JP4971538B2 - Oxidation catalyst polymer and method for producing higher order oxide than alcohol using the same - Google Patents

Description

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって低級アルキル基を表す。）
【００１１】
更に、本発明は、式（１）で表されるＮ−オキシルピペリジノカルバモイル基を有するポリマーの存在下、アルコール化合物を電解酸化することを特徴とするアルコールよりも高次な酸化物の製造方法に係る。アルコールより高次な酸化物としては例えばアルデヒド、ケトン、ラクトン、カルボン酸エステル、カルボン酸化合物等を例示することができる。
【００１２】
本発明者等は、ポリマーと酸化触媒能を有するＮ−オキシル化合物とを化学結合させることにより、電解酸化条件下もしくは後処理条件下で安定にしかも容易に回収が可能となった酸化触媒能を有するポリマーを考案した。更に水溶液中でアルコール化合物を該ポリマーに担持させた状態で電解酸化を行うという、アルコールよりも高次な酸化物の全く新しい製法を開発した。
【００１３】
該ポリマーを用いれば、アルコール化合物を該ポリマーに担持させた状態で酸化反応が行えるため、電流効率の高い水溶液中での電解酸化反応を行うことができ、支持電解質の使用量を減少させることができる。更にポリマーと酸化触媒能を有するＮ−オキシル化合物とを化学結合させることにより、触媒能を有するＮ−オキシル化合物の水溶液中への溶解度を極端に低下させることになり、ほぼ完全に回収、再使用することが可能となる。
【００１４】
このように従来とは全く異なり有機溶媒を使用することなく、酸化触媒能を有するＮ−オキシル化合物と化学結合したポリマーを用いることにより、触媒をほぼ完全な形でリサイクルし得る電解酸化反応を行うことが可能となる。
【００１５】
また、これに伴い、最終的に生成物は該ポリマーのポリマー部に担持された状態となっているため、濾過後、少量の有機溶媒により該ポリマー部を洗浄するだけで、生成物のみを回収できるという高い利点も併せ持っている。またこのとき分離される該ポリマーはそのまま次反応において利用することが可能なため、余分な分離操作が全く必要ない。このように、有機化合物の電解酸化反応系で有機溶媒を使用せず該ポリマーを用いアルコール化合物を電解酸化することにより、目的とするアルデヒド、ケトン、ラクトン化合物等のアルコールよりも高次な酸化物を高収率、高効率で製造しうるという全く新しい事実を見い出し、本発明を完成するに至った。
【００１６】
【発明の実施の形態】
本明細書において、低級アルキル基とは、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基等の炭素数１〜６の直鎖状、分枝状のアルキル基を示す。
【００１７】
本発明の式（１）で表されるＮ−オキシルピロリジノカルバモイル基を有するポリマーは、下記反応式１で表される反応によって製造される。
【００１８】
【化４】
（反応式１）

（式中Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は前記に同じ。）
【００１９】
本反応において用いられる式（２）で表される化合物は、公知の方法で製造されるか、市販品を用いることができる。
本反応においては、ジシクロヘキシルカルボジイミド（ＤＣＣ）等の縮合剤を用い、当該分野で慣用的に行われているカルボン酸とアミンとの脱水縮合反応条件が適用される。
【００２０】
本発明において用いられるポリマーとは、ポリマー分子中に少なくとも１つのカルボキシル基を有するものであれば、特に制限なく使用でき、便宜的に式（３）で表しており、その分子量は重量平均分子量で３００〜５００万程度、好ましくは５００〜３００万程度、更に好ましくは１０００〜１００万程度が好適である。具体的には、例えばカルボキシル基を有するポリマーとしては、ポリ（ｐ−フェニレンベンゾビスチアゾール）等の、上記ポリマーの部分がｐ−フェニレンベンゾビスチアゾールを有するポリマーを例示できるほか、ポリアクリル酸、カルボキシル基を有するイオン交換樹脂等も使用できる。また、ポリエステル類を加水分解してカルボキシル基を生成せしめたものを使用することもできる。
また、ポリエチレン、ポリプロピレン等のポリ炭化水素化合物等、カルボキシル基を有していないポリマーにおいても、従来知られている酸化処理を施すことによって使用することができる。これらポリマーは水、有機溶媒に溶解しないものが好ましい。
【００２１】
本反応において、式（２）で表されるＮ−オキシル化合物の式（３）で表されるポリマーへの含有割合は、現実的に特に制限されるものではないが、用いられるポリマーの重量に対し、式（２）で表されるＮ−オキシル化合物が３〜４０重量％程度、好ましくは５〜２５重量％程度となるように調整すればよい。
【００２２】
例えば本反応は適当な溶媒中で行われる。溶媒としては本反応に不活性なものであれば特に制限されない。溶媒としては、例えば、ヘキサン、シクロヘキサン、ヘプタン等の脂肪族乃至脂環式炭化水素類、ベンゼン、クロロベンゼン、トルエン、キシレン等の芳香族炭化水素類、塩化メチレン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン化炭化水素類、酢酸エチル、酢酸メチル等のエステル類、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類等を挙げることができる。これらは１種単独で又は２種以上混合して使用される。これらの溶媒は、式（３）で表されるポリマー １ｋｇ当たり、通常２〜２００Ｌ程度、好ましくは１０〜１００Ｌ程度使用されるのが良い。
【００２３】
本発明の式（１）で表されるＮ−オキシルピペリジノカルバモイル基を有するポリマー〔以下、式（４）で表されるポリマーとする。〕は酸化触媒として使用することができ、特に、水溶液中でのアルコール化合物の電解酸化反応において好適に使用される。更に、本発明の式（１）で表されるＮ−オキシルピペリジノカルバモイル基を有するポリマーの還元体であるＮ−ヒドロキシ誘導体は、電解酸化反応系内で容易にＮ−オキシル化合物に変換されるため、相当する還元体を使用することも可能である。例えば電解酸化用触媒として、上記Ｎ−オキシル化合物と結合したポリマーの代りに、相当するＮ−ヒドロキシ化合物と結合したポリマーを用いた場合、電解系で容易にＮ−オキシル化合物と結合したポリマーが生成するため本反応に用いることが可能である。電解酸化用触媒は１種を単独で使用でき又は２種以上を併用できる。
【００２４】
本発明の電解酸化法は、例えば式（１）で表されるＮ−オキシルピペリジノカルバモイル基を有するポリマーに原料化合物であるアルコール化合物を担持させた後、これを支持電解質を含む水中に入れ、通常の方法に従って電解酸化することにより行われる。
【００２５】
本発明において、アルコール化合物とは、ポリマーに担持することができるものであればよく、特に水中にほとんど溶出することがないだけの疎水性を有している水に難溶性のアルコール化合物が好ましい。アルコール化合物及びその置換基の種類、式（１）で表されるＮ−オキシルピペリジノカルバモイル基を有するポリマーの 種類によって、アルコール化合物が留まっている度合いが異なるため、アルコール化合物の水溶解度や分子量等で一概に規定できないが、おおよそ一般に水に対して難溶性を示すアルコール化合物が好ましい。事実メタノール、エタノール、エチレングリコール等の水溶解性の高いアルコール化合物の場合、反応は進行しない。従って、一般に電解酸化反応に適応することができるアルコール化合物であって、ポリマーに担持でき且つ水難溶性を示すアルコール化合物であれば特に制限されず、種々のものが使用できる。
【００２６】
アルコール化合物の具体例としては、例えば、ｎ−ブチルアルコール、ｎ−ペンチルアルコール、２−クロロ−ｎ−ペンチルアルコール、３−アセトキシ−ｎ−ペンチルアルコール、２−ブチルアルコール、２−ペンチルアルコール、ベンジルアルコール、２−フェニル−１−エタノール、１−フェニル−１−エタノール等の置換基を有することのあるアルコール類、シクロヘキシルアルコール、シクロペンチルアルコール、４−メトキシシクロヘキシルアルコール等の置換基を有することのある環状アルコール類、ブタンジオール、ペンタンジオール、ヘキサンジオール、ヘプタンジオール、３−メチルヘキサンジオール、３−アセトキシペンタンジオール、３−クロロ−２−メチルヘキサンジオール、シクロヘキサン−１,２−ジエタノール等の置換基を有することのある直鎖状もしくは分岐鎖状ジオール類が挙げられる。更に、トリオール類や４つ以上の水酸基を有するアルコール化合物であっても、水難溶性であって、且つシリカゲルに担持可能なアルコール化合物であれば使用できる。
【００２７】
これらのアルコール化合物に置換できる置換基としては、ハロゲン原子、ニトロ基、シアノ基、アリール基、低級アルキル基、アミノ基、モノ低級アルキルアミノ基、ジ低級アルキルアミノ基、メルカプト基、基ＲＳ−（Ｒは低級アルキル基又はアリール基）で表されるアルキルチオ基又はアリールチオ基、ホルミルオキシ基、基ＲＣＯＯ−（Ｒは前記に同じ）で表されるアシルオキシ基、ホルミル基、基ＲＣＯ−（Ｒは前記に同じ）で表されるアシル基、基ＲＯ−（Ｒは前記に同じ）で表されるアルコキシ基又はアリールオキシ基、カルボキシル基、基ＲＯＣＯ−（Ｒは前記に同じ）で表されるアルコキシカルボニル基又はアリールオキシカルボニル基などが例示できる。ここで低級アルキル基としては炭素数１〜６のアルキル基、アリール基としてはフェニル、トリル、キシリル、ナフチル等を例示できる。
【００２８】
本発明において用いた原料アルコールより高次な酸化物とは、例えば原料アルコールとしてｎ−ブチルアルコールを使用した場合は、ｎ−ブタナール、ｎ−ブタン酸又はｎ−ブタン酸ｎ−ブチルエステルが得られ、１−フェニルエタノールを使用した場合は、アセトフェノンが得られ、１,４−ブタンジオールを使用した場合は、テトラヒドロ−２−フラノンが得られ、１,２−ビス（ヒドロキシメチル）シクロヘキサンを使用した場合は８−オキサビシクロ［４.３.０］ノナン−７−オン等が得られる。
【００２９】
本電解反応は式（１）で表されるＮ−オキシルピペリジノカルバモイル基を有するポリマーに原料を担持した後水中で行われるが、使用量としては、ポリマーとＮ−オキシル化合物との結合数にもよるが、原料アルコール化合物１ｋｇ当たり０.０５〜５０ｋｇ、好ましくは０.１〜５ｋｇの範囲で行うのが良い。
【００３０】
本発明の反応は支持電解質の存在下に行うのが好ましい。使用できる支持電解質としては、水に可溶で通電が可能な塩であればすべて使用可能であるが、例えば塩化リチウム、塩化ナトリウム、塩化カリウム、臭化リチウム、臭化ナトリウム、臭化カリウム、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム等のハロゲン化アルカリ金属塩、塩化ベリリウム、塩化マグネシウム、塩化カルシウム、臭化ベリリウム、臭化マグネシウム、臭化カルシウム、ヨウ化ベリリウム、ヨウ化マグネシウム、ヨウ化カルシウム等のハロゲン化アルカリ土類金属塩、炭酸リチウム、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩、炭酸ベリリウム、炭酸マグネシウム、炭酸カルシウム等のアルカリ土類金属炭酸塩、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム等のアルカリ金属炭酸水素塩、燐酸２水素ナトリウム、燐酸２ナトリウム、燐酸２水素カリウム、燐酸２カリウム等のアルカリ金属燐酸塩、燐酸マグネシウム、燐酸カルシウム等のアルカリ土類金属燐酸塩、塩化アンモニウム、臭化アンモニウム、ヨウ化アンモニウム等のハロゲン化アンモニウム塩、塩化テトラメチルアンモニウム、臭化テトラメチルアンモニウム、ヨウ化テトラメチルアンモニウム、塩化テトラエチルアンモニウム、臭化テトラエチルアンモニウム、ヨウ化テトラエチルアンモニウム、塩化テトラブチルアンモニウム、臭化テトラブチルアンモニウム、ヨウ化テトラブチルアンモニウム等のハロゲン化テトラアルキルアンモニウム、炭酸アンモニウム、炭酸水素アンモニウム等の炭酸アンモニウム塩、燐酸２水素アンモニウム、燐酸２アンモニウム等の燐酸アンモニウム塩、
【００３１】
燐酸２水素テトラエチルアンモニウム、燐酸２水素テトラブチルアンモニウム等の燐酸テトラアルキルアンモニウム塩、硫酸リチウム、硫酸ナトリウム、硫酸カリウム等のアルカリ金属硫酸塩、硫酸水素リチウム、硫酸水素ナトリウム、硫酸水素カリウム等の硫酸水素アルカリ金属塩、硫酸水素テトラエチルアンモニウム、硫酸水素テトラブチルアンモニウム等の硫酸水素テトラアルキルアンモニウム塩、硫酸マグネシウム、硫酸カルシウム等のアルカリ土類金属硫酸塩、次亜塩素酸ナトリウム、次亜塩素酸カリウム、次亜塩素酸カルシウム等の次亜塩素酸塩、過塩素酸リチウム、過塩素酸ナトリウム、過塩素酸マグネシウム等の過塩素酸金属塩、過塩素酸アンモニウム、過塩素酸テトラエチルアンモニウム、過塩素酸テトラブチルアンモニウム等の過塩素酸アンモニウム塩、テトラブチルアンモニウムトシレート等のスルホン酸アンモニウム塩、硼弗化リチウム、硼弗化ナトリウム等の硼弗化金属塩、硼弗化テトラエチルアンモニウム、硼弗化テトラブチルアンモニウム等の硼弗化アンモニウム塩等が挙げられる。
【００３２】
これらの中でも、ハロゲン化アルカリ金属塩、ハロゲン化アルカリ土類金属塩、ハロゲン化テトラアルキルアンモニウム塩、アルカリ金属炭酸塩、アルカリ土類金属炭酸塩が好ましい。
これらの支持電解質は、１種を単独で使用でき、必要に応じて２種以上併用できる。支持電解質の使用量としては、溶媒中、通常０.１〜７０重量％程度、好ましくは０.１〜５０重量％程度の濃度になるようにするのがよい。
【００３３】
本反応で使用する水の使用量としては、特に制限されず、各種反応条件等に応じて適宜選択できるが、通常原料化合物１ｋｇ当たり、通常２〜２０００リットル程度、好ましくは５〜１００リットル程度とするのがよい。水と混合可能な有機溶媒がポリマーに担持された必要な有機物の担持を阻害しない程度であれば適当な溶媒が混入していても反応に支障はない。このような溶媒としては、テトラヒドロフラン、ジオキサン、ジオキソラン等の環状エーテル類、ジメチルホルムアミド、ジエチルホルムアミド、ジメチルアセトアミド等のアミド類、Ｎ−メチルピロリジノン等の環状アミド類、ジメチルスルホキシド等が挙げられる。これらの混入許容量はポリマーの種類、形状、使用量等により異なり、また混入する溶媒によっても異なるが、使用する水に対して３０重量％以下とするのが好ましい。
【００３４】
本電解酸化反応は、通常−５〜１００℃程度、好ましくは０〜６０℃程度の温度下に実施される。
【００３５】
本発明の方法による電解酸化においては、通常の電解反応に用いられる電極を広く利用できる。具体的には、陽極材料として、白金、ステンレス、ニッケル、酸化鉛、炭素、酸化鉄、チタン等が、また陰極材料としては、白金、スズ、アルミニウム、ステンレス、亜鉛、鉛、銅、炭素等が使用できるが、好ましくは陽極材料として白金、炭素、ステンレス等が使用できる。
【００３６】
本発明の電解酸化は陽極と陰極を隔膜で分離してもよいが、とくに分離する必要はなく、単一槽中で行なえることをも特徴としている。
本電解反応は、定電流電解法及び定電圧電解法のいずれをも採用することができるが、装置や操作の簡便さの点で定電流電解法を採用するのが好ましい。電解は、直流または交流電解が可能であるが電流方向を１〜３０秒毎に切り替えて行なうこともできる。電流密度は、通常１〜５００ｍＡ／ｃｍ^２、好ましくは１〜５０ｍＡ／ｃｍ^２の範囲とするのが良い。電気量は用いる電解槽の形状、アルコール化合物の種類、用いる溶媒の種類等により異なり、一概には言えないが、通常２〜２０Ｆ／モル程度、好ましくは２〜８Ｆ／モル程度とするのがよく、上記電気量を通電すれば反応は完結する。
【００３７】
【実施例】
以下に実施例を挙げて、本発明を具体的に説明するが、何らこれらに限定されるものではない。
【００３８】
実施例１
（工程１）
ポリエチレンフィルム１２ｇに９７％発煙硝酸２００ｍｌを加え、８０℃で５０分間攪拌し、得られたフィルムを蒸留水で洗浄した後、蒸留水２００ｍｌに２４時間浸漬させた。このものをろ過してとり、減圧下乾燥して、ポリエチレン主鎖にカルボキシル基が結合したポリマー１０ｇが得られた。
ＩＲ（ｃｍ^−１）：１７１２、１５５４、１４７３
（工程２）
得られたポリマー１.１４ｇ、クロルベンゼン２０ｍｌ、ジシクロヘキシルカルボジイミド４２２.５ｍｇ及び４−アミノ−２,２,６,６−テトラメチルピペリジン−Ｎ−オキシル２２９ｍｇを混合し、５０℃にて２日間反応を行った。反応混合物を減圧濾過し、クロロベンゼン２０ｍｌ、水２０ｍｌ、メタノール２０ｍｌ、エーテル２０ｍｌの順で洗浄を行った後、減圧乾燥を行い、Ｎ−オキシル−２,２,６,６−テトラメチル−４−ピペリジノアミド−ポリエチレン〔ポリマー（Ａ）〕が１.１４ｇ得られた。
ＩＲ（ｃｍ^−１）：１７０４、１６５０、１６４５、１６３０、１５５５、１５２６
【００３９】
実施例２
ポリ（ｐ−フェニレンベンゾビスチアゾール） ３９９ｍｇ、アセトニトリル１０ｍｌ、ジシクロヘキシルカルボジイミド１１９ｍｇ及び４−アミノ−２,２,６,６−テトラメチルピペリジン−Ｎ−オキシル１０５ｍｇを混合し、５０℃で４８時間攪拌した。反応混合物を室温まで冷却して減圧濾過し、得られた固体をアセトニトリルで洗浄し、減圧下で乾燥して、Ｎ−オキシル−２,２,６,６−テトラメチル−４−ピペリジノアミド−ポリ（ｐ−フェニレンベンゾビスチアゾール）〔ポリマー（Ｂ）〕４５１ｍｇが黒色粉末として得られた。
【００４０】
実施例３
１−（ｐ−クロロフェニル）エチルアルコール１５７ｍｇ（１.００ｍｍｏｌ）及びポリマー（Ａ）５００ｍｇにアセトン２ｍｌを加え、５分間激しく撹拌した後、使用したアセトンを減圧留去した。次に支持電解質を含む反応溶媒として２０重量％の臭化ナトリウムを含む飽和重曹水５ｍｌを加え、十分に撹拌した後、２枚の白金電極（１.５×１.０ｃｍ^２）を付し、室温下激しく撹拌しながら電流を３０ｍＡに保ちつつ、２.６時間電解酸化反応を行った（３Ｆ／ｍｏｌ）。反応終了後、反応混合物をろ過し、得られた固形残渣からアセトン５ｍｌで抽出し、抽出液からアセトンを留去すると１−（ｐ−クロロフェニル）エチル−１−オン１３３ｍｇ（収率８６％）が得られた。
１Ｈ ＮＭＲ（２００ＭＨｚ、ＣＤＣｌ_３）δ２.６０（ｓ，３Ｈ），７.４４（ｄ，Ｊ＝８.３Ｈｚ，２Ｈ），７.９０（ｄ，Ｊ＝８.４Ｈｚ，２Ｈ）。
【００４１】
実施例４
実施例１のポリエチレンの硝酸処理条件を以下に変えた以外は、実施例１と同様にしてポリマー（Ａ）を調製し、以下実施例３と同様に反応を行った結果を示す。得られた生成物の１Ｈ ＮＭＲは実施例３で得られたケトン化合物のそれと一致した。

【００４２】
実施例５
実施例３において、電解酸化反応条件（電流と通電時間）を以下に変えた以外は実施例３と同様にして反応を行った結果を示す。得られた生成物の１Ｈ ＮＭＲは実施例３で得られたケトン化合物のそれと一致した。

【００４３】
実施例６
実施例３において、電極を以下に変えた以外は実施例３と同様にして反応を行った結果を示す。得られた生成物の１Ｈ ＮＭＲは実施例３で得られたケトン化合物のそれと一致した。

【００４４】
実施例７
実施例３において、支持電解質を含む反応溶媒を以下に変えた以外は実施例３と同様にして反応を行った結果を示す。得られた生成物の１Ｈ ＮＭＲは実施例３で得られたケトン化合物のそれと一致した。

【００４５】
実施例８
実施例３で最初にろ過された支持電解質を含む重曹溶液を、実施例３で使用する２０重量％の臭化ナトリウムを含む飽和重曹水の代りに用いて反応を行った結果８５％の収率で目的のケトン体を得ることができた。
【００４６】
実施例９
１,４−ブタンジオール９０ｍｇ（１.００ｍｍｏｌ）及び実施例１のポリマー（Ａ）４９３ｍｇにアセトン２ｍｌを加えて５分間攪拌した後、使用したアセトンを減圧留去した。２０重量％の臭化ナトリウムを含む飽和重曹水５ｍｌを加え、十分に撹拌しながら電流を３０ｍＡに保ちつつ、４時間電解酸化反応を行った（４.５Ｆ／ｍｏｌ）。反応終了後、反応混合物をろ過し、得られたポリマーをアセトン５ｍｌで抽出した後、アセトンを留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（酢酸エチル／ヘキサン＝７／１）で精製して、γ−ブチロラクトン７９ｍｇ（収率９２％)が得られた。
１Ｈ ＮＭＲ（２００ＭＨｚ、ＣＤＣｌ_３）δ １.５６−１.７１（ｍ，２Ｈ），２.４７（ｔ，Ｊ＝８.０Ｈｚ，２Ｈ），４.３３（ｔ，Ｊ＝８.８Ｈｚ，２Ｈ）
【００４７】
実施例１０
１−（ｐ−クロロフェニル)エチルアルコール８０ｍｇ（０.５１ｍｍｏｌ）及びポリマー（Ｂ）３９８ｍｇに２０重量％の臭化ナトリウムを含む飽和重曹水５ｍｌを加え、十分に撹拌した後、２枚の白金電極（１.５×１.０ｃｍ^２）を付し、０〜５℃で激しく撹拌しながら電流を２０ｍＡに保ちつつ１時間４０分電解酸化反応を行った（２.５Ｆ／ｍｏｌ）。反応終了後、反応混合物をろ過し、得られた固形残渣を酢酸エチル１５ｍｌで抽出した後、酢酸エチルを留去して１−（ｐ−クロロフェニル)エチル−１−オン６５ｍｇ（収率８２％)が得られた。得られた化合物の１Ｈ ＮＭＲは実施例３のそれに一致した。
【００４８】
実施例１１
実施例１０でろ過、抽出処理された固形残渣をそのまま用いて実施例１０と同様の反応を行った。この操作を５回繰り返し、その結果を以下に示す。得られた生成物の１Ｈ ＮＭＲは実施例３で得られたケトン化合物のそれと一致した。

【００４９】
実施例１２
実施例１０において、電解酸化反応条件（通電時間、通電量）を以下に変えた以外は実施例１０と同様にして反応を行った結果を示す。得られた生成物の１Ｈ
ＮＭＲは実施例３で得られたケトン化合物のそれと一致した。

【００５０】
【発明の効果】
電解酸化反応においてポリマーと化学結合した酸化触媒を用い、原料を担持させた後、電解酸化を行うことにより、有機溶媒を使用することなくアルコール化合物の電解酸化を行うことが可能となり、アルデヒド、ケトン、ラクトン化合物等を高収率、高効率で製造することができる。また、回収されるポリマーと化学結合した酸化触媒はその性質上そのままリサイクルされるため、実質的に電気のみを用いたクリーンな酸化反応の実現が可能となった。
【００５１】
本発明の酸化反応はポリマーに結合した酸化触媒を用い、そのポリマー上に原料を担持させて電解酸化反応を行う方法で、酸化反応の効率の向上と、生成物の単離精製を容易にし、アルデヒド、ケトン、ラクトン化合物等の簡便な合成方法の提供が可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymer having an oxidation catalyst ability. Specifically, the present invention relates to a polymer in which an N-oxyl compound is chemically bonded. The present invention also relates to a method for producing a higher order oxide than alcohol using the polymer as an oxidation catalyst.
[0002]
[Prior art]
In the field of organic synthesis, the oxidation reaction of alcohol is generally widely used and many methods have been developed. In particular, the electrolytic oxidation reaction is attracting attention as a clean oxidation reaction because it performs an electrochemical oxidation reaction, and some of the reactions are performed on an industrial scale.
[0003]
As a conventional electrolytic oxidation method for alcohol, as described in “Organic Electrosynthesis” (Shigeru Torii, 1981, pp. 262-273), a direct electrolytic oxidation method in an organic solvent or a hydrous organic solvent is used. Alternatively, an indirect electrolytic oxidation method using a mediator (electron carrier), an electrolytic oxidation method in a two-layer system of water and an organic solvent not mixed with water (J. Org. Chem., 1991,56, 2416-2421) are generally performed.
[0004]
[Problems to be solved by the invention]
In many reaction systems of these electrolytic oxidation methods, an organic solvent that is difficult to pass an electric current is originally used. Therefore, for example, when N, N-dimethylformamide is used as a solvent, 10 to 50% by weight of a supporting electrolyte is required. A large amount of supporting electrolyte must be used. In addition, since a large amount of the supporting electrolyte is used in this way, complicated operations are required not only in cost and waste problems but also in product isolation and purification.
[0005]
In addition, methods using various metal catalysts as mediators are also known, but these are serious in terms of metal compound costs and post-treatment problems, and those that can be used industrially are limited. Metal catalysts are inevitably recycled due to their high cost, but generally they require complicated operations, and therefore the recovery rate is not excellent.
[0006]
N-oxyl compounds have been reported to be excellent as catalysts for the electrolytic oxidation reaction of alcohol (J. Org. Chem., 1991,56, 2416-2421), all of the reactions introduced in the literature are methylene chloride / water two-layer oxidation reactions, and this reaction is used today because methylene chloride is industrially difficult to use due to environmental problems. It is impossible.
[0007]
In addition, conventionally used N-oxyl compounds are present together with products in the organic layer after the reaction, and usually have to be recovered by column chromatography or fractional crystallization after solvent concentration.
Thus, the electrolytic oxidation method for alcohol compounds still has many problems, and the appearance of a more industrially practical oxidation method has been desired.
[0008]
An object of the present invention is to overcome the drawbacks found in the above-mentioned conventional production methods, provide an excellent oxidation catalyst, and electrolytically oxidize an alcohol compound that is hardly soluble in water to achieve high yield and high efficiency. The purpose of the present invention is to provide a versatile production method capable of producing a higher-order oxide than alcohol.
[0009]
[Means for Solving the Problems]
  The present invention relates to N-oxylpi represented by the formula (1).BaeThe present invention relates to a polymer having a lysinocarbamoyl group.
[0010]
[Chemical Formula 3]

(Wherein R¹, R², R³And R⁴Are the same or different and represent a lower alkyl group. )
[0011]
  Furthermore, the present invention relates to N-oxylpi represented by the formula (1).BaeThe present invention relates to a method for producing a higher-order oxide than alcohol, which comprises electrolytically oxidizing an alcohol compound in the presence of a polymer having a lysinocarbamoyl group. Examples of higher-order oxides than alcohols include aldehydes, ketones, lactones, carboxylic acid esters, and carboxylic acid compounds.
[0012]
The inventors of the present invention have provided an oxidation catalytic ability that can be stably and easily recovered under electrolytic oxidation conditions or after-treatment conditions by chemically bonding a polymer and an N-oxyl compound having an oxidation catalytic ability. Invented a polymer with. Furthermore, we have developed a completely new method for producing higher-order oxides than alcohols, in which electrolytic oxidation is carried out with an alcohol compound supported on the polymer in an aqueous solution.
[0013]
If the polymer is used, an oxidation reaction can be performed in a state where the alcohol compound is supported on the polymer, so that an electrolytic oxidation reaction can be performed in an aqueous solution with high current efficiency, and the amount of supporting electrolyte used can be reduced. it can. Furthermore, by chemically bonding the polymer and N-oxyl compound having oxidation catalytic ability, the solubility of the N-oxyl compound having catalytic ability in the aqueous solution is extremely lowered, and almost completely recovered and reused. It becomes possible to do.
[0014]
Thus, by using a polymer chemically bonded to an N-oxyl compound having an oxidation catalyst ability without using an organic solvent, an electrolytic oxidation reaction that can recycle the catalyst almost completely is performed without using an organic solvent. It becomes possible.
[0015]
Along with this, since the product is finally supported on the polymer part of the polymer, only the product is recovered just by washing the polymer part with a small amount of organic solvent after filtration. It also has the high advantage of being able to. Further, since the polymer separated at this time can be used as it is in the next reaction, no extra separation operation is required. Thus, by subjecting an alcohol compound to electrolytic oxidation without using an organic solvent in an electrolytic oxidation reaction system of an organic compound, an oxide higher in level than an alcohol such as a target aldehyde, ketone, or lactone compound is obtained. Has been found out that it can be produced with high yield and high efficiency, and the present invention has been completed.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
In the present specification, the lower alkyl group is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. 6 linear and branched alkyl groups are shown.
[0017]
The polymer having an N-oxylpyrrolidinocarbamoyl group represented by the formula (1) of the present invention is produced by a reaction represented by the following reaction formula 1.
[0018]
[Formula 4]
(Reaction Formula 1)

(Where R¹, R², R³And R⁴Is the same as above. )
[0019]
The compound represented by Formula (2) used in this reaction can be produced by a known method, or a commercially available product can be used.
In this reaction, a condensing agent such as dicyclohexylcarbodiimide (DCC) is used, and conditions for dehydration condensation reaction of a carboxylic acid and an amine conventionally performed in this field are applied.
[0020]
The polymer used in the present invention is not particularly limited as long as it has at least one carboxyl group in the polymer molecule, and is represented by the formula (3) for convenience, and the molecular weight is a weight average molecular weight. About 3 to 5 million, preferably about 5 to 3 million, more preferably about 1000 to 1 million is suitable. Specifically, as a polymer having a carboxyl group, for example, a polymer in which the polymer part has p-phenylenebenzobisthiazole, such as poly (p-phenylenebenzobisthiazole), polyacrylic acid, carboxyl An ion exchange resin having a group can also be used. Moreover, what hydrolyzed polyester and produced | generated the carboxyl group can also be used.
In addition, polymers that do not have a carboxyl group, such as polyhydrocarbon compounds such as polyethylene and polypropylene, can also be used by performing a conventionally known oxidation treatment. These polymers are preferably those that do not dissolve in water or organic solvents.
[0021]
In this reaction, the content ratio of the N-oxyl compound represented by the formula (2) to the polymer represented by the formula (3) is not particularly limited in practice, but it depends on the weight of the polymer used. On the other hand, the N-oxyl compound represented by the formula (2) may be adjusted to be about 3 to 40% by weight, preferably about 5 to 25% by weight.
[0022]
For example, this reaction is performed in a suitable solvent. The solvent is not particularly limited as long as it is inert to this reaction. Examples of the solvent include aliphatic or alicyclic hydrocarbons such as hexane, cyclohexane and heptane, aromatic hydrocarbons such as benzene, chlorobenzene, toluene and xylene, methylene chloride, dichloroethane, chloroform, carbon tetrachloride and the like. Examples thereof include halogenated hydrocarbons, esters such as ethyl acetate and methyl acetate, and ethers such as diethyl ether, tetrahydrofuran and dioxane. These are used individually by 1 type or in mixture of 2 or more types. These solvents are usually used in an amount of about 2 to 200 L, preferably about 10 to 100 L, per 1 kg of the polymer represented by the formula (3).
[0023]
  N-oxylpi represented by the formula (1) of the present inventionBaePolymer having a lysinocarbamoyl group [hereinafter referred to as a polymer represented by the formula (4). ] Can be used as an oxidation catalyst, and is particularly preferably used in an electrolytic oxidation reaction of an alcohol compound in an aqueous solution. Furthermore, N-oxylpi represented by the formula (1) of the present invention.BaeSince the N-hydroxy derivative which is a reduced form of a polymer having a lysinocarbamoyl group is easily converted into an N-oxyl compound in the electrolytic oxidation reaction system, the corresponding reduced form can be used. For example, when a polymer bonded to the corresponding N-hydroxy compound is used instead of the polymer bonded to the N-oxyl compound as a catalyst for electrolytic oxidation, a polymer bonded easily to the N-oxyl compound is generated in the electrolytic system. Therefore, it can be used for this reaction. The catalyst for electrolytic oxidation can be used individually by 1 type, or can use 2 or more types together.
[0024]
  The electrolytic oxidation method of the present invention is, for example, N-oxylpi represented by the formula (1).BaeAfter the alcohol compound as the raw material compound is supported on a polymer having a lysinocarbamoyl group, this is carried out by placing it in water containing a supporting electrolyte and subjecting it to electrolytic oxidation according to a usual method.
[0025]
  In the present invention, the alcohol compound is not particularly limited as long as it can be supported on a polymer, and in particular, an alcohol compound hardly soluble in water and having hydrophobicity that hardly dissolves in water. Types of alcohol compounds and substituents thereof, N-oxylpi represented by formula (1)BaePolymer having lysinocarbamoyl groupof  seedDepending on the type, the degree of staying of the alcohol compound is different, so it cannot be defined in general by the water solubility or molecular weight of the alcohol compound, but an alcohol compound that is generally poorly soluble in water is preferred. In fact, in the case of alcohol compounds with high water solubility such as methanol, ethanol, ethylene glycol, the reaction does not proceed. Therefore, the alcohol compound is generally not particularly limited as long as it is an alcohol compound that can be adapted to an electrolytic oxidation reaction and can be supported on a polymer and exhibits poor water solubility, and various compounds can be used.
[0026]
Specific examples of the alcohol compound include, for example, n-butyl alcohol, n-pentyl alcohol, 2-chloro-n-pentyl alcohol, 3-acetoxy-n-pentyl alcohol, 2-butyl alcohol, 2-pentyl alcohol, and benzyl alcohol. , 2-phenyl-1-ethanol, alcohols having a substituent such as 1-phenyl-1-ethanol, cyclic alcohols having a substituent such as cyclohexyl alcohol, cyclopentyl alcohol, 4-methoxycyclohexyl alcohol , Butanediol, pentanediol, hexanediol, heptanediol, 3-methylhexanediol, 3-acetoxypentanediol, 3-chloro-2-methylhexanediol, cyclohexane-1,2-diethano And linear or branched diols which may have a substituent such as ruthenium. Furthermore, triols and alcohol compounds having four or more hydroxyl groups can be used as long as they are poorly water-soluble and can be supported on silica gel.
[0027]
Substituents that can be substituted for these alcohol compounds include halogen atoms, nitro groups, cyano groups, aryl groups, lower alkyl groups, amino groups, mono-lower alkylamino groups, di-lower alkylamino groups, mercapto groups, groups RS- ( R is a lower alkyl group or aryl group) alkylthio group or arylthio group, formyloxy group, acyloxy group represented by RCOO- (where R is the same as above), formyl group, group RCO- An alkoxy group represented by an acyl group represented by a group RO- (R is the same as above) or an aryloxy group, a carboxyl group, and a group ROCO- (where R is the same as above). Examples include a group or an aryloxycarbonyl group. Examples of the lower alkyl group include alkyl groups having 1 to 6 carbon atoms, and examples of the aryl group include phenyl, tolyl, xylyl, naphthyl, and the like.
[0028]
For example, when n-butyl alcohol is used as the raw material alcohol, n-butanal, n-butanoic acid or n-butanoic acid n-butyl ester is obtained when the higher-order oxide than the raw material alcohol used in the present invention is used. When 1-phenylethanol was used, acetophenone was obtained, and when 1,4-butanediol was used, tetrahydro-2-furanone was obtained, and 1,2-bis (hydroxymethyl) cyclohexane was used. In such a case, 8-oxabicyclo [4.3.0] nonan-7-one or the like is obtained.
[0029]
  This electrolytic reaction is N-oxylpi represented by the formula (1).BaeAlthough it is carried out in water after supporting the raw material on the polymer having a lysinocarbamoyl group, the amount used depends on the number of bonds between the polymer and the N-oxyl compound, but is 0.05 to 50 kg per kg of the raw alcohol compound, Preferably it is good to carry out in the range of 0.1-5 kg.
[0030]
The reaction of the present invention is preferably carried out in the presence of a supporting electrolyte. As the supporting electrolyte that can be used, any salt that is soluble in water and can be energized can be used. For example, lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide, iodine Alkali metal halides such as lithium iodide, sodium iodide, potassium iodide, beryllium chloride, magnesium chloride, calcium chloride, beryllium bromide, magnesium bromide, calcium bromide, beryllium iodide, magnesium iodide, calcium iodide Halogenated alkaline earth metal salts such as lithium carbonate, sodium carbonate, potassium carbonate and other alkali metal carbonates, beryllium carbonate, magnesium carbonate, calcium carbonate and other alkaline earth metal carbonates, lithium hydrogen carbonate, sodium hydrogen carbonate, Alkali metal hydrogen carbonate such as potassium hydrogen carbonate , Alkali metal phosphates such as sodium dihydrogen phosphate, disodium phosphate, potassium dihydrogen phosphate, dipotassium phosphate, alkaline earth metal phosphates such as magnesium phosphate, calcium phosphate, ammonium chloride, ammonium bromide, ammonium iodide, etc. Ammonium halide salt, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, iodide Tetraalkylammonium halides such as tetrabutylammonium, ammonium carbonates such as ammonium carbonate and ammonium bicarbonate, ammonium dihydrogen phosphate, diammonium phosphate Phosphoric acid ammonium salt of,
[0031]
Tetraalkylammonium phosphates such as tetraethylammonium phosphate, tetrabutylammonium phosphate, alkali metal sulfates such as lithium sulfate, sodium sulfate, and potassium sulfate, hydrogen sulfates such as lithium hydrogen sulfate, sodium hydrogen sulfate, and potassium hydrogen sulfate Alkali metal salts, tetraalkylammonium hydrogensulfates such as tetraethylammonium hydrogensulfate and tetrabutylammonium hydrogensulfate, alkaline earth metal sulfates such as magnesium sulfate and calcium sulfate, sodium hypochlorite, potassium hypochlorite, Hypochlorite such as calcium chlorite, perchlorate metal salts such as lithium perchlorate, sodium perchlorate, magnesium perchlorate, ammonium perchlorate, tetraethylammonium perchlorate, tetrabutyl perchlorate Ammoni Ammonium perchlorate such as tetrabutylammonium tosylate, borofluoride metal salts such as lithium borofluoride and sodium borofluoride, tetraethylammonium borofluoride, tetrabutylammonium borofluoride And ammonium borofluoride salts.
[0032]
Among these, halogenated alkali metal salts, halogenated alkaline earth metal salts, halogenated tetraalkylammonium salts, alkali metal carbonates, and alkaline earth metal carbonates are preferable.
These supporting electrolytes can be used individually by 1 type, and can be used together 2 or more types as needed. The amount of the supporting electrolyte used is usually about 0.1 to 70% by weight, preferably about 0.1 to 50% by weight in the solvent.
[0033]
The amount of water used in this reaction is not particularly limited and can be appropriately selected according to various reaction conditions, etc., but is usually about 2 to 2000 liters, preferably about 5 to 100 liters per 1 kg of the raw material compound. It is good to do. As long as the organic solvent that can be mixed with water does not hinder the loading of the necessary organic substance supported on the polymer, there is no problem in the reaction even if an appropriate solvent is mixed. Examples of such a solvent include cyclic ethers such as tetrahydrofuran, dioxane and dioxolane, amides such as dimethylformamide, diethylformamide and dimethylacetamide, cyclic amides such as N-methylpyrrolidinone, and dimethyl sulfoxide. These admissible amounts vary depending on the type, shape, amount and the like of the polymer, and also vary depending on the solvent to be mixed, but are preferably 30% by weight or less based on the water used.
[0034]
This electrolytic oxidation reaction is usually performed at a temperature of about −5 to 100 ° C., preferably about 0 to 60 ° C.
[0035]
In the electrolytic oxidation according to the method of the present invention, an electrode used for a normal electrolytic reaction can be widely used. Specifically, platinum, stainless steel, nickel, lead oxide, carbon, iron oxide, titanium, etc. are used as the anode material, and platinum, tin, aluminum, stainless steel, zinc, lead, copper, carbon, etc. are used as the cathode material. Although usable, platinum, carbon, stainless steel and the like can be preferably used as the anode material.
[0036]
In the electrolytic oxidation of the present invention, the anode and the cathode may be separated by a diaphragm, but it is not particularly necessary to separate them, and it can be performed in a single tank.
For this electrolysis reaction, either a constant current electrolysis method or a constant voltage electrolysis method can be employed, but it is preferable to employ a constant current electrolysis method from the viewpoint of simplicity of apparatus and operation. The electrolysis can be DC or AC electrolysis, but can also be performed by switching the current direction every 1 to 30 seconds. Current density is usually 1 to 500 mA / cm², Preferably 1 to 50 mA / cm²It is better to be in the range. The amount of electricity varies depending on the shape of the electrolytic cell used, the type of alcohol compound, the type of solvent used, etc., and it cannot be generally stated, but it is usually about 2 to 20 F / mol, preferably about 2 to 8 F / mol. The reaction is completed when the amount of electricity is applied.
[0037]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.
[0038]
Example 1
(Process 1)
To 12 g of polyethylene film, 200 ml of 97% fuming nitric acid was added and stirred at 80 ° C. for 50 minutes. The obtained film was washed with distilled water and then immersed in 200 ml of distilled water for 24 hours. This was filtered off and dried under reduced pressure to obtain 10 g of a polymer having a carboxyl group bonded to the polyethylene main chain.
IR (cm^-1): 1712, 1554, 1473
(Process 2)
1.14 g of the obtained polymer, 20 ml of chlorobenzene, 422.5 mg of dicyclohexylcarbodiimide and 229 mg of 4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl were mixed and reacted at 50 ° C. for 2 days. went. The reaction mixture was filtered under reduced pressure, washed with 20 ml of chlorobenzene, 20 ml of water, 20 ml of methanol, and 20 ml of ether in that order, then dried under reduced pressure, and N-oxyl-2,2,6,6-tetramethyl-4-piperidinoamide. -1.14g of polyethylene [polymer (A)] was obtained.
IR (cm^-1): 1704, 1650, 1645, 1630, 1555, 1526
[0039]
Example 2
399 mg of poly (p-phenylenebenzobisthiazole), 10 ml of acetonitrile, 119 mg of dicyclohexylcarbodiimide and 105 mg of 4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl were mixed and stirred at 50 ° C. for 48 hours. The reaction mixture was cooled to room temperature and filtered under reduced pressure, and the resulting solid was washed with acetonitrile, dried under reduced pressure, and N-oxyl-2,2,6,6-tetramethyl-4-piperidinoamide-poly ( 451 mg of (p-phenylenebenzobisthiazole) [polymer (B)] was obtained as a black powder.
[0040]
Example 3
2 ml of acetone was added to 157 mg (1.00 mmol) of 1- (p-chlorophenyl) ethyl alcohol and 500 mg of the polymer (A), and the mixture was vigorously stirred for 5 minutes, and then used acetone was distilled off under reduced pressure. Next, 5 ml of a saturated sodium bicarbonate solution containing 20% by weight of sodium bromide was added as a reaction solvent containing the supporting electrolyte, and after sufficient stirring, two platinum electrodes (1.5 × 1.0 cm) were added.²The electrolytic oxidation reaction was carried out for 2.6 hours (3F / mol) while maintaining the current at 30 mA with vigorous stirring at room temperature. After completion of the reaction, the reaction mixture was filtered, extracted from the resulting solid residue with 5 ml of acetone, and acetone was distilled off from the extract to give 133 mg of 1- (p-chlorophenyl) ethyl-1-one (yield 86%). Obtained.
1H NMR (200 MHz, CDCl₃) 2.60 (s, 3H), 7.44 (d, J = 8.3 Hz, 2H), 7.90 (d, J = 8.4 Hz, 2H).
[0041]
Example 4
The polymer (A) was prepared in the same manner as in Example 1 except that the nitric acid treatment conditions for polyethylene in Example 1 were changed to the following, and the results of the reaction in the same manner as in Example 3 are shown below. The 1H NMR of the obtained product was consistent with that of the ketone compound obtained in Example 3.

[0042]
Example 5
In Example 3, the result of performing the reaction in the same manner as in Example 3 except that the electrolytic oxidation reaction conditions (current and energization time) were changed as follows. The 1H NMR of the obtained product was consistent with that of the ketone compound obtained in Example 3.

[0043]
Example 6
In Example 3, the result of performing the reaction in the same manner as in Example 3 except that the electrodes were changed as follows. The 1H NMR of the obtained product was consistent with that of the ketone compound obtained in Example 3.

[0044]
Example 7
In Example 3, the result of performing the reaction in the same manner as in Example 3 except that the reaction solvent containing the supporting electrolyte was changed to the following is shown. The 1H NMR of the obtained product was consistent with that of the ketone compound obtained in Example 3.

[0045]
Example 8
The reaction was carried out using the sodium bicarbonate solution containing the supporting electrolyte first filtered in Example 3 in place of the saturated sodium bicarbonate solution containing 20% by weight of sodium bromide used in Example 3. As a result, the yield was 85%. Thus, the desired ketone body could be obtained.
[0046]
Example 9
2 ml of acetone was added to 90 mg (1.00 mmol) of 1,4-butanediol and 493 mg of the polymer (A) of Example 1, and the mixture was stirred for 5 minutes, and then used acetone was distilled off under reduced pressure. 5 ml of a saturated sodium bicarbonate solution containing 20% by weight of sodium bromide was added, and an electrolytic oxidation reaction was carried out for 4 hours while maintaining the current at 30 mA with sufficient stirring (4.5 F / mol). After completion of the reaction, the reaction mixture was filtered, and the resulting polymer was extracted with 5 ml of acetone, and then acetone was distilled off. The obtained residue was purified by silica gel column chromatography (ethyl acetate / hexane = 7/1) to obtain 79 mg of γ-butyrolactone (yield 92%).
1H NMR (200 MHz, CDCl₃) Δ 1.56-1.71 (m, 2H), 2.47 (t, J = 8.0 Hz, 2H), 4.33 (t, J = 8.8 Hz, 2H)
[0047]
Example 10
To 80 mg (0.51 mmol) of 1- (p-chlorophenyl) ethyl alcohol and 398 mg of polymer (B), 5 ml of a saturated sodium bicarbonate solution containing 20% by weight of sodium bromide was added and stirred sufficiently. 1.5 × 1.0cm²The electrolytic oxidation reaction was performed for 1 hour and 40 minutes while maintaining the current at 20 mA with vigorous stirring at 0 to 5 ° C. (2.5 F / mol). After completion of the reaction, the reaction mixture was filtered, and the resulting solid residue was extracted with 15 ml of ethyl acetate, and then the ethyl acetate was distilled off to give 65 mg of 1- (p-chlorophenyl) ethyl-1-one (yield 82%). was gotten. 1H NMR of the obtained compound was consistent with that of Example 3.
[0048]
Example 11
The same reaction as in Example 10 was performed using the solid residue filtered and extracted in Example 10 as it was. This operation was repeated 5 times, and the results are shown below. The 1H NMR of the obtained product was consistent with that of the ketone compound obtained in Example 3.

[0049]
Example 12
In Example 10, the result of having performed reaction similarly to Example 10 except having changed the electrolytic oxidation reaction conditions (energization time, energization amount) into the following is shown. 1H of the product obtained
NMR was consistent with that of the ketone compound obtained in Example 3.

[0050]
【The invention's effect】
By using an oxidation catalyst chemically bonded to the polymer in the electrolytic oxidation reaction, after supporting the raw material, the electrolytic oxidation can be performed to perform the electrolytic oxidation of the alcohol compound without using an organic solvent. , Lactone compounds and the like can be produced with high yield and high efficiency. In addition, since the oxidation catalyst chemically bonded to the recovered polymer is recycled as it is, a clean oxidation reaction using only electricity can be realized.
[0051]
In the oxidation reaction of the present invention, an oxidation catalyst bonded to a polymer is used, and a raw material is supported on the polymer to carry out an electrolytic oxidation reaction. This improves the efficiency of the oxidation reaction and facilitates product isolation and purification. It is possible to provide a simple synthesis method for aldehyde, ketone, lactone compound and the like.

Claims (4)

A method for producing a higher-order oxide than alcohol, characterized in that an alcohol compound is supported on a polymer obtained by the following production method (A) and then subjected to electrolytic oxidation.
Manufacturing method (A)
Polymer having at least one carboxyl group selected from polyolefin having a carboxyl group bonded thereto, poly (p-phenylenebenzobisthiazole) having carboxyl group, polyacrylic acid, ion exchange resin having carboxyl group, polyester having carboxyl group The N-oxylpiperidinocarbamoyl group represented by the formula (1) is incorporated into the polymer, which is obtained by subjecting the N-oxyl compound represented by the formula (2) to a dehydration condensation reaction. Method for producing polymer

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a lower alkyl group.)

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a lower alkyl group.) A method for producing a higher-order oxide than alcohol, which comprises carrying an alcohol compound on a polymer obtained by the following production method (A) and then performing electrolytic oxidation in water in the presence of a supporting electrolyte.
Manufacturing method (A)
Polymer having at least one carboxyl group selected from polyolefin having a carboxyl group bonded thereto, poly (p-phenylenebenzobisthiazole) having carboxyl group, polyacrylic acid, ion exchange resin having carboxyl group, polyester having carboxyl group The N-oxylpiperidinocarbamoyl group represented by the formula (1) is incorporated into the polymer, which is obtained by subjecting the N-oxyl compound represented by the formula (2) to a dehydration condensation reaction. Method for producing polymer

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a lower alkyl group.)

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a lower alkyl group.) The production method according to claim 1 or 2 , wherein the alcohol compound is a compound that is hardly soluble in water. The production method according to claim 1 or 2 , wherein the higher-order oxide than alcohol is an aldehyde or a ketone.