JPH0481576B2 - - Google Patents
Info
- Publication number
- JPH0481576B2 JPH0481576B2 JP59140528A JP14052884A JPH0481576B2 JP H0481576 B2 JPH0481576 B2 JP H0481576B2 JP 59140528 A JP59140528 A JP 59140528A JP 14052884 A JP14052884 A JP 14052884A JP H0481576 B2 JPH0481576 B2 JP H0481576B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- biphenyltetracarboxylic acid
- triphenylphosphine
- ester
- tetrakis
- 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 - Lifetime
Links
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- -1 organic acid salt Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- UEJAKHGKSSMXIS-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid;dihydrate Chemical compound O.O.C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 UEJAKHGKSSMXIS-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- NJIGQKCRWMSZBA-UHFFFAOYSA-N dimethyl 4-[3,4-bis(methoxycarbonyl)phenyl]benzene-1,2-dicarboxylate Chemical compound C1=C(C(=O)OC)C(C(=O)OC)=CC=C1C1=CC=C(C(=O)OC)C(C(=O)OC)=C1 NJIGQKCRWMSZBA-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
〔発明の利用分野〕
本発明はビフエニルテトラカルボン酸の製造方
法に関する。
〔発明の背景〕
従来より次式で示されるビフエニルテトラカル
ボン酸について数種の製造方法が提案されてい
る。
代表的な従来方法は次の通りである。
(1) オルソーフタル酸ジメチルをパラジウムの有
機酸塩の存在下、酸素加圧下に、β−ジケトン
及ぶ／またはエチレンジアミンテトラ酢酸を添
加して脱水素二量化し、その後酸により加水分
解して製造する方法（特公昭50−31148号公報
参照）。
(2) オルソーキンレンを酸素加圧下、パラジウム
の有機酸塩とエチレンジアミンテトラ酢酸の存
在下で脱水素二量化し、更に液相で酸化して製
造する方法（特公昭50−31149号公報参照）。
(3) ４−ハロゲノオルソフタル酸塩を水酸化アル
カリ水溶液中で、金属パラジウムと少量のメタ
ノールの存在下に加熱反応させてカツプリング
させる方法（特開昭55−20705号報参照）。
(4) オルソフタル酸エステルを、有機パラジウム
塩K.1，10−フエナントロリン及び／または
α，α′−ビピリジルの存在下に、酸素加圧下で
酸化カツプリングして合成する方法（特開昭55
−153747号公報参照）。
これらの内、(1)、(2)、(4)の製法では、酸素加圧
下での反応なので特殊な装置を要求され、爆発の
危険性を有し、収率が悪く、異性体が多くできて
選択性が無い等の欠点がある。また(3)の製法では
反応条件は温和だが収率が極めて低いという問題
がある。
〔発明の目的〕
本発明の目的は、高純度のビフエニルテトラカ
ルボン酸を高収率、温和条件で得る方法を提供す
るにある。
〔発明の概要〕
本発明によるビフエニルテトリカルボン酸の製
造方法は、
[Field of Application of the Invention] The present invention relates to a method for producing biphenyltetracarboxylic acid. [Background of the Invention] Several production methods have been proposed for biphenyltetracarboxylic acid represented by the following formula. Typical conventional methods are as follows. (1) Produced by dehydrogenating dimethyl orthophthalate in the presence of an organic acid salt of palladium under oxygen pressure by adding β-diketone and/or ethylenediaminetetraacetic acid, and then hydrolyzing it with acid. Method (see Japanese Patent Publication No. 50-31148). (2) A method of producing orthoquinlen by dehydrogenating and dimerizing it in the presence of an organic acid salt of palladium and ethylenediaminetetraacetic acid under oxygen pressure, and further oxidizing it in the liquid phase (see Japanese Patent Publication No. 50-31149) . (3) A method of coupling 4-halogenorthophthalate by heating it in an aqueous alkali hydroxide solution with metallic palladium in the presence of a small amount of methanol (see JP-A-55-20705). (4) A method for synthesizing orthophthalic acid ester by oxidative coupling under oxygen pressure in the presence of organic palladium salt K.1,10-phenanthroline and/or α,α'-bipyridyl (JP-A-55
-Refer to Publication No. 153747). Among these, manufacturing methods (1), (2), and (4) require special equipment because the reaction is under pressurized oxygen, have the risk of explosion, have poor yields, and produce many isomers. However, there are drawbacks such as lack of selectivity. Furthermore, although the reaction conditions are mild in the production method (3), there is a problem in that the yield is extremely low. [Object of the Invention] An object of the present invention is to provide a method for obtaining highly purified biphenyltetracarboxylic acid in high yield under mild conditions. [Summary of the invention] The method for producing biphenyltetricarboxylic acid according to the present invention includes:
【式】（Ｘはハロゲ
ン、Ｒは望ましくは炭素数が５個以下のアルキル
基）で示されるハローベンゼンカルボン酸ジアル
キルエステルを、テトラキス（トリフエニルホス
フイン）ニツケル、テトラキス（トリフエニルホ
スフイン）パラジウム触媒の少なくとも１種の存
在下でカツプリングさせ、[Formula] (X is halogen, R is preferably an alkyl group having 5 or less carbon atoms) A halobenzenecarboxylic acid dialkyl ester represented by coupling in the presence of at least one catalyst;
【式】で示され
るビフエニルテトラカルボン酸テトラアルキルエ
ステルとした後、これを加水分解することにより
得ることを特徴とする。こうして得られたビフエ
ニルテトラカルボン酸は式
It is characterized in that it is obtained by preparing a biphenyltetracarboxylic acid tetraalkyl ester represented by the formula and then hydrolyzing it. The biphenyltetracarboxylic acid thus obtained has the formula
実施例 １
温度計、撹拌器、窒素ガス吹込口の付いた50ml
のフラスコに、亜鉛粉末0.5ｇ（８ｍmol）とト
リフエニルホスフイン0.5ｇ（２ｍmol）、４−ヨ
ード−ジメチルフタレート2.0ｇ（6.2ｍmol）、
Ｎ，Ｎ−ジメチルホルムアミド（DMF）５mlを
入れ窒素を30分間吹き込んだ。この混合物に、通
常の方法で調節したテトラキス（トリフエニルホ
スフイン）ニツケルのDMF懸濁液（触媒量0.5ｍ
mol）を加える。４時間撹拌した後、希塩酸を加
え、続いてクロロホルムを加えて抽出した。クロ
ロホルム相を取出し、クロロホルムを留去して、
３，3′，４，4′−ビフエニルテトラカルボン酸テ
トラメチルエステルを得た。次いで、10％水酸化
ナトリウム水溶液、メタノール中で、50℃、２時
間撹拌して、エステルを加水分解した。室温に冷
却したのち、クロロホルムを加え、水相を洗浄し
た。分液した水層に塩酸を加え、PHを１以下にし
て、ビフエニルテトラカルボン酸を酸析した。こ
の白色沈澱を口別し、乾燥することにより0.91
ｇ、収率80％で３，3′，４，4′−ビフエニルテト
ラカルボン酸二水和物を得た。生成物の融点を測
定した結果、295℃で分解し、融点は測定できな
かつた。
実施例 ２
触媒としてテトラキス（トリフエニルホスフイ
ン）パラジウム（０）を用いた以外は実施例１と
同様に操作して、３，3′，４，4′−ビフエニルテ
トラカルボン酸二水和物の合成を行つた。その結
果、目的物を0.93ｇ（収率82％）得た。
実施例 ３
ハローベンゼンジカルボン酸ジアルキルエステ
ルとして、４−クロロ−ジメチルフタレートを原
料とした以外は実施例１と同様に操作して、３，
3′，４，4′−ビフエニルテトラカルボン酸二水和
物の合成を行つた。その結果、目的物を0.97ｇ
（収率85％）得た。
実施例 ４
ハローベンゼンジカルボン酸ジアルキルエステ
ルとして、３−ヨード−ジメチルフタレートを用
いた以外は実施例１と同様に操作して、２，2′，
３，3′−ビフエニルテトラカルボン酸二水和物を
0.89ｇ（収率82％）得た。融点は、265℃（分解）
であつた。
〔発明の効果〕
以上説明したように、本発明によれば高純度の
ビフエニルテトラカルボン酸が高収率に温和な条
件で得られるという効果がある。
Example 1 50ml with thermometer, stirrer and nitrogen gas inlet
In a flask, add 0.5 g (8 mmol) of zinc powder, 0.5 g (2 mmol) of triphenylphosphine, 2.0 g (6.2 mmol) of 4-iodo-dimethyl phthalate,
5 ml of N,N-dimethylformamide (DMF) was added and nitrogen was blown in for 30 minutes. To this mixture was added a DMF suspension of tetrakis(triphenylphosphine)nickel prepared in a conventional manner (catalyst amount: 0.5 m).
mol). After stirring for 4 hours, dilute hydrochloric acid was added, followed by chloroform for extraction. Take out the chloroform phase, distill off the chloroform,
3,3',4,4'-biphenyltetracarboxylic acid tetramethyl ester was obtained. Next, the ester was hydrolyzed by stirring in a 10% aqueous sodium hydroxide solution and methanol at 50°C for 2 hours. After cooling to room temperature, chloroform was added to wash the aqueous phase. Hydrochloric acid was added to the separated aqueous layer to adjust the pH to 1 or less to precipitate biphenyltetracarboxylic acid. By separating this white precipitate and drying it, 0.91
g, 3,3',4,4'-biphenyltetracarboxylic acid dihydrate was obtained with a yield of 80%. As a result of measuring the melting point of the product, it was found that it decomposed at 295°C and the melting point could not be measured. Example 2 3,3',4,4'-biphenyltetracarboxylic acid dihydrate was prepared in the same manner as in Example 1 except that tetrakis(triphenylphosphine)palladium(0) was used as a catalyst. Synthesis was carried out. As a result, 0.93 g (yield: 82%) of the target product was obtained. Example 3 3,
3',4,4'-biphenyltetracarboxylic acid dihydrate was synthesized. As a result, the target material was 0.97g
(yield 85%). Example 4 2,2',
3,3'-biphenyltetracarboxylic acid dihydrate
0.89g (yield 82%) was obtained. Melting point is 265℃ (decomposition)
It was hot. [Effects of the Invention] As explained above, the present invention has the effect that highly purified biphenyltetracarboxylic acid can be obtained in high yield under mild conditions.
Claims (1)
テルをテトラキス（トリフエニルホスフイン）ニ
ツケル、テトラキス（トリフエニルホスフイン）
パラジウム触媒の少なくとも１種の存在下でカツ
プリングさせてビフエニルテトリカルボン酸テト
ラアルキルエステルを得、しかる後これを加水分
解することを特徴とするビフエニルテトラカルボ
ン酸の製造方法。1 Halobenzenedicarboxylic acid dialkyl ester is converted into tetrakis(triphenylphosphine)nickel, tetrakis(triphenylphosphine)
A method for producing biphenyltetracarboxylic acid, which comprises coupling in the presence of at least one palladium catalyst to obtain a biphenyltetricarboxylic acid tetraalkyl ester, which is then hydrolyzed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59140528A JPS6122044A (en) | 1984-07-09 | 1984-07-09 | Production of biphenyltetracarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59140528A JPS6122044A (en) | 1984-07-09 | 1984-07-09 | Production of biphenyltetracarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6122044A JPS6122044A (en) | 1986-01-30 |
| JPH0481576B2 true JPH0481576B2 (en) | 1992-12-24 |
Family
ID=15270761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59140528A Granted JPS6122044A (en) | 1984-07-09 | 1984-07-09 | Production of biphenyltetracarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6122044A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4511093B2 (en) * | 2001-12-20 | 2010-07-28 | 本州化学工業株式会社 | Method for producing alicyclic monoolefin carboxylic acid |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1021439C (en) * | 1988-10-11 | 1993-06-30 | 中国科学院长春应用化学研究所 | Syntheses of 3,3', 4,4'-biphenyltetracarboxylic acid and derivatives thereof |
| US5066430A (en) * | 1989-03-20 | 1991-11-19 | E. I. Du Pont De Nemours And Company | Process for centrifugally spinning pitch carbon fibers |
| CN105061124B (en) * | 2015-07-27 | 2017-03-22 | 苏州大学 | Diarylmethane compound preparation method |
-
1984
- 1984-07-09 JP JP59140528A patent/JPS6122044A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4511093B2 (en) * | 2001-12-20 | 2010-07-28 | 本州化学工業株式会社 | Method for producing alicyclic monoolefin carboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6122044A (en) | 1986-01-30 |
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