JPS5942341A - Preparation of oxocarboxylic acid - Google Patents
Preparation of oxocarboxylic acidInfo
- Publication number
- JPS5942341A JPS5942341A JP57153069A JP15306982A JPS5942341A JP S5942341 A JPS5942341 A JP S5942341A JP 57153069 A JP57153069 A JP 57153069A JP 15306982 A JP15306982 A JP 15306982A JP S5942341 A JPS5942341 A JP S5942341A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- iron
- water
- amount
- cyclohexanone
- 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、オキソカルボンｒＩＩ類の製造方法に関する
ものである。オキソカルボン酸の代表的な化合物さして
、合成的に有用な中間体であるアジボアルデヒド酸が知
られているが、従来、このものの製造方法としては、例
えば、シクロヘキサノンを水および銅化合物の存在下、
分子状酸素によ）酸化する方法（特公昭４ｔ７−．２６
７ぶ２号公報）が報告されている。しかしながら拳法は
原料の転化率、目的物の収率がいずれも高くない欠点を
有する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing oxocarboxes rII. A typical compound of oxocarboxylic acids is known as azibaldehyde acid, which is a synthetically useful intermediate. Conventionally, as for the production method of azibaldehyde acid, for example, cyclohexanone is mixed in the presence of water and a copper compound. ,
method of oxidation (by molecular oxygen) (Special Publication Showa 4t7-.26
7bu No. 2) has been reported. However, Kempo has the drawback that both the conversion rate of raw materials and the yield of the target product are not high.
一方、本発明者らは、先にシクロヘキサノンを、水およ
び鉄もしくはイリジウムの化合物の存在下、酸化反応を
行なうと、速やかにアジボアルデヒド酸が生成すること
を見出した。本発明者らはその後、目的物の収率をさら
に高めるべく、引き続き検討を続けた結果、シクロヘキ
サノンを水および鉄化合物、さらに無機イオウ化合物を
存在させてｗＩ累によシ酸化反応を行なうことにより、
アジゼアルデヒド酸をはじめとする、オキソカルボン酸
類の収率が改善されることを見い出し本発明に到達した
。On the other hand, the present inventors have found that when cyclohexanone is first subjected to an oxidation reaction in the presence of water and an iron or iridium compound, azibaldehyde acid is rapidly produced. Subsequently, the present inventors continued to study in order to further increase the yield of the target product, and found that cyclohexanone was oxidized by wI in the presence of water, an iron compound, and an inorganic sulfur compound. ,
The present invention was accomplished by discovering that the yield of oxocarboxylic acids, including azizelaldehyde acid, can be improved.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明においては下記一般式（Ｉ）
ｎ
で表わされるシクロヘキサノン類を、■水、■鉄化合物
ならびに■無機イオウ化合物の存在下、酸素によりｉ化
すゐことによシ下記一般式（ＩＩ）ＲＯＯ（（３Ｈ２）
、０ＯＯＨ・・・・・・・・・・（Ｉｆ）で表わされる
オキソカルボン酸類を製造する。In the present invention, a cyclohexanone represented by the following general formula (I) n is converted to i with oxygen in the presence of (1) water, (2) an iron compound, and (2) an inorganic sulfur compound, thereby converting it into the following general formula (II) ROO ( (3H2)
, 0OOH (If).
一般式（１）および（１）におけるＲは同義であシ、水
素またはアルキル基を示す。アルキル基としては特に限
定されないが炭素数ご以下のものが実用上好ましい。R in general formulas (1) and (1) has the same meaning and represents hydrogen or an alkyl group. The alkyl group is not particularly limited, but those having less than or equal to the number of carbon atoms are practically preferred.
鉄化合物としては水に可溶なものが好オしく、具体的に
例示すると、例えば塩化第一鉄、塩化第二鉄、臭化第二
鉄、硫酸第一鉄、硫酸第二鉄、硝酸第二鉄等の無機酸塩
あるいは酢酸鉄のようが有ｔａＷＩ塩等があげられる。The iron compound is preferably one that is soluble in water; specific examples include ferrous chloride, ferric chloride, ferric bromide, ferrous sulfate, ferric sulfate, and ferrous nitrate. Examples include inorganic acid salts such as diiron, and taWI salts such as iron acetate.
鉄化合物の使用量は人混に変化させ得るが、例えばシク
ロヘキサノン類に対し、鉄として０．７〜７００モル％
、よシ好ましくは／〜３０モル％程度が良い。The amount of iron compound used can vary depending on the person, but for example, 0.7 to 700 mol% of iron relative to cyclohexanone.
, preferably about 1 to 30 mol%.
本発明におしては鉄化合物に加えて、無機イオウ化合物
を使用することが必須である。具体的に例示すると、例
えば、硫化水素、水硫化ナトリウム、チオ硫酸ナトリウ
ム、亜ジチオン酸ナトリウム、ピロ亜硫酸カリウム、ジ
チオン酸カリウム叫が挙げられる。無機イオウ化合物と
しては、二価のイオウ原子を有し、かつ反応系に可溶で
あるものが好ましい。In the present invention, it is essential to use an inorganic sulfur compound in addition to the iron compound. Specific examples include hydrogen sulfide, sodium hydrosulfide, sodium thiosulfate, sodium dithionite, potassium pyrosulfite, and potassium dithionate. The inorganic sulfur compound preferably has a divalent sulfur atom and is soluble in the reaction system.
これらのイオウ化合物の使用量は、鉄に対し、イオウと
して０，１〜１００モル％、よシ好ましくは！〜１００
モル％程度が良い。特に鉄に対し当量以上を使用しない
ことが好ましい。The amount of these sulfur compounds to be used is preferably 0.1 to 100 mol% of sulfur based on iron! ~100
About mol% is good. In particular, it is preferable not to use more than the equivalent amount to iron.
本発明方法を実施するには水の存在が必要であυ、その
使用量はシクロヘキサノン類に対し、Ｍ量比で０．０！
倍ないし／、０００倍、よシ好ましくは０．１倍ないし
１００倍程度とするのが良い。水の使用量によシ、反応
系は均一相あるい ３−
は懸濁相七なるが、本発明方法を実施するにはそのいず
れでも可である。The presence of water is necessary to carry out the method of the present invention, and the amount used is 0.0 in terms of M amount ratio to cyclohexanones!
It is preferable to set the magnification to about 0.1 to 100 times, preferably about 0.1 to 100 times. Depending on the amount of water used, the reaction system can be in a homogeneous phase, a suspended phase, or a suspended phase, and either of these can be used to carry out the method of the present invention.
本反応を実施する際の反応温度はかなり広い範囲にわた
り変化させ得るが、例示すればθ℃〜２００℃、よシ好
ましくは３θ、℃〜りθ℃程度が好適である。圧力は常
圧で十分反応を進行させ得るが、加圧としても良い。The reaction temperature when carrying out this reaction can be varied over a fairly wide range, but for example, θ°C to 200°C, more preferably about 3θ°C to about θ°C. Although the reaction can proceed sufficiently at normal pressure, it may be pressurized.
酸素源としては純酸素を用い得るが、また空気等の希釈
された形態で用いても差し支えない。Pure oxygen may be used as the oxygen source, but it may also be used in a diluted form such as air.
シクロヘキサノン類の転化率は任童に選び得るが、局転
化率では過度酸化生成物が増加する傾向にあり、例えば
ＳＯ％以下に留めると、目的とするオキソカルボン酸類
の選択率がよυ良好となる。The conversion rate of cyclohexanones can be arbitrarily selected, but excessive oxidation products tend to increase at local conversion rates.For example, if the conversion rate is kept below SO%, the selectivity of the target oxocarboxylic acids will be better. Become.
次に実施例によって本発明を史に具体的に：ｉｉｉ！明
するが、本発明はその要旨を越えない限り以下の実施例
に制約されるものではない。Next, the present invention will be explained in detail through examples: iii! However, the present invention is not limited to the following examples unless they go beyond the gist of the invention.
比較例
シクロヘキサノン／ ｆ （／ ０．２ミリモル）、水
／ ０．ｔ ｆ、無水塩化第二鉄θ、／に、ｒ ｙ （
／、θ−４−
ミリモル）の混合物を６０℃に加熱し、激しく撹拌し表
から、常圧で酸素を吸収させた。酸素の吸収量が約２８
９モルに到達したとき反応を停止し、生成物をガスクロ
マトグラフィーにより分析した。結果は次の通シであっ
た。Comparative example cyclohexanone/f (/0.2 mmol), water/0. t f, anhydrous ferric chloride θ, /to, r y (
/, θ-4-mmol) was heated to 60°C and stirred vigorously to absorb oxygen from the surface at normal pressure. The amount of oxygen absorbed is approximately 28
The reaction was stopped when 9 mol was reached and the products were analyzed by gas chromatography. The results were as follows.
（分） （％） （％）
６０ コｊ、タ ６７．７
実施例７〜！
比較例と同一の条件で各種無機イオウ化合物を表−／に
示す量添加して反応を行なわせた。(minute) (%) (%) 60 koj, ta 67.7
Example 7~! A reaction was carried out under the same conditions as in the comparative example by adding various inorganic sulfur compounds in the amounts shown in Table 1.
結果を表−／に示す。The results are shown in Table-/.
Claims (1)
るシクロヘキサノン類を、■水、■鉄化合物ならびに■
無機イオウ化合物の存在下、酸素によシ酸化することを
特徴とする一般式（ＩＩ） Ｂｏｏ（Ｏｎ、）４０００Ｈ・・・・・・・・・・（Ｉ
）（式中Ｒは一般式（１）のＲと同義である。）で表わ
されるオキソカルボン酸類の製造法(1) Cyclohexanones represented by the general formula (1) ) (in the formula, R represents hydrogen or an alkyl group) are mixed with ■water, ■iron compounds, and ■
General formula (II) Boo (On, ) 4000H (I
) (wherein R has the same meaning as R in general formula (1))
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57153069A JPS5942341A (en) | 1982-09-02 | 1982-09-02 | Preparation of oxocarboxylic acid |
| US06/475,646 US4649217A (en) | 1982-04-02 | 1983-03-15 | Process for producing oxocarboxylic acids |
| DE8383103186T DE3360258D1 (en) | 1982-04-02 | 1983-03-30 | A process for producing oxocarboxylic acids |
| EP83103186A EP0091091B1 (en) | 1982-04-02 | 1983-03-30 | A process for producing oxocarboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57153069A JPS5942341A (en) | 1982-09-02 | 1982-09-02 | Preparation of oxocarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5942341A true JPS5942341A (en) | 1984-03-08 |
Family
ID=15554301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57153069A Pending JPS5942341A (en) | 1982-04-02 | 1982-09-02 | Preparation of oxocarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5942341A (en) |
-
1982
- 1982-09-02 JP JP57153069A patent/JPS5942341A/en active Pending
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