JPH02197589A - Production of 3,4,3',4'-biphenyltetracarboxylic ester - Google Patents
Production of 3,4,3',4'-biphenyltetracarboxylic esterInfo
- Publication number
- JPH02197589A JPH02197589A JP1018339A JP1833989A JPH02197589A JP H02197589 A JPH02197589 A JP H02197589A JP 1018339 A JP1018339 A JP 1018339A JP 1833989 A JP1833989 A JP 1833989A JP H02197589 A JPH02197589 A JP H02197589A
- Authority
- JP
- Japan
- Prior art keywords
- prescribed
- general formula
- methanol
- formula
- prepd
- 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.)
- Pending
Links
- -1 3,4,3',4'-biphenyltetracarboxylic ester Chemical class 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000010898 silica gel chromatography Methods 0.000 abstract description 2
- 150000005690 diesters Chemical class 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 239000003115 supporting electrolyte Substances 0.000 abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KWJNTOJAUQZMJO-UHFFFAOYSA-N 4-(4-carboxy-3-methylphenyl)-2-methylbenzoic acid Chemical group C1=C(C(O)=O)C(C)=CC(C=2C=C(C)C(C(O)=O)=CC=2)=C1 KWJNTOJAUQZMJO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は３，４．３’、４’−ビフェニルテトラカルボ
ン酸エステルの製法に関するものであり、更に詳しくは
（式中Ｒはアルキル基を示す、）
で表わされるオルトフタル酸ジエステルを支持塩存在下
、電解酸化することを特徴とするＣＯ□Ｒ
［式中Ｒは前記に同じ、〕で表わされる３、４．３’４
′−ビフェニルテトラカルボン酸エステルの製法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing 3,4.3',4'-biphenyltetracarboxylic acid ester, more specifically (in the formula, R represents an alkyl group, CO□R characterized by electrolytically oxidizing an orthophthalic acid diester represented by ) in the presence of a supporting salt 3,4.3'4 represented by [wherein R is the same as above]
The present invention relates to a method for producing '-biphenyltetracarboxylic acid ester.
従来の技術
これまで３．４．３’、４’−ビフェニルテトラカルボ
ン酸誘導体の製造方法としては、例えば、（１） ３
，３’−ジメチル−４，４′−ジカルボキシビフェニル
を過マンガン酸カリ又は酢酸コバルト存在下酸素で酸化
する方法〔パイルシュタイン（Ｂｅｉｌｓｔｅｉｎ）、
ｉ、 １００３；特開昭４８−５４０４８等〕（２
）４−ヨードフタル酸メチルエステルに銅粉を作用させ
、ウルマン（Ｕｌｌｍａｎｎ）反応により二世化する方
法（パイルシュタイン（Ｂｅｉｌｓｔｅｉｎ） ＋ｆｌ
、 ４３９ ）
（３） オルトキシレンを有機酸のアルカリ金属塩の
存在する中で化学量論量のパラジウム或いは白金の塩と
反応させて二世化する方法〔特開昭３９−２６７１７号
公報〕
（４）フタル酸ジメチルを酸素存在下、触媒量のパラジ
ウム塩を用いて三量化する方法〔特開昭４８〜５２７４
９．５５−１５３７４７．６０−５１１５０．６０−５
１１５１等〕
等が知られている。3.4.3', 4'-Biphenyltetracarboxylic acid derivatives have been produced so far, such as (1) 3
, 3'-dimethyl-4,4'-dicarboxybiphenyl with oxygen in the presence of potassium permanganate or cobalt acetate [Beilstein,
i, 1003; JP-A-48-54048, etc.] (2
) A method of reacting copper powder with 4-iodophthalic acid methyl ester and converting it into a second generation by Ullmann reaction (Beilstein + fl
, 439) (3) A method of converting ortho-xylene by reacting it with a stoichiometric amount of palladium or platinum salt in the presence of an alkali metal salt of an organic acid [JP-A-39-26717] ( 4) A method for trimerizing dimethyl phthalate using a catalytic amount of palladium salt in the presence of oxygen [JP-A-48-5274]
9.55-153747.60-51150.60-5
1151 etc.] are known.
しかしながら上記（１）及び（２）の方法は原料の調製
が非常に困難であるだけでなく、多くの工程を必要とし
、さらには収率も非常に低いという欠点がある。However, methods (1) and (2) above have the disadvantage that not only is it very difficult to prepare the raw materials, but also many steps are required, and the yield is also very low.
上記（３）の方法は高価なパラジウム或いは白金塩を化
学量論量用いる必要があり、又反応系に多量のパラジウ
ム或いは白金金属が析出するなどの欠点があり、工業的
でない。The above method (3) requires the use of stoichiometric amounts of expensive palladium or platinum salts, and also has drawbacks such as a large amount of palladium or platinum metal being deposited in the reaction system, and is not industrially viable.
上記（４）の方法は、触媒量のパラジウム塩で反応が進
行する利点はあるものの１３０〜２２０”Ｃという比較
的高い温度で反応を行わなければならない、さらに、目
的とする二漬化体の収率が低く、その分離・精製が非常
に困難であるという欠点がある。Although the method (4) above has the advantage that the reaction proceeds with a catalytic amount of palladium salt, the reaction must be carried out at a relatively high temperature of 130 to 220"C, and furthermore, it is necessary to carry out the reaction at a relatively high temperature of 130 to 220"C. It has the drawbacks of low yield and very difficult separation and purification.
発明が解決しようとする課題
本発明の目的は上記従来法の如き難点がなく、安全かつ
簡便な操作で、３．４．３’、４’−ビフェニルテトラ
カルボン酸エステルをクリーンな方法で安価に製造する
工業的に有利な方法を提供することにある。Problems to be Solved by the Invention The purpose of the present invention is to produce 3.4.3',4'-biphenyltetracarboxylic acid ester in a clean manner and at low cost, without the drawbacks of the above-mentioned conventional methods, and with safe and simple operations. The object of the present invention is to provide an industrially advantageous manufacturing method.
課題を解決するための手段
本発明は
〔式中Ｒはアルキル基を示す、］
で表わされるオルトフタル酸ジエステルを支持塩存在下
、電解酸化することを特徴とする０１Ｒ
〔式中Ｒは前記に同じ、〕で表わされる３、４．３’。Means for Solving the Problems The present invention is characterized in that an orthophthalic acid diester represented by [in the formula R represents an alkyl group] is electrolytically oxidized in the presence of a supporting salt. , ] 3,4.3'.
４′−ビフェニルテトラカルボン酸エステルの製法に関
するものである。This invention relates to a method for producing 4'-biphenyltetracarboxylic acid ester.
作用
本発明により得られる３、４．３’、４’−ビフェニル
テトラカルボン酸エステルは、高性能エンジニアリング
プラスチックの中で最も耐熱性が高い芳香族ポリイミド
の原料として重要な化合物である。Function The 3,4,3',4'-biphenyltetracarboxylic acid ester obtained by the present invention is an important compound as a raw material for aromatic polyimide, which has the highest heat resistance among high-performance engineering plastics.
このポリイミド樹脂は、宇宙・航空産業、電気・電子産
業をはじめとして、あらゆる産業分野で広く使用されて
いる評価の高い耐熱性樹脂である。This polyimide resin is a highly rated heat-resistant resin that is widely used in all industrial fields, including the space and aviation industries, and the electrical and electronic industries.
本発明においてＲはアルキル基を示す、好ましいアルキ
ル基としてはメチル、エチル、プロピル、イソプロピル
、ブチル、イソブチル、ｔｅｒｔ−ブチル、シクロヘキ
シル等のｃ１〜Ｃ６の直鎖或いは分岐もしくは環状のア
ルキル基を挙げることができる。In the present invention, R represents an alkyl group. Preferred alkyl groups include C1 to C6 linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and cyclohexyl. Can be done.
本発明に用いる支持塩としては金属ハロゲン化物及びテ
トラアルキルアンモニウム塩が挙げられるが、特に塩化
ナトリウム、塩化カリウム、ナトリウムテトラフルオロ
ボレート、テトラアルキルアンモニウムバークロレート
、テトラアルキルアンモニウムテトラフルオロボレート
が好ましく、その使用量としては一般式（１）の化合物
１モル当り５〜５０ｇが好ましい。The supporting salt used in the present invention includes metal halides and tetraalkylammonium salts, and particularly preferred are sodium chloride, potassium chloride, sodium tetrafluoroborate, tetraalkylammonium verchlorate, and tetraalkylammonium tetrafluoroborate, and their use The amount is preferably 5 to 50 g per mole of the compound of general formula (1).
本発明に用いる溶媒としてはアルコール類及びハロゲン
化炭化水素類が挙げられるが、メタノール、エタノール
、塩化メチレン、クロロホルム、四塩化炭素、１．２−
ジクロロエタン等が好ましく、これらが単独又は混合物
で使用される。溶媒の使用量としては、一般式（１）の
化合物１モル当り通常１〜１０１程度、好ましくは１〜
２１が良い。Examples of the solvent used in the present invention include alcohols and halogenated hydrocarbons, including methanol, ethanol, methylene chloride, chloroform, carbon tetrachloride, 1.2-
Dichloroethane and the like are preferred, and these are used alone or in mixtures. The amount of solvent to be used is usually about 1 to 101, preferably 1 to 101, per mole of the compound of general formula (1).
21 is good.
本発明に用いる電極は、通常使用される白金、金、パラ
ジウム、酸化銀、酸化鉄等の酸素過電圧の高い電極が使
用できるが、白金電極が最も好ましい。As the electrode used in the present invention, commonly used electrodes having a high oxygen overvoltage such as platinum, gold, palladium, silver oxide, iron oxide, etc. can be used, but a platinum electrode is most preferable.
実施例 以下に実施例を挙げて本発明を具体的に説明する。Example The present invention will be specifically described below with reference to Examples.
反応器にフタル酸ジメチル（１）１６．５ｄ （１９，
５ｇ。16.5d of dimethyl phthalate (1) (19,
5g.
０．１モル）と塩化カリウム１ｇを秤り取り、メタノー
ル１５０ｄを加え完全に均一になるまでよく撹拌した後
、ガルバノスタットに接続した二枚の白金板（５Ｘ５ｃ
＋Ｊ）を浸し、６輻Ａ／ｃｄの定電流密度で７２時間（
４Ｆ／ｓ＋ｏｌ）通電を行った。なお、電掻間隔は約１
ｃｍに設定した。0.1 mol) and 1 g of potassium chloride, added 150 d of methanol and stirred well until completely homogeneous.
+J) for 72 hours at a constant current density of 6 A/cd (
4F/s+ol) current was applied. In addition, the electric scraping interval is approximately 1
It was set to cm.
反応終了後、メタノールを減圧除去し、シリカゲルクロ
マトグラフィ（メルク社製Ｘｉｅｓｅ１ｇｅｌ ６（Ｌ
Ａｒｔ、９３８５）にて分離精製すると、３，４．３’
、４’−ビフェニルテトラカルボン酸メチル（２）の白
色結晶が５．６ｇ （収率３０％）とフタリド（３）の
白色結晶が４．５ｇ（収率３４％）得られ、未反応原料
（１）が７．０ｇ（３６％）回収された。After the reaction was completed, methanol was removed under reduced pressure, and silica gel chromatography (Xieselgel 6 (L) manufactured by Merck & Co., Ltd.
When separated and purified using Art, 9385), 3,4.3'
, 5.6 g (yield 30%) of white crystals of methyl 4'-biphenyltetracarboxylate (2) and 4.5 g (yield 34%) of white crystals of phthalide (3) were obtained. 1) was recovered in an amount of 7.0 g (36%).
化合物（２） ： ’Ｉｔ−ＮＭＲ（ＣＤＣｈ） δ
３．８０（ｓ、 １２１１．−ＣＯｚＣＨｚ） 。Compound (2): 'It-NMR (CDCh) δ
3.80 (s, 1211.-COzCHz).
６７．２５〜７．７０（ｍ、６）１．Ａｒ）化合物（３
） ： ’Ｈ−ＮＭＩＩ（ＣＤＣｌ２） ６５．２０
（ｓ、２Ｈ，Ａｒ−Ｃ１１ｇ−０）。67.25-7.70 (m, 6)1. Ar) Compound (3
): 'H-NMII (CDCl2) 65.20
(s, 2H, Ar-C11g-0).
６７．０５〜７．８５（ｍ、４Ｈ，Ａｒ）実ｍ二ｌ
実施例１の溶媒、支持塩、電流密度及び電気量等を変え
て表１に示す条件下で反応器ない、化合物（２）〜（５
）を表１に示すような収率で得た。67.05-7.85 (m, 4H, Ar) real m2 l Compound (2 )～(5
) was obtained in the yield shown in Table 1.
表１に記載されていない条件は実施例１と同しである。Conditions not listed in Table 1 are the same as in Example 1.
（Ｍｅはメチル基、Ｅｔはエチル基、Ｂｕはブチル基を
表わす、）
効果
本発明はオルトフタル酸ジエステルを電解酸化するとい
う新規な安全かつ簡便な方法によりビフェニルテトラカ
ルボン酸エステルの製造を可能とする。(Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.) Effect The present invention enables the production of biphenyltetracarboxylic acid ester by a novel safe and simple method of electrolytically oxidizing orthophthalic acid diester. .
（外４名）(4 other people)
Claims (1)
、電解酸化することを特徴とする 一般式 ▲数式、化学式、表等があります▼（２） 〔式中Ｒは前記に同じ。） で表わされる３，４，３′，４′−ビフェニルテトラカ
ルボン酸エステルの製法。[Claims] General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R represents an alkyl group. ] A general formula characterized by electrolytically oxidizing an orthophthalic acid diester represented by the following in the presence of a supporting salt ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (2) [In the formula, R is the same as above. ) A method for producing 3,4,3',4'-biphenyltetracarboxylic acid ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1018339A JPH02197589A (en) | 1989-01-27 | 1989-01-27 | Production of 3,4,3',4'-biphenyltetracarboxylic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1018339A JPH02197589A (en) | 1989-01-27 | 1989-01-27 | Production of 3,4,3',4'-biphenyltetracarboxylic ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02197589A true JPH02197589A (en) | 1990-08-06 |
Family
ID=11968896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1018339A Pending JPH02197589A (en) | 1989-01-27 | 1989-01-27 | Production of 3,4,3',4'-biphenyltetracarboxylic ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02197589A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6191305B1 (en) * | 1998-10-15 | 2001-02-20 | Ube Industries, Ltd. | Preparation of tetraester of 3, 3′, 4, 4′, - biphenyltetracarboxylic acid |
| CN100436649C (en) * | 2005-01-28 | 2008-11-26 | 华东师范大学 | Electrochemical synthesis of biphenyl |
-
1989
- 1989-01-27 JP JP1018339A patent/JPH02197589A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6191305B1 (en) * | 1998-10-15 | 2001-02-20 | Ube Industries, Ltd. | Preparation of tetraester of 3, 3′, 4, 4′, - biphenyltetracarboxylic acid |
| CN100436649C (en) * | 2005-01-28 | 2008-11-26 | 华东师范大学 | Electrochemical synthesis of biphenyl |
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