JPH0456815B2 - - Google Patents
Info
- Publication number
- JPH0456815B2 JPH0456815B2 JP59140530A JP14053084A JPH0456815B2 JP H0456815 B2 JPH0456815 B2 JP H0456815B2 JP 59140530 A JP59140530 A JP 59140530A JP 14053084 A JP14053084 A JP 14053084A JP H0456815 B2 JPH0456815 B2 JP H0456815B2
- Authority
- JP
- Japan
- Prior art keywords
- tetramethylbiphenyl
- reaction
- xylene
- yield
- acid
- 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
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- 239000007818 Grignard reagent Substances 0.000 claims description 5
- 150000004795 grignard reagents Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- -1 organic acid salt Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UXGRXJVMQSSUGS-UHFFFAOYSA-N 1,2-dinitroethane Chemical compound [O-][N+](=O)CC[N+]([O-])=O UXGRXJVMQSSUGS-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- DANMWBNOPFBJSZ-UHFFFAOYSA-N 1-iodo-2,3-dimethylbenzene Chemical group CC1=CC=CC(I)=C1C DANMWBNOPFBJSZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-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
- 239000002253 acid Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
〔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。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a method for producing biphenyltetracarboxylic acid.
従来、テトラメチルビフエニル並びにビフエニ
ルテトラカルボン酸の製造法には幾通りかの方法
が知られている。しかし、これらの従来技術に
は、収率が悪い、反応の選択性がない。爆発の危
険性を伴なうなど多くの問題がある。
Conventionally, several methods are known for producing tetramethylbiphenyl and biphenyltetracarboxylic acid. However, these conventional techniques have poor yields and lack reaction selectivity. There are many problems, including the risk of explosion.
テトラメチルビフエニルの合成法として、次の
方法が知られているが、種々の問題を含んでい
る。例えば、特公昭50−31149号公報に代表され
る、オルソ−キシレンを酸素加圧下、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
下で脱水素二量化する方法、特開昭55−79324号
公報に代表されるオルソ−キシレンをパラジウム
の有機酸塩の存在下、酸素加圧下でカツプリング
する方法が知られている。しかし、これらの方法
には、収率が悪い、反応に選択性がないため異性
体が多く生成する、特殊な合成設備を必要とす
る、爆発の危険性があるなど多くの問題がある。
また、ヨードキシレンと銅粉を作用させる方法
（Ｕ lman反応）は、古くから知られているが、
これも収率が悪い欠点がある。 The following method is known as a method for synthesizing tetramethylbiphenyl, but it involves various problems. For example, a method of dehydrogenizing ortho-xylene in the presence of an organic acid salt of palladium and ethylenediaminetetraacetic acid under oxygen pressure, as typified by Japanese Patent Publication No. 50-31149, and Japanese Patent Publication No. 55-79324 A method is known in which ortho-xylene, typified by: However, these methods have many problems, such as poor yields, lack of selectivity in the reaction, resulting in the production of many isomers, the need for special synthesis equipment, and the risk of explosion.
In addition, the method of reacting iodoxylene and copper powder (U lman reaction) has been known for a long time, but
This also has the drawback of poor yield.
また、ビフエニルテトラカルボン酸の合成方法
にも同様の問題がある。例えば、オルソ−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−ジケトンおよび／またはエチ
レンジアミンテトラ酸素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）、オルソ−キシ
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、さらに液相で酸化して製造する方法（特公昭
50−31149号公報参照）、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
号公報参照）、オルソフタル酸エステルを、有
機パラジウム塩と、１，10−フエナントロリンお
よび／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）、などが知られてい
る。このうち、ととは、酸素加圧下での反
応で特殊な装置を必要とし、爆発の危険性を有す
るだけでなく、収率が悪い、異性体が多く出来て
選択性がないなどの問題点がある。は温和な条
件で反応するが収率が極めて悪い問題がある。 Similar problems also exist in the method for synthesizing biphenyltetracarboxylic acid. For example, dimethyl ortho-phthalate in the presence of an organic acid salt of palladium,
A method in which β-diketone and/or ethylenediaminetetraoxygen is added to dehydrogenate and dimerize under oxygen pressure, and then hydrolyzed with acid (see Japanese Patent Publication No. 1983-31148), ortho-xylene is A method of dehydrogenating and dimerizing palladium in the presence of an organic acid salt of palladium and ethylenediaminetetraacetic acid under pressure, and then oxidizing it in the liquid phase (Tokuko Sho)
50-31149), a method of coupling 4-halogenorthophthalate by heating it in the presence of metallic palladium and a small amount of methanol in an aqueous alkali hydroxide solution (JP-A-55-20705)
(Refer to Japanese Patent Publication No. 2003-111116), a method of synthesizing orthophthalic acid ester by oxidative coupling with an organic palladium salt and 1,10-phenanthroline and/or α,α'-bipyridyl under oxygen pressure (see Japanese Patent Publication No. Publication No. 55-153747), etc. are known. Among these, and requires special equipment because the reaction is carried out under pressurized oxygen, which not only poses the risk of explosion, but also has problems such as poor yield and a lack of selectivity due to the production of many isomers. There is. reacts under mild conditions, but the yield is extremely poor.
本発明の目的は、上記従来技術の問題点のない
比較的少ない工程で、高純度で、収率よく、しか
も温和な条件で、ポリイミドなどの高耐熱性ポリ
マーの原料やエポキシ樹脂の硬化剤として極めて
有用なビフエニルテトラカルボン酸の製造方法を
提供することにある。
The purpose of the present invention is to provide high purity, high yield, and mild conditions for use as a raw material for highly heat-resistant polymers such as polyimide, and as a curing agent for epoxy resins, in a relatively small number of steps without the problems of the above-mentioned conventional techniques. An object of the present invention is to provide a very useful method for producing biphenyltetracarboxylic acid.
本発明のビフエニルテトラカルボン酸は、一般
式
（Ｘはハロゲンを示す）で示されるグリニヤー
ル試薬を塩化銅存在下にカツプリングさせてテト
ラメチルビフエニルを得、しかる後にこれを酸化
剤存在下で酸化することにより得ることを特徴と
する。
The biphenyltetracarboxylic acid of the present invention has the general formula It is characterized in that it is obtained by coupling a Grignard reagent represented by (X represents a halogen) in the presence of copper chloride to obtain tetramethylbiphenyl, and then oxidizing this in the presence of an oxidizing agent.
本発明の代表的方法は次の通りである。 A representative method of the invention is as follows.
（Ｘはハロゲン）で示されるハローオルソキ
シレンと、マグネシウムとを反応させて
で示されるグリニヤール試薬を得る。 (X is halogen) by reacting haloorthoxylene with magnesium. A Grignard reagent is obtained.
上記グリニヤール試薬を塩化銅の存在下にカ
ツプリングさせて
で示されるテトラメチルビフエニルを得る。 Coupling the above Grignard reagent in the presence of copper chloride Tetramethylbiphenyl represented by is obtained.
テトラメチルビフエニルを酸化剤の存在下で
酸化して
で示されるビフエニルテトラカルボン酸を得る。 Oxidizing tetramethylbiphenyl in the presence of an oxidizing agent A biphenyltetracarboxylic acid represented by is obtained.
本発明に使用するハロ−オルソキシレンのハロ
ゲン基は、クロル、ブロム、ヨード基が良い。こ
のハロ−オルソキシレン１当量と、マグネシウム
１〜1.05当量とを常法によつて反応させて得たグ
リニヤール試薬を、塩化銅１〜1.5当量と、ジエ
チルエーテル、テトラヒドロフラン、ジブチルエ
ーテル、トルエン、ベンゼンなどの有機溶媒中
で、０〜100℃の反応温度で、１〜３時間反応さ
せると、カツプリングしてテトラメチルビフエニ
ルが得られる。反応終了後、減圧蒸留など通常の
方法で精製できる。 The halogen group of the halo-orthoxylene used in the present invention is preferably a chloro, bromo, or iodo group. A Grignard reagent obtained by reacting 1 equivalent of this halo-orthoxylene with 1 to 1.05 equivalents of magnesium in a conventional manner is mixed with 1 to 1.5 equivalents of copper chloride, diethyl ether, tetrahydrofuran, dibutyl ether, toluene, benzene, etc. When reacted in an organic solvent at a reaction temperature of 0 to 100°C for 1 to 3 hours, tetramethylbiphenyl is obtained by coupling. After the reaction is complete, it can be purified by conventional methods such as vacuum distillation.
得られたテトラメチルビフエニルを、４当量以
上の酸化剤、例えば過マンガン酸カリウム、重ク
ロム酸カリウム、硝酸などで酸化することによ
り、80％以上の収率でビフエニルテトラカルボン
酸が得られる。 By oxidizing the obtained tetramethylbiphenyl with 4 equivalents or more of an oxidizing agent, such as potassium permanganate, potassium dichromate, nitric acid, etc., biphenyltetracarboxylic acid can be obtained with a yield of 80% or more. .
実施例 １
テトラヒドロフラン72ml中で、金属マグネシウ
ム14ｇと４−ブロモ−０−キシレン74ｇとから通
常の方法で得られた４−ブロモマグネシウム−０
−キシレンのテトラヒドロフラン溶液を、５〜10
℃に冷却した後、塩化銅47.3ｇを加え約１時間撹
拌し、反応を完結した。反応物を水洗し、析出銅
を別した後、溶媒を留去し、残査を、151℃、
10mmHgの条件で減圧蒸留して、３，3′，４，4′−
テトラメチルビフエニル37.7ｇを得た。収率90％
であつた。
Example 1 4-bromomagnesium-0 obtained in a conventional manner from 14 g of metallic magnesium and 74 g of 4-bromo-0-xylene in 72 ml of tetrahydrofuran.
- xylene in tetrahydrofuran solution for 5 to 10
After cooling to ℃, 47.3 g of copper chloride was added and stirred for about 1 hour to complete the reaction. After washing the reaction product with water and separating the precipitated copper, the solvent was distilled off and the residue was heated at 151°C.
Distilled under reduced pressure at 10 mmHg to obtain 3,3',4,4'-
37.7 g of tetramethylbiphenyl was obtained. Yield 90%
It was hot.
実施例 ２
ハロ−０−キシレンとして、４−ヨード−０−
キシレンを92.8ｇ（0.4モル）用いた以外は実施
例１と同様に操作して、３，3′，４，4′−テトラ
メチルビフエニルを合成した。収率38.7ｇで、収
率は92％であつた。Example 2 As halo-0-xylene, 4-iodo-0-
3,3',4,4'-tetramethylbiphenyl was synthesized in the same manner as in Example 1 except that 92.8 g (0.4 mol) of xylene was used. The yield was 38.7 g, which was 92%.
実施例 ３
ハロ−０−キシレンとして、４−クロロ−０−
キシレン56.2ｇ（0.4モル）を用いた以外は実施
例１と同様に操作して、３，3′，４，4′−テトラ
メチルビフエニルを合成した。収量34.9ｇで、収
率は83％であつた。Example 3 As halo-0-xylene, 4-chloro-0-
3,3',4,4'-tetramethylbiphenyl was synthesized in the same manner as in Example 1 except that 56.2 g (0.4 mol) of xylene was used. The yield was 34.9 g, or 83%.
実施例 ４
水3150mlに過マンガン酸カリウム111.3ｇを溶
解し、加熱撹拌する。温度が90℃を越えた後、20
％水酸化カリウム水溶液46.5ｇに、３，3′，４，
4′−テトラメチルビフエニル33.6ｇを混合したス
ラリーを数回に分けて注入し、98〜100℃で５時
間撹拌し反応を完結させた。反応終了後、生成し
たMnO2を別し、液より未反応テトラメチル
ビフエニルをトリクロルエチレンを用いて抽出回
収した。分液した水溶液を4N塩酸を用いて中和
晶析させ、別した沈殿を乾燥して、３，3′，
４，4′−ビフエニルテトラカルボン酸二水和物
51.9ｇを得た。収率は90％であつた。生成物は
295℃で分解を伴つて溶融した。Example 4 Dissolve 111.3 g of potassium permanganate in 3150 ml of water and heat and stir. After the temperature exceeds 90℃, 20
% potassium hydroxide aqueous solution, 3,3',4,
A slurry containing 33.6 g of 4'-tetramethylbiphenyl was injected in several portions and stirred at 98 to 100°C for 5 hours to complete the reaction. After the reaction was completed, the generated MnO 2 was separated, and unreacted tetramethylbiphenyl was extracted and recovered from the liquid using trichlorethylene. The separated aqueous solution was neutralized and crystallized using 4N hydrochloric acid, the separated precipitate was dried, and 3,3′,
4,4'-biphenyltetracarboxylic acid dihydrate
51.9g was obtained. The yield was 90%. The product is
It melted at 295°C with decomposition.
以上説明した通り、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、温和条件で
得られるという効果がある。
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)
ル試薬を塩化銅存在下にカツプリングさせてテト
ラメチルビフエニルを得、しかる後にこれを酸化
剤存在下で酸化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。[Claims] First-order general formula (X represents a halogen) is coupled with a Grignard reagent in the presence of copper chloride to obtain tetramethylbiphenyl, which is then oxidized in the presence of an oxidizing agent to obtain biphenyltetracarboxylic acid. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59140530A JPS6122045A (en) | 1984-07-09 | 1984-07-09 | Method for producing biphenyltetracarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59140530A JPS6122045A (en) | 1984-07-09 | 1984-07-09 | Method for producing biphenyltetracarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6122045A JPS6122045A (en) | 1986-01-30 |
| JPH0456815B2 true JPH0456815B2 (en) | 1992-09-09 |
Family
ID=15270809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59140530A Granted JPS6122045A (en) | 1984-07-09 | 1984-07-09 | Method for producing biphenyltetracarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6122045A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5208471B2 (en) * | 2007-09-26 | 2013-06-12 | 東レ・ファインケミカル株式会社 | Method for producing biphenyl-2,3,2 ', 3'-tetracarboxylic acid |
| WO2012157749A1 (en) | 2011-05-18 | 2012-11-22 | 宇部興産株式会社 | 3,3',4,4'-tetraalkyl cyclohexylbenzene and method for producing same |
-
1984
- 1984-07-09 JP JP59140530A patent/JPS6122045A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6122045A (en) | 1986-01-30 |
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