JPH06211726A - Production of 2-cyclohexenone - Google Patents
Production of 2-cyclohexenoneInfo
- Publication number
- JPH06211726A JPH06211726A JP809293A JP809293A JPH06211726A JP H06211726 A JPH06211726 A JP H06211726A JP 809293 A JP809293 A JP 809293A JP 809293 A JP809293 A JP 809293A JP H06211726 A JPH06211726 A JP H06211726A
- Authority
- JP
- Japan
- Prior art keywords
- cyclohexenone
- cyclohexene
- chromium
- reaction
- compound
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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、シクロヘキセンを酸化
して、２−シクロヘキセノンを製造する方法に関するも
のである。TECHNICAL FIELD The present invention relates to a method for producing 2-cyclohexenone by oxidizing cyclohexene.
【０００２】２−シクロヘキセノンは、レゾルシン誘導
体やアミノフェノール誘導体への転換が可能であり、医
農薬の中間体として有用な化合物である。2-Cyclohexenone is a compound which can be converted into a resorcinol derivative or an aminophenol derivative and is useful as an intermediate for medicines and agricultural chemicals.
【０００３】[0003]
【従来の技術】従来、２−シクロヘキセノンの製造法と
しては、（Ａ）ＶＩＩＩ族の貴金属系触媒を用いシクロ
ヘキセンを酸素酸化し２−シクロヘキセノンとする方法
が知られている（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，８
９，４８０９（１９６７）およびＪ．Ａｍ．Ｃｈｅｍ．
Ｓｏｃ．，９０，４７４３（１９６８））。また、
（Ｂ）シクロヘキセンを酸素酸化し、２−シクロヘキセ
ンヒドロペルオキシドとした後、ヘキサフルオロアセト
ンなどの触媒により分解して２−シクロヘキセノンとす
る方法も知られている（特開昭５８−７２５３３号公
報）。2. Description of the Related Art Conventionally, as a method for producing 2-cyclohexenone, there has been known a method in which a cyclohexene is oxidized with oxygen using a noble metal catalyst of (A) Group VIII to give 2-cyclohexenone (J. Am. Chem. Soc., 8
9, 4809 (1967) and J. Am. Chem.
Soc. , 90, 4743 (1968)). Also,
(B) A method is also known in which cyclohexene is oxygen-oxidized to give 2-cyclohexene hydroperoxide, and then decomposed with a catalyst such as hexafluoroacetone to give 2-cyclohexenone (JP-A-58-72533). .
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、（Ａ）
の方法では副生成物として、シクロヘキセンオキシドや
シクロヘキセノールを生じ２−シクロヘキセノンへの選
択率は良くない。また、（Ｂ）の方法は、比較的２−シ
クロヘキセノンへの選択率は良いが、この方法では中間
体として経由する化学的に不安定な化合物である２−シ
クロヘキセンヒドロペルオキシドをいったん多量に製造
しなければならず、工業的に適した製造プロセスとはい
えない。[Problems to be Solved by the Invention] However, (A)
In the above method, cyclohexene oxide or cyclohexenol is produced as a by-product, and the selectivity to 2-cyclohexenone is not good. In addition, the method (B) has relatively good selectivity to 2-cyclohexenone, but in this method, a large amount of 2-cyclohexene hydroperoxide, which is a chemically unstable compound passing through as an intermediate, is once produced. However, this is not an industrially suitable manufacturing process.
【０００５】本発明者らは、シクロヘキセンの酸素酸化
による２−シクロヘキセノンの製造において、高い選択
率で２−シクロヘキセノンを得、しかも反応中間体とな
る２−シクロヘキセンヒドロペルオキシドを蓄積させず
に２−シクロヘキセノンを得る方法を提供することを目
的として鋭意研究した結果本発明に到達した。The present inventors obtained 2-cyclohexenone with a high selectivity in the production of 2-cyclohexenone by oxygen oxidation of cyclohexene, and further, without accumulating 2-cyclohexene hydroperoxide as a reaction intermediate, The present invention has been achieved as a result of extensive research aimed at providing a method for obtaining cyclohexenone.
【０００６】[0006]
【課題を解決するための手段】すなわち本発明は、シク
ロヘキセンを分子状酸素含有ガスにより酸化して２−シ
クロヘキセノンを製造する際、クロム系化合物を触媒と
し、かつ炭素数７以上のピリジン類の共存下で酸化を行
なうことを特徴とする２−シクロヘキセノンの製造方法
である。Means for Solving the Problems That is, according to the present invention, when cyclohexene is oxidized with a molecular oxygen-containing gas to produce 2-cyclohexenone, a chrome compound is used as a catalyst and a pyridine compound having 7 or more carbon atoms is used. A method for producing 2-cyclohexenone, which comprises performing oxidation in the coexistence.
【０００７】以下に、本発明の製造方法の特徴を詳細に
説明する。The features of the manufacturing method of the present invention will be described in detail below.
【０００８】本発明においてはクロム系化合物を触媒と
し、かつ炭素数７以上のピリジン類の共存下で酸化を行
なうことが重要である。In the present invention, it is important to carry out the oxidation using a chromium compound as a catalyst and in the presence of pyridines having 7 or more carbon atoms.
【０００９】本発明において触媒として用いられるクロ
ム系化合物としては、例えば、酸化クロム、塩化クロム
などの無機クロム化合物、有機酸クロム塩、β−ジケト
ンクロム錯塩などの有機クロム化合物などが挙げられ
る。また、ここでいうクロムとは、２価または３価のク
ロムであり、通常安定な３価を用いる場合が多い。無機
クロム化合物を用いれば反応は不均一系となり、有機ク
ロム化合物を用いれば反応は均一となるが、場合に応じ
て使い分けることができる。Examples of the chromium compound used as a catalyst in the present invention include inorganic chromium compounds such as chromium oxide and chromium chloride, organic acid chromium salts, and organic chromium compounds such as β-diketone chromium complex salts. The term "chromium" as used herein means divalent or trivalent chromium, and usually stable trivalent is often used. If an inorganic chromium compound is used, the reaction becomes heterogeneous, and if an organic chromium compound is used, the reaction becomes uniform, but it can be used properly depending on the case.
【００１０】触媒として用いられるクロム系化合物の使
用量については、クロムイオンとしてシクロへキセンに
対し０．０００１〜１ｗｔ％、好ましくは０．００１〜
０．５ｗｔ％が用いられる。The amount of the chromium compound used as the catalyst is 0.0001 to 1 wt%, preferably 0.001 to 1% by weight, relative to cyclohexene as chromium ions.
0.5 wt% is used.
【００１１】本発明に用いられる炭素数７以上のピリジ
ン類とは、例えばアルキル基、シクロアルキル基または
アリール基などが１以上置換された化合物であって、合
計の炭素数が７以上のピリジン類をいい、エチルピリジ
ンのように１種類の置換基が、ピリジンに１個置換した
化合物であっても、ルチジンのように１種類の置換基
が、ピリジンに複数置換した化合物であっても、２−メ
チル−５−エチルピリジンのように複数種の置換基が、
ピリジンに複数置換した化合物であっても良い。好まし
くは、合計の炭素数が、８〜11のピリジン類が良い。本
発明に用いられる炭素数７以上のピリジン類の好ましい
具体例としては、ルチジン、エチルピリジン、２−メチ
ル−５−エチルピリジン、２−プロピルピリジン、４−
プロピルピリジン、２−ペンチルピリジン、２−シクロ
ヘキシルピリジン、２−フェニルピリジン、４−フェニ
ルピリジンなどが挙げられる。The pyridines having 7 or more carbon atoms used in the present invention are, for example, compounds in which one or more alkyl groups, cycloalkyl groups or aryl groups are substituted, and pyridines having 7 or more carbon atoms in total. A compound in which one kind of substituent is substituted with one pyridine, such as ethylpyridine, or a compound in which one kind of substituent is plurally substituted with pyridine, such as lutidine, 2 A plurality of kinds of substituents such as -methyl-5-ethylpyridine,
A compound in which a plurality of pyridines are substituted may be used. Pyridines having a total carbon number of 8 to 11 are preferable. Specific preferred examples of pyridines having 7 or more carbon atoms used in the present invention include lutidine, ethylpyridine, 2-methyl-5-ethylpyridine, 2-propylpyridine and 4-.
Propyl pyridine, 2-pentyl pyridine, 2-cyclohexyl pyridine, 2-phenyl pyridine, 4-phenyl pyridine, etc. are mentioned.
【００１２】炭素数が７以上のピリジン類の使用量は、
通常、シクロヘキセンに対し０．０００１〜１０ｗｔ
％、好ましくは、０．０１〜５ｗｔ％が用いられる。The amount of pyridines having 7 or more carbon atoms is
Normally, 0.0001 to 10 wt% relative to cyclohexene
%, Preferably 0.01-5 wt%.
【００１３】本発明を実施するにあたってクロム系化合
物、炭素数７以上のピリジン類の添加方法にとくに制限
はなく、シクロヘキセンに、クロム系化合物とピリジン
類を混合しても良く、クロム系化合物とピリジン類の混
合物に、シクロヘキセンを添加しても良い。In carrying out the present invention, the method of adding the chromium compound and the pyridines having 7 or more carbon atoms is not particularly limited, and the chromium compound and the pyridine may be mixed with cyclohexene. Cyclohexene may be added to the mixture of classes.
【００１４】酸化剤として用いる分子状酸素含有ガスと
しては、純酸素や工業排ガスも使用可能であるが、工業
的には通常の空気が最適である。分子状酸素含有ガスの
通気量は、分子状酸素／シクロヘキセンのモル比０．０
１〜１０の範囲が適当である。 反応温度は、通常、０
〜１００℃が適用されるが、好ましくは２０〜７０℃の
範囲で行われる。As the molecular oxygen-containing gas used as the oxidizing agent, pure oxygen and industrial exhaust gas can be used, but industrially normal air is most suitable. The gas permeation amount of the molecular oxygen-containing gas has a molar ratio of molecular oxygen / cyclohexene of 0.0.
A range of 1-10 is suitable. The reaction temperature is usually 0
~ 100 ° C is applied, but preferably in the range of 20-70 ° C.
【００１５】反応圧力は、通常、常圧〜２０ｋｇ／ｃｍ
２で行われる。The reaction pressure is usually atmospheric pressure to 20 kg / cm.
Done in 2 .
【００１６】反応時間は、通常、０．５〜２０時間、ま
たは連続的に反応を行うことも可能であるが、好ましく
は１〜１０時間の範囲で行われる。The reaction time is usually 0.5 to 20 hours, or it is possible to carry out the reaction continuously, but the reaction time is preferably 1 to 10 hours.
【００１７】かくして得られた反応混合物を蒸留するこ
とにより２−シクロヘキセノンを単離することができ
る。2-Cyclohexenone can be isolated by distilling the reaction mixture thus obtained.
【００１８】[0018]
【作用】シクロヘキセンを分子状酸素含有ガスにより酸
化して、２−シクロヘキセノンを製造するにあたり、ク
ロム系化合物を触媒として、添加剤としてピリジンに、
アルキル基、シクロアルキル基、アリール基などが、１
以上置換された化合物で、合計の炭素数が７以上のピリ
ジン類を添加することにより、２−シクロヘキセノン以
外の副生物の精製を押さえ、さらに、中間体の２−シク
ロヘキセンヒドロペルオキシドが多量に蓄積すること無
く、２−シクロヘキセノンを製造することを可能とした
ものである。[Function] In the production of 2-cyclohexenone by oxidizing cyclohexene with a gas containing molecular oxygen, a chromium compound is used as a catalyst and pyridine is used as an additive.
Alkyl group, cycloalkyl group, aryl group, etc. are 1
By adding pyridines having a total carbon number of 7 or more in the above substituted compounds, the purification of by-products other than 2-cyclohexenone is suppressed, and a large amount of intermediate 2-cyclohexene hydroperoxide is accumulated. It is possible to produce 2-cyclohexenone without doing so.
【００１９】本発明の化学的な反応を説明すると、シク
ロヘキセンを分子状酸素含有ガスにより酸化することよ
り、２−シクロヘキセンヒドロペルオキシドが生成す
る。しかし、生成する２−シクロヘキセンヒドロペルオ
キシドは、クロム系化合物と炭素数７以上のピリジン類
により、速やかに分解し２−シクロヘキセノンとなり、
化学的に不安定な２−シクロヘキセンヒドロペルオキシ
ドの蓄積は起こらない。To describe the chemical reaction of the present invention, 2-cyclohexene hydroperoxide is produced by oxidizing cyclohexene with a molecular oxygen-containing gas. However, the produced 2-cyclohexene hydroperoxide is rapidly decomposed into 2-cyclohexenone by the chromium compound and the pyridines having 7 or more carbon atoms,
Accumulation of chemically unstable 2-cyclohexene hydroperoxide does not occur.
【００２０】[0020]
【実施例】以下に実施例を挙げて本発明をさらに詳細に
説明するが、本発明はこれに限定されるものではない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
【００２１】実施例１ １００ｍｌ溶三口フラスコに、シクロヘキセン５０ｇ、
３％ナフテン酸クロム（ＩＩＩ）１．６７ｇ（クロムと
して、シクロヘキセンに対し、０．１ｗｔ％）、２−メ
チル−５−エチルピリジン０．５ｇを添加し、液中に酸
素を３７ｍｌ／ｍｉｎ、（０．１ｍｏｌ／ｈｒ）で通気
撹拌した。反応温度を２０℃に保ち、６時間後反応液の
組成をガスクロマトグラフにて調べた。その結果を表１
に示す。Example 1 50 g of cyclohexene was added to a 100 ml melting three-necked flask.
1.67 g of 3% chromium (III) naphthenate (0.1 wt% as chromium relative to cyclohexene) and 0.5 g of 2-methyl-5-ethylpyridine were added, and oxygen was added to the solution at 37 ml / min, ( It was aerated and stirred at 0.1 mol / hr). The reaction temperature was kept at 20 ° C., and after 6 hours, the composition of the reaction solution was examined by gas chromatography. The results are shown in Table 1.
Shown in.
【００２２】実施例２ 反応温度を６０℃にした以外は、実施例１と同様に反応
を行った。その結果を表１に示す。Example 2 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 60 ° C. The results are shown in Table 1.
【００２３】比較例１ ２−メチル−５−エチルピリジンを添加せずに実施例１
と同様に反応を行った。その結果を表１に示す。Comparative Example 1 Example 1 without the addition of 2-methyl-5-ethylpyridine
The reaction was performed in the same manner as in. The results are shown in Table 1.
【００２４】比較例２ ２−メチル−５−エチルピリジンの代わりに、ピリジン
０．５ｇを添加し実施例２と同様に反応を行った。その
結果を表１に示す。Comparative Example 2 Instead of 2-methyl-5-ethylpyridine, 0.5 g of pyridine was added and the reaction was carried out in the same manner as in Example 2. The results are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】本発明により、高い選択率で２−シクロ
ヘキセノンを得、しかも反応中間体となる２−シクロヘ
キセンヒドロペルオキシドを蓄積させずに２−シクロヘ
キセノンを得ることができた。INDUSTRIAL APPLICABILITY According to the present invention, 2-cyclohexenone can be obtained with a high selectivity and without accumulating 2-cyclohexene hydroperoxide as a reaction intermediate.
Claims (1)
より酸化して２−シクロヘキセノンを製造する際、クロ
ム系化合物を触媒とし、かつ炭素数７以上のピリジン類
の共存下で酸化を行なうことを特徴とする２−シクロヘ
キセノンの製造方法。1. A method for producing 2-cyclohexenone by oxidizing cyclohexene with a gas containing molecular oxygen, wherein oxidation is performed in the coexistence of a pyridine compound having a carbon number of 7 or more with a chromium compound as a catalyst. And a method for producing 2-cyclohexenone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP809293A JPH06211726A (en) | 1993-01-21 | 1993-01-21 | Production of 2-cyclohexenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP809293A JPH06211726A (en) | 1993-01-21 | 1993-01-21 | Production of 2-cyclohexenone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06211726A true JPH06211726A (en) | 1994-08-02 |
Family
ID=11683681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP809293A Pending JPH06211726A (en) | 1993-01-21 | 1993-01-21 | Production of 2-cyclohexenone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06211726A (en) |
-
1993
- 1993-01-21 JP JP809293A patent/JPH06211726A/en active Pending
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