JP4047976B2 - Contains cyclodextrin - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel cyclodextrin-containing material containing a Lewis acid and a nucleophilic reagent reaction catalyst containing the same.
[0002]
[Prior art]
Cyclodextrins are known to interact with various inorganic and organic compounds. Due to this interaction, the properties of cyclodextrin and the above-mentioned inorganic compounds and organic compounds are changed, and applied research using this has been promoted not only in the fields of food, pharmaceuticals and cosmetics but also in the fields of clothing, food and living.
On the other hand, the rare earth salt of bisperfluoroalkylsulfonylimide exhibits Lewis acidity. However, the rare earth salts are difficult to separate and reuse from the reaction system when used as Lewis acid catalysts such as oil or gel in water and organic solvents, or hygroscopic and difficult to handle. There was a problem in terms of practical utility.
[0003]
[Problems to be solved by the invention]
The present invention relates to a solid cyclodextrin-containing product containing an environment-friendly Lewis acid that is easy to handle, easily separated from water and an organic solvent, and can be reused, and a nucleophilic reagent reaction containing the same. The object is to provide a catalyst.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to obtain a solid Lewis acid catalyst that is easy to handle, the present inventors have found a novel cyclodextrin-containing product of a bisperfluoroalkylsulfonylimide rare earth salt. Furthermore, since the cyclodextrin-containing material becomes an effective solid catalyst, it has been found that it can be applied to the reaction of nucleophilic reagents, and the present invention has been completed.
[0005]
  That is, the present invention
1. Obtained by adding a bisperfluoroalkylsulfonylimide rare earth salt represented by the following formula (1) to cyclodextrin,Bisperfluoroalkylsulfonylimide rare earth salt molecule for one cyclodextrin 0.001 ~ Three It is included in the ratio ofContains cyclodextrinA nucleophilic reagent reaction catalyst comprising:
  [(RfSO₂)₂N] nM (1)
(here,Rf Is carbon number 2 ~ 8 A perfluoroalkyl group of M Is a rare earth element selected from ytterbium, lanthanum, scandium and yttriumN is a numerical value equal to the valence of the M element)
[0006]
Hereinafter, the present invention will be described in detail.
The bisperfluoroalkylsulfonylimide rare earth salt used in the present invention is represented by the following formula (1).
[(RfSO₂)₂N]_nM (1)
In the formula, Rf represents a perfluoroalkyl group having 2 or more carbon atoms, preferably a perfluoroalkyl group having 2 to 20 carbon atoms. Examples thereof include a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, a tridecafluorohexyl group, a pentadecafluoroheptyl group, and a heptadecafluorooctyl group.
M represents a rare earth element, and examples thereof include lanthanum series elements, scandium, and yttrium.
[0007]
The cyclodextrins used in the present invention are β, γ-cyclodextrin and β, γ-cyclodextrin derivatives. The cyclodextrin derivative may be a branched cyclodextrin having a glycosyl, maltosyl, galactosyl or mannosyl group, a cyclodextrin derivative having a methyl group, an ethyl group, a hydroxyethyl group, or the like chemically bonded, or a hydroxyl group of the cyclodextrin, such as epichlorohydrin. And co-oligomers and copolymers. In addition, a derivative in which cyclodextrin is chemically bonded to silica gel or the like via a spacer can also be used.
[0008]
The cyclodextrin-containing product of the present invention contains a bisperfluoroalkylsulfonylimide rare earth salt molecule in a ratio of 0.001 to 3 per cyclodextrin, preferably 0.01 to 2, more preferably Includes 0.02-1.
As a method for producing a Lewis acid-containing cyclodextrin-containing product of the present invention, for example, a bisperfluoroalkylsulfonylimide metal salt or a solution of the metal salt solubilized in a water-soluble organic solvent is added to an aqueous solution of cyclodextrin. Under the stirring, a solid that precipitates is obtained, washed with water or an organic solvent, and dried by heating under vacuum.
[0009]
As another method, a small amount of water is added to cyclodextrin, and a paste is added to the metal salt of bisperfluoroalkylsulfonylimide. The mixture is sufficiently stirred and dried by heating under vacuum. In the case of a water-insoluble cyclodextrin derivative, add a bisperfluoroalkylsulfonylimide metal salt to an aqueous suspension of the cyclodextrin derivative, stir well, then filter, wash with water, and then heat and dry in vacuum. Can be obtained.
[0010]
The cyclodextrin-containing product thus obtained is a hygroscopic and is a solid that is hardly soluble in water and a low polar organic solvent and easy to handle. Accordingly, when the solid cyclodextrin-containing material is used as a Lewis acid catalyst, separation and reuse from the reaction system is facilitated.
The cyclodextrin-containing material often has an interaction between the bisperfluoroalkylsulfonylimide rare earth salt and the cyclodextrin.
[0011]
The cyclodextrin-containing product containing a Lewis acid of the present invention can be used as a catalyst for a nucleophilic reagent reaction. Here, the nucleophilic reagent is not particularly limited as long as it has an affinity for the rare earth element cation of the cyclodextrin-containing material and forms a coordination. For example, it is a compound having an element such as oxygen or nitrogen. Specifically, it is a compound group such as ketone, aldehyde, nitrile, ketene, acid anhydride, ester, lactone, ether, alcohol, phenol, carboxylic acid, nitro compound and the like. In addition, compounds such as nucleophilic olefins which have affinity with rare earth element cations and can be coordinated are exemplified. An example of the reaction may be a reaction using a nucleophilic reagent. For example, the Diels-Alder reaction, Michael reaction, Friedel-Craft reaction, aldol reaction, esterification reaction, transesterification reaction, Mannich type reaction and the like can be mentioned. Furthermore, it can be applied to polymerization of olefins.
[0012]
When the cyclodextrin-containing product of the present invention is used as a catalyst, a form using a normal solid catalyst can be appropriately selected and used in either a liquid phase reaction or a gas phase reaction.
As the reaction medium in the liquid phase, a commonly used organic solvent or a mixed solvent with water is used. Preferably, aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons substituted with fluorine or halogen elements, and aromatic hydrocarbons are used.
[0013]
As for the addition amount of the catalyst, 0.0001-fold mol to 10-fold mol can be used as the bisperfluoroalkylsulfonylimide rare earth salt in the cyclodextrin-containing material with respect to the reaction substrate. Preferably it is 0.01 times mol-5 times mol. The use temperature of the catalyst of the present invention is frequently 200 ° C. or less, preferably -80 ° C. to 170 ° C.
The reaction time varies depending on the addition amount of the cyclodextrin-containing material, the content of the bisperfluoroalkylsulfonylimide rare earth salt of the material, the reaction temperature, etc., but several minutes to 72 hours are preferably used.
In the case of a liquid phase reaction, the organic solvent serving as a reaction medium is preferably 1 or more in weight ratio with respect to the cyclodextrin-containing material, more preferably 2 to 1000 times.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be specifically described below with reference to examples.
In the examples¹H-NMR is a JNN-EX400 type nuclear magnetic resonance measuring apparatus manufactured by JEOL Ltd., infrared absorption spectrum is a 1600 type infrared spectrophotometer manufactured by PerkinElmer, and X-ray diffraction is a science using Cu and K-alpha as light sources. It measured using the RINT-2500 X-ray-diffraction apparatus by the electric company. The fluorescence X-ray analyzer was measured using Philips PW2400 manufactured by Philips, and the plasma emission analyzer was measured using IRIS-AP manufactured by Thermosarrel Ash.
[0015]
<Synthesis Example 1>
・ Synthesis of ytterbium salt of bisperfluorobutanesulfonylimide
To a solution obtained by dissolving 5 g of bisperfluorobutanesulfonylimide synthesized from bistrimethylsilylamide sodium salt and perfluorobutanesulfonyl fluoride in a mixed solvent of 15 ml of distilled water and 10 ml of acetonitrile, 1.0 g of ytterbium carbonate was added and stirred. The reaction was carried out at 1 ° C. for 1 hour. Next, unreacted ytterbium carbonate is removed by filtration, and the solvent is removed from the filtrate using a rotary evaporator, followed by vacuum drying at 120 ° C., 1 mmHg, 1 hour. Tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt in the form of white powder 5.3 g was obtained. The infrared absorption spectrum of the synthesized tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt is 1357 cm.^-11141cm^-1, 1089cm^-1SO in the vicinity₂Group and an absorption peak attributed to the C—F group were observed. Composition analysis by X-ray fluorescence analysis (theoretical values in parentheses): F / S / Yb = 55 / 5.8 / 1 atomic ratio (54/6/1)
[0016]
<Synthesis Example 2>
・ Synthesis of yttrium salt of bisperfluorobutanesulfonylimide
A white powdery tris [bis (perfluorobutanesulfonyl) imide] yttrium salt reacted with 5 g of bisperfluorobutanesulfonylimide as in Synthesis Example 1 except that 0.7 g of yttrium carbonate was used instead of ytterbium carbonate. 5.1 g was obtained. Composition analysis by X-ray fluorescence analysis (theoretical values in parentheses): F / S / Y = 54 / 5.9 / 1 atomic ratio (54/6/1)
<Synthesis Example 3>
・ Synthesis of lanthanum salt of bisperfluorooctanesulfonylimide
Bisperfluorooctanesulfonylimide synthesized from bistrimethylsilylamide sodium salt and perfluorooctanesulfonyl fluoride and lanthanum carbonate were reacted in the same manner as in Synthesis Example 1 to obtain tris [bis (perfluorooctanesulfonyl) imide] lanthanum. . The infrared absorption spectrum of the lanthanum salt is 1332 cm.^-11152cm^-11202 cm^-1, 1086cm^-1SO in the vicinity₂Group and an absorption peak attributed to the C—F group were observed. Composition analysis by fluorescent X-ray analysis (theoretical values in parentheses): F / S / La = 101 / 6.1 / 1 atomic ratio (102/6/1).
[0017]
<Synthesis Example 4>
・ Synthesis of yttrium salt of bisperfluorooctanesulfonylimide
Except for using yttrium carbonate in place of lanthanum carbonate, it was reacted with perfluorooctanesulfonylimide in the same manner as in Synthesis Example 3 to obtain a white powdery yttrium salt of the imide. Composition analysis by fluorescent X-ray analysis (theoretical values in parentheses): F / S / Y = 101 / 6.1 / 1 atomic ratio (102/6/1) was shown.
<Synthesis Example 5>
・ Synthesis of scandium salt of bisperfluorobutanesulfonylimide
Bisperfluorobutanesulfonylimide synthesized from bistrimethylsilylamide sodium salt and perfluorobutanesulfonyl fluoride and scandium acetate are reacted in the same manner as in Synthesis Example 1 to obtain a tris [bis (perfluorobutanesulfonyl) imide] scandium salt. It was. Composition analysis by fluorescent X-ray analysis (theoretical value in parentheses): F / S / Sc = 54 / 5.9 / 1 atomic ratio (54/6/1) was shown.
[0018]
<Synthesis Example 6>
・ Synthesis of scandium salt of bisperfluorooctanesulfonylimide
Bisperfluorobutanesulfonylimide synthesized from bistrimethylsilylamide sodium salt and perfluorooctanesulfonyl fluoride and scandium acetate are reacted in the same manner as in Synthesis Example 1 to obtain a tris [bis (perfluorooctanesulfonyl) imide] scandium salt. It was. Composition analysis by fluorescent X-ray analysis (theoretical value in parentheses): F / S / Sc = 102 / 5.9 / 1 atomic ratio (102/6/1) was shown.
[0019]
[Example 1]
1.5 g of β-cyclodextrin was dissolved in 85 ml of water at room temperature. To this solution, 3.0 g of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt was added and stirred at room temperature for 15 hours to form a white precipitate. A white precipitate was obtained by filtration, washed with 10 ml of water, and then vacuum-dried at 80 ° C. for 3 hours at 1 mmHg or less to obtain 2.3 g of a white solid.
The infrared absorption spectrum of this white solid is 2929 cm derived from β-cyclodextrin.^-1Absorption disappeared and shifted to high wavenumber 2937cm^-1  And 1028 cm^-1Characteristic absorption of ytterbium salt derived 1357cm^-1Such characteristic absorption was observed. At 80 ° C in heavy water.¹As a result of measuring HNMR, anomeric H of β-cyclodextrin₁The peak at 4.93 ppm corresponding to 1 disappeared, and the peak appeared at 5.05 ppm shifted by a low magnetic field (TMS standard). The diffraction angle (2θ) was measured with an X-ray diffractometer. The 2θ diffraction peak seen with β-cyclodextrin alone disappears and is not found in the ytterbium salt 12.0, 13.3, 15.2, 17.5, 20.0, 24.1 deg. A new diffraction peak was observed. The ytterbium content by plasma emission analysis was 4.7% by weight.
[0020]
1 g of a white solid which is a cyclodextrin-containing substance of trisbisperfluorobutanesulfonylimide] ytterbium salt synthesized by the above method, 620 μl of methyl vinyl ketone and 560 μl of 2,3-dimethylbutadiene are added to 10 ml of methylene chloride, and suspended at room temperature. The reaction was allowed to stir for 15 hours in a turbid state. The reaction product was analyzed by gas chromatography, and the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 89%.
A solid was obtained from the reaction solution after completion of the reaction by filtration. After washing with 5 ml of methylene chloride, 1 g of a white solid heated to 1 mmHg or less at 60 ° C. and vacuum dried, 620 μl of methyl vinyl ketone and 560 μl of 2,3-dimethylbutadiene are added to 10 ml of methylene chloride, and suspended at room temperature. And stirred for 16 hours. The yield of the reaction product 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 90%.
[0021]
[Example 2]
1.5 g of a white solid which is a cyclodextrin-containing substance of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt synthesized in Example 1, 1330 mg of benzoic anhydride and 500 μl of ethanol were added to 20 ml of toluene at room temperature. The mixture was stirred for 7 hours in a suspended state. The reaction product was analyzed by gas chromatography, and the yield of ethyl benzoate was 94%.
A solid was obtained from the reaction solution after completion of the reaction by filtration. Thereafter, it was washed with 5 ml of toluene, 1.5 g of a white solid which was heated and dried at 60 ° C. at 1 mmHg or less, 1330 mg of benzoic anhydride and 500 μl of ethanol were added to 20 ml of toluene, and the mixture was stirred at room temperature for 7 hours in a suspended state. Reacted. The yield of ethyl benzoate as a reaction product was 92%.
[0022]
[Example 3]
1.5 g of β-cyclodextrin was dissolved in 85 ml of water at room temperature. To this solution, 1.4 g of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt was added and stirred at room temperature for 3 hours to form a white precipitate. This white precipitate was obtained by filtration, washed with 10 ml of water, and then vacuum dried at 80 ° C. for 3 hours at 1 mmHg or less. 2.3 g of a white solid was obtained.
[0023]
The infrared absorption spectrum of this white solid is 2929 cm derived from β-cyclodextrin.^-1Absorption disappeared and shifted to high wavenumber 2935cm^-1  And 1028 cm^-1Characteristic absorption of ytterbium salt derived 1357cm^-1Such characteristic absorption was observed. At 80 ° C in heavy water.¹As a result of measuring H-NMR, anomeric H of β-cyclodextrin₁The peak at 4.93 ppm corresponding to 1 disappeared, and the peak appeared at 5.05 ppm shifted by a low magnetic field (TMS standard). The diffraction angle (2θ) was measured with an X-ray diffractometer. The 2θ diffraction peak seen with β-cyclodextrin alone disappears and is not found in the ytterbium salt 12.0, 13.3, 15.2, 17.5, 20.0, 24.1 deg. A new diffraction peak was observed. The content of ytterbium by plasma emission analysis was 2.9% by weight.
[0024]
2 g of a white solid which is a cyclodextrin-containing substance of trisbisperfluorobutanesulfonylimide] ytterbium salt synthesized by the above method, 1330 mg of benzoic anhydride and 500 μl of ethanol are added to 30 ml of toluene, and 11 in a suspended state at room temperature. The reaction was stirred for an hour. The reaction product was analyzed by gas chromatography, and the yield of ethyl benzoate was 86%.
A solid was obtained from the reaction solution after completion of the reaction by filtration. After washing with 5 ml of toluene, 2.0 g of a white solid which was heated and dried at 60 ° C. at 1 mmHg or less, 1330 mg of benzoic anhydride and 500 μl of ethanol were added to 30 ml of toluene, and the mixture was stirred at room temperature for 11 hours in a suspended state. Reacted. The yield of the reaction product, ethyl benzoate, was 85%.
[0025]
[Example 4]
1.5 g of a white solid which is a cyclodextrin-containing substance of tris [bis (perfluorobutanesulfonylimide) ytterbium salt synthesized in Example 1, 710 μl of benzyl acetate and 1600 μl of ethanol were added to 40 ml of methylene chloride, and suspended at room temperature. The reaction was stirred for 48 hours in a turbid state, and the reaction product was analyzed by gas chromatography, and the yield of ethyl acetate was 79%.
[0026]
[Example 5]
1.7 g of β-cyclodextrin was dissolved in 120 ml of water at room temperature. To this solution, 0.6 g of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt was added and stirred at room temperature for 3 hours to form a white precipitate. This white precipitate was obtained by filtration, washed with 10 ml of water, and then vacuum dried at 80 ° C. for 3 hours at 1 mmHg or less to obtain 2.0 g of a white solid.
The infrared absorption spectrum of this white solid is 2929 cm derived from β-cyclodextrin.^-1Disappeared and shifted to high wavenumber 2933cm^-1And 1028 cm^-1Characteristic absorption of ytterbium salt derived 1357cm^-1Such characteristic absorption was observed. And at 80 ° C in deuterium¹As a result of measuring H-NMR, anomeric H of β-cyclodextrin₁The peak at 4.93 ppm corresponding to 1 disappeared, and a peak appeared at 5.03 ppm shifted by a low magnetic field (TMS standard). The content of ytterbium by plasma emission analysis was 1.8% by weight.
[0027]
Add 0.7 g of white solid, cyclodextrin-containing substance of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt synthesized by the above method, 920 mg of N-benzylideneaniline and 1000 mg of methyltrimethylsilyldimethylketene acetal to 25 ml of methylene chloride. The mixture was stirred for 6 hours in a suspended state at room temperature. The reaction product was analyzed by gas chromatography, and the yield of methyl 3-anilino-2,2-dimethyl-3-phenylpropionate was 71%.
[0028]
[Example 6]
1.5 g of β-cyclodextrin was dissolved in 90 ml of water at room temperature. To this solution, 3.9 g of tris [bis (perfluorooctanesulfonyl) imide] lanthanum salt was added and stirred at room temperature for 15 hours to form a white precipitate. This white precipitate was obtained by filtration, washed with 10 ml of water, and then vacuum dried at 80 ° C. for 3 hours at 1 mmHg or less. 2.1 g of a white solid was obtained.
The infrared absorption spectrum of this white solid is 2929 cm derived from β-cyclodextrin.^-1Absorption disappeared and shifted to high wavenumber 2934cm^-1  And 1029 cm^-11207cm derived from lanthanum salt^-1Such characteristic absorption was observed. And at 80 ° C in deuterium¹As a result of measuring HNMR, anomeric H of β-cyclodextrin₁The peak at 4.93 ppm corresponding to 1 disappeared, and a peak appeared at 5.03 ppm shifted by a low magnetic field (TMS standard). The diffraction angle (2θ) was measured with an X-ray diffractometer. The 2θ diffraction peak seen with β-cyclodextrin alone disappears and is not found in the lanthanum salt 12.0, 13.4, 15.3, 17.6, 20.3, 24.2 deg. A new diffraction peak was observed. The content of lanthanum by plasma emission analysis was 2.4% by weight.
[0029]
Add 2.0 g of white solid which is a cyclodextrin-containing tris [bis (perfluorooctanesulfonyl) imide] lanthanum salt synthesized by the above method, 620 μl of methyl vinyl ketone and 560 μl of 2,3-dimethylbutadiene to 15 ml of dichloroethane, The mixture was stirred and reacted at 40 ° C. for 10 hours in a suspended state. The reaction product was analyzed by gas chromatography, and the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 82%.
[0030]
[Example 7]
β-cyclodextrin 0.7 g was dissolved in 40 ml of water at room temperature. To this solution, 0.9 g of tris [bisperfluorooctanesulfonylimide] lanthanum salt was added and stirred at room temperature for 15 hours to form a white precipitate. This white precipitate was obtained by filtration, washed with 20 ml of water, and then vacuum dried at 80 ° C. for 3 hours at 1 mmHg or less. 1.3 g of a white solid was obtained.
[0031]
The infrared absorption spectrum of this white solid is 2929 cm derived from β-cyclodextrin.^-1Absorption disappeared and shifted to high wavenumber 2934cm^-1  And 1029 cm^-11207cm derived from lanthanum salt^-1Such characteristic absorption was observed. And at 80 ° C in deuterium¹As a result of measuring HNMR, anomeric H of β-cyclodextrin₁The peak at 4.93 ppm corresponding to 1 disappeared, and a peak appeared at 5.03 ppm shifted by a low magnetic field (TMS standard). The diffraction angle (2θ) was measured with an X-ray diffractometer. The 2θ diffraction peak seen with β-cyclodextrin alone disappears and is not found in the lanthanum salt 12.0, 13.4, 15.3, 17.6, 20.3, 24.2 deg. A new diffraction peak was observed. The content of lanthanum by plasma emission analysis was 2.2% by weight.
1.3 g of white solid which is a cyclodextrin-containing tris [bis (perfluorooctanesulfonyl) imide] lanthanum salt synthesized by the above method, 1330 mg of benzoic anhydride and 500 μl of ethanol are added to 20 ml of toluene and suspended. And stirred at 50 ° C. for 4 hours. The reaction product was analyzed by gas chromatography, and the yield of ethyl benzoate was 91%.
[0032]
[Example 8]
1.4 g of β-cyclodextrin is dissolved in 80 ml of water at room temperature. To this solution, 0.6 g of tris [bis (perfluorooctanesulfonyl) imide] lanthanum salt was added and stirred at room temperature for 15 hours to form a white precipitate. This white precipitate was obtained by filtration, washed with 20 ml of water, and then vacuum dried at 80 ° C. for 3 hours at 1 mmHg or less to obtain 1.8 g of a white solid.
[0033]
The infrared absorption spectrum of this white solid is 2929 cm derived from β-cyclodextrin.^-1Disappeared and shifted to high wavenumber 2933cm^-1And 1029 cm^-1Characteristic absorption of lanthanum salt derived from 1216cm^-1Such characteristic absorption was observed. And at 80 ° C in deuterium¹As a result of measuring HNMR, anomeric H of β-cyclodextrin₁The peak at 4.93 ppm corresponding to 1 disappeared, and a peak appeared at 5.03 ppm shifted by a low magnetic field (TMS standard). The diffraction angle (2θ) was measured with an X-ray diffractometer. The 2θ diffraction peak seen with β-cyclodextrin alone disappears and is not found in the lanthanum salt 12.0, 13.4, 15.3, 17.6, 20.3, 24.2 deg. A new diffraction peak was observed. The content of lanthanum by plasma emission analysis was 1.2% by weight.
[0034]
[Example 9]
2.7 g of β-cyclodextrin is dissolved in 160 ml of water at room temperature. When 0.6 g of tris [bis (perfluorooctanesulfonyl) imide] lanthanum salt is added to this solution and stirred for 15 hours at room temperature, a white precipitate is formed. This white precipitate was obtained by filtration, washed with 20 ml of water, and then vacuum dried at 80 ° C. for 3 hours at 1 mmHg or less. 2.7 g of a white solid was obtained.
[0035]
The infrared absorption spectrum of this white solid is 2929 cm derived from β-cyclodextrin.^-1Absorption disappeared and shifted to a high wavenumber of 2932 cm^-1  And 1028 cm^-1Characteristic absorption of lanthanum salt derived from 1217cm^-1Such characteristic absorption was observed. And at 80 ° C in deuterium¹As a result of measuring HNMR, anomeric H of β-cyclodextrin₁The peak at 4.93 ppm corresponding to 1 disappeared, and a peak appeared at 5.03 ppm shifted by a low magnetic field (TMS standard). The diffraction angle (2θ) was measured with an X-ray diffractometer. The 2θ diffraction peak seen with β-cyclodextrin alone disappears and is not found in the lanthanum salt 6.4, 12.2, 15.0, 15.3, 16.1, 18.1, 24.5 deg. . A new diffraction peak was observed. The content of lanthanum by plasma emission analysis was 0.8% by weight.
[0036]
[Example 10]
0.1 g of a white solid, which is a cyclodextrin-containing product of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt synthesized in Example 1, was added at 0 ° C. to a 10 ml solution of methylene chloride containing 510 μl of benzaldehyde and 920 mg of methyltrimethylsilylketene acetal. And stirred for 1 hour in a suspended state at room temperature. The reaction product was analyzed by gas chromatography, and the yield of methyl 3-trimethylsilyloxy-2,2-dimethyl-3-phenylpropionate was 79%.
[0037]
Example 11
White solid 0.3 g which is a cyclodextrin-containing substance of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt synthesized in Example 1, 920 mg of N-benzylideneaniline, 1000 mg of methyltrimethylsilyldimethylketene acetal was added to 10 ml of octafluorotoluene. And stirred for 3 hours in a suspended state at room temperature. The reaction product was analyzed by gas chromatography, and the yield of methyl 3-anilino-2,2-dimethyl-3-phenylpropionate was 73%.
[0038]
Example 12
2.6 g of β-cyclodextrin was dissolved in 180 ml of water at room temperature. To this solution, 0.9 g of tris [bisperfluorobutanesulfonylimide] yttrium salt was added and stirred at room temperature for 3 hours to form a white precipitate. This white precipitate was obtained by filtration, washed with 20 ml of water, and then vacuum dried at 80 ° C. for 3 hours at 1 mmHg or less. White solid 3.0g was obtained.
The content of yttrium by plasma emission analysis was 1.9% by weight. 3.0 g of a white solid, which is a cyclodextrin-containing tris [bis (perfluorooctanesulfonyl) imide] yttrium salt synthesized by the above method, 1330 mg of benzoic anhydride, and 500 μl of ethanol are added to 40 ml of methylene chloride at room temperature. The mixture was stirred for 17 hours in a suspended state. The reaction product was analyzed by gas chromatography, and the yield of ethyl benzoate was 86%.
[0039]
Example 13
2.7 g of β-cyclodextrin was dissolved in 160 ml of water at room temperature. To this solution, 0.6 g of tris [bis (perfluorooctanesulfonyl) imide] scandium salt was added and stirred at room temperature for 15 hours to form a white precipitate. This white precipitate was obtained by filtration, washed with 20 ml of water, and then vacuum dried at 80 ° C. for 3 hours at 1 mmHg or less. White solid 2.2g was obtained.
The scandium content by plasma emission analysis was 0.8% by weight. 2.0 g of a white solid, which is a cyclodextrin-containing tris [bis (perfluorooctanesulfonyl) imide] scandium salt synthesized by the above method, 1330 mg of benzoic anhydride, and 500 μl of ethanol are added to 20 ml of methylene chloride at room temperature. The mixture was stirred for 12 hours in a suspended state. The reaction product was analyzed by gas chromatography, and the yield of ethyl benzoate was 89%.
[0040]
Example 14
1.7 g of γ-cyclodextrin was dissolved in 15 ml of water at room temperature. To this solution, 3.0 g of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt was added and stirred at room temperature for 15 hours to form a white precipitate. This white precipitate was obtained by filtration, washed with 20 ml of water, and then vacuum dried at 80 ° C. for 3 hours at 1 mmHg or less. 2.6 g of white solid was obtained.
The ytterbium content by plasma emission analysis was 4.6% by weight. Add 1.5 g of a white solid, which is a cyclodextrin-containing tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt, 620 μl of methyl vinyl ketone, and 560 μl of 2,3-dimethylbutadiene added to 10 ml of methylene chloride. The mixture was stirred at room temperature for 15 hours in a suspended state. The reaction product was analyzed by gas chromatography, and the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 86%.
[0041]
A solid was obtained from the reaction solution after completion of the reaction by filtration. Thereafter, 1.4 g of white solid which was washed with 5 ml of methylene chloride and vacuum-dried, 620 μl of methyl vinyl ketone and 560 μl of 2,3-dimethylbutadiene were added to 20 ml of methylene chloride, and the mixture was stirred and reacted at room temperature for 20 hours in a suspended state. . The yield of the reaction product 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 88%.
[0042]
Example 15
1.5 g of β-cyclodextrin was dissolved in 85 ml of water at room temperature. To this solution, 3.0 g of tris [bis (perfluorobutanesulfonyl) imide] scandium salt was added and stirred at room temperature for 15 hours to form a white precipitate. This white precipitate was obtained by filtration, washed with 20 ml of water, and then vacuum dried at 80 ° C. for 3 hours at 1 mmHg or less. 2.6 g of white solid was obtained.
The scandium content by plasma emission analysis was 4.8%. Add 1.0 g of white solid, which is a cyclodextrin-containing tris [bis (perfluorobutanesulfonyl) imide] scandium salt, 620 μl of methyl vinyl ketone, and 560 μl of 2,3-dimethylbutadiene to the 10 ml of methylene chloride. The mixture was stirred for 7 hours in a suspended state at room temperature. The reaction product was analyzed by gas chromatography, and the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 89%.
[0043]
Example 16
750 mg of an epichlorohydrin copolymer of β-cyclodextrin (manufactured by Aldrich) was added to 10 ml of water, 1.5 g of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt was added, and the mixture was stirred for 4 hours. Insoluble matter was obtained by filtration, and vacuum drying was performed at 60 ° C. for 3 hours at 1 mmHg or less. As a result, 2.0 g of a solid was obtained.
The infrared absorption spectrum of this solid is 1357 cm derived from ytterbium salt.^-1Such characteristic absorption was observed. The content of ytterbium by plasma emission analysis was 5.7% by weight.
[0044]
2.0 g of solid, which is a mixture of cyclodextrin of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt and epichlorohydrin copolymer synthesized by the above method, 1330 mg of benzoic anhydride, 500 μl of ethanol and 15 ml of methylene chloride And stirred for 9 hours in a suspended state at room temperature. The reaction product was analyzed by gas chromatography, and the yield of ethyl benzoate was 87%.
A solid was obtained from the reaction solution after completion of the reaction by filtration. After washing with 5 ml of methylene chloride, 2.0 g of a solid heated at 60 ° C. under 1 mmHg and vacuum dried, 1330 mg of benzoic anhydride, and 500 μl of ethanol were added to 15 ml of methylene chloride, and suspended at room temperature for 9 hours. The reaction was stirred. The yield of the reaction product, ethyl benzoate, was 85%.
[0045]
[Example 17]
A solid containing 0.5 g of the tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt cyclodextrin and epichlorohydrin copolymer synthesized in Example 16 was mixed with 510 μl of benzaldehyde and 920 mg of methyltrimethylsilylketene acetal. The solution was added to a 10 ml methyl solution at 0 ° C., and allowed to react with stirring for 1 hour in a suspended state at room temperature. The reaction product was analyzed by gas chromatography, and the yield of methyl 3-trimethylsilyloxy-2,2-dimethyl-3-phenylpropionate was 75%.
[0046]
A solid was obtained from the reaction solution after completion of the reaction by filtration. Thereafter, it was washed with 5 ml of methylene chloride, and 0.5 g of a solid heated and dried at 60 ° C. at 1 mmHg or less was added to a solution of 10 ml of methyl chloride containing 510 μl of benzaldehyde and 920 mg of methyltrimethylsilylketene acetal. The reaction was stirred for an hour. The reaction product was analyzed by gas chromatography, and the yield of methyl 3-trimethylsilyloxy-2,2-dimethyl-3-phenylpropionate was 73%. As a result of repeating the third and fourth reactions by exactly the same operation, the yields of methyl 3-trimethylsilyloxy-2-dimethyl-3-phenylpropionate were 74% and 76%, respectively.
[0047]
Example 18
1.0 g of solid, which is a content of cyclodextrin of tris [bis (perfluorobutanesulfonyl) imide] ytterbium salt and epichlorohydrin copolymer synthesized in Example 16, 620 μl of methyl vinyl ketone, 2,3-dimethylbutadiene 560 μl was added to 10 ml of dichloroethane, and the mixture was reacted with stirring at 45 ° C. for 9 hours in a suspended state.
The reaction product was analyzed by gas chromatography, and the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 88%.
A solid was obtained from the reaction solution after completion of the reaction by filtration. Thereafter, it was washed with 5 ml of dichloroethane, 1.0 g of a solid heated at 60 ° C. at 1 mmHg or less, and 620 μl of methyl vinyl ketone and 560 μl of 2,3-dimethylbutadiene were added to 10 ml of dichloroethane, and 45 ° C. in a suspended state. The reaction was allowed to stir for 9 hours. The yield of the reaction product 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 90%.
[0048]
【The invention's effect】
The cyclodextrin-containing material containing a Lewis acid of the present invention is easy to handle, easy to separate from water and an organic solvent, and friendly to the environment that can be reused. In particular, the cyclodextrin-containing material is excellent in reaction activity as a reaction catalyst of a nucleophilic reagent, and can be easily recovered and reused from the reaction system, and is very useful industrially.

Claims (1)

Bisperfluoroalkylsulfonylimide rare earth salt molecule obtained by adding a biperfluoroalkylsulfonylimide rare earth salt represented by the following formula (1) to cyclodextrin is contained in a ratio of 0.001 to 3 per cyclodextrin. A nucleophilic reagent reaction catalyst comprising a cyclodextrin-containing product .
[(RfSO ₂ ) ₂ N] nM (1)
(Here, Rf represents a perfluoroalkyl group having 2 to 8 carbon atoms , M represents a rare earth element selected from ytterbium, lanthanum, scandium, and yttrium, and n represents a value equal to the valence of the M element. )