WO2017034370A1 - Perylene-based compound, preparing method therefor, and fluorescent dye comprising same - Google Patents

Abstract

The present application relates to a novel perylene-based compound, a preparing method therefor, and a fluorescent dye comprising the same.

Description

Perylene-based compound, preparation method thereof, and fluorescent dye comprising the same

The present application relates to a novel perylene-based compound, a preparation method thereof, and a fluorescent dye including the same.

Perylene-based compounds are used as liquid phase fluorescent dyes as polycyclic aromatic hydrocarbon compounds, and are particularly well known as excellent photosafety pigments and bat dyes. Pigments and dyes containing perylene-based compounds show long-wavelength luminescence due to extended resonance, and are used in various fields with very strong fluorescence, and recently, their use as chemiluminescent materials in the display field has greatly increased. Patent Publication No. US2011 / 0251393).

The present application is to provide a novel perylene-based compound, a preparation method thereof and a fluorescent dye comprising the same.

However, the problem to be solved by the present application is not limited to the problem described above, another problem that is not described will be clearly understood by those skilled in the art from the following description.

A first aspect of the present application provides a perylene-based compound represented by Formula 1 below:

[Formula 1]

In the formula 1, wherein R ₁ and said R _{2 are,} each independently, hydrogen, halogen, cyano, C _1-20 alkyl group which may be substituted with a linear or branched, optionally substituted C _3-30 cycloalkyl Alkyl group, C _6-30 aryl group which may be substituted, C _1-20 alkylamine group which may be substituted, C _3-30 cycloalkylamine group which may be substituted, C _6- which may be substituted ₃₀ arylamine group, a linear or branched C _1-20 alkoxy group which may be substituted, a C _3-30 cycloalkoxy group which may be substituted, a C _6-30 aryloxy group which may be substituted, a linear which may be substituted Or a branched C _2-10 alkylcarboxyl group, a substituted C _6-30 arylcarboxyl group, or a substituted C _6-30 arylmercapto group, wherein R ₃ and R ₄ are each independently hydrogen , Halogen group, cyano group, linear or branched C _1-20 alkyl group which may be substituted, C _3-30 cycloalkyl group which may be substituted , A C _6-30 aryl group which may be substituted, a linear or branched C _1-20 alkoxy group which may be substituted, a C _3-30 cycloalkoxy group which may be substituted, or C _6-30 aryl which may be substituted Oxygen.

According to a second aspect of the present invention, a compound represented by the following Chemical Formula 2 may be substituted with a linear or branched C _1-20 alkane compound, a C _3-30 cycloalkane compound which may be substituted, and C ₆ which may be substituted. _-30 aryl compounds, substitutable C _6-30 phenolic compounds, substitutable linear or branched C _1-20 alcohol compounds, substitutable linear or branched C _1-20 alkylamine compounds Preparation of the perylene-based compound according to claim 1 comprising reacting with a C _3-30 cycloalkylamine compound which may be substituted, a C _6-30 arylamine compound which may be substituted, or N-halosuccinimide. Provide a way:

[Formula 2]

In Formula 2, R ₅ to R ₈ are each independently hydrogen, halogen or a linear or branched C _2-10 alkylcarboxyl group which may be substituted.

The third aspect of the present application provides a fluorescent dye comprising a perylene-based compound according to the present application.

The perylene-based compound of the present application is a novel compound which can be used as a green fluorescent dye having a perylene-based nucleus structure and exhibits excellent solubility, in particular, excellent solubility, durability, thermal stability, and luminescence properties in an organic solvent.

1 is a spectrum showing the UV / PL results of the perylene compound according to an embodiment of the present application.

Hereinafter, with reference to the accompanying drawings will be described in detail the embodiments and embodiments of the present application to be easily carried out by those of ordinary skill in the art.

As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise. As used throughout this specification, the terms "about", "substantially" and the like are used at, or in the sense of, numerical values when a manufacturing and material tolerance inherent in the stated meanings is indicated, Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term "step to" or "step of" does not mean "step for."

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B."

Throughout this specification, the term "alkyl" described alone or in combination with other substituents, refers to a linear or branched, C ₁ -C ₂₀ alkyl, C ₁ -C ₁₅ alkyl, C ₁ -C ₁₀ alkyl, or It may include C ₁ -C ₆ alkyl, including, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or all possible isomers thereof It may be, but may not be limited thereto.

Throughout this specification, the term "cycloalkyl", alone or in combination with other substituents, may include C _3-30 cycloalkyl, C _3-20 cycloalkyl, or C _3-10 cycloalkyl, which may be substituted; , Mono- or bicycloaliphatic. For example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, 2,5-cyclohexadienyl, bicyclo [2.2.2] Octyl, adamant-1-yl, decahydronaphthyl, oxocyclohexyl, dioxocyclohexyl, thiocyclohexyl, 2-oxobicyclo [2.2.1] hept-1-yl, or all possible isomers thereof But may not be limited thereto.

Throughout this specification, the term "aryl" described alone or in combination with other substituents, may include C _6-30 aryl, C _6-20 aryl, or C _6-10 aryl, which may be substituted, and the adjacent carbons. Double bonds alternate (resonance) between atoms or suitable heteroatoms. For example, phenyl ring, toluyl ring, naphthalenyl ring, anthracenyl ring, phenanthrene ring, pentarene ring, indene ring, biphenylene ring, phenylene ring, azrene ring, heptarene ring, acenaph Tylene ring, fluorene ring, tetracene ring, triphenylene ring, pyrene ring, chrysene ring, ethyl-crysene ring, pysene ring, perylene ring, pentaphene ring, pentacene ring, tetraphenylene ring, hexa Pen ring, hexasen ring, rubisen ring, coronene ring, trinaphthylene ring, heptaphene ring, heptacene ring, pyrantrene ring, ovaren ring, floranthene ring, benzofloransen ring, 9-an It may be selected from the group consisting of a trilyl group, 2-anthryl group, 9-phenanthryl group, 2-phenanthryl group, 1-pyrenyl group, chrysenyl group, naphthacenyl group, coronyl group and derivatives thereof, It may not be limited.

Throughout this specification, the term "alkoxy" refers to an alkyl group single bond with oxygen, for example, linear or branched C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₅ alkoxy, C ₁ which may be substituted -C ₁₀ alkoxy, or C ₁ -C ₆ alkoxy, and may include, for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, heptyloxy and the like and all possible isomers thereof. It may be, but may not be limited thereto.

Throughout this specification, the term "aryloxy" refers to an aryl group single bond with oxygen, wherein the aryl group single bond with oxygen may be substituted C _6-30 aryl, C _6-20 aryl, or C _6-10 It may include an aryl, for example, a phenyl ring, toluyl ring, naphthalenyl ring, anthracenyl ring, phenanthrene ring, pentarene ring, indene ring, biphenylene ring, phenylene ring, azulene Ring, heptarene ring, acenaphthylene ring, fluorene ring, tetracene ring, triphenylene ring, pyrene ring, chrysene ring, ethyl-chrysene ring, pisene ring, perylene ring, pentaphene ring, pentacene Ring, tetraphenylene ring, hexaphene ring, hexasen ring, rubisen ring, coronene ring, trinaphthylene ring, heptaphene ring, heptacene ring, pyrantrene ring, ovaren ring, floranthene ring, benzo Floransen ring, 9-anthryl group, 2-anthryl group, 9-peh It may be selected from the group consisting of a nanthryl group, 2-phenanthryl group, 1-pyrenyl group, chrysenyl group, naphthasenyl group, coronyl group, and derivatives thereof, but may not be limited thereto.

Throughout this specification, the term "alkylcarboxyl group" includes an alkoxy group mono-bonded with carbon of a carbonyl group in an ester group, wherein the alkoxy group included in the alkylcarboxyl group is, for example, linear or branched C which may be substituted. ₁ -C ₂₀ alkoxy, C ₁ -C ₁₅ alkoxy, C ₁ -C ₁₀ alkoxy, or C ₁ -C ₆ alkoxy, for example, methoxy, ethoxy, propoxy, butoxy, Pentyloxy, heptyloxy, and the like and all possible isomers thereof, but may not be limited thereto.

Throughout this specification, the term "arylcarboxyl group" includes an aryloxy group single-bonded with carbon of a carbonyl group in an ester group, and the aryl group single-bonded with oxygen in the aryloxy group included in the arylcarboxyl group may be substituted. It may include C _6-30 aryl, C _6-20 aryl, or C _6-10 aryl, for example, phenyl ring, toluyl ring, naphthalenyl ring, anthracenyl ring, phenanthrene ring, penta Ylene ring, indene ring, biphenylene ring, phenylene ring, azene ring, heptarene ring, acenaphthylene ring, fluorene ring, tetracene ring, triphenylene ring, pyrene ring, chrysene ring, ethyl- Chrysene ring, pisene ring, perylene ring, pentaphene ring, pentacene ring, tetraphenylene ring, hexaphene ring, hexasengole, rubisen ring, coronene ring, trinaphthylene ring, heptaphen ring, hep Tarsen rings , Pyrantrene ring, ovaren ring, floranthene ring, benzofloransen ring, 9-anthryl group, 2-anthryl group, 9-phenanthryl group, 2-phenanthryl group, 1-pyrenyl group, cry It may be selected from the group consisting of a senyl group, naphthasenyl group, coronyl group, and derivatives thereof, but may not be limited thereto.

Throughout this specification, the term "arylmercapto group" refers to an aryl group single bond with sulfur, wherein the aryl group single bond with sulfur may be substituted C _6-30 aryl, C _6-20 aryl, or C _{6 It} may include _-10 aryl, for example, a phenyl ring, toluyl ring, naphthalenyl ring, anthracenyl ring, phenanthrene ring, pentarene ring, indene ring, biphenylene ring, phenylene ring, Azulene ring, heptarene ring, acenaphthylene ring, fluorene ring, tetracene ring, triphenylene ring, pyrene ring, chrysene ring, ethyl-crisene ring, pysene ring, perylene ring, pentafen ring, Pentacene ring, tetraphenylene ring, hexaphene ring, hexasen ring, rubisen ring, coronene ring, trinaphthylene ring, heptaphene ring, heptacene ring, pyrantrene ring, obarene ring, florene ring , Benzofloransen ring, 9-anthryl group, 2-anthryl group , 9-phenanthryl group, 2-phenanthryl group, 1-pyrenyl group, chrysenyl group, naphthasenyl group, coronyl group, and derivatives thereof may be selected from the group consisting of, but may not be limited thereto.

Throughout this specification, the term “halogen” is a Group 17 element of the periodic table, which may include, for example, F, Cl, Br, or I, but may not be limited thereto.

A first aspect of the present application provides a perylene-based compound represented by Formula 1 below:

[Formula 1]

In the formula 1, wherein R ₁ and said R _{2 are,} each independently, hydrogen, halogen, cyano, C _1-20 alkyl group which may be substituted with a linear or branched, optionally substituted C _3-30 cycloalkyl Alkyl group, C _6-30 aryl group which may be substituted, C _1-20 alkylamine group which may be substituted, C _3-30 cycloalkylamine group which may be substituted, C _6- which may be substituted ₃₀ arylamine group, a linear or branched C _1-20 alkoxy group which may be substituted, a C _3-30 cycloalkoxy group which may be substituted, a C _6-30 aryloxy group which may be substituted, a linear which may be substituted Or a branched C _2-10 alkylcarboxyl group, a substituted C _6-30 arylcarboxyl group, or a substituted C _6-30 arylmercapto group, wherein R ₃ and R ₄ are each independently hydrogen , Halogen group, cyano group, linear or branched C _1-20 alkyl group which may be substituted, C _3-30 cycloalkyl group which may be substituted , A C _6-30 aryl group which may be substituted, a linear or branched C _1-20 alkoxy group which may be substituted, a C _3-30 cycloalkoxy group which may be substituted, or C _6-30 aryl which may be substituted Oxygen.

In one embodiment of the present application, the alkyl group, the alkylamine group, the alkoxy group, and the alkylcarboxyl group independently included in each of R ¹ to R ⁴ may be substituted linearly having about 1 to about 20 carbon atoms. Or branched alkyl groups. As used herein, a linear or branched alkyl group has about 1 to about 20 carbon atoms, about 1 to about 15 carbon atoms, about 1 to about 10 carbon atoms, or about 1 to 6 carbon atoms. It may include an alkyl group, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nona Decyl, eicosanyl, or all possible isomers thereof. For example, it may be an alkyl group having 1 to 12 carbon atoms, that is, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl, undecyl, dodecyl group, Or an alkyl group having 1 to 6 carbon atoms, that is, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group, or an alkyl group having 1 to 4 carbon atoms, that is, a methyl group, an ethyl group, or an i-propyl group. , n-propyl group, t-butyl group, s-butyl group, or n-butyl group.

In one embodiment of the present application, the cycloalkyl group, the cycloalkylamine group, and the cycloalkoxy group independently included in each of R ¹ to R ⁴ include a substituted cycloalkyl group having about 3 to about 30 carbon atoms. This may include a single cyclic ring or a polycyclic ring to which a single cyclic ring is linked or fused. As used herein, a cycloalkyl group includes about 3 to about 30, about 3 to about 25, about 3 to about 20, about 3 to about 15, about 3 to about 10, about 5 to about 30, about 5 to about carbon atoms. 25, about 5 to about 20, about 5 to about 15, about 5 to 10, about 6 to about 30, about 6 to about 25, about 6 to about 20, about 6 to about 15, or about 6 to about 10 It may include a cycloalkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, 2,5-cyclohexadiee Nyl, bicyclo [2.2.2] octyl, adamant-1-yl, decahydronaphthyl, oxocyclohexyl, dioxocyclohexyl, thiocyclohexyl, 2-oxobicyclo [2.2.1] hept-1 -One, or all possible isomers thereof, but may not be limited thereto.

In one embodiment of the present application, may be substituted in the aryl group, the arylamine group, the aryloxy group, the arylcarboxyl group, and the arylmercapto group contained independently of each of R ₁ to R ₄ An aryl group may include a substituted aryl group having about 6 to about 30 carbon atoms, which may be a phenyl group or a polycyclic ring in which two or more phenyl groups are linked or fused. The aryl group may include an aryl group having about 6 to about 30 carbon atoms, about 6 to about 25, about 6 to about 20, about 6 to about 15, or about 6 to about 10 carbon atoms, for example, phenyl Ring, toluyl ring, naphthalenyl ring, anthracenyl ring, phenanthrene ring, pentarene ring, indene ring, biphenylene ring, phenylene ring, azylene ring, heptarene ring, acenaphthylene ring, fluorene Ring, tetracene ring, triphenylene ring, pyrene ring, chrysene ring, ethyl-crysene ring, pisene ring, perylene ring, pentaphene ring, pentacene ring, tetraphenylene ring, hexaphene ring, hexacene Ring, rubisen ring, coronene ring, trinaphthylene ring, heptaphene ring, heptacene ring, pyrantrene ring, ovaren ring, florene ring, benzofloransen ring, 9-anthryl group, 2- Anthryl group, 9-phenanthryl group, 2-phenanthryl group, 1-pyrenyl group, crysenyl group, naph Line group, nose group, and may be selected from the group consisting of their derivatives, may not be limited thereto.

In one embodiment of the present application, the aryl group contained in the aryl group, the arylamine group, the aryloxy group, the arylcarboxyl group or the arylmercapto group independently contained in each of R ₁ to R ₄ , a phenyl group, It may include a biphenyl group or a naphthyl group, but is not limited thereto.

In one embodiment of the present application, the substituents that may be substituted for R ₁ and R ₂ are each independently a halogen group, cyano group, linear or branched C _1-8 alkyl group, or linear or branched C _It may be to include a _1-8 alkoxy group, but is not limited thereto.

In one embodiment of the present application, the substituents that may be independently substituted for each of R ₃ and R ₄ are each independently a halogen group, cyano group, linear or branched C _1-8 alkyl group, or linear or branched group. It may be to include a C _1-8 alkoxy group of the topography, but is not limited thereto.

In one embodiment of the present application, the linear or branched C _1-8 alkyl group or the linear or branched C _1-8 alkoxy group which may be substituted with R ₁ to R ₄ has about 1 to about 8 carbon atoms. It may include, but is not limited to, linear or branched alkyl groups. The linear or branched alkyl group has about 1 to about 8 carbon atoms, about 1 to about 7, about 1 to about 6, about 1 to about 5, about 1 to about 4, about 1 to about 3, or about 1 carbon atoms. To about 2 alkyl groups, including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or all possible isomers thereof. For example, an alkyl group having 1 to 8 carbon atoms, that is, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or an alkyl group having 1 to 6 carbon atoms, that is, a methyl group , An ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group, or an alkyl group having 1 to 4 carbon atoms, that is, methyl group, ethyl group, i-propyl group, n-propyl group, t-butyl group, s It may be a -butyl group, or n-butyl group, but is not limited thereto.

In one embodiment of the present application, the perylene-based compound may include, but may not be limited to:

According to a second aspect of the present disclosure, a C _1-20 alkane compound which may be substituted with a compound represented by Formula 2 below, a C _6-30 cycloalkane compound which may be substituted, a C _6-30 aryl compound which may be substituted, and a substitution C _6-30 phenolic compound which may be substituted, C _1-20 alcoholic compound which may be substituted, C _1-20 alkylamine compound which may be substituted, C _6-30 cycloalkylamine compound which may be substituted, There is provided a process for preparing a perylene based compound according to the first aspect, comprising reacting with a C _6-30 arylamine compound, or N-halosuccinimide, which may be:

[Formula 2]

In Formula 2, R ₅ to R ₈ are each independently hydrogen, halogen or a linear or branched C _2-10 alkylcarboxyl group which may be substituted.

In one embodiment of the present application, substitutable C _6-30 phenolic compounds capable of reacting with the compound represented by Formula 2, for example, are each independently hydroxyphenyl, dihydroxyphenyl, meth Methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, triethoxyphenyl, propoxyphenyl, dipropoxyphenyl, isopropoxyphenyl, diisopropoxyphenyl, butoxyphenyl, hydroxide Hydroxyphenyl, dihydroxyphenyl, cyanophenyl, carboxyphenyl, carboxamidophenyl, N-methylcarboxamidophenyl, acetylaminophenyl, propionylaminophenyl, butyrylaminophenyl, N-phenylaminophenyl, N- (o-tolyl) aminophenyl, N- (m-tolyl) aminophenyl, N- (p-tolyl) aminophenyl, (2-pyridyl) aminophenyl, (3-pyridyl) aminophenyl, (4-pyri Dill) aminophenyl, (2-pyrimidyl) aminophenyl, 4- (4-pyrimidyl) aminophenyl, and all isomers thereof It may include those selected from the group consisting of chedeul However, without being limited thereto.

In one embodiment of the present application, the C _1-20 alcohol-based compound which may be reacted with the compound represented by Formula 2 is, for example, each independently hydroxyethyl, hydroxypropyl, dihydrate Hydroxypropyl, hydroxybutyl, dihydroxybutyl, hydroxypentyl, dihydroxypentyl, hydroxyhexyl, dihydroxyhexyl, hydroxyheptyl, dihydroxyheptyl, and all isomers thereof It may include, but is not limited to.

In one embodiment of the present application, a linear or branched C _1-20 alkylamine compound which may be reacted with the compound represented by Formula 2, a C _3-30 cycloalkylamine compound which may be substituted, And C _6-30 arylamine compounds which may be substituted each independently include, for example, amino groups, methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, diisopropylamino, dibutyl Amino, diisobutylamino, di-tert-butylamino, dipentylamino, dihexylamino, diphenylamino, di-o-tolylamino, di-m-tolylamino, di-p-tolylamino, di (4 Cyanophenyl) amino, and all isomers thereof, but is not limited thereto.

In one embodiment of the present application, the compound represented by the formula (2), phenol, phenyl phenol, di-tert- butyl phenol, hydroxy tert- butyl anisole, N-halo succinimide, hexyl amine, and their It may include reacting with one selected from the group consisting of all isomers.

In one embodiment of the present application, the compound represented by Formula 2 is phenol, 2-phenylphenol, 2,4-di-tert-butylphenol, 4-hydroxy-3-tert-butylanisole, N- And reacting with one selected from the group consisting of bromosuccinimide, hexylamine, and all isomers thereof.

In one embodiment of the present application, the perylene-based compound prepared in the group consisting of halogen, cyanide salt, phenolic compound, naphthol-based compound, alcohol-based compound, thiol-based compound, amine-based compound and boronic acid that can be substituted The reaction may be further performed by adding a material selected from the reaction one to three times.

In one embodiment of the present application, the prepared perylene-based phenol compound and naphthol-based compound, for example, each independently hydroxyphenyl, dihydroxyphenyl, methoxyphenyl, dimethoxyphenyl, Trimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, triethoxyphenyl, propoxyphenyl, dipropoxyphenyl, isopropoxyphenyl, diisopropoxyphenyl, butoxyphenyl, hydroxyphenyl, dihydroxyphenyl , Cyanophenyl, carboxyphenyl, carboxamidophenyl, N-methylcarboxamidophenyl, acetylaminophenyl, propionylaminophenyl, butyrylaminophenyl, N-phenylaminophenyl, N- (o-tolyl) aminophenyl , N- (m-tolyl) aminophenyl, N- (p-tolyl) aminophenyl, (2-pyridyl) aminophenyl, (3-pyridyl) aminophenyl, (4-pyridyl) aminophenyl, (2 -Pyrimidyl) aminophenyl, 4- (4-pyrimidyl) aminophenyl, and all isomers thereof Gin may include is selected from the group, but is not limited to this.

In one embodiment of the present application, the prepared perylene-based alcohol compound is, for example, each independently hydroxyethyl, hydroxypropyl, dihydroxypropyl, hydroxybutyl, dihydroxybutyl , Hydroxypentyl, dihydroxypentyl, hydroxyhexyl, dihydroxyhexyl, hydroxyheptyl, dihydroxyheptyl, and all isomers thereof, but are not limited thereto. no.

In one embodiment of the present application, the prepared perylene-based reactable amine compound is, for example, each independently amino group, methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino , Diisopropylamino, dibutylamino, diisobutylamino, di-tert-butylamino, dipentylamino, dihexylamino, diphenylamino, di-o-tolylamino, di-m-tolylamino, di- p-tolylamino, di (4-cyanophenyl) amino, and all isomers thereof, but are not limited thereto.

In one embodiment of the present invention, the perylene-based compound prepared in the halogen, cyanide salt, phenol, phenylphenol, tert- butyl phenol, di-tert- butyl phenol, naphthol, methyl propanol, cyclohexanol, methoxy thiophenol Reacting by addition of one selected from the group consisting of aniline, phenyl boronic acid, cyanophenyl boronic acid, naphthyl boronic acid, and 2-methylpropyl boronic acid, and all isomers thereof. It may further comprise performing once to three times.

In one embodiment of the present application, the perylene-based compound prepared in the bromine, copper cyanide, phenol, 2-phenylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-naphthol, 2-methyl-2-propanol, cyclohexanol, 4-methoxythiophenol, aniline, phenylboronic acid, 4-cyanophenylboronic acid, 1-naphthylboronic acid, and 2-methylpropyl The reaction may be further performed once to three times by adding the boronic acid, and one selected from the group consisting of all isomers thereof.

In one embodiment of the present application, it may further include, but is not limited to, adding a carbonate salt in some or all of the above reaction step. The carbonate salt forms a basic atmosphere in each reaction step. For example, alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate or alkali metal hydroxides such as sodium hydroxide or potassium hydroxide may be used for the same purpose. However, it is not limited thereto.

In one embodiment of the present application, the reaction may be to include the reaction by dissolving the reactants in an organic solvent, and then precipitated and filtered at room temperature, but is not limited thereto.

In one embodiment of the present disclosure, the reactions range from room temperature to about 200 ° C., for example, room temperature to about 200 ° C., room temperature to about 180 ° C., room temperature to about 160 ° C., room temperature to about 140 ° C., room temperature to about 120 ℃, room temperature to about 100 ℃, room temperature to about 80 ℃, about 70 ℃ to about 200 ℃, about 70 ℃ to about 180 ℃, about 70 ℃ to about 160 ℃, about 70 ℃ to about 140 ℃, about 80 ℃ to It may be performed at a temperature of about 130 ℃, about 100 ℃ to about 130 ℃, about 110 ℃ to about 130 ℃, or about 120 ℃ to about 130 ℃, but is not limited thereto.

In one embodiment of the present application, the preparation method may include a C _1-20 alkane compound which may be substituted with the compound of Formula 2, a C _6-30 cycloalkane compound which may be substituted, in an organic solvent, C _6-30 aryl compound which may be substituted, C _6-30 phenolic compound which may be substituted, C _1-20 alcohol compound which may be substituted, C _1-20 alkylamine compound which may be substituted, may be substituted Adding a C _6-30 cycloalkylamine compound, a substitutable C _6-30 arylamine compound, or N-halosuccinimide, and reacting at a temperature of from about room temperature to about 200 ° C., followed by precipitation and filtration at room temperature. It may be included, but is not limited thereto.

In one embodiment of the present application, the production method is a halogen, cyanide salt, phenolic compound, naphthol-based compound, alcohol-based compound, thiol-based compound, amine-based compound and the above-mentioned perylene-based compound dissolved in an organic solvent By adding a material selected from the group consisting of boronic acid which may be substituted, the reaction may be performed at room temperature to about 200 ° C., followed by precipitation and filtration at room temperature, but is not limited thereto.

In one embodiment of the present application, the organic solvent may be used without limitation so long as it is an organic solvent usable in the art, for example, dimethylformamide, tetrahydrofuran, methylene chloride, acetone, acetonitrile, dimethyl Sulfoxide, hexamethylphosphoamide, pyridine, pyrimidine, imidazole, quinoline, isoquinoline, quinaldine, N-methylpiperidine, N-methylpiperidone, N-methylpyrrolidone, dimethylformamide, dimethyl It may include acetamide, or tetramethylurea, but is not limited thereto. The organic solvent may be used in about 5 g to about 120 g per g of perylene raw material, but is not limited thereto.

The third aspect of the present application provides a fluorescent dye comprising the perylene-based compound according to the present application.

In one embodiment of the present application, the fluorescent dye may be a green fluorescent dye, but may not be limited thereto.

In one embodiment of the invention, the fluorescent dye may be used as, but not limited to, a fluorescent dye for coloring high molecular weight organic and inorganic materials, in particular plastics, paints, printing inks, inorganic-organic composites, and oxide layer systems. You may not. The fluorescent dyes can be used as dispersants, pigment additives for organic pigments and intermediates for producing fluorescent dyes and pigment additives, or dispersants for preparing inkjet inks and aqueous polymer dispersions which absorb and / or emit in the yellow region of the electromagnetic spectrum. It may be used as a pigment additive and an intermediate, but may not be limited thereto. The fluorescent dye may be used as a dispersant, a photoconductor for electrophotography, as a coloring component or color correction component of a luminescent color filter, a semi-transparent color filter, and a retroreflective element, or as an electron emission source of an electroluminescent device and a chemiluminescent device. This may not be limited. In addition, the fluorescent dye may be used as an active component of fluorescence conversion, fluorescent solar collectors, bioluminescent arrays, and photovoltaic, or as a laser dye, but may not be limited thereto.

In one embodiment of the invention, the fluorescent dye is a fluorescent dye for reactive coloring of high molecular weight organic and inorganic materials, in particular plastics, paints, printing inks, inorganic-organic composites, or in the yellow region of the electromagnetic spectrum and / or Or as fluorescent dyes for preparing bleeding-resistant aqueous polymer dispersions, but may not be limited thereto. In addition, the fluorescent dye may be used as a coloring component or color correction component of a luminescent color filter and a semi-transparent color filter and a retroreflective element, or as a migration-stable electron emission source of an electroluminescent device and a chemiluminescent device. This may not be limited

With respect to the fluorescent dye according to this aspect may be applied to all the contents described for the first to second aspects of the present application, but may not be limited thereto.

Hereinafter, the embodiments of the present application will be described in more detail, and the scope of the present application is not limited by the present embodiment.

EXAMPLE

Example 1

Synthesis of Intermediate 1

To a suspension of 1,6,7,12-tetrachloroperylene tetracarboxylic acid dianhydride (2.00 mmol) and 20 mL of water, 10 mL of an aqueous 1 M NaOH solution was added and stirred at 55 ° C. for 30 minutes. . Bromine (1.0 mL) was added and stirred for 24 hours, the precipitate was filtered and dried to afford the compound of intermediate 1 (orange solid, yield: 87%).

MALDI-TOF analysis: calculated molecular weight 705, measured molecular weight 704

-Melting point: 226 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3165, 3016, (Ar C = C) 1667, 1547, (C-Cl) 743, (C-Br) 651.

Synthesis of Compound 1

The intermediate 1 (1.00 mmol) was dissolved in 10 mL of dimethylformamide, followed by addition of phenol (5.00 mmol) and potassium carbonate (5.00 mmol). After stirring at 130 ° C. for 6 hours, the temperature was lowered to room temperature. The reactant was added to 20 mL of 5% aqueous ammonium chloride solution, and the resulting precipitate was filtered and washed with 30 mL of water to yield Compound 1 (yellow solid, yield: 68%).

MALDI-TOF analysis: calculated molecular weight 758, measured molecular weight 756

-Melting Point:> 350 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3060, 2957, (Ar C = C) 1569, 1484, 1431, (COC) 1212, 1149, (C-Cl) 752, 713.

Synthesis of Compound 2

Compound 1 (1.00 mmol) was dissolved in 10 mL of dimethylformamide, and 4-tert-butylbutylphenol (5.00 mmol) and cesium carbonate (5.00 mmol) were added thereto. After stirring at 130 ° C. for 12 hours, the temperature was lowered to room temperature. The reaction was added to 20 mL of 5% aqueous ammonium chloride solution, and the resulting precipitate was filtered and washed with 30 mL of water to yield Compound 2 (yellow solid, yield: 38%).

-MALDI-TOF analysis: calculated molecular weight 1213, measured molecular weight 1212

-Melting point: 311 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 2935, 2821, (Ar C = C) 1565, 1546, 1485, (C-CH ₃ ) 1367, (COC) 1255, 1216, 1167.

Example 2

Synthesis of Compound 3

Intermediate 1 (1.00 mmol) prepared in Example 1 was dissolved in 10 mL of dimethylformamide, and 2-phenylphenol (5.00 mmol) and potassium carbonate (5.00 mmol) were added thereto. After stirring at 130 ° C. for 8 hours, the temperature was lowered to room temperature. The mixture was added to 20 mL of 5% aqueous ammonium chloride solution, and the resulting precipitate was filtered and washed with 30 mL of water to obtain Compound 3 (yellow solid, yield: 78%).

-MALDI-TOF analysis: calculated molecular weight 1063, measured molecular weight 1064

Melting Point:> 350 ℃

FTIR analysis (cm ⁻¹ ) (Ar CH) 3052, 2995, (Ar C = C) 1572, 1521, 1491, (COC) 1256, 1205, (C-Cl) 769, 753.

Example 3

Synthesis of Compound 4

Intermediate 1 (1.00 mmol) prepared in Example 1 was dissolved in 10 mL of dimethylformamide, and then 2,4-ditetrabutylphenol (5.00 mmol) and potassium carbonate (5.00 mmol) were added thereto. After stirring at 130 ° C. for 12 hours, the temperature was lowered to room temperature. The mixture was added to 20 mL of 5% aqueous ammonium chloride solution, and the resulting precipitate was filtered and washed with 30 mL of water to obtain compound 4 (yellow solid, yield: 63%).

-MALDI-TOF analysis: calculated molecular weight 1207, measured molecular weight 1206

Melting Point:> 350 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 2954, 2865, (Ar C = C) 1569, 1482, (C-CH ₃ ) 1394, 1359, (COC) 1211, 1155, 1120, (C-Cl 769, 693.

Example 4

Synthesis of Compound 5

Intermediate 1 (1.00 mmol) prepared as in Example 1 was dissolved in 10 mL of dimethylformamide, followed by addition of 4-hydroxy-3-tetrabutylanisole (5.00 mmol) and potassium carbonate (5.00 mmol). It was. After stirring at 130 ° C. for 12 hours, the temperature was lowered to room temperature. The mixture was added to 20 mL of 5% aqueous ammonium chloride solution, and the resulting precipitate was filtered and washed with 30 mL of water to obtain compound 5 (yellow solid, yield: 42%).

-MALDI-TOF analysis: calculated molecular weight 1103, measured molecular weight 1103

Melting Point:> 350 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3012, 2965, (Ar C = C) 1502, 1499, (C-CH ₃ ) 1386, 1348, (COC) 1202, 1185, 1166, 1058 (C- Cl) 715.

Example 5

Synthesis of Compound 6

Intermediate 1 (1.00 mmol) prepared in Example 1 was dissolved in 10 mL of dimethylformamide, and then hexylamine (5.00 mmol) and triethylamine (5.00 mmol) were added thereto. After stirring at 130 ° C. for 12 hours, the temperature was lowered to room temperature. The mixture was added to 20 mL of 5% aqueous ammonium chloride solution, and the resulting precipitate was filtered and washed with 30 mL of water to obtain compound 6 (orange solid, yield: 76%).

MALDI-TOF analysis: calculated molecular weight 786, measured molecular weight 785

Melting Point:> 350 ℃

FTIR analysis (cm ⁻¹ ): (NH) 3233, (CH ₂ ) 3211, (Ar CH) 3021, 2915, (Ar C = C) 1565, 1501, 1486 (C-CH ₃ ) 1415, 1392, 1331 , (COC) 185 1138 (C-Cl) 775.

Example 6

Synthesis of Compound 7

Compound 1 (1.00 mmol) of Example 1 was dissolved in 10 mL of dimethylformamide, and then phenol (5.00 mmol) and potassium carbonate (5.00 mmol) were added thereto. After stirring at 130 ° C. for 8 days, the temperature was lowered to room temperature. The reactant was added to 20 mL of 5% aqueous ammonium chloride solution, and the resulting precipitate was filtered and washed with 30 mL of water to give compound 7 (yellow solid, yield: 42%).

-MALDI-TOF analysis: calculated molecular weight 989, measured molecular weight 989

-Melting point: 263 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 2975, 2844, (Ar C = C) 1577, 1465, (C-CH ₃ ) 1301, 1287, (COC) 1212, 1192.

Example 7

Synthesis of Compound 8

Compound 1 (1.00 mmol) in Example 1 was dissolved in 10 mL of dimethylformamide, and then cyclohexanol (5.00 mmol) and cesium carbonate (5.00 mmol) were added thereto. After stirring at 130 ° C. for 12 hours, the temperature was lowered to room temperature. The resulting precipitate was filtered by adding the mixed solution to 20 mL of 5% aqueous ammonium chloride solution, and then washed with 30 mL of water to obtain compound 8 (yellow solid, yield: 42%).

-MALDI-TOF analysis: calculated molecular weight 1013, measured molecular weight 1012

-Melting point: 212 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3061, 2931, (Ar C = C) 1575, 1485, (COC) 1206, 1162, (-CH ₂ ) 812, 747.

Example 8

Synthesis of Compound 9

Compound 1 (1.00 mmol) of Example 1 was dissolved in 10 mL of dimethylformamide, and then 2,4-dibutylbutylphenol (5.00 mmol) and cesium carbonate (5.00 mmol) were added thereto. After stirring at 130 ° C. for 12 hours, the temperature was lowered to room temperature. The resulting precipitate was added to 20 mL of 5% aqueous ammonium chloride solution and the resulting precipitate was filtered and washed with 30 mL of water to yield compound 9 (yellow solid, yield: 24%).

-MALDI-TOF analysis: calculated molecular weight 1437, measured molecular weight 1436

-Melting point: 285 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 2954, 2866, (Ar C = C) 1584, 1487, (C-CH ₃ ) 1372, 1303, (COC) 1209, 1121.

Example 9

Synthesis of Compound 10.

Diisobutyl perylene-3,9-dicarboxylate (2.00 mmol) was dissolved in 10 mL of dimethylformamide, N-bromosuccinimide (4.20 mmol) was added, followed by stirring at 80 ° C. for 6 hours. After the temperature was lowered to room temperature. Pour the mixture into 30 mL of methanol and stir for 30 minutes. The resulting crystals were filtered and washed with 20 mL of water and methanol, and then dried to obtain compound 10 (pale orange solid, yield: 83%).

-MALDI-TOF analysis: calculated molecular weight 610, measured molecular weight 610

-Melting point: 351 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 2967, (C = O) 1717, (Ar C = C) 1581, 1502, 1465, (C-CH3) 1393, 1302, (COC) 1155, 1132, (CH) 760.

Synthesis of Compound 11

The compound 10 (1.00 mmol) was dissolved in 5 mL of tetrahydrofuran, and stirred with 3 mL of water, phenylboronic acid (4.00 mmol) and sodium carbonate (4.00 mmol). Pd (PPh ₃ ) ₄ (0.01 mmol) was added as a catalyst and refluxing was performed at 70 ° C. for 12 hours. After the temperature was lowered, the water layer was removed with a separatory funnel, and then poured into 10 mL of methanol to form crystals. The resulting crystals were filtered and washed with 20 mL each of water and methanol to obtain compound 11 (light yellow solid, yield: 30%).

-MALDI-TOF analysis: calculated molecular weight 604, measured molecular weight 604

-Melting point: 395 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3050, 2959, (C = O) 1708, (Ar C = C) 1584, 1515, (C-CH3) 1373, (COC) 1149, 1123, (CH ) 759, 700.

Synthesis of Compound 12

Compound 11 (1.00 mmol) was dissolved in 10 mL of methylene chloride and bromine (2.5 mmol) was added. After stirring for 6 hours at room temperature, the mixture was poured into 30 ml of methanol and stirred for 1 hour to form crystals. The resulting crystals were filtered and washed with 50 mL of methanol to yield compound 12 (orange solid, yield: 70%).

-MALDI-TOF analysis: calculated molecular weight 762, measured molecular weight 761

-Melting point: 345 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3052, 2955, (C = O) 1718, (Ar C = C) 1543, 1487, (C-CH3) 1368, (COC) 1194, 1139, (CH ) 760, 700.

Synthesis of Compound 13

Compound 12 (1.00 mmol) was dissolved in 10 mL of methylene chloride, followed by addition of copper cyanide (4 mmol). After stirring at 150 ° C. for 5 hours, the temperature was lowered and poured into 30 mL of water to form crystals. The resulting crystals were filtered and washed with 50 mL of methanol to yield compound 13 (red solid, yield: 65%).

MALDI-TOF analysis: calculated molecular weight 654, measured molecular weight 654

-Melting point: 420 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3056, 2957, (C≡N) 2214, (C = O) 1720, (Ar C = C) 1589, 1489, 1468, (C-CH3) 1370, (COC) 1192, 1151, (CH) 763, 703.

Example 10

Synthesis of Compound 14

Compound 10 (1.00 mmol) in Example 9 was dissolved in 10 mL methylene chloride, and bromine (3 mmol) was added thereto, followed by stirring at room temperature. After 6 hours, crystals were formed by pouring into 50 mL of methanol and washed three times with a filter and 50 mL of water to obtain Compound 14 (light yellow solid, yield: 76%).

MALDI-TOF analysis: calculated molecular weight 768, measured molecular weight 768

-Melting point: 321 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 2966, (C = O) 1717, (Ar C = C) 1579, 1513, 1452, (C-CH3) 1381, 1331, (COC) 1157, 1136, (CH) 758.

Synthesis of Compound 15

The compound 14 (1.00 mmol) was dissolved in 5 mL of tetrahydrofuran, and stirred with 3 mL of water, phenylboronic acid (6.00 mmol) and sodium carbonate (6.00 mmol). Pd (PPh ₃ ) ₄ (0.01 mmol) was added as a catalyst and refluxing was performed at 70 ° C. for 12 hours. After the temperature was lowered, the water layer was removed with a separatory funnel, and then poured into 10 mL of methanol to form crystals. The resulting crystals were filtered and washed with 20 mL each of water and methanol to give compound 15 (light orange solid, yield: 22%).

MALDI-TOF analysis: calculated molecular weight 756, measured molecular weight 756

-Melting point: 363 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3055, 2958, (C = O) 1717, (Ar C = C) 1598, (C-CH3) 1368, 1256, (COC) 1190, 1145, (CH 756, 698.

Example 11

Synthesis of Compound 16

Compound 14 (1.00 mmol) in Example 10 was dissolved in 10 mL dimethylformamide, and then phenol (6.00 mmol) and potassium carbonate (6.00 mmol) were added. After stirring at 130 ° C. for 12 hours, the temperature was lowered to room temperature. The resulting precipitate was filtered by adding the mixed solution to 20 mL of 5% aqueous ammonium chloride solution, and then washed with 30 mL of water to obtain compound 16 (yellow solid, yield: 63%).

-MALDI-TOF analysis: calculated molecular weight 820, measured molecular weight 820

-Melting point: 353 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3050, 2960, (C = O) 1717, (Ar C = C) 1583, 1502, (C-CH3) 1368, 1301, (COC) 1155, 1102, (CH) 760.

Example 12

Synthesis of Compound 17

Compound 14 (1.00 mmol) in Example 10 was dissolved in 10 mL of dimethylformamide, followed by addition of copper cyanide (6 mmol). After stirring at 150 ° C. for 8 hours, the temperature was lowered and poured into 30 mL of water to form crystals. The resulting crystals were filtered and washed with 50 mL of methanol to yield compound 17 (red solid, yield: 72%).

-MALDI-TOF analysis: calculated molecular weight 554, measured molecular weight 554

Melting Point: 332 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3050, 2963, (C≡N) 2211 (C = O) 1715, (Ar C = C) 1611, 1593, (C-CH3) 1336, 1289, ( COC) 1152, 1129, (CH) 760, 681.

Example 13

Synthesis of Compound 18

Compound 10 (1.00 mmol) in Example 9 was dissolved in 5 mL of tetrahydrofuran, followed by stirring with 3 mL of water, 2-methylpropylboronic acid (4.00 mmol) and sodium carbonate (4.00 mmol). . Pd (PPh ₃ ) ₄ (0.01 mmol) was added as a catalyst and reflux reaction was performed at 70 ° C. for 24 hours. After the temperature was lowered, the water layer was removed with a separatory funnel, and then poured into 10 mL of methanol to form crystals. The resulting crystals were filtered and washed with 20 mL each of water and methanol to give compound 18 (light yellow solid, yield: 20%).

MALDI-TOF analysis: calculated molecular weight 564, measured molecular weight 564

-Melting point: 395 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3050, 2972, (C = O) 1717, (Ar C = C) 1603, 1578, (C-CH3) 1302, 1288, (COC) 1189, 1129, (CH) 760, 700.

Synthesis of Compound 19

Compound 18 (1.00 mmol) was dissolved in 10 mL of methylene chloride and bromine (3 mmol) was added. After stirring for 6 hours at room temperature, the mixture was poured into 30 mL of methanol and stirred for 1 hour to form crystals. The resulting crystals were filtered and washed with 50 mL of methanol to yield compound 19 (dark yellow solid, yield: 59%).

MALDI-TOF analysis: calculated molecular weight 722, measured molecular weight 721

-Melting point: 345 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3057, 2959, (C = O) 1714, (Ar C = C) 1640, 1598, (C-CH3) 1369, 1255, (COC) 1190, 1145, (CH) 755, 698.

Synthesis of Compound 20

The compound 19 (1.00 mmol) was dissolved in 5 mL of tetrahydrofuran, and stirred with 3 mL of water, phenylboronic acid (4.00 mmol) and sodium carbonate (4.00 mmol). Pd (PPh ₃ ) ₄ (0.01 mmol) was added as a catalyst and refluxing was performed at 70 ° C. for 12 hours. After the temperature was lowered, the water layer was removed with a separatory funnel, and then poured into 10 mL of methanol to form crystals. The resulting crystals were filtered and washed with 20 mL each of water and methanol to give compound 20 (orange solid, yield: 23%).

MALDI-TOF analysis: calculated molecular weight 716, measured molecular weight 716

-Melting point: 377 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3060, 2979, (C = O) 1717, (Ar C = C) 1652, 1597, (C-CH3) 1355, 1305, (COC) 1178, 1135, (CH) 761, 698.

Example 14

Synthesis of Compound 21

Compound 10 (1.00 mmol) in Example 9 was dissolved in 10 mL of dimethylformamide, and then stirred at 130 ° C. for 6 hours with phenol (3.00 mmol) and potassium carbonate (3.00 mmol). Lowered. The resulting precipitate was added to 20 mL of 5% aqueous ammonium chloride solution and the resulting precipitate was filtered and washed with 30 mL of water to yield Compound 21 (yellow solid, yield: 68%).

-MALDI-TOF analysis: calculated molecular weight 636, measured molecular weight 638

-Melting point: 373 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3049, 2959, (C = O) 1717, (Ar C = C) 1583, 1502, 1489, (C-CH3) 1367, 1302, (COC) 1155, 1132, (CH) 794, 760.

Example 15

Synthesis of Compound 22

Compound 10 (1.00 mmol) in Example 9 was dissolved in 10 mL of dimethylformamide, and 2-phenylphenol (5.00 mmol) and cesium carbonate (5.00 mmol) were added thereto. After stirring at 130 ° C. for 8 hours, the temperature was lowered to room temperature. The resulting precipitate was added to 20 mL of 5% aqueous ammonium chloride solution and the resulting precipitate was filtered and washed with 30 mL of water to yield Compound 22 (yellow solid, yield: 52%).

MALDI-TOF analysis: calculated molecular weight 788, measured molecular weight 790

-Melting point: 369 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3054, 2958, (C = O) 1717, (Ar C = C) 1581, 1502, 1467, (C-CH3) 1366, 1302, (COC) 1155, 1132, (CH) 759, 698.

Example 16

Synthesis of Compound 23

Compound 10 (1.00 mmol) in Example 9 was dissolved in 10 mL of dimethylformamide, followed by addition of aniline (3.00 mmol) and cesium carbonate (3.00 mmol). After stirring at 130 ° C. for 12 hours, the temperature was lowered to room temperature. The resulting precipitate was filtered by adding the mixed solution to 20 mL of 5% aqueous ammonium chloride solution, and then washed with 30 mL of water to obtain Compound 23 (yellow solid, yield: 48%).

MALDI-TOF analysis: calculated molecular weight 636, measured molecular weight 636

-Melting point: 359 ℃

FTIR analysis (cm ^-1 ): (Ar CH) 3050, 2959, 2873 (C = O) 1717, (Ar C = C) 1581, 1502, 1466, (C-CH3) 1365,1264, (COC) 1156 , 1132, (CH) 760.

Example 17

Synthesis of Compound 24

Compound 10 (1.00 mmol) in Example 9 was dissolved in 10 mL of dimethylformamide, and 2-naphthol (3.00 mmol) and cesium carbonate (3.00 mmol) were added thereto. After stirring at 130 ° C. for 10 hours, the temperature was lowered to room temperature. The resulting precipitate was filtered by adding the mixed solution to 20 mL of 5% aqueous ammonium chloride solution, and then washed with 30 mL of water to obtain compound 24 (dark yellow solid, yield: 62%).

MALDI-TOF analysis: calculated molecular weight 736, measured molecular weight 737

-Melting point: 351 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3050, 2956, (C = O) 1707, (Ar C = C) 1584, 1515, 1463, (C-CH3) 1373, (COC) 1166, 1152, (CH) 758, 700.

Example 18

Synthesis of Compound 25

Compound 10 (1.00 mmol) in Example 9 was dissolved in 10 mL of dimethylformamide, followed by addition of 4-tert-butylbutylphenol (3.00 mmol) and potassium carbonate (3.00 mmol). After stirring at 130 ° C. for 6 hours, the temperature was lowered to room temperature. The resulting precipitate was filtered by adding the mixed solution to 20 mL of 5% aqueous ammonium chloride solution, and then washed with 30 mL of water to obtain Compound 25 (yellow solid, yield: 63%).

MALDI-TOF analysis: calculated molecular weight 748, measured molecular weight 747

-Melting point: 373 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3054, 2958, (C = O) 1716, (Ar C = C) 1584, 1537, 1495, (C-CH3) 1370, 1353, (COC) 1158, (CH) 748, 692.

Example 19

Synthesis of Compound 26

Compound 10 (1.00 mmol) in Example 9 was dissolved in 10 mL tetrahydrofuran and stirred with 3 mL of water, 1-naphthylboronic acid (4.00 mmol), and sodium carbonate (4.00 mmol). Pd (PPh ₃ ) ₄ (0.01 mmol) was added as a catalyst and reflux reaction was performed at 70 ° C. for 8 hours. The temperature was lowered, the water layer was removed with a separatory funnel, and then poured into 10 mL of methanol to form crystals. The resulting crystals were filtered and washed with 20 mL each of water and methanol to give compound 26 (light yellow solid, yield: 24%).

-MALDI-TOF analysis: calculated molecular weight 704, measured molecular weight 704

-Melting point: 382 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3052, (C = O) 1715, (Ar C = C) 1593, 1522, 1502, (C-CH3) 1381, 1372, (COC) 1157, 1102, (CH) 760, 699.

Example 20

Synthesis of Compound 27

Compound 10 (1.00 mmol) in Example 9 was dissolved in 10 mL of dimethylformamide, followed by addition of 2-methyl-2-propanol (5.00 mmol) and cesium carbonate (5.00 mmol). After stirring at 130 ° C. for 24 hours, the temperature was lowered to room temperature. The resulting precipitate was filtered by adding the mixed solution to 20 mL of 5% aqueous ammonium chloride solution and then washed with 30 mL of water to give compound 27 (yellow solid, yield: 38%).

-MALDI-TOF analysis: calculated molecular weight 596, measured molecular weight 596

-Melting point: 348 ℃

FTIR analysis (cm ⁻¹ ): (Ar CH) 3050, 2959, (C = O) 1717, (Ar C = C) 1581, 1502, (C-CH3) 1365, 1302, (COC) 1155, 1132, (CH) 817, 760, 696.

Example 21

Synthesis of Compound 28

Compound 10 (1.00 mmol) in Example 9 was dissolved in 10 mL tetrahydrofuran and stirred with 3 mL of water, 4-cyanophenylboronic acid (4.00 mmol), and sodium carbonate (4.00 mmol). Pd (PPh ₃ ) ₄ (0.01 mmol) was added as a catalyst and refluxing was performed at 70 ° C. for 12 hours. Lower the temperature, remove the water layer with a separatory funnel, and pour into 10 mL of methanol to form crystals. The resulting crystals were filtered and washed with 20 mL each of water and methanol to give compound 28 (light yellow solid, yield: 25%).

MALDI-TOF analysis: calculated molecular weight 654, measured molecular weight 654

-Melting point: 383 ℃

-FTIR analysis (cm ^-1 ): (Ar CH) 3042, 2961, 2880, (C≡N) 2221 (C = O) 1707, (Ar C = C) 1602, 1589, (C-CH3) 1306, 1279 , (COC) 1181, 1152, 1129, (CH) 767, 671.

Example 22

Synthesis of Compound 29

Compound 10 (1.00 mmol) in Example 9 was dissolved in 10 mL of dimethylformamide, followed by addition of 4-methoxythiophenol (4.00 mmol) and cesium carbonate (4.00 mmol). After stirring at 130 ° C. for 24 hours, the temperature was lowered to room temperature. The resulting precipitate was filtered by adding the mixed solution to 20 mL of 5% aqueous ammonium chloride solution, and then washed with 30 mL of water to obtain Compound 29 (orange solid, yield: 63%).

MALDI-TOF analysis: calculated molecular weight 728, measured molecular weight 728

Melting Point: 328 ℃

FTIR analysis (cm ^-1 ): (Ar CH) 3065, 2983, (C = O) 1717, (Ar C = C) 1601, 1581, (C-CH3) 1316, 1298, (COC) 1129, (CH 758.

Experimental Example  One

Propylene glycol monomethyl ether acetate was added to each of the perylene-based compounds (1000 ppm) and stirred for 10 minutes in order to confirm the optical properties of absorption and fluorescence for the perylene-based compounds 1 to 29 synthesized as in Example. Thereafter, additional propylene glycol monomethyl ether acetate was added and the concentration was diluted to 20 ppm, followed by absorption and absorption using a UV / Vis / NIR spectrophotometer (UV3600-shimadzu) and a spectrophotometer (RF-5301PC-shimadzu). Fluorescence was measured and the results are shown in Table 1 below. As a comparative example, commercially available Lumogen F Yellow 083 (BASF) was used. Table 1 shows the maximum absorption wavelength (Λmax), maximum emission wavelength (Λemission) and molar extinction coefficient (ε) for the dye compounds prepared as in the above examples and as a comparative example, Lumogen 083. In Table 1 below, Lumogen 083 did not dissolve and could not exhibit molar extinction coefficient values. As can be seen in Table 1, Lumogen 083 as a comparative example is low solubility is not dissolved in the solvent, the dye compounds according to the examples of the present application was found to show excellent solubility. In the above experiments, it was confirmed that the compounds according to the present example exhibited similar spectral characteristics to those of the comparative example, but had very improved solubility compared to the comparative example.

TABLE 1

FIG. 1 shows the maximum absorption wavelength (solid line) and the maximum emission wavelength (dotted line) of compounds 2, 7 and 9, which are compounds having high solubility in organic solvents and high molar coefficients among dye compounds according to the present example.

Experimental Example  2

The solubility in propylene glycol monomethyl ether acetate (PGMEA) and methyl ethyl ketone (MEK) was evaluated for the perylene-based compounds 1 to 12 prepared as in Example.

The compound and the solvent were mixed in a 25 mL vial bottle at a concentration of about 3% to about 5%, the vial bottle was completely sealed, shaken for 15 minutes, and after 30 minutes, the presence of a liquid precipitate was visually observed. When the precipitate was confirmed, it was determined that the solubility is poor. As a solubility determination criterion, when completely dissolved at 3% or more,? Is indicated by O, when dissolved at 3% or less, and partially dissolved or by X when not dissolved (Table 2). As can be seen in Table 2, it was confirmed that the solubility of the perylene-based compound of the present application is superior to the conventional fluorescent dyes.

TABLE 2

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application. .

Claims (12)

1. Perylene-based compound represented by the following general formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   It said R ₁ and said R _{2 are,} each independently, hydrogen, halogen, cyano, optionally substituted C _1-20 alkyl group, linear or branched which may be substituted, C _3-30 cycloalkyl, optionally substituted C _6-30 aryl group which may be substituted, linear or branched C _1-20 alkylamine group, C _3-30 cycloalkylamine group which may be substituted, C _6-30 arylamine group which may be substituted, A linear or branched C _1-20 alkoxy group which may be substituted, a C _3-30 cycloalkoxy group which may be substituted, a C _6-30 aryloxy group which may be substituted, a linear or branched C which may be substituted _{A 2-10} alkylcarboxyl group, a substituted C _6-30 arylcarboxyl group, or a substituted C _6-30 arylmercapto group,

   R ₃ and R ₄ are each independently hydrogen, a halogen group, a cyano group, a linear or branched C _1-20 alkyl group which may be substituted, a C _3-30 cycloalkyl group which may be substituted, and may be substituted. C _6-30 aryl group, a linear or branched C _1-20 alkoxy group which may be substituted, a C _3-30 cycloalkoxy group which may be substituted, or a C _6-30 aryloxy group which may be substituted.
2. The method of claim 1,

   The alkyl group, the alkylamine group, the alkoxy group, and the substitutable alkyl group contained independently of each of R ₁ to R ₄ may be a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group. Perylene-based compound, comprising a hexyl group, or isomers thereof.
3. The method of claim 1,

   Substituted cycloalkyl groups included in the cycloalkyl group, the cycloalkylamine group, and the cycloalkoxy group independently included in each of R ¹ to R ⁴ are cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or these Perylene-based compound, including isomers of.
4. The method of claim 1,

   Substitutable aryl groups contained in the aryl group, the arylamine group, the aryloxy group, the arylcarboxyl group or the arylmercapto group independently included in each of R ₁ to R ₄ may be phenyl groups or two or more groups. Perylene-based compound that contains a cyclic group fused or fused polycyclic ring.
5. The method of claim 1,

   Substituted aryl groups contained in the aryl group, the arylamine group, the aryloxy group, the arylcarboxyl group or the arylmercapto group contained independently of each of R ₁ to R ₄ are phenyl group, biphenyl group, or A perylene-based compound containing a naphthyl group.
6. The method of claim 1,

   Substituents which may be independently substituted on each of R ₁ and R ₂ include a halogen group, a cyano group, a linear or branched C _1-8 alkyl group, or a linear or branched C _1-8 alkoxy group The perylene compound.
7. The method of claim 1,

   Substituents which may be independently substituted for each of R ₃ and R ₄ include a halogen group, a cyano group, a linear or branched C _1-8 alkyl group, or a linear or branched C _1-8 alkoxy group The perylene compound.
8. To the compound represented by the formula (2), a linear or branched C _1-20 alkane compound which may be substituted, a C _3-30 cycloalkane compound which may be substituted, a C _6-30 aryl compound which may be substituted, to be substituted C _6-30 phenolic compound which may be substituted, linear or branched C _1-20 alcohol compound which may be substituted, linear or branched C _1-20 alkylamine compound which may be substituted, C ₃ which may be substituted A process for preparing a perylene-based compound according to claim 1 comprising reacting with a _-30 cycloalkylamine compound, a substituted C _6-30 arylamine compound, or N-halosuccinimide:

   [Formula 2]

   

   In Chemical Formula 2,

   R ₅ to R ₈ are each independently hydrogen, halogen or a linear or branched C _2-10 alkylcarboxyl group which may be substituted.
9. The method of claim 8,

   From the group consisting of halogen, cyanide salt, phenolic compound, naphthol compound, alcohol compound, thiol compound, amine compound and boronic acid which can be substituted in the perylene compound prepared by the method of claim 8 The method for preparing a perylene-based compound according to claim 1, further comprising performing the step of reacting by adding a substance selected.
10. The method according to claim 8 or 9,

    The method of producing a perylene-based compound according to claim 1, further comprising adding a carbonate salt in some or all of the reaction steps.
11. The method according to claim 8 or 9,

    The reaction is a method of producing a perylene-based compound according to claim 1 comprising dissolving the reactants in an organic solvent to react and then precipitated and filtered at room temperature.
12. The fluorescent dye containing the perylene-type compound in any one of Claims 1-7.

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