JPH0577448B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a nonionic surfactant made of a ferrocene derivative, and more specifically, a nonionic surfactant made of a ferrocene derivative having various hydrophilic groups, particularly a polyoxyalkylene chain. The present invention relates to a method for easily obtaining a highly pure target compound in a high yield by separating polyalkylene glycol mixed in the target compound when producing the target compound. [Prior art and problems to be solved by the invention] An interface for dissolving in water pigments such as phthalocyanine and its derivatives, photosensitive materials, organic conductive materials, insulating materials, paints, and other water-insoluble polymers. Various activators are being studied. The present inventors recently discovered that a surfactant useful for solubilizing this type of water-insoluble pigment, etc.
We have disclosed a ferrocene derivative having a polyoxyalkylene chain, and developed a method for forming a thin film of a hydrophobic organic substance by so-called micelle electrolysis using the ferrocene derivative as a micellar agent. (International Publication WO88/07538, etc.). As mentioned above, compounds having functional groups such as polyoxyalkylene chains as hydrophilic groups (surfactants)
usually requires a step of introducing a functional group such as polyoxyalkylenation during the manufacturing process. Currently, for example, in polyoxyalkylenation, a method is used in which a hydrophobic moiety is reacted with a polyalkylene glycol, and a method in which a hydrophobic moiety and an alkylene oxide are brought into contact and polymerized. However, these methods cannot avoid mixing polyalkylene glycol into the product after the reaction. Conventionally, extraction using an n-butanol-water system has been considered to be the most effective method for separating and removing polyalkylene glycols mixed in compounds with polyoxyalkylene chains as mentioned above (Industrial Chemistry Magazine 64 , 635 (1961)). However, if water is easily dissolved in n-butanol and a large amount of polyalkylene glycol such as polyethylene glycol is mixed, the separation ability will be reduced. Therefore, in order to obtain a highly pure target compound, purification by silica gel chromatography or the like is required. However, this purification by silica gel chromatography has the disadvantage that the operation is complicated and the necessary target compound is adsorbed on the silica gel, resulting in a decrease in yield. Therefore, the present inventors have conducted extensive research in order to develop a manufacturing method that allows for easy separation and removal of polyalkylene glycol mixed into the target compound during the manufacturing stage and that can obtain a highly purified target compound in high yield. Ta. [Means for Solving the Problems] As a result, it has been found that the above problems can be solved by using a carboxylic acid ester-water extraction medium in place of the conventional n-butanol-water extraction medium. The present invention was completed based on this knowledge. That is, the present invention is characterized in that a mixture containing a nonionic surfactant made of a ferrocene derivative and a polyalkylene glycol is brought into contact with a carboxylic acid ester-aqueous extraction medium to separate the ferrocene derivative and the polyalkylene glycol. The present invention provides a method for producing a nonionic surfactant comprising a ferrocene derivative. Various types of ferrocene derivatives can be used in the present invention. For example, general formula

[Formula, R ¹ and R ² are each an alkyl group having 6 or less carbon atoms, an alkoxy group, an amino group, a dimethylamino group, a hydroxyl group, an acetylamino group, a carboxyl group, a methoxycarbonyl group, an acetoxy group, an aldehyde group Or indicates halogen,
R ³ represents hydrogen or a linear or branched alkyl group or alkenyl group having 4 to 18 carbon atoms; R ⁴ and R ⁵
each represents hydrogen or a methyl group. Y represents oxygen or oxycarbonyl group, a is an integer of 0 to 4, b is an integer of 0 to 4, m is an integer of 1 to 18, n
indicates a real number between 2.0 and 70.0. ] The ferrocene derivative represented by the following can be cited as a representative example. Here, the general formula []
Each symbol inside is as described above. That is, as described in the above-mentioned International Publications WO88/07538, WO98/01939, Japanese Patent Application No. 63-233797, Japanese Patent Application No. 2-83386, and others, R ¹ and R ² each have a carbon number of 6 or less. Alkyl groups (methyl group (CH ₃ ), ethyl group (C ₂ H ₅ ), etc.), alkoxy groups (methoxy group (OCH ₃ ), ethoxy group (OC ₂ H ₅ ), etc.), amino group (NH ₂ ), dimethyl Amino group (N(CH ₃ ) ₂ )), hydroxyl group (OH), acetylamino group (NHCOCH ₃ ), carboxyl group (COOH), methoxycarbonyl group (COCH ₃ ), acetoxy group (COOCH ₃ ), aldehyde group (CHO) Or halogen (chlorine, bromine,
fluorine, iodine, etc.). R ¹ and R ² may be the same or different, and even if a plurality of R ¹ and R ² exist in the five-membered ring of ferrocene, the substituents may be the same or different. It's good to wear. In addition, R ³ is hydrogen or has a carbon number of 4 to 18
The straight chain represents a branched alkyl group or alkenyl group. Furthermore, Y is oxygen (-O-) or oxycarbonyl group

[Formula] is shown, and R ⁴ and R ⁵ represent hydrogen or a methyl group (CH ₃ ). Therefore,

[Formula] is -O(CH ₂ CH ₂ O) _o H,

【formula】

【formula】

[Formula] or

【formula】

[Formula] etc. Moreover, m represents an integer of 1 to 18. Therefore, between the ring carbon atom and the above oxygen or oxycarbonyl group, a carbon number of 1 to 18, such as an ethylene group or a propylene group, is added.
with an intervening alkylene group. Further n
indicates the number of repetitions of oxyalkylene groups such as the above oxyethylene group, and means not only integers from 2.0 to 70.0 but also real numbers including these, and indicates the average number of repeats of oxyalkylene groups, etc. . In addition to the ferrocene derivatives represented by the above general formula [], there are various ferrocene derivatives used in the present invention as long as they can be used as nonionic surfactants. 2-
No. 83386), Specification No. 63-233798 (Japanese Unexamined Patent Publication No.
-83387 publication), 63-248600 specification, 63-
Specification No. 248601 (Japanese Unexamined Patent Publication No. 2-96585), Specification of Japanese Patent Application No. 45370 (No.
235895) Publication), as well as Patent Application 2 filed on September 24, 1989, and Patent Applications 2 and 3 filed on March 30 of the same year (all by Tamotsu Otani as agent). Mention may be made of the ferrocene derivatives described in the specification of . In the present invention, these ferrocene derivatives containing a polyoxyethylene group or a polyoxypropylene group as a hydrophilic group are preferably used. These various ferrocene derivatives are manufactured through various manufacturing processes suitable for each structure, but as the final manufacturing step,
The above-mentioned hydrophobic moiety bonded to the ferrocene skeleton

A step of introducing a hydrophilic group such as [Formula] is performed. For example, in the ferrocene derivative of the following general formula in which R ³ to ^{R 5} of the general formula [] are hydrogen,

embedded image A ferrocene derivative in which Y represents oxygen is produced as follows. That is, the general formula HO( _-CH2CH2O ) _{-o ...} [] [n is the same as above. ] Add an alkali metal (metallic sodium, metallic potassium, etc.) to polyethylene glycol represented by the formula, stir at room temperature to 200°C for several minutes to several days, and then

[Formula] [In the formula, X represents a halogen atom. ] By adding a halogen-containing ferrocene compound represented by the formula and reacting with stirring, followed by extraction and purification, a ferrocene derivative represented by the general formula [′] in which Y is oxygen is obtained.

A ferrocene derivative of [chemical formula] is obtained. On the other hand, ferrocene derivatives in which Y in the above general formula ['] is an oxycarbonyl group include polyethylene glycol represented by the above general formula [], mineral acids such as sulfuric acid and hydrochloric acid, aromatic sulfonic acids (e.g.
Add an organic acid such as p-toluenesulfonic acid (p-toluenesulfonic acid), a Lewis acid such as boron fluoride etherate, preferably sulfuric acid or an organic acid, and heat at room temperature to 200°C for several minutes.
Stir for several days, then general formula

A carboxyl group-containing ferrocene compound represented by the formula is added and reacted with stirring, followed by extraction,
It can be obtained by purification. In other words,
By this method, the general formula [′] in which Y is an oxycarbonyl group can be obtained.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples. Example 1 1.0 g (2.6 mmol) of the compound represented by the following formula and polyethylene glycol (average molecular weight 600)
15.6g (26 mmol) and p-toluenesulfonic acid
0.49 g (2.6 mmol) was placed in a 100 ml round bottom flask and dried at 100° C. for 4 hours. The reaction mixture was then transferred to a separatory funnel using 100 ml of 1% aqueous sodium hydroxide solution and extracted with 100 ml of ethyl acetate. After the extraction, the ethyl acetate fraction was dried and concentrated to obtain 2.4 g of the target compound represented by the following formula.
The yield of this product was 98%.

【formula】

[Chemical] Comparative Example 1 The same operation as in Example 1 was carried out except that ethyl acetate in Example 1 was replaced with n-butyl alcohol.
The -butyl alcohol extracted fraction was dried and concentrated to obtain 7.2 g of a mixture of the target product represented by the above formula and polyethylene glycol. Then, to remove polyethylene glycol, silica gel column chromatography (ethyl acetate: methanol = 3:
The target compound represented by the above formula was obtained by purification in step 1). The yield of this product was 74%. Example 2 1.0 g (2.4 mmol) of the compound represented by the following formula and polyethylene glycol (average molecular weight 600)
14.4g (24mmol) and p-toluenesulfonic acid
0.46 g (2.4 mmol) was placed in a 100 ml round bottom flask and stirred at 100°C for 4 hours. The reaction mixture was then transferred to a separatory funnel using 100 ml of 1% aqueous sodium hydroxide solution and extracted with 100 ml of methyl acetate. After the extraction, the methyl acetate fraction was dried and concentrated to obtain 2.4 g of the target compound represented by the following formula.
The yield of this product was 98%.

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Comparative Example 2 The same operation as in Example 2 was carried out except that methyl acetate in Example 2 was replaced with n-butyl alcohol.
The -butyl alcohol extracted fraction was dried and concentrated to obtain 6.5 g of a mixture of the target product represented by the above formula and polyethylene glycol. Then, to remove polyethylene glycol, silica gel column chromatography (ethyl acetate: methanol = 3:
The product was purified in step 1) to obtain 1.8 g of the target compound represented by the above formula. The yield of this product was 74%. Example 3 2.0 g of the compound represented by the following formula and 20 g of polyethylene glycol (average molecular weight 600) were dissolved in 100 ml of water, then extracted with 100 ml of ethyl acetate, and dried and concentrated. As a result, 1.9 g of a highly purified target compound represented by the following formula containing no polyethylene glycol was obtained. The recovery rate for this is 95%
It was hot.

Comparative Example 3 The same operation as in Example 3 was performed except that n-butyl alcohol was used instead of ethyl acetate. As a result, the yield was 8.2 g, which contained a large amount of polyethylene glycol. Examples 4 to 21 The same operations as in Example 3 were performed except that the type of ferrocene derivative was changed as shown below. Table 1 shows the recovery rate of the target product. However, in Example 7, 40g of polyethylene glycol was used,
Further, in Example 20, ethyl propionate was used instead of ethyl acetate.

【table】

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〔Effect of the invention〕

As explained above, according to the production method of the present invention, it is possible to easily separate the target compound after the reaction and the polyalkylene glycol mixed in during the production step, and to obtain a highly pure target compound with only a simple extraction operation. It can be obtained in high yield. Therefore, according to the method of the present invention, ferrocene derivatives useful as nonionic surfactants can be easily produced.

Claims (1)

[Claims] 1. Contacting a mixture containing a nonionic surfactant made of a ferrocene derivative and a polyalkylene glycol with a carboxylic acid ester-aqueous extraction medium to separate the ferrocene derivative and the polyalkylene glycol. A method for producing a nonionic surfactant comprising a ferrocene derivative, characterized by: 2. The manufacturing method according to claim 1, wherein the hydrophilic group of the nonionic surfactant comprising a ferrocene derivative is a polyoxyalkylene group.