JP3166959B2 - Lewis acid catalyst - Google Patents
Lewis acid catalystInfo
- Publication number
- JP3166959B2 JP3166959B2 JP04083994A JP4083994A JP3166959B2 JP 3166959 B2 JP3166959 B2 JP 3166959B2 JP 04083994 A JP04083994 A JP 04083994A JP 4083994 A JP4083994 A JP 4083994A JP 3166959 B2 JP3166959 B2 JP 3166959B2
- Authority
- JP
- Japan
- Prior art keywords
- lewis acid
- reaction
- acid catalyst
- metals
- rfso
- 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.)
- Expired - Fee Related
Links
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
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 for synthesizing organic compounds such as pharmaceuticals, agricultural chemicals, liquid crystals, polymers and intermediates thereof.
【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 a Lewis acid catalyst in an organic reaction, the solubility of the metal salt such as a normal halide, acetate or carbonate in a non-polar solvent such as dichloromethane is considered. Is extremely small, it is necessary to use an aprotic polar solvent such as ether or acetonitrile which has a large coordination ability to a metal ion. However, in these polar solvents, since the solvent molecule is strongly coordinated to the metal ion, the electrophilic Lewis acid catalytic activity of the metal ion 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, an object of the present invention is 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。 すなわち本発明は、一般式（Ｉ） Ｍ［ＲｆＳＯ2 −Ｎ−ＳＯ2 Ｒｆ’］n ・・・（Ｉ） （Ｒｆ及びＲｆ’は、炭素原子数１〜８のペルフルオロ
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、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、及び一般式（ＩＩ） Ｍ［ＲｆＳＯ2 −Ｎ−ＳＯ2 Ｒｆ’］n ・ｍＨ2 Ｏ ・・・（ＩＩ） （Ｒｆ及びＲｆ’は、炭素原子数１〜８のペルフルオロ
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、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、さらには、Ｒｆ及びＲｆ’の炭素原子数が１である
ルイス酸触媒を提供するものである。Means for Solving the Problems As a result of intensive studies, the present inventors have found that various M [RfSO 2 -N-SO 2 Rf ']
By using a metal salt of n (perfluoroalkanesulfonylimide metal salt) and its hydrate, the reaction rate is accelerated in various electrophilic organic reactions, and in particular, in the case of an isomer-forming reaction, its selectivity is increased. And reached the present invention. That is, the present invention relates to a compound represented by the 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; Represents an element selected from the group consisting of alkali metals, alkaline earth metals, transition metals, rare earths, aluminum, gallium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, selenium, and tellurium. valence a Lewis acid catalyst represented by the same number of an integer), and the general formula (II) M [RfSO 2 -N -SO 2 Rf '] n · mH 2 O ··· (II) (Rf and Rf Represents a perfluoroalkyl group having 1 to 8 carbon atoms, and M represents an alkali metal, an alkaline earth metal, a transition metal, a rare earth, aluminum, gallium, thallium, silicon, germanium, tin, lead, or arsenic. , Antimony, bismuth, selenium, tellurium, n represents an integer equal to the valence of the corresponding metal, m
Represents a natural number of 0.5 to 20), and further provides a Lewis acid catalyst in which Rf and Rf ′ have 1 carbon atom.
【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 salt of the present invention is disclosed in French Patent No. 2,527,602,
No. 06217 discloses only the use as an ion conductive material, and other references that were used as a catalyst,
Alternatively, there is no description of the patent, and it is significant to find an effect as a Lewis acid catalyst.
【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 the hydrates thereof used as the catalyst of the present invention are composed of perfluoroalkanesulfonylimidic acid H [RfSO 2 -N-
SO 2 Rf ′] and a compound selected from a corresponding metal carbonate, oxide, hydroxide or a mixture thereof in an aqueous solution at a temperature of 20 to 100 ° C., and the excess water is heated or reduced 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。[0007] These synthesized metal salts and hydrates thereof can be used as long as they are electrophilic organic synthesis reactions, such as the Diels-Alder reaction, the Michael addition reaction, and the like.
Friedel-Crafts reaction and the like. When used in these reactions, the reaction rate is accelerated and the yield is improved. Further, in the reaction for producing an isomer, selectivity can be improved. The reason for this is that the perfluoroalkanesulfonylimide ion [RfSO 2 —N—SO 2 R
f '] - the case of metal salts and counter anions, in addition to the general characteristics of the fluorine-containing organic compound that solubility is relatively large in a non-polar solvent such as dichloromethane, a strong electron-withdrawing fluorine atoms The fluorinated imide ion is stabilized by the force, and the ionic bond with the metal ion is much smaller than that of a normal metal salt. As a result, in nonpolar solvents, the electrophilicity of the desolvated metal ions is increased, 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。Although the catalytic activity appears when the amount of the catalyst added is 0.1 to 20 mol% with respect to the reaction substrate, the amount is 1 to 10 mol in consideration of obtaining a practical reaction rate and economy. % Is preferred. The solvent is hydrocarbon,
Halogenated hydrocarbons, ethers and the like can be used.
【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。The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is 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 MgCOThree・ Mg (OH)Two・ 5HTwoO: 0.2397
g in a flask and add bistrifluoromethanesulfonate
Luimidic acid (HN (CFThreeSOTwo)Two): 1.5 g of water
The mixture 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. and 0.4 m
dried over mHg and Mg ((CFThreeSOTwo) TwoN)Two・ 3H
TwoO was obtained. Further, at 50 ° C., 10-Five1 in mmHg
After drying for 5 hours, Mg ((CFThreeSOTwo)TwoN)Two1.5
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 CaCOThree: Put 0.2289g in a flask,
Trifluoromethanesulfonylimidic acid (HN (CFThreeS
OTwo)Two): 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 ° C, 10-FivemmHg and dried over Ca ((C
FThreeSOTwo)TwoN)Two・ 1.5HTwoO was obtained. One more
35 ° C, 10-Fivedried at 15 mmHg for 15 hours.
FThreeSO Two)TwoN)Two1.3378 g were 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 BaCOThree: Put 0.4849g in a flask
Trifluoromethanesulfonylimidic acid (HN (CFThreeS
OTwo)Two): 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 ° C, 10-3mmHg and dried with Ba ((C
FThreeSOTwo)TwoN)Two・ 1.5HTwoO was obtained. One more
50 ° C, 10-FivemmHg and dried for 15 hours.
FThreeSO Two)TwoN)Two1.6338 g were 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 0.2033 g of ZnO was placed in a flask, and bistrif was added.
Fluoromethanesulfonylimidic acid (HN (CFThreeS
OTwo)Two): Dissolve 1.420 g with 5 g of water and do not stir.
It was dropped. After reacting at 20 ° C., the precipitate was filtered off and washed with water
The solution was dried at 40 ° C. and 0.4 mmHg and Zn ((CF
ThreeSOTwo)TwoN)Two・ 7HTwoO was obtained. 100 more
° C, 10-6dried at 15 mmHg for 15 hours.Three
SOTwo)TwoN) Two1.7966 g were obtained.
【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。Embodiment 5 LaTwoOThree: Put 0.4208g in a flask,
Trifluoromethanesulfonylimidic acid (HN (CFThreeS
OTwo)Two): Dissolve 2.1832 g with 5 g of water and stir
While dripping. After reacting at 100 ° C for 1 hour, the precipitate was
The aqueous solution was separated by filtration and dried at 70 ° C. and 0.4 mmHg to obtain La.
((CFThreeSOTwo)TwoN)Three・ 3HTwoO was obtained. further
60 ° C, 10-3dried at 15 mmHg for 15 hours.
FThreeSO Two)TwoN)Three2.5444 g were 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 A sample was prepared by adding 392.0 mg of methyl vinyl ketone as an internal standard.
392.2 mg of can and CHTwoClTwoAdd 25 ml,
Furthermore, 594.0 mg of cyclopentadiene and CH TwoClTwo
25 ml were added. 17.7 ml of this mixed solution was collected
Mg ((CFThreeSOTwo)TwoN)TwoTo
0.0173 mol (1 mol%) was added. Product
5-acetylbicyclo [2,2,1] hepta-2-e
The increase in the amount of gas is analyzed by gas chromatography,
The reaction rate constant and conversion were determined. The reaction is selective
Advanced. Also, the ratio of endo- and exo-forms of the product
About gas chromatography of the product after the reaction
Determined by Table 1 below shows the reaction speed of this reaction.
Degree constant, conversion and endo and exo forms of the product
Shows the ratio of Also, for comparison,
Rate constant, conversion, and
Shows the ratio of Soviet Union. The reaction temperature was kept at 20 ° C. in each case.
【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 The catalytic effects of the compounds synthesized in Examples 1 to 5 by the same reaction as in Example 6 are shown in Tables 2 and 3 by solvent (dichloromethane, diethyl ether). . Each shows the catalyst concentration, the reaction rate constant, the conversion, and the ratio of the endo- and exo-forms of the product.
【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。The use of the Lewis acid catalyst according to the present invention promotes the production rate of the target compound in the organic synthesis reaction by the electrophilic reaction, thereby improving the yield. In addition, in the production of an isomer, its 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、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. Formula (I) M [RfSO 2 —N—SO 2 Rf ′] n ... (I) (Rf and Rf ′ each represent a perfluoroalkyl group having 1 to 8 carbon atoms; Represents an element selected from the group consisting of alkali metals, alkaline earth metals, transition metals, rare earths, aluminum, gallium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, selenium, and tellurium. A Lewis acid catalyst represented by the following formula:
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、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. 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) And M represents an element selected from alkali metals, alkaline earth metals, transition metals, rare earths, aluminum, gallium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, selenium, tellurium, and n Represents an integer of the same number as the valence of the corresponding metal, and m
Represents 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 JPH07246338A (en) | 1995-09-26 |
| JP3166959B2 true 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) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3250777B2 (en) | 1995-02-13 | 2002-01-28 | セントラル硝子株式会社 | Imides, salts thereof and methods for producing them |
| US5908939A (en) * | 1996-11-11 | 1999-06-01 | Roche Vitamins Inc. | Method of making D,L-A-tocopherol |
| CN100569746C (en) * | 2000-12-15 | 2009-12-16 | 独立行政法人科学技术振兴机构 | Two (perfluoroalkyl group sulfonyl) methane of aryl and metal-salt thereof, and preparation method thereof |
| 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 |
| JP3773824B2 (en) | 2001-03-12 | 2006-05-10 | 独立行政法人科学技術振興機構 | Polymer-supported arylbis (perfluoroalkylsulfonyl) methane |
| ATE370786T1 (en) * | 2001-03-12 | 2007-09-15 | Univ Belfast | USE OF METAL BISTRIFLIMIDE COMPOUNDS |
| CN1273461C (en) * | 2001-12-19 | 2006-09-06 | 财团法人野口研究所 | 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 |
| JP5696465B2 (en) | 2010-12-17 | 2015-04-08 | セントラル硝子株式会社 | Compound having bis (trifluoromethanesulfonyl) ethyl group, acid catalyst, and production method thereof |
-
1994
- 1994-03-11 JP JP04083994A patent/JP3166959B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07246338A (en) | 1995-09-26 |
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