JP2013173726A - Coumarin derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel coumarin derivative having good solubility with respect to a binder resin such as a (meth)acrylic resin and having less influence of concentration quenching, and to provide an organic optical material using the derivative.SOLUTION: There is provided a coumarin derivative represented by general formula (1) (wherein Ris hydrogen or the like; X is oxygen, sulfur or imino; and Y is 2,2-hexafluoroisopropylidene, isopropylidene or the like). There is also provided the use of the derivative in an organic optical material, organic color conversion material or the like.

Description

  The present invention relates to a novel coumarin derivative that can be used as an organic optical material such as an organic color conversion material.

  Coumarin compounds such as coumarin 6 and coumarin 7 are fluorescent dyes that exhibit yellow-green fluorescence when irradiated with ultraviolet rays. Conventionally, a coumarin compound has been used as a fluorescent material such as a colorant for identifying fuel oil and a fluorescent whitening agent for washing, or as a coloring material such as a dye for wavelength correction filters in various displays. In recent years, focusing on the photosensitization function of coumarin compounds, application to applications such as dyes for dye lasers, sensitizing dyes in dye-sensitized solar cells, color conversion filters and light-emitting devices in various displays, etc. Has been. Moreover, about the coumarin compound, the synthesis | combination of various derivatives and its application are tried as it describes in patent documents 1-4.

  When a coumarin compound is used for a color conversion filter, a light emitting device, a wavelength correction filter, etc., for example, a coumarin compound and a binder resin are dissolved and dispersed in a solvent together with a curing agent as an optional component. It is required to form a coating film in which a coumarin compound is uniformly dissolved by preparing a solution and applying the obtained coating solution on a substrate. For this reason, the coumarin compound in the coating solution is, for example, soluble in binder resins such as (meth) acrylic resin, polystyrene, polycarbonate, polyamide, polyimide, epoxy resin, urea resin, melamine resin, benzoguanamine resin, and silicone resin. Is required to be good.

JP 2011-001323 A JP 2009-210745 A JP 2007-273440 A JP 2007-023162 A

  However, known coumarin compounds are not sufficiently soluble in the binder resin. Furthermore, when the known coumarin compound is contained at a high concentration in the coating film, the emission quantum yield decreases, and the phenomenon that the emission intensity is not proportional to the amount of the coumarin compound added, that is, concentration quenching appears remarkably. The emitted color also tends to shift to the long wavelength side.

  An object of the present invention is to provide a novel coumarin derivative that has good solubility in a binder resin and has little influence of concentration quenching, and an organic optical material using the same.

  As a result of intensive studies to solve the above problems, the present inventors have been able to improve the solubility in the binder resin according to the coumarin derivative represented by the following general formula (1), and the concentration The present inventors have found new knowledge that the influence of quenching can be reduced and new knowledge that a coumarin derivative represented by the following general formula (1) is useful as an organic optical material such as an organic color conversion material. It came to complete.

  One aspect of the present invention relates to a coumarin derivative represented by the following general formula (1).

In the formula, R ¹ and R ^1a are the same or different and have the general formula (2):

An N-substituted amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydrogen atom,
R ^2a and R ^2b are the same or different and each represents an alkyl group having 1 to 12 carbon atoms, or R ^2a and R ^2b are bonded to each other to form a 5- to 7-membered nitrogen-containing heterocycle An alkylene group having 4 to 10 carbon atoms, which forms
R ³ , R ^3a , R ⁴ and R ^4a are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or R ¹ and R ^1a represent the above general formula (2). In which R ^2a and R ^2b are bonded to each other to form a 5- to 7-membered nitrogen-containing heterocycle, and R ^2a , R ³ , R ^At least one of a combination of ^2b and R ⁴ , R ^2a and R ^3a , and R ^2b and R ^4a is bonded to each other to form a 5- to 7-membered nitrogen-containing heterocycle, and has 4 to 10 carbon atoms An alkylene group having
R ⁵ and R ^5a are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
R ^6a and R ^6b are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a halogen atom, or a cyano group,
X represents an oxygen atom, a sulfur atom or an imino group,
Y represents the general formula (3):

Or a divalent group represented by formula (4):

A sulfonyl group represented by
R ^7a and R ^7b are the same or different and are an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms or a hydrogen atom is shown.

  Another aspect of the present invention relates to an organic optical material containing a coumarin derivative represented by the general formula (1), and yet another aspect of the present invention is represented by the general formula (1). The present invention relates to an organic color conversion material containing a coumarin derivative.

  The coumarin derivative represented by the above general formula (1) according to the present invention (hereinafter referred to as “coumarin derivative (1)”) has good solubility in a binder resin such as a (meth) acrylic resin. Therefore, when a coumarin derivative (1), a binder resin such as (meth) acrylic resin, and a solvent are mixed, a coating solution in which the coumarin derivative (1) is uniformly dissolved in the binder resin is prepared. Can do. Furthermore, as a result, by using the coumarin derivative (1) of the present invention, it is possible to obtain a coating film in which the coumarin derivative (1) is uniformly dissolved and the coumarin concentration is small. Thereby, the quality of the color conversion filter and the light emitting device can be improved.

  Furthermore, since the coumarin derivative (1) of the present invention is less affected by concentration quenching, the content of the coumarin derivative (1) in the binder resin can be increased. As a result, the optical characteristics of the organic optical material using the coumarin derivative (1) such as a color conversion filter and a light emitting device can be improved.

It is a graph which shows the absorption spectrum about the coumarin derivative and coumarin 6 obtained in Examples 1-4. It is a graph which shows the fluorescence spectrum about the coumarin derivative and coumarin 6 obtained in Examples 1-4. It is a graph which shows the absorption spectrum about the coumarin derivative obtained in Example 5 and 6. It is a graph which shows the fluorescence spectrum about the coumarin derivative obtained in Example 5 and 6. It is a graph which shows the relationship between the fluorescence quantum yield about the coumarin derivative and coumarin 6 obtained in Examples 1-4, and the density | concentration of a fluorescent pigment | dye.

<Coumarin derivative (1)>
The coumarin derivative of the present invention is represented by the following general formula (1). Hereinafter, this coumarin derivative (1) will be described in detail.

In the formula, R ¹ , R ^1a , R ³ , R ^3a , R ⁴ , R ^4a , R ⁵ , R ^5a , R ⁶ , R ^6a , X and Y are the same as described above.

(Coumarin skeleton)
The coumarin derivative (1) has a structure in which two coumarin skeletons represented by the following general formula (5) (hereinafter referred to as “coumarin skeleton (5)”) are bonded via a divalent group Y described later. . The coumarin skeleton (5) includes cases in which the divalent group Y in the general formula (1) is different from the left and right in the general formula (1). In the following description, the divalent group Y in the following general formula (5) Both coumarin skeletons will be described based on the coumarin skeleton shown on the left side. Unless otherwise specified, the details of the groups R ^1a , R ^3a , R ^4a , R ^5a and R ^6a are the same as the corresponding groups R ¹ , R ³ , R ⁴ , R ⁵ and R ⁶ , respectively.

In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and X are the same as described above.

  The coumarin skeleton (5) has a structure in which the carbon atom at the 3-position of the coumarin derivative is bonded to the carbon atom at the II-position of a specific nitrogen-containing heterocyclic ring. The symbols 1 to 8 in the general formula (5) are substitution position numbers in the coumarin derivative, and the symbols I to VII are substitution position numbers in the nitrogen-containing heterocycle.

  X of the nitrogen-containing heterocyclic ring represents an oxygen atom, a sulfur atom or an imino group (> NH), and among these, an oxygen atom is particularly preferable. That is, the coumarin skeleton (5) is represented by the following general formula (5a), (5b) or (5c), and among them, the coumarin skeleton represented by the general formula (5a) is preferable.

In the formula, R ¹ , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as described above.

(Group R ¹ )
R ¹ in the coumarin skeleton (5) is an N-substituted amino group represented by the following general formula (2) (hereinafter referred to as “N-substituted amino group (2)”), an alkyl having 1 to 10 carbon atoms. A group, an alkoxy group having 1 to 10 carbon atoms, or a hydrogen atom;

N-substituted amino group (2) as group R ¹
In the case where the group R ¹ is an N-substituted amino group (2), R ^2a and R ^2b of the N-substituted amino group (2) are
(I) represents the same or different alkyl group having 1 to 12 carbon atoms, or
(Ii) An alkylene group having 4 to 10 carbon atoms which is bonded to each other to form a 5- to 7-membered nitrogen-containing heterocycle.

When R ^2a and R ^2b are the above (i), the alkyl group having 1 to 12 carbon atoms is a group represented by —C _n H _{2n + 1} (n is an integer of 1 to 12), Including all structural isomers. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, isohexyl, 3-methylpentyl, 5-methylpentyl 2-ethylbutyl, 2,2-dimethylbutyl, heptyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 2-methylheptyl, 5,5-dimethylhexyl, 2, Examples include 2-dimethylhexyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and the like. Specifically, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 8, still more preferably 2 to 8, and particularly preferably 2 to 4. The alkyl group may be linear or branched.

In the case where R ^2a and R ^2b are the above (i), R ^2a and R ^2b are preferably the same alkyl group. Preferable embodiments of the N-substituted amino group include, for example, diethylamino, dibutylamino, dihexylamino, dioctylamino, di-2-ethylhexyl and the like, and particularly preferably di-n-butylamino.

In the case where R ^2a and R ^2b are the above (ii), as the alkylene group having 4 to 10 carbon atoms, tetramethylene, pentamethylene and hexamethylene, these alkylene groups as a main chain, and methyl, And groups having a total of 4 to 10 carbon atoms substituted by alkyl side chains such as ethyl, n-propyl, isopropyl and the like.

Other groups R ¹
As the group corresponding to R ¹ , groups other than the N-substituted amino group (2) include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms as described above, and And a hydrogen atom.
Examples of the alkyl group having 1 to 10 carbon atoms include the same alkyl groups as those exemplified as the alkyl group having 1 to 10 carbon atoms corresponding to R ^2a and R ^2b of the N-substituted amino group (2). Is mentioned. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, methyl or ethyl is more preferable, and methyl is particularly preferable.

An alkoxy group having 1 to 10 carbon atoms is a group represented by —OC _m H _{2m + 1} , and when m is 3 to 10, all structural isomers are included. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxyoctyloxy, nonyloxy, decyloxy and the like. It is done.

In general, the coumarin derivative (1) in which the group R ¹ is an N-substituted amino group (2) such as diethylamino absorbs light in the blue region and exhibits fluorescence in the green region. In general, the coumarin derivative (1) in which the group R ¹ is an alkyl group such as methyl, an alkoxy group such as methoxy, and a hydrogen atom absorbs light in the ultraviolet region and exhibits fluorescence in the blue region. Therefore, the group R ¹ may be appropriately selected according to the absorption wavelength and emission wavelength required for the coumarin derivative (1).
R ¹ in the coumarin skeleton (5) is particularly preferably a diethylamino, dibutylamino, methyl, methoxy or hydrogen atom among the above-mentioned groups.

Further, in the coumarin derivative (1) that absorbs light in the blue region and exhibits fluorescence in the green region, R ¹ is diethylamino or dibutylamino from the viewpoint that the absorbance and fluorescence intensity with respect to the light in the wavelength region are strong. Is preferred, and di-n-butylamino is particularly preferred.
In the coumarin derivative (1) that absorbs light in the ultraviolet region and exhibits fluorescence in the blue region, R ¹ is preferably a hydrogen atom from the viewpoint of high absorbance and fluorescence intensity with respect to light in the wavelength region.

(Groups R ³ and R ⁴ )
R ³ and R ⁴ in the coumarin skeleton (5) are
(I) the same or different and represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or (II) when R ^2a and R ^2b are N-substituted amino groups (2) (provided that R ^2a and R ^2b are bonded to each other to form a 5- to 7-membered nitrogen-containing heterocycle), R ^2a and R ³ , R ^2a and R ^3a , R ^2b and R ⁴ , R ^2b and At least one of the combinations of R ^4a represents an alkylene group having 4 to 10 carbon atoms that is bonded to each other to form a 5- to 7-membered nitrogen-containing heterocycle.

When R ³ and R ⁴ are the above (I), the alkyl group having 1 to 10 carbon atoms includes 1 to 10 carbon atoms corresponding to R ^2a and R ^2b of the N-substituted amino group (2). Examples of the alkyl group are the same as those exemplified as the alkyl group having an atom.

In the case where R ³ and R ⁴ are (II) above, the alkylene group having 4 to 10 carbon atoms includes 4 to 10 carbon atoms corresponding to R ^2a and R ^2b of the N-substituted amino group (2). Examples thereof include the same alkylene groups as those exemplified as the alkylene group having an atom.

In the case where R ³ and R ⁴ are the above (II), specific examples of the coumarin skeleton (5) include, for example, a skeleton represented by the following general formula (5x) [R ^2a and R ³ (R ^3a ), and R ^2b and R ⁴ (R ^4a ) are bonded to each other to form a 6-membered nitrogen-containing heterocycle, which is a trimethylene group] or a skeleton represented by the following general formula (5y) [ A 1,1-dimethyltrimethylene group in which R ^2a and R ³ (R ^3a ), and R ^2b and R ⁴ (R ^4a ) are bonded to each other to form a 6-membered nitrogen-containing heterocycle. [If there is].

In the formula, R ⁵ , R ⁶ and X are the same as described above. In addition, R ³ and R ⁴ in the coumarin skeleton (5) are particularly preferably hydrogen atoms among the groups described above.

(Group R ⁵ )
R ⁵ in the coumarin skeleton (5) represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

Examples of the alkyl group having 1 to 10 carbon atoms include the same alkyl groups as those exemplified as the alkyl group having 1 to 10 carbon atoms corresponding to R ^2a and R ^2b of the N-substituted amino group (2). Is mentioned. Of these, an alkyl group having 1 to 4 carbon atoms is preferable.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 3,4- Examples include xylyl, 3,5-xylyl, mesityl, m-cumenyl, 2-indenyl, 1-naphthyl, 2-naphthyl, 2-anthryl, and 2-phenanthryl. Especially, 6-14 are preferable and, as for the number of the carbon atoms of an aryl group, 6-10 are more preferable.
R ⁵ in the coumarin skeleton (5) is particularly preferably a hydrogen atom among the groups described above.

(Group R ⁶ )
R ⁶ in the coumarin skeleton (5) represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a halogen atom, or a cyano group.
Examples of the alkyl group having 1 to 10 carbon atoms include the same alkyl groups as those exemplified as the alkyl group having 1 to 10 carbon atoms corresponding to R ^2a and R ^2b of the N-substituted amino group (2). Is mentioned. Of these, an alkyl group having 1 to 4 carbon atoms is preferable.
Examples of the aryl group having 6 to 30 carbon atoms include the same groups as those exemplified as the aryl group having 6 to 30 carbon atoms corresponding to R ⁵ of the coumarin skeleton (5). Especially, 6-14 are preferable and, as for the number of the carbon atoms of an aryl group, 6-10 are more preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R ⁶ in the coumarin skeleton (5) is particularly preferably a hydrogen atom among the groups described above.

  From the viewpoint of the coumarin skeleton (5), preferred embodiments of the coumarin derivative (1) include compounds represented by the following general formulas (1A), (1B), (1C), (1D) and (1E). .

  In the formula, Y is the same as described above, Et represents an ethyl group, and Bu represents a butyl group.

(Divalent group Y)
The divalent group Y in the coumarin derivative (1) is a divalent group represented by the following general formula (3) (hereinafter referred to as “divalent group (3)”) or a sulfonyl represented by the formula (4). Indicates a group.

R ^7a and R ^7b in the divalent group (3) are the same or different and are an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, 6 to 30 An aryl group having a carbon atom, an aralkyl group having 7 to 30 carbon atoms, or a hydrogen atom is shown.

Examples of the alkyl group having 1 to 10 carbon atoms include the same groups as those exemplified as the alkyl group having 1 to 10 carbon atoms corresponding to R ^2a and R ^2b of the N-substituted amino group (2). Can be mentioned. Among these, methyl and ethyl are preferable, and methyl is particularly preferable.

  As the halogenated alkyl group having 1 to 10 carbon atoms, at least one hydrogen atom in the alkyl group having 1 to 10 carbon atoms is substituted with a halogen such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The thing substituted by the atom is mentioned. Such halogenated alkyl groups include monofluoromethyl, difluoromethyl, perfluoromethyl, monochloromethyl, dichloromethyl, perchloromethyl, monobromomethyl, dibromomethyl, perbromomethyl, monofluoroethyl, difluoroethyl, trifluoro Fluoroethyl, tetrafluoroethyl, perfluoroethyl and the like can be mentioned. Among these, the number of carbon atoms of the halogenated alkyl group is preferably 1 or 2, and more preferably 1. The halogen atom of the halogenated alkyl group is preferably a fluorine atom. Preferable embodiments of the halogenated alkyl group include perfluoromethyl.

Examples of the aryl group having 6 to 30 carbon atoms include the same aryl groups as those exemplified as the aryl group having 6 to 30 carbon atoms corresponding to R ⁵ of the coumarin skeleton (5). Among these, 6-14 are preferable and, as for the number of the carbon atoms of an aryl group, 6-10 are more preferable.

  Examples of the aralkyl group (arylalkyl group) having 7 to 30 carbon atoms include benzyl, phenethyl, diphenylmethyl, trityl, styryl, cinnamyl and the like. Among these, the number of carbon atoms in the aralkyl group is preferably 7 to 13.

The divalent group Y in the coumarin derivative (1) is, among others, 2,2-hexafluoroisopropylidene [1,1,1,3,3,3-hexafluoropropane-2-ylidene, divalent group (3). radicals R ^7a and R ^7b is a trifluoromethyl, group R ^7a and R ^7b is methyl isopropylidene [bivalent group (3)], R ^7a and R methylene [bivalent group (3) Group wherein ^7b is a hydrogen atom] and sulfonyl [formula (4)] are preferred, 2,2-hexafluoroisopropylidene and isopropylidene are more preferred, and 2,2-hexafluoroisopropylidene is particularly preferred.

  The bonding position of the divalent group Y may be any of the carbon atoms from the IV position to the VII position in the coumarin skeleton (5), but is preferably bonded to the carbon atom at the V position or the VI position. It is preferably bonded to the carbon atom at the position. The two coumarin skeletons (5) facing each other through the divalent group Y may be bonded to the divalent group Y at different substitution positions, but are bonded to the divalent group Y at the same substitution position. Is more preferable.

  That is, from the viewpoint of the divalent group Y, preferred embodiments of the coumarin derivative (1) include compounds represented by the following general formulas (1a), (1b), (1c) and (1d).

In the formula, R ¹ , R ^1a , R ³ , R ^3a , R ⁴ , R ^4a , R ⁵ , R ^5a , R ⁶ , R ^6a and X are the same as described above.

  Particularly preferable examples of the coumarin derivative of the present invention include compounds represented by the following formulas (1-1) to (1-8).

  In the formula, Et and Bu are the same as described above.

  The coumarin derivatives represented by the formulas (1-1) to (1-6) absorb light in the blue region and emit light in the green region. On the other hand, the coumarin derivatives represented by the formulas (1-7) and (1-8) absorb light in the ultraviolet region and emit light in the blue region.

<Synthesis Method of Coumarin Derivative (1)>
An example of a method for synthesizing the coumarin derivative (1) is shown below.

  First, as shown in the following reaction formula (I), a coumarin compound (8) is synthesized by a cyclization reaction between a salicylaldehyde compound (6) and diethyl malonate (7). This synthesis reaction can be performed, for example, by dissolving the salicylaldehyde compound (6) and diethyl malonate (7) in a solvent and heating in the presence of piperidine.

In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and Et are the same as described above. Ac represents an acetyl group.

  Next, as shown in the following reaction formula (II), an aldehyde group (—CHO) is introduced into the coumarin compound (8) obtained by the reaction formula (I) to synthesize an aldehyde group-containing coumarin compound (9). . Introduction of an aldehyde group into the coumarin compound (8) can be performed using, for example, phosphoryl chloride and dehydrated dimethylformamide.

In the formula, R ¹ , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as described above.

Furthermore, as shown in the following reaction formula (III), the aldehyde group-containing coumarin compound (9) obtained by the reaction formula (II) is reacted with the compound represented by the following formula (10) to obtain the present invention. Synthesize coumarin derivatives. This reaction can be performed, for example, by dissolving the aldehyde group-containing coumarin compound (9), compound (10) and ammonium acetate in a solvent (glacial acetic acid) and stirring under heating.
In addition, the compound represented by following formula (10) is used so that it may react with the ratio of a 1/2 molar equivalent with respect to an aldehyde group containing coumarin compound (9).

In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , X, Y and Ac are the same as described above.

Another example of the synthesis method of the coumarin derivative (1) is shown below.
As shown in the following reaction formula (IV), the coumarin derivative (1) comprises a salicylaldehyde compound (6), ethyl cyanoacetate (11), a compound represented by the following formula (10), and benzoic acid as a solvent. It is also possible to synthesize in one step by dissolving it in and heating in a nitrogen stream.
In addition, ethyl cyanoacetate (11) was used so as to react at a ratio of equimolar equivalent to the salicylaldehyde compound (6), and the compound represented by the following formula (10) was converted to the salicylaldehyde compound (6). It is used so as to react at a ratio of 1/2 molar equivalent to.

In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , X, Y and Et are the same as described above.

  The coumarin derivative (1) of the present invention has good solubility and is less affected by concentration quenching, and can be used, for example, as an organic optical material or an organic color conversion material.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples.

<Synthesis of Coumarin Derivative (1)>
Example 1 Synthesis of Coumarin Derivative (1-1) A coumarin derivative represented by the above formula (1-1) was synthesized through the steps shown in the following reaction formulas (i) to (iii).

(Synthesis of 7-diethylaminocoumarin (8-1))
1.93 g (10 mmol) of 4-diethylaminosalicylaldehyde (6-1), 3.20 g (20 mmol) of diethyl malonate (7) and 1 mL of piperidine were dissolved in 50 ml of absolute ethanol. The reaction was then carried out with stirring for 6 hours under reflux conditions. After completion of the reaction, ethanol was distilled off under reduced pressure, 10 mL of concentrated hydrochloric acid and 10 mL of glacial acetic acid were added to the reaction mixture, and the mixture was further stirred for 6 hours. After the reaction mixture was cooled to room temperature, it was further cooled by placing it in 200 mL of ice water, and then the pH of the reaction mixture was adjusted to about 5 by dropwise addition of 30% by mass aqueous sodium hydroxide solution to the reaction mixture. After the reaction mixture was stirred for 30 minutes, the resulting precipitate was filtered, washed with water and dried. The precipitate thus obtained was recrystallized from toluene to obtain 7-diethylaminocoumarin represented by the formula (8-1). The yield was 1.74 g (8.0 mmol), and the yield was 80%.
The synthesis process of 7-diethylaminocoumarin (8-1) is shown in reaction formula (i).

  In the formula, Et and Ac are the same as described above.

The measurement result of ¹ H-NMR of 7-diethylaminocoumarin (8-1) is shown below (measurement conditions: 400 MHz, CDCl ₃ ).
δ: 7.55 (d, 1H), 7.23 (d, 1H), 6.59 (d, 1H), 6.51 (s, 1H), 6.06 (d, 1H), 3.42 (M, 4H), 1.21 (t, 6H)

(Synthesis of 7-diethylaminocoumarin-3-aldehyde (9-1))
To a reaction vessel containing 2 mL of phosphoryl chloride, 2 mL of dehydrated dimethylformamide was gradually added dropwise at 0 ° C. in a nitrogen atmosphere, and the mixture was warmed to room temperature and stirred for 30 minutes. Next, 1.50 g (6.91 mmol) of 7-diethylaminocoumarin (8-1) was dissolved in 10 mL of dehydrated dimethylformamide (DMF), placed in a reaction vessel, and stirred at 50 ° C. for 12 hours. The reaction mixture was placed in 200 mL of ice water and 20% by weight aqueous sodium hydroxide solution was added. The resulting precipitate was filtered, washed with water and dried. The precipitate thus obtained was recrystallized from ethanol to obtain 7-diethylaminocoumarin-3-aldehyde represented by the formula (9-1). The yield was 1.20 g (4.89 mmol), and the yield was 70%.
A synthesis step of 7-diethylaminocoumarin-3-aldehyde (9-1) is shown in reaction formula (ii).

  In the formula, Et is the same as described above.

The measurement result of ¹ H-NMR of 7-diethylaminocoumarin-3-aldehyde (9-1) is shown below (measurement conditions: 400 MHz, CDCl ₃ ).
δ: 10.13 (s, 1H), 8.26 (s, 1H), 7.43 (d, 1H), 6.67 (d, 1H), 6.50 (s, 1H), 3.49 (M, 4H), 1.25 (t, 6H)

(Synthesis of Coumarin Derivative (1-1))
2.0 g (8.15 mmol) of 7-diethylaminocoumarin-3-aldehyde (9-1) and 1.49 g (4.08 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoro Propane (10-1) and 12.6 g (163 mmol) of sodium acetate were dissolved in 40 mL of glacial acetic acid and stirred at 90 ° C. for 10 hours. The reaction mixture was then placed in 200 mL of water. The resulting precipitate was filtered, dissolved in dichloromethane, and washed with water in a separatory funnel. The dichloromethane layer collected from the separatory funnel was dried over sodium sulfate and purified by silica gel column chromatography to obtain a coumarin derivative represented by the formula (1-1). The yield was 1.67 g (2.04 mmol), and the yield was 50%.
The synthesis process of the coumarin derivative (1-1) is shown in the reaction formula (iii).

  In the formula, Et and Ac are the same as described above.

The measurement result of ¹ H-NMR of the coumarin derivative (1-1) is shown below (measurement conditions: 400 MHz, CDCl ₃ ).
δ: 8.58 (s, 2H), 8.00 (s, 2H), 7.54 (d, 2H), 7.41 (d, 2H), 7.33 (d, 2H), 6.64 (Dd, 2H), 6.55 (d, 2H), 3.43 (q, 8H), 1.24 (t, 12H)

The measurement result of the absorption spectrum of the coumarin derivative (1-1) is shown in FIG. 1, and the measurement result of the fluorescence spectrum is shown in FIG. The absorption spectrum was measured using an ultraviolet-visible spectrophotometer (“V-650” manufactured by JASCO Corporation). The fluorescence spectrum measured the fluorescence at the time of irradiating the excitation light of the maximum absorption wavelength of each fluorescent dye using the absolute quantum yield measuring apparatus ("C9920-12" made by Hamamatsu Photonics). As a measurement sample, a chloroform solution (concentration: 1 × 10 ⁻⁵ M) of coumarin derivative (1-1) was used for both the absorption spectrum and the fluorescence spectrum.

Example 2: Synthesis of a coumarin derivative (1-2) A coumarin derivative represented by the above formula (1-2) was synthesized through the steps shown in the following reaction formula (iv).

2.0 g (8.15 mmol) of 7-diethylaminocoumarin-3-aldehyde (9-1) and 1.05 g (4.08 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) propane ( 10-2) and 12.6 g (163 mmol) of sodium acetate were dissolved in 40 mL of glacial acetic acid and stirred at 90 ° C. for 10 hours. The reaction mixture was then placed in 200 mL of water. The resulting precipitate was filtered, dissolved in dichloromethane, and washed with water in a separatory funnel. The dichloromethane layer collected from the separatory funnel was dried over sodium sulfate and purified by silica gel column chromatography to obtain a coumarin derivative represented by the formula (1-2). The yield was 1.45 g (2.04 mmol), and the yield was 50%.
The synthesis process of the coumarin derivative (1-2) is shown in the reaction formula (iv).

  In the formula, Et and Ac are the same as described above.

The measurement result of ¹ H-NMR of the coumarin derivative (1-2) is shown below (measurement conditions: 400 MHz, CDCl ₃ ).
δ: 8.58 (s, 2H), 7.81 (s, 2H), 7.41 (t, 4H), 7.12 (d, 2H), 6.63 (dd, 2H), 6.52 (D, 2H), 3.45 (q, 8H), 1.81 (s, 6H), 1.24 (t, 12H)
The measurement result of the absorption spectrum of the coumarin derivative (1-2) is shown in FIG. 1, and the measurement result of the fluorescence spectrum is shown in FIG.

Example 3: Synthesis of a coumarin derivative (1-3) A coumarin derivative represented by the above formula (1-3) was synthesized through the steps shown in the following reaction formula (v).

2.0 g (8.15 mmol) of 7-diethylaminocoumarin-3-aldehyde (9-1) and 1.0 g (4.08 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) sulfone ( 10-3) and 12.6 g (163 mmol) of sodium acetate were dissolved in 40 mL of glacial acetic acid and stirred at 90 ° C. for 10 hours. The reaction mixture was then placed in 200 mL of water. The resulting precipitate was filtered, dissolved in dichloromethane, and washed with water in a separatory funnel. The dichloromethane layer collected from the separatory funnel was dried over sodium sulfate and purified by silica gel column chromatography to obtain a coumarin derivative represented by the formula (1-3). The yield was 1.5 g (2.04 mmol), and the yield was 50%.
The synthesis process of the coumarin derivative (1-3) is shown in the reaction formula (v).

  In the formula, Et and Ac are the same as described above.

The measurement result of ¹ H-NMR of the coumarin derivative (1-3) is shown below (measurement conditions: 400 MHz, CDCl ₃ ).
δ: 8.63 (s, 2H), 8.40 (s, 2H), 7.96 (d, 2H), 7.67 (d, 2H), 7.43 (d, 2H), 6.66 (Dd, 2H), 6.53 (d, 2H)
The measurement result of the absorption spectrum of the coumarin derivative (1-3) is shown in FIG. 1, and the measurement result of the fluorescence spectrum is shown in FIG.

Example 4: Synthesis of a coumarin derivative (1-4) A coumarin derivative represented by the above formula (1-4) was synthesized through the steps shown in the following reaction formula (vi).

  2.49 g (10 mmol) of 4- (di-n-butylamino) salicylaldehyde (6-2), 1.13 g (10 mmol) of ethyl cyanoacetate (11), 1.83 g (5.0 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (10-1) was dissolved in 22 g (250 mmol) of 1-pentanol, and 0.41 g (3.4 mmol) of benzoic acid. And stirred at 135 ° C. for 7 hours under a nitrogen stream. Subsequently, 1-pentanol was distilled off under reduced pressure, and the residue was dissolved in toluene and washed with water. The toluene layer was dried over sodium sulfate, concentrated, and further purified by silica gel column chromatography (developing solvent; hexane-ethyl acetate mixed solvent) to obtain a coumarin derivative represented by the formula (1-4). . The yield was 1.39 g (1.5 mmol), and the yield was 30%.

The measurement result of ¹ H-NMR of the coumarin derivative (1-4) is shown below (measurement conditions: 400 MHz, CDCl ₃ ).
δ: 0.99 (12H, t), 1.36-1.42 (8H, m), 1.59-1.67 (8H, m), 3.37 (8H, t), 6.51 ( 2H, d), 6.63 (2H, dd), 7.32 (2H, d), 7.41 (2H, d), 7.54 (2H, d), 7.99 (2H, s), 8.61 (2H, s)
The measurement result of the absorption spectrum of the coumarin derivative (1-4) is shown in FIG. 1, and the measurement result of the fluorescence spectrum is shown in FIG.

In FIG. 1 and FIG. 2, the measurement result of the absorption spectrum and fluorescence spectrum of coumarin 6 was shown as a comparison object. All the measurement conditions are the same as in Examples 1 to 3.
In addition, in the wavelength shown by the downward arrow in FIG. 2, coumarin derivative (1-4), coumarin derivative (1-3), coumarin derivative (1-1), coumarin derivative (1-2) and coumarin 6 In order, the intensity of the fluorescence spectrum was higher.

Example 5: Synthesis of Coumarin Derivative (1-7) A coumarin derivative represented by the above formula (1-7) was synthesized through the steps shown in the following reaction formulas (vii) to (ix).

(Synthesis of Coumarin (8-2))
1.22 g (10 mmol) of salicylaldehyde (6-3), 3.20 g (20 mmol) of diethyl malonate (7) and 1 mL of piperidine were dissolved in 50 ml of absolute ethanol. The reaction was then carried out with stirring for 6 hours under reflux conditions. After completion of the reaction, ethanol was distilled off under reduced pressure, 10 mL of concentrated hydrochloric acid and 10 mL of glacial acetic acid were added to the reaction mixture, and the mixture was further stirred for 6 hours. After the reaction mixture was cooled to room temperature, it was further cooled by placing it in 200 mL of ice water, and then the pH of the reaction mixture was adjusted to about 5 by dropwise addition of 30% by mass aqueous sodium hydroxide solution to the reaction mixture. After the reaction mixture was stirred for 30 minutes, the resulting precipitate was filtered, washed with water and dried. The precipitate thus obtained was recrystallized from toluene to obtain a coumarin represented by the formula (8-2). The yield was 1.17 g (8.0 mmol), and the yield was 80%.
The synthesis step of coumarin (8-2) is shown in reaction formula (vii).

  In the formula, Et and Ac are the same as described above.

(Synthesis of Coumarin-3-aldehyde (9-2))
To a reaction vessel containing 2 mL of phosphoryl chloride, 2 mL of dehydrated dimethylformamide was gradually added dropwise at 0 ° C. in a nitrogen atmosphere, and the mixture was warmed to room temperature and stirred for 30 minutes. Next, 1.01 g (6.91 mmol) of coumarin (8-2) was dissolved in 10 mL of dehydrated dimethylformamide, placed in a reaction vessel, and stirred at 50 ° C. for 12 hours. The reaction mixture was placed in 200 mL of ice water and 20% by weight aqueous sodium hydroxide solution was added. The resulting precipitate was filtered, washed with water and dried. The thus obtained precipitate was recrystallized with ethanol to obtain a coumarin-3-aldehyde represented by the formula (9-2). The yield was 0.85 g (4.89 mmol), and the yield was 70%.
A synthesis process of coumarin-3-aldehyde (9-2) is shown in reaction formula (viii).

(Synthesis of Coumarin Derivative (1-7))
1.42 g (8.15 mmol) of coumarin-3-aldehyde (9-2) and 1.49 g (4.08 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (10 -1) and 12.6 g (163 mmol) of sodium acetate were dissolved in 40 mL of glacial acetic acid and stirred at 90 ° C. for 10 hours. The reaction mixture was then placed in 200 mL of water. The resulting precipitate was filtered, dissolved in dichloromethane, and washed with water in a separatory funnel. The dichloromethane layer collected from the separatory funnel was dried over sodium sulfate and purified by silica gel column chromatography to obtain a coumarin derivative represented by the formula (1-7). The yield was 1.38 g (2.04 mmol), and the yield was 50%.
The synthesis process of the coumarin derivative (1-7) is shown in the reaction formula (ix).

  In the formula, Et and Ac are the same as described above.

The measurement result of ¹ H-NMR of the coumarin derivative (1-7) is shown below (measurement conditions: 400 MHz, CDCl ₃ ).
δ: 8.81 (s, 2H), 8.10 (s, 2H), 7.62-7.71 (m, 6H), 7.38-7.45 (m, 6H)

  The measurement result of the absorption spectrum of the coumarin derivative (1-7) is shown in FIG. 3, and the measurement result of the fluorescence spectrum is shown in FIG.

Example 6: Synthesis of coumarin derivative (1-8) A coumarin derivative represented by the above formula (1-8) was synthesized through the steps shown in the following reaction formula (x).

1.42 g (8.15 mmol) of coumarin-3-aldehyde (9-2) and 1.05 g (4.08 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) propane (10-2) ) And 12.6 g (163 mmol) of sodium acetate were dissolved in 40 mL of glacial acetic acid and stirred at 90 ° C. for 10 hours. The reaction mixture was then placed in 200 mL of water. The resulting precipitate was filtered, dissolved in dichloromethane, and washed with water in a separatory funnel. The dichloromethane layer collected from the separatory funnel was dried over sodium sulfate and purified by silica gel column chromatography to obtain a coumarin derivative represented by the formula (1-8). The yield was 1.16 g (2.04 mmol), and the yield was 50%.
The synthesis process of the coumarin derivative (1-8) is shown in the reaction formula (x).

  In the formula, Et and Ac are the same as described above.

The measurement result of ¹ H-NMR of the coumarin derivative (1-8) is shown below (measurement conditions: 400 MHz, CDCl ₃ ).
δ: 8.77 (s, 2H), 7.88 (s, 2H), 7.64-7.69 (m, 4H), 7.36-7.51 (m, 6H), 7.31 ( dd, 2H)

  The measurement result of the absorption spectrum of the coumarin derivative (1-8) is shown in FIG. 3, and the measurement result of the fluorescence spectrum is shown in FIG.

<Evaluation of fluorescence characteristics of coumarin derivative (1)>
(Preparation of fluorescent film)
The coumarin derivative (1-1) obtained in Example 1 as a fluorescent dye, the acrylic resin, and toluene are mixed at a predetermined ratio, whereby the coumarin derivative (1-1) is added to the acrylic resin. By making it melt | dissolve, the density | concentration of resin solid content obtained the resin solution of 40 mass%. The obtained resin solution was applied onto a 10 mm square and 1 mm thick glass plate using a spin coater. Next, the obtained coating film was heated and dried at an atmospheric temperature of 80 ° C. to obtain a fluorescent film having a thickness of about 5 μm.
Instead of the coumarin derivative (1-1), a coumarin derivative (1-2) obtained in Example 2 and coumarin 6 were also produced in the same manner as described above.

(Fluorescent dye concentration and fluorescent quantum yield of fluorescent film)
Using an absolute quantum yield measuring apparatus (“C9920-12” manufactured by Hamamatsu Photonics), the fluorescence quantum yield was measured for the fluorescent film when irradiated with excitation light having the maximum absorption wavelength of each fluorescent dye. . The results are shown in Table 1 and FIG.

  When a fluorescent dye is added to a resin film such as an acrylic resin and used as an optical material or a color conversion material, it is necessary to add the fluorescent dye to a certain high concentration in order to obtain sufficient coloring (absorption) and light emission. is there. Further, it is required that the fluorescent dye has high solubility in the resin and that the influence of concentration quenching is small.

  As can be seen from Table 1 and FIG. 5, in the coumarin 6 of Comparative Example 1, the width of the decrease in quantum yield with an increase in the addition concentration appeared greatly. Further, since the fluorescent dye could only be dissolved up to 1% by mass, sufficient coloring (absorption) and light emission could not be obtained.

  In contrast, the coumarin derivatives of Examples 1 to 4 were able to dissolve the coumarin derivative in the acrylic resin at a higher concentration than the coumarin 6 of Comparative Example 1. For example, the coumarin derivative (1-2) of Example 2 can be dissolved in the acrylic resin at a concentration twice that of coumarin 6 of Comparative Example 1, and the coumarin derivative (1-1) of Example 1 can be dissolved. In addition, the coumarin derivative (1-4) of Example 4 could be dissolved at a higher concentration. Moreover, all the coumarin derivatives of Examples 1 to 4 were able to maintain the fluorescence quantum yield at a higher value than the coumarin derivative of Comparative Example 1.

Claims (3)

A coumarin derivative represented by the following general formula (1).

Where
R ¹ and R ^1a are the same or different and have the general formula (2):

An N-substituted amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydrogen atom,
R ^2a and R ^2b are the same or different and each represents an alkyl group having 1 to 12 carbon atoms, or R ^2a and R ^2b are bonded to each other to form a 5- to 7-membered nitrogen-containing heterocycle An alkylene group having 4 to 10 carbon atoms, which forms
R ³ , R ^3a , R ⁴ and R ^4a are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or R ¹ and R ^1a represent the above general formula (2). In which R ^2a and R ^2b are bonded to each other to form a 5- to 7-membered nitrogen-containing heterocycle, and R ^2a , R ³ , R ^At least one of a combination of ^2b and R ⁴ , R ^2a and R ^3a , and R ^2b and R ^4a is bonded to each other to form a 5- to 7-membered nitrogen-containing heterocycle, and has 4 to 10 carbon atoms An alkylene group having
R ⁵ and R ^5a are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
R ^6a and R ^6b are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a halogen atom, or a cyano group,
X represents an oxygen atom, a sulfur atom or an imino group,
Y represents the general formula (3):

Or a divalent group represented by formula (4):

A sulfonyl group represented by
R ^7a and R ^7b are the same or different and are an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms or a hydrogen atom is shown.   An organic optical material containing the coumarin derivative according to claim 1.   An organic color conversion material containing the coumarin derivative according to claim 1.

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