JPH11343260A - Production of tetracarboxylic acid - Google Patents
Production of tetracarboxylic acidInfo
- Publication number
- JPH11343260A JPH11343260A JP10151306A JP15130698A JPH11343260A JP H11343260 A JPH11343260 A JP H11343260A JP 10151306 A JP10151306 A JP 10151306A JP 15130698 A JP15130698 A JP 15130698A JP H11343260 A JPH11343260 A JP H11343260A
- Authority
- JP
- Japan
- Prior art keywords
- tetracarboxylic acid
- ruthenium
- octane
- bicyclo
- formula
- 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.)
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Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、式（１）[0001] The present invention relates to the following formula (1):
【０００２】[0002]
【化３】 Embedded image
【０００３】で表わされるテトラシクロ［６．２．１．
１＜３，６＞．０＜２，７＞］ドデカ−４，９−ジエン
をルテニウム触媒存在下酸化することにより式（２）[0003] Tetracyclo [6.2.1.
1 <3,6>. 0 <2,7>] Dodeca-4,9-diene is oxidized in the presence of a ruthenium catalyst to obtain a compound of the formula (2)
【０００４】[0004]
【化４】 Embedded image
【０００５】で表わされるビシクロ［３．３．０］オク
タン−２，４，６，８−テトラカルボン酸を製造する方
法に関するものである。本発明で得られる前記式（２）
で表わされるビシクロ［３．３．０］オクタン−２，
４，６，８−テトラカルボン酸は、ポリイミド等のポリ
マーの中間体として利用される有用な化合物である。The present invention relates to a method for producing bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid represented by the formula: Formula (2) obtained by the present invention
Bicyclo [3.3.0] octane-2 represented by
4,6,8-Tetracarboxylic acid is a useful compound used as an intermediate of a polymer such as polyimide.
【０００６】[0006]
【従来の技術】一般式（２）で表されるビシクロ［３．
３．０］オクタン−２，４，６，８−テトラカルボン酸
は、例えばジャーナル オブ アメリカン ケミカル
ソサイアティー（Jounal of American Chemical Societ
y）、８１巻、４２７３ページ、１９５９年及びジャー
ナル オブ アメリカン ケミカル ソサイアティー
（Jounal of American Chemical Society）、 ８２巻、
６３４２ページ、１９６０年に報告されている。これ
らの文献では対応するテトラシクロ［６．２．１．１＜
３，６＞．０＜２，７＞］ドデカ−４，９−ジエンより
過マンガン酸カリウムによる酸化反応が主であり、工業
的に利用するのは困難である。また一部オゾン酸化によ
る方法も述べられてあるが、蟻酸溶媒中で過酸化水素処
理を行っており文献にも記載のように極めて発熱が大き
く大変危険を伴い、工業的規模での適用は困難である。2. Description of the Related Art Bicyclo [3.
3.0] Octane-2,4,6,8-tetracarboxylic acid can be obtained, for example, from Journal of American Chemical.
Society (Jounal of American Chemical Societ)
y), 81, 4273, 1959 and the Journal of American Chemical Society, 82,
6342, reported in 1960. In these documents, the corresponding tetracyclo [6.2.1.1 <
3, 6>. 0 <2,7>] Dodeca-4,9-diene is mainly oxidized by potassium permanganate, and it is difficult to use it industrially. Some methods using ozone oxidation are also described, but hydrogen peroxide treatment is performed in formic acid solvent, and as described in the literature, it generates extremely large heat and is very dangerous, making it difficult to apply on an industrial scale. It is.
【０００７】[0007]
【発明が解決しようとする課題】これらの問題を解決す
るために、本発明者らはより穏やかな条件下で酸化反応
が行えるとされるルテニウム触媒を用いる方法につき詳
しく検討を行い本発明を見い出した。本発明の目的は、
テトラシクロ［６．２．１．１＜３，６＞．０＜２，７
＞］ドデカ−４，９−ジエンをルテニウム触媒と反応さ
せることにより、ビシクロ［３．３．０］オクタン−
２，４，６，８−テトラカルボン酸を穏やかな温度条件
下で製造させる方法を提供することにある。In order to solve these problems, the present inventors have studied in detail a method using a ruthenium catalyst which is supposed to be capable of performing an oxidation reaction under milder conditions, and found the present invention. Was. The purpose of the present invention is
Tetracyclo [6.2.1.1 <3,6>. 0 <2,7
>] By reacting dodeca-4,9-diene with a ruthenium catalyst, bicyclo [3.3.0] octane-
An object of the present invention is to provide a method for producing 2,4,6,8-tetracarboxylic acid under mild temperature conditions.
【０００８】[0008]
【課題を解決するための手段】即ち、本発明は、式
（１）That is, the present invention provides a method of formula (1)
【０００９】[0009]
【化５】 Embedded image
【００１０】で表されるテトラシクロ［６．２．１．１
＜３，６＞．０＜２，７＞］ドデカ−４，９−ジエンを
ルテニウム触媒を用いて酸化することにより式（２）The tetracyclo [6.2.1.1 represented by the following formula:
<3, 6>. 0 <2,7>] Dodeca-4,9-diene is oxidized using a ruthenium catalyst to obtain a compound of the formula (2)
【００１１】[0011]
【化６】 Embedded image
【００１２】で表わされるビシクロ［３．３．０］オク
タン−２，４，６，８−テトラカルボン酸の製造方法に
関する。The present invention relates to a process for producing bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid represented by the formula:
【００１３】[0013]
【発明の実施の形態】以下、更に本発明を詳細に説明す
る。本発明で用いるルテニウム触媒としては塩化ルテニ
ウム、塩化ルテニウム水和物、四酸化ルテニウム及び二
酸化ルテニウムの中から選ばれた少なくとも１種のルテ
ニウム触媒を用いることができる。これらの中で、塩化
ルテニウム、塩化ルテニウム水和物が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As the ruthenium catalyst used in the present invention, at least one ruthenium catalyst selected from ruthenium chloride, ruthenium chloride hydrate, ruthenium tetroxide and ruthenium dioxide can be used. Among these, ruthenium chloride and ruthenium chloride hydrate are preferred.
【００１４】本発明方法のルテニウム触媒による酸化の
際に、助酸化剤の存在下に酸化を行うことが、経済上好
ましい。助酸化剤としては過ヨウ素酸ナトリウム、過塩
素酸ナトリウム、過酸化水素や次亜塩素酸ナトリウムな
どが挙げられるが、過ヨウ素酸ナトリウムが好ましい。
触媒量は、原料の前記式（１）で表されるテトラシクロ
［６．２．１．１＜３，６＞．０＜２，７＞］ドデカ−
４，９−ジエンに対して、０．０１〜３０重量％、好ま
しくは、０．１〜１０重量％である。助酸化剤の量は、
前記式（１）で表される原料に対して、４〜２０当量、
好ましくは５〜１０当量である。It is economically preferable to carry out the oxidation in the presence of a co-oxidant during the oxidation with the ruthenium catalyst in the process of the present invention. Examples of the auxiliary oxidizing agent include sodium periodate, sodium perchlorate, hydrogen peroxide and sodium hypochlorite, and sodium periodate is preferable.
The amount of the catalyst is the amount of tetracyclo [6.2.1.1 <3,6>. 0 <2,7>] Dodeca
It is 0.01 to 30% by weight, preferably 0.1 to 10% by weight, based on 4,9-diene. The amount of co-oxidizer is
4 to 20 equivalents to the raw material represented by the formula (1),
Preferably it is 5 to 10 equivalents.
【００１５】本反応は、通常溶媒を用いて行い、有機溶
媒および水の二相系で行うことが出来る。有機溶媒とし
ては四塩化炭素、クロロホルム、ジクロロメタン、１，
２−ジクロロエタン等のハロゲン化炭化水素類、ヘキサ
ン、ヘプタン等の炭化水素類、酢酸エチル等のエステル
類などを用いることができる。また、上記の二相系に対
しアセトニトリルを共溶媒に用いることができ、これに
より効率良く反応が行える。This reaction is usually carried out using a solvent, and can be carried out in a two-phase system of an organic solvent and water. Organic solvents include carbon tetrachloride, chloroform, dichloromethane, 1,
Halogenated hydrocarbons such as 2-dichloroethane, hydrocarbons such as hexane and heptane, and esters such as ethyl acetate can be used. In addition, acetonitrile can be used as a cosolvent for the above two-phase system, whereby the reaction can be performed efficiently.
【００１６】有機溶媒とアセトニトリルと水の混合の割
合は、任意の割合で可能であるが、好ましくは１：１：
２〜０．１：１：１の割合である。溶媒量は通常、基質
１〜１０００倍量用いられ好ましくは２０〜１００倍量
であり、反応温度は−２０℃〜溶媒の沸点まで任意であ
るが好ましくは０℃〜室温で反応させる。The mixing ratio of the organic solvent, acetonitrile and water can be any ratio, but is preferably 1: 1:
The ratio is 2 to 0.1: 1: 1. The amount of the solvent is usually 1 to 1000 times the amount of the substrate, preferably 20 to 100 times, and the reaction temperature is arbitrary from −20 ° C. to the boiling point of the solvent, but the reaction is preferably performed at 0 ° C. to room temperature.
【００１７】尚、本発明の原料化合物である式（１）で
表されるテトラシクロ［６．２．１．１＜３，６＞．０
＜２，７＞］ドデカ−４，９−ジエンは、前記の文献い
ずれにも記載されている方法により得ることができる。
例えば２，５−ノルボルナジエンとジシクロペンタジエ
ンをオートクレーブ中で１９０℃で２０時間反応させる
ことにより得ることができる。The tetracyclo [6.2.1.1 <3,6> .tetracyclo [6.2.1.1] represented by the formula (1) which is a starting compound of the present invention. 0
<2,7>] Dodeca-4,9-diene can be obtained by the methods described in any of the above documents.
For example, it can be obtained by reacting 2,5-norbornadiene and dicyclopentadiene in an autoclave at 190 ° C. for 20 hours.
【００１８】通常反応の進行と共に、生成したテトラカ
ルボン酸はナトリウム塩およびルテニウム塩として析出
してくる。反応終了後２−プロパノール等を加え、反応
活性種である四酸化ルテニウム触媒等を分解させる。そ
の後反応溶液をアセトン：水＝１：１および濃塩酸の混
合溶媒にあけ、式（２）で表わされるビシクロ［３．
３．０］オクタン−２，４，６，８−テトラカルボン酸
へと誘導し溶解させる。その後無機の不溶成分をろ過に
より取り除きろ液の溶媒類を減圧留去し、得られた粗結
晶をろ取、水より再結晶を行うことで、式（２）で表わ
されるビシクロ［３．３．０］オクタン−２，４，６，
８−テトラカルボン酸が得られる。式（２）で表わされ
るビシクロ［３．３．０］オクタン−２，４，６，８−
テトラカルボン酸は２種類の立体異性体が含まれるが、
当然両異性体をも本発明の目的物として得られるもので
ある。Usually, as the reaction proceeds, the generated tetracarboxylic acid is precipitated as a sodium salt and a ruthenium salt. After completion of the reaction, 2-propanol or the like is added to decompose the reactive active species, such as a ruthenium tetroxide catalyst. Thereafter, the reaction solution was poured into a mixed solvent of acetone: water = 1: 1 and concentrated hydrochloric acid, and the bicyclo [3.
3.0] octane-2,4,6,8-tetracarboxylic acid. Thereafter, the inorganic insoluble components were removed by filtration, and the solvent in the filtrate was distilled off under reduced pressure. The obtained crude crystals were collected by filtration and recrystallized from water to give the bicyclo [3.3 represented by the formula (2). .0] octane-2,4,6
8-Tetracarboxylic acid is obtained. Bicyclo [3.3.0] octane-2,4,6,8- represented by the formula (2)
Tetracarboxylic acid includes two types of stereoisomers,
Naturally, both isomers can be obtained as the object of the present invention.
【００１９】[0019]
【実施例】次に実施例を挙げ本発明の内容を具体的に説
明するが、本発明はこれらに限定されるものではない。 実施例１ テトラシクロ［６．２．１．１＜３，６＞．０＜２，７
＞］ドデカ−４，９−ジエン２０．０１ｇを１，２−ジ
クロロエタン２００ｍＬ、アセトニトリル２００ｍＬ、
水３００ｍＬに溶解し、塩化ルテニウム１水和物を１．
１７ｇ加えた。その後、０℃で攪拌しながら過ヨウ素酸
ナトリウムを２７０．９３ｇ１時間掛けて添加した。０
℃で１時間攪拌したところ、ガスクロマトグラフィーに
よりジエン化合物の消失が確認された。その後室温に昇
温し１５時間攪拌した。EXAMPLES The contents of the present invention will now be described specifically with reference to examples, but the present invention is not limited thereto. Example 1 Tetracyclo [6.2.1.1 <3,6>. 0 <2,7
>] 20.01 g of dodeca-4,9-diene was added to 200 mL of 1,2-dichloroethane, 200 mL of acetonitrile,
Dissolve in 300 mL of water and add ruthenium chloride monohydrate to 1.
17 g were added. Thereafter, 270.93 g of sodium periodate was added over 1 hour while stirring at 0 ° C. 0
After stirring at 1 ° C. for 1 hour, disappearance of the diene compound was confirmed by gas chromatography. Thereafter, the temperature was raised to room temperature and the mixture was stirred for 15 hours.
【００２０】次に、この溶液に室温で２−プロパノール
を３００ｍｌ加え室温で発熱が収まるまで攪拌した。反
応溶液を濃塩酸８０ｍＬ、アセトン１０００ｍＬ、水１
０００ｍＬの混合溶液にあけ、更に室温で１時間攪拌を
行った。その後、濾過を行い母液を減圧濃縮、得られた
固形成分を濾取しアセトン、水で洗浄することで粗結晶
を得た。得られた粗結晶を水より再結晶することで、式
（２）のビシクロ［３．３．０］オクタン−２，４，
６，８−テトラカルボン酸２２．９ｇを得た。（収率６
３％）Next, 300 ml of 2-propanol was added to the solution at room temperature, and the mixture was stirred at room temperature until the exotherm stopped. The reaction solution is concentrated hydrochloric acid 80 mL, acetone 1000 mL, water 1
The mixture was poured into 000 mL of the mixed solution, and further stirred at room temperature for 1 hour. Thereafter, filtration was performed, and the mother liquor was concentrated under reduced pressure. The obtained solid component was collected by filtration and washed with acetone and water to obtain a crude crystal. By recrystallizing the obtained crude crystals from water, bicyclo [3.3.0] octane-2,4 of the formula (2) is obtained.
22.9 g of 6,8-tetracarboxylic acid were obtained. (Yield 6
3%)
【００２１】実施例２ 実施例１について、反応溶媒を１，２−ジクロロエタン
からヘキサンに変更して同様の反応を行った。テトラシ
クロ［６．２．１．１＜３，６＞．０＜２，７＞］ドデ
カ−４，９−ジエン０．５０ｇ、ヘキサン５ｍＬ、アセ
トニトリル５ｍＬ、水７．５ｍＬ、塩化ルテニウム水和
物３０ｍｇ、過ヨウ素酸ナトリウム５．４３ｇを用いて
反応を行ったところ、式（２）のビシクロ［３．３．
０］オクタン−２，４，６，８−テトラカルボン酸０．
３８ｇを得た。（収率４２％）Example 2 The same reaction as in Example 1 was carried out except that the reaction solvent was changed from 1,2-dichloroethane to hexane. Tetracyclo [6.2.1.1 <3,6>. 0 <2,7>] Dodeca-4,9-diene 0.50 g, hexane 5 mL, acetonitrile 5 mL, water 7.5 mL, ruthenium chloride hydrate 30 mg, and sodium periodate 5.43 g were reacted. However, the bicyclo [3.3.
0] octane-2,4,6,8-tetracarboxylic acid
38 g were obtained. (Yield 42%)
【００２２】比較例１ テトラシクロ［６．２．１．１＜３，６＞．０＜２，７
＞］ドデカ−４，９−ジエン２０．０５ｇを水１０００
ｍＬに分散させ室温で過マンガン酸カリウム１０８．７
４ｇを４０分かけて加えたが、添加を始めてしばらくし
てから内温が５０℃まで急激に上昇した。その後、室温
で１８時間攪拌し濾過を行った。濾液が約１２０ｍＬに
なるまで濃縮した後、濃塩酸６０ｍＬを加え室温で一晩
放置した。析出してきた粗結晶を濾取し水で洗浄したと
ころ、式（２）のビシクロ［３．３．０］オクタン−
２，４，６，８−テトラカルボン酸７．６４ｇを得た。
（収率２１％）Comparative Example 1 Tetracyclo [6.2.1.1 <3,6>. 0 <2,7
>] Dodeca-4,9-diene (20.05 g) in water (1000)
of potassium permanganate at room temperature.
4 g was added over 40 minutes, but the internal temperature rose rapidly to 50 ° C. shortly after the addition was started. Thereafter, the mixture was stirred at room temperature for 18 hours and filtered. After the filtrate was concentrated to about 120 mL, concentrated hydrochloric acid (60 mL) was added, and the mixture was allowed to stand at room temperature overnight. The precipitated crude crystals were collected by filtration and washed with water to give bicyclo [3.3.0] octane-formula (2).
7.64 g of 2,4,6,8-tetracarboxylic acid was obtained.
(Yield 21%)
【００２３】[0023]
【発明の効果】ルテニウム触媒および過ヨウ素酸ナトリ
ウム等の助酸化剤の組み合わせを酸化剤として用いるこ
とにより、低温の穏やかな条件で反応が行えビシクロ
［３．３．０］オクタン−２，４，６，８−テトラカル
ボン酸を大量に製造することが可能となった。またそれ
に付随して収率的にも改善を計ることができるようにな
った。この方法によりスケールアップも可能となり工業
的生産にも適用できるものである。By using a combination of a ruthenium catalyst and a co-oxidizing agent such as sodium periodate as an oxidizing agent, the reaction can be carried out under a mild condition at a low temperature and bicyclo [3.3.0] octane-2,4,4. It has become possible to mass-produce 6,8-tetracarboxylic acid. In addition, it is possible to improve the yield in connection with it. This method enables scale-up and can be applied to industrial production.
フロントページの続き (72)発明者 中島 康之 千葉県船橋市坪井町722番地１ 日産化学 工業株式会社中央研究所内Continuation of front page (72) Inventor Yasuyuki Nakajima 722-1, Tsuboi-cho, Funabashi-shi, Chiba Pref. Nissan Chemical Industry Co., Ltd. Central Research Laboratory
Claims (4)
０＜２，７＞］ドデカ−４，９−ジエンをルテニウム触
媒を用いて酸化することを特徴とする式（２） 【化２】 で表されるビシクロ［３．３．０］オクタン−２，４，
６，８−テトラカルボン酸の製造方法。(1) Formula (1) The tetracyclo [6.2.1.1 <3,6>.
0 <2,7>] dodeca-4,9-diene is oxidized using a ruthenium catalyst, formula (2) Bicyclo [3.3.0] octane-2,4 represented by
A method for producing 6,8-tetracarboxylic acid.
酸化剤を用いる請求項１記載のテトラカルボン酸の製造
方法。2. The method for producing tetracarboxylic acid according to claim 1, wherein a co-oxidizing agent is used when oxidizing using a ruthenium catalyst.
ルテニウム水和物、四酸化ルテニウム及び二酸化ルテニ
ウムの中から選ばれた少なくとも１種のルテニウム化合
物である請求項１又は２記載のビシクロ［３．３．０］
オクタン−２，４，６，８−テトラカルボン酸の製造方
法。3. The bicyclo [3.3. Ruthenium catalyst according to claim 1 or 2, wherein the ruthenium catalyst is at least one ruthenium compound selected from ruthenium chloride, ruthenium chloride hydrate, ruthenium tetroxide and ruthenium dioxide. 0]
A process for producing octane-2,4,6,8-tetracarboxylic acid.
請求項２に記載のビシクロ［３．３．０］オクタン−
２，４，６，８−テトラカルボン酸の製造方法。4. The bicyclo [3.3.0] octane- according to claim 2, wherein the co-oxidizing agent is sodium periodate.
A method for producing 2,4,6,8-tetracarboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15130698A JP4013005B2 (en) | 1998-06-01 | 1998-06-01 | Method for producing tetracarboxylic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15130698A JP4013005B2 (en) | 1998-06-01 | 1998-06-01 | Method for producing tetracarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11343260A true JPH11343260A (en) | 1999-12-14 |
| JP4013005B2 JP4013005B2 (en) | 2007-11-28 |
Family
ID=15515788
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15130698A Expired - Lifetime JP4013005B2 (en) | 1998-06-01 | 1998-06-01 | Method for producing tetracarboxylic acid |
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| JP (1) | JP4013005B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010095604A1 (en) * | 2009-02-23 | 2010-08-26 | 日産化学工業株式会社 | Alicyclic tetracarboxylic acid manufacturing method |
| JP2015127303A (en) * | 2013-12-27 | 2015-07-09 | 日産化学工業株式会社 | Method of producing alicyclic tetracarboxylic acid |
-
1998
- 1998-06-01 JP JP15130698A patent/JP4013005B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010095604A1 (en) * | 2009-02-23 | 2010-08-26 | 日産化学工業株式会社 | Alicyclic tetracarboxylic acid manufacturing method |
| KR20110129907A (en) * | 2009-02-23 | 2011-12-02 | 닛산 가가쿠 고교 가부시키 가이샤 | Alicyclic tetracarboxylic acid manufacturing method |
| JP5724870B2 (en) * | 2009-02-23 | 2015-05-27 | 日産化学工業株式会社 | Method for producing alicyclic tetracarboxylic acid |
| JP2015127303A (en) * | 2013-12-27 | 2015-07-09 | 日産化学工業株式会社 | Method of producing alicyclic tetracarboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4013005B2 (en) | 2007-11-28 |
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