JPH05107575A - Organic nonlinear optical material - Google Patents

Abstract

PURPOSE:To obtain a nonlinear optical material having excellent nonlinear optical effect which can be used for org. nonlinear optical elements such as a wavelength converter, electro-optic element by constituting the optical material of an org. compd. expressed by specified formula. CONSTITUTION:The optical material consists of an org. compd. expressed by formula I. In the formula I, A is an acceptor substituent, D is a donor substituent, phi1, phi2 are independently aromatic rings or hetero rings, each R1-R3 is independently selected from hydrogen atom, alkyl groups, aryl groups, aralkyl groups, and alkyloxy groups, and i-k are integers >=1. Therefore, by coupling the acceptor substituent A with phi1, the polarization of phi1 is caused to promote the polarization of the whole compd. expressed by the formula I. Thereby, mutually adjacent molecules hardly make a center of symmetry so that the obtd. nonlinear optical material is a novel one having excellent transparency and good nonlinearily.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic nonlinear optical material used in the field of optical information communication or optical information processing, and a nonlinear optical element such as an optical wavelength conversion element and an electro-optical element using the organic nonlinear optical material.

[0002]

BACKGROUND OF THE INVENTION Organic nonlinear optical materials have recently attracted attention in the fields of optical information communication or optical information processing. The non-linear optical material means a material that exhibits a non-linear optical effect such as converting laser light into light of an arbitrary wavelength or changing the refractive index by applying a voltage. / 2 wavelength light (second
A second-order organic nonlinear optical material having a harmonic oscillation effect was reported in 1983 (ACS Symposium Series 233 (1983)).
Since then, it has been attracting attention as a material showing performance exceeding inorganic materials.

Such a secondary organic nonlinear optical material has, for example, an aromatic ring, a donor substituent and an acceptor substituent, and the π electron of the aromatic ring has a donor substituent and an acceptor substituent. A material having a structure that is polarized in the molecule by a group is mentioned. It is considered that this type of material has extremely high nonlinear optical responsivity because nonlinear optical properties occur at the π electron site.

However, when para-nitroaniline, which is expected to have a high nonlinear optical response, is made into a single crystal state which is practically indispensable as a nonlinear optical element such as an optical wavelength conversion element or an electro-optical element, two adjacent molecules are inverted from each other. The resulting structure has a non-linear optical property. As described above, the organic non-linear optical material tends to lose its non-linear optical property when adjacent molecules have central symmetry. Therefore, organic compounds having a substituent that eliminates such symmetry between adjacent molecules or a substituent that imparts optical activity has been synthesized. For example, 2-synthesized in this way
Methyl-4-nitroaniline has been shown to exhibit high nonlinear optical properties.

Organic nonlinear optical materials have higher nonlinear optical properties as the intramolecular polarizability increases. However, if the intramolecular polarization is too high, charge transfer occurs and the transparency of the material is lost. At the same time, the wavelength of the second harmonic matches the maximum absorption wavelength λ _max of the organic nonlinear optical material, and the second harmonic cannot be efficiently extracted.

Further, in order to obtain an organic nonlinear optical material,
A nitro group having a high acceptor property and an amino group having a high donor property are introduced at both ends of a linear molecule such as stilbene. However, the material obtained in this manner has problems that adjacent molecules are likely to have central symmetry and that transparency is poor.

In order to solve these problems, methods such as limiting the length of the π-electron conjugated system in the molecule and introducing a hetero atom into the aromatic ring have been tried, but the fundamental method is No solution has been found.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is a novel organic non-linear structure which is unlikely to have central symmetry between adjacent molecules, has excellent transparency, and has good non-linear optical properties. An object of the present invention is to provide an optical material and a nonlinear optical element such as an optical wavelength conversion element and an electro-optical element in which such an organic nonlinear optical material is used.

[0009]

SUMMARY OF THE INVENTION The organic nonlinear optical material of the present invention has the following general formula (I):

[0010]

[Chemical 2]

(In the formula, A represents an acceptor substituent.
, D represents a donor substituent, and Φ ₁And Φ₂Is German
Standing to represent an aromatic ring or a heterocycle, R₁~ R₃Is
Independently an alkyl group, an aryl group, an aralkyl group and
Represents a group selected from the group consisting of alkyloxy groups,
R₂May further be a hydrogen atom, and i to l are
It is an integer of 1 or more. ) Consists of organic compounds
It is characterized by that.

The nonlinear optical element of the present invention is characterized by being made of such an organic nonlinear optical material.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The organic nonlinear optical material according to the present invention will be specifically described below. The organic nonlinear optical material of the present invention comprises a compound represented by the above formula (I), resulting polarization of [Phi ₁ by acceptor substituent A is bonded to the [Phi _1, total Arawasaru compound of formula (I) Polarization is promoted.

The acceptor substituent A preferably has a Hammett value σ in the range of 0 <σ <0.8. Such substituents are specifically exemplified by nitro group, cyano group, trifluoromethyl group, trifluoromethylmethoxy group, trifluoromethylthio group, carbamoyl group, nitroso group, cyanato group, thiocyanato group, isocyanato group, Formyl group,
Alternatively, an alkoxycarbonyl group such as methoxycarbonyl and ethoxycarbonyl, a halogenated alkoxycarbonyl group, an acetyl group, a propinoyl group, an acyl halide group, a sulfo group, a sulfino group, a sulfeno group, a halogen atom and the like can be mentioned. Of these, a nitro group is preferable.

The acceptor substituent A is and one or more binding to [Phi _1, when a plurality of A is bonded to [Phi _1, each of A being the same or different May be.

Such an acceptor substituent A is Φ
It is preferably bound to Φ ₁ so that the polarization of ₁ is promoted. For example, when Φ ₁ is a benzene ring,
The acceptor substituent A is preferably bonded to Φ ₁ at the para position with respect to the —NR ₂ CO— bond (amide bond), and when there are a plurality of acceptor substituents A, the above It is preferable to bond to Φ ₁ at the para position and the meta position with respect to such an amide bond.

[0017] polarization in [Phi ₂ by donor substituents attached to the same manner [Phi ₂ occurs, the polarization of the entire compound represented by the formula (I) is promoted. The donor substituent D preferably has a Hammett value σ in the range of 0 ≧ σ ≧ −0.83. Specific examples of such a substituent include a dimethylamino group, an amino group, a hydroxy group, an aryloxy group such as a phenoxy group, an alkyloxy group such as a methoxy group, a methyl group, an ethyl group,
n-Propyl group, n-butyl group and other linear alkyl groups, isopropyl group, sec-butyl group, sec-amyl group and other secondary alkyl groups, tert-butyl group, tert-amyl group and other 3
Examples thereof include a primary alkyl group, an aryl group and a thioalkyl group. Of these, a methoxy group is preferable.

The donor substituent D is to one or more binding to [Phi _2, when a plurality of D is attached to [Phi _2, each of the D being the same or different May be.

[0019] Such donor substituents D, as the polarization of the [Phi ₂ is accelerated, it is preferably bonded to the [Phi _2. For example, when Φ ₂ is a benzene ring, the donor substituent D is preferably bonded to Φ ₂ at the para position with respect to the amide bond, and when there are a plurality of donor substituents D. Is preferably bound to Φ ₂ at the para and meta positions with respect to the amide bond as described above.

When Φ ₁ and Φ ₂ are benzene rings, especially when A is bound to Φ ₁ para to the amide bond and D is bound to Φ ₂ para to the amide bond. In this case, the intramolecular polarization effect is highest, which is preferable.

Φ ₁ and Φ ₂ in the above formula (I) are each independently an aromatic ring or a hetero ring, preferably an aromatic ring, a hetero 5-membered ring or a hetero 6-membered ring, particularly a benzene ring or a hetero ring. A 5-membered ring is preferred. These aromatic rings or hetero rings provide a field for electronic resonance, and these rings effectively exert the nonlinear optical effect.
Specific examples of the aromatic ring or hetero ring used for Φ ₁ and Φ ₂ are as follows.

[0022]

[Chemical 3]

[0023]

[Chemical 4]

[0024]

[Chemical 5]

R ₁ to R ₃ in the above formula (I) are each independently a hydrogen atom or a group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and an alkyloxy group. Of these, R ₁ and R ₃ are preferably an alkyl group, particularly preferably a methyl group or an ethyl group, and R ₂ is preferably a hydrogen atom.

The above alkyl group may be linear or branched and has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. As such an alkyl group, specifically, a methyl group, an ethyl group, an n-propyl group,
linear alkyl group such as n-butyl group, isopropyl group,
sec-butyl group, sec-amyl group and other secondary alkyl groups, te
Examples thereof include tertiary alkyl groups such as rt-butyl group and tert-amyl group.

The above aryl group may have a substituent. As such an aryl group, specifically,
Examples thereof include a phenyl group, a naphthyl group, a tolyl group and a xylyl group.

Specific examples of the above aralkyl group include:
Examples thereof include a benzyl group, a phenethyl group, an α-methylbenzyl group and a tolylmethyl group. The alkyloxy group may be linear or branched and has 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. As such an alkyl group, specifically, a linear alkyloxy group such as methyloxy group, ethyloxy group, n-propyloxy group, n-butyloxy group, isopropyloxy group, sec-butyloxy group, sec- Secondary alkyloxy group such as amyloxy group, tert-butyloxy group, tert
Examples include tertiary alkyl groups such as amyloxy group.

In the above compound, adjacent molecules are
R at a position where center symmetry does not occur ₁And / or R₃
Are preferably arranged. For example Φ₁and
Φ₂When is a benzene ring, R₁For the amide bond
Φ in the ortho position₁Is bound to R₃Is amide
Φ in meta position₂Is bound to, or
R₁Is Φ at the meta position with respect to the amide bond₁Is bound to
With R₃Is in the ortho position with respect to the amide bond₂Combined with
Is preferably provided. In this case, two R₁Gazo
Φ at ortho position to amide bond₁Combined with
Or two R₃Are paired with amide bond
And Φ in the ortho position₂May be combined with. Φ₁To
Multiple R₁Are bound, each R₁Are each other
May be the same or different, Φ₂Multiple R in₃But
If bound, each R₃Are identical to each other
Or they may be different.

Further, R ₂ is preferably an optically active group. When R ₂ is an optically active group, the symmetry of the molecule is broken, and when a single crystal is produced, it is difficult for adjacent molecules to have central symmetry, and the nonlinear optical property is effectively maintained. Here, the optically active group means a group having an asymmetric carbon atom, for example, a substituent in which three different groups, a methyl group, an ethyl group, and a hydrogen atom are bonded to one carbon atom.

The compound represented by the above formula (I) preferably has at least one deuterium atom.
Specific examples of the compound represented by the above formula (I) include the following compounds.

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

As the compound represented by the above formula (I), 4- (2,4-) represented by the above chemical formula (7) is particularly preferable.
Dimethoxyphenyl) -3 ', 5'-dinitrobenzamide is preferred.

Such carbohydrazide derivatives are
It can be obtained by performing a condensation reaction of an amine derivative having _one skeleton and an acid chloride having a Φ ₂ skeleton in the presence of a base.

Examples of the base used in this reaction include pyridine, trimethylamine, triethylamine and the like, and pyridine is particularly preferable. Also, these bases can be used in combination.

The carbohydrazide derivative can be obtained through the reaction of the following formula.

[0043]

[Chemical 13]

As is clear from the above reaction formula, HCl is generated during the condensation of the hydrazine derivative and the acid chloride,
In order to proceed the reaction, it is necessary to neutralize this HCl with a base, and usually 1.0 to 5 mol, preferably 2 to 1 mol with respect to 1 mol of the hydrazine derivative or acid chloride.
5 moles of base are used.

The reaction is usually carried out in the liquid phase. In this reaction, a solvent that is chemically inert to the amine derivative and acid chloride used as the starting material and the amide derivative to be formed and that dissolves the amine derivative and the acid chloride used as the starting material is used. Be done. Examples of such a solvent include various solvents such as aromatic hydrocarbon solvents, aliphatic saturated hydrocarbon solvents, aliphatic saturated halogenated hydrocarbon solvents, aliphatic unsaturated hydrocarbon solvents and ether solvents. Is used,
Particularly, dichloromethane and THF are preferable. These solvents are used alone or as a mixture of two or more kinds.

The above reaction is usually carried out in the temperature range of -20 to 100 ° C, preferably 0 to 50 ° C. The reaction can be carried out under reduced pressure, usually under a pressure of 60 kg / cm ² , but is preferably carried out under a pressure of 0 to 30 kg / cm ² , especially 0 to 5 kg / cm ² .
The reaction time is appropriately set depending on the reaction temperature, pressure conditions and the like, and is not particularly limited, but is usually 5 to 100 hours, preferably 1 to 10 hours.

Further, the above reaction is usually carried out under an inert atmosphere such as argon or nitrogen. The organic nonlinear optical material according to the present invention comprises the compound represented by the above formula (I) and is used in a crystallized state.

The crystal of the compound represented by the formula (I) is preferably a single crystal, but may be a eutectic crystal with another component having a similar crystal structure.

[0049]

As described above, the organic nonlinear optical material according to the present invention comprises the organic compound represented by the above formula (I), and a resonance field is given by the Φ ₁ ring and the Φ ₂ ring.
The molecular polarization and the molecular arrangement are controlled in a balanced manner by A, D, R ₁ to R ₃ , and adjacent molecules do not have central symmetry, so that an excellent nonlinear optical effect is obtained.

Therefore, the organic nonlinear optical material according to the present invention is an optical wavelength conversion element utilizing a second-order nonlinear optical effect,
It is suitable for application to nonlinear optical elements such as electro-optical elements.

[0051]

EXAMPLES The present invention will be described below based on more specific examples, but the present invention is not limited to these examples.

[0052]

Example 1 100 ml of dichloromethane and 1.73 g of p-methoxyaniline were placed in a 300 ml three-necked flask.
After stirring at room temperature and further adding 4 cc of pyridine, 2.0 g of p-nitrobenzoyl chloride previously dissolved in dichloromethane was added dropwise to the dropping funnel. A yellow precipitate immediately precipitated. After stirring at room temperature for 12 hours, after confirming the completion of the reaction by thin-layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. After that, reprecipitation was carried out with dichloromethane / hexane to obtain N- (4- represented by the chemical formula (1).
2.0 g of methoxyphenyl) -4-nitrobenzamide was obtained.

When the SHG intensity was measured by the powder method using the obtained powder of the compound, the SHG intensity was superior to that of urea.

[0054]

Example 2 100 ml of dichloromethane and 1.53 g of 2,4-dimethoxyaniline were placed in a 300 ml three-necked flask. After stirring at room temperature and adding 5 cc of pyridine,
2.0 g of p-nitrobenzoyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate immediately precipitated. After stirring for 12 hours at room temperature, after confirming the completion of the reaction by thin layer chromatography,
After a slight decomposition, the oil layer was separated and washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined and vacuum dried. After that, reprecipitation is performed with dichloromethane / hexane, which is represented by the above chemical formula (2).
2.8 g of N- (2,4-dimethoxyphenyl) -4-nitrobenzamide was obtained.

When the SHG intensity was measured by the powder method using the obtained powder of the compound, the SHG intensity was superior to that of urea.

[0056]

Example 3 100 ml of dichloromethane and 1.53 g of 3,5-dimethoxy-aniline were placed in a 300 ml three-necked flask. After stirring at room temperature and further adding 5 cc of pyridine, 2.0 g of p-nitrobenzoyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. 1
After stirring at room temperature for 2 hours and confirming the completion of the reaction by thin layer chromatography, the mixture was placed in a beater containing water, the precipitate was separated, filtered, and washed with an aqueous sodium hydrogencarbonate solution. Was dried under vacuum. After that, reprecipitation was performed with DCM / hexane to give 2.7 g of N- (3,5-dimethoxy) -4-nitrobenzamide represented by the chemical formula (3).
Got

When the SHG intensity was measured by the powder method using the powder of the obtained compound, the SHG intensity was superior to that of urea.

[0058]

Example 4 100 ml of dichloromethane and 1.83 g of 3,4,5-trimethoxyaniline were placed in a 300 ml three-necked flask. After stirring at room temperature and adding 5 cc of pyridine, 1.85 g of p-nitrobenzoyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded.
After stirring at room temperature for 12 hours, after confirming the completion of the reaction by thin-layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. After that, reprecipitation is performed with tetrahydrofuran / hexane to give N- (3,4,5-trimethoxyphenyl) -4-represented by the above chemical formula (4).
3.0 g of nitrobenzamide was obtained.

When the SHG intensity was measured by the powder method using the obtained compound powder, the SHG intensity was superior to that of urea.

[0060]

EXAMPLE 5 100 ml of dichloromethane and 1.23 g of 4-methoxyaniline are placed in a 300 ml three-necked flask.
After stirring at room temperature and adding 5 cc of pyridine, 1.85 g of m-nitrobenzoyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. After stirring at room temperature for 12 hours, after confirming the completion of the reaction by thin-layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. Then, reprecipitation was performed with tetrahydrofuran / hexane to obtain 2.1 g of N- (4-methoxyphenyl) -3-nitrobenzamide represented by the above chemical formula (5).

When the SHG intensity was measured by the powder method using the obtained compound powder, the SHG intensity was superior to that of urea.

[0062]

EXAMPLE 6 100 ml of dichloromethane and 1.53 g of 2,4-dimethoxyaniline are placed in a 300 ml three-necked flask. After stirring at room temperature and adding 5 cc of pyridine,
1.85 g of m-nitrobenzoyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. 12
After stirring at room temperature for an hour, after confirming the completion of the reaction by thin-layer chromatography, hydrolysis was performed, and then an oil layer was separated, washed with a filtered sodium hydrogen carbonate aqueous solution, and then vacuum dried.
After that, reprecipitation was performed with tetrahydrofuran / hexane to obtain 2.7 g of N- (2,4-dimethoxyphenyl) -3-nitrobenzamide represented by the chemical formula (6).

When the SHG intensity was measured by the powder method using the obtained compound powder, the SHG intensity was superior to that of urea.

[0064]

EXAMPLE 7 100 ml of dichloromethane and 1.53 g of 2,4-dimethoxyaniline are placed in a 300 ml three-necked flask. After stirring at room temperature and adding 5 cc of pyridine,
2.3 g of 3,5-dinitrobenzoyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. 1
After stirring at room temperature for 2 hours, after confirming the completion of the reaction by thin layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. After that, reprecipitation was performed with tetrahydrofuran / hexane to obtain 3.47 g of N- (2,4-dimethoxyphenyl) -3,5-dinitrobenzamide represented by the chemical formula (7).

Using the powder of the obtained compound, the SHG intensity was measured by the powder method. A YAG laser was used for input. As a result of comparing SHG intensity with urea, 1
It was 7.3 times.

[0066]

Example 8 100 ml of dichloromethane and 1.23 g of 4-methoxyaniline are placed in a 300 ml three-necked flask.
After stirring at room temperature and adding 5 cc of pyridine, 2.3 g of 3,5-dinitrobenzoyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. After stirring for 12 hours at room temperature, after confirming the completion of the reaction by thin-layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with dichloromethane.
The oil layers were combined and vacuum dried. After that, reprecipitation with tetrahydrofuran / hexane was performed to obtain the above chemical formula (8).
2.8 g of N- (4-methoxyphenyl) -3,5-dinitrobenzamide represented by

When the SHG intensity was measured by the powder method using the powder of the obtained compound, the SHG intensity was superior to that of urea.

[0068]

EXAMPLE 9 100 ml of dichloromethane and 1.84 g of 3,5-dimethoxyaniline are placed in a 300 ml three-necked flask. After stirring at room temperature and adding 5 cc of pyridine,
2.3 g of 3,5-dinitrobenzoyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. 1
After stirring at room temperature for 2 hours, after confirming the completion of the reaction by thin layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. Then, reprecipitation was carried out with tetrahydrofuran / hexane, to obtain 2.3 g of N- (3,5-dimethoxyphenyl) -3,5-dinitrobenzamide represented by the chemical formula (9).

When the SHG intensity was measured by the powder method using the powder of the obtained compound, the SHG intensity was superior to that of urea.

[0070]

Example 10 100 ml of dichloromethane and 1.84 g of 2,5-dimethoxyaniline were placed in a 300 ml three-necked flask. After stirring at room temperature and adding 5 cc of pyridine, 2.3 g of 3,5-dinitrobenzoyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. After stirring at room temperature for 12 hours, after confirming the completion of the reaction by thin-layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. After that, re-precipitation is performed with tetrahydrofuran / hexane to give N- (2,5-dimethoxyphenyl)-represented by the chemical formula (10).
3.02 g of 3,5-dinitrobenzamide was obtained.

When the SHG intensity was measured by the powder method using the obtained powder of the compound, the SHG intensity was superior to that of urea.

[0072]

EXAMPLE 11 100 ml of dichloromethane and 1.94 g of 3,4,5-trimethoxyaniline in a 300 ml three-necked flask.
Put in. After stirring at room temperature and adding 5 cc of pyridine, 2.3 g of 3,5-dinitrobenzoyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. After stirring at room temperature for 12 hours, after confirming the completion of the reaction by thin-layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. After that, reprecipitation was performed with tetrahydrofuran / hexane to obtain 3.7 g of N- (3,4,5-trimethoxyphenyl) -3,5-dinitrobenzamide represented by the chemical formula (11).

When the SHG intensity was measured by the powder method using the obtained compound powder, the SHG intensity was superior to that of urea.

[0074]

EXAMPLE 12 100 ml of dichloromethane and 2.0 g of 2,5-diethoxyaniline are placed in a 300 ml three-necked flask. After stirring at room temperature and adding 5 cc of pyridine,
2.3 g of 3,5-dinitrobenzoyl chloride previously dissolved in 20 cc of dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. After stirring at room temperature for 12 hours, after confirming the completion of the reaction by thin-layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. After that, reprecipitation with tetrahydrofuran / hexane was performed to obtain N- (2,5-diethoxyphenyl)-represented by the chemical formula (12).
3.64 g of 3,5-dinitrobenzamide was obtained.

When the SHG intensity was measured by the powder method using the obtained powder of the compound, the SHG intensity was superior to that of urea.

[0076]

EXAMPLE 13 100 ml of dichloromethane and 2.0 g of 2-amino-6-methoxybenzthiazole are placed in a 300 ml three-necked flask. Stir at room temperature and add 5 more pyridines.
After adding cc, it was dissolved in dichloromethane in advance
2.3 g of 3,5-dinitrobenzoyl chloride is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. After stirring at room temperature for 12 hours, after confirming the completion of the reaction by thin-layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. After that, reprecipitation was performed with tetrahydrofuran / hexane to obtain 2.95 g of N- (6-methoxybenzthiazolyl) -3,5-dinitrobenzamide represented by the chemical formula (13).

When the SHG intensity was measured by the powder method using the obtained compound powder, the SHG intensity was superior to that of urea.

[0078]

Example 14 100 ml of dichloromethane and 2.0 g of 2-amino-6-methoxybenzthiazole are placed in a 300 ml three-necked flask. Stir at room temperature and add 5 more pyridines.
After adding cc, it was dissolved in dichloromethane in advance
4-Nitrobenzoyl chloride 1.85 g is slowly added dropwise from the dropping funnel. A yellow precipitate was deposited as the reaction proceeded. After stirring at room temperature for 12 hours, after confirming the completion of the reaction by thin-layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. After that, reprecipitation was performed with tetrahydrofuran / hexane to obtain 3.07 g of N- (6-methoxybenzthiazolyl) -4-nitrobenzamide represented by the chemical formula (14).

When the SHG intensity was measured by the powder method using the obtained powder of the compound, the SHG intensity was superior to that of urea.

[0080]

Example 15 A 300 ml three-necked flask is charged with 100 ml of dichloromethane and 1.4 g of N, N-dimethyl-p-phenylenediamine. Stir at room temperature and add 5 more pyridines.
After adding cc, it was dissolved in dichloromethane in advance
2.3 g of 3,5-dinitrobenzoyl chloride is slowly added dropwise from the dropping funnel. A precipitate was deposited as the reaction proceeded. After stirring for 12 hours at room temperature, after confirming the completion of the reaction by thin layer chromatography, after hydrolysis, the oil layer was separated,
The extract was washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined and dried under vacuum. After that, reprecipitation was performed with tetrahydrofuran / hexane to obtain 2.36 g of N- (4- (N, N-dimethylamino) phenyl) -3,5-dinitrobenzamide represented by the chemical formula (15).

When the SHG intensity was measured by the powder method using the obtained compound powder, the SHG intensity was superior to that of urea.

[0082]

Example 16 100 ml of dichloromethane and 1.4 g of N, N-dimethyl-p-phenylenediamine are placed in a 300 ml three-necked flask. Stir at room temperature and add 5 more pyridines.
After adding cc, it was dissolved in dichloromethane in advance
4-Nitrobenzoyl chloride 1.85 g is slowly added dropwise from the dropping funnel. A precipitate was deposited as the reaction proceeded. After stirring at room temperature for 12 hours, after confirming the completion of the reaction by thin-layer chromatography, after hydrolysis, the oil layer was separated, washed with an aqueous sodium hydrogen carbonate solution, the aqueous layer was extracted with dichloromethane, and the oil layers were combined, Vacuum dried. After that, reprecipitation was performed with tetrahydrofuran / hexane to obtain N- (4- (N, N-dimethylamino) represented by the chemical formula (16).
2.84 g of phenyl) -4-nitrobenzamide was obtained.

When the SHG intensity was measured by the powder method using the obtained compound powder, the SHG intensity was superior to that of urea.

Claims (6)

[Claims] 1. A compound represented by the general formula (I): (In the formula, A is an acceptor substituent, D is a donor substituent, Φ ₁ and Φ ₂ are each independently an aromatic ring or a heterocycle, and R _{1 to} R ₃ are each independently A hydrogen atom or a group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and an alkyloxy group, and i to 1 are integers of 1 or more.). Organic non-linear optical material. 2. The organic nonlinear optical material according to claim 1, wherein Φ ₁ and Φ ₂ are benzene rings or 5-membered heterocyclic rings. 3. Φ ₁ and Φ ₂ are benzene rings, and A is bound to Φ ₁ in the para position to the amide bond and D is bound to Φ ₂ in the para position to the amide bond. The organic nonlinear optical material according to claim 2, wherein 4. The organic nonlinear optical material according to claim 1, wherein R ₂ is an optically active group. 5. The organic nonlinear optical material according to claim 1, wherein the organic compound represented by the formula (I) has at least one deuterium. 6. An organic nonlinear optical element comprising the organic nonlinear optical material according to claim 1.