JPH05230006A - New hydrazine compound, its production, organic non-linear optical material and non-linear optical element - Google Patents

Abstract

PURPOSE:To provide a new hydrazine compound useful as an organic nonlinear optical material having excellent transparency and non-linear optical effect, crystallizable to form a large-sized single crystal and applicable as a nonlinear optical element such as wavelength conversion element and electrooptical element. CONSTITUTION:The compound of formula I ([A is acceptor-type substituent; PHI1 is aromatic ring or heterocyclic group; R1 to R3 are H, alkyl, aryl, aralkyl or alkyloxy; R4 is H, alkyl or alkenyl which may have substituent (OH or halogen) (a bivalent hetero atom or a bivalent group containing the atom may be present between adjacent C-C atoms) or phenyl; B is direct bond or O; (i) and (j) are integer of >=1], e.g. 4'-nitrophenyl-ethylcarbohydrazide of formula II. The compound can be produced e.g. by reacting a compound of formula III with a compound of formula IV (X is halogen). Since the compound has central asymmetry between adjacent molecules, it has excellent transparency, gives a single crystal as large as >=1mm<3> and enables the generation of second harmonies in high efficiency.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel hydrazine compound, a method for producing the same, an organic nonlinear optical material used in the fields of optical information communication or optical information processing, an optical wavelength conversion element using the same, and an electro-optical element. And other non-linear optical elements.

[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. For example, as a typical inorganic material, KTi
OPO ₄ (KTP) is known, but the development of organic nonlinear optical materials exceeding the nonlinear optical performance of KTP is expected.

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, in the organic nonlinear optical material, the nonlinear optical property tends to be lost when the 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-methyl-4-nitroaniline thus synthesized 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.

Further, in the past, there was a problem that a single crystal organic nonlinear optical material having a size suitable for use as a nonlinear optical element could not be obtained. That is, in most cases, conventional organic nonlinear optical materials are fine needle-shaped crystals or single crystals whose size is 1 mm ³
However, there is a problem in that it is difficult to obtain a single crystal organic nonlinear optical material having a size of 1 mm ³ or more, particularly 5 mm ³ or more.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel hydrazine compound which can be used for the above-mentioned nonlinear optical material and a method for producing the same. I am trying.

Further, according to the present invention, since adjacent molecules are centrally asymmetrical to each other, a novel organic nonlinear optical material having excellent transparency and good nonlinear optical property, particularly nonlinear optical composed of a single crystal of 1 mm ³ or more is provided. It is also intended to provide materials.

A further object of the present invention is to provide a non-linear optical element such as an optical wavelength conversion element, an electro-optical element, etc. in which such an organic non-linear optical material is used.

[0012]

SUMMARY OF THE INVENTION The novel hydrazine compound of the present invention has the following general formula (I):

[0013]

[Chemical 6]

(In the formula, A is an acceptor substituent, Φ ₁ is an aromatic ring or a heterocycle, and R _{1 to} R ₃ are each independently a hydrogen atom or an alkyl group, an aryl group, an aralkyl group and R ₄ is a group selected from the group consisting of an alkyloxy group, R ₄ is a hydrogen atom or a group selected from the group consisting of an alkyl group, an alkenyl group and a phenyl group, and when R ₄ is an alkyl group or an alkenyl group, The alkyl group or alkenyl group may have a hydroxyl group and / or a halogen atom, and contains a divalent hetero atom or a hetero atom between two adjacent carbon atoms in the alkyl group or the alkenyl group. May have a valent group, B is a direct bond,
Alternatively, it is an oxygen atom, and i and j are integers of 1 or more. ) Is represented.

The hydrazine compound represented by the formula (I) is represented by the following general formula (III)

[0016]

[Chemical 7]

(Where A, Φ ₁ , R _{1 to} R ₃ , i and j
Represents the same meaning as described above. ) And a hydrazine compound represented by the general formula (IV) X—CO—B—R ₄ (IV) (wherein R ₄ and B have the same meanings as described above, X
Is a halogen atom. ) And an acid halide represented by

The organic nonlinear optical material according to the present invention is characterized by comprising a hydrazine compound represented by the above formula (I). The nonlinear optical element of the present invention is characterized by being made of such an organic nonlinear optical material.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The novel hydrazine compound of the present invention, the method for producing the same, and the organic nonlinear optical material of the present invention will be specifically described below.

The novel hydrazine compound of the present invention is represented by the above formula (I). Specific examples of such a hydrazine compound include the following compounds (1) to (26).

[0021]

[Chemical 8]

[0022]

[Chemical 9]

[0023]

[Chemical 10]

The novel hydrazine compound represented by the above formula (I) is obtained by subjecting a condensation reaction of the hydrazine compound represented by the above formula (III) to an acid halide represented by the above formula (IV), preferably an acid chloride. Is produced by carrying out in the presence of a base.

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

This hydrazine compound has the following formula (V)

[0027]

[Chemical 11]

A hydrazine compound represented by the following formula (VI) Cl-CO-BR ... (VI) (wherein B is a direct bond or an oxygen atom, and R is a carbon atom having 1 carbon atom). When the acid chloride represented by 4 to 4 is used as a raw material, it is synthesized through the reaction of the following formula.

[0029]

[Chemical 12]

As is clear from the above reaction formula, HCl is generated during the condensation of the hydrazine compound and the acid chloride,
Neutralization of this HCl is necessary to proceed the reaction,
Usually, 1.0 to 5 mol, preferably 2 to 5 mol of a base is used with respect to 1 mol of a hydrazine derivative or an acid chloride.

The reaction is usually carried out in the liquid phase. During this reaction, it is chemically inert to the hydrazine derivative and acid chloride used as raw materials, and the carbohydrazide derivative formed, and,
A solvent that dissolves the hydrazine derivative and the acid chloride used as raw materials is used. As such a solvent, for example, an aromatic hydrocarbon solvent, an aliphatic saturated hydrocarbon solvent, an aliphatic saturated halogenated hydrocarbon solvent,
Various solvents such as aliphatic unsaturated hydrocarbon type solvents and ether type solvents are used, and dichloromethane and THF are particularly 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 100 ° C. Also,
This reaction can be carried out under reduced pressure, usually under a pressure of 60 kg / cm ² , but 0-30 kg / cm ² , especially 0-5 k.
It is preferably carried out under a pressure of g / cm ² . The reaction time is
It 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.

Furthermore, the above reaction is usually carried out in an atmosphere of an inert medium such as argon or nitrogen. The hydrazine compound represented by the above formula (I) of the present invention can also be obtained by a dehydration reaction between a hydrazine compound and a carboxylic acid. During this dehydration reaction, DCC
A dehydrating agent such as (N, N'-dicyclohexylcarbodiimide) is used.

The organic nonlinear optical material according to the present invention comprises a hydrazine compound represented by the above formula (I) and has a diameter of Φ ₁
When the acceptor substituent A is bonded to Φ ₁
Occurs, promoting the polarization of the entire compound represented by formula (I).

The acceptor substituent A preferably has a Hammett value σ in the range of 0 <σ <0.8. Specific examples of such a substituent include a nitro group, a cyano group, a trifluoromethyl group, a trifluoromethoxy group, a trifluoromethylthio group, a carbamoyl group, a nitroso group, a cyanato group, a thiocyanato group, an isocyanato group, and a formyl group. Or 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. Of these, a nitro group or a cyano 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 the para position of Φ ₁ with respect to the —NR ₂ NR ₃ CO— bond, and when there are a plurality of acceptor substituents A, —N is used.
It is preferable that they are bonded at the para and meta positions of Φ ₁ with respect to the R ₂ NR ₃ CO-bond.

Φ ₁ in the above formula (I) is an aromatic ring or a hetero ring, preferably a benzene ring among the aromatic rings, and a hetero 5-membered ring or a hetero 6 ring among the hetero rings.
A membered ring is preferable, and a hetero 5-membered ring is particularly preferable. 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 are as follows.

[0039]

[Chemical 13]

R _{1 to} R ₃ in the above formula (I) are each independently a hydrogen atom or an alkyl group, an aryl group,
It is a group selected from the group consisting of aralkyl groups and alkyloxy groups. Of these, R ₁ is preferably a hydrogen atom or an alkyl group, particularly preferably a methyl group or an ethyl group, and R ₂ and R ₃ are preferably both hydrogen atoms. R ₁ may be bonded to not only the carbon atom forming the aromatic ring or the hetero ring but also the hetero atom forming the hetero ring, for example, the N atom.

The above-mentioned alkyl group may be linear or branched and has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Examples of such an alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group and n-butyl group, secondary alkyl groups such as isopropyl group, sec-butyl group and sec-amyl group, Examples thereof include tertiary alkyl groups such as tert-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 aralkyl group include a benzyl group, a phenethyl group, an α-methylbenzyl group and a tolylmethyl group. The above alkyloxy group may be linear or branched and has 1 carbon atom.
To 6, and preferably 1 to 3 carbon atoms. As such an alkyloxy group, specifically, a linear alkyloxy group such as a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group, an isopropoxy group, a sec-butoxy group, a sec-amyloxy group. Group such as secondary alkyloxy group, tert-butoxy group, tert-amyloxy group, etc.
Primary alkyloxy groups.

In the above compound, adjacent molecules are
R at a position where center symmetry does not occur ₁Is located
Preferably. For example Φ₁Is a benzene ring
Is R₁Is -NR₂NR₃In the ortho position to the CO-bond
Φ₁Is preferably bound to. In this case, 2
R₁Is -NR₂NR₃For CO-bonds
Φ₁May be combined with. Φ₁Multiple R in
₁Are bound, each R₁Are identical to each other
Or they may be different.

Further, R ₂ and / or R ₃ is preferably an optically active group. When R ₂ and / or R ₃ 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 nonlinearity 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.

On the other hand, R ₄ in the above formula (I) is a hydrogen atom or a group selected from the group consisting of an alkyl group, an alkenyl group and a phenyl group, and the alkyl group or the alkenyl group is a linear group. Or may be branched, and may have a hydroxyl group and / or a halogen atom, and further, between adjacent two carbons in the alkyl group or the alkenyl group, O, S, S
a divalent heteroatom such as e, or a divalent group containing not only these divalent heteroatoms but also a heteroatom such as N, B, Si, Ge, etc. Groups may be present.

Examples of such a divalent group include -CO-
Group, -NH- group, -N (CH ₃₎ - group, -BH- group, -
B (CH ₃₎ - group, -SiH ₂ - group, -Si (CH _{3) 2} -
Base,

[0048]

[Chemical 14]

And the like. B in the above formula (I) is a direct bond or an oxygen atom.
If -BR ₄ is an alkyl group, preferably an ethyl group or n- propyl group as the alkyl group. Also −
When BR ₄ is an alkoxy group, a methoxy group is preferable as this alkoxy group.

When the hydrazine compound represented by the above formula (I) is used as the organic nonlinear optical material, the hydrazine compound preferably has at least one deuterium.

The organic nonlinear optical material according to the present invention comprises the compound represented by the above formula (I) and is used in a nonlinear optical element in a crystallized state. For the organic nonlinear optical material according to the present invention, a compound represented by the formula (I) is usually used, but a plurality of compounds represented by the formula (I) may be used.

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

Further, the organic nonlinear optical material according to the present invention may be a composite of the compound represented by the above formula (I) and a transparent polymer. The single crystal as described above may be prepared by dissolving the compound represented by the above formula (I) in a suitable solvent such as dimethylformamide, ethanol, etc., and then evaporating the solvent or changing the temperature of the obtained solution. It is obtained by lowering and crystallizing the compound contained in the solution. Further, the single crystal as described above can be represented by the above formula (I) by a vacuum vapor deposition method, a molecular beam epitaxy method or the like by heating and melting the compound represented by the above formula (I) and then cooling and crystallizing it. It can also be obtained by vapor-phase growth of the compound described above.

According to the organic nonlinear optical material of the present invention, a large single crystal composed of a rectangular parallelepiped having a size of 1 mm ³ or more can be provided by the above method, and in particular, in the above formula (I), methyl-3- (p- Nitrophenyl) carbazate (the compound (7)) is preferable, and a large single crystal of 5 mm ³ or more can be easily provided.

A nonlinear optical element according to the present invention can be obtained by adding a cutting step and a processing step to a large single crystal made of the organic nonlinear optical material according to the present invention as described above.

Further, when the nonlinear optical element according to the present invention is formed from a thin film single crystal, the thickness of the thin film single crystal is preferably 1 μm or more. Further, in the case of a complex of one or more compounds represented by the formula (I) and a transparent polymer as described above, 1 is represented by the formula (I) in the polymer substance. After dispersing one or more compounds, a voltage is applied to this dispersion while heating the resulting dispersion at a temperature above the glass transition point, whereby the compounds contained in this dispersion are Can be obtained by a method of orienting and cooling and solidifying while maintaining this orientation. The nonlinear optical element according to the present invention can also be obtained by processing the thus obtained composite body into a desired shape.

The non-linear optical element according to the present invention as described above is used for a second harmonic generator, an optical switch and the like. FIG. 1 shows an example of a second harmonic generation device, and the second harmonic generation device 10 includes a laser light source 1
1, a condenser lens 12, a non-linear optical element 13, a condenser lens 14 and an infrared cut filter 15.

According to this second harmonic generation device 10, the laser light emitted from the laser light source 11 is condensed in the nonlinear optical element 13 by the condenser lens 12. When laser light is incident on the nonlinear optical element 13 in this manner, the nonlinear optical element 13 generates a second harmonic,
Light including the fundamental wave of the laser light and the light having the second harmonic is emitted from the nonlinear optical element 13. The emitted light is converted into substantially parallel light by the condenser lens 14, and the substantially parallel light is selectively output as light having the second harmonic through the infrared cut filter 15.

FIG. 2 shows another mode using the nonlinear optical element according to the present invention. The second shown in FIG.
The harmonic generator 20 includes a laser light source 21, a condenser lens 22, a core material 23 made of the organic nonlinear optical material according to the present invention, and a clad made of a medium such as highly transparent glass having a refractive index different from that of the core material 23. The material 24 is provided, and the core material 23 is covered with the clad material 24.

According to the second harmonic generation device 20, the laser light emitted from the laser light source 21 enters the core material 23 from one end of the core material 23 through the condenser lens 22 and propagates in the core material 23. To do. In addition, the laser light source 21
The laser light emitted from generates a second harmonic in the process of propagating in the core material 23, and the light having the second harmonic is output from the other end of the core material 23.

The optical modulator 30 shown in FIG. 3 further includes a laser light source 31, a condenser lens 32, and a substrate 34 on which a waveguide 33 made of the organic nonlinear optical material according to the present invention is formed. Of these, the waveguide 33 is bifurcated on the substrate 34 to form two branched paths having the same optical path length, and these branched paths join again.
Further, a pair of electrodes 35 connected to an external power source (not shown) are arranged on both sides of one branch path.

According to the optical modulator 30, the laser light emitted from the laser light source 31 is incident on one end of the waveguide 33 through the condenser lens 32, the laser light is branched along the branching path, and merges again. Then, the light is output from the other end of the waveguide 33. Here, when a voltage is applied between the pair of electrodes 35, the refractive index of the organic nonlinear optical material forming the branched path sandwiched between the pair of electrodes 35 changes, whereby the laser light passing through this branched path is changed. The phase is modulated so that the phase and intensity of the output light, which is the combined light of the laser lights passing through both branch paths, can be changed, and is applied as an optical switch or the like.

[0063]

The present invention provides a novel hydrazine compound represented by the above formula (I).

The novel hydrazine compound according to the present invention is provided with a resonance field by the Φ ₁ ring, and A, R _{1 to} R ₄
Since the molecular polarization and molecular arrangement are controlled in a well-balanced manner and adjacent molecules do not have central symmetry, they have good transparency and exhibit excellent nonlinear optical effects, and at the same time they can be grown into large single crystals. Suitable as a nonlinear optical material.

Further, the organic nonlinear optical material according to the present invention is composed of a novel hydrazine compound having such excellent properties and has excellent transparency and nonlinear optical effect, and at the same time is obtained in the form of a large single crystal or the like. Therefore, the second harmonic can be extracted efficiently.

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

[0067]

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

[0068]

Example 1 50 ml of dichloromethane and 1.54 g of p-nitrophenylhydrazine were placed in a 300 ml three-necked flask, 5 cc of pyridine was added with stirring at room temperature, and then 1.5 cc of propionyl chloride previously dissolved in dichloromethane. When was slowly dropped from the dropping funnel, a yellow precipitate was immediately deposited. After stirring this reaction solution for another 12 hours at room temperature, after confirming the completion of the reaction by thin layer chromatography, excess propionyl chloride was hydrolyzed, and then an aqueous NaHCO ₃ solution was added to react with the aqueous phase. The oily phase, which was rich in product, was separated. Dichloromethane was added to the obtained aqueous phase, and the reaction product remaining in the aqueous phase was extracted and recovered in dichloromethane, the dichloromethane containing the reaction product was mixed with the oil phase, and the mixed solution was dried under vacuum. .. The reaction product thus obtained was reprecipitated with acetone to obtain 1.30 g of a purified product.

The melting point of the purified product obtained by the DSC method was 209 to 210 ° C. In addition, this purified product is D
This solution was dissolved in MSO (dimethyl sulfoxide) and the ¹ H nuclear magnetic resonance spectrum of this purified product was measured using this solution. The chart of the obtained ¹ H nuclear magnetic resonance spectrum is shown in FIG.

The peaks in this chart were analyzed as follows. ¹ H nuclear magnetic resonance (δ ppm) 1.09 (t, 3H, 8 Hz, -CH ₃ ) 2.24 (q, 2H, 7 Hz, -CH _2- ) 6.75 (d, 2H, 9 Hz, ring proton) 8.07 (d, 2H, 9 Hz, ring proton) 9.02 (s, 1H, -NH-) 9.93 (s, 1H, -NH-) Further, the infrared absorption spectrum of this purified product was measured.
The chart of the obtained infrared absorption spectrum is shown in FIG.

From the above results, the obtained purified product was 4'-
It was identified as nitrophenyl-ethylcarbohydrazide (Exemplified compound (2)). Next, the SHG intensity was measured by the powder method using the powder of the compound (2). A YAG laser was used for input. SH of this powder
The G intensity was 24 times the SHG intensity of the urea powder measured in the same manner.

When the powder of the compound (2) was dissolved in a dimethylformamide (DMF) solvent and allowed to stand at room temperature for about 10 days, a single crystal with a size of 8 × 5 × 2 mm ³ was obtained. The size of this single crystal corresponds to about 5 times the size of the single crystal obtained by similarly growing a crystal of 2-methyl-nitroaniline (MNA). In addition, a YAG laser (wavelength: 1064n) was added to the single crystal of the compound (2).
m, continuous wave, output 175 mW), a sharp peak of SH light (532 nm) corresponding to phase matching was obtained only at a specific incident angle. When the SH light intensity was measured, it showed a value three times as large as that when a KTP crystal (sample length: 5 mm) was used.

[0073]

Example 2 70 ml of dichloromethane and 0.8 g of p-nitrophenylhydrazine were placed in a 300 ml three-necked flask, 3 cc of pyridine was added with stirring at room temperature, and then n-butyric acid chloride dissolved in dichloromethane was dissolved. .8cc
When was slowly dropped from the dropping funnel, a yellow precipitate was immediately deposited. After stirring the reaction solution for another 12 hours at room temperature, after confirming the completion of the reaction by thin-layer chromatography, excess n-butyric acid chloride was hydrolyzed, and then NaHCO 3 was added.
₃ Aqueous solution was added to separate the aqueous phase and the oil phase containing a large amount of reaction product. Dichloromethane was added to the obtained aqueous phase, and the reaction product remaining in the aqueous phase was extracted and recovered in dichloromethane, the dichloromethane containing the reaction product was mixed with the oil phase, and the mixed solution was dried under vacuum. .. The reaction product thus obtained was subjected to column chromatography with acetone /
Dichloromethane (volume ratio 1/4) was developed as a developing solution. By reprecipitating the main component thus separated by column chromatography with acetone, 1.3
5 g of purified product was obtained.

The melting point of the purified product obtained by the DSC method was 177 to 178 ° C. Further, as a result of measuring the mass spectrum of this purified product, m / Z was 223 (10
It was 0).

Further, this purified product was dissolved in DMSO (dimethyl sulfoxide), and the ¹ H nuclear magnetic resonance spectrum of this purified product was measured using this solution. The chart of the obtained ¹ H nuclear magnetic resonance spectrum is shown in FIG.

Analysis of the peaks in this chart revealed the following. ¹ H nuclear magnetic resonance (δppm) 0.90 (t, 3H , 8Hz, -CH 3) 1.57 (q, 2H, 7Hz, -CH 2 -) 2.18 (t, 2H, 8Hz, -CH 3 ) 6.75 (d, 2H, 9Hz, ring proton) 8.07 (d, 2H, 9Hz, ring proton) 9.06 (s, 1H, -NH-) 9.93 (s, 1H, -NH-) ) Furthermore, the infrared absorption spectrum of this purified product was measured. The chart of the obtained infrared absorption spectrum is shown in FIG.

From the above results, the purified product obtained was 4'-
It was identified to be nitrophenyl-n-propylcarbohydrazide (Exemplified compound (3)). When the SHG intensity was measured in the same manner as in Example 1 using the obtained powder of the compound (3), the SHG intensity of this powder was 12.1 times the SHG intensity of the urea powder measured in the same manner. there were.

Then, a single crystal of the compound (3) was prepared in the same manner as in Example 1, and a single crystal having a size of 10 × 6 × 4 mm ³ was obtained. When X-ray structural analysis was performed on the thus obtained single crystal of the compound (3), the space group belongs to the orthorhombic system (P2 ₁ 2 ₁ 2 ₁ ) and the lattice constant is a = 12.43 Angstrom, b = 1
It was 9.46 angstroms and c = 4.67 angstroms.

Further, when SH light intensity was measured using the single crystal obtained in the same manner as in Example 1, it was 3.5 times larger than that in the case of using the KTP crystal (sample length: 5 mm). The value was shown.

[0080]

Example 3 50 ml of dichloromethane and 0.77 g of p-nitrophenylhydrazine were placed in a 300 ml three-necked flask, 2.5 cc of pyridine was added with stirring at room temperature, and then trimethylacetyl chloride dissolved in dichloromethane in advance. When 0.9 cc was slowly dropped from the dropping funnel, a yellow precipitate was immediately deposited. After stirring this reaction solution for another 12 hours at room temperature, after confirming the completion of the reaction by thin layer chromatography, the excess trimethylacetyl chloride was hydrolyzed, and then an aqueous NaHCO ₃ solution was added to increase the amount of the aqueous phase and the reaction product. Was separated from the oil phase contained in. Dichloromethane was added to the obtained aqueous phase, and the reaction product remaining in the aqueous phase was extracted and recovered in dichloromethane, the dichloromethane containing the reaction product was mixed with the oil phase, and the mixed solution was dried under vacuum. .. The reaction product thus obtained was developed by column chromatography using acetone / dichloromethane (volume ratio 1/4) as a developing solution. The main component thus separated by column chromatography was reprecipitated with acetone to obtain 0.426 g of a purified product.

The melting point of the purified product obtained by the DSC method was 166 to 167 ° C. In addition, this purified product is D
This solution was dissolved in MSO (dimethyl sulfoxide) and the ¹ H nuclear magnetic resonance spectrum of this purified product was measured using this solution. The chart of the obtained ¹ H nuclear magnetic resonance spectrum is shown in FIG.

Analysis of the peaks in this chart revealed the following. ¹ H nuclear magnetic resonance (δppm) 1.21 (s, 9H , - (CH 3) 3) 6.71 (d, 2H, 9Hz, ring proton) 8.08 (d, 2H, 9Hz, ring proton) 8 .96 (s, 1H, -NH-) 9.79 (s, 1H, -NH-) Further, the infrared absorption spectrum of this purified product was measured.
The chart of the obtained infrared absorption spectrum is shown in FIG.

From the above results, the purified product obtained was 4'-
It was identified to be nitrophenyl-t-butylcarbohydrazide (the exemplified compound (5)). When the SHG intensity of the obtained powder of compound (5) was measured in the same manner as in Example 1, the SHG intensity of this powder was 1.0 times the SHG intensity of the urea powder measured in the same manner. there were.

Then, a single crystal of the compound (5) was prepared in the same manner as in Example, and a single crystal having a size of 5 × 3 × 1 mm ³ was obtained. Further, when SH light intensity was measured using the single crystal obtained in the same manner as in Example 1, it showed a value 0.5 times as compared with the case of using the KTP crystal (sample length: 5 mm). It was

[0085]

Example 4 100 ml of dichloromethane and 0.77 g of p-nitrophenylhydrazine were placed in a 300 ml three-necked flask, and 2.50 cc of pyridine was added thereto with stirring at room temperature, and then methyl chloroformate of 0.20 was diluted with dichloromethane.
When 8 cc was slowly dropped from the dropping funnel, precipitation of a yellow precipitate was observed as the reaction proceeded. After stirring this reaction solution at room temperature for another 12 hours, after confirming the completion of the reaction by thin-layer chromatography, excess methyl chloroformate was hydrolyzed, and then an aqueous NaHCO ₃ solution was added to add a large amount of the aqueous phase and the reaction product. Was separated from the oil phase contained in. Dichloromethane was added to the obtained aqueous phase, and the reaction product remaining in the aqueous phase was extracted and recovered in dichloromethane, the dichloromethane containing the reaction product was mixed with the oil phase, and the mixed solution was dried under vacuum. .. The reaction product thus obtained is reprecipitated with acetone / dichloromethane to give
36 g of purified product was obtained.

The melting point of this purified product obtained by the DSC method was 180 to 181 ° C. Further, as a result of measuring the mass spectrum of this purified product, m / z was 211 (10
It was 0).

The purified product was dissolved in DMSO (dimethyl sulfoxide), and this solution was used to prepare the purified product.
¹ H nuclear magnetic resonance spectrum was measured. The chart of the obtained ¹ H nuclear magnetic resonance spectrum is shown in FIG. 10.

Analysis of the peaks in this chart revealed the following. ¹ H nuclear magnetic resonance (δ ppm) 3.61 (s, 3H, —OCH ₃ ) 6.84 (d, 2H, 9 Hz, ring proton) 8.08 (d, 2H, 9 Hz, ring proton) 9.00 ( s, 1H, -NH-) 9.45 (s, 1H, -NH-) Further, the infrared absorption spectrum of this purified product was measured.
The chart of the obtained infrared absorption spectrum is shown in FIG.

From the above results, the obtained purified product was identified as methyl-3- (p-nitrophenyl) carbazate (the exemplified compound (7)). When the SHG intensity of the obtained powder of compound (7) was measured in the same manner as in Example 1, the SHG intensity of this powder was 19.5 times the SHG intensity of the urea powder measured in the same manner. there were.

Then, a single crystal of the above compound (7) was prepared in the same manner as in Example 1. It was 30 × 12 × 6 mm ^3.
A single crystal with a size of When the X-ray structural analysis was performed on the single crystal of the compound (7) thus obtained, the space group belongs to the orthorhombic system (P2 ₁ 2 ₁ 2 ₁ ) and
The lattice constant is a = 11.48 angstrom, b = 1
It was 8.51 angstrom and c = 4.701 angstrom.

Further, when SH light intensity was measured using the single crystal obtained in the same manner as in Example 1, a value four times larger than that in the case of using the KTP crystal (sample length: 5 mm) was obtained. Indicated.

[0092]

EXAMPLE 5 100 ml of dichloromethane and 0.77 g of p-nitrophenylhydrazine were placed in a 300 ml three-necked flask, and 2.50 cc of pyridine was added with stirring at room temperature, and then ethyl chloroformate was diluted with dichloromethane.
When 00cc was slowly dropped from the dropping funnel, precipitation of a yellow precipitate was observed as the reaction proceeded. After stirring this reaction solution at room temperature for another 12 hours, after confirming the completion of the reaction by thin-layer chromatography, excess ethyl chloroformate was hydrolyzed, and then an aqueous NaHCO ₃ solution was added to increase the amount of the aqueous phase and the reaction product. Was separated from the oil phase contained in. Dichloromethane was added to the obtained aqueous phase, and the reaction product remaining in the aqueous phase was extracted and recovered in dichloromethane, the dichloromethane containing the reaction product was mixed with the oil phase, and the mixed solution was dried under vacuum. .. By reprecipitating the reaction product thus obtained with acetone / dichloromethane,
0.56 g of purified product was obtained.

The melting point of this purified product obtained by the DSC method was 200 to 201 ° C. Further, as a result of measuring the mass spectrum of this purified product, m / z was 225 (10
It was 0).

The purified product was dissolved in DMSO (dimethyl sulfoxide), and this solution was used to prepare the purified product.
¹ H nuclear magnetic resonance spectrum was measured. The chart of the obtained ¹ H nuclear magnetic resonance spectrum is shown in FIG.

Analysis of the peaks in this chart revealed the following. ¹ H nuclear magnetic resonance (δ ppm) 1.20 (s, 3H, —CH ₃ ) 4.09 (s, 2H, —OCH ₂ —) 6.72 (d, 2H, 9 Hz, ring proton) 8.08 ( d, 2H, 9 Hz, ring proton) 8.98 (s, 1H, -NH-) 9.39 (s, 1H, -NH-) Further, the infrared absorption spectrum of this purified product was measured.
The chart of the obtained infrared absorption spectrum is shown in FIG.

From the above results, the obtained purified product was identified as ethyl-3- (p-nitrophenyl) carbazate (the exemplified compound (8)). When the SHG intensity was measured in the same manner as in Example 1 using the obtained powder of the compound (8), the SHG intensity of this powder was 1.0 times the SHG intensity of the urea powder measured in the same manner. there were.

Then, a single crystal of the compound (8) was prepared in the same manner as in Example, and a single crystal having a size of 5 × 3 × 1 mm ³ was obtained. Further, when SH light intensity was measured using the single crystal obtained in the same manner as in Example 1, it showed a value of 0.5 as compared with the case of using the KTP crystal (sample length: 5 mm). ..

[0098]

Example 6 50 ml of dichloromethane and 0.71 g of p-nitrophenylhydrazine were placed in a 200 ml two-necked flask, 2.5 cc of pyridine was added with stirring at room temperature, and then chloroformic acid n dissolved in dichloromethane in advance. -Propyl 0.8cc slowly dropped from the dropping funnel,
Precipitation of a yellow precipitate was observed as the reaction proceeded. After stirring this reaction solution for another 12 hours at room temperature, after confirming the completion of the reaction by thin layer chromatography, excess n-propyl chloroformate was hydrolyzed, and then an aqueous NaHCO ₃ solution was added to the aqueous phase and the reaction product. Was separated from the oil phase containing a large amount of. Dichloromethane was added to the obtained aqueous phase, and the reaction product remaining in the aqueous phase was extracted and recovered in dichloromethane, the dichloromethane containing the reaction product was mixed with the oil phase, and the mixed solution was dried under vacuum. .. The reaction product thus obtained was reprecipitated with acetone / dichloromethane to obtain 0.35 g of a purified product.

The melting point of this purified product obtained by the DSC method was 125-126 ° C. In addition, this purified product is D
This solution was dissolved in MSO (dimethyl sulfoxide) and the ¹ H nuclear magnetic resonance spectrum of this purified product was measured using this solution. The chart of the obtained ¹ H nuclear magnetic resonance spectrum is shown in FIG. 14.

Analysis of the peaks in this chart revealed the following. ¹ H nuclear magnetic resonance (δppm) 0.98 (s, 3H, -CH ₃ ) 1.59 (s, 2H, -CH _2- ) 4.0 (t, 2H, 7Hz, -OCH _2- ) 6. 72 (d, 2H, 9Hz, ring proton) 8.08 (d, 2H, 9Hz, ring proton) 8.98 (s, 1H, -NH-) 9.39 (s, 1H, -NH-) Further this The infrared absorption spectrum of the purified product was measured.
The chart of the obtained infrared absorption spectrum is shown in FIG.

From the above results, the obtained purified product was identified as n-propyl-3- (p-nitrophenyl) carbazate (the exemplified compound (9)). When the SHG intensity of the obtained powder of compound (9) was measured in the same manner as in Example 1, the SHG intensity of this powder was 2.6 times the SHG intensity of the urea powder measured in the same manner. there were.

Then, a single crystal of the compound (9) was prepared in the same manner as in Example, and 6 × 4 × 2.5 mm ³
A single crystal with a size of Further, when SH light intensity was measured using a single crystal obtained in the same manner as in Example 1, it showed a value 0.8 times that in the case of using a KTP crystal (sample length: 5 mm). It was

[0103]

Example 7 50 ml of dichloromethane and 4.62 g of p-nitrophenylhydrazine were placed in a 300 ml three-necked flask. After stirring at room temperature and further adding 5 cc of triethylamine, 4.5 cc of methoxyacetyl chloride was slowly added dropwise from a 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, hydrolysis was performed, and after washing with an aqueous NaHCO ₃ solution, the oil layer was separated, the aqueous layer was washed, and the aqueous layer was extracted with dichloromethane. The oil layers were combined and vacuum dried. Then, the crystals were recrystallized from acetone to obtain 5.735 g of 4'-nitrophenyl-methoxyacetylcarbohydrazide.

The melting point of the purified product obtained by the DSC method was 149 to 150 ° C. In addition, this purified product is D
This solution was dissolved in MSO (dimethyl sulfoxide) and the ¹ H nuclear magnetic resonance spectrum of this purified product was measured using this solution. The chart of the obtained ¹ H nuclear magnetic resonance spectrum is shown in FIG. 16.

The analysis of the peaks in this chart showed the following. ¹ H nuclear magnetic resonance (δ ppm) 4.02 (s, 2H, —CH ₂ —) 4.13 (s, 3H, —OCH ₃ ) 6.75 (d, 2H, 9 Hz, ring proton) 8.07 ( d, 2H, 9 Hz, ring proton) 9.03 (s, 1H, -NH-) 10.14 (s, 1H, -NH-) Further, the infrared absorption spectrum of this purified product was measured.
The chart of the obtained infrared absorption spectrum is shown in FIG.

From the above results, the purified product obtained was 4'-
It was identified as nitrophenyl-methoxyacetylcarbohydrazide (the exemplified compound (12)).

[0107]

EXAMPLE 8 50 ml of dichloromethane and 1.53 g of p-nitrophenylhydrazine are placed in a 300 ml three-necked flask. After stirring at room temperature and adding 3 cc of pyridine, 1.39 g of 3-methylthiopropionyl chloride previously dissolved in dichloromethane is slowly added dropwise from the dropping funnel. A yellow precipitate immediately precipitated. 12
After stirring at room temperature for an hour, after confirming the completion of the reaction by thin layer chromatography, hydrolyzing and washing with an aqueous NaHCO ₃ solution, the oil layer was separated, washed with water, the aqueous layer was extracted with dichloromethane, and the oil layer was extracted. Together, they were vacuum dried. After that, recrystallization was performed with a mixed solvent of methylene chloride / hexane to give 4'-nitrophenyl-3-methylthiopropylcarbohydrazide 1.
91 g were obtained.

The melting point of the purified product obtained by the DSC method was 126 to 127 ° C. The purified product was dissolved in DMSO (dimethyl sulfoxide), and the ¹ H nuclear magnetic resonance spectrum of the purified product was measured using this solution. The chart of the obtained ¹ H nuclear magnetic resonance spectrum is shown in FIG.

Analysis of the peaks in this chart revealed the following. ¹ H nuclear magnetic resonance (δ ppm) 2.10 (s, 3H, —CH ₃ ) 2.51 (t, 2H, 11 Hz, —CH ₂ —) 2.73 (t, 2H, 13 Hz, —CH ₂ —) 6.79 (d, 2H, 9Hz, ring proton) 8.04 (d, 2H, 9Hz, ring proton) 9.07 (s, 1H, -NH-) 10.03 (s, 1H, -NH-) Further, the infrared absorption spectrum of this purified product was measured.
The obtained infrared absorption spectrum chart is shown in FIG.

From the above results, the purified product obtained was 4'-
It was identified to be nitrophenyl-methylthiopropylcarbohydrazide (Exemplified compound (15)).

[Brief description of drawings]

FIG. 1 is a drawing for explaining an example of an apparatus using a nonlinear optical element according to the present invention.

FIG. 2 is a drawing for explaining an example of an apparatus using a nonlinear optical element according to the present invention.

FIG. 3 is a drawing for explaining an example of an apparatus using the nonlinear optical element according to the present invention.

FIG. 4 is a novel hydrazine compound according to the present invention, 4 ′.
^{1 is} a ¹ H nuclear magnetic resonance spectrum chart of -nitrophenyl-ethylcarbohydrazide.

FIG. 5: 4 ′, a novel hydrazine compound according to the present invention
2 is an infrared absorption spectrum chart of -nitrophenyl-ethylcarbohydrazide.

FIG. 6 is a novel hydrazine compound according to the present invention, 4 ′.
^{1 is} a ¹ H nuclear magnetic resonance spectrum chart of -nitrophenyl-n-propylcarbohydrazide.

FIG. 7: 4 ′, a novel hydrazine compound according to the present invention
2 is an infrared absorption spectrum chart of -nitrophenyl-n-propylcarbohydrazide.

FIG. 8: 4 ′, a novel hydrazine compound according to the present invention
^{1 is} a ¹ H nuclear magnetic resonance spectrum chart of -nitrophenyl-t-butylcarbohydrazide.

FIG. 9: 4 ′, a novel hydrazine compound according to the present invention
2 is an infrared absorption spectrum chart of -nitrophenyl-t-butylcarbohydrazide.

FIG. 10 is a ¹ H nuclear magnetic resonance spectrum chart of methyl-3- (p-nitrophenyl) carbazate, which is a novel hydrazine compound according to the present invention.

FIG. 11 is an infrared absorption spectrum chart of methyl-3- (p-nitrophenyl) carbazate, which is a novel hydrazine compound according to the present invention.

FIG. 12 is a ¹ H nuclear magnetic resonance spectrum chart of ethyl-3- (p-nitrophenyl) carbazate, which is a novel hydrazine compound according to the present invention.

FIG. 13 is an infrared absorption spectrum chart of ethyl-3- (p-nitrophenyl) carbazate, which is a novel hydrazine compound according to the present invention.

FIG. 14 is a novel hydrazine compound according to the present invention.
¹ H of n-propyl-3- (p-nitrophenyl) carbazate
It is a nuclear magnetic resonance spectrum chart.

FIG. 15 is a novel hydrazine compound according to the present invention.
3 is an infrared absorption spectrum chart of n-propyl-3- (p-nitrophenyl) carbazate.

FIG. 16 is a novel hydrazine compound according to the present invention.
^{1 is} a ¹ H nuclear magnetic resonance spectrum chart of 4′-nitrophenyl-methoxyacetylcarbohydrazide.

FIG. 17 is a novel hydrazine compound according to the present invention.
3 is an infrared absorption spectrum chart of 4′-nitrophenyl-methoxyacetylcarbohydrazide.

FIG. 18 is a novel hydrazine compound according to the present invention.
^{1 is} a ¹ H nuclear magnetic resonance spectrum chart of 4′-nitrophenyl-methylthiopropylcarbohydrazide.

FIG. 19 is a novel hydrazine compound according to the present invention.
3 is an infrared absorption spectrum chart of 4′-nitrophenyl-methylthiopropylcarbohydrazide.

[Explanation of symbols]

 10, 20 ... Second harmonic generation device 30 ... Optical modulation device 11, 21, 31 ... Laser light source 12, 14, 22, 32 ... Condensing lens 13 ... Non-linear optical element 15・ ・ ・ Infrared cut filter 23 ・ ・ ・ Core material 24 ・ ・ ・ Clad material 33 ・ ・ ・ Waveguide 34 ・ ・ ・ Substrate 35 ・ ・ ・ Electrode

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C07C 323/60 7419-4H C09K 9/02 B 6917-4H G02F 1/35 504 7246-2K

Claims (9)

[Claims] 1. A compound represented by the general formula (I): (In the formula, A is an acceptor substituent, Φ ₁ is an aromatic ring or a heterocycle, and R _{1 to} R ₃ are each independently a hydrogen atom or an alkyl group, an aryl group, an aralkyl group, and an alkyloxy group. R ₄ is a hydrogen atom or a group selected from the group consisting of an alkyl group, an alkenyl group and a phenyl group, and R ₄ is a group selected from the group consisting of:
_{When 4} is an alkyl group or an alkenyl group, the alkyl group or alkenyl group may have a hydroxyl group and / or a halogen atom, and between two adjacent carbon atoms in the alkyl group or the alkenyl group. May have a divalent heteroatom or a divalent group containing a heteroatom, B is a direct bond or an oxygen atom, and i and j are integers of 1 or more. ) A hydrazine compound represented by. 2. A compound represented by the general formula (II): (In the formula, B is a direct bond or an oxygen atom, and R is an alkyl group having 1 to 4 carbon atoms.) The hydrazine compound according to claim 1. 3. A compound represented by the general formula (III): (In the formula, A is an acceptor substituent, Φ ₁ is an aromatic ring or a heterocycle, and R _{1 to} R ₃ are each independently a hydrogen atom or an alkyl group, an aryl group, an aralkyl group, and an alkyloxy group. a group selected from the group consisting of the i and j is an integer of 1 or more. with hydrazine compounds represented by), the general formula (IV) X-CO-B -R 4 ... (IV) ( in the formula, R ₄ is a hydrogen atom or a group selected from the group consisting of an alkyl group, an alkenyl group and a phenyl group,
When R ₄ is an alkyl group or an alkenyl group, the alkyl group or the alkenyl group may have a hydroxyl group and / or a halogen atom, and between two adjacent carbon atoms in the alkyl group or the alkenyl group. Is 2
A valent heteroatom or a divalent group containing a heteroatom may be present, B is a direct bond or is an oxygen atom and X is a halogen atom. ) With an acid halide represented by the general formula (I) (In the formula, A, Φ ₁ , R _{1 to} R ₄ , B, i and j have the same meanings as described above.) A process for producing a hydrazine compound represented by the formula. 4. A compound represented by the general formula (I): In the formula, A is an acceptor substituent, Φ ₁ is an aromatic ring or a heterocycle, and R _{1 to} R ₃ are each independently a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an alkyloxy group. comprising a group selected from the group, R ₄ is a group selected from the group consisting of a hydrogen atom or an alkyl group, alkenyl group and phenyl group, R ₄
Is an alkyl group or an alkenyl group, the alkyl group or alkenyl group may have a hydroxyl group and / or a halogen atom, and between the two adjacent carbon atoms in the alkyl group or the alkenyl group, A divalent heteroatom or a divalent group containing a heteroatom may be present, B is a direct bond or is an oxygen atom and i and j are integers of 1 or greater. ) An organic nonlinear optical material comprising a hydrazine compound represented by 5. The organic nonlinear optical material according to claim 4, wherein Φ ₁ is a benzene ring or a 5-membered heterocyclic ring. 6. Φ ₁ is a benzene ring, and A is −
The organic nonlinear optical material according to claim 5, which is bonded to a para position of Φ ₁ with respect to NR ₂ NR ₃ CO-. 7. The organic nonlinear optical material according to claim 4, wherein R ₂ and / or R ₃ is an optically active group. 8. The organic nonlinear optical material according to claim 4, wherein the hydrazine compound represented by the formula (I) has at least one deuterium. 9. A nonlinear optical element comprising the organic nonlinear optical material according to claim 4.