JP2005097135A - Thiazole derivative and nonlinear optical device and electro-optic device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thiazole derivative which is suitably used in a nonlinear optical device and an electro-optic device, and a nonlinear optical device and an electro-optic device using the same. <P>SOLUTION: The thiazole compound is represented by formula (I) (wherein R<SP>1</SP>and R<SP>2</SP>are each hydrogen or a 1-20C alkyl group which may have a substituent and R<SP>1</SP>and R<SP>2</SP>may be linked with each other to form a ring; R<SP>3</SP>is hydrogen or a 1-6C alkyl group; Ar is a 6-10C aromatic ring or a 4-10C aromatic heterocycle; n is 0 or 1; and E is an electron-attracting group having a σp value of ≥0.3). The nonlinear optical device and the electro-optic device use this compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thiazole derivative, and a nonlinear optical element and an electro-optical element using the same.

    Materials that exhibit nonlinear optical effects (nonlinear optical materials) are attracting attention in the fields of optoelectronics and photonics. The nonlinear optical effect is a phenomenon that shows a nonlinear relationship between the generated electric polarization and the applied electric field when a strong electric field (photoelectric field) is applied to a substance. Refers to a material that exhibits Known as nonlinear optical materials using second-order nonlinear response are materials that generate second harmonics and materials that exhibit the Pockels effect (primary electro-optic effect) that causes a refractive index change in proportion to the first order of the electric field. In particular, application of the latter to electro-optic (EO) light modulation elements and photorefractive elements is being studied.

Conventionally, these nonlinear optical materials have been searched mainly for inorganic nonlinear materials, and devices have been made. However, in recent years, 1) show large nonlinearity, 2) fast response speed, and 3) optical damage. Organic materials are attracting attention because of their high thresholds, 4) the ability to design a wide variety of molecules, and 5) excellent manufacturing suitability. Typical organic materials that have been studied so far include 4-N, N-dimethylamino-4′-nitrostilbene (DANS), 4-N-ethyl-N-hydroxyethylamino-4′-nitroazobenzene ( DR1) and the like.
Generally, organic crystals have a lower hardness than inorganic crystals and have problems in processing into devices, etc., so that they are dispersed in a nonlinear optical molecular polymer matrix or a polymer material having a nonlinear optical response group is used. It is being considered. In order to develop the second-order nonlinear optical effect, it is necessary for the polarization to lack a reversal symmetry center. A molecule or a nonlinear optical response group that exhibits a nonlinear optical effect is oriented in a material by an electric field to align the reversal symmetry center. It is widely arranged to lack the structure. However, organic nonlinear optical materials that have been developed so far are insufficient for practical use as optical elements, and the development of materials suitable for optical elements has been desired.

  Next, the following liquid crystalline compounds are disclosed as compounds related to the compound of the present invention (see, for example, Patent Document 1).

  However, the disclosed compound is different in structure from the present invention in that the phenyl group linked to the 5-position of thiazole does not have an amino group or a dialkylamino group necessary for the expression of high nonlinear optical properties. In addition, the use is different and does not specifically suggest the present invention.

  In the thiazole derivative, a thienyl group having a substituent selected from a halogen, a lower alkyl group and a thienyl group at the 5-position as a substituent, and at least one substituent at the 5-position is a halogen, a lower alkyl group, a lower haloalkyl group, a lower A compound that is a phenyl group having a substituent selected from an alkoxy group, a phenyl group, or a nitro group has been disclosed as a photoactive insecticide (for example, see Patent Document 2).

However, the disclosed compounds require an electron-withdrawing group having a σp value of 0.3 or more necessary for the development of high nonlinear optical properties in the thienyl group linked to the 5-position of thiazole, or the development of high nonlinear optical properties. Connected to the 2-position of thiazole, which has no aromatic ring having 6 to 10 carbon atoms, an aromatic ring having 5 to 10 carbon atoms, and an electron-withdrawing group having a σp value of 0.3 or more The structure is different from the present invention in that the phenyl group does not have an amino group, a monoalkylamino group, or a dialkylamino group necessary for the expression of high nonlinear optical characteristics. Moreover, the use used also differs and does not specifically suggest the present invention.
JP-A-4-128274 International Publication No. 87/06429 Pamphlet

  The present invention provides a thiazole derivative suitably used for a nonlinear optical element and an electro-optical element, and a nonlinear optical element and an electro-optical element using the same, based on the above-described demand.

  The present inventors have found that the object of the present invention is achieved by a compound represented by the following general formula (I), and have reached the present invention. That is, this invention is <1>-<5> shown below.

<1> A compound represented by the following general formula (I).

（式中、Ｒ¹、Ｒ²はそれぞれ独立して水素原子、あるいは置換基を有していても良い炭素数１〜２０のアルキル基を示し、Ｒ¹とＲ²は互いに連結して環を形成してもよい。Ｒ³は、水素原子、あるいは炭素数１から６のアルキル基を示す。Ａｒは炭素数６から１０の芳香環、炭素数４から１０の芳香族性へテロ環を示す。ｎは０、あるいは１を示す。Ｅはσｐ値が０．３以上の電子吸引性基を示す。）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² are connected to each other to form a ring. R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar represents an aromatic ring having 6 to 10 carbon atoms, or an aromatic heterocycle having 4 to 10 carbon atoms. N represents 0 or 1. E represents an electron-withdrawing group having a σp value of 0.3 or more.)

<2> Each of R ¹ and R ² independently represents a hydroxyl group, an amino group, an ester group, an amide group, an ether group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. An optionally substituted alkyl group having 1 to 20 carbon atoms, wherein E is an aldehyde group, a cyano group, a nitro group, —COR ⁴ , —COOR ⁴ , —SO ₂ R ⁴ , —SO ₃ R ⁴ (wherein R ⁴ represents an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, an ester group, an amide group, an ether group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. Or an electron-withdrawing group having a σp value represented by the following general formula (II) of 0.3 or more.

（式中、Ｅ²はシアノ基、ニトロ基、−ＣＯＯＲ⁵、あるいは−ＳＯ₂Ｒ⁵示し、Ｅ³はシアノ基、−ＣＯＯＲ⁵、あるいは−ＳＯ₂Ｒ⁵を示す。式中、Ｒ⁵は炭素数１〜２０のアルキル基を示し、水酸基、アミノ基、エステル基、アミド基、エーテル基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基及びハロゲン原子を有していても良い。）

(In the formula, E ² represents a cyano group, a nitro group, —COOR ⁵ , or —SO ₂ R ⁵ , and E ³ represents a cyano group, —COOR ⁵ , or —SO ₂ R ^{5. In the} formula, R ⁵ represents An alkyl group having 1 to 20 carbon atoms, having a hydroxyl group, an amino group, an ester group, an amide group, an ether group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms and a halogen atom; Is also good.)

<3> The compound according to <1> or <2>, wherein n is 0.
<4> A nonlinear optical element having a layer formed of the compound according to any one of <1> to <3>.
<5> An electro-optical element having a layer formed of the compound according to any one of <1> to <3>.

  According to the present invention, a novel thiazole derivative, and a nonlinear optical element and an electro-optical element using the same can be provided.

  The thiazole derivative of the present invention is a novel compound represented by the following general formula (I), which is not described in any literature, and will be described in detail below.

（式中、Ｒ¹、Ｒ²はそれぞれ独立して水素原子、あるいは置換基を有していても良い炭素数１〜２０のアルキル基を示し、Ｒ¹とＲ²は互いに連結して環を形成してもよい。Ｒ³は水素原子、あるいは炭素数１から６のアルキル基を示す。Ａｒは炭素数６から１０の芳香環、炭素数４から１０の芳香族性へテロ環を示す。ｎは０、あるいは１を示す。Ｅはσｐ値が０．３以上の電子吸引性基を示す。）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² are connected to each other to form a ring. R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Ar represents an aromatic ring having 6 to 10 carbon atoms and an aromatic heterocyclic ring having 4 to 10 carbon atoms. n represents 0 or 1. E represents an electron-withdrawing group having a σp value of 0.3 or more.)

In the general formula (I), R ¹ and R ² each independently represents an optionally substituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 16 carbon atoms, and 1 carbon atom. To 10 are more preferable. Further, it is particularly preferable that either R ¹ or R ² has 1 to 6 carbon atoms.

R ¹ and R ² may each independently have a substituent, and examples of the substituent include a hydroxyl group, an amino group, an ester group, an amide group, an ether group, an alkyl group having 1 to 6 carbon atoms, carbon An alkoxy group having 1 to 6 carbon atoms and a halogen atom are preferable, and an ester group, an amide group, an ether group, and an alkyl group having 1 to 2 carbon atoms are particularly preferable.

R ¹ and R ² may be connected to each other to form a ring, but when forming a ring, it is particularly preferable to form a pyrrolidine ring, a piperidine ring, a piperazine ring, or the like.

R ³ represents an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms.

E represents an electron-withdrawing group having a σp value of 0.3 or more, preferably an electron-withdrawing group having a σp value of 0.4 or more, more preferably 0.45 or more.
In the present invention, Hammett's σp value is applied as a measure of electron withdrawing property. Regarding the σp value of Hammett's rule, the description of “Chem. Rev., 91, 165-195 (1991)” can be applied.

Preferable specific examples of the electron withdrawing group having a σp value of 0.3 or more include an aldehyde group (0.42), a cyano group (0.66), a nitro group (0.78), —COR ⁴ , —COOR. ⁴ , —SO ₂ R ⁴ , —SO ₃ R ⁴ (wherein R ⁴ is a hydroxyl group, an amino group, an ester group, an amide group, an ether group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Group, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom, COMe (0.50), COOMe (0.45).) Or a σp value represented by the following general formula is 0. Examples include electron withdrawing groups of 3 or more.

In the general formula (II), E ² represents a cyano group, a nitro group, —COOR ⁵ , or —SO ₂ R ⁵ , and E ³ represents a cyano group, —COOR ⁵ , or —SO ₂ R ⁵ . In the general formula (II), R ⁵ represents an alkyl group having 1 to 20 carbon atoms, and is a hydroxyl group, amino group, ester group, amide group, ether group, alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. The alkoxy group may have a halogen atom.
Here, when R ⁴ and R ⁵ have a substituent, the substituent is particularly preferably an ester group, an amide group, an ether group, or an alkyl group having 1 to 2 carbon atoms.

  Ar represents an aromatic ring having 6 to 10 carbon atoms or an aromatic hetero ring having 4 to 10 carbon atoms, and is preferably a benzene ring or a thiophene ring. n represents 0 or 1, but n = 0 is preferable.

  Specific examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

  Although the manufacturing method of the compound of this invention is demonstrated below, this invention is not limited to these. The thiazole derivative of the present invention can be synthesized, for example, by the method of Reaction Scheme 1 using a compound represented by the general formula (C1) as a starting material.

<Reaction Scheme 1>

In the formula in the reaction scheme 1, R ¹ , R ² , Ar, E, and n have the same meanings as described above. X represents a bromine atom or an iodine atom.

In the first step, the compound represented by the general formula (C1) is dissolved in a solvent, and tetrakis (triphenylphosphine) palladium is reacted with thiazole in the presence of a base to convert the compound represented by the general formula (C2). be able to.
The solvent used here is not particularly limited, but dimethylformamide (DMF), dimethylacetamide (DMAc), tetrahydrofuran (THF) and the like are preferable.
As the base to be used, inorganic bases and organic bases are adopted, but inorganic bases are preferable, and acetates such as potassium acetate are particularly preferable.
The amount of thiazole to be used is preferably in the range of 0.5 to 10 mol, particularly preferably in the range of 1 to 5 mol, relative to 1 mol of the compound represented by the general formula (C1).
The amount of tetrakis (triphenylphosphine) palladium used is preferably 0.5 to 20 mol%, more preferably 1 to 10 mol%, relative to the compound represented by the general formula (C1).
The reaction temperature is usually the boiling point of the solvent used from room temperature, preferably from 50 ° C. to the boiling point of the solvent. The reaction time is usually 1 hour to 72 hours, preferably 3 hours to 48 hours.

In the second step, the compound represented by the general formula (C2) and the compound represented by the general formula (C3) in the presence of bis (triphenylphosphine) palladium (II) dichloride, triphenylphosphene and copper iodide. Can be converted into the target compound represented by the general formula (I).
The solvent used here is not particularly limited, but dimethylformamide (DMF), dimethylacetamide (DMAc), tetrahydrofuran (THF) and the like are preferable.
As the base to be used, inorganic bases and organic bases are adopted, but inorganic bases are preferable, and carbonates such as cesium carbonate and potassium carbonate are particularly preferable.
The amount of the compound represented by the general formula (C3) to be used is preferably in the range of 0.5 to 4 moles relative to 1 mole of the compound represented by the general formula (C2). It is particularly preferable to use within a range.
The amount of bis (triphenylphosphine) palladium (II) dichloride used is preferably 0.5 to 20 mol%, more preferably 1 to 10 mol%, relative to the compound represented by the formula (III).
The amount of copper iodide used is preferably in the range of 0.5 to 1 mol, based on 1 mol of bis (triphenylphosphine) palladium (II) dichloride, It is particularly preferable to use within a range.
The amount of triphenylphosphine used is preferably in the range of 1 to 4 mol, particularly preferably in the range of 2 to 3 mol, based on 1 mol of bis (triphenylphosphine) palladium (II) dichloride. preferable.
The reaction temperature is usually the boiling point of the solvent used from room temperature, preferably from 50 ° C. to the boiling point of the solvent. The reaction time is usually 1 hour to 72 hours, preferably 3 hours to 48 hours.

  In addition, when the compound of the general formula (I) has various substituents to be introduced, in the above production method, a group that becomes a precursor of the substituent to be introduced in advance is introduced, and the target substitution is performed in an appropriate step. It may be converted into a group. Further, if necessary, a protecting group and a deprotecting step may be employed to introduce a substituent to be introduced.

（式中、Ｅ²はシアノ基、ニトロ基、−ＣＯＯＲ⁵、あるいは−ＳＯ₂Ｒ⁵示す、Ｅ³はシアノ基、−ＣＯＯＲ⁵、あるいは−ＳＯ₂Ｒ⁵を示す。式中、Ｒ⁵は炭素数１〜２０のアルキル基を示し、水酸基、アミノ基、エステル基、アミド基、エーテル基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ハロゲン原子を有していても良い。）で表されるσｐ値が０．３以上での電子吸引基である化合物は、上記のスキーム１で示される方法により合成したＥがアルデヒド基である一般式（Ｉ）の化合物（一般式（Ｄ１）とする）を用いてスキーム２の方法に示される第三工程より合成できる。 Next, in the general formula (I), the E is represented by the following general formula (II):

(In the formula, E ² represents a cyano group, a nitro group, —COOR ⁵ , or —SO ₂ R ⁵ , E ³ represents a cyano group, —COOR ⁵ , or —SO ₂ R ^{5. In the} formula, R ⁵ represents An alkyl group having 1 to 20 carbon atoms, having a hydroxyl group, an amino group, an ester group, an amide group, an ether group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom The compound represented by the general formula (I) in which E is an aldehyde group synthesized by the method shown in Scheme 1 above is a compound that is an electron-withdrawing group having a σp value of 0.3 or more. It can be synthesized from the third step shown in the method of Scheme 2 using the general formula (D1).

<Reaction Scheme 2>

In the reaction scheme 2, R ¹ , R ² , Ar, n, E, E ² and E ³ have the same meanings as in the general formula (I) and general formula (II), respectively.

  In the third step, the compound represented by the general formula (D1) and the compound represented by the general formula (D2) are reacted in the presence of a base to convert the compound represented by the general formula (I). it can. Although the organic solvent used here is not specifically limited, Tetrahydrofuran can be mentioned as a preferable example. The base to be used may or may not be added, but when a base is used, amines are preferred examples, and piperidine is particularly preferred. The amount added may be a catalyst amount. The reaction temperature is usually from room temperature to the boiling point of the solvent used, and the reaction time is usually from 1 minute to 24 hours, preferably from 5 minutes to 1 hour.

(Nonlinear optical element and electro-optical element)
In the present invention, the layer of the “nonlinear optical element (electro-optical element) having a layer formed from a compound” is not limited in shape, thickness, or the like, and refers to a portion containing the compound.

  The nonlinear optical element of the present invention can be manufactured by the following method.

  For example, it can be produced by 1) dissolving a thiazole derivative of the present invention and a polymer medium containing the thiazole derivative in a solvent, 2) applying the composition to a support and drying, and 3) applying an orientation treatment.

In the step of dissolving the composition containing the thiazole derivative of the present invention and the polymer medium holding it in a solvent, the polymer medium to be used is not particularly limited. For example, an acrylic polymer such as PMMA, and an imide such as fluorinated polyimide Examples of such polymers include polycarbonate and polycarbonate. The solvent to be used is not particularly limited. For example, ester solvents such as ethyl acetate, ketone solvents such as methyl ethyl ketone, ether solvents such as tetrahydrofuran, halogen solvents such as chloroform and dichloromethane, and mixed solvents thereof. Is mentioned. Here, dissolving the composition in a solvent means that it may be completely dissolved or incompletely dispersed, but complete dissolution is preferable in terms of transparency. .
Next, in the coating process, the support and the like are not particularly limited, and examples thereof include a glass substrate, a polymer film, and a reflection plate. As a coating method, a known method such as a curtain coating method, an extrusion coating method, a roll coating method, a spin coating method, a dip coating method, a bar coating method, a spray coating method, a slide coating method, or a printing coating method can be employed. The application herein is not particularly limited as long as a layer containing the compound of the present invention can be formed on the support, and includes adhesion and the like.

  In the alignment treatment, corona poling and contact poling methods can be employed.

  The waveguide type electro-optic element of the present invention will be described in detail below, but the present invention is not limited to this.

  FIG. 1 shows an example of a cross-sectional view of a waveguide type electro-optic element which is an embodiment of the present invention. The waveguide type electro-optic element has a core 4 and clad layers 3 and 5 made of an organic material formed above and below the core 4 so as to hold the core 4 on the substrate 1, and the core 4 and the upper and lower clad layers 3 and 5. And a pair of electrodes 2 and 6 for applying an electric field.

(1) Substrate The substrate used in the present invention is not limited, but a substrate having excellent flatness is preferable. For example, a metal substrate, a silicon substrate, a transparent substrate, etc. are mentioned, and can be appropriately selected depending on the form of the waveguide type light modulation element. Preferable examples of the metal substrate include gold, silver, copper, and aluminum substrates, and preferable examples of the transparent substrate include glass and plastic (polyethylene terephthalate, etc.) substrates.

(2) Lower electrode The lower electrode 2 is formed on the entire surface or a part of the substrate 1. The lower electrode 2 may be a metal vapor deposition layer or a transparent electrode layer. Preferred examples of the metal to be deposited include gold, silver, copper, and aluminum. Preferred examples of the transparent electrode layer include indium tin oxide (ITO), fluorine-doped tin oxide, (FTO) antimony-doped tin oxide (ATO), and the like. The substrate 1 may also serve as the lower electrode 2.

(3) Lower Cladding Layer The lower cladding layer 3 is formed on the lower electrode 2. Although the organic material which forms the lower clad layer 3 is not specifically limited, A polyimide, a fluorinated polyimide, etc. are mentioned as a preferable example.

(4) Core The core is preferably composed of a composition containing an oriented thiazole derivative of the present invention and a polymer medium holding the thiazole derivative. In the alignment treatment, corona poling and contact poling methods can be employed.

(5) Upper Cladding Layer An upper cladding layer 5 is formed on the lower cladding layer 3 with the core 4 interposed therebetween. Although the organic material to form the upper cladding layers 3 and 5 is not particularly limited, polyimide, fluorinated polyimide, and the like are preferable examples.

(6) Upper electrode The upper electrode 6 is formed on the entire surface or part of the upper cladding layer 5. The material of the upper electrode 6 is not particularly limited, but an electrode on which gold, silver, copper, aluminum or the like is vapor-deposited is preferable.

(7) Waveguides As waveguides, lightwave optics (Corona (Tokyo) published in 1988), known waveguides described in Chapter 7, page 204, for example, branched waveguide type, Mach-Zehnder type, direction A sex coupler type, a crossed waveguide type, or the like can be adopted. Among these, a branched waveguide type, a Mach-Zehnder type, and a directional coupler type are preferable.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[Example 1] (Production of Compound 1)
-First step-
4-Dimethylaminobromobenzene (7.67 g), thiazole (6.55 g), tetrakis (triphenylphosphine) palladium (1.35 g), and potassium acetate (7.56 g) were added to 77 mL of dimethylacetamide, and the mixture was heated to 140 ° C. Warmed up. After stirring for 12 hours, water was added to the reaction solution, followed by extraction with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel chromatography (eluent: hexane: ethyl acetate = 80: 20), and 5.4 g of 5- (4-dimethylaminophenyl) thiazole. Got.

-Second step-
The obtained 5- (4-dimethylaminophenyl) thiazole (204 mg) was dissolved in 5 mL of dimethylformamide, and 5-bromothiophene-2-carboxaldehyde (191 mg), copper iodide (4 mg), triphenylphosphene ( 15 mg) and bis (triphenylphosphine) palladium (II) dichloride (21 mg) were added and heated to 100 ° C. After stirring for 5 hours, the reaction mixture was concentrated under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel chromatography (eluent: dichloromethane: ethyl acetate = 97: 3) to obtain 5 mg of compound 1.
The obtained crystal was confirmed to be the target compound by ¹ H-NMR and Fab-Mass. The measurement results are shown below.

Fab MASS (M + H) ⁺ = 315
¹ H-NMR: (δ: CDCl ₃ , TMS, ppm) 3.02 (s, 6H), 6.73 (d, 2H), 7.46 (d, 2H), 7.52 (d, 1H) , 7.72 (d, 1H), 7.87 (s, 1H), 9.92 (s, 1H)

  Compounds 2 to 7 and compounds 12 to 15 can also be synthesized by the same method as in Example 1.

[Example 2] (Production of Compound 8)
-Third step-
Compound 1 (31 mg) obtained by the method of Example 1 was dissolved in 1 mL of tetrahydrofuran, malononitrile (7 mg) and 1 drop of hyperidine were added, and the mixture was reacted under reflux conditions for 1 hour. Chloroform was added to the reaction product, washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by recrystallization from acetonitrile to obtain 15 mg of Compound 8.
The obtained crystal was confirmed to be the target compound by ¹ H-NMR and Fab-Mass. The measurement results are shown below.

Fab MASS (M + H) ⁺ = 363
¹ H-NMR: (δ: CDCl ₃ , TMS, ppm) 3.02 (s, 6H), 6.72 (d, 2H), 7.46 (d, 2H), 7.74 (d, 1H) , 7.75 (s, 1H), 7.90 (s, 1H)

  Compounds 9 to 11 and Compound 16 can also be synthesized by the same method as in Example 2.

[Example 3] (Production of Compound 17)
4,4-Dimethylaminobromobenzene of Example 1 was replaced with 4- (N- (hydroxybutyl) -N-methylamino) bromobenzene, and 5-bromothiophene-2-carboxaldehyde was replaced with 2-bromo-5-cyano. Compound 17 was obtained by synthesis in the same manner as in Example 1 except that thiophene was used.
The obtained crystal was confirmed to be the target compound by Fab-Mass. The measurement results are shown below.

Fab MASS (M + H) ⁺ = 370

[Example 4] (Production of Compound 18)
Compound 17 (150 mg) obtained in Example 3 was dissolved in dimethylformamide, acetyl chloride (50 mg) and triethylamine (75 mg) were added, and the mixture was stirred at 40 ° C. for 3 hours. Chloroform was added to the reaction product, washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by recrystallization from acetonitrile to obtain 2 mg of compound 18.
The obtained crystal was confirmed to be the target compound by Fab-Mass. The measurement results are shown below.

Fab MASS (M + H) ⁺ = 412

  Compounds 19 to 24 can also be synthesized according to Example 1 or Example 2.

Example 5 (Manufacture of nonlinear optical element)
A coating solution having the following composition was applied on a glass substrate by spin coating (750 rpm, 20 s). Then, after drying at 50 ° C. under reduced pressure, heating to 110 ° C., applying voltage (tungsten needle, 6 kV, 1.5 cm) using the corona poling method for 5 minutes, then cooling to 60 ° C. while applying voltage. Thus, a nonlinear optical element was manufactured.
The sample obtained above was irradiated with YHG laser infrared light (1.06 μm) to confirm the generation of the second harmonic, and its intensity was measured by the manufacturer fringe method. The results are shown in FIG.

Coating solution composition ────────────────────────────────────
Compound 1 10mg
PMMA 90mg
Chloroform 500mL
────────────────────────────────────

[Comparative Example 1] (Production of nonlinear optical element using DR1 dye)
A coating solution having the following composition was applied on a glass substrate by spin coating (750 rpm, 20 s). Then, after drying at 50 ° C. under reduced pressure and heating to 110 ° C., voltage application (tungsten needle, 6 kV, 1.5 cm) is performed for 5 minutes using the corona poling method, and then to 60 ° C. while applying voltage. The nonlinear optical element was manufactured by cooling.
The sample obtained above was irradiated with YHG laser infrared light (1.06 μm) to confirm the generation of the second harmonic, and its intensity was measured by the manufacturer fringe method. The results are shown in FIG.

Coating solution composition ────────────────────────────────────
DR1 dye 10mg
PMMA 90mg
Cyclohexanone 500mL
────────────────────────────────────

  From the result of FIG. 2 in which the SH intensity (second harmonic intensity) with respect to the orientation degree of the nonlinear optical element obtained in Example 5 and the nonlinear optical element obtained in Comparative Example 1 is shown, it is obtained in Example 5. It can be seen that the obtained nonlinear optical element shows higher SH intensity. From this result, it was proved that the compound of the present invention exhibits a high nonlinear optical effect, and it became clear that the compound is useful for a nonlinear optical element.

[Example 6] (Confirmation of electro-optic effect)
A coating solution having the following composition was applied by spin coating (750 rpm, 20 s) on a glass substrate having a transparent electrode layer as a lower electrode. Then, after drying at 50 ° C. under reduced pressure, heating to 110 ° C., applying voltage (tungsten needle, 6 kV, 1.5 cm) using corona poling method for 5 minutes, then cooling to 60 ° C. while applying voltage. did. Next, aluminum (AL) was vapor-deposited to produce an upper electrode.
The sample obtained above was observed for refractive index modulation by applying an electric field according to the method of “Appl. Phys. Lett., Vol. 56, 1734, 1990”, and the electro-optic effect was confirmed.

Coating solution composition ────────────────────────────────────
Compound 8 10mg
PMMA 90mg
Chloroform 500mL
────────────────────────────────────

1 is an example of a cross-sectional view of a waveguide electro-optical element that is an embodiment of the present invention. It is a plot of SH intensity | strength by the manufacturer fringe method of the nonlinear optical element of Example 5 of this invention and the nonlinear optical element obtained by the comparative example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Silicon substrate 2 ... Lower electrode 3 ... Lower clad layer 4 ... Core 5 ... Upper clad layer 6 ... Upper electrode

Claims (5)

The compound represented by the following general formula (I).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² are connected to each other to form a ring. R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar represents an aromatic ring having 6 to 10 carbon atoms, or an aromatic heterocycle having 4 to 10 carbon atoms. N represents 0 or 1. E represents an electron-withdrawing group having a σp value of 0.3 or more.) R ¹ and R ² each independently have a hydroxyl group, an amino group, an ester group, an amide group, an ether group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. An alkyl group having 1 to 20 carbon atoms, wherein E is an aldehyde group, cyano group, nitro group, —COR ⁴ , —COOR ⁴ , —SO ₂ R ⁴ , —SO ₃ R ⁴ (wherein R ⁴ is Represents an alkyl group having 1 to 20 carbon atoms, and has a hydroxyl group, an amino group, an ester group, an amide group, an ether group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. Or a group represented by the following general formula (II).

(In the formula, E ² represents a cyano group, a nitro group, —COOR ⁵ , or —SO ₂ R ⁵ , and E ³ represents a cyano group, —COOR ⁵ , or —SO ₂ R ^{5. In the} formula, R ⁵ represents An alkyl group having 1 to 20 carbon atoms, having a hydroxyl group, an amino group, an ester group, an amide group, an ether group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms and a halogen atom; Is also good.) The compound according to claim 1 or 2, wherein n is 0. A nonlinear optical element having a layer formed from the compound according to claim 1. An electro-optic element comprising a layer formed from the compound according to claim 1.

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