JPH0633299B2 - Method for producing ferrocene derivative - Google Patents
Method for producing ferrocene derivativeInfo
- Publication number
- JPH0633299B2 JPH0633299B2 JP1076497A JP7649789A JPH0633299B2 JP H0633299 B2 JPH0633299 B2 JP H0633299B2 JP 1076497 A JP1076497 A JP 1076497A JP 7649789 A JP7649789 A JP 7649789A JP H0633299 B2 JPH0633299 B2 JP H0633299B2
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- JP
- Japan
- Prior art keywords
- group
- ferrocene
- general formula
- ferrocene derivative
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、フェロセン誘導体の製造方法に関し、詳しく
は後処理工程が容易で、しかも高純度の目的化合物を高
収率で得ることのできるフェロセン誘導体の製造方法に
関する。Description: TECHNICAL FIELD The present invention relates to a method for producing a ferrocene derivative, more specifically, a ferrocene which can be easily subjected to a post-treatment step and can yield a highly pure target compound in a high yield. The present invention relates to a method for producing a derivative.
フタロシアニンやその誘導体等の色素や感光材料，有機
導電材料，絶縁材料，塗料，その他の水に対して不溶性
のポリマー等、各種の疎水性有機物質を水に溶かすため
の界面活性剤として各種のものが研究されている。Various types of surfactants for dissolving various hydrophobic organic substances in water, such as dyes such as phthalocyanine and its derivatives, photosensitive materials, organic conductive materials, insulating materials, paints, and other water-insoluble polymers Is being studied.
本発明者らは、先般、この種の疎水性有機物質を可溶化
するのに有用な界面活性剤として、フェロセン骨格の五
員環にポリオキシアルキレン鎖とオキシカルボニル基を
有する長鎖置換基を結合した構造のフェロセン誘導体を
開発し、また該フェロセン誘導体をミセル化剤として用
いて所謂ミセル電解法にて疎水性有機物質の薄膜を形成
する方法を開発した（国際公開ＷＯ８８／０７５３
８）。The present inventors have recently proposed a long-chain substituent having a polyoxyalkylene chain and an oxycarbonyl group in the five-membered ring of the ferrocene skeleton as a surfactant useful for solubilizing this type of hydrophobic organic substance. A ferrocene derivative having a bonded structure was developed, and a method of forming a thin film of a hydrophobic organic substance by a so-called micellar electrolysis method using the ferrocene derivative as a micelle agent (International Publication WO88 / 0753)
8).
このようなフェロセン誘導体を製造するには、通常はフ
ェロセン骨格の五員環にエステル基を置換基として導入
した構造のフェロセン化合物とポリアルキレングリコー
ルとを、濃硫酸の存在下で直接反応させて脱水縮合させ
る方法が採用されている。In order to produce such a ferrocene derivative, usually, a ferrocene compound having a structure in which an ester group is introduced as a substituent in a five-membered ring of a ferrocene skeleton and a polyalkylene glycol are directly reacted in the presence of concentrated sulfuric acid for dehydration. A method of condensing is adopted.
しかしながら、この方法では、反応に際してタール状の
分解生成物が生じるため、後処理工程として、シリカゲ
ル等を用いたカラム精製が必要であり、操作が複雑であ
るとともに、その収率も低いものであった。However, in this method, since a tar-like decomposition product is generated during the reaction, column purification using silica gel or the like is required as a post-treatment step, the operation is complicated, and the yield is low. It was
そこで、本発明者らは、上述した如きフェロセン誘導体
を、簡単な工程で、しかも高純度の目的化合物を高収率
で得られる製造方法を開発すべく鋭意研究を重ねた。Therefore, the inventors of the present invention have conducted earnest studies to develop a method for producing the ferrocene derivative as described above in a simple process and in high yield with a high-purity target compound.
その結果、フェロセン化合物とポリアルキレングリコー
ルとの反応に際して、触媒として濃硫酸に代えてトルエ
ンスルホン酸を用いることにより、上記課題を解決でき
ることを見出した。本発明はかかる知見に基いて完成し
たものである。As a result, they have found that the above problem can be solved by using toluenesulfonic acid instead of concentrated sulfuric acid as a catalyst in the reaction between the ferrocene compound and the polyalkylene glycol. The present invention has been completed based on such findings.
すなわち本発明は、一般式 〔式中、Ｒ１及びＲ２はそれぞれ炭素数１〜６のアルキ
ル基，炭素数１〜６のアルコキシ基，ヒドロキシル基，
アミノ基あるいはハロゲンを示す。またＲ３は水素また
は炭素数１〜６のアルキル基を示し、ａは０〜４の整
数，ｂは０〜５の整数，ｍは２〜１８の整数を示す。〕 で表わされるフェロセン化合物と、一般式 〔式中、Ｒ４及びＲ５はそれぞれ水素，メチル基を示
し、ｎは2.０〜50.０の実数を示す。〕 で表わされるポリアルキレングリコールを、トルエンス
ルホン酸の存在下で反応させることを特徴とする一般式 〔式中、Ｒ１，Ｒ２，Ｒ４，Ｒ５，ａ，ｂ，ｍおよびｎ
は前記と同じ。〕 で表わされるフェロセン誘導体の製造方法を提供するも
のである。That is, the present invention has the general formula [In the formula, R 1 and R 2 are each an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group,
Indicates an amino group or halogen. R 3 represents hydrogen or an alkyl group having 1 to 6 carbon atoms, a represents an integer of 0 to 4, b represents an integer of 0 to 5, and m represents an integer of 2 to 18. ] The ferrocene compound represented by [In the formula, R 4 and R 5 each represent hydrogen and a methyl group, and n represents a real number of 2.0 to 50.0. ] A polyalkylene glycol represented by the following general formula characterized by reacting in the presence of toluenesulfonic acid [Wherein R 1 , R 2 , R 4 , R 5 , a, b, m and n
Is the same as above. ] A method for producing a ferrocene derivative represented by
本発明の方法で得られるフェロセン誘導体は、上述の如
く、一般式(III)で表わされるものである。ここで一般
式(III)中の各記号は前述した通りである。つまり、Ｒ
１及びＲ２はそれぞれ炭素数１〜６のアルキル基（メチ
ル基（ＣＨ3），エチル基（Ｃ2Ｈ5），プロピル基（Ｃ3
Ｈ7）等）、炭素数１〜６のアルコキシ基（メトキシ基
（ＯＣＨ3），エトキシ基（ＯＣ2Ｈ5）等）、ヒドロキ
シル基（水酸基（ＯＨ））、アミノ基（ＮＨ2）あるい
はハロゲン（塩素，臭素，フッ素，ヨウ素等）を示す。
なお、Ｒ１及びＲ２は同一であっても異なってもよく、
さらにＲ１及びＲ２がそれぞれ複数個フェロセンの五員
環に存在した場合にも、複数の置換基はそれぞれ同一で
あっても異なってもよい。The ferrocene derivative obtained by the method of the present invention is represented by the general formula (III) as described above. Here, each symbol in the general formula (III) is as described above. That is, R
1 and R 2 are each an alkyl group having 1 to 6 carbon atoms (methyl group (CH 3 ), ethyl group (C 2 H 5 ), propyl group (C 3
H 7 ), etc., an alkoxy group having 1 to 6 carbon atoms (methoxy group (OCH 3 ), ethoxy group (OC 2 H 5 ), etc.), hydroxyl group (hydroxyl group (OH)), amino group (NH 2 ) or halogen. (Chlorine, bromine, fluorine, iodine, etc.) is shown.
Note that R 1 and R 2 may be the same or different,
Further, when a plurality of R 1 and R 2 are present in the five-membered ring of ferrocene, the plurality of substituents may be the same or different.
またｍは２〜１８の整数を示す。したがって、環員炭素
原子と一般式 〔式中、Ｒ４及びＲ５はそれぞれ水素，メチル基を示
す。〕 で表わされるオキシアルキレン基との間にエチレン基，
プロピレン基等の炭素数２〜１８のアルキレン基が介在
したものとなる。さらに、ｎは上記オキシアルキレン基
の繰り返し数を示すもので、2.０〜50.０の整数のみな
らず、これらを含む実数を意味し、オキシアルキレン基
の繰り返し数の平均値を示すものである。Moreover, m shows the integer of 2-18. Therefore, the ring member carbon atom and the general formula [In the formula, R 4 and R 5 represent hydrogen and a methyl group, respectively. ] An ethylene group between the oxyalkylene group represented by
An alkylene group having 2 to 18 carbon atoms such as a propylene group is interposed. Further, n represents the repeating number of the oxyalkylene group and means not only an integer of 2.0 to 50.0 but also a real number including these, and represents an average value of the repeating number of the oxyalkylene group. is there.
本発明では、このような一般式(III)で表わされるフェ
ロセン誘導体を製造するにあたり、前述の如く、前記一
般式（Ｉ）で表わされるフェロセン化合物と、前記一般
式(II)で表わされるポリアルキレングリコールとを、ト
ルエンスルホン酸の存在下で反応させる。In the present invention, when the ferrocene derivative represented by the general formula (III) is produced, as described above, the ferrocene compound represented by the general formula (I) and the polyalkylene represented by the general formula (II) are used. The glycol is reacted in the presence of toluenesulfonic acid.
トルエンスルホン酸としては、ベンゼン環に結合するメ
チル基とスルホン酸基の置換位置がｏ−位，ｍ−位ある
いはｐ−位のいずれのトルエンスルホン酸も用いること
が可能であるが、通常は、ｐ−トルエンスルホン酸を用
いることが好ましい。As the toluenesulfonic acid, it is possible to use any toluenesulfonic acid in which the substitution positions of the methyl group and the sulfonic acid group bonded to the benzene ring are o-position, m-position or p-position, but Preference is given to using p-toluenesulfonic acid.
また反応を行うにあたっては、上記一般式（Ｉ）のフェ
ロセン化合物と一般式(II)のポリアルキレングリコール
を、トルエンスルホン酸と攪拌混合させるだけで反応を
進行させることもできるが、溶媒として、ヘキサン，ヘ
プタン，ベンゼン，トルエン，キシレン，シクロヘキサ
ン等の各種炭化水素、クロロホルム，塩化メチレン，四
塩化炭素等のハロゲン化炭化水素、さらには各種のエー
テル，テトラヒドロフラン，アセトニトリル等の非プロ
トン性極性溶媒を加えることもできる。Further, in carrying out the reaction, the ferrocene compound of the general formula (I) and the polyalkylene glycol of the general formula (II) can be allowed to proceed by simply stirring and mixing with toluenesulfonic acid. , Addition of various hydrocarbons such as heptane, benzene, toluene, xylene and cyclohexane, halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride, and various aprotic polar solvents such as ether, tetrahydrofuran and acetonitrile. You can also
反応温度は、特に制限はないが、一般には室温から２０
０℃の間で行うことができる。また反応時間も、反応を
充分に行う得る時間ならばよく、通常は、３０分以上行
うことが好ましい。Although the reaction temperature is not particularly limited, it is generally from room temperature to 20.
It can be performed between 0 ° C. Further, the reaction time may be any time as long as the reaction can be sufficiently carried out, and usually 30 minutes or more is preferable.
さらに上記一般式（Ｉ），(II)の化合物の配合割合も任
意であるが、通常は、一般式(II)のポリアルキレングリ
コールを、一般式（Ｉ）のフェロセン化合物に対して１
当量以上、特に１〜５０当量加えることが好ましい。ま
た触媒であるトルエンスルホン酸の量は、所謂触媒量で
充分であるが、具体的には一般式（Ｉ）のフェロセン化
合物に対して0.０１当量以上、特に0.１〜１００当量加
えることが好ましい。トルエンスルホン酸の添加量を増
加させると、反応速度を向上させることができるが、0.
０１当量未満では反応進行が充分でなく、実用上好まし
くない。Further, the compounding ratio of the compounds of the above general formulas (I) and (II) is optional, but usually, the polyalkylene glycol of the general formula (II) is added to the ferrocene compound of the general formula (I) at 1%.
It is preferable to add an equivalent amount or more, particularly 1 to 50 equivalent amount. Further, the amount of toluenesulfonic acid as a catalyst is a so-called catalytic amount, but specifically, 0.01 equivalent or more, particularly 0.1 to 100 equivalents relative to the ferrocene compound of the general formula (I) should be added. Is preferred. The reaction rate can be improved by increasing the addition amount of toluenesulfonic acid.
When the amount is less than 01 equivalent, the reaction progress is not sufficient, which is not preferable in practice.
本発明の方法においては、反応終了後の目的生成物、す
なわち一般式(III)で表わされるフェロセン誘導体は、
簡単な後処理、例えば水相から酢酸エチル等で抽出分離
するだけで、高純度のものを高収率で得ることができ
る。In the method of the present invention, the target product after the reaction, that is, the ferrocene derivative represented by the general formula (III) is
A high-purity product can be obtained in a high yield only by a simple post-treatment, for example, extraction and separation from the aqueous phase with ethyl acetate or the like.
次に本発明を実施例及び比較例により、さら詳しく説明
する。Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例１ 下記式で表わされるフェロセン化合物1.０ｇ，ポリエ
チレングリコール（平均分子量６００）１5.６ｇおよび
ｐ−トルエンスルホン酸0.５ｇを丸底フラスコに入れ、
１００℃で４時間攪拌した後、１００mlの水を加えた。
次いで反応生成物を酢酸エチルで抽出し、無水硫酸マグ
ネシウムで乾燥，濃縮し、黄色オイル状の下記式で表
わされるフェロセン誘導体を2.４ｇ得た。このフェロセ
ン誘導体の収率は９6.５％であり、プロトン核磁気共鳴
（1ＨＮＭＲ）スペクトルの測定結果は第１図に示す通
りである。Example 1 1.0 g of a ferrocene compound represented by the following formula, 15.6 g of polyethylene glycol (average molecular weight 600) and 0.5 g of p-toluenesulfonic acid were placed in a round bottom flask,
After stirring at 100 ° C. for 4 hours, 100 ml of water was added.
Then, the reaction product was extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated to obtain 2.4 g of a yellow oily ferrocene derivative represented by the following formula. The yield of this ferrocene derivative was 96.5%, and the measurement result of the proton nuclear magnetic resonance ( 1 HNMR) spectrum is as shown in FIG.
比較例１ 上記式で表わされるフェロセン化合物1.０ｇ，ポリエ
チレングリコール（平均分子量６００）１5.６ｇおよび
濃硫酸1.０ｇを、丸底フラスコに入れ１００℃で１２時
間攪拌した後、１００mlの水を加えた。次いでこの生成
物をｎ−ブチルアルコールで抽出し、無水硫酸マグネシ
ウムで乾燥，濃縮した。得られた生成物は黒色タール状
物質であったため、シリカゲルカラムクロマトグラフー
で精製した。その結果、実施例１と同じ黄色オイル状の
上記式で表わされるフェロセン誘導体を0.８４ｇ得
た。このものの収率は３4.９％であった。 Comparative Example 1 1.0 g of the ferrocene compound represented by the above formula, 15.6 g of polyethylene glycol (average molecular weight 600) and 1.0 g of concentrated sulfuric acid were placed in a round bottom flask and stirred at 100 ° C. for 12 hours, and then 100 ml of water was added. added. Next, this product was extracted with n-butyl alcohol, dried over anhydrous magnesium sulfate, and concentrated. Since the obtained product was a black tar-like substance, it was purified by silica gel column chromatography. As a result, 0.84 g of the same yellow oily ferrocene derivative represented by the above formula as in Example 1 was obtained. The yield of this product was 34.9%.
以上説明したように、本発明の方法によれば、タール状
の分解生成物を副生させることなく反応が進行するた
め、簡単な抽出操作のみで高純度の目的化合物を高収率
で得ることができる。As described above, according to the method of the present invention, the reaction proceeds without producing a tar-like decomposition product as a by-product, and thus a high-purity target compound can be obtained in high yield only by a simple extraction operation. You can
したがって、本発明の方法にしたがえば、界面活性剤や
ミセル化剤として有用なフェロセン誘導体を容易に製造
することができる。Therefore, according to the method of the present invention, a ferrocene derivative useful as a surfactant or a micellizing agent can be easily produced.
第１図は実施例１で得られたフェロセン誘導体の1Ｈ−
ＮＭＲスペクトルを示す。FIG. 1 shows 1 H-of the ferrocene derivative obtained in Example 1.
An NMR spectrum is shown.
Claims (1)
ル基，炭素数１〜６のアルコキシ基，ヒドロキシル基，
アミノ基あるいはハロゲンを示す。またＲ３は水素また
は炭素数１〜６のアルキル基を示し、ａは０〜４の整
数，ｂは０〜５の整数，ｍは２〜１８の整数を示す。〕 で表わされるフェロセン化合物と、一般式 〔式中、Ｒ４及びＲ５はそれぞれ水素，メチル基を示
し、ｎは2.０〜50.０の実数を示す。〕 で表わされるポリアルキレングリコールを、トルエンス
ルホン酸の存在下で反応させることを特徴とする一般式 〔式中、Ｒ１，Ｒ２，Ｒ４，Ｒ５，ａ，ｂ，ｍおよびｎ
は前記と同じ。〕 で表わされるフェロセン誘導体の製造方法。(1) General formula [In the formula, R 1 and R 2 are each an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group,
Indicates an amino group or halogen. R 3 represents hydrogen or an alkyl group having 1 to 6 carbon atoms, a represents an integer of 0 to 4, b represents an integer of 0 to 5, and m represents an integer of 2 to 18. ] The ferrocene compound represented by [In the formula, R 4 and R 5 each represent hydrogen and a methyl group, and n represents a real number of 2.0 to 50.0. ] A polyalkylene glycol represented by the following general formula characterized by reacting in the presence of toluenesulfonic acid [Wherein R 1 , R 2 , R 4 , R 5 , a, b, m and n
Is the same as above. ] The manufacturing method of the ferrocene derivative represented by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1076497A JPH0633299B2 (en) | 1989-03-30 | 1989-03-30 | Method for producing ferrocene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1076497A JPH0633299B2 (en) | 1989-03-30 | 1989-03-30 | Method for producing ferrocene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02256691A JPH02256691A (en) | 1990-10-17 |
| JPH0633299B2 true JPH0633299B2 (en) | 1994-05-02 |
Family
ID=13606861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1076497A Expired - Fee Related JPH0633299B2 (en) | 1989-03-30 | 1989-03-30 | Method for producing ferrocene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0633299B2 (en) |
-
1989
- 1989-03-30 JP JP1076497A patent/JPH0633299B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02256691A (en) | 1990-10-17 |
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