JP2008260704A - Method for removing palladium - Google Patents
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本発明は、パラジウム触媒を用いた有機反応後の溶液からパラジウムを除去する方法に関する。 The present invention relates to a method for removing palladium from a solution after an organic reaction using a palladium catalyst.
従来、リン系配位子とパラジウム化合物からなる触媒を用いた有機反応には、例えば鈴木−宮浦カップリング反応、薗頭クロスカップリング反応、ブッフバルド−ハートウィッグ反応、溝呂木−ヘック反応などがある。これらの反応は、最近では医薬品、農薬、電子材料などの分野で特に有用なトリアルキルホスフィン類とパラジウム化合物からなる触媒を用いたハロゲン化アリールとアミン類のアリールアミノ化反応として知られている。
これらの反応における課題は、目的とする反応生成物に触媒由来のパラジウムが含有することであり、医薬品、農薬、電子材料などの分野ではこのパラジウム含有量の削減が強く求められていた。
Conventional organic reactions using a catalyst comprising a phosphorus-based ligand and a palladium compound include, for example, Suzuki-Miyaura coupling reaction, Sonogashira cross-coupling reaction, Buchwald-Heartwig reaction, Mizorogi-Heck reaction, and the like. These reactions are recently known as arylamination reactions of aryl halides and amines using a catalyst comprising a trialkylphosphine and a palladium compound that are particularly useful in the fields of pharmaceuticals, agricultural chemicals, electronic materials and the like.
The problem in these reactions is that the catalyst-derived palladium is contained in the target reaction product, and reduction of this palladium content has been strongly demanded in the fields of pharmaceuticals, agricultural chemicals, electronic materials and the like.
このため、このパラジウムを除去するための方法が種々検討されており、例えばゼオライト、特に活性白土を用いて吸着除去する方法などが報告されている（例えば、特許文献１参照）。
しかしながら、このゼオライトを用いる除去方法では、吸着剤用として天然ゼオライトを用いた場合であっても比表面積を大きくするなどの処理が必要なために高価になること、また、処理前のパラジウム含有溶液に反応溶媒として用いた水または反応後の水洗などによる水分が混在する場合、パラジウムの除去率が著しく低下するなどの問題があった。このため、混在する水分を共沸溶媒で除去するなどの煩雑な操作が必要のため、経済性ならびに操作面において工業規模の製造プロセスとしては必ずしも未だ満足できるものではなかった。
However, in this removal method using zeolite, even when natural zeolite is used as an adsorbent, it is expensive due to the need for treatment such as increasing the specific surface area, and the palladium-containing solution before treatment In the case where water used as a reaction solvent or water after the reaction is mixed, there is a problem that the palladium removal rate is remarkably lowered. For this reason, complicated operations such as removal of mixed water with an azeotropic solvent are necessary, so that it is not always satisfactory as an industrial scale production process in terms of economy and operation.
本発明は、反応生成物溶液中に水分が混在してもパラジウム除去率を低下させず、また工業的にも安価に使用できる吸着剤を用いた、反応生成物溶液からのパラジウムの除去方法を提供することにある。 The present invention provides a method for removing palladium from a reaction product solution using an adsorbent that does not decrease the palladium removal rate even when water is mixed in the reaction product solution and can be used industrially at a low cost. It is to provide.
本発明は、リン系配位子とパラジウム化合物を含む触媒を用いた有機反応後の溶液を、比表面積が１ｇ当たり５０〜４００ｍ２である活性アルミナで処理することを特徴とするパラジウムの除去方法に関する。 The present invention relates to a method for removing palladium, comprising treating a solution after an organic reaction using a catalyst containing a phosphorus ligand and a palladium compound with activated alumina having a specific surface area of 50 to 400 m 2 per gram. About.
本発明によれば、パラジウム含有溶液を工業的に安価に使用できる活性アルミナで処理することにより、処理溶液中に水分が混在していても反応生成物に対するパラジウム量を１０ｐｐｂ以下まで削減した反応生成物を得ることができる。従って、本発明は、工業的に極めて有用な技術である。 According to the present invention, a palladium-containing solution is treated with activated alumina which can be used industrially at low cost, thereby reducing the amount of palladium to the reaction product to 10 ppb or less even when moisture is mixed in the treatment solution. You can get things. Therefore, the present invention is an industrially extremely useful technique.
以下、本発明について詳細に説明する。
本発明で用いられるパラジウムを除去するための溶液としては、リン系配位子とパラジウム化合物を含む触媒を用いた有機反応溶液であり、その反応としては、特に限定するものではない。この有機反応としては、例えば、有機ホウ素化合物とハロゲン化アリールを反応させる鈴木−宮浦クロスカップリング反応、末端アルキンとハロゲン化アリールを反応させる薗頭クロスカップリング反応、ハロゲン化アリールまたはビニルを末端オレフィンと反応させる溝呂木−ヘック反応、ハロゲン化アリールとアミン類を反応させるブッフバルド−ハートウィッグ反応、有機スズ化合物と有機ハロゲン化物を反応させる右田−小杉−スティルカップリング反応などが挙げられ、特に医薬品、農薬、電子材料などの分野で有用なトリアルキルホスフィン類とパラジウム化合物を含む触媒を用いたハロゲン化アリールとアミン類のアリールアミノ化反応が好適に適用される。
Hereinafter, the present invention will be described in detail.
The solution for removing palladium used in the present invention is an organic reaction solution using a catalyst containing a phosphorus-based ligand and a palladium compound, and the reaction is not particularly limited. Examples of this organic reaction include a Suzuki-Miyaura cross-coupling reaction in which an organoboron compound and an aryl halide are reacted, a Sonogashira cross-coupling reaction in which a terminal alkyne and an aryl halide are reacted, and an aryl halide or vinyl as a terminal olefin. And Mizorogi-Heck reaction, Buchwald-Hartwig reaction in which aryl halides and amines are reacted, and Mita-Kosugi-Still coupling reaction in which organotin compounds are reacted with organic halides. The arylamination reaction of aryl halides and amines using a catalyst containing a trialkylphosphine useful in the field of electronic materials and a palladium compound is preferably applied.
次に、触媒系を構成するリン系配位子としては、パラジウムに配位可能なリン原子を有するものであれば特に限定されず、例えばトリメチルホスフィン、トリエチルホスフィン、トリイソプロピルホスフィン、トリ−ｎ−ブチルホスフィン、トリ−ｉｓｏ−ブチルホスフィン、トリ−ｔｅｒｔ−ブチルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィン、１，２−ビス（ジフェニルホスフィノ）エタン、１，１’−ビス（ジフェニルホスフィノ）フェロセンなどが挙げられる。中でも、トリメチルホスフィン、トリエチルホスフィン、トリイソプロピルホスフィン、トリ−ｎ−ブチルホスフィン、トリ−ｉｓｏ−ブチルホスフィン、トリ−ｔｅｒｔ−ブチルホスフィン、トリシクロヘキシルホスフィンなどのトリアルキルホスフィン類が好ましく、特に好ましくはトリ−ｔｅｒｔ−ブチルホスフィンである。 Next, the phosphorus-based ligand constituting the catalyst system is not particularly limited as long as it has a phosphorus atom capable of coordinating with palladium. For example, trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n- Butylphosphine, tri-iso-butylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,1′-bis (diphenylphosphino) ferrocene, etc. Is mentioned. Among them, trialkylphosphines such as trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-iso-butylphosphine, tri-tert-butylphosphine, and tricyclohexylphosphine are preferable, and tri-phosphine is particularly preferable. tert-Butylphosphine.
また、上記リン系配位子と共に使用されるパラジウム化合物しては、特に限定するものではないが、例えばヘキサクロロパラジウム（ＩＶ）酸ナトリウム四水和物、ヘキサクロロパラジウム（ＩＶ）酸カリウムなどの４価パラジウム化合物類、塩化パラジウム（ＩＩ）、臭化パラジウム（ＩＩ）、酢酸パラジウム（ＩＩ）、パラジウムアセチルアセトナート（ＩＩ）、ジクロロビス（ベンゾニトリル）パラジウム（ＩＩ）、ジクロロビス（アセトニトリル）パラジウム（ＩＩ）、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）、ジクロロテトラアンミンパラジウム（ＩＩ）、ジクロロ（シクロオクタ−１，５−ジエン）パラジウム（ＩＩ）、パラジウムトリフルオロアセテート（ＩＩ）などの２価パラジウム化合物類、トリス（ジベンジリデンアセトン）二パラジウム（０）、トリス（ジベンジリデンアセトン）二パラジウムクロロホルム錯体（０）、テトラキス（トリフェニルホスフィン）パラジウム（０）などの０価パラジウム化合物類が挙げられる。 Moreover, it does not specifically limit as a palladium compound used with the said phosphorus-type ligand, For example, tetravalent, such as sodium hexachloro palladium (IV) acid tetrahydrate, hexachloro palladium (IV) acid potassium, etc. Palladium compounds, palladium chloride (II), palladium bromide (II), palladium acetate (II), palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), Divalent palladium compounds such as dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium trifluoroacetate (II), tris Dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium chloroform complex (0), zero-valent palladium compounds such as tetrakis (triphenylphosphine) palladium (0) and the like.
このリン系配位子とパラジウム化合物を含む触媒を用いた有機反応で使用される反応溶媒としては、特に限定するものではないが、ペンタン、ヘキサン、オクタン、シクロヘキサンなどの脂肪族炭化水素系溶媒、ベンゼン、トルエン、キシレンなどの芳香族炭化水素系溶媒、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフランなどのエーテル系溶媒、酢酸メチル、酢酸エチルなどのエステル系溶媒、アセトン、メチルエチルケトンなどのケトン系溶媒、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシドなどの非プロトン性極性溶媒などが挙げられ、これら反応溶媒は単独若しくは混合して用いても差し支えない。使用される反応溶媒の使用量としては、特に限定するものではないが、反応で得られる生成物に対して、通常、１〜２００重量倍、好ましくは５〜１００重量倍が選ばれる。 The reaction solvent used in the organic reaction using the catalyst containing the phosphorus ligand and the palladium compound is not particularly limited, but is an aliphatic hydrocarbon solvent such as pentane, hexane, octane, cyclohexane, Aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, diisopropyl ether and tetrahydrofuran, ester solvents such as methyl acetate and ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, acetonitrile, N , N-dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide, and the like, and these reaction solvents may be used alone or in combination. The amount of the reaction solvent to be used is not particularly limited, but is usually 1 to 200 times by weight, preferably 5 to 100 times by weight with respect to the product obtained by the reaction.
なお、ハロゲン化アリールとアミン類とのアリールアミノ化反応において、反応中の雰囲気は、窒素、アルゴンなどの不活性ガス雰囲気下であることが好ましく、窒素が最も好ましい。また、常圧下もしくは加圧下いずれでも行うことができる。
また、反応は、好ましくは−２０〜２５０℃、より好ましくは５０〜１５０℃に加熱して反応させることが好ましい。
さらに、反応時間は、用いる原料化合物や反応温度などに依存して変化するため一概に言えないが、通常、１〜４８時間である。
In the arylamination reaction between an aryl halide and an amine, the atmosphere during the reaction is preferably an inert gas atmosphere such as nitrogen or argon, and most preferably nitrogen. Moreover, it can carry out under normal pressure or under pressure.
The reaction is preferably carried out by heating to -20 to 250 ° C, more preferably 50 to 150 ° C.
Furthermore, the reaction time varies depending on the raw material compound used, the reaction temperature, and the like, and thus cannot be generally stated, but is usually 1 to 48 hours.
以上のリン系配位子とパラジウム化合物を含む触媒を用いた有機反応液中のパラジウム含有量は、反応で使用されるパラジウム化合物量にもよるが、通常、０．１ｐｐｍ〜５重量％の範囲である。なお、このパラジウム処理前の溶液には、水洗、分液後の水分が混在していても差し支えない。 The palladium content in the organic reaction liquid using the catalyst containing the phosphorus-based ligand and the palladium compound is usually in the range of 0.1 ppm to 5% by weight, although it depends on the amount of the palladium compound used in the reaction. It is. The solution before the palladium treatment may contain water after washing and liquid separation.
なお、得られる有機反応液は、反応終了後、１０〜９０℃まで冷却し、水を反応溶液に対し１〜２００重量倍程度加えて、析出している塩を溶解し、分液により反応液を分取し、この反応液にパラジウム除去用の活性アルミナを添加して、パラジウムの除去を行う。 The obtained organic reaction liquid is cooled to 10 to 90 ° C. after completion of the reaction, water is added about 1 to 200 times by weight to the reaction solution, the precipitated salt is dissolved, and the reaction liquid is separated by liquid separation. The activated alumina for removing palladium is added to the reaction solution to remove palladium.
ここで、本発明のパラジウム除去で使用する活性アルミナは特に限定するものではないが、通常、１ｇ当たり５０〜４００ｍ２、好ましくは１００〜３００ｍ２の比表面積を有するものであれば問題ない。１ｇ当たり５０ｍ２未満の比表面積を有するアルミナの場合、パラジウムの除去率が低下する傾向にあり、一方、４００ｍ２を超える比表面積を有するアルミナの場合、生成物の収率が低下するため、好ましくない
また、活性アルミナは、表面の処理状態によって酸性、中性、塩基性タイプに分かれるが、どのタイプのものを用いてもよく、通常、工業的に使用される安価な塩基性タイプが選ばれる。
活性アルミナの使用量としては、特に限定するものではないが、処理する反応液に存在する反応生成物１重量部に対して、通常、０．０１〜１００重量部、好ましくは０．２〜３０重量部使用される。０．０１重量部未満では、パラジウムの除去率が低下し、一方、１００重量部を超えると生成物の収率が低下するため、好ましくない。
Here, although not particularly limited activated alumina for use in palladium removal of the present invention, usually, 1g per 50 to 400 m 2, preferably no problem as long as it has a specific surface area of 100 to 300 m 2. In the case of alumina having a specific surface area of less than 50 m 2 per gram, the palladium removal rate tends to decrease, whereas in the case of alumina having a specific surface area exceeding 400 m 2 , the yield of the product is decreased, which is preferable. In addition, activated alumina is divided into acidic, neutral, and basic types depending on the surface treatment state, but any type may be used, and an inexpensive basic type that is usually used industrially is selected. .
The amount of activated alumina used is not particularly limited, but is usually 0.01 to 100 parts by weight, preferably 0.2 to 30 parts per 1 part by weight of the reaction product present in the reaction solution to be treated. Used by weight. If the amount is less than 0.01 parts by weight, the palladium removal rate decreases. On the other hand, if it exceeds 100 parts by weight, the yield of the product decreases, which is not preferable.
本発明の方法でパラジウムを除去する方法としては、通常、活性アルミナとパラジウム含有溶液を混合し、所定時間接触させた後、パラジウムが吸着された活性アルミナをろ過、遠心分離などの一般的な分離手段で分離する方法、活性アルミナが充填された塔内にパラジウム含有溶液を通液するなどの方法が挙げられる。これらパラジウムの除去における処理温度としては、特に限定するものではないが、通常、−３０〜２００℃であり、好ましくは０〜１５０℃である。処理時間は、特に限定するものではないが、通常、０．１〜４８時間、好ましくは０．５〜１０時間である。なお、このパラジウム除去処理は、活性アルミナ中のパラジウムが飽和に達するまで活性アルミナを繰り返し使用しても差し支えない。 As a method for removing palladium by the method of the present invention, generally, activated alumina and a palladium-containing solution are mixed and contacted for a predetermined time, and then the activated alumina on which palladium is adsorbed is filtered, centrifuged, or the like. Examples thereof include a method of separating by means, and a method of passing a palladium-containing solution into a column packed with activated alumina. Although it does not specifically limit as the processing temperature in the removal of these palladium, Usually, it is -30-200 degreeC, Preferably it is 0-150 degreeC. Although processing time is not specifically limited, Usually, it is 0.1 to 48 hours, Preferably it is 0.5 to 10 hours. The palladium removal treatment may be repeated using activated alumina until the palladium in the activated alumina reaches saturation.
以下、本発明を実施例により具体的に説明するが、本発明は実施例のみに限定されるものではない。
なお、反応生成物に含有されるパラジウムの含有量は、採取した試料溶液を溶媒除去した後、その残渣を硫酸と硝酸で湿式分解し、メスアップ後、パラジウム（以下、Ｐｄと略記する。）の含有量が１ｐｐｍ以上の場合はＩＣＰ−Ａｔｏｍｉｃ Ｅｍｉｓｓｉｏｎ Ｓｐｅｃｔｒｏｍｅｔｒｙ（以下、ＩＣＰ−ＡＥＳと略記する。）で分析し、パラジウム含有量が１ｐｐｍ以下の場合はＩＣＰ−Ｍａｓｓ Ｓｐｅｃｔｒｏｍｅｔｒｙ（以下、ＩＣＰ−ＭＳと略記する。）で分析した。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to an Example.
The content of palladium contained in the reaction product was determined by removing the solvent from the collected sample solution, wet-decomposing the residue with sulfuric acid and nitric acid, measuring the volume, and then palladium (hereinafter abbreviated as Pd). When the content of Pb is 1 ppm or more, it is analyzed by ICP-Atomic Emission Spectrometry (hereinafter abbreviated as “ICP-AES”). ).
調製例１
温度計、冷却管を備えた１．０ｌの四つ口フラスコに、４，４’−ジブロモビフェニル ２５．０ｇ（８０ｍｍｏｌ）、ジフェニルアミン ２７．７ｇ（１６３ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド ２３．１ｇ（２４０ｍｍｏｌ）、ｏ−キシレン ５１９．５ｇを仕込み、系内を撹拌しながら、室温下、窒素置換を行った。ついで、酢酸Ｐｄ１８ｍｇ（０．０８ｍｍｏｌ）、トリ（ｔｅｒｔ−ブチル）ホスフィン ４９ｍｇ（０．２４ｍｍｏｌ）を予め少量のｏ−キシレン中で加熱攪拌して調製しておいた触媒溶液を、先の四つ口フラスコに加え、内温を約１３０℃まで加熱し、３時間反応を行った。反応終了後、６０℃まで冷却し、水１４８ｇを加えて析出している塩を溶解し、分液により反応液 ５６６ｇを得た。溶液中のテトラ−Ｎ−フェニルベンジジンの含有量は３８．７ｇであり、Ｐｄの含有量はＩＣＰ−ＡＥＳで分析した結果、テトラ−Ｎ−フェニルベンジジンに対して７９ｐｐｍであった。なお、この得られた反応液中には水分の混在が確認された。
以下、この得られたテトラ−Ｎ−フェニルベンジジン反応液を用いてＰｄの除去を行った。
Preparation Example 1
In a 1.0 l four-necked flask equipped with a thermometer and a condenser tube, 25.0 g (80 mmol) of 4,4′-dibromobiphenyl, 27.7 g (163 mmol) of diphenylamine, 23.1 g (240 mmol) of sodium tert-butoxide ) And 519.5 g of o-xylene were charged, and nitrogen substitution was performed at room temperature while stirring the system. Next, a catalyst solution prepared by previously stirring 18 mg (0.08 mmol) of Pd acetate and 49 mg (0.24 mmol) of tri (tert-butyl) phosphine in a small amount of o-xylene in advance was added to the above four necks. In addition to the flask, the internal temperature was heated to about 130 ° C., and the reaction was carried out for 3 hours. After completion of the reaction, the reaction mixture was cooled to 60 ° C., 148 g of water was added to dissolve the precipitated salt, and 566 g of a reaction solution was obtained by liquid separation. The content of tetra-N-phenylbenzidine in the solution was 38.7 g, and the content of Pd was analyzed by ICP-AES. As a result, it was 79 ppm with respect to tetra-N-phenylbenzidine. In addition, mixing of moisture was confirmed in the obtained reaction solution.
Hereinafter, Pd was removed using the obtained tetra-N-phenylbenzidine reaction solution.
実施例１
温度計、冷却管を備えた１００ｍｌの四つ口フラスコに、調製例１で得られたテトラ−Ｎ−フェニルベンジジン含有溶液 ５０ｇと１ｇ当たり２５０ｍ２の比表面積を有する塩基性タイプの活性アルミナ（和光純薬工業社製、クロマトグラフ用） １０ｇを仕込み、内温６０℃で１時間撹拌した。その後、活性アルミナを減圧濾過し、ろ別した活性アルミナを適当量のｏ−キシレンで洗浄した後、このろ液を濃縮乾固し、ほぼ定量的にテトラ−Ｎ−フェニルベンジジンを回収した。この濃縮乾固後の残渣について、ＩＣＰ−ＭＳ分析を行った結果、Ｐｄの含有量は１０ｐｐｂ以下であり、Ｐｄの除去率は９９．９％以上であった。
Example 1
In a 100 ml four-necked flask equipped with a thermometer and a condenser tube, 50 g of the tetra-N-phenylbenzidine-containing solution obtained in Preparation Example 1 and a basic type activated alumina having a specific surface area of 250 m 2 per g (sum) 10 g of Koto Pure Chemical Industries, Ltd. (for chromatograph) was charged and stirred for 1 hour at an internal temperature of 60 ° C. Thereafter, the activated alumina was filtered under reduced pressure, and the filtered activated alumina was washed with an appropriate amount of o-xylene, and then the filtrate was concentrated to dryness to recover tetra-N-phenylbenzidine almost quantitatively. As a result of ICP-MS analysis of the residue after concentration to dryness, the Pd content was 10 ppb or less, and the Pd removal rate was 99.9% or more.
実施例２〜４
実施例１と同様な容器を用い、活性アルミナの種類および処理条件を表１に示した条件に変更した以外は実施例１と同様に行った。結果を、表１に示す。
Examples 2-4
The same container as in Example 1 was used, and the same procedure as in Example 1 was performed except that the type of activated alumina and the treatment conditions were changed to the conditions shown in Table 1. The results are shown in Table 1.
なお、表１の活性アルミナのうち、塩基性は和光純薬工業社製のクロマトグラフ用、酸性は和光純薬工業社製のスーパーＩ（酸性）、中性は和光純薬工業社製のスーパーＩ（塩基性）を用いた。 Of the activated aluminas in Table 1, basic is for chromatographs manufactured by Wako Pure Chemical Industries, acid is super I (acidic) manufactured by Wako Pure Chemical Industries, and neutral is super manufactured by Wako Pure Chemical Industries. I (basic) was used.
実施例５
直径３５ｍｍのガラス製カラムに、１ｇ当たり２５０ｍ２の比表面積を有する塩基性タイプの活性アルミナ（和光純薬工業社製、クロマトグラフ用） ２０ｇを充填し、次に実施例１で得たテトラ−Ｎ−フェニルベンジジン含有溶液 ５０ｇを室温下、通液した後、カラム中に残存するテトラ−Ｎ−フェニルベンジジンを適当量のｏ−キシレンで洗浄した。カラム処理して得たテトラ−Ｎ−フェニルベンジジン溶液を濃縮乾固し、ほぼ定量的にテトラ−Ｎ−フェニルベンジジンを回収した。この濃縮乾固後の残渣について、ＩＣＰ−ＭＳ分析を行った結果、Ｐｄの含有量は１０ｐｐｂ以下であり、Ｐｄの除去率は９９．９％以上であった。
Example 5
A glass column having a diameter of 35 mm was charged with 20 g of basic type activated alumina having a specific surface area of 250 m 2 per gram (manufactured by Wako Pure Chemical Industries, Ltd., for chromatograph). After passing 50 g of an N-phenylbenzidine-containing solution at room temperature, tetra-N-phenylbenzidine remaining in the column was washed with an appropriate amount of o-xylene. The tetra-N-phenylbenzidine solution obtained by column treatment was concentrated to dryness, and tetra-N-phenylbenzidine was recovered almost quantitatively. As a result of ICP-MS analysis of the residue after concentration to dryness, the Pd content was 10 ppb or less and the Pd removal rate was 99.9% or more.
比較例１
温度計、冷却管を備えた１００ｍｌの四つ口フラスコに、調製例１で得られたテトラ−Ｎ−フェニルベンジジン含有溶液 ５０ｇと活性白土（和光純薬工業社製） １０ｇを仕込み、内温６０℃で１時間撹拌した。その後、活性アルミナを減圧濾過し、ろ別した活性アルミナを適当量のｏ−キシレンで洗浄した後、このろ液を濃縮乾固し、ほぼ定量的にテトラ−Ｎ−フェニルベンジジンを回収した。この濃縮乾固後の残渣について、ＩＣＰ−ＡＥＳ分析を行った結果、Ｐｄの含有量は２０ｐｐｍであり、Ｐｄの除去率は７４．７％であった。
Comparative Example 1
A 100 ml four-necked flask equipped with a thermometer and a condenser tube was charged with 50 g of the tetra-N-phenylbenzidine-containing solution obtained in Preparation Example 1 and 10 g of activated clay (manufactured by Wako Pure Chemical Industries, Ltd.). Stir for 1 hour at ° C. Thereafter, the activated alumina was filtered under reduced pressure, and the filtered activated alumina was washed with an appropriate amount of o-xylene, and then the filtrate was concentrated to dryness to recover tetra-N-phenylbenzidine almost quantitatively. As a result of ICP-AES analysis of the residue after concentration to dryness, the Pd content was 20 ppm and the Pd removal rate was 74.7%.
比較例２〜４
比較例１と同様な容器を用い、ゼオライトの種類および処理条件を表１に示した条件に変更した以外は比較例１と同様に行った。結果を、表２に示す。
Comparative Examples 2-4
The same container as in Comparative Example 1 was used, and the same procedure as in Comparative Example 1 was performed except that the type of zeolite and the treatment conditions were changed to the conditions shown in Table 1. The results are shown in Table 2.
表２中の吸着剤は、以下のとおりである。
Ｙ型ゼオライト：東ソー社製、３２０ＨＯＡ
Ｌ型ゼオライト：東ソー社製、５００−ＫＯＨ
ＺＳＭ−５ ：東ソー社製、ＺＳＭ−５
The adsorbents in Table 2 are as follows.
Y-type zeolite: manufactured by Tosoh Corporation, 320HOA
L-type zeolite: manufactured by Tosoh Corporation, 500-KOH
ZSM-5: manufactured by Tosoh Corporation, ZSM-5
比較例５
直径３５ｍｍのガラス製カラムに、活性白土 ２０ｇを充填し、次に調製例１で得たテトラ−Ｎ−フェニルベンジジン含有溶液 ５０ｇを室温下、通液した後、カラム中に残存するテトラ−Ｎ−フェニルベンジジンを適当量のｏ−キシレンで洗浄した。カラム処理して得たテトラ−Ｎ−フェニルベンジジン溶液を濃縮乾固し、ほぼ定量的にテトラ−Ｎ−フェニルベンジジンを回収した。この濃縮乾固後の残渣について、ＩＣＰ−ＡＥＳ分析を行った結果、Ｐｄの含有量は２５ｐｐｍであり、Ｐｄの除去率は６８．４％であった。
Comparative Example 5
A glass column having a diameter of 35 mm was filled with 20 g of activated clay, and then 50 g of the tetra-N-phenylbenzidine-containing solution obtained in Preparation Example 1 was passed at room temperature, and then remained in the column. Phenylbenzidine was washed with an appropriate amount of o-xylene. The tetra-N-phenylbenzidine solution obtained by column treatment was concentrated to dryness, and tetra-N-phenylbenzidine was recovered almost quantitatively. As a result of ICP-AES analysis of the residue after concentration and drying, the Pd content was 25 ppm and the Pd removal rate was 68.4%.
比較例６
温度計、冷却管を備えた１００ｍｌの四つ口フラスコに、調製例１で得られたテトラ−Ｎ−フェニルベンジジン含有溶液 ５０ｇと１ｇ当たり２０ｍ２の比表面積を有する塩基性タイプのアルミナ（和光純薬工業社製） １０ｇを仕込み、内温６０℃で１時間撹拌した。その後、アルミナを減圧濾過し、ろ別したアルミナを適当量のｏ−キシレンで洗浄した後、このろ液を濃縮乾固し、ほぼ定量的にテトラ−Ｎ−フェニルベンジジンを回収した。この濃縮乾固後の残渣について、ＩＣＰ−ＡＥＳ分析を行った結果、Ｐｄの含有量は６６ｐｐｍであり、Ｐｄの除去率は１６．５％であった。
Comparative Example 6
In a 100 ml four-necked flask equipped with a thermometer and a condenser tube, 50 g of the tetra-N-phenylbenzidine-containing solution obtained in Preparation Example 1 and a basic type alumina having a specific surface area of 20 m 2 per g (Wako Pure) (Manufactured by Yakuhin Kogyo Co., Ltd.) Thereafter, the alumina was filtered under reduced pressure, and the filtered alumina was washed with an appropriate amount of o-xylene, and then the filtrate was concentrated to dryness to recover tetra-N-phenylbenzidine almost quantitatively. As a result of ICP-AES analysis of the residue after concentration to dryness, the Pd content was 66 ppm and the Pd removal rate was 16.5%.
本発明のパラジウムの除去方法は、リン系配位子とパラジウム化合物を含む触媒を用いた有機反応、例えば有機ホウ素化合物とハロゲン化アリールを反応させる鈴木−宮浦クロスカップリング反応、末端アルキンとハロゲン化アリールを反応させる薗頭クロスカップリング反応、ハロゲン化アリールまたはビニルを末端オレフィンと反応させる溝呂木−ヘック反応、ハロゲン化アリールとアミン類を反応させるブッフバルド−ハートウィッグ反応、有機スズ化合物と有機ハロゲン化物を反応させる右田−小杉−スティルカップリング反応などにおいて、パラジウムの除去として有用である。 The palladium removal method of the present invention includes an organic reaction using a catalyst containing a phosphorus-based ligand and a palladium compound, such as a Suzuki-Miyaura cross-coupling reaction in which an organoboron compound and an aryl halide are reacted, a terminal alkyne and a halogenation. Sonogashira cross coupling reaction for reacting aryl, Mizorogi-Heck reaction for reacting aryl halide or vinyl with terminal olefin, Buchwald-Heartwig reaction for reacting aryl halide with amines, organotin compound and organic halide It is useful for removing palladium in the reaction of right rice-Kosugi-still coupling.
Claims (6)
The method for removing palladium according to any one of claims 1 to 5, wherein the amount of activated alumina added is 0.01 to 100 parts by weight with respect to 1 part by weight of the reaction product in the reaction solution.
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| JP2013091057A (en) * | 2011-10-03 | 2013-05-16 | Tosoh Corp | Palladium compound adsorbent and application thereof |
| JP2015074721A (en) * | 2013-10-09 | 2015-04-20 | 東ソー株式会社 | Method for producing arylamine compound |
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