JP2672363B2 - Organic nonlinear optical material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an optical switch, an optical memory used in optical data / information processing or an optical communication system, or an optical bistable element used for optical signal arithmetic processing. The present invention relates to a novel nonlinear optical material having an increased second harmonic generation ability.

Specifically, it relates to a material comprising a salt obtained by reacting an α-cyanocarboxylic acid having a conjugated double bond with an optically active amine.

{Prior Art} The nonlinear optical effect means that when a strong photoelectric field such as laser light is applied to a substance, the electric polarization response of the substance is simply linearly proportional to the magnitude of the applied electric field. It means that the higher-order effect of the size of 2nd or higher appears.

The second-order nonlinear optical effect includes the generation of the second harmonic that converts the wavelength of the incident light by half, the parametric oscillation that converts light of one type into two types of light, and conversely two types of wavelength. Secondary light mixing that emits light of one type of wavelength from
and so on. From these characteristics, materials having a non-linear optical effect will be used in the future as optical switches, optical memories used in optical data / information processing and optical communication systems, or optical bistable elements used in optical signal arithmetic processing. It may be used as a device such as an optical switch.

Generally, in this field, inorganic materials centered on LiNbO ₃ have been studied and studied, but the inorganic materials have a not so large figure of merit, a low response speed, poor morphological processability, and hygroscopicity. However, there is a drawback in that it is difficult to form a desired optical element due to the difficulty of being large.

In recent years, the application of organic substances has become interested in these inorganic materials. It has been confirmed and reported that this is because the response of organic matter mainly complies with π-electron polarization, so that the nonlinear effect is large and the response speed is also large. For example, AC S Symposium Series Volume 233 (ACS Symposium Series Vol.233, 1983) edited by Shemura and Jiss, Non-Linear Optical Materials of Organic Molecules.
And Crystals (Nonlinear Optical Properties)
of Organic Molecules and Crystals, DSChemla, and
J. Zyss edited, Academic Press. 1987) has reported many research examples. The second-order nonlinear optical characteristic which is a main problem in the present invention is a tensor of the third order, and therefore does not become apparent when a symmetry center exists in a molecule or a crystal. For this reason, in the case of an organic substance, in order to use the second harmonic generation as a practical form, even if it has a structure that exhibits a large nonlinear optical effect at the molecular level,
It must be made into a crystal or solid state, but in such a solidification stage, an inversion symmetric structure is often formed preferentially, and as a result, the nonlinear optical effect does not appear as an optical element. was there.

{Objective} The main object of the present invention is to provide a crystalline compound for various nonlinear optical elements, which has an increased second harmonic generation ability, a high molecular polarization ability and no inversion symmetry. It is in.

{Disclosure of the Invention} Generally, the second harmonic generation capability increases as the conjugated system has a large polarization in the molecule and the contribution of the polarization increases. However, the longer the conjugation length, the longer the absorption maximum becomes. It shifts to the side, and it corresponds to 1/2 wavelength of the incident light. At that time, the generated second harmonic may be absorbed and may be burned due to light damage with a change in refractive index, chemical modification, or absorption of heat energy. Therefore, simply increasing the conjugate length is often not advantageous.

Therefore, as a result of intensive studies by the inventors, as shown in the following general formula (I), a carboxyl group on the same carbon,
A group having a high electron absorption property such as a cyano group and a double bond conjugated chain of an appropriate length are used to increase the dipole moment, and an aromatic or aliphatic group is appropriately introduced at the other end of the conjugated bond. Therefore, it was found that it is possible to increase the polarity. For example, when benzene is used as an aromatic group and various substituents are introduced into the benzene nucleus, the above-mentioned various effects are synergized, resulting in a compound with increased molecular polarization, and transfer of electron configuration in the ring. As a result of the effect, a large non-linearity is expected.

Moreover, by appropriately selecting the conjugation length, for example, optical damage due to absorption of the second harmonic light, or physical or chemical damage can be suppressed low.

However, in reality, due to the magnitude of the molecular polarization and the result of the effect of hydrogen bonding between the carboxylic acids, the structure has an inversion symmetry center, and the generation of the second harmonic is often not observed. In general, it is difficult to control the crystal structure, and it is particularly difficult to produce a crystal that breaks the center of symmetry. Therefore, although it is predicted that the material has a large nonlinear susceptibility at the molecular level, there are many cases where the material is not effective as the second harmonic generation material.

As a result of earnest studies, the present inventor has used an optically active amine as a basic substance in the above-mentioned highly polarized carboxylic acid to introduce the optically active asymmetric structure as a carboxylic acid salt or an optically active amine as an amide derivative. As a result of the introduction, they have found that a structure having no center of inversion symmetry can be created, and have reached the present invention. As a result, a large non-linear susceptibility at the molecular level can be expressed as it is as a crystal structure, and it is considered that the contribution to the application to the present technical field is great.

That is, the present invention relates to a non-linear optical material represented by the general formula (I).

Here, R ¹ is -H or -CH ₃ ; n is an integer of 0, 1, 2, and A
Is Z ¹ -Ar-, Is shown.

Ar represents an aromatic group having 6 to 14 carbon atoms, Z ¹ is H-, R ⁵ R
⁶ N−, R ⁷ O−, R ⁸ S−, NC−, R ⁹ OCO−, R ¹⁰ COO−, O ₂ N−, R ¹¹ R
¹² NOC−, R ¹³ CO (R ¹⁴ ) N−, or R ¹⁵ −;

At least one of Z ² , Z ³ and Z ⁴ represents —H, and the rest are each independently a C _{1 to} C ₁₀ alkyl group, R ¹⁶ O—, R ¹⁷ R ¹⁸ N, R ¹⁹ S—, O. ₂ N
-Or two R ¹⁶ represent a group connected to O by R ²⁰ CH.

In the formula, R ² represents H- or a C _{1 to} C ₁₂ alkyl group,
^{5 to} R ²⁰ represent H- or a C _{1 to} C ₁₀ hydrocarbon group.

Z ⁵ are, H-, alkyl _{C 1 ~C 8, O 2 N-} , R 21 O-, R 22 S-, NC-, or indicating the kind of R ²³ R ²⁴ N-.

R ²¹ to R ²⁴ represent H- or a C _{1 to} C ₁₀ hydrocarbon group.

X represents -S-, -O-, NR ²⁸ , and r is 0, 1,
R ²⁸ an integer of 2, 3 is a hydrocarbon group of H-, or C ₁ -C _10.

B is represented by -OH / optically active amine, or -NR ⁴ Y.

Here, R ⁴ represents hydrogen or a single bond, and Y is-(CH _{2 p}
CQ ¹ Q ² Q ³ , where p is 0 or 1, Q ¹ , Q ² and Q ³ are different from each other, and are —H, C _{1 to} C ₅ alkyl groups, phenyl groups, naphthyl groups, —OH, —CH. ₂ OH, -COOR ²⁵ , -CNR ²⁶ R ²⁷ , (R ^{25 to} R ²⁷ represent -H or C _{1 to} C ₈ hydrocarbon group); or a residue obtained by removing an amino group from an α-amino acid skeleton Or -CQ ⁴ Q ⁵ Q ⁶
And Q ⁴ and Q ⁵ are the same as Q ¹ , Q ² and Q ^3, and Q ⁶ _is- (CH _{2 1-4}
Indicates that one bond is connected to R ⁴ .

Of the basic skeleton of the compound group (I), The residue can be shown by being divided into the following residues (II) to (VI).

General formula (II) In the general formula (II), R ¹ is H, Z ¹ is R ⁵ R ⁶ N, R ⁷ O−, R ⁸ S
−, NC−, O ₂ N−, R ⁹ OCO−, R ¹⁰ COO−, R ¹¹ R ¹² NOC−, R ¹³ CO
(R ¹⁴⁾ N-, or ^{R 15 -, (R 5 ~R} 15 is hydrogen or C ₁ -C
₂₀ hydrocarbon groups), and Ar is an aromatic group containing C _{5 to} C ₁₄ carbons. These functional groups amplify the polarization within the molecular structure and contribute to the increase in the second harmonic generation ability.
From this viewpoint, the substitution position is 1,4 with respect to -CH = CH-.
It is most desirable to have the p-position or the peri-position like the 2, 6-position, but the substitution position is not always effective as long as it has the effect of increasing polarization.

Examples of the carboxylic acid having such a residue (II) as a basic skeleton include 3-phenyl-2-cyanopropenoic acid, 3- (p-dimethylaminophenyl) -2-cyanopropenoic acid, 3-
(P-Aminophenyl) -2-cyanopropenoic acid, 3-
(P-Diethylaminophenyl) -2-cyanopropenoic acid, 3- (p-dipropylaminophenyl) -2-cyanopropenoic acid, 3- (p-dibutylaminophenyl)-
2-cyanopropenoic acid, 3- (p-monomethylaminophenyl) -2-cyanopropenoic acid, 3- (p-monoethylaminophenyl) -2-cyanopropenoic acid, and m-, o-substituted derivatives thereof , 3- (p-methoxyphenyl) -2-cyanopropenoic acid, 3- (p-ethoxyphenyl) -2-cyanopropenoic acid, 3- (p-propyloxyphenyl) -2-cyanopropenoic acid, 3- ( p-butyloxyphenyl) -2
-Cyanopropenoic acid, 3- (p-pentyloxyphenyl) -2-cyanopropenoic acid, 3- (pn-hexyloxyphenyl) -2-cyanopropenoic acid, 3- (p-
Decanoxyphenyl) -2-cyanopropenoic acid, and their m-, o-substituted derivatives, 3- (p-methylthiophenyl) -2-cyanopropenoic acid, 3- (p-ethylthiophenyl) -2 -Cyanopropenoic acid, 3- (p-propylthiophenyl) -2-cyanopropenoic acid, 3- (p-butylthiophenyl) -2
-Cyanopropenoic acid, 3- (pn-pentylthiophenyl) -2-cyanopropenoic acid, 3- (pn-hexylthiophenyl) -2-cyanopropenoic acid, 3- (p-
Decanethiophenyl) -2-cyanopropenoic acid, and their m-, o-substituted derivatives, 3- (p-cyanophenyl) -2-cyanopropenoic acid, 3- (m-cyanophenyl) -2-cyano Propenoic acid, 3- (o-cyanophenyl) -2-cyanopropenoic acid, 3- (p-methyloxyphenyl) -2-cyanopropenoic acid, 3- (p-ethyloxyphenyl) -2-cyanopropenoic acid, 3- (p-propyloxyphenyl)
2-Cyanopropenoic acid, and m-, o-substituted derivatives thereof, 3- (p-acetyloxyphenyl) -2-cyanopropenoic acid, 3- (p-propionyloxyphenyl)-
2-Cyanopropenoic acid, 3- (p-butanoyloxyphenyl) -2-cyanopropenoic acid, and their m
-, O-substituted derivative, 3- (p-nitrophenyl) -2-cyanopropenoic acid, 3- (m-nitrophenyl) -2-cyanopropenoic acid, 3- (o-nitrophenyl) -2-cyanopropene Acid, 3- (p-dimethylamidophenyl) -2-cyanopropenoic acid, 3- (p-diethylamidophenyl) -2
-Cyanopropenoic acid, 3- (p-dipropylamidophenyl) -2-cyanopropenoic acid, 3- (p-dibutylamidophenyl) -2-cyanopropenoic acid, and m-, o-substituted derivatives thereof, 3- (p-Atylaminophenyl) -2-cyanopropenoic acid, 3- (p-propionylaminophenyl) -2
-Cyanopropenoic acid, and m-, o-substituted derivatives thereof, 3- (p-methylphenyl) -2-cyanopropenoic acid, 3- (p-ethylphenyl) -2-cyanopropenoic acid, 3- ( p-Propylphenyl) -2-cyanopropenoic acid, 3- (p-butylphenyl) -2-cyanopropenoic acid, 3- (pn-pentylphenyl) -2-cyanopropenoic acid, 3- (pn) -Hexylphenyl) -2-
Cyanopropenoic acid, 3- (p-decanephenyl) -2-
Cyanopropenoic acid, and substituted phenyl 2-cyanopropenoic acid derivatives represented by m-, o-substituted derivatives thereof, 2-cyano-5-phenyl 2,4-pentadienoic acid, 2
-Cyano-5- (p-dimethylaminophenyl) -2,4
-Pentadienoic acid, 2-cyano-5- (p-diethylaminophenyl) -2,4-pentadienoic acid, -cyano-5
-(P-dipropylaminophenyl) -2,4-pentadienoic acid, 2-cyano-5- (p-dibutylaminophenyl) -2,4-pentadienoic acid, 2-cyano-5- (p-
Monomethylaminophenyl) -2,4-pentadienoic acid,
2-Cyano-5- (p-aminophenyl) -2,4-pentadienoic acid and their m-, o-substituted derivatives, 2-cyano-5- (p-methyloxyphenyl) -2,
4-pentadienoic acid, 2-cyano-5- (p-ethyloxyphenyl) -2,4-pentadienoic acid, 2-cyano-
5- (p-propyloxyphenyl) -2,4-pentadienoic acid, 2-cyano-5- (p-butyloxyphenyl) -2,4-pentadienoic acid, and their m-, o-
Substituted derivative, 2-cyano-5- (p-methylthiophenyl) -2,4
-Pentadienoic acid, 2-cyano-5- (p-ethylthiophenyl) -2,4-pentadienoic acid, 2-cyano-5-
(P-Propylthiophenyl) -2,4-pentadienoic acid, 2-cyano-5- (p-butylthiophenyl) -2,
4-pentadienoic acid and m-, o-substituted derivatives thereof, 2-cyano-5- (p-cyanophenyl) -2,4-pentadienoic acid, and m-, o-substituted derivatives thereof, 2. -Cyano-5- (p-methyloxycarbonylphenyl) -2,4-pentadienoic acid, 2-cyano-5- (p
-Ethyloxycarbonylphenyl) -2,4-pentadienoic acid, 2-cyano-5- (p-propyloxycarbonylphenyl) -2,4-pentadienoic acid, 2-cyano-
5- (p-butyloxycarbonylphenyl) -2,4-
Pentadienoic acid and m-, o-substituted derivatives thereof, 2-cyano-5- (p-nitrophenyl) -2,4-pentadienoic acid, and m-, o-substituted derivatives thereof, 2-cyano -5- (p-dimethylamidophenyl)-
2,4-pentadienoic acid, 2-cyano-5- (p-diethylamidophenyl) -2,4-pentadienoic acid, 2-cyano-5- (p-dipropylamidophenyl) -2,4-pentadienoic acid, 2 -Cyano-5- (p-dibutylamidophenyl) -2,4-pentadienoic acid, 2-cyano-5-
(P-Monomethylamidophenyl) -2,4-pentadienoic acid, 2-cyano-5- (p-amidophenyl) -2,4
-Pentadienoic acid, and m-, o-substituted derivatives thereof, 2-cyano-5- (p-acetylaminophenyl)-
2,4-Pentadienoic acid, 2-cyano-5- (p-propionylaminophenyl) -2,4-pentadienoic acid, and m-, o-substituted derivatives thereof, 2-cyano-5- (p-methyl) Phenyl) -2,4-pentadienoic acid, 2-cyano-5- (p-ethylphenyl) -2,4-pentadienoic acid, 2-cyano-5- (p-
Propylphenyl) -2,4-pentadienoic acid, 2-cyano-5- (p-butylphenyl) -2,4-pentadienoic acid, and m-, o-substituted derivatives thereof, substituted phenyl 2- Cyano-2,4-pentadienoic acid derivative, 2-cyano-7-phenyl-2,4,6-heptatrienoic acid, 2-cyano-7- (p-dimethylaminophenyl)
-2,4,6-heptatrienoic acid, 2-cyano-7- (p-
Diethylaminophenyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (p-dipropylaminophenyl) -2,4,6-heptatrienoic acid, 2-cyano-7-
(P-Dibutylaminophenyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (p-monomethylaminophenyl) -2,4,6-heptatrienoic acid, and their m
-, O-substituted derivative, 2-cyano-7- (p-methyloxyphenyl) -2,
4,6-heptatrienoic acid, 2-cyano-7- (p-ethyloxyphenyl) -2,4,6-heptatrienoic acid, 2-
Cyano-7- (p-propyloxyphenyl) -2,4,6
-Heptatrienoic acid, 2-cyano-7- (p-butyloxyphenyl) -2,4,6-heptatrienoic acid, and m-, o-substituted derivatives thereof, 2-cyano-7- (p-methylthiophenyl) ) −2,4,
6-Heptatrienoic acid, 2-cyano-7- (p-ethylthiophenyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (p-propylthiophenyl) -2,4,6-heptatrienoic acid 2-Cyano-7- (p-butylthiophenyl) -2,4,6-heptatrienoic acid, and their m
-, O-substituted derivative, 2-cyano-7- (p-cyanophenyl) -2,4,6-
Heptatrienoic acid, and m-, o-substituted derivatives thereof, 2-cyano-7- (p-methyloxycarbonylphenyl) -2,4,6-heptatrienoic acid, 2-cyano-7-
(P-ethyloxycarbonylphenyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (p-propyloxycarbonylphenyl) -2,4,6-heptatrienoic acid,
2-Cyano-7- (p-butyloxycarbonylphenyl) -2,4,6-heptatrienoic acid and their m-,
o-Substituted derivative, 2-cyano-7- (p-acetyloxyphenyl)-
2,4,6-Heptatrienoic acid, 2-cyano-7- (p-propionyloxyphenyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (p-butanoyloxyphenyl) -2,4 , 6-heptatrienoic acid and their m-,
o-substituted derivative, 2-cyano-7- (p-dimethylamidophenyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (p-diethylamidophenyl) -2,4,6-heptatrienoic acid, 2-Cyano-7- (p-dipropylamidophenyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (p-dibutylamidophenyl) -2,4,6-heptatrienoic acid, 2-cyano -7- (p-monomethylamidophenyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (p-monoethylamidophenyl) -2,4,6-heptatrienoic acid, and their m- , o-Substituted derivative, 2-cyano-7- (p-nitrophenyl) -2,4,6-
Heptatrienoic acid, and m-, o-substituted derivatives thereof, 2-cyano-7- (p-methylphenyl) -2,4,6-
Heptatrienoic acid, 2-cyano-7- (p-ethylphenyl) -2,4,6-heptatrienoic acid, 2-cyano-7-
(P-Propylphenyl) -2,4,6-heptatrienoic acid, and m-, o-substituted derivatives thereof, and phenyl-substituted 2,4,6-heptatrienoic acid derivatives represented by

General formula (III) can be shown as a further preferred residue.

Here, Ar represents an aromatic group having 6 to 14 carbon atoms, and Z ² , Z
^At least one of ³ , Z ⁴ represents -H, and the rest independently H.
-, alkyl group of ^{_{C 1 ~C 8, R 16 O-}} , R 17 R 18 N-, R 19 S-, O 2 N
Indicates-.

As the carboxylic acid having such a residue (III) as a basic skeleton, 3- (3,4-dimethoxyphenyl) -2-cyanopropenoic acid, 3- (3,4-diethoxyphenyl) -2-cyanopropenoic acid, 3- (3,4-dipropyloxyphenyl) -1-cyanopropenoic acid, 3- (2,4-dimethoxyphenyl) -2-cyanopropenoic acid, 3- (2,4-diethoxyphenyl) -2- Cyanopropenoic acid, 3- (2,4
-Dipropyloxyphenyl) -2-cyanopropenoic acid, 3- (3,4-dimethylthiophenyl) -2-cyanopropenoic acid, 3- (3,4-diethylthiophenyl) -2
-Cyanopropenoic acid, 3- (3,4-dipropylthiophenyl) -2-cyanopropenoic acid, 3- (2,4-dimethylthiophenyl) -2-cyanopropenoic acid, 3- (2,4-
Diethyltoxoxyphenyl) -2-cyanopropenoic acid, 3
-(2,4-Dipropylthiophenyl) -2-cyanopropenoic acid, 3- (3,4-dimethylaminophenyl) -2-
Cyanopropenoic acid, 3- (3,4-diethylaminophenyl) -2-cyano-1-propenoic acid, 3- (3,4-dipropylaminophenyl) -2-cyanopropenoic acid, 3-
(2,4-dimethylphenyl) -2-cyanopropenoic acid,
3- (2,4-diethylaminophenyl) -2-cyanopropenoic acid, 3- (2,4-dipropylaminophenyl)-
2-cyanopropenoic acid, 3- (3,4-dinitrophenyl) -2-cyanopropenoic acid, 3- (2,4-dinitrophenyl) -2-cyanopropenoic acid, 5- (3,4-dimethoxyphenyl) -2-cyano-2,4-pentadienoic acid,
5- (3,4-diethoxyphenyl) -2-cyano-2,4-
Pentadienoic acid, 5- (3,4-dipropyloxyphenyl) -2-cyano-2,4-pentadienoic acid, 5- (2,4-
Dimethylthiophenyl) -2-cyano-2,4-pentadienoic acid, 5- (2,4-diethylthiophenyl) -2-cyano-2,4-pentadienoic acid, 5- (2,4-dipropylthiophenyl) ) -2-Cyano-2,4-pentadienoic acid, 5
-(3,4-Dimethylthiophenyl) -2-cyano-2,4-
Pentadienoic acid, 5- (3,4-diethylthiophenyl)
-2-Cyano-2,4-pentadienoic acid, 5- (3,4-dipropylthiophenyl) -2-cyano-2,4-pentadienoic acid, 5- (2,4-dimethylthiophenyl) -2- Cyano-2,4-pentadienoic acid, 5- (2,4-diethylthiophenyl) -2-cyano-2,4-pentadienoic acid, 5-
(2,4-dipropylthiophenyl) -2-cyano-2,4-
Pentadienoic acid, 5- (3,4-dinitrophenyl) -2
-Cyano-2,4-pentadienoic acid, 5- (2,4-dinitrophenyl) -2-cyano-2,4-pentadienoic acid, 7-
(3,4-Dimethoxyphenyl) -2-cyano-2,4,6-hexatrienoic acid, 7- (3,4-diethoxyphenyl)-
2-Cyano-2,4,6-hexatrienoic acid, 7- (3,4-dipropyloxyphenyl) -2-cyano-2,4,6-hexatrienoic acid, 7- (2,4-dimethylthio Phenyl)-
2-Cyano-2,4,6-hexatrienoic acid, 7- (2,4-diethylthiophenyl) -2-cyano-2,4,6-hexatrienoic acid, 7- (2,4-dipropylthio) Phenyl) -2
-Cyano-2,4,6-hexatrienoic acid, 7- (3,4-dimethylthiophenyl) -2-cyano-2,4,6-hexatrienoic acid, 7- (3,4-diethylthiophenyl) 2-Cyano-2,4,6-hexatrienoic acid, 6- (3,4-dipropylthiophenyl) -2-cyano-2,4,6-hexatrienoic acid, 7- (2,4-dimethyl Thiophenyl) -2-cyano-2,4,6-hexatrienoic acid, 7- (2,4-diethylthiophenyl) -2-cyano-2,4,6-hexatrienoic acid, 7- (2,4 -Dipropylthiophenyl) -2-cyano-2,4,6-hexatrienoic acid, 6- (3,4-dinitrophenyl) -2-cyano-2,4,6-hexatrienoic acid, 7
Examples include-(2,4-dinitrophenyl) -2-cyano-2,4,6-hexatrienoic acid.

 Another preferred residue is general formula (IV).

Here, Z ² represents H- or a C ₁ -C ₈ alkyl group,
Ar represents an aromatic group having 6 to 14 carbon atoms.

Examples of the carboxylic acid having the general skeleton of the general formula (IV) include 3- (3,4-dioxymethylenephenyl) -2-cyanopropenoic acid, 2-cyano-5- (3,4-dioxymethylenephenyl) -2,4-pentadienoic acid, 2-cyano-
7- (3,4-dioxymethylenephenyl) -2,4,6-heptatrienoic acid, 3- (3,4-dioxymethylene-6-propylphenyl) -2-cyanoprpenoic acid, 2-cyano- 5- (3,4-dioxymethylene-6-propylphenyl) -2,4-pentadienoic acid, 2-cyano-7- (3,4-
Dioxymethylene-6-propylphenyl) -2,4,6-
Mention may be made of piperonoyl derivatives such as heptatrienoic acid.

As another residue, general formula (V) can be shown.

Wherein, R ¹ represents H- or CH ₃ -, R ² represents an alkyl group of C ₁ -C _12.

Examples of the carboxylic acid include 3-phenyl-2-cyanopropenoic acid, 3- (n-propyl) -2-cyanopropenoic acid, 3- (ethyl) -2
-Cyanopropenoic acid, 3- (methyl) -2-cyanopropenoic acid, 3- (n-butyl) -2-cyanopropenoic acid,
3-Alkyl-substituted 2-cyanopropenoic acid derivative represented by 3- (n-pentyl) -2-cyanopropenoic acid 2-cyano-5-methyl-2,4-pentadienoic acid, 2
-Cyano-5- (n-propyl) -2,4-pentadienoic acid, 2-cyano-5- (n-butyl) -2,4-pentadienoic acid, 2-cyano-5- (n-pentyl) -2 , 4-pentadienoic acid, 2-cyano-5- (n-hexyl) -2,
5-Alkyl-substituted 2,4-pentadienoic acid derivative represented by 4-pentadienoic acid and 2-cyano-5- (n-heptyl) -2,4-pentadienoic acid 2-cyano-5-methyl-2,4-hexadiene Acid, 2
-Cyano-5- (n-propyl) -2,4-hexadienoic acid, 2-cyano-5- (n-butyl) -2,4-hexadienoic acid, 2-cyano-5- (n-pentyl) -2 , 4-hexadienoic acid, 2-cyano-5- (n-hexyl) -2,
4-hexadienoic acid, 5-cyano-5- (n-heptyl) -2,4-hexadienoic acid represented by 5-alkyl-substituted 2,4-hexadienoic acid derivative 2-cyano-7- (methyl) -2,4 , 6-Heptatrienoic acid, 2-cyano-7- (n-propyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (n-butyl) -2,
4,6-heptatrienoic acid, 2-cyano-7- (n-pentyl) -2,4,6-heptatrienoic acid, 2-cyano-7-
7-alkyl-substituted 2,4,6-heptatrienoic acid represented by (n-hexyl) -2,4,6-heptatrienoic acid and 2-cyano-7- (n-heptyl) -2,4,6-heptatrienoic acid Derivative 2-cyano-5- (methyl) -7- (methyl) -2,4,
6-heptatrienoic acid, 2-cyano-5- (methyl)-
7- (n-propyl) -2,4,6-heptatrienoic acid, 2
-Cyano-5- (methyl) -7- (n-butyl) -2,4,
6-heptatrienoic acid, 2-cyano-5- (methyl)-
7- (n-pentyl) -2,4,6-heptatrienoic acid, 2
-Cyano-5- (methyl) -7- (n-hexyl) -2,
4,6-heptatrienoic acid, 2-cyano-5- (methyl)
-7- (n-heptyl) -2,4,6-heptatrienoic acid represented by 7-alkyl, 5-methyl-2,4,6-heptatrienoic acid derivative, 2-cyano-7- (methyl) -2 , 4,6-octatrienoic acid, 2-cyano-7- (n-propyl) -2,4,6-octatrienoic acid, 2-cyano-7- (n-butyl) -2,
4,6-octatrienoic acid, 2-cyano-7- (n-pentyl) -2,4,6-octatrienoic acid, 2-cyano-7-
7-alkyl-substituted 2,4,6-represented by (n-hexyl) -2,4,6-octatrienoic acid and 2-cyano-7- (n-heptyl) -2,4,6-octatrienoic acid Examples thereof include octatrienoic acid derivatives.

Another preferred embodiment is a residue represented by the general formula (VI).

Here, Z ⁵ is an H-, C ₁ -C ₈ alkyl group, O ₂ N-, R ²¹ O.
−, R ²² S−, NC−, or R ²³ R ²⁴ N−. R ²¹
To R ²⁴ represent H-, or a C _{1 to} C ₁₀ hydrocarbon group.

X represents -S-, -O-, or one of NR ²⁸ , and R ²⁸ is H.
−, Or C _{1 to} C ₈ hydrocarbon group.

As a carboxylic acid having such a hetero group-containing residue (VI) as a basic skeleton, 3- (3-thienyl) -2-cyanopropenoic acid, 3-
(2-thienyl) -2-cyanopropenoic acid, 3- (3-
Pyrrolyl) -2-cyanopropenoic acid, 3- (3-furyl) -2-cyanopropenoic acid, 3- (2-furyl) -2
-Cyanopropenoic acid, 3- (2-indolyl) -2-cyanopropenoic acid, 3- (3-indolyl) -2-cyanopropenoic acid, 3- (N-methyl 3-pyrrolyl) -2-
Cyanopropenoic acid, 3- (N-methyl 2-pyrrolyl) -2-cyanopropenoic acid, 3- (N-ethyl 3-
Pyrrolyl) -2-cyanopropenoic acid, 3- (N-ethyl 2-pyrrolyl) -2-cyanopropenoic acid, 3- (N-
Butyl 3-pyrrolyl) -2-cyanopropenoic acid, 3-
(N-butyl 2-pyrrolyl) -2-cyanopropenoic acid, 3- (5-nitro 2-furyl) -2-cyanopropenoic acid, 3- (5-nitro 3-furyl) -2-cyanopropenoic acid, 3 -(5-Nitro 2-thienyl) -2-
Cyanopropenoic acid, 3- (5-nitro-3-thienyl)
2-Cyanopropenoic acid, 3- (5-chloro-3-indolyl) -2-cyanopropenoic acid, etc. 3- (hetero group-containing five-membered ring) -substituted 2-cyanopropenoic acids, 2-cyano-5- (3 -Thienyl) -2,4-pentadienoic acid, 2-cyano-5- (2-thienyl) -2,4-pentadienoic acid, 2-cyano-5- (2-pyrrolyl) -2,
4-pentadienoic acid, 2-cyano-5- (3-pyrrolyl) -2,4-pentadienoic acid, 2-cyano-5- (2-
Furyl) -2,4-pentadienoic acid, 2-cyano-5-
(3-furyl) -2,4-pentadienoic acid, 2-cyano-
5- (2-indolyl) -2,4-pentadienoic acid, 2-
Cyano-5- (3-indolyl) -2,4-pentadienoic acid, 2-cyano-5- (N-methyl 2-pyrrolyl)-
2,4-pentadienoic acid, 2-cyano-5- (N-ethyl-3-pyrrolyl) -2,4-pentadienoic acid, 2-cyano-5- (N-ethyl 2-pyrrolyl) -2,4-pentadienoic acid , 2-cyano-5- (N-butyl 3-pyrrolyl) -2,4-pentadienoic acid, 2-cyano-5- (N-
Butyl 2-pyrrolyl) -2,4-pentadienoic acid, 2-
Cyano-5- (5-nitro-2-furyl) -2,4-pentadienoic acid, 2-cyano-5- (5-nitro-3-furyl) -2,4-pentadienoic acid, 2-cyano-5- (5 −
Nitro 2-thienyl) -2,4-pentadienoic acid, 2-
5- (hetero group-containing penta) such as cyano-5- (5-nitro-3-thienyl) -2,4-pentadienoic acid and 2-cyano-5- (5-chloro-3-indolyl) -2,4-pentadienoic acid Membered ring) -substituted 2,4-pentadienoic acid derivative, 2-cyano-7- (3-thienyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (2-thienyl) -2,4,
6-Heptatrienoic acid, 2-cyano-7- (3-pyrrolyl) -2,4,6-heptatrienoic acid, 2-cyano-7-
(2-Pyrrolyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (3-furyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (2-furyl) -2, 4,6-heptatrienoic acid, 2-cyano-7- (3-indolyl) -2,
4,6-Heptatrienoic acid, 2-cyano-7- (2-indolyl) -2,4,6-heptatrienoic acid, 2-cyano-7
-(N-methyl 3-pyrrolyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (N-methyl 2-pyrrolyl) -2,4,6-heptatrienoic acid, 2-cyano-7-
(N-ethyl 3-pyrrolyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (N-ethyl 2-pyrrolyl)
-2,4,6-heptatrienoic acid, 2-cyano-7- (N-
Butyl 3-pyrrolyl) -2,4,6-heptatrienoic acid,
2-Cyano-7- (N-butyl 2-pyrrolyl) -2,4,
6-Heptatrienoic acid, 2-cyano-7- (5-nitro-2-furyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (5-nitro-3-furyl) -2,4,6- Heptatrienoic acid, 2-cyano-7- (5-nitro-2-thienyl) -2,4,6-heptatrienoic acid, 2-cyano-7-
7- represented by (5-nitro-3-thienyl) -2,4,6-heptatrienoic acid, 2-cyano-7- (5-chloro-3-indolyl) -2,4,6-heptatrienoic acid, etc.
(Hetero group-containing five-membered ring) Substituted-2,4,6-heptatrienoic acid derivative can be mentioned.

Such various carboxylic acid groups (A-1) to (A-
In any of 5), it is preferable that the mutual positions of the double bonds of these conjugated carboxylic acids are in the trans form in terms of structural stability and efficient expression of the nonlinear optical effect. It is not limited.

Examples of B in the present invention include those which show -OH / optically active amine salt.

Here, the optically active amine species are classified into the following three groups.

The optically active amines belonging to the group (B-1) include 1-phenylethylamine, 1-α-naphthylamine, 1-phenyl-2-methylethylamine, 1-phenyl-2-aminopropane and brucine.

The salt from this amine group has a considerably high SHG emission ability,
It has the advantage of easy moldability.

Further, as the optically active amines belonging to the group (B-2), 2-amino-1-butanol and 1-amino-2-
Propanol, 2-amino-1-propanol, 2-amino-1- (p-nitrophenyl) -1,3-propanediol, 2-dimethylamino-1-phenyl-1-benzyl-1-propanol, 1- ( There is N, N-dimethylamino) -1-phenyl-propylamine.

Salts from this amine group have the advantages of relatively high SHG emission ability and excellent resistance to laser light damage, and physical damage such as burning and carbonization even when exposed to laser light for a long time. Tend to be hard to receive.

As the optically active amine belonging to the third group (B-3), an optically active α-amino acid or an optically active α-amino acid derivative is suitably selected. The amino acid may be L-isomer or D-integrated so long as it is optically active.

The α-amino acid derivative used in the present invention has a carboxylic acid residue which is a hydrocarbon ester group having 1 to 20 carbon atoms, or a primary or secondary amide group of hydrocarbon having 1 to 20 carbon atoms. Is desirable. In particular, acidic amino acids have a plurality of carboxylic acid groups, so it is desirable to modify all of them. On the other hand, in a basic amino acid, since there are a plurality of amino groups capable of forming a salt with the above-mentioned conjugated carboxylic acid, a part of them may be modified with an amide group, an imide group or a urethane group. Further, the α-amino acid may form a salt in the molecule, and particularly in the case of a basic amino acid, as a result of the intramolecular salt formation, a basic amino residue is advantageously used for salt formation.

All of the amine groups (B-1) to (B-3) have strong basicity and easily form stable salts with carboxylic acids. The formation of salt may be carried out by a usual neutralization reaction, a solution,
Any state of solid phase may be used.

In order to maintain the optically active purity, it is not preferable to carry out the reaction at an excessively high temperature, and it is desirable to devise a method for suppressing the heat generation of salt formation. The solubility is often significantly different from the starting material due to salt formation, the presence of salt formation can be easily confirmed and is easy to purify.

The optically active amine salt of carboxylic acid thus obtained is
It takes the form of crystals and is excellent in moldability.
Alternatively, it can be shaped into various elements as a solid solution, and can be applied to non-linear optical application fields.

Still another preferable B is an amide derivative represented by -NR ⁴ Y.

Here, R ⁴ represents hydrogen or a single bond, and Y represents — (CH _2
p CQ ¹ Q ² Q ³ (where p is 0 or 1 and Q ¹ , Q ² and Q ³ are different from each other, and are —H, C _{1 to} C ₅ alkyl group, phenyl group, naphthyl group, —OH , -CH ₂ OH, -COOR ²⁵ , -CNR ²⁶ R ²⁷ , (R ²⁵ ~
R ²⁷ represents —H, or a C _{1 to} C ₈ hydrocarbon group)); or a residue obtained by removing an amino group from the α-amino acid skeleton; or a —CQ ⁴ Q ⁵ Q ⁶ , Q ⁴ And Q ⁵ are the same as Q ¹ , Q ² and Q ³ and Q ⁶
_Represents- (CH _{2 1-4} and represents that one bond is connected to R ⁴ .

The general formula Y can be divided into four groups as follows.

That is, it is a group of α-chiral amine derivatives in the case of p = 0, and such α-chiral-substituted alkyl primary amines include 1-methylpropylamine, 1-ethylpropylamine, 1-methylbutylamine, 1-methylpentylamine. Examples thereof include 1-phenylethylamine, 1- (α-naphthyl) ethylamine, 1- (hydroxymethyl) propylamine, and the like.

When p = 1, it is a group of β-chiral amine derivatives, and such β-chiral-substituted primary alkylamines include 2-methylbutylamine, 2-methylpentylamine, 2-phenylpropylamine, 2- (α-naphthyl). ) Compounds such as propylamine, 2-hydroxybutylamine, etc. may be mentioned.

Regarding the α-amino acids and their derivatives, it is desirable that the carboxyl groups of the various amino acids be modified into ester groups, amide groups and the like. An example of this is
It may be an alkyl ester such as α-amino acid methyl ester or ethyl ester, an α-amino acid amide, an α-amino acid anilide, or a peptide from the same or different α-amino acid. Even in the case of this peptide, it is essential that the carboxyl terminal not have an acid structure. Proline is preferably used as the secondary amino α-amino acid.

As the last preferable general formula Y, an optically active cyclic secondary amine represented by L-prolinol can be exemplified as the cyclic compound of CH _{2 1-4} .

These optically active amines may have either the R configuration or the S configuration.

Further, since such derivative formation is an amide formation reaction from the corresponding carboxylic acid and amine, it can be easily carried out by a conventional method. That is, a method of dehydrohalogenation from an acid halide of a carboxylic acid and an amine, a reaction from a carboxylic acid and an amine with a dehydrating agent typified by dicyclohexylcarbodiimide, and a carboxylic acid once activated like a p-nitrophenyl ester. After being modified into an ester, a dealcoholization reaction with an amine can be used.

The optically active amide of the aromatic conjugated carboxylic acid thus obtained has a crystal form and is excellent in formability, and can be formed into various elements as a crystal form as it is, or as a solid solution, and is suitable for nonlinear optical application fields. Although it can be applied, the present derivative is characterized in that it has good solubility in an organic solvent and excellent shapeability.

 Hereinafter, the present invention will be described in more detail with reference to examples.

Synthesis Example 1 2-Cyano-5- (4-dimethylaminophenyl) -2,
Synthesis of 4-pentadienoic acid (1) To a solution of 2.55 g of sodium hydroxide in 100 ml of water was added 5.97 g of methyl cyanoacetate, and 9.55 g of p-dimethylaminocinnamoyl aldehyde was added with stirring and heated to 85 ° C.
Continue stirring for 0 hours. After completion of the reaction, the solid is recovered by adding 50 ml of 12N hydrochloric acid. This solid was recrystallized twice with ethanol to obtain 6.38 g of the desired product. Melting point 218-219 ° C, elemental analysis value C 68.40%, H5.88%, N 11.30%, calculated value C
It was in good agreement with 69.63%, H5.84%, N11.56%. Infrared absorption spectrum: 2216cm ^-1 to CN group, COOH group 1673cm ^-1, 1
Presence of benzene ring and conjugated double bond was observed at 615, 1586, 1551 cm ^-1 . In the NMR spectrum, absorption by a methyl group was observed at 3.08 ppm, and AB absorption based on a benzene ring was observed at 6.80 and 7.60 ppm. Λmax in ethanol was 440 nm.

Synthesis Example 2 2-Cyano-3- (4-dimethylaminophenyl) -2
-Synthesis of propenoic acid (2) After dissolving 34.80 g of methyl cyanoacetate in 400 ml of a sodium hydroxide solution of 13.77 g, add 34.01 g of p-dimethylaminobenzaldehyde under a nitrogen atmosphere and add 200 ml of ethanol to obtain a uniform solution. And After stirring under reflux for 51 hours, the reaction solution is added to 12N hydrochloric acid to obtain a precipitate. This solid was recrystallized with a mixed solution of methanol / ethanol to obtain 2
Repeated times, 13.51 g of needle crystals were obtained. The NMR spectrum shows a methyl group at 3.08 ppm, 6.84-6.82 ppm, and 7.93-7.
Doublet benzene ring at 95ppm and 8.25ppm at −
A peak based on CH = was recognized.

Yield 37%, melting point 226-228 ℃, elemental analysis value C66.82%, H
5.56%, N12.76%, calculated value C66.14%, H5.60%, N
It was in good agreement with 12.96%. Λmax in ethanol is
It was 399 nm.

Synthesis Example 3 2-Cyano-5- (4-dimethoxyphenyl) -2,4-
Synthesis of pentadienoic acid (3) p-Methoxycinnamaldehyde (melting point 45.5) obtained from p-methoxystyrene and phosphorus oxytrichloride (according to the method described in J. Amer. Chem. Soc., 78 , 3209 (1956)). ℃)
Using 16.2 g, 4.8 g of sodium hydroxide, and 11.3 g of methyl cyanoacetate, the compound was synthesized in exactly the same manner as in Synthesis Example (1). Recrystallization from ethanol gave needle crystals with a yield of 69% and a melting point of 240 ° C. Elemental analysis value C68.11%, H4.81
%, N6.10%, calculated value C68.10%, H4.85%, N6.11
It showed a good agreement with%. In the NMR spectrum, a methyl group at 3.83 ppm, a doublet benzene ring at 7.02 to 7.64 ppm, and peaks at -CH = at 7.09, 7.59, and 8.06 ppm were observed. The λmax in ethanol was 372 nm.

Synthesis Example 4 2-Cyano-3- (3,4-methylenedioxyphenyl)
Synthesis of 2-propenoic acid (4) 3,4- (methylenedioxy) benzaldehyde 30.32g
14.20 g of sodium hydroxide and methyl cyanoacetate 33.75 g
Is added to the aqueous solution containing and the stirring is continued for 16 hours at 95 ° C. After the reaction was completed, it was added to a dilute hydrochloric acid aqueous solution to obtain a pale yellow solid.

This solid was recrystallized with ethanol and had a melting point of 233.
C crystals were obtained. Elemental analysis value of this product C61.01%, H3.2
1%, N6.37%, calculated value C60.83%, H3.26%, N6.45
It showed a good agreement with%.

Infrared absorption spectrum is 1677 of -CN at wave number 2224 cm ^-1.
of -COO- in cm ^-1, 1575cm ^-1, absorption of the conjugated system was observed to 1293cm ^-1. In addition, in the NMR spectrum, --CH _2- (6.19
ppm s), -CH = (8.22 ppm s), based on benzene ring-
H (7.12, 7.63, 7.68 ppm) was observed.

Synthesis Example 5 2-Cyano-3- (3,4-dimethoxyphenyl) -2-
Synthesis of chloropentenoic acid (5) 20.50 g of methyl cyanoacetate was added to 150 ml of an aqueous solution of 9.19 g of sodium hydroxide, and 25.38 g of 3,4-dimethoxybenzaldehyde was further added with stirring, and the mixture was heated to 85 ° C and stirred for 40 hours. To continue. After completion of the reaction, the solid is recovered by adding 50 ml of 12N hydrochloric acid. This solid was recrystallized twice with ethanol to obtain 19.84 g of the desired product. Melting point 206.13 ℃, elemental analysis value
C61.94%, H4.78%, N6.04%, calculated value C61.79%,
It showed good agreement with H4.76% and N6.01%.

Infrared absorption spectrum: 2221cm ^-1 to CN group, to 1716cm ^-1 COO
Existence of benzene ring and conjugated double bond was observed in H group, 1596,1573,1512 cm ^-1 . The NMR spectrum shows 3.97-4.0
Absorption by the methyl group was observed at 1 ppm, and ABX absorption based on the benzene ring was observed at 7.00, 7.55, 7.88 ppm. Λm in ethanol
ax was 353 nm.

Synthesis Example 6 Synthesis of 2-cyano-3- (2,4-dinitrophenyl) -2-propenoic acid (6) Instead of 3,4-dimethoxybenzaldehyde, 2,4-
2- (2,4-Dinitrophenyl) -1 was prepared in exactly the same manner as in Synthesis Example 5 except that dinitrobenzaldehyde was used.
-Cyano-1-propenoic acid (6) was obtained. Melting point 210 ° C
And the elemental analysis values are C46.00%, H1.98%, N16.03%,
The calculated values were in good agreement with C46.53%, H1.92%, and N15.97%.

Synthesis Example 7 2-Cyano-5- (3,4-dimethoxyphenyl) -2,4-
Synthesis of pentadienoic acid (7) Using 2- (3,4-dimethoxyphenyl) -1-formyl 1-propenoic acid obtained by reacting 3,4-dimethoxybenzaldehyde with phosphorus oxytrichloride as a starting material , (4, (3,4)
A crystal of -dimethoxyphenyl) -1-cyano-1,3-pentadienoic acid (7) having a melting point of 190 ° C was obtained. Elemental analysis value C6
4.00%, H5.15%, N5.62%, calculated value C64.85%, H
It showed good agreement with 5.06% and N5.40%.

Synthetic Examples 8 to 14 Using the corresponding aldehyde and methyl cyanoacetate, the compounds (8) to (1
4) was synthesized.

Synthesis Example 15 trans, trans, trans, 2-cyano-7- (n-
Pentyl) -2,4,6-heptatriene-1-carboxylic acid (15) Synthesis of trans, trans-2,4-decadienyl 14.85 g,
Add to an aqueous solution of 150 ml containing 6.87 g of sodium hydroxide and 16.40 g of methyl cyanoacetate and continue heating and stirring at 100 ° C. for 16 hours. After completion of the reaction, the mixture was poured into an excess of hydrochloric acid aqueous solution to obtain a viscous solid. This was recrystallized from n-hexane to give crystals having a melting point of 98 to 102 ° C. The elemental analysis values of this crystal are C70.00%, H7.75%, N6.27%, calculated value C7
It showed good agreement with 1.19%, H7.83% and N6.39%. Infrared absorption spectrum, of -CN to the wave number 2211cm ^-1, to 1609cm ^-1 -
Of COO-, 1561cm ^-1, absorption of the conjugated system was observed to 996cm ^-1. Further, in the NMR spectrum, -CH = CH- (6.25 to 7.95p
pm) and absorption of long-chain CH ₂ —, CH ₃ — groups were observed at 0.85 to 2.2 ppm, and the integrated intensity also coincided with the calculated value.

Synthesis Example 16 trans, trans, 2-cyano-5- (n-heptyl)
Synthesis of -2,4-pentadienoic acid (16) Synthesis and purification were carried out in the same manner as in Example 1 except that trans 2-decenal was used as a starting material to obtain crystals. The elemental analysis values were C71.20%, H8.90% and N6.17%, which were in good agreement with the calculated values C70.55%, H8.67% and N6.33%.

Synthesis Example 17 Synthesis of 2-cyano-3- (2-thienyl) -1-propenoic acid (17) Thiophene 2-carboxaldehyde 40.08 g was added to a 160 ml aqueous solution containing 20.97 g of sodium hydroxide and 46.11 g of methyl cyanoacetate, Heat and stir at 90 ° C. for 9 hours. After completion of the reaction, the solid is recovered by adding to excess hydrochloric acid. This was recrystallized with ethanol to obtain needle crystals. Melting point 234 ° C, elemental analysis values are C53.63%, H2.69%, N7.80%, S1
7.70%, calculated value C53.61%, H2.82%, N7.82%, S1
It showed a good agreement with 7.89%. By NMR, 7.34ppm, 8.02pp
A proton of the thiophene ring was observed at m and 8.17 ppm, and a β-position proton was observed at 8.55 ppm. Λmax in ethanol is 335
nm.

Synthesis Example 18 Synthesis of 2-cyano-3- (3-thienyl) -2-propenoic acid (18) Instead of thiophene 2-carboxaldehyde,
Using thiophene 3-carboxaldehyde, the reaction was carried out in the same manner as in Synthesis Example 1 to obtain compound (2). Melting point 21
1 ℃, elemental analysis value is C53.73%, H2.71%, N7.73%, S1
7.52%, calculated value C53.61%, H2.82%, N7.82%, S1
It showed a good agreement with 7.89%. Λmax in ethanol is 307 nm
Met.

Synthesis Example 19 Synthesis of 2-cyano-3- (2-pyrrole) -2-propenoic acid (19) After dissolving 36.93 g of methyl cyanoacetate and 16.94 g of sodium hydroxide in 260 ml of water, pyrrole 2-carboxaldehyde 23.80. g was added, and the mixture was heated and stirred at 95 ° C. for 30 hours, then added to hydrochloric acid, and the resulting solid was recrystallized from an ethanol / methanol mixed solvent to give crystals with a melting point of 213 ° C. The elemental analysis values of this solid were C59.34%, H3.82% and N17.26%, which were in good agreement with the calculated values C59.25%, H3.73% and N17.28%.

Synthesis Example 20 2-Cyano-3- (2-furyl) -2-propenoic acid (2
Synthesis of 0) The synthesis reaction was performed in the same manner as in Synthesis Example 1 except that furfural was used to obtain a compound (4). Melting point 219 ° C. The elemental analysis values of this solid were C59.02%, H2.95%, N8.53%, which showed good agreement with the calculated values C58.89%, H3.10%, N8.59%. Λmax in ethanol was 330 nm.

Synthesis Example 21 Synthesis of 2-cyano-5- (2-furyl) -2,4-pentadienoic acid (21) Reaction was performed in the same manner as in Synthesis Example 1 except that 24.7 g of 3- (2-furyl) acrolene was used. , Compound (5) was obtained. The melting point of this compound is 220 ° C., elemental analysis value, NMR
The structure was confirmed from. Λmax in ethanol was 368 nm.

Synthesis Example 22 Synthesis of 2-cyano-7- (2-furyl) -2,4,6-heptatrienoic acid (22) 5- (2-furyl) -2-cyano-2,4-pentadienoic acid (21) Using the aldehyde obtained by the oxidation reaction with phosphorus oxytrichloride shown in Synthesis Example 3 as a raw material, Synthesis Example 21
Was synthesized in the same manner as described above. From the NMR spectrum, it was confirmed to have a trans structure.

Synthesis Example 23 Synthesis of 2-cyano-3- (3-indolyl) -2-propenoic acid (23) Using Synthesis Example 1 using 21.34 g of indole-3-carboxaldehyde, 9.47 g of sodium hydroxide and 23.46 g of methyl cyanoacetate. The same reaction was performed to obtain pale yellow frame crystals with a yield of 33.5%. 230 ° C. The elemental analysis values of this solid are C68.33%, H3.77%, N13.29%.
2%, H3.80%, N13.20% showed good agreement. Λmax in ethanol was 378 nm.

Example {Evaluation of Second Harmonic Generation Intensity} For the measurement of the second harmonic generation, SK Krutz et al., Journal of Applied Physics (J.Appl.Phys.) Vol. 39. Page 3798 (1968
It was carried out on the powder of the compound of the present invention according to the method described in (Annual). The incident radiation source is Nd: YAG
A 1.06μ beam of laser (2KW / 2Hz pulse) was used to irradiate the powder sample filled in the glass cell to filter out the incident wave, and to further avoid the influence of the incident light intensity, the cell surface method The measurement was performed by detecting the intensity of green light generated in the direction of 55 ° from the line direction. As a sample for comparison, urea powder or m-nitroaniline powder having a particle size of 50 to 90 μ, which had been pulverized and fractionated in advance, was used.
The laser light resistance was measured by irradiating the sample with laser light and visually observing the change in outer shape before and after irradiation.
Generally, the basic performance was measured at a non-focus position because the laser light intensity was strong.

Example 1 2.39 g of the carboxylic acid (1) obtained in Synthesis Example 1 was dissolved in 150 ml of tetrahydrofuran, and L-(−) was added with stirring.
1.18 g of phenylethylamine was added. Precipitation occurred instantaneously, 3.16 g of an orange-red solid was recovered by passing this, and this solid was recrystallized with a mixed solvent of ethanol / methanol to obtain 2.16 g of needle crystals. Elemental analysis value of this crystal C7
2.70%, H6.68%, N11.63%, carboxylic acid (1)
And phenylethylamine showed good agreement with the calculated values assuming salt formation at 1: 1 C72.09%, H6.95%, N11.56%.
Infrared absorption spectrum: 2400~3200cm ^{-1-carboxylate} observed, the carboxylic acid (1), COOH groups for which the absorption on 1673cm ^-1 were observed shift, the presence of salt formation in the vicinity of 1620 cm ^-1 . In the NMR spectrum, the absorption by the methyl group at 2.95 ppm that can be assigned to the carboxylic acid (1), 6.74 to 7.50 ppm
In addition to the absorption of benzene, the absorption by the methyl group of 1-phenylethylamine was observed at 1.50 ppm. The relative ratio of absorption intensities was 2: 1, confirming 1: 1 carboxylic acid / amine salt formation from elemental analysis. In addition, λmax of this salt in ethanol was 420 nm, and it was confirmed that the wavelength was changed by 20 nm, which is lower than that of the corresponding carboxylic acid (1). The melting point of this product was 188 ° C., and the optical rotation [α] _D of Na-D line in methanol was −15 ° C. (C = 0.597). The powder was irradiated with 1.06 μm of an Nd-YAG laser and the second harmonic generation ability was examined. As a result, the intensity was about 3 times that of m-nitroaniline.

Example 2 Using the carboxylic acid (12) shown in the synthesis example, salt formation with L-(-)-1-phenylethylamine was performed in a THF solution in the same manner as in Example 1. Crystals precipitated over time. The crystals were recrystallized from a mixed solvent of methanol / ethanol to obtain pale yellow crystals having a melting point of 172 ° C. The elemental analysis values of this crystal are C75.98%, H6.18%, N8.06%, and the calculated values assuming a 1: 1 salt formation between carboxylic acid (12) and phenylethylamine C76.26%, H6. It showed good agreement with 41% and N8.09%. Infrared absorption spectrum: absorption of a wide range of carboxylates in the range of 2400 to 3200 cm ^-1 and carboxylic acid (12),
COOH groups for which the absorption on 1673cm ^-1 is shifted to the vicinity of 1620 cm ^-1, were observed for the presence of salt formation.

The NMR spectrum gave an integrated intensity suggesting a 1: 1 salt formation of the carboxylic acid and the amine. The optical rotation [α] _D at the Na-D line in methanol was +0.97 degrees (c = 0.597).

The λmax of this salt in ethanol was 355 nm, and it was confirmed that the wavelength was changed by 5 nm lower than that of the corresponding carboxylic acid (1). Nd-YAG laser 1.0
When irradiating 6μ of light and examining the second harmonic generation ability,
The strength was about 1.8 times that of m-nitroaniline.

Examples 3 to 12 In the same manner as in Example 1, the formation of optically active amine salts of various carboxylic acids and the second harmonic generation intensity are summarized in Table 2 below.

Example 13 0.67 g of the carboxylic acid (4) obtained in Synthesis Example 4 was dissolved in 7 ml of tetrahydrofuran and the optically active R-
0.92 g of (-)-α-naphthylethylamine was added.

The generated solid was filtered and recrystallized from ethanol. The melting point is 171 ° C., and the NMR spectrum shows that the integrated intensity ratio of the absorption peak of carboxylic acid (A) and the absorption peak of α-naphthylethylamine is 1: 1, and the elemental analysis value is C71.55%, H5.
20% and N7.21%, which were in good agreement with calculated values of C71.55%, H5.26%, and N7.20% considering the 1: 1 salt formation between carboxylic acid and amine. The crystal obtained in this way was pulverized and the generation of the second harmonic was examined.
It was confirmed to show double emission.

Example 14 0.93 g of the carboxylic acid (1) obtained in Synthesis Example 1 was dissolved in 10 ml of tetrahydrofuran, and S-(-)-1-
0.70 g of (α-naphthyl) ethylamine was added. The resulting solid was collected, washed thoroughly with tetrahydrofuran, and dried to give crystals with a melting point of 171 ° C. The optical rotation [α] _D of this sample in methanol was −30.0 degrees (C = 0.0
4), λmax = 421 nm, which almost coincided with the maximum absorption wavelength of Example 1. The ability of this crystal to generate the second harmonic was 3.9 times that of urea, and no apparent damage was observed even when this crystal powder was exposed to laser light for a long time.

Examples 15 to 19 Optically active amine salts of various carboxylic acids were prepared in the same manner as in Example 14, and the ability to generate second harmonic waves was examined.

Example 20 Thiophene-containing carboxylic acid (17) obtained in Synthesis Example 17
1.54 g was dissolved in 40 ml of tetrahydrofuran and an optically active R-(-)-1-aminophenethylamine 1.46 was added thereto.
g was added. The precipitated solid was collected. Recrystallization from ethanol gave crystals with a melting point of 171 ° C (decomposition point). The elemental analysis values of this crystal are C63.85%, H5.15%, N9.30%, S10.40
%, Which was in good agreement with the calculated values of C63.97%, H5.38%, N9.33%, and S10.17%, which were assumed to be 1: 1 amine salts of carboxylic acids. In addition, the NMR spectrum confirmed that the integrated intensity ratio of the absorption peaks of the carboxylic acid and phenethylamine of Synthesis Example 17 was 1: 1. The maximum absorption wavelength was 322 nm, and when this crystal was pulverized and the second harmonic generation was measured, a green color which was about twice that of urea was observed.

Example 21 1.51 g of the 3-substituted thiophenecarboxylic acid (18) obtained in Synthesis Example 18 was dissolved in 20 ml of tetrahydrofuran, and 1.20 g of R-(-)-1-aminophenethylamine was added thereto. The solid produced was collected, washed thoroughly with tetrahydrofuran, and dried to give crystals with a melting point of 169 ° C (decomposition). The elemental analysis values of this crystal are C63.82%, H5.07%, N
9.31%, S10.57%, calculated value assuming that it is an amine salt of carboxylic acid C63.97%, H5.38%, N9.33%, S10.17
It showed a good agreement with%. In addition, the NMR spectrum confirmed that the absorption peak component intensity ratio of the carboxylic acid and phenethylamine of Synthesis Example 18 was 1: 1. The second harmonic generation capability of this crystal was three times that of urea. The maximum absorption wavelength of ethanol in this sample was 322 nm.

Example 22 0.99 g of the carboxylic acid (21) obtained in Synthesis Example 21 was dissolved in 40 ml of tetrahydrofuran and an optically active R-
0.78 g of (-)-1-aminophenethylamine was added.
n-Hexane was added to collect the precipitated solid. Recrystallization from ethanol gave crystals with a melting point of 121 ° C (decomposition point). The elemental analysis values of this crystal are C69.55%, H5.95%, N9.
The value was 00%, which was in good agreement with the calculated values of C69.65%, H5.86%, and N9.03% of the optically active amine salt of carboxylic acid (21) in Synthesis Example. The light emitted from the Nd-YAG laser was observed to be about 5 times that of urea. The maximum absorption wavelength of this sample in ethanol was 350 nm.

Example 23 3.20 g of trienecarboxylic acid (12) obtained in Synthesis Example 12
Is dissolved in 50 ml of tetrahydrofuran and stirred under R-
2.50 g of (−)-2-amino-1-butanol was added.
Precipitation occurred instantly, and this was passed to collect 3.00 g of a yellow solid. This solid was recrystallized from a mixed solvent of ethanol / methanol to obtain 2.1 g of needle crystals. This product has a melting point
It was 187 ° C., and the optical rotation in the Na—D line in methanol was −16 degrees. The absorption maximum of this sample in methanol was 355 nm.

When the second harmonic generation ability of this powder was examined,
It was 33 times stronger.

Examples 24 to 42 In exactly the same manner as in Example 23, various salts of carboxylic acids and optically active alcohol amines were subjected to a salt-forming reaction, and the second harmonic generating ability of the obtained results was measured.

Example 43 0.89 g of the dimethoxy-substituted conjugated carboxylic acid (7) shown in Synthesis Example 7 was dissolved in 10 ml of THF, and a right-handed R was added thereto.
0.42 g of-(-)-2-amino-1-butanol was obtained.
Excess precipitate is recrystallized from ethanol, melting point 130.
White crystals were obtained at 5 ° C. The NMR spectrum of this solid gave integrated intensities suggesting that the corresponding carboxylic acid and amine were formed in a 1: 1 molar ratio. When this result was pulverized and the second harmonic was measured, a 5.8-fold luminous ability of urea was observed. The absorption maximum of this sample in the ethanol solution was 370 nm. The powder of 2-methyl-4-nitroaniline used for comparison other than Hyoso melted and carbonized under the measurement conditions, but this sample did not show any change in luminescent property over time, and showed good light damage resistance. It was recognized that there is sex.

Example 44 In Example 43, R-(−)-1 was used as the optically active amine.
The amine salt was formed in exactly the same way except using -amino-2-propanol. The ability of this salt to generate the second harmonic was about four times that of urea, and no change with time in luminescence was observed even after long-term exposure to laser light, and high photodamage was observed.

Example 45 In Example 43, the carboxylic acid was obtained in Synthesis Example (5),
The same salt formation was carried out using the dimethoxy compound (5) and exposed to laser light for a long time, but it was confirmed that the luminescence ability did not change and the damage resistance was good.

Example 46 1-Phenylalanine ethyl ester hydrochloride 2.30 g 5
Suspend in 0 ml ether. Triethylamine
Add 0.96 g and add 30 ml water. 10 ml of the supernatant ether phase was collected. This solution was added to a previously prepared solution of 0.26 g of the carboxylic acid (1) in 6 ml of THF. Needle-like crystals were obtained over time. The decomposition point of this crystal was 180 ° C. When the second-harmonic generation ability of this crystal powder was examined, it showed a strength 15 times that of urea.

Example 47 3.30 g of L-valine methyl ester hydrochloride was suspended in 50 ml of ether, and 1.89 g of triethylamine was added thereto to obtain an ale solution of L-valine methyl ester. The needle-shaped crystals were collected by adding 0.12 g of the above-mentioned carboxylic acid (2) prepared separately to a THF solution of 10 ml. When the second-harmonic generating ability of this crystal powder was examined, the strength was three times that of the table.

Examples 48 to 64 In the same manner as in Examples 1 and 2, the amine salts of α-amino acid esters of various carboxylic acids were sought and their second harmonic generation ability was examined. The results are shown in the table.

Example 65 S-(-)-phenethyl-2-cyano-5-phenyl-
Synthesis of 2,4-pentadienoic acid amide (32) 3.3 g of acid chloride of compound (11) obtained by heating compound (11) with thionyl chloride was added to S-
1.8 g of (-)-phenethylamine and 5 g of triethylamine were added to 20 ml of dissolved dioxane with vigorous stirring.
After stirring at room temperature for 3 hours, the reaction product was added to a large amount of water, and the precipitated precipitate was filtered and recrystallized to obtain 2.7 g of yellow needle crystals. Melting point 117 ° C, elemental analysis value C79.50%, H6.05%, N9.30
%, Which was in good agreement with the calculated values of C79.44%, H6.00%, and N9.26%. Infrared absorption spectrum: --NH-- at 3364 cm ^-1
Group, CN group to 2216cm ^-1, to 1649 cm ^-1 and 1522cm ^-1 amide I,
The presence of II was confirmed. The λmax in dioxane was 336 nm.

When the second harmonic generation ability of this crystal was examined,
11 times the intensity was observed, and almost no change was observed in the irradiation of laser light for a long time.

Example 66 S-(-)-phenethyl-2-cyano-7-phenyl-
Synthesis of 2,4,6-heptatrienoic acid amide (33) The acid chloride (melting point 143) of compound (11) obtained by heating compound (12) with thionyl chloride was heated.
C.) 1.79 g was added to 30 ml of THF containing 1.06 g of S-(-)-phenethylamine and 0.70 g of pyridine dissolved therein under vigorous stirring. After the reaction was completed, the reaction product was added to a large amount of water, and the precipitated precipitate was filtered and recrystallized to obtain 1.6 g of crystals.

Melting point 128 ° C, elemental analysis value C80.74%, H6.20%, N8.66%
The calculated values were C80.44%, H6.15% and N8.53%, showing good agreement. Infrared absorption spectrum: --NH-- group at 3360 cm ^-1 , 2
CN groups 216 cm ^-1, amide 1649 cm ^-1 and 1522cm ^-1 I, showed the presence of II. The λmax in ethanol was 370 nm.

In the NMR spectrum, the methyl group of the phenethyl group is 1.5
At 7ppm, absorption based on -CH = 7.99,6.79 ~ 7.05,6.82pp
Observed at m and confirmed the structure.

When the second harmonic generation ability of this crystal was examined,
An intensity of 1.1 times was observed, and almost no change was observed even after irradiation with laser light for a long time.

Example 67 S-(−)-(α-naphthylethyl) 2-cyano-7-
Synthesis of phenyl-2,4,6-heptatrienoic acid amide (34) Dicyclohexylcarbodiimide was added to a dry THF solution of an equivalent mixture of compound (12) and S-(-)-(α-naphthyl) ethylamine, and the mixture was stirred overnight. After removing the precipitated dicyclohexylurea, the mother liquor was concentrated and recrystallized from an ethanol / methanol mixture to give a white solid. It has a melting point of 100 ° C and an infrared absorption spectrum: 3360 cm ^-1.
-NH- group, admitted CN groups 2220Cm ^-1, amide I to 1650 cm ^-1 and 1522cm ^-1, the presence of II in.

When the second harmonic generation ability of this crystal was examined, an intensity four times higher than that of urea was observed, and almost no change was observed even when irradiated with laser light for a long time.

Examples 68 to 72 Optically active acid amides shown in Table 3 were obtained from various carboxylic acids and optically active amines.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kaoru Iwata 4-3-2 Asahigaoka, Hino City, Tokyo Teijin Limited Tokyo Research Center Basic Laboratory

Claims (11)

(57) [Claims] 1. A non-linear optical material represented by the general formula (I). 2. The general formula (I) is The nonlinear optical material according to claim 1, which is represented by: 3. The general formula (I) is The nonlinear optical material according to claim 1, which is represented by: 4. The general formula (I) is The nonlinear optical material according to claim 1, which is represented by: 5. The general formula (I) is The nonlinear optical material according to claim 1, which is represented by: 6. The formula (I) is The nonlinear optical material according to claim 1, which is represented by: 7. The formula (I) is The nonlinear optical material according to claim 1, which is represented by: 8. The general formula (I) is The nonlinear optical material according to claim 1, which is represented by: 9. The general formula (I) is The nonlinear optical material according to claim 1, which is represented by: 10. General formula (I) is The nonlinear optical material according to claim 1, which is represented by: 11. General formula (I) is The nonlinear optical material according to claim 1, which is represented by: