JPS62153240A - Production of p-hydroxybenzaldehyde - Google Patents

Production of p-hydroxybenzaldehyde

Info

Publication number
JPS62153240A
JPS62153240A JP60292491A JP29249185A JPS62153240A JP S62153240 A JPS62153240 A JP S62153240A JP 60292491 A JP60292491 A JP 60292491A JP 29249185 A JP29249185 A JP 29249185A JP S62153240 A JPS62153240 A JP S62153240A
Authority
JP
Japan
Prior art keywords
reaction
cresol
oxidation
para
hydroxybenzaldehyde
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
Application number
JP60292491A
Other languages
Japanese (ja)
Inventor
Hiroshi Kamimura
寛 上村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
C K FINE KEMIKARUZU KK
Original Assignee
C K FINE KEMIKARUZU KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by C K FINE KEMIKARUZU KK filed Critical C K FINE KEMIKARUZU KK
Priority to JP60292491A priority Critical patent/JPS62153240A/en
Publication of JPS62153240A publication Critical patent/JPS62153240A/en
Pending legal-status Critical Current

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PURPOSE:In the production of the title compound by oxidation of p-cresol with molecular oxygen in the presence of a cobalt compound and a base, the reaction is carried out substantially in the absence of iron ion to avoid the activity of catalytic oxidation from lowering whereby the objective compound is selectively obtained. CONSTITUTION:In the production of p-hydroxybenzaldehyde by the oxidation of p-cresol with molecular oxygen in the presence of a cobalt compound and a base, the reaction is carried out substantially in the absence of iron ion, less than 6 ppm, preferably less than 3 ppm, calculated as Fe2O3 to avoid the oxidation activity of the catalyst from lowering and obtain the objective compound advantageously in an amount of less than 1/10 of the conventionally required quantity, namely more than 0.000001 mole or more, preferably 0.0005-0.05 mole per mole of the starting substance. The process according to the present invention can remarkably improve the reaction time and selectivity compared with the conventional processes.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、パラヒドロキシベンズアルデヒドの製造法に
関する。更に詳しくは、パラクレゾールのアルキル基を
分子状酸素で酸化するパラヒドロキシベンズアルデヒド
の製造法の改良に関する。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing parahydroxybenzaldehyde. More specifically, the present invention relates to an improved method for producing para-hydroxybenzaldehyde by oxidizing the alkyl group of para-cresol with molecular oxygen.

〔従来技術〕[Prior art]

パラクレゾール又はパラクレゾール=m体を分子状酸素
で酸化して、選択的にパラヒドロキシベンズアルデヒド
又は、パラヒドロキシベンズアルデヒド誘導体を製造す
る方法としては、Angew、Chem、86,586
 (1975);第12回酸化反応討論会講演要旨集、
P74(197B);特開昭55−81832等に紹介
された方法がある。これらの方法は、コバルト触媒の存
在下、又は不存在下で、塩基化合物を含む有機溶媒中で
分子状酸素で酸化することを特徴としている。
A method for selectively producing para-hydroxybenzaldehyde or para-hydroxybenzaldehyde derivatives by oxidizing para-cresol or para-cresol m-form with molecular oxygen is described in Angew, Chem, 86,586.
(1975); Collection of lecture abstracts of the 12th Oxidation Reaction Symposium,
P74 (197B): There is a method introduced in Japanese Patent Application Laid-Open No. 55-81832. These methods are characterized by oxidation with molecular oxygen in an organic solvent containing a basic compound in the presence or absence of a cobalt catalyst.

〔問題を解決するための手段〕[Means to solve the problem]

従来技術、中でも特開昭55−81832の方法は高い
技術水準にある。
The prior art, especially the method disclosed in Japanese Patent Application Laid-Open No. 55-81832, is at a high level of technology.

本発明者はこの方法で触媒として使用されるコバルト化
合物に対し微量の鉄イオンがその酸化触媒能を太き(低
下させることを確認し本発明を完成した。
The present inventor completed the present invention by confirming that a trace amount of iron ions increases (decreases) the oxidation catalytic ability of the cobalt compound used as a catalyst in this method.

鉄イオンはコバルト化合物の酸化触媒能を大きく低下さ
せ、ご(微量でも負の触媒作用を示し、パラクレゾール
の反応性を低下させるだけではな(、パラヒド口キシベ
ンズアルデヒドへの選択率も低下させ、副生成物特に重
合物の生成を増大させろ。
Iron ions greatly reduce the oxidation catalytic ability of cobalt compounds, exhibiting a negative catalytic effect even in small amounts, and not only reduce the reactivity of para-cresol (but also reduce the selectivity to parahydride-oxybenzaldehyde, Increase the production of by-products, especially polymers.

本発明により、実質的に鉄イオンの不存在下での反応に
よれば、コバルト化合物の使用量は、特開昭55−81
832で述べている量の10分の1つまりパラクレゾー
ルに対してO,OOOOO1倍モルでも効果がある。
According to the present invention, the amount of cobalt compound used can be adjusted according to the reaction substantially in the absence of iron ions.
Even one-tenth of the amount stated in 832, that is, 1 times the mole of O,OOOOOO to para-cresol, is effective.

また、斯かる鉄イオンを実質的に含有しない反応条件の
選択により反応時間及び選択率の面で特開昭55−81
832に較べて、著しい改善が望める。
In addition, by selecting reaction conditions that do not substantially contain iron ions, it is possible to improve the reaction time and selectivity of JP-A-55-81.
A significant improvement can be expected compared to 832.

本発明は、鉄イオンが実質的に不存在下の反応条件下で
行うが、実質的に不存在とは、反応液全量に対してFe
、03換算で6ppm以下好ましくは、3ppm以下を
意味する。
The present invention is carried out under reaction conditions in which iron ions are substantially absent.
, 6 ppm or less, preferably 3 ppm or less in terms of 0.03.

本発明方法では出発原料として、パラクレゾールを使用
する。又、触媒として使用するコバルト化合物の量は、
パラクレゾールに対してo、oooooi倍モル以上で
あることが望ましく、好ましくは、0.0005倍モル
〜0.05倍モルの範囲である。
The method of the invention uses para-cresol as a starting material. Also, the amount of cobalt compound used as a catalyst is
It is desirable that the amount is o,oooooi times or more in mole relative to para-cresol, and preferably in the range of 0.0005 to 0.05 times in mole.

本発明で使用する塩基としては、カセイソーダ、カセイ
カリ、水酸化リチウム等のアルカリ金属の水酸化物、ナ
トリウムアルコキシド、カリウムアルコキシド等の金属
アルコキシドがある。その使用量は、パラクレゾールに
対して、1.5倍モル以上好ましくは、2倍モル〜5倍
モルの範囲である。
Examples of the base used in the present invention include alkali metal hydroxides such as caustic soda, caustic potash, and lithium hydroxide, and metal alkoxides such as sodium alkoxide and potassium alkoxide. The amount used is 1.5 times mole or more, preferably 2 times mole to 5 times mole, relative to para-cresol.

反応溶媒として使用するアルコールとしては、メタノー
ル、エタノールイソプロパノール等の低級アルコールが
使用できる。特に好ましいのはメタノールである。勿論
これら塩基、アルコール類の選択にあたっては、鉄イオ
ン、への配慮が必要である。
As the alcohol used as the reaction solvent, lower alcohols such as methanol and ethanol isopropanol can be used. Particularly preferred is methanol. Of course, when selecting these bases and alcohols, consideration must be given to iron ions.

本発明方法は、60〜80℃の温度範囲で実施するのが
好ましく、50℃以下では、反応速度が低下し、一方8
0℃以上では、溶媒酸化又は副反応による副生物が増大
する。
The method of the present invention is preferably carried out in the temperature range of 60 to 80°C; below 50°C, the reaction rate decreases;
At temperatures above 0°C, by-products due to solvent oxidation or side reactions increase.

酸化剤として使用する分子状酸素としては、酸素ガス、
空気等があり、圧力は通常1気圧以上が適用される。
Molecular oxygen used as an oxidizing agent includes oxygen gas,
There is air, etc., and the pressure is usually 1 atm or more.

反応混合物よりの目的物の分離精製は、有機溶剤による
抽出、再結晶法によることができる。
The target product can be separated and purified from the reaction mixture by extraction with an organic solvent or recrystallization method.

以下で実施例により本発明を具体的に説明する。The present invention will be specifically explained below using Examples.

実施例1 温度計、液及びガスの供給管及び抜き出し管を備えた内
容積1gの攪拌機付のオートクレーブに予めパラクレゾ
ール(59,5N、0.55モル)塩化コバルトろ水塩
(1゜4薦g、0.000006モル)、カセイソーダ
(70,98、)、1.65モル)およびメタノール(
180ミリリツトル)を仕込み反応温度60℃にて1気
圧の酸素雰囲気下で4時間攪拌した。
Example 1 Para-cresol (59.5 N, 0.55 mol) and cobalt chloride filtrate (1°4 recommended) were placed in advance in an autoclave equipped with a thermometer, a stirrer, and an internal volume of 1 g, equipped with a thermometer, a supply pipe for liquid and gas, and a discharge pipe. g, 0.000006 mol), caustic soda (70,98, ), 1.65 mol) and methanol (
180 ml) was charged and stirred for 4 hours at a reaction temperature of 60° C. under an oxygen atmosphere of 1 atm.

本例での反応液中の鉄イオン(Fc、、0.換算)の含
有量は、3ppmであった。
The content of iron ions (Fc, .0.0.0) in the reaction solution in this example was 3 ppm.

反応混合物を高速液体クロマトグラフで分析した結果は
、次のとおりであった。
The reaction mixture was analyzed by high performance liquid chromatography, and the results were as follows.

パラクレゾールの転化率   65.4%パラヒドロキ
シベンズアルデヒドの選択率72.0% 実施例2 実施例1において塩化コバルトろ水塩の量を1.51 
!!(0,0O55モル)に変えた以外は、実施例1と
同様に反応させた。本例での反応液中の鉄イオン(Fe
203換算)の含″有量は、5ppmであった。
Conversion rate of para-cresol 65.4% Selectivity of para-hydroxybenzaldehyde 72.0% Example 2 In Example 1, the amount of cobalt chloride filtrate was changed to 1.51%.
! ! The reaction was carried out in the same manner as in Example 1, except that the amount was changed to (0,0O55 mol). In this example, iron ions (Fe
203 conversion) was 5 ppm.

反応の結果は次のとおりであった。The results of the reaction were as follows.

パラクレゾールの転化率   95,1%パラヒドロキ
シベンズアルデヒドの選択率82.6係 比較例1 実施例1において、鉄含有量の多い苛性ソーダを使用し
反応液中の鉄イオン(Fe20゜換算)の含有量を7p
pmとして反応を行った。
Conversion rate of para-cresol 95.1% Selectivity of para-hydroxybenzaldehyde 82.6 Comparative Example 1 In Example 1, caustic soda with a high iron content was used, and the content of iron ions (Fe20° conversion) in the reaction solution was 7p
The reaction was carried out as pm.

反応の結果は次のとおりであった。The results of the reaction were as follows.

パラクレゾールの転化率   57.3%パラヒドロキ
シベンズアルデヒドの選択率55.8% 比較例2 実施例2において、1.D、法の苛性ソーダを使用し反
応液中の鉄イオン(Fe203換算)の含有量を10p
pmとして反応を行った。
Conversion rate of para-cresol 57.3% Selectivity of para-hydroxybenzaldehyde 55.8% Comparative Example 2 In Example 2, 1. D. Using method caustic soda, the content of iron ions (Fe203 equivalent) in the reaction solution was reduced to 10p.
The reaction was carried out as pm.

反応の結果は次のとおりであった。The results of the reaction were as follows.

パラクレゾールの転化率   894%パラヒドロキシ
ベンズアルデヒドの選択率70.0%
Conversion rate of para-cresol 894% Selectivity of para-hydroxybenzaldehyde 70.0%

Claims (1)

【特許請求の範囲】[Claims] パラクレゾールをコバルト化合物および塩基の共存下酸
素または酸素含有ガスで酸化するパラヒドロキシベンズ
アルデヒドの製造にあたり、反応を実質的に鉄イオンの
不存在下で行うことを特徴とするパラヒドロキシベンズ
アルデヒドの製造法。
1. A method for producing para-hydroxybenzaldehyde, which comprises oxidizing para-cresol with oxygen or an oxygen-containing gas in the presence of a cobalt compound and a base, the reaction being carried out in the substantial absence of iron ions.
JP60292491A 1985-12-27 1985-12-27 Production of p-hydroxybenzaldehyde Pending JPS62153240A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60292491A JPS62153240A (en) 1985-12-27 1985-12-27 Production of p-hydroxybenzaldehyde

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60292491A JPS62153240A (en) 1985-12-27 1985-12-27 Production of p-hydroxybenzaldehyde

Publications (1)

Publication Number Publication Date
JPS62153240A true JPS62153240A (en) 1987-07-08

Family

ID=17782506

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60292491A Pending JPS62153240A (en) 1985-12-27 1985-12-27 Production of p-hydroxybenzaldehyde

Country Status (1)

Country Link
JP (1) JPS62153240A (en)

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