JPH0283387A - Novel ferrocene derivative, surfactant containing the same derivative and production of organic thin film - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R<1> and R<2> are 1-14C chain alkylene] X<1> and X<2> are -O- or oxycarbonyl; A<1> and A<2> are group shown by formula II (R' is H or methyl; r is 2-70); Z<1> and Z<2> are H, amino, etc.; a and b are 1-4)]. EXAMPLE:A compound shown by formula III. USE:A surfactant to solubilize a hydrophobic organic substance in an aqueous medium useful in forming a thin film of hydrophobic organic substance and extremely improving production efficiency of organic thin film. PREPARATION:For example, ferrocene is reacted with an alkoxycarbonylalkanoic acid halide shown by formula IV (R<3> is alkyl) to give a compound shown by formula V, which is is hydrolyzed, a reaction product shown by formula VI is subjected to Clemensen reduction and then a formed compound shown by formula VII is condensed through dehydration with polyethylene glycol to give a compound shown by formula I wherein X<1> and X<2> are oxycarbonyl, R<1> and R<2> are (n+1)C alkylene, A<1> and A<2> are oxyethylene and and Z and Z' are H.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel ferrocene derivative, a surfactant containing the same, and a method for producing an organic thin film. A novel ferrocene derivative having a configuration, and containing the ferrocene derivative,
The present invention relates to a surfactant capable of solubilizing a hydrophobic organic substance such as phthalocyanine, and a method for producing a thin film of a hydrophobic organic substance using this surfactant.

[Prior art and problems to be solved by the invention]-g, dyes such as phthalocyanine or its derivatives are insoluble in water, and dimethylformamide (DM
Although it is soluble in organic solvents such as F) and tetrahydrofuran (THF), the amount of solubilization is small, and the solubility is only about a few square centimeters.

Surfactants for dissolving phthalocyanine and the like in water have been researched for some time, but a satisfactory solution has not yet been developed. It has been reported that functional group-substituted phthalocyanine derivatives can be slightly dissolved in water using sulfonic surfactants, but their solubility is not always sufficiently high, and unsubstituted phthalocyanine cannot be dissolved at all.

Furthermore, surfactants are being researched to dissolve water-insoluble polymers in the same way as mentioned above.
The current situation is that sufficient results have not yet been obtained.

The group of the present inventors has developed a ferrocene derivative having a polyoxyethylene chain as a surfactant that solubilizes pigments such as carp, phthalocyanine and its derivatives, or water-insoluble polymers. We have developed a method for forming organic thin films using the so-called micelle electrolysis method (Japanese Patent Application No. 62-212718).

The present inventors have conducted extensive research in order to improve the above-mentioned surfactant, further improve the ability to solubilize hydrophobic organic substances in micelle electrolysis, and develop a method for increasing the production efficiency of organic thin films.

As a result, by changing the number of chain substituents consisting of a hydrophobic group and a hydrophilic group bonded to the ferrocene skeleton from one to two in the above ferrocene derivative, the solubilization ability was greatly improved. It has been found that the film-forming ability is significantly improved when an organic thin film is formed using this method. The present invention was completed based on this knowledge.

[Means to solve the problem]

That is, the present invention is directed to the general formula [wherein R1 and R2 each represent a linear or branched alkylene group having 1 to 14 carbon atoms, and Xl and X2 each represent 10- or -0-0-. Further, A' and A2 are +CH, CHO)-, H(R' is R' hydrogen or a methyl group, respectively, and r is a real number from 2 to 70.

), Zl and Z2 are each hydrogen.

Methyl group, methoxy group, amino group, dimethylamino group,
It represents a hydroxyl group, an acetylamino group, a carboxyl group, a methoxycarbonyl group, an acetoxy group, an aldehyde group, or a halogen. a and b each represent an integer of 1 to 4. ] A novel ferrocene derivative represented by the following is provided, and a surfactant containing this novel ferrocene derivative is provided. Furthermore, the present invention solubilizes a hydrophobic organic substance in an aqueous medium with a surfactant containing the novel ferrocene derivative, and electrolyzes the resulting micellar solution to form a thin film of the hydrophobic organic substance on an electrode. A method for producing an organic thin film is also provided.

The ferrocene derivative of the present invention is represented by -i formula CI]. Here, each symbol in the -1'IQ formula [I] is as described above. That is, R1 and R2 are each a linear alkylene group or a branched alkylene group having 1 to 14 carbon atoms (for example, a methylene group, an ethylene group, a propylene group,
butylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, etc.), which constitutes a hydrophobic group. In addition, Xl and x2 are each oxygen (-0-) or oxycarbonyl group (-C-O-)
shows. Further, A1 and A2 are respectively (-CH2CH2)-, H R', that is, (-CH2CH20)-, H or +CH2CHO)-, H CH.

(r is a real number from 2 to 70). This AI and A2 are hydrophilic groups, and here oxyethylene group (-CH2CH
, O-) or l-methyloxyethylene group (-CH
rCH indicates the number of repetitions of 2CHO−).

means not only an integer between 2 and 70 but also a real number including these, but this refers to the oxyethylene group or l
- It shows the average value of the number of repeating methyloxyethylene groups.

Furthermore, Zl and Z2 are hydrogen and methyl group (CH
3), methoxy group (OCH3), amino group (NH2).

Dimethylamino group (N(CH3)), hydroxyl group (OH).

Acetylamino group (NHCOCHff), carboxyl group (C00H), methoxysulfonyl group (CO, CH,
).

Acetoxy group (OCOCR3), aldehyde group (CHO
) or halogen (chlorine, bromine, fluorine, etc.).

The novel ferrocene derivative represented by the formula (1) can be produced by various methods. Specifically, for example, Xl and X2 are both oxycarbonyl groups, R1 and R2 are both alkylene groups (polymethylene groups) having n+1 carbon atoms, A' and A2 are both oxyethylene groups with a repeating number (r) of p, Zl and When Z2 is both hydrogen, alkoxycarbonyl of general formula (lCo(CH2)l, C00R3 (R' is an alkyl group) etc.) is added to ferrocene in a solvent such as methylene chloride, carbon disulfide, carbon tetrachloride, or nitrobenzene. Alkanoic acid halides are treated with free sol fluorocarbon catalysts (e.g. AA C13, FeC42
□.

FeCI! ,3+sbc! , ) to obtain a compound represented by , which is then reacted with alkali hydroxide (KOH, Na
OH etc.) to obtain a compound represented by the general formula. After that, alcohol (methanol, ethanol, etc.) is added to this compound of general formula (1).
, in a solvent such as dioxane, toluene, acetic acid, etc., using zinc or zinc amalgam and concentrated hydrochloric acid as a reducing agent to reduce the compound represented by the - format (wherein R4 is hydrogen or an alkyl group). obtain. Thereafter, polyethylene glycol (degree of polymerization: p) is subjected to dehydration condensation to produce the desired new ferrocene derivative.

Further, for example, Xl and X2 are both oxygen, R1 and R2 are both alkylene groups (polymethylene groups) having n+1 carbon atoms,
When A1 and A2 are both oxyethylene groups with a repeating number (r) of p, and Zl and Z2 are both hydrogen, -form χ' C0 (CHz), lX" (X is a halogen such as chlorine) An acid halide represented by 5X (indicates a halogen such as bromine) is reacted in a solvent such as methylene chloride, carbon disulfide, carbon tetrachloride, or nitrobenzene using the above-mentioned free sol fluorine catalyst, - A compound represented by the formula is obtained.Furthermore, this compound of the -form (V) is subjected to Clemenzene reduction in the same manner as described above to obtain a compound represented by the general formula.After that, this is combined with polyethylene glycol (degree of polymerization; p). When treated with an alkali metal such as 1-lium metal or potassium metal and condensed, a new ferrocene derivative of the desired general formula is produced.

The novel ferrocene derivative of the present invention obtained by the method described above is effective as a surfactant, and can particularly be used as a surfactant (micellar agent) for soluble hydrophobic organic substances in an aqueous medium. .

The surfactant of the present invention contains a ferrocene derivative represented by the above-mentioned formula [I] (including the general formulas (1') and (I'')) as a main component, and also contains various other substances as necessary. It is also possible to add appropriate additives.

By using the surfactant of the present invention, it is possible to solubilize various hydrophobic organic substances in an aqueous medium. There are various types of such hydrophobic organic substances, such as phthalocyanine, metal complexes of phthalocyanine and derivatives thereof, naphthalocyanine, metal complexes of naphthalocyanine and derivatives of gore, porphyrin, metal complexes of porphyrin and these. 1,1°-diheptyl 4.4″, including optical memory dyes and organic dyes such as derivatives of
-Bipyridinium dibromide 11″ didodecyl-4
, 4'-bipyridinium dibromide, and photosensitive materials such as 6-nitro-1,3,3-1-limethylspiro (2''-11°-benzopyran-2,2°-indoline) (commonly known as spiropyran). Photochromic materials), optical sensor materials, liquid crystal display pigments such as p-azoxyanisole, and electronics listed in "Color Chemical Encyclopedia" CMC Co., Ltd., published March 28, 1988, pages 542-717. Dye for printing, dye for recording.

Environmental chromism pigments, photographic pigments, energy pigments, biomedical pigments 1 food and cosmetic pigments, dyes,
Examples include hydrophobic compounds of pigments and special coloring dyes. Also, 7,7.88-tetracyanoquinone dimethane (TCNQ) and tetrathiafulvalene (TTF)
organic conductive materials and gas sensor materials such as 1:1 complexes with , photocurable paints such as pentaerythritol diacrylate, insulating materials such as stearic acid, diazo type photosensitive materials and paints such as 1-phenylazo-2-naphthol. etc. can be given. Furthermore, water-insoluble polymers such as polycarbonate polystyrene, polyethylene, polypropylene.

polyamide, polyphenylene sulfide (PPS),
General-purpose polymers such as polyphenylene oxide (PPO) and polyacrylonitrile (PAN), polyphenylene, polypyrrole, polyaniline, polythiophene, acetylcellulose, polyvinyl acetate, polyvinyl butyral, and various other polymers (such as polyvinylpyridine) or copolymers (methacrylic acid) copolymers of methyl and meccrylic acid, etc.).

There are various ways in which the novel ferrocene derivative of the present invention can be used as a surfactant, but it is particularly effective when used as a micelle agent in the method for producing an organic thin film of the present invention. In the method of the invention, the above-format CI)
Add a surfactant (micelle-forming agent) made of a new ferrocene derivative (4 degrees is above the critical micelle concentration), a supporting salt, and a hydrophobic organic substance, and thoroughly disperse them using ultrasound, a homogenizer, a stirrer, etc. to form micelles. is formed, and then, if necessary, excess hydrophobic organic substances are removed,
The obtained micelle solution is electrolytically treated using the above-mentioned electrode while it is left standing or with slight stirring. Also,
The hydrophobic organic substance may be supplemented and added to the micelle solution during the electrolytic treatment, or the micelle solution near the anode may be extracted from the system, the hydrophobic organic substance may be added to the extracted micelle solution, and the mixture is thoroughly mixed and stirred. A circulation circuit for returning this liquid to the vicinity of the cathode later may also be provided. The electrolytic conditions at this time may be selected appropriately depending on various situations, but usually the liquid temperature is 0 to 7.
0°C1 preferably 20~30゛C1 voltage 0.03~1
．． 5■, preferably 0.1 to 0.5■, and the current density is 1
0+nA/cm” or less, preferably 50 to 300μA/
Let it be Cm2.

When this electrolytic treatment is performed, the redox reaction of the ferrocene derivative proceeds. Focusing on the behavior of Fe ions in ferrocene derivatives, we can see that at the anode, the Fe'' of ferrocene is
e'', the micelles collapse, and particles of hydrophobic organic substances (approximately 600 to 900 particles) are deposited on the anode.Meanwhile, at the cathode, the Fe3° oxidized at the anode is reduced to Fe''. Since the original micelles are restored, membrane forming operations can be performed repeatedly using the same solution. The new ferrocene derivative used in the method of the present invention has a structure in which the ferrocene skeleton is interposed between the main chain and the hydrophilic group, so the efficiency of the above redox reaction is very high, and a thin film can be formed in a short time. be done.

Through such electrolytic treatment, a thin film of about 600 to 900 particles of the desired hydrophobic organic substance is formed on the anode.

The supporting salt (supporting electrolyte) used in the method of the present invention is added as necessary to adjust the electrical conductivity of the aqueous medium. The amount of supporting salt added is usually about 0 to 300 times the concentration of the surfactant (micelle forming agent), preferably about 10 to 200 times. Although electrolysis can be performed without adding this supporting salt, in this case, a highly pure thin film containing no supporting salt can be obtained.

In addition, when using a supporting salt, the type of supporting salt is particularly limited as long as it can adjust the electrical conductivity of the aqueous medium without interfering with the formation of micelles or the precipitation of the hydrophobic organic substance on the electrode. There isn't.

Specifically, sulfates (salts of lithium, potassium, sodium rubidium aluminum, etc.), which are generally widely used as supporting salts, and vinegar 11 (lithium, potassium,
Sodium, rubidium.

salts such as helium, magnesium, calcium, strontium barium, and aluminum).

Halide salts (salts of lithium, potassium, sodium rubidium, calcium, magnesium, aluminum, etc.), 5 water-soluble oxide salts (salts of lithium, potassium, sodium, rubidium, calcium, magnesium, aluminum, etc.) are preferred.

Further, the electrode used in the method of the present invention may be any metal or conductor that has a higher oxidation potential than ferrocene (+0.15 V vs. saturated red electrode). Specific examples include IT○ (mixed oxide of indium oxide and tin oxide), platinum, gold, silver, grady carbon, conductive metal oxides, organic polymer conductors, and the like.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Production Example 1 (1) In the presence of 9.4 g of anhydrous aluminum chloride, 6.5 g of ferrocene and 10.6 g of 3-methoxycarbonylpropionic acid chloride were reacted in a methylene chloride solvent at room temperature for 2 hours.

After the reaction was completed, the reaction mixture was treated with dilute hydrochloric acid and then loaded in a silica gel column to obtain 8.6 g of methyl biferrocenoylniprobionic acid represented by the following formula.

(2) 8.6 g of methyl 1,1'-ferrocenoylniprobionic acid synthesized in (1) above and 4.1 g of potassium hydroxide
g was refluxed in an ethanol solvent for 2 hours and then treated with an acid to obtain 8.0 g of 11'-ferrocenoyl nipropionic acid represented by the following formula.

(3) 1 synthesized in (2) above in the presence of zinc amalgam prepared from 17.4 g of zinc and 7.2 g of mercuric chloride.
, 8.0 g of 1'-ferrocenoylnipropionic acid were reacted in a mixed solvent of concentrated hydrochloric acid and ethanol at 80°C for 3 hours.

After the reaction was completed, the mixture was extracted with ethyl acetate and purified using a silica gel column to obtain 6.0 g of ethyl 1,1'ferrocenenibutyrate represented by the following formula.

Example 1 To ethyl 1,1'-ferrocene dibutyrate 6,00 g obtained in Production Example 1 above, 173.8 g of polyethylene glycol (average molecular weight ffi 600) and 0.1 cc of concentrated sulfuric acid were added, and the mixture was heated at 80°C. React for 6 hours, and add this reaction solution to water and n
- Extracted with an isostatic mixture of butanol.

After washing the extract with water, it was developed using a silica gel column and a mixture of benzene and ethanol (benzene:ethanol=5:1) as a solvent for chromatographic purification.

After drying, the obtained purified product had a yield of 40.5% and a yield of 8.9
It was 1g.

The elemental analysis values for this substance are 56.1% carbon and 8.0% hydrogen.
% and nitrogen 0.0%, and the measurement results of proton nuclear magnetic resonance spectrum ('H-NMR) were as shown in FIG.

From the above results, it was found that the purified product was a ferrocene derivative having the following structure.

Production Example 2 (1) Instead of 3-methoxycarbonylpropionic acid chloride in Production Example 1 (1), 26.7 g of 4-methoxycarbonylbutyric acid chloride, 21.6 g of anhydrous aluminum chloride, and 15.1 g of ferrocene were added. The same operation as in Production Example 1 (1) was carried out except that 1. of the following formula was used. Methyl Beeferocenoyl Nibutyrate 19.4g
I got it.

(2) Instead of ethyl 1.1'-ferrocenoylnipropionate in Production Example 1 (2), 1 obtained in (1) above was used.
, 19.4 g of methyl 1'-ferrocenoylnibutyrate, and 11.5 g of potassium hydroxide were used in the same manner as in Production Example 1 (2) to obtain 1. of the following formula. 18.1 g of beeferosenoyl diacetic acid was obtained.

(3) Production Example 1 (3) 1. 1,1'-obtained in (2) above in place of beeferosenoyl nipropionic acid
The same operation as in Production Example 1 (3) was performed except that 1 g of ferrocenoylnibutyric acid 1B, 52.3 g of zinc, and 21.7 g of mercuric chloride were used to produce 1 shown by the following formula.
9.1 g of ethyl 1'-ferrocene divalerate was obtained.

Example 2 Ethyl 1,1'-ferrocene divalerate obtained in Production Example 2 above9. 406.0 g of polyethylene glycol (average molecular weight 1000) and 0.1 cc of concentrated sulfuric acid were added to OOg, reacted at 80°C for 6 hours, and the reaction solution was extracted with an isostatic mixture of water and n-butanol. .

After washing the extract with water, it was developed using a silica gel column and a mixture of benzene and ethanol (benzene:ethanol=5:1) as a solvent for chromatographic purification.

After drying, the obtained purified product had a yield of 43.0% and a yield of 20.0%.
It was 5g.

The elemental analysis values for this material are 57.1% carbon and 11% hydrogen.
9% and nitrogen 0.0%, and the measurement results of proton nuclear magnetic resonance spectrum ('H-NMR) were as shown in FIG.

From the above results, it was found that the purified product was a ferrocene derivative having the following structure.

Production Example 3 (1) Instead of 3-methoxycarbonylpropionic acid chloride in Production Example 1 (1), 2.2 g of ethyl 5-methoxycarbonylvalerate, 1.6 g of anhydrous aluminum chloride, and 2.3 g of ferrocene were added. The same operation as in Production Example 1 (1) was carried out except that 4.0 g
of ethyl ferrocenoylvalerate was obtained.

Further, a similar reaction was carried out using 2.8 g of 3-methoxycarbonylpropionic acid chloride and 1.6 g of anhydrous aluminum chloride, and 3.2 g of ethyl 1,1' ferrocenoylprobionic acid valerate of the following formula was obtained. Obtained.

(2) Instead of ethyl 1,1'-ferrocenoylnipropionate in Production Example 1 (2), ethyl 1,1'-ferrocenoylpropionate obtained in Production Example 3 (1) above; ethyl valerate; The same operation as in Production Example 1 (2) was carried out except that 3.2 g and 1.6 g of potassium hydroxide were used to prepare 1,1' ferrocenoylpropionate valerate 2,
9g was obtained.

(3) Production Example 1 (3) 1. 1,1 obtained in Production Example 3 (2) above in place of beef erosenoyl nipropionic acid
The same operation as in Production Example 1 (3) was carried out except that 2.9 g of '-ferrocenoylpropionate valeric acid, 8.7 g of zinc, and 3.6 g of mercuric chloride were used, and the following formula was obtained. 1. Ethyl p-ferrocenebutyrate Ethyl hexanoate 2.3
I got g.

Example 3 To 2.30 g of ethyl I,1'-ethylhexanoate obtained in Production Example 3 above, 111.0 g of polyethylene glycol (average molecular weight Lt1000) and 0.0 g of concentrated sulfuric acid were added.
1 cc of the mixture was added and reacted at 80°C for 6 hours, and the reaction solution was extracted with an isostatic mixture of water and n-butanol.

After washing the extract with water, it was developed using a silica gel column and a mixture of benzene and ethanol (benzene: ethanol = 5:1) as a solvent for chromatographic purification.

After drying, the obtained purified product had a yield of 38.4% and a yield of 4.9%.
It was 4g.

The elemental analysis values for this substance are 56.2% carbon and 9.1% hydrogen.
% and nitrogen 0.0%, and the measurement results of proton nuclear magnetic resonance spectrum (IH-NMR) were as shown in FIG.

From the above results, it was found that the purified product was a ferrocene derivative having the following structure.

Production Example 4 (1) Instead of 3-methoxycarbonylpropionic acid chloride in Production Example 1 (1), 6.3 g of 6-methoxycarbonylhexanoic acid chloride, 4.2 g of anhydrous aluminum chloride, and 3.2 g of ferrocene were added. The same operation as in Production Example 1 (]) was carried out except that Og was used, and methyl 1,1' ferrocenoylnihexanoate 5.5 of the following formula was prepared.
In place of methyl 1,1'-ferrocenoylnibropionate in Production Example 1 (2), 1,1'-ferrocenoylnihexane obtained in Production Example 4 (1) was used. The same operation as in Production Example 1 (2) was performed except that 5.5 g of methyl acid and 2.2 g of potassium hydroxide were used to prepare 1.1'-fecosenoylnihexanoic acid 5,
2g was obtained.

(3) Instead of 1.1′ to ferrocenoyl nipropionic acid in Production Example 1 (3), 1 obtained in Production Example 4 (2) above,
5.2 g of 1'-ferrocenoylnihexanoic acid, and 9,
The same j= production as in Production Example 1 (3) was carried out except that 9 g of zinc and 4.1 g of mercurous chloride were used, and 1. 3.0 g of ethyl beeferroceneniheptanoate was obtained.

Production Example 5 (1) 4-bromobutyric acid chloride synthesized from 10.8 g of 4-bromobutyric acid and 30.6 g (7) thionyl chloride;
0 g of anhydrous aluminum chloride and 6.0 g of ferrocene were reacted in a methylene chloride solvent at room temperature for 3 hours.

After the reaction was completed, it was treated with diluted hydrochloric acid and purified using a silica gel column to obtain the following formula 1. Obtained 9-7 g of PC (4-butenyl bromide) ferrocenyl ketone.

(2) 1,1'-di(4-butenyl bromide) ferrocenyl synthesized in Production Example 5 (1) in the presence of an amalgam prepared with 20.7 g of zinc and 8.6 g of mercuric chloride. 9.7 g of ketone was refluxed for 6 hours in a mixed solvent of J hydrochloric acid and ethanol.

After the reaction is completed, it is extracted with ethyl acetate and purified with a silica gel column to obtain the following formula 1. 5.1 g of beef elosenni (4-bromide butane) was obtained.

Example 5 53.0 g of polyethylene glycol (average molecular ff1
600), add 0.60g of metallic sodium to 7
The mixture was stirred at 0°C overnight. Next, 1,1'-ferrocene (tetrabromide butane) 5 obtained in 'J Preparation Example 5 is added to this.
．． 03g was added and reacted at 110°C for 10 hours.

This reaction solution was extracted with an equal mixture of water and n-butanol.

After washing the extract with water, it was developed using a silica gel column and a mixture of benzene and ethanol (benzene:ethanol-5=1) as a solvent for chromatographic purification.

After drying, the obtained purified product had a yield of 41.2% and a yield of 6.9
It was 3g.

The elemental analysis of this material is 54.9% carbon and 8.7% hydrogen.
% and nitrogen 0.0%, and the measurement results of proton nuclear magnetic resonance spectrum (IH-NMR) were as shown in FIG.

From the above results, it was found that the purified product was a ferrocene derivative having the following structure.

Production Example 6 (1) Instead of 4-bromobutyric acid in Production Example 5 (1), 8.
The same operation as in Production Example 5 (1) was carried out, except that 2 g of 6-brominated hexanoic acid, 5 or 6 g of anhydrous aluminum chloride, and 3.9 g of ferrocene and 40.0 g of thionyl chloride were used. 8.6 g of 11'-di(6-hexynyl bromide)ferrocenyl ketone of the following formula was obtained.

(2) Instead of 1,1'-di(4-bromide butenyl)ferrocenyl ketone in Production Example 5(2), the above Production Example 6 (1
) Production example 5 (2 ) to obtain 1,1'-ferrocenni (6
- Bromide hexane) 4.6 g was obtained.

Example 6 70.2 g of polyethylene glycol (average molecular weight 110
00), add 0.50g of metallic sodium to 70
The mixture was stirred at °C overnight. Next, add 4.56g of 1
, 1'-ferrocene (6-bromide hexane) was added to 11
The reaction was carried out at 0°C for 10 hours.

This reaction solution was extracted with an equal mixture of water and n-butanol.

After washing the extract with water, it was developed using a silica gel column and a mixture of benzene and ethanol (benzene:ethanol-5:1) as a solvent for chromatographic purification.

After drying, the obtained purified product had a yield of 37.2% and a yield of 7.8%.
It was 9g.

The elemental analysis values for this substance are 57.2% carbon and 9.2% hydrogen.
% and nitrogen 0.0%, and the measurement results of proton nuclear magnetic resonance spectrum ('H-NMR) were as shown in FIG.

From the above results, it was found that the purified product was a ferrocene derivative having the following structure.

Examples 7 to 15 and Comparative Example 1 A predetermined ferrocene derivative was added as a surfactant (micelle agent) to 100 cc of water to give a concentration of 2 mM, and 100 mg of a predetermined dye was added to 20 cc of this solution, and 1
The mixture was stirred for 0 minutes to disperse and solubilize.

Furthermore, after stirring with a stirrer for two days and nights, the obtained micelle solution (dispersed solution) was centrifuged at 200 rpm for 30 minutes. The visible absorption spectrum of this supernatant liquid is shown in Figures 7 to 15 (marked A).

From this, the above dye is solubilized (dispersed) in the micelle solution.
It was confirmed that The solubilization ability was as shown in Table 1. LiBr was added to this solution as a supporting salt to give a concentration of 0.1M, and the mixture was stirred with a stirrer for 10 minutes.

Using this solution as an electrolyte, constant potential electrolysis was carried out at a temperature of 25°C, an applied voltage of 0.5 V, and a predetermined current density using an ITO transparent glass electrode as an anode, platinum as a cathode, and a saturated sweetened electrode as a reference electrode. It lasted 30 minutes.

As a result, a thin film of the above dye was obtained on the TTO transparent glass electrode. The visible absorption spectra of the dye thin film on this ITO transparent glass electrode are shown in Figures 7 to 15 (mark B).

By matching marks A and B in each figure, it was confirmed that one film on the ITO transparent glass electrode was a solubilized dye. Moreover, the thickness of this thin film was measured by UV absorption spectrum. These results are summarized in Table 1.

〔Effect of the invention〕

The ferrocene derivative of the present invention is a new compound that has never existed before, and contains a surfactant (micellar agent), a catalyst, a combustion improver, a flotation agent, a lubricating aid, and a dispersant.

It can be used for various purposes such as liquid crystal. In particular, when this ferrocene derivative is used as a surfactant (micelle agent), it forms micelles in an aqueous solution system and solubilizes various hydrophobic organic substances such as pigments such as phthalocyanine and various hydrophobic polymers, which have a wide range of applications. be able to. Further, by adding this surfactant (micelle forming agent) and following the method of the present invention which utilizes the aggregation number of micelles by aqueous electrolysis, it is possible to form an extremely thin organic film. Furthermore, since the surfactant has excellent solubilizing ability, the film forming ability is extremely high.

The organic thin film formed by the method of the present invention is expected to be effectively used in various fields including photoelectric conversion materials, photosensitive materials, and solar cells.

[Brief explanation of the drawing]

1 to 6 show IH-NMR of the ferrocene derivatives obtained in Examples 1 to 6, respectively. Marks A in Figs. 7 to 15 indicate the visible absorption spectra of the supernatant liquids obtained in Examples 7 to 15, respectively, and marks B in Figs. 7 to 15 indicate the visible absorption spectra of the supernatant liquids obtained in Examples 7 to 15, respectively. The visible absorption spectrum of the obtained thin film on TTO is shown. FIG. 16 is a scanning electron micrograph (30,000x magnification) showing the surface structure of the thin film obtained in Example 8. Procedural amendment (voluntary) May 9, 1989

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 each represent a linear or branched alkylene group having 1 to 14 carbon atoms, and ^2
Each indicates -O- or ▲There is a mathematical formula, chemical formula, table, etc.▼. In addition, A^1 and A^2 each indicate ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R' is hydrogen or a methyl group, and r is a real number from 2 to 70.), and Z^1 and Z ^2 is hydrogen, methyl group, methoxy group, amino group, dimethylamino group, hydroxyl group, respectively.
Indicates an acetylamino group, carboxyl group, methoxycarbonyl group, acetoxy group, aldehyde group, or halogen. a and b each represent an integer of 1 to 4. ] A novel ferrocene derivative represented by (2) A surfactant containing the novel ferrocene derivative according to claim 1. (3) A hydrophobic organic substance is solubilized in an aqueous medium with a surfactant containing the novel ferrocene derivative according to claim 1, and the resulting micellar solution is electrolyzed to coat the hydrophobic organic substance on an electrode. A method for producing an organic thin film, the method comprising forming a thin film.