JP2005502446A - Novel catalyst formulations and their preparation - Google Patents

Abstract

The present invention describes a general methodology for formulating composite solids useful for catalyzing various reactions. The present invention relates in particular to heterogeneous catalysts as formulations comprising a solid support on which a catalytically active material is deposited, which is in particular insoluble in various liquid media, the insoluble material being suitable Composed of secondary building blocks derived from various organometallic active ingredients, and the organometallic active ingredients are molecularly modified to introduce two or more negatively charged functional groups, these This molecularly modified organometallic component interacts with the salts of Ca ²⁺ , Sr ²⁺ and Ba ²⁺ to provide a virtually insoluble solid material.

Description

例えば、この固形ホスフィンは、温度を５℃未満に制御しつつ、少しずつ、発煙硫酸に加えられ、次いで、所望の程度のスルホン化が達成されるまで、例えば、２０〜８０℃まで加熱される。次いで、この反応混合物は、直ちに冷却されて、ホスフィンがそれ以上スルホン化または酸化するのを止め、待たずに、これに水を加えて、温度が３０℃より高くなるのを回避し、該プロトン化ホスフィン塩は、アルカリ溶液で中和される。アルカリスルホン酸塩およびアルカリ硫酸塩を含有する混合物は、水を蒸発させることにより、濃縮される。この水の蒸発中にて、アルカリ硫酸塩が沈殿し、これは、濾過により除去され、この母液に、メタノールが混合される。このアルカリ硫酸塩の殆どが沈殿すると、このメタノール中に、スルホン化ホスフィンが抽出される。メタノールを蒸発させると、固形物として、スルホン化ホスフィンが得られる。適切な溶媒（例えば、水またはエタノール）に溶解し、そこから再結晶すると、その粗製第三級ホスフィン金属スルホン酸塩がさらに精製され得る。
【００６９】
このスルホン化はまた、Ａｌｂａｎｅｓｅらの米国特許第５６８４１８１号および米国特許第５７８０６７４号で記述されているように、ホウ酸および三酸化イオウ錯体を使用して、濃硫酸媒体中で、実行できる。このような手順の利点は、酸化ホスフィンの形成を少なくすることにある。同様に、このスルホン化反応のワークアップはまた、クエンチしたスルホン化混合物を亜リン酸トリブチルまたはトリイソオクチルアミン有機相（これは、引き続いて、アルカリ溶液で抽出される）で抽出することにより、修正され得る。このような手順の利点は、ホスフィンが対応する酸化物から選択的に分離できることにある。ホスフィンの酸化物は、このようなスルホン化ホスフィン配位子中でしばしば生じる汚染物である。酸化ホスフィンが存在していても、遷移金属と組み合わせて、この配位子の触媒挙動に影響を与えない。このような酸化ホスフィンは、金属と配位せず、そこで、酸化ホスフィンが原因の汚染は、触媒反応の目的のためには、許容され得ることが分かる。酸化ホスフィンの存在は、二座配位子および二座キラル配位子の場合には、許容され得ない。この分野の専門家は、以来、二座配位子のホスフィンモノオキシドが異なる配位挙動を示す状況を容易に理解できる。この状況は、エナンチオ選択性反応の触媒を調製している間に、さらに複雑になる。このような場合、酸化ホスフィンの除去が望ましく、これは、亜リン酸トリブチルまたはトリイソオクチルアミンの溶液から抽出的に分離することにより、あるいはＨｅｒｍａｎｎら、Ａｎｇｅｗ．Ｃｈｅｍ．Ｉｎｔ．Ｅｎｇ．著、２９（１９９０）Ｎｏ（４）３９１〜３９３で記述されているように、改変デキストラン（例えば、ＳＥＰＨＡＤＥＸ Ｇ１５（登録商標））のゲルから分別することにより、達成され得る。
【００７０】
スルホン化されるこのような配位子は、リチウム燐化物、グリニヤール試薬および三塩化リンなどを使用する種々の方法により、調製できる。このような配位子の知見および理解は、当業者に公知の文献で教示されている。例えば、Ｋｏｓｏｌａｐｏｆｔ Ｇ．Ｍ．，Ｍａｉｅｒ Ｌ．Ｏｒｇａｎｉｃ Ｐｈｏｓｐｈｏｒｕｓ Ｃｏｍｐｏｕｎｄｓ，Ｖｏｌｕｍｅ １，２８８，Ｗｉｌｅｙ Ｉｎｔｅｒｓｃｉｅｎｃｅ，Ｎｅｗ Ｙｏｒｋ，（著作権）１９７２．／Ｅｎｇｌ Ｒ．ｓｙｎｔｈｅｓｉｓ ｏｆ ｃａｒｂｏｎ ｐｈｏｓｐｈｏｒｕｓ ｂｏｎｄｓ，（著作権）ＣＲＣ Ｐｒｅｓｓ １９８８．／Ｔｒｉｐｅｔｔ Ｓ．Ａ．Ａ ｓｐｅｃｉａｌｉｓｔ Ｐｅｒｉｏｄｉｃａｌ Ｒｅｐｏｒｔ ｏｆ Ｏｒｇａｎｏｐｈｏｓｐｈｏｒｕｓ Ｃｈｅｍｉｓｔｒｙ，Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ Ｌｏｎｄｏｎ（著作権）１９７０。このような合成の具体的な例は、（Ｍａｎｎ，Ｆ．Ｇ．ら、Ｊ．Ｃｈｅｍ．Ｓｏｃ．１９３７，５２７〜５３５；米国特許第４，４８３，８０２号および米国特許第４，７３１，４８６号で説明されている）。同様に、窒素含有配位子は、当該技術分野で公知の特殊な化学合成により、調製できる（Ｅｉｔ Ｄｒｅｎｔ、米国特許第５，１６６，４１１号）。このような配位子の合成、製造および精製は、明らかに、本願の範囲から外れる。このような配位子のスルホン化に関係している知見もまた、周知であることは、明らかに理解できる。同様に、他のアニオン的に荷電した官能基（例えば、−ＣＯＯ⁻、−ＰＯ_３ ^２−）を備えた配位子もまた、一連の特定の有機合成（ホスホン酸およびカルボン酸を含有する配位子の合成）により、調製できる。本発明は、一般的な触媒処方物（これは、固形物であり、触媒として使用される）を調製するために、このような周知の配位子をさらに利用することを請求している。さらに処理することによるこのような公知の配位子の利用は、本願の範囲（ｓｃｏｐｅおよびｐｕｒｖｉｅｗ）内であり、そして本発明の好ましい実施形態の１つである。好ましいアニオン性配位子およびそれらの遷移金属錯体および四級化合物の例には、以下のようなものが挙げられる。これらが例にすぎず、包括的ではないことは、言うまでもない。
アニオン性配位子
【００７１】
【化２】

四級化合物の一部の例には、以下がある：
アニオン性四級化合物
【００７２】
【化３】

上記ポリアニオン性配位子および四級化合物は、アルカリ金属、四級アンモニウムまたはプロトンの塩として存在している。このような化合物がこのような配位子と遷移金属との水溶性の組合せであり、それらの錯体へのアクセスを与えることは、当該技術分野で周知である。触媒活性部分の一部の例には、以下がある：
触媒活性アニオン性部分
【００７３】
【化４】

先に述べた錯体は、文献の記載で公知の種々の方法により、調製できる。広義には、このような金属錯体は、以下のように分類できる：
１．金属塩およびアニオン性配位子からの金属錯体の合成；
２．不安定な配位子のアニオン性配位子による置換。
【００７４】
例えば、ＰｄＣｌ_２ビス（トリフェニルホスフィントリスルホネート三ナトリウム）のような錯体は、水性エタノール中にて、ＰｄＣｌ_４ ^２−とトリフェニルトリフェニルホスフィントリスルホネート三ナトリウムとを反応させることにより、塩化ルテニウムとトリフェニルトリフェニルホスフィントリスルホネート三ナトリウムとを反応させることにより調製され、後者の場合、シクロオクタジエンまたはアセチルアセトネートのような不安定な配位子を置換することにより、ＨＲｈＣＯ（ＴＰＰＴＳ）_３、ＲＵＣｌ_２ＢＩＮＡＰのような錯体が調製される。スルホン化フタロシアニン（ｐｔｈａｌｏｃｙｎｉｎｅ）のような錯体は、配位子と錯体とを同時に形成することにより、調製される。先に述べたように、このような錯体の合成は、当業者に周知の知見である。このような錯体の合成は、本発明の範囲（ｓｃｏｐｅおよびｐｕｒｖｉｅｗ）を超える。このような錯体をさらに利用して触媒用途のための不溶性固形処方物を形成することは、本発明の明白な実施形態である。
【００７５】
異なる金属および多様な配位子を含有するいくつかの異なる金属錯体が合成された。このような金属錯体は、マグネシウム化合物以外の第ＩＩＡ族金属化合物と相互作用するときはいつでも、固形物を提供し、これらは、水、有機溶媒に不溶であった。それらの沈殿物は、２００℃まで固形物であり、非昇華性であった。実施例で記述したいくつかの実験を行い、提案された仮説を検証して、ポリアニオンは、第ＩＩＡ族金属と相互作用するとき、種々の液体に不溶な沈殿物を形成するとの論理的な結論を推定した。本願のさらに別の好ましい実施形態では、触媒活性ポリアニオンおよび触媒不活性アニオンの混合物は、大部分の液体に不溶な沈殿物を形成するのに好ましい。触媒不活性添加剤がさらに存在している理由は、共通イオン効果という周知の現象により、水中で沈殿した錯体の溶解度を低下させることにある。また、錯体を形成するのに使用される追加配位子を加えることも、好ましい。追加配位子の存在は、配位している液相で触媒処方物を使用するつもりの場合、または関与している配位子が一座である場合、特に好ましい。
【００７６】
該触媒処方物の触媒活性物質は、沈殿により、触媒不活性添加剤の溶液と、触媒活性要素と第ＩＩＡ族金属カチオンの溶液との相互作用により、形成される。触媒不活性添加剤の溶液、触媒活性要素は、第ＩＩＡ族金属カチオンの溶液と接触したとき、２つの溶液が拡散を開始し、引き続いて、第ＩＩＡ族金属のカチオンがポリアニオンとの衝突に遭遇したときはいつでも、固化が開始し、固形物のクラスターがゆっくりと形成される。このような沈殿物では、触媒不活性添加剤は、少なくとも２個またはそれ以上の負電荷を有するアニオン、配位子化合物から別個に選択され、該配位子化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィンに由来の少なくとも１個のラジカルを含有し、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻およびそれらの組合せから別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、そして触媒活性要素は、金属錯体、四級化合物、金属オキソアニオンおよびポリオキソメタレートまたはそれらの組合せから別個に選択される。
【００７７】
この触媒活性は、金属錯体が以下の一般式を有するように、選択され得る：
（Ｍ）_ｘ（Ｌ）_ｙ（Ｌ^＊）_ｚ
ここで、Ｍは、元素の周期表の第ＩＩＩＢ族、第ＩＶＢ族、第ＶＢ族、第ＶＩＢ族、第ＶＩＩＢ族、第ＩＢ族または第ＩＩＢ族に由来の遷移金属の配位錯体の触媒金属原子またはイオンであり、そして別個に選択された適切な遷移金属イオンであり得、原子には、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎが挙げられる。好ましくは、この金属錯体は、元素の周期表の第ＶＩＩＩ族に由来の金属原子またはイオンを含有し、ｘは、１〜６０であり、Ｌは、脂肪族化合物、芳香族化合物および複素環化合物であり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有し、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合した、オキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し；ｙは、少なくとも１であり、Ｌ^＊は、有機アニオン、無機アニオンおよび配位子化合物から選択されるラジカルであり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベン、＝Ｃ：由来の少なくとも１個のラジカルを含有し、このラジカルは、このラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、Ｚは、０〜７である。四級アンモニウム化合物は、以下の一般式を有する：
［（Ｙ^＋）（Ｒ^＊）_Ｉ］［Ｚ⁻］
ここで、Ｙ^＋＝Ｎ^＋、Ｐ^＋、Ａｓ^＋に対して、Ｉ＝４である；Ｙ^＋＝Ｓ^＋に対して、Ｉ＝３であり、そしてＲ^＊は、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルから別個に選択され、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備え、そしてＺは、有機アニオン、無機アニオンおよび配位錯体アニオンから選択されるアニオンである。
【００７８】
従って、先の実施形態に記述したように、本発明者は、多元的な触媒要素を固化する一般的な技術を開発し、これは、異なる理論および機構に従って、機能する。このような固化は、先に述べた触媒要素をイオン性固形物に取り込むことにより達成され、これは、それだけで、ポリアニオン性触媒要素、ポリアニオン性添加剤および第ＩＩＡ族金属イオンの相互作用により、形成される。
【００７９】
本発明の触媒処方物（ここで、先に述べた触媒物質）は、その固体支持体の表面で支持される。形成された不溶性の触媒物質は、液体に溶解できず、それゆえ、この固体支持体で支持できないことが思い起こされる。従って、沈殿により、この固体支持体の表面にて、このような物質を直接的に形成する技術が必要とされていた。
【００８０】
それにより、複合材料触媒の最終的な形成は、この支持体表面で触媒活性物質を沈殿することにより、実行できる。沈殿または共沈による触媒の形成は、それゆえ、この点で、中心となる重要なものである。しかしながら、沈殿は、複雑な現象であり、この支持体表面に触媒を堆積するには、いくつかの補助的な技術を開発する必要がある。それにもかかわらず、いくつかの触媒関連物質（特に、支持物質）について、沈殿は、最も頻繁に適用される方法である。この点で、このような沈殿は、液体の大部分でクラスターおよび粒子を発生し得るので、面倒である。固形触媒活性物質の形成の具体的な取り扱いは、第ＩＩＡ族金属イオンおよびポリアニオン要素として分類される２つの成分が相互作用するときに沈殿物を生じるので、共沈という用語により、うまく記述されている。共沈は、相互作用している種の化学量論が明確であるとき、その支持物質にてこのような物質の均一な分布を生じるのに極めて適切な技術である。以前の経験から、共沈により、その支持体表面での良好な分散を得ることができ、これは、それなしでは、考慮中の触媒アセンブリを得るのが困難であることが公知の事実である。それゆえ、そのバルク共沈プロセスは、複合材料系のアセンブリを得るように改良する必要がある。
【００８１】
好ましくは、この共沈は、アニオン性要素（触媒活性要素および触媒不活性添加剤）を含有する前駆体溶液および第ＩＩＡ族金属溶液が支持体の表面の近くで拡散するか不溶なクラスターの形成が支持体の表面の近くで開始するような様式で、実行される。以下、アニオン性成分を含有する溶液は、溶液Ａと呼び、そして第ＩＩＡ族金属を含有する溶液は、溶液Ｂと呼ぶ。先に述べた実施形態の触媒処方物を組み立てる種々の方法を概説することは、本発明の他の実施形態である。これらの組立技術は、広義には、種々の沈殿技術に従って分類され、そして実施形態の記述を保証して記述されている。
【００８２】
固形複合材料として不均一触媒処方物を調製する方法（該固形複合材料は、その上に触媒活性固形物を堆積した多孔性固体支持体から構成されている）の１つは、不溶性固体支持体を液相に懸濁する工程により特徴付けられ、該液相には、触媒不活性添加剤および触媒活性要素の溶液ならびに第ＩＩＡ族金属カチオン溶液が激しくかき混ぜつつ同時に加えられて１〜４８時間熟成され、ここで、該支持体は、反応媒体中にて、機械的に頑丈で熱的に安定な固体であり、約３〜３０００Åの範囲の細孔直径を有し、そして粉末、顆粒、定形または不定形のフレークまたはパレット、シート、モノリス、ロープおよび繊維固形物織布として存在し、そして該触媒不活性添加剤は、有機化合物、無機化合物、またはＯ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有する化合物から選択される少なくとも２個またはそれ以上の負電荷を有するアニオンから別個に選択され、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有する。
【００８３】
該触媒活性要素は、金属錯体、四級化合物、メタルオキソアニオン、ポリオキソメタレートおよびそれらの組合せから別個に選択され、該金属錯体は、以下の一般式を有する：
（Ｍ）_ｘ（Ｌ）_ｙ（Ｌ^＊）_ｚ
ここで、Ｍは、元素の周期表の第ＩＩＩＢ族、第ＩＶＢ族、第ＶＢ族、第ＶＩＢ族、第ＶＩＩＢ族、第ＩＢ族または第ＩＩＢ族に由来の遷移金属の配位錯体の触媒金属原子またはイオンであり、そして別個に選択された適切な遷移金属イオンであり得、原子には、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎが挙げられる。好ましくは、この金属錯体は、元素の周期表の第ＶＩＩＩ族に由来の金属原子またはイオンを含有し、ｘは、１〜６０であり、Ｌは、脂肪族化合物、芳香族化合物および複素環化合物であり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有し、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、ｙは、少なくとも１であり、Ｌ^＊は、有機アニオン、無機アニオンおよび配位子化合物から選択されるラジカルであり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベン、＝Ｃ：由来の少なくとも１個のラジカルを含有し、このラジカルは、このラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、そしてｚは、０〜７である；そして該四級アンモニウム化合物は、以下の一般式を有する：
［（Ｙ^＋）（Ｒ^＊）_Ｉ］［Ｚ⁻］
ここで、Ｙ^＋＝Ｎ^＋、Ｐ^＋、Ａｓ^＋に対して、Ｉ＝４である；Ｙ^＋＝Ｓ^＋に対して、Ｉ＝３であり、そしてＲ^＊は、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルから別個に選択され、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備え、そしてＺは、有機アニオン、無機アニオンおよび配位錯体アニオンから選択されるアニオンである。該第ＩＩＡ族金属カチオンは、Ｃａ^２＋、Ｓｒ^２＋およびＢａ^２＋の化合物から選択される。
【００８４】
上で述べた方法は、−７８〜２００℃の範囲の温度、好ましくは、−５〜１００℃の間の温度で実行される。この方法用の溶媒は、水性溶媒、水混和性有機溶媒またはそれらの混合物から選択される。
【００８５】
上記方法では、触媒不活性添加剤および触媒活性要素の溶液ならびに第ＩＩＡ族金属カチオンの溶液は、１０〜１５００分間にわたって、同時に加えられる。この処理が完了した後、前記触媒は、遠心分離、デカンテーション、重力沈降または他の固液分離技術により回収され、引き続いて、真空中にて、固体乾燥される。本明細書中で記述した方法は、粘度、溶媒および溶解度調節剤の影響下にて、沈殿物の成分が固形物質をゆっくりと生じるとき、使用可能である。固形物質の種がゆっくりと発生するので、この沈殿物の種が支持体表面に沈降するのに十分な時間がある。以下で記述の他の方法は、瞬間的に起こる共沈に適切である。このような方法は、通常、それに特殊な単位操作が必要なことから、重要であり、また、製造には、特別な設備が必要である。
【００８６】
不均一触媒処方物を調製する別の方法（ここで、固形複合材料は、その上に触媒活性固形物を堆積した多孔性固体支持体から構成される）は、該固体支持体を触媒活性要素および触媒不活性添加剤で含浸する工程に続いて、乾燥させる工程により特徴付けられ、乾燥した支持体は、その上に触媒活性要素が堆積され、触媒不活性添加剤は、同時にかき混ぜつつ、第ＩＩＡ族金属化合物の溶液に加えられる。懸濁液は、かき混ぜつつ、１〜４８時間熟成され、従って、該方法は、−７８〜２００℃の範囲の温度、好ましくは、−５〜１００℃の間の温度で実行される。
【００８７】
この場合、支持体は、反応媒体中にて、機械的に頑丈で熱的に安定な固体であり、約３〜３０００Åの範囲の細孔直径を有し、そして粉末、顆粒、定形または不定形のフレークまたはパレット、シート、モノリス、ロープおよび繊維固形物織布として存在し、そして触媒不活性添加剤は、有機化合物、無機化合物、またはＯ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有する化合物であり得る少なくとも２個またはそれ以上の負電荷を有するアニオンから別個に選択され、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有する。
【００８８】
該触媒活性要素は、金属錯体、四級化合物、メタルオキソアニオンおよびポリオキソメタレートまたはそれらの組合せから別個に選択され、該金属錯体は、以下の一般式を有する：
（Ｍ）_ｘ（Ｌ）_ｙ（Ｌ^＊）_ｚ
ここで、Ｍは、元素の周期表の第ＩＩＩＢ族、第ＩＶＢ族、第ＶＢ族、第ＶＩＢ族、第ＶＩＩＢ族、第ＩＢ族または第ＩＩＢ族に由来の遷移金属の配位錯体の触媒金属原子またはイオンであり、そして別個に選択された適切な遷移金属イオンであり得、原子には、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎが挙げられる。好ましくは、この金属錯体は、元素の周期表の第ＶＩＩＩ族に由来の金属原子またはイオンを含有し、ｘは、１〜６０であり、Ｌは、脂肪族化合物、芳香族化合物および複素環化合物であり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有し、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、ｙは、少なくとも１であり、Ｌ^＊は、有機アニオン、無機アニオンおよび配位子化合物から選択されるラジカルであり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベン、＝Ｃ：由来の少なくとも１個のラジカルを含有し、このラジカルは、このラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、そしてｚは、０〜７である；そして四級アンモニウム化合物は、以下の一般式を有する：
［（Ｙ^＋）（Ｒ^＊）_Ｉ］［Ｚ⁻］
ここで、Ｙ^＋＝Ｎ^＋、Ｐ^＋、Ａｓ^＋に対して、Ｉ＝４である；Ｙ^＋＝Ｓ^＋に対して、Ｉ＝３であり、そしてＲ^＊は、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルから別個に選択され、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備え、そしてＺは、有機アニオン、無機アニオンおよび配位錯体アニオンから選択されるアニオンである。該第ＩＩＡ族金属カチオンは、Ｃａ^２＋、Ｓｒ^２＋およびＢａ^２＋の化合物から選択される。考慮中の方法によれば、アニオン性成分および第ＩＩＡ族金属カチオンを溶解するのに使用する溶媒は、水性溶媒、水混和性有機溶媒またはそれらの混合物である。
【００８９】
この方法の改良が採用され得、ここで、その上に触媒活性要素および触媒不活性添加剤を堆積した支持体は、特定の方法要件に依存して、１０〜１５００分間にわたって同時にかき混ぜつつ、第ＩＩＡ族金属化合物の溶液に加えられる。この方法は、従って、遠心分離、デカンテーション、重力沈降または他の固液分離技術により触媒を回収することにより、引き続いて、真空中にて、乾燥することにより、完結する。
【００９０】
さらに、固形複合材料として不均一触媒処方物を調製するさらに別の好ましい方法によれば、固形複合材料は、その上に触媒活性固形物を堆積した多孔性固体支持体から構成され、該方法は、固体支持体を触媒活性要素および触媒不活性添加剤の溶液で含浸する工程に続いて、乾燥する工程によって特徴付けられる。その上に触媒不活性添加剤および触媒活性要素を堆積した固体支持体は、水混和性溶媒に懸濁され、該水混和性溶媒に、激しくかき混ぜつつ、第ＩＩＡ族金属化合物の溶液が加えられ、同時に、溶媒の低沸点画分または共沸画分が除去される。該懸濁液は、１〜４８時間熟成され、ここで、該方法は、従って、７０〜２００℃の範囲の温度で、実行される。
【００９１】
この場合の該支持体は、反応媒体中にて、機械的に頑丈で熱的に安定な固体であり、約３〜３０００Åの範囲の細孔直径を有し、そして粉末、顆粒、定形または不定形のフレークまたはパレット、シート、モノリス、ロープおよび繊維固形物織布として存在し、そして触媒不活性添加剤は、有機化合物、無機化合物、またはＯ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有する化合物であり得る少なくとも２個またはそれ以上の負電荷を有するアニオンから別個に選択され、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有する。
【００９２】
触媒活性要素は、金属錯体、四級化合物、メタルオキソアニオンおよびポリオキソメタレートまたはそれらの組合せから別個に選択され、該金属錯体は、以下の一般式を有する：
（Ｍ）_ｘ（Ｌ）_ｙ（Ｌ^＊）_ｚ
ここで、Ｍは、元素の周期表の第ＩＩＩＢ族、第ＩＶＢ族、第ＶＢ族、第ＶＩＢ族、第ＶＩＩＢ族、第ＩＢ族または第ＩＩＢ族に由来の遷移金属から選択される配位錯体の触媒金属原子またはイオンであり、そして別個に選択された適切な遷移金属イオンであり得、原子には、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎが挙げられる。好ましくは、この金属錯体は、元素の周期表の第ＶＩＩＩ族に由来の金属原子またはイオンを含有し、ｘは、１〜６０の範囲であり、Ｌは、脂肪族化合物、芳香族化合物および複素環化合物から選択され、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有し、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、ｙは、少なくとも１であり、Ｌ^＊は、有機アニオン、無機アニオンおよび配位子化合物から選択されるラジカルであり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベン、＝Ｃ：由来の少なくとも１個のラジカルを含有し、このラジカルは、このラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、そしてｚは、０〜７である；そして該四級アンモニウム化合物は、以下の一般式を有する：
［（Ｙ^＋）（Ｒ^＊）_Ｉ］［Ｚ⁻］
ここで、Ｙ^＋＝Ｎ^＋、Ｐ^＋、Ａｓ^＋に対して、Ｉ＝４である；Ｙ^＋＝Ｓ^＋に対して、Ｉ＝３であり、そしてＲ^＊は、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルから別個に選択され、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備え、そしてＺは、有機アニオン、無機アニオンおよび配位錯体アニオンから選択されるアニオンである。該第ＩＩＡ族金属カチオンは、Ｃａ^２＋、Ｓｒ^２＋およびＢａ^２＋の化合物から選択される。
【００９３】
第ＩＩＡ族金属イオンの溶液を形成するのに使用する溶媒は、水性溶媒、水混和性有機溶媒またはそれらの混合物であり、そして、支持体を懸濁するのに使用する溶媒は、４０〜２００℃の範囲の沸点を有する水混和性有機溶媒である。本発明の方法は、遠心分離、デカンテーション、重力沈降または他の固液分離技術により触媒を回収することにより、引き続いて、真空中にて、乾燥することにより、完結する。
【００９４】
固形複合材料として不均一触媒処方物を調製する方法では、その上に第ＩＩＡ族金属化合物を堆積した多孔性固体支持体から構成された該固形複合材料は、引き続いて、乾燥される。その上に第ＩＩＡ族金属を堆積した固体支持体は、水混和性溶媒で懸濁され、該水混和性溶媒に、激しくかき混ぜつつ、触媒活性要素および触媒不活性添加剤の溶液が加えられ、同時に、溶媒の低沸点画分または共沸画分が除去される。この共沸蒸留工程は、従って、７０〜２００℃の範囲の温度で、実行される。溶媒の共沸除去工程で使用される液状媒体は、４０〜２００℃の範囲の沸点を有する水混和性有機溶媒である。それらは、懸濁後、１〜４８時間熟成される。
【００９５】
この場合、支持体は、反応媒体中にて、機械的に頑丈で熱的に安定な固体であり、約３〜３０００Åの範囲の細孔直径を有し、そして粉末、顆粒、定形または不定形のフレークまたはパレット、シート、モノリス、ロープおよび繊維固形物織布として存在し、そして該触媒不活性添加剤は、有機化合物、無機化合物、またはＯ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有する化合物であり得る少なくとも２個またはそれ以上の負電荷を有するアニオンから別個に選択され、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有する。
【００９６】
該触媒活性要素は、金属錯体、四級化合物、メタルオキソアニオンおよびポリオキソメタレートまたはそれらの組合せから別個に選択され、該金属錯体は、以下の一般式を有する：
（Ｍ）_ｘ（Ｌ）_ｙ（Ｌ^＊）_ｚ
ここで、Ｍは、元素の周期表の第ＩＩＩＢ族、第ＩＶＢ族、第ＶＢ族、第ＶＩＢ族、第ＶＩＩＢ族、第ＩＢ族または第ＩＩＢ族に由来の遷移金属から選択される配位錯体の触媒金属原子またはイオンであり、そして別個に選択された適切な遷移金属イオンであり得、原子には、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎが挙げられる。好ましくは、この金属錯体は、元素の周期表の第ＶＩＩＩ族に由来の金属原子またはイオンを含有し、ｘは、１〜６０であり、Ｌは、脂肪族化合物、芳香族化合物および複素環化合物であり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有し、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、ｙは、少なくとも１であり、Ｌ^＊は、有機アニオン、無機アニオンおよび配位子化合物から選択されるラジカルであり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベン、＝Ｃ：に由来の少なくとも１個のラジカルを含有し、このラジカルは、このラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、そしてｚは、０〜７である；そして該四級アンモニウム化合物は、以下の一般式を有する：
［（Ｙ^＋）（Ｒ^＊）_Ｉ］［Ｚ⁻］
ここで、Ｙ^＋＝Ｎ^＋、Ｐ^＋、Ａｓ^＋に対して、Ｉ＝４である；Ｙ^＋＝Ｓ^＋に対して、Ｉ＝３であり、そしてＲ^＊は、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルから別個に選択され、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備え、そしてＺは、有機アニオン、無機アニオンおよび配位錯体アニオンから選択されるアニオンである。該第ＩＩＡ族金属カチオンは、Ｃａ^２＋、Ｓｒ^２＋およびＢａ^２＋の化合物から選択される。第ＩＩＡ族金属イオンの溶液を形成するのに使用する溶媒は、水性溶媒、水混和性有機溶媒またはそれらの混合物である。有機混和性液体および低沸点液体の除去後、遠心分離、デカンテーション、重力沈降または他の固液分離技術、引き続いて、真空中にて、固体乾燥することにより、触媒を回収する。
【００９７】
固形複合材料として不均一触媒処方物を調製する方法は、気体の流れに固体支持体を流動化させる工程を包含する。該触媒活性要素および該触媒不活性添加剤の溶液は、触媒活性要素および触媒不活性添加剤が該固体支持体に堆積されるように、噴霧され、該固形物の流動体化は、１〜４８時間継続される。第ＩＩＡ族金属化合物の溶液は、引き続いて、噴霧され、そして固形物の流動体化は、さらに、１〜４８時間継続され、そして固形物が回収される。この流動体化の方法は、２０〜２００℃の範囲の温度で実行され、ここで、この場合、支持体は、反応媒体中にて、機械的に頑丈で熱的に安定な固体であり、約３〜３０００Åの範囲の細孔直径を有し、そして粉末、顆粒、定形または不定形のフレークまたはパレット、シート、モノリス、ロープおよび繊維固形物織布として存在し、そして該触媒不活性添加剤は、有機化合物、無機化合物、またはＯ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有する化合物であり得る少なくとも２個またはそれ以上の負電荷を有するアニオンから別個に選択され、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し；該触媒活性要素は、金属錯体、四級化合物、メタルオキソアニオンおよびポリオキソメタレートまたはそれらの組合せから別個に選択され、該金属錯体は、以下の一般式を有する：
（Ｍ）_ｘ（Ｌ）_ｙ（Ｌ^＊）_ｚ
ここで、Ｍは、元素の周期表の第ＩＩＩＢ族、第ＩＶＢ族、第ＶＢ族、第ＶＩＢ族、第ＶＩＩＢ族、第ＩＢ族または第ＩＩＢ族に由来の遷移金属の配位錯体の触媒金属原子またはイオンであり、そして別個に選択された適切な遷移金属イオンであり得、原子には、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎが挙げられる。好ましくは、この金属錯体は、元素の周期表の第ＶＩＩＩ族に由来の金属原子またはイオンを含有し、ｘは、１〜６０であり、Ｌは、脂肪族化合物、芳香族化合物および複素環化合物であり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有し、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、ｙは、少なくとも１であり、Ｌ^＊は、有機アニオン、無機アニオンおよび配位子化合物から選択されるラジカルであり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベン、＝Ｃ：に由来の少なくとも１個のラジカルを含有し、このラジカルは、このラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有し、そしてｚは、０〜７である；そして四級アンモニウム化合物は、以下の一般式を有する：
［（Ｙ^＋）（Ｒ^＊）_Ｉ］［Ｚ⁻］
ここで、Ｙ^＋＝Ｎ^＋、Ｐ^＋、Ａｓ^＋に対して、Ｉ＝４である；Ｙ^＋＝Ｓ^＋に対して、Ｉ＝３であり、そしてＲ^＊は、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルから別個に選択され、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備え、そしてＺは、有機アニオン、無機アニオンおよび配位錯体アニオンから選択されるアニオンである。第ＩＩＡ族金属カチオンは、Ｃａ^２＋、Ｓｒ^２＋およびＢａ^２＋の化合物から選択される。第ＩＩＡ族金属イオンの溶液を形成するのに使用する溶媒は、水性溶媒、水混和性有機溶媒またはそれらの混合物である。
【００９８】
本発明は、さらに、本発明による触媒を製造する別の好ましい方法に及ぶ。この方法によれば、アニオン的に荷電した要素およびアニオン的に荷電した添加剤は、この固体支持体に堆積され、引き続いて、溶媒を同時に除去しつつ、第ＩＩＡ族金属塩溶液を噴霧することにより、硬化される。
【００９９】
従って、固形複合材料として不均一触媒処方物を調製する方法は、不活性な気体の流れの下で回転パンにて固体支持体を回転する工程を包含する。触媒活性要素および触媒不活性添加剤の溶液は、該触媒活性要素および触媒不活性添加剤が該固体支持体に均一に堆積されるように、噴霧される。該固形物の回転は、１〜４８時間継続される。第ＩＩＡ族金属化合物の溶液は、引き続いて、噴霧され、そして湿った固形物の回転は、さらに、１〜４８時間継続され、そして固形物が回収される。従って、記述の方法は、２０〜２００℃の範囲の温度で実行される。該不活性気体流れの加熱またはパン（これは、支持体を含む）の回転のいずれかにより、この方法の温度が達成され得る。本発明の処方物を形成するのに使用する実験室装置は、図６で表わされ、このような装置は、容量要件に依存して、適切に縮尺され得る。
【０１００】
本明細書中で使用可能な支持体材料は、反応媒体中にて、機械的に頑丈で熱的に安定な固体であり、約３〜３０００Åの範囲の細孔直径を有し、そして粉末、顆粒、定形または不定形のフレークまたはパレット、シート、モノリス、ロープおよび繊維固形物織布として存在する。
【０１０１】
触媒不活性添加剤は、有機化合物、無機化合物、またはＯ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有する化合物であり得る少なくとも２個またはそれ以上の負電荷を有するアニオンから別個に選択され、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有する。さらに、この触媒不活性添加剤は、複数のアニオン性電荷を備える重合体であり得る。
【０１０２】
触媒活性要素は、金属錯体、四級化合物、メタルオキソアニオンおよびポリオキソメタレートまたはそれらの組合せから別個に選択される。触媒活性である金属錯体要素は、以下の一般式を有するように選択される：
（Ｍ）_ｘ（Ｌ）_ｙ（Ｌ^＊）_ｚ
ここで、Ｍは、元素の周期表の第ＩＩＩＢ族、第ＩＶＢ族、第ＶＢ族、第ＶＩＢ族、第ＶＩＩＢ族、第ＩＢ族または第ＩＩＢ族に由来の遷移金属の配位錯体の触媒金属原子またはイオンであり、そして別個に選択された適切な遷移金属イオンであり得、原子には、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎが挙げられる。好ましくは、この金属錯体は、元素の周期表の第ＶＩＩＩ族に由来の金属原子またはイオンを含有し、接尾辞ｘは、錯体に存在するこのような触媒遷移金属の数を示し、このような金属要素の数は、１〜６０である。金属錯体の成分Ｌは、脂肪族化合物、芳香族化合物および複素環化合物であり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベンに由来の少なくとも１個のラジカルを含有し、該ラジカルは、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える、ラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有する。接尾辞ｙは、配位している配位子（これは、それより低い配位状態にある金属を保持する）の数を示し、ｙは、少なくとも１である必要がある。Ｌ^＊は、有機アニオン、無機アニオンおよび配位子化合物から選択されるラジカルであり、該化合物は、Ｏ、Ｎ、Ｓ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、オレフィン、カルベン、＝Ｃ：に由来の少なくとも１個のラジカルを含有し、このラジカルは、このラジカルに結合したオキシ、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルを有する。接尾辞ｚは、このような非参加（ｎｏｎ−ｐａｒｔｉｃｉｐａｔｉｎｇ）配位子の数を示す。これらの配位子は複数または異なって存在する場合、同一であり得るが、総数は０〜７の範囲である。あるいは、別の種類の触媒活性要素（これは、単独で、または上記遷移金属錯体と併用して、使用可能である）は、該四級アンモニウム化合物であり、以下の一般式を有する：
［（Ｙ^＋）（Ｒ^＊）_Ｉ］［Ｚ⁻］
ここで、選択され得る化合物は、窒素、リン、ヒ素およびイオウの四級化合物に属し得る。窒素、リン、ヒ素含有化合物に属する場合、Ｙ^＋＝Ｎ^＋、Ｐ^＋に対して、接尾辞Ｉ＝４である；そしてイオウ化合物について、Ｙ^＋＝Ｓ^＋に対して、Ｉ＝３であり、そしてＲ^＊は、アルキル、アリール、アリールアルキル、アルキルアリール、アルコキシ、アリールオキシ、シクロアルキルから別個に選択され、−ＳＯ_３ ⁻、−ＳＯ_２ ⁻、−ＰＯ_３ ^２−、−ＣＯＯ⁻、−Ｏ⁻、ＡｓＯ_３ ^２−および−Ｓ⁻から別個に選択される少なくとも１個またはそれ以上の負電荷官能基を備える；Ｚは、有機アニオン、無機アニオンおよび配位錯体アニオンから選択されるアニオンである。大部分の場合、実際の触媒要素は、アニオンＺ⁻であることが暗示される。四級化合物は、固化に対するアンカーを与えるだけでなく、アニオンＺ⁻が逃げないように、必要な静電場を提供する。
【０１０３】
第ＩＩＡ族金属カチオンは、Ｃａ^２＋、Ｓｒ^２＋およびＢａ^２＋の化合物から選択される。先に記述のように被覆パンにて触媒を形成する方法では、溶液を形成するのに使用する溶媒は、好ましくは、水性溶媒、水混和性有機溶媒またはそれらの混合物である。このような溶液は、この方法に従って、同時または順次に噴霧される。
【０１０４】
触媒処方物を形成するのに使用される方法とは無関係に、該固体触媒アンサンブルは、気相または液体スラリーにて、多様な反応を触媒するのに使用できる。頑丈な固形物である触媒は、反応物および生成物の物理的状態および特性に依存して、種々の反応器構成（例えば、固定床、トリッケル床、流動床およびスラリー反応器）にて、有機化合物を製造するのに適当な反応器構成を選択する機会が得られる。
【０１０５】
本発明の固体触媒は、必要に応じて、改変でき、ここで、この固体触媒には、必要に応じて、高沸点液体または低融点固形物のフィルムが堆積される。この改変は、必要な生成物に対して高い選択性を得るために、反応物の局所溶解度を高めるか触媒部位の環境を改善するように、選定できる。
【０１０６】
特定の反応に対して先に記述の実施形態に従って調合する触媒は、液相にてこのような反応を触媒する類似の触媒から選択される；類似の要素は、そこに負電荷を導入するように適切に機能化することにより、均一系のこのような親触媒から誘導される。触媒活性要素は、必要条件に依存して、金属錯体、四級化合物、金属オキソアニオンおよびポリオキソメタレートまたはそれらの組合せから別個に誘導される。アニオン性官能基を除いて、触媒要素の残りの構造は、このような要素の固化には重要ではない。各個の溶解性触媒に由来のアニオン的に荷電した要素の誘導体の一部の例を、以下の表に示す。表で示した種類の反応は、代表的なものにすぎず、触媒要素は、添付の請求の範囲の範囲内に入る。それゆえ、その触媒要素が、触媒する反応とは無関係に、一般的な技術で固化される固体触媒処方物を記述することは、実施形態を明白にすることになる。このような触媒要素は、明らかに、請求の範囲で請求されている。
【０１０７】
アニオン的に官能化した溶解性触媒要素およびそれらの適用の一部の例を、以下の表に列挙する。
【０１０８】
【表１】

本発明に従って支持された触媒は、記述した試験により実証されるように、非常に活性であり、これは、以下の例で示されている。実際、これらの実施例は、このような支持した触媒を、公知の分子触媒理論に従って異なる機構により触媒される多様な反応に適用することに関する。これらの支持した触媒の均一相での反応を比較すると、相当な程度まで触媒活性を保持しつつ、容易な分離が簡単に達成できることが証明される。これにより、触媒は、連続プロセスに適切となり、それにより、触媒のプロセス経済性が高まる。本質的に固形である該触媒処方物は、不均一相での所望の触媒変換後、簡単に回収できる。それらは、次いで、新たな仕込量の反応物を触媒するために再使用でき、この操作は、連続的であるか繰り返し可能であるかいずれかであり、ここで、この触媒は、数回、再生できる。その有利な事実としては、触媒処方物は、その活性が相当に低下することなしに、数回、繰り返し可能であることがある。
【０１０９】
触媒を触媒反応の目的に供する前に、安定性および不適合性を評価することが必須である。この理由のために、種々の化学的なストレスを加えて、触媒処方物が実際の反応に適用したときに遭遇するストレスをシミュレートした。反応中または後処理中に遭遇するストレスには、溶媒および媒体が原因の溶媒和ストレスがある。適用できる範囲の溶媒には、反応および後処理（例えば、洗浄）に使用される液体がある。洗浄は、吸着した物質を除去し、他の化学処理により活性化するように触媒を再生するのに好ましいプロセスである。
【０１１０】
この理由のために、先に記述した方法に従って、異なる金属（例えば、ロジウム、ルテニウム、イリジウム、パラジウム、白金、コバルト、ニッケル、モリブデンおよび鉄）を含有する種々の触媒が調製され、そして図３で詳述した装置にて、水、酢酸、メタノール、イソプロパノール、エーテル、テトラヒドロフラン、酢酸エチル、アセトン、アセトニトリル、トルエン、シクロヘキサンのような溶媒の沸騰温度で、抽出された。この抽出は、数時間継続され、引き続いて、溶媒を変えた。金属含量の感知できる損失はなく、視覚的な比較による物理的形態が検出された。ヒドロキシ、メトキシおよび他の塩基性ラジカルを含む部位が破壊されることは、明らかに正しい。これらの実験は、触媒は、多様な範囲の溶媒で安定であり、特定の種類の溶媒に制限する必要はないことを示す。同様に、触媒は、酸およびアルカリ水溶液に浸出され、遷移金属または第ＩＩＡ族金属を含む金属の損失が検出された。
【０１１１】
研究した触媒の活性は、実施例にて、通常の様式で、回転数が測定されるが、これは、理想的な条件下にて、単位時間あたり、触媒活性要素に対する触媒反応により変換される分子の数、すなわち、所定時間にわたる収量を規定する。
【０１１２】
種々の予備実験を実行し、本発明の触媒の適用性を確認した。これらの予備実験は、分子触媒を理解することを目的としていた。この理由のために、２種の生成物が不斉な位置選択性と共に形成される反応が選択された。ヒドロホルミル化は、このような反応の１つであり、ここで、反応速度および位置選択性は、分子環境が変わるために、著しく変化する。これらの理由のために、ヘキサンをＨＲｈＣＯ（ＴＰＰＴＳ）_３でヒドロホルミル化することは、反応条件での触媒を理解する適切なプローブとして、考慮された。
【０１１３】
ヒドロホルミル化反応は、基質としてのヘキセンおよび活性触媒要素としてのＨＲｈＣＯ（ＴＰＰＴＳ）_３（ロジウム１ｇ／支持体１ｇ）、含水量（ｐｐｍ）、支持体としてのシリカおよび過剰でない配位子について、実行した。完全な変換が得られ、その触媒を、遠心分離で回収し、トルエンで洗浄し、そして真空中で乾燥した。乾燥触媒粉末を、水中でのアリルアルコールのヒドロホルミル化に再使用した。触媒は、ヒドロホルミル化に活性であり、アルデヒドが得られた。反応後の触媒は、遠心分離で回収され、真空中で乾燥され、そしてヘキセンヒドロホルミル化に再使用され、アルデヒドを生成することが分かった。この実験により、基質とは無関係に、種々の溶媒にて、反応を連続的に触媒する実行可能性が明らかとなった。
【０１１４】
従って、支持体の必要性は、ＨＲｈＣＯ（ＴＰＰＴＳ）_３を硝酸バリウムで沈殿させることにより、確認された。沈殿物は、ヘキセンヒドロホルミル化を触媒するのに使用された。２４時間後、転化率は、１％未満であった。
【０１１５】
反応は、固体状態で起こり、反応条件下での錯体の浸出（これは、最終的に、固形物に戻る）では起こらないことを確認するために。これは、触媒種および追加配位子の移動度の規準を使用することにより、検証される。溶解性触媒の場合、追加配位子は、可動状態にあり、それが原因で、活性種と相互作用でき、低い速度および高いｎ／Ｉ比にすることにより、そのようになる。存在している追加配位子と共に触媒を調製したとき、活性および選択性の変化は、観察されなかった。この観察は、配位子および触媒の不動状態に起因していた。配位子が移動できないために、それらの活性種との相互作用は、完全に遅延され、それにより、速度およびｎ／ｉ比に影響を与えない。
【０１１６】
触媒の不動性は、さらに、この固体触媒に水を加えることにより、検証された。低い含水量（ｐｐｍ／ｇ）では、高い転化率が得られた。含水量が高くなると、活性は、かなり低下した。同じ触媒は、乾燥したとき、その最初の活性に戻った。この実験は、最終的に、固体状態で反応が起こることを立証している。
【０１１７】
従って、その触媒の寿命、その安定性および耐久性を示す重大な評価は、触媒５ｇを使用して、管状トリカル床反応器（Φ１／２”）にて、８０℃および３００ｐｓｉ Ｈ_２／ＣＯ（１：１）で、触媒をヒドロホルミル化にかけることにより、管状固定床反応器にて、実行された。トルエン中の５％デセンを、１０ｍｌ／ｈｒの給送速度で、連続的にポンプ上げした。変換レベルは、定常状態に達した後、アルデヒドについて、２０％であった（ｎ／ｉ ２．１）。この反応は、７２時間継続したが、活性の損失はなかった。その液体の給送を中止することにより、反応を停止し、１時間にわたって、水をポンプ上げした。その後、反応物の給送を再開した。最初は、変換がなかったが、これは、１０時間にわたって、徐々に再開した。この観察は、その触媒表面で水のフィルムが形成されたことに起因しており、これは、デセンと触媒表面との接触を物理的に遅らせる。さらに、水は、錯体触媒を洗い流さず、このことは、固体状態で反応が起こることの決定的証拠となる。
【０１１８】
固体触媒処方物の技術は、本発明で確立され、それによれば、固体触媒は、多様な溶媒中で反応を触媒するために調合され適用できる。本明細書中で引用した触媒処方物は、さらに別の実施形態に従って、種々の反応に適用された。触媒処方物が使用可能である代表的な種類の反応は、次の節で記述する。ここで記述する種類の反応は、例にすぎず、先に記述したような触媒活性要素の範囲により限定されない。本明細書中で記述した種々の種類の反応は、考慮中の触媒処方物の範囲を概説する目的であり、ここで、複数の有機化合物の製造に適用するとき、触媒の分離、操作の安定性および利便性に重点が置かれている。本明細書中で記述した種類の反応には、ヒドロホルミル化、水素化、カルボニル化、Ｈｅｃｋ型反応およびＳｕｚｉｋｉ型反応による炭素−炭素結合形成、異性化（ｉｓｏｍａｒｉｚａｔｉｏｎ）、エポキシ化、Ｗａｃｋｅｒ酸化、Ｍｉｃｈｅｌ付加およびＫｎｏｖｅｎｇｅｌ縮合がある。
【０１１９】
オレフィンへの一酸化炭素および水素の金属触媒付加により、アルデヒドへのアクセスが得られ、ある場合には、それに続いて、水素化される。広範囲の多様なオレフィンは、対応するアルデヒドにヒドロホルミル化できる。種々のオレフィスンは、古典的なＷｉｌｋｉｎｓｏｎ触媒の類似物で、ヒドロホルミル化された。種々のオレフィン（例えば、ヘキセン、スチレン、シクロヘキセンおよび酢酸ビニル）は、ヒドロホルミル化された。同様に、ヘキセンは、選択性を制御するために、異なる配位子で改変されたロジウムでヒドロホルミル化された。従って、ヒドロホルミル化に活性な他の金属（例えば、コバルトおよびパラジウム）もまた、試験された。
【０１２０】
パラジウムホスフィン錯体は、均一反応系にて、ハロゲン化物、アルコールおよびオレフィンのカルボニル化を触媒する。このようなパラジウム錯体の類似物は、スチレン、スチリルアルコール、フェニルアセチレンおよびブロモベンゼンについて調整され、そして試験された。各場合において、合理的な活性が得られ、触媒は、再利用できる。
【０１２１】
種々のホスフィンアミン、Ｚｒ、Ｈｆ、Ｖ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔの亜リン酸塩錯体は、種々の官能基の水素化に有用である。オレフィン、カルボニルおよびニトロ芳香族化合物の水素化は、本発明で調合した触媒を使って、試験した。
【０１２２】
ビニル炭素中心にて炭素−炭素結合を直接形成することにより置換アルケンを伸長することは、種々の有機合成物の製造に有用な反応である。このような合成手順は、従来の有機合成で達成することは困難である。そのパラジウム錯体（Ｐｄ０）は、この意味で、有効であることが判明した。ホスフィン、メタレートホスフィンおよび亜リン酸塩を含めた種々のパラジウム錯体は、有用な触媒である。他の金属（例えば、ニッケルおよびパラジウム）もまた、この点で、有用である。臭化アリールのオレフィン化は、本発明の触媒処方物を使って、立証された。
【０１２３】
アリールまたはビニルボロン酸とハロゲン化アリールとのパラジウムで触媒した交差カップリング反応は、当該技術分野で周知である。このようなカップリング反応は、非極性媒体だけでなく極性媒体でも実行される。パラジウムホスフィン錯体は、この点で、有用である。種々のビアリール化合物は、この反応によって、アクセス可能である。本発明の触媒処方物はまた、この種の反応に適切である。
【０１２４】
二重結合の異性化（ｉｓｏｍａｒｉｚａｔｉｏｎ）は、オレフィンを異性化オレフィンに変換する際に有用な反応である。種々の遷移金属錯体は、この種の反応を触媒する。この点で有用な金属錯体には、白金、パラジウム、ロジウムおよびコバルトがある。本発明の触媒処方物はまた、この反応を触媒する際に有用である。
【０１２５】
現在の触媒処方物はまた、オレフィンをエポキシドおよび酸に酸化するのに適切である。例えば、モリブデン酸塩イオンは、四級アンモニウムイオン対として不均一化するとき、オレフィンのエポキシ化を触媒できる。種々のフタロシアニン（ｐｔｈａｌｏｃｙａｎｉｎｅ）もまた、この点で、有用である。
【０１２６】
メソメリック（ｍｅｓｏｍｅｒｉｃ）アニオンの活性化オレフィン（例えば、αβ不飽和オレフィン）への求核付加は、Ｍｉｃｈｅｌ反応として、公知である。比較的に酸性のプロトンを有する電子吸引基を含有する化合物は、メソメリックアニオンを形成するのに適当な化合物である。このような化合物には、例えば、Ｒ−ＣＨ_２−Ｚがあり、ここで、Ｚは、電子吸引基（例えば、ＣＮ、ＣＯＯＲ、ＮＯ_２、ＣＨＯなど）であり、そしてＲは、アルキルアリールであり得るか、またはＺは、先に定義したとおりである。強塩基の存在下では、アニオンＲ−ＣＨ^（−）−Ｚに対する化合物は、β位置にて、α−β−不飽和オレフィンに付加する。活性化オレフィンは、Ｃ＝Ｃ−Ｚとして表わされ得、ここで、Ｚに結合した炭素は、αであり、そして隣接した炭素は、βである。
【０１２７】
一般に、該メソメリックイオンを形成するのに使用する触媒には、強塩基（例えば、Ｈ⁻、ＯＨ⁻、ＭｅＯ⁻など）がある。アニオン断片それ自体は、固化するのが困難であり、従って、このようなものに対して選択される対カチオンは、四級アンモニウム化合物であり、これらは、アニオン性官能基で官能化され、そしてイオン対は、全体として、固体支持体に沈殿される。アルコキシイオン対として四級アルミニウム化合物が存在している場合、固化した四級化合物の処方物は、使用前に、アルコキシアニオンの溶液で首尾よく洗浄される。マロン酸ジエチルを、アクリル酸エチル、マレイン酸ジエチル、アクリロニトリルで縮合することは、以下の実施例で示されている。
【０１２８】
アルデヒドまたはケトンの縮合（これは、通常、α水素を含有せず、オレフィンを形成するために、Ｒ−ＣＨ_２−Ｚの形態の化合物を使う）は、Ｋｎｏｖｅｎｇｅｌ反応と呼ばれており（Ｊｏｎｅｓ，Ｏｒｇ．ｒｅａｃｔ．１９６７，１５，２０４〜５９９）、ここで、Ｚは、ＣＨＯ、ＣＯＲ、ＣＯＯＨ、ＣＯＯＲ、ＣＮ、ＮＯ_２であり得る。この反応に一般に使用可能である触媒には、塩基性アミン、ヒドロキシルアニオンまたはアルコキシアニオンがある。アニオン断片は、それ自体、固化するのが困難であり、従って、このようなものに選択される対カチオンは、四級アンモニウム化合物であり、これは、アニオン性官能基で官能化され、イオン対は、全体として、固体支持体で沈殿される。アルコキシイオン対として四級アルミニウム化合物が存在している場合、固化した四級化合物の処方物は、使用前に、アルコキシアニオンの溶液で首尾よく洗浄される。ブチルアルデヒドを２−エチルヘキサナール、ベンズアルデヒドに縮合し、アセトンを、ジベンジリデンアセトン、ベンズアルデヒドに縮合し、アセトニトリルをシンナモニトリルに縮合することは、以下の添付の実施例で示されている。
【０１２９】
これらの記述から、アニオン的に荷電した触媒要素を適当に形成することにより、多様な溶解性触媒が調合できることは、明らかである。これらの要素は、構造上、これらの溶解性触媒要素と類似している。これに関連して使用可能な触媒には、金属錯体、四級アンモニウム化合物があり、ここで、コンプリメンタリー（ｃｏｍｐｌｉｍｅｎｔａｒｙ）アニオンは、触媒である（コンプリメンタリーアニオンは、金属錯体、有機金属アニオンまたは無機アニオンであり得る）。
【０１３０】
本発明は、一部の特定の理論に従って、該固体触媒処方物を以下の特定の機構で触媒される１つの特定の種類の錯体または反応に限定することなく、着想された。高い表面積を有する固体支持体により、不溶な触媒物質が物理的に移植される機械的強度および表面が得られると認知されている。この不溶物質は、２個またはそれ以上のアニオン性官能基を含む他の溶解性錯体触媒と、カルシウム塩、ストロンチウム塩およびバリウム塩の溶液との相互作用から、生じる。この物質は、ビヒクルとして、この固体支持体の表面で形成される。そこから得られた複合性固形アセンブリは、固体触媒として、適当に使用できる。
【０１３１】
さらに、出願人の好ましい触媒処方物を再利用し再生することは、経過時間により決定されようと基質の消費または他のパラメータによりモニターされようと、例えば、所定のバッチ運転にて、許容できる変換レベルが起こったとき、公知の方法および手順を使用して、容易に達成される。その容器は、室温にして残留圧力（もしあれば）を吐き出すことだけが必要である。この反応混合物は、その後、簡単にデカントすることより、単に、触媒から分離される。この触媒処方物は、濾過され、多分、後の再使用のために適当な液体で洗浄されるか、単に、必要に応じて、供給原料で再充填され、次の反応が開始する。
【０１３２】
触媒の寿命は、実験室または商業設定のいずれかで、特定の触媒処方物を繰り返し再生して作業することにより、よく理解できるので、適当な液体で洗浄するか特定の化学処理にかけるかいずれかにより、時々、触媒を再生することが、さらに望まれ得る。出願人の好ましい触媒を使って、それらの不溶性と浸出または他の崩壊に対する耐性とを考慮して、連続反応プロセスもまた、実行可能である。このようなプロセスは、当該技術分野で通例の公知手順を使用して、設計され実行できる。
【０１３３】
本発明の触媒および方法をさらによく理解し易くする目的のために、それらの調製および使用の具体的な場合について、以下の実施例が参照される。これらの実施例は、代表的なものにすぎず、出願人の発明の範囲を限定するものではない。本発明の種々の改良および変更は、当業者に明らかであり、このような改良および変更は、本願の範囲および添付の請求の範囲の性質および範囲に含まれることが理解できるはずである。
【実施例】
【０１３４】
（実験１（仮説の検証））
この比較例は、２個またはそれ以上の負電荷を有するアニオンが、Ｍｇ^２＋以外の第ＩＩＡ族金属カチオンと相互作用するとき、常に、沈殿物を生じ、これは、事実上、有機溶媒（非極性溶媒、極性溶媒（プロトン性溶媒および非プロトン性溶媒）を含めて）に不溶であり、そして、ある場合には、水性溶媒に難溶性であるという仮説の有効性を説明する。この仮説は、以下のようにして検証した。異なるアニオンの溶液を、第ＩＩＡ族金属イオンと相互作用した。アニオン成分の溶液（溶液Ａ）０．１モルおよび第ＩＩＡ族金属カチオン成分の溶液（溶液Ｂ）０．１モルを調製した。１０ｍｌの溶液Ｂを、沸騰チューブにて、５０ｍｌの溶液Ａと混合した。溶液を、１０時間にわたって、振盪機にて、十分に混合した。得られた懸濁液を遠心分離し、上澄み液をデカントすることにより、沈殿物を除去した。残留沈殿物を蒸留水で希釈し、続いて、遠心分離およびデカンテーションを３回繰り返した。この沈殿物に、メタノール１０ｍｌを加え、遠心分離およびデカンテーションの手順を繰り返した。得られた湿潤沈殿物を、５０℃で、真空乾燥した。沈殿物が観察されなかった混合物を捨てた。乾燥した沈殿物のバリウムおよびストロンチウムは、水、メタノール、エタノール、プロパノール、ブタノール、酢酸、ベンゼン、キシレン、石油エーテル、酢酸エチル、アセトン、メチルエチルケトン、アセトニトリル、ジメチルホルムアミド、クロロホルム、テトラヒドロフランに不溶であることが分かった。これに対して、カルシウムの一部の塩は、難溶性であることが分かった。
【０１３５】
結果は、以下の表に要約する。
【０１３６】
【表２】

これらに加えて、ＥＤＴＡアセチルアセトネート、カルシウムの水素化化合物は、硫酸ナトリウム、リン酸ナトリウムと相互作用して、不溶な沈殿物を生じた。
【０１３７】
（実験２）
（高純度発煙硫酸の合成）
２リットルの三ッ口フラスコに、蒸留冷却器、添加漏斗を装着し、他の末端に、底部排水弁付きの収集容器を装着した。蒸留冷却器には、また、圧力逃しノンリターン弁を備え付けた。フラスコにて、磁性棒を設置し、５００ｇのＰ_２Ｏ_５を充填した。収集容器に、４５ｍｌの濃Ｈ_２ＳＯ_４を入れた。添加漏斗に、４００ｍｌの濃Ｈ_２ＳＯ_４を入れた。添加は、２時間にわたって、同時に磁気かき混ぜしつつ、開始した。三酸化イオウがゆっくりと留出し始めるまで、フラスコの温度をゆっくりと上げた。収集容器中の液体の全容量が１４８ｍｌに達するまで、濃Ｈ_２ＳＯ_４中にて、三酸化イオウを集め、加熱を停止し、アセンブリを解体した。
【０１３８】
（実験３）
（トリフェニルホスフィントリスルホネートの合成）
以下の手順により、トリフェニルホスフィントリスルホネートを合成した。トリフェニルホスフィン５０ｇをスルホン化反応器に入れ、続いて、真空アルゴン脱気を行い、アルゴンで覆った。スルホン化反応器を５℃まで冷却し、反応器の温度が１０℃を超えない（ｃｒｏｓｓ）ようにして、スルホン化反応器に、硫酸２００ｇを充填した。硫酸の添加は、２時間にわたって、機械攪拌機で絶えず攪拌しつつ、実行した。反応混合物は、淡黄色を呈した。この反応器に、６０分間にわたって、先の実験により調製した６５％発煙硫酸２８０ｇを充填した。このスルホン化反応器の温度を２２℃まで上げ、反応を７６時間継続した。その後、その反応の温度を０℃まで下げ、３〜４時間にわたって、温度が５℃を超えて上昇しないようにして、このスルホン化反応器に、蒸留し脱気した水５０ｍｌを導入した。この溶液を、水５００ｍｌで、さらに希釈した。希釈した溶液を３リットルのジャケット付き容器に移し、そして５℃まで冷やし、最終的に、５０重量％のＮａＯＨ水溶液（これは、予め脱気した）で中和した。中和点では、溶液は、鮮やかな黄色を呈した。この場合、ＮａＯＨの添加を中止し、濃硫酸を加えることにより、ｐＨを６まで下げた。中和の間に形成された硫酸ナトリウムは、部分的に沈殿し、これを濾過により除去し、得られた溶液を、減圧下にて、３００ｍｌまで濃縮した。形成された硫酸ナトリウムを、濾過により除去した。ＴＰＰＴＳを含有する母液を、さらに、脱気メタノール２０００ｍｌで希釈し、そして２時間還流し、その間、その硫酸ナトリウムの殆どは沈殿し、メタノール中のＴＰＰＴＳの上澄み抽出物は、濾過により除去した。メタノール中のＴＰＰＴＳ抽出物を乾燥状態まで蒸発して、白色固体を得た（Ｐ^３１ＮＭＲにより、９５％を超える純度）。この固体を最低量の水に溶解し、脱気エタノールで再沈して、９９％を超える純度のＴＰＰＴＳを得た。
【０１３９】
（実験４）
（Ｐ−フェニル−３，３’−ホスフィンジアリビス（ベンゼンスルホン酸）二ナトリウムの合成）
オルトホウ酸（４８ｇ）を９８％濃硫酸（２００ｍｌ）に溶解し、これに、６５％発煙硫酸２００ｍｌを加えた。その溶液の温度を６０℃まで上げ、高真空下にて、酸化カルシウムを含むガストラップ付属装置を設けることにより、過剰の三酸化イオウを除去した（トラップは、−１０℃まで冷やした）。オルトホウ酸および三酸化イオウの溶液を５℃まで冷却し、アルゴンブランケット下にて、トリフェニルホスフィン３０ｇを加えた。得られた混合物を機械攪拌機でかき混ぜ、その反応器の温度を５８℃まで上げ、反応を９０時間継続した。その温度を０℃まで下げ、脱気した水５００ｍｌで加水分解した。この溶液を、中和するまで５０重量％水酸化ナトリウム水溶液で中和し、形成された沈殿物を濾過により除去し、そして母液を３００ｍｌまで濃縮し、メタノール１０００ｍｌで希釈し、２時間還流した。得られた沈殿物を、濾過により除去した。そのメタノール中の抽出物を蒸発させると、固体が得られ、これを、メタノール１０００ｍｌに懸濁し、これに、微結晶セルロースアビセル（ａｖｉｃｅｌ）５０ｇを加え、続いて、濃Ｈ_２ＳＯ_４（２０ｍｌ）を加え、アルゴンブランケット下にて、６時間還流した。溶液を冷却し、そして濾過して、アビセルを除去した。これに、Ａｖｉｃｅｌ（登録商標）５０ｇを再び加え、さらに６時間還流した。懸濁液を濾過し、含メタノール抽出物を５０重量％ＮａＯＨで中和し、そして濾過した。溶液を蒸発し、白色化合物の正確な元素分析を得た。
【０１４０】
（実験５）
（３，３’，３”−ホスフィントリアルトリス（４−メチルベンゼンスルホネート）三ナトリウムの合成）
オルトホウ酸（ｇ、６．６ｍｍｏｌ）を濃硫酸（９６％、３．７５ｍｌ）に溶解し、これに、反応混合物中にて、（２−メチルフェニル）ホスフィン（０．５０ｇ、１．４ｍｍｏｌ）を溶解した。反応混合物の温度を０℃にしつつ、発煙硫酸（６．７５ｍｌ、６５重量％）を滴下した。２５℃で７２時間攪拌した後、その温度を０℃まで下げ、脱気した水５ｍｌを加えることにより、その混合物を加水分解した。この溶液を、中和するまで５０重量％水酸化ナトリウム水溶液で中和し、形成された沈殿物を濾過により除去し、そして母液を３ｍｌまで濃縮し、メタノール１０ｍｌで希釈し、２時間還流した。得られた沈殿物を、濾過により除去した。そのメタノール抽出物を蒸発させると、固体が得られ、これを、メタノール１０ｍｌに懸濁し、これに、微結晶セルロースアビセル０．５ｇを加え、続いて、濃Ｈ_２ＳＯ_４（０．５ｍｌ）を加え、アルゴンブランケット下にて、６時間還流した。溶液を冷却し、そして濾過して、アビセルを除去した。これに、アビセル０．５ｇを再び加え、さらに６時間還流した。懸濁液を濾過し、含メタノール抽出物を５０重量％ＮａＯＨで中和し、そして濾過した。溶液を蒸発させて、白色化合物の正確な元素分析を得た。
【０１４１】
（実験６）
（スルホン化トリベンジルホスフィンのナトリウム塩の合成）
正確なスルホン化度を確立しなかったこと以外は、トリフェニルホスフィンと同様にして、トリベンジルホスフィンのスルホン化を実行した。さらなる実験のために、ジおよびトリスルホン化ホスフィンを含有する反応混合物を使用した。
【０１４２】
（実験７）
（１−３ビス−ジフェニルホスフィノプロパンのスルホン化）
ジフェニルホスフィノプロパン４．９５ｇ（１２ｍｍｏｌ）を、オルトホウ酸４ｇ（６４．７ｍｍｏｌ）の反応混合物３７．５ｍｌ（９８％）溶液に溶解し、０℃まで冷却し、これに、２時間にわたって、６５％発煙硫酸６７．５ｍｌを滴下した。添加後、反応混合物を２５℃にし、そして４８時間攪拌した。この後、反応混合物を０℃にし、そして脱気した水５０ｍｌで加水分解した。この溶液を、ｐＨ７まで５０重量％水酸化ナトリウム水溶液で中和し、形成された沈殿物を濾過により除去し、そして母液を３０ｍｌまで濃縮し、メタノール１００ｍｌで希釈し、２時間還流した。得られた沈殿物を、濾過により除去した。そのメタノール抽出物を蒸発させると、固体が得られ、これを、メタノール１００ｍｌに懸濁し、これに、微結晶セルロースアビセル５ｇを加え、続いて、濃Ｈ_２ＳＯ_４（１ｍｌ）を加え、アルゴンブランケット下にて、６時間還流した。溶液を冷却し、そして濾過して、アビセルを除去した。これに、アビセル５ｇを再び加え、さらに６時間還流した。懸濁液を濾過し、含メタノール抽出物を５０重量％ＮａＯＨで中和し、そして濾過した。溶液を蒸発させて、白色化合物を得た。
【０１４３】
（実施例８）
（１−２ビス−ジフェニルホスフィノエタンのスルホン化）
先の実験で説明した類似の様式で、調製を実行した。
【０１４４】
（実験９）
（２，２’−ビス（ジフェニルホスフィノメチル）−１，１’−ビフェニル（ビスビ）の合成およびスルホン化）
３リットルの三ッ口フラスコに、密封機械攪拌機、還流冷却器および温度計を備え付ける。このフラスコ中にて、フェナントレン８９ｇ（０．５ｍｏｌ）を氷酢酸１リットルに溶解し、そして水浴にて、８５℃まで温める。４０分間で、３０％過酸化水素溶液３４５ｍｌ（４ｍｏｌ）を導入し、温度を約８０℃まで低下させ、６時間継続し、減圧下にて酢酸および水を除去して、褐色固体を得た。この残留物を２Ｎ水酸化ナトリウム溶液で分解し、そして粉末木炭４ｇを加え、その混合物を７５℃まで温め、そして濾過する。濾液を、濃ＨＣｌで、ｐＨ２まで酸性化した。白色沈殿物を濾過し、そして５０℃（融点１０９℃）で乾燥した。得られた６９％の物質８３ｇは、さらなる合成のために十分な純度である。
【０１４５】
３リットルの三ッ口フラスコに、密封機械攪拌機、還流冷却器および温度計を備え付ける。フラスコを、氷塩浴にて、０℃まで冷却した。反応容器に、ジフェン酸２４．２ｇ（０．１ｍｏｌ）およびホウ水素化ナトリウム１５．１２ｇ（０．４ｍｏｌ）を充填した。この固形粉末に、泡立ちができるだけ少なくなるような様式で、乾燥テトラヒドロフラン２００ｍｌを加えた。１時間後、懸濁液は、均一になり、これに、温度を０℃で維持しつつ、２時間にわたって、１００ｍｌテトラヒドロフラン中の０．２ｍｏｌＨ_２ＳＯ_４を加えた。添加が終わった後、混合物を、室温で、２４時間攪拌させた。この白色懸濁液に、３０％ＮａＯＨ（１００ｍｌ）を加え、４時間還流し、そして液体を室温にし、クロロホルムで抽出して、白色固体を得た。これを、精製することなく、さらに使用した。
【０１４６】
上で述べた調製由来のジオール中間体（０．０８ｍｏｌ）をクロロホルムに溶解し、そして二ッ口フラスコ（そこには、冷却器およびガードチューブ、圧力均等添加容器を装着した）に移した。フラスコに、ピリジン１滴を加え、塩化チオニル０．２ｍｏｌをクロロホルム２５ｍｌに溶解し、そして添加容器に充填した。室温で、丸底フラスコに、塩化チオニルを加えた。添加の間、ガードチューブから、かなりの量の二酸化イオウおよび塩化水素が逃げた。クロロホルムが還流し始めるまで、このフラスコの温度を上げた。５時間後、水を加えることにより、反応をクエンチした。クロロホルムを、炭酸水素塩溶液に続いて水で抽出し、そして硫酸ナトリウム床に通すことにより、乾燥した。クロロホルムを、減圧下にて、５０℃で蒸発させて、黄色油状物（皮膚に刺激性で炎症性）を得、これを、高真空下にて、蒸留して、淡黄色油状物を得た。
【０１４７】
（以下の手順は、米国特許第４，８７９，４１６号から採用した）
機械攪拌機、サーモウェル、添加漏斗および冷却器を備えた５００ｍｌフラスコに、トリフェニルホスフィン１６．７７ｇ（０．０６４ｍｏｌ）、テトラヒドロフラン６４ｍｌおよびリチウムワイヤ０．８８ｇ（０．１２８原子）を加えた。このフラスコを、１５℃まで冷却した。反応混合物を一晩攪拌して、リチウムが完全に溶解した赤色溶液を得た。このフラスコをさらに５℃まで冷却し、塩化第三級ブチル５．９２ｇ（０．０６４ｍｏｌ）を加え、温度を５０℃まで上げ、そして２時間維持した。反応混合物を冷却し、これに、上記の二塩化物７．５ｇをゆっくりと加えた。この反応混合物の温度を、穏やかに沸騰するように、上げた。メタノール５ｍｌを加えることにより、反応をクエンチした。この反応混合物を蒸発させて、粘着性の塊を得、これを、十分なジエチルエーテルに溶解し、そして水で洗浄した。ジエチルエーテルを蒸発すると、淡黄色の粘着性の塊が得られ、これを、ＴＨＦ／メタノールから再結晶して、白色物質の微結晶を得た。
【０１４８】
この物質を、ジフェニルホスフィノプロパンについて記述した方法に従って、スルホン化した。白色化合物を生成するために、水に溶解性であった。
【０１４９】
（実験１０）
（（Ｒ）ＢＩＮＡＰ（２，２’−ビスジフェニルホスフィノ−１，１’−ビナフチル）のスルホン化）
スルホン化の手順は、米国特許第５７５６８３８号から採用した。（Ｒ）ＢＩＮＡＰ（０．５ｇ）を、アルゴン下にて、１０℃で、濃硫酸１．７５ｍｌに溶解した。その後、２〜３時間にわたって、発煙硫酸（４０重量％）７．５ｍｌを滴下し、得られた混合物を、１０℃で、７６時間攪拌した。攪拌後、この混合物を、氷１００ｇにゆっくりと注ぎ、続いて、溶液がｐＨ７に中和されるまで、５０重量％ＮａＯＨを滴下した。得られた溶液を、減圧下にて、３０ｍｌまで濃縮した。硫酸ナトリウムを沈殿するために、これに、メタノール１００ｍｌを加えた。減圧下にて、含メタノール抽出物を蒸発させて、固体を得、これを、メタノールに溶解し、そして濾過した。メタノールを蒸発させて、白色固体を得た。同様に、ｓＢＩＮＡＰをスルホン化した。
【０１５０】
（実験１１）
（（Ｓ，Ｓキラホス）（Ｓ）（Ｓ）２，３−ビスジフェニルホスフィノブタンのスルホン化）
スルホン化の手順は、Ａｌａｒｉｏら、Ｊ．Ｃｈｅｍ．Ｓｏｃ．，Ｃｈｅｍ．Ｃｏｍｍｕｎ．，１９８６，２０２から採用した。
【０１５１】
（実験１２）
（Ｒプロホス１，２（Ｓ）ビスジフェニルホスフィノプロパンのスルホン化）
スルホン化の手順は、Ａｍｒａｎｉら、Ｏｒｇａｎｏｍｅｔａｌｌｉｃｓ １９８９，８，５４２から採用した。
【０１５２】
（実験１３）
（Ｒ，Ｒ ２−５，ビスジフェニルホスフィノペンタンのスルホン化）
スルホン化の手順は、Ａｍｒａｎｉら、Ｏｒｇａｎｏｍｅｔａｌｌｉｃｓ １９８９，８，５４２ Ｓｕｌｆｏｎａｔｉｏｎ ｏｆ ２−ｐｙｒｉｄｙｌ ｐｈｏｓｐｈｉｎｅから採用した。
【０１５３】
（実験１４）
（トリフェニルアミンのスルホン酸ナトリウム塩の合成）
反応器に、トリフェニルアミン２ｇを充填し、それに、濃硫酸２０ｃｃを加えた。このアミンが溶解するまで、この混合物を攪拌した。急速に攪拌しつつ、この混合物に、発煙硫酸（６５％）２０ｃｃを加え、その反応器を、約２０℃まで冷却した。発煙硫酸を加えた後、これらの反応物および内容物を５０℃まで加熱し、この温度で、４８時間維持した。この反応器およびその内容物を冷却し、その反応混合物に、蒸留水（１０ｃｃ）を加え、この発煙硫酸をクエンチした。その硫酸溶液が中和されるまで、冷却（１０℃）下にて、この溶液に、５０％ＮａＯＨ溶液を加えた。この溶液を濃縮し、次いで、メタノールを加えて、その硫酸ナトリウム粉末から、水溶性配位子を抽出した。このメタノールを蒸発させて、トリフェニルアミノスルホン酸（１．６ｇ）の水溶性ナトリウム塩を得た。この生成物は、ビスおよび９５％より多いトリススルホン化生成物の混合物から成る。これらは、触媒作用用の金属錯体の合成において、そのまま使用できる。
【０１５４】
（実験１５）
（トリベンジルアミントリスルホン酸三ナトリウム塩）
反応器に、トリベンジルアミン２ｇを充填し、それに、濃硫酸２０ｃｃを加えた。このアミンが溶解するまで、この混合物を攪拌した。急速に攪拌しつつ、この混合物に、発煙硫酸（６５％）２０ｃｃを加え、その反応器を、約２０℃まで冷却した。発煙硫酸を加えた後、これらの反応物および内容物を５０℃まで加熱し、この温度で、４８時間維持した。この反応器およびその内容物を冷却し、その反応混合物に、蒸留水（１０ｃｃ）を加え、この発煙硫酸をクエンチした。その硫酸溶液が中和されるまで、冷却（１０℃）下にて、この溶液に、５０％ＮａＯＨ溶液を加えた。この溶液を濃縮し、次いで、メタノールを加えて、その硫酸ナトリウム粉末から、水溶性配位子を抽出した。このメタノールを蒸発させて、トリベンジルアミノスルホン酸（１．７ｇ）の水溶性ナトリウム塩を得た。スルホン化度は、Ｈ^１ＮＭＲおよび元素分析により、確立した。
【０１５５】
（実験１６）
（２，２’−ビピリジンのスルホン酸ナトリウム塩の合成）
反応器に、２，２’−ビピリジン２ｇを充填し、それに、濃硫酸２０ｃｃを加えた。このアミンが溶解するまで、この混合物を攪拌した。急速に攪拌しつつ、この混合物に、発煙硫酸（６５％）２０ｃｃを加え、その反応器を、約２０℃まで冷却した。発煙硫酸を加えた後、これらの反応物および内容物を５０℃まで加熱し、この温度で、４８時間維持した。この反応器およびその内容物を冷却し、その反応混合物に、蒸留水（１０ｃｃ）を加え、この発煙硫酸をクエンチした。その硫酸溶液が中和されるまで、冷却（１０℃）下にて、この溶液に、５０％ＮａＯＨ溶液を加えた。この溶液を濃縮し、次いで、メタノールを加えて、その硫酸ナトリウム粉末から、水溶性配位子を抽出した。このメタノールを蒸発させて、２，２’−ビピリジンジスルホン酸（１．２ｇ）の水溶性ナトリウム塩を得た。この生成物は、元素分析および^１Ｈ ＮＭＲにより明らかなように、ビススルホン化生成物の混合物から成る。これらは、触媒作用用の金属錯体の合成において、そのまま使用できる。
【０１５６】
（実験１７）
（２−フェニルピリジンのスルホン化）
反応器に、２−フェニルピリジン２ｇを充填し、それに、濃硫酸２０ｃｃを加えた。このアミンが溶解するまで、この混合物を攪拌した。急速に攪拌しつつ、この混合物に、発煙硫酸（６５％）２０ｃｃを加え、その反応器を、約２０℃まで冷却した。発煙硫酸を加えた後、これらの反応物および内容物を５０℃まで加熱し、この温度で、４８時間維持した。この反応器およびその内容物を冷却し、その反応混合物に、蒸留水（１０ｃｃ）を加え、この発煙硫酸をクエンチした。その硫酸溶液が中和されるまで、冷却（１０℃）下にて、この溶液に、５０％ＮａＯＨ溶液を加えた。この溶液を濃縮し、次いで、メタノールを加えて、その硫酸ナトリウム粉末から、水溶性配位子を抽出した。このメタノールを蒸発させて、２−フェニルピリジンスルホン酸（１．２ｇ）の水溶性ナトリウム塩を得た。この生成物は、元素分析により明らかなように、ビススルホン化生成物の混合物から成る。これらは、触媒作用用の金属錯体の合成において、そのまま使用できる。
【０１５７】
（実験１８）
（２−３ビスジフェニルホスフィノコハク酸ナトリウム塩の合成）
マレイン酸ジメチル（５０ｇ）のクロロホルム（１００ｍｌ）溶液を含有する反応系に、２時間にわたって、臭素（１５ｍｌ）のクロロホルム１００ｍｌ溶液を加えた。この反応混合物を、２時間攪拌した。反応の終わりに、混合物を飽和チオ硫酸ナトリウム１００ｍｌで２回洗浄し、次いで、水１００ｍｌで２回洗浄した。有機部分を硫酸ナトリウム５ｇに通し、引き続いて、活性炭で処理した。クロロホルムをストリップして、油状物６０ｇを得た。引き続いた反応は、２５０ｍｌ三ッ口ガラス容器（これは、添加漏斗、電磁攪拌機およびゴム製隔壁を備えている）で設定した。アセンブリをアルゴンでフラッシュした。この容器に、細かく切断したリチウムリボン（５００ｍｇ）を加え、アセンブリを脱気し、そしてアルゴンを再充填した。このアセンブリに、アルゴンブランケットを維持しつつ、気密注釈器を使って、テトラヒドロフラン５０ｍｌを加えた。添加漏斗に、クロロジフェニルホスフィン８．３ｍｌを入れ、脱気し、そしてアルゴンで再充填した。添加漏斗の内容物をリチウム懸濁液に落とし、リチウム溶解中にて、溶液は、赤色を呈し始め、リチウムが完全に溶解した後、反応混合物を４時間攪拌した。
【０１５８】
別の２５０ｍｌ容器（これは、還流冷却器およびゴム製隔壁を備えている）に、注射器で、乾燥テトラヒドロフラン３０ｍｌを入れ、アセンブリを脱気し、そしてアルゴンを再充填した。これに、注射器で、臭化マレイン酸ジエチル４．５２ｇを移し、続いて、リン化リチウム（ｌｉｔｈｉｕｍ ｐｈｏｓｐｈｉｅｄ）溶液３０ｍｌ（赤色）を移した。その反応混合物の内容物を、８０℃で、１２時間維持した。この反応混合物に、メタノール１ｍｌを加え、減圧下にて、テトラヒドロフランを除去した。シロップ状の橙色液体を、エーテル２５ｍｌで２回洗浄した。このシロップ状の橙色生成物１ｇを、三ッ口丸底フラスコ（そこには、還流冷却器を装着した）に移し、アルゴンで十分にフラッシュし、そして２％水酸化ナトリウム２０ｍｌを還流した。その反応混合物を５℃まで冷却すると、ジホスフィンの白色物質が沈殿し、濾過により回収すると、１ｇが得られた。
【０１５９】
（実験１９）
（塩化ベンジルでのトリベンジルアミントリスルホネートの四級化）
トリベンジルアミントリスルホネート（０．１ｍｏｌ）および塩化ベンジル（０．２ｍｏｌ）の混合物に、水５０ｍｌおよびジメチルホルムアミド５０ｍｌを加えた。溶液を、７０℃で、７６時間攪拌し、反応は、塩化ベンジルの消失により、モニターした。減圧下にて、反応混合物を蒸発させて、固体の塊を得、これを、最小量の水に溶解し、水溶液を、ジエチルエーテルで洗浄した。減圧下にて、水性抽出物を乾燥し、固体を、乾燥状態で保存した。
【０１６０】
（実験２０）
（水酸化四級アンモニウムの合成）
硝酸銀１７ｇ（０．１ｍｏｌ）を蒸留水１７０ｍｌに溶解し、そして８５℃まで温め、そこに、水酸化ナトリウム３．９ｇ（０．０９７ｍｏｌ）を加えた。沈殿物の凝固が完結するまで、混合物を激しくかき混ぜた。沈殿物を遠心分離で回収し、そして水１００ｍｌに懸濁し、そこに、上記四級アンモニウム化合物（０．０９ｍｏｌ）を加えた。窒素下にて、反応混合物を３時間攪拌し、そして濾過した。減圧下にて、室温で、液体を蒸発させて、固体を得た。
【０１６１】
（実験２１）
（塩化ベンジルでのトリフェニルアミンの四級化）
トリフェニルアミントリスルホネート（０．１ｍｏｌ）および塩化ベンジル（０．２ｍｏｌ）の混合物に、水５０ｍｌおよびジメチルホルムアミド５０ｍｌを加えた。溶液を、７０℃で、７６時間攪拌し、反応は、塩化ベンジルの消失により、モニターした。減圧下にて、反応混合物を蒸発させて、固体の塊を得、これを、最小量の水に溶解し、水溶液を、ジエチルエーテルで洗浄した。減圧下にて、水性抽出物を乾燥し、固体を、乾燥状態で保存した。
【０１６２】
（実験２２）
（ｎベンジルトリフェニルアミンの四級アンモニウム塩の水酸化四級アンモニウムの形成）
（実験２３）
（ヒドリドカルボニルトリス（トリフェニルホスフィントリスルホン酸三ナトリウム）ロジウム（Ｉ）の合成）
この手順は、Ｄａｖｉｓらの１９９１年２月１９日付けの米国特許第４，９９４，４２７号から採用された。アセチルアセトネートジカルボニルロジウム（Ｉ）５００ｍｇを、水中のトリフェニルホスフィントリスルホネートナトリウム４ｇの激しく攪拌し脱気した水溶液１０ｍｌに加えた。溶解が完結した後、１：１のＨ_２／ＣＯの雰囲気下にて、攪拌を６時間継続した。次いで、この溶液を遠心分離し、沈殿したロジウムを除去した。この溶液に、１：１のＨ_２／ＣＯで飽和した無水エタノール８０ｍｌを加えて、所望の錯体を沈殿させた。沈殿物を回収し、そして真空乾燥した。
【０１６３】
（実験２４）
（ジクロロビス（トリストリフェニルホスフィンスルホナト三ナトリウム）パラジウム（ＩＩ））
この手順は、Ｊｉａｎｇら、Ｊ．Ｍｏｌ．Ｃａｔａｌ．Ａ：Ｃｈｅｍｉｃａｌ １３０（１９９８）７９〜８４から採用し、シュレン（ｓｃｈｌｅｎｋ）クフラスコに、ＰｄＣｌ_２（１００ｍｇ）および２Ｍ ＨＣｌ（２ｍｌ）を加え、その混合物を、ＰｄＣｌ_２が完全に溶解するまで、５０℃で、攪拌した。このフラスコを室温まで冷却しアルゴンでフラッシュした後、攪拌しながら、そのフラスコに、ＴＰＰＴＳ（０．８０ｇ）を加えた。その溶液の色は、直ちに、暗赤色から黄色に変わった。１０分間攪拌した後、エタノール１５ｍｌを加え、明るい黄色粉末が沈殿し、混合物を３０分間攪拌した。濾過した沈殿物を、９５％温エタノール３０ｍｌで、３回洗浄し、そして真空中で乾燥した。
【０１６４】
（実験２５）
（トランス−ＰｔＣｌ_２（ＴＰＰＴＳ）_２の合成）
白金錯体ＰｔＣｌ_２（ＮＣＰｈ）_２（２３５ｍｇ、０．５ｍｍｏｌ）を、トルエン１０ｍｌに溶解した。この溶液に、ＴＰＰＴＳ（５６８ｍｇ、１ｍｍｏｌ）の水溶液（１０ｍｌ）を加えた。この混合物に、イソプロパノール３ｍｌを加え、反応混合物を、５０℃で、１０時間攪拌した。ＰｔＣｌ_２（ＴＰＰＴＳ）_２・６Ｈ_２Ｏ（６２０ｍｇ）を蒸発させることにより、水相から、錯体を回収した。
【０１６５】
（実験２６）
（ＮｉＣｌ_２／ＴＰＰＴＳの合成）
溶解するのに十分な水中にて、塩化ニッケル六水和物（０．０５ｍｏｌ）をｔｐｐｔｓ（０．１２ｍｏｌ）と反応させ、形成された錯体を、エタノールで沈殿した。
【０１６６】
（実験２７）
（ＩｒＣｌ（ＣＯＤ）／ＴＰＰＴＳの合成）
ＩｒＣｌ（ＣＯＤ）（０．０１ｍｏｌ）を最小量のトルエンに溶解し、そして最小量の水に溶解したｔｐｐｔｓ（０．０４ｍｏｌ）と交換した。トルエン層を除去し、そして水層を乾燥した。
【０１６７】
（実験２８）
（［Ｒｕ（Ｃｌ）（μ−Ｃｌ）（ＴＰＰＴＳ）_２］の合成）
この方法は、Ｍ．Ｈｅｒｎａｎｄｅｚら、Ｊ．Ｍｏｌ．Ｃａｔａｌ．Ａ：Ｃｈｅｍｉｃａｌ １１６（１９９７）１１７〜１３０から採用した。ＲｕＣｌ_２（ＰＰｈ_３）_３（５．８ｇ、６ｍｍｏｌ）をテトラヒドロフラン１５０ｍｌに溶解し、そして６０℃まで加熱した。激しいく攪拌しながら、ＴＰＰＴＳ（６．３ｇ、１０．１ｍｏｌ）の水溶液３０ｍｌを滴下した。その二相媒体を、さらに、６０℃で、３０分間攪拌した。室温まで冷却した後、橙色有機層１４０ｍｌを除去した。得られた溶液を、濾過により除いた。次いで、その深紅色水相を、乾燥状態まで蒸発させ、さらに、真空中で乾燥した。
【０１６８】
（実験２９）
（［Ｒｕ（Ｈ）（Ｃｌ）（ＴＰＰＴＳ）_３］の合成）
この方法は、Ｍ．Ｈｅｒｎａｎｄｅｚら、Ｊ．Ｍｏｌ．Ｃａｔａｌ．Ａ：Ｃｈｅｍｉｃａｌ １１６（１９９７）１１７〜１３０から採用した。この錯体は、［Ｒｕ（Ｈ）（Ｃｌ）（ＰＰｈ_３）_３］から調製した。ＰｈＣＨ_３（３ｇ、３．３ｍｍｏｌ）を、テトラヒドロフラン１２０ｍｌ；ＴＰＰＴＳ（５ｇ、８ｍｍｏｌ）；Ｈ_２Ｏ（３０ｍｌ）に溶解した。水相から、明紫色固体を回収した。
【０１６９】
（実験３０）
（［Ｒｕ（Ｈ）_２（ＴＰＰＴＳ）_４］の合成）
ＲｕＣｌ_３・３Ｈ_２Ｏ（０．１ｇ、０．３８ｍｍｏｌ）およびＴＰＰＴＳ（１．０７ｇ、１．７２ｍｍｏｌ）を、蒸留水１０ｍｌに溶解した。その深褐色溶液を、水素流れを通しつつ、室温で攪拌した。１０分後、ＮａＢＨ_４（０．１７ｇ、約４．５ｍｍｏｌ）を加えた。溶液は、激しく泡立つと共に、即座に黄褐色に変わった。その混合物を、１０分間にわたって、５０℃まで加熱し、冷却し、乾燥状態まで蒸発させると、固体が得られた。
【０１７０】
（実験３１）
（Ｒｕ／ビナフ（Ｂｉｎａｐｔ）錯体の合成）
１：８のベンゼンエタノール混合物中にて、［Ｒｕ（ベンゼン）Ｃｌ_２］_２（０．０１ｇ）と２当量（０．０５ｇ）のＲ−ビナフ４ＳＯ_３Ｎａとを反応させることにより、ルテニウムビナフ４ＳＯ_３Ｎａ触媒を調製し、４．５ｍｌの［Ｒｕ（ベンゼン）Ｃｌ］Ｒ−ビナフ４ＳＯ_３Ｎａを得た。得られた溶液を、真空乾燥した。
【０１７１】
（実験３２）
（Ｒｈ^＋／キラホステトラスルホネート錯体の合成）
水中にて、室温で、過剰の過塩素酸ナトリウムの存在下にて、［Ｒｈ（ＣＯＤ）Ｃｌ］_２と２モル当量のスルホネート配位子とを反応させることにより、Ｒｈ^＋／チラホステトラスルホネート触媒を調製し、カチオン錯体を形成した。
【０１７２】
（実験３３）
（酢酸パラジウムスルホネート−ビピリジル錯体の合成）
合成手順は、Ｂｒｉｎｋら、Ｃｈｅｍ．Ｃｏｍｍｕｎ，１９９８，２３５９〜２３６０から採用した。Ｐｄ（ＯＡｃ）_２（０．１ｍｍｏｌ）およびスルホン化ビピリジル（０．１ｍｍｏｌ）を、水４２．５ｇと共に一晩攪拌して、透明な橙色溶液を得、これを、乾燥状態まで蒸発させた。
【０１７３】
（実験３４）
（コバルト（ＩＩ）４，４’，４”，４”’−テトラスルホフタロシアニンの四ナトリウム塩（手順は、Ｉｎｏｒｇ．Ｃｈｅｍ．Ｖｏｌ ４，Ｎｏ．４ １９６５年４月、４６９〜４７１）から採用する）
４−スルホフタル酸の一ナトリウム塩（４．３２ｇ、０．０１６２ｍｏｌ）、塩化アンモニウム（０．４７ｇ、０．００９ｍｏｌ）、尿素（５．８ｇ、０．０９７ｍｏｌ）、モリブデン酸アンモニウム（０．０６８ｇ、０．００００６ｍｏｌ）および硫酸コバルト（ＩＩ）・２Ｈ_２Ｏ（１．３６ｇ、０．００４８ｍｏｌ）およびセリット１００ｍｌを、ニトロベンゼン中にて、共に粉砕して、均一ペーストを形成し、そして丸底フラスコ（これには、還流冷却器を装着した）にて、ニトロベンゼンで、５０ｍｌまで希釈した。その反応混合物を、１８０℃まで加熱した。この反応混合物を、温度を１８０〜１９０℃で維持しつつ、オーバーヘッド攪拌と共に、ゆっくりと加熱した。その不均一混合物を、１８０℃で、６時間加熱した。反応混合物を冷却してニトロベンゼンを除去することにより、その粗生成物を回収した。ニトロベンゼンが除去されるまで、固形ケークをヘキサンで洗浄し、続いて、メタノールで洗浄した。その固形残留物を、１Ｎ塩酸（これは、塩化ナトリウムで飽和した）１１０ｍｌに移した。その混合物を沸騰するまで簡単に加熱し、室温まで冷却し、そして濾過した。得られた溶液を、０．１Ｎ ＮａＯＨ（７０ｍｌ）に溶解した。この溶液を８０℃まで加熱し、そして不溶な不純物を、濾過により、直ちに分離した。溶液に、塩化ナトリウム（２７ｇ）を加え、アンモニアの発生が止まるまで、スラリーを８０℃まで加熱した。反応混合物を室温まで冷却し、そして濾過した。この再沈プロセスを２回繰り返し、固体を濾過し、そして濾液が硝酸銀溶液で試験したときに塩素イオンを含まなくなるまで、８０％エタノールで洗浄した。この固体を、４時間にわたって、エタノール２０ｍｌ中で還流して、純粋な生成物を得、これを、Ｐ_２Ｏ_５で乾燥して、６５％の正確な元素を得た。
【０１７４】
（実験３５）
（銅（ＩＩ）４，４’，４”，４”’−テトラスルホフタロシアニンの四ナトリウム塩）
この化合物は、硫酸銅・５Ｈ_２Ｏ（０．００４８ｍｏｌ）以外は、類似のモル比の反応物を使用して、コバルト（ＩＩ）４，４’，４”，４”’−テトラスルホフタロシアニンの四ナトリウム塩について記述したようにして、調製し精製した。
【０１７５】
（実験３６）
（マンガン（ＩＩ）４，４’，４”，４”’−テトラスルホフタロシアニンの四ナトリウム塩）
この化合物は、酢酸マンガン（０．００４８ｍｏｌ）以外は、類似のモル比の反応物を使用して、コバルト（ＩＩ）４，４’，４”，４”’−テトラスルホフタロシアニンの四ナトリウム塩について記述したようにして、調製し精製した。
【０１７６】
（実験３７）
（鉄（ＩＩＩ）４，４’，４”，４”’−テトラスルホフタロシアニンの酸化付加物の四ナトリウム塩）
この化合物は、塩化鉄（ＩＩＩ）（０．００４８ｍｏｌ）以外は、類似のモル比の反応物を使用して、コバルト（ＩＩ）４，４’，４”，４”’−テトラスルホフタロシアニンの四ナトリウム塩について記述したようにして、調製し精製した。
【０１７７】
（実験３８）
（水溶性コバルト（ＩＩ）錯体Ｎ，Ｎ’−エチレンビス（サリチルジアミン５−ナトリウムスルホネート））
この錯体の合成は、Ｋｅｖｉｎら、Ｊ．Ｃｈｅｍ．Ｓｏｃ．，Ｄａｌｔｏｎ Ｔｒａｎｓ．１９８２，１０９に従って、実行した。
【０１７８】
濃硫酸（９５ｃｍ^３）に、Ｎ−フェニルサリチルジアミン（３５ｇ）を加え、温度を１００±５℃に保ちつつ、混合物を、時々攪拌して、２時間加熱し、冷却後、溶液をゆっくりと氷水に注いで、黄色沈殿物を得、これを、引き続いて、水から再結晶して、結晶性黄色化合物（２０ｇ）を得た。
【０１７９】
上記生成物２５．５ｇを水５００ｍｌに溶解し、この溶液に、無水炭酸ナトリウム８．４ｇをゆっくりと加え、泡立ちが止まるまで、攪拌した。アニリンを蒸気蒸留し、水溶液を真空乾燥して、固体を得、これを、水およびエタノールから沈殿することにより、精製した。
【０１８０】
（Ｎａ_２［Ｃｏ（ＳＯ_３塩（ｓａｌ））］・３Ｈ_２Ｏ）
この化合物であるＣｏＣｌ_２・６Ｈ_２Ｏ（６ｇ、２５ｍｍｏｌ）を水３０ｃｃに溶解し、そしてサリチルアルデヒド５スルホン酸二ナトリウム（１３．２ｇ、５０ｍｍｏｌ）の水２０ｃｃ溶液に加え、混合物を１０分間加熱した。濾過後、溶液を濃縮し、そして冷却して、結晶性錯体１２ｇを得た。
【０１８１】
（Ｎ，Ｎ’−エチレンビス（サリチルジアミン５−ナトリウムスルホネート））
Ｎａ_２［Ｃｏ（ＳＯ_３塩）］_２・３Ｈ_２Ｏ（５．５ｇ、１０ｍｍｏｌ）に、エタノール１００ｃｃ、水１５ｃｃおよびエチレンジアミン（０．６ｇ、１０ｍｍｏｌ）を加え、混合物を、窒素雰囲気下にて、１時間還流した。暗褐色の羽毛状沈殿物を回収した。
【０１８２】
（実験３９）
（触媒調製用の支持体の作製）
全ての支持体材料は、業者から調達し、さらに寸法を小さくすることなく、使用した。支持体の仕様は、適当な仕様で提供した。支持体材料は、図３で記述のアセンブリを使用して、ヘキサン、エーテル、メタノールおよび水から抽出した。
【０１８３】
（第ＩＩＡ族イオンでの表面飽和）
各支持体を、２５ｇのロットに分割し、５％硝酸バリウム溶液５００ｍｌに懸濁した。その懸濁液を、２４時間還流した。懸濁液を室温にし、固体を濾過し、そして図３で記述の抽出器に移して、水５００ｍｌ、アセトンおよび石油エーテル（沸点６０〜８０℃）で抽出した。固体を真空乾燥し、さらに使用するために保存した。
【０１８４】
上記支持体を、以下の手順により、使用直前に脱気した。必要量を丸底フラスコ（これは、二方向弁を備えている）に移し、０．１ｍｍＨｇで脱気し、温度を１５０℃に上げ、真空を維持しつつ、この温度で１時間保った。真空入口を閉じ、アルゴンを導入し、フラスコを室温まで冷却した。この手順を少なくとも３回繰り返し、固体を、アルゴン下にて、さらに使用するために保存した。従って、以下の支持体を作製した：シリカ、ガンマアルミナ、ジルコニア、チタニア、珪藻土、ベントナイト、ハイフロスーパーセル、アスベスト粉末、マグネシウムヒドロタルサイト、硫酸バリウム、木炭、骨灰。
【０１８５】
（実施例１〜８４）
（共沈による触媒処方物の調製）
以下の実施例は、バルク液体中での共沈として公知の調合方法に従って、本発明の触媒処方物を調製する手順の１つを説明する。
【０１８６】
不均一触媒処方物を調製する一般手順は、アニオン的に荷電した触媒要素の溶液、触媒不活性アニオン添加剤（溶液Ａと呼ぶ）および第ＩＩＡ族金属溶液（溶液Ｂと呼ぶ）の製造として、本明細書中で記述している。先に記述のように前処理した支持体を、水性溶媒または水混和性溶媒に懸濁し、得られた懸濁液を激しくかき混ぜ、長時間にわたって、この懸濁溶液Ａおよび溶液Ｂに加え、得られた懸濁液を、規定時間にわたって、さらにかき混ぜた。懸濁液を遠心分離し、固体を、水、メタノールおよびジエチルエーテルで繰り返し洗浄し、続いて、真空中で乾燥した。乾燥粉末を、気密容器にて、アルゴン下で保存したが、これは、そこに取り込んだ触媒活性要素に依存して、適当な反応に使用できる。
【０１８７】
注記１：溶液Ａは、アニオン成分（これは、均一溶液を製造するアニオン錯体および添加剤を含有する）を脱気溶媒に溶解することにより、調製される。得られた溶液はまた、アルゴンをパージすることにより、脱気される。
【０１８８】
注記２：溶液Ｂは、第ＩＩＡ族金属塩を溶解することにより、調製される。溶液は、使用前に脱気した。
【０１８９】
注記３：ＡおよびＢの添加は、特に明記しない限り、室温で実行される。
【０１９０】
【表３】

（実施例８５〜１６８）
（堆積沈殿による触媒処方物の調製）
以下の実施例は、固体支持体の表面近くでの共沈として公知の処方方法に従って、本発明の触媒処方物を調製する手順の１つを説明する。
【０１９１】
不均一触媒処方物を調製する一般手順は、アニオン的に荷電した触媒要素の溶液、触媒不活性アニオン添加剤（溶液Ａと呼ぶ）および第ＩＩＡ族金属イオン溶液（溶液Ｂと呼ぶ）の製造として、本明細書中で記載している。先に記述のように前処理した規定量の支持体を、固形物を溶液で湿潤させることにより溶液Ａで含浸し、続いて、蒸発して、溶液Ａのアニオン成分を有する乾燥固体支持体を得る。この固形粉末を、規定時間にわたって、溶液Ｂに徐々に加える。得られた懸濁液を、規定時間にわたって、さらにかき混ぜる。懸濁液を遠心分離し、固形物を、水で繰り返し洗浄し、続いて、真空中で乾燥した。乾燥粉末を、気密容器にて、アルゴン下で保存した。これらの固体触媒処方物は、そこに取り込んだ触媒活性要素に依存して、適当な反応に使用できる。
【０１９２】
注記１：溶液Ａは、アニオン成分（これは、均一溶液を製造するアニオン錯体および添加剤を含有する）を脱気溶媒に溶解することにより、調製される。得られた溶液はまた、アルゴンをパージすることにより、脱気される。
【０１９３】
注記２：溶液Ｂは、第ＩＩＡ族金属塩を溶解することにより、調製される。溶液は、使用前に脱気した。
【０１９４】
注記３：固体支持体での溶液の含浸は、特に明記しない限り、固形物を溶液Ａで湿潤させ、そして真空中で、５０℃で蒸発させることにより、実行される。
【０１９５】
注記４：Ａの成分を有する含浸固形物の溶液Ｂへの添加は、特に明記しない限り、環境温度で実行される。
【０１９６】
【表４】

（実施例１６９〜２５２）
（水を同時に除去しつつ堆積沈殿による触媒処方物の調製）
以下の実施例は、固体支持体の表面近くでの共沈として公知の処方の方法に従って、本発明の触媒処方物を調製する手順の１つを例示する。
【０１９７】
不均一な触媒処方物を調製する一般手順は、アニオン的に荷電した触媒要素の溶液、触媒不活性アニオン添加剤（溶液Ａと呼ぶ）および第ＩＩＡ族金属溶液（溶液Ｂと呼ぶ）の製造として、本明細書中で記述している。先に記述のように前処理した規定量の支持体を、固形物を溶液で湿潤させることにより溶液Ａで含浸し、続いて、エバポレートして、溶液Ａのアニオン成分を有する乾燥固体支持体を得る。この固形粉末を、水混和性溶媒、または溶液Ｂの溶媒成分と共沸混合物を形成する溶媒に懸濁させる。その懸濁液を撹拌し、そして温度を上げて溶媒の蒸留を開始した。この条件下にて、溶液Ｂをゆっくりとポンピングした。同時に、固形物を懸濁した溶媒もまた、蒸留速度と類似の速度で、ポンピングする。一旦、全ての溶液Ｂを加えると、規定時間にわたって、懸濁液を攪拌する。得られた懸濁液を、規定時間にわたって、さらに撹拌する。懸濁液を遠心分離し、固形物を、水で繰り返し洗浄し、そして真空中で乾燥した。乾燥粉末を、気密容器にて、アルゴン下で保存した。これらの固体触媒処方物は、そこに取り込んだ触媒活性要素に依存して、適当な反応に使用できる。
【０１９８】
注記１：溶液Ａを、アニオン成分（これは、均一溶液を作製するアニオン錯体および添加剤を含有する）を脱気溶媒に溶解することにより、調製する。得られた溶液をまた、アルゴンをパージすることにより、脱気する。
【０１９９】
注記２：溶液Ｂを、第ＩＩＡ族金属塩を溶解することにより、調製する。溶液は、使用前に脱気した。
【０２００】
注記３：固体支持体での溶液の含浸は、特に明記しない限り、固形物を溶液Ａで湿潤させることにより、そして減圧中で、５０℃でエバポレートすることにより、実行される。
【０２０１】
注記４：Ａの成分を有する含浸固形物の溶液Ｂへの添加は、特に明記しない限り、周囲温度で実行される。
【０２０２】
注記５：溶液Ａの含浸を、回避し得、その代わりに、以下の手順が使用し得る。支持体を溶媒に懸濁し、それに、溶液Ａの溶媒成分を同時に除去しつつ溶液をポンピングする。溶媒はまた、その容器の液体容量が同じになるような速度で、ポンピングする。この溶液Ｂを加えた後、熟成し、先に記述したように、固形物の単離を実行する。
【０２０３】
【表５】

（実施例２５３〜３３６）
（流動床での堆積沈殿による触媒処方物の調製）
以下の実施例は、流動床にて固体支持体の表面近くでの共沈として公知の調合方法に従って、本発明の触媒処方物を調製する手順の１つを説明する。
【０２０４】
不均一触媒処方物を調製する一般手順は、アニオン的に荷電した触媒要素の溶液、触媒不活性アニオン添加剤（溶液Ａと呼ぶ）および第ＩＩＡ族金属溶液（溶液Ｂと呼ぶ）の製造として、本明細書中で記述している。先に記述のように前処理した規定量の支持体を、流動化容器に充填し、そして固形物をアルゴン流れで流動化した。この流動化チャンバの温度を、規定温度まで上げた。固形物が塊を形成しないような様式で、規定時間にわたって、この床に、溶液Ａを噴霧した。規定時間にわたって、流動化をさらに継続し、溶液Ｂを同様に噴霧して、規定時間にわたって、流動化を継続した。固形物を容器から排出し、そして規定時間にわたって、熟成した。そのように形成した触媒処方物を、水、メタノールおよびジエチルエーテルで洗浄し、続いて、真空中で乾燥した。乾燥粉末を、気密容器にてアルゴン下で保存した。これらの固体支持体処方物は、そこに取り込んだ触媒活性要素に依存して、適当な反応に使用できる。
【０２０５】
注記１：溶液Ａは、アニオン成分（これは、均一溶液を製造するアニオン錯体および添加剤を含有する）を脱気溶媒に溶解することにより、調製される。得られた溶液はまた、アルゴンをパージすることにより、脱気される。
【０２０６】
注記２：溶液Ｂは、第ＩＩＡ族金属塩を溶解することにより、調製される。溶液は、使用前に脱気した。
【０２０７】
注記３：流動床堆積は、図４で記述の設備にて、実行した。
【０２０８】
【表６】

（実施例３３７〜４２０）
（被覆パンでの堆積沈殿による触媒処方物の調製）
以下の実施例は、固体支持体の表面近くでの共沈として公知の調合方法に従って、本発明の触媒処方物を調製する手順の１つを説明する。
【０２０９】
不均一触媒処方物を調製する一般手順は、アニオン的に荷電した触媒要素の溶液、触媒不活性アニオン添加剤（溶液Ａと呼ぶ）および第ＩＩＡ族金属溶液（溶液Ｂと呼ぶ）の製造として、本明細書中で記述している。先に記述のように前処理した規定量の支持体を、パンに充填し、これを、引き続いて、回転に設定した。この手順中にて、固形物を回転させた。その回転パンの温度を、規定温度まで上げた。アルゴン流れの下で、規定時間にわたって固形物の床に溶液Ａを噴霧し、続いて溶液Ｂを噴霧した。得られた固形物を、規定時間回転させ、そして真空中で乾燥した。固形物を、水、メタノールおよびジエチルエーテルで洗浄し、そして乾燥した。乾燥粉末を気密容器にてアルゴンの下で保存した。これらの固体支持体処方物は、そこに取り込んだ触媒活性要素に依存して、適当な反応に使用できる。
【０２１０】
注記１：溶液Ａは、アニオン成分（これは、均一溶液を製造するアニオン錯体および添加剤を含有する）を脱気溶媒に溶解することにより、調製される。得られた溶液はまた、アルゴンをパージすることにより、脱気される。
【０２１１】
注記２：溶液Ｂは、第ＩＩＡ族金属塩を溶解することにより、調製される。溶液は、使用前に脱気した。
【０２１２】
【表７】

（実施例４２１〜４２９）
（種々の有機溶媒中での触媒の安定性）
これらの実施例は、液相中での触媒の安定性を説明する。触媒の安定性を、液相反応での触媒の完全性および回復力を確証するために、評価した。図３の装置を組み立て、その抽出容器に、触媒５ｇを加えた。抽出容器に、溶媒０．５リットルを充填した。この抽出器中の固形物をかき混ぜ、その丸底フラスコ中の溶媒が沸騰するように設定した。固体触媒を、２４時間にわたって、連続的に浸出した。沸騰している液体を室温にし、第ＩＩＡ族金属および遷移金属について分析した。触媒活性物質の浸出は、明らかではなかった。
【０２１３】
【表８】

（実施例４３０）
（プローブとしてのヒドロホルミル化反応）
本実施例は、この触媒処方物の液相反応への適用性を説明し、ここで、２種の気体は、液相にて、基質と反応する。本実施例はまた、いかにして固体触媒が反応を触媒するのに使用できるか、そして、それを回収し再生する好ましい方法を説明する。
【０２１４】
触媒の仕様：
【０２１５】
【表９】

反応手順：アルゴン雰囲気下にて、そのマイクロ反応器に、触媒１ｇおよびオクテン２５ｍｌを充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で６００ｐｓｉまで加圧し、この温度で維持した。液状懸濁液を９００ｒｐｍで攪拌した。反応を２４０分間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。
【０２１６】
転化率１４^＊１０^−３モルのオクテン
６０分でのターンオーバー周波数は、８９４時間^−１であった。
【０２１７】
２４０分後のターンオーバー数は、１２９６．２９モルであった。２４０分後の触媒ｎ／ｉ比のモル^−１は、２．７であった（ここで、ｎは、直鎖アルデヒドであり、そしてＩは、イソアルデヒドである）。
【０２１８】
回収した触媒の色：淡褐色。
【０２１９】
この触媒を遠心分離により回収し、反応器を、窒素雰囲気下にて、トルエンで繰り返し洗浄した。固体触媒を、減圧下にて、乾燥し、これを再生して、先に記述したように反応を実行し、同等の活性および選択性を得た。触媒の色は、淡褐色であった。
【０２２０】
（実施例４３１）
（支持体の必要性）
これらの比較例は、最適な装填を行うプロトコルを決定するために、この触媒処方物での固体支持体の必要性および固体支持体に対する触媒活性固形物質の装填効果を説明する。
【０２２１】
ヘキサンのヒドロホルミル化
触媒の仕様：
【０２２２】
【表１０】

手順：
アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２０ｍｌ中にて、触媒２ｇおよびヘキサン０．５ｇ（５．２^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。８９％のオレフィンが、１．８０のｎ／Ｉ選択性で、アルデヒドに変換された。同一条件化でロジウム触媒の４^＊１０^−７モルバリウム塩は、いずれの反応もまったく促進しなかった。
【０２２３】
（実施例４３２）
（追加配位子の効果）
これらの比較例は、触媒処方物中での追加配位子の必要性を説明する。これらの実施例はまた、最適な装填を決定するために、この触媒処方物中での固体支持体および固体支持体に対する触媒活性固形物質の装填効果を説明する。
【０２２４】
触媒の調製。触媒の変化する仕様は、以下の方法によって調製された。
【０２２５】
ヘキサンのヒドロホルミル化
触媒の調製：
触媒の仕様：
【０２２６】
【表１１】

手順：
アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２０ｍｌ中にて、触媒２ｇおよびヘキサン０．５ｇ（５．２^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。
【０２２７】
その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。約８９％のオレフィンが、１．８０のｎ／Ｉ選択性で、アルデヒドに変換した。
【０２２８】
（実施例４３３）
（追加水の効果−ヘキセンのヒドロホルミル化）
触媒の仕様：
【０２２９】
【表１２】

手順：
アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２０ｍｌ中にて、触媒２ｇおよびヘキサン０．５ｇ（５．２^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。８９％のオレフィンが、１．８０のｎ／Ｉ選択性で、アルデヒドに変換された。
【０２３０】
同じ反応充填物条件下にて、水１ｇを加えると、２４時間後、類似のｎ／Ｉ比で、５％の転化率しか得られなかった。
【０２３１】
（実施例４３４）
（継続的な固定床実験）
触媒の仕様：
【０２３２】
【表１３】

手順：従って、その触媒の寿命、その安定性および耐久性を示す重大な評価は、触媒５ｇを使用して、管状トリカル床反応器（Φ１／２”）にて、８０℃および３００ｐｓｉ Ｈ_２／ＣＯ（１：１）で、触媒をヒドロホルミル化にかけることにより、管状固定床反応器にて、実行された。トルエン中の５％デセンを、１０ｍｌ／ｈｒの給送速度で、連続的にポンプ上げした。変換レベルは、定常状態に達した後（５時間）、アルデヒドについて、２０％（±２％変動）であった（ｎ／ｉ ２．１）。この反応は、７６時間さらに継続したが、活性の損失はなかった。その液体の給送を中止することにより、反応を停止し、１時間にわたって、水をポンプ上げした。その後、反応物の給送を再開した。最初は、変換がなかったが、これは、１０時間にわたって、より早いレベルで徐々に再開した。この観察は、その触媒表面で水のフィルムが形成されたことに起因しており、これは、デセンと触媒表面との接触を物理的に遅らせる。さらに、水は、錯体触媒を洗い流さず、このことは、固体状態で反応が起こることの決定的証拠を提供する。
【０２３３】
（実施例４３５）
（ヘキセンのヒドロホルミル化）
触媒の仕様：
【０２３４】
【表１４】

手順：
アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２ｍｌ中にて触媒２００ｍｇおよびヘキセン０．０５ｇ（５．２^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。８９％のオレフィンが、１．９１のｎ／Ｉ選択性で、アルデヒドに変換された。反応器をトルエンで数回洗浄することにより、この触媒を回収した。遠心分離により、触媒を回収し、トルエンおよびジエチルエーテルで繰り返し洗浄した。触媒を減圧下にて乾燥し、そして再生して、同等の活性を得た。
【０２３５】
（実施例４３６）
（スチレンのヒドロホルミル化）
（触媒の調製）
触媒の仕様：
【０２３６】
【表１５】

アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２ｍｌ中にて、触媒２００ｍｇおよびスチレン０．０５ｇ（４．８^＊１０^−４）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。９１％のオレフィンが、０．４４９のｎ／Ｉ比で、アルデヒドに変換された。反応器をトルエンで数回洗浄することにより、この触媒を回収した。遠心分離により、触媒を回収し、トルエンおよびジエチルエーテルで繰り返し洗浄した。触媒を減圧下にて乾燥し、そして再生して、同等の活性を得た。
【０２３７】
（実施例４３７）
（シクロヘキサンのヒドロホルミル化）
（触媒の調製）
触媒の仕様：
【０２３８】
【表１６】

アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２ｍｌ中にて、触媒２００ｍｇおよびシクロヘキサン０．０５ｇ（６．１^＊１０^−４）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。４７％のオレフィンが、アルデヒドに変換された。反応器をトルエンで数回洗浄することにより、この触媒を回収した。遠心分離により、触媒を回収し、トルエンおよびジエチルエーテルで繰り返し洗浄した。触媒を減圧下にて乾燥し、そして再生して、同等の活性を得た。
【０２３９】
（実施例４３８）
（アリルアルコールのヒドロホルミル化）
触媒の仕様：
【０２４０】
【表１７】

手順：アルゴン雰囲気下にて、このマイクロ反応器に、水２ｍｌ中にて、触媒２００ｍｇおよびアリルアルコール０．０５ｇ（８．７^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。２０％のオレフィンが、１のｎ／ｉ比で、アルデヒドに変換された。反応器をトルエンで数回洗浄することにより、この触媒を回収した。遠心分離により、触媒を回収し、トルエンおよびジエチルエーテルで繰り返し洗浄した。触媒を減圧下にて乾燥し、そして再生して、同等の活性を得た。
【０２４１】
（実施例４３９）
（ヘキセンのヒドロホルミル化）
触媒の仕様：
【０２４２】
【表１８】

アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２ｍｌ中にて、触媒２００ｍｇおよびヘキセン０．５ｇ（５．９^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。６８％のオレフィンが、１．７８のｎ／Ｉ選択性で、アルデヒドに変換された。反応器をトルエンで数回洗浄することにより、この触媒を回収した。遠心分離により、触媒を回収し、トルエンおよびジエチルエーテルで繰り返し洗浄した。触媒を減圧下にて乾燥し、そして再生して、同等の活性を得た。
【０２４３】
（実施例４４０）
（ヘキセンのヒドロホルミル化）
触媒の仕様：
【０２４４】
【表１９】

アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２ｍｌ中にて、触媒２００ｍｇおよびヘキセン０．０５ｇ（５．９^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。７８％のオレフィンが、１７．８８のｎ／Ｉ選択性で、アルデヒドに変換された。反応器をトルエンで数回洗浄することにより、この触媒を回収した。遠心分離により、触媒を回収し、トルエンおよびジエチルエーテルで繰り返し洗浄した。触媒を減圧下にて乾燥し、そして再生して、同等の活性を得た。
【０２４５】
（実施例４４１）
（ヘキセンのヒドロホルミル化）
触媒の仕様：
【０２４６】
【表２０】

アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２ｍｌ中にて、触媒２００ｍｇおよびヘキセン０．０５ｇ（５．９^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。８０％のオレフィンが、０．６のｎ／Ｉ選択性で、アルデヒドに変換された。反応器をトルエンで数回洗浄することにより、この触媒を回収した。遠心分離により、触媒を回収し、トルエンおよびジエチルエーテルで繰り返し洗浄した。触媒を減圧下にて乾燥し、そして再生して、同等の活性を得た。
【０２４７】
（実施例４４２）
（ヘキセンのヒドロホルミル化）
触媒の仕様：
【０２４８】
【表２１】

アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２ｍｌ中にて、触媒２００ｍｇおよびヘキセン０．０５ｇ（５．９^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。８０％のオレフィンが、０．９２のｎ／Ｉ選択性で、アルデヒドに変換された。反応器をトルエンで数回洗浄することにより、この触媒を回収した。遠心分離により、触媒を回収し、トルエンおよびジエチルエーテルで繰り返し洗浄した。触媒を減圧下にて乾燥し、そして再生して、同等の活性を得た。
【０２４９】
（実施例４４３）
（コバルト触媒ヒドロホルミル化）
触媒の仕様：
【０２５０】
【表２２】

アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２ｍｌ中にて、触媒２００ｍｇおよびヘキセン０．０５ｇ（５．９^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。３０％のオレフィンが、１．３８のｎ／ｉ選択性で、アルデヒドに変換された。反応器をトルエンで数回洗浄することにより、この触媒を回収した。遠心分離により、触媒を回収し、トルエンおよびジエチルエーテルで繰り返し洗浄した。触媒を減圧下にて乾燥し、そして再生して、同等の活性を得た。
【０２５１】
（実施例４４４）
（白金触媒ヒドロホルミル化）
触媒の調製：不均一塩化白金−ホスフィン錯体を、ジクロロメタンおよび塩化第一スズと共に沸騰し、引き続いて、ジクロロメタンで抽出した。
【０２５２】
触媒の仕様：
【０２５３】
【表２３】

手順：アルゴン雰囲気下にて、このマイクロ反応器に、トルエン２ｍｌ中にて、触媒２００ｍｇおよびヘキセン０．０５ｇ（５．９^＊１０^−４ｍｏｌ）を充填した。この反応器をＨ_２／ＣＯ混合物でフラッシュし、反応器を７５℃まで加熱し、そしてＨ_２／ＣＯ混合物（１：１のモル比）で加圧し、この温度で維持した。液状懸濁液を、外部磁気かき混ぜで攪拌した。反応を２４時間継続した。その生成物の分析により、オレフィンがアルデヒドに変換したことが確認された。５７％のオレフィンが、１０．４７のｎ／Ｉ選択性で、アルデヒドに変換された。反応器をトルエンで数回洗浄することにより、この触媒を回収した。遠心分離により、触媒を回収し、トルエンおよびジエチルエーテルで繰り返し洗浄した。触媒を減圧下にて乾燥し、そして再生して、同等の活性を得た。
【０２５４】
（実施例４４５）
（スチレンのカルボニル化）
触媒の仕様：
【０２５５】
【表２４】

手順：磁気攪拌棒を備えた１５ｍｌ反応器に、触媒２００ｍｇおよびスチレン５００ｍｇ（４．９０ １０^−３ｍｍｏｌ）およびｐ−トルエンスルホン酸５ｍｇ、Ｎ，Ｎ−ジメチルアニリン２５ｍｇおよびメタノール１０ｍｌを充填した。マイクロ反応器をアルゴンでフラッシュし、そして一酸化炭素８００ｐｓｉで加圧し、混合物を、７０℃で、２４時間攪拌した。反応混合物を、ガスクロマトグラフにより分析した。フェニルアセチレン８７％が、プロピオン酸メチル２フェニルに対して９９％の選択性で、カルボニル化された。反応混合物を遠心分離して、固体触媒を回収し、これを、引き続いて、メタノールで繰り返し洗浄した。触媒をジエチルエーテルでさらに洗浄し、そして減圧下にて乾燥した。
【０２５６】
（実施例４４６）
（スチリルアルコールのカルボニル化）
触媒の調製
触媒の仕様：
【０２５７】
【表２５】

手順：磁気攪拌棒を備えた１５ｍｌ反応器に、触媒２００ｍｇおよびスチリルアルコール５００ｍｇ（８．９^＊１０^−３ｍｍｏｌ）およびｐトルエンスルホン酸５ｍｇおよびメタノール１０ｍｌを充填した。マイクロ反応器をアルゴンでフラッシュし、そして一酸化炭素８００ｐｓｉで加圧し、混合物を、１００℃で、２４時間攪拌した。反応混合物を、ガスクロマトグラフにより分析した。フェニルアセチレン５２％が、２−プロピオン酸フェニルより多く、プロピオン酸メチル２フェニルに対して９１％の選択性で、カルボニル化された。反応混合物を遠心分離して、固体触媒を回収し、これを、引き続いて、メタノールで繰り返し洗浄した。触媒をジエチルエーテルでさらに洗浄し、そして減圧下にて乾燥した。
【０２５８】
（実施例４４７）
（フェニルアセチレンのカルボニル化）
触媒の仕様：
【０２５９】
【表２６】

手順：磁気攪拌棒を備えた１５ｍｌ反応器に、触媒２００ｍｇおよびフェニルアセチレン５００ｍｇ（４．９０ １０^−３ｍｍｏｌ）およびｐ−トルエンスルホン酸５ｍｇ、Ｎ，Ｎ−ジメチルアニリン２５ｍｇおよびメタノール１０ｍｌを充填した。マイクロ反応器をアルゴンでフラッシュし、そして一酸化炭素１００ｐｓｉで加圧し、混合物を、９０℃で、１２時間攪拌した。反応混合物を、ガスクロマトグラフにより分析した。フェニルアセチレン８０％が、メチルデビトロアトロペート（ｄｅｈｙｄｒｏａｔｒｏｐａｔｅ）に対して９６％の選択性で、カルボニル化された。反応混合物を遠心分離して、固体触媒を回収し、これを、引き続いて、メタノールで繰り返し洗浄した。触媒をジエチルエーテルでさらに洗浄し、そして減圧下にて乾燥した。
【０２６０】
（実施例４４８）
（スチレンの水素化）
触媒の仕様：
【０２６１】
【表２７】

手順：磁気攪拌棒を備えた１５ｍｌ反応器に、エタノール１０ｍｌ中にて、触媒２００ｍｇおよびスチレン５００ｍｇ（４．８^＊１０^−３ｍｍｏｌ）を充填した。マイクロ反応器をアルゴンでフラッシュし、そして水素５００ｐｓｉで加圧し、混合物を、９０℃で、１２時間攪拌した。反応混合物を、ガスクロマトグラフにより分析した。スチレン９８％が、エチルベンゼンに水素化された。反応混合物を遠心分離して、固体触媒を回収し、これを、引き続いて、メタノールで繰り返し洗浄した。触媒をジエチルエーテルでさらに洗浄し、そして減圧下にて乾燥した。触媒を再生し、同等の活性を得た。
【０２６２】
（実施例４４９）
（ケイ皮酸メチルの水素化）
触媒の仕様：
【０２６３】
【表２８】

手順：磁気攪拌棒を備えた１５ｍｌ反応器に、メタノール１０ｍｌ中にて、触媒２００ｍｇおよびケイ皮酸メチル５００ｍｇ（３．０８^＊１０^−３ｍｍｏｌ）を充填した。マイクロ反応器をアルゴンでフラッシュし、そして水素１０００ｐｓｉで加圧し、混合物を、５０℃で、１２時間攪拌した。反応混合物を、ガスクロマトグラフにより分析した。ケイ皮酸メチル８０％が、プロピオン酸メチル３フェニルに水素化された。反応混合物を遠心分離して、固体触媒を回収し、これを、引き続いて、メタノールで繰り返し洗浄した。触媒をジエチルエーテルでさらに洗浄し、そして減圧下にて乾燥した。触媒を再生し、同等の活性を得た。
【０２６４】
（実施例４５０）
（シンナモニトリルの水素化）
触媒の仕様：
【０２６５】
【表２９】

手順：磁気攪拌棒を備えた１５ｍｌ反応器に、メタノール１０ｍｌ中にて、触媒２００ｍｇおよびシンナモニトリル５００ｍｇ（３．８７^＊１０^−３ｍｍｏｌ）を充填した。マイクロ反応器をアルゴンでフラッシュし、そして水素５００ｐｓｉで加圧し、混合物を、５０℃で、１２時間攪拌した。反応混合物を、ガスクロマトグラフにより分析した。シンナモニトリル７９％が、６０％の選択性で、３−フェニルプロピオニトリルに水素化された。反応混合物を遠心分離して、固体触媒を回収し、これを、引き続いて、メタノールで繰り返し洗浄した。触媒をジエチルエーテルでさらに洗浄し、そして減圧下にて乾燥した。触媒を再生し、同等の活性を得た。
【０２６６】
（実施例４５１）
（デヒドロナプロキセンの水素化）
触媒の仕様：
【０２６７】
【表３０】

手順：磁気攪拌棒を備えた１５ｍｌ反応器に、トルエン１０ｍｌ中にて、触媒２００ｍｇおよびデヒドロナプロキセン１２８ｍｇ（１．２６^＊１０^−３ｍｏｌ）およびトリエチルアミン１２８ｍｇ（１．２６^＊１０^−３ｍｏｌ）を充填した。メタノール（３：２ｖ/ｖ）マイクロ反応器をアルゴンでフラッシュし、そして水素１００ｂａｒで加圧し、混合物を、０℃で、４８時間攪拌した。反応混合物を遠心分離して、固体触媒を回収し、これを、引き続いて、メタノールで繰り返し洗浄した。全ての洗浄物および反応混合物を組合せ、そして真空中で乾燥した。そのように得た固形物をジクロロメタンに溶解し、そして希ＨＣｌで洗浄し、続いて、水で洗浄した。ジクロロメタンを蒸発させて、ナプロキセンを得た。生成物の分析：生成物は、ＷＨＥＬＫ−Ｏカラム（Ｍｅｒｃｋ製）を使うＨＰＬＣで分析した。ナプロキセンの収率は、９８％および９２％ｅ．ｅであった。
【０２６８】
第二リサイクルは、９８％およびｅ．ｅ．９４％であった。
【０２６９】
（実施例４５２）
（ヘプタアルデヒドの水素化）
触媒の仕様：
【０２７０】
【表３１】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填した。これに、トルエン２ｍｌの溶液として、ヘプタアルデヒド５０ｍｇ（４．３８^＊１０^−４ｍｏｌ）を加えた。マイクロ反応器をアルゴンでフラッシュし、そして９０℃まで加熱した。磁気かき混ぜを開始した。その温度に達した後、反応器を水素５００−ｐｓｉで加圧した。この反応器を、これらの条件下にて、２４時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。ヘプタアルデヒド９９％が変換された。
【０２７１】
反応器をトルエンで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０２７２】
（実施例４５３）
（シンナムアルデヒドの水素化）
触媒の仕様：
【０２７３】
【表３２】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填した。これに、テトラヒドロフラン２ｍｌの溶液として、シンナムアルデヒド５００ｍｇ（３．７８＊１０^−３ｍｏｌ）を加えた。マイクロ反応器をアルゴンでフラッシュし、そして９０℃まで加熱した。磁気攪拌を開始した。その温度に達した後、反応器を水素５００ｐｓｉで加圧した。この反応器を、これらの条件下にて、２４時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。シンナムアルデヒド８８％が変換された。シンナミルアルコールに対する選択性は、７３％であった。
【０２７４】
反応器をテトラヒドロフランで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０２７５】
（実施例４５４）
（アセト酢酸エチルの水素化）
触媒の仕様：
【０２７６】
【表３３】

手順：この触媒１ｇを、このマイクロ反応器に充填した。これに、メタノール１５ｍｌ中の３−オキソブタン酸エチル５ｇを加えた。得られた懸濁液をマイクロ反応器に充填し、これを、アルゴンおよび水素でフラッシュした。この反応器の温度を９０℃まで上げ、反応器に、水素１５０ｐｓｉを充填した。この反応器を、これらの条件下にて、２４時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。３−オキソブタン酸エチルは、定量的に、対応するアルコールに変換された。反応器をメタノールで数回洗浄することにより、触媒を回収した。合わせた画分を分別して、触媒を回収した。回収した触媒を、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０２７７】
生成物の光学純度は、新鮮な触媒で９２％、そして再生した触媒は、９４％である。
【０２７８】
（実施例４５５）
（ベンジレデンアセトンの水素化）
触媒の仕様：
【０２７９】
【表３４】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填した。これに、テトラヒドロフラン２ｍｌの溶液として、ベンジレデンアセトン５００ｍｇ（３．４２＊１０^−３ｍｏｌ）を加えた。マイクロ反応器をアルゴンでフラッシュし、そして９０℃まで加熱した。磁気攪拌を開始した。その温度に達した後、反応器を水素５００ｐｓｉで加圧した。この反応器を、これらの条件下にて、２４時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。全てのベンジレデンアセトンが変換された。反応器をテトラヒドロフランで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０２８０】
（実施例４５６）
（ニトロトルエンの水素化）
触媒の仕様：
【０２８１】
【表３５】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填した。これに、酢酸エチル２ｍｌの溶液として、ｏ−ニトロトルエン５００ｍｇ（３．６４９＊１０^−３ｍｏｌ）を加えた。マイクロ反応器をアルゴンでフラッシュし、そして９０℃まで加熱した。磁気攪拌を開始した。その温度に達した後、反応器を水素５００ｐｓｉで加圧した。この反応器を、これらの条件下にて、２４時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。全てのｏ−ニトロトルエンがｏ−トルエン（ｔｏｌｕｄｅｎｅ）に変換された。
【０２８２】
反応器を酢酸エチルで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０２８３】
（実施例４５７）
（ｏ−クロロニトロベンゼンの水素化）
触媒の仕様：
【０２８４】
【表３６】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填した。これに、酢酸エチル２ｍｌの溶液として、ｏ−クロロニトロベンゼン５００ｍｇ（３．９５２＊１０^−３ｍｏｌ）を加えた。マイクロ反応器をアルゴンでフラッシュし、そして９０℃まで加熱した。磁気攪拌を開始した。その温度に達した後、反応器を水素５００ｐｓｉで加圧した。この反応器を、これらの条件下にて、２４時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。全てのｏ−クロロニトロベンゼンがｏ−クロロアニリンに変換された。
【０２８５】
反応器を酢酸エチルで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０２８６】
（実施例４５８）
（ヨードベンゼンおよびアクリル酸メチル）
触媒の仕様：
【０２８７】
【表３７】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填した。これに、トルエン５ｍｌの溶液として、水酸化テトラブチルアンモニウム１ｍｇ、酢酸ナトリウム０．４１ｍｇ（５＊１０^−３）、アクリル酸エチル０．５ｇ（５＊１０^−３）およびヨードベンゼン０．５０９ｇ（２．５＊１０^−３）を加えた。マイクロ反応器をアルゴンでフラッシュし、そして９０℃まで加熱し、その温度に達した後、磁気攪拌を開始した。この反応器を、これらの条件下にて、４８時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。アクリル酸エチル８６％が生成物に変換された。反応器をトルエンで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０２８８】
回収した触媒の色を観察すると、暗黄色であった。
【０２８９】
（実施例４５９）
（ヨードベンゼンおよびアクリロニトリル）
触媒の仕様：
【０２９０】
【表３８】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填した。これに、トルエン５ｍｌの溶液として、水酸化テトラブチルアンモニウム１ｍｇ、酢酸ナトリウム０．４１ｍｇ、アクリロニトリル０．２６５ｇ（５＊１０^−３）およびヨードベンゼン０．５０９ｇ（２．５＊１０^−３）を加えた。マイクロ反応器をアルゴンでフラッシュし、そして９０℃まで加熱し、その温度に達した後、磁気攪拌を開始した。この反応器を、これらの条件下にて、４８時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。アクリロニトリル９０％が生成物に変換された。
【０２９１】
反応器をトルエンで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０２９２】
回収した触媒の色を観察すると、暗黄色であった。
【０２９３】
（実施例４６０）
（ヨードベンゼンおよびスチレン）
触媒の仕様：
【０２９４】
【表３９】

手順：この触媒１ｇを、このマイクロ反応器に充填した。これに、トルエン１０ｍｌの溶液として、水酸化テトラブチルアンモニウム５ｍｇ、炭酸カリウム０．６６ｍｇ、スチレン０．５ｇ（４．８＊１０^−３ｍｏｌ）およびヨードベンゼン１．９５７ｇ（９．６＊１０^−３ｍｏｌ）を加えた。マイクロ反応器をアルゴンでフラッシュし、そして９０℃まで加熱し、その温度に達した後、磁気攪拌を開始した。この反応器を、これらの条件下にて、７６時間維持した。反応器を０℃まで冷却することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。スチレン４４％がスチルベンに変換された。
【０２９５】
反応器をトルエンで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０２９６】
（実施例４６１）
（ヨードベンゼンおよびエチレン）
触媒の仕様：
【０２９７】
【表４０】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填した。これに、アセトニトリル１０ｍｌの溶液として、水酸化テトラブチルアンモニウム１ｍｇ、酢酸ナトリウム０．４１ｇおよびヨードベンゼン０．５０９ｇ（２．５＊１０^−３）を加えた。マイクロ反応器を窒素でフラッシュし、そして１２０℃まで加熱し、反応器をエチレンで加圧し、磁気攪拌を開始した。この反応器を、これらの条件下にて、７６時間維持した。反応器を０℃まで冷却することにより、反応を停止した。反応器の気体を抜くことにより、反応器を減圧した。反応器を開き、液体をガスクロマトグラフにより分析した。ヨードベンゼン３０％がスチレンに変換された。
【０２９８】
反応器をトルエンで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０２９９】
（実施例４６２）
（ブロモベンゼンおよびｏ−トリルボロン酸）
触媒の仕様：
【０３００】
【表４１】

手順：十分に乾燥した５００ｍｌフラスコに、温度計、磁気攪拌棒、冷却器、添加漏斗および二方向弁を備え付けた。このフラスコに、マグネシウムターニング１２．２ｇ（０．５ａｔｏｍ）を入れた。二方向弁を通じて、アセンブリを十分に脱気し、そして窒素を満たし、マグネシウムを６時間攪拌した。これに、ヨウ素の結晶、テトラヒドロフラン（これは、ナトリウムベンゾフェノンケチルで蒸留した）１００ｍｌおよび１，２−ジブロモエタン２００μｌを加えた。マグネシウムターニングの表面が白く輝いた後、温度が沸騰まで上昇するような速度で、ブロモベンゼン７８．５ｇ（０．５ｍｏｌ）を加えた。ヒーター−攪拌機を取り除くことにより、このフラスコを断続的に冷却しつつ、反応を継続した。一旦、反応が鎮静すると、マグネシウムが溶解するまで、混合物を還流した。反応混合物を、ガラスウールで詰めたＳｈｌｅｎｋチューブに移した。
【０３０１】
（ｍ−トリルボロン酸）
完全に乾燥したフランジ付きフラスコ（これには、密封機械スタッフィングボックスおよび滴下漏斗および還流冷却器（融解塩化カルシウムガードチューブ付き）を装着した）を組み立てた。このフラスコの温度を、アセトンおよび液体窒素で−７５℃にした。このフラスコに、エーテル１５０ｍｌ中のホウ酸トリブチル４０．５ｇを加えた。かなり急速に攪拌しつつ、温度を−７０℃より上昇させることなく、ｏ−トリル臭化マグネシウムの溶液を加えた。同じ温度で、３時間、攪拌を継続した。このフラスコの温度を、氷浴で、１２時間にわたって、５℃まで維持した。この反応混合物を、１０％冷硫酸１５０ｍｌに加えた。エーテルで抽出し、そしてエバポレートした。これに、水１００ｍｌを加え、そしてＮａＯＨで、僅かにアルカリ性に塩基性化した。酸性化し、沸騰水で抽出し、そして結晶性物質（５ｇ）として収集した。
【０３０２】
この触媒１ｇを、還流冷却器を装着した丸底フラスコに充填し、磁気棒を、丸底フラスコに加えた。これに、トルエン２０ｍｌ溶液として、水酸化テトラブチルアンモニウム１ｍｇ、炭酸ナトリウム７５ｍｇ、ｏ−トリルボロン酸０．１３６ｇ（１０^−３ｍｏｌ）およびヨードベンゼン０．２２４ｇ（１．１＊１０^−３）を加えた。アセンブリを、窒素でフラッシュし、９０℃まで加熱した。この反応器を、これらの条件下で２４時間維持した。反応器を０℃まで冷却することにより、反応を停止した。液体を、ガスクロマトグラフにより分析した。ヨードベンゼン９５％を、２−メチル−１，１’−ビフェニルに変換した。
【０３０３】
反応器をトルエンで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、炭酸ナトリウム、水、メタノールおよびジエチルエーテルで洗浄し、そして触媒を減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。触媒を再生して、同等の転化率および選択性を得た。
【０３０４】
（実施例４６３）
（フェニル臭化マグネシウムおよびヨードベンゼン）
触媒の仕様：
【０３０５】
【表４２】

手順：
（グリニャール試薬の調製）
十分に乾燥した５００ｍｌフラスコに、温度計、磁気攪拌棒、冷却器、添加漏斗および二方向弁を備え付けた。このフラスコに、マグネシウムターニング０．６１ｇ（０．０２５ａｔｏｍ）を入れた。二方向弁を通じて、アセンブリを十分に脱気し、そして窒素を満たし、マグネシウムを６時間攪拌した。これに、ヨウ素の結晶、テトラヒドロフラン（これは、ナトリウムベンゾフェノンケチルで蒸留した）５０ｍｌおよび１，２−ジブロロエタン２００μｌを加えた。マグネシウムターニングの表面が白く輝いた後、温度が沸騰まで上昇するような速度で、ｔｈｆ ２０ｍｌ中のブロモベンゼン３．９２２ｇ（０．０２５ｍｏｌ）を加えた。ヒーター−攪拌機を取り除くことにより、このフラスコを断続的に冷却しつつ、反応を継続した。一旦、反応が鎮静すると、マグネシウムが溶解するまで、混合物を還流した。反応混合物を、ガラスウールで詰めたＳｈｌｅｎｋチューブに移した。
【０３０６】
十分に乾燥した２５０ｍｌフラスコに、温度計、磁気攪拌棒、冷却器、添加漏斗および二方向弁を備え付け、触媒５ｇ、テトラヒドロフラン（これは、青色のナトリウムベンゾフェノンケチルで新たに蒸留した）５０ｍｌを充填した。先に記述したように、アセンブリを窒素で満たした。これに、ヨードベンゼン５．０９ｇ（０．０２５ｍｏｌ）を加えた。添加容器に、予め調製したグリニャール試薬６０ｍｌを充填した。このフラスコの内容物（これは、５℃まで予め冷却した）に、グリニャール試薬をゆっくりと加えた。このフラスコの温度を、５℃で、２４時間維持した。反応混合物を室温まで冷却し、これに、水２０ｍｌに続いて飽和塩化アンモニウム２０ｍｌをゆっくりと加えた。得られた懸濁液を濾過して、固形物を除去し、引き続いて、テトラヒドロフランおよび水で十分に洗浄した。濾液をジクロロメタンで抽出して、収率８９％で、ビフェニルを得た。濾過後に残った残留物を、水、テトラヒドロフランおよびエーテルで洗浄し、そして減圧下にて乾燥した。
【０３０７】
（実施例４６４）
（イソブチル臭化マグネシウムおよびヨードベンゼン）
触媒の調製：触媒は、ナトリウムワイヤ上の沸騰ＴＨＦで抽出することにより、予め乾燥し、続いて、真空にかけ、そして五酸化リンで保存した。
【０３０８】
触媒の仕様：
【０３０９】
【表４３】

手順：
（グリニャール試薬の調製）
十分に乾燥した５００ｍｌフラスコに、温度計、磁気攪拌棒、冷却器、添加漏斗および二方向弁を備え付けた。このフラスコに、マグネシウムターニング２．４４ｇ（０．１ａｔｏｍ）を入れた。二方向弁を通じて、アセンブリを十分に脱気し、そして窒素を満たし、マグネシウムを６時間攪拌した。これに、ヨウ素の結晶、テトラヒドロフラン（これは、ナトリウムベンゾフェノンケチルで蒸留した）５０ｍｌおよび１，２−ジブロロエタン２００μｌを加えた。マグネシウムターニングの表面が白く輝いた後、温度が沸騰まで上昇するような速度で、臭化イソブチル９．２ｇ（０．１ｍｏｌ）を加えた。ヒーター−攪拌機を取り除くことにより、このフラスコを断続的に冷却しつつ、反応を継続した。一旦、反応が鎮静すると、マグネシウムが溶解するまで、混合物を還流した。反応混合物を、ガラスウールで詰めたカニューレを用いてＳｈｌｅｎｋチューブに移した。
【０３１０】
十分に乾燥した５００ｍｌフラスコに、温度計、磁気攪拌棒、冷却器、添加漏斗および二方向弁を備え付け、触媒５ｇ、テトラヒドロフラン（これは、青色のナトリウムベンゾフェノンケチルで新たに蒸留した）５０ｍｌを充填した。先に記述したように、アセンブリを窒素で満たした。これに、ヨードベンゼン２０．３９ｇ（０．１ｍｏｌ）を加えた。添加容器に、予め調製したグリニャール試薬５０ｍｌを充填した。このフラスコの内容物（これは、０℃まで冷却した）に、グリニャール試薬をゆっくりと加えた。このフラスコの温度を、５０〜０℃まで上げた。反応混合物を室温まで冷却し、これに、水２５ｍｌに続いて飽和塩化アンモニウム２５ｍｌをゆっくりと加えた。得られた懸濁液を濾過して、固形物を除去し、引き続いて、テトラヒドロフランおよび水で十分に洗浄した。濾液をジクロロメタンで抽出して、収率９２％で、イソブチルベンゼンを得た。濾過後に残った残留物を、水、ｔｈｆおよびエーテルで洗浄し、そして減圧下にて乾燥した。
【０３１１】
（実施例４６５）
（ボロン酸アリールのアリル化）
触媒の仕様：
【０３１２】
【表４４】

手順：触媒２ｇｍに、テトラヒドロフラン２０ｍｌを加え、この溶液に、フェニルリチウム２．９ｍｍｏｌを含有する冷溶液５ｍｌを加えた。その混合物を、攪拌下にて、０℃まで冷却し、これに、Ｂ（ＯＣＨ_３）_３（０．４２ｍｌ、３．６２ｍｍｏｌ）をゆっくりと加え、続いて、炭酸アリルメチル１．４４ｍｍｏｌを加えた。次いで、温度を６０℃まで上げ、そして反応を１２時間継続した。固体触媒から液体を分離し、そしてヘキサン２０ｍｌおよび飽和塩化アンモニウム２０ｍｌの混合物に注いだ。有機層により、３−フェニルプロペンが形成されたことが明らかとなった。
【０３１３】
回収した触媒を、飽和炭酸水素塩、テトラヒドロフランおよびジエチルエーテルで洗浄し、そして真空中で乾燥後、再生した。
【０３１４】
（実施例４６６）
（ヘキセンの異性化）
触媒の仕様：
【０３１５】
【表４５】

手順：以下の手順に従って、異性化を実行した。触媒５ｇｍをマイクロ反応器に充填し、これを、引き続いて、窒素でフラッシュし、そして１−ヘキセン（純度９２％）５ｇおよびシクロヘキサン４５ｍｌの脱気混合物を充填した。この反応器の温度を１００℃まで上げ、そして７６時間維持した。１−ヘキセンの転化率は、７３％であった。そして２種の異性化生成物を観察した。触媒を遠心分離し、そして液体を分離した。触媒を、シクロヘキサンで繰り返し洗浄した。単離した触媒を、同じ条件下にて再生して、同等の収率を得た。
【０３１６】
（実施例４６７）
（Ｎ，Ｎ−ジエチレリルアミン（ｄｉｅｔｈｙｌｎｅｒｙｌ ａｍｉｎｅ）の異性化）
触媒の仕様：
【０３１７】
【表４６】

手順：触媒の乾燥
異性化は、固体触媒に合うように変更した（Ｈｅｌｖｅｔｉｃａ Ｃｈｅｍｉｃａ Ａｃｔａ ｖｏｌ．７１，（１９８８）８９７〜９２０）から採用される手順のように実行した。触媒２ｇｍを、Ｆｉｓｃｈｅｒ−ポーターボトルに充填し、そして脱気した。引き続いて、ボトルを窒素でフラッシュし、そしてＮ，Ｎ−エチレリルアミン１１．３７ｇ（５０ｍｍｏｌ）（ｇｃ９２の面積％による純度）および無水テトラヒドロフラン５０ｍｌの脱気混合物を充填した。このボトルの温度を８０℃まで上げ、そして７６時間維持した。触媒を、遠心分離し、そして液体を分離した。テトラヒドロフランによる触媒の繰り返し洗浄物を合わせ、そしてエバポレートして、淡黄色オイルを得、これを、水５０ｍｌ中の５０％酢酸に溶解し、０℃で、１０分間攪拌し、そしてヘキサン５０ｍｌを加え、液体を、室温で、３０分間攪拌した。ヘキサン層を分離し、そして水層をヘキサンで洗浄した。ヘキサン抽出物を、飽和炭酸水素塩溶液で洗浄した。抽出物を分別すると、（Ｓ）シトロネロール（Ｎ，Ｎ−ジエチレリルアミンに基づいて、９０％）７．３５ｇが得られた。この物質の光学純度は、旋光分析（ｃ＝５、ＣＨＣｌ_３、ランプＤ、２０℃）により、９８％であることが分かった。単離した触媒を、同じ条件下にて再生して、同等の収率を得た。
【０３１８】
（実施例４６８）
（１，４−ジアセトキシブテンの異性化）
触媒の仕様：
【０３１９】
【表４７】

手順：以下の手順に従って、異性化を実行した。触媒１００ｍｇをマイクロ反応器に充填し、これを、引き続いて、窒素でフラッシュで、そして１，４−ジアセトキシブテン５０ｍｇ（３＊１０^−４ｍｏｌ）およびトルエン２ｍｌの脱気混合物を充填した。この反応器の温度を１００℃まで上げ、そして７６時間維持した。触媒を遠心分離し、そして液体を分離した。トルエンにより、触媒を繰り返し洗浄した。１，４−ジアセトキシブテンの転化率は、５７％であった。単離した触媒を、同じ条件下にて再生して、同等の収率を得た。
【０３２０】
（実施例４６９）
（ヘキセンのワッカー）
触媒の仕様：
【０３２１】
【表４８】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填し、これに、ヘキセン中の２０％ｖ／ｖ溶液として、ヘキセン１ｍｌを加えた。マイクロ反応器を空気（４５０ｐｓｉ）で加圧し、そして９０℃まで加熱した。その温度に達した後、磁気攪拌を開始した。この反応器を、２４時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。シクロヘキセン３６％が、ヘキサン−２−オンについて９０％の選択性で、生成物に変換された。残りの生成物は、異性化オレフィンおよび一部の未知生成物であると推定された。
【０３２２】
反応器をシクロヘキサンで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を水で補強して、水５０重量％を含有させた。この触媒を再生して、同等の活性および選択性を得た。
【０３２３】
回収した触媒の観察色は、暗黄色であった。
【０３２４】
（実施例４７０）
（デセンのワッカー）
触媒の仕様：
【０３２５】
【表４９】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填し、これに、ヘキセン中の２０％溶液として、デセン１ｍｌを加えた。マイクロ反応器を空気（４５０ｐｓｉ）で加圧し、そして９０℃まで加熱した。その温度に達した後、磁気攪拌を開始した。この反応器を、２４時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。デセン１９％が、デカン−２−オンについて８７％の選択性で、生成物に変換された。残りの生成物は、異性化オレフィンおよび一部の未知生成物であると推定された。
【０３２６】
反応器をシクロヘキサンで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を水で補強して、水５０重量％を含有させた。この触媒を再生して、同等の活性および選択性を得た。
【０３２７】
回収した触媒の観察色は、暗黄色であった。
【０３２８】
（実施例４７１）
（シクロヘキセンのワッカー）
触媒の仕様：
【０３２９】
【表５０】

手順：この触媒１００ｍｇを、このマイクロ反応器に充填し、これに、ヘキセン中の２０％溶液として、シクロヘキセン１ｍｌを加えた。マイクロ反応器を空気（４５０ｐｓｉ）で加圧し、そして９０℃まで加熱した。その温度に達した後、磁気攪拌を開始した。この反応器を、２４時間維持した。反応器を０℃まで冷却して減圧することにより、反応を停止した。反応器を開き、液体をガスクロマトグラフにより分析した。シクロヘキセン７％が、シクロヘキサノンについて３０％の選択性で、生成物に変換された。残りの生成物は、推定されなかった。
【０３３０】
反応器をシクロヘキサンで数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を水で補強して、水５０重量％を含有させた。この触媒を再生して、同等の活性および選択性を得た。
【０３３１】
回収した触媒の観察色は、暗黄色であった。
【０３３２】
（実施例４７２）
スチレンのエポキシ化
触媒の調製：Ｐｈ（ＣＨ_２）−Ｎ^＋（Ｐｈ_ｍＳＯ_３ ⁻）_３・ＯＨ⁻を、被覆パンでの堆積沈殿として先に記述の方法に従って記載されるように不均一化した。固形物を水に懸濁し、これに、３モル当量のＯＨ⁻が存在している（標準的な酸での滴定により概算した）懸濁液、７０℃で、４時間攪拌した。固形物を回収し、そして水で１２時間抽出し、続いて、真空中で乾燥した。
【０３３３】
触媒の仕様：
【０３３４】
【表５１】

手順：この触媒５ｇを、５００ｍｌガラス製反応容器（これには、機械攪拌機、温度計ポケットおよび添加容器を備え付けた）に充填し、これに、酢酸７５ｍｌ中のスチレン３０ｇ（０．２９ｍｏｌ）を加えた。反応容器を、流体クライオスタットを循環しつつ、５℃まで冷却した。その温度に達した後、攪拌を開始した。３０分間にわたって、３４％過酸化水素３０ｍｌを加えた。この反応容器の温度および攪拌を、２４時間維持した。反応器を開け、液体をガスクロマトグラフで分析した。スチレン７２％が、スチレンオキシドについて８９％の選択性で、生成物に変換された。残りの生成物は、推定されなかった。
【０３３５】
反応器を酢酸で数回洗浄することにより、触媒を回収した。合わせた画分を遠心分離して、触媒を回収した。回収した触媒を、メタノール、エーテルで洗浄し、そして乾燥した。この触媒を再生して、同等の活性および選択性を得た。
【０３３６】
（実施例４７３）
（クロロフェノールの酸化）
触媒の調製：流動床中の沈殿物として、記述の方法に従って、触媒を調製した。
【０３３７】
触媒の仕様：
【０３３８】
【表５２】

手順：還流冷却器を装着した５０ｍｌ丸底フラスコに、アセトニトリル５ｍｌおよび０．１Ｍ酢酸塩緩衝液（ｐＨ７）１５ｍｌを加え、そこに、トリクロロフェノール１８１ｍｇ（１０^−３ｍｏｌ）を加えた。触媒２．５ｇを加え、懸濁液を磁気針で攪拌した。この懸濁液の温度を、６０℃まで上げた。上記懸濁液に、水中の３４％Ｈ_２Ｏ_２（０．３ｍｌ）を加えた。その反応混合物を、５時間継続した。トリクロロフェノールが全て消失したことを観察し、硝酸銀溶液にて、溶液中の塩化物イオンを検出した。
【０３３９】
（実施例４７４）
（フマル酸ジエチルおよびマロン酸ジエチルのプロパン−１，１，２，３−テトラカルボキシレートへの縮合）
触媒の仕様：
【０３４０】
【表５３】

手順：効率的還流冷却器、磁気攪拌棒および滴下漏斗を取り付けた１００ｍｌフラスコに、触媒５ｇｍを充填した。攪拌しつつ、マロン酸ジエチル１．６ｇ（０．００１ｍｏｌ）および無水エタノール２５ｍｌを加えた。反応混合物を暖め、そしてフマル酸ジエチル１．４ｇｍ（０．００８１ｍｏｌ）を加えた。混合物を、８時間還流した。反応混合物を冷却し、そして懸濁液を遠心分離して、触媒を回収した。反応液を分析すると、マロン酸ジエチルについて、９０％の転化率が明らかとなった。生成物を、８ｍｍの減圧下にて、１８０〜１９０℃で蒸留して、プロパン−１，１，２，３−テトラカルボキシレート（収率８５％）を得た。
【０３４１】
触媒を回収し、エタノール、ジエチルエーテルで洗浄し、そして減圧下にて、乾燥した。
【０３４２】
触媒を再生して、同等の活性を得た。
【０３４３】
（実施例４７５）
（マロン酸ジエチルおよびホルムアルデヒドのテトラエチルプロパン−１，１，３，３−テトラカルボキシレートへの縮合）
触媒の仕様：
【０３４４】
【表５４】

手順：蒸留したマロン酸ジエチル１．６ｇ（０．００１ｍｏｌ）、エタノール２５ｍｌおよび４０％ホルムアルデヒド０．４ｇ（５＊１０^−４ｍｏｌ）の混合物（これは、５０ｍｌ丸底フラスコに含まれる）を０℃まで冷却し、そして触媒５ｇｍを加え、混合物を、室温で、２４時間攪拌し、次いで、１２時間還流した。懸濁液を遠心分離して、触媒を回収した。反応液を分析すると、マロン酸ジエチルが８０％転化したことが明らかとなった。液体を、エバポレートし、ジエチルエーテルで抽出した。抽出物を、硫酸ナトリウムで乾燥した。触媒を、エタノール、ジエチルエーテルで洗浄し、そして減圧下にて、乾燥した。触媒を再生して、同等の活性を得た。
【０３４５】
（実施例４７６）
（アセトンおよびクロロホルムのクロロブトールへの縮合）
触媒の仕様：
【０３４６】
【表５５】

手順：還流冷却器を備え付けた１００ｍｌ丸底フラスコに、触媒５ｇｍを充填し、そこに、アセトン溶液２５ｍｌ中の溶液として、１．１９ｇ（０．０１ｍｏｌ）のクロロホルムの溶液を充填した。この反応混合物に磁気攪拌棒を加え、反応混合物を、室温で２４時間攪拌した。懸濁液を遠心分離して、触媒を回収した。反応液を分析すると、クロロホルムの全てが転化したことが明らかとなった。触媒を、エタノール、ジエチルエーテルで洗浄し、そして減圧下にて乾燥した。触媒を再生して、同等の活性を得た。
【０３４７】
（実施例４７７）
（ベンズアルデヒドおよびアセトニトリルのシンナモニトリルへの縮合）
触媒の仕様：
【０３４８】
【表５６】

手順：還流冷却器を備え付けた２５０ｍｌ丸底フラスコに、触媒５ｇｍを充填し、そこに、アセトニトリル溶液１００ｍｌ中の溶液として、１０．６ｇ（０．１ｍｏｌ）のベンズアルデヒドの溶液を充填した。この反応混合物に磁気攪拌棒を加え、反応混合物を、還流温度で２４時間攪拌した。懸濁液を遠心分離して、触媒を回収した。反応液を分析すると、ベンズアルデヒドの８８％の転化率およびシンナモニトリルの９８％の選択性が明らかとなった。シンナモニトリルを、分別蒸留で回収した（ベンズアルデヒドに基づいて、８０％）。
【０３４９】
触媒を、エタノール、ジエチルエーテルで洗浄し、そして減圧下にて乾燥した。触媒を再生して、同等の活性を得た。
【０３５０】
（実施例４７８）
（ベンズアルデヒドおよびアセトンのベンザリレデン（ｂｅｎｚａｙｌｅｄｅｎｅ）アセトンへの縮合）
触媒の仕様：
【０３５１】
【表５７】

手順：還流冷却器を備え付けた２５０ｍｌ丸底フラスコに、触媒５ｇｍを充填し、そこに、アセトン溶液１００ｍｌ中の溶液として、１０．６ｇ（０．１ｍｍｏｌ）のベンズアルデヒドの溶液を充填した。この反応混合物に磁気攪拌棒を加え、反応混合物を、室温で２４時間攪拌した。懸濁液を遠心分離して、触媒を回収した。反応液を分析すると、ベンズアルデヒドの７７％の転化率が明らかとなった。触媒を、エタノール、ジエチルエーテルで洗浄し、そして減圧下にて乾燥した。触媒を再生して、同等の活性を得た。
【０３５２】
（実施例４７９）
（ブタルアルデヒドおよび２−エチルヘキセナールの縮合）
触媒の仕様：
【０３５３】
【表５８】

手順：還流冷却器を備え付けた１００ｍｌ丸底フラスコに、触媒５ｇｍを充填し、そこに、トルエン溶液５０ｍｌ中の溶液として、７．２ｇ（０．１ｍｍｏｌ）のブタルアルデヒドの溶液を充填した。この反応混合物に磁気攪拌棒を加え、反応混合物を、２４時間還流した。懸濁液を遠心分離して、触媒を回収した。反応液を分析すると、ブタルアルデヒドの９０％の転化率が明らかとなった。触媒を、エタノール、ジエチルエーテルで洗浄し、そして減圧下にて乾燥した。触媒を再生して、同等の活性を得た。
【０３５４】
（実施例４８０）
ヨードベンゼンホスフィン化の触媒の仕様：
【０３５５】
【表５９】

手順：還流冷却器を備え付けた丸底フラスコに、触媒５ｇｍを充填した。これに、無水脱気ジエチルホルムアミド３０ｍｌ中のジフェニルホスフィン１ｍｌ（５．７５ｍｍｏｌ）の溶液を、室温で加えた。懸濁液を、繰り返し真空およびアルゴンフラッシングして、脱気した。３０分間にわたって１００℃まで加熱した後、ジメチルホルムアミド３０ｍｌ中のヨードベンゼン１０ｍｍｏｌ（２．０４ｇｍ）およびジアザビシクロオクタン２０ｍｍｏｌ（２．２５ｇｍ）を加え、得られた溶液を、１００℃で維持した。その後、１２時間間隔で、各１ｍｌのジフェニルホスフィンの３つの追加部分を加えた。反応を、７６時間継続した。フラスコを室温まで冷却することにより、反応を停止した。遠心分離により、触媒を回収し、そしてジメチルホルムアミドで洗浄した。濾液を合わせ、そしてエバポレートして、粘着性残留物を得、これを、テトラヒドロフラン５０ｍｌで希釈した。溶液を、^３１Ｐ ＮＭＲで分析した。
【０３５６】
以下の化合物を検出した：トリフェニルホスフィン、トリフェニルホスフィンオキシド、ジフェニルホスフィンおよびジフェニルホスフィンオキシド。
【０３５７】
ヨードベンゼンに基づいたトリフェニルホスフィンの収率は、９２％であった；ヨードベンゼンの転化は、ガスクロマトグラフィーにより確認されるように完結した。
【０３５８】
回収した触媒の色を観察すると、新鮮な触媒よりも暗かった。
【０３５９】
触媒の回収および再生：回収した触媒を同じ条件下にて再生して、ヨードベンゼンに基づいて８８％のトリフェニルホスフィンを得た。３番目に再生した触媒については、２５０ｍｇ ＮｉＣｌ_２・６Ｈ_２Ｏ（これは、水中の５０％エタノールに溶解した）とともに、６時間還流した。触媒を、水、エタノールで抽出し、そして乾燥した。この触媒を再生して、９０％のトリフェニルホスフィンを得た。
【０３６０】
溶媒としてのシクロヘキサン中の同じ条件下での新鮮な触媒は、ニッケルの浸出を示さないが、トリフェニルホスフィンの収率は、７６時間後、約１０％であった。
【０３６１】
（実施例４８１）
（ブロモアニソールのホスフィン化）
触媒の調製：被覆パンでの堆積沈殿として記述した方法に従って、触媒を調製した。
【０３６２】
触媒の仕様：
【０３６３】
【表６０】

手順：還流冷却器を備え付けた丸底フラスコに、触媒５ｇｍを充填した。これに、無水脱気ジエチルホルムアミド３０ｍｌ中のジフェニルホスフィン１ｍｌ（５．７５ｍｍｏｌ）の溶液を、室温で加えた。懸濁液を、繰り返し真空およびアルゴンフラッシングして、脱気した。３０分間にわたって１００℃まで加熱した後、ジメチルホルムアミド３０ｍｌ中の２−ブロモアニソール１０ｍｍｏｌ（１．８７ｇｍ）およびジアザビシクロオクタン２０ｍｍｏｌ（２．２５ｇｍ）を加え、得られた溶液を、１００℃で維持した。その後、１２時間間隔で、各１ｍｌのジフェニルホスフィンの３つの追加部分を加えた。反応を、７６時間継続した。フラスコを室温まで冷却することにより、反応を停止した。遠心分離により、触媒を回収し、そしてジメチルホルムアミドで洗浄した。濾液を合わせ、そしてエバポレートして、粘着性残留物を得、これを、テトラヒドロフラン５０ｍｌで希釈した。溶液を、先の実施例で記述のように、^３１Ｐ ＮＭＲで分析した。２−ブロモアニソールの８３％の転化率が観察された。ホスフィンの定量的な概算値は、決定しなかった。
【０３６４】
（実施例４８２）
（Ｃ_６Ｈ_６からＣ_６Ｄ_６への重水素化）
触媒の仕様：
【０３６５】
【表６１】

触媒の前処理：触媒を、重水３ｍｌで２回還流し、遠心分離で回収し、そして減圧下にて乾燥した。これは、固体支持体にてプロトンを除去するのに必須であった。
【０３６６】
手順：この触媒１００ｍｇを、外部磁気攪拌機を備え付けたマイクロ反応器に充填し、ベンゼン０．０１ｍｏｌ（０．７８ｇ）および重水２ｍｌを加えた。外部加熱を使って、反応容器を１１０℃まで加熱した。その温度に達した後、攪拌を開始した。反応器を、これらの状態で、２４時間維持した。反応器を−５℃まで冷却し、液体を回収し、そして有機液体をＮＭＲ（内部標準としてクロロホルムを使用して、重水素で８８％の標識化）で分析した。
【０３６７】
触媒を遠心分離で回収し、そして回収した触媒を、減圧下にて乾燥した。この触媒を再生して、同等の活性および選択性を得た。
【０３６８】
本発明は、その好ましい実施形態に関して、詳しく示され記述されているものの、本発明の精神および範囲から逸脱することなく、形態および詳細について、前述の変更および他の変更が行われ得ることは、当業者に理解される。
【図面の簡単な説明】
【０３６９】
【図１】図１は、この触媒処方物の概念的な描写の概略図である。
【図２】図２は、この触媒処方物の表面の半現実的な拡大図である。触媒活性物質を堆積した支持体、単一または複数の反応物は、この触媒物質に達し、これは、活性部位を含み、それから、反応物は、生成物に変換され、そしてバルク液体に戻って放出される。
【図３】図３は、固形物の連続液状抽出器の概略図であり、ここで、ａは、単方向気体バブラー（これは、冷却器に連結されている）であり、ｂは、この冷却器であり、ｃは、抽出容器（これは、磁気針と、浸出／抽出する固形物とを保持する）であり、ｄは、磁気攪拌機ユニットであり、ｅは、抽出液を保持する容器であり、ｆは、高温浴である。
【図４】図４は、触媒処方物が処理される流動床の概略図であり、ここで、ａは、一定温度の流体がそこを通って循環するジャケットであり、ｂは、液体がそこを通って噴霧されるアトマイザーであり、ｃは、気体固体分離メッシュであり、ｄは、溶液Ａの入口であり、ｅは、溶液Ｂの入口であり、Ｖ１およびＶ２は、弁である。
【図５】図５は、液体を同時に除去する触媒調製ユニットの概略図であり、ここで、ａは、不活性ガス入口であり、ｂは、溶液ＡおよびＢの入口であり、ｃは、磁気針、支持体および液体を保持する容器であり、ｄは、不活性ガス出口であり、ｅは、冷却器であり、ｆは、液体コレクタであり、ｇは、液体コレクタアームである。
【図６】図６は、触媒調製ユニットの概略図であり、ここで、ａは、溶液ＡおよびＢ用の入口であり、ｂは、真空ラインであり。ｃは、被覆パン用のモーターであり、ｄは、被覆パンであり、ｅは、液体ＡおよびＢ用のノズルであり、ｆは、高温浴であり、ｇは、縮合した液体用の収集容器である。【Technical field】
[0001]
(Technical field)
The present invention relates to a new class of heterogeneous catalysts, whose methodology is useful for preparing solid catalysts for various chemical reactions. In particular, the present invention relates to a catalyst system composed of a chemical formulation consisting of an insoluble material having the desired catalytic properties and a support, which are assembled together by special techniques. This catalyst is useful for promoting reactions in the gas phase or liquid phase. A unique feature of this catalyst system is that the entire catalyst formulation remains as a solid composite without decomposition during the reaction. The present invention primarily describes a technique in which a soluble catalyst is converted to an insoluble material by appropriate molecular modification. The invention further relates to a preferred method of preparing such a catalyst formulation.
[Background]
[0002]
(Background technology)
Soluble molecular catalysts, especially transition metal complexes, are well known in the art. Such catalysts are also known to catalyze a variety of useful organic transformations. These transformations include, for example, hydrogenation, hydroformylation, carbonylation, amination, isomerization, telomerization, Heck olefination, Suzuki coupling, metathesis, epoxidation and the like. Such transformations have found a variety of useful applications in pharmaceuticals, pesticides, solvents, and other valuable products of industrial and consumption importance.
[0003]
In established methods known in the art, mainly catalytically active transition metal complexes are applied in uniform form as a solution in the reactant phase. For example, in the case of hydroformylation of olefins using a rhodium and phosphine ligand complex catalyst, where the phosphine ligand has no ionic charge (eg, tributylphosphine, triphenylphosphine, etc.) and the reaction medium It is soluble in Although such catalysts are very effective in terms of productivity and selectivity, their application in practical areas is often limited to volatile products. In the case of homogeneous catalyst reactions involving high molecular weight products (particularly non-volatile products), catalyst separation is a significant problem. Due to the high cost of the catalyst, high sensitivity to high temperatures, and strict product specifications, quantitative catalyst separation is required. Conventional unit operations (eg, distillation and crystallization) are of least importance because organometallic complexes are inherently delicate and cannot withstand the separation stresses (especially the thermal stresses encountered during distillation). Other separation techniques cannot be used in an effective manner because they are inefficient in separating such small amounts of catalyst. In addition, the high purity of the product is important in products such as pharmaceuticals, requiring strict separation of the catalyst from the product stream. Therefore, the use of homogeneous catalysts per se inherently makes it difficult to recover these catalysts from the reaction product. Efficient catalyst recovery and reuse is a central issue for the economic viability of the process, as complexes and ligands are often expensive.
[0004]
It is also known to use aqueous solutions of sulfonated aryl phosphines and many other water soluble compounds and transition metal complex catalysts derived therefrom to cause the reaction. As disclosed in the patent (US Pat. No. 4,248,802), all such reactions are operated under two-phase conditions, where the catalyst phase is aqueous and the product And the reactants are dissolved in the organic phase. Similar reverse two-phase techniques can also be applied, where the catalyst is dissolved in the organic phase and the products and reactants are in the aqueous phase. Depending on the solubility of the reactants and products, a sensible choice is required while utilizing a two-phase catalyst system. In either case, at the end of the reaction, the catalyst and product phases are separated, so the catalyst phase is regenerated and the product phase is further directed to downstream processing.
[0005]
However, due to the limited solubility of organic reactants in this catalytic phase, it has been observed that two-phase media have low catalytic activity. Furthermore, such a two-phase reaction requires a high reactor pressure in the case of a gas-liquid reaction. In order to achieve practical reaction rates, catalyst loading must be increased or larger process equipment must be used, which is usually prohibitively expensive. Furthermore, these reactions require a number of auxiliary equipment to separate the liquid-liquid fraction under the reaction conditions.
[0006]
Over the past quarter century, attempts have been made to heterogenize this universal species of soluble catalyst. As natural catalyst species, several methods have been developed that retain high activity and selectivity, which facilitate separation by simple filtration, centrifugation or gravity sedimentation.
[0007]
One technique for forming a solid catalyst is to use a metal salt or precursor complex with a solid support, which is suitably functionalized with an organic functional group capable of forming a coordinate bond with the metal. Interaction is involved. The support used in this connection is either an organic polymer matrix or an inorganic matrix. These supports are chemically functionalized to have amino, phosphino and carboxylato functional groups on the support surface. Studies related to this technology are described in Catalysis Reviews, 16, 17-37 (1974); Chemical Reviews, 81, 109, (1981); Tetrahedron Asymmetry, 6, 1109-1116 (1995); Tetrahedron Letters 5-37, 37, 37; 3378 (1996). “Catalysis by supported complexes”, Studies in surface science and catalysis, Vol. 8, Elsevier Publishing Co. Amsterdam, 1981 describes a complex grafted onto an inorganic support.
[0008]
From a practical point of view, these catalysts are not widely used because their activity is often lower than the corresponding homogeneous catalysts. In addition, there are complications due to the polymer nature of the support (eg, expansion and contraction of the matrix-these alter diffusion resistance). Also, over the long term, it has been found that when exposed to oxygen, the metal bound to the support is lost in the solution, thereby degrading the activity of the catalyst.
[0009]
Supported liquid phase catalysts (such as those described in US Pat. No. 3,855,307 (1974) and US Pat. No. 4,994,427 (1991)) are available for the properties of the reaction medium. It is very sensitive and is often leached into the reaction medium depending on the nature of the solvent. The application of such catalysts is limited only to vapor phase reactions. Its teaching is described in US Pat. No. 4,994,427 (1991), where a solution of a water soluble catalyst is dispersed in a high surface area solid. The aqueous film of the catalyst-containing solution remains insoluble in the non-polar organic solvent, so that after the reaction, the solid catalyst can be recovered by simple filtration. Application of such catalysts is limited to reactions involving water-insoluble reaction media. Furthermore, such catalysts are sensitive to water content.
[0010]
Incorporation of this catalyst into a porous material (eg, zeolite) is described by Balkus et al. Inclusion Phenom. Mol. Recognit. Chem. , 21 (1-4), 159-84 (English) 1995. This catalyst is encapsulated in a three-dimensional network of zeolites, where the catalyst cannot diffuse out of the zeolite due to size exclusion, but smaller sized reactants diffuse and form inside the zeolite. The resulting product subsequently diffuses. Still another paper, J.H. Catal, 163 (2), 457-464 1996, describes a method for incorporating a catalyst into its polymer matrix, but due to its diffusion resistance, the efficiency of the catalyst is questionable.
[0011]
Despite several known techniques for heterogenizing soluble molecular catalysts, there are no known methods that can be conveniently used for a variety of catalyst elements using a common protocol. Furthermore, the catalyst formed by such a protocol needs to provide a solid catalyst that can be used not only in non-polar reaction media but also in polar reaction media. Indeed, there is a particular need for such a technique for forming a catalyst, and the present invention aims to meet these needs.
DISCLOSURE OF THE INVENTION
[Means for Solving the Problems]
[0012]
(Disclosure of the Invention)
Significantly, the general background as well as the specific background of the art does not teach or suggest a heterogeneous catalyst similar to the supported metal catalyst, where the catalytically active material is its solid support. The formation as a whole can be used as a heterogeneous catalyst useful not only for nonpolar solvents but also for catalysis in polar solvents. Therefore, an object of the present invention is to provide a novel catalyst useful for promoting various chemical reactions. More particularly, the present invention relates to a catalyst system comprising a calcium salt, a strontium salt, a barium salt of a ligand containing at least two or more acidic functional groups, and an organometallic catalyst produced therefrom. These salts are supported on a solid surface of an inert vehicle or carrier. This catalyst is useful for facilitating reactions in aqueous, polar and non-polar organic media.
[0013]
Many anionically charged phosphines and other ligand compounds, as well as their various salts, are known in the art. Also, the ligands and complexes are water soluble, but importantly, in the published literature, patents or any known reference, alkaline earth metal salts of anionically charged ligands There is no disclosure or suggestion that recognizes the importance of forming insoluble materials as their complexes. Furthermore, in the references known to the applicant, the importance of such an insoluble organometallic complex or the particular type, classification or characteristics of its catalytic application is directly related to the recovery and reuse of the catalyst. There is no disclosure or suggestion to prove.
[0014]
It has now been discovered that reactions catalyzed by soluble catalysts can be catalyzed by the solid catalysts of the present invention. The solid catalyst is a formulation rather than a chemically defined single component catalyst system as referred to herein, where the solid support and the catalytically active material are both Assembled to form a solid catalyst. This support is a multi-component, which is catalytically inert by itself, but provides a physical vehicle, filler and provides a high surface area in which the catalytically active material is disposed. The agglomerates of support and catalytically active material are assembled in a specific manner in which the support surface is covered or deposited with the catalytically active material, rather than a simple random physical mixture. Such a concept, as described in the background of the present invention, has been previously known, but provides a catalyst suitable only for the gas phase or special liquid phase. For example, there is a supported aqueous phase catalyst (hereinafter referred to as SAPC) or a supported liquid phase catalyst (hereinafter referred to as SLPC). For example, SAPC can only be used when the reaction medium is a water-miscible organic medium. Similarly, SLPC is only suitable in the gas phase and not in the general liquid phase.
[0015]
A surprising element of the present invention is the discovery of a general technique in which a natural catalyst (which is soluble) is converted to a solid material and becomes virtually insoluble in organic and aqueous media. Catalytically active materials, as referred to herein, are composed of secondary structural blocks that are derived from catalytically active moieties and are naturally built in a homogeneous phase when placed on a high surface area solid. It catalyzes the reaction catalyzed by the seed, but at the same time remains as a solid disposed on the support. For this reason, the catalyst as a whole can be separated from the reaction mixture by simple solid-liquid separation.
[0016]
Such a catalyst formulation is highly advantageous over catalyzing reactions with homogeneous or heterogeneous catalysts. This catalyst was devised in a manner similar to a supported heterogeneous catalyst, but the supported active phase is composed of molecular elements, which in effect catalyze the actual reaction. This particular formulation synergistically combines the desired easy separation and high specificity of the molecular catalyst. The obvious advantages of the present invention are the following:
(A) a solid catalyst that provides inherent separation;
(B) similar activity and selectivity to soluble molecular catalysts since the active site is structurally isotropic;
(C) The formulation as a whole is a mechanically robust material;
(D) The modularity of the assembly is such that the desired selection elements, supports and additives assemble the catalyst, depending on the need.
[0017]
As described herein, the central theme of this discovery is an invention in which a soluble catalytic material is converted to a solid, which is effectively insoluble in a variety of liquid media due to systematic molecular modification. It is in. It has been observed that alkali metal ammonium salts and quaternary ammonium salts are obtained when the soluble catalyst species is modified to have two or more anionic groups present with protons. The soluble catalyst modification referred to herein implies that anionic functional groups are introduced while synthesizing the components of the catalyst or modifying the catalyst itself. This anionically functionalized salt provides a solid material that is insoluble in various liquid media when interacting with the Group IIA metal. This solid material is composed of building blocks of catalytic elements crosslinked with a Group IIA metal cation.
[0018]
Surprisingly, in previous patents (US Pat. No. 4,248,802 and US Pat. No. 4,994,427) alkaline earth metal salts of such anion-functionalized compounds are generally water soluble. Was billed as being. In the present disclosure, the present inventor discloses that the alkaline earth metal salt of this anion functionalized compound is insoluble in organic media and is insoluble or insoluble in aqueous media. Therefore, inactive salt admixtures that are catalyst inert are used to control water solubility. This admixture is primarily aimed at suppressing the solubility of ionic solids by a phenomenon commonly known as the common ionic effect.
[0019]
In the manner described above, a wide variety of catalyst complexes can be converted to solid materials by a common protocol. Such solid materials have been found to be stable under the reaction environment normally encountered. In other respects, soluble catalysts for various types of reactions (eg, hydrogenation, hydroformylation, carbonylation, olefination, telomerization, isomerization, oxidation, etc.) can be solidified. Yet another aspect of the present invention is to formulate this material and a solid support to form a catalyst. The support involved here can be selected independently of the catalyst element to be formulated and the catalyst inert additive to be mixed. The most interesting aspect of the present invention is that this catalyst formulation (also referred to as a catalyst ensemble or catalyst assembly) remains as a solid without its components disintegrating upon dissolution. This ensemble can be used to catalyze chemical reactions in a slurry or fixed bed reactor configuration.
[0020]
Therefore, an accurate object of the present invention is to provide a solid catalyst in which the catalytic element with which it participates is a molecularly defined isotropic species. Furthermore, the synthesis technique should be a common set of techniques that allow the desired catalyst species to be heterogeneous by simple means. An important object of the present invention is that the catalytically active solid formulation should not disintegrate or decompose not only under the reaction conditions but also under liquid flow. Another desired (although not essential) objective is to provide a solid catalyst that mimics its solubility analog while being easily separable due to the advantages inherent in solid catalysts. The term “natural” is used in this context to mean the catalyst element before it modifies and interacts with the Group IIA metal salt to yield a solid. Other objects and advantages of the present invention will be readily apparent from the following description and appended claims.
[0021]
Thus, the general aspects of the present invention can be described as the discovery of routine techniques by which solid catalysts can be prepared. A system of catalysts that are similar in composition, characteristics, and advantages are referred to herein generically. A characteristic of this family of catalysts is that they are chemically defined organometallic elements in which they are homogeneous but the active sites are physically present as solids. These organometallic elements are analogs derived from equivalent homogeneous catalytic elements. The homogeneous catalyst element referred to herein includes all types of soluble catalysts. Their natural structure consists of negatively charged functional groups (e.g. -SO₃ ⁻, -PO₃ ^2-Or -COO⁻) To be chemically modified. When synthesizing such materials, they exist as soluble salts, depending on the counterion associated with the anionic functional group. Due to the most interesting phenomenon observed in the present invention, the present invention can itself be referred to as general, which is an organometallic element modified as described above, and a Group IIA metal salt It can be converted into a solid substance by interacting with. The solid that is formed is ultimately a Group IIA metal salt. This observation is confirmed by converting a large variety of chemical structures into insoluble solids as previously described. Furthermore, a method has been developed for assembling such solids on the support surface.
[0022]
(Description of Preferred Embodiment)
In order to facilitate understanding of the principles of the present invention, several embodiments described in the examples are referred to and specifically described to illustrate them. Nonetheless, it is not to be construed as limiting the scope of the invention, and such changes and further improvements in these embodiments, as well as the invention as described herein. It will be appreciated that still other applications of the principles are contemplated as would normally occur to those skilled in the art to which the present invention pertains.
[0023]
In one embodiment, the present invention provides a novel heterogeneous catalyst composition, the catalyst composition containing a solid support having a catalytically active material deposited thereon, wherein the catalytically active material can be a variety of liquids. Insoluble in the medium, this solid material consists of catalytically active anionic elements with Group IIA metal ions, which are well defined molecularly.
[0024]
In another embodiment of the present invention, the catalytically active elements are deposited on the outer and pore surfaces of the solid support, the pores being primarily greater than about 20 mm in diameter, and the solid support fines. The pores have a pore diameter in the range of about 3 to 3000 mm.
[0025]
In yet another embodiment, the solid support is a chemically inert solid material and is present as a powder, granule, shaped or amorphous flake or pallet, sheet, monolith, rope and fiber solid woven fabric. And this porous solid support is a mechanically robust and thermally stable solid and insoluble in the reaction medium.
[0026]
In yet another embodiment, the catalytically active element is insoluble in the reaction medium, the reaction medium is selected from an organic phase, an aqueous phase, a powder, a non-aqueous ionic liquid and a supercritical fluid phase, and 100 ° C. A thermally stable solid material with a higher melting point.
[0027]
In yet another embodiment, the catalytically active material is a non-sublimable solid.
[0028]
In yet another embodiment, the present invention provides a catalyst comprised of a solid support having a catalytically active element deposited thereon, the catalytically active element being stable in the gas phase, liquid phase and gas-liquid phase. Remaining as a composite solid, the liquid phase is selected from organic, aqueous, powder, non-aqueous ionic liquid and supercritical fluid phases or mixtures thereof, the mixture comprising reactants, products Products and accelerators.
[0029]
In still other embodiments, the catalyst is in the gas phase or liquid phase as a physically stable composite solid over a temperature range of −78 ° C. to 300 ° C. and over a pressure range of 5 to 5000 psi. It remains.
[0030]
In still other embodiments, the Group IIA metal used is a cation with a +2 charge and is selected from calcium, strontium, barium and mixtures thereof.
[0031]
In still other embodiments, the Group IIA metal used is selected alone or in combination with other Group IIA metals.
[0032]
In still other embodiments, the catalytically active element is an anion having two or more negative charges and is separate from metal complexes, quaternary compounds, metal oxoanions, polyoxometalates and combinations thereof. Selected.
[0033]
In yet another embodiment, the present invention provides a catalyst, wherein the metal complex has the following general formula:
(M)_x(L)_y(L^*)_z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Is an atom or ion and is separately selected, x is in the range of 1-60, L is selected from aliphatic, aromatic and heterocyclic compounds, which are O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, containing at least one radical derived from carbene, the radical being —SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded to a radical with at least one or more negatively charged functional groups selected separately from wherein y is at least 1 and L^*Is a radical selected from organic anions, inorganic anions and ligand compounds, which compounds are O, N, S, Se, Te, P, As, Sb, Bi, Si, olefins, carbenes, = C Containing at least one radical derived from, the radical having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to the radical, and Z is from 0 to 7 It is a range.
[0034]
In yet another embodiment, the quaternary compound has the general formula:
[(Y⁺) (R^*)_I] [Z⁻]
Where Y⁺= N⁺, P⁺, As⁺For I = 4; Y⁺= S⁺For I = 3 and R^*Are independently selected from alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, and -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻With at least one or more negatively charged functional groups selected separately from Z and Z is an anion selected from organic anions, inorganic anions and coordination complex anions.
[0035]
In yet another embodiment, the insoluble catalytically active material optionally contains a catalyst inert additive, the catalyst inert additive is an anion having two or more negative charges, And it is selected separately from organic anions, inorganic anions or combinations thereof.
[0036]
In yet another embodiment, the catalyst inert additive is selected from a ligand compound, wherein the ligand compound is O, N, S, Se, Te, P, As, Sb, Bi, Contains at least one radical derived from Si, olefin, carbene, which radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical having at least one or more negatively charged functional groups selected from
[0037]
In still other embodiments, the amount of catalytically active element used is 40% or less, and the amount of catalytically inert additive used is a proportion of 0-200% by weight of the catalytically active element. .
[0038]
In yet another embodiment, the catalyst can be used for catalytic reactions in the gas phase or slurry phase.
[0039]
In yet another embodiment, the catalyst further comprises a high boiling liquid film deposited on the solid support.
[0040]
As stated above, a major aspect of Applicants' invention is directed to a solid formulation as a catalyst comprised of a solid support having a catalytically active material deposited thereon. Therefore, the catalyst formulation referred to herein is in the physical sense a solid and an organized ensemble of chemical components that are combined together to perform the task of catalyzing the reaction. . The definition of the assembly is written down in a narrow sense in the following embodiments in order to devise a catalyst suitable for real life. This multi-component catalyst is a compromise that balances the support fluid flow, activity and physical integrity around the catalyst particles. The relative importance of these factors has a direct impact on the reaction, reactor design, process conditions and economics. Many catalytic materials are composed of a single component (eg, zeolite, prop clay, metal alloy and metal oxide), but cannot reliably catalyze a wide variety of reactions. A multi-component catalyst as considered in this embodiment provides a choice of physicochemical properties, whereas it can be selected from different materials as salts, oxides, metal aggregates or organometallic materials. In order to achieve the previously mentioned features, this embodiment describes a general construction draft of the catalyst formulation of the present invention, as illustrated in FIGS.
[0041]
Referring to the drawing detailed in FIG. 1, the components of the formulation are divided into two categories. These two categories are catalytic passivity and catalytic activity. Passive components are supports and other additives, which inevitably give the catalyst formulation solid properties and can be selected regardless of the active ingredient, depending on the application. Of course, it can be seen that the selection of the support cannot be made randomly, and that the selection is totally dependent on the process. For example, silica supports cannot be used in strong alkaline solutions. This is because it dissolves and loses its integrity. Thus, the support associated with this embodiment is believed to be a reagent that acts as a vehicle that imparts physical shape and morphology to the catalyst particles to enhance mobility.
[0042]
From the previous discussion, it is sufficiently clear that catalytically active materials are often expensive and sometimes valuable, and the latter often applies to reactions catalyzed by organometallic complex catalysts. The activity of such materials depends on factors such as surface area, porosity, shape, and resistance to surface fouling when supported on a solid. In an effort to optimize these factors, it is common practice to disperse the active ingredients on the surface of an inert solid commonly known as a support or carrier. Although these materials are considered diluents, sometimes they play an important multifunctional role in directing catalytic activity. This can include chemical reactions with catalytically active materials, which are only to distinguish them from bifunctional catalysts, where the support plays an important role in terms of catalytic function. Shown to be inactive. Embodiments of the present invention implicitly assume the possibility of forming such synergistic multifunctional combinations in some cases.
[0043]
Accordingly, the purpose of using the support is strongly attributed to a number of factors such as economic needs, process needs and desired physicochemical properties. The economic reason considered by the inventor is mainly cost reduction by expanding the availability of expensive catalytically active materials. More process needs recognized by the inventor include providing the catalyst with sufficient mechanical strength, adjusting the bulk density of the formed catalyst, providing an endothermic source and thermal buffer, and excessively It was to dilute the active phase. In addition, the inventor recognizes that the catalyst geometry needs (which are mainly met by the support) can be described as an increase in catalyst surface area, optimization of the overall design porosity. ing. Other chemical features that the inventor believes need to be explicitly stated in this embodiment include that the support provides a means of reducing sintering or inactivation, and that acidic or basic centers. (These may act synergistically with the catalytically active material).
[0044]
In principle, any stable solid material with high surface area, porosity, strength and required dough is suitable, depending on the particular application considered. Almost stable ranges of solids that can be used herein include alumina, silica, magnesia, titania, zirconia, aluminophosphate, charcoal, organic polymers, and densified clay. These materials are preferred because of their high surface area, porosity and strength. Apart from these properties, they also have a low coefficient of thermal expansion.
[0045]
Almost all insulating solids are useful as supports, but for economic reasons silica and alumina are preferred supports. From previous reports it has been observed that alumina, silica, zirconia and tria tend to be acidic. These properties are either not important or can be eliminated by selective toxicity. Many naturally occurring materials belong to this group (eg, pumice asbestos, calcined clay (eg, bentonite), leptite and diatomaceous earth). As a result of the significant change in structure, solids provide a range of surface areas and porosity. A synthetic form of a material may be preferred in that it provides a more closely defined range of properties. If a concerted reaction is required, one of the reactions can be catalyzed on the support itself. This support catalyzes the reaction because of the acidic and basic sites thereon or because of the intentional formation of metallic sites thereon. In such cases, the support itself is another solid catalyst formed from a metal supported by a solid catalyst. Examples of supports belonging to this category of supports include 5% palladium on carbon, 1% Ni on alumina-copper-chromite (which was calcined and reduced before use), ruthenium on silica. And platinum sulfide on carbon. Considering the individual factors that govern the choice of support, the final choice depends on comparing these factors in relation to the application in which the catalyst is used.
[0046]
As evidence, the catalytic reaction rate is governed by the chemical reaction rate at the surface when the observed activity is a function of the surface area of the solid support. In practice, however, the overall reaction rate is usually affected by mass transfer or heat transfer, where the porosity and shape of the catalyst particles becomes increasingly important. As a result, the choice of support depends on the surface area of the catalyst available to the reactants and on the porosity of the catalyst.
[0047]
In the context of the present invention, surface area optimization is an important factor, which is related to other properties such as fabric and strength. Therefore, it can be easily extrapolated that surface area and porosity are closely related, and that porosity and mechanical strength are also related to each other. It is clear to the designer to ensure the long life required to obtain a stable structure in which the catalyst is strongly bonded together. Certainly this is not the case if the porosity is too high. In the case of naturally occurring supports, it is difficult to systematically modify the porosity. Zeolite or carbon molecular sieves limit the passage of reactant molecules because most of their surface area is in the channels and their width is narrow. Some gamma aluminas have a pore size distribution in the range of 100-200 mm, whereas foamed alumina has few micropores. The pore diameter can also be increased by carefully precipitating the material with a pore mouse.
[0048]
Thus, in addition to acting as a physical vehicle for the catalytic site, the support can have a significant effect on the catalytic reaction itself, where, for example, the local pH can be different. Alternatively, the bulk of the support can sterically affect the reaction process and even prevent the reaction from taking place.
[0049]
As mentioned earlier, apart from the chemical behavior of its active phase, the support has been found to play an important role in defining the catalytic properties. Such characteristics can be utilized depending on the process requirements. If the effect of the support on this active catalyst phase can be minimized, it is quite advantageous, but this is often difficult with heterogeneous catalysts. By separating the effect of the active phase from the effect of the support, the catalyst morphology can be modified by selecting the support and the active phase independently of each other.
[0050]
Thus, the support in this catalyst formulation is a porous solid and its pores are primarily larger than about 20 mm in diameter and have a pore diameter in the range of about 3 to 3000 mm. Also, the support material can be a substrate, intermediate, product of the reaction unless a concerted series reaction sequence (the one or more reactions are catalyzed by the support itself) is desired. And inert to the solvent. A suitable catalyst support is any solid that is insoluble in the reaction medium, thermally stable and has a high melting point. Examples of these support materials include pumice, alumina gel, silica gel, silica-alumina gel, aged or inactivated silica-alumina cracking catalyst, magnesia, diatomaceous earth, bauxite, titania, zirconia, clay (natural and acid treatment) Both), attapulgite, bentonite, lime, calcium carbonate. Calcium silicate, magnesium silicate, carborundum, activated carbon and non-activated carbon, adsorptive carbon, zeolite, zeolite molecular sieve, hydrotalcite, solid foam (for example, ceramic honeycomb), porous organic polymer (for example, macroreticular) Ion exchange resins), microporous polymers, porous crosslinked polystyrene-sulfonates, calcium alginate, barium sulfate, powdered cellulose, woven mesh, foamed paper, functionalized polymers, but are not limited thereto. The support can also be a supported metal catalyst. The support material can be used as regular and irregular particles, capillaries, meshes, woven meshes and space elements (eg, molded articles, extrudates, ceramic rods, balls, debris, lash rings, tiles). The support material may also have modifiers or deactivators present from the impregnation process or spray process or other foaming operations.
[0051]
As described in previous embodiments, the present invention relates to solid phase multi-component formulations, wherein the catalytically active material is disposed on the surface of the solid support. Soluble catalytic materials (eg, organometallic complexes) can form a catalytically active solid phase, if made insoluble, where the active site is defined as an isotropic molecular element (otherwise It exists only in solution. Such insoluble materials can form a simple solid catalyst of choice when dispersed and supported on the surface of the solid support. The example depicted in FIG. 2 outlines the strategy foreseen by the inventor.
[0052]
The active ingredient is composed of a solid phase, which is catalytically active, i.e. mainly responsible for the desired chemical transformation. Unlike supports, the general idea of selecting such materials is rarely available, and compositions must be reasonably developed within the framework of the laws of related chemistry. As is well known, a variety of materials can catalyze the same reaction, but some materials cannot necessarily catalyze a diverse range of reactions. Accordingly, it is another specific embodiment of the present invention whereby the soluble molecular catalyst is suitably modified so that it can be incorporated into a solid material.
[0053]
Desirable properties of such catalytically active solid materials include the following:
1. The substance should not dissolve or wilted in a wide range of reaction media and reaction conditions;
2. The material should have sufficient mechanical and fracture strength;
3. Such materials should be made from organometallic building blocks;
4). The material should have a strong tendency to agglomerate with respect to the support and the overall formulation is not only in liquids, including aqueous, organic and inorganic, but also in the acidic and alkaline conditions, Over time (e.g., -78 to 300 <0> C), should remain as a composite material;
5. The material should have a high melting point and be non-sublimable;
6). The catalytically active solid material is thermally stable and should not be pyrolyzed at the reaction temperature; and
7). One of the building blocks of the material is the molecular component responsible for the specific reaction it catalyzes.
[0054]
The reaction medium mentioned above is a very wide variety of liquids and not only can be selected depending on the solubility of the substrate and other components, but the product should be recovered cleanly. Examples of liquids that can be used as reaction medium include petroleum fractions of different boiling points, cycloalkanes (eg cyclohexane, cycloheptane, cyclodecane), aromatic compounds (eg benzene, toluene, xylene, ethylbenzene, butylbenzene), Alcohols (including methanol, ethanol, propanol, butanol, amyl alcohol (straight and branched), higher alcohols, cyclohexanol, phenol, xylinol, cresol), acids (eg, acetic acid, propionic acid, butyric acid), amides (Eg, formamide, dimethylformamide, pyrrolidone, n-methylpyrrolidone), nitrile (eg, acetonitrile, propinitrile, benzonitrile), ester (eg, ethyl acetate, methyl acetate, methyl propionate, benzoate) Methyl, methyl propionate), ethers (eg, diethyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, dioxane, furan), ketones (eg, acetone, methyl ethyl ketone, pentan-2-one, cyclohexanone), nitroaliphatic compounds (eg, Nitromethane, natroethane, nitropropane), nitroaromatic compounds (eg, nitrobenzene, 2-nitrotoluene), halogenated solvents (eg, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene) However, it is not limited to these. Other high-boiling solvents used for specific purposes include hexadecane, octadecane, hexatracontan, squalene, chlorinated hydrocarbon oil, liquid paraffin, mineral oil, naphthalene, phenanthrene, methylnaphthalene, high-boiling substituted and unsubstituted organics. Alcohol, glycol, polyglycol, ether, polyether (eg, glycerol, carbitol, dulcitol, erythritol, polyethylene glycol, propylene glycol, diglycerol, diethylene glycol, polypropylene glycol, tetraethylene glycol, 2-ethyl-1,3-hexane Diol, 1,5-pentanediol, methoxypolyethylene glycol, 1,2,4-butanediol, polyphenyl ether, methylbenzyl ether, bis (phenoxy Ether), tetraethyleneglycodimethyl ether), high-boiling esters (eg, diisooctyl phthalate, dibuty phthalate, dioctyl phthalate, bis (2-ethylhexyl) phthalate, dinonyl phthalate, butyl benzyl phthalate, bis phthalate ( 2-tetrahydrofurfuryl), dipropyl tetrachlorophthalate, dioctyl sebacate, bis (2-ethylhexyl) sebacate)). Inorganic solvents that can be used include water, room temperature ionic liquids, powder solvents and supercritical dense phases. It is also possible to use two or more solvent media for the reaction, depending on the solubility of the reactants and products. The selection criteria for the solvent is the chemical and physical requirements of the reaction rather than the components of the catalyst formulation. The catalyst formulation as a whole is stable in a variety of reaction media, and practically any liquid can be used as the solvent for the reaction, as is the case with conventional heterogeneous catalysts. Of course, in order to obtain the optimum performance of this catalyst, it will be appreciated that very few liquids are suitable and have to be selected accordingly.
[0055]
The properties described above for catalytically active solid materials are generally found in materials such as ceramics. It is well known in the art that ceramics contain metallic and non-metallic elements, which are bound by ionic bonds, covalent bonds, or both. These substances have their structural composition (A_mX_nAre the most common examples). A is a metal cation with a charge of + m and X is a multivalent anion with a charge of -n. An ionic substance has no free electrons and becomes a poor conductor of heat and electricity. Furthermore, the very stable and directional ionic bonds increase the melting range of the ceramic. Usually, ceramics are also hard and resistant to physical and chemical changes. Other factors that affect the relationship between the structure and properties of a ceramic material can be described as the ratio of radius and the difference in electronegativity between the cation and anion, but the net negative charge on the material is Zero. Clearly, therefore, it was foreseen that the catalytic material should have properties similar to ceramics.
[0056]
Therefore, another embodiment of this work consists in developing a solid material in which the unit block is composed of defined catalyst elements. Another purpose of this study is to develop a strategy without limiting the catalyst formulation to one specific type of complex or reaction, and subsequently to develop a specific mechanism according to a specific theory. A_mX_nType material (where A_mIs an alkaline earth metal cation, and X is an anion having a structure involved in catalyzing a specific reaction), if formed, the resulting material has similar properties to a ceramic. Thought to have. Furthermore, ionic such materials are not soluble in organic solvents and they are typically assumed to be used as solvents, while at the same time such materials are soluble in their aqueous solvents. Can be ignored when the medium is aqueous.
[0057]
In order to confirm and hypothesize this hypothesis, several comparative experiments cited in the examples were conducted. Two or more negatively charged anions interacted with the Group IIA metal cation in solution. Various Group IIA compounds (including salts, complexes, alkyls and hydrides) interacted with various anion and polyanion compounds having negative charges in the range of -1 to -3. Various Group IIA compounds used for this purpose are magnesium chloride, magnesium acetate, magnesium nitrate, magnesium acac, magnesium complex of ethylenediaminetetraacetic acid disodium salt, bytyl magnesium chloride, calcium hydroxide, calcium chloride, calcium nitrate, Calcium hydride, calcium acac, calcium complex of ethylenediaminetetraacetic acid disodium salt, strontium acetate, strontium chloride, strontium acac, strontium complex of ethylenediaminetetraacetic acid disodium salt, barium nitrate, barium hydroxide, barium acetate, barium chloride It was done. Such a compound was used as a Group IIA cation source in solution. These cations interacted with negatively charged anions and polyanionic compounds of -1, -2 and -3. Such anions in solution include sodium nitrate, sodium propionate, sodium p-toluenesulfonate, disodium m-benzenedisulfonate, disodium oxalate, disodium sulfate, disodium phenylphosphonate, disodium phosphate. Obtained from hydrogen, sodium hydrogen phthalate, ammonium molybdate, sodium carboxymethylcellulose, sodium polyvinyl sulfonate. Group IIA metal ions other than magnesium ions were finally confirmed to form insoluble salts when interacting with at least two or more negatively charged anions. Such a salt is insoluble in a mixture of an organic substance and an aqueous organic substance, and has a very low solubility in water.
[0058]
Therefore, the cation (A^{n +}The hypothesis is confirmed that the alkali metal salt containing (where n> 1)), when interacted, yields a material that is insoluble in most organic solvents as well as aqueous solvents. Such a proposal was confirmed by the interaction of the various anionic compounds described in Experiment 1, which are based on a variety of anionic structures. It has been observed that salts of alkaline earth metals and anions (which have two or more negative charges) give solids. A deliberate conclusion was drawn by systematically changing the molecular capacity of the polyanion, its anionic functional group, and the electron density of the alkali metal cation. The only requirement for the material to form insolubles is that the anion (X) described above should have at least two anionically charged functional groups. Subsequent experiments have shown that an anion as small as nitrate and an anion as large as polyvinyl sulfonate form a substance that is almost insoluble in water and completely insoluble in organic solvents. If a polyanionic property is introduced at the peripheral position of the catalyst molecule so as not to disturb or affect the catalytic reaction, the anion (X) described above is obtained.
[0059]
An anionic compound is an acid having a proton as a counter cation in a normal sense. Moreover, it is preferable to introduce a highly acidic functional group into the originally catalytically active species. Strongly acidic groups are preferred because they cannot be protonated in contact with strong acids, which may be present in the reaction medium. Therefore, a highly acidic functional group is, for example, -SO₃ ^-1, -PO₃ ^2-Are preferably selected from other groups such as -COO⁻) Is also suitable provided that the reaction medium is not acidic.
[0060]
The catalytically active species described in the previous embodiment is a molecular element having structural features necessary for the desired catalysis. Such molecular elements are, for example, metal complex catalysts, metal oxoanions or ion pairs. The peripheral positions of such catalytically active elements are anionic functional groups (e.g. -SO₃ ⁻, -PO₃ ^2-, -COO⁻) And the degree of substitution is effectively> 1.
[0061]
The substitution / modification described herein specifically includes an anionic functional group (eg, —COO⁻, -SO₃ ^-1, -PO₃ ^2-Etc.) means the molecular modification of the element. The term modified does not necessarily mean that the modified element is chemically derived from the parent element, but refers to an analog of the separately synthesized parent structure. It is further specified that such an anionic functional group is attached to one of the carbon atoms of the parent element.
[0062]
Therefore, in the explicit description of the preferred embodiment, the catalyst formulation is a combination of the solid support described in the previous embodiment (with a catalytically active solid material deposited thereon) and the ensemble as a whole is: It exists as a stable composite material in the gas phase or liquid phase. The liquid phase is composed of an aqueous liquid, an organic liquid or a mixture thereof (which contains reactants, products and promoters). The catalyst formulation of this embodiment is a composite solid that is physically stable in the gas phase or liquid phase over the temperature range of -78 to 300 ° C., over the pressure range of 5 to 5000 psi, or in the gas phase or It remains as a physically stable composite solid in the liquid phase. The catalytically active material of this embodiment is an insoluble salt, which is composed of a Group IIA metal, a catalytically inert additive, and a catalytically active element. To further describe this Group IIA metal, it exists as a cation with a +2 charge. The Group IIA metal cation of the catalytically active material is selected from calcium, strontium and barium. Specifically, magnesium is excluded. The Group IIA metal that forms the catalytically active material can be selected alone or in combination with other Group IIA metals. The catalytic material is formed by a polyanionic catalytically active element and a catalytically inactive polyanionic element together with the Group IIA metal ions described above.
[0063]
The addition of the inert additive is largely due to a decrease in the solubility of the catalytically active solid in the aqueous solvent. As stated, an ionic substance tends to dissociate in water, thereby dissolving in the liquid phase if it happens to be liquid. In order to suppress this, another ionic substance needs to be further present in order to reduce the solubility due to the common ionic effect (a phenomenon well known in the literature) at the expense of solubility. In addition, such additives are also foreseen to impart microporosity to the material. Addition of a catalyst inert material (which itself is one of the components of the metal ligand complex) gives this solid material excessive coordination performance, which is an important buffer Acts as a liquid, allowing the transition metal coordinated in the complex to be retained. Conversely, it implies that the presence of additional ligands as catalytically active additives also prevents the loss of transition metals. Furthermore, it can be seen that the catalyst inert additive may be present as needed depending on the adsorbability of the support, the fluid stress on the solid particles and the coordination tendency of the reactants and solvent. The catalytically active element can be selected separately from the metal complex, quaternary compound, metal oxoanion and polyoxymetalate or combinations thereof.
[0064]
The metal complex described above has the general formula:
(M)_x(L)_y(L^*)_z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Atom or ion and can be a suitably selected suitable transition metal, including atoms Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Examples include Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and Zn. Preferably, the metal complex contains a metal atom or ion from group VIII of the periodic table of elements, the suffix x means the number of metal atoms or ions present, Yes, L is an aliphatic compound, an aromatic compound and a heterocyclic compound, and the compound is at least one derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene And the radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded to a radical having at least one or more negatively charged functional groups selected separately from , At least 1. L^*Is a radical selected from organic anions, inorganic anions and ligand compounds, the compounds derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, olefins, carbenes, = C Wherein the radical has an oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl optionally attached to the radical, and Z is 0 It is the range of ~ 7.
[0065]
As described in the previous embodiment, the catalyst inert additive is optionally selected from a ligand compound, wherein the ligand compound is O, N, S, Se, Te, P , As, Sb, Bi, Si, olefin, containing at least one radical derived from carbene, wherein the radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected from
[0066]
As described in one of the previous embodiments, the quaternary compound has the general formula:
[(Y⁺) (R^*)_I] [Z⁻]
Where Y⁺= N⁺, P⁺, As⁺For I = 4; Y⁺= S⁺For I = 3 and R^*Are independently selected from alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, and -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻With at least one or more negatively charged functional groups selected separately from Z and Z is an anion selected from organic anions, inorganic anions and coordination complex anions.
[0067]
Sulfonated quaternary phosphine metal salt ligands of this type of anionically charged ligand that can be used in the present invention and / or methods for their preparation are well known or described, for example, in “J. Chem. .Soc. ", Pp. 276-288 (1958), U.S. Pat. Nos. 4,483,802 and 4,731,486. For example, such a ligand may be a di- or polysulfonated phosphine predominantly protonated by sulfonation of the corresponding aromatic tertiary phosphine with fuming sulfuric acid under controlled temperature conditions, such as the following compounds: Can be prepared by forming:
[0068]
[Chemical 1]

For example, the solid phosphine is added in portions to the fuming sulfuric acid while controlling the temperature below 5 ° C. and then heated to, for example, 20-80 ° C. until the desired degree of sulfonation is achieved. . The reaction mixture is then immediately cooled to stop further sulfonation or oxidation of the phosphine, and without waiting, water is added to avoid the temperature from rising above 30 ° C. The phosphine chloride salt is neutralized with an alkaline solution. The mixture containing alkali sulfonate and alkali sulfate is concentrated by evaporating the water. During the evaporation of the water, the alkali sulfate precipitates and is removed by filtration, and the mother liquor is mixed with methanol. When most of the alkali sulfate is precipitated, sulfonated phosphine is extracted into the methanol. When the methanol is evaporated, the sulfonated phosphine is obtained as a solid. The crude tertiary phosphine metal sulfonate can be further purified by dissolving in a suitable solvent (eg, water or ethanol) and recrystallizing therefrom.
[0069]
This sulfonation can also be carried out in concentrated sulfuric acid media using boric acid and sulfur trioxide complexes, as described in Albanese et al. US Pat. No. 5,684,181 and US Pat. No. 5,780,674. The advantage of such a procedure is that it reduces the formation of phosphine oxide. Similarly, the sulfonation reaction work-up can also be accomplished by extracting the quenched sulfonation mixture with a tributyl phosphite or triisooctylamine organic phase, which is subsequently extracted with an alkaline solution. Can be modified. The advantage of such a procedure is that the phosphine can be selectively separated from the corresponding oxide. Phosphine oxides are contaminants that often occur in such sulfonated phosphine ligands. The presence of phosphine oxide does not affect the catalytic behavior of this ligand in combination with a transition metal. It can be seen that such phosphine oxides do not coordinate with the metal, so that contamination due to phosphine oxide can be tolerated for the purpose of catalysis. The presence of phosphine oxide is unacceptable in the case of bidentate and bidentate chiral ligands. Experts in this field can then readily understand the situation in which the bidentate phosphine monooxide exhibits different coordination behavior. This situation is further complicated while preparing the catalyst for the enantioselective reaction. In such cases, removal of phosphine oxide is desirable, which can be accomplished by extractively separating from a solution of tributyl phosphite or triisooctylamine, or by Hermann et al., Angew. Chem. Int. Eng. It can be achieved by fractionating from a gel of modified dextran (eg, SEPHADEX G15®) as described by the author, 29 (1990) No (4) 391-393.
[0070]
Such sulfonated ligands can be prepared by a variety of methods using lithium phosphide, Grignard reagent, phosphorus trichloride and the like. Knowledge and understanding of such ligands are taught in the literature known to those skilled in the art. For example, Kosolasoft G. M.M. Maier L., et al. Organic Phosphorus Compounds, Volume 1,288, Wiley Interscience, New York, (Copyright) 1972. / Engl R.D. synthesis of carbon phosphorous bonds, (copyright) CRC Press 1988. / Tripett S. A. A special Periodic Report of Organophosphorus Chemistry, Chemical Society London (Copyright) 1970. Specific examples of such synthesis are (Mann, FG, et al., J. Chem. Soc. 1937, 527-535; US Pat. No. 4,483,802 and US Pat. No. 4,731,486). Explained in the issue). Similarly, nitrogen-containing ligands can be prepared by specialized chemical synthesis known in the art (Eit Drent, US Pat. No. 5,166,411). The synthesis, production and purification of such ligands is clearly outside the scope of this application. It can be clearly understood that the knowledge relating to the sulfonation of such ligands is also well known. Similarly, other anionically charged functional groups (eg, —COO⁻, -PO₃ ^2-)) Can also be prepared by a series of specific organic syntheses (synthesis of ligands containing phosphonic and carboxylic acids). The present invention claims to further utilize such well-known ligands to prepare a general catalyst formulation, which is a solid and used as a catalyst. The use of such known ligands by further processing is within the scope of this application (scope and purview) and is one of the preferred embodiments of the present invention. Examples of preferred anionic ligands and their transition metal complexes and quaternary compounds include the following. It goes without saying that these are examples only and are not comprehensive.
Anionic ligand
[0071]
[Chemical 2]

Some examples of quaternary compounds include:
Anionic quaternary compounds
[0072]
[Chemical 3]

The polyanionic ligands and quaternary compounds exist as alkali metal, quaternary ammonium or proton salts. It is well known in the art that such compounds are water soluble combinations of such ligands and transition metals and provide access to their complexes. Some examples of catalytically active moieties include the following:
Catalytically active anionic moiety
[0073]
[Formula 4]

The complexes described above can be prepared by various methods known in the literature. In a broad sense, such metal complexes can be classified as follows:
1. Synthesis of metal complexes from metal salts and anionic ligands;
2. Substitution of unstable ligands with anionic ligands.
[0074]
For example, PdCl₂Complexes such as bis (triphenylphosphine trisulfonate trisodium) can be synthesized in aqueous ethanol using PdCl₄ ^2-Prepared by reacting ruthenium chloride with trisodium triphenyltriphenylphosphine trisulfonate by reacting with trisodium triphenyltriphenylphosphine trisulfonate, in the latter case of cyclooctadiene or acetylacetonate. HRhCO (TPPTS) by replacing such labile ligands₃, RUCl₂A complex such as BINAP is prepared. Complexes such as sulfonated phthalocyanines are prepared by simultaneously forming a ligand and a complex. As mentioned earlier, the synthesis of such complexes is a knowledge well known to those skilled in the art. The synthesis of such complexes is beyond the scope of the present invention (scope and purview). It is an obvious embodiment of the present invention to further utilize such complexes to form insoluble solid formulations for catalytic applications.
[0075]
Several different metal complexes containing different metals and various ligands have been synthesized. Such metal complexes provided solids whenever they interacted with Group IIA metal compounds other than magnesium compounds, which were insoluble in water and organic solvents. The precipitates were solid up to 200 ° C. and were non-sublimable. A number of experiments described in the examples were conducted to verify the proposed hypothesis and the logical conclusion that polyanions form precipitates that are insoluble in various liquids when interacting with Group IIA metals. Estimated. In yet another preferred embodiment of the present application, a mixture of catalytically active polyanions and catalytically inert anions is preferred to form a precipitate that is insoluble in most liquids. The reason for the further presence of the catalyst inert additive is to reduce the solubility of the complex precipitated in water due to the well-known phenomenon of common ion effect. It is also preferred to add additional ligands used to form the complex. The presence of additional ligands is particularly preferred if the catalyst formulation is intended to be used in a coordinating liquid phase or if the ligand involved is monodentate.
[0076]
The catalytically active material of the catalyst formulation is formed by precipitation, by interaction of a solution of the catalyst inert additive and a solution of the catalytically active element and the Group IIA metal cation. The solution of the catalyst inert additive, the catalytically active element, when in contact with the Group IIA metal cation solution, the two solutions begin to diffuse and subsequently the Group IIA metal cation encounters a collision with the polyanion. Whenever it does, solidification begins and a cluster of solids is slowly formed. In such precipitates, the catalyst inert additive is selected separately from at least two or more negatively charged anions, ligand compounds, the ligand compounds being O, N, S, Contains at least one radical derived from Se, Te, P, As, Sb, Bi, Si, olefin, the radical being —SO 2₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻And having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical, having at least one or more negatively charged functional groups selected separately from combinations thereof And the catalytically active element is separately selected from metal complexes, quaternary compounds, metal oxoanions and polyoxometalates or combinations thereof.
[0077]
This catalytic activity can be selected such that the metal complex has the following general formula:
(M)_x(L)_y(L^*)_z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Atom or ion, and can be a suitably selected suitable transition metal ion, including atoms Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru , Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and Zn. Preferably, the metal complex contains a metal atom or ion derived from group VIII of the periodic table of elements, x is 1-60, L is an aliphatic compound, aromatic compound and heterocyclic compound And the compound contains at least one radical derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, and the radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups independently selected from , At least 1 and L^*Is a radical selected from organic anions, inorganic anions and ligand compounds, which are O, N, S, Se, Te, P, As, Sb, Bi, Si, olefins, carbenes, = C Contains at least one radical derived from, the radical having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded to the radical, Z being from 0 to 7 It is. Quaternary ammonium compounds have the following general formula:
[(Y⁺) (R^*)_I] [Z⁻]
Where Y⁺= N⁺, P⁺, As⁺For I = 4; Y⁺= S⁺For I = 3 and R^*Are independently selected from alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, and -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻With at least one or more negatively charged functional groups selected separately from Z and Z is an anion selected from organic anions, inorganic anions and coordination complex anions.
[0078]
Thus, as described in previous embodiments, the inventor has developed a general technique for solidifying multi-dimensional catalyst elements, which functions according to different theories and mechanisms. Such solidification is achieved by incorporating the previously described catalyst element into an ionic solid, which by itself is due to the interaction of the polyanionic catalyst element, the polyanionic additive and the Group IIA metal ion. It is formed.
[0079]
The catalyst formulation of the present invention (wherein the catalyst materials mentioned above) are supported on the surface of the solid support. It is recalled that the insoluble catalyst material formed cannot be dissolved in the liquid and therefore cannot be supported on this solid support. Therefore, a technique for forming such a substance directly on the surface of the solid support by precipitation has been required.
[0080]
Thereby, the final formation of the composite catalyst can be carried out by precipitating the catalytically active substance on the surface of the support. The formation of the catalyst by precipitation or coprecipitation is therefore of central importance in this respect. However, precipitation is a complex phenomenon and several auxiliary techniques need to be developed to deposit the catalyst on the support surface. Nevertheless, for some catalyst related materials (especially support materials) precipitation is the most frequently applied method. In this respect, such precipitation is troublesome because it can generate clusters and particles in the majority of the liquid. The specific treatment of the formation of the solid catalytically active material is well described by the term coprecipitation because it produces a precipitate when the two components classified as Group IIA metal ions and polyanion elements interact. Yes. Coprecipitation is a very suitable technique for producing a uniform distribution of such materials in the support material when the stoichiometry of the interacting species is clear. From previous experience, coprecipitation can obtain good dispersion at its support surface, which is a fact known to be difficult without it to obtain the catalyst assembly under consideration. . Therefore, the bulk coprecipitation process needs to be improved to obtain composite-based assemblies.
[0081]
Preferably, this coprecipitation forms a precursor solution containing anionic elements (catalytically active elements and catalytically inert additives) and a Group IIA metal solution which diffuses near the surface of the support or forms insoluble clusters. Is carried out in such a way that it starts near the surface of the support. Hereinafter, the solution containing the anionic component is referred to as Solution A, and the solution containing the Group IIA metal is referred to as Solution B. It is another embodiment of the present invention that outlines various methods of assembling the catalyst formulations of the previously described embodiments. These assembly techniques are broadly categorized according to various precipitation techniques and are described with assurance of the description of the embodiments.
[0082]
One method for preparing a heterogeneous catalyst formulation as a solid composite, which is composed of a porous solid support having a catalytically active solid deposited thereon, is an insoluble solid support. Is suspended in the liquid phase, to which the catalyst inert additive and the catalyst active element solution and the Group IIA metal cation solution are simultaneously added with vigorous stirring and aged for 1 to 48 hours. Wherein the support is a mechanically robust and thermally stable solid in the reaction medium, has a pore diameter in the range of about 3 to 3000 mm, and is a powder, granule, shaped Or present as amorphous flakes or pallets, sheets, monoliths, ropes and fiber solid fabrics, and the catalyst-inert additive is an organic compound, an inorganic compound, or O, N, S, Se, Te, P , A , Sb, Bi, Si, olefins, is independently selected from anions having at least two or more negative charges is selected from compounds containing at least one radical from the carbene, the radical, -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected from
[0083]
The catalytically active element is separately selected from metal complexes, quaternary compounds, metal oxoanions, polyoxometalates and combinations thereof, wherein the metal complex has the following general formula:
(M)_x(L)_y(L^*)_z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Atom or ion, and can be a suitably selected suitable transition metal ion, including atoms Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru , Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and Zn. Preferably, the metal complex contains a metal atom or ion derived from group VIII of the periodic table of elements, x is 1-60, L is an aliphatic compound, aromatic compound and heterocyclic compound And the compound contains at least one radical derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, and the radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected separately from At least 1 and L^*Is a radical selected from organic anions, inorganic anions and ligand compounds, which compounds are O, N, S, Se, Te, P, As, Sb, Bi, Si, olefins, carbenes, = C Containing at least one radical derived from, the radical having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to the radical, and z is from 0 to And the quaternary ammonium compound has the general formula:
[(Y⁺) (R^*)_I] [Z⁻]
Where Y⁺= N⁺, P⁺, As⁺For I = 4; Y⁺= S⁺For I = 3 and R^*Are independently selected from alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, and -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻With at least one or more negatively charged functional groups selected separately from Z and Z is an anion selected from organic anions, inorganic anions and coordination complex anions. The Group IIA metal cation is Ca²⁺, Sr²⁺And Ba²⁺Selected from the following compounds:
[0084]
The process described above is carried out at a temperature in the range of −78 to 200 ° C., preferably between −5 to 100 ° C. The solvent for this process is selected from aqueous solvents, water-miscible organic solvents or mixtures thereof.
[0085]
In the above method, the catalyst inert additive and the catalyst active element solution and the Group IIA metal cation solution are added simultaneously over a period of 10 to 1500 minutes. After this treatment is complete, the catalyst is recovered by centrifugation, decantation, gravity sedimentation or other solid-liquid separation techniques, followed by solid drying in vacuum. The methods described herein can be used when the components of the precipitate slowly produce solid material under the influence of viscosity, solvent and solubility modifiers. There is sufficient time for the seed of the sediment to settle on the support surface because the seed of solid material develops slowly. The other methods described below are suitable for instantaneous coprecipitation. Such a method is important because it usually requires special unit operations, and the production requires special equipment.
[0086]
Another method of preparing a heterogeneous catalyst formulation, wherein the solid composite material is comprised of a porous solid support having a catalytically active solid deposited thereon, the solid support as a catalytically active element. And a step of impregnating with a catalyst inert additive followed by a drying step, wherein the dried support has a catalytically active element deposited thereon, while the catalyst inert additive is agitated at the same time while stirring. Added to the solution of the Group IIA metal compound. The suspension is aged for 1 to 48 hours with stirring, so the process is carried out at a temperature in the range of −78 to 200 ° C., preferably between −5 to 100 ° C.
[0087]
In this case, the support is a mechanically robust and thermally stable solid in the reaction medium, has a pore diameter in the range of about 3 to 3000 mm, and is a powder, granule, shaped or amorphous Flakes or pallets, sheets, monoliths, ropes and fiber solid woven fabrics, and catalyst inert additives are organic compounds, inorganic compounds, or O, N, S, Se, Te, P, As, Sb , Bi, Si, olefin, carbene, which are separately selected from at least two or more negatively charged anions, which may be compounds containing at least one radical,₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected from
[0088]
The catalytically active element is separately selected from metal complexes, quaternary compounds, metal oxoanions and polyoxometalates or combinations thereof, the metal complexes having the following general formula:
(M)_x(L)_y(L^*)_z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Atom or ion, and can be a suitably selected suitable transition metal ion, including atoms Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru , Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and Zn. Preferably, the metal complex contains a metal atom or ion derived from group VIII of the periodic table of elements, x is 1-60, L is an aliphatic compound, aromatic compound and heterocyclic compound And the compound contains at least one radical derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, and the radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected separately from At least 1 and L^*Is a radical selected from organic anions, inorganic anions and ligand compounds, which compounds are O, N, S, Se, Te, P, As, Sb, Bi, Si, olefins, carbenes, = C Containing at least one radical derived from, the radical having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to the radical, and z is from 0 to And the quaternary ammonium compound has the following general formula:
[(Y⁺) (R^*)_I] [Z⁻]
Where Y⁺= N⁺, P⁺, As⁺For I = 4; Y⁺= S⁺For I = 3 and R^*Are independently selected from alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, and -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻With at least one or more negatively charged functional groups selected separately from Z and Z is an anion selected from organic anions, inorganic anions and coordination complex anions. The Group IIA metal cation is Ca²⁺, Sr²⁺And Ba²⁺Selected from the following compounds: According to the method under consideration, the solvent used to dissolve the anionic component and the Group IIA metal cation is an aqueous solvent, a water-miscible organic solvent or a mixture thereof.
[0089]
An improvement of this method may be employed, wherein the support on which the catalytically active element and the catalyst inert additive are deposited is mixed with the first while stirring for 10 to 1500 minutes, depending on the specific process requirements. Added to the solution of the Group IIA metal compound. This method is therefore completed by recovering the catalyst by centrifugation, decantation, gravity sedimentation or other solid-liquid separation techniques, followed by drying in vacuum.
[0090]
Furthermore, according to yet another preferred method of preparing a heterogeneous catalyst formulation as a solid composite material, the solid composite material is comprised of a porous solid support having a catalytically active solid deposited thereon, the method comprising: Characterized by the step of impregnating the solid support with a solution of the catalytically active element and the catalytically inert additive followed by drying. The solid support on which the catalyst inert additive and the catalyst active element are deposited is suspended in a water-miscible solvent, and a solution of the Group IIA metal compound is added to the water-miscible solvent with vigorous stirring. At the same time, the low-boiling or azeotropic fraction of the solvent is removed. The suspension is aged for 1 to 48 hours, where the process is therefore carried out at a temperature in the range of 70 to 200 ° C.
[0091]
The support in this case is a mechanically robust and thermally stable solid in the reaction medium, has a pore diameter in the range of about 3 to 3000 mm, and is a powder, granule, shaped or irregular Present as regular flakes or pallets, sheets, monoliths, ropes and fiber solid woven fabrics, and catalyst inert additives are organic compounds, inorganic compounds, or O, N, S, Se, Te, P, As, Separately selected from at least two or more negatively charged anions, which may be compounds containing at least one radical derived from Sb, Bi, Si, olefin, carbene, which radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected from
[0092]
The catalytically active element is separately selected from metal complexes, quaternary compounds, metal oxoanions and polyoxometalates or combinations thereof, the metal complexes having the following general formula:
(M)_x(L)_y(L^*)_z
Wherein M is a coordination complex selected from a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Catalytic metal atoms or ions, and can be appropriately selected suitable transition metal ions, including atoms such as Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn are mentioned. Preferably, the metal complex contains a metal atom or ion derived from group VIII of the periodic table of elements, x is in the range of 1-60, L is an aliphatic compound, aromatic compound and complex. Selected from ring compounds, said compound containing at least one radical derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, said radical being- SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected separately from At least 1 and L^*Is a radical selected from organic anions, inorganic anions and ligand compounds, which compounds are O, N, S, Se, Te, P, As, Sb, Bi, Si, olefins, carbenes, = C Containing at least one radical derived from, the radical having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to the radical, and z is from 0 to And the quaternary ammonium compound has the general formula:
[(Y⁺) (R^*)_I] [Z⁻]
Where Y⁺= N⁺, P⁺, As⁺For I = 4; Y⁺= S⁺For I = 3 and R^*Are independently selected from alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, and -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻With at least one or more negatively charged functional groups selected separately from Z and Z is an anion selected from organic anions, inorganic anions and coordination complex anions. The Group IIA metal cation is Ca²⁺, Sr²⁺And Ba²⁺Selected from the following compounds:
[0093]
The solvent used to form the Group IIA metal ion solution is an aqueous solvent, a water-miscible organic solvent or mixtures thereof, and the solvent used to suspend the support is 40-200. It is a water-miscible organic solvent having a boiling point in the range of ° C. The method of the present invention is completed by recovering the catalyst by centrifugation, decantation, gravity sedimentation or other solid-liquid separation techniques, followed by drying in vacuum.
[0094]
In the method of preparing a heterogeneous catalyst formulation as a solid composite, the solid composite comprised of a porous solid support having a Group IIA metal compound deposited thereon is subsequently dried. The solid support on which the Group IIA metal is deposited is suspended in a water miscible solvent, and a solution of the catalytically active element and the catalyst inert additive is added to the water miscible solvent with vigorous stirring. At the same time, the low-boiling or azeotropic fraction of the solvent is removed. This azeotropic distillation step is therefore carried out at a temperature in the range of 70-200 ° C. The liquid medium used in the solvent azeotropic removal step is a water-miscible organic solvent having a boiling point in the range of 40-200 ° C. They are aged 1 to 48 hours after suspension.
[0095]
In this case, the support is a mechanically robust and thermally stable solid in the reaction medium, has a pore diameter in the range of about 3 to 3000 mm, and is a powder, granule, shaped or amorphous Flakes or pallets, sheets, monoliths, ropes and fiber solid fabrics, and the catalyst inert additives are organic compounds, inorganic compounds, or O, N, S, Se, Te, P, As, Separately selected from at least two or more negatively charged anions, which may be compounds containing at least one radical derived from Sb, Bi, Si, olefin, carbene, which radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected from
[0096]
The catalytically active element is separately selected from metal complexes, quaternary compounds, metal oxoanions and polyoxometalates or combinations thereof, the metal complexes having the following general formula:
(M)_x(L)_y(L^*)_z
Wherein M is a coordination complex selected from a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Catalytic metal atoms or ions, and can be appropriately selected suitable transition metal ions, including atoms such as Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn are mentioned. Preferably, the metal complex contains a metal atom or ion derived from group VIII of the periodic table of elements, x is 1-60, L is an aliphatic compound, aromatic compound and heterocyclic compound And the compound contains at least one radical derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, and the radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected separately from At least 1 and L^*Is a radical selected from organic anions, inorganic anions and ligand compounds, which compounds are O, N, S, Se, Te, P, As, Sb, Bi, Si, olefins, carbenes, = C Containing at least one radical derived from: the radical having an oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to the radical, and z is 0 And the quaternary ammonium compound has the general formula:
[(Y⁺) (R^*)_I] [Z⁻]
Where Y⁺= N⁺, P⁺, As⁺For I = 4; Y⁺= S⁺For I = 3 and R^*Are independently selected from alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, and -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻With at least one or more negatively charged functional groups selected separately from Z and Z is an anion selected from organic anions, inorganic anions and coordination complex anions. The Group IIA metal cation is Ca²⁺, Sr²⁺And Ba²⁺Selected from the following compounds: The solvent used to form the Group IIA metal ion solution is an aqueous solvent, a water-miscible organic solvent, or a mixture thereof. After removal of the organic miscible liquid and low boiling liquid, the catalyst is recovered by centrifugation, decantation, gravity sedimentation or other solid-liquid separation technique followed by solid drying in vacuo.
[0097]
A method of preparing a heterogeneous catalyst formulation as a solid composite includes fluidizing a solid support in a gas stream. The solution of the catalytically active element and the catalytically inert additive is sprayed such that the catalytically active element and the catalytically inert additive are deposited on the solid support; Continue for 48 hours. The solution of the Group IIA metal compound is subsequently sprayed and the fluidization of the solid is further continued for 1-48 hours and the solid is recovered. This fluidization process is carried out at a temperature in the range of 20 to 200 ° C., in which case the support is a mechanically robust and thermally stable solid in the reaction medium, Having a pore diameter in the range of about 3 to 3000 mm and present as powders, granules, shaped or irregular flakes or pallets, sheets, monoliths, ropes and fiber solid woven fabrics, and the catalyst-inert additive Can be an organic compound, an inorganic compound, or a compound containing at least one radical derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene Or independently selected from negatively charged anions, wherein the radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded to a radical, having at least one or more negatively charged functional groups selected from The elements are separately selected from metal complexes, quaternary compounds, metal oxoanions and polyoxometalates or combinations thereof, the metal complexes having the following general formula:
(M)_x(L)_y(L^*)_z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Atom or ion, and can be a suitably selected suitable transition metal ion, including atoms Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru , Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and Zn. Preferably, the metal complex contains a metal atom or ion derived from group VIII of the periodic table of elements, x is 1 to 60, L is an aliphatic compound, aromatic compound and heterocyclic compound And the compound contains at least one radical derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, and the radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected separately from At least 1 and L^*Is a radical selected from organic anions, inorganic anions and ligand compounds, which are O, N, S, Se, Te, P, As, Sb, Bi, Si, olefins, carbenes, = C Containing at least one radical derived from: the radical having an oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to the radical, and z is 0 And the quaternary ammonium compound has the following general formula:
[(Y⁺) (R^*)_I] [Z⁻]
Where Y⁺= N⁺, P⁺, As⁺For I = 4; Y⁺= S⁺For I = 3 and R^*Are independently selected from alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, and -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻With at least one or more negatively charged functional groups selected separately from Z and Z is an anion selected from organic anions, inorganic anions and coordination complex anions. Group IIA metal cations are Ca²⁺, Sr²⁺And Ba²⁺Selected from the following compounds: The solvent used to form the Group IIA metal ion solution is an aqueous solvent, a water-miscible organic solvent, or a mixture thereof.
[0098]
The invention further extends to another preferred method for producing the catalyst according to the invention. According to this method, an anionically charged element and an anionically charged additive are deposited on this solid support and subsequently sprayed with a Group IIA metal salt solution while simultaneously removing the solvent. Is cured.
[0099]
Thus, a method of preparing a heterogeneous catalyst formulation as a solid composite material includes rotating a solid support in a rotating pan under an inert gas stream. A solution of the catalytically active element and the catalytically inert additive is sprayed such that the catalytically active element and the catalytically inert additive are uniformly deposited on the solid support. The rotation of the solid is continued for 1 to 48 hours. The solution of the Group IIA metal compound is subsequently sprayed and the spinning of the wet solid is continued for an additional 1 to 48 hours and the solid is recovered. The described method is therefore carried out at a temperature in the range of 20-200 ° C. The temperature of the process can be achieved by either heating the inert gas stream or rotating the pan (which includes the support). The laboratory equipment used to form the formulations of the present invention is represented in FIG. 6, and such equipment can be appropriately scaled depending on the capacity requirements.
[0100]
Support materials that can be used herein are mechanically robust and thermally stable solids in the reaction medium, have a pore diameter in the range of about 3 to 3000 mm, and are powders, Present as granules, regular or irregular flakes or pallets, sheets, monoliths, ropes and fiber solid fabrics.
[0101]
The catalyst inert additive is an organic compound, an inorganic compound, or a compound containing at least one radical derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene. Independently selected from at least two or more negatively charged anions, wherein the radical is -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected from Further, the catalyst inert additive can be a polymer with multiple anionic charges.
[0102]
The catalytically active element is separately selected from metal complexes, quaternary compounds, metal oxoanions and polyoxometalates or combinations thereof. A metal complex element that is catalytically active is selected to have the following general formula:
(M)_x(L)_y(L^*)_z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Atom or ion, and can be a suitably selected suitable transition metal ion, including atoms Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru , Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and Zn. Preferably, the metal complex contains a metal atom or ion from group VIII of the periodic table of elements and the suffix x indicates the number of such catalytic transition metals present in the complex, such as The number of metal elements is 1-60. Component L of the metal complex is an aliphatic compound, an aromatic compound or a heterocyclic compound, and the compound is derived from O, N, S, Se, Te, P, As, Sb, Bi, Si, an olefin, and a carbene. At least one radical of the formula₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻Having oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to a radical with at least one or more negatively charged functional groups selected from The suffix y indicates the number of ligands that are coordinated (which retains the metal in a lower coordination state), and y must be at least 1. L^*Is a radical selected from organic anions, inorganic anions and ligand compounds, which are O, N, S, Se, Te, P, As, Sb, Bi, Si, olefins, carbenes, = C Containing at least one radical derived from: the radical having an oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached to the radical. The suffix z indicates the number of such non-participating ligands. These ligands may be the same when present in plural or different, but the total number ranges from 0-7. Alternatively, another type of catalytically active element, which can be used alone or in combination with the above transition metal complex, is the quaternary ammonium compound and has the following general formula:
[(Y⁺) (R^*)_I] [Z⁻]
The compounds that can be selected here can belong to the quaternary compounds of nitrogen, phosphorus, arsenic and sulfur. Y belongs to a compound containing nitrogen, phosphorus or arsenic.⁺= N⁺, P⁺The suffix I = 4; and for sulfur compounds, Y⁺= S⁺For I = 3 and R^*Are independently selected from alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, and -SO₃ ⁻, -SO₂ ⁻, -PO₃ ^2-, -COO⁻, -O⁻, AsO₃ ^2-And -S⁻With at least one or more negatively charged functional groups selected independently from Z; Z is an anion selected from organic anions, inorganic anions and coordination complex anions. In most cases, the actual catalytic element is an anion Z⁻Is implied. Quaternary compounds not only provide anchors for solidification, but also anions Z⁻Provide the necessary electrostatic field so that it does not escape.
[0103]
Group IIA metal cations are Ca²⁺, Sr²⁺And Ba²⁺Selected from the following compounds: In the method of forming the catalyst in the coated pan as described above, the solvent used to form the solution is preferably an aqueous solvent, a water-miscible organic solvent or a mixture thereof. Such solutions are sprayed simultaneously or sequentially according to this method.
[0104]
Regardless of the method used to form the catalyst formulation, the solid catalyst ensemble can be used to catalyze a variety of reactions in the gas phase or liquid slurry. Catalysts that are rugged solids are organic in various reactor configurations (eg, fixed bed, trickle bed, fluidized bed and slurry reactor), depending on the physical state and properties of the reactants and products. There is an opportunity to select a suitable reactor configuration to produce the compound.
[0105]
The solid catalyst of the present invention can be modified as needed, wherein a film of a high boiling liquid or a low melting solid is deposited on the solid catalyst as needed. This modification can be selected to increase the local solubility of the reactants or improve the environment of the catalyst site in order to obtain high selectivity for the required product.
[0106]
The catalyst formulated according to the previously described embodiment for a particular reaction is selected from similar catalysts that catalyze such reactions in the liquid phase; similar elements may introduce a negative charge therein. Derived from such a parent catalyst in a homogeneous system by proper functionalization. The catalytically active element is derived separately from metal complexes, quaternary compounds, metal oxoanions and polyoxometalates or combinations thereof, depending on the requirements. With the exception of anionic functional groups, the remaining structure of the catalytic element is not critical to the solidification of such element. Some examples of derivatives of anionically charged elements derived from each individual soluble catalyst are shown in the table below. The types of reactions shown in the table are merely representative and the catalytic elements fall within the scope of the appended claims. Therefore, describing a solid catalyst formulation whose catalytic element is solidified by common techniques, regardless of the reaction it catalyzes, will clarify the embodiment. Such catalytic elements are clearly claimed in the claims.
[0107]
Some examples of anionically functionalized soluble catalyst elements and their applications are listed in the table below.
[0108]
[Table 1]

The catalysts supported according to the invention are very active, as demonstrated by the tests described, and this is illustrated in the following examples. Indeed, these examples relate to the application of such supported catalysts to a variety of reactions catalyzed by different mechanisms according to known molecular catalyst theory. Comparison of the reactions in the homogeneous phase of these supported catalysts demonstrates that easy separation can be easily achieved while retaining catalytic activity to a significant extent. This makes the catalyst suitable for a continuous process, thereby increasing the process economy of the catalyst. The catalyst formulation, which is essentially solid, can be easily recovered after the desired catalyst conversion in the heterogeneous phase. They can then be reused to catalyze a new charge of reactants, this operation being either continuous or repeatable, where the catalyst is several times Can play. As an advantageous fact, the catalyst formulation may be repeatable several times without a substantial decrease in its activity.
[0109]
It is essential to assess stability and incompatibility before subjecting the catalyst to catalytic reaction purposes. For this reason, various chemical stresses were applied to simulate the stresses encountered when the catalyst formulation was applied to the actual reaction. Stresses encountered during reaction or after-treatment include solvation stress due to solvent and medium. Applicable ranges of solvents include liquids used in reactions and workups (eg, washing). Washing is a preferred process for removing the adsorbed material and regenerating the catalyst so that it is activated by other chemical treatments.
[0110]
For this reason, various catalysts containing different metals (eg, rhodium, ruthenium, iridium, palladium, platinum, cobalt, nickel, molybdenum and iron) were prepared according to the method described above and in FIG. In the apparatus described in detail, it was extracted at the boiling temperature of a solvent such as water, acetic acid, methanol, isopropanol, ether, tetrahydrofuran, ethyl acetate, acetone, acetonitrile, toluene, cyclohexane. This extraction was continued for several hours and subsequently the solvent was changed. There was no appreciable loss of metal content and physical morphology was detected by visual comparison. It is clearly correct that sites containing hydroxy, methoxy and other basic radicals are destroyed. These experiments show that the catalyst is stable in a wide range of solvents and need not be limited to a particular type of solvent. Similarly, the catalyst was leached in acid and alkaline aqueous solutions and loss of metals including transition metals or Group IIA metals was detected.
[0111]
The activity of the studied catalyst is measured in the usual manner in the examples in the rotational speed, which is converted by a catalytic reaction to the catalytically active element per unit time under ideal conditions. Define the number of molecules, ie the yield over a given time.
[0112]
Various preliminary experiments were performed to confirm the applicability of the catalyst of the present invention. These preliminary experiments were aimed at understanding molecular catalysts. For this reason, a reaction was chosen in which the two products were formed with asymmetric regioselectivity. Hydroformylation is one such reaction where the reaction rate and regioselectivity change significantly as the molecular environment changes. For these reasons, hexane is replaced with HRhCO (TPPTS).₃Hydroformylation was considered as a suitable probe to understand the catalyst at the reaction conditions.
[0113]
The hydroformylation reaction involves hexene as a substrate and HRhCO (TPPTS) as an active catalytic element.₃(Rhodium 1 g / support 1 g), water content (ppm), silica as support and non-excessive ligand. Complete conversion was obtained and the catalyst was recovered by centrifugation, washed with toluene and dried in vacuo. The dried catalyst powder was reused for the hydroformylation of allyl alcohol in water. The catalyst was active for hydroformylation and an aldehyde was obtained. The post-reaction catalyst was recovered by centrifugation, dried in vacuo, and reused for hexene hydroformylation to produce an aldehyde. This experiment revealed the feasibility of continuously catalyzing the reaction in various solvents, regardless of the substrate.
[0114]
Therefore, the need for a support is HRhCO (TPPTS)₃Was confirmed by precipitation with barium nitrate. The precipitate was used to catalyze hexene hydroformylation. After 24 hours, the conversion was less than 1%.
[0115]
To make sure that the reaction takes place in the solid state and does not take place with the leaching of the complex under the reaction conditions (which eventually returns to the solid). This is verified by using the catalyst species and additional ligand mobility criteria. In the case of a soluble catalyst, the additional ligand is in a mobile state, which allows it to interact with the active species, and so on by having a low rate and a high n / I ratio. No changes in activity and selectivity were observed when the catalyst was prepared with additional ligand present. This observation was attributed to the immobile state of the ligand and catalyst. Since the ligands cannot move, their interaction with the active species is completely delayed, thereby not affecting the rate and n / i ratio.
[0116]
The catalyst immobility was further verified by adding water to the solid catalyst. High conversion was obtained at low water content (ppm / g). The activity decreased considerably with increasing water content. The same catalyst returned to its original activity when dried. This experiment finally proves that the reaction takes place in the solid state.
[0117]
Thus, a critical assessment of the lifetime of the catalyst, its stability and durability is that a 5 g catalyst is used in a tubular tri-bed reactor (Φ1 / 2 ″) at 80 ° C. and 300 psi H₂This was carried out in a tubular fixed bed reactor by subjecting the catalyst to hydroformylation with / CO (1: 1). 5% decene in toluene was pumped continuously at a feed rate of 10 ml / hr. The conversion level was 20% for aldehydes after reaching steady state (n / i 2.1). This reaction continued for 72 hours with no loss of activity. By stopping the feeding of the liquid, the reaction was stopped and the water was pumped for 1 hour. Thereafter, the feeding of the reactant was resumed. Initially there was no conversion, but this gradually resumed over 10 hours. This observation is due to the formation of a film of water on the catalyst surface, which physically delays contact between the decene and the catalyst surface. Furthermore, water does not wash away the complex catalyst, which is definitive evidence that the reaction occurs in the solid state.
[0118]
The technology of solid catalyst formulations is established in the present invention, according to which solid catalysts can be formulated and applied to catalyze reactions in a variety of solvents. The catalyst formulations cited herein were applied to various reactions according to yet another embodiment. The typical types of reactions for which catalyst formulations can be used are described in the next section. The types of reactions described here are only examples and are not limited by the scope of catalytically active elements as described above. The various types of reactions described herein are intended to outline the range of catalyst formulations under consideration, where when applied to the production of multiple organic compounds, separation of the catalyst, stability of operation Emphasis is placed on sex and convenience. The types of reactions described herein include hydroformylation, hydrogenation, carbonylation, carbon-carbon bond formation by Heck-type and Suzuki-type reactions, isomerization, epoxidation, Wacker oxidation, Michel addition. And Knovegel condensation.
[0119]
Metal-catalyzed addition of carbon monoxide and hydrogen to the olefin provides access to the aldehyde, which in some cases is subsequently hydrogenated. A wide variety of olefins can be hydroformylated to the corresponding aldehyde. Various orophisins were hydroformylated with analogs of the classic Wilkinson catalyst. Various olefins (eg hexene, styrene, cyclohexene and vinyl acetate) have been hydroformylated. Similarly, hexene was hydroformylated with rhodium modified with different ligands to control selectivity. Accordingly, other metals active in hydroformylation (eg, cobalt and palladium) were also tested.
[0120]
The palladium phosphine complex catalyzes the carbonylation of halides, alcohols and olefins in a homogeneous reaction system. Such palladium complex analogs were prepared and tested for styrene, styryl alcohol, phenylacetylene and bromobenzene. In each case, reasonable activity is obtained and the catalyst can be reused.
[0121]
Various phosphineamines, Zr, Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt phosphite complexes have various functional groups It is useful for hydrogenation. Hydrogenation of olefins, carbonyls and nitroaromatic compounds was tested using the catalyst formulated in this invention.
[0122]
Extending a substituted alkene by directly forming a carbon-carbon bond at the vinyl carbon center is a useful reaction for the preparation of various organic compounds. Such synthetic procedures are difficult to achieve with conventional organic synthesis. The palladium complex (Pd0) was found to be effective in this sense. Various palladium complexes including phosphine, metalate phosphine and phosphite are useful catalysts. Other metals such as nickel and palladium are also useful in this regard. Olefination of aryl bromides has been demonstrated using the catalyst formulation of the present invention.
[0123]
Palladium catalyzed cross-coupling reactions of aryl or vinyl boronic acids with aryl halides are well known in the art. Such a coupling reaction is carried out not only in non-polar media but also in polar media. Palladium phosphine complexes are useful in this regard. Various biaryl compounds are accessible by this reaction. The catalyst formulation of the present invention is also suitable for this type of reaction.
[0124]
Double bond isomerization is a useful reaction in converting olefins to isomerized olefins. Various transition metal complexes catalyze this type of reaction. Useful metal complexes in this regard include platinum, palladium, rhodium and cobalt. The catalyst formulations of the present invention are also useful in catalyzing this reaction.
[0125]
Current catalyst formulations are also suitable for oxidizing olefins to epoxides and acids. For example, molybdate ions can catalyze olefin epoxidation when heterogenized as quaternary ammonium ion pairs. Various phthalocyanines are also useful in this regard.
[0126]
Nucleophilic addition of mesomeric anions to activated olefins (eg, αβ unsaturated olefins) is known as the Michel reaction. A compound containing an electron withdrawing group having a relatively acidic proton is a suitable compound for forming a mesomeric anion. Such compounds include, for example, R—CH₂-Z, where Z is an electron withdrawing group (eg, CN, COOR, NO₂, CHO, etc.) and R can be alkylaryl or Z is as defined above. In the presence of a strong base, the anion R—CH^(-)Compounds for -Z add to an α-β-unsaturated olefin at the β position. The activated olefin may be represented as C = C-Z, where the carbon attached to Z is α and the adjacent carbon is β.
[0127]
In general, the catalyst used to form the mesomeric ion includes a strong base (eg, H⁻, OH⁻, MeO⁻and so on. Anionic fragments themselves are difficult to solidify, so the counter cation chosen for such is a quaternary ammonium compound, which is functionalized with an anionic functional group, and The ion pair as a whole is precipitated on the solid support. When a quaternary aluminum compound is present as an alkoxy ion pair, the solidified quaternary compound formulation is successfully washed with a solution of alkoxy anions prior to use. The condensation of diethyl malonate with ethyl acrylate, diethyl maleate, acrylonitrile is demonstrated in the examples below.
[0128]
Condensation of aldehydes or ketones (which usually do not contain alpha hydrogen and to form olefins, R-CH₂(Using compounds in the form of -Z) is referred to as the Knovengel reaction (Jones, Org. React. 1967, 15, 204-599), where Z is CHO, COR, COOH, COOR, CN, NO₂It can be. Catalysts that can generally be used for this reaction include basic amines, hydroxyl anions or alkoxy anions. Anionic fragments themselves are difficult to solidify, so the counter cation chosen for such is a quaternary ammonium compound, which is functionalized with an anionic functional group, Are precipitated on the solid support as a whole. When a quaternary aluminum compound is present as an alkoxy ion pair, the solidified quaternary compound formulation is successfully washed with a solution of alkoxy anions prior to use. Condensation of butyraldehyde to 2-ethylhexanal, benzaldehyde, condensation of acetone to dibenzylideneacetone, benzaldehyde, and condensation of acetonitrile to cinnamonitrile are shown in the accompanying examples below.
[0129]
From these descriptions it is clear that a variety of soluble catalysts can be formulated by appropriately forming anionically charged catalyst elements. These elements are structurally similar to these soluble catalyst elements. Catalysts that can be used in this connection include metal complexes and quaternary ammonium compounds, where complementary anions are catalysts (complementary anions are metal complexes, organometallic anions or inorganics). Anion).
[0130]
The present invention was conceived in accordance with some specific theory without limiting the solid catalyst formulation to one specific type of complex or reaction catalyzed by the following specific mechanism. It is recognized that a solid support having a high surface area provides mechanical strength and a surface to which insoluble catalyst material is physically implanted. This insoluble material arises from the interaction of other soluble complex catalysts containing two or more anionic functional groups with solutions of calcium, strontium and barium salts. This material is formed as a vehicle on the surface of the solid support. The composite solid assembly obtained therefrom can be suitably used as a solid catalyst.
[0131]
Furthermore, recycling and regenerating Applicant's preferred catalyst formulation can be tolerated, for example, in a given batch run, whether determined by elapsed time or monitored by substrate consumption or other parameters. When a level occurs, it is easily achieved using known methods and procedures. The container need only be brought to room temperature and expelled residual pressure (if any). This reaction mixture is then simply separated from the catalyst by simple decanting. The catalyst formulation is filtered and possibly washed with a suitable liquid for later reuse or simply refilled with the feedstock as needed to initiate the next reaction.
[0132]
The life of a catalyst can be well understood by repeatedly regenerating and working a specific catalyst formulation in either a laboratory or commercial setting, so it can be either washed with an appropriate liquid or subjected to a specific chemical treatment. Depending on the occasion, it may be further desired to regenerate the catalyst from time to time. Using Applicants' preferred catalysts, continuous reaction processes are also feasible, taking into account their insolubility and resistance to leaching or other decay. Such a process can be designed and implemented using known procedures routine in the art.
[0133]
For the purpose of facilitating a better understanding of the catalysts and methods of the present invention, reference is made to the following examples for specific cases of their preparation and use. These examples are merely representative and do not limit the scope of Applicants' invention. Various modifications and alterations of this invention will be apparent to those skilled in the art and it should be understood that such improvements and modifications fall within the scope and nature of this application and the appended claims.
【Example】
[0134]
(Experiment 1 (Verification of hypothesis))
This comparative example shows that two or more negatively charged anions are Mg²⁺Whenever it interacts with other Group IIA metal cations, a precipitate is formed, which is effectively in organic solvents (including nonpolar solvents, polar solvents (protic and aprotic solvents)). Explains the effectiveness of the hypothesis that it is insoluble and in some cases sparingly soluble in aqueous solvents. This hypothesis was verified as follows. Solutions of different anions interacted with Group IIA metal ions. An anion component solution (solution A) 0.1 mol and a Group IIA metal cation component solution (solution B) 0.1 mol were prepared. 10 ml of solution B was mixed with 50 ml of solution A in a boiling tube. The solution was mixed thoroughly on a shaker for 10 hours. The resulting suspension was centrifuged and the supernatant was decanted to remove the precipitate. The residual precipitate was diluted with distilled water, followed by repeated centrifugation and decantation three times. To this precipitate, 10 ml of methanol was added, and the procedure of centrifugation and decantation was repeated. The resulting wet precipitate was vacuum dried at 50 ° C. The mixture in which no precipitate was observed was discarded. The barium and strontium in the dried precipitate may be insoluble in water, methanol, ethanol, propanol, butanol, acetic acid, benzene, xylene, petroleum ether, ethyl acetate, acetone, methyl ethyl ketone, acetonitrile, dimethylformamide, chloroform, tetrahydrofuran. I understood. In contrast, some calcium salts were found to be sparingly soluble.
[0135]
The results are summarized in the following table.
[0136]
[Table 2]

In addition to these, EDTA acetylacetonate, a calcium hydride compound, interacted with sodium sulfate and sodium phosphate to form insoluble precipitates.
[0137]
(Experiment 2)
(Synthesis of high purity fuming sulfuric acid)
A 2-liter three-necked flask was equipped with a distillation condenser and addition funnel, and at the other end was fitted with a collection container with a bottom drain valve. The distillation cooler was also equipped with a pressure relief non-return valve. In a flask, a magnetic bar is installed, and 500 g of P₂O₅Filled. In a collection container, 45 ml of concentrated H₂SO₄Put. Add 400 ml of concentrated H to the addition funnel₂SO₄Put. The addition was started over 2 hours with simultaneous magnetic stirring. The flask temperature was slowly increased until sulfur trioxide began to distill slowly. Concentrate H until the total volume of liquid in the collection container reaches 148 ml₂SO₄Inside, sulfur trioxide was collected, heating was stopped, and the assembly was disassembled.
[0138]
(Experiment 3)
(Synthesis of triphenylphosphine trisulfonate)
Triphenylphosphine trisulfonate was synthesized by the following procedure. 50 g of triphenylphosphine was placed in the sulfonation reactor followed by vacuum argon degassing and covered with argon. The sulfonation reactor was cooled to 5 ° C., and the sulfonation reactor was charged with 200 g of sulfuric acid so that the temperature of the reactor did not exceed 10 ° C. The addition of sulfuric acid was carried out over 2 hours with constant stirring with a mechanical stirrer. The reaction mixture had a pale yellow color. The reactor was charged with 280 g of 65% fuming sulfuric acid prepared by the previous experiment over 60 minutes. The temperature of the sulfonation reactor was raised to 22 ° C. and the reaction was continued for 76 hours. Thereafter, the temperature of the reaction was lowered to 0 ° C., and 50 ml of distilled and degassed water was introduced into the sulfonation reactor over a period of 3-4 hours so that the temperature did not rise above 5 ° C. This solution was further diluted with 500 ml of water. The diluted solution was transferred to a 3 liter jacketed vessel and cooled to 5 ° C. and finally neutralized with 50 wt% aqueous NaOH (which was previously degassed). At the neutralization point, the solution had a bright yellow color. In this case, the addition of NaOH was stopped and the pH was lowered to 6 by adding concentrated sulfuric acid. Sodium sulfate formed during neutralization partially precipitated and was removed by filtration, and the resulting solution was concentrated to 300 ml under reduced pressure. The formed sodium sulfate was removed by filtration. The mother liquor containing TPPTS was further diluted with 2000 ml of degassed methanol and refluxed for 2 hours, during which time most of the sodium sulfate precipitated and the supernatant extract of TPPTS in methanol was removed by filtration. The TPPTS extract in methanol was evaporated to dryness to give a white solid (P³¹Purity> 95% by NMR). This solid was dissolved in a minimum amount of water and reprecipitated with degassed ethanol to obtain a TPPTS with a purity exceeding 99%.
[0139]
(Experiment 4)
(Synthesis of P-phenyl-3,3'-phosphine dialibis (benzenesulfonic acid) disodium)
Orthoboric acid (48 g) was dissolved in 98% concentrated sulfuric acid (200 ml), and 200 ml of 65% fuming sulfuric acid was added thereto. Excess sulfur trioxide was removed by raising the temperature of the solution to 60 ° C. and providing a gas trap attachment device containing calcium oxide under high vacuum (the trap was cooled to −10 ° C.). The solution of orthoboric acid and sulfur trioxide was cooled to 5 ° C., and 30 g of triphenylphosphine was added under an argon blanket. The resulting mixture was stirred with a mechanical stirrer, the reactor temperature was raised to 58 ° C. and the reaction was continued for 90 hours. The temperature was lowered to 0 ° C. and hydrolyzed with 500 ml of degassed water. The solution was neutralized with 50 wt% aqueous sodium hydroxide until neutralized, the formed precipitate was removed by filtration, and the mother liquor was concentrated to 300 ml, diluted with 1000 ml of methanol and refluxed for 2 hours. The resulting precipitate was removed by filtration. Upon evaporation of the extract in methanol, a solid was obtained, which was suspended in 1000 ml of methanol, to which 50 g of microcrystalline cellulose avicel was added, followed by concentrated H₂SO₄(20 ml) was added and refluxed for 6 hours under an argon blanket. The solution was cooled and filtered to remove Avicel. To this, 50 g of Avicel (registered trademark) was added again, and the mixture was further refluxed for 6 hours. The suspension was filtered, the methanol-containing extract was neutralized with 50 wt% NaOH and filtered. The solution was evaporated to give an accurate elemental analysis of the white compound.
[0140]
(Experiment 5)
(Synthesis of 3,3 ', 3 "-phosphine trialtris (4-methylbenzenesulfonate) trisodium)
Orthoboric acid (g, 6.6 mmol) was dissolved in concentrated sulfuric acid (96%, 3.75 ml), and (2-methylphenyl) phosphine (0.50 g, 1.4 mmol) was added to the reaction mixture. Dissolved. While the temperature of the reaction mixture was 0 ° C., fuming sulfuric acid (6.75 ml, 65% by weight) was added dropwise. After stirring for 72 hours at 25 ° C., the temperature was lowered to 0 ° C. and the mixture was hydrolyzed by adding 5 ml of degassed water. The solution was neutralized with 50 wt% aqueous sodium hydroxide until neutralized, the precipitate formed was removed by filtration, and the mother liquor was concentrated to 3 ml, diluted with 10 ml of methanol and refluxed for 2 hours. The resulting precipitate was removed by filtration. Upon evaporation of the methanol extract, a solid is obtained, which is suspended in 10 ml of methanol, to which 0.5 g of microcrystalline cellulose Avicel is added, followed by concentrated H₂SO₄(0.5 ml) was added and refluxed for 6 hours under an argon blanket. The solution was cooled and filtered to remove Avicel. To this, 0.5 g of Avicel was added again and the mixture was further refluxed for 6 hours. The suspension was filtered, the methanol-containing extract was neutralized with 50 wt% NaOH and filtered. The solution was evaporated to give an accurate elemental analysis of the white compound.
[0141]
(Experiment 6)
(Synthesis of sodium salt of sulfonated tribenzylphosphine)
Sulfonation of tribenzylphosphine was performed in the same manner as triphenylphosphine, except that the exact degree of sulfonation was not established. For further experiments, a reaction mixture containing di- and trisulfonated phosphine was used.
[0142]
(Experiment 7)
(Sulphonation of 1-3 bis-diphenylphosphinopropane)
4.95 g (12 mmol) of diphenylphosphinopropane are dissolved in 37.5 ml (98%) of a reaction mixture of 4 g (64.7 mmol) of orthoboric acid and cooled to 0 ° C., over which 65% 67.5 ml of fuming sulfuric acid was added dropwise. After the addition, the reaction mixture was brought to 25 ° C. and stirred for 48 hours. After this, the reaction mixture was brought to 0 ° C. and hydrolyzed with 50 ml of degassed water. The solution was neutralized with 50 wt% aqueous sodium hydroxide to pH 7, the precipitate formed was removed by filtration, and the mother liquor was concentrated to 30 ml, diluted with 100 ml methanol and refluxed for 2 hours. The resulting precipitate was removed by filtration. Upon evaporation of the methanol extract, a solid is obtained, which is suspended in 100 ml of methanol, to which 5 g of microcrystalline cellulose avicel is added, followed by concentrated H₂SO₄(1 ml) was added and refluxed for 6 hours under an argon blanket. The solution was cooled and filtered to remove Avicel. To this, 5 g of Avicel was added again, and the mixture was further refluxed for 6 hours. The suspension was filtered, the methanol-containing extract was neutralized with 50 wt% NaOH and filtered. The solution was evaporated to give a white compound.
[0143]
(Example 8)
(Sulfonation of 1-2 bis-diphenylphosphinoethane)
Preparation was performed in a similar manner as described in previous experiments.
[0144]
(Experiment 9)
(Synthesis and sulfonation of 2,2'-bis (diphenylphosphinomethyl) -1,1'-biphenyl (bisbi))
A 3 liter three-necked flask is equipped with a sealed mechanical stirrer, reflux condenser and thermometer. In this flask, 89 g (0.5 mol) of phenanthrene is dissolved in 1 liter of glacial acetic acid and warmed to 85 ° C. in a water bath. In 40 minutes, 345 ml (4 mol) of 30% hydrogen peroxide solution was introduced, the temperature was lowered to about 80 ° C., continued for 6 hours, and acetic acid and water were removed under reduced pressure to give a brown solid. The residue is decomposed with 2N sodium hydroxide solution and 4 g of powdered charcoal are added, the mixture is warmed to 75 ° C. and filtered. The filtrate was acidified to pH 2 with concentrated HCl. The white precipitate was filtered and dried at 50 ° C. (melting point 109 ° C.). The resulting 69% of 69% material is sufficiently pure for further synthesis.
[0145]
A 3 liter three-necked flask is equipped with a sealed mechanical stirrer, reflux condenser and thermometer. The flask was cooled to 0 ° C. in an ice salt bath. A reaction vessel was charged with 24.2 g (0.1 mol) of diphenic acid and 15.12 g (0.4 mol) of sodium borohydride. To this solid powder, 200 ml of dry tetrahydrofuran was added in such a way as to minimize foaming. After 1 hour, the suspension became homogeneous and was maintained at 0.2 mol H in 100 ml tetrahydrofuran over 2 hours while maintaining the temperature at 0 ° C.₂SO₄Was added. After the addition was complete, the mixture was allowed to stir at room temperature for 24 hours. To this white suspension was added 30% NaOH (100 ml) and refluxed for 4 hours, and the liquid was brought to room temperature and extracted with chloroform to give a white solid. This was used further without purification.
[0146]
The diol intermediate (0.08 mol) from the preparation described above was dissolved in chloroform and transferred to a two-necked flask (which was equipped with a condenser and guard tube, pressure equalization addition vessel). One drop of pyridine was added to the flask, 0.2 mol of thionyl chloride was dissolved in 25 ml of chloroform, and the addition vessel was filled. At room temperature, thionyl chloride was added to the round bottom flask. A significant amount of sulfur dioxide and hydrogen chloride escaped from the guard tube during the addition. The temperature of the flask was raised until the chloroform began to reflux. After 5 hours, the reaction was quenched by adding water. Chloroform was dried by extracting with bicarbonate solution followed by water and passing through a sodium sulfate bed. Chloroform was evaporated at 50 ° C. under reduced pressure to give a yellow oil (irritating and irritating to the skin) which was distilled under high vacuum to give a pale yellow oil. .
[0147]
(The following procedure was taken from US Pat. No. 4,879,416)
To a 500 ml flask equipped with a mechanical stirrer, thermowell, addition funnel and condenser was added 16.77 g (0.064 mol) triphenylphosphine, 64 ml tetrahydrofuran and 0.88 g (0.128 atoms) lithium wire. The flask was cooled to 15 ° C. The reaction mixture was stirred overnight to give a red solution with complete dissolution of lithium. The flask was further cooled to 5 ° C., 5.92 g (0.064 mol) of tert-butyl chloride was added, the temperature was raised to 50 ° C. and maintained for 2 hours. The reaction mixture was cooled and to this was slowly added 7.5 g of the above dichloride. The temperature of the reaction mixture was raised to gently boil. The reaction was quenched by adding 5 ml of methanol. The reaction mixture was evaporated to give a sticky mass that was dissolved in enough diethyl ether and washed with water. Diethyl ether was evaporated to give a pale yellow sticky mass, which was recrystallized from THF / methanol to give fine crystals of white material.
[0148]
This material was sulfonated according to the method described for diphenylphosphinopropane. It was soluble in water to produce a white compound.
[0149]
(Experiment 10)
(Sulfonation of (R) BINAP (2,2'-bisdiphenylphosphino-1,1'-binaphthyl))
The sulfonation procedure was taken from US Pat. No. 5,756,838. (R) BINAP (0.5 g) was dissolved in 1.75 ml of concentrated sulfuric acid at 10 ° C. under argon. Then, over 2 to 3 hours, 7.5 ml of fuming sulfuric acid (40 wt%) was added dropwise, and the resulting mixture was stirred at 10 ° C. for 76 hours. After stirring, the mixture was slowly poured into 100 g of ice, followed by dropwise addition of 50 wt% NaOH until the solution was neutralized to pH7. The resulting solution was concentrated to 30 ml under reduced pressure. To precipitate sodium sulfate, 100 ml of methanol was added thereto. The methanol-containing extract was evaporated under reduced pressure to give a solid, which was dissolved in methanol and filtered. Methanol was evaporated to give a white solid. Similarly, sBINAP was sulfonated.
[0150]
(Experiment 11)
(Sulphonation of (S, S Kiraphos) (S) (S) 2,3-bisdiphenylphosphinobutane)
The sulfonation procedure is described in Alario et al. Chem. Soc. , Chem. Commun. , 1986, 202.
[0151]
(Experiment 12)
(Sulfonation of R-Prophos 1,2 (S) bisdiphenylphosphinopropane)
The sulfonation procedure was taken from Amrani et al., Organometallics 1989, 8, 542.
[0152]
(Experiment 13)
(Sulfonation of R, R 2-5, bisdiphenylphosphinopentane)
The sulfonation procedure was adopted from Amrani et al., Organometallics 1989, 8, 542 Sulphonation of 2-pyridine phosphine.
[0153]
(Experiment 14)
(Synthesis of triphenylamine sulfonic acid sodium salt)
The reactor was charged with 2 g of triphenylamine, and 20 cc of concentrated sulfuric acid was added thereto. The mixture was stirred until the amine was dissolved. To this mixture with rapid stirring, 20 cc of fuming sulfuric acid (65%) was added and the reactor was cooled to about 20 ° C. After the fuming sulfuric acid was added, the reactants and contents were heated to 50 ° C. and maintained at this temperature for 48 hours. The reactor and its contents were cooled and distilled water (10 cc) was added to the reaction mixture to quench the fuming sulfuric acid. To this solution was added 50% NaOH solution under cooling (10 ° C.) until the sulfuric acid solution was neutralized. The solution was concentrated and then methanol was added to extract the water soluble ligand from the sodium sulfate powder. The methanol was evaporated to give a water-soluble sodium salt of triphenylaminosulfonic acid (1.6 g). This product consists of a mixture of bis and greater than 95% trissulfonated product. These can be used as they are in the synthesis of catalytic metal complexes.
[0154]
(Experiment 15)
(Tribenzylamine trisulfonic acid trisodium salt)
The reactor was charged with 2 g of tribenzylamine, and 20 cc of concentrated sulfuric acid was added thereto. The mixture was stirred until the amine was dissolved. To this mixture with rapid stirring, 20 cc of fuming sulfuric acid (65%) was added and the reactor was cooled to about 20 ° C. After the fuming sulfuric acid was added, the reactants and contents were heated to 50 ° C. and maintained at this temperature for 48 hours. The reactor and its contents were cooled and distilled water (10 cc) was added to the reaction mixture to quench the fuming sulfuric acid. To this solution was added 50% NaOH solution under cooling (10 ° C.) until the sulfuric acid solution was neutralized. The solution was concentrated and then methanol was added to extract the water soluble ligand from the sodium sulfate powder. The methanol was evaporated to obtain a water-soluble sodium salt of tribenzylaminosulfonic acid (1.7 g). The degree of sulfonation is H¹Established by NMR and elemental analysis.
[0155]
(Experiment 16)
(Synthesis of 2,2'-bipyridine sulfonic acid sodium salt)
The reactor was charged with 2 g of 2,2'-bipyridine, and 20 cc of concentrated sulfuric acid was added thereto. The mixture was stirred until the amine was dissolved. To this mixture with rapid stirring, 20 cc of fuming sulfuric acid (65%) was added and the reactor was cooled to about 20 ° C. After the fuming sulfuric acid was added, the reactants and contents were heated to 50 ° C. and maintained at this temperature for 48 hours. The reactor and its contents were cooled and distilled water (10 cc) was added to the reaction mixture to quench the fuming sulfuric acid. To this solution was added 50% NaOH solution under cooling (10 ° C.) until the sulfuric acid solution was neutralized. The solution was concentrated and then methanol was added to extract the water soluble ligand from the sodium sulfate powder. The methanol was evaporated to obtain a water-soluble sodium salt of 2,2'-bipyridinedisulfonic acid (1.2 g). This product is used for elemental analysis and¹As apparent from 1 H NMR, it consists of a mixture of bissulfonated products. These can be used as they are in the synthesis of catalytic metal complexes.
[0156]
(Experiment 17)
(Sulfonation of 2-phenylpyridine)
The reactor was charged with 2 g of 2-phenylpyridine, and 20 cc of concentrated sulfuric acid was added thereto. The mixture was stirred until the amine was dissolved. To this mixture with rapid stirring, 20 cc of fuming sulfuric acid (65%) was added and the reactor was cooled to about 20 ° C. After the fuming sulfuric acid was added, the reactants and contents were heated to 50 ° C. and maintained at this temperature for 48 hours. The reactor and its contents were cooled and distilled water (10 cc) was added to the reaction mixture to quench the fuming sulfuric acid. To this solution was added 50% NaOH solution under cooling (10 ° C.) until the sulfuric acid solution was neutralized. The solution was concentrated and then methanol was added to extract the water soluble ligand from the sodium sulfate powder. The methanol was evaporated to give a water-soluble sodium salt of 2-phenylpyridine sulfonic acid (1.2 g). This product consists of a mixture of bissulfonated products, as evidenced by elemental analysis. These can be used as they are in the synthesis of catalytic metal complexes.
[0157]
(Experiment 18)
(Synthesis of 2-3 bisdiphenylphosphinosuccinic acid sodium salt)
To a reaction system containing a solution of dimethyl maleate (50 g) in chloroform (100 ml) was added bromine (15 ml) in chloroform (100 ml) over 2 hours. The reaction mixture was stirred for 2 hours. At the end of the reaction, the mixture was washed twice with 100 ml of saturated sodium thiosulfate and then twice with 100 ml of water. The organic portion was passed through 5 g of sodium sulfate and subsequently treated with activated carbon. The chloroform was stripped to give 60 g of oil. Subsequent reactions were set up in a 250 ml three-necked glass vessel (which was equipped with an addition funnel, a magnetic stirrer and a rubber septum). The assembly was flushed with argon. To this vessel was added a finely cut lithium ribbon (500 mg), the assembly was degassed and refilled with argon. To this assembly, 50 ml of tetrahydrofuran was added using an airtight annotator while maintaining an argon blanket. The addition funnel was charged with 8.3 ml of chlorodiphenylphosphine, degassed and refilled with argon. The contents of the addition funnel were dropped into the lithium suspension and the solution began to turn red during the lithium dissolution, and after the lithium was completely dissolved, the reaction mixture was stirred for 4 hours.
[0158]
In a separate 250 ml container (which is equipped with a reflux condenser and a rubber septum), a syringe was charged with 30 ml of dry tetrahydrofuran, the assembly was evacuated and refilled with argon. To this, 4.52 g of diethyl maleate bromide was transferred with a syringe, followed by 30 ml of lithium phosphide solution (red). The contents of the reaction mixture were maintained at 80 ° C. for 12 hours. To this reaction mixture, 1 ml of methanol was added, and tetrahydrofuran was removed under reduced pressure. The syrupy orange liquid was washed twice with 25 ml of ether. 1 g of this syrupy orange product was transferred to a three-necked round bottom flask equipped with a reflux condenser, flushed thoroughly with argon and refluxed with 20 ml of 2% sodium hydroxide. When the reaction mixture was cooled to 5 ° C., a white material of diphosphine precipitated and was collected by filtration to give 1 g.
[0159]
(Experiment 19)
(Quaternization of tribenzylamine trisulfonate with benzyl chloride)
To a mixture of tribenzylamine trisulfonate (0.1 mol) and benzyl chloride (0.2 mol), 50 ml of water and 50 ml of dimethylformamide were added. The solution was stirred at 70 ° C. for 76 hours and the reaction was monitored by the disappearance of benzyl chloride. The reaction mixture was evaporated under reduced pressure to give a solid mass which was dissolved in a minimum amount of water and the aqueous solution was washed with diethyl ether. The aqueous extract was dried under reduced pressure and the solid was stored dry.
[0160]
(Experiment 20)
(Synthesis of quaternary ammonium hydroxide)
17 g (0.1 mol) of silver nitrate was dissolved in 170 ml of distilled water and warmed to 85 ° C., to which 3.9 g (0.097 mol) of sodium hydroxide was added. The mixture was stirred vigorously until the precipitate solidified. The precipitate was collected by centrifugation and suspended in 100 ml of water, to which the quaternary ammonium compound (0.09 mol) was added. The reaction mixture was stirred for 3 hours under nitrogen and filtered. The liquid was evaporated under reduced pressure at room temperature to give a solid.
[0161]
(Experiment 21)
(Quaternization of triphenylamine with benzyl chloride)
To a mixture of triphenylamine trisulfonate (0.1 mol) and benzyl chloride (0.2 mol), 50 ml of water and 50 ml of dimethylformamide were added. The solution was stirred at 70 ° C. for 76 hours and the reaction was monitored by the disappearance of benzyl chloride. The reaction mixture was evaporated under reduced pressure to give a solid mass which was dissolved in a minimum amount of water and the aqueous solution was washed with diethyl ether. The aqueous extract was dried under reduced pressure and the solid was stored dry.
[0162]
(Experiment 22)
(Formation of quaternary ammonium hydroxide of quaternary ammonium salt of n-benzyltriphenylamine)
(Experiment 23)
(Synthesis of hydridocarbonyltris (trisodium triphenylphosphine trisulfonate) rhodium (I))
This procedure was taken from US Pat. No. 4,994,427 issued February 19, 1991 to Davis et al. 500 mg of acetylacetonate dicarbonylrhodium (I) was added to 10 ml of a vigorously stirred and degassed aqueous solution of 4 g sodium triphenylphosphine trisulfonate in water. After dissolution is complete, 1: 1 H₂Stirring was continued for 6 hours under an atmosphere of / CO. The solution was then centrifuged to remove precipitated rhodium. To this solution, 1: 1 H₂80 ml of absolute ethanol saturated with / CO was added to precipitate the desired complex. The precipitate was collected and dried in vacuo.
[0163]
(Experiment 24)
(Dichlorobis (tristriphenylphosphine sulfonate trisodium) palladium (II))
This procedure is described in Jiang et al. Mol. Catal. A: Adopted from Chemical 130 (1998) 79-84 and placed in a Schlenk flask with PdCl₂(100 mg) and 2M HCl (2 ml) are added and the mixture is added to PdCl₂The mixture was stirred at 50 ° C. until it completely dissolved. The flask was cooled to room temperature and flushed with argon, and then TPPTS (0.80 g) was added to the flask with stirring. The color of the solution immediately changed from dark red to yellow. After stirring for 10 minutes, 15 ml of ethanol was added and a bright yellow powder precipitated and the mixture was stirred for 30 minutes. The filtered precipitate was washed 3 times with 30 ml of 95% warm ethanol and dried in vacuo.
[0164]
(Experiment 25)
(Trans-PtCl₂(TPPTS)₂Synthesis)
Platinum complex PtCl₂(NCPh)₂(235 mg, 0.5 mmol) was dissolved in 10 ml of toluene. To this solution was added an aqueous solution (10 ml) of TPPTS (568 mg, 1 mmol). To this mixture was added 3 ml of isopropanol and the reaction mixture was stirred at 50 ° C. for 10 hours. PtCl₂(TPPTS)₂・ 6H₂The complex was recovered from the aqueous phase by evaporating O (620 mg).
[0165]
(Experiment 26)
(NiCl₂/ TPPTS synthesis)
Nickel chloride hexahydrate (0.05 mol) was reacted with tppts (0.12 mol) in enough water to dissolve and the formed complex was precipitated with ethanol.
[0166]
(Experiment 27)
(Synthesis of IrCl (COD) / TPPTS)
IrCl (COD) (0.01 mol) was dissolved in a minimum amount of toluene and replaced with tppts (0.04 mol) dissolved in a minimum amount of water. The toluene layer was removed and the aqueous layer was dried.
[0167]
(Experiment 28)
([Ru (Cl) (μ-Cl) (TPPTS)₂]
This method is described in M.M. Hernandez et al. Mol. Catal. A: Adopted from Chemical 116 (1997) 117-130. RuCl₂(PPh₃)₃(5.8 g, 6 mmol) was dissolved in 150 ml of tetrahydrofuran and heated to 60 ° C. While stirring vigorously, 30 ml of an aqueous solution of TPPTS (6.3 g, 10.1 mol) was added dropwise. The biphasic medium was further stirred at 60 ° C. for 30 minutes. After cooling to room temperature, 140 ml of the orange organic layer was removed. The resulting solution was removed by filtration. The crimson aqueous phase was then evaporated to dryness and further dried in vacuo.
[0168]
(Experiment 29)
([Ru (H) (Cl) (TPPTS)₃]
This method is described in M.M. Hernandez et al. Mol. Catal. A: Adopted from Chemical 116 (1997) 117-130. This complex is represented by [Ru (H) (Cl) (PPh₃)₃It was prepared from. PhCH₃(3 g, 3.3 mmol) was added to 120 ml of tetrahydrofuran; TPPTS (5 g, 8 mmol);₂Dissolved in O (30 ml). A light purple solid was recovered from the aqueous phase.
[0169]
(Experiment 30)
([Ru (H)₂(TPPTS)₄]
RuCl₃・ 3H₂O (0.1 g, 0.38 mmol) and TPPTS (1.07 g, 1.72 mmol) were dissolved in 10 ml of distilled water. The deep brown solution was stirred at room temperature while passing a stream of hydrogen. 10 minutes later, NaBH₄(0.17 g, about 4.5 mmol) was added. The solution foamed vigorously and instantly turned tan. The mixture was heated to 50 ° C. for 10 minutes, cooled and evaporated to dryness to give a solid.
[0170]
(Experiment 31)
(Synthesis of Ru / Binapt Complex)
In a 1: 8 benzene ethanol mixture, [Ru (benzene) Cl₂]₂(0.01 g) and 2 equivalents (0.05 g) of R-binaphth 4SO₃Ruthenium Binaphth 4SO by reacting with Na₃Na catalyst was prepared and 4.5 ml of [Ru (benzene) Cl] R-binaphth 4SO₃Na was obtained. The resulting solution was vacuum dried.
[0171]
(Experiment 32)
(Rh⁺/ Synthesis of Kiraphos Tetrasulfonate Complex)
[Rh (COD) Cl] in water at room temperature in the presence of excess sodium perchlorate₂Is reacted with 2 molar equivalents of a sulfonate ligand to give Rh⁺/ Tilaphos tetrasulfonate catalyst was prepared to form a cation complex.
[0172]
(Experiment 33)
(Synthesis of palladium acetate sulfonate-bipyridyl complex)
The synthetic procedure is described by Brink et al., Chem. Commun, 1998, 2359-2360. Pd (OAc)₂(0.1 mmol) and sulfonated bipyridyl (0.1 mmol) were stirred overnight with 42.5 g of water to give a clear orange solution, which was evaporated to dryness.
[0173]
(Experiment 34)
(Cobalt (II) 4,4 ′, 4 ″, 4 ″ ′-tetrasulfophthalocyanine tetrasodium salt (procedure is Inorg. Chem. Vol 4, No. 4 April 1965, 469-471) )
4-sulfophthalic acid monosodium salt (4.32 g, 0.0162 mol), ammonium chloride (0.47 g, 0.009 mol), urea (5.8 g, 0.097 mol), ammonium molybdate (0.068 g, 0 0.00006 mol) and cobalt sulfate (II) · 2H₂O (1.36 g, 0.0048 mol) and 100 ml of celite were ground together in nitrobenzene to form a uniform paste and in a round bottom flask (which was equipped with a reflux condenser) Dilute to 50 ml with nitrobenzene. The reaction mixture was heated to 180 ° C. The reaction mixture was heated slowly with overhead stirring while maintaining the temperature at 180-190 ° C. The heterogeneous mixture was heated at 180 ° C. for 6 hours. The crude product was recovered by cooling the reaction mixture to remove nitrobenzene. The solid cake was washed with hexane until the nitrobenzene was removed, followed by methanol. The solid residue was transferred to 110 ml of 1N hydrochloric acid (saturated with sodium chloride). The mixture was briefly heated to boiling, cooled to room temperature and filtered. The resulting solution was dissolved in 0.1N NaOH (70 ml). The solution was heated to 80 ° C. and insoluble impurities were immediately separated by filtration. To the solution, sodium chloride (27 g) was added and the slurry was heated to 80 ° C. until ammonia evolution ceased. The reaction mixture was cooled to room temperature and filtered. This reprecipitation process was repeated twice, the solid was filtered and washed with 80% ethanol until the filtrate was free of chloride ions when tested with silver nitrate solution. The solid is refluxed in 20 ml of ethanol for 4 hours to give a pure product which is converted to P₂O₅To give 65% of the correct element.
[0174]
(Experiment 35)
(Copper (II) 4,4 ', 4 ", 4"'-tetrasulfophthalocyanine tetrasodium salt)
This compound is copper sulfate 5H₂Except for O (0.0048 mol), a similar molar ratio of the reactants was used as described for the tetrasodium salt of cobalt (II) 4,4 ′, 4 ″, 4 ″ ′-tetrasulfophthalocyanine. Prepared and purified.
[0175]
(Experiment 36)
(Manganese (II) 4,4 ', 4 ", 4"'-tetrasulfophthalocyanine tetrasodium salt)
This compound is used for the tetrasodium salt of cobalt (II) 4,4 ′, 4 ″, 4 ″ ′-tetrasulfophthalocyanine, using a similar molar ratio reactant, except for manganese acetate (0.0048 mol). Prepared and purified as described.
[0176]
(Experiment 37)
(Tetrasodium salt of oxidation adduct of iron (III) 4,4 ', 4 ", 4"'-tetrasulfophthalocyanine)
This compound uses four reactants of cobalt (II) 4,4 ′, 4 ″, 4 ″ ′-tetrasulfophthalocyanine using a similar molar ratio of reactants except for iron (III) chloride (0.0048 mol). Prepared and purified as described for the sodium salt.
[0177]
(Experiment 38)
(Water-soluble cobalt (II) complex N, N'-ethylenebis (salicyldiamine 5-sodium sulfonate))
The synthesis of this complex is described in Kevin et al. Chem. Soc. Dalton Trans. Performed according to 1982,109.
[0178]
Concentrated sulfuric acid (95cm³), N-phenylsalicyldiamine (35 g) is added, the mixture is stirred occasionally and heated for 2 hours while keeping the temperature at 100 ± 5 ° C., after cooling, the solution is slowly poured into ice water to give a yellow color A precipitate was obtained, which was subsequently recrystallized from water to give a crystalline yellow compound (20 g).
[0179]
25.5 g of the above product was dissolved in 500 ml of water, and 8.4 g of anhydrous sodium carbonate was slowly added to this solution and stirred until bubbling ceased. The aniline was steam distilled and the aqueous solution was dried in vacuo to give a solid that was purified by precipitation from water and ethanol.
[0180]
(Na₂[Co (SO₃Salt)] 3H₂O)
This compound, CoCl₂・ 6H₂O (6 g, 25 mmol) was dissolved in 30 cc of water and added to a 20 cc solution of salicylaldehyde 5 disodium sulfonate (13.2 g, 50 mmol) in water and the mixture was heated for 10 minutes. After filtration, the solution was concentrated and cooled to give 12 g of crystalline complex.
[0181]
(N, N'-ethylenebis (salicyldiamine 5-sodium sulfonate))
Na₂[Co (SO₃salt)]₂・ 3H₂To O (5.5 g, 10 mmol) was added 100 cc of ethanol, 15 cc of water and ethylenediamine (0.6 g, 10 mmol) and the mixture was refluxed for 1 hour under nitrogen atmosphere. A dark brown feathery precipitate was collected.
[0182]
(Experiment 39)
(Preparation of support for catalyst preparation)
All support materials were procured from commercial suppliers and used without further reduction in dimensions. Support specifications were provided with appropriate specifications. The support material was extracted from hexane, ether, methanol and water using the assembly described in FIG.
[0183]
(Surface saturation with Group IIA ions)
Each support was divided into 25 g lots and suspended in 500 ml of 5% barium nitrate solution. The suspension was refluxed for 24 hours. The suspension was brought to room temperature, the solid was filtered and transferred to the extractor described in FIG. 3 and extracted with 500 ml of water, acetone and petroleum ether (bp 60-80 ° C.). The solid was vacuum dried and stored for further use.
[0184]
The said support body was deaerated just before use with the following procedures. The required amount was transferred to a round bottom flask (which is equipped with a two-way valve), degassed with 0.1 mm Hg, the temperature was raised to 150 ° C. and maintained at this temperature for 1 hour while maintaining the vacuum. The vacuum inlet was closed, argon was introduced, and the flask was cooled to room temperature. This procedure was repeated at least 3 times and the solid was stored for further use under argon. Accordingly, the following supports were prepared: silica, gamma alumina, zirconia, titania, diatomaceous earth, bentonite, hyflo supercell, asbestos powder, magnesium hydrotalcite, barium sulfate, charcoal, bone ash.
[0185]
(Examples 1 to 84)
(Preparation of catalyst formulation by coprecipitation)
The following example illustrates one procedure for preparing the catalyst formulation of the present invention according to a formulation method known as coprecipitation in bulk liquid.
[0186]
The general procedure for preparing a heterogeneous catalyst formulation is as the production of a solution of an anionically charged catalyst element, a catalyst inert anion additive (referred to as Solution A) and a Group IIA metal solution (referred to as Solution B) Described in this specification. The support pretreated as described above is suspended in an aqueous or water-miscible solvent and the resulting suspension is vigorously stirred and added over a long time to the suspensions A and B to obtain The resulting suspension was further agitated for a specified time. The suspension was centrifuged and the solid was washed repeatedly with water, methanol and diethyl ether and subsequently dried in vacuo. The dry powder was stored in an airtight container under argon, which can be used for an appropriate reaction, depending on the catalytically active element incorporated therein.
[0187]
Note 1: Solution A is prepared by dissolving an anionic component (which contains an anionic complex and additives that produce a homogeneous solution) in a degassed solvent. The resulting solution is also degassed by purging with argon.
[0188]
Note 2: Solution B is prepared by dissolving the Group IIA metal salt. The solution was degassed before use.
[0189]
Note 3: Addition of A and B is performed at room temperature unless otherwise specified.
[0190]
[Table 3]

(Examples 85-168)
(Preparation of catalyst formulation by sedimentation)
The following example illustrates one procedure for preparing the catalyst formulation of the present invention according to a formulation method known as coprecipitation near the surface of a solid support.
[0191]
The general procedure for preparing a heterogeneous catalyst formulation is as the production of a solution of an anionically charged catalyst element, a catalyst inert anion additive (referred to as Solution A) and a Group IIA metal ion solution (referred to as Solution B). As described herein. A defined amount of support pretreated as described above is impregnated with solution A by wetting the solid with the solution, followed by evaporation to form a dry solid support having the anionic component of solution A. obtain. The solid powder is gradually added to Solution B over a specified time. The resulting suspension is further stirred for a specified time. The suspension was centrifuged and the solid was washed repeatedly with water followed by drying in vacuo. The dry powder was stored under argon in an airtight container. These solid catalyst formulations can be used in suitable reactions, depending on the catalytically active element incorporated therein.
[0192]
Note 1: Solution A is prepared by dissolving an anionic component (which contains an anionic complex and additives that produce a homogeneous solution) in a degassed solvent. The resulting solution is also degassed by purging with argon.
[0193]
Note 2: Solution B is prepared by dissolving the Group IIA metal salt. The solution was degassed before use.
[0194]
Note 3: Impregnation of the solution on the solid support is carried out by wetting the solid with solution A and evaporating in vacuo at 50 ° C. unless otherwise stated.
[0195]
Note 4: Addition of impregnated solid with component A to solution B is performed at ambient temperature unless otherwise specified.
[0196]
[Table 4]

(Examples 169 to 252)
(Preparation of catalyst formulation by sedimentation while simultaneously removing water)
The following example illustrates one procedure for preparing the catalyst formulation of the present invention according to the method of formulation known as coprecipitation near the surface of the solid support.
[0197]
The general procedure for preparing a heterogeneous catalyst formulation is as the production of a solution of an anionically charged catalyst element, a catalyst inert anion additive (referred to as Solution A) and a Group IIA metal solution (referred to as Solution B). As described herein. A defined amount of support pretreated as described above is impregnated with solution A by wetting the solids with the solution, followed by evaporation to form a dry solid support having the anionic component of solution A. obtain. The solid powder is suspended in a water miscible solvent or a solvent that forms an azeotrope with the solvent component of Solution B. The suspension was stirred and the temperature was raised to start the distillation of the solvent. Under this condition, Solution B was slowly pumped. At the same time, the solvent in which the solids are suspended is also pumped at a rate similar to the distillation rate. Once all the solution B is added, the suspension is stirred for a specified time. The resulting suspension is further stirred for a specified time. The suspension was centrifuged and the solid was washed repeatedly with water and dried in vacuo. The dry powder was stored under argon in an airtight container. These solid catalyst formulations can be used in suitable reactions, depending on the catalytically active element incorporated therein.
[0198]
Note 1: Solution A is prepared by dissolving the anionic component (which contains the anion complex and additives to make a homogeneous solution) in a degassed solvent. The resulting solution is also degassed by purging with argon.
[0199]
Note 2: Solution B is prepared by dissolving the Group IIA metal salt. The solution was degassed before use.
[0200]
Note 3: Impregnation of the solution on the solid support is carried out by wetting the solid with solution A and evaporating at 50 ° C. under reduced pressure unless otherwise specified.
[0201]
Note 4: Addition of impregnated solid with component A to solution B is performed at ambient temperature unless otherwise specified.
[0202]
Note 5: Solution A impregnation can be avoided and the following procedure can be used instead. The support is suspended in a solvent and the solution is pumped into it while simultaneously removing the solvent component of solution A. The solvent is also pumped at a rate such that the liquid volume of the container is the same. After this solution B is added, it is aged and isolation of the solid is carried out as described above.
[0203]
[Table 5]

(Examples 253 to 336)
(Preparation of catalyst formulation by sedimentation in a fluidized bed)
The following example illustrates one procedure for preparing the catalyst formulation of the present invention according to a formulation method known as coprecipitation near the surface of a solid support in a fluidized bed.
[0204]
The general procedure for preparing a heterogeneous catalyst formulation is as the production of a solution of an anionically charged catalyst element, a catalyst inert anion additive (referred to as Solution A) and a Group IIA metal solution (referred to as Solution B) Described in this specification. A defined amount of support, pretreated as described above, was charged into a fluidization vessel and the solids fluidized with a stream of argon. The temperature of the fluidization chamber was raised to a specified temperature. Solution A was sprayed onto the bed for a specified time in such a way that the solids did not form lumps. Fluidization was continued further for a specified time, and solution B was sprayed in the same manner, and fluidization was continued for a specified time. The solid was drained from the container and aged for a specified time. The catalyst formulation so formed was washed with water, methanol and diethyl ether and subsequently dried in vacuo. The dry powder was stored under argon in an airtight container. These solid support formulations can be used in suitable reactions, depending on the catalytically active element incorporated therein.
[0205]
Note 1: Solution A is prepared by dissolving an anionic component (which contains an anionic complex and additives that produce a homogeneous solution) in a degassed solvent. The resulting solution is also degassed by purging with argon.
[0206]
Note 2: Solution B is prepared by dissolving the Group IIA metal salt. The solution was degassed before use.
[0207]
Note 3: Fluidized bed deposition was performed with the equipment described in FIG.
[0208]
[Table 6]

(Examples 337 to 420)
(Preparation of catalyst formulation by sedimentation in a coated pan)
The following example illustrates one procedure for preparing the catalyst formulation of the present invention according to a formulation method known as coprecipitation near the surface of a solid support.
[0209]
The general procedure for preparing a heterogeneous catalyst formulation is as the production of a solution of an anionically charged catalyst element, a catalyst inert anion additive (referred to as Solution A) and a Group IIA metal solution (referred to as Solution B) Described in this specification. A defined amount of support pre-treated as described above was filled into a pan, which was subsequently set to rotation. During this procedure, the solid was rotated. The temperature of the rotating pan was raised to a specified temperature. Solution A was sprayed onto the bed of solids for a specified time under a stream of argon followed by Solution B. The resulting solid was spun for a specified time and dried in vacuo. The solid was washed with water, methanol and diethyl ether and dried. The dry powder was stored under argon in an airtight container. These solid support formulations can be used in suitable reactions, depending on the catalytically active element incorporated therein.
[0210]
Note 1: Solution A is prepared by dissolving an anionic component (which contains an anionic complex and additives that produce a homogeneous solution) in a degassed solvent. The resulting solution is also degassed by purging with argon.
[0211]
Note 2: Solution B is prepared by dissolving the Group IIA metal salt. The solution was degassed before use.
[0212]
[Table 7]

(Examples 421 to 429)
(Stability of catalyst in various organic solvents)
These examples illustrate the stability of the catalyst in the liquid phase. The stability of the catalyst was evaluated to confirm the catalyst integrity and resilience in the liquid phase reaction. The apparatus of FIG. 3 was assembled and 5 g of catalyst was added to the extraction container. An extraction vessel was filled with 0.5 liter of solvent. The solids in the extractor were agitated and the solvent in the round bottom flask was set to boil. The solid catalyst was leached continuously over 24 hours. The boiling liquid was brought to room temperature and analyzed for Group IIA metals and transition metals. The leaching of the catalytically active material was not obvious.
[0213]
[Table 8]

(Example 430)
(Hydroformylation reaction as a probe)
This example illustrates the applicability of this catalyst formulation to liquid phase reactions, where the two gases react with the substrate in the liquid phase. This example also illustrates how a solid catalyst can be used to catalyze the reaction and a preferred method for recovering and regenerating it.
[0214]
Catalyst specifications:
[0215]
[Table 9]

Reaction procedure: Under an argon atmosphere, the microreactor was charged with 1 g of catalyst and 25 ml of octene. This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized to 600 psi with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred at 900 rpm. The reaction was continued for 240 minutes. Analysis of the product confirmed that the olefin was converted to an aldehyde.
[0216]
Conversion 14^*10^-3Mole octene
The turnover frequency at 60 minutes is 894 hours^-1Met.
[0217]
The turnover number after 240 minutes was 1296.29 mol. Molar of catalyst n / i ratio after 240 minutes^-1Was 2.7, where n is a linear aldehyde and I is an isoaldehyde.
[0218]
Color of recovered catalyst: light brown.
[0219]
The catalyst was recovered by centrifugation, and the reactor was washed repeatedly with toluene under a nitrogen atmosphere. The solid catalyst was dried under reduced pressure and regenerated to carry out the reaction as described above to obtain comparable activity and selectivity. The color of the catalyst was light brown.
[0220]
(Example 431)
(Necessity of support)
These comparative examples illustrate the need for a solid support in this catalyst formulation and the loading effect of catalytically active solid material on the solid support to determine the optimal loading protocol.
[0221]
Hydroformylation of hexane
Catalyst specifications:
[0222]
[Table 10]

procedure:
In an argon atmosphere, the microreactor was charged with 2 g of catalyst and 0.5 g of hexane (5.2 g) in 20 ml of toluene.^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 89% of the olefin was converted to an aldehyde with n / I selectivity of 1.80. 4 of rhodium catalyst under the same conditions^*10^-7The morbarium salt did not promote any reaction at all.
[0223]
(Example 432)
(Effect of additional ligand)
These comparative examples illustrate the need for additional ligands in the catalyst formulation. These examples also illustrate the loading effect of the solid support and the catalytically active solid material on the solid support in this catalyst formulation to determine the optimal loading.
[0224]
Preparation of catalyst. The changing specifications of the catalyst were prepared by the following method.
[0225]
Hydroformylation of hexane
Catalyst preparation:
Catalyst specifications:
[0226]
[Table 11]

procedure:
Under an argon atmosphere, this microreactor was charged with 2 g of catalyst and 0.5 g of hexane (5.2 g) in 20 ml of toluene.^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours.
[0227]
Analysis of the product confirmed that the olefin was converted to an aldehyde. About 89% of the olefin was converted to aldehyde with n / I selectivity of 1.80.
[0228]
(Example 433)
(Effect of additional water-hydroformylation of hexene)
Catalyst specifications:
[0229]
[Table 12]

procedure:
Under an argon atmosphere, this microreactor was charged with 2 g of catalyst and 0.5 g of hexane (5.2 g) in 20 ml of toluene.^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 89% of the olefin was converted to an aldehyde with n / I selectivity of 1.80.
[0230]
When 1 g of water was added under the same reaction charge conditions, after 24 hours, only 5% conversion was obtained with similar n / I ratio.
[0231]
(Example 434)
(Continuous fixed bed experiment)
Catalyst specifications:
[0232]
[Table 13]

Procedure: Therefore, a critical assessment of the lifetime of the catalyst, its stability and durability was made at 80 ° C. and 300 psi H in a tubular tri-bed reactor (Φ1 / 2 ″) using 5 g of catalyst.₂This was carried out in a tubular fixed bed reactor by subjecting the catalyst to hydroformylation with / CO (1: 1). 5% decene in toluene was pumped continuously at a feed rate of 10 ml / hr. The conversion level was 20% (± 2% variation) for aldehydes after reaching steady state (5 hours) (n / i 2.1). This reaction continued for an additional 76 hours, but there was no loss of activity. By stopping the feeding of the liquid, the reaction was stopped and the water was pumped for 1 hour. Thereafter, the feeding of the reactant was resumed. Initially, there was no conversion, but this gradually resumed at an earlier level over 10 hours. This observation is due to the formation of a film of water on the catalyst surface, which physically delays contact between the decene and the catalyst surface. Furthermore, water does not wash away the complex catalyst, which provides definitive evidence that the reaction occurs in the solid state.
[0233]
(Example 435)
(Hydrocene hydroformylation)
Catalyst specifications:
[0234]
[Table 14]

procedure:
Under an argon atmosphere, the microreactor was charged with 200 mg of catalyst and 0.05 g of hexene (5.2 in 2 ml of toluene).^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 89% of the olefin was converted to an aldehyde with n / I selectivity of 1.91. The catalyst was recovered by washing the reactor several times with toluene. The catalyst was recovered by centrifugation and washed repeatedly with toluene and diethyl ether. The catalyst was dried under reduced pressure and regenerated to obtain comparable activity.
[0235]
(Example 436)
(Hydroformylation of styrene)
(Preparation of catalyst)
Catalyst specifications:
[0236]
[Table 15]

Under an argon atmosphere, this microreactor was charged with 200 mg of catalyst and 0.05 g of styrene (4.8 g) in 2 ml of toluene.^*10^-4). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 91% of the olefin was converted to an aldehyde with an n / I ratio of 0.449. The catalyst was recovered by washing the reactor several times with toluene. The catalyst was recovered by centrifugation and washed repeatedly with toluene and diethyl ether. The catalyst was dried under reduced pressure and regenerated to obtain comparable activity.
[0237]
(Example 437)
(Hydroformylation of cyclohexane)
(Preparation of catalyst)
Catalyst specifications:
[0238]
[Table 16]

Under an argon atmosphere, the microreactor was charged with 200 mg catalyst and 0.05 g cyclohexane (6.1 g) in 2 ml toluene.^*10^-4). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 47% of the olefin was converted to aldehyde. The catalyst was recovered by washing the reactor several times with toluene. The catalyst was recovered by centrifugation and washed repeatedly with toluene and diethyl ether. The catalyst was dried under reduced pressure and regenerated to obtain comparable activity.
[0239]
(Example 438)
(Hydroformylation of allyl alcohol)
Catalyst specifications:
[0240]
[Table 17]

Procedure: Under argon atmosphere, the microreactor was charged with 200 mg catalyst and 0.05 g allyl alcohol (8.7 g in 2 ml water).^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 20% of the olefin was converted to an aldehyde with an n / i ratio of 1. The catalyst was recovered by washing the reactor several times with toluene. The catalyst was recovered by centrifugation and washed repeatedly with toluene and diethyl ether. The catalyst was dried under reduced pressure and regenerated to obtain comparable activity.
[0241]
(Example 439)
(Hydrocene hydroformylation)
Catalyst specifications:
[0242]
[Table 18]

Under an argon atmosphere, this microreactor was charged with 200 mg of catalyst and 0.5 g of hexene (5.9 g) in 2 ml of toluene.^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 68% of the olefin was converted to an aldehyde with an n / I selectivity of 1.78. The catalyst was recovered by washing the reactor several times with toluene. The catalyst was recovered by centrifugation and washed repeatedly with toluene and diethyl ether. The catalyst was dried under reduced pressure and regenerated to obtain comparable activity.
[0243]
(Example 440)
(Hydrocene hydroformylation)
Catalyst specifications:
[0244]
[Table 19]

Under an argon atmosphere, the microreactor was charged with 200 mg of catalyst and 0.05 g of hexene (5.9 g) in 2 ml of toluene.^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 78% of the olefins were converted to aldehydes with an n / I selectivity of 17.88. The catalyst was recovered by washing the reactor several times with toluene. The catalyst was recovered by centrifugation and washed repeatedly with toluene and diethyl ether. The catalyst was dried under reduced pressure and regenerated to obtain comparable activity.
[0245]
(Example 441)
(Hydrocene hydroformylation)
Catalyst specifications:
[0246]
[Table 20]

Under an argon atmosphere, the microreactor was charged with 200 mg of catalyst and 0.05 g of hexene (5.9 g) in 2 ml of toluene.^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 80% of the olefin was converted to an aldehyde with an n / I selectivity of 0.6. The catalyst was recovered by washing the reactor several times with toluene. The catalyst was recovered by centrifugation and washed repeatedly with toluene and diethyl ether. The catalyst was dried under reduced pressure and regenerated to obtain comparable activity.
[0247]
(Example 442)
(Hydrocene hydroformylation)
Catalyst specifications:
[0248]
[Table 21]

Under an argon atmosphere, the microreactor was charged with 200 mg of catalyst and 0.05 g of hexene (5.9 g) in 2 ml of toluene.^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 80% of the olefin was converted to an aldehyde with an n / I selectivity of 0.92. The catalyst was recovered by washing the reactor several times with toluene. The catalyst was recovered by centrifugation and washed repeatedly with toluene and diethyl ether. The catalyst was dried under reduced pressure and regenerated to obtain comparable activity.
[0249]
(Example 443)
(Cobalt catalyzed hydroformylation)
Catalyst specifications:
[0250]
[Table 22]

Under an argon atmosphere, this microreactor was charged with 200 mg of catalyst and 0.05 g of hexene (5.9 g) in 2 ml of toluene.^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 30% of the olefin was converted to an aldehyde with an n / i selectivity of 1.38. The catalyst was recovered by washing the reactor several times with toluene. The catalyst was recovered by centrifugation and washed repeatedly with toluene and diethyl ether. The catalyst was dried under reduced pressure and regenerated to obtain comparable activity.
[0251]
(Example 444)
(Platinum-catalyzed hydroformylation)
Catalyst preparation: The heterogeneous platinum chloride-phosphine complex was boiled with dichloromethane and stannous chloride and subsequently extracted with dichloromethane.
[0252]
Catalyst specifications:
[0253]
[Table 23]

Procedure: Under argon atmosphere, the microreactor was charged with 200 mg of catalyst and 0.05 g of hexene (5.9 g) in 2 ml of toluene.^*10^-4mol). This reactor is H₂/ CO mixture, the reactor is heated to 75 ° C. and H₂Pressurized with a / CO mixture (1: 1 molar ratio) and maintained at this temperature. The liquid suspension was stirred by external magnetic stirring. The reaction was continued for 24 hours. Analysis of the product confirmed that the olefin was converted to an aldehyde. 57% of the olefin was converted to an aldehyde with an n / I selectivity of 10.47. The catalyst was recovered by washing the reactor several times with toluene. The catalyst was recovered by centrifugation and washed repeatedly with toluene and diethyl ether. The catalyst was dried under reduced pressure and regenerated to obtain comparable activity.
[0254]
(Example 445)
(Carbonylation of styrene)
Catalyst specifications:
[0255]
[Table 24]

Procedure: A 15 ml reactor equipped with a magnetic stir bar was charged with 200 mg of catalyst and 500 mg of styrene (4.90 10^-3mmol) and 5 mg of p-toluenesulfonic acid, 25 mg of N, N-dimethylaniline and 10 ml of methanol. The microreactor was flushed with argon and pressurized with 800 psi carbon monoxide and the mixture was stirred at 70 ° C. for 24 hours. The reaction mixture was analyzed by gas chromatograph. 87% phenylacetylene was carbonylated with 99% selectivity to methyl 2-phenylpropionate. The reaction mixture was centrifuged to recover the solid catalyst, which was subsequently washed repeatedly with methanol. The catalyst was further washed with diethyl ether and dried under reduced pressure.
[0256]
(Example 446)
(Carbonylation of styryl alcohol)
Catalyst preparation
Catalyst specifications:
[0257]
[Table 25]

Procedure: A 15 ml reactor equipped with a magnetic stir bar was charged with 200 mg of catalyst and 500 mg of styryl alcohol (8.9).^*10^-3mmol) and 5 mg p-toluenesulfonic acid and 10 ml methanol. The microreactor was flushed with argon and pressurized with 800 psi carbon monoxide and the mixture was stirred at 100 ° C. for 24 hours. The reaction mixture was analyzed by gas chromatograph. 52% of phenylacetylene was carbonylated with more selectivity than phenyl 2-propionate and 91% selectivity to methyl 2-propionate. The reaction mixture was centrifuged to recover the solid catalyst, which was subsequently washed repeatedly with methanol. The catalyst was further washed with diethyl ether and dried under reduced pressure.
[0258]
(Example 447)
(Carbonylation of phenylacetylene)
Catalyst specifications:
[0259]
[Table 26]

Procedure: A 15 ml reactor equipped with a magnetic stir bar was charged with 200 mg of catalyst and 500 mg of phenylacetylene (4.90 10^-3mmol) and 5 mg of p-toluenesulfonic acid, 25 mg of N, N-dimethylaniline and 10 ml of methanol. The microreactor was flushed with argon and pressurized with 100 psi carbon monoxide and the mixture was stirred at 90 ° C. for 12 hours. The reaction mixture was analyzed by gas chromatograph. 80% of phenylacetylene was carbonylated with 96% selectivity to methyldehydroatropate. The reaction mixture was centrifuged to recover the solid catalyst, which was subsequently washed repeatedly with methanol. The catalyst was further washed with diethyl ether and dried under reduced pressure.
[0260]
(Example 448)
(Styrene hydrogenation)
Catalyst specifications:
[0261]
[Table 27]

Procedure: In a 15 ml reactor equipped with a magnetic stir bar, in 10 ml of ethanol, 200 mg of catalyst and 500 mg of styrene (4.8)^*10^-3mmol). The microreactor was flushed with argon and pressurized with 500 psi of hydrogen and the mixture was stirred at 90 ° C. for 12 hours. The reaction mixture was analyzed by gas chromatograph. Styrene 98% was hydrogenated to ethylbenzene. The reaction mixture was centrifuged to recover the solid catalyst, which was subsequently washed repeatedly with methanol. The catalyst was further washed with diethyl ether and dried under reduced pressure. The catalyst was regenerated and the same activity was obtained.
[0262]
(Example 449)
(Hydrogenation of methyl cinnamate)
Catalyst specifications:
[0263]
[Table 28]

Procedure: A 15 ml reactor equipped with a magnetic stir bar was charged with 200 mg of catalyst and 500 mg of methyl cinnamate (3.08) in 10 ml of methanol.^*10^-3mmol). The microreactor was flushed with argon and pressurized with 1000 psi of hydrogen and the mixture was stirred at 50 ° C. for 12 hours. The reaction mixture was analyzed by gas chromatograph. 80% of methyl cinnamate was hydrogenated to methyl 3-phenylpropionate. The reaction mixture was centrifuged to recover the solid catalyst, which was subsequently washed repeatedly with methanol. The catalyst was further washed with diethyl ether and dried under reduced pressure. The catalyst was regenerated and the same activity was obtained.
[0264]
(Example 450)
(Hydrogenation of cinnamonitrile)
Catalyst specifications:
[0265]
[Table 29]

Procedure: In a 15 ml reactor equipped with a magnetic stir bar, in 10 ml of methanol, 200 mg of catalyst and 500 mg of cinnamonitrile (3.87).^*10^-3mmol). The microreactor was flushed with argon and pressurized with 500 psi of hydrogen and the mixture was stirred at 50 ° C. for 12 hours. The reaction mixture was analyzed by gas chromatograph. Cinnamonitrile 79% was hydrogenated to 3-phenylpropionitrile with a selectivity of 60%. The reaction mixture was centrifuged to recover the solid catalyst, which was subsequently washed repeatedly with methanol. The catalyst was further washed with diethyl ether and dried under reduced pressure. The catalyst was regenerated and the same activity was obtained.
[0266]
(Example 451)
(Hydrogenation of dehydronaproxen)
Catalyst specifications:
[0267]
[Table 30]

Procedure: A 15 ml reactor equipped with a magnetic stir bar was charged with 200 mg of catalyst and 128 mg of dehydronaproxen (1.26 in 10 ml of toluene).^*10^-3mol) and 128 mg (1.26) of triethylamine^*10^-3mol). A methanol (3: 2 v / v) microreactor was flushed with argon and pressurized with 100 bar of hydrogen and the mixture was stirred at 0 ° C. for 48 hours. The reaction mixture was centrifuged to recover the solid catalyst, which was subsequently washed repeatedly with methanol. All washings and reaction mixtures were combined and dried in vacuo. The so obtained solid was dissolved in dichloromethane and washed with dilute HCl followed by water. Dichloromethane was evaporated to give naproxen. Product analysis: The product was analyzed by HPLC using a WHELK-O column (Merck). Naproxen yields were 98% and 92% e.e. e.
[0268]
The second recycle is 98% and e. e. 94%.
[0269]
(Example 452)
(Hydrogenation of heptaldehyde)
Catalyst specifications:
[0270]
[Table 31]

Procedure: 100 mg of the catalyst was charged to the microreactor. To this, 50 mg of heptaldehyde (4.38) was added as a solution of 2 ml of toluene.^*10^-4mol) was added. The microreactor was flushed with argon and heated to 90 ° C. Magnetic stirring was started. After reaching that temperature, the reactor was pressurized with 500-psi hydrogen. The reactor was maintained under these conditions for 24 hours. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. 99% heptaldehyde was converted.
[0271]
The catalyst was recovered by washing the reactor several times with toluene. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0272]
(Example 453)
(Hydrogenation of cinnamaldehyde)
Catalyst specifications:
[0273]
[Table 32]

Procedure: 100 mg of the catalyst was charged to the microreactor. To this, 500 mg of cinnamaldehyde (3.78 * 10) was added as a solution of 2 ml of tetrahydrofuran.^-3mol) was added. The microreactor was flushed with argon and heated to 90 ° C. Magnetic stirring was started. After reaching that temperature, the reactor was pressurized with 500 psi of hydrogen. The reactor was maintained under these conditions for 24 hours. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. Cinnamaldehyde 88% was converted. The selectivity for cinnamyl alcohol was 73%.
[0274]
The catalyst was recovered by washing the reactor several times with tetrahydrofuran. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0275]
(Example 454)
(Hydrogenation of ethyl acetoacetate)
Catalyst specifications:
[0276]
[Table 33]

Procedure: 1 g of the catalyst was charged to the microreactor. To this was added 5 g of ethyl 3-oxobutanoate in 15 ml of methanol. The resulting suspension was charged to a microreactor, which was flushed with argon and hydrogen. The reactor temperature was raised to 90 ° C. and the reactor was charged with 150 psi of hydrogen. The reactor was maintained under these conditions for 24 hours. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. Ethyl 3-oxobutanoate was quantitatively converted to the corresponding alcohol. The catalyst was recovered by washing the reactor several times with methanol. The combined fractions were fractionated to recover the catalyst. The recovered catalyst was washed with water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0277]
The optical purity of the product is 92% with fresh catalyst and 94% with regenerated catalyst.
[0278]
(Example 455)
(Hydrogenation of benzyledeneacetone)
Catalyst specifications:
[0279]
[Table 34]

Procedure: 100 mg of the catalyst was charged to the microreactor. To this, as a solution of 2 ml of tetrahydrofuran, 500 mg of benzyledeneacetone (3.42 * 10^-3mol) was added. The microreactor was flushed with argon and heated to 90 ° C. Magnetic stirring was started. After reaching that temperature, the reactor was pressurized with 500 psi of hydrogen. The reactor was maintained under these conditions for 24 hours. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. All benzyledene acetone was converted. The catalyst was recovered by washing the reactor several times with tetrahydrofuran. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0280]
(Example 456)
(Nitrotoluene hydrogenation)
Catalyst specifications:
[0281]
[Table 35]

Procedure: 100 mg of the catalyst was charged to the microreactor. To this, 500 mg (3.649 * 10) of o-nitrotoluene was added as a solution of 2 ml of ethyl acetate.^-3mol) was added. The microreactor was flushed with argon and heated to 90 ° C. Magnetic stirring was started. After reaching that temperature, the reactor was pressurized with 500 psi of hydrogen. The reactor was maintained under these conditions for 24 hours. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. All o-nitrotoluene was converted to o-toluene.
[0282]
The catalyst was recovered by washing the reactor several times with ethyl acetate. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0283]
(Example 457)
(Hydrogenation of o-chloronitrobenzene)
Catalyst specifications:
[0284]
[Table 36]

Procedure: 100 mg of the catalyst was charged to the microreactor. To this, as a solution of 2 ml of ethyl acetate, 500 mg of o-chloronitrobenzene (3.952 * 10^-3mol) was added. The microreactor was flushed with argon and heated to 90 ° C. Magnetic stirring was started. After reaching that temperature, the reactor was pressurized with 500 psi of hydrogen. The reactor was maintained under these conditions for 24 hours. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. All o-chloronitrobenzene was converted to o-chloroaniline.
[0285]
The catalyst was recovered by washing the reactor several times with ethyl acetate. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0286]
(Example 458)
(Iodobenzene and methyl acrylate)
Catalyst specifications:
[0287]
[Table 37]

Procedure: 100 mg of the catalyst was charged to the microreactor. To this, as a solution of 5 ml of toluene, 1 mg of tetrabutylammonium hydroxide and 0.41 mg of sodium acetate (5 * 10^-3), 0.5 g of ethyl acrylate (5 * 10^-3) And 0.509 g (2.5 * 10) iodobenzene^-3) Was added. The microreactor was flushed with argon and heated to 90 ° C., after which temperature magnetic stirring was started. The reactor was maintained for 48 hours under these conditions. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. 86% ethyl acrylate was converted to product. The catalyst was recovered by washing the reactor several times with toluene. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0288]
When the color of the recovered catalyst was observed, it was dark yellow.
[0289]
(Example 459)
(Iodobenzene and acrylonitrile)
Catalyst specifications:
[0290]
[Table 38]

Procedure: 100 mg of the catalyst was charged to the microreactor. To this, as a solution of 5 ml of toluene, 1 mg of tetrabutylammonium hydroxide, 0.41 mg of sodium acetate, 0.265 g of acrylonitrile (5 * 10^-3) And 0.509 g (2.5 * 10) iodobenzene^-3) Was added. The microreactor was flushed with argon and heated to 90 ° C., after which temperature magnetic stirring was started. The reactor was maintained for 48 hours under these conditions. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. 90% of acrylonitrile was converted to product.
[0291]
The catalyst was recovered by washing the reactor several times with toluene. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0292]
When the color of the recovered catalyst was observed, it was dark yellow.
[0293]
(Example 460)
(Iodobenzene and styrene)
Catalyst specifications:
[0294]
[Table 39]

Procedure: 1 g of the catalyst was charged to the microreactor. To this, as a solution of toluene 10 ml, tetrabutylammonium hydroxide 5 mg, potassium carbonate 0.66 mg, styrene 0.5 g (4.8 * 10^-3mol) and 1.957 g (9.6 * 10) of iodobenzene.^-3mol) was added. The microreactor was flushed with argon and heated to 90 ° C., after which temperature magnetic stirring was started. The reactor was maintained under these conditions for 76 hours. The reaction was stopped by cooling the reactor to 0 ° C. The reactor was opened and the liquid was analyzed by gas chromatograph. Styrene 44% was converted to stilbene.
[0295]
The catalyst was recovered by washing the reactor several times with toluene. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0296]
(Example 461)
(Iodobenzene and ethylene)
Catalyst specifications:
[0297]
[Table 40]

Procedure: 100 mg of the catalyst was charged to the microreactor. To this, as a solution of 10 ml of acetonitrile, 1 mg of tetrabutylammonium hydroxide, 0.41 g of sodium acetate and 0.509 g of iodobenzene (2.5 * 10^-3) Was added. The microreactor was flushed with nitrogen and heated to 120 ° C., the reactor was pressurized with ethylene and magnetic stirring was started. The reactor was maintained under these conditions for 76 hours. The reaction was stopped by cooling the reactor to 0 ° C. The reactor was depressurized by venting the reactor. The reactor was opened and the liquid was analyzed by gas chromatograph. 30% iodobenzene was converted to styrene.
[0298]
The catalyst was recovered by washing the reactor several times with toluene. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0299]
(Example 462)
(Bromobenzene and o-tolylboronic acid)
Catalyst specifications:
[0300]
[Table 41]

Procedure: A well-dried 500 ml flask was equipped with a thermometer, magnetic stir bar, condenser, addition funnel and two-way valve. This flask was charged with 12.2 g (0.5 atom) of magnesium turning. The assembly was thoroughly degassed through a two-way valve and filled with nitrogen and the magnesium was stirred for 6 hours. To this was added iodine crystals, 100 ml of tetrahydrofuran (which was distilled with sodium benzophenone ketyl) and 200 μl of 1,2-dibromoethane. After the magnesium turning surface shines white, 78.5 g (0.5 mol) of bromobenzene was added at such a rate that the temperature rose to boiling. The reaction was continued while the flask was intermittently cooled by removing the heater-stirrer. Once the reaction subsided, the mixture was refluxed until the magnesium was dissolved. The reaction mixture was transferred to a Shlenk tube packed with glass wool.
[0301]
(M-Tolylboronic acid)
A fully dried flanged flask (which was fitted with a sealed mechanical stuffing box and dropping funnel and reflux condenser (with molten calcium chloride guard tube)) was assembled. The temperature of the flask was brought to −75 ° C. with acetone and liquid nitrogen. To this flask was added 40.5 g of tributyl borate in 150 ml of ether. A solution of o-tolyl magnesium bromide was added while stirring fairly rapidly without raising the temperature above -70 ° C. Stirring was continued for 3 hours at the same temperature. The temperature of the flask was maintained at 5 ° C. with an ice bath for 12 hours. The reaction mixture was added to 150 ml of 10% cold sulfuric acid. Extracted with ether and evaporated. To this was added 100 ml of water and basified slightly with NaOH. Acidified, extracted with boiling water and collected as crystalline material (5 g).
[0302]
1 g of this catalyst was charged into a round bottom flask equipped with a reflux condenser, and a magnetic rod was added to the round bottom flask. To this, as a 20 ml solution of toluene, 1 mg of tetrabutylammonium hydroxide, 75 mg of sodium carbonate, 0.136 g of o-tolylboronic acid (10^-3mol) and 0.224 g (1.1 * 10) of iodobenzene^-3) Was added. The assembly was flushed with nitrogen and heated to 90 ° C. The reactor was maintained under these conditions for 24 hours. The reaction was stopped by cooling the reactor to 0 ° C. The liquid was analyzed by gas chromatograph. 95% iodobenzene was converted to 2-methyl-1,1'-biphenyl.
[0303]
The catalyst was recovered by washing the reactor several times with toluene. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with sodium carbonate, water, methanol and diethyl ether and the catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity. The catalyst was regenerated to obtain comparable conversion and selectivity.
[0304]
(Example 463)
(Phenyl magnesium bromide and iodobenzene)
Catalyst specifications:
[0305]
[Table 42]

procedure:
(Preparation of Grignard reagent)
A fully dry 500 ml flask was equipped with a thermometer, magnetic stir bar, condenser, addition funnel and two-way valve. To this flask, 0.61 g (0.025 atom) of magnesium turning was added. The assembly was thoroughly degassed through a two-way valve and filled with nitrogen and the magnesium was stirred for 6 hours. To this was added iodine crystals, 50 ml of tetrahydrofuran (which was distilled with sodium benzophenone ketyl) and 200 μl of 1,2-dibromoethane. After the magnesium turning surface shines white, 3.922 g (0.025 mol) of bromobenzene in 20 ml of thf was added at such a rate that the temperature rose to boiling. The reaction was continued while the flask was intermittently cooled by removing the heater-stirrer. Once the reaction subsided, the mixture was refluxed until the magnesium was dissolved. The reaction mixture was transferred to a Shlenk tube packed with glass wool.
[0306]
A well-dried 250 ml flask was equipped with a thermometer, magnetic stir bar, condenser, addition funnel and two-way valve and charged with 5 g of catalyst, 50 ml of tetrahydrofuran (freshly distilled with blue sodium benzophenone ketyl). . The assembly was filled with nitrogen as previously described. To this, 5.09 g (0.025 mol) of iodobenzene was added. The addition container was filled with 60 ml of Grignard reagent prepared in advance. To the contents of the flask (which was pre-cooled to 5 ° C.), the Grignard reagent was slowly added. The temperature of the flask was maintained at 5 ° C. for 24 hours. The reaction mixture was cooled to room temperature and to this was slowly added 20 ml of water followed by 20 ml of saturated ammonium chloride. The resulting suspension was filtered to remove solids, followed by thorough washing with tetrahydrofuran and water. The filtrate was extracted with dichloromethane to give biphenyl in 89% yield. The residue remaining after filtration was washed with water, tetrahydrofuran and ether and dried under reduced pressure.
[0307]
(Example 464)
(Isobutyl magnesium bromide and iodobenzene)
Catalyst preparation: The catalyst was pre-dried by extraction with boiling THF on sodium wire, followed by vacuum and storage with phosphorus pentoxide.
[0308]
Catalyst specifications:
[0309]
[Table 43]

procedure:
(Preparation of Grignard reagent)
A fully dry 500 ml flask was equipped with a thermometer, magnetic stir bar, condenser, addition funnel and two-way valve. To this flask, 2.44 g (0.1 atom) of magnesium turning was added. The assembly was thoroughly degassed through a two-way valve and filled with nitrogen and the magnesium was stirred for 6 hours. To this was added iodine crystals, 50 ml of tetrahydrofuran (which was distilled with sodium benzophenone ketyl) and 200 μl of 1,2-dibromoethane. After the surface of the magnesium turning shined white, 9.2 g (0.1 mol) of isobutyl bromide was added at such a rate that the temperature rose to boiling. The reaction was continued while the flask was intermittently cooled by removing the heater-stirrer. Once the reaction subsided, the mixture was refluxed until the magnesium was dissolved. The reaction mixture was transferred to a Shlenk tube using a cannula filled with glass wool.
[0310]
A fully dry 500 ml flask was equipped with a thermometer, magnetic stir bar, condenser, addition funnel and two-way valve and charged with 5 g of catalyst, 50 ml of tetrahydrofuran (freshly distilled with blue sodium benzophenone ketyl). . The assembly was filled with nitrogen as previously described. To this, 20.39 g (0.1 mol) of iodobenzene was added. The addition container was filled with 50 ml of Grignard reagent prepared in advance. To the contents of the flask (which was cooled to 0 ° C.), the Grignard reagent was slowly added. The temperature of the flask was raised to 50-0 ° C. The reaction mixture was cooled to room temperature and to this was slowly added 25 ml of water followed by 25 ml of saturated ammonium chloride. The resulting suspension was filtered to remove solids, followed by thorough washing with tetrahydrofuran and water. The filtrate was extracted with dichloromethane to give isobutylbenzene in 92% yield. The residue remaining after filtration was washed with water, thf and ether and dried under reduced pressure.
[0311]
(Example 465)
(Allylation of aryl boronates)
Catalyst specifications:
[0312]
[Table 44]

Procedure: To 2 gm of catalyst was added 20 ml of tetrahydrofuran, and to this solution was added 5 ml of a cold solution containing 2.9 mmol of phenyllithium. The mixture is cooled under stirring to 0 ° C. and to this is added B (OCH₃)₃(0.42 ml, 3.62 mmol) was added slowly followed by 1.44 mmol allylmethyl carbonate. The temperature was then raised to 60 ° C. and the reaction was continued for 12 hours. The liquid was separated from the solid catalyst and poured into a mixture of 20 ml hexane and 20 ml saturated ammonium chloride. It was revealed that 3-phenylpropene was formed by the organic layer.
[0313]
The recovered catalyst was washed with saturated bicarbonate, tetrahydrofuran and diethyl ether and regenerated after drying in vacuo.
[0314]
(Example 466)
(Isomerization of hexene)
Catalyst specifications:
[0315]
[Table 45]

Procedure: Isomerization was performed according to the following procedure. 5 gm of catalyst was charged to the microreactor, which was subsequently flushed with nitrogen and charged with 5 g of 1-hexene (92% purity) and 45 ml of cyclohexane. The reactor temperature was raised to 100 ° C. and maintained for 76 hours. The conversion of 1-hexene was 73%. Two isomerized products were observed. The catalyst was centrifuged and the liquid was separated. The catalyst was washed repeatedly with cyclohexane. The isolated catalyst was regenerated under the same conditions to obtain an equivalent yield.
[0316]
(Example 467)
(Isomerization of N, N-dietyrylamine)
Catalyst specifications:
[0317]
[Table 46]

Procedure: Drying the catalyst
The isomerization was carried out as the procedure adopted from (Helvetica Chema Acta vol. 71, (1988) 897-920) adapted to suit the solid catalyst. 2 gm of catalyst was charged to a Fischer-Porter bottle and degassed. Subsequently, the bottle was flushed with nitrogen and charged with a degassed mixture of 11.37 g (50 mmol) of N, N-ethylerylamine (purity according to area percentage of gc92) and 50 ml of anhydrous tetrahydrofuran. The bottle temperature was raised to 80 ° C. and maintained for 76 hours. The catalyst was centrifuged and the liquid was separated. The combined washings of catalyst with tetrahydrofuran and combined were evaporated to give a pale yellow oil which was dissolved in 50% acetic acid in 50 ml water, stirred at 0 ° C. for 10 minutes, and 50 ml hexane was added, The liquid was stirred for 30 minutes at room temperature. The hexane layer was separated and the aqueous layer was washed with hexane. The hexane extract was washed with saturated bicarbonate solution. Fractionation of the extract gave 7.35 g of (S) citronellol (90% based on N, N-dierylylamine). The optical purity of this material is determined by optical rotation analysis (c = 5, CHCl₃, Lamp D, 20 ° C.), it was found to be 98%. The isolated catalyst was regenerated under the same conditions to obtain an equivalent yield.
[0318]
(Example 468)
(Isomerization of 1,4-diacetoxybutene)
Catalyst specifications:
[0319]
[Table 47]

Procedure: Isomerization was performed according to the following procedure. 100 mg of catalyst was charged into the microreactor which was subsequently flushed with nitrogen and 50 mg of 1,4-diacetoxybutene (3 * 10^-4mol) and 2 ml of toluene in a degassed mixture. The reactor temperature was raised to 100 ° C. and maintained for 76 hours. The catalyst was centrifuged and the liquid was separated. The catalyst was washed repeatedly with toluene. The conversion of 1,4-diacetoxybutene was 57%. The isolated catalyst was regenerated under the same conditions to obtain an equivalent yield.
[0320]
(Example 469)
(Hexen Wacker)
Catalyst specifications:
[0321]
[Table 48]

Procedure: 100 mg of this catalyst was charged to the microreactor, to which 1 ml of hexene was added as a 20% v / v solution in hexene. The microreactor was pressurized with air (450 psi) and heated to 90 ° C. After reaching that temperature, magnetic stirring was started. The reactor was maintained for 24 hours. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. Cyclohexene 36% was converted to product with 90% selectivity to hexane-2-one. The remaining products were presumed to be isomerized olefins and some unknown products.
[0322]
The catalyst was recovered by washing the reactor several times with cyclohexane. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was reinforced with water to contain 50% by weight of water. This catalyst was regenerated to obtain comparable activity and selectivity.
[0323]
The observed color of the recovered catalyst was dark yellow.
[0324]
(Example 470)
(Desen's Wacker)
Catalyst specifications:
[0325]
[Table 49]

Procedure: 100 mg of the catalyst was charged to the microreactor, to which 1 ml of decene was added as a 20% solution in hexene. The microreactor was pressurized with air (450 psi) and heated to 90 ° C. After reaching that temperature, magnetic stirring was started. The reactor was maintained for 24 hours. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. 19% of the decene was converted to product with 87% selectivity for decan-2-one. The remaining products were presumed to be isomerized olefins and some unknown products.
[0326]
The catalyst was recovered by washing the reactor several times with cyclohexane. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was reinforced with water to contain 50% by weight of water. This catalyst was regenerated to obtain comparable activity and selectivity.
[0327]
The observed color of the recovered catalyst was dark yellow.
[0328]
(Example 471)
(Cyclohexene Wacker)
Catalyst specifications:
[0329]
[Table 50]

Procedure: 100 mg of the catalyst was charged to the microreactor, to which 1 ml of cyclohexene was added as a 20% solution in hexene. The microreactor was pressurized with air (450 psi) and heated to 90 ° C. After reaching that temperature, magnetic stirring was started. The reactor was maintained for 24 hours. The reaction was stopped by cooling the reactor to 0 ° C. and reducing the pressure. The reactor was opened and the liquid was analyzed by gas chromatograph. Cyclohexene 7% was converted to product with 30% selectivity for cyclohexanone. The remaining product was not estimated.
[0330]
The catalyst was recovered by washing the reactor several times with cyclohexane. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was reinforced with water to contain 50% by weight of water. This catalyst was regenerated to obtain comparable activity and selectivity.
[0331]
The observed color of the recovered catalyst was dark yellow.
[0332]
(Example 472)
Epoxidation of styrene
Catalyst preparation: Ph (CH₂-N⁺(Ph_mSO₃ ⁻)₃・ OH⁻Was homogenized as described according to the method described above as a sedimentation precipitate in a coated pan. Suspend the solid in water and add it to 3 molar equivalents of OH.⁻In water (estimated by titration with standard acid) and stirred at 70 ° C. for 4 hours. The solid was collected and extracted with water for 12 hours followed by drying in vacuo.
[0333]
Catalyst specifications:
[0334]
[Table 51]

Procedure: 5 g of this catalyst was charged into a 500 ml glass reaction vessel (which was equipped with a mechanical stirrer, thermometer pocket and addition vessel) and to this was added 30 g (0.29 mol) of styrene in 75 ml of acetic acid. It was. The reaction vessel was cooled to 5 ° C. while circulating through the fluid cryostat. After reaching that temperature, stirring was started. Over 30 minutes, 30 ml of 34% hydrogen peroxide was added. The temperature and stirring of the reaction vessel was maintained for 24 hours. The reactor was opened and the liquid was analyzed by gas chromatography. 72% of styrene was converted to product with 89% selectivity for styrene oxide. The remaining product was not estimated.
[0335]
The catalyst was recovered by washing the reactor several times with acetic acid. The combined fractions were centrifuged to recover the catalyst. The recovered catalyst was washed with methanol, ether and dried. This catalyst was regenerated to obtain comparable activity and selectivity.
[0336]
(Example 473)
(Oxidation of chlorophenol)
Catalyst preparation: The catalyst was prepared according to the method described as a precipitate in the fluidized bed.
[0337]
Catalyst specifications:
[0338]
[Table 52]

Procedure: To a 50 ml round bottom flask equipped with a reflux condenser, 5 ml of acetonitrile and 15 ml of 0.1 M acetate buffer (pH 7) were added, and 181 mg (10^-3mol) was added. 2.5 g of catalyst was added and the suspension was stirred with a magnetic needle. The temperature of the suspension was raised to 60 ° C. To the above suspension, 34% H in water₂O₂(0.3 ml) was added. The reaction mixture was continued for 5 hours. It was observed that all of the trichlorophenol had disappeared, and chloride ions in the solution were detected with a silver nitrate solution.
[0339]
(Example 474)
(Condensation of diethyl fumarate and diethyl malonate to propane-1,1,2,3-tetracarboxylate)
Catalyst specifications:
[0340]
[Table 53]

Procedure: A 100 ml flask equipped with an efficient reflux condenser, magnetic stir bar and dropping funnel was charged with 5 gm of catalyst. While stirring, 1.6 g (0.001 mol) of diethyl malonate and 25 ml of absolute ethanol were added. The reaction mixture was warmed and 1.4 gm (0.0081 mol) of diethyl fumarate was added. The mixture was refluxed for 8 hours. The reaction mixture was cooled and the suspension was centrifuged to recover the catalyst. Analysis of the reaction solution revealed a 90% conversion for diethyl malonate. The product was distilled at 180-190 ° C. under a reduced pressure of 8 mm to obtain propane-1,1,2,3-tetracarboxylate (yield 85%).
[0341]
The catalyst was recovered, washed with ethanol, diethyl ether and dried under reduced pressure.
[0342]
The catalyst was regenerated to obtain comparable activity.
[0343]
(Example 475)
(Condensation of diethyl malonate and formaldehyde to tetraethylpropane-1,1,3,3-tetracarboxylate)
Catalyst specifications:
[0344]
[Table 54]

Procedure: 1.6 g (0.001 mol) of distilled diethyl malonate, 25 ml of ethanol and 0.4 g of 40% formaldehyde (5 * 10^-4mol) mixture (contained in a 50 ml round bottom flask) was cooled to 0 ° C. and 5 gm of catalyst was added and the mixture was stirred at room temperature for 24 hours and then refluxed for 12 hours. The suspension was centrifuged to recover the catalyst. Analysis of the reaction mixture revealed that 80% conversion of diethyl malonate. The liquid was evaporated and extracted with diethyl ether. The extract was dried over sodium sulfate. The catalyst was washed with ethanol, diethyl ether and dried under reduced pressure. The catalyst was regenerated to obtain comparable activity.
[0345]
(Example 476)
(Condensation of acetone and chloroform to chlorobutol)
Catalyst specifications:
[0346]
[Table 55]

Procedure: A 100 ml round bottom flask equipped with a reflux condenser was charged with 5 gm of catalyst, which was charged with a solution of 1.19 g (0.01 mol) chloroform as a solution in 25 ml acetone solution. A magnetic stir bar was added to the reaction mixture and the reaction mixture was stirred at room temperature for 24 hours. The suspension was centrifuged to recover the catalyst. Analysis of the reaction solution revealed that all of the chloroform had been converted. The catalyst was washed with ethanol, diethyl ether and dried under reduced pressure. The catalyst was regenerated to obtain comparable activity.
[0347]
(Example 477)
(Condensation of benzaldehyde and acetonitrile to cinnamonitrile)
Catalyst specifications:
[0348]
[Table 56]

Procedure: A 250 ml round bottom flask equipped with a reflux condenser was charged with 5 gm of catalyst, which was charged with a solution of 10.6 g (0.1 mol) of benzaldehyde as a solution in 100 ml of acetonitrile solution. A magnetic stir bar was added to the reaction mixture and the reaction mixture was stirred at reflux temperature for 24 hours. The suspension was centrifuged to recover the catalyst. Analysis of the reaction revealed 88% conversion of benzaldehyde and 98% selectivity for cinnamonitrile. Cinnamonitrile was recovered by fractional distillation (80% based on benzaldehyde).
[0349]
The catalyst was washed with ethanol, diethyl ether and dried under reduced pressure. The catalyst was regenerated to obtain comparable activity.
[0350]
(Example 478)
(Condensation of benzaldehyde and acetone to benzayledene acetone)
Catalyst specifications:
[0351]
[Table 57]

Procedure: A 250 ml round bottom flask equipped with a reflux condenser was charged with 5 gm of catalyst, which was charged with a solution of 10.6 g (0.1 mmol) benzaldehyde as a solution in 100 ml acetone solution. A magnetic stir bar was added to the reaction mixture and the reaction mixture was stirred at room temperature for 24 hours. The suspension was centrifuged to recover the catalyst. Analysis of the reaction revealed a 77% conversion of benzaldehyde. The catalyst was washed with ethanol, diethyl ether and dried under reduced pressure. The catalyst was regenerated to obtain comparable activity.
[0352]
(Example 479)
(Condensation of butalaldehyde and 2-ethylhexenal)
Catalyst specifications:
[0353]
[Table 58]

Procedure: A 100 ml round bottom flask equipped with a reflux condenser was charged with 5 gm of catalyst, which was charged with a solution of 7.2 g (0.1 mmol) of butalaldehyde as a solution in 50 ml of toluene solution. A magnetic stir bar was added to the reaction mixture and the reaction mixture was refluxed for 24 hours. The suspension was centrifuged to recover the catalyst. Analysis of the reaction solution revealed a 90% conversion of butalaldehyde. The catalyst was washed with ethanol, diethyl ether and dried under reduced pressure. The catalyst was regenerated to obtain comparable activity.
[0354]
(Example 480)
Specification of iodobenzene phosphination catalyst:
[0355]
[Table 59]

Procedure: A round bottom flask equipped with a reflux condenser was charged with 5 gm of catalyst. To this was added a solution of 1 ml (5.75 mmol) of diphenylphosphine in 30 ml of anhydrous degassed diethylformamide at room temperature. The suspension was degassed by repeated vacuum and argon flushing. After heating to 100 ° C. for 30 minutes, 10 mmol (2.04 gm) iodobenzene and 20 mmol (2.25 gm) diazabicyclooctane in 30 ml dimethylformamide were added and the resulting solution was maintained at 100 ° C. Thereafter, at 12 hour intervals, three additional portions of 1 ml each of diphenylphosphine were added. The reaction was continued for 76 hours. The reaction was stopped by cooling the flask to room temperature. The catalyst was recovered by centrifugation and washed with dimethylformamide. The filtrates were combined and evaporated to give a sticky residue which was diluted with 50 ml of tetrahydrofuran. The solution³¹Analyzed by P NMR.
[0356]
The following compounds were detected: triphenylphosphine, triphenylphosphine oxide, diphenylphosphine and diphenylphosphine oxide.
[0357]
The yield of triphenylphosphine based on iodobenzene was 92%; iodobenzene conversion was complete as confirmed by gas chromatography.
[0358]
Observing the color of the recovered catalyst was darker than the fresh catalyst.
[0359]
Catalyst recovery and regeneration: The recovered catalyst was regenerated under the same conditions to yield 88% triphenylphosphine based on iodobenzene. For the third regenerated catalyst, 250 mg NiCl₂・ 6H₂Refluxed with O (which was dissolved in 50% ethanol in water) for 6 hours. The catalyst was extracted with water, ethanol and dried. The catalyst was regenerated to give 90% triphenylphosphine.
[0360]
Fresh catalyst under the same conditions in cyclohexane as solvent showed no nickel leaching, but the yield of triphenylphosphine was about 10% after 76 hours.
[0361]
(Example 481)
(Phosphonation of bromoanisole)
Catalyst preparation: The catalyst was prepared according to the method described as sedimentation precipitation in a coated pan.
[0362]
Catalyst specifications:
[0363]
[Table 60]

Procedure: A round bottom flask equipped with a reflux condenser was charged with 5 gm of catalyst. To this was added a solution of 1 ml (5.75 mmol) of diphenylphosphine in 30 ml of anhydrous degassed diethylformamide at room temperature. The suspension was degassed by repeated vacuum and argon flushing. After heating to 100 ° C. over 30 minutes, 10 mmol (1.87 gm) 2-bromoanisole and 20 mmol (2.25 gm) diazabicyclooctane in 30 ml dimethylformamide were added and the resulting solution was maintained at 100 ° C. . Thereafter, at 12 hour intervals, three additional portions of 1 ml each of diphenylphosphine were added. The reaction was continued for 76 hours. The reaction was stopped by cooling the flask to room temperature. The catalyst was recovered by centrifugation and washed with dimethylformamide. The filtrates were combined and evaporated to give a sticky residue which was diluted with 50 ml of tetrahydrofuran. Solution as described in previous examples,³¹Analyzed by P NMR. An 83% conversion of 2-bromoanisole was observed. A quantitative estimate of phosphine was not determined.
[0364]
(Example 482)
(C₆H₆To C₆D₆Deuteration)
Catalyst specifications:
[0365]
[Table 61]

Catalyst pretreatment: The catalyst was refluxed twice with 3 ml of heavy water, recovered by centrifugation and dried under reduced pressure. This was essential to remove protons on the solid support.
[0366]
Procedure: 100 mg of this catalyst was charged into a microreactor equipped with an external magnetic stirrer and 0.01 mol of benzene (0.78 g) and 2 ml of heavy water were added. The reaction vessel was heated to 110 ° C. using external heating. After reaching that temperature, stirring was started. The reactor was maintained at these conditions for 24 hours. The reactor was cooled to −5 ° C., the liquid was collected, and the organic liquid was analyzed by NMR (88% labeling with deuterium using chloroform as internal standard).
[0367]
The catalyst was recovered by centrifugation and the recovered catalyst was dried under reduced pressure. This catalyst was regenerated to obtain comparable activity and selectivity.
[0368]
Although the invention has been shown and described in detail with respect to preferred embodiments thereof, it will be appreciated that the foregoing and other changes may be made in form and detail without departing from the spirit and scope of the invention. It will be understood by those skilled in the art.
[Brief description of the drawings]
[0369]
FIG. 1 is a schematic representation of a conceptual depiction of this catalyst formulation.
FIG. 2 is a semi-realistic enlarged view of the surface of this catalyst formulation. The support on which the catalytically active material is deposited, the single or multiple reactants, reaches this catalytic material, which contains the active sites, and then the reactants are converted into products and returned to the bulk liquid. Released.
FIG. 3 is a schematic view of a continuous liquid extractor of solids, where a is a unidirectional gas bubbler (which is connected to a cooler) and b is this A cooler, c is an extraction container (which holds the magnetic needle and solids to be leached / extracted), d is a magnetic stirrer unit, and e is a container holding the extract And f is a hot bath.
FIG. 4 is a schematic diagram of a fluidized bed in which a catalyst formulation is processed, where a is a jacket through which a constant temperature fluid circulates, and b is a liquid there. An atomizer sprayed through, c is a gas solid separation mesh, d is an inlet for solution A, e is an inlet for solution B, and V1 and V2 are valves.
FIG. 5 is a schematic diagram of a catalyst preparation unit that simultaneously removes liquid, where a is an inert gas inlet, b is an inlet for solutions A and B, and c is A magnetic needle, a support, and a container holding a liquid, d is an inert gas outlet, e is a cooler, f is a liquid collector, and g is a liquid collector arm.
FIG. 6 is a schematic diagram of a catalyst preparation unit, where a is the inlet for solutions A and B, and b is the vacuum line. c is a motor for a coated pan, d is a coated pan, e is a nozzle for liquids A and B, f is a hot bath, and g is a collection container for condensed liquid It is.

Claims (86)

A novel heterogeneous catalyst composition comprising a solid support having a catalytically active material deposited thereon, the catalytically active material being substantially insoluble in various liquid media, The solid material consists of catalytically active anionic elements with Group IIA metal ions,
Composition. The catalyst according to claim 1, wherein the catalytically active substance is well defined molecularly. The catalyst of claim 1, wherein the catalytically active element is deposited on an outer surface and a pore surface of the solid support, wherein the pores are predominantly greater than about 20 mm in diameter. The catalyst of claim 1, wherein the pores of the solid support have a pore diameter in the range of about 3 to 3000 mm. The catalyst of claim 1, wherein the solid support is a chemically inert solid material. The catalyst according to claim 1, wherein the porous solid support is a powder, granule, regular or irregular flake or pallet, sheet, monolith, rope and fiber solid woven fabric. The catalyst according to claim 1, wherein the porous solid support is a mechanically robust and thermally stable solid and is insoluble in the reaction medium. The catalyst according to claim 1, wherein the catalytically active element is insoluble in the reaction medium, and the reaction medium is selected from an organic phase, an aqueous phase, a powder, a non-aqueous ionic liquid and a supercritical fluid phase. The catalyst of claim 1, wherein the catalytically active solid support is a thermally stable solid material having a melting point higher than 100 ° C. The catalyst according to claim 1, wherein the catalytically active substance is a non-sublimable solid. 2. The solid support according to claim 1, comprising a solid support on which a catalytically active element is deposited, the catalytically active element remaining as a composite solid that is stable in the gas phase, liquid phase and gas-liquid phase. catalyst. The liquid phase is selected from organic, aqueous, powder, non-aqueous ionic liquid and supercritical fluid phases or mixtures thereof, wherein the mixture contains reactants, products and promoters. 11. The catalyst according to 11. The catalyst of claim 1 remaining as a physically stable composite solid in the gas phase or liquid phase over a temperature range of -78C to 300C. The catalyst of claim 1 remaining as a physically stable composite solid in the gas phase or liquid phase over a pressure in the range of 5 to 5000 psi. The catalyst according to claim 1, wherein the Group IIA metal used is a cation with a charge of +2. The catalyst according to claim 1, wherein the Group IIA metal used is selected from calcium, strontium, barium and mixtures thereof. 2. A catalyst according to claim 1, wherein the Group IIA metal used is selected alone or in combination with other Group IIA metals. The catalyst of claim 1, wherein the catalytically active element is an anion having two or more negative charges. The catalyst of claim 1, wherein the catalytically active element is separately selected from metal complexes, quaternary compounds, metal oxoanions, polyoxometalates, and combinations thereof. The catalyst of claim 19, wherein the metal complex has the general formula:
(M) _x (L) _y (L ^* ) _z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Is an atom or ion and is separately selected, x is in the range of 1 to 60, L is selected from aliphatic compounds, aromatic compounds and heterocyclic compounds, the compounds being O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, at least one radical derived from carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded thereto containing, the ^{_{radical, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- separately little is selected from Comprising at least one or more negatively charged functional groups, y is at least 1, L ^* is a radical selected from organic anions, inorganic anions and ligand compounds, the compounds comprising O N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene bonded thereto = C, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl At least one radical, and Z is in the range of 0-7.
catalyst. 20. A catalyst according to claim 19, wherein the quaternary compound has the general formula:
_{^{[(Y +) (R *}} ) I] [Z -]
Where, for Y ⁺ = N ⁺ , P ⁺ , As ⁺ , I = 4; for Y ⁺ = S ⁺ , I = 3 and R ^* is alkyl, aryl, arylalkyl , alkylaryl, alkoxy, aryloxy, independently selected from ^{_{cycloalkyl, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- from Comprising at least one or more negatively charged functional groups selected separately, and Z is an anion selected from organic anions, inorganic anions and coordination complex anions,
catalyst. The catalyst according to claim 1, wherein the insoluble catalytically active substance optionally contains a catalyst inert additive. 23. A catalyst according to claim 22, wherein the catalyst inert additive is an anion having two or more negative charges. 23. A catalyst according to claim 22, wherein the catalyst inert additive is selected separately from organic anions, inorganic anions or combinations thereof. The catalyst inert additive is selected from a ligand compound, wherein the ligand compound is O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, Contains at least one radical derived from a bonded carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, wherein the radical is —SO ₃ ^— , —SO ₂ ^— , — ^{_{PO 3 2-, -COO -, -O}} -, AsO 3 2- and -S ^- comprising at least one or more negatively charged functional groups are independently selected from a catalyst according to claim 22. The catalyst according to claim 1, wherein the amount of catalytically active element used is 40% by weight or less. The catalyst according to claim 1, wherein the amount of catalyst inert additive used is a proportion of 0 to 200% by weight of the catalytically active element. The catalyst according to claim 1, which can be used for a catalytic reaction in a gas phase or a slurry phase. The catalyst of claim 1 further comprising a high boiling liquid film deposited on the solid support. A novel heterogeneous catalyst composition comprising a solid support having a catalytically active material deposited thereon, the catalytically active material being substantially insoluble in various liquid media, The solid material consists of a catalytically active anionic element with a Group IIA metal ion and a catalytically inert anionic additive,
Composition. 32. The catalyst of claim 30, wherein the catalytically active material is well defined molecularly. 31. The catalyst of claim 30, wherein the catalytically active element is deposited on the outer and pore surfaces of the solid support, the pores being primarily greater than about 20 mm in diameter. 32. The catalyst of claim 30, wherein the pores of the solid support have a pore diameter in the range of about 3 to 3000 mm. 32. The catalyst of claim 30, wherein the solid support is a chemically inert solid material. 31. The catalyst of claim 30, wherein the porous solid support is a powder, granule, regular or amorphous flake or pallet, sheet, monolith, rope and fiber solid woven fabric. 31. The catalyst of claim 30, wherein the porous solid support is a mechanically robust and thermally stable solid and is insoluble in the reaction medium. 31. The catalyst of claim 30, wherein the catalytically active element is insoluble in the reaction medium, and the reaction medium is selected from an organic phase, an aqueous phase, a powder, a non-aqueous ionic liquid and a supercritical fluid phase. 32. The catalyst of claim 30, wherein the catalytically active solid support is a thermally stable solid material having a melting point higher than 100 <0> C. 32. The catalyst of claim 30, wherein the catalytically active material is a non-sublimable solid. 31. The solid support according to claim 30, comprising a solid support on which a catalytically active element is deposited, the catalytically active element remaining as a composite solid that is stable in the gas phase, liquid phase and gas-liquid phase. catalyst. The liquid phase is selected from organic, aqueous, powder, non-aqueous ionic liquid and supercritical fluid phases or mixtures thereof, wherein the mixture contains reactants, products and promoters. 41. The catalyst according to 40. 31. The catalyst of claim 30, remaining as a physically stable composite solid in the gas phase or liquid phase over a temperature range of -78C to 300C. 31. The catalyst of claim 30, remaining as a physically stable composite solid in the gas phase or liquid phase over a pressure in the range of 5 to 5000 psi. 31. The catalyst according to claim 30, wherein the Group IIA metal used is a cation with a charge of +2. 31. Catalyst according to claim 30, wherein the Group IIA metal used is selected from calcium, strontium, barium and mixtures thereof. 31. A catalyst according to claim 30, wherein the Group IIA metal used is selected alone or in combination with other Group IIA metals. 32. The catalyst of claim 30, wherein the catalytically active element is an anion having two or more negative charges. 32. The catalyst of claim 30, wherein the catalytically active element is separately selected from metal complexes, quaternary compounds, metal oxoanions, polyoxometalates, and combinations thereof. 31. A catalyst according to claim 30, wherein the amount of catalytically active element used is 40% by weight or less. 31. A catalyst according to claim 30, wherein the amount of catalyst inert additive used is a proportion of 0 to 200% by weight of the catalytically active element. The catalyst according to claim 30, which can be used for a catalytic reaction in a gas phase or a slurry phase. 32. The catalyst of claim 30, further comprising a high boiling liquid film deposited on the solid support. A method of preparing a catalytically active material comprising the steps of interacting a solution comprising a catalytically inert additive and a catalytically active element with a solution of a Group IIA metal cation and obtaining a precipitate; Wherein the catalyst inert additive is separately selected from at least two or more negatively charged anions, ligand compounds and combinations thereof, wherein the ligand compounds are O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, at least one radical derived from carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded thereto containing, the ^{_{radical, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and - ^- at least one or comprises more negatively charged functional groups independently selected from: the catalyst activity elements, metal complexes, quaternary compounds, independently selected metal oxo anions, the polyoxometalate and combinations thereof And the metal complex has the following general formula:
(M) _x (L) _y (L ^* ) _z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Is an atom or ion and is separately selected, x is in the range of 1 to 60, L is selected from aliphatic compounds, aromatic compounds and heterocyclic compounds, the compounds being O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, at least one radical derived from carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded thereto containing, the ^{_{radical, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- separately little is selected from Comprising at least one or more negatively charged functional groups, y is at least 1, L ^* is a radical selected from organic anions, inorganic anions and ligand compounds, the compounds comprising O N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene bonded thereto = C, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl And z ranges from 0 to 7; and the quaternary ammonium compound has the general formula:
_{^{[(Y +) (R *}} ) I] [Z -]
Where, for Y ⁺ = N ⁺ , P ⁺ , As ⁺ , I = 4; for Y ⁺ = S ⁺ , I = 3 and R ^* is alkyl, aryl, arylalkyl , alkylaryl, alkoxy, aryloxy, independently selected from ^{_{cycloalkyl, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- from Comprising at least one or more negatively charged functional groups selected separately, and Z is an anion selected from an organic anion, an inorganic anion and a coordination complex anion; and the Group IIA metal cation is: Selected from compounds of Ca ²⁺ , Sr ²⁺ and Ba ²⁺ ,
Method. 54. The method of claim 53, wherein the reaction is carried out at a temperature in the range of -70 to 200 <0> C, preferably between -5 and 100 <0> C. 54. A process according to claim 53, wherein the amount of catalytically active element used is not more than 40% by weight. 54. A process according to claim 53, wherein the amount of catalytically inert additive used is a proportion of 0 to 200% by weight of the catalytically active element. 54. The method of claim 53, which can be used for catalytic reactions in the gas phase or slurry phase. 54. The method of claim 53, further comprising a film of high boiling liquid deposited on the solid support. A method for preparing a heterogeneous catalyst formulation as a solid composite comprising a porous solid support having a catalytically active solid deposited thereon, the method comprising an insoluble solid support In which the catalyst inert additive and the catalytically active element and the Group IIA metal cation solution are added simultaneously with vigorous stirring and aged for 1 to 48 hours, Wherein the support is a mechanically robust and thermally stable solid in the reaction medium, has a pore diameter in the range of about 3 to 3000 mm, and is a powder, granule, shaped or amorphous Flakes or pallets, sheets, monoliths, ropes and fiber solid fabrics, and the catalyst inert additives are organic compounds, inorganic compounds, or O, N, S, Se, Te, P, As, Sb, Bi, at least two selected from compounds containing at least one radical derived from i, olefin, carbene bonded thereto, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl are independently selected from anions having a more negative charge, the ^{_{radical, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- from Comprising at least one or more separately selected negatively charged functional groups; the catalytically active element is separately selected from metal complexes, quaternary compounds, metal oxoanions, polyoxometalates and combinations thereof; The metal complex has the following general formula:
(M) _x (L) _y (L ^* ) _z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Is an atom or ion and is separately selected, x is in the range of 1 to 60, L is selected from aliphatic compounds, aromatic compounds and heterocyclic compounds, the compounds being O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, at least one radical derived from carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded thereto containing, the ^{_{radical, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- separately little is selected from Comprising at least one or more negatively charged functional groups, y is at least 1, L ^* is a radical selected from organic anions, inorganic anions and ligand compounds, the compounds comprising O N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene bonded thereto = C, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl And z is in the range of 0 to 7; and the quaternary ammonium compound has the following general formula:
_{^{[(Y +) (R *}} ) I] [Z -]
Where, for Y ⁺ = N ⁺ , P ⁺ , As ⁺ , I = 4; for Y ⁺ = S ⁺ , I = 3 and R ^* is alkyl, aryl, arylalkyl , alkylaryl, alkoxy, aryloxy, independently selected from ^{_{cycloalkyl, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- from Comprising at least one or more negatively charged functional groups selected separately, and Z is an anion selected from an organic anion, an inorganic anion and a coordination complex anion; and the Group IIA metal cation is: Selected from compounds of Ca ²⁺ , Sr ²⁺ and Ba ²⁺ ,
Method. 60. The method of claim 59, wherein the reaction is carried out at a temperature in the range of -70 to 200 <0> C, preferably between -5 and 100 <0> C. 60. The method of claim 59, wherein the solvent used is selected from aqueous solvents, water-miscible organic solvents and mixtures thereof. 60. The method of claim 59, wherein the catalytically inert additive and catalytically active element solution and the Group IIA metal cation solution are added simultaneously over a period of 10 to 1500 minutes. 60. The method of claim 59, wherein the catalyst is recovered by centrifugation, decantation, gravity sedimentation or other solid-liquid separation techniques, followed by solid drying in a vacuum. A method for preparing a heterogeneous catalyst formulation as a solid composite, the solid composite comprising a porous solid support having a catalytically active solid deposited thereon, the method comprising the solid support Followed by a step of impregnating the catalyst active element and the catalyst inert additive with a drying step, wherein the dried support has the catalytic active element deposited thereon and the catalyst inert additive is Is added to the solution of the Group IIA metal compound with simultaneous stirring, and the suspension is aged with stirring for 1-48 hours, where the support is mechanically stirred in the reaction medium. A tough, thermally stable solid having a pore diameter in the range of about 3 to 3000 mm, and a powder, granule, shaped or irregular flake or pallet, sheet, monolith, rope and fiber solid woven fabric Exist and then The catalyst inert additive is an organic compound, an inorganic compound, or O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, oxy, alkyl, aryl, aryl bonded thereto Separately selected from at least two or more negatively charged anions selected from compounds containing at least one radical derived from alkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, ^{_{-SO 3 -, -SO 2 -,}} -PO 3 2-, -COO -, -O - at least one or more negatively charged functional groups independently selected from ^-, _AsO ^{3 2-} and -S The catalytically active element comprises a metal complex, a quaternary compound, a metal oxoanion and a polyoxometalate or a combination thereof Selected Luo separately, the metal complex has the following general formula:
(M) _x (L) _y (L ^* ) _z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Is an atom or ion and is separately selected, x is in the range of 1 to 60, L is selected from aliphatic compounds, aromatic compounds and heterocyclic compounds, the compounds being O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, at least one radical derived from carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded thereto containing, the ^{_{radical, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- separately little is selected from Comprising at least one or more negatively charged functional groups, y is at least 1, L ^* is a radical selected from organic anions, inorganic anions and ligand compounds, the compounds comprising O N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene bonded thereto = C, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl And z ranges from 0 to 7; and the quaternary ammonium compound has the general formula:
_{^{[(Y +) (R *}} ) I] [Z -]
Where, for Y ⁺ = N ⁺ , P ⁺ , As ⁺ , I = 4; for Y ⁺ = S ⁺ , I = 3 and R ^* is alkyl, aryl, arylalkyl , alkylaryl, alkoxy, aryloxy, independently selected from ^{_{cycloalkyl, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- from Comprising at least one or more negatively charged functional groups selected separately, and Z is an anion selected from an organic anion, an inorganic anion and a coordination complex anion; and the Group IIA metal cation is: Selected from compounds of Ca ²⁺ , Sr ²⁺ and Ba ²⁺ ,
Method. 65. A process according to claim 64, wherein the reaction is carried out at a temperature in the range of -70 to 200 <0> C, preferably between -5 and 100 <0> C. 65. The method of claim 64, wherein the solvent used is selected from aqueous solvents, water miscible organic solvents and mixtures thereof. 65. The method of claim 64, wherein the support on which the catalytically active element and catalyst inert additive are deposited is added to the solution of the Group IIA metal compound over 10 to 1500 minutes with simultaneous agitation. 65. The method of claim 64, wherein the catalyst is recovered by centrifugation, decantation, gravity sedimentation or other solid-liquid separation techniques, followed by solid drying in vacuum. A method for preparing a heterogeneous catalyst formulation as a solid composite, the solid composite comprising a porous solid support having a catalytically active solid deposited thereon, the method comprising the solid support Following the step of impregnating the catalyst active element and the catalyst inert additive with the catalyst, the drying process and the solid support on which the catalyst inert additive and the catalyst active element are deposited are suspended in a water-miscible solvent. A solution of a Group IIA metal compound is added with vigorous stirring to the water-miscible solvent, and at the same time the low-boiling or azeotropic fraction of the solvent is removed and the suspension is The suspension is aged for 1 to 48 hours, wherein the support is a mechanically robust and thermally stable solid in the reaction medium and has a pore diameter in the range of about 70 to 3000 mm. And powder, granule, regular or irregular shape Present as woven or pallet, sheet, monolith, rope and fiber solid woven fabrics, and the catalyst inert additive is an organic compound, an inorganic compound, or O, N, S, Se, Te, P, As, At least selected from compounds containing at least one radical derived from Sb, Bi, Si, olefin, carbene bonded thereto, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl Separately selected from two or more negatively charged anions, the radicals being —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ²⁻ , —COO ⁻ , —O ⁻ , AsO ₃ ²⁻ and -S ^- independently selected from the comprising at least one or more negatively charged functional groups; the catalyst activity elements, metal Body, quaternary compounds, separately selected from metal oxo anions and polyoxometalates or combinations thereof, the metal complex has the following general formula:
(M) _x (L) _y (L ^* ) _z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Is an atom or ion and is separately selected, x is in the range of 1 to 60, L is selected from aliphatic compounds, aromatic compounds and heterocyclic compounds, the compounds being O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, at least one radical derived from carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded thereto containing, the ^{_{radical, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- separately little is selected from Comprising at least one or more negatively charged functional groups, y is at least 1, L ^* is a radical selected from organic anions, inorganic anions and ligand compounds, the compounds comprising O N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene bonded thereto = C, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl And z is in the range of 0 to 7; and the quaternary ammonium compound has the following general formula:
_{^{[(Y +) (R *}} ) I] [Z -]
Where, for Y ⁺ = N ⁺ , P ⁺ , As ⁺ , I = 4; for Y ⁺ = S ⁺ , I = 3 and R ^* is alkyl, aryl, arylalkyl , alkylaryl, alkoxy, aryloxy, independently selected from ^{_{cycloalkyl, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- from Comprising at least one or more negatively charged functional groups selected separately, and Z is an anion selected from an organic anion, an inorganic anion and a coordination complex anion; and the Group IIA metal cation is: Selected from compounds of Ca ²⁺ , Sr ²⁺ and Ba ²⁺ ,
Method. 70. The method of claim 69, wherein the reaction is performed at a temperature in the range of -70 to 200 <0> C. 70. The method of claim 69, wherein the solvent used to form the Group IIA metal solution is selected from aqueous solvents, water-miscible organic solvents, and mixtures thereof. 70. The method according to claim 69, wherein the solvent used is a water miscible organic solvent and has a boiling point in the range of 40-200 <0> C. 70. The method of claim 69, wherein the catalyst is recovered by centrifugation, decantation or gravity sedimentation, or other solid-liquid separation techniques and subsequently dried in a vacuum. A method of preparing a heterogeneous catalyst formulation as a solid composite material, the solid composite material comprising a porous solid support having a Group IIA metal compound deposited thereon, followed by The solid support on which the Group IIA metal has been deposited is dried and suspended in a water-miscible solvent, to which the solution of catalytically active element and catalyst inert additive is added with vigorous stirring. At the same time, the low-boiling or azeotropic fraction of the solvent is removed and the suspension is aged for 1 to 48 hours, where the support is mechanically A tough, thermally stable solid having a pore diameter in the range of about 3 to 3000 mm, and a powder, granule, shaped or irregular flake or pallet, sheet, monolith, rope and fiber solid woven fabric And exist as The solvent inert additive is an organic compound, an inorganic compound, or O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene bonded thereto, oxy, alkyl, aryl, arylalkyl. Independently selected from an anion having at least two or more negative charges selected from compounds containing at least one radical derived from, alkylaryl, alkoxy, aryloxy, cycloalkyl, wherein the radical is- At least one or more negatively charged functional groups independently selected from SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ²⁻ , —COO ⁻ , —O ⁻ , AsO ₃ ²⁻ and —S ⁻ The catalytically active element is from a metal complex, a quaternary compound, a metal oxoanion and a polyoxometalate or combinations thereof; Selected pieces, the metal complex has the following general formula:
(M) _x (L) _y (L ^* ) _z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Is an atom or ion and is separately selected, x is in the range of 1 to 60, L is selected from aliphatic compounds, aromatic compounds and heterocyclic compounds, the compounds being O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, at least one radical derived from carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded thereto containing, the ^{_{radical, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- separately little is selected from Comprising at least one or more negatively charged functional groups, y is at least 1, L ^* is a radical selected from organic anions, inorganic anions and ligand compounds, the compounds comprising O N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene bonded thereto = C, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl And z ranges from 0 to 7; and the quaternary ammonium compound has the general formula:
_{^{[(Y +) (R *}} ) I] [Z -]
Where, for Y ⁺ = N ⁺ , P ⁺ , As ⁺ , I = 4; for Y ⁺ = S ⁺ , I = 3 and R ^* is alkyl, aryl, arylalkyl , alkylaryl, alkoxy, aryloxy, independently selected from ^{_{cycloalkyl, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- from Comprising at least one or more negatively charged functional groups selected separately, and Z is an anion selected from an organic anion, an inorganic anion and a coordination complex anion; and the Group IIA metal cation is: Selected from compounds of Ca ²⁺ , Sr ²⁺ and Ba ²⁺ ,
Method. 75. The method of claim 74, wherein the reaction is performed at a temperature in the range of -70 to 200 <0> C. 75. The method of claim 74, wherein the solvent used to form the Group IIA metal solution is selected from aqueous solvents, water-miscible organic solvents, and mixtures thereof. 75. The method of claim 74, wherein the solvent used is a water miscible organic solvent and has a boiling point in the range of 40 to 200 <0> C. 75. The method of claim 74, wherein the catalyst is recovered by centrifugation, decantation or gravity sedimentation, or other solid-liquid separation techniques and subsequently dried in vacuum. A method of preparing a heterogeneous catalyst formulation as a solid composite comprising fluidizing a solid support in a gas stream, and a catalytically active element and a catalyst inert additive on the solid support. Spraying the catalytically active element and the catalytically inert additive as deposited, fluidizing the solid is continued for 1 to 48 hours, and the solution of the Group IIA metal compound is , Followed by spraying and fluidization of the solids is continued for a further 1 to 48 hours, and the solids are recovered, wherein the support is mechanically robust in the reaction medium. As a thermally stable solid, having a pore diameter in the range of about 70 to 3000 mm, and as a powder, granule, regular or irregular flake or pallet, sheet, monolith, rope and fiber solid woven fabric Exists, and The catalyst inert additive is an organic compound, an inorganic compound, or O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, oxy, alkyl, aryl, aryl bonded thereto Separately selected from at least two or more negatively charged anions selected from compounds containing at least one radical derived from alkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, ^{_{-SO 3 -, -SO 2 -,}} -PO 3 2-, -COO -, -O - at least one or more negatively charged functional groups independently selected from ^-, _AsO ^{3 2-} and -S The catalytically active element comprises a metal complex, a quaternary compound, a metal oxoanion and a polyoxometalate or a combination thereof Selected Luo separately, the metal complex has the following general formula:
(M) _x (L) _y (L ^* ) _z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Is an atom or ion and is separately selected, x is in the range of 1-60, L is selected from aliphatic, aromatic and heterocyclic compounds, said compounds being O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl attached thereto, at least one radical containing, the ^{_{radical, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- separately little is selected from With at least one or more negatively charged functional groups, y is at least 1, L ^* is a radical selected from organic anions, inorganic anions and ligand compounds, the compounds comprising O , N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene bonded thereto = C, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl And z is in the range of 0 to 7; and the quaternary ammonium compound has the following general formula:
_{^{[(Y +) (R *}} ) I] [Z -]
Where, for Y ⁺ = N ⁺ , P ⁺ , As ⁺ , I = 4; for Y ⁺ = S ⁺ , I = 3 and R ^* is alkyl, aryl, arylalkyl , alkylaryl, alkoxy, aryloxy, independently selected from ^{_{cycloalkyl, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- from Comprising at least one or more negatively charged functional groups selected separately, and Z is an anion selected from an organic anion, an inorganic anion and a coordination complex anion; and the Group IIA metal cation is: Selected from compounds of Ca ²⁺ , Sr ²⁺ and Ba ²⁺ ,
Method. 80. The method of claim 79, wherein the reaction is performed at a temperature in the range of -70 to 200 <0> C. 80. The method of claim 79, wherein the solvent used to form the Group IIA metal solution is selected from aqueous solvents, water-miscible organic solvents, and mixtures thereof. A method for preparing a heterogeneous catalyst formulation as a solid composite comprising the step of rotating a solid support in a rotating pan under a stream of gas comprising the catalytically active element and the catalyst inert The additive solution is sprayed such that the catalytically active element and catalytically inert additive are deposited on the solid support, the solid rotation is continued for 1 to 48 hours, and the Group IIA metal The solution of the compound is subsequently sprayed and the rotation of the solid is continued for a further 1 to 48 hours and the solid is recovered, where the support is mechanically loaded in the reaction medium. Tough and thermally stable solids, having a pore diameter in the range of about 70 to 3000 mm, and woven powders, granules, shaped or irregular flakes or pallets, sheets, monoliths, ropes and fiber solids Exists as a cloth, The catalyst inert additive is an organic compound, an inorganic compound, or O, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, oxy, alkyl, aryl bonded thereto, Separately selected from at least two or more negatively charged anions selected from compounds containing at least one radical derived from arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl, ^{_{, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O - at least one or more negatively charged functional groups independently selected from ^-, _AsO ^{3 2-} and -S The catalytically active element comprises a metal complex, a quaternary compound, a metal oxoanion and a polyoxometalate or a combination thereof Independently selected from, the metal complex has the following general formula:
(M) _x (L) _y (L ^* ) _z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Is an atom or ion and is separately selected, x is in the range of 1 to 60, L is selected from aliphatic compounds, aromatic compounds and heterocyclic compounds, the compounds being O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, at least one radical derived from carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded thereto containing, the ^{_{radical, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- separately little is selected from Comprising at least one or more negatively charged functional groups, y is at least 1, L ^* is a radical selected from organic anions, inorganic anions and ligand compounds, the compounds comprising O N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene bonded thereto = C, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl And z is in the range of 0 to 7; and the quaternary ammonium compound has the following general formula:
_{^{[(Y +) (R *}} ) I] [Z -]
Where, for Y ⁺ = N ⁺ , P ⁺ , As ⁺ , I = 4; for Y ⁺ = S ⁺ , I = 3 and R ^* is alkyl, aryl, arylalkyl , alkylaryl, alkoxy, aryloxy, independently selected from ^{_{cycloalkyl, -SO 3 -, -SO 2 -}} , -PO 3 2-, -COO -, -O -, AsO 3 2- and -S ^- from Comprising at least one or more negatively charged functional groups selected separately, and Z is an anion selected from an organic anion, an inorganic anion and a coordination complex anion; and the Group IIA metal cation is: Selected from compounds of Ca ²⁺ , Sr ²⁺ and Ba ²⁺ ,
Method. 83. The method of claim 82, wherein the reaction is performed at a temperature in the range of -70 to 200 <0> C. 84. The method of claim 82, wherein the solvent used to form the solution is selected from aqueous solvents, water miscible organic solvents, and mixtures thereof. 83. The method of claim 82, wherein the solution is sprayed simultaneously or sequentially. Use of the catalyst according to claim 1 in a reaction, wherein the reaction is selected from similar reactions catalyzed by a catalytically active element in the liquid phase, the catalytically active element comprising a metal complex, a quaternary compound Independently selected from metal oxoanions and polyoxometalates or combinations thereof, the metal complex has the following general formula:
(M) _x (L) _y (L ^* ) _z
Here, M is a catalytic metal of a coordination complex of a transition metal derived from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB, Group IB or Group IIB of the periodic table of elements. Is an atom or ion and is separately selected, x is in the range of 1 to 60, L is selected from aliphatic compounds, aromatic compounds and heterocyclic compounds, the compounds being O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, at least one radical derived from carbene, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl bonded thereto Y is at least 1 and L ^* is a radical selected from an organic anion, an inorganic anion and a ligand compound, the compound comprising O, N, S , Se, Te, P, As, Sb, Bi, Si, olefin, carbene bonded thereto = C, oxy, alkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, cycloalkyl And Z ranges from 0 to 7; and the quaternary ammonium compound has the general formula:
_{^{[(Y +) (R *}} ) I] [Z -]
Where, for Y ⁺ = N ⁺ , P ⁺ , As ⁺ , I = 4; for Y ⁺ = S ⁺ , I = 3 and R ^* is alkyl, aryl, arylalkyl Independently selected from alkylaryl, alkoxy, aryloxy, cycloalkyl, and Z is an anion selected from organic anions, inorganic anions and coordination complex anions,
Method.

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