JPH0717932A - Improved production of ketazines - Google Patents
Improved production of ketazinesInfo
- Publication number
- JPH0717932A JPH0717932A JP15932393A JP15932393A JPH0717932A JP H0717932 A JPH0717932 A JP H0717932A JP 15932393 A JP15932393 A JP 15932393A JP 15932393 A JP15932393 A JP 15932393A JP H0717932 A JPH0717932 A JP H0717932A
- Authority
- JP
- Japan
- Prior art keywords
- ketazine
- hydrogen peroxide
- producing
- compound
- working solution
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ケタジンの合成方法と
そのヒドラジン製造への応用に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for synthesizing ketazine and its application to the production of hydrazine.
【０００２】[0002]
【従来の技術】ケタジン類はヒドラジン合成における安
定な中間体として有効な化合物であり、従来から種々の
ケタジン製造法が開発されている。そのなかでケトン、
アンモニア、酸化剤として過酸化水素を用いる方法はエ
ネルギー効率が高く、副生する塩もないことから近年注
目を集めており、有機ひ素化合物を触媒とする方法（特
公昭６１−４１５０９）、ニトリルやアミドを共反応剤
として用いる方法（特開昭４７−１３７１、同４７−１
４０９８、同４９−１８８１５）などが提案されてい
る。酸化剤として用いられる過酸化水素は、温度上昇或
は不純物に非常に敏感な物質であり、なかでも重金属に
より著しい分解をうけることが知られている。Ketazines are compounds effective as stable intermediates in hydrazine synthesis, and various methods for producing ketazine have been developed. Ketone,
The method using ammonia and hydrogen peroxide as an oxidant has been attracting attention in recent years because it has high energy efficiency and there is no salt produced as a by-product. Method using amide as co-reactant (JP-A-47-1371, JP-A-47-1
4098 and 49-18815). Hydrogen peroxide, which is used as an oxidant, is a substance that is very sensitive to temperature rise and impurities, and it is known that hydrogen peroxide undergoes remarkable decomposition among them.
【０００３】また、工業規模における製造においては、
原料に混在する重金属や反応容器等装置材質表面からの
溶出重金属による共反応剤や触媒又はそれらを含有する
液（以後、便宜的に作動溶液と呼ぶ）の汚染は避けられ
ず、さらに重金属は何らかの処理をしなければ蓄積して
過酸化水素の分解をますます助長する。すなわち、過酸
化水素を酸化剤として用いる工業規模のケタジンの効率
的な合成においては、作動液の重金属による汚染、重金
属の蓄積は、大きな障害となる。例えばケタジンを製造
するには、作動溶液に原料たるアンモニア、過酸化水
素、カルボニル化合物を反応させ、反応後分離した生成
ケタジン相と作動溶液相を分け、作動溶液相は反応によ
り生成した水を除去、場合により未反応物を回収した
後、反応系に循環させるという方法がおこなわれるが、
この作動溶液の循環利用により前記汚染は、ますます顕
著なものになる。作動溶液に蓄積した重金属類は、過酸
化水素の分解を促進し、ケタジン収率の低下、副成物の
生成等を引き起こすので、工業的なケタジンの製造を困
難にしてしまう。Further, in manufacturing on an industrial scale,
Contamination of co-reactants and catalysts or liquids containing them (hereinafter referred to as working solutions for convenience) with heavy metals dissolved in the raw materials and from the surface of equipment materials such as reaction vessels is unavoidable. If left untreated, it accumulates and further promotes the decomposition of hydrogen peroxide. That is, in efficient industrial scale synthesis of ketazine using hydrogen peroxide as an oxidant, contamination of the working fluid by heavy metals and accumulation of heavy metals are major obstacles. For example, to produce ketazine, the working solution is reacted with the raw materials ammonia, hydrogen peroxide, and a carbonyl compound, the generated ketazine phase and the working solution phase separated after the reaction are separated, and the working solution phase removes water generated by the reaction. In some cases, after collecting the unreacted material, it is circulated in the reaction system.
The recycling of this working solution makes the contamination more pronounced. The heavy metals accumulated in the working solution accelerate the decomposition of hydrogen peroxide, reduce the yield of ketazine, and produce by-products, which makes industrial production of ketazine difficult.
【０００４】これに対して、従来の方法では、反応系
に、例えばニトリロトリ酢酸、エチレンジアミンテトラ
酢酸、１、２−シクロヘキサンジアミン−Ｎ，Ｎ，
Ｎ’，Ｎ’−テトラ酢酸等のアルキレンポリアミンのポ
リカルボキシ誘導体、或は、リン酸、ピロリン酸、クエ
ン酸等の重金属の封鎖能を有する、いわゆる過酸化水素
の安定剤を添加することがなされているが、いずれの安
定剤及びその金属キレート化合物体もその作動溶液にた
いする溶解度が生成するケタジンに対する溶解度よりも
高く、生成するケタジン相に殆ど溶解しない。一方、先
に例示した共反応剤や触媒を含め、ケタジン合成を目的
として提案されている共反応剤や触媒もまたすべて生成
するケタジンへの溶解度は極めて小さい。よって従来用
いられている安定剤及びその金属キレート体は、溶解に
おいて、共反応剤や触媒すなわち作動溶液と同一な挙動
をとることになり、重金属は作動溶液中に蓄積する。こ
のことから本質的に過酸化水素の分解要因たる重金属を
作動溶液から除去する為には、従来は、高価な共反応剤
や触媒を含有する作動溶液と共に安定剤及びその金属キ
レート体を廃棄する、あるいは、作動溶液から安定剤及
びその金属キレート体を分離した後、安定剤及びその金
属キレート体を廃棄する、等、甚だしく経済的に不利
な、或は複雑な手段を講じなければならなかった。On the other hand, in the conventional method, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, 1,2-cyclohexanediamine-N, N, is added to the reaction system.
A polycarboxy derivative of an alkylene polyamine such as N ′, N′-tetraacetic acid, or a so-called hydrogen peroxide stabilizer capable of sequestering heavy metals such as phosphoric acid, pyrophosphoric acid and citric acid is added. However, any of the stabilizers and the metal chelate compound thereof have a higher solubility in the working solution than that of the formed ketazine, and are hardly dissolved in the formed ketazine phase. On the other hand, all the co-reactants and catalysts proposed for the purpose of synthesizing ketazine, including the co-reactants and catalysts exemplified above, also have extremely low solubility in ketazine. Therefore, the conventionally used stabilizer and its metal chelate will behave in the same manner as the co-reactant and the catalyst, that is, the working solution in dissolution, and the heavy metal will be accumulated in the working solution. Therefore, in order to remove the heavy metal, which is essentially a factor for decomposing hydrogen peroxide, from the working solution, the stabilizer and its metal chelate are conventionally discarded together with the working solution containing an expensive co-reactant or catalyst. Or, after the stabilizer and its metal chelate are separated from the working solution, the stabilizer and its metal chelate must be discarded, and other serious economically disadvantageous or complicated measures must be taken. .
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、連続
的なケタジン類の製造において、重金属による過酸化水
素の分解を防ぎ、ケタジン類を収率よくしかも効率よく
製造することにある。SUMMARY OF THE INVENTION An object of the present invention is to prevent the decomposition of hydrogen peroxide by heavy metals in the continuous production of ketazines and to produce the ketazines in high yield and efficiently.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、前述の如
き安定剤の欠点を解消し、ケタジンに易溶性なキレート
剤を用いることにより、重金属を金属キレート体とし
て、ケタジンとともに作動溶液から除去し、ケタジンが
収率よくしかも効率よく製造されることを見いだし、本
発明を完成させた。Means for Solving the Problems The present inventors have solved the above-mentioned drawbacks of stabilizers and used a chelating agent that is easily soluble in ketazine so that a heavy metal can be used as a metal chelate from a working solution together with ketazine. After removal, it was found that ketazine was produced in good yield and efficiently, and the present invention was completed.
【０００７】本発明は、アンモニア及び一般式The present invention is directed to ammonia and the general formula
【化１】Ｒ1（Ｒ2）Ｃ＝Ｏ （式中Ｒ1 及びＲ2 は、それぞれ炭素数１２以下の直鎖
状もしくは分枝状アルキル基、環状アルキル基または芳
香核を有する炭化水素基であり、Ｒ1 及びＲ2 は同一で
あっても異なるものであってもよく、Ｒ1 とＲ2 が互い
に結合しカルボニル基の炭素原子と共に環を形成するも
のであってもよい。）であらわされるカルボニル化合物
と過酸化水素を用いて、一般式Embedded image R 1 (R 2 ) C═O (wherein R 1 and R 2 are each a linear or branched alkyl group having 12 or less carbon atoms, a cyclic alkyl group, or a hydrocarbon group having an aromatic nucleus) And R 1 and R 2 may be the same or different, and R 1 and R 2 may be bonded to each other to form a ring together with the carbon atom of the carbonyl group.). Using a carbonyl compound represented by hydrogen peroxide and a general formula
【化２】Ｒ1（Ｒ2）Ｃ＝Ｎ−Ｎ＝Ｃ（Ｒ1）Ｒ2 （式中Ｒ1 及びＲ2 は、それぞれ炭素数１２以下の直鎖
状もしくは分枝状アルキル基、環状アルキル基または芳
香核を有する炭化水素基であり、Ｒ1 及びＲ2 は同一で
あっても異なるものであってもよく、Ｒ1 とＲ2 が互い
に結合しカルボニル基の炭素原子と共に環を形成するも
のであってもよい。）であらわされるケタジンを合成す
るに際して、ケタジンに易溶なキレート化合物の存在下
に反応を行い、生成したケタジンと作動溶液の分離を静
置分離、または液−液抽出、またはこれらの組合せによ
り行うことを特徴とするケタジンの製造法に係わる。Embedded image R 1 (R 2 ) C═N—N═C (R 1 ) R 2 (wherein R 1 and R 2 are each a linear or branched alkyl group having 12 or less carbon atoms, a cyclic group). An alkyl group or a hydrocarbon group having an aromatic nucleus, R 1 and R 2 may be the same or different, and R 1 and R 2 are bonded to each other to form a ring with the carbon atom of the carbonyl group. In the case of synthesizing ketazine represented by the formula (1), the reaction is performed in the presence of a chelate compound which is easily soluble in ketazine, and the generated ketazine and working solution are separated by static separation or liquid-liquid. The present invention relates to a method for producing ketazine, which is characterized by performing extraction or a combination thereof.
【０００８】本発明に於けるキレート化合物としては、
ケタジンへの溶解度が高いキレート化合物が好適に使用
される。具体的には、生成ケタジンへの溶解度が２０℃
において０．５％以上、好ましくは１．０％以上であれ
ばよい。本発明に於けるキレート化合物としては、より
具体的には、８−ヒドロキシキノリン等のキノリノール
類、メチル−８−キノリノール、エチル−８−キノリノ
ール、７（１−ノニル−２−プロペニル）−８−キノリ
ノール（Schering社、商品名ＫＥＬＥＸ−１００）等の
置換キノリノール類、１−ヒドロキシ−２−エチルヘキ
シル−１'−エチルペンチル−ケトンオキシム（Henkel
社、商品名ＬＩＸ６３）、１−ヒドロキシ−４−ドデル
ヘキシル−ベンゾフェノンオキシム（Henkel社、商品名
ＬＩＸ６５）等の脂肪族および芳香族ヒドロキシオキシ
ム化合物が例示される。このなかでもキノリノール類お
よび置換キノリノール類が好ましく、長鎖アルキル置換
キノリノール類が特に好ましい。As the chelate compound in the present invention,
A chelate compound having a high solubility in ketazine is preferably used. Specifically, the solubility in the produced ketazine is 20 ° C.
At 0.5% or more, preferably 1.0% or more. As the chelate compound in the present invention, more specifically, quinolinols such as 8-hydroxyquinoline, methyl-8-quinolinol, ethyl-8-quinolinol, 7 (1-nonyl-2-propenyl) -8- Substituted quinolinols such as quinolinol (Schering Co., trade name KELEX-100), 1-hydroxy-2-ethylhexyl-1′-ethylpentyl-ketone oxime (Henkel
Examples thereof include aliphatic and aromatic hydroxy oxime compounds such as 1-hydroxy-4-doderhexyl-benzophenone oxime (Henkel, trade name LIX65). Of these, quinolinols and substituted quinolinols are preferable, and long-chain alkyl-substituted quinolinols are particularly preferable.
【０００９】キレート化合物の使用量は特に限定される
ものではないが、反応系中、０．１〜０．０００１重量
％という極めて少ない使用量で有効な効果を示す。もち
ろんこの量より多く添加しても反応を阻害するものでは
ない。本発明のケタジンへの溶解度が高いキレート化合
物が極めて少量で大きな効果を示す理由は、明らかでな
いが、過酸化水素の分解要因である重金属が、反応中、
キレート化合物と錯化し、さらに静置分離、または液−
液抽出、またはこれらの組合せによる分離にてケタジン
とともに作動溶液より除去され、作動溶液中の重金属濃
度が低濃度に維持されることによる為と考えられる。キ
レート化合物の添加方式は、市販の形態のまま、溶剤に
溶かして、あるいは、原料に含有させるなど特に限定さ
れない。また、複数の本発明のキレート化合物を組み合
わせて用いてもよく、それ以外のキレート化合物と組み
合わせて用いてもよい。The amount of the chelate compound used is not particularly limited, but an effective effect can be obtained with an extremely small amount of 0.1 to 0.0001% by weight in the reaction system. Of course, adding more than this amount does not hinder the reaction. It is not clear why the chelate compound of the present invention having a high solubility in ketazine exhibits a large effect even when the amount is very small, but a heavy metal which is a factor for decomposing hydrogen peroxide, during the reaction,
Complex with a chelate compound and then separate by standing or liquid
It is considered that this is because the heavy metal concentration in the working solution is maintained at a low concentration by removing it together with ketazine from the working solution by liquid extraction or separation by a combination thereof. The addition method of the chelate compound is not particularly limited, such as being in a commercially available form, dissolved in a solvent, or contained in a raw material. Further, a plurality of chelate compounds of the present invention may be used in combination, or may be used in combination with other chelate compounds.
【００１０】本発明における作動溶液は、有機または無
機のオキシ酸、そのアンモニウム塩およびその誘導体、
例えば無水物、エステル、アミド、ニトリル、過酸化ア
シルまたはこれらの混合物の中から選択された１種また
は複数の化合物を溶液にすることによって調製すること
ができる。好ましくは、アミド、アンモニウム塩及びニ
トリルを使用する。前記アミドとしては、ホルムアミ
ド、アセトアミド、モノクロルアセトアミド及びプロピ
オンアミドが好ましい。好ましいアンモニウム塩は、リ
ン酸塩、酢酸塩モノクロロ酢酸塩、プロピオン酸塩、フ
ェニルアルソンサン塩及びカコジル酸塩である。また、
好ましいニトリルは、アセトニトリルとプロピオニトリ
ルである。作動溶液の溶媒としては、１価もしくは多価
アルコール溶媒、水と１価もしくは多価アルコールとの
混合溶媒、特に好ましくは、水と１価の脂肪族低級アル
コールとの混合溶媒および水と１価の脂肪族低級アルコ
ールとグリコールとの混合溶媒が挙げられる。The working solution in the present invention is an organic or inorganic oxyacid, its ammonium salt and its derivative,
For example, it can be prepared by bringing one or more compounds selected from an anhydride, an ester, an amide, a nitrile, an acyl peroxide, or a mixture thereof into a solution. Preference is given to using amides, ammonium salts and nitrites. As the amide, formamide, acetamide, monochloroacetamide and propionamide are preferable. Preferred ammonium salts are phosphate, acetate monochloroacetate, propionate, phenylarsonsan and cacodylate. Also,
Preferred nitriles are acetonitrile and propionitrile. As the solvent of the working solution, a monohydric or polyhydric alcohol solvent, a mixed solvent of water and a monohydric or polyhydric alcohol, particularly preferably a mixed solvent of water and a monohydric aliphatic lower alcohol and water and a monohydric alcohol are used. And a mixed solvent of the aliphatic lower alcohol and glycol.
【００１１】本発明に於ける具体的なカルボニル化合物
の例としては、ケトンが好適で、アセトン、メチルエチ
ルケトン、２―ペンタノン、３―メチル―２―ブタノ
ン、３―メチル―２―ペンタノン、４―メチル―２―ペ
ンタノン、メチルシクロヘキシルケトン、アセトフェノ
ン、ベンゾフェノン、シクロペンタノン、シクロヘキサ
ノン、シクロヘプタノン、シクロオクタノン、シクロデ
カノン、シクロドデカノン等を挙げることが出来る。も
し、ケタジンを製造する目的がケタジンを水で加水分解
してヒドラジンを製造することである場合には、これら
のケトンのうちアセトン及びメチルエチルケトンが取り
扱いやすく経済的である点で好ましい。本発明において
は、反応系中の水分濃度が少ない程、反応速度が速くな
り、且選択率も向上する傾向にあるので、使用する過酸
化水素は濃度の高いものが好ましい。通常３０〜９０重
量％、好ましくは６０〜８５重量％の過酸化水素水が使
用される。アンモニアはアンモニア水としても、或はア
ンモニアガスとして導入してもよい。反応は液相条件下
に０〜１２０゜Ｃ、好ましくは３０〜１００゜Ｃの温度
で、常圧または加圧下に実施される。As a specific example of the carbonyl compound in the present invention, a ketone is preferable, and acetone, methyl ethyl ketone, 2-pentanone, 3-methyl-2-butanone, 3-methyl-2-pentanone, 4-methyl. -2-Pentanone, methylcyclohexylketone, acetophenone, benzophenone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone, cyclododecanone and the like can be mentioned. If the purpose of producing ketazine is to hydrolyze ketazine with water to produce hydrazine, of these ketones, acetone and methyl ethyl ketone are preferable because they are easy to handle and economical. In the present invention, the lower the concentration of water in the reaction system, the faster the reaction rate and the higher the selectivity. Therefore, the hydrogen peroxide used has a high concentration. Usually, 30 to 90% by weight, preferably 60 to 85% by weight of hydrogen peroxide solution is used. Ammonia may be introduced as aqueous ammonia or as ammonia gas. The reaction is carried out under liquid phase conditions at a temperature of 0 to 120 ° C., preferably 30 to 100 ° C. under normal pressure or pressure.
【００１２】[0012]
【実施例】以下、実施例を挙げて説明する。 実施例−１ ステンレス鋼（ＳＵＳ３０４）を使用した１５００ｃｃ
の攪拌機付き反応器にカコジル酸５重量％、酢酸アンモ
ニウム３０重量％、プロピレングリコール５０重量％、
水１５重量％からなる作動溶液５００ｃｃを仕込み、５
０゜Ｃに加温しアンモニアガスを連続的に吹き込みなが
ら、メチルエチルケトン３０５ｇ、８０％過酸化水素９
０ｇ、作動溶液に対して７（１−ノニル−２−プロペニ
ル）−８−キノリノール（Schering社、商品名ＫＥＬＥ
Ｘ−１００）０．００１重量％を同時に添加し、４時間
反応させた。反応後液は、メチルエチルケタジン相と作
動溶液相とに静置分離し、各相のメチルエチルケタジン
量を機器分析および滴定分析にて定量したところ添加し
た過酸化水素にたいし８５％の収率で、メチルエチルケ
タジンがえられた。ステンレス鋼（ＳＵＳ３０４）製充
填材（充填空間部９００ｃｃ）が充填された内径５０ｍ
ｍ、高さ５００ｍｍのステンレス鋼（ＳＵＳ３０４）製
蒸留器を用いて、分離した前記作動溶液より反応生成
水、過酸化水素媒体水を留去し作動溶液を５００ｃｃま
で濃縮し、得られた作動溶液を用いて前記メチルエチル
ケタジン合成反応を繰り返し実施した。この操作を１０
０回行い、決められた間隔にてメチルエチルケタジンの
収率を調べたところ、収率低下は認められなかった。こ
の間作動溶液中の鉄の濃度は、０．１ｐｐｍで一定に推
移した。EXAMPLES Examples will be described below. Example-1 1500cc using stainless steel (SUS304)
In a reactor equipped with a stirrer, 5% by weight of cacodylic acid, 30% by weight of ammonium acetate, 50% by weight of propylene glycol,
Charge 500 cc of working solution consisting of 15% by weight of water, 5
While warming to 0 ° C and continuously blowing ammonia gas, methyl ethyl ketone 305g, 80% hydrogen peroxide 9
0 g, 7 (1-nonyl-2-propenyl) -8-quinolinol (Schering Co., trade name KELE) for the working solution
X-100) 0.001% by weight was added at the same time, and the reaction was carried out for 4 hours. After the reaction, the liquid was allowed to stand and separate into a methylethylketazine phase and a working solution phase, and the amount of methylethylketazine in each phase was determined by instrumental analysis and titration analysis. The yield of methyl ethyl ketazine was obtained. Inner diameter 50m filled with stainless steel (SUS304) filler (filling space 900cc)
m, a height of 500 mm, using a stainless steel (SUS304) distiller, the reaction product water and hydrogen peroxide medium water were distilled off from the separated working solution to concentrate the working solution to 500 cc. Was used to repeatedly carry out the methylethylketazine synthesis reaction. Do this operation 10
When the yield of methyl ethyl ketazine was examined 0 times and determined at regular intervals, no decrease in yield was observed. During this period, the concentration of iron in the working solution remained constant at 0.1 ppm.
【００１３】実施例−２ 実施例−１と同一の反応器、蒸留器をもちいた。反応器
にカコジル酸２重量％、ｔ−ブタノール２０重量％、プ
ロピレングリコール１０重量％、からなる作動溶液５０
０ｃｃを仕込み、５０゜Ｃに加温しアンモニアガスを連
続的に吹き込みながら、メチルエチルケトン３０５ｇ、
８０％過酸化水素９０ｇ、８−ヒドロキシキノリン０．
００１ｇを同時に添加し４時間反応させた。反応後の液
は均一相で、過酸化水素にたいし８５％の収率で、メチ
ルエチルケタジンがえられた。反応後の液よりトルエン
にて生成ケタジンを液−液抽出した後、分離された作動
溶液より蒸留器にて反応生成水、過酸化水素媒体水を留
去し作動溶液を５００ｃｃまで濃縮し、得られた作動溶
液を用いて前記メチルエチルケタジン合成反応を繰り返
し実施した。この操作を１００回行い、決められた間隔
にてメチルエチルケタジンの収率を調べたところ、収率
低下は認められなかった。この間作動溶液中の鉄の濃度
は、０．２ｐｐｍで一定に推移した。Example-2 The same reactor and distiller as in Example-1 were used. Working solution 50 consisting of 2% by weight of cacodylic acid, 20% by weight of t-butanol and 10% by weight of propylene glycol in a reactor.
Charge 0 cc, warm to 50 ° C., continuously blow ammonia gas, and add 305 g of methyl ethyl ketone.
80% hydrogen peroxide 90 g, 8-hydroxyquinoline 0.
001 g was added at the same time and reacted for 4 hours. The liquid after the reaction was a homogeneous phase, and methyl ethyl ketazine was obtained in a yield of 85% with respect to hydrogen peroxide. After liquid-liquid extraction of the formed ketazine from the liquid after the reaction with toluene, the reaction product water and hydrogen peroxide medium water are distilled off from the separated working solution with a distiller to concentrate the working solution to 500 cc. The methyl ethyl ketazine synthesis reaction was repeatedly performed using the working solution thus obtained. This operation was repeated 100 times, and the yield of methylethylketazine was examined at a predetermined interval. No decrease in yield was observed. During this time, the concentration of iron in the working solution remained constant at 0.2 ppm.
【００１４】比較例−１ キレート化合物として７（１−ノニル−２−プロペニ
ル）−８−キノリノールの代わりに同量のエチレンジア
ミンテトラ酢酸を添加した以外は、実施例−１と同様に
繰り返し反応を行った。メチルエチルケタジン収率は初
期には８５％であったが、繰り返しとともに収率の低下
が認められ、１０回の繰り返し反応により収率は６０％
にまで低下した。又、１０回目の反応後の作動溶液中の
鉄の濃度は、１０ｐｐｍにまで上昇していた。Comparative Example-1 The same reaction as in Example-1 was carried out except that the same amount of ethylenediaminetetraacetic acid was added instead of 7 (1-nonyl-2-propenyl) -8-quinolinol as the chelate compound. It was The yield of methylethylketazine was 85% at the beginning, but the yield decreased with repetition, and the yield was 60% after 10 repeated reactions.
Fell to. Further, the concentration of iron in the working solution after the 10th reaction had risen to 10 ppm.
【００１５】[0015]
【発明の効果】本発明によれば、連続的なケタジン類の
製造において、重金属による過酸化水素の分解を防ぎ、
ケタジン類を収率よくしかも効率よく製造することがで
きる。According to the present invention, in the continuous production of ketazines, the decomposition of hydrogen peroxide by heavy metals is prevented,
Ketazines can be produced in high yield and efficiently.
Claims (8)
基を有する化合物を作動液と接触させケタジンを合成す
るに際して、生成するケタジンに易溶なキレート化合物
の存在下に反応を行い、生成したケタジンを作動液と分
離することを特徴とするケタジン類の製造法。1. When synthesizing ketazine by bringing a compound having ammonia, hydrogen peroxide and a carbonyl group into contact with a working fluid, the reaction is carried out in the presence of a chelate compound which is easily soluble in the ketazine produced, and the ketazine produced is actuated. A method for producing ketazines, which comprises separating from a liquid.
解度が２０℃において０．５％以上であるキレート化合
物であることを特徴とする請求項１に記載のケタジン類
の製造法。2. The method for producing ketazine according to claim 1, wherein the chelating agent is a chelating compound having a solubility of 0.5% or more at 20 ° C. in the formed ketazine.
ン、メチルエチルケトン及びメチルイソブチルケトンよ
りなる群の中から選択されることを特徴とする請求項１
または２に記載のケタジン類の製造法。3. The compound containing a carbonyl group is selected from the group consisting of acetone, methyl ethyl ketone and methyl isobutyl ketone.
Alternatively, the method for producing the ketazine according to item 2.
過酸化水素１モルに対し１.８〜３モルであることを特
徴とする請求項１〜３のいずれか一項に記載のケタジン
類の製造法。4. The amount of the compound containing a carbonyl group is
The method for producing a ketazine according to any one of claims 1 to 3, wherein the amount of hydrogen peroxide is 1.8 to 3 mol with respect to 1 mol of hydrogen peroxide.
に対して０.１〜１Ｋｇの間であることを特徴とする請
求項１〜４のいずれか一項に記載のケタジン類の製造
法。5. The ketazine compound according to claim 1, wherein the amount of the working solution is between 0.1 and 1 kg per mol of hydrogen peroxide. Manufacturing method.
置分離、液−液抽出またはこれらの組合せにより行うこ
とを特徴とする請求項１に記載のケタジン類の製造法。6. The method for producing ketazine according to claim 1, wherein the produced ketazine and the working fluid are separated by static separation, liquid-liquid extraction, or a combination thereof.
換キノリノール類および脂肪族または芳香族ヒドロキシ
オキシム化合物からなる群から選ばれた少なくとも１種
であることを特徴とする請求項２に記載のケタジン類の
製造法。7. The ketazine according to claim 2, wherein the chelating agent is at least one selected from the group consisting of quinolinols, substituted quinolinols, and aliphatic or aromatic hydroxyoxime compounds. Manufacturing method.
ノリノール類であることを特徴とする請求項７に記載の
ケタジン類の製造法。8. The method for producing ketazine according to claim 7, wherein the chelating agent is a long-chain alkyl-substituted quinolinol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15932393A JP3279394B2 (en) | 1993-06-29 | 1993-06-29 | Improved production of ketazines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15932393A JP3279394B2 (en) | 1993-06-29 | 1993-06-29 | Improved production of ketazines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0717932A true JPH0717932A (en) | 1995-01-20 |
| JP3279394B2 JP3279394B2 (en) | 2002-04-30 |
Family
ID=15691302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15932393A Expired - Lifetime JP3279394B2 (en) | 1993-06-29 | 1993-06-29 | Improved production of ketazines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3279394B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262159A (en) * | 2006-03-27 | 2007-10-11 | Nippon Shokubai Co Ltd | Method for producing polyvinylpyrrolidone |
-
1993
- 1993-06-29 JP JP15932393A patent/JP3279394B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262159A (en) * | 2006-03-27 | 2007-10-11 | Nippon Shokubai Co Ltd | Method for producing polyvinylpyrrolidone |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3279394B2 (en) | 2002-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Polyakov et al. | Imine exchange in O‐aryl and O‐alkyl oximes as a base reaction for aqueous ‘dynamic’combinatorial libraries. A kinetic and thermodynamic study | |
| CN113840799B (en) | Improved process for preparing hydrazine hydrate with oxime recycle | |
| JPH0959238A (en) | Synthesis of ketazine | |
| JP2003183237A (en) | Method for producing oxime | |
| Schneider et al. | A new triphasic solid-solid-liquid catalytic system for the inexpensive and selective oxidation of secondary alcohols by calcium hypochlorite | |
| KR950002838B1 (en) | Process for the preparation of azines | |
| JP3279394B2 (en) | Improved production of ketazines | |
| EP0070155B1 (en) | Process of preparing a ketazine from a ketone | |
| JP3309413B2 (en) | Method for inhibiting thermal decomposition of cycloalkanone oxime | |
| JP4414091B2 (en) | Method for preparing hydrazine hydrate | |
| US4049712A (en) | Method for manufacturing hydrazodicarbonamide | |
| KR100653586B1 (en) | Method for preparing hydrazine hydrate | |
| US3984451A (en) | Method for preparing hydrazo-bis-acetonitriles | |
| JP4418109B2 (en) | Method for preparing hydrazine hydrate | |
| JP2004059553A (en) | Method for producing amide compound | |
| JP3528859B2 (en) | Synthetic method of ketazine | |
| JP4743975B2 (en) | Method for producing lactone | |
| JP3460714B2 (en) | Method for inhibiting thermal decomposition of cycloalkanone oxime | |
| JP4131025B2 (en) | Method for producing ketazine and hydrated hydrazine | |
| US3972874A (en) | Method for preparing symmetrical and unsymmetrical ketazines and mixtures thereof | |
| JP3133585B2 (en) | Method for producing acid amide | |
| CN113840800A (en) | Improved process for making hydrazine hydrate with pyrazoline recycle | |
| JP2000072738A (en) | Production of oxime | |
| McLaren et al. | Enantioselective Synthesis of α-Methyl-β-Aminoacid Derivatives via Aza-Aldol reaction of Acylcamphorsultam Enolates | |
| JP2003104968A (en) | Method for producing amide compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080222 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090222 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20100222 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100222 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 9 Free format text: PAYMENT UNTIL: 20110222 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120222 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 10 Free format text: PAYMENT UNTIL: 20120222 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 11 Free format text: PAYMENT UNTIL: 20130222 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140222 Year of fee payment: 12 |
|
| EXPY | Cancellation because of completion of term |