JP4000820B2 - Process for producing β-hydroxyhydroperoxides and ketones and catalyst thereof - Google Patents

Description

（式中、Ｒ¹およびＲ²はそれぞれ同一または相異なって、置換されていてもよいアルキル基、置換されていてもよいアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基、置換されていてもよいアラルキル基、置換されていてもよいアラルキルオキシ基、置換されていてもよいアシル基、置換されていてもよいカルボアルコキシ基、置換されていてもよいカルボアリールオキシ基、置換されていてもよいカルボアラルキルオキシ基、カルボキシル基、ハロゲン原子を表わす。また、Ｒ¹とＲ²が一緒になって環構造の一部を形成してもよい。）
で示されるオレフィン類が挙げられる。
【００２１】
置換されていてもよいアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−デシル基、シクロプロピル基、２，２−ジメチルシクロプロピル基、シクロペンチル基、シクロヘキシル基、メンチル基等の直鎖状、分枝鎖状または環状の炭素数１〜２０のアルキル基およびこれらアルキル基が、後述するアルコキシ基、アリールオキシ基、アラルキルオキシ基、ハロゲン原子、アシル基、カルボアルコキシ基、カルボアリールオキシ基、カルボアラルキルオキシ基、カルボキシル基等で置換されていてもよく、かかる置換基で置換されたアルキル基としては、例えばクロロメチル基、フルオロメチル基、トリフルオロメチル基、メトキシメチル基、エトキシメチル基、メトキシエチル基、カルボメトキシメチル基、１−カルボエトキシ−２，２−ジメチル−３−シクロプロピル基等が挙げられる。
【００２２】
置換されていてもよいアルコキシ基としては、前記置換されていてもよいアルキル基と酸素原子とから構成されるものが挙げられ、例えばメトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、イソブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−デシルオキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基、メンチルオキシ基等の直鎖状、分枝鎖状または環状の炭素数１〜２０のアルコキシ基およびこれらアルコキシ基が、例えばハロゲン原子、アルコキシ基等の置換基で置換されたもの、例えばクロロメトキシ基、フルオロメトキシ基、トリフルオロメトキシ基、メトキシメトキシ基、エトキシメトキシ基、メトキシエトキシ基等が挙げられる。
【００２３】
置換されていてもよいアリール基としては、例えばフェニル基、ナフチル基等およびこれらフェニル基、ナフチル基等を構成する芳香環が上記したアルキル基、アリール基、アルコキシ基、後述するアラルキル基、アリールオキシ基、アラルキルオキシ基、ハロゲン原子等の置換基で置換された、例えば２−メチルフェニル基、４−クロロフェニル基、４−メチルフェニル基、４−メトキシフェニル基、３−フェノキシフェニル基等が挙げられる。置換されていてもよいアリールオキシ基としては、前記置換されていてもよいアリール基と酸素原子とから構成されるものが挙げられ、例えばフェノキシ基、２−メチルフェノキシ基、４−クロロフェノキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、３−フェノキシフェノキシ基等が挙げられる。
【００２４】
置換されていてもよいアラルキル基としては、前記置換されていてもよいアリール基と上記したアルキル基とから構成されるものが挙げられ、例えばベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、３−フェノキシベンジル基、２，３，５，６−テトラフルオロベンジル基、２，３，５，６−テトラフルオロ−４−メチルベンジル基、２，３，５，６−テトラフルオロ−４−メトキシベンジル基、２，３，５，６−テトラフルオロ−４−メトキシメチルベンジル基等が挙げられる。また、置換されていてもよいアラルキルオキシ基としては、前記置換されていてもよいアラルキル基と酸素原子とから構成されるものが挙げられ、例えばベンジルオキシ基、４−クロロベンジルオキシ基、４−メチルベンジルオキシ基、４−メトキシベンジルオキシ基、３−フェノキシベンジルオキシ基、２，３，５，６−テトラフルオロベンジルオキシ基、２，３，５，６−テトラフルオロ−４−メチルベンジルオキシ基、２，３，５，６−テトラフルオロ−４−メトキシベンジルオキシ基、２，３，５，６−テトラフルオロ−４−メトキシメチルベンジルオキシ基等が挙げられる。
【００２５】
ハロゲン原子としては、例えばフッ素原子、塩素原子、臭素原子等が挙げられる。
【００２６】
置換されていてもよいアシル基としては、カルボニル基と前記置換されていてもよいアルキル基、置換されていてもよいアリール基および置換されていてもよいアラルキル基とから構成されるものが挙げられ、例えばカルボメチル基、カルボエチル基、カルボフェニル基、カルボベンジル基等が挙げられる。
【００２７】
置換されていてもよいカルボアルコキシ基、置換されていてもよいカルボアリールオキシ基および置換されていてもよいカルボアラルキルオキシ基としては、それぞれカルボニル基と前記置換されていてもよいアルコキシ基、置換されていてもよいアリールオキシ基および置換されていてもよいアラルキルオキシ基とから構成されるものが挙げられ、例えばカルボメトキシ基、カルボエトキシ基、カルボフェノキシ基、カルボベンジルオキシ基等が挙げられる。
【００２８】
かかる置換基が一緒になって環構造の一部を形成する場合の環構造としては、例えばシクロペンタン環、シクロヘキサン環、シクロペンテン環、シクロヘキセン環等が挙げられる。
【００２９】
かかる二置換末端オレフィン類（以下、オレフィン類と略記する）としては、例えばイソブテン、２−メチル−１−ペンテン、２，４，４−トリメチル−１−ペンテン、２−エチル−１−ブテン、α−メチルスチレン、４−クロロ−α−メチルスチレン、α−フェニルスチレン、メチレンシクロブタン、メチレンシクロペンタン、メチレンシクロヘキサン、β−ピネン、１，３，３−トリメチル−２−メチレンインドリン等が挙げられる。
【００３０】
オレフィン類の中には、その分子内に不斉炭素を有しており、光学異性体が存在するものがあるが、本発明には、光学異性体の単独または混合物のいずれも用いることができる。
【００３１】
本反応は、前記した金属酸化物触媒の存在下に、オレフィン類と過酸化水素を反応させるものであり、オレフィン類の炭素−炭素二重結合部位が酸化されたβ−ヒドロキシヒドロペルオキシド類と、オレフィン類の炭素−炭素二重結合が酸化開裂したケトン類が、ギ酸と共に生成する。
【００３２】
オレフィン類として、上記一般式（１）で示されるオレフィン類を用いた場合には、炭素−炭素二重結合が酸化された、一般式（２）

（式中、Ｒ¹およびＲ²は上記と同一の意味を表わす。）
で示されるβ−ヒドロキシヒドロペルオキシド類と、炭素−炭素二重結合が酸化開裂した一般式（４）

（式中、Ｒ¹およびＲ²は上記と同一の意味を表わす。）
で示されるケトン類が、ギ酸と共に生成する。なお、本反応においては、オレフィン類の別の酸化物であるジオール類やアルデヒド類が、副生物として生成することがある。上記一般式（１）で示されるオレフィン類の場合には、一般式（３）

（式中、Ｒ¹およびＲ²は上記と同一の意味を表わす。）
で示されるジオール類や一般式（５）

（式中、Ｒ¹およびＲ²は上記と同一の意味を表わす。）
で示されるアルデヒド類が副生物として挙げられる。
【００３３】
具体的なオレフィン類を例として、さらに具体的に説明すると、例えば原料オレフィン類としてα−メチルスチレンを用いた場合には、２−ヒドロペルオキシ−２−フェニル−１−プロパノールおよびアセトフェノンがギ酸と共に得られる。また、原料オレフィン類として、例えばメチレンシクロヘキサンを用いた場合には、1−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロヘキサンおよびシクロヘキサノンがギ酸と共に得られる。
【００３４】
オレフィン類と過酸化水素との反応の触媒である金属酸化物の使用量は、オレフィン類に対して、通常０．００１モル倍以上であり、その上限は特にないが、経済的な面を考慮すると、実用的には、オレフィン類に対して、１モル倍以下である。
【００３５】
過酸化水素は、通常水溶液として用いられる。もちろん過酸化水素の有機溶媒溶液を用いてもよい。過酸化水素水もしくは有機溶媒溶液中の過酸化水素濃度は特に制限されないが、容積効率、安全面等を考慮すると、実用的には１〜６０重量％である。過酸化水素水は、通常市販のものをそのままもしくは必要に応じて、希釈、濃縮等により濃度調整を行なった後用いられる。過酸化水素の有機溶媒溶液は、例えば過酸化水素水を有機溶媒で抽出処理する、もしくは有機溶媒の存在下に蒸留処理する等の手段により、調製することができる。
【００３６】
過酸化水素の使用量は、オレフィン類に対して、通常１モル倍以上であり、使用量の上限は特にないが、経済的な面も考慮すると、実用的には、オレフィン類に対して、１０モル倍以下である。なお、触媒として、金属化合物と過酸化水素を反応せしめてなる金属酸化物調製液を用いる場合は、該調製液中の過酸化水素量を含めて、過酸化水素の使用量を設定してもよい。
【００３７】
本反応は、通常水溶媒または有機溶媒中で実施される。有機溶媒としては、例えばジエチルエーテル、メチルｔｅｒｔ−ブチルエーテル、テトラヒドロフラン等のエーテル系溶媒、酢酸エチル等のエステル系溶媒、メタノール、エタノール、ｔｅｒｔ−ブタノール等のアルコール系溶媒、アセトニトリル、プロピオニトリル等のニトリル系溶媒等が挙げられる。水溶媒または有機溶媒の使用量は特に制限されないが、容積効率等を考慮すると、実用的には、オレフィン類に対して、１００重量倍以下である。
【００３８】
なお、本反応においては、生成物の生成比率は、オレフィン類の構造や反応条件等により異なるため、目的とする生成物に応じて、適宜反応条件を選択すればよい。例えばβ−ヒドロキシヒドロペルオキシド類を目的とする場合には、有機溶媒中で反応を実施することが好ましい。また、β−ヒドロキシヒドロペルオキシド類を目的とする場合には、無水条件下で反応を実施することが好ましい。無水条件下で反応を実施する方法としては、例えば反応系内に脱水剤を共存させる方法等が挙げられる。脱水剤としては、例えば無水硫酸マグネシウム、無水硫酸ナトリウム、無水ホウ酸、ポリリン酸、五酸化二リン等が挙げられ、その使用量は、反応系内に存在する水を脱水除去可能な量以上であれば十分である。
【００３９】
反応温度は、通常０〜２００℃であるが、反応温度が低いほど、β−ヒドロキシヒドロペルオキシド類が生成しやすく、反応温度が高いほど、ケトン類が生成しやすい。
【００４０】
本反応は、通常オレフィン類、過酸化水素および金属酸化物触媒を接触、混合することにより実施されるが、その混合順序は特に制限されない。また、例えば金属化合物、過酸化水素およびオレフィン類を接触、混合させて、金属酸化物触媒の調製操作と、オレフィン類と過酸化水素との反応を、同時に行ってもよい。
【００４１】
本反応は、常圧条件下で実施してもよいし、加圧条件下で実施してもよい。また、反応の進行は、例えばガスクロマトグラフィ、高速液体クロマトグラフィ、薄層クロマトグラフィ、核磁気共鳴スペクトル分析、赤外吸収スペクトル分析等の通常の分析手段により確認することができる。
【００４２】
また、本反応は、例えば無水ホウ酸等のホウ素化合物の共存下に実施してもよく、ホウ素化合物としては、例えば無水ホウ酸、メタホウ酸、正ホウ酸、メタホウ酸アルカリ金属塩、メタホウ酸アルカリ土類金属塩、正ホウ酸アルカリ金属塩、正ホウ酸アルカリ土類金属塩等が挙げられ、その使用量は特に制限されないが、あまり多すぎても経済的に不利になるため、実用的には、オレフィン類に対して、通常１モル倍以下である。
【００４３】
反応終了後、例えば反応液を濃縮処理、カラムクロマトグラフィ処理等することにより、反応液から、β−ヒドロキシヒドロペルオキシド類およびケトン類を分離し、取り出すことができる。また、反応液に、必要に応じて水および／または水に不溶の有機溶媒を加え、抽出処理し、得られる有機層を濃縮処理することにより、これら生成物を分離し、取り出すことができる。取り出したβ−ヒドロキシヒドロペルオキシド類およびケトン類は、例えば蒸留、カラムクロマトグラフィ等の手段によりさらに精製してもよい。
【００４４】
水に不溶の有機溶媒としては、例えばトルエン、キシレン等の芳香族炭化水素系溶媒、例えばジクロロメタン、クロロホルム、クロロベンゼン等のハロゲン化炭化水素系溶媒、例えばジエチルエーテル、メチルｔｅｒｔ−ブチルエーテル、テトラヒドロフラン等のエーテル系溶媒、例えば酢酸エチル等のエステル系溶媒等が挙げられ、その使用量は特に制限されない。
【００４５】
なお、前記したとおり、本反応においては、ジオール類やアルデヒド類が副生物として生成するが、上記と同様の処理により、反応液からジオール類やアルデヒド類を取り出すこともできる。
【００４６】
β−ヒドロキシヒドロペルオキシド類およびケトン類を取り出した後の濾液や水層中には、本反応の触媒である金属酸化物が含まれているため、該水層をそのままもしくは必要に応じて濃縮処理等を行った後、再度オレフィン類と過酸化水素との反応の触媒として使用することができる。
【００４７】
オレフィン類として、光学活性体を用いた場合には、不斉炭素の位置に応じて、光学活性な生成物が得られる。
【００４８】
かくして得られるβ−ヒドロキシヒドロペルオキシド類としては、例えば２−ヒドロペルオキシ−２−メチル−１−プロパノール、２，４，４−トリメチル−２−ヒドロペルオキシ−１−ペンタノール、２−エチル−２−ヒドロペルオキシ−１−ブタノール、２−メチル−２−ヒドロペルオキシ−１−ペンタノール、２−ヒドロペルオキシ−２−フェニル−１−プロパノ-ル、２−ヒドロペルオキシ−２−（４−クロロフェニル）−１−プロパノール、２，２−ジフェニル−２−ヒドロペルオキシエタノール、１−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロブタン、１−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロペンタン、１−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロヘキサン、ビシクロ［３．１．１］−２−ヒドロペルオキシ−２−（ヒドロキシメチル）−６，６−ジメチルヘプタン、１，３，３−トリメチル−２−ヒドロペルオキシ−２−（ヒドロキシメチル）インドリン等が挙げられる。
【００４９】
また、ケトン類としては、例えばアセトン、２−ペンタノン、４，４−ジメチルペンタン−２−オン、ジエチルケトン、メチルプロピルケトン、アセトフェノン、シクロブタノン、シクロペンタノン、シクロヘキサノン、ベンゾフェノン、ノピノン、１，３，３−トリメチルインドリノン等が挙げられる。
【００５０】
生成したβ−ヒドロキシヒドロペルオキシド類は、アルカリ処理または熱処理することにより、該β−ヒドロキシヒドロペルオキシド類が分解し、ケトン類をホルムアルデヒドと共に得ることができる。例えば、上記した一般式（２）で示されるβ−ヒドロキシヒドロペルオキシド類からは、上記一般式（４）

（式中、Ｒ¹およびＲ²は上記と同一の意味を表わす。）
で示されるケトン類がホルムアルデヒドと共に得られる。具体的な化合物を例にしてさらに詳しく説明すると、例えばα−メチルスチレンから得られる２−ヒドロペルオキシ−２−フェニル−１−プロパノールからは、アセトフェノンがホルムアルデヒドと共に得られる。また、原料オレフィン類として、例えばメチレンシクロヘキサンから得られる１−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロヘキサンからはシクロヘキサノンがホルムアルデヒドと共に得られる。
【００５１】
アルカリ処理する場合のアルカリとしては、例えばナトリウムメチラート等のアルカリ金属アルコラート等が挙げられ、その使用量は、β−ヒドロキシヒドロペルオキシド類に対して、通常０．０１モル倍以上であり、その上限は特にない。熱処理する温度は、通常６０〜２００℃である。
【００５２】
また、生成したβ−ヒドロキシヒドロペルオキシド類は、第Va族元素化合物、第VIIa族元素化合物、第VIII族元素化合物、第Ib族元素化合物、第IIb族元素化合物、第IIIb族元素化合物、第IVb族元素化合物、第Vb族元素化合物およびランタニド化合物からなる群から選ばれる少なくとも１種の化合物を作用させることにより、該β−ヒドロキシヒドロペルオキシド類が分解し、ケトン類がホルムアルデヒドと共に得られる。
【００５３】
第Va族元素化合物としては、例えばバナジウム金属、酸化バナジウム、バナジン酸アンモニウム、バナジウム金属と過酸化水素を反応させてなるバナジウム酸化物、バナジウムカルボニル錯体等のバナジウム化合物、例えばニオブ金属、酸化ニオブ、塩化ニオブ（V）（NbCl₅）、ニオブカルボニル錯体等のニオブ化合物等が挙げられる。第VIIa族元素化合物としては、例えばレニウム金属、塩化レニウム等のレニウム化合物等が挙げられる。第VIII族元素化合物としては、例えば鉄金属、塩化鉄、Fe(CO)₅、Fe(acac)₃等の鉄化合物、例えばルテニウム金属、塩化ルテニウム、Ru₃(CO)₁₂、Ru(acac)₃、RuCl₂(PPh₃)₃等のルテニウム化合物、例えばコバルト金属、酢酸コバルト、[Co₂(CO)₈]₂等のコバルト化合物、例えばロジウム金属、塩化ロジウム、Rh₄(CO)₁₂等のロジウム化合物、例えばイリジウム金属、塩化イリジウム等のイリジウム化合物、例えばニッケル金属、Ni(CO)₄等のニッケル化合物、例えばパラジウム金属、酢酸パラジウム、パラジウムカーボン等のパラジウム化合物等が挙げられる。
【００５４】
第Ib族元素化合物としては、例えば銅金属、例えば塩化第一銅、塩化第二銅、臭化第一銅、臭化第二銅等の銅化合物等が挙げられる。第IIb族元素化合物としては、例えば亜鉛金属、例えば塩化亜鉛等の亜鉛化合物等が挙げられる。第IIIb族元素化合物としては、例えば三フッ化ホウ素等のホウ素化合物、例えばアルミニウム金属、塩化アルミニウム等のアルミニウム化合物等が挙げられる。第IVb族元素化合物としては、例えばスズ金属、塩化スズ等のスズ化合物物等が挙げられる。第Vb族元素化合物としては、例えばビスマス金属、塩化ビスマス(BiCl₃)等のビスマス化合物、例えばアンチモン金属、塩化アンチモン（V）（SbCl₅）、塩化アンチモン（III）（SbCl₃）等のアンチモン化合物等が挙げられる。ランタニド化合物としては、例えばサマリウム金属、サマリウムトリフラート（Sm(OTf)₂）等のサマリウム化合物、例えばガドリニウム金属等のガドリニウム化合物、例えばジスプロシウム金属、ジスプロシウムトリフラート（Dy(OTf)₃）等のジスプロシウム化合物等が挙げられ、ジスプロシウム化合物が好ましい。
【００５５】
かかる化合物の中でも、バナジウム化合物、銅化合物、ルテニウム化合物、パラジウム化合物およびこれらの混合物が好適である。なお、かかる化合物は、単独で用いてもよいし、混合して用いてもよい。
【００５６】
かかる化合物の使用量は、β−ヒドロキシヒドロペルオキシド類に対して、通常０．００１モル倍以上であり、その上限は特にないが、経済的な面も考慮すると、実用的には１モル倍以下である。
【００５７】
β−ヒドロキシヒドロペルオキシド類にかかる化合物を作用させるとは、その両者を混合すればよく、その混合温度は、通常−２０〜１００℃である。また通常β−ヒドロキシヒドロペルオキシド類が溶解する溶媒の存在下に行われる。かかる溶媒としては、例えばジエチルエーテル、メチルｔｅｒｔ−ブチルエーテル、テトラヒドロフラン等のエーテル系溶媒、例えば酢酸エチル等のエステル系溶媒、例えばメタノール、エタノール、ｔｅｒｔ−ブタノール等のアルコール系溶媒、例えばアセトニトリル、プロピオニトリル等のニトリル系溶媒等が挙げられ、その使用量はβ−ヒドロキシヒドロペルオキシド類が溶解すればよく、その上限は特にないが、容積効率等を考慮すると、実用的には、β−ヒドロキシヒドロペルオキシド類に対して、１００重量倍以下である。
【００５８】
なお、オレフィン類を前記した例えばタングステン金属、ホウ化タングステン等で酸化して得られるβ−ヒドロキシヒドロペルオキシド類を含む反応液を用いる場合は、該反応液にそのまま前記化合物を作用させてもよいし、該反応液から、抽出処理等によりβ−ヒドロキシヒドロペルオキシド類を取り出した後、前記化合物を作用させてもよい。
【００５９】
かくして得られるケトン類としては、既に上記したオレフィン類との酸化反応で得られるケトン類が挙げられる。
【００６０】
また、β−ヒドロキシヒドロペルオキシド類を還元剤で還元処理することにより、ジオール類を得ることもできる。一般式（２）で示されるβ−ヒドロキシヒドロペルオキシド類を還元処理すると、一般式（３）

（式中、Ｒ¹およびＲ²はそれぞれ上記と同一の意味を表わす。）
で示されるジオール類が生成する。還元処理は、通常β−ヒドロキシヒドロペルオキシド類と還元剤を混合することにより実施され、還元剤としては、例えばチオ硫酸ナトリウム等の無機還元剤、例えばジメチルスルフィド等の有機還元剤等が挙げられる。かかる還元剤の使用量は、β−ヒドロキシヒドロペルオキシド類に対して、通常１モル倍以上であり、その上限は特にないが、実用性を考慮すると、β−ヒドロキシヒドロペルオキシド類に対して５モル倍以下である。
【００６１】
還元処理の温度は、通常１０〜１００℃の範囲である。本還元処理も、通常β−ヒドロキシヒドロペルオキシド類が溶解する溶媒の存在下に実施される。また、オレフィン類を前記した例えばタングステン金属、ホウ化タングステン等で酸化して得られるβ−ヒドロキシヒドロペルオキシド類を含む反応液を用いる場合は、該反応液をそのまま還元剤と混合してもよいが、反応液中に未反応の過酸化水素等酸化性物質が残存している場合が多いため、該反応液から、抽出処理等によりβ−ヒドロキシヒドロペルオキシド類を取り出した後、還元剤と混合することが経済的な面で好ましい。
【００６２】
ジオール類としては、例えば２−メチル−１，２−プロパンジオール、２−メチル−１，２−ペンタンジオール、２，４，４−トリメチル−１，２−ペンタンジオール、２−エチル−１，２−ブタンジオール、２−フェニル−１，２−プロパンジオール、２−（４−クロロフェニル）−１，２−プロパンジオール、１，１−ジフェニル−１，２−エタンジオール、１−（ヒドロキシメチル）シクロブタノール、１−（ヒドロキシメチル）シクロペンタノール、１−（ヒドロキシメチル）シクロヘキサノール、ビシクロ［４．１．１］−２−ヒドロキシメチル−６，６−ジメチルヘプタン−２−オール、１，３，３−トリメチル−２−ヒドロキシ−２−（ヒドロキシメチル）インドリン等が挙げられる。
【００６３】
【実施例】
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれら実施例により限定されるものではない。なお、ガスクロマトグラフィ分析（以下、ＧＣ分析と略記する。）および高速液体クロマトグラフィ分析（以下、ＬＣ分析と略記する。）の各条件は、以下のとおりである。
【００６４】
＜ＧＣ分析条件＞
カラム：ＤＢ−１（φ０．２５μｍ×３０ｍ、膜厚１．０μｍ）
キャリアガス：ヘリウム（流速：１ｍ／分）
スプリット比：１／１０、試料注入量：１μＬ
カラム温度：１００℃（０分）→１８０℃（昇温速度：２℃／分、１８０℃での保持時間：０分）→３００℃（昇温速度：１０℃／分、３００℃での保持時間：１５分）
注入口温度：２００℃、検出器温度：２５０℃
【００６５】

【００６６】
実施例１＜タングステン金属と過酸化水素との反応による酸化物の調製＞
ビーカーに、タングステン金属粉末４ｇを加え、さらに１５重量％過酸化水素水溶液５０ｇを加え、室温で攪拌させた。酸素ガスを発生しながら、タングステン金属粉末が溶解していき（内温は６０℃まで上昇した）、薄い黄褐色に着色した均一の透明液が得られた。この溶液を室温まで冷却し、白金網を用いて残存する過酸化水素を分解した後、室温でロータリーエバポレーターを用いて、前記溶液から水を留去し、淡黄色の固体（タングステン酸化物）を得た。この固体を常温、空気開放系で恒量になるまで乾燥し、５．８ｇの固体を得た。
【００６７】
濃縮前の均一透明液のＵＶスペクトル
λ^H2O _max：２０４，２３８ｎｍ
濃縮前の均一透明液のＩＲスペクトル（水溶液；４０００〜７５０ｃｍ^-1）
ν_max：３３４２，１２７５，１０３０，９６７，８３７ｃｍ^-1
得られた固体のＩＲスペクトル（ＫＢｒ）
ν_max：３５３１，３４５２，２９４５，１６５３，１６１９，９７３，９０６，６３８，５５１ｃｍ^-1
元素分析値；Ｗ：６３．９，Ｏ：３１．２，Ｈ：１．６
【００６８】
実施例２＜ホウ化タングステンと過酸化水素との反応による酸化物の調製＞
磁気回転子および還流冷却管を備えた１００ｍＬフラスコに、ホウ化タングステン粉末４．２ｇおよび水２５ｇを加え、内温４０℃で、攪拌しながら、６０重量％過酸化水素水溶液１８ｇを２時間かけて滴下した。同温度で２時間さらに保温し、白色の結晶がわずかに浮遊した無色溶液が得られた。この溶液を室温まで冷却し、白金網を用いて残存する過酸化水素を分解した後、室温でロータリーエバポレーターを用いて、前記溶液から水を留去し、白色の固体（酸化物）を得、これを常温、空気開放系で恒量になるまで乾燥し、５．８ｇの固体を得た。
【００６９】
濃縮前の無色溶液のＵＶスペクトル
λ^H2O _max：２００，２３５（ｓ）ｎｍ
濃縮前の無色溶液のＩＲスペクトル（水溶液；４０００〜７５０ｃｍ^-1）
ν_max：３３５０，２８３６，１２７５，１１５８，９６５，８３６ｃｍ^-1
得られた固体のＩＲスペクトル（ＫＢｒ）
ν_max：３５２７，３２２０，２３６０，２２６１，１６２２，１４６９，１１９６，９７３，９０４．５，８８４，７９１，６４０，５４９ｃｍ^-1
元素分析値；Ｗ：５１．２，Ｏ：３９．０，Ｈ：２．２，Ｂ：３．９８
【００７０】
実施例３＜硫化タングステンと過酸化水素との反応による酸化物の調製＞
実施例２において、ホウ化タングステン粉末に代えて、硫化タングステン５．４ｇを用い、水の量を１２ｇとした以外は実施例２と同様に実施して、淡黄色固体１０．１ｇを得た。
【００７１】
濃縮前の溶液のＵＶスペクトル
λ^H2O _max：２００，２４０（ｓ）ｎｍ
濃縮前の無色溶液のＩＲスペクトル（水溶液；４０００〜７５０ｃｍ^-1）
ν_max：３３７３，１１８７，１０４４，９７４，８７８，８３７ｃｍ^-1
得られた固体のＩＲスペクトル（ＫＢｒ）
ν_max：３４３５，３３５９，１７３０，１６３２，１３２０，１２８５，１１７８，１１０３，１０７０，１００８，９８１，８８７，８３９，８５１，６６０，６１５，５７８ｃｍ^-1
元素分析値；Ｗ：３５．３，Ｏ：４７．７，Ｈ：３．０，Ｓ：１２．４
【００７２】
実施例４＜モリブデン金属と過酸化水素との反応による酸化物の調製＞
実施例２において、ホウ化タングステン粉末に代えて、モリブデン金属２．１ｇを用い、水の量を１２ｇとし、６０重量％過酸化水素水溶液の使用量を１２ｇとした以外は実施例２と同様に実施して、黄色固体４．０ｇを得た。
【００７３】
濃縮前の溶液のＵＶスペクトル
λ^H2O _max：２０７，３００ｎｍ
濃縮前の無色溶液のＩＲスペクトル（水溶液；４０００〜７５０ｃｍ^-1）
ν_max：３３５９，２４８０，１３７２，９７４，８６６ｃｍ^-1
得られた固体のＩＲスペクトル（ＫＢｒ）
ν_max：３５３０，１６２１，９６４，９２７，９０２，８４０，６３３，５５７，５３０，５２２ｃｍ^-1
元素分析値；Ｍｏ：４７．８，Ｏ：４６．２，Ｈ：２．１
【００７４】
実施例５＜ホウ化モリブデンと過酸化水素との反応による酸化物の調製＞
実施例２において、ホウ化タングステン粉末に代えて、ホウ化モリブデン２．３ｇを用い、水の量を１２ｇとし、６０重量％過酸化水素水溶液の使用量を１２ｇとした以外は実施例２と同様に実施して、黄色固体５．２ｇを得た。
【００７５】
濃縮前の溶液のＵＶスペクトル
λ^H2O _max：２００，３１０ｎｍ
得られた固体のＩＲスペクトル（ＫＢｒ）
ν_max：３２２１，２５２０，２３６１，２２６２，１６２０，１４６３，１４３９，１１９５，９６５，９２７，８８７，８４０，７９９，６７４，６３４，５４７，５２９ｃｍ^-1
元素分析値；Ｍｏ：３５．５，Ｏ：５１．０，Ｈ：２．９，Ｂ：４．１
【００７６】
比較例１＜タングステン酸と過酸化水素との反応による酸化化合物の調製＞
ビーカーに、タングステン酸（Ｈ₂ＷＯ₄）５．４ｇを加え、さらに１５重量％過酸化水素水溶液５０ｇを加え、室温で攪拌させた。タングステン酸の結晶が完溶しなかったので、内温を５５℃に昇温し、さらに２時間攪拌、保持した。冷却後、未反応結晶を濾別し、得られた溶液を白金網を用いて残存する過酸化水素を分解した後、室温でロータリーエバポレーターを用いて前記溶液から水を留去し、淡黄色の固体を得た。この固体を常温、空気開放系で恒量になるまで乾燥し、３．０ｇの固体を得た。
【００７７】
濃縮前の溶液のＵＶスペクトル
λ^H2O _max：２１０，２５０（ｓ）ｎｍ
濃縮前の溶液のＩＲスペクトル（水溶液；４０００〜７５０ｃｍ^-1）
ν_max：３４００，２８３３，１３５５，９６７，８３６ｃｍ^-1
得られた固体のＩＲスペクトル（ＫＢｒ）
ν_max：３４１６，１６２３，１３８５，９７５，８８０，８３９，７４９，７００，６４３，６２５，５５０ｃｍ^-1
元素分析値；Ｗ：６３．９，Ｏ：３１．２，Ｈ：１．６
これらのスペクトルデータを前記実施例１で得られたタングステン金属と過酸化水素との反応で得られた酸化物と比較したが、異なる酸化物であった。
【００７８】
実施例６
磁気回転子と還流冷却管を備えた５０ｍＬフラスコに、３０重量％過酸化水素水２５０ｍｇおよびタングステン金属粉末４０ｍｇを仕込み、内温４０℃に昇温した。同温度で０．５時間攪拌、保持した後、６０重量％過酸化水素水５００ｍｇ、ｔｅｒｔ−ブタノール１．５ｇおよび硫酸マグネシウム５３０ｍｇを加えて、３０分攪拌した後に、α−メチルスチレン２６０ｍｇとｔｅｒｔ−ブタノール５００ｍｇを２０分かけて滴下し、その後、内温６０℃のオイルバスで３時間加熱攪拌した。反応終了後、反応液にメチル−ｔｅｒｔ−ブチルエーテル１０ｇと水５ｇを加え、硫酸マグネシウムを溶解、分液し、有機層を得た。該有機層をＬＣ分析し、アセトフェノンの生成を確認した。有機層をＧＣ分析（内部標準法）したところ、アセトフェノンの収量は１２８ｍｇ（収率：４８．５％）であった。
【００７９】
実施例７
磁気回転子と還流冷却管を備えた５０ｍＬフラスコに、３０重量％過酸化水素水１．０ｇおよび炭化タングステン２０ｍｇを仕込み、内温４０℃に昇温した。同温度で０．５時間攪拌、保持した後、３０重量％過酸化水素水１．８ｇおよびα−メチルスチレン１．３ｇを加え、内温７５℃のオイルバスで３時間加熱攪拌した。反応終了後、反応液にメチル−ｔｅｒｔ−ブチルエーテル１０ｇと水５ｇを加え、分液し、有機層を得た。該有機層をＬＣ分析し、アセトフェノンの生成を確認した。有機層をＧＣ分析（内部標準法）したところ、アセトフェノンの収量は１２３ｍｇ（収率：９．３％）であり、原料α−メチルスチレンが９０％回収された。
【００８０】
実施例８
実施例７において、炭化タングステン２０ｍｇに代えて、硫化タングステン３０ｍｇを用い、反応時間を３時間から１０時間に代えた以外は実施例７と同様に実施した。アセトフェノンの収量：３１８ｍｇ（収率：２４％）、原料α−メチルスチレン３６％回収。
【００８１】
実施例９
実施例８において、硫化タングステン３０ｍｇに代えてモリブデン金属４０ｍｇを用い、ｔｅｒｔ−ブタノール５ｇを加えて反応を行った以外は実施例８と同様に実施した。アセトフェノンの収量：５０２ｍｇ（収率：３８％）。原料α−メチルスチレン１５％回収。副生物として、２−フェニルプロピオンアルデヒドが収率２１％で生成していた。
【００８２】
実施例１０
実施例６において、α−メチルスチレン２６０ｍｇに代えて、メチレンシクロヘキサン２１１ｍｇを用いた以外は実施例６と同様に実施し、シクロヘキサノン６２ｍｇを得た。収率：２９％。
【００８３】
実施例１１
磁気回転子と還流冷却管を備えた５０ｍＬフラスコに、３０重量％過酸化水素水２５０ｍｇおよびタングステン金属粉末４０ｍｇを仕込み、内温４０℃に昇温した。同温度で０．５時間攪拌、保持した後、６０重量％過酸化水素水５００ｍｇ、ｔｅｒｔ−ブタノール１．５ｇおよび硫酸マグネシウム５３０ｍｇを加えて、３０分攪拌した後に、α−メチルスチレン２６０ｍｇとｔｅｒｔ−ブタノール５００ｍｇを２０分かけて滴下し、その後、内温２５℃のオイルバスで２時間加熱攪拌した。反応終了後、反応液にメチル−ｔｅｒｔ−ブチルエーテル１０ｇと水５ｇを加え、硫酸マグネシウムを溶解、分液し、有機層を得た。該有機層をＬＣ分析し、２−ヒドロペルオキシ−２−フェニル−１−プロパノールの生成を確認した。なおアセトフェノンは、微量生成しているだけであった。該有機層をＧＣ分析（内部標準法）したところ、２−ヒドロペルオキシ−２−フェニル−１−プロパノールは注入口部で熱分解し、アセトフェノンとして検出されることが分かったため、アセトフェノンの収率をＧＣ分析（内部標準法）の結果から算出し、それを２−ヒドロペルオキシ−２−フェニル−１−プロパノールの収率とした。２−ヒドロペルオキシ−２−フェニル−１−プロパノールの収率：５０％。なお、原料α−メチルスチレンが１８％回収された。
【００８４】
実施例１２
磁気回転子と還流冷却管を備えた５０ｍＬフラスコに、上記実施例１１で得た２−ヒドロペルオキシ−２−フェニル−１−プロパノールを含む有機層と五酸化バナジウム２０ｍｇを仕込み、内温６０℃で４時間攪拌、保持した。反応液をＬＣ分析したところ、２−ヒドロペルオキシ−２−フェニル−１−プロパノールのピークは消失しており、アセトフェノンの生成が確認された。ＧＣ分析によりアセトフェノンの収率を求めたところ、５０％であった（α−メチルスチレン基準）。
【００８５】
実施例１３
実施例１１と同様に実施して、２−ヒドロペルオキシ−２−フェニル−１−プロパノールを含む有機層を得た。該有機層に、１０重量％チオ硫酸ナトリウム水溶液１０ｇを加え、内温２５℃で１４時間攪拌、保持した。反応液をＧＣ分析（内部標準法）したところ、２−フェニル−１，２−プロパンジオール２３９ｍｇが生成していた。収率：７１％。
【００８６】
実施例１４
磁気回転子および還流冷却管を付した１００ｍＬフラスコに、タングステン金属粉末８０ｍｇを仕込み、３０重量％過酸化水素水５００ｍｇを少しずつ加えた後３０分、室温にて攪拌し無色の均一溶液を得た。この溶液に、６０重量％過酸化水素水６００ｍｇ、ｔｅｒｔ−ブタノール３ｇ、無水硫酸マグネシウム１．０６ｇを加えた後、３０分室温にて攪拌後、メチレンシクロヘキサン４２２ｍｇとｔｅｒｔ−ブタノール１．５ｇからなる混合液を３０分かけて滴下した。内温２５℃で１６時間攪拌、保持した後、反応液にトルエン１０ｇと水５ｇを加えて攪拌後に分液してトルエン溶液２０ｇを得た。該トルエン溶液をＬＣ分析したところ、１−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロヘキサンと１−ヒドロキシメチルシクロヘキサノールが生成していた。シクロヘキサノンの生成は確認できなかった。該トルエン溶液をＧＣ分析（内部標準法）したところ、１−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロヘキサンは注入口部で熱分解して、シクロヘキサノンとして検出されたため、ＧＣ分析（内部標準法）により、シクロヘキサノンの収率を算出し、該収率を１−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロヘキサンの収率とした。収率：２９％。また、１−ヒドロキシ−１−（ヒドロキシメチル）シクロヘキサンの収率は１５％であった。
【００８７】
実施例１５
磁気回転子および還流冷却管を備えた５０ｍＬフラスコに、塩化銅（II）５０ｍｇを仕込み、上記実施例１４で得た１−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロヘキサンを含むトルエン溶液１０ｇを加え、内温２５℃で１６時間攪拌した。得られた反応液をＬＣ分析したところ、１−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロヘキサンのピークは消失していた。ＧＣ分析（内部標準法）したところ、シクロヘキサノン２１１ｍｇが生成していた。シクロヘキサノンの収率：４９％（メチレンシクロヘキサン基準）。
【００８８】
実施例１６
磁気回転子および還流冷却管を備えた５００ｍＬフラスコに、上記実施例１４で得た１−ヒドロペルオキシ−１−（ヒドロキシメチル）シクロヘキサンを含むトルエン溶液１０ｇ仕込み、１０重量％チオ硫酸ナトリウム水溶液１０ｇを加え、内温２５℃で１６時間攪拌した後、分液して濃縮し、白色結晶２７０ｍｇを得た。該白色結晶を¹Ｈ-ＮＭＲで分析したところ、高純度の１−（ヒドロキシメチル）シクロヘキサノールであることを確認した。収率：９３％。
【００８９】
実施例１７
磁気回転子および還流冷却管を備えた５０ｍＬフラスコに、３０重量％過酸化水素水２００ｍｇ、ｔｅｒｔ−ブタノール１．５ｇ、無水ホウ酸１６ｍｇおよびタングステン金属粉末４０ｍｇを仕込み、内温６０℃に昇温した。同温度で１時間攪拌、保持後、無水硫酸マグネシウム５３０ｍｇを加え、さらに２，４，４−トリメチル−１−ペンテン２４７ｍｇ、ｔｅｒｔ−ブタノール１．５ｇおよび３０重量％過酸化水素水３５０ｍｇからなる混合液を２０分かけて滴下した。滴下終了後、内温６０℃で６時間攪拌、保持した。反応液をＧＣ分析し、４，４−ジメチルペンタン−２−オンの生成を確認した（ＧＣ分析の面積百分率値：５１％）。
【００９０】
実施例１８
磁気回転子と還流冷却管を備えた５０ｍＬフラスコに、３０重量％過酸化水素水２５０ｍｇおよびホウ化タングステン粉末４５ｍｇを仕込み、内温４０℃に昇温した。同温度で０．５時間攪拌、保持した後、６０重量％過酸化水素水５００ｍｇ、ｔｅｒｔ−ブタノール１．５ｇおよび硫酸マグネシウム５３０ｍｇを加えて、３０分攪拌した後に、β−ピネン４００ｍｇとｔｅｒｔ−ブタノール５００ｍｇを１０分かけて滴下し、その後、内温２５℃で２０時間加熱攪拌した。反応液をガスクロマトグラフィ分析し、ノピノンの生成を確認した（ＧＣ分析の面積百分率値：ノピノン＝２９％、原料β−ピネン＝２９％）。
【００９１】
【発明の効果】
本発明の方法によれば、入手が容易なタングステン金属、モリブデン金属、ホウ化タングステン等のタングステン化合物、ホウ化モリブデン等のモリブデン化合物の存在下に、二置換末端オレフィン類と安価な過酸化水素を反応させることにより、β−ヒドロキシヒドロペルオキシド類およびケトン類を容易に得ることができ、また該β−ヒドロキシヒドロペルオキシド類から、ジオール類およびケトン類も容易に得ることができるため、工業的に有利である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing β-hydroxyhydroperoxides and ketones important as various chemical products and synthetic intermediates thereof, and a catalyst thereof.
[0002]
[Prior art]
Hydrogen peroxide has attracted attention in recent years as a clean and excellent oxidant that is inexpensive, easy to handle and harmless after the reaction, and various oxidation methods using hydrogen peroxide have been reported. .
[0003]
As a method for obtaining β-hydroxyhydroperoxides by oxidizing disubstituted terminal olefins with hydrogen peroxide, for example, Mo (acac)₂A method of reacting isobutene with anhydrous hydrogen peroxide in the presence of a catalyst (J. Chem. Soc. Chem. Comm., 1198 (1970)), α-methylstyrene and hydrogen peroxide in the presence of a Ti zeolite catalyst. (Chem. Ber.,1291453 (1996)), but none of the methods are industrially satisfactory because of low yields.
[0004]
Examples of a method for producing ketones by reacting terminal disubstituted olefins with hydrogen peroxide include (1) a method using a tungstic acid catalyst (Chem. Lett., 857 (1989)), (2 ) Although a method using a methylrhenium trioxide catalyst (WO98 / 47847) has been reported, the former method (1) is low in yield of the desired ketones and the latter (2). These methods are not always satisfactory from an industrial point of view in that the methyl rhenium trioxide catalyst is expensive and disadvantageous economically.
[0005]
Examples of the method for producing ketones from β-hydroxyhydroperoxides include a method of thermal decomposition at high temperature and a method of acid decomposition (Chem. Ber.,129, 1453 (1996)), a method of alkali decomposition (J. Org. Chem.,43, 1760 (1978)) and the like, but further development of an industrially advantageous method has been demanded.
[0006]
In addition, a method for producing diols by reducing β-hydroxyhydroperoxides is a method of reducing with triphenylphosphine (Chem. Ber.,129, 1453 (1996)), but since expensive triphenylphosphine is used and an operation to separate the generated diols and by-product triphenylphosphine oxide is necessary, It was not necessarily a method.
[0007]
[Problems to be solved by the invention]
Under such circumstances, the present inventors have eagerly developed a method for industrially producing β-hydroxyhydroperoxides and ketones by oxidizing disubstituted terminal olefins with hydrogen peroxide. As a result, it was found that a metal oxide obtained by reacting a tungsten compound such as tungsten metal or tungsten boride, which is easily available, or a molybdenum compound such as molybdenum metal or molybdenum boride with hydrogen peroxide is a disubstituted terminal olefin. It exhibits high catalytic activity for oxidation reaction, and β-hydroxyhydroperoxides and ketones are obtained by reacting disubstituted terminal olefins with hydrogen peroxide in the presence of the oxide catalyst, By treating hydroxy hydroperoxides with specific metal compounds, the decomposition reaction proceeds and ketones are obtained. It, by reducing processing the β- hydroxy hydroperoxides, found that diol is obtained, leading to the present invention.
[0008]
[Means for Solving the Problems]
That is, the present invention relates to a tungsten compound comprising a disubstituted terminal olefin and hydrogen peroxide, tungsten metal, molybdenum metal, tungsten and a group IIIb, group IVb, group Vb or a group VIb element excluding oxygen and Metal oxide obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of molybdenum and a group IIIb, group IVb, group Vb or a group VIb element excluding oxygen. It is intended to provide a process for producing β-hydroxyhydroperoxides and ketones characterized by reacting in the presence of a catalyst and the catalyst.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
First, the catalyst used when reacting disubstituted terminal olefins with hydrogen peroxide will be described.
Catalysts include tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb or tungsten compound consisting of group VIb excluding oxygen and molybdenum and group IIIb, group IVb, group Vb. Alternatively, a metal oxide obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of molybdenum compounds composed of Group VIb elements excluding oxygen is used.
[0010]
Examples of the tungsten compound composed of tungsten and a group IIIb element include tungsten boride, and examples of the tungsten compound composed of tungsten and a group IVb element include tungsten carbide, tungsten silicide, and the like. Examples of tungsten compounds composed of elements include tungsten nitride and tungsten phosphide. Examples of tungsten compounds composed of Group VIb elements other than tungsten and oxygen include tungsten sulfide.
[0011]
Examples of molybdenum compounds composed of molybdenum and Group IIIb elements include molybdenum boride, and examples of molybdenum compounds composed of molybdenum and Group IVb elements include molybdenum carbide and molybdenum silicide. Examples of molybdenum compounds composed of elements include molybdenum nitride and molybdenum phosphide, and examples of molybdenum compounds composed of molybdenum and Group VIb elements excluding oxygen include molybdenum sulfide.
[0012]
Among these metal compounds, tungsten metal, molybdenum metal, tungsten boride, molybdenum boride, tungsten sulfide, and molybdenum sulfide are preferable. Such metal compounds may be used alone or in combination of two or more. In addition, it is preferable to use a metal compound having a small particle size in that the preparation of a metal oxide as a catalyst is easy.
[0013]
As the hydrogen peroxide to be reacted with the metal compound, an aqueous solution is usually used. Of course, an organic solvent solution of hydrogen peroxide may be used, but it is preferable to use a hydrogen peroxide solution in terms of easier handling. The concentration of hydrogen peroxide in the hydrogen peroxide solution or the organic solvent solution of hydrogen peroxide is not particularly limited, but is practically 1 to 60% by weight in consideration of volume efficiency, safety and the like. As the hydrogen peroxide solution, a commercially available one may be used as it is or after adjusting the concentration by dilution, concentration or the like, if necessary. As the organic solvent solution of hydrogen peroxide, a solution prepared by a means such as extraction treatment of an aqueous hydrogen peroxide solution with an organic solvent or distillation treatment in the presence of an organic solvent may be used.
[0014]
The amount of hydrogen peroxide used in preparing the metal oxide is usually 3 mol times or more, preferably 5 mol times or more, relative to the metal compound, and there is no particular upper limit.
[0015]
The reaction between the metal compound and hydrogen peroxide is usually carried out in an aqueous solution. Of course, for example, ether solvents such as diethyl ether, methyl tert-butyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and tert-butanol, nitrile solvents such as acetonitrile and propionitrile, etc. You may implement in an organic solvent or the mixed solvent of this organic solvent and water.
[0016]
The reaction between the metal compound and hydrogen peroxide is usually carried out by mixing and contacting the two, and the metal compound is sufficiently dispersed in the metal oxide preparation solution to improve the contact efficiency between the metal compound and hydrogen peroxide. It is preferable to carry out the reaction while stirring. In addition, it is preferable to use a metal compound having a small particle diameter, such as a powdered metal compound, in order to increase the contact efficiency between the metal compound and hydrogen peroxide and to facilitate control during preparation of the metal oxide. The preparation temperature at the time of preparation of the metal oxide is usually −10 to 100 ° C.
[0017]
By reacting a metal compound and hydrogen peroxide in water, an organic solvent, or a mixed solvent of water and an organic solvent, all or part of the metal compound is dissolved, and a homogeneous solution or suspension containing a metal oxide However, the metal oxide may be taken out of the preparation solution by, for example, concentration treatment and used as a catalyst, or the preparation solution may be used as it is as a catalyst.
[0018]
Next, the reaction between disubstituted terminal olefins and hydrogen peroxide using the metal oxide as a catalyst will be described.
[0019]
Disubstituted terminal olefins include olefinic carbon-carbon double bonds, and two substituents are bonded to one carbon atom of the carbon atom forming the double bond, and the other carbon atom. Any one may be used as long as two hydrogen atoms are bonded to each other. In addition, the two substituents couple | bonded with one carbon atom of the carbon atom which forms the carbon-carbon double bond of disubstituted terminal olefins may combine, and may form the ring.
[0020]
Examples of such disubstituted terminal olefins include those represented by the general formula (1)

(Wherein R¹And R²Are the same or different and each may be an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aryloxy group, or an optionally substituted A good aralkyl group, an optionally substituted aralkyloxy group, an optionally substituted acyl group, an optionally substituted carboalkoxy group, an optionally substituted carboaryloxy group, an optionally substituted Represents a carboaralkyloxy group, a carboxyl group, or a halogen atom. R¹And R²Together may form part of the ring structure. )
And olefins represented by
[0021]
Examples of the alkyl group which may be substituted include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as decyl group, cyclopropyl group, 2,2-dimethylcyclopropyl group, cyclopentyl group, cyclohexyl group and menthyl group, and these alkyl groups May be substituted with an alkoxy group, an aryloxy group, an aralkyloxy group, a halogen atom, an acyl group, a carboalkoxy group, a carboaryloxy group, a carboaralkyloxy group, a carboxyl group, etc., which will be described later. Examples of the substituted alkyl group include a chloromethyl group, a fluoromethyl group, and a trifluoro group. Butyl group, methoxymethyl group, ethoxymethyl group, methoxyethyl group, carbomethoxymethyl group, 1-carbethoxy-2,2-dimethyl-3-cyclopropyl group and the like.
[0022]
Examples of the optionally substituted alkoxy group include those composed of the optionally substituted alkyl group and an oxygen atom. For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n -Butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-decyloxy group, cyclopentyloxy group, cyclohexyloxy group, menthyloxy group, etc. A cyclic alkoxy group having 1 to 20 carbon atoms and a group in which these alkoxy groups are substituted with a substituent such as a halogen atom or an alkoxy group, such as a chloromethoxy group, a fluoromethoxy group, a trifluoromethoxy group, a methoxymethoxy group, An ethoxymethoxy group, a methoxyethoxy group, etc. are mentioned.
[0023]
Examples of the aryl group which may be substituted include, for example, a phenyl group, a naphthyl group and the like, and an aromatic ring constituting the phenyl group, naphthyl group and the like, an alkyl group, an aryl group, an alkoxy group, an aralkyl group and an aryloxy described later. A 2-methylphenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a 3-phenoxyphenyl group, and the like substituted with a substituent such as a group, an aralkyloxy group, or a halogen atom. . Examples of the optionally substituted aryloxy group include those composed of the optionally substituted aryl group and an oxygen atom, such as a phenoxy group, 2-methylphenoxy group, 4-chlorophenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 3-phenoxyphenoxy group and the like can be mentioned.
[0024]
Examples of the aralkyl group which may be substituted include those composed of the aryl group which may be substituted and the alkyl group described above. For example, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group. 4-methoxybenzyl group, 3-phenoxybenzyl group, 2,3,5,6-tetrafluorobenzyl group, 2,3,5,6-tetrafluoro-4-methylbenzyl group, 2,3,5,6 -Tetrafluoro-4-methoxybenzyl group, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl group and the like. Examples of the optionally substituted aralkyloxy group include those composed of the optionally substituted aralkyl group and an oxygen atom, such as a benzyloxy group, 4-chlorobenzyloxy group, 4- Methylbenzyloxy group, 4-methoxybenzyloxy group, 3-phenoxybenzyloxy group, 2,3,5,6-tetrafluorobenzyloxy group, 2,3,5,6-tetrafluoro-4-methylbenzyloxy group 2,3,5,6-tetrafluoro-4-methoxybenzyloxy group, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyloxy group, and the like.
[0025]
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
[0026]
Examples of the optionally substituted acyl group include those composed of a carbonyl group and the optionally substituted alkyl group, the optionally substituted aryl group, and the optionally substituted aralkyl group. Examples thereof include carbomethyl group, carboethyl group, carbophenyl group, carbobenzyl group and the like.
[0027]
As the optionally substituted carboalkoxy group, the optionally substituted carboaryloxy group and the optionally substituted carboaralkyloxy group, a carbonyl group and the above optionally substituted alkoxy group, substituted Examples thereof include an aryloxy group which may be substituted and an aralkyloxy group which may be substituted, such as a carbomethoxy group, a carboethoxy group, a carbophenoxy group, a carbobenzyloxy group and the like.
[0028]
Examples of the ring structure when such substituents together form a part of the ring structure include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a cyclohexene ring, and the like.
[0029]
Examples of such disubstituted terminal olefins (hereinafter abbreviated as olefins) include isobutene, 2-methyl-1-pentene, 2,4,4-trimethyl-1-pentene, 2-ethyl-1-butene, α -Methylstyrene, 4-chloro-α-methylstyrene, α-phenylstyrene, methylenecyclobutane, methylenecyclopentane, methylenecyclohexane, β-pinene, 1,3,3-trimethyl-2-methyleneindoline and the like.
[0030]
Some olefins have an asymmetric carbon in the molecule and have optical isomers, but in the present invention, any one or a mixture of optical isomers can be used. .
[0031]
In this reaction, olefins and hydrogen peroxide are reacted in the presence of the metal oxide catalyst described above, and β-hydroxyhydroperoxides in which the carbon-carbon double bond sites of the olefins are oxidized; Ketones in which carbon-carbon double bonds of olefins are oxidatively cleaved are formed together with formic acid.
[0032]
When the olefin represented by the general formula (1) is used as the olefin, the general formula (2) in which the carbon-carbon double bond is oxidized.

(Wherein R¹And R²Represents the same meaning as above. )
And a general formula (4) in which a carbon-carbon double bond is oxidatively cleaved.

(Wherein R¹And R²Represents the same meaning as above. )
Is produced together with formic acid. In this reaction, diols and aldehydes, which are other oxides of olefins, may be generated as by-products. In the case of the olefins represented by the general formula (1), the general formula (3)

(Wherein R¹And R²Represents the same meaning as above. )
Diols represented by the general formula (5)

(Wherein R¹And R²Represents the same meaning as above. )
The aldehydes represented by can be mentioned as by-products.
[0033]
More specifically, taking specific olefins as examples, for example, when α-methylstyrene is used as the raw material olefins, 2-hydroperoxy-2-phenyl-1-propanol and acetophenone are obtained together with formic acid. It is done. When methylenecyclohexane is used as the raw material olefin, for example, 1-hydroperoxy-1- (hydroxymethyl) cyclohexane and cyclohexanone are obtained together with formic acid.
[0034]
The amount of metal oxide used as a catalyst for the reaction between olefins and hydrogen peroxide is usually 0.001 mol times or more with respect to olefins, and there is no upper limit, but considering the economical aspect. Then, it is 1 mol times or less practically with respect to olefins.
[0035]
Hydrogen peroxide is usually used as an aqueous solution. Of course, an organic solvent solution of hydrogen peroxide may be used. The hydrogen peroxide concentration in the hydrogen peroxide solution or the organic solvent solution is not particularly limited, but is practically 1 to 60% by weight in consideration of volume efficiency, safety and the like. As the hydrogen peroxide solution, a commercially available one is usually used as it is or after adjusting the concentration by dilution, concentration or the like, if necessary. The organic solvent solution of hydrogen peroxide can be prepared, for example, by means such as extraction treatment of hydrogen peroxide water with an organic solvent or distillation treatment in the presence of an organic solvent.
[0036]
The amount of hydrogen peroxide used is usually 1 mol times or more with respect to olefins, and there is no particular upper limit of the amount used, but considering economic aspects, practically, with respect to olefins, It is 10 mol times or less. In addition, when using a metal oxide preparation liquid obtained by reacting a metal compound and hydrogen peroxide as a catalyst, the amount of hydrogen peroxide used may be set including the amount of hydrogen peroxide in the preparation liquid. Good.
[0037]
This reaction is usually carried out in an aqueous solvent or an organic solvent. Examples of the organic solvent include ether solvents such as diethyl ether, methyl tert-butyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and tert-butanol, and nitriles such as acetonitrile and propionitrile. System solvents and the like. The amount of water solvent or organic solvent used is not particularly limited, but considering volume efficiency and the like, it is practically 100 weight times or less with respect to olefins.
[0038]
In this reaction, since the product production ratio varies depending on the structure of olefins, reaction conditions, and the like, the reaction conditions may be appropriately selected according to the target product. For example, when β-hydroxyhydroperoxides are intended, the reaction is preferably carried out in an organic solvent. In addition, when β-hydroxyhydroperoxides are intended, it is preferable to carry out the reaction under anhydrous conditions. Examples of the method for carrying out the reaction under anhydrous conditions include a method in which a dehydrating agent is allowed to coexist in the reaction system. Examples of the dehydrating agent include anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous boric acid, polyphosphoric acid, diphosphorus pentoxide and the like, and the amount used is more than the amount capable of dehydrating and removing water present in the reaction system. If there is enough.
[0039]
The reaction temperature is usually 0 to 200 ° C., but β-hydroxyhydroperoxides are likely to be generated as the reaction temperature is low, and ketones are likely to be generated as the reaction temperature is high.
[0040]
This reaction is usually carried out by contacting and mixing olefins, hydrogen peroxide and a metal oxide catalyst, but the mixing order is not particularly limited. Further, for example, a metal compound, hydrogen peroxide, and olefins may be contacted and mixed, and the preparation operation of the metal oxide catalyst and the reaction of the olefins and hydrogen peroxide may be performed simultaneously.
[0041]
This reaction may be carried out under normal pressure conditions or under pressurized conditions. In addition, the progress of the reaction can be confirmed by ordinary analysis means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, nuclear magnetic resonance spectrum analysis, infrared absorption spectrum analysis and the like.
[0042]
In addition, this reaction may be carried out in the presence of a boron compound such as boric anhydride. Examples of the boron compound include boric anhydride, metaboric acid, orthoboric acid, alkali metal borate, and alkali metal borate. Examples include earth metal salts, alkali metal salts of normal borates, and alkaline earth metal salts of borates, and the amount used is not particularly limited. Is usually 1 mol times or less with respect to olefins.
[0043]
After completion of the reaction, β-hydroxyhydroperoxides and ketones can be separated and removed from the reaction solution, for example, by subjecting the reaction solution to concentration treatment, column chromatography treatment, or the like. Moreover, these products can be separated and taken out by adding water and / or an organic solvent insoluble in water to the reaction solution as necessary, performing an extraction treatment, and concentrating the resulting organic layer. The removed β-hydroxyhydroperoxides and ketones may be further purified, for example, by means such as distillation or column chromatography.
[0044]
Examples of the organic solvent insoluble in water include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as dichloromethane, chloroform, and chlorobenzene, and ethers such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran. Examples of the solvent include ester solvents such as ethyl acetate, and the amount used is not particularly limited.
[0045]
As described above, in this reaction, diols and aldehydes are produced as by-products, but diols and aldehydes can also be extracted from the reaction solution by the same treatment as described above.
[0046]
Since the filtrate and aqueous layer after removing β-hydroxyhydroperoxides and ketones contain a metal oxide which is a catalyst for this reaction, the aqueous layer is concentrated as it is or as necessary. Then, it can be used again as a catalyst for the reaction between olefins and hydrogen peroxide.
[0047]
When an optically active substance is used as the olefin, an optically active product is obtained depending on the position of the asymmetric carbon.
[0048]
Examples of the β-hydroxyhydroperoxides thus obtained include 2-hydroperoxy-2-methyl-1-propanol, 2,4,4-trimethyl-2-hydroperoxy-1-pentanol, 2-ethyl-2- Hydroperoxy-1-butanol, 2-methyl-2-hydroperoxy-1-pentanol, 2-hydroperoxy-2-phenyl-1-propanol, 2-hydroperoxy-2- (4-chlorophenyl) -1 -Propanol, 2,2-diphenyl-2-hydroperoxyethanol, 1-hydroperoxy-1- (hydroxymethyl) cyclobutane, 1-hydroperoxy-1- (hydroxymethyl) cyclopentane, 1-hydroperoxy-1- ( Hydroxymethyl) cyclohexane, bicyclo [3.1.1] -2 Hydroperoxy-2- (hydroxymethyl) -6,6-dimethyl-heptane, 1,3,3-trimethyl-2-hydroperoxy-2- (hydroxymethyl) indoline and the like.
[0049]
Examples of the ketones include acetone, 2-pentanone, 4,4-dimethylpentan-2-one, diethyl ketone, methyl propyl ketone, acetophenone, cyclobutanone, cyclopentanone, cyclohexanone, benzophenone, nopinone, 1,3, 3-trimethylindolinone etc. are mentioned.
[0050]
The produced β-hydroxyhydroperoxides are subjected to an alkali treatment or a heat treatment, whereby the β-hydroxyhydroperoxides are decomposed to obtain ketones together with formaldehyde. For example, from the β-hydroxyhydroperoxides represented by the above general formula (2), the above general formula (4)

(Wherein R¹And R²Represents the same meaning as above. )
Is obtained together with formaldehyde. More specifically, taking a specific compound as an example, acetophenone is obtained together with formaldehyde from 2-hydroperoxy-2-phenyl-1-propanol obtained from, for example, α-methylstyrene. Moreover, as a raw material olefin, cyclohexanone is obtained with formaldehyde from 1-hydroperoxy-1- (hydroxymethyl) cyclohexane obtained from, for example, methylenecyclohexane.
[0051]
Examples of the alkali in the alkali treatment include alkali metal alcoholates such as sodium methylate, and the amount used is usually 0.01 mol times or more with respect to β-hydroxyhydroperoxides, and the upper limit thereof. There is no particular. The temperature for the heat treatment is usually 60 to 200 ° C.
[0052]
Further, the produced β-hydroxy hydroperoxides are Group Va element compound, Group VIIa element compound, Group VIII element compound, Group Ib element compound, Group IIb element compound, Group IIIb element compound, Group IVb. By acting at least one compound selected from the group consisting of Group element compounds, Group Vb element compounds and lanthanide compounds, the β-hydroxyhydroperoxides are decomposed, and ketones are obtained together with formaldehyde.
[0053]
Examples of the Group Va element compound include vanadium metal, vanadium oxide, ammonium vanadate, vanadium oxide obtained by reacting vanadium metal with hydrogen peroxide, vanadium compounds such as vanadium carbonyl complex, such as niobium metal, niobium oxide, and chloride. Niobium (V) (NbCl_Five) And niobium compounds such as niobium carbonyl complexes. Examples of Group VIIa element compounds include rhenium compounds such as rhenium metal and rhenium chloride. Examples of Group VIII element compounds include iron metal, iron chloride, and Fe (CO)._Five, Fe (acac)_ThreeIron compounds such as ruthenium metal, ruthenium chloride, Ru_Three(CO)₁₂, Ru (acac)_Three, RuCl₂(PPh_Three)_ThreeRuthenium compounds such as cobalt metal, cobalt acetate, [Co₂(CO)₈]₂Cobalt compounds such as rhodium metal, rhodium chloride, Rh_Four(CO)₁₂Rhodium compounds such as iridium metal, iridium compounds such as iridium chloride, such as nickel metal, Ni (CO)_FourNickel compounds such as palladium metal, palladium compounds such as palladium acetate, palladium carbon and the like.
[0054]
Examples of the Group Ib element compound include copper metal such as copper compounds such as cuprous chloride, cupric chloride, cuprous bromide and cupric bromide. Examples of the group IIb element compound include zinc compounds such as zinc compounds such as zinc chloride. Examples of the group IIIb element compound include boron compounds such as boron trifluoride, and aluminum compounds such as aluminum metal and aluminum chloride. Examples of Group IVb element compounds include tin compounds such as tin metal and tin chloride. Examples of Group Vb element compounds include bismuth metal and bismuth chloride (BiCl_Three) Bismuth compounds such as antimony metal, antimony chloride (V) (SbCl_Five), Antimony (III) chloride (SbCl_Three) And the like. Examples of lanthanide compounds include samarium metal and samarium triflate (Sm (OTf)₂) Samarium compounds, such as gadolinium compounds such as gadolinium metal, such as dysprosium metal, dysprosium triflate (Dy (OTf))_Three) And the like, and dysprosium compounds are preferred.
[0055]
Among these compounds, vanadium compounds, copper compounds, ruthenium compounds, palladium compounds, and mixtures thereof are preferable. Such compounds may be used alone or in combination.
[0056]
The amount of the compound used is usually 0.001 mol times or more with respect to β-hydroxyhydroperoxides, and there is no particular upper limit, but considering the economical aspect, it is practically 1 mol times or less. It is.
[0057]
To make a compound related to β-hydroxyhydroperoxides act, both of them may be mixed, and the mixing temperature is usually −20 to 100 ° C. Usually, it is carried out in the presence of a solvent in which β-hydroxyhydroperoxides are dissolved. Examples of such solvents include ether solvents such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol, and tert-butanol, such as acetonitrile and propionitrile. The use amount of β-hydroxyhydroperoxides is not particularly limited as long as β-hydroxyhydroperoxides are dissolved. However, in consideration of volumetric efficiency, β-hydroxyhydroperoxide is practically used. 100 weight times or less with respect to a kind.
[0058]
When using a reaction solution containing β-hydroxyhydroperoxides obtained by oxidizing olefins with, for example, tungsten metal, tungsten boride or the like, the compound may be allowed to act on the reaction solution as it is. The β-hydroxyhydroperoxides may be extracted from the reaction solution by extraction or the like, and then reacted with the compound.
[0059]
Examples of the ketones thus obtained include ketones already obtained by the oxidation reaction with olefins described above.
[0060]
Also, diols can be obtained by reducing β-hydroxyhydroperoxides with a reducing agent. When the β-hydroxyhydroperoxides represented by the general formula (2) are reduced, the general formula (3)

(Wherein R¹And R²Represents the same meaning as above. )
Is produced. The reduction treatment is usually carried out by mixing β-hydroxyhydroperoxides and a reducing agent, and examples of the reducing agent include inorganic reducing agents such as sodium thiosulfate, and organic reducing agents such as dimethyl sulfide. The amount of the reducing agent to be used is usually 1 mol or more with respect to β-hydroxyhydroperoxides, and there is no particular upper limit, but considering practicality, 5 mol with respect to β-hydroxyhydroperoxides. Is less than double.
[0061]
The temperature of the reduction treatment is usually in the range of 10 to 100 ° C. This reduction treatment is also usually performed in the presence of a solvent in which β-hydroxyhydroperoxides are dissolved. In the case of using a reaction liquid containing β-hydroxyhydroperoxides obtained by oxidizing olefins with, for example, tungsten metal, tungsten boride or the like, the reaction liquid may be directly mixed with a reducing agent. In many cases, unreacted hydrogen peroxide and other oxidizing substances remain in the reaction solution, so that β-hydroxyhydroperoxides are extracted from the reaction solution by extraction or the like and then mixed with a reducing agent. It is preferable in terms of economy.
[0062]
Examples of the diol include 2-methyl-1,2-propanediol, 2-methyl-1,2-pentanediol, 2,4,4-trimethyl-1,2-pentanediol, and 2-ethyl-1,2 -Butanediol, 2-phenyl-1,2-propanediol, 2- (4-chlorophenyl) -1,2-propanediol, 1,1-diphenyl-1,2-ethanediol, 1- (hydroxymethyl) cyclo Butanol, 1- (hydroxymethyl) cyclopentanol, 1- (hydroxymethyl) cyclohexanol, bicyclo [4.1.1] -2-hydroxymethyl-6,6-dimethylheptan-2-ol, 1,3 Examples include 3-trimethyl-2-hydroxy-2- (hydroxymethyl) indoline.
[0063]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. The conditions for gas chromatography analysis (hereinafter abbreviated as GC analysis) and high performance liquid chromatography analysis (hereinafter abbreviated as LC analysis) are as follows.
[0064]
<GC analysis conditions>
Column: DB-1 (φ0.25 μm × 30 m, film thickness 1.0 μm)
Carrier gas: helium (flow rate: 1 m / min)
Split ratio: 1/10, sample injection volume: 1 μL
Column temperature: 100 ° C. (0 min) → 180 ° C. (temperature rising rate: 2 ° C./min, holding time at 180 ° C .: 0 min) → 300 ° C. (temperature rising rate: 10 ° C./min, holding at 300 ° C.) (Time: 15 minutes)
Inlet temperature: 200 ° C, detector temperature: 250 ° C
[0065]

[0066]
Example 1 <Preparation of oxide by reaction of tungsten metal and hydrogen peroxide>
4 g of tungsten metal powder was added to the beaker, and 50 g of a 15 wt% aqueous hydrogen peroxide solution was further added, and the mixture was stirred at room temperature. While the oxygen gas was generated, the tungsten metal powder was dissolved (internal temperature increased to 60 ° C.), and a uniform transparent liquid colored pale yellowish brown was obtained. After cooling this solution to room temperature and decomposing the remaining hydrogen peroxide using a platinum net, water was distilled off from the solution at room temperature using a rotary evaporator to obtain a pale yellow solid (tungsten oxide). Obtained. This solid was dried to a constant weight at room temperature and in an open air system to obtain 5.8 g of solid.
[0067]
UV spectrum of homogeneous transparent liquid before concentration
λ^H2O _max: 204, 238 nm
IR spectrum of homogeneous transparent liquid before concentration (aqueous solution; 4000 to 750 cm^-1)
ν_max: 3342, 1275, 1030, 967, 837 cm^-1
IR spectrum (KBr) of the obtained solid
ν_max: 3531,3452,2945,1653,1619,973,906,638,551cm^-1
Elemental analysis value; W: 63.9, O: 31.2, H: 1.6
[0068]
Example 2 <Preparation of oxide by reaction of tungsten boride and hydrogen peroxide>
To a 100 mL flask equipped with a magnetic rotor and a reflux condenser, 4.2 g of tungsten boride powder and 25 g of water were added, and 18 g of a 60 wt% hydrogen peroxide aqueous solution was stirred for 2 hours at an internal temperature of 40 ° C. It was dripped. The mixture was further kept warm at the same temperature for 2 hours to obtain a colorless solution in which white crystals slightly floated. After cooling this solution to room temperature and decomposing the remaining hydrogen peroxide using a platinum net, water was distilled off from the solution using a rotary evaporator at room temperature to obtain a white solid (oxide). This was dried to a constant weight at room temperature and in an open air system to obtain 5.8 g of a solid.
[0069]
UV spectrum of colorless solution before concentration
λ^H2O _max: 200, 235 (s) nm
IR spectrum of colorless solution before concentration (aqueous solution; 4000-750 cm^-1)
ν_max: 3350, 2836, 1275, 1158, 965, 836 cm^-1
IR spectrum (KBr) of the obtained solid
ν_max: 3527, 3220, 2360, 2261, 1622, 1469, 1196, 973, 904.5, 884, 791, 640, 549 cm^-1
Elemental analysis value; W: 51.2, O: 39.0, H: 2.2, B: 3.98
[0070]
Example 3 <Preparation of oxide by reaction of tungsten sulfide and hydrogen peroxide>
In Example 2, it replaced with the tungsten boride powder, and it implemented similarly to Example 2 except having used 5.4 g of tungsten sulfide and having changed the quantity of water to 12 g, and obtained 10.1 g of pale yellow solid.
[0071]
UV spectrum of the solution before concentration
λ^H2O _max: 200, 240 (s) nm
IR spectrum of colorless solution before concentration (aqueous solution; 4000-750 cm^-1)
ν_max: 3373, 1187, 1044, 974, 878, 837 cm^-1
IR spectrum (KBr) of the obtained solid
ν_max: 3435, 3359, 1730, 1632, 1320, 1285, 1178, 1103, 1070, 1008, 981, 887, 839, 851, 660, 615, 578 cm^-1
Elemental analysis value; W: 35.3, O: 47.7, H: 3.0, S: 12.4
[0072]
Example 4 <Preparation of Oxide by Reaction of Molybdenum Metal with Hydrogen Peroxide>
In Example 2, instead of tungsten boride powder, 2.1 g of molybdenum metal was used, the amount of water was 12 g, and the amount of 60 wt% aqueous hydrogen peroxide was 12 g. Carried out 4.0 g of yellow solid.
[0073]
UV spectrum of the solution before concentration
λ^H2O _max: 207,300nm
IR spectrum of colorless solution before concentration (aqueous solution; 4000-750 cm^-1)
ν_max: 3359, 2480, 1372, 974, 866cm^-1
IR spectrum (KBr) of the obtained solid
ν_max: 3530, 1621, 964, 927, 902, 840, 633, 557, 530, 522 cm^-1
Elemental analysis value; Mo: 47.8, O: 46.2, H: 2.1
[0074]
Example 5 <Preparation of oxide by reaction of molybdenum boride and hydrogen peroxide>
In Example 2, instead of tungsten boride powder, 2.3 g of molybdenum boride was used, the amount of water was 12 g, and the amount of 60 wt% aqueous hydrogen peroxide solution was 12 g. To obtain 5.2 g of a yellow solid.
[0075]
UV spectrum of the solution before concentration
λ^H2O _max: 200, 310 nm
IR spectrum (KBr) of the obtained solid
ν_max: 3221, 2520, 2361, 2262, 1620, 1463, 1439, 1195, 965, 927, 887, 840, 799, 674, 634, 547, 529 cm^-1
Elemental analysis value; Mo: 35.5, O: 51.0, H: 2.9, B: 4.1
[0076]
Comparative Example 1 <Preparation of oxidized compound by reaction of tungstic acid and hydrogen peroxide>
In a beaker, tungstic acid (H₂WO_Four5.4 g was added, and 50 g of a 15 wt% aqueous hydrogen peroxide solution was further added, and the mixture was stirred at room temperature. Since the crystals of tungstic acid were not completely dissolved, the internal temperature was raised to 55 ° C., and further stirred and held for 2 hours. After cooling, unreacted crystals were filtered off, and the resulting solution was decomposed with hydrogen peroxide using a platinum net, and then water was distilled off from the solution at room temperature using a rotary evaporator. A solid was obtained. This solid was dried to a constant weight at room temperature and in an open air system to obtain 3.0 g of a solid.
[0077]
UV spectrum of the solution before concentration
λ^H2O _max: 210, 250 (s) nm
IR spectrum of the solution before concentration (aqueous solution; 4000 to 750 cm^-1)
ν_max: 3400, 2833, 1355, 967, 836cm^-1
IR spectrum (KBr) of the obtained solid
ν_max: 3416, 1623, 1385, 975, 880, 839, 749, 700, 643, 625, 550 cm^-1
Elemental analysis value; W: 63.9, O: 31.2, H: 1.6
These spectral data were compared with the oxide obtained by the reaction between the tungsten metal obtained in Example 1 and hydrogen peroxide, but they were different oxides.
[0078]
Example 6
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 250 mg of 30 wt% aqueous hydrogen peroxide and 40 mg of tungsten metal powder, and the temperature was raised to 40 ° C. After stirring and holding at the same temperature for 0.5 hours, 500 mg of 60 wt% aqueous hydrogen peroxide, 1.5 g of tert-butanol and 530 mg of magnesium sulfate were added and stirred for 30 minutes, and then 260 mg of α-methylstyrene and tert- Butanol (500 mg) was added dropwise over 20 minutes, and then the mixture was heated and stirred in an oil bath having an internal temperature of 60 ° C. for 3 hours. After completion of the reaction, 10 g of methyl tert-butyl ether and 5 g of water were added to the reaction solution, and magnesium sulfate was dissolved and separated to obtain an organic layer. LC analysis of the organic layer confirmed the formation of acetophenone. When the organic layer was analyzed by GC (internal standard method), the yield of acetophenone was 128 mg (yield: 48.5%).
[0079]
Example 7
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 1.0 g of 30 wt% hydrogen peroxide water and 20 mg of tungsten carbide, and the temperature was raised to 40 ° C. inside temperature. After stirring and holding at the same temperature for 0.5 hour, 1.8 g of 30 wt% hydrogen peroxide water and 1.3 g of α-methylstyrene were added, and the mixture was heated and stirred for 3 hours in an oil bath with an internal temperature of 75 ° C. After completion of the reaction, 10 g of methyl-tert-butyl ether and 5 g of water were added to the reaction solution, and the mixture was separated to obtain an organic layer. LC analysis of the organic layer confirmed the formation of acetophenone. When the organic layer was subjected to GC analysis (internal standard method), the yield of acetophenone was 123 mg (yield: 9.3%), and 90% of the raw material α-methylstyrene was recovered.
[0080]
Example 8
In Example 7, it replaced with 20 mg of tungsten carbide, and implemented similarly to Example 7 except having changed the reaction time from 3 hours to 10 hours using 30 mg of tungsten sulfide. Acetophenone yield: 318 mg (yield: 24%), raw material α-methylstyrene 36% recovered.
[0081]
Example 9
In Example 8, 40 mg of molybdenum metal was used instead of 30 mg of tungsten sulfide, and the reaction was performed by adding 5 g of tert-butanol. Yield of acetophenone: 502 mg (yield: 38%). Recovery of 15% raw material α-methylstyrene. As a by-product, 2-phenylpropionaldehyde was produced in a yield of 21%.
[0082]
Example 10
In Example 6, it carried out similarly to Example 6 except having replaced with 260 mg of alpha methyl styrene, and having used 211 mg of methylenecyclohexane, and obtained 62 mg of cyclohexanone. Yield: 29%.
[0083]
Example 11
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 250 mg of 30 wt% aqueous hydrogen peroxide and 40 mg of tungsten metal powder, and the temperature was raised to 40 ° C. After stirring and holding at the same temperature for 0.5 hours, 500 mg of 60 wt% aqueous hydrogen peroxide, 1.5 g of tert-butanol and 530 mg of magnesium sulfate were added and stirred for 30 minutes, and then 260 mg of α-methylstyrene and tert- Butanol (500 mg) was added dropwise over 20 minutes, and then the mixture was heated and stirred in an oil bath with an internal temperature of 25 ° C. for 2 hours. After completion of the reaction, 10 g of methyl tert-butyl ether and 5 g of water were added to the reaction solution, and magnesium sulfate was dissolved and separated to obtain an organic layer. LC analysis of the organic layer confirmed the formation of 2-hydroperoxy-2-phenyl-1-propanol. Note that acetophenone was only produced in a trace amount. GC analysis of the organic layer (internal standard method) revealed that 2-hydroperoxy-2-phenyl-1-propanol was thermally decomposed at the inlet and detected as acetophenone. It calculated from the result of GC analysis (internal standard method), and made it the yield of 2-hydroperoxy-2-phenyl-1-propanol. Yield of 2-hydroperoxy-2-phenyl-1-propanol: 50%. In addition, 18% of raw material α-methylstyrene was recovered.
[0084]
Example 12
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with the organic layer containing 2-hydroperoxy-2-phenyl-1-propanol obtained in Example 11 and 20 mg of vanadium pentoxide at an internal temperature of 60 ° C. Stir and hold for 4 hours. When the reaction solution was analyzed by LC, the peak of 2-hydroperoxy-2-phenyl-1-propanol disappeared, and the production of acetophenone was confirmed. The yield of acetophenone was determined by GC analysis and found to be 50% (based on α-methylstyrene).
[0085]
Example 13
In the same manner as in Example 11, an organic layer containing 2-hydroperoxy-2-phenyl-1-propanol was obtained. To the organic layer was added 10 g of a 10 wt% aqueous sodium thiosulfate solution, and the mixture was stirred and held at an internal temperature of 25 ° C for 14 hours. GC analysis (internal standard method) of the reaction solution revealed that 239 mg of 2-phenyl-1,2-propanediol was produced. Yield: 71%.
[0086]
Example 14
A 100 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 80 mg of tungsten metal powder, and 500 mg of 30 wt% hydrogen peroxide was added little by little, followed by stirring at room temperature for 30 minutes to obtain a colorless uniform solution. . To this solution was added 60% by weight hydrogen peroxide solution 600 mg, tert-butanol 3 g, and anhydrous magnesium sulfate 1.06 g, and after stirring at room temperature for 30 minutes, a mixture consisting of 422 mg of methylenecyclohexane and 1.5 g of tert-butanol was added. The liquid was added dropwise over 30 minutes. After stirring and holding at an internal temperature of 25 ° C. for 16 hours, 10 g of toluene and 5 g of water were added to the reaction solution, followed by liquid separation after stirring to obtain 20 g of a toluene solution. When the toluene solution was analyzed by LC, 1-hydroperoxy-1- (hydroxymethyl) cyclohexane and 1-hydroxymethylcyclohexanol were produced. The formation of cyclohexanone could not be confirmed. When this toluene solution was subjected to GC analysis (internal standard method), 1-hydroperoxy-1- (hydroxymethyl) cyclohexane was thermally decomposed at the inlet and detected as cyclohexanone. The yield of cyclohexanone was calculated, and the yield was defined as the yield of 1-hydroperoxy-1- (hydroxymethyl) cyclohexane. Yield: 29%. The yield of 1-hydroxy-1- (hydroxymethyl) cyclohexane was 15%.
[0087]
Example 15
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 50 mg of copper (II) chloride, and 10 g of a toluene solution containing 1-hydroperoxy-1- (hydroxymethyl) cyclohexane obtained in Example 14 was added. The mixture was stirred at an internal temperature of 25 ° C. for 16 hours. When the obtained reaction liquid was analyzed by LC, the peak of 1-hydroperoxy-1- (hydroxymethyl) cyclohexane disappeared. As a result of GC analysis (internal standard method), 211 mg of cyclohexanone was produced. Cyclohexanone yield: 49% (based on methylenecyclohexane).
[0088]
Example 16
A 500 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 10 g of a toluene solution containing 1-hydroperoxy-1- (hydroxymethyl) cyclohexane obtained in Example 14, and 10 g of a 10 wt% aqueous sodium thiosulfate solution was added. After stirring at an internal temperature of 25 ° C. for 16 hours, the mixture was separated and concentrated to obtain 270 mg of white crystals. The white crystals¹When analyzed by 1 H-NMR, it was confirmed to be high-purity 1- (hydroxymethyl) cyclohexanol. Yield: 93%.
[0089]
Example 17
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 200 mg of 30 wt% hydrogen peroxide, 1.5 g of tert-butanol, 16 mg of boric anhydride and 40 mg of tungsten metal powder, and the temperature was raised to 60 ° C. . After stirring and holding at the same temperature for 1 hour, 530 mg of anhydrous magnesium sulfate was added, and further a mixture of 247 mg of 2,4,4-trimethyl-1-pentene, 1.5 g of tert-butanol and 350 mg of 30% by weight hydrogen peroxide solution. Was added dropwise over 20 minutes. After completion of dropping, the mixture was stirred and held at an internal temperature of 60 ° C. for 6 hours. GC analysis of the reaction solution confirmed the formation of 4,4-dimethylpentan-2-one (area percentage value of GC analysis: 51%).
[0090]
Example 18
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 250 mg of 30 wt% aqueous hydrogen peroxide and 45 mg of tungsten boride powder and heated to an internal temperature of 40 ° C. After stirring and holding at the same temperature for 0.5 hours, 500 mg of 60 wt% aqueous hydrogen peroxide, 1.5 g of tert-butanol and 530 mg of magnesium sulfate were added and stirred for 30 minutes, and then 400 mg of β-pinene and tert-butanol were added. 500 mg was added dropwise over 10 minutes, and then heated and stirred at an internal temperature of 25 ° C. for 20 hours. The reaction solution was analyzed by gas chromatography to confirm the formation of nopinone (GC analysis area percentage value: nopinone = 29%, raw material β-pinene = 29%).
[0091]
【The invention's effect】
According to the method of the present invention, disubstituted terminal olefins and inexpensive hydrogen peroxide are added in the presence of easily available tungsten metal such as tungsten metal, molybdenum metal, tungsten boride, and molybdenum compound such as molybdenum boride. By reacting, β-hydroxyhydroperoxides and ketones can be easily obtained, and diols and ketones can be easily obtained from the β-hydroxyhydroperoxides, which is industrially advantageous. It is.

Claims (24)

Tungsten compounds consisting of disubstituted terminal olefins and hydrogen peroxide, tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb or group VIb elements excluding oxygen and molybdenum and group IIIb In the presence of a metal oxide catalyst obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of molybdenum compounds consisting of Group IVb, Group Vb or Group VIb elements excluding oxygen. A process for producing β-hydroxyhydroperoxides and ketones, characterized by reacting. Disubstituted terminal olefins are represented by the general formula (1)

(In the formula, R ¹ and R ² are the same or different and each may be an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, or a substituent which may be substituted. Aryloxy group, aralkyl group which may be substituted, aralkyloxy group which may be substituted, acyl group which may be substituted, carboalkoxy group which may be substituted, carboaryl which may be substituted Represents an oxy group, an optionally substituted carboaralkyloxy group, a carboxyl group, or a halogen atom, and R ¹ and R ² may combine to form part of the ring structure.)
The method for producing β-hydroxyhydroperoxides and ketones according to claim 1, wherein the olefins are represented by the formula: The method for producing β-hydroxyhydroperoxides and ketones according to claim 1, wherein the Group IIIb element is boron. The method for producing β-hydroxyhydroperoxides and ketones according to claim 1, wherein the Group IVb element is carbon. The method for producing β-hydroxyhydroperoxides and ketones according to claim 1, wherein the Group Vb element is nitrogen or phosphorus. The method for producing β-hydroxyhydroperoxides and ketones according to claim 1, wherein the Group VIb element excluding oxygen is sulfur. The manufacturing method of (beta) -hydroxy hydroperoxide and ketones of Claim 1 using hydrogen peroxide water. Tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb or tungsten compound consisting of group VIb excluding oxygen and molybdenum and group IIIb, group IVb, group Vb or oxygen are excluded A β-hydroxy hydroperoxide and a ketone are obtained by oxidizing a disubstituted terminal olefin by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of molybdenum compounds consisting of Group VIb elements. Metal oxide catalyst for manufacturing. Tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb or tungsten compound consisting of group VIb excluding oxygen and molybdenum and group IIIb, group IVb, group Vb or oxygen are excluded Β-hydroxy hydroperoxides and ketones obtained by oxidizing disubstituted terminal olefins by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of molybdenum compounds consisting of Group VIb elements Metal oxide catalyst aqueous solution for producing A metal oxide catalyst solution for producing β-hydroxyhydroperoxides and ketones by oxidizing disubstituted terminal olefins comprising the metal oxide catalyst aqueous solution according to claim 9 and an organic solvent. Tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb or tungsten compound consisting of group VIb excluding oxygen and molybdenum and group IIIb, group IVb, group Vb or oxygen are excluded A disubstituted terminal olefin characterized in that at least one metal compound selected from the group consisting of molybdenum compounds consisting of Group VIb elements and hydrogen peroxide solution are reacted with stirring so that the metal compound is sufficiently dispersed. Of a metal oxide catalyst aqueous solution for the production of β-hydroxyhydroperoxides and ketones by oxidizing alkynes. A β-hydroxyhydroperoxide is obtained by the method according to claim 1, and then the β-hydroxyhydroperoxide is decomposed by alkali treatment or heat treatment. A method for producing ketones characterized by the following. A β-hydroxyhydroperoxide is obtained by the method according to claim 1, and then the β-hydroxyhydroperoxide is added to a group Va element compound, a group VIIa element compound, a group VIII element compound. And at least one compound selected from the group consisting of a group Ib element compound, a group IIb element compound, a group IIIb element compound, a group IVb element compound, a group Vb element compound and a lanthanide compound, A method for producing ketones, which comprises decomposing β-hydroxyhydroperoxides. The method for producing a ketone according to claim 13, wherein the Group Va element compound is a vanadium compound or a niobium compound. The method for producing ketones according to claim 13, wherein the Group VIIa element compound is a rhenium compound. The method for producing ketones according to claim 13, wherein the Group VIII element compound is an iron compound, a ruthenium compound, a cobalt compound, a rhodium compound, an iridium compound, a nickel compound or a palladium compound. The method for producing ketones according to claim 13, wherein the Group Ib element compound is a copper compound. The method for producing ketones according to claim 13, wherein the Group IIb element compound is a zinc compound. The method for producing ketones according to claim 13, wherein the Group IIIb element compound that acts on β-hydroxyhydroperoxides is a boron compound or an aluminum compound. The method for producing ketones according to claim 13, wherein the Group IVb element compound that acts on β-hydroxyhydroperoxides is a tin compound. Group Vb element compounds, method for producing ketones placing serial to claim 1 3 a bismuth compound or antimony compound to be applied to the β- hydroxy hydroperoxides. The method for producing a ketone according to claim 13, wherein the lanthanide compound is a dysprosium compound. A process for producing diols, comprising obtaining β-hydroxyhydroperoxides by the method according to claim 1, and then reducing the β-hydroperoxides with a reducing agent. The method for producing a diol according to claim 23, wherein the reducing agent is an inorganic reducing agent or sulfides.