JPH06179638A - Production of dimethylbiphenyldicarboxylic acid - Google Patents
Production of dimethylbiphenyldicarboxylic acidInfo
- Publication number
- JPH06179638A JPH06179638A JP3102243A JP10224391A JPH06179638A JP H06179638 A JPH06179638 A JP H06179638A JP 3102243 A JP3102243 A JP 3102243A JP 10224391 A JP10224391 A JP 10224391A JP H06179638 A JPH06179638 A JP H06179638A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acid
- dimethylbiphenyl
- dimethylbiphenyldicarboxylic
- dicarboxylic 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.)
- Pending
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、オルトトルイル酸アル
キルの酸化カップリング反応によって得られるジメチル
ビフェニルジカルボン酸ジアルキルエステルを加水分解
する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for hydrolyzing dimethylbiphenyldicarboxylic acid dialkyl ester obtained by oxidative coupling reaction of alkyl orthotoluate.
【従来の技術及びその問題点】特開平２−１１５１４３
号公報には、Ｐｄ触媒を用いたオルトトルイル酸アルキ
ルの酸化カップリング反応で二量化物であるジメチルビ
フェニルジカルボン酸ジアルキルエステルを合成する方
法が開示されており、この方法では異性体として、主に
３，３′−ジメチルビフェニル−４，４′−ジカルボン
酸ジアルキルエステル及び３，４′−ジメチルビフェニ
ル−４，３′−ジカルボン酸ジアルキルエステルが高収
率で、その他、４，４′−ジメチルビフェニル−３，
３′−ジカルボン酸ジアルキルエステル等が得られる。
これらの二量化物は、液晶ポリマーとして注目されてい
るポリエステル、ポリアミドなどの原料として有用な化
合物である。2. Description of the Related Art JP-A-2-115143
The publication discloses a method for synthesizing a dimer dimethylbiphenyldicarboxylic acid dialkyl ester by an oxidative coupling reaction of an alkyl orthotoluate using a Pd catalyst. In this method, as the isomer, mainly 3 , 3'-Dimethylbiphenyl-4,4'-dicarboxylic acid dialkyl ester and 3,4'-dimethylbiphenyl-4,3'-dicarboxylic acid dialkyl ester were obtained in high yield, and other 4,4'-dimethylbiphenyl- Three
A 3'-dicarboxylic acid dialkyl ester or the like is obtained.
These dimers are useful compounds as raw materials for polyesters, polyamides, etc., which are attracting attention as liquid crystal polymers.
【０００２】さらに上記公報には、酸化カップリング反
応で得られた二量化物の異性体の、蒸留、再結晶化によ
る分離精製方法も記載されている。通常、これら異性体
のエステル化合物は、ＫＯＨ、ＮａＯＨなどのアルカリ
をエステル基に対して等モル以上使用する加水分解反応
および塩酸などの酸による中和反応からなる、良く知ら
れたエステル加水分解法によってジカルボン酸化合物に
転化される。この場合、生成物のジカルボン酸化合物は
固体として析出し、これを重合物製造の原料として用い
るためには、析出固体からＮａＣｌ、ＫＣｌなどのアル
カリ中和塩を充分除去し、原料中の塩素含有量をできる
限り小さくしなければならない。しかし、加水分解反応
後、析出固体の水捌が悪く、短時間の簡単な水洗ではア
ルカリ中和塩の除去が不充分であり、従って、高純度の
ジカルボン酸化合物を製造するためには、煩雑な水洗、
濾過処理を必要とする。Further, the above publication also describes a method for separating and purifying the isomers of the dimer obtained by the oxidative coupling reaction by distillation and recrystallization. Usually, the ester compound of these isomers is a well-known ester hydrolysis method comprising a hydrolysis reaction using an alkali such as KOH and NaOH in an equimolar amount or more with respect to the ester group and a neutralization reaction with an acid such as hydrochloric acid. Is converted to a dicarboxylic acid compound. In this case, the product dicarboxylic acid compound precipitates as a solid, and in order to use this as a raw material for the production of a polymer, alkali neutralization salts such as NaCl and KCl are sufficiently removed from the precipitated solid, and the chlorine-containing raw material is contained. The amount should be as small as possible. However, after the hydrolysis reaction, the precipitated solid is poorly handled and the alkaline neutralization salt is insufficiently removed by a short time simple water washing. Therefore, in order to produce a high-purity dicarboxylic acid compound, it is complicated. Clean water,
Requires filtration treatment.
【０００３】[0003]
【問題点解決のための技術的手段】本発明は、オルトト
ルイル酸アルキルの酸化カップリング反応によって得ら
れる二量化物であるジメチルビフェニルジカルボン酸ジ
アルキルエステルの改良された加水分解方法を提供す
る。本発明は、オルトトルイル酸アルキルの酸化カップ
リング反応によって得られるジメチルビフェニルジカル
ボン酸ジアルキルエステルを、５〜１００ｋｇ／ｃｍ２
の圧力下、１５０〜３００℃で加水分解することを特徴
とするジメチルビフェニルジカルボン酸の製造方法に関
する。上記エステル化合物におけるアルキル基は、炭素
数１〜５の脂肪族炭化水素基である。The present invention provides an improved process for the hydrolysis of dimer dimethylbiphenyldicarboxylic acid dialkyl esters which are dimers obtained by the oxidative coupling reaction of alkyl orthotoluates. The present invention provides dimethylbiphenyldicarboxylic acid dialkyl ester obtained by oxidative coupling reaction of alkyl orthotoluyl acid in an amount of 5 to 100 kg / cm 2.
The method for producing dimethylbiphenyldicarboxylic acid is characterized in that it is hydrolyzed at 150 to 300 ° C. under a pressure of 1. The alkyl group in the ester compound is an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
【０００４】本発明においては、酸化カップリング反応
終了後、反応混合物から減圧蒸留および／あるいは再結
晶化によって各々の異性体に分離されたジメチルビフェ
ニルジカルボン酸ジアルキルエステル類を、別々に加圧
下で加熱加水分解し、それぞれのジカルボン酸化合物を
製造することができる。また、酸化カップリング反応終
了後、異性体の混合物を加圧下で加熱加水分解し、それ
ぞれの異性体のジカルボン酸化合物を混合物として製造
し、そのあとジカルボン酸化合物を分離することもでき
る。本発明の加水分解反応において、水の使用量は特に
制限はないが、通常エステル化合物１重量部に対して２
〜５０重量部の水を用い、５〜１００ｋｇ／ｃｍ２の圧
力下、特に好ましくは１０〜５０ｋｇ／ｃｍ２の圧力
下、反応温度１５０〜３００℃、特に好ましくは１８０
〜２５０℃で反応を行う。反応圧力が５ｋｇ／ｃｍ２未
満であったり、反応温度が１５０℃未満であると、反応
速度が非常に遅く、あるいは全く反応が起こらず、ま
た、３００℃を越えると、好ましくない分解反応が起こ
り、経済的ではない。In the present invention, after completion of the oxidative coupling reaction, dimethylbiphenyldicarboxylic acid dialkyl esters separated into respective isomers from the reaction mixture by distillation under reduced pressure and / or recrystallization are separately heated under pressure. Each dicarboxylic acid compound can be produced by hydrolysis. Further, after the completion of the oxidative coupling reaction, the mixture of isomers may be heated and hydrolyzed under pressure to produce a dicarboxylic acid compound of each isomer as a mixture, and then the dicarboxylic acid compound may be separated. In the hydrolysis reaction of the present invention, the amount of water used is not particularly limited, but it is usually 2 per 1 part by weight of the ester compound.
To 50 parts by weight of water and a pressure of 5 to 100 kg / cm 2 , particularly preferably a pressure of 10 to 50 kg / cm 2 , and a reaction temperature of 150 to 300 ° C., particularly preferably 180.
The reaction is carried out at ~ 250 ° C. If the reaction pressure is less than 5 kg / cm 2 or the reaction temperature is less than 150 ° C., the reaction rate is very slow or no reaction occurs. If it exceeds 300 ° C., an undesired decomposition reaction occurs. , Not economical.
【０００５】反応の進行に伴って、反応中に脱離する炭
素数１〜５のアルコールを水蒸気と共に系外に抜き出
し、抜き出した水と等量の熱水を圧入する。エステルか
ら酸への平衡反応を酸生成に向ける前記操作を、脱離ア
ルコールが検出されなくなるまで繰り返し、通常反応終
了まで１〜３０時間要する。生成物の酸化分解を避ける
ために、窒素などの不活性ガス雰囲気下に加水分解反応
を行うことが好ましい。本発明において、反応温度を下
げ、反応時間を短縮するために、硫酸、ｐ−トルエンス
ルホン酸などの触媒を使用することができる。これらの
酸触媒の添加量は、通常エステル化合物１重量部に対し
て１／１０以下である。With the progress of the reaction, the alcohol having 1 to 5 carbon atoms that is desorbed during the reaction is withdrawn from the system together with water vapor, and hot water in an amount equal to the withdrawn water is injected under pressure. The above operation of directing an equilibrium reaction from an ester to an acid to produce an acid is repeated until no eliminated alcohol is detected, and usually 1 to 30 hours are required until the reaction is completed. In order to avoid oxidative decomposition of the product, it is preferable to carry out the hydrolysis reaction under an atmosphere of an inert gas such as nitrogen. In the present invention, a catalyst such as sulfuric acid or p-toluenesulfonic acid can be used in order to lower the reaction temperature and shorten the reaction time. The addition amount of these acid catalysts is usually 1/10 or less with respect to 1 part by weight of the ester compound.
【０００６】[0006]
【実施例】以下に本発明の実施例を説明する。 実施例１ オートクレーブ（５００ｍｌ）中に、３，３′−ジメチ
ルビフェニル−４，４′−ジカルボン酸ジメチル１０ｇ
および水２５０ｍｌを仕込み、３００ｒｐｍの攪拌下
に、圧力２６ｋｇ／ｃｍ２、２２５℃で４時間加水分解
反応を行った。次いで水蒸気を冷却捕集で水として約１
００ｍｌ抜き出し、その後、熱水１００ｍｌを窒素ガス
で圧入し反応を続けた。反応開始から７時間および１０
時間後に水蒸気抜き出し操作を行い、１２時間後にメタ
ノールの留出がほとんどないことを確かめ反応を終了し
た。オートクレーブ冷却後、内容物を簡単な濾過、水
洗、乾燥によって、３，３′−ジメチルビフェニル−
４，４′−ジカルボン酸８．８８ｇ（収率９８％）を製
造することができた。EXAMPLES Examples of the present invention will be described below. Example 1 10 g of dimethyl 3,3'-dimethylbiphenyl-4,4'-dicarboxylate in an autoclave (500 ml)
Then, 250 ml of water was charged, and the hydrolysis reaction was carried out at a pressure of 26 kg / cm 2 and 225 ° C. for 4 hours under stirring at 300 rpm. Then, the steam is cooled and collected to be about 1 as water.
00 ml was taken out, and then 100 ml of hot water was injected under pressure with nitrogen gas to continue the reaction. 7 hours and 10 from the start of the reaction
After a lapse of time, steam extraction operation was performed, and after 12 hours, it was confirmed that almost no methanol was distilled off, and the reaction was completed. After cooling in an autoclave, the contents were subjected to a simple filtration, washing with water and drying to obtain 3,3'-dimethylbiphenyl-
It was possible to produce 8.88 g (yield 98%) of 4,4'-dicarboxylic acid.
【０００７】実施例２ ３，３′−ジメチルビフェニル−４，４′−ジカルボン
酸ジメチル５０ｇ、硫酸１．０ｇ、および水２５０ｍｌ
を仕込み、圧力１９ｋｇ／ｃｍ２、反応温度２１０℃に
した以外は実施例１と同様に加水分解反応を行い、３，
３′−ジメチルビフェニル−４，４′−ジカルボン酸４
４．２ｇ（収率９８％）を製造することができた。 実施例３ 硫酸の代わりにｐ−トルエンスルホン酸２ｇを用いた以
外は、実施例２と同様に加水分解反応を行い、３，３′
−ジメチルビフェニル−４，４′−ジカルボン酸４４．
０ｇ（収率９７％）を製造することができた。Example 2 50 g of dimethyl 3,3'-dimethylbiphenyl-4,4'-dicarboxylate, 1.0 g of sulfuric acid, and 250 ml of water
Was charged, and the hydrolysis reaction was performed in the same manner as in Example 1 except that the pressure was 19 kg / cm 2 and the reaction temperature was 210 ° C.
3'-Dimethylbiphenyl-4,4'-dicarboxylic acid 4
It was possible to produce 4.2 g (yield 98%). Example 3 A hydrolysis reaction was carried out in the same manner as in Example 2 except that 2 g of p-toluenesulfonic acid was used instead of sulfuric acid to give 3,3 ′.
-Dimethylbiphenyl-4,4'-dicarboxylic acid 44.
It was possible to produce 0 g (97% yield).
【０００８】実施例４ ３，３′−ジメチルビフェニル−４，４′−ジカルボン
酸ジメチルの代わりに３，４′−ジメチルビフェニル−
４，３′−ジカルボン酸ジメチルを用いた以外は、実施
例２と同様に加水分解反応を行い、３，４′−ジメチル
ビフェニル−４，３′−ジカルボン酸４４．４ｇ（収率
９８％）を製造することができた。 実施例５ ３，３′−ジメチルビフェニル−４，４′−ジカルボン
酸ジメチルと３，４′−ジメチルビフェニル−４，３′
−ジカルボン酸ジメチル（モル比１：１）の混合物５０
ｇを用いた以外は、実施例２と同様に加水分解反応を行
い、３，３′−ジメチルビフェニル−４，４′−ジカル
ボン酸と３，４′−ジメチルビフェニル−４，３′−ジ
カルボン酸（モル比１：１）の混合物４４．４ｇ（収率
９８％）を製造することができた。EXAMPLE 4 3,3'-Dimethylbiphenyl-4,4'-dicarboxylate Instead of dimethyl 3,4'-dimethylbiphenyl-
The hydrolysis reaction was performed in the same manner as in Example 2 except that dimethyl 4,3'-dicarboxylic acid was used, and 44.4 g (yield 98%) of 3,4'-dimethylbiphenyl-4,3'-dicarboxylic acid. Could be manufactured. Example 5 Dimethyl 3,3′-dimethylbiphenyl-4,4′-dicarboxylate and 3,4′-dimethylbiphenyl-4,3 ′
A mixture of dimethyl dicarboxylate (molar ratio 1: 1) 50
Hydrolysis reaction was carried out in the same manner as in Example 2 except that g was used to obtain 3,3'-dimethylbiphenyl-4,4'-dicarboxylic acid and 3,4'-dimethylbiphenyl-4,3'-dicarboxylic acid. It was possible to produce 44.4 g (yield 98%) of a mixture (molar ratio 1: 1).
【０００９】比較例１ 加水分解反応を１００℃で１２時間行った以外は、実施
例１と同様に反応を行ったところ、加水分解は全く起こ
らなかった。 比較例２ 加水分解反応を１００℃で１２時間行った以外は、実施
例２と同様に反応を行ったところ、加水分解は全く起こ
らなかった。 （以下余白）Comparative Example 1 When the reaction was carried out in the same manner as in Example 1 except that the hydrolysis reaction was carried out at 100 ° C. for 12 hours, no hydrolysis occurred at all. Comparative Example 2 When the reaction was carried out in the same manner as in Example 2 except that the hydrolysis reaction was carried out at 100 ° C. for 12 hours, hydrolysis did not occur at all. (Below margin)
Claims (1)
ング反応によって得られるジメチルビフェニルジカルボ
ン酸ジアルキルエステルを、５〜１００ｋｇ／ｃｍ２の
圧力下、１５０〜３００℃で加水分解することを特徴と
するジメチルビフェニルジカルボン酸の製造方法。1. A dimethylbiphenyldicarboxylic acid characterized by hydrolyzing a dimethylbiphenyldicarboxylic acid dialkylester obtained by an oxidative coupling reaction of an alkyl orthotoluylate at 150 to 300 ° C. under a pressure of 5 to 100 kg / cm 2. Method for producing acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3102243A JPH06179638A (en) | 1991-02-08 | 1991-02-08 | Production of dimethylbiphenyldicarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3102243A JPH06179638A (en) | 1991-02-08 | 1991-02-08 | Production of dimethylbiphenyldicarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06179638A true JPH06179638A (en) | 1994-06-28 |
Family
ID=14322181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3102243A Pending JPH06179638A (en) | 1991-02-08 | 1991-02-08 | Production of dimethylbiphenyldicarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06179638A (en) |
-
1991
- 1991-02-08 JP JP3102243A patent/JPH06179638A/en active Pending
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