JP2001233849A - Method for producing sulfonimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple method for producing a sulfonimide. SOLUTION: This method for producing a sulfonimide represented by the general formula (3): [(RfSO2)2N]nM (3) [Rf, M and (n) are each as described in the specification], characterized by the imidization reaction of (2 moles) one or more sulfonic acid halides represented by the general formula (1): RfSO2X (1) with (one mole) a carboxamide which is represented by acetic amide and may have a halogen substituent, in the presence of a basic metal salt-based catalyst such as sodium carbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful method for producing a sulfonimide having a perhalogen group.

[0002]

2. Description of the Related Art Perhalogenated alkylsulfonimides are compounds useful as pharmaceutical intermediates, battery electrolyte intermediates, Lewis acid catalysts, and the like.

Conventionally, [(RfSO ₂ ) ₂ N] _n M [wherein Rf, M and n have the same meanings as in claim 1]. Is synthesized by amidating the corresponding perhalogenated alkyl sulfonic acid halide by using liquid ammonia and then dimerizing using hexamethyldisilazane. (D. DesMarteau et al., Ino
rganic Chem., 1984, 23, 3720-37.
23).

However, this method is not an industrial production method because it involves many reaction steps, uses expensive substances, and has a small yield of about 50%.

Further, there has been proposed a method of synthesizing a tertiary amine salt of sulfonimide by treating a corresponding perhalogenated alkylsulfonic acid halide with liquid ammonia and a tertiary amine at a low temperature of about -40 ° C. (JP-A-8-81436). However, reaction conditions at a low temperature using liquid ammonia require a large-scale cooling device and also require safety considerations because it handles dangerous gas such as ammonia.

As described above, a method for easily producing a sulfonimide having a perhalogen group such as a perhalogenated alkylsulfonimide on an industrial scale has not been established.

[0007]

An object of the present invention is to provide a simple method for producing a sulfonimide having a perhalogen group.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for producing a perhalogenated alkylsulfonimide derivative. As a result, when an imidation reaction was carried out by combining specific raw materials, the obtained reaction intermediate was obtained. The body is easily decomposed to amide due to the electron withdrawing property of perhalogen group,
It has been found that the desired sulphonimide can be easily produced in a short step by further imidizing the amide.

In addition, two different sulfonic halides (halides) with different perhalogenated alkyl substituents and halides, such as Rf ¹ SO ₂ X ¹ and Rf ² SO ₂ X
With ^2, it found that halide high yield by the reaction of the difference (halogen species), certain N- asymmetric sulfonimide with high selectivity ^(Rf ₁ SO 2 NHSO ₂ Rf ²⁾ is obtained ( Theoretically, three types of sulfonimides are obtained, but one is preferentially produced in this reaction due to a difference in reactivity.) Based on such findings, the present invention has been completed.

That is, the present invention relates to a compound represented by the general formula (1): RfSO ₂ X (1) wherein Rf represents a perhalogenated alkyl or alkenyl group having 1 to 22 carbon atoms or a perhalogenated aromatic group. Represent. X represents a halogen atom. 1 represented by
One or two kinds of sulfonic acid halides and a general formula (2) RCONH ₂ (2) wherein R represents an alkyl group which may have a halogen substituent. Is carried out in the presence of a basic metal salt catalyst containing a metal selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal and a transition metal. (3) [(RfSO ₂ ) ₂ N] _n M (3) wherein two Rf are the same or different and are the same as those described in the general formula (1). M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a rare earth metal or a transition metal. n represents an integer of 1 to 6. A method for producing a sulfonimide represented by the formula:

In the present invention, a sulfonimide represented by the general formula (3) [(RfSO ₂ ) ₂ N] _n M (3) is obtained by the following steps (a) and (b). And a method for producing a sulfonimide represented by the general formula (3). (a) General formula (1) RfSO ₂ X (1) [wherein, Rf has the same meaning as in claim 1. And one or two kinds of sulfonic acid halides represented by the general formula (2) RCONH ₂ (2) [wherein, R has the same meaning as in claim 1]. ]
The carboxylic acid amide represented by an alkali metal, an alkaline earth metal, a rare earth metal or a metal selected from the group of transition metals in the presence of a basic metal salt-based catalyst having a metal component selected from the group, a general formula (4) RfSO ₂ NHCOR (4) [wherein Rf and R represent the general formulas (1) and (2)
Has the same meaning as described in (B) an imide represented by the general formula (4) is further subjected to an imidation reaction with a sulfonic acid halide represented by the general formula (1) to obtain an imide represented by the general formula (3). A) obtaining a sulfonimide represented by

At the same time, the present invention provides a compound represented by the general formula (1): RfSO ₂ X (1) wherein Rf is as defined in claim 1. And a sulfonic acid halide represented by the general formula (2) RCONH ₂ (2) [wherein, R has the same meaning as defined in claim 1]. ]
Is subjected to an imidation reaction in the presence of a basic catalyst to obtain a carboxylic acid amide represented by the general formula (4): RfSO ₂ NHCOR (4) [wherein Rf and R represent the general formulas (1) and (2)
Has the same meaning as described in To obtain an imide represented by the formula
Furthermore, the imide represented by the general formula (4) is hydrolyzed, wherein the general formula (5) RfSO ₂ NH ₂ (5) wherein Rf is a compound represented by the general formula (1) Is synonymous with A method for producing a sulfonamide represented by the formula:

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Rf in a sulfonic acid halide represented by the general formula (1) is exemplified by a perhalogenated alkyl or alkenyl group having 1 to 22 carbon atoms or a perhalogenated aromatic group. Is done. Among them, from the viewpoint of reactivity, a perfluoroalkyl group, a perchloroalkyl group, a perfluoroaromatic group, a perchloroaromatic group, and the like are preferable.

X in the sulfonic acid halide represented by the general formula (1) is a halogen atom, and F, Cl,
Examples of Br and I include, preferably, F and Cl.

Specific examples of the sulfonic acid halide represented by the general formula (1) include perhalogenated alkanes (C
1-22) sulfonic acid chloride, perhalogenated alkane (C1-22) sulfonic acid fluoride, perhalogenated alkane (C1-22) sulfonic acid bromide, perhalogenated alkene (C2-22) sulfonic acid chloride,
Perhalogenated alkene (C2-22) sulfonic acid fluoride, perhalogenated alkene (C2-22) sulfonic acid bromide and perhalogenated benzenesulfonic acid chloride, perhalogenated benzenesulfonic acid fluoride, perhalogenated benzenesulfonic acid bromide, etc. Perhalogenated aromatic sulfonic acid halide and the like. Among them, perhalogenated alkanes (C1-22)
Sulfonic acid halides (F, Cl) or perhalogenated benzene sulfonic acid halides (F, Cl) are recommended.

The group R in the carboxylic acid amide represented by the general formula (2) is not particularly limited as long as it is an alkyl group, and may have a halogen substituent. In consideration of the above, those having a small steric hindrance and a small molecular weight are preferable, and examples thereof include an alkyl group having 1 to 12 carbon atoms, and more specifically, an alkyl group such as a methyl, ethyl, propyl, isopropyl, butyl, or isobutyl group. And a trifluoromethyl group, a trichloromethyl group, a difluoromethyl group, a dichloromethyl group, a monofluoromethyl group, a monochloromethyl group and the like.

Specific examples of the compound in the carboxylic acid amide represented by the general formula (2) include carboxylic acid amides such as acetic acid amide, propionic acid amide, butyric acid amide, monofluoroacetic acid amide, difluoroacetic acid amide, and trifluoroacetic acid. Halogenated alkylcarboxylic acid amides such as acetic acid amide, monochloroacetic acid amide, dichloroacetic acid amide, and trichloroacetic acid amide are exemplified, and among them, acetic acid amide, trifluoroacetic acid amide, and trichloroacetic acid amide are recommended.

Alkali metals and alka usable in the present invention
Selected from the group of lithium earth metals, rare earth metals or transition metals
Examples of basic metal salt catalysts containing a metal as a component include M ′
_mA _nAre exemplified.

[0019] M _'m A _n M in the metal salts represented by' is an alkali metal, alkaline earth metal, transition metal or rare earth metal is exemplified. m and n are the same or different and each represents an integer of 1 to 6. Examples of the alkali metal include lithium (Li), potassium (K), and sodium (Na). Examples of the alkaline earth metal include beryllium (Be), magnesium (Mg), and calcium (C).
a), strontium (Sr) and the like, and as the transition metal, titanium (Ti), iron (Fe), cobalt (C
o), nickel (Ni), copper (Cu), zinc (Zn),
Ruthenium (Ru), rhodium (Rh), silver (Ag),
Tungsten (W) and the like are exemplified, and as the rare earth metal, neodymium (Nd), europium (Eu), terbium (Tb), cerium (Ce), erbium (E
r), ytterbium (Yb), samarium (Sm) and the like.

[0020] Also, M _'m A A of _n represents an anion, in particular hydroxide anions as monovalent anion (O
H ⁻ ), nitrate anion (NO ₃ ⁻ ), cyan anion (CN ⁻ ), and hydride anion (H ⁻ ) are carbonate anions (CO ₃ ²⁻ ) and sulfate anions (SO ₄ ²⁻ ) as divalent anions. but phosphate anion _(PO ^{4 3-),} and the like as a trivalent anion.

Among the above anions, a hydroxide anion,
A carbonate anion or the like is recommended, and more preferably a carbonate anion.

Further, an anion having four or more valences can be used. For example, a ferricyan anion [Fe (CN) ₆ ]
^{4- and the} like.

In addition, an anion represented by the general formula R- (COO) _x , an anion represented by the general formula R ′-(SO ₃ ) _x , and various organic acids such as R ″-(OSO ₃ ) _x An anion can also be used, wherein R, R 'and R "each represent an alkyl group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an aromatic group or a heterocyclic group. x shows the integer of 1-6.

As the basic metal salt catalyst used in the present invention,
Specifically, Li₂CO₃, LiOH, Na₂CO₃, N
aOH, NaH, K₂CO₃, KOH, KH, BeCO
₃, MgCO₃, Ca₂CO₃, SrCO₃, Ti
₂(CO₃)₂, FeCO₃, CoCO₃, NiC
O₃, CuCO₃, ZnCO₃, Ru₂(CO₃)₃,
Rh₂(CO₃)₃, Ag₂CO₃, Nd₂(CO₃)
₃, Eu₂(CO₃)₃, Tb ₂(CO₃)₃, Ce₂
(CO₃)₃, Sm₂(CO₃)₃Etc. are exemplified.
But Li₂CO₃, LiOH, K₂CO₃, KOH, N
a₂CO₃, NaOH, MgCO₃, CaCO₃Etc. are anti
It is recommended from the viewpoint of responsiveness, and more preferably Li₂CO₃,
Na₂CO₃, K₂CO₃, MgCO₃, CaCO₃But
Recommended.

In the present invention, a basic metal salt-based catalyst is used as a catalyst. In addition, amines such as primary amines, secondary amines and tertiary amines which are common basic catalysts can be used. is there. For example, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, pyridine and the like are exemplified.

Further, metal catalysts such as lithium metal, potassium metal, sodium metal, and magnesium metal, and oxides thereof can also be used.

The sulfonimide represented by the general formula (3) according to the present invention comprises one or two of the sulfonimides represented by the general formula (1).
Is obtained by an imidation reaction between a sulfonic acid halide of any kind and a carboxylic acid amide represented by the general formula (2) in the presence of a basic metal salt-based catalyst (this reaction is carried out with sulfonic acid halide and carboxylic acid). Amide and a 2: 1 molar ratio reaction).

Rf in the sulfonimide represented by the general formula (3) has the same meaning as that described in the general formula (1).

M in the sulfonimide represented by the general formula (3) is the basic metal salt catalyst M ′ used in the reaction.
or it is derived from _m A _n, or are those in which a desalted hydrogen atoms, specifically, a hydrogen atom, an alkali metal, alkaline earth metal, transition metal or rare earth metal is exemplified.

Specific examples of the sulfonimide compound represented by the general formula (3) include: 1) N-symmetric type (a compound in which two identical substituents are bonded to a nitrogen atom). (C _x F _{2x + 1} SO ₂ ) ₂ N _n M (x = 1 to 2
_{2), · (C x Cl} 2x + 1 SO 2) 2 N n M (x = 1~2
_{2), · (C x F} 2x-1 SO 2) 2 N n M (x = 2~2
2), · (C _nx Cl _2nx-1 SO ₂ ) ₂ N _nm (x = 2 to ₂ )
_{22), · (C 6 F} 5 SO 2) 2 N n M, · (CF 3 -C 6 F 5 SO 2) 2 N n M, · (CCl 3 -C 6 Cl 5 SO 2) 2 N n M , 2) N-asymmetric (of different substituents on the nitrogen atom is bonded _{two) · (C x F 2x +} 1 SO 2) (C y F 2y + 1 SO 2)
_{N n M (x, y =} 1~22), · (C x Cl 2x + 1 SO 2) (C y Cl 2y + 1 SO
₂ ) N _n M (x, y = 1 to 22), (C _x F _{2x + 1} SO ₂ ) (C _y Cl _{2y + 1} S
_{O 2) N n M (x} , y = 1~22), · (C x F 2x-1 SO 2) (C y F 2y-1 SO 2)
_{N n M (x, y =} 2~22), · (C x Cl 2x-1 SO 2) (C y Cl 2y-1 SO
₂ ) N _n M (x, y = 2 to 22), (C _x F _2x-1 SO ₂ ) (C _y Cl _2y-1 S
(O ₂ ) N _n M (x, y = 2 to 22), (C ₆ F ₅ SO ₂ ) (C _x F _{2x + 1} SO ₂ ) N _n M
(X = 1 to 22), (CF ₃ -C ₆ F ₄ SO ₂ ) (C _x F _{2x + 1} S
O ₂ ) N _n M (x = 1 to 22), (CCl ₃ -C ₆ Cl ₄ SO ₂ ) (C _x F _{2x + 1} S
O ₂ ) N _n M (x = 1 to 22), (C ₆ Cl ₅ SO ₂ ) (C _x F _{2x + 1} SO ₂ ) N _n
M (x = 1 to 22), (C ₆ F ₅ SO ₂ ) (C _x Cl _{2x + 1} SO ₂ ) N _n
M (x = 1 to 22), (C ₆ Cl ₅ SO ₂ ) (C _x Cl _{2x + 1} SO ₂ ) N
_n M (x = _1~22), etc. are exemplified.

Among them, it is preferable to use an N-symmetric type: (C _x F _{2x + 1} SO ₂ ) ₂ N _n M (x = 1 to ₂ )
_{2), · (C x Cl} 2x + 1 SO 2) 2 N n M (x = 1~2
_{2), · (C 6 F} 5 SO 2) 2 N n M, · (CCl 3 -C 6 Cl 5 SO 2) 2 N n M is recommended, N- asymmetric as _{· (C x F 2x + 1} SO 2 _{) (C y F 2y + 1} SO 2)
_{N n M (x, y =} 1~22), · (C 6 F 5 SO 2) (C x F 2x + 1 SO 2) N n M
(X = 1 to 22), etc. are recommended.

A specific method for producing the imide represented by the general formula (3) is based on the following three steps (scheme 1).

Scheme 1

First Step (Route a) One or two sulfonic acid halides represented by the general formula (1) RfSO ₂ X (1) and the general formula (2) RCONH ₂ (2) By subjecting the perhalogenated carboxylic acid amide to an imidization reaction in an organic solvent under a basic catalyst,
General formula (4) RfSO ₂ NHCOR as a reaction intermediate (4) An imide represented by the following formula is obtained.

Second Step (Route b) The imide of general formula (4) is hydrolyzed under the reaction conditions to form a sulfonamide of general formula (5) RfSO ₂ NH ₂ (5).

Third Step (Route c) The sulfonamide represented by the general formula (5) further undergoes an imidation reaction with the sulfonic acid halide represented by the general formula (1) to obtain the desired compound represented by the general formula (3) ).

The above three-stage reaction can be isolated at each stage, but is preferably performed in one pot. In particular, the imide represented by the general formula (4) is hydrolyzed to form a sulfonamide represented by the general formula (5) (route c), and the imide represented by the general formula (1) It is conceivable that the perhalogenated alkylcarbonyl group is eliminated while reacting to give the desired sulfonimide salt represented by the general formula (3) (route d).
(However, the sulfonamide represented by the general formula (5) can be isolated, and route c is considered to be the main route.)

When an amine catalyst such as a primary amine, a secondary amine or a tertiary amine is used as a reaction catalyst for imidization, the reaction stops at the first stage (route a),
The resulting product may be an imide represented by the general formula (4).

[0039] In contrast, when a basic metal salt-based catalyst represented by M _'m A _n, imides represented by the general formula (4) is easily hydrolyzed, amides of the general formula (5) To form the desired sulfonimide of the general formula (3).

Hereinafter, the imidization reaction of the present invention will be described in detail. Regarding the reaction conditions of the imidation reaction, the routes a, b, and c, the solvents, the reaction temperatures, and the like are all the same, and even if the reaction is performed in one pot from the route a to the route c, the routes a, b , C can be applied individually, the following reaction conditions can be applied.

As the organic solvent used for the imidization reaction, an aprotic solvent is used, and examples thereof include ether solvents such as THF, diethyl ether and diglyme, amide solvents such as dimethylformamide and diethylformamide, and DMSO. Examples include preferably THF, which has high solubility of various substrates (sulfonic acid halides, carboxylic acid amides, and catalysts) and is easily post-treated.

The amount of the solvent used is not particularly limited, but is preferably 1 to 100 parts by weight based on the total amount (1 part by weight) of the sulfonic acid halide and the carboxylic acid amide in consideration of economy, reaction rate and the like. Parts by weight, preferably 3 to 30
Use about parts by weight.

In this reaction, the sulfonic acid halide and the carboxylic acid amide are reacted at a molar ratio of 2: 1. Therefore, the amount of the sulfonic acid halide and the carboxylic acid amide used is 2 moles per 2 moles of the sulfonic acid halide. Examples of the carboxylic acid amide include 0.5 to 2.5 mol, preferably 0.1 to 2.5 mol.
8-1.5 moles is recommended.

The amount of the basic catalyst (basic metal salt-based or amine-based catalyst) is not particularly limited, but considering the reaction yield and the like, it is necessary to trap by-product halogen ions during the reaction. About 1.0 to 10.0 moles, preferably 2.0 moles per mole of halide
~ 6.0 mol is recommended.

When it is desired to terminate the reaction with the compound of the general formula (4), an amine-based catalyst is advantageous. On the other hand, when the reaction is further carried out to obtain an imide of the general formula (3), M ′ _{n Am} The metal salt-based catalysts represented are advantageous.

As will be described later, the reaction is represented by the general formula (5)
In If you want to stop an amide represented, M as the catalyst _'n
Using a metal salt catalyst represented by A _m, further, as the amount of the sulfonic acid halide and a carboxylic acid amide, a molar ratio, the carboxylic acid amide 0.5 to sulfonic acid halide mole. 5 moles, preferably 0.8-1.
It is recommended to use 2 moles.

The reaction pressure for the imidization reaction may be normal pressure or under pressure, for example, 1 to 1000 atm, preferably 1 to 10 atm.

The reaction temperature is, for example, from -70 ° C to 150 ° C, preferably from 30 to 130 ° C.

The reaction time varies depending on the reaction conditions and the type of the starting material, but is preferably 1 hour to 100 hours, and preferably 1 hour to 10 hours.

In the present invention, when two kinds of sulfonic acid halides having different alkyl substituents are used as the sulfonic acid halide represented by the general formula (1), for example, they are represented by the general formula (6) In the case of a mixture of a compound and a compound represented by the general formula (7), Rf ¹ —SO ₂ X ¹ (6) Rf ² —SO ₂ X ² (7) [wherein, Rf ¹ and Rf ² are different from each other. And is synonymous with Rf. X ¹ and X ² are different from each other and have the same meaning as X. In the first step, the sulfonic acid halide (6) having a highly reactive halogen selectively undergoes an imidization reaction to form an imide represented by the general formula (4). The imide is subsequently decomposed into an amide represented by the general formula (5), and then reacted with a sulfonic acid halide (7) having a halogen with low reactivity, thereby obtaining a sulfone represented by the general formula (3). An imide (here represented by the general formula (8)) is obtained. The above steps are shown in Scheme 2. Here, Rf ¹ and Rf ² are different and have the same meaning as Rf, and X ¹ and X ² are also different and have the same meaning as X. Furthermore, the reactivity of the halogen shall have higher X ¹ than X ^2.

Scheme 2

The method for preferentially obtaining a specific sulfonimide using two kinds of sulfonic acid halides having different reactivities according to the present invention is as follows: 1) X ¹ and X ² as halides having different reactivities 2) that the sulfonic acid halide structure has an electron-withdrawing group such as a perhalogenated alkyl group; 3) the basicity of the basic catalyst used is moderate It requires basicity of about sodium, potassium carbonate and lithium carbonate.), And the obtained intermediate compound of the general formula (4) is easily decomposed by this base. What you get.

Particularly, theoretically, in addition to the compound represented by the general formula (8), (Rf ¹ SO ₂ ) ₂ NH, (Rf ² SO
_{Although 2} ) ₂ NH should be obtained, it is epoch-making that the compound of the general formula (8) can be preferentially produced due to the difference in reactivity between X ¹ and X ² .

Further, the present invention provides a method for producing a sulfonamide represented by the general formula (5). This production method was found in the step of producing a sulfonimide represented by the general formula (3) using a sulfonic acid halide of the general formula (1) and a carboxylic acid amide as raw materials.

That is, the method for producing the sulfonamide represented by the general formula (5) is achieved through the route a and the route b in the scheme 1.

Accordingly, the sulfonic acid halide, carboxylic acid amide and metal catalyst of the general formula (1) as starting materials are as follows:
Those used in the process for producing the sulfonimide represented by the general formula (3) can be diverted.

Among them, the molar ratio of the sulfonic acid halide and the carboxylic acid amide used as raw materials is 1 mol of the carboxylic acid amide to 1 mol of the carboxylic acid amide.
By carrying out the reaction using 5 to 1.5 mol, preferably 0.8 to 1.2 mol, the sulfonamide represented by the general formula (5) is preferentially obtained (this reaction is carried out using sulfonic acid The reaction between the halide and the carboxylic acid amide is a 1: 1 molar ratio).

The sulfonimide represented by the general formula (3) or the sulfonamide represented by the general formula (5) obtained by the above method can be purified by a conventionally known purification method such as crystallization and column chromatography (ion chromatography). (Exchange, silica gel) or the like.

The sulfonimide represented by the general formula (3) obtained by the production method of the present invention is usually obtained as a salt of a basic catalyst used as a catalyst (where M = alkali in the general formula (3)) Metal, alkaline earth metal, rare earth metal or transition metal) in many cases. In this case, 1N-HC
1, free form by treatment with a dilute acid such as 1N-H ₂ SO ₄ or ion exchange treatment (M =
H).

The sulfonimide obtained in the present invention has a lithium salt useful as an electrolyte for a lithium battery,
Further, alkali metal salts such as sodium and potassium, rare earth complexes such as lanthanum, and transition metal complexes such as scandium are useful as Lewis acid catalysts and catalysts for various reactions.

Further, a complex of a rare earth metal ion such as Eu and Nd with a sulfonimide is very useful as a light emitting material.

[0062]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

¹⁹ F, ¹³ C and ¹ H-NMR were measured using JEOL NMR EX-270. -IR was measured using Perkin-Elmer 1720-X. -The absorption characteristics were measured using Shimadzu UV-2100. Elemental analysis was measured using Perkin-Elmer 240C. -The light emission characteristic was measured using JASCO SS-25.

Example 1 Preparation of C ₄ F ₉ SO ₂ NKSO ₂ C ₄ F _{9 In} a 100 ml three-necked flask equipped with a cooling tube, 30 m of THF was added.
1, CF ₃ CONH ₂ (3.3 g, 28 mmol) (manufactured by Wako Pure Chemical Industries, Ltd.) and potassium carbonate (10.0 g, 72 mm)
ol) (manufactured by Kanto Chemical Co.) at room temperature under nitrogen atmosphere
Stirred for hours. Subsequently, C ₄ F ₉ SO ₂ F (8.5
g, 28 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) and refluxed for 3 hours. At this point, the reaction mixture was analyzed and found to be C
It was confirmed that ₄ F ₉ SO ₂ NH ₂ was generated. Then, C ₄ F ₉ SO ₂ F (8.5 g, 2
8 mmol), and the mixture was further refluxed for 3 hours.

Subsequently, THF was distilled off under reduced pressure.
Dissolve the residue in acetone,₂C0 ₃, KF and other insoluble salts
Were removed by filtration. Continue to evaporate acetone
The obtained solid is washed with ether, and further washed with ethanol.
Recrystallized in water to give colorless needle crystals C₄F₉SO₂NKSO
₂C₄F₉(13.4 g, yield 77%) was obtained.

¹⁹ F-NMR (solvent CD ₃ OD, standard reagent hexafluorobenzene): −79.37 (t, 6
_{F, CF 3), - 111.57} (t, 4F, CF 2),
_{-119.29 (br, 4F, CF 2} ), - 124.3
5 (br, 4F, CF ₂ ) ppm

IR: 1347 (S = O), 1235 (C
-F), 1201 (CF), 1126 (SO) cm
^-1

Example 2 C₆F₅S0₂NKSO₂C₆
F₅ In Example 1, C₄F₉SO₂Instead of using F
C₆F₅SO₂Cl (15.0 g, 56 mmol) (East
(Kyo Kasei Co., Ltd.)₃CONH ₂Instead of
CH₃CONH₂(1.7 g, 28 mmol mol)
The same procedure as in Example 1 was repeated except that white crystals C were used.
₆F₅SO₂NKSO₂C₆F₅(7.8 g, yield 54
%).

19F-NMR (solvent CD ₃ OD, standard reagent hexafluorobenzene): -137.13 (o-, 4F,
_{CF 2), - 153.00 (p-} , 2F, CF), - 1
_{61.66 (m-, 4F, CF 2} ) ppm

IR: 1489 (C ₆ F ₅ ), 1306
(S = O), 1252 (C-F), 1226 (C-
F), 1116 (SO) cm ^-1

Example 3 C ₈ F ₁₇ SO ₂ NKSO ₂ C ₈ F _{17 In} a 100 ml three-necked flask equipped with a condenser, 30 m of THF was added.
1, CF ₃ CONH ₂ (3.3 g, 28 mmol) (manufactured by Wako Pure Chemical Industries) and triethylamine (11.5 g, 11
4 mmol), and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour. Subsequently, C ₈ F ₁₇ SO ₂ F (14.1 g, 28
mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) and refluxed for 3 hours. At this point, it was confirmed that a triethylamine salt of C ₈ F ₁₇ SO ₂ NHCOCF ₃ was generated.
The reaction solution was poured into ether, and the ether layer was washed with ion-exchanged water. Further, the ether layer was dried using magnesium sulfate, and then the ether layer was concentrated to obtain C ₈ F ₁₇ S
O ₂ NHCOCF ₃ triethylamine salt (15.6
g, 80%).

19F-NMR (solvent CD ₃ OD, standard reagent hexafluorobenzene): -73.29 (m, 3F, CF
_{3), - 79.23 (t,} 3F, CF 3), - 112.
_{32 (t, 2F, CF 2} ), - 118.32 (br, 2
_{F, CF 2), - 120.05} (br, 6F, C
F ₂ ), -124.40 (br, 2F, CF ₂ ) ppm

1H-NMR (CD ₃ OD, standard reagent hexafluorobenzene): 1.3 (t, 9H, CH 3),
3.3 (q, 6H, CH2) ppm

IR: 3106 (NH), 2822 (C
-H), 1664 (C = O), 1326 (S = O), 1
220 (CF), 1138 ((CF), 1122
(SO) cm ^-1

Subsequently, C ₈ F ₁₇ SO ₂ NHCOCF ₃
-Dissolve the triethylamine salt in THF (30 ml), further add potassium carbonate (15.0 g) and C ₈ F ₁₇
SO ₂ F (14.1 g, 28 mmol) was added and refluxed for 3 hours. During the reaction, the reaction solution was analyzed by HPLC, and it was found that C ₈ F ₁₇ SO ₂ NH ₂ was partially generated. Thereafter, THF was distilled off under reduced pressure, and the residue was dissolved in acetone, and insoluble salts such as K ₂ CO ₃ and KF were removed by filtration. Subsequently, acetone was distilled off, and the solid obtained was washed with ether and further recrystallized in ethanol to obtain colorless needle crystals C ₈ F ₁₇ SO ₂ N
KSO ₂ C ₈ F ₁₇ (20.5 g, yield 72%) was obtained.

¹⁹ F-NMR (solvent CD ₃ OD, standard reagent hexafluorobenzene): −79.20 (t, 6F, C
F ₃ ), −112.57 (t, 4F, CF ₂ ), −11
_{8.27 (br, 4F, CF 2} ), - 119.39 (b
_{r, 12F, CF 2),} - 120.61 (br, 4F,
_{CF 2), - 124.17 (br} , 4F, CF 2) ppm

IR: 1354 (S = O), 1249 (C
-F), 1202 (CF), 1152 (SO) cm
^-1

Example 4 Instead of using C ₄ F ₉ SO ₂ NKSO ₂ C ₆ F ₅ C ₄ F ₉ SO ₂ F, C ₄ F ₉ SO ₂ F
(8.5 g, 28 mmol) and C ₆ F ₅ SO ₂ Cl
(7.5 g, 28 mmol mol) _C 4 _F 9 _SO 2 in the same way as any other embodiment 1 using NKS0 ₂ C ₆ F
₅ was obtained as white crystals (10.8 g, yield 68%).

¹⁹ F-NMR (solvent CD ₃ OD, standard reagent hexafluorobenzene): −79.38 (m, 3
_{F, CF 3), - 111.57} (t, 2F, CF 2),
_{-119.29 (br, 2F, CF 2} ), - 124.3
_{4 (br, 2F, CF 2} ), - 135.56 (o-, 2
_{F, CF 2), - 151.12} (p-, 1F, CF),
_{-162.20 (m-, 2F, CF 2} ) ppm

IR: 1495 (C6F5), 1349
(S = O), 1236 (C-F), 1205 (C-
F), 1149 (SO) cm ^-1

UV (solvent methanol): 227 nm (K
Absorption band), 268 nm (B absorption band)

Example 5 30 ml of THF was added to a 100 ml three-necked flask equipped with a C ₄ F ₉ SO ₂ NH ₂ condenser under a nitrogen atmosphere, and then CF ₃ CONH
₂ (3.3 g, 28 mmol) (manufactured by Wako Pure Chemical Industries) and potassium carbonate (10.0 g) (manufactured by Kanto Chemical Co., Ltd.) were added, and the mixture was stirred for 1 hour. Subsequently, C ₄ F ₉ SO ₂ F (6.5 g, 22 mm
ol) (manufactured by Tokyo Chemical Industry Co., Ltd.) and refluxed under normal pressure for 3 hours. Subsequently, THF was distilled off under reduced pressure, and the residue was dissolved in ether, washed with water three times, dried over magnesium sulfate, filtered, and then ether was distilled off. Subsequently, the residue was sublimated at 2 mmHg and 55 ° C. to obtain white crystals C ₄ F ₉ SO ₂ NH ₂ (3.7 g, 58%).

19F-NMR (solvent acetone-d ₆ , standard reagent hexafluorobenzene): -79.33 (t, 3F,
_{CF 3), - 112.21 (t} , 2F, CF 2), - 1
_{19.51 (p, 2F, CF 2} ), - 124.33
(H, 2F, CF ₂ ) ppm

1H-NMR (solvent acetone-d ₆ , standard reagent hexafluorobenzene): 8.1 (br, H, NH)
ppm

IR: 3347, 3181, 3071 (N
-H), 1379 (S = O), 1200 (C-F), 1
140 (CF), 1045 (SF) cm ^-1

Example 6 In a 100 ml three-necked flask equipped with a C ₄ F ₉ SO ₂ NKSO ₂ C ₆ F ₅ condenser, THF 20 m
l, C ₄ F ₉ SO ₂ NH ₂ obtained in Example 5 (5.6 g,
19 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) and potassium carbonate (1
(0.0 g, 72 mmol) and stirred for 1 hour at room temperature under a nitrogen atmosphere. Subsequently, C ₆ F ₅ SO ₂ Cl
(5.0 g, 19 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was refluxed under normal pressure for 3 hours. Subsequently, THF was distilled off under reduced pressure, and the residue was dissolved in acetone, and K ₂ CO ₃ , KF and the like were removed by filtration. Subsequently, the residue obtained by distilling off acetone is washed with ether and then recrystallized in ethanol to give C ₄ F ₉ SO ₂ NKSO ₂ C
The ₆ F ₅ as a white crystalline (10.4 g, yield 94
%).

¹⁹ F-NMR (solvent CD ₃ OD, standard reagent hexafluorobenzene): −79.37 (m, 3F, C
_{F 3), - 111.57 (t} , 2F, CF 2), - 11
_{9.29 (br, 2F, CF 2} ), - 124.35 (b
_{r, 2F, CF 2),} - 135.56 (o-, 2F, C
F ₂ ), −151.11 (p−, 1F, CF), −16
_{2.20 (m-, 2F, CF 2} ) ppm

IR: 1495 (C6F5), 1347
(S = O), 1235 (C-F), 1203 (C-
F), 1147 (SO) cm ^-1

UV (solvent methanol): 227 nm (K
Absorption band), 268 nm (B absorption band)

[0090] _{C 4 F 9 SO 2 NKSO C} 4 F 9 SO 2 obtained in desalination Example 6 _{2 C 6 F 5 NKSO 2 C} 6 F 5
(10.4 g, 18 mmol) was stirred in a 25% H ₂ SO ₄ aqueous solution for 1 hour, the reaction solution was extracted with ether, and the ether layer was further distilled off.
C ₄ F ₉ SO ₂ NHSO ₂ C ₆
F ₅ (7.8 g, yield 80%) was obtained.

¹⁹ F-NMR (solvent CD ₃ OD, standard reagent hexafluorobenzene): −79.39 (m, 3
_{F, CF 3), - 111.54} (t, 2F, CF 3),
-119.27 (br, 2F, CF2), -124.3
4 (br, 2F, CF2), -135.32 (o-, 2
F, CF), -149.53 (p-, 1F, CF),-
_{161.50 (m-, 2F, CF 3} ) ppm

IR: 1495 (C ₆ F ₅ ), 1345
(S = O), 1235 (C-F), 1202 (C-
F), 1146 (SO) cm ^-1

UV: (solvent methanol) 227 nm (K
Absorption band), 268 nm (B absorption band)

Application Example C ₈ F ₁₇ SO ₂ NKSO ₂ C ₈ F ₁₇ obtained in Example 3
(20.5 g, 20 mmol) was stirred in a 25% H ₂ SO ₄ aqueous solution for 1 hour, the reaction solution was extracted with ether, and the ether layer was further distilled off.
By sublimation at C ₈ F ₁₇ SO ₂ NHSO ₂ C
₈ F ₁₇ (16.0 g, 82%) was obtained.

C ₈ F ₁₇ SO ₂ NHSO ₂ C ₈ F
₁₇ (1.0 g, 1 mmol) was dissolved in 30 ml of distilled water, and then Nd ₂ O ₃ (600 mg, 1.8 mmol) was dissolved.
lmol) and stirred at room temperature for 3 days. The precipitated solid was filtered, washed with water, dissolved in methanol and centrifuged,
Unreacted Nd ₂ O ₃ was removed by filtration. The methanol was distilled off and the complex [(C ₈ F ₁₇ SO ₂ ) ₂ N] ₃ Nd
(206 mg, 20% yield).

[0096] The resulting complex was dissolved in acetone -d ₆ (concentration 0.05 mol / l), to measure the emission characteristics using JASCO Corp. SS-25. As a result, the excitation wavelength 5
85 nm, emission wavelength 1.06 μm, quantum yield 3.2%,
The light emission lifetime was 13 μs.

[0097]

According to the production method of the present invention, the sulfonic acid halide and the carboxylic acid amide are imidized under mild conditions in the presence of a basic metal salt-based catalyst, thereby facilitating the reaction in a short step. It has become possible to produce sulfonimide. Patent applicant Shin Nippon Rika Co., Ltd.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (reference) // C07B 61/00 300 C07B 61/00 300 C07F 1/06 C07F 1/06 F term (reference) 4H006 AA02 AC61 BA02 BA06 BA08 BA10 BA14 BA17 BA32 BA34 BA36 BA69 BC31 BE12 4H039 CA80 CD10 CD20 CD90 4H048 AA02 AC61 BA02 BA03 BA05 BA06 BA07 BA08 BA10 BA19 BA20 BA21 BA23 BA24 BA28 BA29 BA32 BE12 VA11 VA30 VA50 VB10

Claims (9)

[Claims] 1. A compound represented by the general formula (1): RfSO ₂ X (1) wherein Rf represents a perhalogenated alkyl or alkenyl group having 1 to 22 carbon atoms, or a perhalogenated aromatic group. X represents a halogen atom. 1 represented by
One or two kinds of sulfonic acid halides and a general formula (2) RCONH ₂ (2) wherein R represents an alkyl group which may have a halogen substituent. Is carried out in the presence of a basic metal salt catalyst containing a metal selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal and a transition metal. General formula
(3) [(RfSO ₂ ) ₂ N] _n M (3) [wherein the two Rf are the same or different and are the same as those described in the general formula (1). M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a rare earth metal or a transition metal. n represents an integer of 1 to 6. ] The manufacturing method of the sulfonimide represented by this. 2. Formula (3) [(RfSO ₂ ) ₂ N] _n M (3) wherein Rf, M and n are the same as above. The sulfonimide represented by the following formula (3) is obtained by the following steps (a) and (b):
A method for producing a sulfonimide represented by the formula: (a) General formula (1) RfSO ₂ X (1) wherein Rf and X are the same as described above. And one or two sulfonic acid halides represented by the general formula (2) RCONH ₂ (2) wherein R is the same as defined above. A carboxylic acid amide represented by the formula (I) in the presence of a basic metal salt catalyst containing a metal selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal and a transition metal; Formula (4) RfSO ₂ NHCOR (4) [wherein Rf and R represent the general formulas (1) and (2)
Is the same as that described in the above. (B) an imide represented by the general formula (4) is further subjected to an imidation reaction with a sulfonic acid halide represented by the general formula (1) to obtain an imide represented by the general formula (3). A) obtaining a sulfonimide represented by 3. The formula (3) [(RfSO ₂ ) ₂ N] _n M (3) wherein Rf, M and n are the same as above. The sulfonimide represented by the formula (3) is obtained by the following steps (a) to (d):
A method for producing a sulfonimide represented by the formula: (a) General formula (1) RfSO ₂ X (1) wherein Rf is the same as above. And one or two sulfonic acid halides represented by the general formula (2) RCONH ₂ (2) wherein R is the same as defined above. A carboxylic acid amide represented by the formula (I) in the presence of a basic metal salt catalyst containing a metal selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal and a transition metal; Formula (4) RfSO ₂ NHCOR (4) wherein Rf and R are the same as above. (C) an imide represented by the general formula (4) is decomposed by the basic metal salt-based catalyst to obtain an imide represented by the general formula (5): RfSO ₂ NH ₂ (5) , Rf have the same meanings as those described in formula (1). (D) forming a sulfonamide represented by the formula:
A step in which a sulfonamide represented by the general formula (5) further undergoes an imidation reaction with a sulfonic acid halide represented by the general formula (1) to form a sulfonimide represented by the general formula (3). 4. One or two kinds represented by the general formula (1)
4. The method according to claim 1, wherein the carboxylic acid amide represented by the general formula (2) is used in an amount of 0.5 to 1.5 mol per 2 mol of the sulfonic acid halide. The method for producing a sulfonimide described in the above item. 5. A compound represented by the general formula (6) and a compound represented by the general formula (7) wherein the sulfonic acid halide represented by the general formula (1) is Rf ¹ SO ₂ X ¹ (6) Rf ² SO ₂ X ² (7) [wherein, Rf ¹ and Rf ² are different from each other and have the same meaning as Rf. X ¹ and X ² are different from each other and have the same meaning as X. Wherein the sulfonimide represented by the general formula (3) is represented by the general formula (8): (Rf ¹ SO ₂ ) (Rf ² SO ₂ ) N _n M (8) wherein Rf ¹ and Rf ² , M and n are the same as above. The method for producing a sulfonimide according to any one of claims 1 to 3, which is represented by the following formula: 6. A carboxylic acid amide represented by the general formula (2)
Group R in CH is CH ₃, CCl₃Or CF₃Is
The sulfonimide according to any one of claims 1 to 3.
Manufacturing method. 7. The method according to claim 1, wherein the basic metal salt-based catalyst is Li ₂ CO ₃ ,
_2. One or more kinds selected from the group consisting of Na ₂ CO ₃ , K ₂ CO ₃ , MgCO ₃ , and CaCO _3.
The method for producing a sulfonimide according to any one of claims 1 to 3. 8. A general formula (1) RfSO ₂ X (1) wherein Rf is the same as described above. And a sulfonic acid halide represented by the general formula (2): RCONH ₂ (2) wherein R is the same as defined above. Is subjected to an imidation reaction in the presence of a basic catalyst,
General formula (4) RfSO ₂ NHCOR as a reaction intermediate (4) wherein Rf and R are the same as above. RfSO ₂ NH ₂ (5) wherein the imide represented by the general formula (4) is hydrolyzed, and the imide represented by the general formula (4) is hydrolyzed. Is the same as ] The manufacturing method of the sulfonamide represented by this. 9. A carboxylic acid amide represented by the general formula (2) is used in an amount of 0.5 to 1.5 mol per 1 mol of the sulfonic acid halide represented by the general formula (1). The method for producing a sulfonamide according to claim 8.