JPH07246338A - Lewis acid catalyst - Google Patents
Lewis acid catalystInfo
- Publication number
- JPH07246338A JPH07246338A JP6040839A JP4083994A JPH07246338A JP H07246338 A JPH07246338 A JP H07246338A JP 6040839 A JP6040839 A JP 6040839A JP 4083994 A JP4083994 A JP 4083994A JP H07246338 A JPH07246338 A JP H07246338A
- Authority
- JP
- Japan
- Prior art keywords
- lewis acid
- acid catalyst
- reaction
- metal
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は医薬、農薬、液晶、ポリ
マーあるいはそれらの中間体等の有機化合物の合成反応
に有用に利用されるルイス酸触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Lewis acid catalyst which is useful in the synthetic reaction of organic compounds such as pharmaceuticals, agricultural chemicals, liquid crystals, polymers and their intermediates.
【０００２】[0002]
【従来の技術および解決すべき問題点】従来、金属塩を
ルイス酸触媒として有機反応に用いる場合は、通常のハ
ロゲン化物、酢酸塩、炭酸塩などの金属塩ではジクロロ
メタンなどの非極性溶媒に対する溶解度が極めて小さい
ために、金属イオンに対する配位能が大きいエーテルや
アセトニトリルなどの非プロトン性極性溶媒を用いる必
要がある。しかしながらこれらの極性溶媒中では金属イ
オンに溶媒分子が強く配位するために反応基質に対する
金属イオンの親電子的なルイス酸触媒活性が極端に減少
してしまう。2. Description of the Related Art Conventionally, when a metal salt is used as an Lewis acid catalyst in an organic reaction, the solubility of ordinary metal salts such as halides, acetates and carbonates in a non-polar solvent such as dichloromethane is high. Since it is extremely small, it is necessary to use an aprotic polar solvent such as ether or acetonitrile which has a large coordination ability for metal ions. However, in these polar solvents, the solvent molecule strongly coordinates with the metal ion, so that the electrophilic Lewis acid catalytic activity of the metal ion with respect to the reaction substrate is extremely reduced.
【０００３】本発明の目的とするところは、上記問題点
に鑑み、求電子反応による有機反応における触媒活性を
増大させるルイス酸触媒を提供することにある。In view of the above problems, it is an object of the present invention to provide a Lewis acid catalyst which increases the catalytic activity in an organic reaction by an electrophilic reaction.
【０００４】[0004]
【問題点を解決するための手段】本発明者らは、鋭意検
討の結果、種々のＭ［ＲｆＳＯ2 −Ｎ−ＳＯ2 Ｒｆ’］
n （ペルフルオロアルカンスルホニルイミド金属塩）な
る金属塩及びその水和物を用いることにより、種々の求
電子反応の有機反応において反応速度が促進され、特に
異性体を生成する反応においては、その選択性を向上さ
せることを見出し本発明に到達した。[Means for Solving the Problems]
As a result of discussion, various M [RfSO2-N-SO2Rf ']
n(Perfluoroalkanesulfonylimide metal salt)
By using metal salts and hydrates of
The reaction rate is accelerated in the organic reaction of the electron reaction,
In a reaction that produces an isomer, its selectivity is improved.
The inventors have reached the present invention by finding that they can.
【０００５】本発明のペルフルオロアルカンスルホニル
イミド金属塩は、フランス特許２５２７６０２号、２６
０６２１７号にイオン伝導材料としての利用のみが開示
されており、その他触媒として利用されたという文献、
あるいは特許の記述はなく、ルイス酸触媒としての効果
を見出したことは意義あることである。The perfluoroalkanesulfonylimide metal salts of the present invention are described in French Patent No. 2527602, 26.
No. 06217 discloses use only as an ion conductive material, and is used as a catalyst for other catalysts,
Alternatively, there is no description in the patent, and it is significant that the effect as a Lewis acid catalyst was found.
【０００６】本発明の触媒として用いられる一般式
（Ｉ）、一般式（ＩＩ）で示されるペルフルオロアルカ
ンスルホニルイミド金属塩及びその水和物は、ペルフル
オロアルカンスルホニルイミド酸Ｈ［ＲｆＳＯ2 −Ｎ−
ＳＯ2 Ｒｆ’］と該当する金属の炭酸塩、酸化物、水酸
化物あるいはそれらの混合物から選ばれる化合物を用い
て水溶液中で温度２０〜１００℃で反応させ余剰の水を
加熱あるいは減圧下で乾燥し合成させる。The perfluoroalkanesulfonylimide metal salts represented by the general formulas (I) and (II) and their hydrates used as the catalyst of the present invention are perfluoroalkanesulfonylimidic acid H [RfSO 2 —N-
SO 2 Rf ′] and a compound selected from carbonates, oxides, hydroxides or a mixture thereof of the corresponding metal are reacted in an aqueous solution at a temperature of 20 to 100 ° C. and excess water is heated or under reduced pressure. Dry and synthesize.
【０００７】これら合成された金属塩およびその水和物
は求電子反応の有機合成反応で有れば利用が可能で、た
とえばディールス−アルダー反応、マイケル付加反応、
フリーデル−クラフト反応等である。これらの反応に使
用すると反応速度が加速され、また収率が向上する。さ
らに異性体を生成する反応においては選択性を向上させ
ることができる。この理由としてはペルフルオロアルカ
ンスルホニルイミドイオン［ＲｆＳＯ2 −Ｎ−ＳＯ2 Ｒ
ｆ’］- を対アニオンとする金属塩の場合は、ジクロロ
メタンなどの非極性溶媒中での溶解度が比較的大きいと
いう含フッ素有機化合物の一般的な特徴に加えて、フッ
素原子の強力な電子吸引力によって含フッ素イミドイオ
ンが安定化され金属イオンとの間のイオン結合が通常の
金属塩に比べてはるかに小さいという特徴を持ってい
る。この結果非極性溶媒中では脱溶媒和した金属イオン
の親電子性が大きくなり、これらの金属塩のルイス酸触
媒活性が非常に増大することによる。These synthesized metal salts and hydrates thereof can be used as long as they are organic synthesis reactions of electrophilic reaction. For example, Diels-Alder reaction, Michael addition reaction,
Friedel-Crafts reaction and the like. When used in these reactions, the reaction rate is accelerated and the yield is improved. Further, the selectivity can be improved in the reaction for producing the isomer. The reason for this is that perfluoroalkanesulfonylimide ion [RfSO 2 —N—SO 2 R
In the case of a metal salt having f ′] − as a counter anion, in addition to the general characteristic of a fluorine-containing organic compound that solubility in a non-polar solvent such as dichloromethane is relatively large, strong electron withdrawing of a fluorine atom is performed. It is characterized in that the fluorinated imide ion is stabilized by the force, and the ionic bond with the metal ion is much smaller than that of ordinary metal salts. As a result, the electrophilicity of the desolvated metal ion is increased in the nonpolar solvent, and the Lewis acid catalytic activity of these metal salts is greatly increased.
【０００８】触媒としての添加量は反応基質に対して
０．１〜２０ｍｏｌ％で触媒能が現れるが、実用的な反
応速度を得ること、また経済性を考慮した場合、添加量
は１〜１０ｍｏｌ％が好ましい。また溶媒は炭化水素、
ハロゲン化炭化水素、エーテル等の使用が可能である。The catalytic activity appears when the amount added as a catalyst is 0.1 to 20 mol% with respect to the reaction substrate, but the amount added is 1 to 10 mol in consideration of obtaining a practical reaction rate and economical efficiency. % Is preferred. The solvent is hydrocarbon,
It is possible to use halogenated hydrocarbons, ethers and the like.
【０００９】[0009]
【実施例】以下、実施例において具体的に説明するが係
る実施例に限定されるものではない。EXAMPLES Hereinafter, the examples will be specifically described, but the examples are not limited thereto.
【００１０】実施例１ ＭｇＣＯ3 ・Ｍｇ（ＯＨ）2 ・５Ｈ2 Ｏ：０．２３９７
ｇをフラスコにいれ、ビストリフルオロメタンスルホニ
ルイミド酸（ＨＮ（ＣＦ3 ＳＯ2 ）2 ）：１．５ｇを水
５ｇで溶かして攪拌しながら滴下した。２０℃で２時間
反応させた後沈澱物を濾別し水溶液を５０℃、０．４ｍ
ｍＨｇで乾燥しＭｇ（（ＣＦ3 ＳＯ2 ） 2 Ｎ）2 ・３Ｈ
2 Ｏを得た。また、さらに５０℃、１０-5ｍｍＨｇで１
５時間乾燥させＭｇ（（ＣＦ3 ＳＯ2 ）2 Ｎ）2 １．５
ｇを得た。Example 1 MgCO3・ Mg (OH)2・ 5H2O: 0.2397
Add g to the flask and add bistrifluoromethanesulfone.
Lumidic acid (HN (CF3SO2)2): 1.5 g water
It was dissolved in 5 g and added dropwise with stirring. 2 hours at 20 ° C
After the reaction, the precipitate was separated by filtration and the aqueous solution was heated at 50 ° C. for 0.4 m.
After drying with mHg, Mg ((CF3SO2) 2N)2・ 3H
2O was obtained. In addition, further 50 ℃, 10-Five1 in mmHg
After drying for 5 hours, Mg ((CF3SO2)2N)21.5
g was obtained.
【００１１】実施例２ ＣａＣＯ3 ：０．２２８９ｇをフラスコにいれ、ビスト
リフルオロメタンスルホニルイミド酸（ＨＮ（ＣＦ3 Ｓ
Ｏ2 ）2 ）：１．２９０７ｇを水５ｇで溶かして攪拌し
ながら滴下した。２０℃で反応させた後沈澱物を濾別し
水溶液を２０℃、１０-5ｍｍＨｇで乾燥させＣａ（（Ｃ
Ｆ3 ＳＯ2 ）2 Ｎ）2 ・１．５Ｈ2 Ｏを得た。さらに１
３５℃、１０-5ｍｍＨｇで１５時間乾燥させＣａ（（Ｃ
Ｆ3 ＳＯ 2 ）2 Ｎ）2 １．３３７８ｇを得た。Example 2 CaCO3: 0.2289g in a flask
Lifluoromethanesulfonylimidic acid (HN (CF3S
O2)2): 1.2907 g was dissolved in 5 g of water and stirred
While dripping. After reacting at 20 ° C., the precipitate was filtered off
Aqueous solution at 20 ℃, 10-FiveDry with mmHg Ca ((C
F3SO2)2N)2・ 1.5H2O was obtained. 1 more
35 ° C, 10-FiveAfter drying for 15 hours at mmHg, Ca ((C
F3SO 2)2N)21.3378 g was obtained.
【００１２】実施例３ ＢａＣＯ3 ：０．４８４９ｇをフラスコにいれ、ビスト
リフルオロメタンスルホニルイミド酸（ＨＮ（ＣＦ3 Ｓ
Ｏ2 ）2 ）：１．３８６５ｇを水５ｇで溶かして攪拌し
ながら滴下した。４０℃で反応させた後沈澱物を濾別し
水溶液を６０℃、１０-3ｍｍＨｇで乾燥させＢａ（（Ｃ
Ｆ3 ＳＯ2 ）2 Ｎ）2 ・１．５Ｈ2 Ｏを得た。さらに１
５０℃、１０-5ｍｍＨｇで１５時間乾燥させＢａ（（Ｃ
Ｆ3 ＳＯ 2 ）2 Ｎ）2 １．６３３８ｇを得た。Example 3 BaCO3: Add 0.4849g to the flask and bistro
Lifluoromethanesulfonylimidic acid (HN (CF3S
O2)2): 1.3865 g was dissolved in 5 g of water and stirred
While dripping. After reacting at 40 ° C., the precipitate was filtered off
Aqueous solution at 60 ℃, 10-3After drying with mmHg, Ba ((C
F3SO2)2N)2・ 1.5H2O was obtained. 1 more
50 ° C, 10-FiveAfter drying at mmHg for 15 hours, Ba ((C
F3SO 2)2N)21.6338 g was obtained.
【００１３】実施例４ ＺｎＯ：０．２０３３ｇをフラスコにいれ、ビストリフ
ルオロメタンスルホニルイミド酸（ＨＮ（ＣＦ3 Ｓ
Ｏ2 ）2 ）：１．４２０ｇを水５ｇで溶かして攪拌しな
がら滴下した。２０℃で反応させた後沈澱物を濾別し水
溶液を４０℃、０．４ｍｍＨｇで乾燥させＺｎ（（ＣＦ
3 ＳＯ2 ）2 Ｎ）2 ・７Ｈ2 Ｏを得た。さらに１００
℃、１０-6ｍｍＨｇで１５時間乾燥させＺｎ（（ＣＦ3
ＳＯ2 ）2 Ｎ） 2 １．７９６６ｇを得た。Example 4 ZnO: 0.2033 g was placed in a flask and bistrif.
Luoromethanesulfonylimidic acid (HN (CF3S
O2)2): Dissolve 1.420 g with 5 g of water and do not stir
It was dripped. After reacting at 20 ° C, the precipitate was filtered off and filtered with water.
The solution was dried at 40 ° C. and 0.4 mmHg, and Zn ((CF
3SO2)2N)2・ 7H2O was obtained. 100 more
℃, 10-6After drying for 15 hours at mmHg, Zn ((CF3
SO2)2N) 2Obtained was 1.7966 g.
【００１４】実施例５ Ｌａ2 Ｏ3 ：０．４２０８ｇをフラスコにいれ、ビスト
リフルオロメタンスルホニルイミド酸（ＨＮ（ＣＦ3 Ｓ
Ｏ2 ）2 ）：２．１８３２ｇを水５ｇで溶かして攪拌し
ながら滴下した。１００℃１時間反応させた後沈澱物を
濾別し水溶液を７０℃、０．４ｍｍＨｇで乾燥させＬａ
（（ＣＦ3 ＳＯ2 ）2 Ｎ）3 ・３Ｈ2 Ｏを得た。さらに
６０℃、１０-3ｍｍＨｇで１５時間乾燥させＬａ（（Ｃ
Ｆ3 ＳＯ 2 ）2 Ｎ）3 ２．５４４４ｇを得た。Example 5 La2O3: Add 0.4208g to the flask, bisto
Lifluoromethanesulfonylimidic acid (HN (CF3S
O2)2): 2.1832 g was dissolved in 5 g of water and stirred
While dripping. After reacting at 100 ° C for 1 hour, the precipitate was removed.
It is filtered off and the aqueous solution is dried at 70 ° C. and 0.4 mmHg to obtain La.
((CF3SO2)2N)3・ 3H2O was obtained. further
60 ° C, 10-3Lam ((C
F3SO 2)2N)32.5444 g was obtained.
【００１５】実施例６、比較例１ メチルビニルケトン３９２．０ｍｇに内部標準としてデ
カン３９２．２ｍｇとＣＨ2 Ｃｌ2 ２５ｍｌを加え、さ
らにシクロペンタジエン５９４．０ｍｇとＣＨ 2 Ｃｌ2
２５ｍｌを加えた。この混合溶液を１７．７ｍｌ採取し
実施例１で示したＭｇ（（ＣＦ3 ＳＯ2 ）2 Ｎ）2 を
０．０１７３ｍｏｌ（１ｍｏｌ％）加えた。生成物であ
る５−アセチルビシクロ〔２，２，１〕ヘプタ−２−エ
ンの増加量をガスクロマトグラフィーによって分析し、
反応速度定数および転化率を求めた。反応は、選択的に
進行した。また生成物のエンド体およびエキソ体の比に
ついては反応終了後の生成物のガスクロマトグラフィー
によって決定した。以下の表１にこの反応による反応速
度定数、転化率および生成物のエンド体およびエキソ体
の比を示す。また比較のために触媒無添加時の場合の反
応速度定数、転化率および生成物のエンド体およびエキ
ソ体の比を示す。反応温度はいずれも２０℃に保った。Example 6, Comparative Example 1 392.0 mg of methyl vinyl ketone was used as an internal standard.
392.9 mg of can and CH2Cl2Add 25 ml,
Cyclopentadiene 594.0 mg and CH 2Cl2
25 ml was added. 17.7 ml of this mixed solution was sampled
The Mg ((CF3SO2)2N)2To
0.0173 mol (1 mol%) was added. Is a product
5-acetylbicyclo [2,2,1] hept-2-e
Gas chromatographic analysis for increased amounts of
The reaction rate constant and conversion rate were determined. The reaction is selective
Progressed. In addition, the ratio of the endo-form and exo-form of the product
Gas chromatography of the product after the reaction
Determined by The reaction speed of this reaction is shown in Table 1 below.
Degree constant, conversion and endo- and exo-forms of the product
The ratio of In addition, for comparison, the reaction when no catalyst was added
Response rate, conversion and end product and exhaust of product
The ratio of the so body is shown. The reaction temperature was kept at 20 ° C. in all cases.
【００１６】[0016]
【表１】 [Table 1]
【００１７】実施例７〜１６、比較例２ 実施例６と同様の反応で実施例１〜５で合成した化合物
の触媒効果を溶媒別（ジクロロメタン、ジエチルエーテ
ル）に表２、表３に示した。それぞれに触媒濃度、反応
速度定数、転化率および生成物のエンド体およびエキソ
体の比を示す。Examples 7 to 16 and Comparative Example 2 Tables 2 and 3 show the catalytic effects of the compounds synthesized in Examples 1 to 5 in the same reaction as in Example 6 for each solvent (dichloromethane, diethyl ether). . The catalyst concentration, the reaction rate constant, the conversion rate, and the ratio of the endo-form and the exo-form of the product are shown for each.
【００１８】[0018]
【表２】 [Table 2]
【００１９】[0019]
【表３】 [Table 3]
【００２０】[0020]
【発明の効果】本発明におけるルイス酸触媒を用いるこ
とにより、求電子反応による有機合成反応において、目
的物の生成速度が促進され、收率の向上をもたらす。ま
た、異性体の生成においては、その選択性を大幅に向上
させることができる。EFFECT OF THE INVENTION By using the Lewis acid catalyst of the present invention, the production rate of the target substance is promoted in the organic synthesis reaction by the electrophilic reaction, and the yield is improved. In addition, in the production of isomers, the selectivity can be greatly improved.
Claims (3)
アルキル基を表し、Ｍはアルカリ金属、アルカリ土類金
属、遷移金属、希土類、アルミニウム、ガリウム、イリ
ジウム、タリウム、ケイ素、ゲルマニウム、スズ、鉛、
ヒ素、アンチモン、ビスマス、セレン、テルルから選ば
れた元素を表し、ｎは該当する金属の原子価と同数の整
数を表す）で示されるルイス酸触媒。1. General formula (I) M [RfSO 2 —N—SO 2 Rf ′] n ... (I) (Rf and Rf ′ represent a perfluoroalkyl group having 1 to 8 carbon atoms, and M Is an alkali metal, alkaline earth metal, transition metal, rare earth, aluminum, gallium, iridium, thallium, silicon, germanium, tin, lead,
Lewis acid catalyst represented by an element selected from arsenic, antimony, bismuth, selenium, and tellurium, and n represents an integer equal to the valence of the corresponding metal.
アルキル基を表し、Ｍはアルカリ金属、アルカリ土類金
属、遷移金属、希土類、アルミニウム、ガリウム、イリ
ジウム、タリウム、ケイ素、ゲルマニウム、スズ、鉛、
ヒ素、アンチモン、ビスマス、セレン、テルルから選ば
れた元素を表し、ｎは該当する金属の原子価と同数の整
数を表し、ｍは０．５〜２０の自然数を表す）で示され
るルイス酸触媒。2. General formula (II) M [RfSO 2 —N—SO 2 Rf ′] n · mH 2 O (II) (Rf and Rf ′ are perfluoroalkyl groups having 1 to 8 carbon atoms. Represents M, alkali metal, alkaline earth metal, transition metal, rare earth, aluminum, gallium, iridium, thallium, silicon, germanium, tin, lead,
Lewis acid catalyst represented by an element selected from arsenic, antimony, bismuth, selenium, and tellurium, n is an integer having the same number as the valence of the corresponding metal, and m is a natural number of 0.5 to 20). .
請求項１または請求項２に記載のルイス酸触媒。3. The Lewis acid catalyst according to claim 1, wherein Rf and Rf ′ have 1 carbon atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04083994A JP3166959B2 (en) | 1994-03-11 | 1994-03-11 | Lewis acid catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04083994A JP3166959B2 (en) | 1994-03-11 | 1994-03-11 | Lewis acid catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07246338A true JPH07246338A (en) | 1995-09-26 |
| JP3166959B2 JP3166959B2 (en) | 2001-05-14 |
Family
ID=12591785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04083994A Expired - Fee Related JP3166959B2 (en) | 1994-03-11 | 1994-03-11 | Lewis acid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3166959B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998021197A3 (en) * | 1996-11-11 | 1998-07-23 | Hoffmann La Roche | PROCESS FOR MANUFACTURING d,l-α-TOCOPHEROL |
| US6235921B1 (en) | 1995-02-13 | 2001-05-22 | Central Glass Company, Limited | Amines or salts thereof and methods of preparing same |
| EP1344772A1 (en) * | 2000-12-15 | 2003-09-17 | Japan Science and Technology Corporation | Arylbis (perfluoroalkylsulfonyl) methane, metal salt of the same, and processes for producing these |
| JP2004200015A (en) * | 2002-12-19 | 2004-07-15 | Sanyo Electric Co Ltd | Electrolyte for nonaqueous battery, its manufacturing method, and nonaqueous battery electrolytic solution |
| JP2004531492A (en) * | 2001-03-12 | 2004-10-14 | ザ クイーンズ ユニバーシティ オブ ベルファスト | Metal bistriflimide compound and method for synthesizing metal bistriflimide compound |
| US7026409B2 (en) | 2001-03-12 | 2006-04-11 | Japan Science And Technology Agency | Polymer-supported arylbis(perfluoroalkylsulfonyl)-methane |
| US7193113B2 (en) | 2000-12-15 | 2007-03-20 | Japan Science And Technology Corporation | Arylbis(perfluoroalkylsulfonyl) methane and metallic salt thereof, and methods for producing the same |
| DE10297356B4 (en) * | 2001-12-19 | 2011-04-28 | Asahi Kasei Kabushiki Kaisha | Lewis acid catalyst composition |
| DE112011103786T5 (en) | 2010-12-17 | 2013-09-12 | Central Glass Company, Limited | Bis (trifluoromethanesulfonyl) ethyl bearing compound and acid catalyst and process for producing the same |
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1994
- 1994-03-11 JP JP04083994A patent/JP3166959B2/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6235921B1 (en) | 1995-02-13 | 2001-05-22 | Central Glass Company, Limited | Amines or salts thereof and methods of preparing same |
| WO1998021197A3 (en) * | 1996-11-11 | 1998-07-23 | Hoffmann La Roche | PROCESS FOR MANUFACTURING d,l-α-TOCOPHEROL |
| EP1344772A1 (en) * | 2000-12-15 | 2003-09-17 | Japan Science and Technology Corporation | Arylbis (perfluoroalkylsulfonyl) methane, metal salt of the same, and processes for producing these |
| US7339082B2 (en) | 2000-12-15 | 2008-03-04 | Japan Science And Technology Corporation | Arylbis (perfluoroalkylsulfonyl)methane and metallic salt thereof, and methods for producing the same |
| US7193113B2 (en) | 2000-12-15 | 2007-03-20 | Japan Science And Technology Corporation | Arylbis(perfluoroalkylsulfonyl) methane and metallic salt thereof, and methods for producing the same |
| EP1344772A4 (en) * | 2000-12-15 | 2005-03-16 | Japan Science & Tech Agency | Arylbis (perfluoroalkylsulfonyl) methane, metal salt of the same, and processes for producing these |
| US7026409B2 (en) | 2001-03-12 | 2006-04-11 | Japan Science And Technology Agency | Polymer-supported arylbis(perfluoroalkylsulfonyl)-methane |
| JP2004531492A (en) * | 2001-03-12 | 2004-10-14 | ザ クイーンズ ユニバーシティ オブ ベルファスト | Metal bistriflimide compound and method for synthesizing metal bistriflimide compound |
| EP1857432A2 (en) * | 2001-03-12 | 2007-11-21 | The Queen's University of Belfast | Synthesis of metal bis-triflimide compounds and methods for purification thereof |
| EP1857432A3 (en) * | 2001-03-12 | 2008-05-14 | The Queen's University of Belfast | Synthesis of metal bis-triflimide compounds and methods for purification thereof |
| US7781625B2 (en) | 2001-03-12 | 2010-08-24 | The Queen's University Of Belfast | Process catalysed by bis-trifilmide compounds |
| DE10297356B4 (en) * | 2001-12-19 | 2011-04-28 | Asahi Kasei Kabushiki Kaisha | Lewis acid catalyst composition |
| JP2004200015A (en) * | 2002-12-19 | 2004-07-15 | Sanyo Electric Co Ltd | Electrolyte for nonaqueous battery, its manufacturing method, and nonaqueous battery electrolytic solution |
| DE112011103786T5 (en) | 2010-12-17 | 2013-09-12 | Central Glass Company, Limited | Bis (trifluoromethanesulfonyl) ethyl bearing compound and acid catalyst and process for producing the same |
| US9314782B2 (en) | 2010-12-17 | 2016-04-19 | Central Glass Company, Limited | Bis(trifluoromethanesulfonyl)ethyl-bearing compound and acid catalyst, and method for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3166959B2 (en) | 2001-05-14 |
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