JP2006124333A - Styrylamine derivative and method for sythesizing styrylamine derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a styrylamine derivative with an excellent chemically stable structure to realize an organic electronics using the styrylamine derivative, excellent in carrier transporting property and amorphous property and to provide a method for producing the styrylamine derivative. <P>SOLUTION: The invention relates to the method for synthesizing styrylamine derivative represented by general formula (1) in which three synthetic method is exemplified by using a specific intermediate. (In the formula R<SB>1</SB>-R<SB>6</SB>are each independently a H, a halogen atom, or the like, A<SB>1</SB>-A<SB>3</SB>, B<SB>1</SB>, B<SB>2</SB>are each independently a H, a hydrocarbon group or the like.). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a styrylamine derivative and a method for synthesizing the styrylamine derivative, and more particularly to a styrylamine derivative having high charge transporting properties and excellent chemical stability, and a method for synthesizing such a styrylamine derivative.

  In recent years, organic electronics using organic materials with carrier (charge) transport capability, such as organic electroluminescence (EL) elements, organic solar cells, organic transistors, organic memories, etc., have been in the spotlight and energetically in industry and academia. Research is underway.

  In particular, organic electroluminescence devices are attracting attention as next-generation display technologies, and materials are being actively developed. There are many organic compounds studied in this field, such as phthalocyanine derivatives, aluminum quinolinol complexes, aromatic amine derivatives, oxadiazole derivatives, stilbene derivatives, merocyanine derivatives, and coumarin derivatives. Among these, styrylamine-based materials are considered to be promising materials as thin film device materials because they have not only high carrier transportability but also excellent film forming characteristics. For this reason, in the following Patent Document 1, the following Patent Document 2, and the like, styrylamine derivatives for organic electroluminescence devices have been proposed, and organic electroluminescence can be obtained by using the styrylamine derivative having the structure proposed here. It is said that the light emission efficiency and light emission lifetime of the element can be improved.

WO02 / 20459 Japanese Patent Laid-Open No. 11-40359

However, the present inventors examined the synthesis of the following compound 1 having the structure described in Patent Document 1 and the following compound 2 having the structure described in Patent Document 2, but column chromatography using a silica gel agent was performed. When purification was performed with a fee, it was difficult to change the quality and improve the purity.

  Although the mechanism by which these compounds 1 and 2 are altered is not grasped, it is considered that a chemical reaction similar to the reaction in which aniline is oxidized and polymerized under acidic conditions and aniline black is generated. In other words, in the column of the silica gel agent, it is considered that the silanol group proton contained in the silica gel agent acts as an acid catalyst and promotes alteration.

  Further, the inventors have experienced a phenomenon that supports the alteration of the above compound under such acidic conditions. That is, when a solution for NMR measurement is prepared for the compound 1 using a deuterated chloroform solvent not containing a commercially available stabilizer, a light yellow transparent solution having fluorescence is obtained. The solution turns dark brown and turns to black after a further day. In this case, deuterated chloroform without a stabilizer is easily decomposed to generate an acid, and this deuterated chloroform becomes a source of acid. FIGS. 1 to 4 show the results of absorption fluorescence measurement of a deuterated chloroform solution of Compound 1 (for NMR measurement) immediately after adjustment (after 15 minutes) and after storage for 2 days (2 days). In these figures, it is shown that the deuterated chloroform solution of Compound 1 reaches a maximum wavelength of 600 nm of the absorption spectrum and the fluorescence spectrum becomes longer after storage for 2 days. This result suggests that the delocalization energy of the π electrons of Compound 1 increases with time, that is, the molecule is increased. And this is very similar to the polymerization process that aniline black produces.

  As described above, although it is a styrylamine derivative that has poor acid resistance and is difficult to purify, it has not only high carrier transportability, particularly hole transportability, but also excellent amorphous properties. Accordingly, since crystallization is suppressed even in a thin film, it can be said that the material is suitable for a thin film device such as an organic electroluminescent element.

  Therefore, the present invention provides a styrylamine derivative having a structure excellent in chemical stability in order to realize organic electronics using a styrylamine derivative excellent in carrier transportability and amorphousness, and further provides this styrylamine. It aims at providing the synthesis method of a derivative | guide_body.

  As a result of intensive studies by the present inventors in order to achieve the above object, arylene derived from naphthalene bonded at the 2nd and 6th positions is arranged between the double bond and the amino group in the styrylamine derivative. As a result, a novel styrylamine derivative having excellent chemical stability and easy purification while maintaining carrier transportability and a method for producing the same were found, and the present invention was achieved.

That is, the styrylamine derivative of the present invention is represented by the following general formula (1).

  In the general formula (1), R1 to R6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, a saturated or unsaturated hydrocarbon group, a saturated or unsaturated hydrocarbon. It represents an oxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a saturated or unsaturated hydrocarbon amino group, and a substituted or unsubstituted arylamino group. A1 to A3, B1, and B2 each independently represent a hydrogen atom, a saturated or unsaturated hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R1 to R6, A1 to A3, B1, and B2 other than these hydrogen atom, halogen atom, cyano group, and nitro group are bonded to each other to form a saturated or unsaturated carbocycle. Also good.

  In the styrylamine derivative represented by the general formula (1), an arylene derived from naphthalene bonded at the 2-position and the 6-position is arranged between the double bond and the amino group in the styrylamine derivative. Increase delocalization energy of π electrons including heavy bonds. This stabilizes the entire molecule of the styrylamine derivative represented by the general formula (1).

  In particular, a structure in which at least one group represented by A1 to A3 in the general formula (1) is substituted with an aryl group, or at least one pair of adjacent substituents of R1 to R6 are bonded to each other to form a naphthalene moiety. By forming a condensed ring having a structure containing three or more rings, the conjugation length including a double bond is further increased, thereby further stabilizing the molecule.

  For example, as a structure in which at least one group represented by A1 to A3 in the general formula (1) is substituted with an aryl group, at least one of A1 to A3 is an aryl group represented by the following general formula (2): can do.

  And preferably, A2 in the general formula (1) is an E-form of the following general formula (3) having an aryl group of the general formula (2) or a styrylamine derivative of the Z-form to effectively conjugate The length can be increased to stabilize the molecule. In particular, as shown in the general formula (3), the conjugate length can be most effectively increased by using the E body.

  R′1 to R′6 in the general formula (2) and the general formula (3) are defined in the same manner as R1 to R6 in the general formula (1). Moreover, C1 and C2 in General formula (2) and General formula (3) are defined similarly to B1 and B2 in the said General formula (1).

  As a more specific configuration in the general formula (3), an E-form represented by the following general formula (4) or a styrylamine derivative of the Z-form is shown.

  In the general formula (4), R ″ 1 to R ″ 20 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, a saturated or unsaturated hydrocarbon group, a saturated or unsaturated group. Saturated hydrocarbonoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, saturated or unsaturated hydrocarbon amino group, substituted or unsubstituted arylamino Represents a group. In R ″ 1 to R ″ 20, adjacent groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group may be bonded to each other to form a saturated or unsaturated carbocycle.

  Moreover, this invention is also a synthesis method of the styrylamine derivative demonstrated using General formula (1)-(4), and the 1st-3rd synthesis method is illustrated with an intermediate body.

  The first synthesis method is a method via an intermediate represented by the following general formula (5).

  In this case, an ethylene derivative represented by the following general formula (6) is used together with the intermediate of the general formula (5), and one of them is derived into a boronic acid or a boronic ester compound and coupled in the presence of a palladium catalyst. Let

  In general formula (5) and general formula (6), R1 to R6, A1 to A3, B1 and B2 have the same meaning as defined in general formula (1).

  As a modified example of the first synthesis method via the intermediate of the general formula (5), at least the intermediate of the general formula (5) and the intermediate of the following general formula (7) Using an intermediate and one of the ethylene derivatives represented by the following general formula (8) or general formula (9), one of these is derived into a boronic acid or boronic ester compound, and a palladium catalyst Coupling may be performed in the presence.

  In the general formula (7), R′1 to R′6, C1, and C2 represent the same meaning as defined in the general formula (3). And A1-A3 in General formula (8) and General formula (9) represents the same meaning as what was defined by General formula (1).

  As described above, in the modified example of the first synthesis method, when both the intermediate of the general formula (5) and the intermediate of the following general formula (7) are used, the styryl represented by the general formula (3) is used. An amine derivative is obtained. This synthesis method includes the case where the intermediate of the general formula (5) and the intermediate of the general formula (7) have the same structure.

  Further, the second synthesis method goes through an intermediate represented by the following general formula (10). In this case, the intermediate is coupled in the presence of low atomized titanium. Thereby, the target styrylamine derivative is obtained across the double bond.

  In addition, R1-R6, B1, B2 in General formula (10) represents the same meaning as what was defined by General formula (1).

  Furthermore, the third synthesis method goes through an intermediate represented by the following general formula (11) or general formula (12). In this case, the selected intermediate and the carbonyl compound having A2 and A3 in the general formula (1) are coupled in the presence of a base.

  In addition, R1-R6 in General formula (11) and General formula (12) represents the same meaning as what was defined by General formula (1). A1 in the general formula (11) and the general formula (12) represents a hydrogen atom, a saturated or unsaturated hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Further, X- in the general formula (11) represents a halide ion, and T1 and T2 in the general formula (12) each independently represent a saturated hydrocarbon group.

  As described above, according to the present invention, in the styrylamine derivative having charge transporting property and amorphous property, arylene derived from naphthalene bonded at the 2nd and 6th positions is arranged between the double bond and the amino group. With the configuration, it is possible to improve chemical stability. As a result, it is possible to improve the durability of organic electronics using, for example, this styrylamine derivative in the thin film layer.

  Moreover, according to the synthesis method of the present invention, it is possible to obtain a styrylamine derivative having excellent chemical stability as described above. As a result, alteration of the styrylamine derivative under acidic conditions is prevented and purification becomes easy, and a styrylamine derivative with high purity can be obtained.

  Embodiments of the present invention will be described in the order of a styrylamine derivative and a synthesis method of the styrylamine derivative.

<Styrylamine derivative>
R1 to R6, R′1 to R′6, A1 to A3, B1, B2, C1, C2, R ″ 1 to R ″ 20 in the general formulas (1) to (4) representing the styrylamine derivative of the present invention. As described above, a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, a saturated or unsaturated hydrocarbon group, a saturated or unsaturated hydrocarbon oxy group, a substituted or unsubstituted aryl group Represents a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a saturated or unsaturated hydrocarbon amino group, a substituted or unsubstituted arylamino group, and the like.

  Among the above, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Specific examples of the saturated or unsaturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, trifluoromethyl group, cyclopentyl group, cyclohexyl group, and adamantyl. Group, vinyl group, allyl group, propenyl group, stearyl group, trityl group, benzyl group, styryl group, phenethyl group, cinnamyl group, benzhydryl group and the like.

  Specific examples of the saturated or unsaturated hydrocarbon oxy group include methoxy group, ethoxy group, propoxy group, butoxy group, trifluoromethoxy group, perfluoroethoxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group. Vinyloxy group, allyloxy group, propenyloxy group, trityloxy group, benzyloxy group, styryloxy group, phenethyloxy group, cinnamyloxy group, benzhydryloxy group, and the like.

  Specific examples of the substituted or unsubstituted aryl group include phenyl group, naphthyl group, acenaphthylenyl group, acenaphthenyl group, phenanthryl group, phenalenyl group, anthryl group, naphthacenyl group, fluorenyl group, chrysenyl group, pyrenyl group, triphenylenyl group, perylenyl. Group, fluoranthenyl group, tolyl group, xylyl group, mesityl group, biphenyl group, naphthylphenyl group, terphenyl group, biphenylnaphthyl group, spirobifluorenyl group, tetraphenylphenyl group, tetraxylylphenyl group, etc. is there.

  Specific examples of the substituted or unsubstituted aryloxy group include phenoxy group, naphthyloxy group, acenaphthinyloxy group, acenaphthenyloxy group, phenanthryloxy group, phenalenyloxy group, anthryloxy group, Naphthacenyloxy group, fluorenyloxy group, chrysenyloxy group, pyrenyloxy group, triphenylenyloxy group, perylenyloxy group, fluoranthenyloxy group, tolyloxy group, xylyloxy group, mesityloxy group, biphenyloxy group, naphthylphenyloxy group Terphenyloxy group, biphenylnaphthyloxy group, spirobifluorenyloxy group, tetraphenylphenyloxy group, tetraxylphenyloxy group and the like.

  Specific examples of the substituted or unsubstituted heterocyclic group include pyridyl group, furyl group, thienyl group, quinolyl group, isoquinolyl group, phthalazinyl group, quinoxalyl group, biphenylquinoline group, phenanthridyl group, acridinyl group, carbazolyl group, Examples include phenanthrazinyl group, benzofuranyl group, oxadiazolyl group, triazolyl group, imidazolyl group, benzoxazolyl group, thiazolyl group, triazinyl group, benzothiazolyl group, and bipyridyl group.

  Specific examples of the unsaturated hydrocarbon amino group include a dimethylamino group, a diethylamino group, a dipropylamino group, and a dibutylamino group.

  Specific examples of the substituted or unsubstituted arylamino group include diphenylamino group, ditolylamino group, phenylnaphthylamino group, dinaphthylamino group, ditolylamino group, bis (biphenyl) amino group, bis (naphthylphenyl) amino group, bis (Benzylphenyl) amino group and the like.

  Considering the use of the styrylamine derivative as described above as a deposition film forming material in the manufacturing process of organic electronics, for example, R1 to R6 and R′1 to R ′ described above so that the overall molecular weight can be suppressed to 1000 or less. It is preferable to set '6, A1 to A3, B1, B2, C1, C2, and R ″ 1 to R ″ 20.

  Based on this, in the above general formula (1), when R1 to R6 are groups having carbon, the carbon number of each group constituting R1 to R6 is the hydrocarbon group and hydrocarbon oxy. Group: C1-20, aryl group and aryloxy group: C6-25, heterocyclic group: C2-25, hydrocarbon amino group: C1-8, arylamino group: C6 35 is preferred. Moreover, when A1-A3, B1, B2 in General formula (1) is group which has carbon, the carbon number is saturated or unsaturated hydrocarbon group: C1-C20, substituted or unsubstituted aryl Group: 6-45 carbon atoms, substituted or unsubstituted heterocyclic group: preferably 2-30 carbon atoms.

  In addition, when R′1 to R′6, C1, C2, and R ″ 1 to R ″ 20 in the general formulas (2) to (4) are carbon-containing groups, the carbon number of each of these groups is as described above. In the general formula (1), A1 to A3 are set within the range of the carbon number in the case of being a group having carbon.

Hereinafter, although the specific structure of a styrylamine derivative is illustrated, the styrylamine derivative of this invention is not limited to the following structures. In the structural formula, Me represents a methyl group, and n-Pr represents a normal propyl group.

  In particular, when the styrylamine derivative described using the general formulas (1) to (4) is used for the blue light emitting layer of the organic electroluminescent element, R1 to R6 in the general formula (1) described above are carbon. If it is group which has these, carbon number of each group which comprises these R1-R6 is hydrocarbon group and hydrocarbon oxy group: C1-C6, aryl group and aryloxy group: C6-C12, Heterocyclic group: preferably 2 to 10 carbon atoms, hydrocarbon amino group: 1 to 8 carbon atoms, arylamino group: 6 to 35 carbon atoms. Moreover, when A1-A3 is group which has carbon, it is preferable that they are hydrocarbon group: C1-C20, aryl group: C6-C45, heterocyclic group: C2-C30. Furthermore, when B1 and B2 are groups having carbon, it is preferable that the aryl group has 6 to 15 carbon atoms and the heterocyclic group has 2 to 15 carbon atoms.

  Therefore, the styrylamine derivatives represented by the general formulas (1) to (4) and the structural formulas (A1) to (A53), the structural formulas (B1) to (B10), and the structural formulas (C1) to (C20). Among these, a styrylamine derivative included in the above-described range is suitably used as a constituent material of the blue light emitting layer of the organic electroluminescent element.

  Since the styrylamine derivatives as described above are excellent in chemical stability, carrier transportability, and amorphous properties, they can be suitably used as organic thin film materials constituting organic electronics. Specifically, the styrylamine derivative is used in the following organic electronics as follows.

1) Organic electroluminescent device In an organic electroluminescent device having an organic light emitting layer sandwiched between an anode and a cathode, a hole transport layer and a hole injection layer inserted between the organic light emitting layer and the anode, In this organic light emitting layer, a thin film layer made of the styrylamine derivative of the present invention is used. In particular, when the organic electroluminescent element is a blue light emitting element, blue light emission excellent in color purity can be obtained by using a styrylamine derivative having a limited effective conjugate length as the organic light emitting layer as described above. Furthermore, the styrylamine derivative having a cyano group as an example of A33 and the styrylamine derivative containing a heterocyclic ring as an example of A39 to A44 can also improve the electron transport property. For this reason, the use in the electron carrying layer inserted between an organic light emitting layer and a cathode is also possible.

2) Organic transistor In an organic transistor using an organic thin film as a semiconductor layer in contact with a source electrode and a drain electrode, the styrylamine derivative of the present invention is used as the organic thin film constituting the semiconductor layer. In this case, it can be used by mixing with other materials. For example, the source / drain diffusion layer may be formed by selectively introducing impurities.

3) Organic memory In an organic memory in which an organic thin film is sandwiched by a conductive material typified by metal and charges can be stored and released by applying a voltage, the organic thin film of the present invention is used as the organic thin film. A styrylamine derivative is used. In this case, it can also be used by mixing with other substances.

4) Organic Solar Cell In a dye-sensitized organic solar cell, the styrylamine derivative of the present invention can be used as a photosensitizer. A wide range of light in the ultraviolet, visible, and infrared regions can be converted into an electric current by mixing with the material of the present invention or other substances having different absorption wavelengths.

5) Organic imaging device In the organic imaging device, the styrylamine derivative of the present invention is used for the light conversion layer, the hole transport layer, and the hole injection layer. Moreover, like an organic electroluminescent element, among the styrylamine derivatives of the present invention, a styrylamine derivative having a cyano group and a styrylamine derivative containing a heterocyclic ring are also used as an electron transport layer.

<First Synthesis Method (Part 1)>
As a first synthesis method (part 1) of the styrylamine derivative described above, the synthesis route of the styrylamine derivative of the structural formula A3 is shown in the following synthesis formula (1). The following synthesis formula (1) shows an example in which a styrylamine derivative of A3 is synthesized by a Suzuki coupling reaction in which a halide and a boronic acid or a boronic ester are coupled with a palladium catalyst.

尚、合成式（１）において末端のメチル基は省略した。

In addition, the terminal methyl group was abbreviate | omitted in the synthetic formula (1).

  In this synthesis formula (1), intermediate 1 which is an example of general formula (5) is derived into a boronic acid ester compound (intermediate 2). A styrylamine derivative of A3 is obtained by coupling this intermediate 2 with an intermediate 3 as an example of the ethylene derivative of the general formula (6) synthesized by another route in the presence of a palladium catalyst. .

<First Synthesis Method (Part 2)>
As a first synthesis method (part 2) of the styrylamine derivative described above, the synthesis route of the styrylamine derivative of the structural formula A1 is shown in the following synthesis formula (2).

  In this synthesis formula (2), intermediate 4 which is an example of general formula (5) is derived into a boronic acid ester compound (intermediate 5). The intermediate 5 and an ethylene derivative (Br2H2), which is an example of the general formula (8), are coupled in the presence of a palladium catalyst. Thereby, an intermediate 6 as an example of the ethylene derivative of the general formula (6) was synthesized, and this intermediate 6 was further coupled with a derivative having any one of A1 to A3 in the presence of a palladium catalyst, A styrylamine derivative of A1 is obtained.

<Second synthesis method>
As a second method for synthesizing the styrylamine derivative described above, the synthesis route of the C17 styrylamine derivative is shown in the following synthesis formula (3). In the following synthesis formula (3), an example in which a compound of C17 is synthesized by an McMurry reaction in which a carbonyl compound is coupled with low-valent titanium is shown. By using the McMurry reaction, it is possible to reduce the number of synthesis steps for a compound having high symmetry around the double bond portion.

  In this synthesis formula (3), an intermediate 7 as an example of the general formula (10) is synthesized, and this intermediate 7 is coupled in the presence of low-atom titanium to obtain a styrylamine derivative of C17. .

<Third synthesis method>
As a third synthesis method of the styrylamine derivative described above, a synthesis route of the styrylamine derivative of A2 is shown in the following synthesis example (4). In the following synthesis formula (4), an example in which the compound of A2 is synthesized by a Wittig reaction or Horner-Emmmons reaction in which a carbonyl compound and a phosphonium salt or phosphite ester are coupled in the presence of a base is shown.

尚、合成式（４）において末端のメチル基は省略した。

In addition, the terminal methyl group was abbreviate | omitted in the synthetic formula (4).

  In this synthesis formula (4), an intermediate 9 as an example of the general formula (11) is synthesized via an intermediate 8 as an example of the general formula (5). Then, this intermediate 9 is combined with a carbonyl compound to obtain a styrylamine derivative of A2. (Wittig reaction)

  Further, in Synthesis Example 2, as shown in parentheses in Synthesis Formula (4), Intermediate 10 that is an example of General Formula (12) is synthesized via Intermediate 8. Then, this intermediate 10 is combined with a carbonyl compound to obtain a styrylamine derivative of A2. (Horner-Emmmons reaction)

  The synthesis method described above is merely an example, and the synthesis method of the styrylamine derivative of the present invention is not limited to the above-described three examples. In the process of synthesizing the styrylamine derivative of the present invention, isomerization of the double bond portion is likely to occur due to light and heat. Therefore, the synthesis route using the double bond site formation reaction in the latter half of the reaction is possible. Is preferable.

  Next, specific examples 1 and 2 of the present invention, comparative examples for these examples, and evaluation results of styrylamine derivatives synthesized in the examples and comparative examples will be described.

Example 1 The above styrylamine derivative of C1 was synthesized as shown in the following synthesis formula (5).

  First, in a 300 ml eggplant type flask, a stir bar, 75.9 g (0.34 mol) of 6-bromo-2-naphthol, 144 ml (1.58 mol) of aniline, 13.3 g (0.07 mol) of p-toluenesulfonic acid monohydrate, 114 ml of xylene The reaction vessel was placed in an argon atmosphere and reacted at 120 ° C. for 15 hours while stirring with a stirrer. Meanwhile, water was removed using a Dean-Stark apparatus. The reaction solution was allowed to cool, and then 17.1 g (0.21 mol) of sodium acetate and 460 ml of ethanol were added. The mixture was refluxed and then cooled, and the precipitated crystals were separated by filtration. Washing with 250 ml of ethanol gave 88 g (Crude) of white crystals of Intermediate 11.

  Next, 70.0 g (0.23 mol) of the intermediate 11 in the 300 ml eggplant type flask, 116.3 g (0.57 mol) of iodobenzene, 143 g (1.03 mol) of potassium carbonate, 9.4 g (0.15 mol) of copper powder, 18-Crown- 8.7 g (0.032 mol) of 6 and 235 ml of o-dichlorobenzene were added and refluxed for 6 hours under a nitrogen atmosphere. The reaction solution was filtered through celite and purified by chromatography to obtain 56 g of white crystals of intermediate 12 [corresponding to general formula (5)]. The yield was 65%.

  Next, 55.9 g (0.15 mol) of intermediate 12 and 450 ml of dehydrated THF were placed in a 500 ml three-necked flask, and the reaction vessel was placed in an argon atmosphere. Thereafter, the reaction vessel was cooled to −50 to −45 ° C. with calcium chloride and dry ice, and 115 ml (0.18 mol) of 1.58 mol / l BuLi was added. After stirring at the same temperature for 1 hour, a solution obtained by diluting 21 ml of DMF with 90 ml of dehydrated THF was added dropwise over 5 minutes. After completion of the dropwise addition, the mixture was stirred for 3.5 hours, and 60 ml of dilute hydrochloric acid and 600 ml of toluene were added for liquid separation. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Hexane was added to the obtained oil for crystallization, and after filtration, recrystallization was performed to obtain 36.0 g of yellow crystals of intermediate 13 [corresponding to general formula (10)]. The yield was 74.2%.

  Thereafter, 16.0 g (0.05 mol) of intermediate 13 and 495 ml of dehydrated dioxane and 9.8 g (0.15 mol) of zinc powder were placed in a 1 liter three-necked flask, and titanium tetrachloride was cooled while cooling the reaction vessel in an ice bath. 11.0 ml (0.10 mol) was added dropwise and refluxed for 15 hours under an argon atmosphere. A 10% aqueous potassium carbonate solution and toluene were added to the reaction solution to carry out liquid separation. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was purified twice by column chromatography to obtain 4.3 g of yellow crystals of the styrylamine derivative shown in C1. The yield was 28%.

尚、合成式（６）において末端のメチル基は省略した。 Example 2 The styrylamine derivative of C2 was synthesized as shown in the following synthesis formula (6).

In addition, the terminal methyl group was abbreviate | omitted in the synthetic formula (6).

  First, in a 300 ml eggplant-shaped flask, a stir bar, 125 g (0.56 mol) of 6-bromo-2-naphthol, 224 g (2.11 mol) of p-toluidine, 13.3 g (0.11 mol) of p-toluenesulfonic acid monohydrate, 200 ml of xylene was added, the inside of the reaction vessel was placed in an argon atmosphere, and the mixture was reacted at 120 ° C. for 15 hours while stirring with a stirrer. Meanwhile, water was removed using a Dean-Stark apparatus. After allowing the reaction solution to cool, 28.2 g (0.34 mol) of sodium acetate and 760 ml of ethanol were added, and after refluxing, the mixture was cooled and the precipitated crystals were separated by filtration. Washing with ethanol gave 154.4 g of intermediate 14 white crystals. The yield was 88%.

  Next, 140 g (0.45 mol) of the intermediate 14, 269 g (1.96 mol) of potassium carbonate, 18 g (0.28 mol) of copper powder, 16.7 g (0.063 mol) of 18-Crown-6 in a 3 liter reaction vessel, And 2 l of decalin were added and refluxed for 6 hours under a nitrogen atmosphere. THF2l was added to the reaction solution, filtered through Celite, and purified by chromatography to obtain 109 g of white crystals of intermediate 15 [corresponding to general formula (5)]. The yield was 60%.

  Next, 78.0 g (0.19 mol) of intermediate 15 and 660 ml of dehydrated THF were placed in a 1-liter three-necked flask, and the inside of the reaction vessel was placed under an argon atmosphere. Thereafter, the reaction vessel was cooled to −50 to −45 ° C. with calcium chloride and dry ice, and 149 ml (0.24 mol) of 1.58 mol / l BuLi was added. After stirring at the same temperature for 1 hour, a solution obtained by diluting 27 ml of DMF with 120 ml of dehydrated THF was added dropwise over 5 minutes. After completion of the dropwise addition, the mixture was stirred for 2 hours, and liquid separation was performed by adding 80 ml of water and 800 ml of toluene. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained oil was purified by chromatography to obtain 49 g of crystals of intermediate 16 [corresponding to general formula (10)]. The yield was 73%.

  Thereafter, intermediate 16: 48 g (0.14 mol), dehydrated dioxane: 900 ml, and zinc powder: 28.0 g (0.43 mol) were placed in a 2-liter three-necked flask, and the reaction vessel was cooled in an ice bath. Titanium tetrachloride: 24 ml (0.22 mol) was added dropwise and refluxed for 15 hours under an argon atmosphere. A 10% aqueous potassium carbonate solution and toluene were added to the reaction solution to carry out liquid separation. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was purified twice by column chromatography to obtain 8.2 g of styrylamine derivative yellow crystals shown in C2. The yield was 9%.

<Comparative Example> Compound 1 shown in the problem to be solved by the invention was synthesized as shown in the following synthesis formula (7).

  First, 2- (4-bromophenyl) -1,3 dioxolane: 9.160 g (0.040 mol), N-phenyl-2-naphthylamine: 8.770 g (0.04 mol), palladium acetate in a 1-liter three-necked flask (II): 0.180 g (0.8 mmol), sodium t-butoxide: 4.610 g (0.048 mol), and xylene: 700 ml were added, and 32 ml of tri-t-butylphosphine 0.1 mol / l xylene solution was stirred with a stirrer. (3.2 mmol) was slowly added dropwise, and the reaction was carried out at 110 ° C. for 7.5 hours under a nitrogen atmosphere. Thereafter, liquid separation treatment and purification by column chromatography were performed three times to obtain 10.23 g of Intermediate 17. The yield was 70%.

  Next, Intermediate 17: 10.23 g, Acetone: 600 ml, Water: 140 ml, and p-Toluenesulfonic acid pyridinium salt: 0.754 g (0.003 mol) were placed in a 1 liter three-necked flask at room temperature for 30 minutes. The mixture was stirred with a stir bar at 50 ° C. for 3 hours. Thereafter, separation treatment and purification by column chromatography were performed twice, and about 8.07 g of intermediate 18 was obtained. The yield was 92%.

  Thereafter, 0.91 g of zinc (0.014 mol) and 77 ml of THF were placed in a 500 ml three-necked flask, and while cooling the reaction vessel in an ice bath, 0.78 ml (0.007 mol) of titanium tetrachloride, 3.8 pyridine. ml was added dropwise and stirred with a stir bar. Next, 1.03 g (0.003 mol) of Intermediate 2 was dissolved in 33 ml of THF and added dropwise over 30 minutes. Thereafter, the reaction solution is put in a nitrogen atmosphere, reacted at room temperature for 20 minutes at 60 ° C. for 5 hours, added with 10% aqueous potassium carbonate solution, subjected to liquid separation treatment and purification by column chromatography 5 times, and 0.346 g of Compound 1 ( 0.56 mmol) was obtained. The yield was 19%.

<Evaluation result-1>
The NMR spectra of each intermediate, styrylamine derivative, and compound shown in the synthesis of Examples 1 and 2 and Comparative Example 3 are shown in FIGS.

  From these NMR spectra, it was confirmed that each intermediate, styrylamine derivative, and compound 1 shown in the synthesis formula (5) to the synthesis formula (7) were synthesized in each synthesis process.

<Evaluation result-2>
The styrylamine derivative synthesized in Examples 1 and 2 and the compound 1 synthesized in the Comparative Example were dissolved in a heavy chloroform solvent (product number 22578-9) manufactured by Aldrich, and the absorbance with an absorption peak on the longest wavelength side of about 0.1 was obtained. The absorption spectrum and the fluorescence spectrum after 15 minutes, 30 minutes, and 180 minutes were measured. The absorption spectrum and fluorescence spectrum of each synthesized product are shown in FIG. 11, FIG. 12, and FIG. For the measurement of absorption spectrum and fluorescence spectrum, Hitachi U3300 type spectrophotometer and Hitachi F4500 type spectrofluorometer were used, respectively.

  Focusing on the peak on the longest wavelength side with respect to the absorption spectrum and comparing the spectra after 15 minutes and 180 minutes with respect to Compound 1 of Comparative Example, the intensity decreases to 24% at 396 nm. As a result, the styrylamine derivative C1 maintained 53% strength at 408 nm, and the styrylamine derivative C2 of Example 2 maintained 43% strength at 417 nm.

  On the other hand, regarding the fluorescence spectrum, attention was paid to the peak of the fluorescence spectrum obtained by excitation at the longest wavelength peak of the absorption spectrum. When the spectra of Comparative Compound 1 after 15 minutes and 180 minutes were compared, respectively, the fluorescence intensity decreased to 1% at 444 nm. In contrast to the above results, the fluorescence spectrum of the styrylamine derivative C1 of Example 1 maintained 28% fluorescence intensity at 461 nm, and the fluorescence spectrum of the styrylamine derivative C2 of Example 2 maintained 21% fluorescence intensity at 474 nm. Results were obtained.

  As described above, it was confirmed that the novel styrylamine derivative of the present invention is a compound capable of suppressing alteration even in deuterated chloroform not containing a stabilizer.

<Evaluation result-3>
The styrylamine derivatives C1 and C2 synthesized in Examples 1 and 2 and the compound 1 synthesized in Comparative Example were each dissolved in a toluene solution and subjected to double development of thin layer chromatography (TLC). For the TLC plate, a 25TLC aluminum sheet (adsorbent: silica gel 60F254) manufactured by MERCK was used, and as a developing solvent, a mixed solvent of toluene: cyclohexane = 1: 3 was used.

  With regard to the styrylamine derivatives C1 and C2 synthesized in Examples 1 and 2, spots other than C1 and C2 were not observed in the second development, and it was confirmed that there was no alteration. On the other hand, the compound 1 of the comparative example showed tailing even in the second development, and it was confirmed that the compound 1 was altered.

  As described above, the styrylamine derivative of the present invention was able to improve alteration during silica gel TLC development. Similar silica gel is used for the chromatographic packing material and the TLC adsorbent for the compound purification, and the above results reflect the state of alteration during the compound purification. Therefore, it was confirmed that the styrylamine derivative of the present invention can be easily purified by silica gel column chromatography.

It is a figure which shows the time-dependent change of the absorption spectrum of the compound 1, and a fluorescence spectrum. 2 is a diagram showing an NMR spectrum of intermediate 11 synthesized in Example 1. FIG. 2 is a diagram showing an NMR spectrum of intermediate 13 synthesized in Example 1. FIG. 2 is a diagram showing an NMR spectrum of a C1 styrylamine derivative synthesized in Example 1. FIG. 4 is a diagram showing an NMR spectrum of intermediate 14 synthesized in Example 2. FIG. 4 is a diagram showing an NMR spectrum of intermediate 15 synthesized in Example 2. FIG. 4 is a diagram showing an NMR spectrum of intermediate 16 synthesized in Example 2. FIG. 3 is a diagram showing an NMR spectrum of a styrylamine derivative of C2 synthesized in Example 2. FIG. It is a figure which shows the NMR spectrum of the intermediate body 18 synthesize | combined by the comparative example. It is a figure which shows the NMR spectrum of the compound 1 synthesize | combined by the comparative example. 2 is a graph showing an absorption spectrum and a fluorescence spectrum of a styrylamine derivative of C1 synthesized in Example 1. FIG. 2 is a graph showing an absorption spectrum and a fluorescence spectrum of a C2 styrylamine derivative synthesized in Example 2. FIG. It is a figure which shows the absorption spectrum and fluorescence spectrum of the compound 1 synthesize | combined by the comparative example.

Claims (18)

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

[In the general formula (1),
R1 to R6 are each independently
Hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, amino group saturated or unsaturated hydrocarbon group,
Saturated or unsaturated hydrocarbon oxy groups,
A substituted or unsubstituted aryl group,
A substituted or unsubstituted aryloxy group,
A substituted or unsubstituted heterocyclic group,
A saturated or unsaturated hydrocarbon amino group,
Represents a substituted or unsubstituted arylamino group,
Adjacent groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group may be bonded to each other to form a saturated or unsaturated carbocycle.
A1 to A3, B1, and B2 are each independently
Hydrogen atom,
Saturated or unsaturated hydrocarbon groups,
A substituted or unsubstituted aryl group,
Represents a substituted or unsubstituted heterocyclic group,
Adjacent groups may be bonded to each other to form a saturated or unsaturated carbocycle. ] The styrylamine derivative according to claim 1, wherein
A styrylamine derivative, wherein at least one of A1 to A3 in the general formula (1) is represented by the following general formula (2).

[In general formula (2),
R′1 to R′6 are each independently
Hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, amino group,
Saturated or unsaturated hydrocarbon groups,
Saturated or unsaturated hydrocarbon oxy groups,
A substituted or unsubstituted aryl group,
A substituted or unsubstituted aryloxy group,
A substituted or unsubstituted heterocyclic group,
A saturated or unsaturated hydrocarbon amino group,
Represents a substituted or unsubstituted arylamino group,
Adjacent groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group may be bonded to each other to form a saturated or unsaturated carbocycle.
C1 to C2 are each independently
Hydrogen atom,
Saturated or unsaturated hydrocarbon groups,
A substituted or unsubstituted aryl group,
Represents a substituted or unsubstituted heterocyclic group,
Adjacent groups may be bonded to each other to form a saturated or unsaturated carbocycle. ] The styrylamine derivative according to claim 2,
A styrylamine derivative of E form represented by the following general formula (3), wherein A2 in the general formula (1) is the above general formula (2), or a Z form thereof.

In the styrylamine derivative according to claim 3,
E-form represented by the following general formula (4), or styrylamine derivative of Z-form.

[In the general formula (4),
R ″ 1 to R ″ 20 are each independently
Hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, amino group,
Saturated or unsaturated hydrocarbon groups,
Saturated or unsaturated hydrocarbon oxy groups,
A substituted or unsubstituted aryl group,
A substituted or unsubstituted aryloxy group,
A substituted or unsubstituted heterocyclic group,
A saturated or unsaturated hydrocarbon amino group,
Represents a substituted or unsubstituted arylamino group,
Adjacent groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group may be bonded to each other to form a saturated or unsaturated carbocycle. The styrylamine derivative according to claim 4,
An E-form represented by the following structural formula (1), or a styrylamine derivative of the Z-form.

The styrylamine derivative according to claim 4,
An E-form represented by the following structural formula (2), or a styrylamine derivative of the Z-form.

The styrylamine derivative according to claim 4,
E-form represented by the following structural formula (3), or a styrylamine derivative of Z-form.

In the general formula (1) representing the styrylamine derivative according to claim 1,
R1 to R6 are each independently
Hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, amino group saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms,
A saturated or unsaturated hydrocarbon oxy group having 1 to 20 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 25 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 25 carbon atoms,
A substituted or unsubstituted heterocyclic group having 2 to 25 carbon atoms,
A saturated or unsaturated hydrocarbon amino group having 1 to 8 carbon atoms,
Represents a substituted or unsubstituted arylamino group having 6 to 35 carbon atoms,
Adjacent groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group may be bonded to each other to form a saturated or unsaturated carbocycle,
A1 to A3, B1, and B2 are each independently
Hydrogen atom,
A saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 45 carbon atoms,
Represents a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms,
A styrylamine derivative, wherein adjacent groups may be bonded to each other to form a saturated or unsaturated carbocyclic ring. In the general formula (1) representing the styrylamine derivative according to claim 1,
R1 to R6 are each independently
Hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, amino group saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms,
A saturated or unsaturated hydrocarbon oxy group having 1 to 6 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 12 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms,
A substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms,
A saturated or unsaturated hydrocarbon amino group having 1 to 8 carbon atoms,
Represents a substituted or unsubstituted arylamino group having 6 to 35 carbon atoms,
Adjacent groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group may be bonded to each other to form a saturated or unsaturated carbocycle,
A1 to A3 are each independently
Hydrogen atom,
A saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 45 carbon atoms,
Represents a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms,
Adjacent groups may be bonded to each other to form a saturated or unsaturated carbocycle,
B1 and B2 are each independently
A substituted or unsubstituted aryl group having 6 to 15 carbon atoms,
Represents a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms,
A styrylamine derivative, wherein adjacent groups may be bonded to each other to form a saturated or unsaturated carbocyclic ring. The styrylamine derivative according to any one of claims 1 to 9, which is used as an organic thin film material constituting organic electronics. The styrylamine derivative according to claim 10, wherein the organic electronics is an organic electroluminescence device, an organic transistor, an organic memory device, an organic solar cell, or an organic imaging device. A method for synthesizing a styrylamine derivative represented by the following general formula (1),
A method for synthesizing a styrylamine derivative characterized by passing through an intermediate represented by the following general formula (5).

[In General Formula (1) and General Formula (5),
R1 to R6 are each independently
Hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, amino group saturated or unsaturated hydrocarbon group,
Saturated or unsaturated hydrocarbon oxy groups,
A substituted or unsubstituted aryl group,
A substituted or unsubstituted aryloxy group,
A substituted or unsubstituted heterocyclic group,
A saturated or unsaturated hydrocarbon amino group,
Represents a substituted or unsubstituted arylamino group,
Adjacent groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group may be bonded to each other to form a saturated or unsaturated carbocycle.
A1 to A3, B1, and B2 are each independently
Hydrogen atom,
Saturated or unsaturated hydrocarbon groups,
A substituted or unsubstituted aryl group,
Represents a substituted or unsubstituted heterocyclic group,
Adjacent groups may be bonded to each other to form a saturated or unsaturated carbocycle. ] The method for synthesizing a styrylamine derivative according to claim 12,
Using an intermediate of the general formula (5) and an ethylene derivative represented by the following general formula (6), one of these is derived into a boronic acid or a boronic ester compound and coupled in the presence of a palladium catalyst. A method for synthesizing a styrylamine derivative.

[In General Formula (6), A1 to A3 each have the same meaning as defined in claim 12. ] The method for synthesizing a styrylamine derivative according to claim 12,
Of the intermediate of the general formula (5) and the intermediate of the following general formula (7), at least the intermediate of the general formula (5) and ethylene represented by the following general formula (8) or the general formula (9) A method for synthesizing a styrylamine derivative, wherein one of these derivatives is used, and one of them is derived into a boronic acid or a boronic ester compound and coupled in the presence of a palladium catalyst.

[In general formula (7),
R′1 to R′6 are each independently
Hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, amino group,
Saturated or unsaturated hydrocarbon groups,
Saturated or unsaturated hydrocarbon oxy groups,
A substituted or unsubstituted aryl group,
A substituted or unsubstituted aryloxy group,
A substituted or unsubstituted heterocyclic group,
A saturated or unsaturated hydrocarbon amino group,
Represents a substituted or unsubstituted arylamino group,
Adjacent groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group may be bonded to each other to form a saturated or unsaturated carbocycle.
C1 to C2 are each independently
Hydrogen atom,
Saturated or unsaturated hydrocarbon groups,
A substituted or unsubstituted aryl group,
Represents a substituted or unsubstituted heterocyclic group,
Adjacent groups may be bonded to each other to form a saturated or unsaturated carbocycle.
In general formula (8) and general formula (9), A1-A3 represent the same meaning as defined in claim 12, respectively. ] A method for synthesizing a styrylamine derivative represented by the following general formula (1),
A method for synthesizing a styrylamine derivative characterized by passing through an intermediate represented by the following general formula (10).

[In General Formula (1) and General Formula (10),
R1 to R6 are each independently
Hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, amino group saturated or unsaturated hydrocarbon group,
Saturated or unsaturated hydrocarbon oxy groups,
A substituted or unsubstituted aryl group,
A substituted or unsubstituted aryloxy group,
A substituted or unsubstituted heterocyclic group,
A saturated or unsaturated hydrocarbon amino group,
Represents a substituted or unsubstituted arylamino group,
Adjacent groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group may be bonded to each other to form a saturated or unsaturated carbocycle.
A1 to A3, B1, and B2 are each independently
Hydrogen atom,
Saturated or unsaturated hydrocarbon groups,
A substituted or unsubstituted aryl group,
Represents a substituted or unsubstituted heterocyclic group,
Adjacent groups may be bonded to each other to form a saturated or unsaturated carbocycle. ] The method for synthesizing a styrylamine derivative according to claim 15,
A method for synthesizing a styrylamine derivative, wherein the intermediate of the general formula (10) is coupled in the presence of low atomized titanium. A method for synthesizing a styrylamine derivative represented by the following general formula (1),
A method for synthesizing a styrylamine derivative characterized by passing through an intermediate represented by the following general formula (11) or general formula (12).

[In General Formula (1), General Formula (11), and General Formula (12),
R1 to R6 are each independently
Hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, amino group saturated or unsaturated hydrocarbon group,
Saturated or unsaturated hydrocarbon oxy groups,
A substituted or unsubstituted aryl group,
A substituted or unsubstituted aryloxy group,
A substituted or unsubstituted heterocyclic group,
A saturated or unsaturated hydrocarbon amino group,
Represents a substituted or unsubstituted arylamino group,
Adjacent groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group may be bonded to each other to form a saturated or unsaturated carbocycle.
A1 to A3, B1, and B2 are each independently
Hydrogen atom,
Saturated or unsaturated hydrocarbon groups,
A substituted or unsubstituted aryl group,
Represents a substituted or unsubstituted heterocyclic group,
Adjacent groups may be bonded to each other to form a saturated or unsaturated carbocycle.
X- represents a halide ion.
T1 and T2 each independently represent a saturated hydrocarbon group. ] The method for synthesizing a styrylamine derivative according to claim 17,
The intermediate of the general formula (11) or the intermediate of the general formula (12) and the carbonyl compound having A2 and A3 in the general formula (1) are coupled in the presence of a base, A method for synthesizing a styrylamine derivative.

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