JPS61221265A - Functional dye containing long-chain alkyl group - Google Patents

Abstract

NEW MATERIAL:Rhodamine compounds of formula I, wherein R1, R3 are each lower alkyl; R2 is lower alkyl, 10C or higher long-chain alkyl; R4 is 10C or higher long-chain alkyl; X<-> is an anion, or squarylium compounds of formula II, wherein R2 is 10C or higher long-chain alkyl. EXAMPLE:3,6-(N,N'-Diethyl-N,N'-dioctadecyl) diamino-9-(2-carboxypheyl) xanthi lium perchlorate. USE:Matherials for molecular electronics, which are suitable for use as materials for photoelectric converter, optical memory, etc. PREPARATION:2-(4-N,N'-Diethylamino-2-hydroxybenzoyl)-benzoic acid, which is a condensate between N-ethyl-N-octadecyl-m-hydroxyaniline and phthalic anhydride, is reacted with N-ethyl-N-octadecyl-m-hydroxyaniline to obtain the compd. of formula I.

Description

[Detailed description of the invention] Industrial application field> The present invention relates to an electrically or photochemically active ultra-thin film material, and mainly aims to provide a material that can be applied to molecular-level electronics in the field of electronic engineering. This is the purpose.

<Prior Art> In the field of electronics, the miniaturization of integrated circuits has progressed, and very large scale integrated circuits have appeared. Current microfabrication technology has already reached its limit in order to increase the degree of integration in the future, and processing and construction at the molecular level, which is different from conventional methods, is being explored.

<Problems to be solved by the invention> As processing at the molecular level is required,
As a result of various studies, the inventors of the present invention have developed a dye that is a photochemically active compound, in other words, a dye that absorbs light and effectively releases electrons, and that has been modified into a form that makes it easy to arrange them regularly at the molecular level. We believe that the provision will help us achieve our objectives. However, no satisfactory dyes with such properties have been provided so far.

Among the various existing dyes, rhodamine B and squalium dyes are preferred as photochemically active compounds. The former is highly desirable as a photochemically active compound, as it is known that r electrons generated by photoexcitation can be transferred to anthracene without loss. Furthermore, squalium dyes are used as photoelectron-generating dyes in electrophotography, and are also excellent in photostability.

Generally, the Langmuir-Blodgett method is known as a technique for accurately arranging molecules in a single layer.

The present inventors introduced a long-chain alkyl group into a photochemically active compound and investigated the synthesis of a dye capable of forming a monomolecular film by the Langmuir-Blodgett method. As a result, the general formula (11, (II) I have completed the present invention as shown.

General formula ([) (In the formula, R, R is a lower alkyl group such as methyl, ethyl, propyl, etc., R2 is a lower alkyl group such as methyl, ethyl, propyl, etc., or a carbon number of 10 E, l, preferably carbon Long chain alkyl group from number 12 to 22, Ra It R#
l'lk 10 represents a long chain alkyl group on Cl, preferably from 12 to 22 carbon atoms.

X- represents a 7-ion such as CF or Br-1I-1CIO4-. ) A rhodamine dye having a long-chain alkyl group.

General formula (9) (In the formula, R8 is a lower alkyl group such as methyl, ethyl, propyl, etc., and R is a group having 10 or more carbon atoms, preferably 12 carbon atoms.
represents a long-chain alkyl group from to 22. ] A squalium dye having a long-chain alkyl group.

These compounds can be dissolved in a bath medium such as chloroform to form a monomolecular film on the water surface either alone or in combination with a long chain fatty acid such as arachidic acid.

In the present invention, the compound of general formula (i) can be synthesized according to the general synthesis method of rhodamine B, for example, from N-ethyl-N-octadecyl-m-hydroxyaniline and phthalic anhydride; N-ethyl-N
It can be obtained by reacting -octadecyl-m-hydroxyaniline.

The general formula (TI) can also be obtained from, for example, N-ethyl-N-ocdadecyl-m-hydroxyaniline and squalic acid according to the usual squalium dye synthesis method. This gives dyes in much better yields than those without hydroxyl groups.

Function> The dyes having a novel long-chain alkyl group of the present invention have a function of 10
"~10-' M chloroform solution is spread in distilled water to form a stable monomolecular film, and by the Langminia-Blodgett method, glass, Nesa glass, platinum, gold, silver,
It is possible to create a cumulative film of the desired thickness by stacking the aluminum translucent electrode in a single layer or in a regular manner. These can be used in the field of electronics as ultra-thin photoelectric conversion elements, optical memories, nonlinear optical elements, etc.

Hereinafter, methods for producing rhodamine and squalium dyes having long-chain alkyl groups will be explained using specific examples.

<Example 1> Method for producing L6-(N, N'-diethyl-N, N'-dioctadecyl)diamino-9-(2-carboxylphenyl)xanthylium verchlorate.

300% N-ethyl-N-octadecyl-m-hydroxyaniline and 126% phthalic anhydride were heated and stirred in a 150"C oil bath for 4 hours. Dissolved in chloroform at room temperature and treated with 10% aqueous ammonia. After fco, separate the organic layer,
Wash with water, dry, and concentrate. The resulting amorphous was dissolved in 5 ml of acetone and 0.0.4 g of 70% HCl. After adding and diluting with water.

Precipitated 8,6-(N,N'-diethyl-N,N
Crude crystals of dioctadecyl)diamino-9-(2-carboxylphenyl)xanthylium verchlorate were prepared in a furnace. Purification was performed by silica gel column chromatography to obtain the desired product 207 Misaki.

Melting point 62-64'C Maximum absorption value 550 nm (methanol) <Example 2
~4. > The following dye represented by general formula (I) was obtained in the same manner as in Example 1.

Rice does not show a clear melting point.

<Example 5>8-N,N-diethylamino-6-(N'-ethyl-N
Method for producing '-octadecyl)amino-9-(2-carboxylphenyl)xanthylium verchlorate.

1 g of N,N-diethyl-m-hydroxyaniline and 90,011 g of phthalic anhydride were refluxed in 10 txl of toluene for 2 hours, and after cooling, the precipitated crystals were recrystallized from ethanol in the furnace belly to form 2-(4-N,N-diethylamino). -2-hydroxybenzoyl)-benzoic acid door 6011
I got g. 700 mg of the obtained compound was dissolved in N-ethyl-N
-octadecyl-m-hydroxyaniline 850m11
/ After melting once at 100"C, let it cool and add concentrated sulfuric acid 0.8
Add xl and melt again at 130°C for 3 hours. After cooling and washing with water, dissolve in chloroform and treat with 10% aqueous ammonia.

Separate the organic layer, wash with water, dry, and concentrate. The obtained amorphous is acetone 5J! l? Ni/IIril, TO%H
After adding CI Oa O,4tel and diluting with water, 3-N,N-diethylamino-6-(N'-ethyl-N'-octadecyl)ami, no 9-(2-carboxylphenyl)xanthiylium bar precipitates. Crude crystals of chlorate were crushed in a furnace. Purification was performed by silica gel column chromatography to obtain 3801 #l of the desired product.

Melting point: 77-80°C Maximum absorption value: 547 nm (methanol) <Example 6
1. Method for producing 3-bis-(4-((N-ethyl-N-octadecyl)amino)-2-hydroxyphenyl]-2,4-dihydroxycyclobutenediylium inner salt.

200 ml of N-ethyl-N-octadecyl-m-hydroxyaniline and 30 ml of Squaric acid were refluxed for 3 hours in a mixture of N-butan/tk 40 s benzene and 10 ml of benzene. After cooling, the precipitated crystals were removed from the furnace. Ko.

After thorough washing with methanol, it was recrystallized with a mixture of chloroform and methanol to obtain 1,8-bis-C4-((N-ethyl-N-octadecyl)amino)-2-hydroxyphenyl]-2,4-dihydroxycyclo. Butenediylium inner salt 16
Get 5TIg.

Chloroform with melting point of 126 and absorption maximum of 644 nm [Examples 7 to 9] In the same manner as in Example 6, the following dye represented by general formula (II) was obtained.

<Effects of the Invention> The novel rhodamine dyes and squalium dyes having long-chain alkyl groups of the present invention can be produced by the Langmier-Prodgett method on glass, nesagaras, and platinum.

Gold, silver, aluminum, and semi-transparent electrodes can be used to form monomolecular films or cumulative films, making them useful as materials for molecular electronics and charging conversion elements.

It can be used as an optical memory, a nonlinear optical element, etc. and applicant
Japan Photosensitive Pigment Research Institute Co., Ltd. Commissioner of the Patent Office Shiga
Gakuden dye 3 Relationship with the case of the person making the amendment Patent applicant 5 Contents of the amendment Engraving of the patent axis and specification (no change in content) 6 Attached documents

Claims (2)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_3 are lower alkyl groups, R_2 is lower alkyl groups or long chain alkyl groups with 10 or more carbon atoms, R_
4 represents a long chain alkyl group having 10 or more carbon atoms. X^- represents an anion. ) A rhodamine dye having a long-chain alkyl group. (2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_1 represents a lower alkyl group, and R_2 represents a long chain alkyl group with 10 or more carbon atoms.) Squarium dye with an alkyl group.