JP4210091B2 - Metal cation exchange montmorillonite catalyst - Google Patents
Metal cation exchange montmorillonite catalyst Download PDFInfo
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- JP4210091B2 JP4210091B2 JP2002277215A JP2002277215A JP4210091B2 JP 4210091 B2 JP4210091 B2 JP 4210091B2 JP 2002277215 A JP2002277215 A JP 2002277215A JP 2002277215 A JP2002277215 A JP 2002277215A JP 4210091 B2 JP4210091 B2 JP 4210091B2
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- cation
- montmorillonite
- catalyst
- metal cation
- carbon atoms
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims description 43
- 229910052901 montmorillonite Inorganic materials 0.000 title claims description 42
- 239000003054 catalyst Substances 0.000 title claims description 40
- 229910052751 metal Inorganic materials 0.000 title claims description 38
- 239000002184 metal Substances 0.000 title claims description 38
- 238000005341 cation exchange Methods 0.000 title claims description 16
- -1 scandium cation Chemical class 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 33
- 150000001768 cations Chemical class 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 229910052706 scandium Inorganic materials 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 14
- 238000006845 Michael addition reaction Methods 0.000 claims description 12
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 12
- 150000002576 ketones Chemical class 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 claims description 5
- 125000004450 alkenylene group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- KVLCHQHEQROXGN-UHFFFAOYSA-N aluminium(1+) Chemical compound [Al+] KVLCHQHEQROXGN-UHFFFAOYSA-N 0.000 description 2
- 229940007076 aluminum cation Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003431 steroids Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical class O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- CFMUQQVWLGSGJL-UHFFFAOYSA-K dodecane-1-sulfonate;scandium(3+) Chemical compound [Sc+3].CCCCCCCCCCCCS([O-])(=O)=O.CCCCCCCCCCCCS([O-])(=O)=O.CCCCCCCCCCCCS([O-])(=O)=O CFMUQQVWLGSGJL-UHFFFAOYSA-K 0.000 description 1
- JOHCLLAMYIRJOJ-UHFFFAOYSA-K dodecyl sulfate;scandium(3+) Chemical compound [Sc+3].CCCCCCCCCCCCOS([O-])(=O)=O.CCCCCCCCCCCCOS([O-])(=O)=O.CCCCCCCCCCCCOS([O-])(=O)=O JOHCLLAMYIRJOJ-UHFFFAOYSA-K 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JHZPNBKZPAWCJD-UHFFFAOYSA-N ethyl 2-oxocyclopentane-1-carboxylate Chemical compound CCOC(=O)C1CCCC1=O JHZPNBKZPAWCJD-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- DNHDRUMZDHWHKG-UHFFFAOYSA-N wieland–miescher ketone Chemical compound C1CC(=O)C=C2CCCC(=O)C21C DNHDRUMZDHWHKG-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、金属カチオンをイオン交換しているモンモリロナイトを含有する触媒に関する。
【０００２】
【従来の技術】
マイケル付加反応は、最も重要な炭素−炭素結合形成反応の一つであり、１，３−ジカルボニル化合物とα，β−不飽和ケトンの反応等、種々の有機化合物の合成に用いられ、得られた有機化合物は種々の用途に用いられている。（例えば、ステロイドやテルペノイドの合成において重要な中間体となるWieland-Miescherケトンは、この反応を用いて得られた１，５−ジカルボニル化合物から合成できる）。
このような、マイケル付加反応を用いた有機化合物の製造には、強塩基が触媒として用いられていたが、副反応が多い等の問題があった。そこで、この問題を解決するためルイス酸を触媒として用いる方法が提案され、さらに、触媒活性を向上したルイス酸触媒としてスカンジウムトリス（ドデシルサルフェート）やスカンジウムトリスドデカンスルフォネート等の使用が知られている（Tetrahedron Letters ４１， (2000) 3107-3111）。
しかし、このような触媒を用いた均一系の反応の場合は、反応後の触媒等の分離・回収が困難であり、又環境上の問題等も生じていた。そこで、このような問題の生じない固体触媒が望まれていたが、マイケル付加反応を用いた有機化合物の合成に優れた活性を有する固体触媒は見出されていなかった。
【０００３】
【発明が解決しようとする課題】
本発明は、固体触媒であってかつマイケル付加反応を用いた有機反応の合成に優れた活性を示すものを提供することを目的とする。
本発明者は、前記の従来の触媒の問題を解決した触媒を開発するべく鋭意検討した結果、金属カチオンをイオン交換しているモンモリロナイトが、固体触媒として用いられ、１，３−ジカルボニル化合物とα，β−不飽和ケトンのマイケル付加反応に優れた活性を有することを見出した。
本発明者はさらに、金属カチオンが、スカンジウムカチオン（Ｓｃ３＋）、イッテルビウムカチオン（Ｙｂ３＋）の場合、触媒活性が特に高いこと、１，３−ジカルボニル化合物とα，β−不飽和ケトンのマイケル付加反応以外にも優れた触媒活性を示すことを見出し、本発明を完成した。
【０００４】
【課題を解決するための手段】
すなわち、本発明は、金属カチオンをイオン交換しているモンモリロナイトを含有し、１，３−ジカルボニル化合物とα，β−不飽和ケトンのマイケル付加反応に用いられることを特徴とする金属カチオン交換モンモリロナイト触媒において、金属カチオンが、スカンジウムカチオン（Ｓｃ ３＋ ）、イッテルビウムカチオン（Ｙｂ ３＋ ）及びチタニウムカチオン（Ｔｉ ４＋ ）から選ばれることを特徴とする金属カチオン交換モンモリロナイト触媒を提供するものである。
【０００５】
本発明は、又、スカンジウムカチオン（Ｓｃ３＋）又はイッテルビウムカチオン（Ｙｂ３＋）をイオン交換しているモンモリロナイトを含有し、１，３−ジカルボニル化合物とα，β−不飽和ケトンのマイケル付加反応に用いられることを特徴とする金属カチオン交換モンモリロナイト触媒を提供する。
【０００６】
本発明は、さらに、金属カチオンをイオン交換しているモンモリロナイトを含有する触媒の存在下、下記一般式（Ｉ）で表される化合物
下記一般式（II）で表される化合物
【０００７】
【発明の実施の形態】
本発明の触媒に含有される、金属カチオンをイオン交換しているモンモリロナイトにおいて、金属カチオンとしては、スカンジウムカチオン（Ｓｃ３＋）、イッテルビウムカチオン（Ｙｂ３＋）及びチタニウムカチオン（Ｔｉ４＋）が例示される。
中でも、スカンジウムカチオン（Ｓｃ３＋）及びイッテルビウムカチオン（Ｙｂ３＋）、とりわけスカンジウムカチオン（Ｓｃ３＋）の場合、１，３−ジカルボニル化合物とα，β−不飽和ケトンのマイケル付加反応において優れた触媒活性が得られる。
なお、金属カチオンをイオン交換しているモンモリロナイトとは、金属カチオンを保持しているモンモリロナイトとの意味である。
【０００８】
モンモリロナイトとは、層状粘土鉱物であり、種々の金属カチオンを層間に容易にイオン交換でき、そのカチオンの種類によって酸性を制御できる特徴を持つ。通常、下記一般式（ＩＶ）で示される。
(Ｘ，Ｙ)２〜３Ｚ４Ｏ１０（ＯＨ）２・ｍＨ２Ｏ・（Ｗｗ） （ＩＶ）
（式中、Ｘは、Ａｌ、Ｆｅ３＋、Ｍｎ３＋、又はＣｒ３＋であり、Ｙは、Ｍｇ、Ｆｅ２＋、Ｍｎ２＋、Ｎｉ、Ｚｎ又はＬｉであり、ＺはＳｉ又はＡｌであり、Ｗは、Ｋ、Ｎａ等のアルカリ金属又はＣａ等のアルカリ土類金属であり、そしてＨ２Ｏは層間水である。又、ｗは１／３である。）
モンモリロナイトの中でも、下記式（Ｖ）で表されるものが代表的なものとして挙げられる。
Ａｌ５／３Ｍｇ１／３Ｓｉ４Ｏ１０（ＯＨ）２Ｗ１／３・ｍＨ２Ｏ （Ｖ）（式中、ｍ及びＷは、前記と同じ意味を表す。Ａｌの一部はＦｅ３＋で置換されていてもよく、Ｓｉの一部はＡｌで置換されていてもよい。）
【０００９】
金属カチオンをイオン交換しているモンモリロナイトは、モンモリロナイトと、金属カチオンが溶解した溶液、例えば当該金属の塩の水溶液を接触することにより製造することができる。
特に、スカンジウムカチオン（Ｓｃ３＋）の場合、（ＣＦ３ＳＯ３）３Ｓｃ（スカンジウムトリフラート）水溶液と接触させて得られたものは高い触媒活性を示すので好ましい。
本発明の金属カチオン交換モンモリロナイト触媒は、このようにして得られた金属カチオンをイオン交換しているモンモリロナイトを、好ましくは主成分として、含有するものである。
【００１０】
本発明の金属カチオン交換モンモリロナイト触媒は、１，３−ジカルボニル化合物とα，β−不飽和ケトンを反応させることによる１，５−ジカルボニル化合物の合成等のいわゆるマイケル付加反応を利用した製造方法や、その他の有機反応を利用した方法において優れた触媒活性を発揮する。
ここで１，３−ジカルボニル化合物としては、前記の一般式（Ｉ）で表される化合物が例示され、α，β−不飽和ケトンとしては、前記の一般式（II）で表される化合物が例示される。一般式（Ｉ）で表される化合物と一般式（II）で表される化合物を、本発明の金属カチオン交換モンモリロナイト触媒の存在下、反応することにより一般式（III）で表される化合物が得られる。
【００１１】
一般式（Ｉ）で表される化合物のより具体的な例として、下記式（I-1）で表される化合物が挙げられる。
又、一般式（II）で表される化合物のより具体的な例として、下記式（II-1）で表される化合物が挙げられる。
一般式（Ｉ-1）で表される化合物と一般式（II-1）で表される化合物を、本発明の金属カチオン交換モンモリロナイト触媒の存在下、反応することにより下記式（III-1）で表される化合物が得られる。
一般式（Ｉ-1）で表される化合物と一般式（II-1）で表される化合物の反応は、通常、無溶媒条件下又はトルエン、ジクロロエタン等の溶媒中で行われる。金属カチオン交換モンモリロナイト触媒は、一般式（Ｉ-1）で表される化合物１モル当たり、好ましくは１〜１００ｇ、より好ましくは１０〜５０ｇ用いられる。
反応温度は、１０℃程度〜１１０℃程度が採用できるが、３０℃〜８０℃程度が好ましい。
【００１５】
通常、一般式（II-1）で表される化合物は、一般式（Ｉ-1）で表される化合物より１〜１．５倍モル程度過剰に用いることが好ましい。
反応は、一般式（Ｉ-1）で表される化合物、一般式（II-1）で表される化合物、触媒、及び必要によりさらに溶媒を混合し、攪拌しながら所定の温度に保つことにより進行させることができる。反応容器としてオートクレーブ等の圧力容器を用い加圧下で行ってもよい。反応時間は限定されないが、スカンジウムカチオン（Ｓｃ３＋）交換モンモリロナイト触媒等の高活性な触媒を用いた場合は、１０時間以内で反応はほぼ完結する。
【００１６】
反応後、金属カチオン交換モンモリロナイト触媒は、濾過等の方法により容易に回収できる。回収された触媒は、活性の低下はなく、再使用が可能である。
【００１７】
【発明の効果】
本発明の金属カチオン交換モンモリロナイト触媒は、固体触媒であり、かつマイケル付加反応を用いた有機化合物の合成反応に優れた触媒活性を示す。固体触媒であるので、その回収は容易であり、その結果、反応工程、装置、反応管理等を簡単に容易にすることができる。又、本発明の金属カチオン交換モンモリロナイト触媒は、無害であり、反応に使用して回収されてもほとんど触媒活性は低下せず繰返しの再使用が可能である。
特に、金属カチオンとして、スカンジウムカチオン（Ｓｃ３＋）又はイッテルビウムカチオン（Ｙｂ３＋）、（とりわけスカンジウムカチオン（Ｓｃ３＋））を用いたものは、触媒活性が高い。
【００１８】
【実施例】
以下、実施例を挙げ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よりなんら限定されるものではない。
【００１９】
実施例１ スカンジウムカチオン（Ｓｃ３＋）交換モンモリロナイト触媒の合成３ｇのナトリウム−モンモリロナイト（クニピア、クニミネ工業株式会社製）を、２００ｍｌの５×１０−３モル濃度のスカンジウムトリフラート水溶液に加え、５０℃で２４時間攪拌した。得られたスラリーを濾過し、蒸留水で洗浄後、１１０℃で乾燥することにより、スカンジウムカチオン（Ｓｃ３＋）交換モンモリロナイト触媒が得られた。
【００２０】
実施例２、４および参考例１ イッテルビウムカチオン（Ｙｂ３＋）、アルミニウムカチオン（Aｌ3 ＋）又はチタニウムカチオン（Ｔｉ４＋）交換モンモリロナイト触媒の合成
スカンジウムトリフラート水溶液の代わりに、イッテルビウムトリフラート、塩化アルミニウム又は塩化チタンの水溶液を用いた以外は実施例１と同様に行うことにより、それぞれ、イッテルビウムカチオン（Ｙｂ３＋）、アルミニウムカチオン（Aｌ3 ＋）又はチタニウムカチオン（Ｔｉ４＋）カチオン交換モンモリロナイト触媒が得られた。
【００２１】
エチル２−オキソ−シクロペンタンカルボキシレート（式（I-1）の化合物）の４ミリモル、２−シクロペンタン−１−オン（式（II-1）の化合物）の６ミリモル、及び実施例１〜４で得られた金属カチオン交換モンモリロナイト触媒の０．１ｇを反応容器に加え、攪拌下８０℃に６時間保ち反応を行った。
反応終了後、生成物をガスクロマトグラフィーで分析し、その結果から式（III-1）の化合物の収率を求めた。その結果を、表１にしめす。
【表１】
比較例１
金属カチオン交換モンモリロナイト触媒の代わりに、スカンジウムトリフラートを用いた以外は上記実施例と同様に行ったが、式（III-1）の化合物の収率は２５％であった。
【００２３】
比較例２
金属カチオン交換モンモリロナイト触媒の代わりに、ナトリウム−モンモリロナイト（クニピア、monｔＫ-10、ＳＯ４ ２−／ＺｒＯ２、H+-beta、H+-USY、H+-mordenite、H+-ZSM-5、クニミネ工業株式会社製の無機固体酸触媒）、を用いた以外は上記実施例と同様に行ったが、式（III-1）の化合物の収率は３０％程度であった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a catalyst containing montmorillonite in which metal cations are ion-exchanged.
[0002]
[Prior art]
The Michael addition reaction is one of the most important carbon-carbon bond formation reactions, and is used in the synthesis of various organic compounds such as the reaction of 1,3-dicarbonyl compounds with α, β-unsaturated ketones. The obtained organic compounds are used in various applications. (For example, Wieland-Miescher ketone, which is an important intermediate in the synthesis of steroids and terpenoids, can be synthesized from 1,5-dicarbonyl compounds obtained using this reaction).
In the production of such an organic compound using the Michael addition reaction, a strong base was used as a catalyst, but there were problems such as many side reactions. Therefore, in order to solve this problem, a method using a Lewis acid as a catalyst has been proposed. Further, as a Lewis acid catalyst having improved catalytic activity, use of scandium tris (dodecyl sulfate), scandium trisdodecane sulfonate, or the like is known. (Tetrahedron Letters 41, (2000) 3107-3111).
However, in the case of a homogeneous reaction using such a catalyst, it is difficult to separate and recover the catalyst after the reaction, and environmental problems have occurred. Therefore, a solid catalyst that does not cause such a problem has been desired, but no solid catalyst having an activity excellent in the synthesis of an organic compound using the Michael addition reaction has been found.
[0003]
[Problems to be solved by the invention]
It is an object of the present invention to provide a solid catalyst that exhibits excellent activity for the synthesis of organic reactions using the Michael addition reaction.
As a result of intensive studies to develop a catalyst that solves the problems of the conventional catalysts described above, the present inventor has used montmorillonite in which a metal cation is ion-exchanged as a solid catalyst, and a 1,3-dicarbonyl compound and It has been found that it has excellent activity in the Michael addition reaction of α, β-unsaturated ketones.
The present inventor further shows that when the metal cation is scandium cation (Sc 3+ ) or ytterbium cation (Yb 3+ ), the catalytic activity is particularly high, and Michael of 1,3-dicarbonyl compound and α, β-unsaturated ketone. The present invention was completed by finding that it exhibits excellent catalytic activity other than the addition reaction.
[0004]
[Means for Solving the Problems]
That is, the present invention contains montmorillonite that ion-exchanges a metal cation, and is used for the Michael addition reaction of a 1,3-dicarbonyl compound and an α, β-unsaturated ketone. In the catalyst , a metal cation exchange montmorillonite catalyst is provided , wherein the metal cation is selected from a scandium cation (Sc 3+ ), an ytterbium cation (Yb 3+ ), and a titanium cation (Ti 4+ ) .
[0005]
The present invention also includes a montmorillonite ion-exchanged with a scandium cation (Sc 3+ ) or an ytterbium cation (Yb 3+ ), and is used for a Michael addition reaction of a 1,3-dicarbonyl compound and an α, β-unsaturated ketone. The present invention provides a metal cation exchange montmorillonite catalyst characterized by being used .
[0006]
The present invention further relates to a compound represented by the following general formula (I) in the presence of a catalyst containing montmorillonite in which a metal cation is ion-exchanged.
Compound represented by the following general formula (II)
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the montmorillonite in which the metal cation is ion-exchanged contained in the catalyst of the present invention, examples of the metal cation include scandium cation (Sc 3+ ), ytterbium cation (Yb 3+ ), and titanium cation (Ti 4+ ).
In particular, in the case of scandium cation (Sc 3+ ) and ytterbium cation (Yb 3+ ), especially scandium cation (Sc 3+ ), excellent catalytic activity in the Michael addition reaction of a 1,3-dicarbonyl compound and an α, β-unsaturated ketone. Is obtained.
In addition, the montmorillonite which ion-exchanged the metal cation means the montmorillonite holding the metal cation.
[0008]
Montmorillonite is a layered clay mineral, and has a feature that various metal cations can be easily ion-exchanged between layers, and the acidity can be controlled by the kind of the cations. Usually, it is represented by the following general formula (IV).
(X, Y) 2~3 Z 4 O 10 (OH) 2 · mH 2 O · (W w) (IV)
( Wherein X is Al, Fe 3+ , Mn 3+ , or Cr 3+ , Y is Mg, Fe 2+ , Mn 2+ , Ni, Zn or Li, Z is Si or Al, and W is , K, Na, etc. or Ca, etc., and alkaline earth metals such as Ca, and H 2 O is interlayer water, and w is 1/3.)
Among the montmorillonites, those represented by the following formula (V) can be cited as typical examples.
Al 5/3 Mg 1/3 Si 4 O 10 (OH) 2 W 1/3 · mH 2 O (V) (wherein m and W have the same meanings as described above. Part of Al is Fe 3+ And a part of Si may be substituted with Al.)
[0009]
Montmorillonite in which the metal cation is ion-exchanged can be produced by contacting montmorillonite with a solution in which the metal cation is dissolved, for example, an aqueous solution of the metal salt.
In particular, in the case of a scandium cation (Sc 3+ ), a product obtained by contact with an aqueous solution of (CF 3 SO 3 ) 3 Sc (scandium triflate) is preferable because it exhibits high catalytic activity.
The metal cation exchange montmorillonite catalyst of the present invention contains the montmorillonite obtained by ion exchange of the metal cation thus obtained, preferably as a main component.
[0010]
The metal cation exchange montmorillonite catalyst of the present invention is a production method using a so-called Michael addition reaction such as synthesis of a 1,5-dicarbonyl compound by reacting a 1,3-dicarbonyl compound with an α, β-unsaturated ketone. In addition, it exhibits excellent catalytic activity in methods utilizing other organic reactions.
Examples of the 1,3-dicarbonyl compound include compounds represented by the general formula (I), and examples of the α, β-unsaturated ketone include compounds represented by the general formula (II). Is exemplified. By reacting the compound represented by the general formula (I) and the compound represented by the general formula (II) in the presence of the metal cation exchange montmorillonite catalyst of the present invention, the compound represented by the general formula (III) is obtained. can get.
[0011]
More specific examples of the compound represented by the general formula (I) include a compound represented by the following formula (I-1).
A more specific example of the compound represented by the general formula (II) is a compound represented by the following formula (II-1).
By reacting the compound represented by the general formula (I-1) and the compound represented by the general formula (II-1) in the presence of the metal cation exchange montmorillonite catalyst of the present invention, the following formula (III-1) Is obtained.
The reaction of the compound represented by the general formula (I-1) and the compound represented by the general formula (II-1) is usually performed under solvent-free conditions or in a solvent such as toluene or dichloroethane. The metal cation exchange montmorillonite catalyst is preferably used in an amount of 1 to 100 g, more preferably 10 to 50 g, per 1 mol of the compound represented by the general formula (I-1).
The reaction temperature can be about 10 ° C to about 110 ° C, preferably about 30 ° C to 80 ° C.
[0015]
Usually, the compound represented by the general formula (II-1) is preferably used in an excess of about 1 to 1.5 times the molar amount of the compound represented by the general formula (I-1).
The reaction is carried out by mixing the compound represented by the general formula (I-1), the compound represented by the general formula (II-1), a catalyst, and, if necessary, a solvent, and maintaining the mixture at a predetermined temperature while stirring. Can be advanced. The reaction may be performed under pressure using a pressure vessel such as an autoclave. The reaction time is not limited, but when a highly active catalyst such as a scandium cation (Sc3 +) exchanged montmorillonite catalyst is used, the reaction is almost completed within 10 hours.
[0016]
After the reaction, the metal cation exchange montmorillonite catalyst can be easily recovered by a method such as filtration. The recovered catalyst is not reduced in activity and can be reused.
[0017]
【The invention's effect】
The metal cation exchange montmorillonite catalyst of the present invention is a solid catalyst and exhibits excellent catalytic activity in the synthesis reaction of organic compounds using the Michael addition reaction. Since it is a solid catalyst, its recovery is easy, and as a result, the reaction process, equipment, reaction management, etc. can be easily facilitated. Further, the metal cation exchange montmorillonite catalyst of the present invention is harmless, and even when recovered by use in the reaction, the catalytic activity is hardly lowered and it can be reused repeatedly.
In particular, those using scandium cation (Sc 3+ ) or ytterbium cation (Yb 3+ ) (particularly scandium cation (Sc 3+ )) as the metal cation have high catalytic activity.
[0018]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.
[0019]
Example 1 Synthesis of Scandium Cation (Sc 3+ ) Exchanged Montmorillonite Catalyst 3 g of sodium-montmorillonite (Kunipia, manufactured by Kunimine Industries, Ltd.) was added to 200 ml of 5 × 10 −3 molar aqueous scandium triflate solution at 24 ° C. Stir for hours. The obtained slurry was filtered, washed with distilled water, and dried at 110 ° C. to obtain a scandium cation (Sc 3+ ) exchanged montmorillonite catalyst.
[0020]
Examples 2 and 4 and Reference Example 1 Synthesis of Ytterbium Cation (Yb 3+ ), Aluminum Cation (Al 3 + ) or Titanium Cation (Ti 4+ ) Exchanged Montmorillonite Catalyst Instead of an aqueous scandium triflate solution, ytterbium triflate, aluminum chloride or titanium chloride A ytterbium cation (Yb 3+ ), an aluminum cation (Al 3 + ), or a titanium cation (Ti 4+ ) cation-exchanged montmorillonite catalyst was obtained in the same manner as in Example 1 except that an aqueous solution of was used.
[0021]
4 mmol of ethyl 2-oxo-cyclopentanecarboxylate (compound of formula (I-1)), 6 mmol of 2-cyclopentan-1-one (compound of formula (II-1)), and Examples 1 to 0.1 g of the metal cation exchange montmorillonite catalyst obtained in 4 was added to the reaction vessel, and the reaction was carried out while stirring at 80 ° C. for 6 hours.
After completion of the reaction, the product was analyzed by gas chromatography, and the yield of the compound of formula (III-1) was determined from the result. The results are shown in Table 1.
[Table 1]
Comparative Example 1
Although it carried out similarly to the said Example except having used scandium triflate instead of the metal cation exchange montmorillonite catalyst, the yield of the compound of Formula (III-1) was 25%.
[0023]
Comparative Example 2
Sodium-montmorillonite (Kunipia, montK-10, SO 4 2− / ZrO 2 , H + -beta, H + -USY, H + -mordenite, H + -ZSM-5, manufactured by Kunimine Industries Co., Ltd. instead of metal cation exchange montmorillonite catalyst The inorganic solid acid catalyst) was used in the same manner as in the above Example, but the yield of the compound of the formula (III-1) was about 30%.
Claims (6)
下記一般式（II）で表される化合物
Compound represented by the following general formula (II)
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