JP2004285009A - Method for producing aminotris(disubstituted amino)phosphonium chloride - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for safely/easily producing an aminotris(disubstituted amino)phosphonium chloride in high yield and high selectivity on an industrial scale without the need of isolatedly handling phosphorus pentachloride. <P>SOLUTION: The method for producing the aminotris(disubstituted amino)phosphonium chloride comprises the following process: Phosphorus trichloride and chlorine are reacted with each other in the presence of an aromatic hydrocarbon to form phosphorus pentachloride, subsequently in a condition of reaction mixture without isolation/refining of the phosphorus pentachloride, the phosphorus pentachloride in the reaction mixture and a disubstituted amine are reacted with each other to form a chlorotris(disubstituted amino)phosphonium chloride, which is then reacted with ammonia. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００１４】
（式中、Ｒは二置換アミノ基の同種または異種の置換基を表すが、二個の置換基Ｒが互いに結合して二置換アミノ基が環状アミノ基となる場合もある。）で表される化合物である。
本発明の方法において、溶媒として用いる芳香族炭化水素類としては、ベンゼン、アルキル置換芳香族炭化水素、ハロゲン化芳香族炭化水素、ハロゲン化アルキル置換芳香族炭化水素などが挙げられる。
【００１５】
具体的には、たとえば、ベンゼン；トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、エチルベンゼン、ノルマルプロピルベンゼン、クメン、１，２，３−トリメチルベンゼン、１，２，４−トリメチルベンゼン、メシチレン、テトラリン、ブチルベンゼン、ｐ−シメン、シクロヘキシルベンゼン、１，２−ジエチルベンゼン、１，３−ジエチルベンゼン、１，４−ジエチルベンゼン、１，２−ジイソプロピルベンゼン、１，３−ジイソプロピルベンゼン、１，４−ジイソプロピルベンゼン、１，２，４−トリエチルベンゼン、１，３，５−トリエチルベンゼンまたはドデシルベンゼンなどの炭素原子数７〜２０個のアルキル置換芳香族炭化水素；クロロベンゼン、ｏ−ジクロロベンゼン、ｍ−ジクロロベンゼン、１，２，４−トリクロロベンゼン、１，２，３，４−テトラクロロベンゼン、ブロモベンゼン、ｏ−ジブロモベンゼン、ｍ−ジブロモベンゼン、１−ブロモ−２−クロロベンゼン、１−ブロモ−３−クロロベンゼン、１−ブロモナフタレンまたは１−クロロナフタレンなどの炭素数原子数６〜１４個かつハロゲン原子数１〜４個のハロゲン化芳香族炭化水素；２−クロロトルエン、３−クロロトルエン、４−クロロトルエン、２−ブロモトルエン、３−ブロモトルエン、２，４−ジクロロトルエン、３，４−ジクロロトルエン、１−ブロモ−２−エチルベンゼン、１−ブロモ−４−エチルベンゼン、２−クロロエチルベンゼン、１−クロロ−４−エチルベンゼン、１−クロロ−４−イソプロピルベンゼン、１−ブロモ−４−イソプロピルベンゼン、メシチルクロリド、４−クロロ−ｏ−キシレンまたは２−クロロ−ｐ−キシレンなどの炭素原子数７〜２０個かつハロゲン原子数１〜４個のハロゲン化アルキル置換芳香族炭化水素；などが好ましく挙げられる。これらの他、本発明目的を損なわない限りにおいて、すなわち、反応を阻害しない限り如何なる芳香族炭化水素類を溶媒として用いても構わない。これらのうち、より好ましくは、ベンゼン；トルエン、ｍ−キシレン、エチルベンゼン、メシチレンなどの炭素原子数７〜９個のアルキル置換芳香族炭化水素；クロロベンゼン、ｏ−ジクロロベンゼンまたは１，２，４−トリクロロベンゼンなどの炭素原子数６〜１４個かつ塩素原子数１〜４個の塩素化芳香族炭化水素；２−クロロトルエン、４−クロロトルエン、１−クロロ−４−エチルベンゼンまたはメシチルクロリドなどの炭素原子数７〜９個かつ塩素原子数１〜４個の塩素化アルキル置換芳香族炭化水素である。
【００１６】
これら芳香族炭化水素類の溶媒は単独で用いても複数種を併用しても構わない。また、これらの溶媒そのものが、生成する五塩化りん、クロロトリス（二置換アミノ）ホスホニウムクロリドまたはアミノトリス（二置換アミノ）ホスホニウムクロリドを完全に溶解する必要はない。これらの溶媒の使用量は特に限定されないが、通常、原料の三塩化りん１重量部に対して３００重量部以下であり、好ましくは１〜１５０重量部であり、より好ましくは２〜３０重量部である。
【００１７】
本発明の方法に用いられる三塩化りんは、市販されているものをそのまま使用できるが、必要であれば蒸留などの精製工程を施した後で使用してもよい。
本発明の方法において、前記芳香族炭化水素類の存在下、三塩化りんと塩素とを反応させて五塩化りんを生成させるに際し、用いる塩素の量は、三塩化りん１モルに対して、通常０．９〜１．５モルであり、好ましくは０．９５〜１．２モルである。塩素は、通常、連続的または間欠的に前記芳香族炭化水素類溶媒と三塩化りんとが装入されている反応器に、気体、液体または溶液のいずれかの状態で仕込む。これらのうちでは、気体での装入が好ましい。塩素を気体で反応器に導入する場合には、たとえば、窒素、ヘリウムまたはアルゴン等の不活性ガスで希釈して用いても構わない。
【００１８】
この反応における反応温度は、通常０〜６０℃であり、好ましくは１０〜４０℃である。反応時の圧力は、通常０．００１〜１．０ＭＰａ（絶対圧、以降同じ。）、好ましくは０．１〜０．５ＭＰａである。反応時間は特に制限されないが、通常、塩素の仕込み時間も含め２０時間以内であり、好ましくは０．１〜１０時間である。
【００１９】
反応終了後、塩素を過剰に用いた場合には、次反応での副生物抑制の点から残存する未反応の塩素を除去することが好ましい。未反応塩素の除去方法としては、一般的な方法を適宜選択して用いることができるが、減圧による除去、不活性ガスの流通による除去、およびこれらの組み合わせによる方法などが好ましく用いられる。未反応塩素の除去の程度は、特に限定されないが、通常、反応混合物中の残存塩素濃度として０．２重量％以下であり、特に０．１重量％以下が好ましい。
【００２０】
このようにして反応器内で生成させた五塩化りんは、単離・精製することなく、芳香族炭化水素類溶媒などを含む反応混合物のままで、次の二置換アミンとの反応に用いる。
本発明の方法に用いる二置換アミンは、Ｒ_２ＮＨの構造を有する化合物で、二つの置換基（Ｒ）が、同種または異種の炭化水素基であり、好ましくは炭素原子数１〜１０個の炭化水素基である二置換アミンである。置換基（Ｒ）としては、具体的には、たとえば、メチル、エチル、ｎ−プロピル、イソプロピル、アリル、ｎ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、２−ブテニル、１−ペンチル、２−ペンチル、３−ペンチル、２−メチル−１−ブチル、イソペンチル、ｔｅｒｔ−ペンチル、３−メチル−２−ブチル、ネオペンチル、ｎ−ヘキシル、４−メチル−２−ペンチル、シクロペンチル、シクロヘキシル、１−ヘプチル、３−ヘプチル、１−オクチル、２−オクチル、２−エチル−１−ヘキシル、１，１−ジメチル−３，３−ジメチルブチル（通称、ｔｅｒｔ−オクチル）、ノニル、デシル、フェニル、４−トルイル、ベンジル、１−フェニルエチルまたは２−フェニルエチル等の脂肪族または芳香族の炭化水素基から選ばれる。これらのうち、好ましくは、メチル、エチル、ｎ−プロピル、イソプロピル、ｔｅｒｔ−ブチル、ｔｅｒｔ−ペンチルまたは１，１−ジメチル−３，３−ジメチルブチルなどの炭素原子数１〜１０個の脂肪族炭化水素基であり、より好ましくは、メチル、エチル、ｎ−プロピルおよびイソプロピルなどの炭素原子数１〜３個の脂肪族炭化水素基であり、メチル基またはエチル基がさらに好ましい。
【００２１】
また、前記二置換アミンとして、２個の置換基（Ｒ）が互いに結合した環状二級アミンも用いることができる。この場合の環状二級アミンとしては、ピロリジン、ピペリジン、モルホリンおよびヘキサメチレンイミン、またはそれらにメチルまたはエチルなどのアルキル基が置換した５〜７員環の環状二級アミンが挙げられる。これらのうち、好ましくは、５〜７員環の無置換環状二級アミンであり、より好ましくは、ピロリジン、ピペリジンまたはモルホリンである。
【００２２】
これらの二置換アミンは、単独で用いることもできるが複数種を組み合わせて用いることもできる。複数種の二置換アミンを組み合わせて用いる場合、あらかじめ混合した状態で五塩化りんと反応させる方法の他、それぞれの二置換アミンを逐次的に五塩化りんと反応させる方法もとることができる。
反応器内で生成させた五塩化りん（反応混合物中に含まれる五塩化りん）と前記二置換アミンとを反応させてクロロトリス（二置換アミノ）ホスホニウムクロリドを生成させるに際し、用いる二置換アミンの量は、反応収率確保の点から、始めに用いた三塩化りん１モルに対して通常５．８０〜６．３０モルであり、好ましくは６．００〜６．２０モルである。前記二置換アミンは、通常、連続的または間欠的に、芳香族炭化水素類溶媒と生成した五塩化りんとを含む反応混合物に、気体、液体または溶液のいずれかの状態で加える。二置換アミンを気体で反応混合物に加える場合には、たとえば、窒素、ヘリウムまたはアルゴン等の不活性ガスで希釈して用いても構わない。
【００２３】
この反応における反応温度は、通常０〜８０℃であり、好ましくは１０〜７０℃である。反応時の圧力は、通常０．００１〜１．０ＭＰａであり、好ましくは０．１〜０．５ＭＰａである。反応時間は特に制限されないが、通常、二置換アミンの仕込み時間も含め４０時間以内であり、好ましくは０．５〜３０時間であり、より好ましくは１〜１５時間である。
【００２４】
このようにして得られたクロロトリス（二置換アミノ）ホスホニウムクロリドは、下記式（１）
【００２５】
【化４】

【００２６】
（式中、Ｒは二置換アミノ基の同種または異種の置換基を表すが、二個の置換基Ｒが互いに結合して二置換アミノ基が環状アミノ基となる場合もある。）で表される化合物である。なお、式中Ｒは、前記の反応に用いた二置換アミンの置換基Ｒと対応している。
このクロロトリス（二置換アミノ）ホスホニウムクロリドは、次のアンモニアとの反応に用いるに際して、場合によっては単離して供することもできるが、通常は芳香族炭化水素類溶媒および副生物である二置換アミンの塩酸塩を含む反応混合物そのままで用いることができる。
【００２７】
上記反応で生成させたクロロトリス（二置換アミノ）ホスホニウムクロリドと、アンモニアとを反応させて、アミノトリス（二置換アミノ）ホスホニウムクロリドを製造するに際し、用いるアンモニアの量は、収率および経済性の点から始めに用いた三塩化りんの１モルに対して、通常１．８〜５０モルであり、好ましくは２〜２０モルである。アンモニアは、通常、連続的または間欠的に、気体、液体または溶液のいずれかの状態で、クロロトリス（二置換アミノ）ホスホニウムクロリドを含む反応混合物へ加える。これらのうちでは、気体で加えることが好ましい。アンモニアを気体で反応混合物に加える場合には、たとえば、窒素、ヘリウムまたはアルゴン等の不活性ガスで希釈して用いても構わない。
【００２８】
この反応の温度は、通常０〜６０℃であり、好ましくは１０〜５０℃である。反応時の圧力は、通常０．００１〜１．０ＭＰａであり、好ましくは０．１〜０．５ＭＰａである。反応時間は特に制限されないが、通常、アンモニアの仕込み時間も含め４０時間以内であり、好ましくは０．５〜３０時間であり、より好ましくは１〜１５時間である。この反応に前段の反応混合物をそのまま用いる場合には、該反応混合物には前段の反応の副生物である二置換アミンの塩酸塩が含まれている。この二置換アミンの塩酸塩は、通常、過剰に存在するアンモニアによって全部または一部が置きかわり、塩化アンモニウムと二置換アミンを生成する。
【００２９】
また、この反応に単離したクロロトリス（二置換アミノ）ホスホニウムクロリドを使用する場合には、溶媒として上述の芳香族炭化水素類を用いることが好ましい。溶媒の使用量は特に限定されないが、通常、使用するクロロトリス（二置換アミノ）ホスホニウムクロリドのモル数を三塩化りんに換算した１重量部に対し、上述の重量部の範囲で用いる。
【００３０】
このようにして得られたアミノトリス（二置換アミノ）ホスホニウムクロリドは、下記式（２）
【００３１】
【化５】

【００３２】
で表される化合物であり、式中Ｒは、前記の反応に用いたクロロトリス（二置換アミノ）ホスホニウムクロリドの置換基Ｒと対応している。
なお、本発明の方法により製造したアミノトリス（二置換アミノ）ホスホニウムクロリドは、場合によっては反応混合物のまま、次の用途（たとえば、ホスファゼン化合物の合成など）に供することもできるが、分離して取り出すこともできる。
【００３３】
通常、前記反応混合物中には、アミノトリス（二置換アミノ）ホスホニウムクロリドが塩化アンモニウムおよび二置換アミン塩酸塩の固体と共に固体として存在しているが、アミノトリス（二置換アミノ）ホスホニウムクロリドは、加熱すると溶解する。そこで、なおも不溶である塩化アンモニウムおよび二置換アミン塩酸塩を濾過などの通常の固液分離法により除いたのち、冷却することにより析出してくるアミノトリス（二置換アミノ）ホスホニウムクロリドの固体を通常の固液分離法で分離することができる。この方法で得られたアミノトリス（二置換アミノ）ホスホニウムクロリドは充分に純度は高いが、必要ならば改めて再結晶などの精製工程を施すこともできる。
【００３４】
【発明の効果】
本発明の方法によれば、芳香族炭化水素類の存在下、三塩化りんと塩素とを反応させて五塩化りんを生成させ、ついで二置換アミンを反応させ、さらにアンモニアを反応させるため、五塩化りんを単離して取り扱う必要がなくなり、アミノトリス（二置換アミノ）ホスホニウムクロリドを、工業的なスケールで安全かつ効率的に製造することができる。すなわち、本発明によれば、アミノトリス（二置換アミノ）ホスホニウムクロリドを簡便に高収率かつ高選択率で得ることができる。
【００３５】
【実施例】
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、下記の実施例中で用いた分析装置および分析手法は以下の通りである。
（１）^３１Ｐ−ＮＭＲ分析
日本電子株式会社製Ａ−５００型ＮＭＲ分析装置（５００ＭＨｚ）を用いて行った。
（２）滴定法（反応混合物中の残存塩素分の分析）
試料約１０ｇを２００ｍｌ三角フラスコに秤量し、氷水により冷却しながら、純水２０ｍｌと１０重量％ヨウ化カリウム水溶液１０ｍｌおよび１０重量％酢酸水溶液１０ｍｌを加え、緩やかに攪拌した。この試料溶液を０．０１ｍｏｌ／ｌチオ硫酸ナトリウム水溶液にて滴定を行なった。澱粉指示薬（約０．５重量％澱粉水溶液（煮沸済み））を、試料溶液が極薄い黄色になってから約１ｍｌ加え、この試料溶液の紫色が消失した点を終点とした。
【００３６】
【実施例１】
窒素雰囲気下で、１Ｌのガラス製反応器に、三塩化りん２７．５ｇ（２００ｍｍｏｌ）とｏ−ジクロロベンゼン２４５ｇを仕込んだ。この溶液を緩やかに攪拌しながら３０℃に保ち、常圧条件下にガス導入管を介して塩素ガス１３．９ｇ（１９６ｍｍｏｌ、三塩化りんに対して０．９８倍ｍｏｌ）を６０分かけて吹込み、さらに６０分攪拌を続けた。
【００３７】
次にこの反応液に、ジメチルアミン５４．６ｇ（１２１０ｍｍｏｌ、三塩化りんに対して６．０５倍ｍｏｌ）をガス状態で４時間かけて吹込んだ。反応は常圧で、温度は３０℃を保持するように冷却を行ないながら実施した。吹込み終了後、同温度で３０分攪拌した後、３０分かけて６０℃まで昇温し、さらに６０分攪拌を続けた。反応液は白色の懸濁液となった。
【００３８】
次に、温度を４０℃まで下げ、アンモニア８．３ｇ（４９０ｍｍｏｌ、三塩化りんに対して２．４５倍ｍｏｌ）をガス状態で２時間かけて吹込んだ。反応は常圧で、温度は４０℃で行なった。吹込み終了後、同温度でさらに６０分攪拌を続けた。反応液は白色の懸濁液であった。得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
【００３９】
濾別された白色固体の重水素化クロロホルム溶媒中での^３１Ｐ−ＮＭＲによる分析では五塩化りんは検出されず、全て反応していることが判った。また重水素化ジメチルスルホキシド溶媒を用い、りん酸トリ−ノルマル−ブチルを内部標準とした^３１Ｐ−ＮＭＲによる分析から、この白色固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは１６２ｍｍｏｌであった。一方、濾液についても前記白色固体と同様に分析したところ、五塩化りんは検出されず、アミノトリス（ジメチルアミノ）ホスホニウムクロリドは２８ｍｍｏｌ含まれていた。これ以外に極微量の不明ピークが認められた。濾液および固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは合計で１９０ｍｍｏｌであり、収率は９５．０％であった。
【００４０】
【実施例２】
実施例１における塩素ガス量を１２．８ｇ（１８０ ｍｍｏｌ、三塩化りんに対して０．９０倍ｍｏｌ）に変更し、塩素ガスの吹込み温度を１５℃に変更した以外は、実施例１と全く同様に反応を行なった。反応液は白色の懸濁液であった。
【００４１】
得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
濾別された白色固体および濾液を実施例１の方法に従って分析したところ、白色固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは１４９ｍｍｏｌであり、濾液中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは２７ｍｍｏｌであった。これ以外に少量の不明ピークが認められた。濾液および固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは合計で１７６ｍｍｏｌであり、収率は８８．０％であった。
【００４２】
【実施例３】
窒素雰囲気下で、１Ｌのガラス製反応器に、三塩化りん２７．５ｇ（２００ｍｍｏｌ）とｏ−ジクロロベンゼン４１０ｇを仕込んだ。この溶液を緩やかに攪拌しながら１０℃に保ち、常圧条件下にガス導入管を介して塩素ガス１７．０ｇ（２４０ｍｍｏｌ、三塩化りんに対して１．２０倍ｍｏｌ）を６０分かけて吹込み、３０℃に昇温した後、さらに６０分攪拌を続けた。その後、ガス導入管を介して窒素ガスを約２０ｇ／ｈで６０分間吹込み、過剰分の未反応塩素を除去した。反応混合物中の残留塩素分を滴定法により分析した結果６０ｐｐｍであった。
【００４３】
次にこの反応液に、ジメチルアミン５４．６ｇ（１２１０ｍｍｏｌ、三塩化りんに対して６．０５倍ｍｏｌ）をガス状態で４時間かけて吹込んだ。反応は常圧で、温度は３０℃を保持するように冷却を行ないながら実施した。吹込み終了後、同温度で３０分攪拌した後、３０分かけて６０℃まで昇温し、さらに６０分攪拌を続けた。反応液は白色の懸濁液となった。
【００４４】
次に、温度を４０℃まで下げ、アンモニア８．３ｇ（４９０ｍｍｏｌ、三塩化りんに対して２．４５倍ｍｏｌ）をガス状態で２時間かけて吹込んだ。反応は常圧で、温度は４０℃で行なった。吹込み終了後、同温度でさらに６０分攪拌を続けた。反応液は白色の懸濁液であった。得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
【００４５】
濾別された白色固体および濾液を実施例１の方法に従って分析したところ、白色固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは１５６ｍｍｏｌであり、濾液中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは３９ｍｍｏｌであった。これ以外に極微量の不明ピークが認められた。濾液および固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは合計で１９５ｍｍｏｌであり、収率は９７．５％であった。
【００４６】
【実施例４】
あらかじめ良く乾燥し窒素置換した容積５Ｌのオートクレーブ反応器（内壁：グラスライニング）に、三塩化りん１３７．３ｇ（１．００ｍｏｌ）とｏ−ジクロロベンゼン２０４６ｇを仕込んだ。この溶液を緩やかに攪拌しながら４０℃に保つとともに、窒素ガスを導入して内部圧力を０．１５ＭＰａ（絶対圧、以降同様）に調整した。ここにガス導入管を介して塩素ガス７０．９ｇ（１．００ｍｏｌ、三塩化りんに対して１．００倍ｍｏｌ）を３．５時間かけて吹込んだ。反応時の最大圧力は０．１６ＭＰａであった。吹込み終了後、４０℃に保ったままでさらに１．５時間攪拌を続けた。その後、気相部のガスを大気圧まで放出し、窒素ガスで０．２０ＭＰａまで加圧し大気圧まで放出する気相部置換操作を３回繰り返した。反応混合物中の残留塩素分を滴定法により分析した結果１７５ｐｐｍであった。
【００４７】
次に、反応液を６０℃に昇温し、窒素ガスを導入して内部圧力を０．１０ＭＰａに調整した後、ガス導入管を介してジメチルアミン２７５．０ｇ（６．１０ｍｏｌ、三塩化りんに対して６．１０倍ｍｏｌ）をガス状態で６．５時間かけて吹込んだ。反応は、温度が６０℃を保持するように制御して行なった。反応時の最大圧力は０．１８ＭＰａであった。吹込み終了後、同温度でさらに１時間攪拌を続けた。その後、気相部のガスを大気圧まで放出し、窒素ガスで０．２０ＭＰａまで加圧し大気圧まで放出する気相部置換操作を３回繰り返した。
【００４８】
次に、温度を４０℃まで下げ、窒素ガスを導入して内部圧力を０．１０ＭＰａに調整した後、ガス導入管を介してアンモニア６８．１ｇ（４．００ｍｏｌ、三塩化りんに対して４．００倍ｍｏｌ）をガス状態で３時間かけて吹込んだ。反応は、温度が４０℃を保持するように制御して行なった。反応時の最大圧力は０．２５ＭＰａであった。吹込み終了後、同温度でさらに１時間攪拌を続けた。反応終了後、気相部のガスを大気圧まで放出し、窒素ガスで置換操作を行なった後、オートクレーブを開放して反応混合物を取り出した。反応液は白色の懸濁液であり、得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
【００４９】
濾別された白色固体および濾液を実施例１の方法に従って分析したところ、白色固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは０．７６８ｍｏｌであり、濾液中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは０．１９３ｍｏｌであった。これ以外に極微量の不明ピークが認められた。濾液および固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは合計で０．９６１ｍｏｌであり、収率は９６．１％であった。
【００５０】
【実施例５】
実施例４におけるジメチルアミン量を２６１．５ｇ（５．８０ｍｏｌ、三塩化りんに対して５．８０倍ｍｏｌ）に変更し、ジメチルアミンの吹込み温度を４０℃に変更した以外は、実施例４と全く同様に反応を行なった。
反応液は白色の懸濁液であり、得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
【００５１】
濾別された白色固体および濾液を実施例１の方法に従って分析したところ、白色固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは０．７０５ｍｏｌであり、濾液中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは０．１７８ｍｏｌであった。これ以外に微量の不明ピークが認められた。濾液および固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは合計で０．８８３ｍｏｌであり、収率は８８．３％であった。
【００５２】
【実施例６】
実施例４におけるジメチルアミン量を２７９．５ｇ（６．２０ｍｏｌ、三塩化りんに対して６．２０倍ｍｏｌ）に変更し、ジメチルアミンの吹込み温度を１０℃に変更し、ジメチルアミン吹込み終了後に６０℃に昇温して１時間攪拌した以外は、実施例４と全く同様に反応を行なった。
【００５３】
反応液は白色の懸濁液であり、得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
濾別された白色固体および濾液を実施例１の方法に従って分析したところ、白色固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは０．７１２ｍｏｌであり、濾液中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは０．１８３ｍｏｌであった。これ以外に微量の不明ピークが認められた。濾液および固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは合計で０．８９５ｍｏｌであり、収率は８９．５％であった。
【００５４】
【実施例７】
実施例１における塩素ガス量を１４．２ｇ（２００ｍｍｏｌ、三塩化りんに対して１．００倍ｍｏｌ）に変更し、ジメチルアミン量を５４．１ｇ（１２００ｍｍｏｌ、三塩化りんに対して６．００倍ｍｏｌ）に変更し、アンモニア量を６．８ｇ（４００ｍｍｏｌ、三塩化りんに対して２．００倍ｍｏｌ）に変更した以外は、実施例１と全く同様に反応を行なった。
【００５５】
反応液は白色の懸濁液であった。得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
濾別された白色固体および濾液を実施例１の方法に従って分析したところ、白色固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは１６４ｍｍｏｌであり、濾液中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは３０ｍｍｏｌであった。これ以外に極微量の不明ピークが認められた。濾液および固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは合計で１９４ｍｍｏｌであり、収率は９７．０％であった。
【００５６】
【実施例８】
実施例１におけるｏ−ジクロロベンゼンをトルエン３４３ｇに変更した以外は、実施例１と全く同様に反応を行なった。
反応液は白色の懸濁液であった。得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
【００５７】
濾別された白色固体および濾液を実施例１の方法に従って分析したところ、白色固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは１７１ｍｍｏｌであり、濾液中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは１２ｍｍｏｌであった。これ以外に微量の不明ピークが認められた。濾液および固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは合計で１８３ｍｍｏｌであり、収率は９１．５％であった。
【００５８】
【実施例９】
実施例１におけるｏ−ジクロロベンゼンを４−クロロトルエン３４３ｇに変更した以外は、実施例１と全く同様に反応を行なった。
反応液は白色の懸濁液であった。得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
【００５９】
濾別された白色固体および濾液を実施例１の方法に従って分析したところ、白色固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは１６５ｍｍｏｌであり、濾液中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは２１ｍｍｏｌであった。これ以外に微量の不明ピークが認められた。濾液および固体中に含まれるアミノトリス（ジメチルアミノ）ホスホニウムクロリドは合計で１８６ｍｍｏｌであり、収率は９３．０％であった。
【００６０】
【実施例１０】
実施例１におけるジメチルアミンガスの吹込みに代えて、ピロリジン８６．８ｇ（１２２０ｍｍｏｌ、三塩化りんに対して６．１０倍ｍｏｌ）を液状で２時間かけて反応液に滴下した以外は、実施例１と全く同様に反応を行なった。
反応液は白色の懸濁液であった。得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
【００６１】
濾別された白色固体および濾液を実施例１の方法に準じて分析したところ、白色固体中に含まれるアミノトリ（ピロリジン−１−イル）ホスホニウムクロリドは１４１ｍｍｏｌであり、濾液中に含まれるアミノトリ（ピロリジン−１−イル）ホスホニウムクロリドは３９ｍｍｏｌであった。これ以外に少量の不明ピークが認められた。濾液および固体中に含まれるアミノトリ（ピロリジン−１−イル）ホスホニウムクロリドは合計で１８０ｍｍｏｌであり、収率は９０．０％であった。
【００６２】
【実施例１１】
実施例１におけるジメチルアミンガスの吹込みに代えて、モルホリン１０６．３ｇ（１２２０ｍｍｏｌ、三塩化りんに対して６．１０倍ｍｏｌ）を同重量のｏ−ジクロロベンゼンで希釈した５０重量％溶液２１２．６ｇを使用し、この溶液を３時間かけて反応液に滴下した以外は、実施例１と全く同様に反応を行なった。
【００６３】
反応液は白色の懸濁液であった。得られた懸濁液を窒素加圧で濾過して白色の固体を濾別した。濾液は無色透明な液であった。
濾別された白色固体および濾液を実施例１の方法に準じて分析したところ、白色固体中に含まれるアミノトリ（モルホリン−４−イル）ホスホニウムクロリドは１３９ｍｍｏｌであり、濾液中に含まれるアミノトリ（モルホリン−４−イル）ホスホニウムクロリドは４０ｍｍｏｌであった。これ以外に少量の不明ピークが認められた。濾液および固体中に含まれるアミノトリ（モルホリン−４−イル）ホスホニウムクロリドは合計で１７９ｍｍｏｌであり、収率は８９．５％であった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to the reaction of phosphorus trichloride with chlorine to produce phosphorus pentachloride, which is used without isolation, reacted with a disubstituted amine, and then reacted with ammonia to form aminotris (disubstituted amino) phosphonium. It relates to a simple and efficient method for producing chloride. Aminotris (disubstituted amino) phosphonium chloride is an extremely important and useful compound as a synthetic intermediate of a phosphazene compound or a phosphazenium compound used for an alkylene oxide polymerization catalyst, a flame retardant, a lubricating oil, and the like.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Conventionally, as a method for producing aminotris (disubstituted amino) phosphonium chloride, a method for producing aminotris (dimethylamino) phosphonium chloride by reacting dimethylamine and ammonia with phosphorus pentachloride in a methylene chloride solvent has been disclosed. (See Non-Patent Document 1).
[0003]
As an improved method, there is disclosed a method for producing aminotris (dimethylamino) phosphonium chloride in which water introduced into the reaction system is restricted and phosphorus pentachloride is reacted with dimethylamine and ammonia using aromatic hydrocarbons as a solvent. (See Patent Document 1).
In all of these methods, phosphorus pentachloride is used as a starting material.However, phosphorus pentachloride is a highly reactive solid compound at room temperature, reacts easily with moisture in the air, and reacts with hydrogen chloride gas. Care must be taken when handling because it is disassembled while generating. Usually, when handling a relatively small amount in a laboratory or the like, a glove box or the like replaced with an inert gas such as dry nitrogen can be used to perform weighing and transfer operations in the glove box. When used in relatively large quantities, it is very difficult to deal with equipment and ensure safety. Further, since phosphorus pentachloride has a property of solidifying under its own weight, it is more difficult to handle an industrially required amount.
[0004]
For these reasons, the use of phosphorus pentachloride as a starting material in the production of aminotris (disubstituted amino) phosphonium chloride was not an industrially preferable method.
Further, as another method for producing aminotris (dimethylamino) phosphonium chloride, hexamethylphosphoric triamide is reacted with phosgene to produce tris (dimethylamino) phosphonium dichloride, which is then reacted with ammonia to obtain aminotris (dimethylamino) phosphonium. A method for producing (amino) phosphonium chloride has also been disclosed (see Non-Patent Documents 2 and 3).
[0005]
However, this method also uses a very dangerous compound called phosgene, and thus involves special measures for ensuring safety and protecting the environment. .
The present inventors have conducted intensive studies in view of the above circumstances, and using phosphorus trichloride which is a liquid at room temperature as a starting material, reacting phosphorus trichloride and chlorine in the presence of aromatic hydrocarbons. It has been found that aminotris (disubstituted amino) phosphonium chloride can be easily and safely produced by reacting the produced phosphorus pentachloride with a disubstituted amine without isolation and purification, and then reacting with ammonia. Thus, the present invention has been completed.
[0006]
[Non-patent document 1]
"Liebig Anna-Len", 1996, p. 1067 (Liebigs Ann., 1067 (1996)).
[Patent Document 1]
JP-A-11-152293
[Non-patent document 2]
"Nahiriten Hemy Technique Laboratorium", Vol. 38, No. 10, 1990, page 1216 (Nachr. Chem. Tech. Lab., 38 (10) 1216 (1990)).
[Non-Patent Document 3]
"Liebig Anna-Len", 1996, p. 1066 (Liebigs Ann., 1066 (1996)).
[0007]
[Object of the invention]
An object of the present invention is to provide a method for easily and safely producing aminotris (disubstituted amino) phosphonium chloride by an industrially more efficient method.
[0008]
Summary of the Invention
The process for producing aminotris (disubstituted amino) phosphonium chloride of the present invention comprises reacting phosphorus trichloride with chlorine in the presence of an aromatic hydrocarbon to produce phosphorus pentachloride, It is used in the form of a reaction mixture without isolation and purification, and the phosphorus pentachloride contained in the reaction mixture is reacted with a disubstituted amine to produce chlorotris (disubstituted amino) phosphonium chloride. It is characterized in that aminotris (disubstituted amino) phosphonium chloride is obtained by reacting disubstituted amino) phosphonium chloride with ammonia.
[0009]
In the production method of the present invention, the chlorine may be used in an amount of 0.9 to 1.5 mol per 1 mol of phosphorus trichloride, and the phosphorus may be reacted with chlorine at a temperature of 0 to 60 ° C. preferable.
In the production method of the present invention, the disubstituted amine is used in an amount of 5.80 to 6.30 mol based on 1 mol of phosphorus trichloride initially used, and the phosphorus pentachloride and the disubstituted amine are used in an amount of 0 to 6.30 mol. The reaction is preferably performed at a temperature of 80 ° C.
[0010]
Further, in the present invention, the two substituents of the disubstituted amine are the same or different aliphatic hydrocarbon groups having 1 to 3 carbon atoms, or the disubstituted amine is 5 to 7 It is preferably a membered unsubstituted cyclic secondary amine.
In the present invention, the aromatic hydrocarbons include benzene, an alkyl-substituted aromatic hydrocarbon having 7 to 9 carbon atoms, a chlorinated aromatic hydrocarbon having 1 to 4 carbon atoms, or 7 to 9 carbon atoms. Preferably it is selected from nine chlorinated alkyl-substituted aromatic hydrocarbons.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described specifically.
The process of the present invention comprises reacting phosphorus trichloride with chlorine in the presence of aromatic hydrocarbons to produce phosphorus pentachloride, which is used without isolation, reacted with a disubstituted amine, and then reacted with ammonia. Reacting to produce aminotris (disubstituted amino) phosphonium chloride.
[0012]
The aminotris (disubstituted amino) phosphonium chloride obtained by the production method of the present invention is represented by the following formula (2)
[0013]
Embedded image

[0014]
(In the formula, R represents the same or different substituent of a disubstituted amino group, but two substituents R may be bonded to each other to form a disubstituted amino group into a cyclic amino group.) Compound.
In the method of the present invention, examples of the aromatic hydrocarbon used as a solvent include benzene, alkyl-substituted aromatic hydrocarbon, halogenated aromatic hydrocarbon, and halogenated alkyl-substituted aromatic hydrocarbon.
[0015]
Specifically, for example, benzene; toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, normal propylbenzene, cumene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, mesitylene , Tetralin, butylbenzene, p-cymene, cyclohexylbenzene, 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 1,2-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-diisopropyl Alkyl-substituted aromatic hydrocarbons having 7 to 20 carbon atoms such as benzene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene or dodecylbenzene; chlorobenzene, o-dichlorobenzene, m-dichlorobenzene , 1,2,4-tric Robenzene, 1,2,3,4-tetrachlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, 1-bromo-2-chlorobenzene, 1-bromo-3-chlorobenzene, 1-bromonaphthalene or 1-chloro Halogenated aromatic hydrocarbons having 6 to 14 carbon atoms and 1 to 4 halogen atoms such as naphthalene; 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, 2-bromotoluene, 3-bromo Toluene, 2,4-dichlorotoluene, 3,4-dichlorotoluene, 1-bromo-2-ethylbenzene, 1-bromo-4-ethylbenzene, 2-chloroethylbenzene, 1-chloro-4-ethylbenzene, 1-chloro-4 -Isopropylbenzene, 1-bromo-4-isopropylbenzene, mesitylclo De, 4-chloro--o- xylene or 2-chloro -p- halogenated alkyl-substituted aromatic hydrocarbons having 7 to 20 carbon atoms and the number 1-4 halogen atoms, such as xylene; and the like preferably. In addition to these, any aromatic hydrocarbon may be used as a solvent as long as the object of the present invention is not impaired, that is, as long as the reaction is not inhibited. Of these, benzene; alkyl-substituted aromatic hydrocarbons having 7 to 9 carbon atoms such as toluene, m-xylene, ethylbenzene, and mesitylene; chlorobenzene, o-dichlorobenzene, and 1,2,4-triene Chlorinated aromatic hydrocarbons having 6 to 14 carbon atoms and 1 to 4 carbon atoms such as chlorobenzene; carbons such as 2-chlorotoluene, 4-chlorotoluene, 1-chloro-4-ethylbenzene or mesityl chloride It is a chlorinated alkyl-substituted aromatic hydrocarbon having 7 to 9 atoms and 1 to 4 chlorine atoms.
[0016]
These solvents of aromatic hydrocarbons may be used alone or in combination of two or more. Also, these solvents do not need to completely dissolve the resulting phosphorus pentachloride, chlorotris (disubstituted amino) phosphonium chloride or aminotris (disubstituted amino) phosphonium chloride. The use amount of these solvents is not particularly limited, but is usually 300 parts by weight or less, preferably 1 to 150 parts by weight, more preferably 2 to 30 parts by weight based on 1 part by weight of phosphorus trichloride as a raw material. It is.
[0017]
As the phosphorus trichloride used in the method of the present invention, a commercially available one can be used as it is, but if necessary, it may be used after a purification step such as distillation.
In the method of the present invention, when phosphorus trichloride is reacted with chlorine in the presence of the aromatic hydrocarbons to produce phosphorus pentachloride, the amount of chlorine used is usually 0 to 1 mol of phosphorus trichloride. 0.9 to 1.5 mol, preferably 0.95 to 1.2 mol. Chlorine is usually charged in a gas, liquid or solution state into a reactor in which the aromatic hydrocarbon solvent and phosphorus trichloride are charged continuously or intermittently. Of these, gas charging is preferred. When chlorine is introduced into the reactor as a gas, it may be diluted with an inert gas such as nitrogen, helium or argon.
[0018]
The reaction temperature in this reaction is usually from 0 to 60 ° C, preferably from 10 to 40 ° C. The pressure during the reaction is usually 0.001 to 1.0 MPa (absolute pressure, the same applies hereinafter), preferably 0.1 to 0.5 MPa. The reaction time is not particularly limited, but is usually within 20 hours including the charging time of chlorine, preferably 0.1 to 10 hours.
[0019]
When chlorine is used excessively after completion of the reaction, it is preferable to remove remaining unreacted chlorine from the viewpoint of suppressing by-products in the next reaction. As a method for removing unreacted chlorine, a general method can be appropriately selected and used, but a method using a reduced pressure, a method using an inert gas flow, and a combination thereof are preferably used. The degree of removal of unreacted chlorine is not particularly limited, but is usually 0.2% by weight or less, preferably 0.1% by weight or less, as the residual chlorine concentration in the reaction mixture.
[0020]
The phosphorus pentachloride thus produced in the reactor is used for the next reaction with the disubstituted amine without isolation and purification, as is, in the reaction mixture containing the aromatic hydrocarbon solvent and the like.
The disubstituted amine used in the method of the present invention is R ₂ In the compound having the structure of NH, two substituents (R) are the same or different hydrocarbon groups, preferably a disubstituted amine having 1 to 10 carbon atoms. Specific examples of the substituent (R) include, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, tert-butyl, 2-butenyl, 1-pentyl, 2-pentyl , 3-pentyl, 2-methyl-1-butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, -Heptyl, 1-octyl, 2-octyl, 2-ethyl-1-hexyl, 1,1-dimethyl-3,3-dimethylbutyl (commonly referred to as tert-octyl), nonyl, decyl, phenyl, 4-toluyl, benzyl Or an aliphatic or aromatic hydrocarbon group such as 1-phenylethyl or 2-phenylethyl. Among these, preferably, an aliphatic carbon having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl or 1,1-dimethyl-3,3-dimethylbutyl. A hydrogen group, more preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl and isopropyl; and a methyl group or an ethyl group is further preferable.
[0021]
Further, as the disubstituted amine, a cyclic secondary amine in which two substituents (R) are bonded to each other can also be used. Examples of the cyclic secondary amine in this case include pyrrolidine, piperidine, morpholine, hexamethyleneimine, and a 5- to 7-membered cyclic secondary amine in which an alkyl group such as methyl or ethyl is substituted. Of these, a 5- to 7-membered unsubstituted cyclic secondary amine is preferred, and pyrrolidine, piperidine or morpholine is more preferred.
[0022]
These disubstituted amines can be used alone or in combination of two or more. When a plurality of types of disubstituted amines are used in combination, a method of reacting each disubstituted amine with phosphorus pentachloride sequentially, in addition to a method of reacting with phosphorus pentachloride in a mixed state in advance, can be used.
In reacting phosphorus pentachloride (phosphorus pentachloride contained in the reaction mixture) generated in the reactor with the disubstituted amine to form chlorotris (disubstituted amino) phosphonium chloride, the amount of disubstituted amine used Is usually 5.80 to 6.30 mol, preferably 6.00 to 6.20 mol, per 1 mol of phosphorus trichloride initially used, from the viewpoint of securing the reaction yield. The disubstituted amine is usually or continuously added to the reaction mixture containing the aromatic hydrocarbon solvent and the formed phosphorus pentachloride in a gaseous, liquid or solution state. When the disubstituted amine is added to the reaction mixture as a gas, it may be used after dilution with an inert gas such as nitrogen, helium, or argon.
[0023]
The reaction temperature in this reaction is usually 0 to 80 ° C, preferably 10 to 70 ° C. The pressure during the reaction is usually from 0.001 to 1.0 MPa, preferably from 0.1 to 0.5 MPa. Although the reaction time is not particularly limited, it is generally 40 hours or less, including the charging time of the disubstituted amine, preferably 0.5 to 30 hours, more preferably 1 to 15 hours.
[0024]
The thus obtained chlorotris (disubstituted amino) phosphonium chloride has the following formula (1)
[0025]
Embedded image

[0026]
(In the formula, R represents the same or different substituent of a disubstituted amino group, but two substituents R may be bonded to each other to form a disubstituted amino group into a cyclic amino group.) Compound. In the formula, R corresponds to the substituent R of the disubstituted amine used in the above reaction.
This chlorotris (disubstituted amino) phosphonium chloride can be optionally isolated and used in the subsequent reaction with ammonia, but it is usually used as a solvent for aromatic hydrocarbons and disubstituted amine which is a by-product. The reaction mixture containing the hydrochloride can be used as it is.
[0027]
In producing chlorotris (disubstituted amino) phosphonium chloride by reacting chlorotris (disubstituted amino) phosphonium chloride produced by the above reaction with ammonia, the amount of ammonia used depends on the yield and economy. Is usually 1.8 to 50 mol, preferably 2 to 20 mol, per 1 mol of phosphorus trichloride used initially. Ammonia is usually added continuously or intermittently, either as a gas, liquid or solution, to a reaction mixture containing chlorotris (disubstituted amino) phosphonium chloride. Among these, it is preferable to add with a gas. When ammonia is added to the reaction mixture as a gas, it may be used after dilution with an inert gas such as nitrogen, helium, or argon.
[0028]
The reaction temperature is usually 0 to 60 ° C, preferably 10 to 50 ° C. The pressure during the reaction is usually from 0.001 to 1.0 MPa, preferably from 0.1 to 0.5 MPa. The reaction time is not particularly limited, but is usually within 40 hours including the time for charging ammonia, preferably 0.5 to 30 hours, more preferably 1 to 15 hours. When the reaction mixture of the former step is used as it is in this reaction, the reaction mixture contains hydrochloride of disubstituted amine which is a by-product of the reaction of the former step. The disubstituted amine hydrochloride is usually wholly or partially replaced by excess ammonia to form ammonium chloride and the disubstituted amine.
[0029]
When chlorotris (disubstituted amino) phosphonium chloride is used in this reaction, it is preferable to use the above-mentioned aromatic hydrocarbons as a solvent. Although the amount of the solvent used is not particularly limited, it is usually used in the above-mentioned range by weight based on 1 part by weight of the moles of chlorotris (disubstituted amino) phosphonium chloride converted to phosphorus trichloride.
[0030]
The aminotris (disubstituted amino) phosphonium chloride thus obtained is represented by the following formula (2)
[0031]
Embedded image

[0032]
Wherein R corresponds to the substituent R of chlorotris (disubstituted amino) phosphonium chloride used in the above reaction.
The aminotris (disubstituted amino) phosphonium chloride produced by the method of the present invention may be used as it is in the reaction mixture for the next use (for example, synthesis of a phosphazene compound). You can also take it out.
[0033]
Usually, aminotris (disubstituted amino) phosphonium chloride is present as a solid in the reaction mixture along with ammonium chloride and disubstituted amine hydrochloride solids. Then it dissolves. Therefore, after removing ammonium chloride and disubstituted amine hydrochloride which are still insoluble by a usual solid-liquid separation method such as filtration, the solid of aminotris (disubstituted amino) phosphonium chloride which precipitates by cooling is removed. It can be separated by a usual solid-liquid separation method. The aminotris (disubstituted amino) phosphonium chloride obtained by this method has a sufficiently high purity, but if necessary, may be subjected to another purification step such as recrystallization.
[0034]
【The invention's effect】
According to the method of the present invention, phosphorus pentachloride is produced by reacting phosphorus trichloride with chlorine in the presence of aromatic hydrocarbons, then reacting with disubstituted amine, and further reacting ammonia. The need to isolate and handle phosphorus is eliminated, and aminotris (disubstituted amino) phosphonium chloride can be produced safely and efficiently on an industrial scale. That is, according to the present invention, aminotris (disubstituted amino) phosphonium chloride can be easily obtained with high yield and high selectivity.
[0035]
【Example】
Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
In addition, the analyzer and the analysis method used in the following Examples are as follows.
(1) ³¹ P-NMR analysis
The analysis was performed using an A-500 type NMR analyzer (500 MHz) manufactured by JEOL Ltd.
(2) Titration method (analysis of residual chlorine in reaction mixture)
About 10 g of the sample was weighed in a 200 ml Erlenmeyer flask, and while cooling with ice water, 20 ml of pure water, 10 ml of a 10% by weight aqueous solution of potassium iodide and 10 ml of an aqueous solution of 10% by weight of acetic acid were added, followed by gentle stirring. This sample solution was titrated with a 0.01 mol / l aqueous solution of sodium thiosulfate. About 1 ml of a starch indicator (about 0.5% by weight starch aqueous solution (boiled)) was added after the sample solution became extremely pale yellow, and the point at which the purple color of the sample solution disappeared was regarded as the end point.
[0036]
Embodiment 1
Under a nitrogen atmosphere, 27.5 g (200 mmol) of phosphorus trichloride and 245 g of o-dichlorobenzene were charged into a 1 L glass reactor. This solution was kept at 30 ° C. while being gently stirred, and 13.9 g (196 mmol, 0.98 times mol relative to phosphorus trichloride) of chlorine gas was blown through the gas inlet tube at normal pressure over 60 minutes. And continued stirring for another 60 minutes.
[0037]
Next, 54.6 g (1210 mmol, 6.05 times the mol of phosphorus trichloride) of dimethylamine was blown into the reaction solution in a gas state over 4 hours. The reaction was carried out at normal pressure while cooling to maintain the temperature at 30 ° C. After completion of the blowing, the mixture was stirred at the same temperature for 30 minutes, then heated to 60 ° C. over 30 minutes, and further stirred for 60 minutes. The reaction became a white suspension.
[0038]
Next, the temperature was lowered to 40 ° C., and 8.3 g (490 mmol, 2.45 times the mol of phosphorus trichloride) of ammonia was blown in a gas state over 2 hours. The reaction was carried out at normal pressure and at a temperature of 40 ° C. After the blowing, stirring was continued at the same temperature for another 60 minutes. The reaction was a white suspension. The resulting suspension was filtered under nitrogen pressure to separate a white solid. The filtrate was a colorless and transparent liquid.
[0039]
Filtered white solid in deuterated chloroform solvent ³¹ P-NMR analysis did not detect phosphorus pentachloride, indicating that all had reacted. In addition, using a deuterated dimethyl sulfoxide solvent, tri-n-butyl phosphate was used as an internal standard. ³¹ From analysis by P-NMR, the amount of aminotris (dimethylamino) phosphonium chloride contained in this white solid was 162 mmol. On the other hand, when the filtrate was analyzed in the same manner as the white solid, phosphorus pentachloride was not detected, and 28 mmol of aminotris (dimethylamino) phosphonium chloride was contained. In addition, a trace amount of unknown peak was observed. The aminotris (dimethylamino) phosphonium chloride contained in the filtrate and the solid was 190 mmol in total, and the yield was 95.0%.
[0040]
Embodiment 2
Example 1 was repeated except that the amount of chlorine gas in Example 1 was changed to 12.8 g (180 mmol, 0.90 times mol with respect to phosphorus trichloride), and the blowing temperature of chlorine gas was changed to 15 ° C. The reaction was performed exactly the same. The reaction was a white suspension.
[0041]
The resulting suspension was filtered under nitrogen pressure to separate a white solid. The filtrate was a colorless and transparent liquid.
When the white solid and the filtrate separated by filtration were analyzed according to the method of Example 1, the amount of aminotris (dimethylamino) phosphonium chloride contained in the white solid was 149 mmol, and the amount of aminotris (dimethylamino) phosphonium contained in the filtrate was 149 mmol. Chloride was 27 mmol. In addition, a small amount of unknown peak was observed. The aminotris (dimethylamino) phosphonium chloride contained in the filtrate and the solid was 176 mmol in total, and the yield was 88.0%.
[0042]
Embodiment 3
Under a nitrogen atmosphere, 27.5 g (200 mmol) of phosphorus trichloride and 410 g of o-dichlorobenzene were charged into a 1 L glass reactor. The solution was maintained at 10 ° C. with gentle stirring, and 17.0 g of chlorine gas (240 mmol, 1.20 times mol relative to phosphorus trichloride) was blown through the gas introduction tube at normal pressure over 60 minutes. After the mixture was heated to 30 ° C., stirring was continued for another 60 minutes. Thereafter, nitrogen gas was blown in at a rate of about 20 g / h for 60 minutes through a gas inlet tube to remove excess unreacted chlorine. As a result of analyzing the residual chlorine content in the reaction mixture by a titration method, it was 60 ppm.
[0043]
Next, 54.6 g (1210 mmol, 6.05 times the mol of phosphorus trichloride) of dimethylamine was blown into the reaction solution in a gas state over 4 hours. The reaction was carried out at normal pressure while cooling to maintain the temperature at 30 ° C. After completion of the blowing, the mixture was stirred at the same temperature for 30 minutes, then heated to 60 ° C. over 30 minutes, and further stirred for 60 minutes. The reaction became a white suspension.
[0044]
Next, the temperature was lowered to 40 ° C., and 8.3 g (490 mmol, 2.45 times the mol of phosphorus trichloride) of ammonia was blown in a gas state over 2 hours. The reaction was carried out at normal pressure and at a temperature of 40 ° C. After the blowing, stirring was continued at the same temperature for another 60 minutes. The reaction was a white suspension. The resulting suspension was filtered under nitrogen pressure to separate a white solid. The filtrate was a colorless and transparent liquid.
[0045]
When the white solid and the filtrate separated by filtration were analyzed according to the method of Example 1, the amount of aminotris (dimethylamino) phosphonium chloride contained in the white solid was 156 mmol, and the amount of aminotris (dimethylamino) phosphonium contained in the filtrate was 156 mmol. Chloride was 39 mmol. In addition, a trace amount of unknown peak was observed. The aminotris (dimethylamino) phosphonium chloride contained in the filtrate and the solid was 195 mmol in total, and the yield was 97.5%.
[0046]
Embodiment 4
137.3 g (1.00 mol) of phosphorus trichloride and 2046 g of o-dichlorobenzene were charged into a 5 L autoclave reactor (inner wall: glass lining) which had been thoroughly dried and purged with nitrogen in advance. The solution was maintained at 40 ° C. with gentle stirring, and the internal pressure was adjusted to 0.15 MPa (absolute pressure, hereinafter the same) by introducing nitrogen gas. 70.9 g of chlorine gas (1.00 mol, 1.00-fold mol relative to phosphorus trichloride) was blown into the gas through a gas introduction tube over 3.5 hours. The maximum pressure during the reaction was 0.16 MPa. After completion of the blowing, stirring was further continued for 1.5 hours while maintaining the temperature at 40 ° C. Thereafter, the gas phase replacement operation of releasing the gas in the gas phase to atmospheric pressure, increasing the pressure to 0.20 MPa with nitrogen gas, and releasing the gas to atmospheric pressure was repeated three times. As a result of analyzing the residual chlorine content in the reaction mixture by a titration method, it was 175 ppm.
[0047]
Next, the temperature of the reaction solution was raised to 60 ° C., and nitrogen gas was introduced to adjust the internal pressure to 0.10 MPa. Then, 275.0 g (6.10 mol, dimethylamine was added to phosphorus trichloride) through a gas introduction tube. (6.10 times mol) was blown in a gaseous state over 6.5 hours. The reaction was performed while controlling the temperature at 60 ° C. The maximum pressure during the reaction was 0.18 MPa. After the blowing, stirring was continued at the same temperature for another hour. Thereafter, the gas phase replacement operation of releasing the gas in the gas phase to atmospheric pressure, increasing the pressure to 0.20 MPa with nitrogen gas, and releasing the gas to atmospheric pressure was repeated three times.
[0048]
Next, the temperature was lowered to 40 ° C., nitrogen gas was introduced to adjust the internal pressure to 0.10 MPa, and then 68.1 g of ammonia (4.00 mol, 4.0% with respect to phosphorus trichloride) through a gas introduction pipe. (00-fold mol) was blown in a gas state over 3 hours. The reaction was performed while controlling the temperature at 40 ° C. The maximum pressure during the reaction was 0.25 MPa. After the blowing, stirring was continued at the same temperature for another hour. After the completion of the reaction, the gas in the gas phase was released to the atmospheric pressure, and after performing a replacement operation with nitrogen gas, the autoclave was opened and the reaction mixture was taken out. The reaction solution was a white suspension, and the obtained suspension was filtered under nitrogen pressure to separate a white solid by filtration. The filtrate was a colorless and transparent liquid.
[0049]
The filtered white solid and the filtrate were analyzed according to the method of Example 1. As a result, the aminotris (dimethylamino) phosphonium chloride contained in the white solid was 0.768 mol, and the aminotris (dimethylamino) contained in the filtrate was 0.768 mol. ) The phosphonium chloride was 0.193 mol. In addition, a trace amount of unknown peak was observed. The aminotris (dimethylamino) phosphonium chloride contained in the filtrate and the solid was 0.961 mol in total, and the yield was 96.1%.
[0050]
Embodiment 5
Example 4 Example 4 was repeated except that the amount of dimethylamine in Example 4 was changed to 261.5 g (5.80 mol, 5.80 times the mol of phosphorus trichloride) and the blowing temperature of dimethylamine was changed to 40 ° C. The reaction was performed in exactly the same manner as described above.
The reaction solution was a white suspension, and the obtained suspension was filtered under nitrogen pressure to separate a white solid by filtration. The filtrate was a colorless and transparent liquid.
[0051]
When the white solid and the filtrate separated by filtration were analyzed in accordance with the method of Example 1, the amount of aminotris (dimethylamino) phosphonium chloride contained in the white solid was 0.705 mol, and the amount of aminotris (dimethylamino) contained in the filtrate was 0.75 mol. ) Phosphonium chloride was 0.178 mol. In addition, a small amount of unknown peak was observed. The aminotris (dimethylamino) phosphonium chloride contained in the filtrate and the solid was 0.883 mol in total, and the yield was 88.3%.
[0052]
Embodiment 6
The amount of dimethylamine in Example 4 was changed to 279.5 g (6.20 mol, 6.20 times the mol of phosphorus trichloride), the blowing temperature of dimethylamine was changed to 10 ° C., and the blowing of dimethylamine was completed. The reaction was carried out in exactly the same manner as in Example 4, except that the temperature was raised to 60 ° C. and stirred for 1 hour.
[0053]
The reaction solution was a white suspension, and the obtained suspension was filtered under nitrogen pressure to separate a white solid by filtration. The filtrate was a colorless and transparent liquid.
When the white solid and the filtrate separated by filtration were analyzed according to the method of Example 1, the amount of aminotris (dimethylamino) phosphonium chloride contained in the white solid was 0.712 mol, and the amount of aminotris (dimethylamino) contained in the filtrate was 0.712 mol. ) The phosphonium chloride was 0.183 mol. In addition, a small amount of unknown peak was observed. The aminotris (dimethylamino) phosphonium chloride contained in the filtrate and the solid was 0.895 mol in total, and the yield was 89.5%.
[0054]
Embodiment 7
The amount of chlorine gas in Example 1 was changed to 14.2 g (200 mmol, 1.00 times mol with respect to phosphorus trichloride), and the amount of dimethylamine was 54.1 g (1200 mmol, 6.00 times with respect to phosphorus trichloride). mol) and the amount of ammonia was changed to 6.8 g (400 mmol, 2.00-fold mol based on phosphorus trichloride), and the reaction was carried out in exactly the same manner as in Example 1.
[0055]
The reaction was a white suspension. The resulting suspension was filtered under nitrogen pressure to separate a white solid. The filtrate was a colorless and transparent liquid.
The filtered white solid and the filtrate were analyzed according to the method of Example 1. As a result, the amount of aminotris (dimethylamino) phosphonium chloride contained in the white solid was 164 mmol, and the amount of aminotris (dimethylamino) phosphonium contained in the filtrate was Chloride was 30 mmol. In addition, a trace amount of unknown peak was observed. The total amount of aminotris (dimethylamino) phosphonium chloride contained in the filtrate and the solid was 194 mmol, and the yield was 97.0%.
[0056]
Embodiment 8
The reaction was carried out in exactly the same manner as in Example 1, except that o-dichlorobenzene in Example 1 was changed to 343 g of toluene.
The reaction was a white suspension. The resulting suspension was filtered under nitrogen pressure to separate a white solid. The filtrate was a colorless and transparent liquid.
[0057]
When the white solid and the filtrate separated by filtration were analyzed in accordance with the method of Example 1, the amount of aminotris (dimethylamino) phosphonium chloride contained in the white solid was 171 mmol, and the amount of aminotris (dimethylamino) phosphonium contained in the filtrate was 171 mmol. Chloride was 12 mmol. In addition, a small amount of unknown peak was observed. Aminotris (dimethylamino) phosphonium chloride contained in the filtrate and the solid was 183 mmol in total, and the yield was 91.5%.
[0058]
Embodiment 9
The reaction was carried out in exactly the same manner as in Example 1, except that o-dichlorobenzene in Example 1 was changed to 343 g of 4-chlorotoluene.
The reaction was a white suspension. The resulting suspension was filtered under nitrogen pressure to separate a white solid. The filtrate was a colorless and transparent liquid.
[0059]
When the white solid and the filtrate separated by filtration were analyzed according to the method of Example 1, the amount of aminotris (dimethylamino) phosphonium chloride contained in the white solid was 165 mmol, and the amount of aminotris (dimethylamino) phosphonium contained in the filtrate was Chloride was 21 mmol. In addition, a small amount of unknown peak was observed. The total amount of aminotris (dimethylamino) phosphonium chloride contained in the filtrate and the solid was 186 mmol, and the yield was 93.0%.
[0060]
Embodiment 10
Example 8 Example 8 was repeated except that pyrrolidine 86.8 g (1220 mmol, 6.10 times the mol of phosphorus trichloride) was dropped into the reaction solution over 2 hours in place of the blowing of dimethylamine gas in Example 1. The reaction was carried out exactly as in 1.
The reaction was a white suspension. The resulting suspension was filtered under nitrogen pressure to separate a white solid. The filtrate was a colorless and transparent liquid.
[0061]
When the white solid and the filtrate separated by filtration were analyzed in accordance with the method of Example 1, the amount of aminotri (pyrrolidin-1-yl) phosphonium chloride contained in the white solid was 141 mmol, and the amount of aminotri (pyrrolidine) contained in the filtrate was 141 mmol. -1-yl) phosphonium chloride was 39 mmol. In addition, a small amount of unknown peak was observed. Aminotri (pyrrolidin-1-yl) phosphonium chloride contained in the filtrate and the solid was 180 mmol in total, and the yield was 90.0%.
[0062]
Embodiment 11
In place of blowing dimethylamine gas in Example 1, 106.3 g (1220 mmol, 6.10 times mol based on phosphorus trichloride) of morpholine was diluted with the same weight of o-dichlorobenzene. The reaction was carried out in exactly the same manner as in Example 1 except that 6 g of the solution was used and the solution was dropped into the reaction solution over 3 hours.
[0063]
The reaction was a white suspension. The resulting suspension was filtered under nitrogen pressure to separate a white solid. The filtrate was a colorless and transparent liquid.
When the white solid and the filtrate separated by filtration were analyzed in accordance with the method of Example 1, the amount of aminotri (morpholin-4-yl) phosphonium chloride contained in the white solid was 139 mmol, and the amount of aminotri (morpholine -4-yl) phosphonium chloride was 40 mmol. In addition, a small amount of unknown peak was observed. The total amount of aminotri (morpholin-4-yl) phosphonium chloride contained in the filtrate and the solid was 179 mmol, and the yield was 89.5%.

Claims (8)

In the presence of aromatic hydrocarbons, react phosphorus trichloride and chlorine to produce phosphorus pentachloride,
Next, the phosphorus pentachloride is used in the form of a reaction mixture without isolation and purification, and phosphorus pentachloride contained in the reaction mixture is reacted with a disubstituted amine to be represented by the following formula (1). Producing chlorotris (disubstituted amino) phosphonium chloride,
Then, a method for producing aminotris (disubstituted amino) phosphonium chloride represented by the following formula (2), characterized by reacting the chlorotris (disubstituted amino) phosphonium chloride with ammonia;

(In the formula (1), R represents the same or different substituent of a disubstituted amino group, but two substituents R may be bonded to each other to form a disubstituted amino group into a cyclic amino group.)

(In the formula (2), R is the same as R in the formula (1).) The method for producing aminotris (disubstituted amino) phosphonium chloride according to claim 1, wherein the chlorine is used in an amount of 0.9 to 1.5 mol per 1 mol of phosphorus trichloride. The method for producing aminotris (disubstituted amino) phosphonium chloride according to claim 1 or 2, wherein the phosphorus trichloride and chlorine are reacted at a temperature of 0 to 60 ° C. The aminotris (disubstituted) according to any one of claims 1 to 3, wherein the disubstituted amine is used in an amount of 5.80 to 6.30 mol based on 1 mol of phosphorus trichloride used initially. Method for producing amino) phosphonium chloride. The method for producing aminotris (disubstituted amino) phosphonium chloride according to any one of claims 1 to 4, wherein the phosphorus pentachloride and the disubstituted amine are reacted at a temperature of 0 to 80 ° C. The aminotris according to any one of claims 1 to 5, wherein the two substituents of the disubstituted amine are the same or different aliphatic hydrocarbon groups having 1 to 3 carbon atoms. Method for producing disubstituted amino) phosphonium chloride. The method for producing aminotris (disubstituted amino) phosphonium chloride according to any one of claims 1 to 6, wherein the disubstituted amine is a 5- to 7-membered unsubstituted cyclic secondary amine. The aromatic hydrocarbon is benzene, an alkyl-substituted aromatic hydrocarbon having 7 to 9 carbon atoms, a chlorinated aromatic hydrocarbon having 1 to 4 chlorine atoms, or chlorine having 7 to 9 carbon atoms. The method for producing aminotris (disubstituted amino) phosphonium chloride according to any one of claims 1 to 7, wherein the method is selected from alkylated aromatic substituted aromatic hydrocarbons.