JPH0662655B2 - Novel ferrocene derivative, surfactant containing the same, and method for producing organic thin film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel ferrocene derivative, a surfactant containing the same, and a method for producing an organic thin film. More specifically, the main carbon chain as a substituent thereof has a branched chain. , A novel ferrocene derivative having a structure in which a substituted or unsubstituted phenyl group is bonded,
And a surfactant containing the ferrocene derivative and 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.

[Problems to be Solved by Prior Art and Invention]

Generally, a dye such as phthalocyanine or a derivative thereof is insoluble in water and soluble in an organic solvent such as dimethylformamide (DMF) and tetrahydrofuran (THF), but its solubilization amount is small, It has a solubility of only a few mg.

Although a surfactant for dissolving the phthalocyanine or the like in water has been studied so far, a satisfactory one has not been developed yet. It has been reported that the phthalocyanine derivative substituted with a functional group can be slightly dissolved in water with a sulfone-based surfactant, but its solubility is not necessarily sufficiently high, and an unsubstituted phthalocyanine cannot be dissolved at all.

Also, for water-insoluble polymers, surfactants for dissolving in water have been studied in the same manner as described above,
The current situation is that sufficient results have not been obtained yet.

The group of the present inventors has recently developed a ferrocene derivative having a polyoxyethylene chain as a surfactant for solubilizing a dye such as phthalocyanine or a derivative thereof or a water-insoluble polymer, and further A method for forming an organic thin film by using the so-called micelle electrolysis method was developed (PCT / JP88 / 00855).

The present inventors have improved the above-mentioned surfactant to improve the electrolytic performance during the micelle electrolysis method while maintaining a high solubilizing ability of the hydrophobic organic substance, and facilitate the redox reaction of the ferrocene derivative. We have conducted intensive research to develop a method of further advancing the production efficiency of organic thin films.

As a result, they have found that a ferrocene derivative having a novel structure in which a substituted or unsubstituted phenyl group is bonded as a branched chain to the main carbon chain of the substituent can achieve the object. The present invention has been completed based on such findings.

[Means for Solving the Problems]

That is, the present invention has the general formula [In the formula, R ¹ and R ² each represent a methyl group, a methoxy group, an amino group, a dimethylamino group, a hydroxyl group or halogen. R ³ represents hydrogen, a methyl group or an ethyl group, and X is —O— or And R ⁴ represents hydrogen or a methyl group. a is an integer of 0 to 4, b is an integer of 0 to 5, and k and m are 0 ≦, respectively.
It represents a positive integer that satisfies k + m ≦ 10, and n represents a real number of 2 to 70. ] And a surfactant containing the novel ferrocene derivative. Furthermore, the present invention solubilizes a hydrophobic organic substance with a surfactant containing the novel ferrocene derivative in an aqueous medium, and a method for solubilizing a hydrophobic organic substance, and this solubilizing method. Also provided is a method for producing an organic thin film, which comprises electrolyzing the resulting micelle solution to form a thin film of the hydrophobic organic substance on an electrode.

The ferrocene derivative of the present invention is represented by the general formula [I]. Here, each symbol in general formula [I] is as described above. That is, R ¹ and R ² are each a methyl group (CH ₃ ), a methoxy group (OCH ₃ ), an amino group (NH ₂ ), a dimethylamino group (N (CH ₃ ) ₂ ), a hydroxyl group (OH) or a halogen (chlorine). , Bromine, fluorine, etc.). R ¹ and R ² may be the same or different, and when R ¹ and R ² are respectively present in the 5-membered ring of a plurality of ferrocenes, a plurality of substituents may be the same or different. May be.

R ³ is hydrogen, methyl group (CH ₃ ), or ethyl group (CH 3
₂ CH ₃ ). The substitution position may be o-, m- or p-. X is oxygen (-O-) or oxycarbonyl group Indicates. Further, R ⁴ is hydrogen or a methyl group (CH ₃ ). Therefore, Is -O (CH ₂ CH ₂ O) _n H, Or Is. Here, n represents the number of repeating oxyethylene groups or 1-methyloxyethylene groups, and is 2 to 7
It means not only an integer of 0 but also a real number including them, and shows the average value of the number of repetitions of these groups.

The length of the main carbon chain having a substituted or unsubstituted phenyl group bonded to the five-membered ring of the ferrocene skeleton, that is, Where k and m are positive integers that satisfy 0 ≦ k + m ≦ 10. k is preferably 1 to 5, and m is preferably 1 to 5. The ferrocene derivative having k + m of more than 10 has deteriorated electrolytic performance.

The compound of the present invention has a phenyl group in the main carbon chain. Methylphenyl group Or ethylphenyl group Are linked as a branched chain.

The novel ferrocene derivative represented by the general formula [I] can be produced by various methods. Specifically, X is an oxycarbonyl group , Methylene chloride, carbon disulfide, carbon tetrachloride,
General formula in a solvent such as nitrobenzene (Wherein R ¹ , R ² , a and b are the same as above), and the substituted or unsubstituted ferrocene is represented by the general formula (In the formula, R ³ , k and m are the same as above.) A dicarboxylic acid anhydride having a substituted or unsubstituted phenyl group is treated with a Friedel-Crafts catalyst (for example, AlCl 2).
₃ , FeCl ₂ , FeCl ₃ , SbCl ₅ , SnCl _4, etc.) in the presence of −20 ° C.
Reaction at reflux temperature (In the formula, R ¹ , R ² , R ³ , a, b, k and m are the same as above.). Next, the compound represented by the above general formula [IV] is used in a solvent such as alcohol (methanol or ethanol), dimethyl ether, toluene, acetic acid or the like, using zinc or zinc amalgam and concentrated hydrochloric acid as a reducing agent at 20 to 120 ° C. Clemensen reduction at (In the formula, R ¹ , R ² , R ³ , a, b, k and m are the same as the above.) The compound represented by the formula is produced. After this (N and R ⁴ are the same as above), that is, HO (CH ₂ CHO) _n H or Is dehydrated and condensed in the presence of a catalyst such as p-toluenesulfonic acid or sulfuric acid to give the desired general formula (Wherein R ¹ , R ² , R ³ , R ⁴ , a, b, k, m and n are the same as above), a novel ferrocene derivative is prepared.

Further, for example, when X is oxygen (-O-), the compound of the general formula [I
I] to the compound represented by the general formula (In the formula, R ³ , k and m are the same as above.) The compound represented by the above general formula [II] and [III]
Under the same conditions as in the reaction of (In the formula, R ¹ , R ² , R ³ , a, b, k and m are the same as above.). Then, the compound represented by the general formula [IV ′] is esterified by refluxing it with methyl alcohol or ethyl alcohol under a catalyst such as p-toluenesulfonic acid or sulfuric acid for 3 to 10 hours to give the compound represented by the general formula [VI ] (In the formula, R ¹ , R ² , R ³ , a, b, k and m are the same as above,
R ⁵ represents a methyl group or an ethyl group. ) Is obtained. Further, the compound of the general formula (VI), in the presence of a reducing agent such as sodium borohydride (NaBH ₄ ) or lithium aluminum hydride (LiAlH ₄ ),
Tetrahydrofuran; 1,4-dioxane; diethyl ether; in an aprotic polar solvent such as dimethyl ether, by refluxing for 0.5 to 10 hours, the general formula (In the formula, R ¹ , R ² , R ³ , a, b, k and m are the same as the above.). Then, the general formula [VI
I) compound, carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine in chloroform solvent.
Reflux for 5 to 6 hours to halogenate the compound of the general formula (In the formula, R ¹ , R ² , R ³ , a, b, k and m are the same as above,
Y represents chlorine or bromine. ) Is produced. In this reaction, when carbon tetrachloride is used as a reaction raw material, this carbon tetrachloride may be used as a solvent.

The compound of the general formula [VIII] obtained by the above reaction is represented by the formula (N and R ⁴ are the same as above) and 50 ° C. to 200 ° C., 3 to 3 in the presence of a polyethylene glycol compound and an alkali metal such as sodium, lithium or potassium.
After reacting for 0 hours, the general formula (Wherein R ¹ , R ² , R ³ , R ⁴ , a, b, k, m and n are the same as above), and a new ferrocene derivative is produced.

The novel ferrocene derivative of the present invention obtained by the method as described above is effective as a surfactant, and can be particularly used as a surfactant (micelling agent) for solubilizing a hydrophobic organic substance in an aqueous medium. When the ferrocene derivative of the present invention is used as the micellizing agent, it can be used alone or as a mixture of two or more kinds of ferrocene derivatives.

The surfactant of the present invention contains a ferrocene derivative represented by the above general formula [I] (including the above general formulas [I ′] and [I ″]) as a main component, and other various kinds as necessary. It is also possible to appropriately add the additive.

By using the surfactant of the present invention, various hydrophobic organic substances can be solubilized in an aqueous medium. There are various kinds of such hydrophobic organic substances, for example, phthalocyanine, a metal complex of phthalocyanine and their derivatives, naphthalocyanine, a metal complex of naphthalocyanine and their derivatives, porphyrin, a metal complex of porphyrin and their derivatives. 1,1'-diheptyl-4, including dyes for optical memory such as derivatives and organic dyes,
Electrochromic materials such as 4'-bipyridinium dibromide, 1,1'-didodecyl-4,4'-bipyridinium dibromide, 6-nitro-1,3,3-trimethylspiro- (2'H-1'-benzopyran -2
Photosensitive materials (photochromic materials) such as 2'-indoline (commonly called spiropyran), photosensor materials, liquid crystal display dyes such as p-azoxyanisole, and "Color Chemical Dictionary" CMC Co., Ltd., March 1988.
Electronic dyes, recording dyes, environmental chromism dyes, photographic dyes, energy dyes, biomedical dyes, food / cosmetic dyes, dyes, pigments listed on pages 542 to 717 issued on the 8th. Among the special coloring pigments, there are hydrophobic compounds. Also,
7,7,8,8-Tetracyanoquinone dimethane (TCN
Q) and tetrathiafulvalene (TTF) 1: 1 complex organic conductive materials and gas sensor materials, pentaerythritol diacrylate and other photocurable paints, stearic acid and other insulating materials, 1-phenylazo-2-naphthol Examples of such materials include diazo type photosensitive materials and paints. Further, water-insoluble polymers such as polycarbonate, polystyrene, polyethylene, polypropylene, polyamide, polyphenylene sulfide (PPS), polyphenylene oxide (PPO), polyacrylonitrile (PAN), and other general-purpose polymers, and polyphenylene, polypyrrole, polyaniline, polythiophene , Acetyl cellulose, polyvinyl acetate, polyvinyl butyral, and various other polymers (such as polyvinyl pyridine) or copolymers (such as copolymers of methyl methacrylate and methacrylic acid)
Can be raised.

There are various modes for using the novel ferrocene derivative of the present invention as a surfactant, and it is particularly effective to use it as a micellizing agent in the method for producing an organic thin film of the present invention. In the method of the present invention, the above-mentioned general formula [I]
Add a surfactant (micelling agent) consisting of the new ferrocene derivative (concentration is above the limit micelle concentration), supporting salt and hydrophobic organic substance, and disperse them sufficiently by ultrasonic wave, homogenizer or stirrer to form micelles. Excuse me. It is usually carried out for 1 hour to 10 days. Thereafter, if necessary, excess hydrophobic organic substance is removed, and the resulting micelle solution is subjected to electrolytic treatment using the electrode described later while standing or with some stirring. Alternatively, a hydrophobic organic substance may be supplementarily added to the micelle solution during the electrolytic treatment, or the micelle solution in the vicinity of the anode may be extracted from the system, and the hydrophobic organic substance may be added to the extracted micelle solution and sufficiently mixed and stirred. After that, a circulation circuit for returning this liquid to the vicinity of the cathode may be additionally provided. The electrolysis conditions at this time may be appropriately selected according to various situations, but the liquid temperature is usually 0 to 70 ° C., preferably 20.
-30 ° C, voltage 0.03-1.00V, preferably 0.15-0.7V
And the current density is 10 mA / cm ² or less, preferably 50 to 30
0 μA / cm ² .

When this electrolytic treatment is performed, the redox reaction of the ferrocene derivative proceeds. Focusing on the behavior of Fe ions in the ferrocene derivative, Fe ²⁺ of ferrocene becomes Fe ³⁺ at the anode, micelles collapse, and particles of hydrophobic organic substance (60
0 to 900Å) is deposited on the anode. On the other hand, at the cathode, Fe ³⁺ oxidized at the anode returns to the original micelles when it is reduced to Fe ²⁺ , so that the film forming operation can be repeated with the same solution. The novel ferrocene derivative used in the method of the present invention is a ferrocene derivative having a substituted or unsubstituted phenyl group as a branched chain in the main carbon chain, has a high solubilizing ability for hydrophobic substances, and further has the above-mentioned oxidation. The reduction reaction is very efficient and a thin film is formed in a short time.

By such electrolytic treatment, a thin film of particles of the desired hydrophobic organic substance having a particle size of about 600 to 900 Å is formed on the anode.

The supporting salt (supporting electrolyte) used in the method of the present invention is added as necessary in order to adjust the electric conductivity of the aqueous medium. The amount of the supporting salt added is usually about 0 to 300 times, preferably about 10 to 200 times the concentration of the above-mentioned surfactant (micelling agent). Electrolysis can be performed without adding this supporting salt, but in this case, a thin film having high purity containing no supporting salt can be obtained.
When a supporting salt is used, the type of the supporting salt is not particularly limited as long as it can control the electric conductivity of the aqueous medium without hindering the formation of micelles or the deposition of the hydrophobic organic substance on the electrode. There is no.

Specifically, sulfates (lithium, potassium, sodium, rubidium,
Salts such as aluminum), acetates (salts such as lithium, potassium, sodium, rubidium, beryllium, magnesium, calcium, strontium, barium, aluminum), halide salts (lithium, potassium, sodium, rubidium, calcium, magnesium, aluminum) Etc.), water-soluble oxide salts (lithium, potassium, sodium, rubidium, calcium,
Salts of magnesium, aluminum, etc.) are preferred.

Further, the electrode used in the method of the present invention may be a metal or a conductor that is more noble than the oxidation potential of ferrocene (+0.15 V vs. saturated sweet koh electrode). Specific examples thereof include ITO (mixed oxide of indium oxide and tin oxide), platinum, gold, silver, glassy carbon, conductive metal oxide, and organic polymer conductor.

〔Example〕

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

Production Example 1 (1) In the presence of 14.6 g of anhydrous aluminum chloride, 9.4 g of ferrocene and 10.0 g of 2-phenylglutaric anhydride were reacted in a methylene chloride solvent at room temperature for 2 hours.

After the reaction was completed, it was treated with dilute hydrochloric acid and then extracted with methylene chloride.
Alkali extraction and acid treatment were carried out to obtain 16.6 g (yield 86%) of the following compound and isomer mixture.

(2) In the presence of zinc amalgam prepared from 9.6 g of zinc and 4.4 g of mercuric chloride, 8.3 g of a mixture of the compound and
80% in a mixed solvent of concentrated hydrochloric acid and 1,2-dimethoxyethane
The reaction was carried out at 0 ° C for 2 hours. After completion of the reaction, extraction with ethyl acetate and purification with a silica gel column were performed to obtain 3.9 g (yield 49%) of a mixture of the following compounds and isomers.

Example 1 Compound obtained in Preparation Example 1 and isomer mixture thereof 3.9
g, 66 g of polyethylene glycol (average molecular weight 6
00) and 0.5 ml of concentrated sulfuric acid were added and reacted at 80 ° C. for 8 hours.

The reaction solution was extracted with a water-n-butanol equivalent mixture. The extract was washed with water, developed using a silica gel column and a mixture of ethyl acetate-methanol (4: 1) as a developing solvent, and purified by chromatography.

After drying, the amount of the obtained purified product was 3.5 g (yield 34%). The elemental analysis value of this product is carbon 61.0%, hydrogen 8.2
%, And the measurement result of ¹ H-NMR was as shown in FIG. 1.

From the above results, the purified product was identified as a ferrocene derivative having the following structure (isomer).

Example 2 After adding the ferrocene derivative obtained in Example 1 to 100 cc of water to make a 2 mM solution, 20 ml of this micelle solution was added.
0.1 g of phthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the above, and the mixture was dispersed by ultrasonic waves for 10 minutes to solubilize it. Furthermore, after stirring with a stirrer for two days and nights, the obtained dispersible micelle solution was centrifuged at 2000 rpm for 30 minutes. From the visible absorption spectrum of this supernatant, it was confirmed that the phthalocyanine was dispersed, and from the absorbance, it was found that the solubilizing ability of the micelle forming agent was 8.4 mM / 2 mM micelle forming agent.

Lithium bromide was added to the dispersion-solubilized micelle solution to a concentration of 0.1 M, and the mixture was stirred with a stirrer for 10 minutes. This solution was used as an electrolytic solution, an ITO transparent glass electrode was used as an anode, a platinum plate was used as a cathode, and a saturated sweet-coal electrode was used as a reference electrode, and constant potential electrolysis was performed at 25 ° C. and an applied voltage of 0.5V. At this time, the current density was 9.8 μA / cm ² , the energization time was 30 minutes,
The amount of electricity passed was 0.015 coulomb (C).

As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. Since the absorption spectrum of phthalocyanine on the ITO transparent glass electrode and the absorption spectrum of the dispersion-solubilized micelle solution match, it was found that the thin film on the ITO transparent glass electrode was phthalocyanine and the film thickness was 2.2 μm from the absorbance. It was

On the other hand, lithium bromide as a supporting salt was added to the micellar solution at
In addition to M, the oxidation-reduction potential was measured by cyclic voltammetry to find that it was 0.192 V, and the potential difference between the oxidation and reduction peaks was 60 mV.

Production Example 2 (1) 8.0 g of the mixture of the compound obtained in Production Example 1 (1) and was refluxed for 5 hours in an ethanol solvent in the presence of 1 cc of sulfuric acid. After completion of the reaction, concentration, alkali treatment and ether extraction were performed, and after drying, ether was distilled off to obtain 8.1 g of the following compound and isomer mixture.

(2) A mixture of the compound obtained in (1) above and 8.
1 g, 8.0 g of anhydrous aluminum chloride and 3.8 g of sodium borohydride were refluxed in a tetrahydrofuran solvent for 2 hours. After completion of the reaction, the mixture was treated with dilute hydrochloric acid, extracted with ethyl acetate, and purified with a silica gel column to obtain 4.2 g (yield 60%) of an isomer mixture of the following compound.

(3) A mixture of the compound obtained in (2) above and 4.
2g, triphenylphosphine 4.7g, carbon tetrabromide 6.0g
Was refluxed in chloroform solvent for 3 hours. After the reaction,
Concentrate, extract with n-pentane, and purify with a silica gel column to give the following compound and isomer mixture of 3.4.
g (yield 69%) was obtained.

Example 3 42 g of polyethylene glycol (average molecular weight 1000)
0.30 g of metallic sodium was added to the mixture, and the mixture was stirred at 80 ° C. overnight. Next, 3.3 g of the compound and isomer mixture obtained in Production Example 2 (3) was added thereto, and the mixture was reacted at 110 ° C. for 10 hours. The reaction was extracted with a water-n-butal equivalent mixture. After washing the extract with water, a silica gel column was used, and ethyl acetate-methanol (4:
Chromatographic purification was performed using the mixture of 1).

The amount of the purified product obtained was 3.9 g (yield 37%), and the elemental analysis values of this product were carbon 58.5%, hydrogen 8.1%, ¹ H-
The NMR measurement results were as shown in FIG.

From the above results, it was possible to identify that the purified product was a ferrocene derivative having the following structure (isomer).

Example 4 The ferrocene derivative obtained in Example 3 was added to 100 cc of water to make a 2 mM solution, and then 20 cc of this micelle solution was added.
0.1 g of phthalocyanine (manufactured by Tokyo Kasei) was added, and the mixture was sonicated for 10 minutes and then solubilized. Furthermore, after stirring for two days with a stirrer, the obtained dispersion-solubilized micelle solution was centrifuged at 2000 rpm for 30 minutes.
From the visible absorption spectrum of this supernatant, it was confirmed that the phthalocyanine was dispersed, and from the absorbance, it was found that the solubilizing ability of the micelle forming agent was 7.9 mM / 2 mM micelle forming agent.

Lithium bromide was added to the dispersion-solubilized micelle solution to a concentration of 0.1 M, and the mixture was stirred with a stirrer for 10 minutes.

This solution was used as an electrolytic solution, an ITO transparent glass electrode was used as an anode, a platinum plate was used as a cathode, and a saturated sweet candy electrode was used as a reference electrode, and constant potential electrolysis was performed at an applied voltage of 0.5V. At this time, the current density was 9.4 μA / cm ² , the energization time was 30 minutes, and the energization amount was 0.02 C.

As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. Since the absorption spectrum of phthalocyanine on the ITO transparent glass electrode and the absorption spectrum of the dispersion-solubilized micelle solution match, it was found that the thin film on the ITO transparent glass electrode was phthalocyanine, and the thin thickness was 1.9 μm due to the absorbance. .

On the other hand, 0.1M lithium bromide as a supporting salt was added to the micelle solution.
As a result of measuring the oxidation-reduction potential by cyclic voltammetry, it was 0.189 V, and the potential difference between the oxidation and reduction peaks was 55 mV.

Comparative Example 1 Instead of the compound obtained in Example 1 in Example 2, Using the compound of Example 1, in the same manner as in Example 2, a dispersion-solubilized micelle solution of phthalocyanine was obtained. It was found that the solubilizing ability of this product was 8.2 mM / 2 mM micellizing agent.

Using this micellizing agent, potentiostatic electrolysis was performed in the same manner as in Example 2. At this time, the current density was 16.7 μA / cm ² , the energization time was 30 minutes, and the energization amount was 0.03C.

It was found from the absorption spectrum that the obtained thin film was phthalocyanine, and the film thickness was 1.85 μm from the absorbance.

Further, the redox potential was measured in the same manner as in Example 2 and found to be 0.239 V, and the potential difference between the oxidation and reduction peaks was 8
It was 8 mV.

Comparative Example 2 Instead of the compound obtained in Example 1 in Example 2, a compound of formula Using the compound of Example 1, in the same manner as in Example 2, a dispersion-solubilized micelle solution of phthalocyanine was obtained. It was found that the solubilizing ability of this product was 1.8 mM / 2 mM micelle forming agent.

Using this micellizing agent, potentiostatic electrolysis was performed in the same manner as in Example 2. At this time, the current density was 11.9 μA / cm ² , the energization time was 30 minutes, and the energization amount was 0.02C.

It was found from the absorption spectrum that the obtained thin film was phthalocyanine, and the film thickness was 0.05 μm from the absorbance.

Further, the redox potential was measured in the same manner as in Example 2 and found to be 0.124 V, and the potential difference between the oxidation and reduction peaks was 3
It was 5 mV.

〔The invention's effect〕

The ferrocene derivative of the present invention is a novel compound that has never been used, and is to be used for various purposes such as a surfactant (micelle agent), a catalyst, a combustion improver, a flotation agent, a lubricating aid, a dispersant, and a liquid crystal. You can In particular, when this ferrocene derivative is used as a surfactant (micelling agent), it forms micelles in an aqueous solution system and solubilizes various hydrophobic organic substances such as dyes such as phthalocyanine and various hydrophobic polymers, which have a wide range of applications. be able to. Further, according to the method of the present invention in which the surfactant (micelling agent) is added and the aggregated discrete micelles are utilized by aqueous solution electrolysis, an extremely thin organic film can be formed. Moreover, since the above-mentioned surfactant has excellent redox efficiency, the film forming ability is remarkably 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 description of drawings]

FIG. 1 shows ¹ H-of the ferrocene derivative obtained in Example 1.
NMR is shown, and FIG. 2 shows ¹ H-NMR of the ferrocene derivative obtained in Example 3.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // H01L 31/04 31/08

Claims (4)

[Claims] 1. A general formula [In the formula, R ¹ and R ² each represent a methyl group, a methoxy group, an amino group, a dimethylamino group, a hydroxyl group or halogen. R ³ represents hydrogen, a methyl group or an ethyl group, and X is —O— or And R ⁴ represents hydrogen or a methyl group. a is an integer of 0 to 4, b is an integer of 0 to 5, and k and m are 0 ≦, respectively.
It represents a positive integer that satisfies k + m ≦ 10, and n represents a real number of 2 to 70. ] The novel ferrocene derivative represented by these. 2. A surfactant containing the novel ferrocene derivative according to claim 1. 3. A hydrophobic organic material in an aqueous medium.
A method for solubilizing a hydrophobic organic substance, which comprises solubilizing with a surfactant containing the novel ferrocene derivative described. 4. A hydrophobic organic material in an aqueous medium.
A method for producing an organic thin film, which comprises solubilizing with a surfactant containing the novel ferrocene derivative described above and electrolyzing the resulting micelle solution to form a thin film of the hydrophobic organic substance on an electrode.