JPH06321845A - Production of carboxilic acid - Google Patents
Production of carboxilic acidInfo
- Publication number
- JPH06321845A JPH06321845A JP5109000A JP10900093A JPH06321845A JP H06321845 A JPH06321845 A JP H06321845A JP 5109000 A JP5109000 A JP 5109000A JP 10900093 A JP10900093 A JP 10900093A JP H06321845 A JPH06321845 A JP H06321845A
- Authority
- JP
- Japan
- Prior art keywords
- group
- catalyst
- amount
- alcohol
- lead
- 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.)
- Granted
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】本発明はカルボン酸の製造方法、
更に詳しくは各種脂肪酸エステルの製造原料及び抗炎症
剤、鎮痛剤等の医薬品として広い用途を有するカルボン
酸の製造方法に関する。The present invention relates to a method for producing a carboxylic acid,
More specifically, the present invention relates to a method for producing a carboxylic acid, which has a wide range of uses as a raw material for producing various fatty acid esters and a drug such as an anti-inflammatory agent and an analgesic.
【０００２】[0002]
【従来の技術】一級アルコールをカルボン酸に変換する
に当り、過マンガン酸塩、重クロム酸塩等の重金属系酸
化剤がしばしば使用される。しかしながらこれらの酸化
剤を用いる方法は、目的化合物の収率や選択性が充分高
くないことに加えて、高価で有害な試薬を化学量論量必
要とするため反応の後処理が繁雑であり、産業廃棄物を
多量に副生する等多くの欠点があった。2. Description of the Related Art In converting a primary alcohol into a carboxylic acid, a heavy metal oxidant such as permanganate or dichromate is often used. However, in the method using these oxidizing agents, in addition to the yield and selectivity of the target compound not being sufficiently high, a post-treatment of the reaction is complicated because an expensive and harmful reagent requires a stoichiometric amount, There were many drawbacks such as producing a large amount of industrial waste.
【０００３】一方前記欠点を解消する技術として芳香族
アルコールを酸化してフェニル酢酸誘導体を得るに当
り、貴金属触媒存在下に含酸素ガスで酸化する方法（特
開昭５２−１０２３３号公報）、白金又はパラジウムに
助触媒として鉛又は鉛化合物を添加して含酸素ガスで酸
化する方法（特開昭５４−１３２５４７号公報）が開示
されている。これらの方法では安価な酸化剤で比較的収
率良くカルボン酸誘導体が生成する点で改善がされてい
るものの、未だ高価な貴金属系触媒を比較的多量に使用
しなければならないことに加えて、触媒の失活が著しい
ために触媒の回収再使用が困難であり、従って触媒金属
単位重量当りのカルボン酸取得量が極めて少ないためコ
スト高となり、未だ工業的に有利な技術となり得ていな
い。On the other hand, as a technique for solving the above-mentioned drawbacks, a method of oxidizing an aromatic alcohol to obtain a phenylacetic acid derivative, and oxidizing it with an oxygen-containing gas in the presence of a noble metal catalyst (Japanese Patent Laid-Open No. 52-10233), platinum. Alternatively, a method of adding lead or a lead compound as a co-catalyst to palladium and oxidizing it with an oxygen-containing gas (Japanese Patent Laid-Open No. 54-132547) is disclosed. Although these methods have been improved in that a carboxylic acid derivative is produced in a relatively high yield with an inexpensive oxidizing agent, in addition to the fact that an expensive precious metal-based catalyst still has to be used in a relatively large amount, It is difficult to recover and reuse the catalyst due to the remarkable deactivation of the catalyst. Therefore, the amount of carboxylic acid obtained per unit weight of the catalyst metal is extremely small, resulting in high cost, and it has not yet become an industrially advantageous technique.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、斯か
る従来技術の欠点を解消して一級アルコールを酸化する
に際して貴金属触媒の失活を著しく抑制し、これによっ
て触媒金属単位重量当りの生成物取得量を飛躍的に増大
させ工業的に実施可能なカルボン酸の製造方法を確立す
ることにある。SUMMARY OF THE INVENTION The object of the present invention is to overcome the disadvantages of the prior art and remarkably suppress the deactivation of the noble metal catalyst during the oxidation of the primary alcohol, thereby forming the catalyst per unit weight of the metal. The purpose of the present invention is to establish a method for producing a carboxylic acid that can be industrially implemented by dramatically increasing the amount of material obtained.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、特開昭５
４−１３２５４７号公報に記載の技術を詳細に検討した
結果、触媒の活性が低下することと原料アルコールの転
化率との間に密接な関連性があることを見い出した。即
ち原料アルコールの種類や反応液中の酸素濃度にも依る
が、例えば転化率が９５％を越え、酸素濃度に比べて被
酸化物濃度が小さくなると触媒を不活性化させることを
掴んだ。この傾向は原料アルコールを１００％生成物に
転化する条件においてとりわけ顕著であり、回収触媒の
再使用が不可能となることを見い出した。更に失活した
触媒を解析することにより、触媒活性低下の原因は触媒
表面が酸素により非可逆的に酸化され、酸化パラジウム
又は酸化白金の層を形成するためであることを突き止め
た。Means for Solving the Problems The inventors of the present invention have disclosed in Japanese Patent Laid-Open No.
As a result of detailed study of the technique described in JP-A-4-132547, it was found that there is a close relationship between the decrease in the activity of the catalyst and the conversion rate of the raw material alcohol. That is, although it depends on the type of the raw material alcohol and the oxygen concentration in the reaction solution, for example, it was found that the catalyst is inactivated when the conversion rate exceeds 95% and the concentration of oxides becomes smaller than the oxygen concentration. It has been found that this tendency is particularly remarkable under the condition that 100% of the raw material alcohol is converted into a product, and the reuse of the recovered catalyst becomes impossible. Further, by analyzing the deactivated catalyst, it was found that the cause of the decrease in the catalytic activity was that the surface of the catalyst was irreversibly oxidized by oxygen to form a layer of palladium oxide or platinum oxide.
【０００６】これらの知見をもとに本発明者らは、一級
アルコールをパラジウム、白金又はこれらの化合物に助
触媒として鉛又は鉛化合物を添加した触媒の存在下で含
酸素ガスと反応させてカルボン酸を得るに際して、触媒
の長寿命化を達成し、触媒金属単位重量当りの目的物取
得量を著しく増大させる方法を鋭意検討し、ついに本発
明を完成するに至った。Based on these findings, the inventors of the present invention reacted a primary alcohol with an oxygen-containing gas in the presence of palladium, platinum or a catalyst obtained by adding lead or a lead compound as a co-catalyst to the carbon dioxide. When obtaining an acid, the inventors have earnestly studied a method of achieving a long life of the catalyst and remarkably increasing the amount of the target substance acquired per unit weight of the catalyst metal, and finally completed the present invention.
【０００７】即ち、本発明は、一般式 Ｒ−ＣＨ2 ＯＨ （１） 〔式中Ｒは置換基として水酸基もしくは炭素数１〜５の
アルコキシ基を有していてもよい炭素数１〜１９の直鎖
又は分枝鎖状のアルキル基、置換基として水酸基もしく
は炭素数１〜５のアルコキシ基を有していてもよい直鎖
又は環状アルキレン基、或いは芳香核上に水酸基、フッ
素原子、シアノ基、炭素数１〜５のアルキル基及び炭素
数１〜５のアルコキシ基からなる群より選ばれた置換基
を有していてもよい炭素数６〜１２のアルアルキル基を
示す。〕で表わされる一級アルコールをパラジウム、白
金又はこれらの化合物と助触媒として鉛又は鉛化合物と
を含有する触媒の存在下で酸化する方法において、触媒
を含む反応系に含酸素ガスと共に原料アルコール及びア
ルカリ水溶液を連続的に供給しつつ、反応系から供給量
と同量の反応混合物を取り出すことを特徴とするカルボ
ン酸の製造方法に係る。That is, the present invention provides a compound represented by the general formula R-CH 2 OH (1) [wherein R is a C 1-19 carbon atom which may have a hydroxyl group or a C 1-5 alkoxy group as a substituent. A linear or branched alkyl group, a linear or cyclic alkylene group which may have a hydroxyl group or an alkoxy group having 1 to 5 carbon atoms as a substituent, or a hydroxyl group, a fluorine atom or a cyano group on the aromatic nucleus. Shows an aralkyl group having 6 to 12 carbon atoms which may have a substituent selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms. ] In the method of oxidizing a primary alcohol represented by the following in the presence of a catalyst containing palladium, platinum or a compound thereof and lead or a lead compound as a cocatalyst, a raw material alcohol and an alkali together with an oxygen-containing gas are added to a reaction system containing the catalyst. The present invention relates to a method for producing a carboxylic acid, characterized in that the same amount of the reaction mixture as the amount supplied is taken out from the reaction system while continuously supplying the aqueous solution.
【０００８】本発明で処理対象となる上記一般式（１）
の一級アルコールとしては、従来公知のものを広く使用
でき、例えば２−フェニルエタノール、２−（２−メト
キシフェニル）エタノール、２−（３−メトキシフェニ
ル）エタノール、２−（４−メトキシフェニル）エタノ
ール、２−（４−メトキシフェニル）−２−メチルエタ
ノール、２−（２−ヒドロキシフェニル）エタノール、
２−（３−ヒドロキシフェニル）エタノール、２−（４
−ヒドロキシフェニル）エタノール、２−（４−ヒドロ
キシフェニル）−２−メチルエタノール、２−（４−ヒ
ドロキシフェニル）−２−エチルエタノール、２−（４
−ヒドロキシフェニル）−２−イソプロピルエタノー
ル、２−（４−イソブチルフェニル）−２−メチルエタ
ノール、２−（４−シアノフェニル）エタノール、２−
（４−フルオロフェニル）エタノール、２−（２−フル
オロフェニル）エタノール、２−メチル−２−フェニル
エタノール、３−フェニルプロパノール、３−（２−メ
トキシフェニル）プロパノール、３−（４−メトキシフ
ェニル）プロパノール、３−（２−ヒドロキシフェニ
ル）プロパノール、３−（４−ヒドロキシフェニル）プ
ロパノール、３−（４−ヒドロキシフェニル）−３−メ
チルプロパノール、２−（３，４−メチレンジオキシフ
ェニル）エタノール、２−（４−ヒドロキシ−３，５−
ジメトキシフェニル）エタノール、２−（３，４−ジメ
トキシフェニル）エタノール、４−フェニルブタノー
ル、４−（４−メトキシフェニル）ブタノール、４−
（４−ヒドロキシフェニル）ブタノール、５−フェニル
ペンタノール、５−（４−メトキシフェニル）ペンタノ
ール、５−（４−ヒドロキシフェニル）ペンタノール、
ベンジルアルコール、４−メトキシベンジルアルコー
ル、ケイヒアルコール、４−メトキシケイヒアルコー
ル、２−（２−ナフチル）エタノール、２−メチル−２
−（６−メトキシ−２−ナフチル）エタノール、メタノ
ール、エタノール、プロパノール、シクロペンチルメタ
ノール、ヘキサノール、２−シクロヘキシルエタノー
ル、オクタノール、デカノール、ラウリルアルコール、
ドデセノール、オクタデシルアルコール、エチレングリ
コール、プロピレングリコール、１，４−ブタンジオー
ル、１，６−ヘキサンジオール、１，１０−デカンジオ
ール、エチレングリコールモノメチルエーテル、エチレ
ングリコールモノエチルエーテル、プロビレングリコー
ルモノメチルエーテル、６−メトキシヘキサノール、１
０−メトキシデカノール等を例示できる。The above general formula (1) to be processed in the present invention
As the primary alcohol, conventionally known alcohols can be widely used, and examples thereof include 2-phenylethanol, 2- (2-methoxyphenyl) ethanol, 2- (3-methoxyphenyl) ethanol, and 2- (4-methoxyphenyl) ethanol. , 2- (4-methoxyphenyl) -2-methylethanol, 2- (2-hydroxyphenyl) ethanol,
2- (3-hydroxyphenyl) ethanol, 2- (4
-Hydroxyphenyl) ethanol, 2- (4-hydroxyphenyl) -2-methylethanol, 2- (4-hydroxyphenyl) -2-ethylethanol, 2- (4
-Hydroxyphenyl) -2-isopropylethanol, 2- (4-isobutylphenyl) -2-methylethanol, 2- (4-cyanophenyl) ethanol, 2-
(4-fluorophenyl) ethanol, 2- (2-fluorophenyl) ethanol, 2-methyl-2-phenylethanol, 3-phenylpropanol, 3- (2-methoxyphenyl) propanol, 3- (4-methoxyphenyl) Propanol, 3- (2-hydroxyphenyl) propanol, 3- (4-hydroxyphenyl) propanol, 3- (4-hydroxyphenyl) -3-methylpropanol, 2- (3,4-methylenedioxyphenyl) ethanol, 2- (4-hydroxy-3,5-
Dimethoxyphenyl) ethanol, 2- (3,4-dimethoxyphenyl) ethanol, 4-phenylbutanol, 4- (4-methoxyphenyl) butanol, 4-
(4-hydroxyphenyl) butanol, 5-phenylpentanol, 5- (4-methoxyphenyl) pentanol, 5- (4-hydroxyphenyl) pentanol,
Benzyl alcohol, 4-methoxybenzyl alcohol, cinnamic alcohol, 4-methoxycinnamic alcohol, 2- (2-naphthyl) ethanol, 2-methyl-2
-(6-methoxy-2-naphthyl) ethanol, methanol, ethanol, propanol, cyclopentylmethanol, hexanol, 2-cyclohexylethanol, octanol, decanol, lauryl alcohol,
Dodecenol, octadecyl alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, 6 -Methoxyhexanol, 1
Examples thereof include 0-methoxydecanol.
【０００９】本発明の方法で使用する触媒はパラジウ
ム、白金又はこれらの化合物に助触媒として鉛又は鉛化
合物を含有するものである。これらの触媒は通常、適当
な担体に担持させて用いるのが効果的である場合が多
い。担体としては、活性炭、シリカ、アルミナ、マグネ
シア等が好適であるが、これらの限定されず一般に使用
されるものが利用できる。担体へのパラジウム、白金又
はこれらの化合物の担持量は０．１〜２０重量％、特に
０．５〜１０重量％の範囲が好ましい。助触媒は鉛又は
鉛化合物であり、金属鉛、酢酸鉛、硝酸鉛、硫酸鉛、水
酸化鉛、酸化鉛等を用いることができる。これらの鉛又
は鉛化合物の担体上への担持量は０．０１〜１０重量
％、特に０．０５〜５重量％が好ましい。The catalyst used in the method of the present invention is palladium, platinum or a compound containing lead or a lead compound as a cocatalyst. Usually, it is often effective to support these catalysts on a suitable carrier before use. As the carrier, activated carbon, silica, alumina, magnesia and the like are preferable, but those commonly used are not limited to these. The amount of palladium, platinum or a compound thereof supported on the carrier is preferably 0.1 to 20% by weight, particularly preferably 0.5 to 10% by weight. The co-catalyst is lead or a lead compound, and metallic lead, lead acetate, lead nitrate, lead sulfate, lead hydroxide, lead oxide and the like can be used. The amount of lead or lead compound supported on the carrier is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight.
【００１０】上記触媒は、例えば塩化パラジウム等のパ
ラジウム化合物又は塩化白金酸塩等の白金化合物と酢酸
鉛等の鉛化合物を含む水溶液中に上記した担体を浸漬さ
せ塩基性条件下で水素ガス、ヒドラジン等の還元剤を作
用させて処理した後、水洗及び乾燥する通常の方法で調
製できる。またパラジウム又は白金を担持した市販の触
媒を鉛化合物を含む水溶液に浸漬し、次いで水溶液を塩
基性にして単離した後水洗及び乾燥したものも本発明の
方法に使用できる。The above catalyst is prepared by immersing the above carrier in an aqueous solution containing a palladium compound such as palladium chloride or a platinum compound such as chloroplatinate and a lead compound such as lead acetate under a basic condition with hydrogen gas and hydrazine. It can be prepared by a usual method of treating with a reducing agent such as the above, followed by washing with water and drying. Also, a commercially available catalyst supporting palladium or platinum may be immersed in an aqueous solution containing a lead compound, and then the aqueous solution may be made basic, isolated, washed with water and dried, and used in the method of the present invention.
【００１１】本発明の方法は、水又は水を主成分として
含有する混合溶媒中で実施することが好ましい。水と混
合して用いる溶媒としては水に可溶でしかも本発明の方
法の条件下で安定なものであれば特に制限されないが、
例えばアセトン、ジオキサン、ジメチルホルムアミド等
が適している。The method of the present invention is preferably carried out in water or a mixed solvent containing water as a main component. The solvent used by mixing with water is not particularly limited as long as it is soluble in water and stable under the conditions of the method of the present invention,
For example, acetone, dioxane, dimethylformamide and the like are suitable.
【００１２】本発明の方法は、反応選択性と反応速度を
共に高く保つため通常塩基性条件下で実施するのが望ま
しい。使用する塩基としては、例えば水酸化ナトリウ
ム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム等
が好適である。使用する塩基の量は、通常原料アルコー
ルに対して等モル〜３倍モルの範囲でよい。It is usually desirable to carry out the process of the present invention under basic conditions in order to keep both the reaction selectivity and the reaction rate high. As the base used, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like are suitable. The amount of the base used may usually be in the range of equimolar to 3 times the molar amount of the starting alcohol.
【００１３】本発明の方法は室温〜１５０℃で実施でき
るが、特に４０〜１００℃が好ましい。酸化剤は含酸素
ガスであり、殊に空気又は酸素が好適に使用できる。反
応圧力は常圧〜１０kg／cm2 で実施できるが、５kg／cm
2 以下で反応させるのが有利である。The method of the present invention can be carried out at room temperature to 150 ° C., particularly preferably 40 to 100 ° C. The oxidant is an oxygen-containing gas, and air or oxygen can be preferably used. The reaction pressure can be carried out at atmospheric pressure to 10 kg / cm 2 , but 5 kg / cm
It is advantageous to react at 2 or less.
【００１４】本発明の方法は、触媒を含む反応系（触媒
床）に酸化剤と共に原料アルコール及びアルカリ水溶液
を連続的に供給しつつ、反応系から供給量と同量の反応
混合物を取り出すことを特徴とする。In the method of the present invention, while the raw material alcohol and the alkaline aqueous solution are continuously supplied together with the oxidizing agent to the reaction system containing the catalyst (catalyst bed), the same amount of the reaction mixture as the supply amount is taken out from the reaction system. Characterize.
【００１５】触媒床の形式は懸濁床でも固定床でもよ
い。これに供給する原料アルコールは前記した水溶性溶
媒に溶解させることもできるし、アルカリ水溶液に溶解
又は分散させて供給することもできる。The type of catalyst bed may be a suspension bed or a fixed bed. The raw material alcohol to be supplied to this can be dissolved in the above-mentioned water-soluble solvent, or can be dissolved or dispersed in an alkaline aqueous solution and supplied.
【００１６】本発明において触媒の長寿命化を達成し、
触媒金属単位重量当りの目的物取得量を飛躍的に増大さ
せるためには触媒床に単位時間当り供給する原料アルコ
ールの量（モル／ｈｒ）を反応で生成するカルボン酸の
量（モル／ｈｒ）より過剰にすることが重要である。供
給する原料アルコールの量は、アルコールの種類、反応
温度、反応時の圧力等により異なり一概には言えない
が、通常触媒貴金属１ｇ当り０．０１〜１０モル／ｈｒ
がよく、０．１〜３モル／ｈｒがより好適である。In the present invention, the life of the catalyst is prolonged,
In order to dramatically increase the amount of the target substance obtained per unit weight of the catalyst metal, the amount of the raw material alcohol supplied per unit time to the catalyst bed (mol / hr) is the amount of the carboxylic acid produced by the reaction (mol / hr) It is important to make more excess. The amount of the raw material alcohol to be supplied varies depending on the type of alcohol, the reaction temperature, the pressure during the reaction, etc. and cannot be generally stated, but it is usually 0.01 to 10 mol / hr per 1 g of the catalyst precious metal.
Is preferable, and 0.1 to 3 mol / hr is more preferable.
【００１７】本発明の方法は触媒床に単位時間当りに生
成するカルボン酸の量（モル／ｈｒ）より過剰量のアル
コールを供給しそれと等しい量のアルコールと生成物の
混合物を触媒床から抜き出しながら反応を連続的に進め
る。触媒床から抜き出す反応液の変換率（原料アルコー
ルと生成物の混合物中に占める生成物のモル分率）は、
好ましくは５０〜９５％であり、より好ましくは７０〜
９０％である。According to the method of the present invention, an excess amount of alcohol is supplied to the catalyst bed over the amount of carboxylic acid formed per unit time (mol / hr), and an equal amount of the mixture of alcohol and product is withdrawn from the catalyst bed. The reaction proceeds continuously. The conversion rate of the reaction liquid extracted from the catalyst bed (the mole fraction of the product in the mixture of the raw material alcohol and the product) is
It is preferably 50 to 95%, more preferably 70 to 95%.
90%.
【００１８】このようにして得た本発明の反応液からの
原料アルコールと生成物との分離は容易に実施できる。
即ち、生成物はアルカリ塩として反応液中に均一溶解し
ており、一方原料アルコールは通常アルカリ水溶液に不
溶であるので、デカンテーション又は溶媒抽出により一
旦アルコールを分離する。分離したアルコールは再度反
応に供することができる。一方生成物を含むアルカリ水
溶液は中和処理を施すことにより結晶を析出させるか、
適当な溶媒で抽出することにより簡単に単離できる。The starting alcohol and the product can be easily separated from the reaction solution of the present invention thus obtained.
That is, the product is uniformly dissolved in the reaction solution as an alkali salt, while the raw material alcohol is usually insoluble in the alkaline aqueous solution, so the alcohol is once separated by decantation or solvent extraction. The separated alcohol can be subjected to the reaction again. On the other hand, the alkaline aqueous solution containing the product is subjected to neutralization treatment to precipitate crystals, or
It can be easily isolated by extraction with a suitable solvent.
【００１９】[0019]
【発明の効果】本発明によれば一級アルコールを酸化す
るに際して貴金属触媒の活性を充分長期間維持し、これ
により触媒金属単位重量当りの生成物取得量を飛躍的に
増大させることが可能となり、工業的に実施できるカル
ボン酸の製造方法が提供できる。EFFECTS OF THE INVENTION According to the present invention, the activity of the noble metal catalyst can be maintained for a sufficiently long period when the primary alcohol is oxidized, whereby the product acquisition amount per unit weight of the catalytic metal can be dramatically increased. A method for producing a carboxylic acid that can be industrially implemented can be provided.
【００２０】[0020]
実施例１ 触媒は、市販の５％パラジウム活性炭粉末６．６ｇを水
３００mlに分散させ、これに酢酸鉛三水塩０．５ｇを水
５０mlに溶解した液を撹拌下で加えた。次にこの液に１
０％苛性ソーダ水溶液２０mlを撹拌下で加え、１５分間
撹拌した後濾過して単離し、水洗することにより調製し
た。Example 1 As a catalyst, 6.6 g of commercially available 5% palladium activated carbon powder was dispersed in 300 ml of water, and a solution prepared by dissolving 0.5 g of lead acetate trihydrate in 50 ml of water was added thereto with stirring. Then add 1 to this liquid
It was prepared by adding 20 ml of 0% aqueous sodium hydroxide solution with stirring, stirring for 15 minutes, filtering and isolating, and washing with water.
【００２１】酸素導入管、原料導入管、先端に濾布を装
着した反応液を抜き出し管、温度計及び撹拌器を装着し
た５００mlのステンレス製オートクレーブに、先に調製
した触媒全量、水酸化ナトリウム８．２ｇを水２００ml
に溶解した液及び４−メトキシフェネチルアルコール１
５．４ｇ（０．１０１モル）を仕込み、気相を酸素で置
換した。次に混合物を撹拌器で充分掻き混ぜながら昇温
し、９０℃で酸素ガスを導入しながら内圧を３kg／cm2
に保って反応した。反応の進行に合せて連続的に４−メ
トキシフェネチルアルコール１５．４ｇ、水酸化ナトリ
ウム８．２ｇ及び水２００mlの組成からなる混合液を導
入し、それと同液量の反応液を連続的に抜き出した。こ
の時変換率が８０〜９０％となるように原料液の導入量
と反応液の抜き出し量を調整した。反応を８２時間継続
して、合計１０１６ｇの原料アルコールを供給した。抜
き出した反応液をデカンテーションすることにより油層
として４−メトキシフェネチルアルコールを１５１ｇ回
収した。一方水層を１０％硫酸水溶液で中和し、生じた
白色沈殿を濾過して単離し、水洗と乾燥を行なって白色
結晶を９３０ｇ得た。このもののＮＭＲ及びＧＣスペク
トルは標品４−メトキシフェニル酢酸のそれと一致し
た。変換率は８５％であり、４−メトキシフェニル酢酸
の選択性は９８％であった。使用した金属パラジウム１
ｇ当りの４−メトキシフェニル酢酸取得量は２．８２kg
であり、反応は８２時間後も更に継続できる状態であっ
た。結果を表１及び表２にまとめて示した。Into a 500 ml stainless steel autoclave equipped with an oxygen introduction tube, a raw material introduction tube, a reaction cloth with a filter cloth attached at the tip, a thermometer and a stirrer, the total amount of the catalyst prepared above and sodium hydroxide 8 0.2 g of water 200 ml
And 4-methoxyphenethyl alcohol 1 dissolved in
5.4 g (0.101 mol) was charged and the gas phase was replaced with oxygen. Next, the temperature of the mixture was raised with thorough stirring with a stirrer, and the internal pressure was raised to 3 kg / cm 2 while introducing oxygen gas at 90 ° C.
I kept it at and reacted. Along with the progress of the reaction, a mixed solution consisting of 15.4 g of 4-methoxyphenethyl alcohol, 8.2 g of sodium hydroxide and 200 ml of water was continuously introduced, and the same amount of the reaction solution was continuously withdrawn. . At this time, the introduction amount of the raw material liquid and the withdrawal amount of the reaction liquid were adjusted so that the conversion rate was 80 to 90%. The reaction was continued for 82 hours to supply a total of 1016 g of raw material alcohol. The extracted reaction liquid was decanted to collect 151 g of 4-methoxyphenethyl alcohol as an oil layer. On the other hand, the aqueous layer was neutralized with a 10% aqueous sulfuric acid solution, the white precipitate formed was isolated by filtration, washed with water and dried to obtain 930 g of white crystals. The NMR and GC spectra of this product coincided with those of the standard 4-methoxyphenylacetic acid. The conversion was 85% and the selectivity of 4-methoxyphenylacetic acid was 98%. Metal Palladium used 1
The amount of 4-methoxyphenylacetic acid obtained per g is 2.82 kg.
The reaction was in a state where it could be continued even after 82 hours. The results are summarized in Tables 1 and 2.
【００２２】実施例２〜９ 実施例１と同様にして調製した触媒を用いて各種一級ア
ルコールをカルボン酸に変換した。結果を表１及び表２
にまとめて示した。全ての例において反応は表２中に示
した時間後も更に継続できる状態であった。Examples 2 to 9 Various primary alcohols were converted to carboxylic acids using the catalyst prepared in the same manner as in Example 1. The results are shown in Table 1 and Table 2.
Are summarized in. In all the examples, the reaction was in a state where it could be further continued after the time shown in Table 2.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】実施例１０ ５％パラジウム活性炭粉末６．６ｇを市販の５％白金活
性炭粉末に加えた以外は実施例１と同様にして触媒を調
製した。この触媒を用い、４−メトキシフェネチルアル
コール、水酸化ナトリウム及び水を実施例１と同様にオ
ートクレーブに仕込み、５０℃で酸素ガスを導入しなが
ら内圧を２kg／cm2 に保って反応した。反応の進行に合
せて連続的に４−メトキシフェネチルアルコール１５．
４ｇ及び４％水酸化ナトリウム水溶液２００mlの組成か
らなる混合液を供給し、それと同液量の反応液を連続的
に抜き出した。この間変換率が８０〜９０％となるよう
に原料液の供給量と反応液の抜き出し量を調整した。反
応を７８時間行なって合計６９４ｇの原料を供給した。
実施例１と同様に後処理をして４−メトキシフェニル酢
酸５５９ｇと４−メトキシフェネチルアルコール１２５
ｇを回収した。変換率８２％、４−メトキシフェニル酢
酸の選択性は９０％であった。金属白金１ｇ当りの４−
メトキシフェニル酢酸取得量は１．６９kgであり、反応
は７８時間後も更に継続できる状態であった。Example 10 A catalyst was prepared in the same manner as in Example 1 except that 6.6 g of 5% palladium activated carbon powder was added to commercially available 5% platinum activated carbon powder. Using this catalyst, 4-methoxyphenethyl alcohol, sodium hydroxide and water were charged in an autoclave in the same manner as in Example 1 and reacted at 50 ° C. while introducing oxygen gas while maintaining the internal pressure at 2 kg / cm 2 . 4-methoxyphenethyl alcohol 15.
A mixed solution having a composition of 4 g and 200 ml of a 4% sodium hydroxide aqueous solution was supplied, and the same amount of the reaction solution was continuously withdrawn. During this period, the supply amount of the raw material liquid and the withdrawal amount of the reaction liquid were adjusted so that the conversion rate was 80 to 90%. The reaction was run for 78 hours, supplying a total of 694 g of raw material.
Post-treatment was carried out in the same manner as in Example 1 to give 559 g of 4-methoxyphenylacetic acid and 125 of 4-methoxyphenethyl alcohol.
g was recovered. The conversion rate was 82% and the selectivity for 4-methoxyphenylacetic acid was 90%. 4-per 1 g of metallic platinum
The amount of methoxyphenylacetic acid obtained was 1.69 kg, and the reaction could be continued even after 78 hours.
【００２６】比較例 実施例１と同様にして調製した触媒、水酸化ナトリウム
８．２ｇを水２００mlに溶解した液及び４−メトキシフ
ェネチルアルコール１５．４ｇ（０．１０１モル）を５
００mlのステンレス製オートクレーブに仕込み、気相を
酸素で置換した。内容物を撹拌器で充分掻き混ぜ、酸素
ガスを導入しながら内圧を３kg／cm2 に保って９０℃で
２時間反応した（この反応を１バッチ目とする）。反応
液を冷却し濾過して触媒と反応液を分離した。反応液は
１０％硫酸水で中和後エーテル抽出し、抽出液をガスク
ロマトグラフィー（ＧＣ）で定量することにより４−メ
トキシフェニル酢酸が１５．４ｇ（０．０９３モル）生
成し、原料アルコールが０．１１ｇ回収された。変換率
９９．３％、収率９１．７％であった。ここで回収した
触媒を再び同じ反応器に仕込み１バッチ目と同様にして
原料、水酸化ナトリウム及び水を仕込んで反応及び後処
理を行なった（２バッチ目）。４−メトキシフェニル酢
酸が１４．９ｇ生成し、原料が０．９５ｇ回収された。
変換率９３．８％、収率８９．１％であった。同様にし
て５バッチ目まで触媒を繰返し使用して得た結果を表３
に示した。Comparative Example A catalyst prepared in the same manner as in Example 1, a solution prepared by dissolving 8.2 g of sodium hydroxide in 200 ml of water, and 15.4 g (0.101 mol) of 4-methoxyphenethyl alcohol were added to 5 parts.
It was charged into a 00 ml stainless steel autoclave and the gas phase was replaced with oxygen. The contents were thoroughly stirred with a stirrer and reacted at 90 ° C. for 2 hours while maintaining the internal pressure at 3 kg / cm 2 while introducing oxygen gas (this reaction is the first batch). The reaction solution was cooled and filtered to separate the catalyst and the reaction solution. The reaction solution was neutralized with 10% sulfuric acid water, extracted with ether, and the extracted solution was quantified by gas chromatography (GC) to produce 15.4 g (0.093 mol) of 4-methoxyphenylacetic acid, and the raw material alcohol was obtained. 0.11 g was recovered. The conversion rate was 99.3% and the yield was 91.7%. The catalyst recovered here was charged again into the same reactor, and the raw materials, sodium hydroxide and water were charged in the same manner as in the first batch to carry out reaction and post-treatment (second batch). 14.9 g of 4-methoxyphenylacetic acid was produced and 0.95 g of the raw material was recovered.
The conversion rate was 93.8% and the yield was 89.1%. Similarly, the results obtained by repeatedly using the catalyst up to the fifth batch are shown in Table 3.
It was shown to.
【００２７】[0027]
【表３】 [Table 3]
【００２８】表３から明らかなように３バッチまでに触
媒の活性低下が徐々に現われ、４バッチ目で一挙に失活
した。これ以降繰返し使用しても触媒能が回復すること
はなかった。３バッチ目までで４−メトキシフェニル酢
酸を４３．５ｇ得た。金属パラジウム１ｇ当りの取得量
は０．１３kgであった。As is apparent from Table 3, the catalyst activity gradually decreased by the third batch, and the catalyst was deactivated at the fourth batch. Even after repeated use, the catalytic ability was not recovered. By the third batch, 43.5 g of 4-methoxyphenylacetic acid was obtained. The amount acquired per 1 g of metallic palladium was 0.13 kg.
【００２９】実施例２〜９で使用した原料をそれぞれ用
いて上記と同様に反応と触媒の回収使用を繰返した結
果、パラジウム１ｇ当りのカルボン酸取得量は０．０６
〜０．１５kgであった。As a result of repeating the reaction and recovering and using the catalyst in the same manner as above using each of the raw materials used in Examples 2 to 9, the obtained amount of carboxylic acid per 1 g of palladium was 0.06.
Was 0.15 kg.
【００３０】また実施例１０と同様にして調製した触媒
を用いて４−メトキシフェネチルアルコールの酸化と触
媒の回収使用を繰返した結果、白金１ｇ当りの４−メト
キシフェニル酢酸取得量は０．０８kgであった。The oxidation of 4-methoxyphenethyl alcohol and the recovery and use of the catalyst were repeated using the catalyst prepared in the same manner as in Example 10. As a result, the amount of 4-methoxyphenylacetic acid obtained per 1 g of platinum was 0.08 kg. there were.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 53/132 8930−4Ｈ 57/03 8930−4Ｈ 57/30 8930−4Ｈ 57/58 8930−4Ｈ 59/01 8930−4Ｈ 59/125 Ａ 8930−4Ｈ 59/52 8930−4Ｈ 59/68 8930−4Ｈ 253/30 255/57 9357−4Ｈ // Ｃ０７Ｂ 61/00 ３００ (72)発明者 諸岡 良彦 神奈川県横浜市緑区藤が丘２−41−21− 404─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical indication C07C 53/132 8930-4H 57/03 8930-4H 57/30 8930-4H 57/58 8930-4H 59/01 8930-4H 59/125 A 8930-4H 59/52 8930-4H 59/68 8930-4H 253/30 255/57 9357-4H // C07B 61/00 300 (72) Inventor Yoshihiko Morooka Kanagawa 2-41-21-404, Fujigaoka, Midori-ku, Yokohama-shi
Claims (1)
アルコキシ基を有していてもよい炭素数１〜１９の直鎖
又は分枝鎖状のアルキル基、置換基として水酸基もしく
は炭素数１〜５のアルコキシ基を有していてもよい直鎖
又は環状アルキレン基、或いは芳香核上に水酸基、フッ
素原子、シアノ基、炭素数１〜５のアルキル基及び炭素
数１〜５のアルコキシ基からなる群より選ばれた置換基
を有していてもよい炭素数６〜１２のアルアルキル基を
示す。〕で表わされる一級アルコールをパラジウム、白
金又はこれらの化合物と助触媒として鉛又は鉛化合物と
を含有する触媒の存在下で酸化する方法において、触媒
を含む反応系に含酸素ガスと共に原料アルコール及びア
ルカリ水溶液を連続的に供給しつつ、反応系から供給量
と同量の反応混合物を取り出すことを特徴とするカルボ
ン酸の製造方法。1. A compound represented by the general formula: R—CH 2 OH, wherein R is a straight chain or branched chain having 1 to 19 carbon atoms and optionally having a hydroxyl group or an alkoxy group having 1 to 5 carbon atoms as a substituent. Alkyl group, a linear or cyclic alkylene group which may have a hydroxyl group or a C1-5 alkoxy group as a substituent, or a hydroxyl group, a fluorine atom, a cyano group, or a C1-5 group on the aromatic nucleus. It represents an aralkyl group having 6 to 12 carbon atoms which may have a substituent selected from the group consisting of an alkyl group and an alkoxy group having 1 to 5 carbon atoms. ] In the method of oxidizing a primary alcohol represented by the following in the presence of a catalyst containing palladium, platinum or a compound thereof and lead or a lead compound as a cocatalyst, a raw material alcohol and an alkali together with an oxygen-containing gas are added to a reaction system containing the catalyst. A method for producing a carboxylic acid, which comprises continuously supplying an aqueous solution and removing a reaction mixture in the same amount as the supply amount from a reaction system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10900093A JP3240424B2 (en) | 1993-05-11 | 1993-05-11 | Method for producing carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10900093A JP3240424B2 (en) | 1993-05-11 | 1993-05-11 | Method for producing carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06321845A true JPH06321845A (en) | 1994-11-22 |
| JP3240424B2 JP3240424B2 (en) | 2001-12-17 |
Family
ID=14499035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10900093A Expired - Fee Related JP3240424B2 (en) | 1993-05-11 | 1993-05-11 | Method for producing carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3240424B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11246471A (en) * | 1998-02-27 | 1999-09-14 | Kao Corp | Oxidation of aliphatic primary alcohol |
| WO2008041325A1 (en) * | 2006-10-03 | 2008-04-10 | Mitsubishi Rayon Co., Ltd. | METHOD OF PRODUCING α,β-UNSATURATED ALDEHYDE AND/OR α,β-UNSATURATED CARBOXYLIC ACID |
| JP2015057386A (en) * | 2013-09-16 | 2015-03-26 | アームストロング ワールド インダストリーズ インコーポレーテッド | Method for producing methacrylic acid from biobased starting material |
-
1993
- 1993-05-11 JP JP10900093A patent/JP3240424B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11246471A (en) * | 1998-02-27 | 1999-09-14 | Kao Corp | Oxidation of aliphatic primary alcohol |
| WO2008041325A1 (en) * | 2006-10-03 | 2008-04-10 | Mitsubishi Rayon Co., Ltd. | METHOD OF PRODUCING α,β-UNSATURATED ALDEHYDE AND/OR α,β-UNSATURATED CARBOXYLIC ACID |
| US8173838B2 (en) | 2006-10-03 | 2012-05-08 | Mitsubishi Rayon Co., Ltd. | Method for producing at least one of α, β-unsaturated aldehyde and α, β-unsaturated carboxylic acid |
| JP2015057386A (en) * | 2013-09-16 | 2015-03-26 | アームストロング ワールド インダストリーズ インコーポレーテッド | Method for producing methacrylic acid from biobased starting material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3240424B2 (en) | 2001-12-17 |
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