JPH0633298B2 - Ferrocene derivatives and surfactants containing the same - Google Patents

Description

Detailed Description of the Invention Technical Field The present invention relates to a ferrocene derivative and a surfactant containing the same, and more particularly to a novel ferrocene derivative having a polyoxyethylene chain, and a surfactant containing the ferrocene derivative and capable of solubilizing dyes such as phthalocyanines.

BACKGROUND ART Generally, dyes such as phthalocyanine and its derivatives are insoluble in water, but are soluble in organic solvents such as dimethylformamide (DMF) and tetrahydrofuran (THF), but the amount of solubility is small, at only a few milligrams.

Although surfactants for dissolving phthalocyanines in water have been studied, no satisfactory solution has yet been developed. It has been reported that functionally substituted phthalocyanine derivatives can be slightly dissolved in water with sulfone surfactants, but the solubility is not necessarily sufficiently high, and unsubstituted phthalocyanines cannot be dissolved at all.

In addition, surfactants have been researched to dissolve water-insoluble polymers in water, as mentioned above.
The current situation is that sufficient results have not yet been achieved.

The present inventors have conducted extensive research in order to develop a surfactant that can solubilize dyes such as phthalocyanines and their derivatives, or water-insoluble polymers.

During the course of this research, the inventors discovered that ferrocene derivatives are promising surfactants with the above-mentioned properties. Based on this discovery, the inventors continued their research and discovered that new ferrocene derivatives, in which specific substituents containing polyoxyethylene chains have been introduced into ferrocene or its derivatives, can achieve the objective. At the same time, they discovered that water-insoluble (hydrophobic) organic thin films can be efficiently produced by electrochemical techniques using these new ferrocene derivatives.

The present invention was completed through such research process.

Disclosure of the Invention That is, the present invention provides a compound represented by the general formula [I] [wherein R ¹ and R ² each represent a hydrogen atom, a methyl group, or an ethyl group; m is 1 to 4; n is 1 to 5; and r is 1.
represents an integer of 1 to 18, and s represents a real number of 2.0 to 45.0.] or general formula [II] [wherein w represents an integer of 2 to 20; R ¹ , R ² , m.
n and s are the same as above.], and also to provide a surfactant containing the ferrocene derivative represented by the above general formula [I] or [II].

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an explanatory diagram showing the principle of the method for producing an organic thin film using a surfactant of the present invention, in which 1 represents a ferrocene derivative, 2 represents a hydrophobic organic substance, 3 represents a micelle, 4 represents an oxidized ferrocene derivative, 5 represents an anode, 6 represents a cathode, Fc represents ferrocene, and ^e- represents an electron.

FIG. 2 shows the ^1H- of the ferrocene derivative obtained in Example 1.
FIG. 3 shows ^{the 1} H-NMR of the ferrocene derivative obtained in Example 2, FIG. 4 shows ^{the 1} H-NMR of the ferrocene derivative obtained in Example 3, FIG. 5 shows ^{the 1} H-NMR of the ferrocene derivative obtained in Example 4, and FIG. 6 shows the 1 H-NMR of the ferrocene derivative obtained in Example 5.
7 shows ^{the 1} H-NMR of the ferrocene derivative obtained in Example 6, and FIG. 8 shows ^{the 1} H-NMR of the ferrocene derivative obtained in Example 7.
^1H -NMR of the ferrocene derivative obtained in 1 is shown.

FIG. 9 shows the visible absorption spectra of the supernatants obtained in Examples 8 to 12, and FIG. 10 shows the visible absorption spectra of the thin dye films on ITO obtained in Examples 13 and 14.

FIG. 11 shows the visible absorption spectrum of the supernatant obtained in Example 15 and the visible absorption spectrum of the dye thin film on ITO, FIG. 12 shows the visible absorption spectrum of the supernatant obtained in Example 16 and the visible absorption spectrum of the dye thin film on ITO, FIG. 13 shows the visible absorption spectrum of the supernatant obtained in Example 17 and the visible absorption spectrum of the dye thin film on ITO, FIG. 14 shows the visible absorption spectrum of the supernatant obtained in Example 18 and the visible absorption spectrum of the dye thin film on ITO, FIG. 15 shows the visible absorption spectrum of the supernatant obtained in Example 19 and the visible absorption spectrum of the dye thin film on ITO, and FIG. 16 shows the visible absorption spectrum of the supernatant obtained in Example 20.
16 shows the visible absorption spectrum of the supernatant obtained in Example 15 and the visible absorption spectrum of the dye thin film on ITO, and FIG. 17 shows the visible absorption spectrum of the supernatant obtained in Example 21 and the visible absorption spectrum of the dye thin film on ITO.
1 shows the visible absorption spectrum of a thin film of the dye on SiO.

Figure 18 is an SEM photograph showing the surface structure of the thin film formed in Example 13, Figure 19 is an SEM photograph showing the surface structure of the thin film formed in Example 15, Figure 20 is an SEM photograph showing the surface structure of the thin film formed in Example 16, and Figure 21 is an SEM photograph showing the surface structure of the thin film formed in Example 17.

BEST MODE FOR CARRYING OUT THE INVENTION The ferrocene derivative of the present invention is represented by the general formula [I] or [II].
In the formula, ^R1 and ^R2 each represent a hydrogen atom, a methyl group, or an ethyl group; m is 1 to 4; n is 1 to 5; and r is 11 to 15.
r is an integer of 11 to 18, and s is a real number of 2.0 to 45.0. Since r is an integer of 11 to 18 as described above, an alkylene group (polymethylene group) having 11 to 18 carbon atoms, such as an undecamethylene group, a dodecamethylene group, or a tridecamethylene group, is interposed between the ring carbon atom and the etheric oxygen atom closest to said carbon atom.
It means not only integers between 2.0 and 45.0 but also real numbers including these, _and indicates the average number of repetitions of oxyethylene groups ( _-CH2CH2O- ) constituting the ferrocene derivative.

On the other hand, since w in the general formula [II] represents an integer of 2 to 20, an alkylene group (polymethylene group) having 2 to 20 carbon atoms, such as an ethylene group or a propylene group, is interposed between the ring carbon atom and the oxycarbonyl group.
R ¹ , R ² , m, n and s are the same as defined above.

The ferrocene derivatives represented by the general formula [I] or [II] can be produced by various methods. For example, the ferrocene derivatives represented by the general formula [I] can be produced as follows. (where s is the same as above), an alkali metal (such as metallic sodium or metallic potassium) is added to polyethylene glycol represented by the formula (1), and the mixture is stirred at room temperature to 200°C for several minutes to several days,
Then the general formula [wherein X represents a halogen atom; and R ¹ , R ² ,
The halogen-containing ferrocene compound of the general formula [IV] can be obtained by, for example, reacting an ω-halogenocarboxylic acid of the general formula HOOC(CH ₂ ) _r-1 X (wherein r and X are the same as above) with a suitable halogenating agent (such as thionyl chloride) to form a ferrocene derivative of the general formula [I].
An acid halide (acylated product) represented by the general formula X ¹ OC(OH ₂ ) _r-1 X (wherein X ¹ represents a halogen atom derived from a halogenating agent, and r and X are the same as above) is prepared, and this is converted into an acid halide (acylated product) represented by the general formula [wherein R ¹ , R ² , m and n are the same as above] to form a compound represented by the general formula: [wherein R ¹ , R ² , m, n and r are the same as defined above] is obtained, and the halogen-containing ferrocene compound of general formula [IV] can be produced by further reducing this.

On the other hand, the ferrocene derivative represented by the general formula [II] can be prepared by adding concentrated sulfuric acid to the polyethylene glycol represented by the general formula [III] and stirring the mixture at room temperature to 200° C. for several minutes, followed by adding the mixture to the polyethylene glycol represented by the general formula [III]. [wherein R ¹ , R ² , m, n and w are the same as above], and react with stirring, followed by extraction and purification.
The carboxyl group-containing ferrocene compound represented by the general formula [I] can be produced, for example, as follows: That is, by reacting an alkoxycarbonyl acid halide represented by the general formula ^X2OC ( _CH2 ) _w-1COOR (wherein ^X2 represents a halogen atom, R represents an alkyl group, and w is the same as above) with ferrocene represented by the general formula [V] or a derivative thereof to produce a carboxyl group-containing ferrocene compound represented by the general formula [I] [wherein R ¹ , R ² , m, n and w are the same as above.], which is then hydrolyzed to the corresponding carboxylic acid, and then reduced, or reduced and then hydrolyzed, to produce the carboxyl group-containing ferrocene compound represented by general formula [VII].

The ferrocene derivatives of the present invention represented by the general formula [I] or [II] can be produced as described above.
In producing these ferrocene derivatives, similar polyethers can be used in place of the polyethylene glycol of general formula [III]. After the reaction, extraction treatment can be carried out using alcohol, THF, etc., and purification can be carried out by chromatography, etc.

The ferrocene derivatives of the present invention represented by the general formula [I] or [II] obtained by the above-mentioned method are effective as surfactants, and in particular can be used as surfactants (micelle forming agents) for solubilizing hydrophobic organic substances in water or aqueous media.

The surfactant of the present invention is a compound represented by the general formula [I] or [I
I] as a main component, and various additives can also be added as needed. By using this surfactant of the present invention, various hydrophobic organic substances can be solubilized in water or an aqueous medium. There are various hydrophobic organic substances, and examples of such hydrophobic organic substances include optical memory dyes and organic dyes such as phthalocyanine, phthalocyanine derivatives, metal complexes of phthalocyanine, metal complexes of phthalocyanine derivatives, naphthalocyanine, naphthalocyanine derivatives, metal complexes of naphthalocyanine, metal complexes of naphthalocyanine derivatives, porphyrin, porphyrin derivatives (e.g., tetraphenylporphyrin), metal complexes of porphyrin, and metal complexes of porphyrin derivatives, as well as 1,1'-diheptyl-4,
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) and optical sensor materials such as 2'-indoline (commonly known as spiropyran), dyes for liquid crystal displays such as p-azoxyanisole,
Examples of suitable materials include organic conductive materials and gas sensor materials such as a 1:1 complex of 8-tetracyanoquinone dimethane (TCNQ) and tetrathiafulvalene (TTF), photocurable coating materials such as pentaerythritol diacrylate, insulating materials such as stearic acid, and diazo-type photosensitive materials and coating materials such as 1-phenylazo-2-naphthol. Furthermore, examples include water-insoluble polymers, such as general-purpose polymers such as polycarbonate, polystyrene, polyethylene, polypropylene, polyamide, polyphenylene sulfide (PPS), polyphenylene oxide (PPO), and polyacrylonitrile (PAN), as well as polyphenylene, polypyrrole, polyaniline, polythiophene, acetylcellulose, polyvinyl acetate, and polyvinyl butyral, as well as various polymers (e.g., polyvinylpyridine) and copolymers (e.g., copolymers of methyl methacrylate and methacrylic acid).

The ferrocene derivatives of the present invention can be used as surfactants in various ways, but are particularly effective as micellizers in the production of organic thin films. To produce such organic thin films, a surfactant (micelleizer) consisting of a ferrocene derivative represented by the general formula [I] or [II], a supporting salt, and a hydrophobic organic substance are first added to an aqueous medium and thoroughly dispersed using ultrasound, a homogenizer, or a stirrer to form micelles. If necessary, excess hydrophobic organic substance is removed, and the resulting micellar solution is electrolyzed using the electrodes described above, with the solution remaining stationary or with slight stirring. Alternatively, the hydrophobic organic substance may be replenished during electrolysis. Alternatively, a circulation circuit may be provided in which the micellar solution near the anode is removed from the system, the hydrophobic organic substance is added to the removed micellar solution, and the resulting solution is thoroughly mixed and stirred, and then the resulting solution is returned to the cathode.
The electrolysis conditions may be appropriately selected depending on the circumstances. Generally, the solution temperature is 0 to 70°C, preferably 20 to 30°C.
°C, voltage 0.03 to 1.5 V, preferably 0.1 to 0.5 V, current density 10 mA/ ^cm2 or less, preferably 50 to 3
00 μA/cm ² .

When this electrolysis is carried out, the reaction proceeds as shown in Figure 1. When we focus on the behavior of the Fe ions in the ferrocene derivative, the Fe ²⁺ of ferrocene becomes Fe ³⁺ at the anode 5.
As a result, the micelles 3 collapse, and particles (about 600 to 900 Å) of the hydrophobic organic substance 2 are deposited on the anode.
At the cathode 6, the Fe ³⁺ oxidized at the anode 5 is reduced to Fe ²⁺ and returns to the original micelles 3, so that the film formation operation can be carried out repeatedly using the same solution.

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

Supporting salt (supporting electrolyte) used in the method for producing the organic thin film
is added as needed to adjust the electrical conductivity of the aqueous medium. The amount of the supporting salt added is usually about 10 to 300 times, preferably about 50 to 200 times, the concentration of the surfactant (micelle forming agent). There are no particular restrictions on the type of supporting salt, as long as it can adjust the electrical conductivity of the aqueous medium without preventing micelle formation or precipitation of the hydrophobic organic substance on the electrode.

Specifically, sulfates (lithium, potassium, sodium, rubidium,
Preferred are acetates (salts of lithium, potassium, sodium, rubidium, beryllium, magnesium, calcium, strontium, barium, aluminum, etc.), and acetates (salts of lithium, potassium, sodium, rubidium, beryllium, magnesium, calcium, strontium, barium, aluminum, etc.).

The electrode used in the above-mentioned method for producing an organic thin film may be made of a metal or conductor that is more noble than the oxidation potential of ferrocene (+0.15 V vs. saturated calomel electrode).
(mixed oxide of indium oxide and tin oxide), platinum,
Examples include gold, silver, glassy carbon, conductive metal oxides, and organic polymer conductors.

[Example]

The present invention will now be explained in more detail using examples.

Synthesis Example 1 (1) 11-Undecanoic acid chloride, synthesized from 50.0 g of 11-bromoundecanoic acid and 90.0 g of thionyl chloride, was reacted with 37.0 g of anhydrous aluminum chloride and 35.0 g of ferrocene in methylene chloride solvent at 5° C. for 3 hours. After completion of the reaction, the reaction mixture was treated with dilute hydrochloric acid and purified on a silica gel column to obtain 56.9 g of 10-bromodecanylferrocenyl ketone represented by the following formula:

(2) In the presence of an amalgam prepared from 65.4 g of zinc and 27.2 g of mercuric chloride, the 10-
56.9 g of decanyl bromide ferrocenyl ketone was refluxed in a mixed solvent of concentrated hydrochloric acid and ethanol for 6 hours to carry out a reduction reaction.

After the reaction was completed, the mixture was extracted with ethyl acetate and purified with a silica gel column to obtain 1-ferrocenyl-11-
42.1 g of undecane bromide was obtained.

Example 1 6.5 g of polyethylene glycol (average molecular weight 600)
0.064 g of metallic sodium was added to the mixture, and the mixture was stirred at 70° C. for 24 hours.
11-bromoundecane (obtained in Synthesis Example 1 above)
The reaction mixture was added and reacted at 110° C. for 10 hours, and the reaction mixture was extracted with an equal mixture of water and n-butanol. The extract was washed with water, and then a silica gel column was used to extract the extract with a mixture of benzene and ethanol (benzene:ethanol=
The column was developed using a 5:1 mixture and purified by chromatography.
The purified product was obtained in a yield of 41% and in an amount of 0.96 g.
The elemental analysis of this product was carbon 60.21%, hydrogen 9.46%.
%, and nitrogen 0.00%. The results of measurement of the proton nuclear magnetic resonance spectrum ( ¹ H-NMR) are shown in FIG.

From the above results, it can be seen that the purified substance is a ferrocene derivative having the following synthesis.

Example 2 The same procedure as in Example 1 was carried out, except that polyethylene glycol having an average molecular weight of 1,000 was used. The purified product obtained was in a yield of 31% and in an amount of 2.15 g. The results of ^1H -NMR analysis of this product are shown in Figure 3.

From the above results, it is clear that the purified product is a ferrocene derivative having the following structure:

Synthesis Example 2 (1) In the presence of 9.6 g of anhydrous aluminum chloride, 13.5 g of ferrocene and 11-ethoxycarbonylundecanoic acid chloride (J. Amer. Chem. Soc., 69, 2350 (194
7)) was reacted in 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 purified with a silica gel column to obtain 13.7 g of ethyl ferrocenoylundecanoate represented by the following formula.

(2) 12.4 g of ethyl ferrocenoylundecanoate synthesized in (1) above and 2.9 g of potassium hydroxide were refluxed in ethanol solvent for 2 hours, followed by acid treatment to obtain 11.3 g of ferrocenoylundecanoic acid represented by the following formula.

(3) In the presence of zinc amalgam prepared from 6.5 g of zinc and 2.7 g of mercuric chloride, 6.0 g of the ferrocenoylundecanoic acid synthesized in (2) above was 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 ferrocenyl dodecanoic acid represented by the following formula:
4.8 g was obtained.

Example 3 The same procedure as in Example 1 was carried out, except that 6 g of polyethylene glycol (average molecular weight 600) and 0.1 cc of concentrated sulfuric acid were added to 0.29 g of ferrocenyldodecanoic acid (obtained in Synthesis Example 2 above), and the mixture was reacted at 80°C for 6 hours. The purified product obtained was in a yield of 62% and weighed in at 0.44 g. ^{The 1H} -NMR measurement results of this product are shown in Figure 4.

From the above results, it is clear that the purified product is a ferrocene derivative having the following structure:

Synthesis Example 3 (1) Instead of the 11-ethoxycarbonylundecanoic acid chloride shown in Synthesis Example 2 (1), 35.0 g of 10-ethoxycarbonyldecanoic acid chloride was used, and 17.7 g of 10-ethoxycarbonyldecanoic acid chloride was used.
The same procedure as in Synthesis Example 2(1) was carried out except that 24.7 g of anhydrous aluminum chloride was used and reacted with 24.7 g of ferrocene, thereby obtaining 23.0 g of ethyl ferrocenoyldecanoate represented by the following formula.

(2) The same procedure as in Synthesis Example 2(2) was carried out, except that 5.0 g of ethyl ferrocenoyldecanoate (obtained in (1) above) was used instead of the ethyl ferrocenoylundecanoate shown in Synthesis Example 2(2) and 1.2 g of potassium hydroxide was used, to obtain 4.7 g of ferrocenoyldecanoic acid represented by the following formula.

(3) Instead of the ferrocenoylundecanoic acid shown in Synthesis Example 2(3), 4.7 g of ferrocenoyldecanoic acid (see above (2)) was used.
The same procedure as in Synthesis Example 2(3) was carried out except that 6.6 g of zinc and 2.7 g of mercuric chloride were used to obtain ferrocenylundecanoic acid represented by the following formula:
3.4 g was obtained.

Example 4 3.02 g of ferrocenylundecanoic acid obtained in the above Synthesis Example 3
The same procedure as in Example 1 was carried out, except that 39.14 g of polyethylene glycol (average molecular weight 600) and 0.1 cc of concentrated sulfuric acid were added to the mixture and reacted at 80°C for 6 hours. The yield of the purified product was 4.00 g, at a yield of 51.5%. The results of ^1H -NMR analysis of this product are shown in Figure 5. The elemental analysis values were as follows:

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

Synthesis Example 4 (1) The same procedure as in Synthesis Example 2(1) was carried out, except that 19.3 g of 9-ethoxycarbonylnonanoic acid chloride was used instead of the 11-ethoxycarbonylundecanoic acid chloride shown in Synthesis Example 2(1), and 10.4 g of anhydrous aluminum chloride was used to react with 14.0 g of ferrocene, to obtain 2-ethyl ferrocenoylnonanoate represented by the following formula:
3.4 g was obtained.

(2) The same procedure as in Synthesis Example 2(2) was carried out, except that 20.5 g of ethyl ferrocenoylnonanoate (obtained in (1) above) was used instead of ethyl ferrocenoylundecanoate shown in Synthesis Example 2(2), and 5.1 g of potassium hydroxide was used, to obtain 19.7 g of ferrocenoylnonanoic acid represented by the following formula.

(3) Instead of the ferrocenoylundecanoic acid shown in Synthesis Example 2(3), 11.1 g of ferrocenoylnonanoic acid (see above) was used.
The same procedure as in Synthesis Example 2 was repeated except that 13.1 g of zinc and 5.5 g of mercuric chloride were used.
The same procedure as in (3) was carried out to obtain 8.3 g of ferrocenyldecanoic acid represented by the following formula.

Example 5 To 8.19 g of the ferrocenyldecanoic acid obtained in Synthesis Example 4,
82.72 g of polyethylene glycol (average molecular weight 60
The same procedure as in Example 1 was carried out, except that 0.1 cc of 1,000 ml of toluene (0.01 ml) and 0.1 cc of concentrated sulfuric acid were added and the mixture was reacted at 80°C for 6 hours. The yield of the purified product was 10.60 g, with a yield of 49.2%. The results of ^1H -NMR analysis of this product are shown in Figure 6. The elemental analysis values were as follows:

From the above results, it is clear that the purified product is a ferrocene derivative having the following structure:

Synthesis Example 5 (1) The same procedure as in Synthesis Example 2(1) was carried out, except that 29.0 g of 5-ethoxycarbonylvaleryl chloride was used instead of the 11-ethoxycarbonylundecanoyl chloride shown in Synthesis Example 2(1), and 32.4 g of anhydrous aluminum chloride was used to react with 45.2 g of ferrocene, to obtain 44.4 g of ethyl ferrocenoylvalerate represented by the following formula.
1 g was obtained.

(2) The same procedure as in Synthesis Example 2(2) was repeated except that 44.1 g of ethyl ferrocenoylvalerate (obtained in (1) above) was used instead of the ferrocenoylundecanoic acid shown in Synthesis Example 2(2) and 13.3 g of potassium hydroxide was used to obtain ferrocenoylvaleric acid 36.
0 g was obtained.

(3) Instead of the ferrocenoylundecanoic acid shown in Synthesis Example 2(3), 9.4 g of ferrocenoylvaleric acid (obtained in the above (2)) was used, and 13.1 g of zinc and 5.5 g of ferrocenoylvaleric acid were used.
The same procedure as in Synthesis Example 2(3) was carried out except that 1.0 g of mercuric chloride was used, thereby obtaining 6.9 g of ferrocenylhexanoic acid represented by the following formula.

Example 6 6.90 g of ferrocenylhexanoic acid obtained in Synthesis Example 5 above
The same procedure as in Example 1 was carried out, except that 184.80 g of polyethylene glycol (average molecular weight 1000) and 0.1 cc of concentrated sulfuric acid were added to the mixture and reacted at 80° C. for 6 hours.
The purified product was obtained in a yield of 39.5% and in an amount of 11.68 g. The results of ¹ H-NMR analysis of this product are shown in Figure 7. The elemental analysis values were as follows:

From the above results, it is clear that the purified product is a ferrocene derivative having the following structure:

Synthesis Example 6 (1) In place of ferrocene in Synthesis Example 2 (1), octamethylferrocene (Chem. Ztg., 1976, 100(3), 1
43 (Ger)) was used, and instead of 11-ethoxycarbonylundecanoic acid chloride,
The same procedure as in Synthesis Example 2(1) was carried out except that 13.3 g of 9-ethoxycarbonylnonanoic acid chloride and 7.2 g of anhydrous aluminum chloride were used and reacted with 16.1 g of ferrocene, thereby obtaining 6.4 g of ethyl octamethylferrocenoylnonanoate represented by the following formula.

(2) The same procedure as in Synthesis Example 2(2) was repeated, except that 6.4 g of ethyl octamethylferrocenoylnonanoate (obtained in (1) above) was used instead of ethyl ferrocenoylundecanoate shown in Synthesis Example 2(2), and 1.1 g of potassium hydroxide was used, to obtain 6.0 g of octamethylferrocenoylnonanoic acid represented by the following formula.

(3) The same procedure as in Synthesis Example 2(3) was carried out, except that 6.0 g of octamethylferrocenoylnonanoic acid (obtained in (2) above) was used instead of the ferrocenoylundecanoic acid shown in Synthesis Example 2(3), and 8.1 g of zinc and 3.3 g of mercuric chloride were used, to obtain 2.1 g of octamethylferrocenyldecanoic acid represented by the following formula.

Example 7 Octamethylferrocenyldecanoic acid obtained in Synthesis Example 6 above
To 2.03 g of the solution, add 86.64 g of polyethylene glycol (average molecular weight 2000) and 0.1 cc of concentrated sulfuric acid, and heat for 6 hours at 80°C.
The same procedure as in Example 1 was carried out, except that the reaction was carried out for 1 hour. The yield of the purified product was 15.2%, and the yield was 1.61 g. The results of ^1H -NMR analysis of this product are shown in Figure 8. The elemental analysis values were as follows:

From the above results, it is clear that the purified product is a ferrocene derivative having the following structure:

Example 8: 1.13 mg of the ferrocene derivative obtained in Example 1 was added as a surfactant (micelle agent) to 31.5 ml of water, and 10 mg of phthalocyanine was added thereto and dispersed and dissolved by ultrasonic stirring for 10 minutes. After further stirring for two days and nights with a stirrer, the resulting micelle solution was stirred at 2,000 rpm for 1 minute.
The resulting solution was centrifuged for 1 hour. The visible absorption spectrum of the supernatant is shown in Figure 9 (mark A). This confirmed that phthalocyanine was solubilized in the micellar solution. The solubility was 4.4 mM/4 mM micellization agent solution.

Example 9 The same procedure as in Example 8 was carried out, except that phthalocyanine was replaced with a phthalocyanine-iron complex. The visible absorption spectrum of the supernatant is shown in Figure 9 (point B). This confirmed that phthalocyanine was solubilized in the micellar solution. The solubility was 0.72 mM/4 mM micellization agent solution.

Example 10 The same procedure as in Example 8 was carried out, except that phthalocyanine was replaced with a phthalocyanine-cobalt complex. The visible absorption spectrum of the supernatant is shown in Figure 9 (C). This confirmed that phthalocyanine was solubilized in the micellar solution. The solubility was 0.22 mM/4 mM micellization agent solution.

Example 11 The same procedure as in Example 8 was carried out, except that phthalocyanine was replaced with a phthalocyanine copper complex. The visible absorption spectrum of the supernatant is shown in Figure 9 (point D). This confirmed that phthalocyanine was solubilized in the micellar solution. The solubility was 0.11 mM/4 mM micellization agent solution.

Example 12 The same procedure as in Example 8 was carried out, except that phthalocyanine was replaced with a phthalocyanine zinc complex. The visible absorption spectrum of the supernatant is shown in Figure 9 (point E). This confirmed that phthalocyanine was solubilized in the micellar solution. The solubility was 0.41 mM/4 mM micellization agent solution.

Example 13: 0.22 g of lithium sulfate ( _Li2SO4 ) was added to 10 ml of the micellar solution prepared in Example 8 to obtain a 0.44 mM phthalocyanine/2 mM micellization agent/0.2 M lithium sulfate solution. This was used as the electrolyte, and constant-potential electrolysis was carried out at 25°C for ₂ hours at an applied voltage of 0.5 V and a current of 7 μA using ITO as the anode, platinum as the cathode, and a saturated calomel electrode as the reference electrode.
As a result, a dye thin film having primary particles with an average particle size of 1000 Å was formed on the ITO. A scanning electron microscope (SEM) photograph (magnification 20000, JEOL Ltd., JSM-T220) of this dye thin film is shown in Figure 18.
In addition, the visible absorption spectrum of the dye thin film on ITO was measured.
The visible absorption spectra of Fig. 10 (mark A) and Fig. 9 (mark A) match, and the dye thin film on the ITO was identified as consisting of phthalocyanine.

Example 14 The same procedure as in Example 13 was carried out, except that the electrolysis time was changed to 40 minutes.

The visible absorption spectrum of the produced dye thin film is shown in Figure 10 (Line B). Comparing Line A and Line B in Figure 10, the thin film produced here has a smaller absorption spectrum than that of Example 13, and it is clear that the film thickness can be controlled by the electrolysis time.

Example 15: 0.193 g of the ferrocene derivative obtained in Example 3 was added as a surfactant (micelle agent) to 100 cc of water, and 100 mg of phthalocyanine was added thereto, and the mixture was dispersed and solubilized by ultrasonic stirring for 10 minutes. After further stirring for two days and nights with a stirrer, the resulting micelle solution (dispersion solution) was
The mixture was centrifuged at 200 rpm for 30 minutes. The visible absorption spectrum of the resulting supernatant is shown in Figure 11 (mark A). This confirmed that phthalocyanine was solubilized (dispersed) in the micelle solution. The solubilization ability was
The solution was a 6.4 mM phthalocyanine/2 mM micellization agent solution. LiBr was added to this solution as a supporting salt to make the concentration 0.1 M, and the mixture was stirred with a stirrer for 10 minutes.

The obtained solution was used as an electrolyte, and the anode was an ITO transparent glass electrode, the cathode was platinum, and the reference electrode was a saturated calomel electrode. The anode was a platinum transparent glass electrode, and the reference electrode was a saturated calomel electrode. The anode was a platinum transparent glass electrode, and the current density was 45 μA/cm ² at 25° C. with an applied voltage of 0.5 V.
The constant potential electrolysis was carried out for 30 minutes.
It was 0.09 coulombs.

As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. The visible absorption spectrum of the phthalocyanine on this ITO transparent glass electrode is shown in Figure 11 (mark B). Since Figure 11 (mark A) and Figure 11 (mark B) match, it was confirmed that the thin film on the ITO transparent glass electrode was phthalocyanine. Furthermore, the ultraviolet (UV) absorption spectrum revealed that the thickness of this thin film was 0.31 μm.

An SEM photograph (magnification: 30,000 times, JSM-T220, manufactured by JEOL Ltd.) of the obtained thin film is shown in FIG.

Example 16: 0.190 g of the ferrocene derivative obtained in Example 4 was added as a surfactant (micelle agent) to 100 cc of water, and 100 mg of phthalocyanine was added thereto, and the mixture was dispersed and solubilized by ultrasonic stirring for 10 minutes. After further stirring for two days and nights with a stirrer, the resulting micelle solution (dispersion solution) was
The mixture was centrifuged at 2000 rpm for 30 minutes. The visible absorption spectrum of the resulting supernatant is shown in Figure 12 (mark A). This confirmed that phthalocyanine was solubilized (dispersed) in the micelle solution. The solubilization ability was
The solution was a 7.8 mM phthalocyanine/2 mM micellization agent solution. LiBr was added to this solution as a supporting salt to make the concentration 0.1 M, and the mixture was stirred with a stirrer for 10 minutes.

The obtained solution was used as an electrolyte, and the anode was an ITO transparent glass electrode, the cathode was platinum, and the reference electrode was a saturated calomel electrode. The applied voltage was 0.5 V at 25°C and the current density was 48 μA/cm ^{2 .}
The constant potential electrolysis was carried out for 30 minutes.
It was 0.09 coulombs.

As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. The visible absorption spectrum of the phthalocyanine on this ITO transparent glass electrode is shown in Figure 12 (Circle B). The agreement between Figure 12 (Circle A) and Figure 12 (Circle B) confirmed that the thin film on the ITO transparent glass electrode was phthalocyanine. Furthermore, the UV absorption spectrum revealed that the thickness of this thin film was 1.05 μm.

An SEM photograph (magnification: 30,000 times, JSM-T220, manufactured by JEOL Ltd.) of the obtained thin film is shown in FIG.

Example 17: To 100 cc of water, 0.187 g of the ferrocene derivative obtained in Example 5 was added as a surfactant (micelle agent),
100 mg of phthalocyanine was added to this and ultrasonicated for 10 minutes.
The mixture was stirred for 1 minute to disperse and solubilize the mixture. After further stirring for 2 days and 30 minutes with a stirrer, the resulting micellar solution (dispersed solution) was centrifuged at 2000 rpm for 30 minutes. The visible absorption spectrum of the resulting supernatant is shown in Figure 13 (Point A).
This confirms that phthalocyanine is solubilized (dispersed) in the micellar solution. The solubilizing ability was 8.2 mM phthalocyanine/2 mM micellization agent solution. LiBr was added to this solution as a supporting salt to make the concentration 0.1 M, and the solution was stirred with a stirrer for 10 minutes.

The obtained solution was used as an electrolyte, and the anode was an ITO transparent glass electrode, the cathode was platinum, and the reference electrode was a saturated calomel electrode. The applied voltage was 0.5 V at 25°C and the current density was 72 μA/cm ^{2 .}
The constant potential electrolysis was carried out for 30 minutes.
It was 0.13 coulombs.

As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. The visible absorption spectrum of the phthalocyanine on this ITO transparent glass electrode is shown in Figure 13 (mark B). Since Figure 13 (mark A) and Figure 13 (mark B) match, it was confirmed that the thin film on the ITO transparent glass electrode was phthalocyanine. In addition, the thickness of this thin film was U
The V absorption spectrum revealed that the wavelength was 1.85 μm.

An SEM photograph (magnification: 30,000 times, JSM-T220, manufactured by JEOL Ltd.) of the obtained thin film is shown in FIG.

Example 18: To 100 cc of water, 0.176 g of the ferrocene derivative obtained in Example 6 was added as a surfactant (micelle agent),
100 mg of phthalocyanine was added to this and ultrasonicated for 10 minutes.
The mixture was stirred for 1 minute to disperse and solubilize the mixture. After further stirring for two days and nights using a stirrer, the resulting micellar solution (dispersed solution) was centrifuged at 2000 rpm for 30 minutes. The visible absorption spectrum of the resulting supernatant is shown in Figure 14 (Point A).
This confirms that phthalocyanine is solubilized (dispersed) in the micellar solution. The solubilizing ability was 1.8 mM phthalocyanine/2 mM micellization agent solution. LiBr was added to this solution as a supporting electrolyte to make the concentration 0.1 M, and the solution was stirred with a stirrer for 10 minutes.

The obtained solution was used as an electrolyte, and the anode was an ITO transparent glass electrode, the cathode was platinum, and the reference electrode was a saturated calomel electrode. The applied voltage was 0.5 V at 25°C and the current density was 17 μA/cm ^{2 .}
The constant potential electrolysis was carried out for 30 minutes.
It was 0.04 coulombs.

As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. The visible absorption spectrum of the phthalocyanine on this ITO transparent glass electrode is shown in Figure 14 (mark B). Since Figure 14 (mark A) and Figure 14 (mark B) match, it was confirmed that the thin film on the ITO transparent glass electrode was phthalocyanine. In addition, the thickness of this thin film was U
The V absorption spectrum revealed that the wavelength was 0.04 μm.

Example 19: 0.210 g of the ferrocene derivative obtained in Example 7 was added as a surfactant (micelle agent) to 100 cc of water.
100 mg of phthalocyanine was added to this and ultrasonicated for 10 minutes.
The mixture was stirred for 1 minute to disperse and solubilize the mixture. After further stirring for 2 days and 30 minutes with a stirrer, the resulting micellar solution (dispersed solution) was centrifuged at 2000 rpm for 30 minutes. The visible absorption spectrum of the resulting supernatant is shown in Figure 15 (Point A).
This confirms that phthalocyanine is solubilized (dispersed) in the micellar solution. The solubilizing ability was 4.0 mM phthalocyanine/2 mM micellization agent solution. LiBr was added to this solution as a supporting electrolyte to make the concentration 0.1 M, and the solution was stirred with a stirrer for 10 minutes.

The resulting solution was used as an electrolyte, and the anode was an ITO transparent glass electrode, the cathode was a platinum electrode, and the reference electrode was a saturated calomel electrode. The applied voltage was 0.5 V and the current density was 124 μA/cm at 25°C.
The constant potential electrolysis of ² was carried out for 30 minutes. The amount of current applied was 0.23 coulombs.

As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. The visible absorption spectrum of the phthalocyanine on this ITO transparent glass electrode is shown in Figure 15 (Circle B). The agreement between Figure 15 (Circle A) and Figure 15 (Circle B) confirmed that the thin film on the ITO transparent glass electrode was phthalocyanine. Furthermore, the UV absorption spectrum revealed that the thickness of this thin film was 4.6 μm.

Example 20 0.188 g of the ferrocene derivative obtained in Example 1 was added as a surfactant (micelle agent) to 100 cc of water.
100 mg of phthalocyanine iron complex was added to the mixture, and the mixture was dispersed and solubilized by ultrasonic stirring for 10 minutes. After further stirring for two days and nights, the resulting micellar solution (dispersion solution) was centrifuged at 2000 rpm for 30 minutes.
The visible absorption spectrum of the obtained supernatant is shown in Figure 16 (mark A). This confirmed that the phthalocyanine iron complex was solubilized (dispersed) in the micellar solution. The solubilizing ability was 4.1 mM/2 m
The solution was a micellization agent solution containing Li as a supporting salt.
Br was added to the solution to a concentration of 0.1 M, and the mixture was stirred with a stirrer for 10 minutes.

The obtained solution was used as an electrolyte, and the anode was an ITO transparent glass electrode, the cathode was platinum, and the reference electrode was a saturated calomel electrode. The applied voltage was 0.5 V at 25°C and the current density was 14 μA/cm ^{2 .}
The constant potential electrolysis was carried out for 30 minutes.
It was 0.03 coulombs.

As a result, a thin film of the phthalocyanine iron complex was obtained on the ITO transparent glass electrode. The visible absorption spectrum of the phthalocyanine iron complex on the ITO transparent glass electrode is shown in Figure 16 (Circle B). Figure 16 (Circle A) and Figure 16 (Circle B)
The thin film on the ITO transparent glass electrode was confirmed to be a phthalocyanine iron complex. The thickness of this thin film was 0.16 mm from the UV absorption spectrum.
It was found to be μm.

Example 21 0.188 g of the ferrocene derivative obtained in Example 1 was added as a surfactant (micelle agent) to 100 cc of water.
100 mg of phthalocyanine copper complex was added to the mixture, and the mixture was dispersed and solubilized by ultrasonic stirring for 10 minutes. After further stirring for two days and nights with a stirrer, the resulting micellar solution (dispersion solution) was centrifuged at 2000 rpm for 30 minutes.
The visible absorption spectrum of the obtained supernatant is shown in Figure 17 (mark A). This confirmed that the phthalocyanine copper complex was solubilized (dispersed) in the micellar solution. The solubilizing ability was 3.8 mM/2 ml of the phthalocyanine copper complex.
The solution was a micellization agent solution containing Li as a supporting salt.
Br was added to the solution to a concentration of 0.1 M, and the mixture was stirred with a stirrer for 10 minutes.

The obtained solution was used as an electrolyte, and the anode was an ITO transparent glass electrode, the cathode was platinum, and the reference electrode was a saturated calomel electrode. The applied voltage was 0.5 V at 25°C and the current density was 43 μA/cm ^{2 .}
The constant potential electrolysis was carried out for 30 minutes.
It was 0.11 coulombs.

As a result, a thin film of the phthalocyanine copper complex was obtained on the ITO transparent glass electrode. The visible absorption spectrum of the phthalocyanine copper complex on the ITO transparent glass electrode is shown in Figure 17 (Circle B). Figure 17 (Circle A) and Figure 17 (Circle B)
The thin film on the ITO transparent glass electrode was confirmed to be a phthalocyanine copper complex. The thickness of this thin film was 0.08 mm from the UV absorption spectrum.
It was found to be μm.

The ferrocene derivative of the present invention is a novel compound that has not been previously found and can be used in a variety of applications, including as a surfactant (micelle agent), catalyst, combustion improver, flotation agent, and dispersant. In particular, when this ferrocene derivative is used as a surfactant (micelle agent), it forms micelles in an aqueous system, which can solubilize dyes such as phthalocyanine, which have a wide range of applications, and various hydrophobic polymers. Furthermore, by adding this surfactant (micelle agent) and following the method of the present invention, which utilizes the aggregation and dispersion of micelles by aqueous electrolysis, it is possible to form extremely thin organic thin films.

Claims (2)

[Claims] [Claim 1] General formula [wherein R ¹ and R ² each represent a hydrogen atom, a methyl group, or an ethyl group; m is 1 to 4; n is 1 to 5; and r is 1.
represents an integer of 1 to 18, and s represents a real number of 2.0 to 45.0.] or a general formula [wherein w represents an integer of 2 to 20; R ¹ , R ² , m,
n and s are the same as defined above. 2. A surfactant containing the ferrocene derivative according to claim 1.