JP2004051497A - Method for producing adamantanediols - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing adamantanediols by recovering an organic solvent to recycle it. <P>SOLUTION: The production method comprises reacting adamantanes with hypochlorites using a ruthenium compound in a water/organic solvent double phase system, and then adding a 4-8C alcohol to the reaction liquid mixture to extract adamantanediols. In this case, in recovering the organic solvent from the reaction liquid mixture to reuse for the above reaction, the alcohol content in the organic solvent is made to be 0.5 wt.% or less. <P>COPYRIGHT: (C)2004,JPO

Description

（式中、Ｒは水素原子、アルキル基、アリール基、シクロアルキル基、アルコキシ基、アリールオキシ基、アシルオキシ基、ハロゲン基を示す）
【０００９】
ここでアルキル基には、メチル、エチル、プロピル、ブチル、ヘキシル基などの炭素数１〜１０アルキル基、好ましくは炭素数１〜６アルキル基、特に炭素数１〜４アルキル基が含まれる。アリール基には、フェニル基、ナフチル基等が含まれ、シクロアルキル基には、シクロヘキシル、シクロオクチル基等が含まれる。アルコキシ基には、メトキシ、エトキシ、プロポキシ、ブトキシ、ヘキシルオキシ基等の炭素数１〜１０アルコキシ基が含まれる。アリールオキシ基には、例えば、フェノキシ基等が含まれる。アシルオキシ基には、アセチルオキシ、プロピオニルオキシ、ブチリルオキシ基等の炭素数２〜６アシルオキシ基等が含まれる。ハロゲン基には、クロル基、ブロム基、ヨード基等が含まれる。
【００１０】
本発明のアダマンタンジオール類は、１，３−アダマンタンジオール、１，２−アダマンタンジオール、１，４−アダマンタンジオールが挙げられ、これらは置換基を有していてもよい。
【００１１】
本発明のルテニウム化合物は、ルテニウム金属、二酸化ルテニウム、四酸化ルテニウム、水酸化ルテニウム、塩化ルテニウム、臭化ルテニウム、ヨウ化ルテニウム、硫酸ルテニウムまたはそれらの水和物等を単独または混合物で用いることができる。ルテニウム化合物は、原料のアダマンタン１モルに対して０．００５〜２．０モル、より好ましくは０．０１〜０．２の割合で使用する。使用量がこの範囲より少ないと反応速度が低下し、多いと高価なルテニウム化合物を多量に使用することになり、共に工業的見地から好ましくない。
【００１２】
本発明に用いる次亜塩素酸塩類としては、次亜塩素酸ナトリウムが好ましい。次亜塩素酸塩類は、６〜３５重量％の水溶液として使用する。次亜塩素酸塩類の濃度がこの範囲より低いと水相の量が多くなり、生成物の水相からの抽出効率が低下し、廃液処理にも負担をかける。一方、次亜塩素酸塩類の濃度がこの範囲より高いと副反応が起こりやすくなりアダマンタンジオール類の収率が低下する。
【００１３】
次亜塩素酸塩類の添加量は、アダマンタン類１モルに対し、１．５〜４．０モル、好ましくは２．０〜３．０モルの範囲とする。次亜塩素酸塩類の添加量がこの範囲より少ない場合は未反応の基質あるいはアダマンタンモノオール類が大量に残り、アダマンタンジオール類の選択率が低い。一方、添加量がこの範囲より多い場合は、アダマンタントリオール類生成などの副反応の割合が増え、やはりアダマンタンジオール類の選択率が低下する。
【００１４】
本発明の方法において、効率的かつ高収率でアダマンタンジオール類を得るためには、次亜塩素酸塩は一度に添加せずに滴下しながら反応することが好ましい。一度に添加すると副反応の割合が増え、アダマンタン類およびアダマンタンモノオール類の転化率が低下する。
【００１５】
反応中のｐＨは３〜１０の範囲で任意に選ぶことができる。ｐＨが１０を超えると触媒活性の低い過ルテニウムイオンが生成するため好ましくない。また、ｐＨが３を下回ると塩素が発生し、反応に悪影響を及ぼす。
【００１６】
反応中のｐＨを調整するために酸を添加することができる。添加する酸としては、水溶性の酸である蟻酸、酢酸、プロピオン酸等の有機酸、塩酸、硫酸、硝酸、リン酸等の無機酸のいずれでも良いが、生成物の精製から考えると無機酸が好ましく、反応に影響を与える可能性が低い塩酸および硫酸が更に好ましい。用いる酸の濃度に特に制限はない。
【００１７】
本発明において使用する有機溶媒としては、水との相溶性が低く、高酸化状態のルテニウムの溶解性が高く、本発明の反応に対し不活性な溶媒を選択する。相溶性が高いと溶媒回収コストが上昇し、高酸化状態のルテニウムの溶解性が低いと反応が進行しにくくなる。そのような有機溶媒の例としては、ハロゲン化アルキル類［例えばジクロロメタン、１，２−ジクロロエタン、クロロホルム、四塩化炭素など］、エステル類［例えば酢酸メチル、酢酸エチル、酢酸イソプロピルなど］、炭化水素類［例えばヘキサン、シクロヘキサン、ヘプタンなど］の溶媒を挙げることができる。この中で特に１，２−ジクロロエタン、酢酸エチルが好ましい。これらの溶媒は、単独でも２種以上の溶媒を混合した系でも使用できる。溶媒は、原料として用いるアダマンタン１重量部に対して、１〜５０重量部、好ましくは３〜１０重量部の割合で使用する。
【００１８】
反応温度は１０〜１００℃、好ましくは３０〜７０℃の範囲である。反応温度がこの範囲よりも低い場合は反応速度が著しく低下し、逆に高い場合は、次亜塩素酸塩の分解や副反応の増加によるアダマンタンジオール類選択率の低下が起こり、いずれも不利になる場合が多い。反応時間は、１００〜６００分が好ましい。使用する反応器は、特に制限はなく公知の攪拌機付き反応器で行うことができる。
【００１９】
反応後の混合液にアルカリを添加し、ルテニウム化合物を水相に分離後、炭素数４〜８のアルコールを添加して抽出することにより、アダマンタンジオール類とルテニウム化合物がそれぞれ有機相と水相に分離され、アダマンタンジオール類が有機相から得られる。炭素数４〜８のアルコールとしては１−ブタノール、１−ペンタノール、１−ヘキサノール、２−ブタノール、２−メチル−１−プロパノール、３−メチル−１−ブタノールまたはベンジルアルコールが好ましい。有機相からは、濾過、濃縮、蒸留、晶析、再結晶等の公知方法でアダマンタンジオール類が分離される。また、水相のルテニウム化合物は濾過もしくは酸化状態にして有機溶媒で抽出することにより、反応に再利用することができる。
【００２０】
有機溶媒の回収方法について、抽出溶媒として用いたアルコールの含有率を０．５重量％以下にする必要がある。アルコールの含有率が０．５重量％を超えると反応収率が低下してしまう。具体的な回収方法として、前記のアルコール抽出後の有機相から蒸留により回収することが挙げられる。また、別法として、反応混合液へのアルコールの添加前に蒸留により回収することが挙げられる。
【００２１】
一方、抽出溶媒の再利用に関しては、有機溶媒の混入量に関係なく次反応に再利用可能である。
【００２２】
【実施例】
以下、実施例及び比較例により本発明をさらに具体的に説明する。但し、本発明はこれらの実施例により限定されるものではない。
【００２３】
実施例１
攪拌機、温度計、ジムロート冷却器、ｐＨ電極をつけた３ｌの５つ口ジャケット付きフラスコにアダマンタン６５．５ｇ（４８２ｍｍｏｌ）、酢酸エチル４３４ｇ、塩化ルテニウム・ｎ水和物３．１８ｇ、水７７ｇを仕込んだ後、４６℃に加温した。ｐＨコントローラーに次亜塩素酸ナトリウム注入用定量ポンプ及び硫酸注入用ポンプを接続し、ｐＨ５を維持するように両者を滴下していき、次亜塩素酸ナトリウム水溶液を７２０ｇ（１．２ｍｏｌ）添加した。
【００２４】
次亜塩素酸ナトリウムの添加終了後、２５重量％ＮａＯＨ１３ｇを加えて水相を中和した。ヘキサノール５４０ｇを添加してアダマンタンジオール類を溶解し、有機相と水相を分離した。ガスクロマトグラフィーで分析した結果　、アダマンタンの転化率は１００％、１−アダマンタノール収率は７％、１，３−アダマンタンジオール収率は７０％、１，３，５−アダマンタントリオール収率は１６％であった。有機相を濃縮し、ヘキサノールを８％含む酢酸エチルを留分として４２０ｇ得た。これをさらに段数２０の精留塔により精製しヘキサノールを０．１２％含む酢酸エチル３８０ｇを回収した。
【００２５】
回収した酢酸エチルを用いた以外は、上記と同様に再度反応および後処理を行い有機相および水相をガスクロマトグラフィーで分析した結果　、アダマンタンの転化率は１００％、１−アダマンタノール収率は９％、１，３−アダマンタンジオール収率は７０％、１，３，５−アダマンタントリオール収率は１４％であった。
【００２６】
実施例２
実施例１と同様に反応、抽出および濃縮後、濃縮の際に得られた留分を段数２０の精留塔により精製しヘキサノールを０．４６％含む酢酸エチル３８０ｇを回収した。回収した酢酸エチルを用いた以外は、上記と同様に再度反応および後処理を行い有機相および水相をガスクロマトグラフィーで分析した結果　、アダマンタンの転化率は１００％、１−アダマンタノール収率は１３％、１，３−アダマンタンジオール収率は５９％、１，３，５−アダマンタントリオール収率は１４％であった。
【００２７】
比較例１
実施例１と同様に反応、抽出および濃縮後、濃縮の際に得られた留分を段数１０の精留塔により精製しヘキサノールを０．９％含む酢酸エチル３８０ｇを回収した。回収した酢酸エチルを用いた以外は、上記と同様に再度反応および後処理を行い有機相および水相をガスクロマトグラフィーで分析した結果　、アダマンタンの転化率は１００％、１−アダマンタノール収率は４９％、１，３−アダマンタンジオール収率は３５％、１，３，５−アダマンタントリオール収率は６％であった。
【００２８】
比較例２
実施例１と同様に反応、抽出および濃縮後、濃縮の際得られたヘキサノールを８％含む酢酸エチル４２０ｇを用いた以外は実施例１と同様に再度反応を行ったが、アダマンタンジオールの生成は確認できなかった。
【００２９】
実施例３
実施例１と同様に反応を行い、２５重量％ＮａＯＨ１３ｇを加えて水相の中和を行った。次に混合液を５０℃に加熱し常圧から徐々に２００ｔｏｒｒまで減圧することにより酢酸エチル４２０ｇおよび水３０ｇを留去した。ヘキサノール５４０ｇを添加してアダマンタンジオール類を溶解し、有機相と水相を分離した。ガスクロマトグラフィーで分析した結果　、アダマンタンの転化率は１００％、１−アダマンタノール収率は７％、１，３−アダマンタンジオール収率は７０％、１，３，５−アダマンタントリオール収率は１６％であった。
【００３０】
留去した酢酸エチルを用いた以外は、実施例１と同様に再度反応および後処理を行い有機相および水相をガスクロマトグラフィーで分析した結果　、アダマンタンの転化率は１００％、１−アダマンタノール収率は９％、１，３−アダマンタンジオール収率は７０％、１，３，５−アダマンタントリオール収率は１４％であった。
【００３１】
【発明の効果】
本発明により、有機溶媒を簡便に回収、再利用が可能であり、アダマンタンジオール類を効率的に製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing adamantanediols useful as raw materials for highly functional polymers, synthetic lubricating oils and plasticizers, or as intermediates for organic chemicals such as medical and agricultural chemicals.
[0002]
[Prior art]
The present inventors have proposed a method in Japanese Patent Application Laid-Open No. 2000-219646 in which adamantane is reacted with a ruthenium compound and hypochlorous acid or a salt thereof in a water / organic solvent two-phase system. According to this method, adamantanediols can be obtained selectively and in high yield.
[0003]
Furthermore, in JP-A-2000-344696, after reacting adamantane with a ruthenium compound and hypochlorous acid or a salt thereof in a water / organic solvent two-phase system, an alcohol having 4 to 8 carbon atoms is used as an extraction solvent. A method of extracting the added and produced adamantanediols was proposed. According to this method, the operation of isolating the adamantanediols is simplified, and the adamantanediols can be produced more efficiently.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing an adamantanediol more efficiently by collecting and reusing an organic solvent in the production of the adamantanediol.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on the reuse of an organic solvent, and as a result, have found that the organic solvent can be reused by reducing the alcohol content in the organic solvent to a certain ratio or less, and have completed the present invention. .
[0006]
That is, the present invention provides an adamantane diol which is obtained by reacting adamantane with a ruthenium compound and a hypochlorite in a water / organic solvent two-phase system, and adding an alcohol having 4 to 8 carbon atoms to the mixed solution after the reaction. In the method of producing adamantanediols by extracting the organic solvent from the mixed solution after the reaction, when the recovered organic solvent is reused in the reaction, the alcohol content in the recycled organic solvent is 0%. The present invention relates to a method for producing adamantanediols, which is not more than 0.5% by weight.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Adamantane used as a raw material in the present invention is represented by the following general formula.
[0008]
Embedded image

(Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an acyloxy group, or a halogen group)
[0009]
Here, the alkyl group includes an alkyl group having 1 to 10 carbon atoms, such as a methyl, ethyl, propyl, butyl, and hexyl group, preferably an alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms. The aryl group includes a phenyl group, a naphthyl group and the like, and the cycloalkyl group includes a cyclohexyl, cyclooctyl group and the like. The alkoxy group includes a C1 to C10 alkoxy group such as methoxy, ethoxy, propoxy, butoxy, and hexyloxy groups. The aryloxy group includes, for example, a phenoxy group and the like. The acyloxy group includes an acyloxy group having 2 to 6 carbon atoms such as acetyloxy, propionyloxy and butyryloxy. Halogen groups include chloro, bromo, and iodo groups.
[0010]
The adamantanediols of the present invention include 1,3-adamantanediol, 1,2-adamantanediol, and 1,4-adamantanediol, and these may have a substituent.
[0011]
The ruthenium compound of the present invention can be used alone or as a mixture of ruthenium metal, ruthenium dioxide, ruthenium tetroxide, ruthenium hydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium sulfate or a hydrate thereof. . The ruthenium compound is used in a proportion of 0.005 to 2.0 mol, more preferably 0.01 to 0.2, per mol of adamantane as a raw material. If the amount used is less than this range, the reaction rate will be reduced, and if it is too large, a large amount of expensive ruthenium compound will be used, both of which are undesirable from an industrial point of view.
[0012]
As the hypochlorite used in the present invention, sodium hypochlorite is preferable. The hypochlorites are used as a 6-35% by weight aqueous solution. If the concentration of hypochlorites is lower than this range, the amount of the aqueous phase increases, the efficiency of extracting the product from the aqueous phase decreases, and a burden is imposed on waste liquid treatment. On the other hand, if the concentration of hypochlorite is higher than this range, a side reaction is likely to occur, and the yield of adamantanediols decreases.
[0013]
The amount of hypochlorite to be added is in the range of 1.5 to 4.0 mol, preferably 2.0 to 3.0 mol, per 1 mol of adamantane. If the amount of hypochlorite is less than this range, a large amount of unreacted substrate or adamantane monool remains and the selectivity for adamantanediol is low. On the other hand, when the addition amount is larger than this range, the ratio of side reactions such as the formation of adamantanetriols increases, and the selectivity of adamantanediols also decreases.
[0014]
In the method of the present invention, in order to obtain adamantanediols efficiently and in a high yield, it is preferable to react while adding hypochlorite dropwise without adding it all at once. If added at once, the proportion of side reactions increases, and the conversion of adamantane and adamantane monol decreases.
[0015]
The pH during the reaction can be arbitrarily selected within the range of 3 to 10. If the pH exceeds 10, undesired perruthenium ions having low catalytic activity are generated. Further, when the pH is lower than 3, chlorine is generated, which adversely affects the reaction.
[0016]
An acid can be added to adjust the pH during the reaction. The acid to be added may be any of water-soluble organic acids such as formic acid, acetic acid, and propionic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Are preferred, and hydrochloric acid and sulfuric acid which are unlikely to affect the reaction are more preferred. There is no particular limitation on the concentration of the acid used.
[0017]
As the organic solvent used in the present invention, a solvent having low compatibility with water, high solubility of ruthenium in a high oxidation state, and inert to the reaction of the present invention is selected. If the compatibility is high, the cost of recovering the solvent increases, and if the solubility of the ruthenium in a highly oxidized state is low, the reaction hardly proceeds. Examples of such organic solvents include alkyl halides [eg, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, etc.], esters [eg, methyl acetate, ethyl acetate, isopropyl acetate, etc.], hydrocarbons. [For example, hexane, cyclohexane, heptane, etc.] can be mentioned. Of these, 1,2-dichloroethane and ethyl acetate are particularly preferred. These solvents can be used alone or in a system in which two or more solvents are mixed. The solvent is used in a proportion of 1 to 50 parts by weight, preferably 3 to 10 parts by weight, based on 1 part by weight of adamantane used as a raw material.
[0018]
The reaction temperature ranges from 10 to 100C, preferably from 30 to 70C. When the reaction temperature is lower than this range, the reaction rate is remarkably reduced.On the contrary, when the reaction temperature is higher, the selectivity of adamantanediols is reduced due to decomposition of hypochlorite and an increase in side reactions, and both are disadvantageous. Often. The reaction time is preferably from 100 to 600 minutes. The reactor used is not particularly limited and can be a known reactor equipped with a stirrer.
[0019]
An alkali is added to the mixed solution after the reaction, the ruthenium compound is separated into an aqueous phase, and an alcohol having 4 to 8 carbon atoms is added and extracted, so that the adamantanediols and the ruthenium compound are converted into an organic phase and an aqueous phase, respectively. Separated, adamantanediols are obtained from the organic phase. As the alcohol having 4 to 8 carbon atoms, 1-butanol, 1-pentanol, 1-hexanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol or benzyl alcohol is preferred. Adamantanediols are separated from the organic phase by a known method such as filtration, concentration, distillation, crystallization, and recrystallization. The ruthenium compound in the aqueous phase can be reused in the reaction by filtering or oxidizing and extracting with an organic solvent.
[0020]
Regarding the method of recovering the organic solvent, the content of the alcohol used as the extraction solvent needs to be 0.5% by weight or less. If the alcohol content exceeds 0.5% by weight, the reaction yield will decrease. As a specific recovery method, there is a method of recovering from the organic phase after the alcohol extraction by distillation. Another alternative is to recover by distillation before adding the alcohol to the reaction mixture.
[0021]
On the other hand, regarding the reuse of the extraction solvent, it can be reused in the next reaction regardless of the amount of the organic solvent mixed.
[0022]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited by these examples.
[0023]
Example 1
In a 3 l 5-neck jacketed flask equipped with a stirrer, thermometer, Dimroth condenser, and pH electrode, 65.5 g (482 mmol) of adamantane, 434 g of ethyl acetate, 3.18 g of ruthenium chloride / n-hydrate, and 77 g of water were charged. After that, the mixture was heated to 46 ° C. A metering pump for injecting sodium hypochlorite and a pump for injecting sulfuric acid were connected to the pH controller, and both were dropped so as to maintain pH 5, and 720 g (1.2 mol) of an aqueous solution of sodium hypochlorite was added.
[0024]
After the completion of the addition of sodium hypochlorite, 13 g of 25% by weight of NaOH was added to neutralize the aqueous phase. Hexanol (540 g) was added to dissolve the adamantanediols, and the organic phase and the aqueous phase were separated. As a result of analysis by gas chromatography, the conversion of adamantane was 100%, the yield of 1-adamantanol was 7%, the yield of 1,3-adamantanediol was 70%, and the yield of 1,3,5-adamantanetriol was 16%. %Met. The organic phase was concentrated, and 420 g of ethyl acetate containing 8% of hexanol was obtained as a fraction. This was further purified by a rectification column having 20 stages to recover 380 g of ethyl acetate containing 0.12% of hexanol.
[0025]
Except that the recovered ethyl acetate was used, the reaction and post-treatment were performed again in the same manner as above, and the organic phase and the aqueous phase were analyzed by gas chromatography. As a result, the conversion of adamantane was 100%, and the yield of 1-adamantanol was 100%. 9%, 1,3-adamantanediol yield was 70%, and 1,3,5-adamantanetriol yield was 14%.
[0026]
Example 2
After the reaction, extraction and concentration in the same manner as in Example 1, the fraction obtained during the concentration was purified by a rectification column having 20 stages to recover 380 g of ethyl acetate containing 0.46% of hexanol. Except that the recovered ethyl acetate was used, the reaction and post-treatment were performed again in the same manner as above, and the organic phase and the aqueous phase were analyzed by gas chromatography. As a result, the conversion of adamantane was 100%, and the yield of 1-adamantanol was 100%. 13%, 1,3-adamantanediol yield was 59%, and 1,3,5-adamantanetriol yield was 14%.
[0027]
Comparative Example 1
After the reaction, extraction and concentration in the same manner as in Example 1, the fraction obtained at the time of concentration was purified by a rectification column having 10 stages to recover 380 g of ethyl acetate containing 0.9% of hexanol. Except that the recovered ethyl acetate was used, the reaction and post-treatment were performed again in the same manner as above, and the organic phase and the aqueous phase were analyzed by gas chromatography. As a result, the conversion of adamantane was 100%, and the yield of 1-adamantanol was 100%. 49%, the yield of 1,3-adamantanediol was 35%, and the yield of 1,3,5-adamantanetriol was 6%.
[0028]
Comparative Example 2
After the reaction, extraction and concentration in the same manner as in Example 1, the reaction was carried out again in the same manner as in Example 1 except that 420 g of ethyl acetate containing 8% of hexanol obtained at the time of concentration was used. I could not confirm.
[0029]
Example 3
The reaction was carried out in the same manner as in Example 1, and the aqueous phase was neutralized by adding 13 g of 25% by weight of NaOH. Next, the mixture was heated to 50 ° C., and the pressure was gradually reduced from normal pressure to 200 torr, whereby 420 g of ethyl acetate and 30 g of water were distilled off. Hexanol (540 g) was added to dissolve the adamantanediols, and the organic phase and the aqueous phase were separated. As a result of analysis by gas chromatography, the conversion of adamantane was 100%, the yield of 1-adamantanol was 7%, the yield of 1,3-adamantanediol was 70%, and the yield of 1,3,5-adamantanetriol was 16%. %Met.
[0030]
The reaction and post-treatment were carried out again in the same manner as in Example 1 except that the distilled ethyl acetate was used, and the organic phase and the aqueous phase were analyzed by gas chromatography. As a result, the conversion of adamantane was 100% and 1-adamantanol was obtained. The yield was 9%, the 1,3-adamantanediol yield was 70%, and the 1,3,5-adamantanetriol yield was 14%.
[0031]
【The invention's effect】
According to the present invention, an organic solvent can be easily recovered and reused, and adamantanediols can be efficiently produced.

Claims (2)

The adamantane is reacted with a ruthenium compound and a hypochlorite in a water / organic solvent two-phase system, and an alcohol having 4 to 8 carbon atoms is added to the mixed solution after the reaction to extract the adamantane diol and the adamantane diol is extracted. In the method for producing the organic solvents, the organic solvent is recovered from the mixed solution after the reaction, and when the recovered organic solvent is reused in the reaction, the alcohol content in the recycled organic solvent is 0.5% by weight or less. A method for producing adamantanediols. The method according to claim 1, wherein the organic solvent is recovered before adding the alcohol.