JP2000086617A - Production of bisperfluoroalkylsulfonimide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject compound useful as a Lewis acid catalyst or an organic ionic conductor by reacting a perfluoroalkylsulfonyl chloride with a mixture comprising anhydrous ammonia and a tertiary amine. SOLUTION: A perfluoroalkylsufonyl chloride represented by the formula RfSO2Cl (Rf is a 1-6C perfluoroalkyl) is reacted with a mixture comprising anhydrous ammonia and a tertiary amine represented by the formula R1R2R3N (R1 to R3 are each a 1-5C alkyl) or a heterocyclic amine or an aromatic amine, as necessary, in a solvent to thereby simply, efficiently and industrially produce the objective compound represented by the formula (RfSO2)2NM (M is a monovalent cation).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing a bisperfluoroalkylsulfonimide compound which is useful as a Lewis acid catalyst and an organic ion conductor.

[0002]

2. Description of the Related Art Bisperfluoroalkylsulfonylimide compounds, that is, bisperfluoroalkylsulfonylimides or salts thereof are useful in the field of organic synthesis and electric materials as Lewis acid catalysts and organic ion conductors. As a method of producing a bisperfluoroalkylsulfonimide compound proposed so far, for example, a method of reacting a perfluoroalkylsulfonyl halide with an alkali metal salt of N-trimethylsilylperfluoroalkylsulfonimide (EP 364340,
JP-A-9-173856, etc.) 2R _f SO ₂ X + (Me ₃ Si) ₂ NLi → (R _f SO ₂ ) ₂ NLi + 2Me ₃ SiX [wherein, X represents a halogen. Method of reacting perfluoroalkylsulfonyl fluoride with an alkali metal salt of perfluoroalkylsulfonamide (J. Fluorine Chem., 52, 7, 1991, etc.) R _f SO ₂ F + R _f SO ₂ NHLi → (R _f SO ₂ ) ₂ NLi + HF Method of reacting perfluoroalkylsulfonic anhydride with urea or ammonium halide
No. 56805) (R _f SO ₂ ) ₂ O + CO (NH ₂ ) ₂ → (R _f SO ₂ ) ₂ NH + NH ₃ + CO ₂ (R _f SO ₂ ) ₂ O + NH ₄ X → ( _{R f SO 2) 2 NH +} H 2 O + HX [ wherein, X represents a halogen method of reacting perfluoroalkyl sulfonyl halide and a metal nitride (WO90 / 11999, _{etc.) 2R f SO 2 X + Li} 3 N → (R _f SO ₂ ) ₂ NLi + 2LiX wherein X represents a halogen. Perfluoroalkylsulfonyl fluoride is reacted with ammonia or perfluoroalkylsulfonamide in the presence of a tertiary amine or a heterocyclic amine. Method (WO97 / 23448, JP-A-8-81436)
2R _f SO ₂ F + NH ₃ + 3NR ¹ R ² R ³ → (R _f SO ₂ ) ₂ NNHR ¹ R ² R ³ + 2
R ¹ R ² R ³ NHF R _f SO ₂ F + R _f SO ₂ NH ₂ + NR ¹ R ² R ³ → (R _f SO ₂ ) ₂ NH + R ¹ R ²
R ³ NHF wherein R ¹ , R ² and R ³ are the same or different and each represent an alkyl group having 1 to 5 carbon atoms. Oxidation of bis (perfluoroalkylthio) amine with sodium hypochlorite (Inorg. Chem., 35, 1918,
1996 etc.) (R _f S) ₂ NH + 4NaClO → (R _f SO ₂ ) ₂ NNa + HCl + 3NaCl, etc. are known. However, all of the above methods (1) to (4) require the reaction to be carried out under high pressure, so that an expensive pressurized reactor must be used. Furthermore, these methods are not industrial methods because they require many steps and use expensive silazane derivatives.
Is difficult to purify the product, and the isolation yield is very low. The method is not industrial because it uses a metal nitride which is unstable in the air. The method (1) uses a corrosive oxidizing agent, and the method (2) requires an expensive corrosion-resistant reaction apparatus because hydrogen fluoride, which is a toxic corrosive gas, is generated in the step of purifying the product. As described above, no satisfactory method has been found for an efficient method for synthesizing a bisperfluoroalkylsulfonimide compound using a simple apparatus.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a simple and efficient industrial process for producing a bisperfluoroalkylsulfonimide compound which has solved the above problems.

[0004]

As a result of intensive studies to achieve the above object, the present inventors have found an industrial production method of a perfluoroalkylsulfonimide compound by using perfluoroalkylsulfonyl chloride as an imidizing agent. According to the invention, bisperfluoroalkylsulfonimides can be easily prepared from perfluoroalkylsulfonyl chloride, anhydrous ammonia and tertiary or heterocyclic or aromatic amines without using a pressurized reactor, especially under normal pressure. Compounds can be prepared. That is, the present invention provides a compound represented by the general formula (II): R _f SO ₂ Cl (II) wherein R _f represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms. A perfluoroalkylsulfonyl chloride represented by the general formula (III): R ¹ R ² R ³ N (III) wherein R ¹ , R ² and R ³ are the same or different; Represents an alkyl group of the formulas 1 to 5. The third shown by
A general formula (I): (R _f SO ₂ ) ₂ NM (I) wherein an amine or a mixture comprising a heterocyclic or aromatic amine is reacted in a solvent or without a solvent. R _f represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, and M represents a monovalent cation. ] The method for producing a bisperfluoroalkylsulfonimide compound represented by the formula:

The present invention also relates to a tertiary amine represented by the general formula (III): R ¹ R ² R ³ N (III) or a heterocyclic or aromatic amine in a solvent or under solvent-free conditions. Production of bisperfluoroalkylsulfonimide compound characterized by introducing anhydrous ammonia into a mixed solution of perfluoroalkylsulfonyl chloride represented by the formula (II): R _f SO ₂ Cl (II) and reacting the mixture. And a method in which anhydrous ammonia is dissolved in a tertiary amine represented by the general formula (III): R ¹ R ² R ³ N (III) or a heterocyclic or aromatic amine in a solvent or under solvent-free conditions. the liquid the general formula (II): production of R _f SO ₂ was added perfluoroalkyl sulfonyl chloride represented by Cl (II), bis perfluoroalkyl sulfonimide compound characterized by reacting Including the law. The composition and yield of the product are almost the same regardless of the above three methods.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The target substance of the present invention is a bisperfluoroalkylsulfonimide compound represented by the general formula (I): (R _f SO ₂ ) ₂ NM (I), wherein R _f is a group having 1 to 6 carbon atoms. Is a linear or branched perfluoroalkyl group, preferably CF ₃ , C ₂ F ₅ , C ₃ F ₇ or C ₄ F ₉ . M represents a monovalent cation, preferably H ⁺ , Li ⁺ , Na ⁺ , Me ₄ N ⁺ , Et ₄ N
⁺ , Et ₃ MeN ⁺ , and Bu ₄ N ⁺ .

In the present invention, the tertiary amine represented by the general formula (III) used for producing the bisperfluoroalkylsulfonimide compound represented by the general formula (I) includes, for example, tributylamine and tributylamine. Examples include propylamine, triethylamine, diethylmethylamine, and dimethylbutylamine; examples of the heterocyclic amine include pyridine; and examples of the aromatic amine include dimethylaniline, but are not limited thereto. Not something.

The organic solvent used in the above reaction is preferably an inert solvent which does not react with the starting materials and products in the reaction step, for example, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, methylene chloride, ethylene chloride Suitable examples include, but are not limited to, halogenated carbons such as chloroform, carbon tetrachloride and the like, and hydrocarbons such as benzene, toluene, xylene and hexane.
The above reaction can be carried out at a temperature in the range of 0 ° C. to 100 ° C., and most preferably 20 ° C. to 80 ° C.

The reaction formula of the present invention is shown as follows. 2R _f SO ₂ Cl + NH ₃ + 3R ¹ R ² R ³ N → (R _f SO ₂ ) ₂ NNHR ¹ R ² R ³ +
2R ¹ R ² R ³ NHCl The above ammonium sulfonimidate salt releases an amine by reacting with a strong acid such as sulfuric acid, hydrochloric acid, tosylic acid, trifluoromethane sulfonic acid, ion exchange resin and the like to form a corresponding free sulfonimide. Can be manufactured. By distilling the reaction mixture, it is possible to separate the ammonium salt from the ammonium salt, and a high-purity sulfonimide can be easily isolated. That is, if this is shown by a reaction formula, it is as follows. (R _f SO ₂ ) ₂ NHR ¹ R ² R ³ + HX → (R _f SO ₂ ) ₂ NH + XHNR ¹ R ² R ³ [wherein, X represents a halogen or sulfonyl derivative. The above sulfonimide reacts with a base such as a hydroxide, oxide or carbonate containing an alkali metal to cause cation exchange, whereby a corresponding sulfonimide metal salt can be produced. The reaction formula in the case of using lithium carbonate is shown below. 2 (R _f SO ₂ ) ₂ NH + Li ₂ CO ₃ → 2 (R _f SO ₂ ) ₂ NL
i + H ₂ O + CO _{2 In} addition, the above sulfonimide can undergo cation exchange by reacting with another quaternary ammonium salt to produce a corresponding ammonium sulfonimidate salt. That is, if this is shown by a reaction formula, it is as follows. _{2 (R f SO 2) 2} NH + R 4 R 5 R 6 R 7 NX
→ 2 (R _f SO ₂ ) ₂ NNR ⁴ R ⁵ R ⁶ R ⁷ + HX wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different,
X represents an alkyl group having 1 to 5 carbon atoms, and X represents a monovalent anion. ]

[0010]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 (Production of bistrifluoromethanesulfonimide) After replacing a 500-ml three-necked flask equipped with a condenser with nitrogen, 100 ml of anhydrous triethylamine was charged and cooled to -60 ° C on a dry ice / ethanol bath. After dissolving 2.5 g of ammonia in this, 100 g of trifluoromethanesulfonyl chloride was added dropwise with vigorous stirring.
Thereafter, the reaction was carried out at room temperature for 3 hours and at reflux for 1 hour. After the reaction solution was extracted with methylene chloride, it was washed twice with water. The organic layer was dried over anhydrous magnesium sulfate and then filtered. The solvent was distilled off from the filtrate under reduced pressure to obtain 54.9 g of a mixture of triethylammonium bistrifluoromethanesulfonimide and ammonium chloride. 60 g of concentrated sulfuric acid was added to the above crude product, followed by distillation under reduced pressure to obtain 31.0 g of bistrifluoromethanesulfonimide: (CF ₃ SO ₂ ) ₂ NH (yield: 75).
%: Based on ammonia). The physical properties of the obtained substance were as follows. Melting point: 49 ° C. ¹ H-NMR (acetone-d6, δ): 11.11 (bs, 1H, NH) ¹⁹ F-NMR (DMSO, δ): −73.9 (S) IR (KBr, cm ⁻¹ ): 3425 ( NH), 1325 (SO ₂ ), 1206 (C
F), 1140 (SO ₂ ), 1059 (SO ₂ ) Example 2 (Production of lithium bistrifluoromethanesulfonimide) After replacing the 100 ml glass reactor equipped with a condenser with nitrogen, the bistrifluoro obtained in Example 1 was replaced. 26.5 g of methanesulfonimide and 60 ml of anhydrous isopropyl ether were charged to obtain a homogeneous solution. While stirring at room temperature, 8.3 g of lithium carbonate (4N product of Honjo Chemical Co., Ltd.) was added little by little. After generation of carbon dioxide gas was no longer observed, the mixture was heated gradually and reacted under boiling reflux for 2 hours. After the reaction solution was cooled under a nitrogen stream, anhydrous magnesium sulfate was added and dried for 1 hour. The solution was filtered under reduced pressure through a membrane filter (manufactured by Nippon Millipol) having a pore size of 0.2 μm to remove undissolved lithium carbonate and magnesium sulfate. After evaporating the solvent from the filtrate under reduced pressure, anhydrous methylene chloride was added. The crystallized crystals were separated by filtration and dried at 150 ° C. As a result, lithium bistrifluoromethanesulfonimide having a purity of 99% or more and a water content of 100 ppm or less: (CF ₃ SO ₂ ) ₂ NLi 2
6.5 g (98% yield) was obtained. The physical properties of the obtained substance were as follows. Melting point: 230 ° C. ¹³ C-NMR (DMSO, δ): 120.9 (q, J = 320 Hz) ¹⁹ F-NMR (DMSO, δ): -73.9 (S) Example 3 (tetrabutylammonium bistrifluoromethanesulfonylimidate) Production) 15.7 g of the bistrifluoromethanesulfonimide obtained in Example 1 and 170 ml of pure water were charged into a 200 ml glass reactor to form a homogeneous solution. To this, 16.1 g of tetrabutylammonium bromide was added and reacted at room temperature for 1 hour. After the crystallized white crystals were separated by filtration, they were sufficiently washed with water. The obtained crystal was dried at 120 ° C., and tetrabutylammonium bistrifluoromethanesulfonylimidate: (CF ₃ SO
₂₎ to give a ₂ NNBu ₄ 18.0g (70% yield).

Example 4 (Production of bispentafluoroethanesulfonimide) The reaction was carried out under the same conditions as in Example 1 except that pentafluoroethanesulfonyl chloride was used instead of trifluoromethanesulfonyl chloride. Ethane sulfonimide: (C ₂ F ₅ SO ₂ ) ₂ NH was obtained. The yield was 73% (based on ammonia). The physical properties of the obtained substance were as follows. Melting point: 42 ° C. ¹ H-NMR (CD ₃ CN, δ): 8.20 (bs, 1 H, NH) ¹⁹ F-NMR (CD ₃ CN, δ): -78.6 (6F, S), -116.9
(4F, S) IR (KBr, cm ^-1 ): 3425 (NH), 1345 (SO ₂ ), 1226 (CF
₂ ), 1189 (CF ₃ ), 1146 (SO ₂ ), 1099 (SO ₂ ), 984, 783, 746,
650, 621, 532 Example 5 (Production of lithium bispentafluoroethanesulfonimide) The reaction was carried out under the same conditions as in Example 2 except that bispentafluoroethanesulfonimide was used instead of bistrifluoromethanesulfonimide. As a result, lithium bispentafluoroethanesulfonimide: (C ₂ F ₅ SO ₂ ) ₂ NLi was obtained. The yield was 98%. The physical properties of the obtained substance were as follows. ¹⁹ F-NMR (CD ₃ CN, δ): -78.6 (6F, S), -117.0
(4F, S) IR (KBr, cm ^-1 ): 1367 (SO ₂ ), 133
5 (SO ₂ ), 1223 (CF ₂ ), 1181 (C
F ₃ ), 1098 (SO ₂ ), 980, 780,
760, 746, 649, 606, 525

Claims (3)

[Claims] 1. A compound of the general formula (I): (R _f SO ₂ ) ₂ NM (I) wherein R _f is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, and M is 1 Represents a valent cation. A method for producing a bisperfluoroalkylsulfonimide compound represented by the general formula (II): R _f SO ₂ Cl (II) wherein R _f is as defined above. A perfluoroalkylsulfonyl chloride represented by the general formula (III): R ¹ R ² R ³ N (III) wherein R ¹ , R ² and R ³ are the same or different; Represents an alkyl group of the formulas 1 to 5. The third shown by
A process for producing a bisperfluoroalkylsulfonimide compound, comprising reacting an amine or a mixture comprising a heterocyclic or aromatic amine in a solvent or without a solvent. 2. Formula (I): (R _f SO ₂ ) ₂ NM (I) wherein R _f is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, and M is 1 Represents a valent cation. A method for producing a bisperfluoroalkylsulfonimide compound represented by the general formula (III): R ¹ R ² R ³ N (III) in a solvent or under non-solvent conditions, wherein R ¹ , R ² and R ³ are the same or different and each represent an alkyl group having 1 to 5 carbon atoms. A tertiary amine, or a heterocyclic or aromatic amine,
General formula (II): R _f SO ₂ Cl (II) wherein R _f is as defined above. A method for producing a bisperfluoroalkylsulfonimide compound, characterized by introducing anhydrous ammonia into a mixed solution in which perfluoroalkylsulfonyl chloride is dissolved and reacting the mixture. 3. A compound of the formula (I): (R _f SO ₂ ) ₂ NM (I) wherein R _f is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, and M is 1 Represents a valent cation. A method for producing a bisperfluoroalkylsulfonimide compound represented by the general formula (III): R ¹ R ² R ³ N (III) wherein R ¹ , R ² and R ³ are the same or different and each represent an alkyl group having 1 to 5 carbon atoms. The third shown by
An amine or a mixed solution obtained by dissolving anhydrous ammonia in a heterocyclic or aromatic amine is mixed with a general formula (II): R _f SO ₂ Cl (II) wherein R _f is as defined above. A method for producing a bisperfluoroalkylsulfonimide compound, which comprises adding perfluoroalkylsulfonyl chloride represented by the formula