JPS61152647A - Diazo compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula (X is nitro, carboxyl or cyano; Y is 7-17C alkyl; Z is H or 7-17C alkyl). EXAMPLE:N-Heptyl-4-[4-nitrophenyl]azobenzeneamine. USE:An organic optical material. It has non-linear optical effect and forms a monomolecular film having oriented molecules. PREPARATION:p-Nitroaniline or p-aminobenzoic acid is dissolved in dilute hydrochloric acid under heating, cooled to obtain a hydrochloride, and added with sodium nitrite dropwise under cooling to obtain diazonium salt. An N-alkyl- substituted aniline is dissolved in an organic solvent containing suspended sodium acetate to prevent the ionization of the amino group, cooled, and made to react with the diazonium salt by adding the aqueous solution of the salt dropwise to obtain the compound of formula.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a novel diazo compound, and more specifically,
This invention relates to diazo compounds useful as organic optical materials.

[Technical background of the invention and its problems] A compound having a structure in which an electron donor and an electron acceptor are bonded in a conjugated system has a large dipole moment, and
It is known as a material that exhibits electro-optical properties or second-order nonlinear optical properties.

Examples of such compounds include p-nitroaniline and 4-nitro-4'-dimethylaminostilbene.

Conventionally, these organic compounds have been made into single crystals and their optical properties have been studied, but when they are made into thin films, it is difficult to control the orientation of molecules. Therefore, these organic compounds are unsuitable as materials for optical devices, and there has been a strong desire for the emergence of organic compounds that can be used as such materials.

[Purpose of the invention] The object of the present invention is to eliminate the above-mentioned drawbacks.

An object of the present invention is to provide a novel diazo compound that can form a thin film with one molecule oriented without losing its optical properties.

[Summary of the Invention] The diazo compound of the present invention has the general formula: Y (wherein, X represents a nitro group, carboxyl group or cyano group, Y represents an alkyl group having 7 to 17 carbon atoms,
represents a hydrogen atom or an alkyl group having 7 to 17 carbon atoms.

In the above formula, what is an alkyl group having 7 to 17 carbon atoms?

For example, it means a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, and a heptadecyl group.

Examples of the diazo compound of the present invention include:

Toheptyl-4-[4-nitrophenyl azobenzenamine, N,N-diheptyl-4-[4-nitrophenyl azobenzenamine, toheptyl-4-[4-carboxyphenyl azobenzenamine, N,N-diheptyl-4 -[4-carboxyphenylene, N-heptyl-4-[4-cyanophenyl azobenzenamine, N,N-diheptyl-4-[4-cyanophenyl azobenzenamine, tododecyl-4-[4
-nitrophenyl 17-tubenzenamine, N,N-didodecyl-4-[4-nitrophenyl 1 azobenzenamine, tododecyl-4-14-carboxyphenyl 1 azobenzenamine, N,N-didodecyl-4-[4-carboxyphenyl Azobenzenamine, N-dodecyl-
4-[4-cyanophenyl-1azobenzenamine, N,
N-didodecyl-4-[4-cyanophenyl-azobenzenamine, N-dodecyl-1-hepty-4-rho-nitrophenyl-1 azobenzenamine, N-dodecyl-1-hebutyl-4-[4-carboxyphenyl-azobenzenamine , N-dodecylbutyl-4-[4-cyanophenyl-1 azobenzenamine, N-tetradecylute-undecyl-4-[4-nitrophenyl-1-azobenzenamine, totitradecylute-undecyl-4-[4-carboxy Phenyl l-azobenzenamine, totytradecylate undecyl-4-[4-cyanophenyl l-azobenzenamine, N-octylate totecyl-4-[4-
Nitrophenyl azobenzenamine, octylate dodecyl-4-[4-carboxyphenyl azobenzenamine, N-octyl-N-F decyl-4-[4-cyanophenyl azobenzenamine, N-decyl-N-heptadecyl -4-[4-nitrophenyl-azobenzenamine, tohexadecyl-N-heptadecyl-
Examples include 4-local boxyphenyl azobenzenamine and tohexadecyl-N-heptadecyl-4-[4-cyanophenyl azobenzenamine.

It was confirmed that from the diazo compound of the present invention (Example 1), a monomolecular film stack could be formed on a quartz substrate using a monomolecular film production apparatus.

In addition, this laminated film was coated with 1.06# using a YAG laser.
When irradiated with Lgt pulsed light, it was observed that a pulsed light of 0.541 4 m was output, confirming its effectiveness as a second harmonic generation element. Because of these properties, the diazo compound of the present invention is expected to be used as a useful organic optical material.

Next, one method for producing the diazo compound of the present invention will be explained. The diazo compound of the present invention is produced according to a general diazotization reaction. First, p-nitroaniline or p-
Dissolve 7-minobenzoic acid in dilute hydrochloric acid by heating, then cool to obtain the hydrochloride. Next, while cooling the whole in a water bath, sodium nitrite is added dropwise to obtain the diazonium salt. Here, in addition to chloride ion, the counter anion of diazonium salt is
Nitrate ion, boron tetrafluoride ion.

perchlorate ion, perbromate ion, periodate ion,
Examples include bromine ion and iodine ion. Since the obtained diazonium salt is easily thermally decomposed, it is desirable to quickly filter it using a cooled funnel and store it in a water bath.

Next, in order to prevent the ionization of the amine 7 group, the toalkyl-substituted aniline was dissolved in an organic solvent in which sodium acetate was suspended, and the solution was sufficiently cooled in a water bath. was added dropwise and reacted to obtain a diazo compound. Here, the organic solvent may be any solvent as long as it is soluble in water and capable of dissolving the N-alkyl-substituted aniline, and examples thereof include dioxane, acetone, and ethanol. Also.

The solution changes from black to red at the same time as the diazonium salt is added dropwise, but it is important to control the dropwise addition so that the internal temperature does not exceed 5°C.

At the end of the dropwise addition, a large amount of red precipitate is formed, which is filtered and thoroughly washed with water. The obtained precipitate contains raw materials or by-products and is purified by recrystallization. Examples of the recrystallization solvent include methanol and ethanol. Purified crystals are yellow to red solids with IR
, was identified by NNR.

1) According to the 1-NMR spectrum, the α-methylene proton of the long-chain alkylamino group is significantly shifted downfield compared to the normal chemical shift value, while the amino group is significantly positive. It is shown that it has a large dipole moment.

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples and Application Examples.

[Example of the invention] 10L (Synthesis example) Put 2.0g of p-nitroaniline, 365ml of concentrated hydrochloric acid, and 5+*jL of pure water into a 1QQmJL 3-tube flask, stir with a stirrer, and then heat and dissolve in a hot water bath. . Thereafter, it is cooled to precipitate crystals. Add log ice to bring the internal temperature to 5°C. 1.01g of sodium nitrite in water lO■
Gradually drip the dissolved material. The internal temperature is 7~
The temperature rose to around 10℃. After adding the sodium nitrite aqueous solution dropwise over a period of about 40 minutes, the mixture was cooled in a water bath for another 40 minutes and stirring was continued. Then, using a cooled extraction funnel,
Filter the reaction mixture and store in water cooling.

N-n-dodecylaniline 3.8g, aceto 725si
, 5 g of sodium acetate was placed in a Mitsuro flask, stirred with a stirrer, and cooled in a water bath. to this.

The previously prepared aqueous diazonium salt solution was added dropwise little by little. After completion of the addition, stirring was continued for an additional hour. 8. The reaction product was filtered, thoroughly washed with a large amount of water, and then vacuum dried at room temperature.

1.5 g of the obtained precipitate (8.48 g) was recrystallized in ethanol. Yellow powdery crystals of oflg were obtained. The melting point was 60-61°C.

, Spectrum 2930, 2850cm''1 (alkyl (azo group)
, 1590c■4 (benzene ring), 1510.

1330cm-Toro group on Otori).

') l-NIIR spectrum δ direct Chloroform 0,
88ppm (methyl group, triplet), 1.2-1
, 7pp■ (methylene group), 4.3pp■ (methylene group next to nitrogen atom, triplet), 7.1-8.
3pp tooth (benzene ring proton and amino group); area ratio 12: 83: 8: 3? (Calculated value 12: 8
0:8:311).

(Synthesis example) 2.00 g of p-7 minobenzoic acid, 4.5 g of concentrated hydrochloric acid,
Add 15mM of water to a 100ml Mitsuro flask and heat and dissolve in a hot water bath while stirring with a stirrer.

Thereafter, it was cooled to precipitate crystals. Add ice cubes to this and bring the temperature inside the flask to 5°C.

) + t” M 32% Melt-1-
k II ＾ J- 1 nl+y
4. InamOL- Gradually add the dissolved material dropwise. The temperature inside the flask rose to about 7-10°C.
After the dropwise addition took about 40 minutes, stirring was continued for an additional 40 minutes while cooling in a water bath. The reaction mixture is then filtered using a chilled extraction funnel and stored in water cooling.

Put 3.8 g of Nn-dodecylaniline, 25 layers of acetone, and 6 g of sodium acetate into a three-layered flask, stir with a stirrer, and cool in a water bath. To this, the diazonium salt aqueous solution prepared earlier was added dropwise little by little. After the addition is complete, continue stirring for an additional hour. Filter the reaction product, wash thoroughly with plenty of water, and dry under vacuum at room temperature. Of the obtained precipitate (5.09 g), 2.3 g was recrystallized in methanol to obtain 1.1 g of red crystals. The melting point was 88-90°C.

-, spectrum 21330, 2850cs→ (alkyl group),
1680cm-'(carbonyl)&), 1800c
■( (benzene ring).

1580cs → (azo group).

'H-NMR spell δ acetone 0.87pp
■(Methyl group, triplet), 1.2-1.7pp
m (methylene group), 4.4pp garden (methylene group next to nitrogen atom, triplet), 7.0-8.19p ■
(benzene ring proton, amino group and carboxyl group); area ratio 12: 80: 7: 37 (calculated value 1
2:80:8:4G).

Example of Forming a Medium Molecular Layer Laminated Film A monomolecular film forming apparatus manufactured by Joyce Label Co., Ltd. was used as a monomolecular film forming apparatus.

The compound synthesized in Example 1 was added to 5 X to' mol
Dissolve in benzene at a concentration of /i to prepare a developing solution.

For the aqueous phase, double-distilled water was used, and disodium hydrogen phosphate was used.
゛2 of/4, pH adjusted to 7. with sodium hydroxide-hydrochloric acid.
Prepare to 5. The water temperature was set at 25° C., and three Y-layer films were laminated on a quartz glass substrate. S thickness is estimated to be 50 to 70 people.

The compound synthesized in Example 2 was added to 5 x 104■ol/
Dissolve in chloroform at the same concentration to make a developing solution.

For the aqueous phase, double-distilled water is used to make a cadmium chloride solution of 5×1G4mal/liter. The water temperature was set to 25℃.
Three Y layer films were laminated on a quartz glass substrate.

The thickness of the film is estimated to be 50 to 70 people.

Observation of second-order nonlinear optical properties The laminated film obtained in Example 3 was injected with YAG-Nd3+ laser (input = 1 OBons) (Ia optical pulse light (repetition 10 Hz, pulse width 10 nsec, pulse output 10 mW)
) was applied at an angle of 45°, and the reflected light was measured at a measurement angle of 30°.* It was confirmed that a secondary high frequency was generated by photoelectric conversion through a filter that transmits only 530 nm and observation with an oscilloscope. did. If the intensity of the incident light is Io and the intensity of the second harmonic is l2ca, then γ”
(I2t,,/I,2)34 is 104~
There was 104esu.

[Effects of the Invention] As detailed above, the diazo compound of the present invention has a nonlinear optical effect and can form a monomolecular film with oriented molecules, so it can be usefully used as an organic optical material. Its industrial value is extremely large.

Claims (1)

[Claims] General formula: ▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, X represents a nitro group, carboxyl group or cyano group, Y represents an alkyl group having 7 to 17 carbon atoms, and Z
represents a hydrogen atom or an alkyl group having 7 to 17 carbon atoms.