JPH0665217A - Triazine compound - Google Patents

Abstract

PURPOSE:To provide a triazine compound exhibiting excellent nonlinear optical effect in crystalline state and useful as a nonlinear optical material. CONSTITUTION:The compound of formula I (X is OH, halogen, alkyl, alkoxy, aryl, arylalkyl, nitro-substituted phenylamino, nitro-substituted phenylalkylamino, nitro-substituted stilbenylamino or nitro-substituted stilbenylalkylamino; Y is aryl or arylalkyl; Z is nitro-substituted stilbenylamino or nitro-substituted stilbenylalkylamino), e.g. (4-chloro-6-phenyl-1,3,5-triazin-2-yl)-(4'-nitrostilbenyl)- amine of formula II. The compound can be produced by condensing an aryl- substituted triazine compound with a p-nitroaniline compound of a 4-amino-4'- nitrostilbene compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a triazine compound useful as a nonlinear optical material.

[0002]

2. Description of the Related Art A nonlinear optical effect is a strong coherent photoelectric field such as laser light and the interaction between a substance and an electric polarization response of the substance does not show a proportional relationship with the photoelectric field. , The second and higher order effects of the photoelectric field appear. As a typical example, second harmonic generation (SHG), sum frequency generation, Pockels effect, three-wave parametric oscillation, etc.
Third harmonic generation (THG) for the third-order nonlinear optical effect,
Degenerate four-wave mixing (DFWM), optical Kerr effect, etc. are known. Materials having such a nonlinear optical effect are used as optical switch elements, optical memory elements, optical bistable elements, etc.
In the future, it is expected to play an important role in the field of next-generation optical industry such as optical communication and optical computer.

Conventionally, lithium niobate (LiNbO ₃ ) is mainly used as a non-linear optical material, and potassium niobate (KNbO ₃ ) and potassium dihydrogen phosphate (KH ₂ PO ₄ ,
Research on inorganic materials such as KDP has been conducted. However, in general, inorganic materials have such a low figure of merit, a non-linear optical effect is caused by the lattice vibration of crystals, so that the response speed is low, the hygroscopicity is large, it is difficult to process, and the optical threshold is low. From this point, it was difficult to manufacture a practical optical element except a part.

In recent years, organic materials have been actively researched for these inorganic materials. The characteristics of organic materials are that the nonlinear optical effect is derived from the polarization of the π-electron system, so a high response speed and a large nonlinear optical constant may be obtained, chemical modification is easy, and processability is high. High, high light threshold, and the like. Organic non-linear compounds include urea and p-nitroaniline (p-N).
A), 2-methyl-4-nitroaniline (MNA), and many other compounds have been found (AC Symposium Serie, Volume 233).
s, Vol.233 (1983)), organic nonlinear optical materials, Kato et al. (CMC, 1985), new organic nonlinear optical materials I and II, Kobayashi et al. (CMC, 1991)
Year) etc.).

[0005]

However, the above-mentioned conventional organic nonlinear optical material has various problems and has not yet been put to practical use. For example, as in p-NA and 4-dimethylamino-4′-nitrostilbene (DANS), the second-order nonlinearity of the molecule (second-order supramolecular polarizability β) is large, but in the crystalline state it has a symmetric central structure. Because of this, there are many cases in which the second-order nonlinear optical effect does not appear.

In order to solve this problem, as one of the methods for causing the organic compound that does not exhibit the secondary nonlinear optical effect due to the crystal structure to exhibit the secondary nonlinear optical effect, the organic compound is used as a liquid crystal or polymer. Attempts have been made to control the molecular orientation of an organic compound by dispersing it in a compound and applying an electric field or a magnetic field to express a second-order nonlinear optical effect. However, there are drawbacks such that the molecular orientation is disturbed over time and the nonlinear optical effect is attenuated. Further, as another method, a molecular modification is introduced into an organic compound to introduce a substituent asymmetrically, a chiral structure such as an asymmetric carbon is introduced, or a hydrogen bond is introduced.
Attempts have been made to prevent the crystal structure from having a center of symmetry by introducing a Λ type structure, reducing the dipole moment in the ground state to 0, forming a molecular salt, and the like. However, satisfactory results have not yet been obtained. The present invention has been made in view of the above circumstances, and an object thereof is to provide an organic compound having an excellent nonlinear optical effect.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have heretofore unknown aryl-substituted triazine compounds and p-type compounds.
The inventors have found that a condensate with a nitroaniline-based compound or a 4-amino-4′-nitrostilbene-based compound can exhibit a second-order nonlinear optical effect, and completed the present invention. In order to solve the above problems, the present invention provides a triazine compound represented by the following general formula (I).

[0008]

[Chemical 2]

(In the formula, X is a hydroxyl group, a halogen atom, an alkyl group, an alkoxyl group, an aryl group, an arylalkyl group, a nitro-substituted phenylamino group, a nitro-substituted phenylalkylamino group, a nitro-substituted stilbenylamino group, and a nitro group. It is any one group or atom selected from the group consisting of substituted stilbenylalkylamino groups and may have a substituent, Y is either an aryl group or an arylalkyl group and has a substituent Optionally, Z is either a nitro-substituted stilbenylamino group or a nitro-substituted stilbenylalkylamino group, which may have a substituent.)

The present invention will be described in detail below. In the general formula (I), X is a hydroxyl group, a halogen atom, an alkyl group, an alkoxyl group, an aryl group, an arylalkyl group, a nitro-substituted phenylamino group, a nitro-substituted phenylalkylamino group, a nitro-substituted stilbenylamino group,
And a nitro-substituted stilbenylalkylamino group.

Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms, and chlorine atom is preferably used. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n
-Butyl group, sec-butyl group, t-butyl group, n-amyl group, i-amyl group, t-amyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, pentadecyl group, etc. And a lower alkyl group is preferably used. Examples of the alkoxyl group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, seci-butoxy group, t-
Butoxy group, n-amyloxy group, i-amyloxy group, t
-Amyloxy group, hexyloxy group, heptoxy group, octoxy group, nonanoxy group, decyloxy group, dodecyloxy group, pentadecyloxy group, and the like, and preferably a lower alkoxy group is used. Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group and the like. Examples of arylalkyl groups include benzyl group, phenethyl group, 2-phenylethyl group, 3-phenylpropyl group, 2-phenylpropyl group, 1-phenylpropyl group, benzhydryl group, trityl group and the like.

Examples of the nitro-substituted phenylamino group include 4-nitroanilino group, 3-nitroanilino group and 2
-Nitroanilino group, 3,5-dinitroanilino group,
2,4-dinitro-anilino group, 2-methyl-3-nitroanilino group, 2-methyl-4-nitro-anilino group, and the like, and particularly, the position of the nitro substituent is the meta position or para position of the terminal benzene ring. Are preferred. Examples of the nitro-substituted phenylalkylamino group include N-methyl-4-nitroanilino group, N-methyl-3-nitroanilino group, N-ethyl-4-nitroanilino group, N-ethyl-3-nitroanilino group and N-propyl. -4-nitroanilino group, N-propyl-3-nitroanilino group,
Examples thereof include N-methyl-3,5-dinitroanilino group and the like, and those in which the position of the nitro substituent is at the meta position or para position of the terminal benzene ring are particularly preferable. Examples of the nitro-substituted stilbenylamino group include a 4'-nitro-p-stilbenylamino group, 4'-nitro-3-methyl-p-stilbenylamino group, and the like. The position is preferably the meta position or para position of the terminal benzene ring. Examples of the nitro-substituted stilbenylalkylamino group include N-methyl-4′-nitro-p-stilbenylamino group and N-methyl-4′-nitro-3-methyl-p-stilbenylamino group. And the like, and those in which the position of the nitro substituent is at the meta position or para position of the terminal benzene ring are particularly preferable.

In the above general formula (I), Y is either an aryl group or an arylalkyl group. Here, examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group. Examples of the arylalkyl group include benzyl group, phenethyl group, 2-
Examples thereof include a phenylethyl group, a 3-phenylpropyl group, a 2-phenylpropyl group, a 1-phenylpropyl group, a benzhydryl group and a trityl group.

In the above general formula (I), Z is either a nitro-substituted stilbenylamino group or a nitro-substituted stilbenylalkylamino group. Here, examples of the nitro-substituted stilbenylamino group include a 4'-nitro-p-stilbenylamino group, a 4'-nitro-3-methyl-p-stilbenylamino group, and the like. It is preferred that the position of the substituent is at the meta position or para position of the terminal benzene ring. Further, examples of the nitro-substituted stilbenylalkylamino group include N-methyl-4 ′.
-Nitro-p-stilbenylamino group, N-methyl-
Examples thereof include a 4'-nitro-3-methyl-p-stilbenylamino group, and those in which the position of the nitro substituent is the meta or para position of the terminal benzene ring are particularly preferable.

However, these X, Y, and Z are not limited to the above-exemplified elements and substituents. Specific examples (Compounds 1 to 66) of the compound of the present invention are shown below, but the triazine compound of the present invention is not limited to these exemplified compounds.

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

[0026]

[Chemical 13]

[0027]

[Chemical 14]

[0028]

[Chemical 15]

[0029]

[Chemical 16]

[0030]

[Chemical 17]

[0031]

[Chemical 18]

[0032]

[Chemical 19]

[0033]

[Chemical 20]

[0034]

[Chemical 21]

[0035]

[Chemical formula 22]

[0036]

[Chemical formula 23]

[0037]

[Chemical formula 24]

These compounds can be synthesized, for example, according to the following synthetic routes (synthetic routes 1 to 8).

[0039]

[Chemical 25]

[0040]

[Chemical formula 26]

[0041]

[Chemical 27]

[0042]

[Chemical 28]

[0043]

[Chemical 29]

[0044]

[Chemical 30]

[0045]

[Chemical 31]

[0046]

[Chemical 32]

The base used in the synthetic route 1 is
Inorganic bases such as alkali metal or alkaline earth metal carbonates, hydrogen carbonates, hydroxides, hydrides, alkyl lithium, trialkyl amines, 1,8-diazabicyclo [5,4,0] -7-undecene, etc. Organic bases of can be used. Examples of the solvent include hydrocarbons such as n-hexane, ketones such as acetone, aromatic hydrocarbons such as benzene and toluene, ethers such as tetrahydrofuran, and aprotic substances such as N, N-dimethylformamide and dimethylsulfoxide. A polar solvent and nitriles such as acetonitrile are used.

The solvent used in Synthesis Route 2 is
An aprotic polar solvent such as N, N-dimethylformamide or dimethylsulfoxide can be used. In the synthetic route 3, alcohol or its sodium or potassium salt is used as R ³ OH or R ³ OM. As the solvent, an alcohol corresponding to R ³ OH or R ³ OM, N, N-dimethylformamide, dimethylsulfoxide or the like can be used. Alternatively, ketones such as acetone, aprotic polar solvents such as ethers such as tetrahydrofuran, and nitriles such as acetonitrile can be used.

In the synthetic route 4, alkylation is carried out using a Grineer reagent such as R ³ MgCl or a lithium compound such as R ³ Li. As the solvent, an aprotic polar solvent such as ether, benzene, N, N-dimethylformamide, dimethylsulfoxide or the like can be used. In the synthesis route 5, an alkali metal or an alkali metal hydride is preferably used as the base, and a Grignard reagent such as Ar ¹ MgBr or Ar ¹ Li is used.
Arylation is carried out using a lithium compound such as.

In the synthetic route 6, a Grignard reagent such as Ar ¹ MgBr or R ³ MgCl, or Ar ¹
Arylation and alkylation are carried out using a lithium compound such as Li or R ³ Li. As a base, synthetic route 1
Organic bases similar to can be used. Further, as the solvent,
Ether, benzene, N, N-dimethylformamide,
An aprotic polar solvent such as dimethyl sulfoxide can be used.

Biguanide in the synthetic route 7 or 8 (biguanide is Yuki et al., Polymer Chemistry, vol 30,
p720 (1973), etc., and can be synthesized. Also,
This reaction can also be performed according to these methods of Yuki et al.)
In the reaction of an acid anhydride or an acid halide with an inorganic base such as an alkali metal or alkaline earth metal carbonate, hydrogencarbonate, hydroxide or hydride as a base, alkyllithium or trialkylamine ,
Organic bases such as 1,8-diazabicyclo [5,4,0] -7-undecene can be used. As the solvent, ketones such as acetone are preferable. Also, polyphosphoric acid can be used. The nitration reaction is performed with potassium nitrate and concentrated sulfuric acid.

[0052]

[Examples] Examples of synthesizing representative compounds will be shown below as Examples of the present invention.

Example 1 Compound 1 [(4-chloro-6-phenyl-1,3,5-
Triazin-2-yl)-(4′-nitrostilbenyl) -amine] Synthesis of 2,4-dichloro-6-phenyl-1,3,5-triazine Under nitrogen atmosphere 1,3,5- Trichlorotriazine 10
mmol (1.84 g) was dissolved in 20 ml of dry benzene, and phenylmagnesium bromide ether solution (3
(mmol / ml) 3.4 ml was added dropwise. After dropping, the mixture was stirred at room temperature for 1 hour. The reaction solution was washed with 10 ml of ice water, and the benzene layer was dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the obtained crystals were purified by sublimation. Synthesis of title compound First, 4'-nitro-4-aminostilbene was synthesized according to a conventional method (JN Ashley, et al, J. Chem. Soc., P112 (19).
42 years)). Next, in a nitrogen atmosphere, 10 mmol (2.26 g) of 2,4-dichloro-6-phenyl-1,3,5-triazine obtained in this example was dried with 20 m of benzene.
4'-nitro-4-aminostilbene 10
A benzene solution (20 ml) of mmol (2.40 g) was added, and the mixture was heated under reflux for 5 hours. After cooling, the generated crystals were filtered, washed with benzene and n-hexane, and dried to give compound 1
Was obtained (3.66 g, yield 85%). Elemental analysis value C H N O Cl theoretical value 64.27% 3.75% 16.29% 7.44% 8.25% actual value 64.29 3.79 16.32 7.65 8.12 NMR spectrum (DMSO-d ₆ ) δ 7.15 to 7.89 (m, 11H, aromatic, olefin) δ8.23 (d, 2H, aromatic) δ8.51 (d, 2H, aromatic) δ9.89 (s, 1H, NH)

(Example 2) Compound 2 [(4-hydroxy-6-phenyl-1,3,3
5-Triazin-2-yl)-(4′-nitrostilbenyl) -amine] 10 mmol (4.30) of Compound 1 obtained in Example 1
g) was dissolved in a mixed solvent of 20 ml of dimethyl sulfoxide and 1 ml of water, and the reaction was carried out while stirring at 100 ° C for 5 minutes. The reaction solution was cooled and then poured into 100 ml of water, and the formed precipitate was filtered off. Then, it was washed with water, ethanol and n-hexane and dried to obtain compound 2 (3.79 g, yield 92%). Elemental analysis value C H N O theoretical value 67.15% 4.17% 17.02% 11.67% measured value 67.23 4.26 17.09 11.44 NMR spectrum (DMSO-d ₆ ) δ7.20 to 7.90 (m, 11H, aromatic, olefin) δ8.25 ( d, 2H, aromatic) δ8.53 (d, 2H, aromatic) δ9.21 (s, 1H, NH) δ1
0.85 (s, 1H, OH)

Example 3 Compound 3 [(4-methoxy-6-phenyl-1,3,5
-Triazin-2-yl)-(4'-nitrostilbenyl) -amine] under a nitrogen atmosphere, the compound 1 obtained in Example 1 10 mm
(4.30 g) was suspended in 50 ml of dry methanol, and sodium methoxide 28
% Methanol solution (10 mmol, 1.94 g) was added. The reaction was carried out at room temperature for 8 hours. The reaction solution was poured into 100 ml of water, filtered, and washed with water. The composition organism was purified by silica gel chromatography (methylene chloride) to obtain compound 3 (3.49 g, yield 82%). Elemental analysis value C H N O theoretical value 67.76% 4.50% 16.46% 11.28% measured value 67.66 4.42 16.59 11.13 NMR spectrum (DMSO-d ₆ ) δ3.85 (s, 3H, OMe) δ7.25 to 7.90 (m, 11H) , Aromatic, olefin) δ8.20 (d, 2H, aromatic) δ8.53 (d, 2H, aromatic) δ10.3 (s, 1H, NH)

Example 4 Compound 4 [(4-methyl-6-phenyl-1,3,5-
Triazin-2-yl)-(4′-nitrostilbenyl) -amine] Synthesis of compound 1 obtained in Example 1 10 mm under nitrogen atmosphere
Ol (4.30 g) was suspended in dry benzene (20 ml), the adjusted methylmagnesium iodide ether solution (0.33 ml, 11 mmol) was added dropwise, and the mixture was heated under reflux for 1 hour for reaction. The reaction solution was poured into 100 ml of ice water, filtered, washed with water and dried. The crude product was purified by silica gel chromatography (methylene chloride) to obtain compound 4 (3.28 g, yield 80%). Elemental analysis value C H N O theoretical value 70.40% 4.68% 17.10% 7.82% measured value 70.52 4.42 17.29 7.61 NMR spectrum (DMSO-d ₆ ) δ3.23 (s, 3H, Me) δ7.15 to 7.84 (m, 11H) , Aromatic, olefin) δ8.23 (d, 2H, aromatic) δ8.60 (d, 2H, aromatic) δ9.35 (s, 1H, N
H)

Example 5 Synthesis of Compound 5 [(4,6-diphenyl-1,3,5-triazin-2-yl)-(4'-nitrostilbenyl) -amine] 2-chloro-4 Synthesis of 3,6-diphenyl-1,3,5-triazine 1,3,5-trichlorotriazine 10 under nitrogen atmosphere
mmol (1.84 g) was dissolved in 30 ml of dry benzene, and the phenylmagnesium bromide ether solution (3
(mmol / ml) 6.8 ml was added dropwise. After the dropping, the mixture was stirred at room temperature for 4 days, the solvent was distilled off under reduced pressure, and the residue was extracted with petroleum ether. After drying over anhydrous sodium sulfate and evaporating the solvent under reduced pressure, the obtained crystals were recrystallized from an alcohol / benzene mixed solvent. Synthesis of title compound 2-chloro-4 obtained in this example under nitrogen atmosphere,
6-diphenyl-1,3,5-triazine 10 mmol
(2.26 g) was dissolved in 20 ml of dry benzene, and 4'-nitro-4-aminostilbene 1 was synthesized according to a conventional method.
0 mmol (2.40 g) of benzene solution (20 ml)
Was added and the mixture was heated under reflux for 5 hours. After cooling, the generated crystals were filtered, washed with benzene and n-hexane, and dried to obtain compound 5 (3.66 g, yield 85%). Elemental analysis value C H N O theoretical value 73.87% 4.49% 14.85% 6.79% measured value 73.69 4.25 14.77 6.67 NMR spectrum (DMSO-d ₆ ) δ7.20 to 7.89 (m, 14H, aromatic, olefin) δ8.34 ( d, 2H, aromatic) δ8.65 (m, 4H, aromatic) δ10.20 (s, 1H, NH)

Example 6 Compound 6 [(4-benzyl-6-phenyl-1,3,5
-Triazin-2-yl)-(4'-nitrostilbenyl) -amine] 2-chloro-4-benzyl-6-phenyl-1,
Synthesis of 3,5-triazine 2,4-dichloro-6-phenyl-1,3,5-trichlorotriazine 1 obtained in Example 1 under nitrogen atmosphere
0 mmol (2.26 g) was dissolved in 30 ml of dry benzene, and 11 ml of an ether solution of benzylmagnesium bromide (1 mmol / ml) was added dropwise under ice cooling. After the dropping, the mixture was stirred at room temperature for 4 days, the solvent was distilled off under reduced pressure, and the residue was extracted with petroleum ether. After drying over anhydrous sodium sulfate and evaporating the solvent under reduced pressure, the obtained crystals were recrystallized from an alcohol / benzene mixed solvent. Synthesis of the title compound 2-chloro-4- obtained in this example under nitrogen atmosphere
Benzyl-6-phenyl-1,3,5-triazine 10
mmol (2.82 g) was dissolved in 20 ml of dry benzene, and 10 mmol (2.40 g) of 4'-nitro-4-aminostilbene synthesized according to a conventional method in a benzene solution (2
0 ml) was added and the mixture was heated under reflux for 5 hours. After cooling, the generated crystals were filtered, washed with benzene and n-hexane, and dried to obtain compound 6 (4.13 g, yield 85%). Elemental analysis value C H N O theoretical value 68.33% 4.82% 15.94% 10.92% measured value 68.44 4.65 15.87 10.68 NMR spectrum (DMSO-d ₆ ) δ4.25 (s, 2H, CH ₂ Ph) δ7.15 to 7.95 (m , 16H, aromatic, olefin) δ8.27 (d, 2H, aromatic) δ8.63 (d, 2H, aromatic) δ10.25 (s, 1H, NH)

Example 7 Compound 13 [(4-chloro-6-tolyl-1,3,5-
Triazin-2-yl)-(4′-nitrostilbenyl) -amine] Synthesis of 2,4-dichloro-6-tolyl-1,3,5-triazine Under nitrogen atmosphere 1,3,5- Trichlorotriazine 10
mmol (1.84 g) was dissolved in 20 ml of dry benzene, and tolyl magnesium bromide ether solution (3 m
(mol / ml) 3.4 ml was added dropwise. After the dropping, the mixture was stirred at room temperature for 1 hour. The reaction solution was washed with 10 ml of ice water and the benzene layer was dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the obtained crystals were purified by sublimation. Synthesis of title compound 2,4-dichloro-6-tolyl-1,3,5-triazine 10 mmol obtained in this example under nitrogen atmosphere
(2.40 g) was dissolved in 20 ml of dry benzene, and 4'-nitro-4-aminostilbene 1 was synthesized according to a conventional method.
0 mmol (2.40 g) of benzene solution (20 ml)
Was added and the mixture was heated under reflux for 5 hours. After cooling, the generated crystals were filtered, washed with benzene and n-hexane, and dried to obtain compound 13 (3.55 g, yield 80%). Elemental analysis value C H N O Cl theoretical value 64.94% 4.09% 15.78% 7.21% 7.99% measured value 65.01 4.31 15.70 7.11 7.89 NMR spectrum (DMSO-d ₆ ) δ2.30 (s, 3H, Me) δ7.15 to 7.91 (m, 10H, aromatic, olefin) δ8.30 (d, 2H, aromatic) δ8.63 (d, 2H, aromatic) δ10.25 (s, 1H, NH)

Example 8 Compound 20 [(4-chloro-6- (4-dimethylaminophenyl) -1,3,5-triazin-2-yl-
Synthesis of (4′-nitrostilbenyl) -amine] Synthesis of 2,4-dichloro-6- (4-dimethylaminophenyl) -1,3,5-triazine Under nitrogen atmosphere 1,3,5-trichloro Triazine 10
mmol (1.84 g) was dissolved in 20 ml of dry benzene, and 3.4 ml of 4-dimethylaminomagnesium ether bromide solution (3 mmol / ml) was added dropwise under ice cooling. After dropping, the mixture was stirred at room temperature for 1 hour. The reaction solution was washed with 10 ml of ice water, and the benzene layer was dried over anhydrous sodium sulfate.
After distilling off the solvent under reduced pressure, the obtained crystals were purified by sublimation. Synthesis of the title compound 2,4-dichloro-6- (4-dimethylaminophenyl) -1,3,5-obtained in this example under nitrogen atmosphere
Triazine (10 mmol, 2.69 g) was dissolved in dry benzene (20 ml) and synthesized according to a conventional method.
A benzene solution (20 ml) of 4-aminostilbene 10 mmol (2.40 g) was added, and the mixture was heated under reflux for 5 hours.
After cooling, the generated crystals were filtered, washed with benzene and n-hexane, and dried to obtain compound 20 (3.88 g, yield 82%). Elemental analysis value C H N O Cl theoretical value 63.49% 4.78% 17.77% 6.77% 7.50% actual value 63.35 4.80 17.51 6.79 7.61 NMR spectrum (DMSO-d ₆ ) δ3.42 (s, 6H, NMe ₂ ) δ7.15〜 8.00 (m, 10H, aromatic, olefin) δ8.36 ~ 8.57
(m, 4H, aromatic) δ8.97 (s, 1H, NH)

Example 9 Compound 23 [(4-chloro-6-benzyl-1,3,5
-Triazin-2-yl)-(4'-nitrostilbenyl) -amine] Synthesis of 2,4-dichloro-6-benzyl-1,3,5-triazine Under nitrogen atmosphere 1,3,5 -Trichlorotriazine 10
mmol (1.84 g) was dissolved in 20 ml of dry benzene, and the solution of benzyl bromide bromide (3 ml / m) under ice cooling.
l) 3.4 ml was added dropwise. After dropping, the mixture was stirred at room temperature for 1 hour. The reaction solution was washed with 10 ml of ice water and the benzene layer was dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure,
The obtained crystal was purified by sublimation. 2) Synthesis of title compound 2,4-dichloro-6-benzyl-1,3,5-triazine 10 mmol obtained in this example under nitrogen atmosphere
(2.40 g) was dissolved in 20 ml of dry benzene, and 4'-nitro-4-aminostilbene 1 was synthesized according to a conventional method.
0 mmol (2.40 g) of benzene solution (20 ml)
Was added and the mixture was heated under reflux for 5 hours. After cooling, the generated crystals were filtered, washed with benzene and n-hexane, and dried to obtain compound 23 (3.76 g, yield 85%). Elemental analysis value C H N O Cl theoretical value 65.09% 3.87% 15.81% 7.23% 8.01% actual value 64.81 3.81 15.62 7.11 8.15 NMR spectrum (DMSO-d ₆ ) δ4.17 (s, 2H, CH ₂ Ph) δ7.20 ~ 7.89 (m, 13H, aromatic, olefin) δ8.32 (d, 2H, aromatic) δ10.00 (s, 1H, NH)

Example 10 Compound 39 [(4- (4-nitrophenylamino) -6
-Phenyl-1,3,5-triazin-2-yl)-
Synthesis of (4′-nitrostilbenyl) -amine] Under nitrogen atmosphere, compound 1 obtained in Example 1 10 mm
ol (4.30 g) and p-nitroaniline 20 mm
ol (2.76 g) with dry dimethylformamide 50
It was dissolved in ml and reacted at 100 ° C. for 20 hours. The reaction solution was poured into 100 ml of water, filtered and washed with water. The obtained composition organism was purified by silica gel chromatography (methylene chloride) to obtain compound 39 (3.30 g, yield 62).
%). Elemental analysis value C H N O theoretical value 65.53% 3.98% 18.45% 12.04% actual value 65.41 3.78 18.20 12.18 NMR spectrum (DMSO-d ₆ ) δ7.20 to 7.94 (m, 13H, aromatic, olefin) δ8.16 to 8.31
(m, 4H, aromatic) δ8.57 (d, 2H, aromatic) δ10.23 (s, 2H, NH)

Example 11 Synthesis of Compound 48 [(6-phenyl-bis (4'-nitrostilbenylamino) -1,3,5-triazine] Compound 1 obtained in Example 1 under nitrogen atmosphere 10 mm
Ol (4.30 g) and 4′-nitro-4-aminostilbene 20 mmol (4.80 g) were dissolved in 50 ml of dry dimethylformamide and reacted at 100 ° C. for 20 hours. The reaction solution was poured into 100 ml of water, filtered and washed with water. The obtained composition organism was purified by silica gel chromatography (methylene chloride) to obtain compound 48 (3.68).
g, yield 58%). Elemental analysis value C H N O theoretical value 70.13% 4.30% 15.47% 10.10% measured value 70.00 4.12 15.40 10.23 NMR spectrum (DMSO-d ₆ ) δ 7.15 to 7.93 (m, 22H, aromatic, olefin) δ 8.40 ( d, 4H, aromatic) δ8.61 (d, 4H, aromatic) δ10.25 (s, 2H, NH)

Further, the crystals of the compounds 1 to 6, 13, 20, 23, 39 and 48 obtained in the above Examples 1 to 11 were crushed and filled in a 0.3 mm thick glass cell, and Nd was added. : When irradiated with YAG laser light (1064 nm), the second harmonic (5
32 nm) was observed.

[0065]

As described above, according to the present invention, it is possible to provide a triazine compound which can exhibit an excellent nonlinear optical effect in a crystalline state and is useful as a nonlinear optical material.

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[Procedure amendment]

[Submission date] August 12, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

However, these X, Y, and Z are not limited to the above-exemplified elements and substituents. Specific examples of the compound of the present invention are shown below, but the triazine compound of the present invention is not limited to these exemplified compounds.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[0027]

[Chemical 14]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

[0028]

[Chemical 15]

Claims (3)

[Claims] 1. A triazine compound represented by the following general formula (I): [Chemical 1] (In the formula, X is a hydroxyl group, a halogen atom, an alkyl group, an alkoxyl group, an aryl group, an arylalkyl group, a nitro-substituted phenylamino group, a nitro-substituted phenylalkylamino group, a nitro-substituted stilbenylamino group, and a nitro-substituted stilbenyl group. A group or atom selected from the group consisting of alkylalkylamino groups, which may have a substituent. Y represents either an aryl group or an arylalkyl group which may have a substituent. Good, Z is either a nitro-substituted stilbenylamino group or a nitro-substituted stilbenylalkylamino group, which may have a substituent.) 2. Z is either a nitro-substituted stilbenylamino group or a nitro-substituted stilbenylalkylamino group having a nitro substituent at either the meta or para position of the terminal benzene ring. The triazine compound according to claim 1. 3. A nitro-substituted phenylamino group, a nitro-substituted phenylalkylamino group, a nitro-substituted stilbenylamino group or nitro, wherein X has a nitro substituent at either the meta or para position of the terminal benzene ring. The triazine compound according to claim 1, which is one of substituted stilbenylalkylamino groups.