JP2001328954A - Reaction in water-based medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of reaction in a water-based medium and further a method of reaction easy to separate and reuse a proton acid catalyst in the method of reaction. SOLUTION: This method of reaction comprises using a bisperfluoroalkylsulfonylimide, a trisperfluoroalkylsulfonylmethide or perfluoroalkylsulfonic acid and reacting in the water-based medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a reaction method using a proton acid catalyst.

[0002]

2. Description of the Related Art Organic compounds have a slow reaction due to poor solubility in an aqueous medium, and there is a problem in industrial practicality. On the other hand, reactions using organic solvents generally have environmental problems such as often harmful to humans. Therefore, a reaction method in which the reaction sufficiently proceeds even in an aqueous medium has been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a reaction method in an aqueous medium, and further to provide a reaction method in which the proton acid catalyst can be easily separated and reused. It is assumed that.

[0004]

Means for Solving the Problems The present inventors have intensively studied a reaction method in an aqueous medium and a reaction method in which a protonic acid can be easily separated and reused. The above object can be achieved by using sulfonylimide, trisperfluoroalkylsulfonylmethide or perfluoroalkylsulfonic acid as an aqueous medium, and further performing a reaction using an aqueous medium composed of water and a fluorine-based reaction medium. And completed the present invention.

That is, the present invention provides: [1] A reaction in an aqueous medium using at least one kind selected from proton acids represented by the following formulas (1), (2) and (3) as an acid catalyst. reaction _{wherein, (Rf1SO 2) (Rf2SO 2} ) NH (1) (Rf1SO 2) (Rf2SO 2) (Rf3SO 2) CH (2) Rf2SO 3 H (3) ( wherein, each independently of the Rf1 and Rf3 Represents a perfluoroalkyl group having 1 or more carbon atoms.
The above perfluoroalkyl groups are shown. [2] The reaction method according to [1], wherein the aqueous medium comprises water and a fluorine-based reaction medium.

Hereinafter, the present invention will be described in detail. The bisperfluoroalkylsulfonylimide, trisperfluoroalkylsulfonylmethide and perfluoroalkylsulfonic acid used in the present invention are represented by the following formulas (1), (2) and (3), respectively. _{(Rf1SO 2) (Rf2SO 2)} NH (1) (Rf1SO 2) (Rf2SO 2) (Rf3SO 2) CH (2) Rf2SO in ₃ H (3) formula, Rf1 and Rf3 are 1 carbon atoms each independently
The above perfluoroalkyl groups are shown, preferably perfluoroalkyl groups having 1 to 20 carbon atoms, more preferably perfluoroalkyl groups having 4 to 20 carbon atoms.
Specific examples of Rf1 and Rf3 include, for example, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadeca Examples thereof include a fluorooctyl group. Rf2 represents a perfluoroalkyl group having 2 or more carbon atoms, preferably 4 to 4 carbon atoms.
And 20 represents a perfluoroalkyl group. Specific examples of Rf2 include, for example, a nonafluorobutyl group, an undecafluoropentyl group, a tridecafluorohexyl group, a pentadecafluoroheptyl group, and a heptadecafluorooctyl group.

The bisperfluoroalkylsulfonylimide represented by the above formula (1) is described, for example, in German Patent 2,
No. 239,817, for example, a tetrahydrofuran solution of bistrimethylsilylamide sodium salt and perfluoroalkylsulfonyl fluoride are reacted at room temperature, and thereafter,
It is synthesized by distilling off tetrahydrofuran, further adding perfluoroalkylsulfonyl fluoride to the residue, reacting in dioxane at 130 ° C., distilling off dioxane under reduced pressure, and neutralizing with sulfuric acid.

[0008] Trisperfluoroalkylsulfonyl methide represented by the formula (2) is described in, for example, US Pat.
For example, perfluoroalkylsulfonyl fluoride is added to a solution of methylmagnesium chloride in tetrahydrofuran, and after the reaction, treated with sulfuric acid and then with cesium carbonate. Isolate as a salt. It is synthesized by treating this cesium salt with sulfuric acid.

[0009] The perfluoroalkylsulfonic acid represented by the formula (3) can be easily produced by hydrolyzing perfluoroalkylsulfonyl fluoride. In the present invention, at least one selected from the protonic acids represented by the above formulas (1), (2) and (3)
It is necessary to use the species as an acid catalyst, and from the viewpoint of catalytic activity, it is preferably at least one selected from the protic acids represented by the formulas (1) and (2).

The protonic acid used in the present invention can be applied to ordinary acid-catalyzed reactions. For example, a Diels-Alder reaction, a Michael reaction, a Friedel-Crafts reaction, an aldol reaction, a Mannich type reaction, a hydrolysis reaction, a hydration reaction, a formylation reaction, an alkylation reaction, an olefin isomerization and the like can be mentioned. Furthermore, dehydration reaction of alcohol, o-glycosylation reaction, polymerization of olefins, oxidation reaction using hydrogen peroxide, organic peroxide and the like can be mentioned.

It is necessary to use an aqueous medium as the reaction medium for the liquid phase reaction of the present invention. As the aqueous medium, water alone or a mixed medium of water and a fluorine-based reaction medium is used. Among them, the use of a mixed medium of water and a fluorine-based reaction medium facilitates separation of the protonic acid used in the present invention,
It is preferable because the protonic acid can be reused. The content of the fluorine-based reaction medium with respect to the aqueous medium is preferably 5 to 90% by volume, more preferably 20 to 80% by volume. If the amount of the fluorine-based reaction medium is less than 5% by volume, it tends to be difficult to recover the protonic acid. If the amount exceeds 90% by volume, the separation of the product and the catalyst phase tends to be difficult.

In the present invention, the fluorine-based reaction medium refers to a fluorine-based aromatic hydrocarbon or a fluorine-based aliphatic hydrocarbon. The fluorine-based aromatic hydrocarbons are perfluorinated aromatic hydrocarbons and partially fluorine-substituted aromatic hydrocarbons, such as hexafluorobenzene, octafluorotoluene, 1,2,3-trifluorobenzene,
Examples thereof include 2,4-trifluorobenzene and 1,3,5-trifluorobenzene. Further, it is an aromatic hydrocarbon having an alkyl group partially substituted with fluorine, for example, α, α, α-trifluorotoluene, α, α, α, α, α
', Α', α'-hexafluoro-o, m, p-xylene, 2-methylbenzotrifluoride, hexafluoropropylbenzene and the like can also be mentioned.

The fluorinated aliphatic hydrocarbon is preferably a fluorinated aliphatic hydrocarbon which does not solidify around room temperature.
For example, a linear compound, a branched compound, or a cyclic compound is used, and examples thereof include perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorocyclohexane, and perfluoromethylcyclohexane. It also includes those having one part substituent, for example, those substituted with halogen or the like,
And perfluorooctyl halide.

The above-mentioned fluorine-based reaction medium may be one component or two components.
A mixed system of components or more can also be used. From the viewpoint of phase separation between the product and the catalyst, a fluorine-based aliphatic hydrocarbon or a mixed medium of a fluorine-based aliphatic hydrocarbon and a fluorine-based aromatic hydrocarbon is preferably used. A mixed medium of hydrocarbons and fully substituted fluoroaromatics is used. In the case of a mixed medium, the content of the fluorinated aromatic hydrocarbon is preferably 5 to 50% by volume based on the mixed medium.

The amount of the protic acid as a catalyst is 0.0001 as bisperfluoroalkylsulfonylimide, trisperfluorosulfonylmethide and / or perfluoroalkylsulfonic acid relative to the reaction substrate.
A 1-fold to 10-fold mol can be used. 0.
If it is less than 0001 mol, the reaction yield is low, and if it exceeds 10 mol, it is economically disadvantageous. Preferably 0.
It is from 01 times mol to 2 times mol. The use temperature of the catalyst of the present invention is frequently 200 ° C. or lower, and is preferably −80 ° C. or less.
170 ° C.

The reaction time varies depending on the amount of bisperfluoroalkylsulfonylimide, trisperfluoroalkylsulfonylmethide or perfluoroalkylsulfonic acid added, and the reaction temperature, but is preferably from several minutes to 72 hours. From the viewpoint of improving the reaction yield, the amount of the aqueous medium used is preferably 1 or more by weight relative to bisperfluoroalkylsulfonylimide, trisperfluoroalkylsulfonylmethide and / or perfluoroalkylsulfonic acid used as the catalyst. Preferably, it is more preferably 2 to 10,000.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION

[0018]

Example 1 124 μl of methyl vinyl ketone, 2,3-
112 μl of dimethylbutadiene were added in 3 ml of water. Next, 8 mol% of tris (perfluorobutanesulfonyl) methide was added to 2,3-dimethylbutadiene, and the mixture was stirred and reacted at room temperature for 20 hours. After completion of the reaction, 3 ml of methylene chloride was added to the reaction solution, and the reaction product in the methylene chloride phase was analyzed by gas chromatography, and the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 71%. Met.

[0019]

Example 2 124 μl of methyl vinyl ketone, 2,3-
112 μl of dimethylbutadiene were added in 3 ml of water. Next, 7 mol% of bis (perfluorooctanesulfonyl) imide was added to 2,3-dimethylbutadiene, and the mixture was stirred and reacted at room temperature for 18 hours. After completion of the reaction, 3 ml of methylene chloride was added to the reaction solution, and the reaction product in the methylene chloride phase was analyzed by gas chromatography, and the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 70%. Met.

[0020]

Example 3 124 μl of methyl vinyl ketone, 2,3-
112 μl of dimethylbutadiene were added in 3 ml of water. Next, 15 mol% of perfluorooctanesulfonic acid was added to 2,3-dimethylbutadiene, and the mixture was stirred and reacted at room temperature for 40 hours. After the completion of the reaction, methylene chloride 3
of the methylene chloride phase was analyzed by gas chromatography, and 5-acetyl-2,
The yield of 3-dimethyl-cyclohex-2-ene is 53%.
Met.

[0021]

Example 4 124 μl of methyl vinyl ketone, 2,3-
112 μl of dimethylbutadiene was added to a mixed solvent of 4 ml of water, 5 ml of perfluorohexane, and 1.5 ml of perfluorobenzene. Next, 10 mol% of tris (perfluorobutanesulfonyl) methide was added to 2,3-dimethylbutadiene, and the mixture was stirred and reacted at room temperature for 37 hours. After the completion of the reaction, the perfluorohexane and perfluorobenzene phases were withdrawn, and 3 m
The reaction product in the methylene chloride phase was analyzed by gas chromatography, and the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 63%.
The perfluorohexane and perfluoropentene phases containing tris (perfluorobutanesulfonyl) methide were reused under the above reaction conditions to carry out the reaction. As a result, the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 64%.

[0022]

Example 5 124 μl of methyl vinyl ketone, 2,3-
112 μl of dimethylbutadiene was added to a mixed solvent of 4 ml of water, 3 ml of perfluoromethylcyclohexane, and 1 ml of perfluorobenzene. Next, 10 mol% of bis (perfluorooctanesulfonyl) imide was added to 2,3-dimethylbutadiene, and the mixture was stirred and reacted at room temperature for 40 hours. After the reaction is completed, the perfluoromethylcyclohexane and perfluorobenzene phases are extracted,
3 ml of methylene chloride was added to the remaining liquid, and the reaction product of the methylene chloride phase was analyzed by gas chromatography, and the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 67%. The perfluoromethylcyclohexane and perfluoropentene phases containing bis (perfluorooctanesulfonyl) imide were reused under the above reaction conditions to carry out the reaction. As a result, the yield of 5-acetyl-2,3-dimethyl-cyclohex-2-ene was 65%.

[0023]

Comparative Example 1 Methyl vinyl ketone 124 μl, 2,3-
Add 112 μl of dimethylbutadiene into 3 ml of water,
The reaction was stirred at room temperature for 20 hours. The reaction product was obtained in Example 1.
Analysis by gas chromatography in the same manner as in
-Acetyl-2,3-dimethyl-cyclohex-2-
The ene yield was 8%.

[0024]

Comparative Example 2 Methyl vinyl ketone 124 μl, 2,3-
Add 112 μl of dimethylbutadiene into 3 ml of water,
10 mol% of trifluoromethanesulfonic acid was added to 2,3-dimethylbutadiene, and the mixture was stirred and reacted at room temperature for 20 hours. The reaction product was analyzed by gas chromatography in the same manner as in Example 1, and 5-acetyl-2,
The yield of 3-dimethyl-cyclohex-2-ene was 9%.

[0025]

Comparative Example 3 Methyl vinyl ketone 124 μl, 2,3-
Add 112 μl of dimethylbutadiene into 3 ml of water,
Bis (trifluoromethylsulfonyl) imide
10 mol% was added to -dimethylbutadiene, and the mixture was stirred and reacted at room temperature for 20 hours. The reaction product was analyzed by gas chromatography in the same manner as in Example 1, and 5-
The yield of acetyl-2,3-dimethyl-cyclohex-2-ene was 10%.

[0026]

Example 6 150 mg of 2-adamantanone and 690 mg of a 30% aqueous hydrogen peroxide solution were added to 3 ml of water, and 3 mol% of tris (perfluorobutanesulfonyl) methide was added to 2-adamantanone. The mixture was stirred and reacted for hours. After completion of the reaction, methylene chloride 4
The reaction product in the methylene chloride phase was analyzed by gas chromatography, and the yield of the lactone by the Bayer-Villiger reaction of 2-adamantanone was 56%.

[0027]

Example 7 150 mg of 2-adamantanone and 690 mg of a 30% aqueous solution of hydrogen peroxide were added to 3 ml of water, and bis (perfluorooctanesulfonyl) imide was added at 3 mol% based on 2-adamantanone. The mixture was stirred and reacted for hours. After completion of the reaction, methylene chloride 4
The reaction product in the methylene chloride phase was analyzed by gas chromatography, and the yield of the lactone by the Bayer-Villiger reaction of 2-adamantanone was 54%.

[0028]

Comparative Example 4 150 mg of 2-adamantanone and 690 mg of a 30% aqueous hydrogen peroxide solution were added to 3 ml of water, and the mixture was stirred and reacted at room temperature for 20 hours. The reaction product was analyzed by gas chromatography, and the yield of the lactone by the Bayer-Villiger reaction of 2-adamantanone was 2%.

[0029]

Comparative Example 5 150 mg of 2-adamantanone and 690 mg of a 30% aqueous solution of hydrogen peroxide were added to 3 ml of water, 3 mol% of trifluoromethanesulfonic acid was added to 2-adamantanone, and the mixture was stirred and reacted at room temperature for 20 hours. Was.
The reaction product was analyzed by gas chromatography,
The yield of the lactone form from the Adamantanone by the Bayer-Villiger reaction was 7%.

[0030]

Comparative Example 6 150 mg of 2-adamantanone and 690 mg of a 30% aqueous hydrogen peroxide solution were added to 3 ml of water, and bis (trifluoromethylsulfonyl) imide was added at 3 mol% based on 2-adamantanone. The mixture was stirred and reacted for hours. The reaction product was analyzed by gas chromatography, and the yield of the lactone by the Bayer-Villiger reaction of 2-adamantanone was 12%.

[0031]

Example 8 216 mg of benzaldehyde and 480 mg of methyltrimethylsilylketene acetal were added to 6 ml of water, and 5 mol% of tris (perfluorobutanesulfonyl) methide was added to benzaldehyde, followed by a stirring reaction at room temperature for 3 hours. After completion of the reaction, 6 ml of methylene chloride was added to the reaction solution, and the reaction product in the methylene chloride phase was analyzed by gas chromatography, and the conversion of benzaldehyde was 50%.

[0032]

Example 9 216 mg of benzaldehyde and 480 mg of methyltrimethylsilylketene acetal were added to 6 ml of water.
Tris (perfluorooctanesulfonyl) methide was added to a mixed solvent of 5 ml of perfluoromethylcyclohexane and 1 ml of perfluorotoluene at 10 mol% with respect to benzaldehyde, and the mixture was stirred and reacted at room temperature for 5 hours. After completion of the reaction, the perfluoromethylcyclohexane and perfluorotoluene phases were withdrawn, 6 ml of methylene chloride was added to the remaining liquid, and the conversion of benzaldehyde in the methylene chloride phase was analyzed by gas chromatography.
%Met. The perfluoromethylhexane and perfluorotoluene phases containing tris (perfluorooctanesulfonyl) methide were reused under the above reaction conditions to carry out the reaction. As a result, the conversion of benzaldehyde was 50%.

[0033]

Comparative Example 7 216 mg of benzaldehyde and 480 mg of methyltrimethylsilylketene acetal were added to 6 ml of water, and the mixture was stirred and reacted at room temperature for 3 hours. The conversion of benzaldehyde was analyzed by gas chromatography and found to be 3%.

[0034]

Comparative Example 8 216 mg of benzaldehyde and 480 mg of methyltrimethylsilylketene acetal were added to 6 ml of water, and 5 mol% of trifluoromethanesulfonic acid was added to benzaldehyde, followed by a stirring reaction at room temperature for 3 hours. The conversion of benzaldehyde was analyzed by gas chromatography and found to be 4%.

[0035]

Comparative Example 9 216 mg of benzaldehyde and 480 mg of methyltrimethylsilylketene acetal were added to 6 ml of water, 5 mol% of bis (trifluoromethylsulfonyl) imide was added to benzaldehyde, and the mixture was stirred and reacted at room temperature for 3 hours. The conversion of benzaldehyde was analyzed by gas chromatography and found to be 13%.

[0036]

The reaction in an aqueous medium using bisperfluoroalkylsulfonylimide, trisperfluoroalkylsulfonylmethide or perfluoroalkylsulfonic acid is promoted, and the reaction of the acid with water and a fluorine-based reaction medium is accelerated. The catalyst can be separated and reused.

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Claims (2)

[Claims] 1. A reaction method comprising reacting in an aqueous medium using at least one selected from proton acids represented by the following formulas (1), (2) and (3) as an acid catalyst. _{(Rf1SO 2) (Rf2SO 2)} NH (1) [(Rf1SO 2) (Rf2SO 2) (Rf3SO 2) CH (2) Rf2SO 3 H (3) ( wherein, Rf1 and Rf3 each independently 1 or more carbon atoms And Rf2 represents a carbon atom having 2 carbon atoms.
The above perfluoroalkyl groups are shown. ) 2. The method according to claim 1, wherein the aqueous medium comprises water and a fluorine-based reaction medium.