrosinnamaldehyde (0.5 mmol) or nitrochalcon (0.5 mmol) , 1.0 mmol of benzyl cyanide and 5 mol% of CuI dissolved with Cs ₂ CO ₃ (1 eq.) In 5 mL THF were added. Thereafter, each reaction mixture was refluxed under open air conditions for 6 to 10 hours until the reaction shown by TLC was completed. Then, the solvent was removed using a rotary evaporator under reduced pressure, and a residue was obtained. The residue was purified by flash column chromatography using silica gel to isolate the pure product.

Characterization data for all compounds were as follows:

2-1. 6-phenyl-5H- Benzo [b] carbazole -11- Carbonite reel [6-Phenyl-5H-benzo [b] carbazole-11-carbonitrile; 3a]

Compound 3a was obtained as a yellow solid according to the above synthesis method; mp 230-232 ° C. Obtained by column chromatography-Yield: 61% (97 mg) and hexane: ethyl acetate (9: 1) obtained by recrystallization step -52% (82 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.80 (d, J = 7.8 Hz, 1H), 8.49 (d, J = 8.4 Hz, 1H), 7.93 (s, 1H), 7.85 (d, J = 8.4 Hz , 1H), 7.68-7.53 (m, 7H), 7.49 (t, J = 7.8 Hz, 1H), 7.37 (d, J = 8.4 Hz, 1H), 7.34 (t, J = 7.8 Hz, 1H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 142.4, 136.7, 135.2, 130.29, 129.9, 129.4, 129.4, 129.1, 128.7, 127.6, 126.1, 125.4, 125.4, 125.3, 124.0, 123.2, 121.1, 120.4, 118.0, 110.6 , 98.9; IR (neat) 3337, 2211, 1465, 1396, 1237, 739, 603 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₃ H ₁₄ N ₂ : 318. 1157. Found: 318. 1158.

2-2. 8- methyl -6- (p- Tolyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [8-Methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile; 3b]

Compound 3b was obtained as a yellow solid according to the above synthesis method; mp 213-215 ° C. Yield: 61% (97 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.73 (d, J = 7.9 Hz, 1H), 8.33 (d, J = 8.5 Hz, 1H), 7.95 (s, 1H), 7.61 (s, 1H), 7.50 (t, J = 7.5 Hz, 1H), 7.45-7.41 (m, 5H), 7.34 (d, J = 8.2 Hz, 1H), 7.29 (t, J = 7.5 Hz, 1H), 2.51 (s, 3H) , 2.46 (s, 3 H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 142.2, 138.4, 136.9, 135.8, 132.2, 130.2, 130.0, 128.99, 127.7, 127.5, 126.6, 124.9, 124.1, 123.4, 122.9, 121.1, 120.1, 118.1, 110.4, 98.4 , 21.8, 21.3; IR (neat) 3316, 2228, 1750, 1603, 1438, 1230, 1080, 707 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₅ H ₁₈ N ₂ : 346. 1470. Found: 346. 1466.

2-3. 10- methyl -6- (o- Tolyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [10-Methyl-6- (o- tolyl ) -5H-benzo [b] carbazole-11-carbonitrile; 3c]

Compound 3c was obtained as a yellow solid according to the above synthesis method; mp 245-247 ° C. Yield: 55% (95 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 9.01 (d, J = 8.0 Hz, 1H), 7.70 (s, 1H), 7.58-7.52 (m, 1H), 7.50-7.46 (m, 2H), 7.46- 7.39 (m, 2H), 7.38-7.33 (m, 3H), 7.31 (t, J = 7.4 Hz, 2H), 3.31 (s, 3H), 1.94 (s, 3H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 142.6, 137.5, 136.2, 134.9, 134.6, 131.1, 130.8, 130.3, 129.2, 128.9, 128.9, 128.3, 128.0, 126.6, 125.7, 124.4, 124.3, 123.7, 121.5, 121.13 , 120.2, 110.4, 97.5, 23.8, 19.6; IR (neat) 3320, 2209, 1624, 1470, 1346, 1230, 1087, 746 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₅ H ₁₈ N ₂ : 346. 1470. Found: 346. 1470.

2-4. 8-ethyl-6- (4- Ethyl phenyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [8-Ethyl-6- (4- ethylphenyl ) -5H-benzo [b] carbazole-11-carbonitrile; 3d]

Compound 3d was obtained as a yellow solid according to the above synthesis method; mp 195-197 ° C. Yield: 60% (112 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.77 (d, J = 7.9 Hz, 1H), 8.40 (d, J = 8.6 Hz, 1H), 7.93 (s, 1H), 7.64 (s, 1H), 7.52 (dd, J = 11.2, 4.1 Hz, 1H), 7.50-7.44 (m, 5H), 7.35 (d, J = 8.1 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H), 2.83 (q, J = 7.6 Hz, 2H), 2.76 (q, J = 7.6 Hz, 2H), 1.39 (t, J = 7.6 Hz, 3H), 1.25 (t, J = 7.6 Hz, 3H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 144.6, 142.3, 142.2, 136.9, 132.5, 130.3, 130.1, 129.0, 128.9, 128.58, 127.8, 126.7, 126.7, 125.2, 123.7, 123.0, 123.0, 121.2, 120.2, 118.2 , 110.5, 98.5, 29.2, 28.7, 15.5, 15.4; IR (neat) 3329, 2213, 1708, 1620, 1516, 1459, 1339, 1185, 1134, 1041, 816, 746 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₇ H ₂₂ N ₂ : 374. 1783. Found: 374. 1779.

2-5. 8-isopropyl-6- (4- Isopropylphenyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [8-Isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11-carbonitrile; 3e]

Compound 3e was obtained as a yellow solid according to the above synthesis method; mp 175-177 ° C. Yield: 59% (118 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.74 (d, J = 7.9 Hz, 1H), 8.39 (d, J = 8.7 Hz, 1H), 7.92 (s, 1H), 7.65 (s, 1H), 7.54 -7.41 (m, 6H), 7.33 (d, J = 8.1 Hz, 1H), 7.28 (t, J = 7.5 Hz, 1H), 3.05 (m, 1H), 2.99 (m, 1H), 1.37 (d, J = 6.9 Hz, 6H), 1.24 (d, J = 6.9 Hz, 6H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 149.2, 146.6, 142.2, 136.9, 132.6, 130.2, 130.1, 129.0, 128.0, 127.8, 127.4, 127.1, 126.8, 125.3, 125.0, 123.9, 123.0, 121.8, 121.2, 120.1 , 118.2, 110.5, 98.4, 34.4, 34.0, 24.0, 23.8; IR (neat) 3324, 2217, 1753, 1608, 1447, 1334, 1234, 750 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₉ H ₂₆ N ₂ : 402. 2096. Found: 402.2099.

2-6. 10- Methoxy -6- (2- Methoxyphenyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [10- Methoxy -6- (2-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile; 3f]

Compound 3f was obtained as a yellow solid according to the above synthesis method; mp 280-282 ° C. Yield: 58% (109 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.97 (d, J = 8.0 Hz, 1H), 7.80 (s, 1H), 7.48-7.41 (m, 2H), 7.26 (m, 4H), 7.19-7.16 ( m, 1H), 7.13-7.05 (m, 2H), 6.80 (d, J = 7.5 Hz, 1H), 4.05 (s, 3H), 3.58 (s, 3H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 157.45 155.50 142.0, 137.4, 132.1, 132.0, 130.3, 128.8, 128.2, 125.7, 123.8, 123.8, 121.7, 121.2, 120.8, 120.5, 120.1, 119.8, 118.2, 111.8, 110.2 , 103.6, 96.3, 55.6; IR (neat) 3342, 2909, 2212, 1608, 1520, 1422, 1376, 1353, 1228, 987, 794 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₅ H ₁₈ N ₂ O ₂ : 378.1368. Found: 378.1366.

2-7. 8- Methoxy -6- (4- Methoxyphenyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [8- Methoxy -6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile; 3g]

According to the above synthesis method, 3 g of a compound was obtained as a yellow solid; mp 365-367 ° C. Yield: 64% (120 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.72 (d, J = 7.9 Hz, 1H), 8.34 (d, J = 9.1 Hz, 1H), 7.90 (s, 1H), 7.50 (t, J = 7.6 Hz , 1H), 7.46 (d, J = 8.1 Hz, 2H), 7.34 (d, J = 8.1 Hz, 1H), 7.30 (t, J = 7.6 Hz, 1H), 7.28-7.23 (m, 1H), 7.15 (d, J = 8.1 Hz, 2H), 7.12 (d, J = 1.6 Hz, 1H), 3.93 (s, 3H), 3.77 (s, 3H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 159.7, 157.8, 141.9, 137.5, 131.6, 131.2, 128.7, 127.9, 127.3, 126.8, 125.5, 124.8, 122.7, 121.3, 120.2, 118.4, 114.9, 113.7, 110.4, 103.5 , 98.6, 55.4, 55.2; IR (neat) 3333, 2913, 2207, 1601, 1509, 1462, 1376, 1355, 1218, 763 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₅ H ₁₈ N ₂ O ₂ : 378. 1368. Found: 378.1367.

2-8. 8- Ethynyl -6- (4- Ethynylphenyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [8- Ethynyl -6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile; 3h]

Compound 3h was obtained as a yellow solid according to the above synthesis method except that CuI was not used; mp> 300 ° C. Yield: 64% (117 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.77 (d, J = 7.9 Hz, 1H), 8.42 (d, J = 8.7 Hz, 1H), 7.95 (d, J = 14.6 Hz, 2H), 7.78 (d , J = 8.1 Hz, 2H), 7.65 (dd, J = 8.7, 1.5 Hz, 1H), 7.57 (dd, J = 11.2, 4.0 Hz, 1H), 7.52 (d, J = 8.1 Hz, 2H), 7.39 (d, J = 8.1 Hz, 1H), 7.36 (t, J = 7.6 Hz, 1H), 3.22 (s, 1H), 3.15 (s, 1H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 142.5, 137.0, 135.1, 133.3, 130.3, 129.9, 129.4, 129.1, 128.5, 128.2, 128.1, 125.5, 123.3, 123.0, 122.8, 120.9, 120.8, 120.0, 117.5, 110.7 , 99.4, 83.6, 82.8, 78.8, 78.7; IR (neat) 3363, 2949, 2208, 1624, 1507, 1484, 1336, 1378, 1229, 754 cm ^-1 ; HRMS m / z (M ₊ ) calcd for C ₂₇ H ₁₄ N ₂ : 366.1157. Found: 366.1154.

2-9. 6-([1,1’- Biphenyl ] -4-yl) -8-phenyl-5H- Benzo [b] carbazole -11- Carbonite reel [6-([1,1'-Biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile; 3i]

Compound 3i was obtained as a yellow solid according to the above synthesis method; mp> 300 ° C. Yield: 58% (150 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.81 (d, J = 7.9 Hz, 1H), 8.56 (d, J = 8.8 Hz, 1H), 8.11 (d, J = 1.5 Hz, 1H), 8.03 (s , 1H), 7.92-7.85 (m, 3H), 7.76-7.71 (m, 2H), 7.67 (d, J = 7.9 Hz, 2H), 7.64-7.60 (m, 2H), 7.59-7.55 (m, 1H) ), 7.52 (t, J = 7.8 Hz, 2H), 7.44-7.39 (m, 4H), 7.35 (q, J = 7.9 Hz, 2H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 142.5, 141.6, 140.7, 140.2, 138.9, 137.1, 134.03, 130.7, 130.2, 129.4, 129.0, 128.9, 128.4, 128.2, 127.8, 127.6, 127.5, 127.1, 125.9, 125.4 , 123.9, 123.2, 123.1, 121.2, 120.5, 118.0, 110.6, 98.9; IR (neat) 3364, 2218, 1624, 1505, 1474, 1339, 1358, 1239, 764 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₃₅ H ₂₂ N ₂ : 470.1783. Found: 470.1784.

2-10. 8-( Trifluoromethoxy ) -6- (4- ( Trifluoromethoxy ) Phenyl) -5H- Benzo [b] carbazole -11- Carbonite reel [8- (Trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl) -5H-benzo [b] carbazole-11-carbonitrile; 3j]

Compound 3j was obtained as a yellow solid according to the above synthesis method; mp 265-267 ° C. Yield: 61% (148 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.76 (d, J = 8.0 Hz, 1H), 8.51 (d, J = 9.2 Hz, 1H), 7.97 (s, 1H), 7.59 (t, J = 7.9 Hz , 4H), 7.53 (d, J = 8.1 Hz, 2H), 7.50 (d, J = 9.2 Hz, 1H), 7.42 (d, J = 8.1 Hz, 1H), 7.37 (t, J = 7.6 Hz, 1H ); ¹³ C NMR (150 MHz, CDCl ₃ ) d 149.7, 147.3, 142.4, 137.5, 133.0, 131.7, 130.2, 130.0, 128.1, 127.6, 127.0, 123.2, 122.1, 122.0, 121.3, 120.9, 120.7, 119.6, 119.6, 117.3 , 115.5, 110.8, 99.6; IR (neat) 3315, 2219, 1597, 1502, 1457, 1375, 1368, 1268, 742 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₅ H ₁₂ F ₆ N ₂ O ₂ : 486.0803. Found: 486.0801.

2-11. 8- Chloro -6- (4- Chlorophenyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [8- Chloro -6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile; 3k]

Compound 3k was obtained as a yellow solid according to the above synthesis method; mp> 300 ° C. Yield: 55% (106 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.75 (d, J = 8.0 Hz, 1H), 8.40 (d, J = 9.0 Hz, 1H), 7.91 (s, 1H), 7.74 (d, J = 1.9 Hz , 1H), 7.65 (d, J = 8.3 Hz, 2H), 7.60-7.53 (m, 2H), 7.48 (d, J = 8.3 Hz, 2H), 7.39 (d, J = 8.1 Hz, 1H), 7.35 (t, J = 7.6 Hz, 1H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 142.4, 137.3, 135.2, 132.9, 132.6, 131.6, 130.5, 130.1, 30.0, 129.8, 127.8, 127.1, 127.0, 126.4, 123.7, 123.2, 121.6, 120.8, 117.4, 110.7 , 99.5; IR (neat) 3356, 2206, 1750, 1601, 1448, 1344, 1230, 1088, 807 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₃ H ₁₂ C _l2 N ₂ : 386.0378. Found: 386.0377.

2-12. 8-( Trifluoromethyl ) -6- (4- ( Trifluoromethyl ) Phenyl) -5H- Benzo [b] carbazole -11- Carbonite reel [8- (Trifluoromethyl) -6- (4- (trifluoromethyl) phenyl) -5H-benzo [b] carbazole-11-carbonitrile; 3l]

Compound 3l was obtained as a yellow solid according to the above synthesis method; mp = 240-242 ° C. Yield: 63% (143 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.79 (d, J = 8.0 Hz, 1H), 8.59 (d, J = 8.8 Hz, 1H), 8.04 (s, 1H), 8.00-7.94 (m, 3H) , 7.78 (d, J = 8.8 Hz, 1H), 7.72 (d, J = 7.8 Hz, 2H), 7.62 (t, J = 7.7 Hz, 1H), 7.43 (d, J = 8.1 Hz, 1H), 7.38 (t, J = 7.6 Hz, 1H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 142.7, 138.1, 137.3, 131.6, 131.4, 130.7, 130.5, 129.8, 129.3, 128.4, 126.8, 126.7, 124.9, 123.4, 123.1, 123.1, 122.9, 122.6, 121.1, 120.6 , 117.1, 110.9, 99.9; IR (neat) 3324, 2231, 1584, 1515, 1461, 1394, 1355, 1266, 752 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₅ H ₁₂ F ₆ N ₂ : 454.0905. Found: 454.0903.

2-13. 4- Methoxy -6-phenyl-5H- Benzo [b] carbazole -11- Carbonite reel [4- Methoxy -6-phenyl-5H-benzo [b] carbazole-11-carbonitrile; 4a]

Compound 4a was obtained as a yellow solid according to the above synthesis method; mp 252-254 ° C. Yield: 63% (109 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.49 (d, J = 8.4 Hz, 1H), 8.39 (d, J = 8.0 Hz, 1H), 8.04 (s, 1H), 7.84 (d, J = 8.6 Hz , 1H), 7.65 (t, J = 7.4 Hz, 2H), 7.60 (m, 2H), 7.56 (d, J = 7.7 Hz, 2H), 7.50-7.45 (m, 1H), 7.28 (t, J = 7.9 Hz, 1H), 7.04 (d, J = 7.8 Hz, 1H), 3.97 (s, 3H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 145.2, 136.4, 135.2, 132.9, 130.3, 129.9, 129.4, 129.2, 128.6, 127.9, 126.0, 125.4, 125.2, 124.6, 121.9, 120.8, 118.0, 115.2, 109.2, 107.5 , 99.1, 55.5; IR (neat) 3362, 2217, 1742, 1516, 1458, 1339, 1185, 1134, 816, 745 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₄ H ₁₆ N _{2 O} : 348.1263. Found: 348.1260.

2-14. 4- Methoxy -8- methyl -6- (p- Tolyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [4- Methoxy -8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile; 4b]

Compound 4b was obtained as a yellow solid according to the above synthesis method; mp 293-295 ° C. Yield: 60% (112 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.34 (t, J = 7.8 Hz, 2H), 8.00 (s, 1H), 7.58 (s, 1H), 7.46-7.35 (m, 5H), 7.22 (t, J = 4.0 Hz, 1H), 6.99 (d, J = 7.8 Hz, 1H), 3.93 (s, 3H), 2.51 (s, 3H), 2.44 (s, 3H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 145.2, 138.3, 136.7, 135.8, 132.7, 132.2, 130.2, 130.1, 130.1, 127.9, 127.6, 127.0, 125.1, 124.2, 124.0, 122.1, 120.6, 118.1, 115.1, 108.9 , 98.7, 55.5, 21.9, 21.4; IR (neat) 3343, 2912, 2208, 1601, 1503, 1452, 1397, 1349, 1223, 982, 791 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₆ H ₂₀ N _{2 O} : 376.1576. Found: 376.1576.

2-15. 6-phenyl-3- ( Trifluoromethyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [6-Phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole-11-carbonitrile; 4c]

Compound 4c was obtained as a yellow solid according to the above synthesis method; mp 205-207 ° C. Yield: 64% (123 mg). ¹ H NMR (600 MHz, DMSO-d ₆ ) d 11.43 (s, 1H), 8.74 (d, J = 8.3 Hz, 1H), 8.36 (d, J = 8.4 Hz, 1H), 7.86 (s, 1H) , 7.78 (d, J = 8.6 Hz, 1H), 7.73 (dd, J = 14.1, 6.7 Hz, 3H), 7.69-7.65 (m, 2H), 7.62 (dd, J = 11.2, 4.2 Hz, 1H), 7.60-7.57 (m, 2H); ¹³ C NMR (150 MHz, DMSO-d ₆ ) d 142.7, 137.3, 134.4, 130.3, 129.9, 129.2, 128.9, 128.7, 128.1, 126.8, 126.1, 125.3, 125.2, 124.5, 123.5, 122.6, 122.4, 117.3, 115.8 , 108.7, 98.3; IR (neat) 3298, 2935, 2231, 1653, 1521, 1382, 1351, 1227, 993, 794 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₄ H ₁₃ F ₃ N ₂ : 386.1031. Found: 386.1028.

2-16. 3- Chloro -6-phenyl-5H- Benzo [b] carbazole -11- Carbonite reel [3- Chloro -6-phenyl-5H-benzo [b] carbazole-11-carbonitrile; 4d]

Compound 4d was obtained as a yellow solid according to the above synthesis method; mp 258-260 ° C. Yield: 55% (96 mg). ¹ H NMR (600 MHz, CDCl ₃ + DMSO-d ₆ ) d 10.46 (s, 1H), 8.55 (d, J = 8.4 Hz, 1H), 8.34 (d, J = 8.4 Hz, 1H), 7.74 (d , J = 8.6 Hz, 1H), 7.59 (t, J = 7.6 Hz, 2H), 7.53 (dd, J = 16.3, 8.0 Hz, 2H), 7.49 (d, J = 6.3 Hz, 2H), 7.45 (s , 1H), 7.44-7.39 (m, 1H), 7.17 (d, J = 8.5 Hz, 1H); ¹³ C NMR (150 MHz, CDCl ₃ + DMSO-d ₆ ) d 143.7, 137.5, 136.5, 134.6, 133.9, 129.8, 129.3, 128.4, 128.0, 127.6, 126.2, 125.2, 124.8, 124.6, 124.0, 123.8, 122.5, 119.2, 117.2, 110.8, 97.4; IR (neat) 3321, 2235, 1648, 1521, 1485, 1333, 1121, 1134, 812, 747 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₃ H ₁₃ ClN ₂ : 352.0767. Found: 352.0768.

2-17. 3- Chloro -8- methyl -6- (p- Tolyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [3- Chloro -8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile; 4e]

Compound 4e was obtained as a yellow solid according to the above synthesis method; mp> 300 ° C. Yield: 58% (110 mg). ¹ H NMR (600 MHz, CDCl ₃ + DMSO-d ₆ ) d 10.29 (s, 1H), 8.49 (d, J = 8.4 Hz, 1H), 8.20 (d, J = 8.5 Hz, 1H), 7.50 (d , J = 5.6 Hz, 1H), 7.44-7.31 (m, 6H), 7.13 (d, J = 8.4 Hz, 1H), 2.47 (s, 3H), 2.38 (s, 3H); ¹³ C NMR (150 MHz, CDCl ₃ + DMSO-d ₆ ) d 143.4, 139.7, 137.1, 136.7, 134.9, 134.6, 133.5, 131.7, 131.6, 129.6, 129.1, 126.4, 125.2, 123.2, 122.6, 119.1, 118.4, 117.8, 117.3, 111.9, 97.0, 21.1, 20.6; IR (neat) 3353, 2919, 2209, 1602, 1501, 1442, 1396, 1359, 1228, 997, 799 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₅ H ₁₇ ClN ₂ : 380.1080. Found: 380.1083.

2-18. 3- Chloro -8- Methoxy -6- (4- Methoxyphenyl ) -5H- Benzo [b] carbazole -11- Carbonite reel [3- Chloro -8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile; 4f]

Compound 4f was obtained as a yellow solid according to the above synthesis method; mp 283-285 ° C. Yield: 62% (127 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.53 (d, J = 8.4 Hz, 1H), 8.26 (d, J = 9.2 Hz, 1H), 7.82 (s, 1H), 7.40 (d, J = 8.4 Hz , 2H), 7.24-7.16 (m, 3H), 7.11 (d, J = 8.4 Hz, 2H), 7.06 (d, J = 2.0 Hz, 1H), 3.88 (s, 3H), 3.71 (s, 3H) ; ¹³ C NMR (150 MHz, CDCl ₃ ) d 159.8, 158.0, 142.4, 137.6, 134.5, 131.8, 131.23, 127.0, 126.8, 125.0, 124.7, 123.5, 122.8, 120.8, 120.0, 118.7, 117.9, 115.0, 110.6, 103.6 , 98.7, 55.4, 55.2; IR (neat) 3314, 2203, 170t, 1625, 1516, 1454, 1333, 1181, 1138, 826, 745 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₅ H ₁₇ ClN ₂ O ₂ : 412.0979. Found: 412.0981.

2-19. 7- (naphthalen-1-yl) -8H- Naphtho [2,1-b] carbazole -13- Carbonite reel [7- ( Naphthalen -One- yl ) -8H-naphtho [2,1-b] carbazole-13-carbonitrile; 5a]

Compound 5a was obtained as a yellow solid according to the above synthesis method; mp> 300 ° C. Yield: 58% (121 mg). ¹ H NMR (600 MHz, DMSO-d ₆ ) d 11.17 (s, 1H), 9.92 (d, J = 8.6 Hz, 1H), 8.93 (d, J = 8.1 Hz, 1H), 8.23 (d, J = 8.3 Hz, 1H), 8.14 (d, J = 8.3 Hz, 1H), 7.95 (d, J = 7.7 Hz, 1H), 7.81 (m, 2H), 7.75-7.61 (m, 3H), 7.55-7.46 ( m, 3H), 7.37 (t, J = 7.5 Hz, 1H), 7.28 (t, J = 7.6 Hz, 1H), 7.22 (d, J = 9.2 Hz, 1H), 7.08 (d, J = 8.5 Hz, 1H); ¹³ C NMR (150 MHz, DMSO-d ₆ ) d 143.0, 137.8, 133.6, 132.7, 131.8, 131.4, 129.6, 129.0, 128.9, 128.8, 128.7, 128.5, 127.4, 127.1, 126.8, 126.7, 126.2, 126.2, 126.1 , 125.1, 124.1, 123.9, 121.8, 121.1, 120.0, 119.6, 111.8, 96.1; IR (neat) 3354, 2219, 1754, 1584, 1455, 1337, 1188, 746 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₃₁ H ₁₈ N ₂ : 418.1470. Found: 418.1467.

2-20. 9- Methoxy -7- (naphthalen-1-yl) -8H- Naphtho [2,1-b] carbazole -13- Carbonite reel [9- Methoxy -7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile; 5b]

Compound 5b was obtained as a yellow solid according to the above synthesis method; mp> 300 ° C. Yield: 62% (138 mg). ¹ H NMR (600 MHz, CDCl ₃ + DMSO-d ₆ ) d 9.91 (d, J = 8.6 Hz, 1H), 8.52 (d, J = 8.2 Hz, 1H), 8.38 (s, 1H), 7.95 (d , J = 8.3 Hz, 1H), 7.88 (d, J = 8.3 Hz, 1H), 7.71 (d, J = 7.6 Hz, 1H), 7.66-7.61 (m, 1H), 7.60-7.54 (m, 1H) , 7.51 (t, J = 7.4 Hz, 1H), 7.46 (d, J = 6.3 Hz, 1H), 7.37 (dd, J = 17.7, 8.5 Hz, 2H), 7.16 (dd, J = 15.8, 8.5 Hz, 2H), 7.08 (dd, J = 11.1, 4.1 Hz, 1H), 7.01 (d, J = 8.5 Hz, 1H), 6.86 (d, J = 7.8 Hz, 1H), 3.71 (s, 3H); ¹³ C NMR (150 MHz, CDCl ₃ + DMSO-d ₆ ) d 145.0, 137.1, 133.6, 132.5, 132.2, 131.8, 131.5, 129.9, 129.2, 128.9, 128.3, 128.2, 128.1, 127.3, 126.9, 126.8, 126.4, 126.4, 126.1, 125.5, 125.1, 124.5, 124.1, 124.0, 121.9, 121.0, 120.3, 114.7, 108.3, 97.2, 55.0; IR (neat) 3309, 2216, 1592, 1507, 1453, 1398, 1322, 1269, 743 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₃₂ H ₂₀ N _{2 O} : 448.1576. Found: 448.1576.

2-21. 11- Chloro -7- (naphthalen-1-yl) -8H- Naphtho [2,1-b] carbazole -13- Carbonite reel [11- Chloro -7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile; 5c]

Compound 5c was obtained as a yellow solid according to the above synthesis method; mp> 300 ° C. Yield: 60% (135 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 10.05 (d, J = 8.5 Hz, 1H), 9.05 (d, J = 2.0 Hz, 1H), 8.13 (d, J = 8.3 Hz, 1H), 8.05 (d , J = 8.3 Hz, 1H), 7.87 (d, J = 7.7 Hz, 1H), 7.84-7.78 (m, 2H), 7.75 (dd, J = 8.3, 6.9 Hz, 1H), 7.71-7.66 (m, 1H), 7.67-7.63 (m, 1H), 7.58 (d, J = 9.1 Hz, 1H), 7.55 (ddd, J = 8.0, 6.8, 1.0 Hz, 1H), 7.48 (dd, J = 8.6, 2.0 Hz , 1H), 7.38 (d, J = 9.1 Hz, 1H), 7.29 (ddd, J = 8.1, 6.8, 1.1 Hz, 1H), 7.25 (s, 1H), 7.20 (d, J = 8.5 Hz, 1H) ; ¹³ C NMR (150 MHz, CDCl ₃ ) d 140.0, 137.9, 134.0, 132.6, 132.0, 130.8, 129.5, 129.5, 128.8, 128.8, 128.6, 128.6, 128.3, 127.4, 127.1, 126.7, 126.0, 125.9, 125.9, 125.7 , 125.5, 125.0, 124.2, 124.1, 122.7, 122.6, 120.9, 111.6, 98.1; IR (neat) 3324, 2227, 1708, 1617, 1514, 1398, 1184, 1133, 816, 744 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₃₁ H ₁₇ ClN ₂ : 452.1080. Found: 452.1083.

2-22. 7- (naphthalen-1-yl) -10- ( Trifluoromethyl ) -8H- Naphtho [2,1-b] carbazole -13- Carbonite reel [7- (Naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile; 5d]

Compound 5d was obtained as a yellow solid according to the above synthesis method; mp = 270-272 ° C. Yield: 65% (157 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 10.04 (d, J = 8.6 Hz, 1H), 9.18 (d, J = 8.4 Hz, 1H), 8.13 (d, J = 8.3 Hz, 1H), 8.04 (d , J = 8.3 Hz, 1H), 7.97 (s, 1H), 7.88 (d, J = 7.7 Hz, 1H), 7.80 (t, J = 7.8 Hz, 1H), 7.77-7.72 (m, 1H), 7.68 (t, J = 7.3 Hz, 1H), 7.65-7.56 (m, 4H), 7.54 (t, J = 7.4 Hz, 1H), 7.40 (d, J = 9.2 Hz, 1H), 7.28 (t, J = 7.5 Hz, 1H), 7.18 (d, J = 8.5 Hz, 1H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 140.8, 138.1, 134.1, 132.4, 132.0, 131.9, 131.2, 130.2, 130.0, 129.6, 129.5, 128.8, 128.7, 128.6, 127.6, 127.2, 126.7, 126.2, 126.0, 125.9 , 125.5, 125.3, 125.2, 125.0, 124.4, 124.1, 123.7, 123.4, 121.0, 117.0 (q, J = 3 Hz), 107.9 (q, J = 3 Hz), 98.5; IR (neat) 3307, 2210, 1595, 1505, 1456, 1395, 1325, 1262, 747 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₃₂ H ₁₇ F ₃ N ₂ : 486.1344. Found: 486.1345.

2-23. 13- (naphthalen-2-yl) -12H- Naphtho [1,2-b] carbazole -7- Carbonite reel [13- ( Naphthalen -2- yl ) -12H-naphtho [1,2-b] carbazole-7-carbonitrile; 5e]

Compound 5e was obtained as a yellow solid according to the above synthesis method; mp = 298-300 ° C. Yield: 59% (123 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.80 (d, J = 7.9 Hz, 1H), 8.42 (d, J = 9.0 Hz, 1H), 8.13 (d, J = 8.3 Hz, 1H), 8.11 (s , 1H), 8.04 (d, J = 8.0 Hz, 1H), 7.97-7.91 (m, 2H), 7.87 (d, J = 7.8 Hz, 1H), 7.84 (d, J = 9.0 Hz, 1H), 7.80 (d, J = 8.6 Hz, 1H), 7.68-7.62 (m, 2H), 7.54-7.49 (m, 2H), 7.43 (t, J = 7.2 Hz, 1H), 7.35 (t, J = 8.0 Hz, 2H), 7.02 (dd, J = 11.4, 4.1 Hz, 1H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 141.5, 138.8, 136.8, 134.2, 133.1, 133.1, 130.5, 130.2, 129.3, 128.8, 128.6, 128.2, 128.1, 127.9, 127.8, 127.7, 127.2, 127.0, 127.0, 126.7 , 126.5, 125.6, 125.5, 124.9, 124.0, 122.8, 121.0, 120.5, 118.3, 110.7, 100.5; IR (neat) 3291, 2224, 1743, 1595, 1494, 1457, 1392, 1150, 818, 741 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₃₁ H ₁₈ N ₂ : 418.1470. Found: 418.1468.

2-24. 11- Methoxy -13- (naphthalen-2-yl) -12H- Naphtho [1,2-b] carbazole -7- Carbonite reel [11- Methoxy -13- (naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile; 5f]

Compound 5f was obtained as a yellow solid according to the above synthesis method; mp> 300 ° C. Yield: 61% (136 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.43 (d, J = 9.0 Hz, 1H), 8.39 (d, J = 8.1 Hz, 1H), 8.14 (d, J = 8.3 Hz, 1H), 8.11 (s , 1H), 8.05 (d, J = 8.0 Hz, 1H), 8.03 (s, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.86 (dd, J = 12.1, 8.4 Hz, 2H), 7.73 (d, J = 8.6 Hz, 1H), 7.69-7.61 (m, 2H), 7.52 (dd, J = 8.3, 1.6 Hz, 1H), 7.42 (t, J = 7.4 Hz, 1H), 7.29 (t, J = 7.9 Hz, 1H), 7.01 (dd, J = 10.2, 4.6 Hz, 2H), 3.90 (s, 3H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 145.3, 138.4, 136.7, 134.2, 133.1, 133.1, 132.0, 130.5, 130.2, 129.4, 128.6, 128.3, 128.1, 128.0, 127.8, 127.8, 127.2, 126.9, 126.9, 126.7 , 126.5, 126.0, 125.5, 125.2, 124.0, 121.9, 120.9, 118.2, 114.8, 108.5, 100.7, 55.4; IR (neat) 3319, 2234, 1751, 1532, 1498, 1447, 1332, 1157, 817, 743 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₃₂ H ₂₀ N _{2 O} : 448.1576. Found: 448.1578.

2-25. 12-phenyl-13H- Dibenzo [a, h] carbazole -7- Carbonite reel [12-Phenyl-13H- dibenzo [a, h] carbazole -7-carbonitrile; 6a]

Compound 6a was obtained as a yellow solid according to the above synthesis method; mp 294-292 ° C. Yield: 48% (88 mg). ¹ H NMR (600 MHz, CDCl ₃ + DMSO-d ₆ ) d 10.89 (s, 1H), 8.70 (d, J = 8.7 Hz, 1H), 8.62 (d, J = 8.2 Hz, 1H), 8.39 (d , J = 8.4 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.75 (d, J = 8.5 Hz, 1H), 7.63 (dd, J = 8.0, 5.2 Hz, 3H), 7.59-7.49 (m, 5H), 7.46 (t, J = 7.5 Hz, 1H), 7.43-7.36 (m, 1H); ¹³ C NMR (150 MHz, CDCl ₃ + DMSO-d ₆ ) d 139.9, 134.6, 133.7, 132.9, 130.6, 129.9, 129.2, 128.1, 127.8, 127.6, 127.5, 126.4, 126.0, 125.5, 124.9, 124.4, 124.1, 123.6, 123.4, 122.8, 122.1, 119.5, 118.8, 114.6, 99.3; IR (neat) 3314, 2212, 1645, 1562, 1459, 1395, 1175, 817, 745 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₇ H ₁₆ N ₂ : 368.1313. Found: 368.1316.

2-26. 10- methyl -12- (p- Tolyl ) -13H- Dibenzo [a, h] carbazole -7- Carbonite reel [10-Methyl-12- (p- tolyl ) -13H-dibenzo [a, h] carbazole-7-carbonitrile; 6b]

Compound 6b was obtained as a yellow solid according to the above synthesis method; mp 297-299 ° C. Yield: 45% (89 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.51 (d, J = 8.7 Hz, 1H), 8.25 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.75 (t, J = 8.3 Hz , 2H), 7.45 (d, J = 8.7 Hz, 1H), 7.38 (s, 1H), 7.33-7.25 (m, 3H), 7.20 (d, J = 8.7 Hz, 2H), 7.12 (t, J = 8.7 Hz, 1H), 6.97 (s, 1H), 2.30 (s, 3H), 2.21 (s, 3H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 139.0, 138.6, 136.2, 135.5, 133.7, 132.2, 130.2, 130.2, 129.7, 129.5, 129.1, 128.2, 128.1, 127.1, 126.8, 125.8, 125.0, 124.3, 121.1, 121.0 , 120.3, 120.2, 118.5, 116.4, 97.6, 21.94, 21.4; IR (neat) 3323, 2216, 1621, 1571, 1452, 1365, 1134, 1031, 826, 747 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₉ H ₂₀ N ₂ : 396.1626. Found: 396.1623.

2-27. 10- Methoxy -12- (4- Methoxyphenyl ) -13H- Dibenzo [a, h] carbazole -7- Carbonite reel [10- Methoxy -12- (4-methoxyphenyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile; 6c]

Compound 6c was obtained as a yellow solid according to the above synthesis method; mp 285-287 ° C. Yield: 40% (85 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 8.75 (d, J = 8.7 Hz, 1H), 8.52 (s, 1H), 8.39 (d, J = 9.1 Hz, 1H), 8.02 (dd, J = 13.5, 7.7 Hz, 2H), 7.72 (d, J = 8.7 Hz, 1H), 7.58-7.56 (m 4H), 7.33-7.29 (m, 1H), 7.23 (d, J = 7.8 Hz, 2H), 7.17 (s , 1H), 3.98 (t, J = 8.8 Hz, 3H), 3.80 (t, J = 3.2 Hz, 3H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 159.8, 157.5, 138.6, 136.8, 133.6, 131.3, 131.0, 129.1, 128.0, 127.3, 126.7, 126.0, 125.8, 125.5, 123.3, 121.0, 121.0, 120.3, 120.1, 118.7 , 118.4, 116.6, 115.1, 103.6, 97.7, 55.46, 55.2; IR (neat) 3354, 2208, 1584, 1458, 1325, 1285, 1134, 1081, 851, 756 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₉ H ₂₀ N ₂ O ₂ : 428.1525. Found: 428.1525.

2-28. 7- (naphthalen-1-yl) -8H- Benzo [a] naphtho [1,2-h] carbazole -15- Carbonite reel [7- ( naphthalen -One- yl ) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile; 6d]

Compound 6d was obtained as a yellow solid according to the above synthesis method; mp> 300 ° C. Yield: 45% (105 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 10.10 (d, J = 8.6 Hz, 1H), 9.12 (d, J = 8.9 Hz, 1H), 8.51 (s, 1H), 8.17 (d, J = 8.3 Hz , 1H), 8.07 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.91-7.87 (m, 2H), 7.82-7.76 (m, 3H), 7.73 (d, J = 6.7 Hz, 1H), 7.68 (t, J = 7.3 Hz, 1H), 7.55 (dd, J = 8.6, 5.0 Hz, 3H), 7.48 (t, J = 7.5 Hz, 1H), 7.37 (d, J = 9.1 Hz, 1H), 7.26 (t, J = 8.9 Hz, 2H); ₁₃ C NMR (150 MHz, CDCl ₃ ) d 138.5, 136.7, 134.1, 133.4, 132.9, 132.2, 132.1, 129.6, 129.5, 128.96, 128.7, 128.6, 128.6, 127.5, 127.5, 127.3, 127.1, 126.8, 126.8, 126.7 , 126.4, 125.9, 125.7, 125.7, 125.2, 124.5, 124.4, 121.6, 121.2, 121.1, 120.5, 120.3, 116.9, 96.9; IR (neat) 3314, 2231, 1707, 1620, 1511, 1458, 1359, 1182, 823, 754 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₃₅ H ₂₀ N ₂ : 468.1626. Found: 468.1629.

2-29. 10- (thiophen-3-yl) -9H- Thieno [2,3-b] carbazole -4- Carbonite reel [10- ( Thiophen -3- yl ) -9H-thieno [2,3-b] carbazole-4-carbonitrile; 7]

Compound 7 was obtained as a brown solid according to the above synthesis method; mp = 275-277 ° C. Yield: 43% (70 mg). ¹ H NMR (600 MHz, DMSO-d ₆ ) d 11.43 (s, 1H), 8.48 (d, J = 7.9 Hz, 1H), 8.16 (dd, J = 2.8, 1.2 Hz, 1H), 7.95 (dt, J = 4.5, 2.8 Hz, 1H), 7.73-7.61 (m, 3H), 7.59-7.54 (m, 1H), 7.40-7.24 (m, 2H); ¹³ C NMR (150 MHz, DMSO-d ₆ ) d 142.0, 140.8, 137.1, 135.4, 135.0, 135.0, 129.2, 128.0, 127.8, 126.5, 123.6, 120.6, 119.9, 119.6, 118.7, 117.8, 116.5, 112.2, 93.8 ; IR (neat) 3305, 2225, 1720, 1630, 1518, 1452, 1357, 1182, 827 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₁₉ H ₁₀ N ₂ S ₂ : 330.0285. Found: 330.0284.

2-30. 6-([1,1’- Biphenyl ] -4-day) -10- Methoxy -5H- Benzo [b] carbazole -11- Carbonite reel [6-([1,1'-Biphenyl] -4-yl) -10-methoxy-5H-benzo [b] carbazole-11-carbonitrile; 8a]

Compound 8a was obtained as a yellow solid according to the above synthesis method; mp = 297-299 ° C. Yield: 40% (85 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 9.06 (d, J = 8.0 Hz, 1H), 7.95 (s, 1H), 7.85 (d, J = 7.8 Hz, 2H), 7.72 (d, J = 7.7 Hz , 2H), 7.60 (t, J = 7.0 Hz, 2H), 7.51 (m, 4H), 7.39 (m, 4H), 6.91 (d, J = 7.5 Hz, 1H), 4.16 (s, 3H); ¹³ C NMR (150 MHz, CDCl ₃ ) d 155.5, 142.4, 140.3, 134.5, 131.7, 130.7, 130.3, 129.1, 129.0, 128.0, 127.8, 127.1, 127.0, 126.0, 123.9, 121.6, 120.6, 120.4, 119.7, 118.0 , 110.3, 103.8, 96.4, 55.7; IR (neat) 3320, 2231, 1720, 1631, 1509, 1445, 1356, 1175, 758 cm ^-1 ; HRMS m / z (M ₊ ) calcd for C ₃₀ H ₂₀ N _2O : 424.1576. Found: 424.1579.

2-31. 10- Methoxy -6-phenyl-5H- Benzo [b] carbazole -11- Carbonite reel [10- methoxy -6-phenyl-5H-benzo [b] carbazole-11-carbonitrile; 8b]

Compound 8b was obtained as a yellow solid according to the above synthesis method; mp = 289-291 ° C. Yield: 55% (96 mg). ¹ H NMR (600 MHz, CDCl ₃ ) d 9.05 (d, J = 8.0 Hz, 1H), 7.87 (s, 1H), 7.63 (t, J = 7.4 Hz, 2H), 7.54 (m, 4H), 7.40 -7.31 (m, 4H), 6.90 (dd, J = 6.8, 1.3 Hz, 1H), 4.14 (s, 3H) .; ¹³ C NMR (150 MHz, CDCl ₃ ) d 155.5, 142.4, 137.0, 135.6, 131.7, 130.3, 129.3, 129.0, 128.6, 128.2, 125.9, 123.9, 123.5, 121.6, 120.9, 120.3, 119.7, 118.0, 110.3, 103.7 , 96.4, 55.7; IR (neat) 3324, 2213, 1695, 1516, 1435, 1345, 1176, 827, 758 cm ^-1 ; HRMS m / z (M ⁺ ) calcd for C ₂₄ H ₁₆ N _{2 O} : 348.1263. Found: 348.1263.

< Experimental example  1> Cu ^{2 +}  Ionic Sensing  Characteristics check

Over the past decade, the development of selective fluorescent sensors for the detection of biologically and environmentally important metal ions has been an important field of research. Among them, divalent copper ion (Cu ^{+ 2)} are very important to living organisms, in particular, shows a significant effect on the human body. For example, excess accumulation of Cu ^{2 +} is Alzheimer's disease, Wilson's disease, cause neurodegenerative diseases, oxidative stress, such as men Kes's disease, while insufficient intake of Cu ^{2 +} is a bone non-normalized, anemia, leukopenia, etc. Can cause Therefore, it can be said that the development of chemical sensors capable of selectively detecting divalent copper ions that are biologically and environmentally important is very urgent.

Thus, in the present invention, in order to check the copper ion sensing characteristics of the carbazole derivatives obtained in Examples 1 to Synthesis Examples, compounds 3f and 5d (c = 5 X 10 ^-3 M) dissolved in DMSO are Al ^{3 +} , Zn. ^{2 +} , Hg ^{2 +} , Cu ⁺ , Co ^{3 +} , Ca ^{2 +} , Pb ²⁺ , Ni ^{2 +} , Cu ^{2 +} and mixed with an aqueous solution ( c = 10 μM) in which various metal ions are dissolved. , Fluorescence spectroscopy of the mixed solution was performed. All fluorescence measurements were performed using Hitechi-7000 at room temperature and at various wavelengths after 5 minutes incubation at a scan rate of 240 nm / min using a slit width of 5 nm and a photomultiplier tube of 400 V.

As a result, as shown in Figure 4, when caused at 285 nm, it was confirmed that it causes a significant quenching in the fluorescence intensity of the compound 3f. In addition, referring to FIG. 5, the concentration of Cu ²⁺ ions in compounds 3f (at 475 nm) and 5d (448 nm) increases (5 μM to 50 μM), and the fluorescence reaction and the fluorescence intensity of compounds A linear relationship was observed.

Fluorescence quenching of such compounds 3f and 5d are, presumably due to complex formation between the Cu ^{2 +} ions, nitrogen, oxygen or π- electron, as shown in Fig.

Thus compounds 3f and 5d it was all confirmed that this can be used as the fluorescence sensor of Cu ^{2 +} ions.

In addition, in order to obtain insight into the photophysical properties of the carbazole compounds synthesized above, a fluorescence spectrum dependent on solvent polarity was confirmed. 8- (trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl) -5H-benzo [b] carbazole-11-carbonitrile (3j) and 7- (naphthalen-1-yl)- 10- (trifluoromethyl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile (5d) compounds are four solvents: hexane, chloroform, ethyl acetate and dimethylsulfoxide (DMSO It was confirmed that when the polarity of hexane from hexane to DMSO was increased in the solvent of) at 285 nm, a positive solvent-dependent solvatochromism appeared in the fluorescence spectrum (not shown).

In particular, in the case of compound 3j, a red shift phenomenon of 55 nm was observed as the solvent was changed from hexane to DMSO. In addition, in compound 5d, 35 nm red shift was observed as the solvent was changed from hexane to DMSO. These results indicate that the synthesized compounds have solvent-dependent color development characteristics, which means that they can be used as a new sensitive fluorescent probe for solvent polarity. It is believed that a significant change in the dipole moment between the ground state and the excited state due to the charge transfer characteristics of the fluorescence state is the main cause of the redshift phenomenon in which each compound 3j and 5d is seen in a polar solvent.

As described above, specific parts of the present invention have been described in detail. For those skilled in the art, this specific technique is only a preferred embodiment, and it is obvious that the scope of the present invention is not limited thereby. Do. That is, the substantial scope of the present invention is defined by the appended claims and their equivalents.

Claims (13)

Carbazole derivatives represented by the following formula (1) or (2):
[Formula 1]

In Chemical Formula 1,
R ¹ and R ² may be the same or different, and each is a substituent selected from the group consisting of hydrogen, (C1 to C3) alkoxy, tri (halogen) (C1 to C4) alkyl, and halogen, or R ¹ and R ² are linked to each other to form a benzene ring;
R ³ and R ⁴ may be the same or different, hydrogen, (C1 to C4) alkyl, (C1 to C3) alkoxy, ethynyl, aryl, tri (halogen) (C1 to C3) alkoxy, halogen, And tri (halogen) (C1 ~ C4) alkyl, or one substituent selected from the group consisting of, or R ³ and R ⁴ are connected to each other to form a benzene ring;
[Formula 2]

In Chemical Formula 2,
X is any one of S, N or O,
Y is a 5-membered heteroaryl ring containing any one of S, N or O. The method of claim 1, wherein in Formula 1,
R ¹ and R ² may be the same or different, and each is a substituent selected from the group consisting of hydrogen, methoxy, trifluoromethyl, and chloro, or R ¹ and R ² are connected to each other to form a benzene ring To form;
R ³ and R ⁴ may each be the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, methoxy, ethynyl, phenyl, trifluoromethoxy, chloro, and trifluoromethyl Carbazole derivative characterized in that it is any one substituent, or R ³ and R ⁴ are connected to each other to form a benzene ring. The method of claim 1, wherein in Formula 2,
X is S, Y is a carbazole derivative, characterized in that thiazole. The method of claim 1, wherein the carbazole derivative is 6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [6-Phenyl-5H-benzo [b] carbazole-11-carbonitrile], 8-methyl- 6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 10-methyl -6- (o-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [10-Methyl-6- (o-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 8- Ethyl-6- (4-ethylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Ethyl-6- (4-ethylphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Isopropyl-6- (4-isopropylphenyl) -5H-benzo [b] carbazole-11 -carbonitrile], 10-methoxy-6- (2-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [10-Methoxy-6- (2-methoxyphenyl) -5H-benzo [b ] carbazole-11-carbonitrile], 8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Methoxy-6- (4-methoxyphenyl) -5H -benzo [b] carbazole-11-carbonitri le], 8-ethynyl-6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Ethynyl-6- (4-ethynylphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 6-([1,1'-biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile [6-([1,1 '-Biphenyl] -4-yl) -8-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 8- (trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl)- 5H-benzo [b] carbazole-11-carbonitrile [8- (Trifluoromethoxy) -6- (4- (trifluoromethoxy) phenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8-chloro-6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile [8-Chloro-6- (4-chlorophenyl) -5H-benzo [b] carbazole-11-carbonitrile], 8- (tri Fluoromethyl) -6- (4- (trifluoromethyl) phenyl) -5H-benzo [b] carbazole-11-carbonitrile [8- (Trifluoromethyl) -6- (4- (trifluoromethyl) phenyl)- 5H-benzo [b] carbazole-11-carbonitrile], 4-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [4-Methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 4-methoxy- 8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [4-Methoxy-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole- 11-carbonitrile], 6-phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole-11-carbonitrile [6-Phenyl-3- (trifluoromethyl) -5H-benzo [b] carbazole- 11-carbonitrile], 3-chloro-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile], 3- Chloro-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-8-methyl-6- (p-tolyl) -5H-benzo [b] carbazole-11-carbonitrile], 3-chloro-8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile [3-Chloro-8-methoxy-6- (4-methoxyphenyl) -5H-benzo [b] carbazole-11-carbonitrile], 7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile [7- (Naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 9-methoxy-7- (naphthalen-1-yl) -8H-naphtho [2,1-b ] Carbazole-13-carbonitrile [9-Methoxy-7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carba zole-13-carbonitrile], 11-chloro-7- (naphthalen-1-yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile [11-Chloro-7- (naphthalen-1 -yl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 7- (naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b ] Carbazole-13-carbonitrile [7- (Naphthalen-1-yl) -10- (trifluoromethyl) -8H-naphtho [2,1-b] carbazole-13-carbonitrile], 13- (naphthalen-2-yl ) -12H-naphtho [1,2-b] carbazole-7-carbonitrile [13- (Naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile], 11- Methoxy-13- (naphthalen-2-yl) -12H-naphtho [1,2-b] carbazole-7-carbonitrile [11-Methoxy-13- (naphthalen-2-yl) -12H-naphtho [ 1,2-b] carbazole-7-carbonitrile; 5f], 12-phenyl-13H-dibenzo [a, h] carbazole-7-carbonitrile [12-Phenyl-13H-dibenzo [a, h] carbazole-7-carbonitrile], 10-methyl-12- ( p-tolyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile [10-Methyl-12- (p-tolyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile], 10 -Methoxy-12- (4-methoxyphenyl) -13H-dibenzo [a, h] carbazole-7-carbonitrile [10-Methoxy-12- (4-methoxyphenyl) -13H-dibenzo [a, h ] carbazole-7-carbonitrile], 7- (naphthalen-1-yl) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile [7- (naphthalen-1-yl) -8H-benzo [a] naphtho [1,2-h] carbazole-15-carbonitrile], 10- (thiophen-3-yl) -9H-thieno [2,3-b] carbazole-4-carbonite Reel [10- (Thiophen-3-yl) -9H-thieno [2,3-b] carbazole-4-carbonitrile], 6-([1,1'-biphenyl] -4-yl) -10-me Methoxy-5H-benzo [b] carbazole-11-carbonitrile [6-([1,1'-Biphenyl] -4-yl) -10-methoxy-5H-benzo [b] carbazole-11-carbonitrile], And 10-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonitrile [10-methoxy-6-phenyl-5H-benzo [b] carbazole-11-carbonit rile] carbazole derivative, characterized in that selected from the group consisting of. A composition for detecting a divalent copper ion (Cu ²⁺ ) comprising a carbazole derivative represented by the following Chemical Formula 1 or 2, or a pharmaceutically acceptable salt thereof as an active ingredient:
[Formula 1]

In Chemical Formula 1,
R ¹ and R ² may be the same or different, and each is a substituent selected from the group consisting of hydrogen, (C1 to C3) alkoxy, tri (halogen) (C1 to C4) alkyl, and halogen, or R ¹ and R ² are linked to each other to form a benzene ring;
R ³ and R ⁴ may be the same or different, hydrogen, (C1 to C4) alkyl, (C1 to C3) alkoxy, ethynyl, aryl, tri (halogen) (C1 to C3) alkoxy, halogen and Tri (halogen) (C1 ~ C4) alkyl is any one substituent selected from the group consisting of, or R ³ and R ⁴ are connected to each other to form a benzene ring;
[Formula 2]

In Chemical Formula 2,
X is any one of S, N or O,
Y is a 5-membered heteroaryl ring containing any one of S, N or O. Kit for detecting a divalent copper ion (Cu ^{2 +} ) comprising the composition according to claim 5 as an active ingredient. delete delete In the presence of a copper catalyst and the base Cs ₂ CO ₃ , a) a 2-nitrocinnamaldehyde derivative; And b) one or more compounds selected from the group consisting of substituted or unsubstituted benzyl cyanide derivatives, 5-ring heteroaryl cyanide derivatives, and 1,2-diphenylethan-1-one; Method for producing sol derivatives. 10. The method of claim 9, wherein the copper catalyst is CuI. 10. The method of claim 9, wherein the 2-nitrocinnamaldehyde derivative is represented by Formula 3 below:
[Formula 3]

In Chemical Formula 3,
Z is hydrogen or a phenyl group,
R ⁵ and R ⁶ may be the same or different from each other, hydrogen, (C1 to C3) alkoxy, tri (halogen) (C1 to C4) alkyl, and any one substituent selected from the group consisting of halogen, or, R, ⁵ and R ⁶ are connected to each other to form a benzene ring. 10. The method of claim 9, wherein the benzyl cyanide derivative is represented by Formula 4 below:
[Formula 4]

In Chemical Formula 4,
R ⁷ and R ⁸ may be the same or different, hydrogen, (C1 to C4) alkyl, (C1 to C3) alkoxy, ethynyl, aryl, tri (halogen) (C1 to C3) alkoxy, halogen and Tri (halogen) (C1 ~ C4) alkyl is any one substituent selected from the group consisting of, or, R ⁷ and R ⁸ are connected to each other to form a benzene ring. 10. The method of claim 9, wherein the 5-ring heteroaryl cyanide derivative is represented by Formula 5 below:
[Formula 5]

X 'is any one of S, N or O.

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