JP2002145872A - Method of manufacturing epoxy compound - Google Patents
Method of manufacturing epoxy compoundInfo
- Publication number
- JP2002145872A JP2002145872A JP2000334966A JP2000334966A JP2002145872A JP 2002145872 A JP2002145872 A JP 2002145872A JP 2000334966 A JP2000334966 A JP 2000334966A JP 2000334966 A JP2000334966 A JP 2000334966A JP 2002145872 A JP2002145872 A JP 2002145872A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- hydrogen peroxide
- reaction
- pyrophosphate
- epoxy 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
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- Epoxy Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、オレフィン化合物
を原料とするエポキシ化合物の製造方法に関するもので
ある。更に詳しくは、本発明は、オレフィン化合物と過
酸化水素をニトリル化合物の存在下に反応させることに
より、高価な触媒を使用せず、オレフィン化合物と過酸
化水素を効率良く使用することを可能とした、経済的な
エポキシ化合物の製造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing an epoxy compound using an olefin compound as a raw material. More specifically, the present invention makes it possible to use an olefin compound and hydrogen peroxide efficiently by reacting an olefin compound and hydrogen peroxide in the presence of a nitrile compound without using an expensive catalyst. And an economical method for producing an epoxy compound.
【０００２】[0002]
【従来の技術】従来より、選択率の高いエポキシ化合物
の製造方法としては、触媒に遷移金属ポリフィリン化合
物（特開昭６３−２５５２７２号公報）、アンチモン化
合物（特開昭５８−３９６７６号公報）、セレン化合物
（特開昭５９−７６０７７号公報）やチタン化合物（特
公昭５６−３５９４１号公報）等を用いる方法が提案さ
れているが、このような従来の製造方法には、前記触媒
が高価であったり、助触媒が必要であったり、更には有
害な廃棄物が発生するなど、多くの問題があった。2. Description of the Related Art Conventionally, methods for producing an epoxy compound having a high selectivity include a transition metal porphyrin compound (JP-A-63-255272), an antimony compound (JP-A-58-39676), and a catalyst. A method using a selenium compound (JP-A-59-76077), a titanium compound (JP-B-56-35941) and the like has been proposed. However, such a conventional production method requires an expensive catalyst. There were many problems such as the presence of a cocatalyst and the generation of harmful waste.
【０００３】また、過酸化水素とニトリル化合物を用い
るエポキシ化合物の製造方法としては、Ｐａｙｎｅ酸化
による方法が有名である（Ｊ．Ｏｒｇ．Ｃｈｅｍ．１９
６８．ｖｏｌ．２６，ｐ６６０）が、この方法には、過
酸化水素を反応の進行に合わせて継続的に添加する必要
がある等の不便があった。更には、オレフィン化合物と
過酸化水素をニトリル化合物とアルカリ金属塩の存在下
で反応させる方法（特開平７−２０６８３５号公報）が
提案されていて、この方法では最高収率７１％でエポキ
シ化合物を製造することができるとされるが、オレフィ
ン化合物に対して大量の過酸化水素を必要とするため、
経済的とは言い難いという問題があった。As a method for producing an epoxy compound using hydrogen peroxide and a nitrile compound, a method using Payne oxidation is famous (J. Org. Chem. 19).
68. vol. 26, p660), but this method has inconvenience such as the need to continuously add hydrogen peroxide as the reaction proceeds. Furthermore, a method has been proposed in which an olefin compound and hydrogen peroxide are reacted with a nitrile compound in the presence of an alkali metal salt (JP-A-7-206835). In this method, an epoxy compound is produced at a maximum yield of 71%. It is said that it can be produced, but requires a large amount of hydrogen peroxide for olefin compounds,
There was a problem that it was hardly economical.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、上記
のようなオレフィン化合物と過酸化水素からニトリル化
合物の存在下でエポキシ化合物を製造する方法であっ
て、高価な触媒を使用することなく、オレフィン化合物
と過酸化水素とを効率的に反応させることができ、しか
も安全で経済的なエポキシ化合物の製造方法を提供する
ことにある。An object of the present invention is to provide a method for producing an epoxy compound from the above-mentioned olefin compound and hydrogen peroxide in the presence of a nitrile compound without using an expensive catalyst. Another object of the present invention is to provide a safe and economical method for producing an epoxy compound which can efficiently react an olefin compound with hydrogen peroxide.
【０００５】[0005]
【発明が解決しようとする手段】本発明者らは、上記本
発明の目的を達成すべく鋭意検討した結果、オレフィン
化合物と過酸化水素を、ニトリル化合物の存在下、所定
の成分を含有する水溶液中で反応させると、高価な触媒
を使用しないで、当該反応が効率的に行われ、エポキシ
化合物が高選択的に得られることを見い出し、本発明を
完成した。The present inventors have conducted intensive studies to achieve the above object of the present invention. As a result, an olefin compound and hydrogen peroxide were dissolved in an aqueous solution containing a predetermined component in the presence of a nitrile compound. When the reaction was carried out in an aqueous solution, it was found that the reaction was carried out efficiently without using an expensive catalyst, and an epoxy compound was obtained with high selectivity, thereby completing the present invention.
【０００６】即ち、本発明の要旨は、オレフィン化合物
と過酸化水素を、ニトリル化合物存在下に、ピロリン酸
塩−ピロリン酸水溶液中で反応させることを特徴とする
エポキシ化合物の製造方法に存する。That is, the gist of the present invention resides in a method for producing an epoxy compound, comprising reacting an olefin compound with hydrogen peroxide in the presence of a nitrile compound in a pyrophosphate-pyrophosphate aqueous solution.
【０００７】[0007]
【発明の実施の形態】以下、本発明のエポキシ化合物の
製造方法について、更に詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the method for producing an epoxy compound of the present invention will be described in more detail.
【０００８】本発明によりエポキシ化合物を製造するた
めの原料として使用されるオレフィン化合物としては、
特に限定されないが、例えば、プロピレン、１−ブテ
ン、ｔ−２−ブテン、ｃ−２−ブテン、１−ペンテン、
イソペンテン、シクロペンテン、１−ヘキセン、２−ヘ
キセン、シクロヘキセン、ノルボルネン、１−オクテン
等の炭素数３〜１５のモノオレフィン化合物、又は、ブ
タジエン、ｔ−１，３−ペンタジエン、ｃ−１，３−ペ
ンタジエン、シクロペンタジエン、シクロヘキサジエ
ン、ノルボルナジエン、シクロオクタジエン、ビニルシ
クロヘキセン等の炭素数３〜１５のポリオレフィン化合
物、ポリエステルやポリイミド等の分子内に炭素−炭素
二重結合を有するポリマー等を挙げることができる。The olefin compound used as a raw material for producing an epoxy compound according to the present invention includes:
Although not particularly limited, for example, propylene, 1-butene, t-2-butene, c-2-butene, 1-pentene,
Monoolefin compounds having 3 to 15 carbon atoms such as isopentene, cyclopentene, 1-hexene, 2-hexene, cyclohexene, norbornene, 1-octene, or butadiene, t-1,3-pentadiene, c-1,3-pentadiene And polyolefin compounds having 3 to 15 carbon atoms such as cyclopentadiene, cyclohexadiene, norbornadiene, cyclooctadiene, and vinylcyclohexene; and polymers having a carbon-carbon double bond in the molecule such as polyester and polyimide.
【０００９】本発明において、上記オレフィン化合物と
の反応に供される過酸化水素は、通常、市販されている
２０〜７０％水溶液を用いることができる。In the present invention, a commercially available 20 to 70% aqueous solution can be used as the hydrogen peroxide to be subjected to the reaction with the olefin compound.
【００１０】上記過酸化水素の使用量は、オレフィン化
合物に対して、例えば０．０５〜１０倍モル、特に０．
１〜１．０倍モルとすることが、過酸化水素の効率的使
用の面から好ましい。The amount of the hydrogen peroxide to be used is, for example, 0.05 to 10 times, especially 0.1 to 10 times the mol of the olefin compound.
The molar ratio is preferably 1 to 1.0 times from the viewpoint of efficient use of hydrogen peroxide.
【００１１】本発明において、上記オレフィン化合物と
過酸化水素はニトリル化合物の存在下に反応するもので
あり、このようなニトリル化合物としては、アセトニト
リル、プロピオニトリル、ベンゾニトリル等が用いら
れ、特にアセトニトリルが入手容易であることから好ま
しい。尚、ニトリル化合物の使用量は限定されないが、
過酸化水素に対して、例えば１〜５０倍モル、特に１〜
１０倍モルであることが好ましく、この範囲を大きく外
れると、反応速度が低下するおそれがある。In the present invention, the olefin compound and hydrogen peroxide react in the presence of a nitrile compound. As such a nitrile compound, acetonitrile, propionitrile, benzonitrile and the like are used. Is preferred because it is easily available. The amount of the nitrile compound used is not limited,
For example, 1 to 50 times mol, particularly
The molar ratio is preferably 10-fold, and if it is largely out of this range, the reaction rate may decrease.
【００１２】上記反応における溶媒としては、ニトリル
化合物が溶媒を兼ねることができるので、別途に溶媒を
使用することは必須ではないが、必要に応じてアルコー
ル類、芳香族炭化水素類、塩素化炭化水素類等を用いる
こともできる。As a solvent in the above reaction, it is not essential to use a separate solvent since a nitrile compound can also serve as a solvent. However, alcohols, aromatic hydrocarbons, chlorinated carbon Hydrogens and the like can also be used.
【００１３】上記溶媒としては、例えば、メタノール、
エタノール、イソプロパノール、ｎ−ブタノール、ｔ−
ブタノール、ｔ−アミルアルコール、シクロヘキサノー
ル等の炭素数１〜６の直鎖、分岐、環状アルコール等の
アルコール類；ベンゼン、トルエン、キシレン等の芳香
族炭化水素類；又は、塩化メチレン、１、２−ジクロロ
メタン、クロロホルム、四塩化炭素等の塩素化炭化水素
類等を挙げることができる。As the solvent, for example, methanol,
Ethanol, isopropanol, n-butanol, t-
Alcohols having 1 to 6 carbon atoms such as linear, branched and cyclic alcohols such as butanol, t-amyl alcohol and cyclohexanol; aromatic hydrocarbons such as benzene, toluene and xylene; or methylene chloride, 1, 2 -Chlorinated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride.
【００１４】これらの溶媒を使用する場合、その使用量
はオレフィン化合物に対して、例えば０．１〜５０倍モ
ルであり、特に０．５〜１０倍モルであることが好まし
い。When these solvents are used, the amount of the solvent used is, for example, 0.1 to 50 times, preferably 0.5 to 10 times the mol of the olefin compound.
【００１５】而して、本発明のエポキシ化合物の製造方
法では、上記説明したオレフィン化合物と過酸化水素
を、ニトリル化合物存在下に反応させるに際し、この反
応をピロリン酸塩−ピロリン酸水溶液中で行うことを特
徴とするものである。According to the method for producing an epoxy compound of the present invention, when the above-described olefin compound and hydrogen peroxide are reacted in the presence of a nitrile compound, this reaction is carried out in a pyrophosphate-pyrophosphate aqueous solution. It is characterized by the following.
【００１６】上記ピロリン酸塩−ピロリン酸水溶液は、
ニトリル化合物と共存させることによって、従来のオレ
フィン化合物と過酸化水素をニトリル化合物の存在下の
反応で必要とされていたアルコール溶媒の使用や、水の
使用量を極力減らしたりすることを不必要とし、また、
生成するエポキシ化合物と当量のアミドが生成するとさ
れているＰａｙｎｅ酸化と比べて、反応後にニトリル化
合物から生成するアミドの量を極めて少なくし、オレフ
ィン化合物と過酸化水素を効率良く反応させることを可
能とするものである。The pyrophosphate-pyrophosphate aqueous solution is
By coexisting with the nitrile compound, it is not necessary to use an alcohol solvent or reduce the amount of water used as much as required in the reaction of the conventional olefin compound and hydrogen peroxide in the presence of the nitrile compound. ,Also,
Compared with the Payne oxidation, which is said to produce an equivalent amount of amide with the epoxy compound to be produced, the amount of amide produced from the nitrile compound after the reaction is extremely small, making it possible to efficiently react the olefin compound with hydrogen peroxide. Is what you do.
【００１７】本発明で使用するピロリン酸塩としては、
例えば、ピロリン酸カリウム、ピロリン酸ナトリウム等
のピロリン酸アルカリ金属塩やピロリン酸アンモニウム
塩を挙げることができ、特にピロリン酸カリウムが好ま
しい。The pyrophosphate used in the present invention includes:
For example, alkali metal salts of pyrophosphate such as potassium pyrophosphate and sodium pyrophosphate and ammonium pyrophosphate can be mentioned, and potassium pyrophosphate is particularly preferable.
【００１８】上記反応においては、反応系のｐＨにより
ェポキシ化合物の収率と選択率が影響され、中でも収率
は、反応系のｐＨが７．５〜１０．５、特に８．０〜
９．５であることが好ましい。ｐＨが７．５未満では、
ェポキシ化合物が加水分解してアルコールを生じ、逆に
ｐＨ１０．５を超えると反応自体が進みにくく、何れも
エポキシ化合物の収率が低くなり、選択率も下がって生
産性が極めて悪くなる。In the above reaction, the yield of the epoxy compound and the selectivity are affected by the pH of the reaction system, and the yield is preferably from 7.5 to 10.5, particularly from 8.0 to 8.0.
It is preferably 9.5. If the pH is less than 7.5,
When the epoxy compound is hydrolyzed to produce alcohol, and conversely, when the pH exceeds 10.5, the reaction itself does not easily proceed, and in any case, the yield of the epoxy compound decreases, the selectivity decreases, and the productivity becomes extremely poor.
【００１９】尚、反応系のｐＨは、ピロリン酸塩と併用
するピロリン酸との配合比率によって、調整することが
でき、この他、反応速度を高めるためにアルキルスルホ
ン酸アルカリ金属塩等の界面活性剤を使用しても良い。The pH of the reaction system can be adjusted by adjusting the mixing ratio of pyrophosphate and pyrophosphoric acid to be used in combination. An agent may be used.
【００２０】本発明のエポキシ化合物の製造方法では、
上記の各原料を反応器に同時に投入しても良いし、任意
の順序で投入しても良い。特に、過酸化水素は一度に加
えても、反応の進行と平行して断続的にまたは継続的に
加えても良い。In the method for producing an epoxy compound of the present invention,
The above-mentioned raw materials may be simultaneously charged into the reactor, or may be charged in an arbitrary order. In particular, hydrogen peroxide may be added all at once, or intermittently or continuously in parallel with the progress of the reaction.
【００２１】上記反応系における各原料の濃度として
は、オレフィン化合物に対して、例えば、過酸化水素
０．０５〜１０倍モル（特に０．１〜１．０倍モル）、
ニトリル化合物０．０５〜５００倍モル（特に０．０５
〜１００倍モル）［過酸化水素に対して１〜５０倍モル
（特に１〜１０倍モル）］、ピロリン酸塩−ピロリン酸
０．１〜１００倍モル（特に０．１〜１０倍モル）であ
ることが好ましい。The concentration of each raw material in the above-mentioned reaction system is, for example, 0.05 to 10 times mol (particularly 0.1 to 1.0 times mol) of hydrogen peroxide with respect to the olefin compound.
Nitrile compound 0.05 to 500-fold molar (particularly 0.05
1 to 50 times mol (especially 1 to 10 times mol) relative to hydrogen peroxide], pyrophosphate-pyrophosphoric acid 0.1 to 100 times mol (especially 0.1 to 10 times mol) It is preferred that
【００２２】また、上記エポキシ化合物を得るための反
応は、液相中、大気圧下で行うことができるが、オレフ
ィン化合物がガス状である場合は、それを液相中に溶解
させるのに十分な圧力を保つことが好ましい。尚、反応
温度は０℃〜９０℃、特に２０℃〜７０℃であることが
好ましく、反応時間は１〜１００時間、特に６〜５０時
間であることが好ましい。The reaction for obtaining the epoxy compound can be carried out in a liquid phase at atmospheric pressure. However, when the olefin compound is in a gaseous state, it is sufficient to dissolve it in the liquid phase. It is preferable to maintain an appropriate pressure. The reaction temperature is preferably 0 ° C to 90 ° C, particularly preferably 20 ° C to 70 ° C, and the reaction time is preferably 1 to 100 hours, particularly preferably 6 to 50 hours.
【００２３】反応終了後は、有機相を回収し、目的のエ
ポキシ化合物を公知の方法で精製することができるが、
本発明のエポキシ化合物の製造方法では、反応後にニト
リル化合物から生成するアミドの量が極めて少ないため
に、この後、新たに過酸化物とオレフィン化合物を追加
するだけで、水相はそのまま再利用することが可能であ
る。After completion of the reaction, the organic phase is recovered, and the desired epoxy compound can be purified by a known method.
In the method for producing an epoxy compound of the present invention, since the amount of amide generated from the nitrile compound after the reaction is extremely small, the aqueous phase is reused as it is only by newly adding a peroxide and an olefin compound. It is possible.
【００２４】このように、本発明のエポキシ化合物の製
造方法は、オレフィン化合物と過酸化水素を、ニトリル
化合物存在下に、ピロリン酸塩−ピロリン酸水溶液中で
反応させることにより実施されるものであり、本発明に
よれば、典型的なエポキシ化合物を選択率７５％以上で
製造することができる。As described above, the method for producing an epoxy compound of the present invention is carried out by reacting an olefin compound with hydrogen peroxide in an aqueous solution of pyrophosphate and pyrophosphate in the presence of a nitrile compound. According to the present invention, a typical epoxy compound can be produced with a selectivity of 75% or more.
【００２５】[0025]
【実施例】以下に本発明を実施例によって詳細に説明す
るが、本発明はこれら実施例に限定されるものではな
い。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
【００２６】実施例１ 反応容器にピロリン酸カリウム６０１ｍｇ、ピロリン酸
３２．４ｍｇ、過酸化水素１１３ｍｇ、水４．０ｇ、ア
セトニトリル６．０ｇ、４−ビニルシクロヘキセン２．
１６ｇ、ドデシルスルホン酸ナトリウム２５ｍｇを入
れ、２０℃で２４時間撹拌した。反応時ｐＨは８．８７
であった。反応終了後、ガスクロマト分析を行ったとこ
ろ、４−ビニルシクロヘキセン−１，２−エポキシドの
過酸化水素基準の収率は５６％、選択率は９２％であっ
た。このとき反応系にはアセトアミドが生成したが、過
酸化水素基準の収率は６．１％と少なく、アミドがエポ
キシ化合物と当量生成するとされるＰａｙｎｅ酸化とは
異なる反応であることがわかった。Example 1 In a reaction vessel, 601 mg of potassium pyrophosphate, 32.4 mg of pyrophosphoric acid, 113 mg of hydrogen peroxide, 4.0 g of water, 6.0 g of acetonitrile, 4-vinylcyclohexene 2.
16 g and 25 mg of sodium dodecylsulfonate were added and stirred at 20 ° C. for 24 hours. During the reaction, the pH was 8.87.
Met. After completion of the reaction, gas chromatographic analysis showed that the yield of 4-vinylcyclohexene-1,2-epoxide based on hydrogen peroxide was 56% and the selectivity was 92%. At this time, acetamide was produced in the reaction system, but the yield based on hydrogen peroxide was as low as 6.1%, and it was found that the reaction was different from Payne oxidation in which amide was produced in an equivalent amount to the epoxy compound.
【００２７】実施例２ 反応温度を６０℃としたこと以外は実施例１と同じ条件
で反応を行った。過酸化水素基準の収率は７９％、選択
率は８５％であった。Example 2 A reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 60 ° C. The yield based on hydrogen peroxide was 79%, and the selectivity was 85%.
【００２８】実施例３ 反応時ｐＨを１０．３６としたこと以外は実施例１と同
じ条件で反応を行った。過酸化水素基準の収率は２１
％、選択率は９３％であった。Example 3 The reaction was carried out under the same conditions as in Example 1 except that the pH during the reaction was 10.36. The yield based on hydrogen peroxide is 21.
% And selectivity was 93%.
【００２９】実施例４ 反応時ｐＨを９．８４としたこと以外は実施例１と同じ
条件で反応を行った。過酸化水素基準の収率は３６％、
選択率は８６％であった。Example 4 The reaction was carried out under the same conditions as in Example 1 except that the pH during the reaction was 9.84. The yield based on hydrogen peroxide is 36%,
The selectivity was 86%.
【００３０】実施例５ 反応時ｐＨを９．３２としたこと以外は実施例１と同じ
条件で反応を行った。過酸化水素基準の収率は５１％、
選択率は８４％であった。Example 5 A reaction was carried out under the same conditions as in Example 1 except that the pH during the reaction was changed to 9.32. The yield based on hydrogen peroxide is 51%,
The selectivity was 84%.
【００３１】実施例６ 反応時ｐＨを９．１９としたこと以外は実施例１と同じ
条件で反応を行った。過酸化水素基準の収率は５１％、
選択率は８７％であった。Example 6 The reaction was carried out under the same conditions as in Example 1 except that the pH during the reaction was 9.19. The yield based on hydrogen peroxide is 51%,
The selectivity was 87%.
【００３２】実施例７ 反応時ｐＨを９．０７としたこと以外は実施例１と同じ
条件で反応を行った。過酸化水素基準の収率は５６％、
選択率は８８％であった。Example 7 A reaction was carried out under the same conditions as in Example 1 except that the pH during the reaction was set to 9.07. The yield based on hydrogen peroxide is 56%,
The selectivity was 88%.
【００３３】実施例８ 反応時ｐＨを８．７７としたこと以外は実施例１と同じ
条件で反応を行った。過酸化水素基準の収率は５５％、
選択率は８８％であった。Example 8 A reaction was carried out under the same conditions as in Example 1 except that the pH during the reaction was 8.77. The yield based on hydrogen peroxide is 55%,
The selectivity was 88%.
【００３４】実施例９ 反応時ｐＨを８．３５としたこと以外は実施例１と同じ
条件で反応を行った。過酸化水素基準の収率は３６％、
選択率は８１％であった。Example 9 The reaction was carried out under the same conditions as in Example 1 except that the pH during the reaction was 8.35. The yield based on hydrogen peroxide is 36%,
The selectivity was 81%.
【００３５】実施例１０ 反応時ｐＨを７．９９としたこと以外は実施例１と同じ
条件で反応を行った。過酸化水素基準の収率は２９％、
選択率は８５％であった。Example 10 The reaction was carried out under the same conditions as in Example 1 except that the pH during the reaction was 7.99. The yield based on hydrogen peroxide is 29%,
The selectivity was 85%.
【００３６】実施例１１ ４−ビニルシクロヘキセンの代わりに１−オクテン２．
２４ｇを使用したこと以外は実施例１と同じ条件で反応
を行った。オクテン−１，２−エポキシドの過酸化水素
基準の収率は２９％、選択率は８５％であった。Example 11 1-octene in place of 4-vinylcyclohexene
The reaction was carried out under the same conditions as in Example 1 except that 24 g was used. The yield of octene-1,2-epoxide based on hydrogen peroxide was 29%, and the selectivity was 85%.
【００３７】実施例１２ ４−ビニルシクロヘキセンの代わりにｔ−２−ブテン
１．１２ｇを使用したこと以外は実施例１と同じ条件で
反応を行った。ｔ−２−ブテン−２，３−エポキシドの
過酸化水素基準の収率は３９％、選択率は８２％であっ
た。Example 12 A reaction was carried out under the same conditions as in Example 1 except that 1.12 g of t-2-butene was used instead of 4-vinylcyclohexene. The yield of t-2-butene-2,3-epoxide based on hydrogen peroxide was 39%, and the selectivity was 82%.
【００３８】実施例１３ ４−ビニルシクロヘキセンの代わりに１−ブテン１．１
２ｇを使用したこと以外は実施例１と同じ条件で反応を
行った。ブテン−１，２−エポキシドの過酸化水素基準
の収率は３１％、選択率は８１％であった。Example 13 1-butene 1.1 instead of 4-vinylcyclohexene
The reaction was carried out under the same conditions as in Example 1 except that 2 g was used. The yield of butene-1,2-epoxide based on hydrogen peroxide was 31%, and the selectivity was 81%.
【００３９】実施例１４ 実施例１３の反応終了後、有機相を回収したのち、過酸
化水素と１−ブテンを実施例１３と同量となるように補
充したのち、実施例１３と同じ条件で再び反応を行っ
た。新たに生成したブテン−１，２−エポキシドの過酸
化水素基準の収率は３６％、選択率は８３％であった。Example 14 After completion of the reaction of Example 13, the organic phase was recovered, and hydrogen peroxide and 1-butene were replenished to the same amounts as in Example 13. The reaction was performed again. The yield of newly formed butene-1,2-epoxide based on hydrogen peroxide was 36%, and the selectivity was 83%.
【００４０】比較例１ ピロリン酸カリウムおよびピロリン酸を使用しないこと
以外は実施例１と同じ条件で反応を行った。４−ビニル
シクロヘキセン−１，２−エポキシドの過酸化水素基準
の収率は０％であった。Comparative Example 1 A reaction was carried out under the same conditions as in Example 1 except that potassium pyrophosphate and pyrophosphoric acid were not used. The yield based on hydrogen peroxide of 4-vinylcyclohexene-1,2-epoxide was 0%.
【００４１】比較例２ アセトニトリルの代わりにメタノールを使用したこと以
外は実施例１と同じ条件で反応を行った。４−ビニルシ
クロヘキセン−１，２−エポキシドの過酸化水素基準の
収率は０％であった。Comparative Example 2 A reaction was carried out under the same conditions as in Example 1 except that methanol was used instead of acetonitrile. The yield based on hydrogen peroxide of 4-vinylcyclohexene-1,2-epoxide was 0%.
【００４２】上記実施例及び比較例から明らかなよう
に、本発明によれば、高価な触媒を使用せず、オレフィ
ン化合物と過酸化水素とを効率的に反応させることがで
き、目的のエポキシ化合物を高選択的に得ることができ
た。また、本発明は、アルコール溶媒や水の使用量に対
する配慮を必要とせず、しかも反応後にニトリル化合物
から生成するアミドの量はごく僅かであり、前述のＰａ
ｙｎｅ酸化とは異なる新規な反応であることがわかる。As is clear from the above Examples and Comparative Examples, according to the present invention, an olefin compound and hydrogen peroxide can be efficiently reacted without using an expensive catalyst, and the desired epoxy compound Was obtained with high selectivity. Further, the present invention does not require consideration for the amount of alcohol solvent or water used, and the amount of amide generated from the nitrile compound after the reaction is very small.
It turns out that it is a novel reaction different from yne oxidation.
【００４３】[0043]
【発明の効果】本発明によれば、オレフィン化合物と過
酸化水素を、ニトリル化合物の存在下、ピロリン酸塩−
ピロリン酸水溶液中で反応させることで、オレフィン化
合物と過酸化水素とを効率的に使用することが可能で、
しかもエポキシ化合物を安全で経済的且つ効率的に得る
ことができ、加えて、反応後にニトリル化合物から生成
するアミドの量が極めて少ないために、ピロリン酸塩−
ピロリン酸水溶液はそのまま再利用が可能である。According to the present invention, an olefin compound and hydrogen peroxide are reacted with a pyrophosphate salt in the presence of a nitrile compound.
By reacting in a pyrophosphoric acid aqueous solution, it is possible to use the olefin compound and hydrogen peroxide efficiently,
In addition, the epoxy compound can be obtained safely, economically and efficiently, and in addition, the amount of amide generated from the nitrile compound after the reaction is extremely small, so that the pyrophosphate-
The aqueous pyrophosphoric acid solution can be reused as it is.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１３年１月９日（２００１．１．９）[Submission date] January 9, 2001 (2001.1.9)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００３[Correction target item name] 0003
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００３】また、過酸化水素とニトリル化合物を用い
るエポキシ化合物の製造方法としては、Ｐａｙｎｅ酸化
による方法が有名である（Ｊ．Ｏｒｇ．Ｃｈｅｍ．１９
６４．ｖｏｌ．２６，ｐ６６０）が、この方法には、過
酸化水素を反応の進行に合わせて継続的に添加する必要
がある等の不便があった。更には、オレフィン化合物と
過酸化水素をニトリル化合物とアルカリ金属塩の存在下
で反応させる方法（特開平７−２０６８３５号公報）が
提案されていて、この方法では最高収率７１％でエポキ
シ化合物を製造することができるとされるが、オレフィ
ン化合物に対して大量の過酸化水素を必要とするため、
経済的とは言い難いという問題があった。As a method for producing an epoxy compound using hydrogen peroxide and a nitrile compound, a method using Payne oxidation is famous (J. Org. Chem. 19).
6 4. vol. 26, p660), but this method has inconvenience such as the need to continuously add hydrogen peroxide as the reaction proceeds. Furthermore, a method has been proposed in which an olefin compound and hydrogen peroxide are reacted with a nitrile compound in the presence of an alkali metal salt (JP-A-7-206835). In this method, an epoxy compound is produced at a maximum yield of 71%. It is said that it can be produced, but requires a large amount of hydrogen peroxide for olefin compounds,
There was a problem that it was hard to say that it was economical.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２３[Correction target item name] 0023
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２３】反応終了後は、有機相を回収し、目的のエ
ポキシ化合物を公知の方法で精製することができるが、
本発明のエポキシ化合物の製造方法では、反応後にニト
リル化合物から生成するアミドの量が極めて少ないため
に、この後、新たに過酸化水素とオレフィン化合物を追
加するだけで、水相はそのまま再利用することが可能で
ある。After completion of the reaction, the organic phase is recovered, and the desired epoxy compound can be purified by a known method.
In the production method of the epoxy compound of the present invention, because the amount of the amide generated from a nitrile compound after the reaction is very small, and thereafter, only adding a new hydrogen peroxide and an olefin compound, the aqueous phase is reused It is possible.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４３[Correction target item name] 0043
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４３】[0043]
【発明の効果】本発明によれば、オレフィン化合物と過
酸化水素を、ニトリル化合物の存在、ピロリン酸塩−ピ
ロリン酸水溶液中で反応させることで、高価な媒体を使
用することなく、オレフィン化合物と過酸化水素とを効
率的に使用することが可能で、しかもエポキシ化合物を
安全で経済的且つ効率的に得ることができ、加えて、反
応後にニトリル化合物から生成するアミドの量が極めて
少ないために、ピロリン酸塩−ピロリン酸水溶液はその
まま再利用が可能である。 ─────────────────────────────────────────────────────
According to the present invention, an olefin compound and hydrogen peroxide are reacted in the presence of a nitrile compound in a pyrophosphate-pyrophosphate aqueous solution to use an expensive medium.
Without use, it can be effectively used an olefin compound with hydrogen peroxide, moreover epoxy compound safe, economical and the can be obtained efficiently, in addition, to produce the nitrile compound after the reaction Since the amount of the amide is extremely small, the pyrophosphate-pyrophosphate aqueous solution can be reused as it is. ────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１３年８月１７日（２００１．８．１
７）[Submission date] August 17, 2001 (2001.8.1)
7)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４３[Correction target item name] 0043
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４３】[0043]
【発明の効果】本発明によれば、オレフィン化合物と過
酸化水素を、ニトリル化合物の存在、ピロリン酸塩−ピ
ロリン酸水溶液中で反応させることで、高価な触媒を使
用することなく、オレフィン化合物と過酸化水素とを効
率的に使用することが可能で、しかもエポキシ化合物を
安全で経済的且つ効率的に得ることができ、加えて、反
応後にニトリル化合物から生成するアミドの量が極めて
少ないために、ピロリン酸塩−ピロリン酸水溶液はその
まま再利用が可能である。According to the present invention, by reacting an olefin compound with hydrogen peroxide in the presence of a nitrile compound in an aqueous solution of pyrophosphate-pyrophosphate, the olefin compound can be reacted with the olefin compound without using an expensive catalyst. Hydrogen peroxide can be used efficiently, and an epoxy compound can be obtained safely, economically and efficiently. In addition, the amount of amide generated from the nitrile compound after the reaction is extremely small. The pyrophosphate-pyrophosphate aqueous solution can be reused as it is.
Claims (4)
リル化合物存在下に、ピロリン酸塩−ピロリン酸水溶液
中で反応させることを特徴とするエポキシ化合物の製造
方法。1. A method for producing an epoxy compound, comprising reacting an olefin compound and hydrogen peroxide in an aqueous solution of pyrophosphate-pyrophosphate in the presence of a nitrile compound.
はピロリン酸ナトリウムである請求項１に記載のエポキ
シ化合物の製造方法。2. The method for producing an epoxy compound according to claim 1, wherein the pyrophosphate is potassium pyrophosphate or sodium pyrophosphate.
７．５〜１０．５のものである請求項１又は２に記載の
エポキシ化合物の製造方法。3. An aqueous solution of pyrophosphate-pyrophosphate having a pH of
The method for producing an epoxy compound according to claim 1, wherein the epoxy compound has a viscosity of 7.5 to 10.5.
ロピオニトリル又はべンゾニトリルである請求項１に記
載のエポキシ化合物の製造方法。4. The method for producing an epoxy compound according to claim 1, wherein the nitrile compound is acetonitrile, propionitrile or benzonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000334966A JP2002145872A (en) | 2000-11-01 | 2000-11-01 | Method of manufacturing epoxy compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000334966A JP2002145872A (en) | 2000-11-01 | 2000-11-01 | Method of manufacturing epoxy compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002145872A true JP2002145872A (en) | 2002-05-22 |
Family
ID=18810789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000334966A Pending JP2002145872A (en) | 2000-11-01 | 2000-11-01 | Method of manufacturing epoxy compound |
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| Country | Link |
|---|---|
| JP (1) | JP2002145872A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009256260A (en) * | 2008-04-18 | 2009-11-05 | Daiso Co Ltd | Production method of epoxy alcohol |
| JP2013518835A (en) * | 2010-02-02 | 2013-05-23 | モーメンテイブ・スペシヤルテイ・ケミカルズ・インコーポレーテツド | Method for producing 1,2-epoxide and apparatus for carrying out the method |
| WO2014065239A1 (en) | 2012-10-25 | 2014-05-01 | 日産化学工業株式会社 | Method for producing epoxy compound |
| US8729282B2 (en) | 2008-08-01 | 2014-05-20 | Momentive Specialty Chemicals Inc. | Process for the manufacture of a 1,2-epoxide |
| US8735613B2 (en) | 2009-11-27 | 2014-05-27 | Momentive Specialty Chemicals Inc. | Process for the manufacture of propylene oxide |
| US8802873B2 (en) | 2008-08-01 | 2014-08-12 | Momentive Specialty Chemicals Inc. | Process for the manufacture of epichlorohydrin |
| US8975423B2 (en) | 2010-02-02 | 2015-03-10 | Hexion Inc. | Epoxidation process |
| US9024048B2 (en) | 2011-06-22 | 2015-05-05 | Evonik Degussa Gmbh | Apparatus and methods to preserve catalyst activity in an epoxidation process |
| US9145378B2 (en) | 2010-02-02 | 2015-09-29 | Hexion Inc. | Manufacture of an epoxyethyl ethers or glycidyl ethers |
| US9174955B2 (en) | 2010-02-02 | 2015-11-03 | Hexion Inc. | Manufacture of an epoxyethyl carboxylate or glycidyl carboxylate |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62114979A (en) * | 1985-11-13 | 1987-05-26 | Sanyo Kokusaku Pulp Co Ltd | Epoxidization of olefin |
| JPH06343872A (en) * | 1993-05-07 | 1994-12-20 | Bp Chem Internatl Ltd | Catalyst and method for epoxidization of olefin compound |
| JPH07206835A (en) * | 1994-01-26 | 1995-08-08 | Idemitsu Kosan Co Ltd | Production of styrene oxide derivative |
| JPH07206736A (en) * | 1994-01-18 | 1995-08-08 | Maruzen Petrochem Co Ltd | Oxidation of hydrocarbon |
| JPH08103659A (en) * | 1994-09-30 | 1996-04-23 | Maruzen Petrochem Co Ltd | Crystalline titanium-silicalite coated catalyst for epoxidation of olefin compound |
| WO1998043736A1 (en) * | 1997-04-02 | 1998-10-08 | Arco Chemical Technology, L.P. | Catalyst compositions derived from titanium-containing molecular sieves |
| WO1998043735A1 (en) * | 1997-04-02 | 1998-10-08 | Arco Chemical Technology, L.P. | Tellurium, titanium and silicon-containing molecular sieves |
| WO1999026936A2 (en) * | 1997-11-24 | 1999-06-03 | E.I. Du Pont De Nemours And Company | Process for the selective oxidation of organic compounds |
| JPH11171880A (en) * | 1997-12-05 | 1999-06-29 | Daiso Co Ltd | Epoxidation of halogenated allyls and regeneration of used catalyst |
| WO1999048884A1 (en) * | 1998-03-26 | 1999-09-30 | Repsol Quimica, S.A. | Process for epoxydation of olefinic compounds with hydrogen peroxide |
| JPH11309378A (en) * | 1998-04-28 | 1999-11-09 | Asahi Chem Ind Co Ltd | Catalyst for oxidizing olefin |
| JP2000026440A (en) * | 1997-04-22 | 2000-01-25 | Uop Llc | Epoxidation of olefin using catalyst containing titanostannosilicalite |
-
2000
- 2000-11-01 JP JP2000334966A patent/JP2002145872A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62114979A (en) * | 1985-11-13 | 1987-05-26 | Sanyo Kokusaku Pulp Co Ltd | Epoxidization of olefin |
| JPH06343872A (en) * | 1993-05-07 | 1994-12-20 | Bp Chem Internatl Ltd | Catalyst and method for epoxidization of olefin compound |
| JPH07206736A (en) * | 1994-01-18 | 1995-08-08 | Maruzen Petrochem Co Ltd | Oxidation of hydrocarbon |
| JPH07206835A (en) * | 1994-01-26 | 1995-08-08 | Idemitsu Kosan Co Ltd | Production of styrene oxide derivative |
| JPH08103659A (en) * | 1994-09-30 | 1996-04-23 | Maruzen Petrochem Co Ltd | Crystalline titanium-silicalite coated catalyst for epoxidation of olefin compound |
| WO1998043736A1 (en) * | 1997-04-02 | 1998-10-08 | Arco Chemical Technology, L.P. | Catalyst compositions derived from titanium-containing molecular sieves |
| WO1998043735A1 (en) * | 1997-04-02 | 1998-10-08 | Arco Chemical Technology, L.P. | Tellurium, titanium and silicon-containing molecular sieves |
| JP2000026440A (en) * | 1997-04-22 | 2000-01-25 | Uop Llc | Epoxidation of olefin using catalyst containing titanostannosilicalite |
| WO1999026936A2 (en) * | 1997-11-24 | 1999-06-03 | E.I. Du Pont De Nemours And Company | Process for the selective oxidation of organic compounds |
| JPH11171880A (en) * | 1997-12-05 | 1999-06-29 | Daiso Co Ltd | Epoxidation of halogenated allyls and regeneration of used catalyst |
| WO1999048884A1 (en) * | 1998-03-26 | 1999-09-30 | Repsol Quimica, S.A. | Process for epoxydation of olefinic compounds with hydrogen peroxide |
| JPH11309378A (en) * | 1998-04-28 | 1999-11-09 | Asahi Chem Ind Co Ltd | Catalyst for oxidizing olefin |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009256260A (en) * | 2008-04-18 | 2009-11-05 | Daiso Co Ltd | Production method of epoxy alcohol |
| US8802873B2 (en) | 2008-08-01 | 2014-08-12 | Momentive Specialty Chemicals Inc. | Process for the manufacture of epichlorohydrin |
| US8729282B2 (en) | 2008-08-01 | 2014-05-20 | Momentive Specialty Chemicals Inc. | Process for the manufacture of a 1,2-epoxide |
| US8735613B2 (en) | 2009-11-27 | 2014-05-27 | Momentive Specialty Chemicals Inc. | Process for the manufacture of propylene oxide |
| JP2015061841A (en) * | 2010-02-02 | 2015-04-02 | モーメンテイブ・スペシヤルテイ・ケミカルズ・インコーポレーテツド | Process for producing 1,2-epoxide and device for carrying out the process |
| US8859790B2 (en) | 2010-02-02 | 2014-10-14 | Momentive Specialty Chemicals Inc. | Process for the manufacture of a 1,2-epoxide and a device for carrying out said process |
| US8975423B2 (en) | 2010-02-02 | 2015-03-10 | Hexion Inc. | Epoxidation process |
| JP2013518835A (en) * | 2010-02-02 | 2013-05-23 | モーメンテイブ・スペシヤルテイ・ケミカルズ・インコーポレーテツド | Method for producing 1,2-epoxide and apparatus for carrying out the method |
| US9102640B2 (en) | 2010-02-02 | 2015-08-11 | Evonik Degussa Gmbh | Process for the manufacture of a 1,2-epoxide and a device for carrying out said process |
| US9145378B2 (en) | 2010-02-02 | 2015-09-29 | Hexion Inc. | Manufacture of an epoxyethyl ethers or glycidyl ethers |
| US9174955B2 (en) | 2010-02-02 | 2015-11-03 | Hexion Inc. | Manufacture of an epoxyethyl carboxylate or glycidyl carboxylate |
| US9024048B2 (en) | 2011-06-22 | 2015-05-05 | Evonik Degussa Gmbh | Apparatus and methods to preserve catalyst activity in an epoxidation process |
| WO2014065239A1 (en) | 2012-10-25 | 2014-05-01 | 日産化学工業株式会社 | Method for producing epoxy compound |
| KR20150070190A (en) | 2012-10-25 | 2015-06-24 | 닛산 가가쿠 고교 가부시키 가이샤 | Method for producing epoxy compound |
| CN104797576A (en) * | 2012-10-25 | 2015-07-22 | 日产化学工业株式会社 | Method for producing epoxy compound |
| US9464074B2 (en) | 2012-10-25 | 2016-10-11 | Nissan Chemical Industries, Ltd. | Method for producing epoxy compound |
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