JP2009215200A - Imidazolium derivative salt and its application - Google Patents

Abstract

〔式中、Ｒ^１はセチル基などを表し、Ｒ^２はメチル基などを表し、Ｒ^３はフェニル基などを表し、Ｘａ⁻はＩ⁻などを表す。〕
で表される化合物。
【選択図】なしPROBLEM TO BE SOLVED: To provide an ionic liquid having antibacterial activity.
The following general formula (I)
[Chemical 1]

Wherein, ^{R 1} represents a cetyl group, ^{R 2} represents a a methyl group, ^{R 3} represents a phenyl group, Xa ^- is I ^- represents the like. ]
A compound represented by
[Selection figure] None

Description

  The present invention relates to novel imidazolium derivative salts, pyrrolidinium derivative salts, and piperidinium derivative salts. These compounds can be used as antibacterial agents and the like.

  Ordinary salts such as salt are solid at room temperature, but there are also salts that are liquid at room temperature. Such a salt is generally called an ionic liquid. The ionic liquid has 1) vapor pressure close to zero, 2) flame retardancy, 3) excellent thermal stability, 4) ionic but low viscosity, 5) high partial pressure electrolysis, It is used for various applications such as solvents and battery electrolytes.

  Many compounds having properties as an ionic liquid have been reported for a long time, and the present inventor has also found a compound having properties as an ionic liquid among the derivatives of pyrimidine, and has previously filed an application (Patent Document 1). .

JP 2001-247572 A

  An object of the present invention is to provide a novel ionic liquid compound.

  As a result of intensive studies to solve the above problems, the present inventor has found a compound exhibiting properties as an ionic liquid in imidazolium derivative salts, pyrrolidinium derivative salts, and piperidinium derivative salts. Moreover, it discovered that the compound which shows high antibacterial activity was contained in these ionic liquid compounds. The present invention has been completed based on these findings.

  That is, the present invention provides the following (1) to (10).

(1) The following general formula (I)

〔式中、Ｒ^１は下記置換基群Ａから選ばれた１若しくは２以上の置換基によって置換されていてもよい炭素数４〜２０の直鎖状又は分岐鎖状のアルキル基、又は下記置換基群Ａから選ばれた１若しくは２以上の置換基によって置換されていてもよい炭素数２〜２０の直鎖状又は分岐鎖状のアルキニル基を表し、Ｒ^２は水素原子又は炭素数１〜３の直鎖状又は分岐鎖状のアルキル基を表し、Ｒ^３は下記置換基群Ａから選ばれた１若しくは２以上の置換基によって置換されていてもよいフェニル基又は下記置換基群Ａから選ばれた１若しくは２以上の置換基によって置換されていてもよい炭素数２〜２０の直鎖状又は分岐鎖状のアルキニル基を表し、Ｘａ⁻はＦ⁻、Ｃｌ⁻、Ｂｒ⁻、Ｉ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＣＦ_３ＢＦ_３ ⁻、Ｃ_２Ｆ_５ＢＦ_３ ⁻、又は（ＣＦ_３ＳＯ_３）_２Ｎ⁻を表し、置換基群Ａはハロゲン原子、トリメチルシリル基、エチルシリル基、及びフェニル基からなる群である。〕
で表される化合物。

[Wherein, R ¹ is a linear or branched alkyl group having 4 to 20 carbon atoms which may be substituted with one or more substituents selected from the following substituent group A, or the following substitution Represents a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted by one or more substituents selected from the group A, and R ² represents a hydrogen atom or a carbon number 1 to 1 3 represents a linear or branched alkyl group, and R ³ represents a phenyl group which may be substituted with one or more substituents selected from the following substituent group A or from the following substituent group A. Represents a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted with one or more selected substituents, and Xa ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , I ^{−. _{, BF 4 -, PF 6 -}} , CF 3 BF 3 - C ₂ F ₅ BF ₃ ^-, or _{(CF 3 SO 3) 2 N} - represents the, substituent group A is a group consisting of a halogen atom, a trimethylsilyl group, ethylsilyl group and a phenyl group. ]
A compound represented by

(2) The compound according to (1), wherein R ¹ in the general formula (I) is a linear alkyl group having 10 to 12 carbon atoms.

(3) The compound according to (1) or (2), wherein R ² in the general formula (I) is a methyl group.

(4) The compound according to (1) or (2), wherein R ² in the general formula (I) is a hydrogen atom.

(5) The compound according to any one of (1) to (4), wherein R ³ in the general formula (I) is a phenyl group substituted by a fluorine atom.

(6) The compound according to any one of (1) to (4), wherein R ³ in the general formula (I) is an ethynyl group.

(7) The compound according to any one of (1) to (6), wherein Xa in the general formula (I) is CF ₃ BF ₃ ^— .

(8) The following general formula (II)

〔式中、Ｒ^４は水素原子又は下記置換基群Ｂから選ばれた１若しくは２以上の置換基によって置換されていてもよい炭素数１〜５の直鎖状又は分岐鎖状のアルキル基を表し、Ｒ^５は下記置換基群Ｂから選ばれた１若しくは２以上の置換基によって置換されていてもよい炭素数１〜２０の直鎖状又は分岐鎖状のアルキル基、又は下記置換基群Ｂから選ばれた１若しくは２以上の置換基によって置換されていてもよい炭素数２〜２０の直鎖状又は分岐鎖状のアルキニル基を表し、Ｘｂ⁻はＦ⁻、Ｃｌ⁻、Ｂｒ⁻、Ｉ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＣＦ_３ＢＦ_３ ⁻、Ｃ_２Ｆ_５ＢＦ_３ ⁻、又は（ＣＦ_３ＳＯ_３）_２Ｎ⁻を表し、置換基群Ｂはハロゲン原子、及びトリメチルシリル基からなる群である。〕
で表される化合物。

[Wherein, R ⁴ represents a linear or branched alkyl group having 1 to 5 carbon atoms which may be substituted by a hydrogen atom or one or more substituents selected from the following substituent group B. R ⁵ represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with one or more substituents selected from the following substituent group B, or the following substituent group Represents a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted by one or more substituents selected from B, Xb ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , Represents I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ BF ₃ ⁻ , C ₂ F ₅ BF ₃ ⁻ , or (CF ₃ SO ₃ ) ₂ N ⁻ , and the substituent group B includes a halogen atom and a trimethylsilyl group. It is a group. ]
A compound represented by

〔式中、Ｒ^６は水素原子又は下記置換基群Ｃから選ばれた１若しくは２以上の置換基によって置換されていてもよい炭素数１〜５の直鎖状又は分岐鎖状のアルキル基を表し、Ｒ^７は下記置換基群Ｃから選ばれた１若しくは２以上の置換基によって置換されていてもよい炭素数１〜２０の直鎖状又は分岐鎖状のアルキル基、又は下記置換基群Ｃから選ばれた１若しくは２以上の置換基によって置換されていてもよい炭素数２〜２０の直鎖状又は分岐鎖状のアルキニル基を表し、Ｘｃ⁻はＦ⁻、Ｃｌ⁻、Ｂｒ⁻、Ｉ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＣＦ_３ＢＦ_３ ⁻、Ｃ_２Ｆ_５ＢＦ_３ ⁻、又は（ＣＦ_３ＳＯ_３）_２Ｎ⁻を表し、置換基群Ｃはハロゲン原子、及びトリメチルシリル基からなる群である。〕
で表される化合物。 (9) The following general formula (III)

[In the formula, R ⁶ represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms which may be substituted with one or more substituents selected from the following substituent group C. R ⁷ represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with one or more substituents selected from the following substituent group C, or the following substituent group Represents a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted by one or more substituents selected from C, Xc ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ BF ₃ ⁻ , C ₂ F ₅ BF ₃ ⁻ , or (CF ₃ SO ₃ ) ₂ N ⁻ , and the substituent group C is a halogen atom and a trimethylsilyl group. It is a group. ]
A compound represented by

(10) An antibacterial agent comprising the compound according to any one of (1) to (9).

  The present invention provides novel imidazolium derivative salts, pyrrolidinium derivative salts, and piperidinium derivative salts. Since these compounds exhibit ionic liquid or properties equivalent thereto, they are useful as lubricants, solvents, electrolyte solutions, and the like. In addition, since some have antibacterial activity, they can also be used as antibacterial agents.

  Hereinafter, the present invention will be described in detail.

  In the present invention, the “halogen atom” is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  In the present invention, the “linear or branched alkyl group having 4 to 20 carbon atoms” means, for example, n-butyl, isobutyl, s-butyl, tert-butyl, n-pentyl, n-hexyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-cetyl, n-heptadecyl, n-octadecyl, n- Nonadecyl, n-eicosyl, 4,4,4-trimethylbutyl, 5,5,5-trimethylpentyl, 6,6,6-trimethylhexyl and the like.

  In the present invention, the “linear or branched alkynyl group having 2 to 20 carbon atoms” means, for example, ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octynyl, 1-noninyl, 1-decynyl, 1-undecynyl, 1-dodecynyl, 1-tridecynyl, 1-tetradecynyl, 1-pentadecynyl, 1-hexadecynyl, 1-heptadecynyl, 1-octadecynyl, 1-nonadecynyl, 1- Eicosinyl and the like.

  In the present invention, the “linear or branched alkyl group having 1 to 3 carbon atoms” includes, for example, methyl, ethyl, n-propyl, isopropyl and the like.

  In the present invention, “a linear or branched alkyl group having 4 to 20 carbon atoms which may be substituted with one or more substituents selected from substituent group A” means the carbon described above. In addition to the linear or branched alkyl group of 4 to 20, for example, 4- (trimethylsilyl) butyl, 5- (trimethylsilyl) pentyl, 6- (trimethylsilyl) hexyl, 4,4,4-trifluorobutyl 5,5,5-trifluoropentyl, 6,6,6-trifluorohexyl and the like.

  In the present invention, “a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted by one or more substituents selected from substituent group A” refers to the carbon described above. In addition to the linear or branched alkynyl group of 2 to 20, for example, 4- (trimethylsilyl) -1-butynyl, 5- (trimethylsilyl) -1-pentynyl, 6- (trimethylsilyl) -1-hexynyl, 4,4,4-trifluoro-1-butynyl, 5,5,5-trifluoro-1-pentynyl, 6,6,6-trifluoro-1-hexynyl and the like.

  In the present invention, the “phenyl group optionally substituted by one or more substituents selected from the following substituent group A” includes, for example, phenyl, 2-fluorophenyl, 3-fluorophenyl, 4- Fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl 3,5-difluorophenyl, 2,6-difluorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 2,4-dibromophenyl, 2,5- Dibromophenyl, 3,5-dibromophenyl, 2,6-dibromophenyl, , 3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,3,4-trichlorophenyl, 2,3,5-trichlorophenyl, 2,3 , 6-trichlorophenyl, 2,3,4-tribromophenyl, 2,3,5-tribromophenyl, 2,3,6-tribromophenyl, 2,4-chloro-5-fluorophenyl, pentafluorophenyl , Pentachlorophenyl, pentabromophenyl and the like.

  In the present invention, “a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with one or more substituents selected from substituent group B” means, for example, 4 -(Trimethylsilyl) butyl, 5- (trimethylsilyl) pentyl, 6- (trimethylsilyl) hexyl, 4,4,4-trifluorobutyl, 5,5,5-trifluoropentyl, 6,6,6-trifluorohexyl, etc. It is.

  In the present invention, “a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted by one or more substituents selected from substituent group B” means, for example, 4 -(Trimethylsilyl) -1-butynyl, 5- (trimethylsilyl) -1-pentynyl, 6- (trimethylsilyl) -1-hexynyl, 4,4,4-trifluoro-1-butynyl, 5,5,5-trifluoro -1-pentynyl, 6,6,6-trifluoro-1-hexynyl and the like.

  In the present invention, “a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with one or more substituents selected from substituent group C” means, for example, 4 -(Trimethylsilyl) butyl, 5- (trimethylsilyl) pentyl, 6- (trimethylsilyl) hexyl, 4,4,4-trifluorobutyl, 5,5,5-trifluoropentyl, 6,6,6-trifluorohexyl, etc. It is.

  In the present invention, “a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted by one or more substituents selected from substituent group C” means, for example, 4 -(Trimethylsilyl) -1-butynyl, 5- (trimethylsilyl) -1-pentynyl, 6- (trimethylsilyl) -1-hexynyl, 4,4,4-trifluoro-1-butynyl, 5,5,5-trifluoro -1-pentynyl, 6,6,6-trifluoro-1-hexynyl and the like.

In the general formula (I), R ¹ is preferably a linear alkyl group having 10 to 20 carbon atoms, and more preferably a linear alkyl group having 10 to 12 carbon atoms.

In the general formula (I), R ² is preferably a methyl group or a hydrogen atom.

In the general formula (I), R ³ is preferably a phenyl group substituted by a fluorine atom or an ethynyl group.

In the general formula (I), Xa is preferably CF ₃ BF ₃ ^— .

  The compound represented by the general formula (I) can be produced, for example, by the following Step 1 and Step 2.

上記式中、Ｒ^１、Ｒ^２、Ｒ^３及びＸａは前記と同意義を示し、Ｙ^１及びＹ^２は臭素原子などのハロゲン原子を表し、Ｚａ^＋はカリウムイオンなどの陽イオンを表す。

In the above formula, R ¹ , R ² , R ³ and Xa are as defined above, Y ¹ and Y ² represent a halogen atom such as a bromine atom, and Za ⁺ represents a cation such as a potassium ion.

  Step 1 is a step in which a compound represented by the general formula (A) and a compound represented by the general formula (B) are reacted in the presence of a solvent and a catalyst to obtain a compound represented by the general formula (C). is there.

  The solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include tetrahydrofuran, dioxane, chloroform, dimethylformamide and the like. These solvents may be used alone or as a mixture of two or more kinds as necessary.

  The catalyst used is not particularly limited, and examples thereof include tetrabutylammonium iodide, tetraethylammonium iodide, potassium iodide and the like.

  The amount ratio of the compound represented by the general formula (a) and the compound represented by the general formula (b) is not particularly limited, but the latter is preferably 0.5 to 1.0 mol with respect to 1 mol of the former, 0.8 to More preferably, it is 1.0 mol.

  Although reaction temperature is not specifically limited, It is preferable to set it as 50-100 degreeC, and it is still more preferable to set it as 80-100 degreeC.

  The reaction time is not particularly limited, but is preferably 10 to 24 hours, and more preferably 10 to 15 hours.

  In Step 2, in the presence of a solvent and a catalyst, the compound represented by the general formula (c), the compound represented by the general formula (d), and the compound represented by the general formula (e) are reacted to form a general formula ( This is a step of obtaining a compound represented by I).

  The solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include tetrahydrofuran, dioxane, chloroform, dimethylformamide and the like. These solvents may be used alone or as a mixture of two or more kinds as necessary.

  The catalyst used is not particularly limited, and examples thereof include tetrabutylammonium iodide, tetraethylammonium iodide, potassium iodide and the like.

  The amount ratio of the compound represented by the general formula (c), the compound represented by the general formula (d), and the compound represented by the general formula (e) is not particularly limited, but is represented by the general formula (c). It is preferable that the compound represented by the general formula (d) is 1 to 2 mol and the compound represented by the general formula (e) is 0.1 to 1.0 mol per 1 mol of the compound represented by the general formula (d). More preferably, the compound represented by 1.0 to 1.5 mol and the compound represented by formula (e) are 0.1 to 0.5 mol.

  Although reaction temperature is not specifically limited, It is preferable to set it as 10-100 degreeC, and it is still more preferable to set it as 15-35 degreeC.

Although the reaction time is not particularly limited, it is preferably 10 to 48 hours, more preferably 15 to 20 hours. The compound represented by the general formula (II) can be produced by the following step 3. .

上記式中、Ｒ^４、Ｒ^５及びＸｂは前記と同意義を示し、Ｙ^３は臭素原子などのハロゲン原子を表し、Ｚｂ^＋はカリウムイオンなどの陽イオンを表す。

In the above formula, R ⁴ , R ⁵ and Xb are as defined above, Y ³ represents a halogen atom such as a bromine atom, and Zb ⁺ represents a cation such as a potassium ion.

  In step 3, in the presence of a solvent and a catalyst, the compound represented by the general formula (f), the compound represented by the general formula (g), and the compound represented by the general formula (h) are reacted to form the general formula ( This is a step of obtaining a compound represented by II).

  The solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include tetrahydrofuran, dioxane, chloroform, dimethylformamide and the like. These solvents may be used alone or as a mixture of two or more kinds as necessary.

  The catalyst used is not particularly limited, and examples thereof include tetrabutylammonium iodide, tetraethylammonium iodide, potassium iodide and the like.

  The amount ratio of the compound represented by the general formula (f), the compound represented by the general formula (g), and the compound represented by the general formula (h) is not particularly limited, but is represented by the general formula (f). It is preferable that the compound represented by the general formula (g) is 1 to 2 mol and the compound represented by the general formula (h) is 0.1 to 1 mol per 1 mol of the compound. It is more preferable that the compound represented by 1 to 1.5 mol and the compound represented by the general formula (h) be 0.1 to 0.5 mol.

  The reaction temperature is not particularly limited, but is preferably 10 to 100 ° C, and more preferably 60 to 90 ° C.

Although the reaction time is not particularly limited, it is preferably 10 to 48 hours, more preferably 15 to 24 hours. The compound represented by the general formula (III) can be produced by the following step 4. .

上記式中、Ｒ^６、Ｒ^７及びＸｃは前記と同意義を示し、Ｙ^４は臭素原子などのハロゲン原子を表し、Ｚｃ^＋はカリウムイオンなどの陽イオンを表す。

In the above formula, R ⁶ , R ⁷ and Xc are as defined above, Y ⁴ represents a halogen atom such as a bromine atom, and Zc ⁺ represents a cation such as a potassium ion.

  In step 4, in the presence of a solvent and a catalyst, the compound represented by the general formula (i), the compound represented by the general formula (j), and the compound represented by the general formula (k) are reacted, and the general formula ( This is a step of obtaining a compound represented by III).

  The solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include tetrahydrofuran, dioxane, chloroform, dimethylformamide and the like. These solvents may be used alone or as a mixture of two or more kinds as necessary.

  The catalyst used is not particularly limited, and examples thereof include tetrabutylammonium iodide, tetraethylammonium iodide, potassium iodide and the like.

  The amount ratio of the compound represented by the general formula (i), the compound represented by the general formula (j), and the compound represented by the general formula (k) is not particularly limited, but is represented by the general formula (i). It is preferable that the compound represented by the general formula (j) is 1 to 2 mol and the compound represented by the general formula (k) is 0.1 to 1 mol per 1 mol of the compound represented by the general formula (j). More preferably, the compound represented by 1 to 1.5 mol and the compound represented by formula (k) are 0.1 to 0.5 mol.

  The reaction temperature is not particularly limited, but is preferably 10 to 100 ° C, and more preferably 60 to 90 ° C.

Although the reaction time is not particularly limited, it is preferably 10 to 48 hours, more preferably 15 to 25 hours, since the compounds represented by the general formulas (I) to (III) have antibacterial activity. Can be used as an antibacterial agent. The antibacterial agent can be used as an antibacterial agent for humans and foods, but is preferably used as an industrial antibacterial agent. Specifically, (1) Prevention of paint quality deterioration due to bacteria, (2) Prevention of decay of adhesives and pastes such as casein, polyvinyl alcohol, starch, etc. (3) For papermaking such as wet pulp and chips Prevention of spoilage of raw materials, quality deterioration due to bacteria, (4) Prevention of bacterial contamination and quality deterioration of processed products and materials such as wood and plywood, (5) Prevention of contamination of fiber and deterioration of quality, ( 6) Prevention of quality deterioration due to bacteria in emulsions, (7) Prevention of quality deterioration due to bacteria in surfactants, (8) Prevention of quality deterioration due to bacteria such as hydraulic fluids, (9) Due to bacteria such as plastic and rubber It can be used for applications such as prevention of quality deterioration and (10) prevention of slime damage caused by bacteria during the paper making process.

  The antibacterial agent of the present invention is used by spraying, coating, adding or the like to the above-mentioned various industrial products or raw materials. At this time, the concentration of the compounds represented by the general formulas (I) to (III) in the industrial product is not particularly limited as long as it is within the range of exhibiting antibacterial activity, but is preferably 0.00001 to 10% by weight. 0.001 to 10% by weight is more preferable.

  When the compounds represented by the general formulas (I) to (III) are used as antibacterial agents, they may be used together with an appropriate solid or liquid carrier. The carrier is not particularly limited as long as it is commonly used as a carrier contained in an antibacterial agent. For example, mineral powders (kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, phosphorus, Lime, white carbon, slaked lime, quartz sand, ammonium sulfate, urea, etc.), vegetable powder (soybean flour, wheat flour, wood flour, starch, crystalline cellulose, etc.), alumina, silicate, sugar polymer, highly dispersible silicic acid, waxes , Water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, chlorobenzene, cumene, methylnaphthalene) Etc.), halogenated hydrocarbons (chloroform) , Carbon tetrachloride, dichloromethane, chloroethylene, trichlorofluoromethane, dichlorodifluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexane, methyl isobutyl ketone, etc.), Esters (ethyl acetate, butyl acetate, ethylene glycol acetate, dioctyl phthalate, amyl acetate, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether) Ethylene glycol monoethyl ether, 1-methoxy-2-propanol, etc.), amines (ethylamine, dimethylamine, trimer Lumine, isobutylamine, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, solvent naphtha, etc.), and petroleum fractions (paraffins, kerosene, light oil, etc.) Etc. can be used.

  The dosage form of the antibacterial agent is not particularly limited, and dosage forms such as powders, emulsions, wettable powders, sols (flowable agents), granules, aerosols, solid agents, and coating agents can be used. The content of the compounds represented by the general formulas (I) to (III) in the antibacterial agent is not particularly limited, but is preferably 0.00001 to 10% by weight, and more preferably 0.001 to 10% by weight.

  The microorganisms that are the targets of the antibacterial agent are not particularly limited, and a wide variety of microorganisms such as bacteria (including both gram-positive bacteria and gram-negative bacteria), yeasts, and filamentous fungi can be used as antibacterial objects.

  Since the compounds represented by the general formulas (I) to (III) exhibit ionic liquids or properties equivalent thereto, they can be used in the same applications as known ionic liquids. Ionic liquids are used for lubricants, solvents, electrolyte solutions, physiologically active substances, and high refractive index liquids, and compounds represented by general formulas (I) to (III) should also be used for these applications. Can do. In addition, the compounds represented by the general formulas (I) to (III) can be used for applications such as cationic surfactants, DNA and protein extractants, and assistants for organizing carbon or gold nanomaterials. I can expect.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Synthesis Example 1] 1-cetyl 2-methylimidazole Into a flask, methylimidazole (50 mmol), cetyl bromide (16.8 g, 55 mmol), sodium hydride (2.2 g, 1.7 eq.), Tetrabutylammonium iodide (0.89 ml, 0.05 eq.) was added and further dried tetrahydrofuran (150 ml) was added. The mixture was stirred at room temperature for 20 hours. After extracting the product with ethyl acetate, the extract was dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, 1-cetyl 2-methylimidazole was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.14 Hz), 1.25 (22 H), 1.59 (4 H), 1.70 (2 H, m), 2.37 (3 H), 3.80 ( 2 H, t, J = 7.14 Hz), 6.80 (1 H, d, J = 1.37 Hz), 6.90 (1 H, d, J = 1.37 Hz).

[Synthesis Example 2] 1-tetradecyl-2-methylimidazole 1-tetradecyl-2-methylimidazole was obtained in the same manner as in Synthesis Example 1, except that tetradecyl bromide was used instead of cetyl bromide.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 6.73 Hz), 1.25 (24 H, m), 2.36 (3 H, s), 3.80 (2 H, q), 6.80 (1 H , d, J = 0.69 Hz), 6.90 (1 H, d).

Synthesis Example 3 1-Tedecyl-2-methylimidazole was obtained in the same manner as in Synthesis Example 1 except that dodecyl bromide was used instead of cetyl bromide.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 6.82 Hz), 1.21-1.30 (16 H, m), 1.69-1.82 (4 H, m), 2.37 (3 H, s), 3.80 (2 H, q), 6.80 (1 H, d, J = 1.22 Hz), 6.89 (1 H, d), 7.27 (1 H, s)

[Example 1] 1-cetyl 2-methyl-3-benzylimidazolium iodide 1-cetyl 2-methylimidazole (0.84 g, 3 mmol), benzyl bromide (1.23 g), potassium iodide (4,98) After adding g) and chloroform (100 ml), the inside of the flask was replaced with argon. After the mixture was reacted at 80 ° C. for 12 hours, the solvent was distilled off under reduced pressure to obtain 1-cetyl 2-methyl-3-benzylimidazolium iodide (Compound 1).
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 6.87 Hz), 1.22-1.32 (28 H, m), 1.60 (2 H, m),
1.80-1.90 (2 H, m)

[Example 2] 1-dodecyl-2-methyl-3-benzylimidazolium iodide
1-dodecyl-2-methyl-3-benzylimidazolium iodide (compound) was prepared in the same manner as in Example 1 except that 1-dodecyl-2-methylimidazole was used instead of 1-cetyl-2-methylimidazole. 2) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.08 Hz), 1.25-1.33 (18 H, m), 1.82-1.85 (2 H, m), 2.82 (3 H, s), 4.18 (2 H, Q), 5.55 (2 H, S), 7.27-7.47

[Example 3] 1-tetradecyl-2-methyl-3-benzylimidazolium iodide
1-tetradecyl-2-methyl-3-benzylimidazolium iodide (compound 3) in the same manner as in Example 1 except that 1-tetradecylimidazole was used instead of 1-hexadecyl-2-methylimidazole Got.

[Example 4] 1-cetyl 2-methyl-3- (2-fluoro) benzylimidazolium iodide Iodine was prepared in the same manner as in Example 1 except that 2-fluorobenzyl bromide was used instead of benzyl bromide. 1-cetyl 2-methyl-3- (2-fluoro) benzylimidazolium (compound 4) was obtained.
¹ H NMR (CDCl ₃ ): δ0.88 (3 H, t, J = 7.08 Hz), 1.22-1.34 (24 H), 1.58 (2 H), 1.86 (2 H, m), 2.90 (3 H) , 4.15 (2 H, t, J = 7.08 Hz), 5.56 (2 H, s), 7.11 (1 H, m), 7.39-7.47 (4 H), 7.71 (1 H, m). ¹⁹ F NMR ( _{CDCl 3):.. δ44.7 ppm} from ext C 6 F 6 13 C NMR (CDCl 3): δ12.10, 13.13, 14.34, 15.35, 32.38, 27.04, 29.34-31.36, 32.61, 47.80, 50.01, 116.64 ( d, J = 148.0 Hz), 120.80 (d, J = 145.5 Hz), 122.46 (dd, J = 199.9, 21.3 Hz), 125.85 (d, J = 149.5 Hz), 132.39 (d, J = 132.0 Hz), 144.34, 160.32, 162.77.

[Example 5] 1-tetradecyl-2-methyl-3- (2-fluoro) benzylimidazolium iodide
Except that 1-tetradecyl-2-methylimidazole was used instead of 1-cetyl-2-methylimidazole and 2-fluorobenzylbromide was used instead of benzylbromide, the same method as in Example 1, 1-tetradecyl-2-methyl-3- (2-fluoro) benzylimidazolium iodide (Compound 5) was obtained.
¹ H NMR (CDCl ₃ ): δ0.88 (3 H, t, J = 7.08 Hz), 1.24-1.32 (22 H), 1.85 (2 H, m), 2.90 (3 H), 4.17 (2 H, t, J = 7.08 Hz), 5.56 (2 H, s), 7.10-7.71 (6 H, m) 19 F NMR (CDCl 3):.. δ44.7 (m) ppm from ext C 6 F 6.

[Example 6] 1-cetyl 2-methyl-3- (3-fluoro) benzylimidazolium iodide Iodine was prepared in the same manner as in Example 1 except that 3-fluorobenzyl bromide was used instead of benzyl bromide. 1-cetyl 2-methyl-3- (3-fluoro) benzylimidazolium (compound 6) was obtained.
¹ H NMR (CDCl ₃ ): δ0.88 (3 H, t, J = 7.08 Hz), 1.25-1.37 (24 H), 1.58 (2 H), 1.87 (2 H, m), 2.83 (3 H) , 4.14 (2 H, t, J = 7.08 Hz), 5.56 (2 H, s), 7.00 (1 H, m), 7.10 (1 H, m), 7.20-7.44 (4 H). ¹⁹ F NMR ( CDCl ₃ ): δ 51.2 ppm from ext. C ₆ F ₆ .

[Example 7] 1-cetyl 2-methyl-3- (4-fluoro) benzylimidazolium iodide Iodine was prepared in the same manner as in Example 1 except that 4-fluorobenzyl bromide was used instead of benzyl bromide. 1-cetyl 2-methyl-3- (4-fluoro) benzylimidazolium (compound 7) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.08 Hz), 1.23-1.37 (24 H), 1.56 (2 H), 1.85 (2 H, m), 2.85 (3 H), 4.14 (2 H, t, J = 7.08 Hz), 5.54 (2 H, s), 6.96-7.46 (6 H). ¹⁹ F NMR (CDCl ₃ ): δ 50.5 ppm from ext. C ₆ F _6. ¹³ C NMR (CDCl ₃ ): δ 11.65, 12.66, 13.47, 14.48, 22.49, 26.19, 28.93-30.51, 31.73, 49.07, 51.46, 116.08 (d, J = 138.0 Hz), 121.63 (dd, J = 119.9, 33.6 Hz) , 128.78, 130.98 (dd, J = 144.9, 34.3 Hz), 143.48, 161.41, 163.88.

[Example 8] 1-dodecyl-2-methyl-3- (2,3-difluoro) benzylimidazolium bromide Into a flask, 1-dodecyl-2-methylimidazole (0.05 g, 0.2 mmol), 2,3-difluoro After adding benzyl bromide (33.1 ml, 0.26 mmol) and methylene chloride (1.17 ml) and heating to reflux for 22 hours, the solvent was distilled off under reduced pressure to give 1-dodecyl-2-methyl-3- (2, 3-Difluoro) benzylimidazolium (compound 8) was obtained with a yield of 85%.
¹ H NMR (300 MHz, CDCl ₃ ): δ 0.88 (t, J = 7 Hz, 3 H), 1.20-1.39 (m, 18 H), 1.77-1.89 (m, 2 H), 2.90 (s, 3 H), 4.18 (t, J = 7.5 Hz, 2 H), 5.79 (s, 2 H), 7.14-7.26 (m, 2 H), 7.45 (s, 1 H), 7.61-7.69 (m, 1 H ), 7.71 (br s, 1 H).

[Example 9] 1-cetyl 2-methyl-3- (2,4-difluoro) benzylimidazolium iodide Same as Example 1 except that 2,4-difluorobenzyl bromide was used instead of benzyl bromide By the method, 1-cetyl 2-methyl-3- (2,4-difluoro) benzylimidazolium iodide (compound 9) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.08 Hz), 1.23-1.37 (24 H), 1.56 (2 H), 1.85 (2 H, m), 2.85 (3 H), 4.14 (2 H, t, J = 7.08 Hz), 5.54 (2 H, s), 6.96-7.46 (6 H) 13 C NMR (CDCl 3):. δ 11.02, 12.03, 12.91, 13.44, 21.94, 25.62, 27.92-29.15, 29.99, 31.17, 48.62, 50.49, 103.15, 104.61, 110.20, 111.65, 121.30 (dd, J = 119.9, 48.8 Hz), 136.19 (dd, J = 9.92, 9.15 Hz), 143.26, 162.42 (dd, J = 250.3, 12.9 Hz).

Example 10 1-Tetradecyl-2-methyl-3- (2,4-difluoro) benzylimidazolium iodide
Example 1 except that 1-tetradecyl-2-methylimidazole was used instead of 1-hexadecyl-2-methylimidazole, and 2,4-difluorobenzylbromide was used instead of benzylbromide. By the method, 1-tetradecyl-2-methyl-3- (2,4-difluoro) benzylimidazolium iodide (Compound 10) was obtained.

Example 11 1-Dodecyl-2-methyl-3- (2,4-difluoro) benzylimidazolium bromide
1-dodecyl-2-methyl-3- (2,4-difluoro bromide) was prepared in the same manner as in Example 8, except that 2,4-difluorobenzyl bromide was used instead of 2,3-difluorobenzyl bromide. ) Benzylimidazolium (Compound 11) was obtained.
81% yield. ¹ H NMR (300 MHz, CDCl ₃ ) δ 0.88 (t, J = 7 Hz, 3 H), 1.20-1.39 (m, 18 H), 1.76-1.89 (m, 2 H), 2.90 ( s, 3 H), 4.15 (t, J = 7.5 Hz, 2 H), 5.70 (s, 2 H), 6.85 (ddd, J = 10, 9, 3 Hz, 1 H), 6.94-7.02 (m, 1 H), 7.33 (d, J = 2 Hz, 1 H), 7.59 (d, J = 2 Hz, 1 H), 7.98 (dt, J = 6, 9 Hz, 1 H).

[Example 12] 1-cetyl 2-methyl-3- (2,5-difluoro) benzylimidazolium iodide Same as Example 1 except that 2,5-difluorobenzyl bromide was used instead of benzyl bromide By the method, 1-cetyl 2-methyl-3- (2,5-difluoro) benzylimidazolium iodide (compound 12) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.08 Hz), 1.25-1.37 (20 H), 1.54-1.64 (6 H), 1.86 (2 H, m), 2.89 (3 H ), 4.13 (2 H, t, J = 7.08 Hz), 5.59 (2 H, s), 7.08-7.43 (5 H). ¹⁹ F NMR (CDCl ₃ ): δ 39.1 (m), 46.1 (m) ppm from ext. C ₆ F ₆ .

[Example 13] 1-tetradecyl-2-methyl-3- (2,5-difluoro) benzylimidazolium iodide
Example 1 except that 1-tetradecyl-2-methylimidazole was used instead of 1-hexadecyl-2-methylimidazole, and 2,5-difluorobenzylbromide was used instead of benzylbromide. By the method, 1-tetradecyl-2-methyl-3- (2,5-difluoro) benzylimidazolium iodide (compound 13) was obtained.

[Example 14] 1-cetyl 2-methyl-3- (3,5-difluoro) benzylimidazolium iodide Same as Example 1 except that 3,5-difluorobenzyl bromide was used instead of benzyl bromide By the method, 1-cetyl 2-methyl-3- (3,5-difluoro) benzylimidazolium iodide (compound 14) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.08 Hz), 1.20-1.38 (20 H), 1.59 (6 H), 1.88 (2 H, m), 2.83 (3 H), 4.14 (2 H, t, J = 7.08 Hz), 5.65 (2 H, s), 6.82-6.92 (2 H, m), 7.26-7.51 (3 H). ¹⁹ F NMR (CDCl ₃ ): δ 54.9- 55.0 ppm from ext. C ₆ F ₆ .

[Example 15] 1-tetradecyl-2-methyl-3- (2,6-difluoro) benzylimidazolium iodide
Example 1 except that 1-tetradecyl-2-methylimidazole was used instead of 1-hexadecyl-2-methylimidazole, and 2,6-difluorobenzylbromide was used instead of benzylbromide. By the method, 1-tetradecyl-2-methyl-3- (2,6-difluoro) benzylimidazolium iodide (compound 15) was obtained.

Example 16 1-Dodecyl-2-methyl-3- (2,3,4-trifluoro) benzylimidazolium bromide
1-dodecyl-2-methyl-3- (2,3 bromide) in the same manner as in Example 8, except that 2,3,4-difluorobenzyl bromide was used instead of 2,3-difluorobenzyl bromide. , 4-trifluoro) benzylimidazolium (Compound 16) was obtained.
38% yield. ¹ H NMR (300 MHz, CDCl ₃ ) δ 0.88 (t, J = 7 Hz, 3 H), 1.20-1.38 (m, 18 H), 1.77-1.89 (m, 2 H), 2.90 ( s, 3 H), 4.14 (t, J = 7.5 Hz, 2 H), 5.81 (s, 2 H), 7.08 (ddt, J = 7, 2, 9 Hz, 1 H), 7.32 (s, 1 H ), 7.71 (s, 1 H), 7.81-7.90 (m, 1 H).

[Example 17] 1-dodecyl-2-methyl-3- (2,3,5-trifluoro) benzylimidazolium bromide
1-dodecyl-2-methyl-3- (2,3 bromide) in the same manner as in Example 8, except that 2,3,5-difluorobenzyl bromide was used instead of 2,3-difluorobenzyl bromide. , 5-trifluoro) benzylimidazolium (Compound 17) was obtained.
68% yield. ¹ H NMR (300 MHz, CDCl ₃ ) δ 0.88 (t, J = 7 Hz, 3 H), 1.22-1.40 (m, 18 H), 1.79-1.92 (m, 2 H), 2.90 ( s, 3 H), 4.13 (t, J = 7.5 Hz, 2 H), 5.83 (s, 2 H), 6.95-7.05 (m, 1 H), 7.25-7.31 (m, 1 H), 7.42-7.50 (m, 1 H), 7.63-7.68 (m, 1 H).

[Example 18] 1-dodecyl-2-methyl-3- (2,3,6-trifluoro) benzylimidazolium bromide
1-dodecyl-2-methyl-3- (2,3 bromide) in the same manner as in Example 8, except that 2,3,6-difluorobenzyl bromide was used instead of 2,3-difluorobenzyl bromide. , 6-Trifluoro) benzylimidazolium (Compound 18) was obtained.
68% yield. ¹ H NMR (300 MHz, CDCl ₃ ) δ 0.88 (t, J = 7 Hz, 3 H), 1.20-1.40 (m, 18 H), 1.78-1.90 (m, 2 H), 2.94 ( s, 3 H), 4.22 (t, J = 7.5 Hz, 2 H), 5.63 (s, 2 H), 6.99 (ddt, J = 4, 2, 9 Hz, 1 H), 7.27 (dq, J = 5, 9 Hz, 1 H), 7.39 (br s, 1 H), 7.46-7.50 (m, 1 H).

Example 19 1-dodecyl-2-methyl-3- (2,4-dichloro-5-fluoro) benzylimidazolium bromide
1-dodecyl-2-methyl-3- (2) bromide in the same manner as in Example 8, except that 2,4-dichloro-5-fluorobenzyl bromide was used instead of 2,3-difluorobenzyl bromide. , 4-Dichloro-5-fluoro) benzylimidazolium (Compound 19) was obtained.
73% yield. ¹ H NMR (300 MHz, CDCl ₃ ) δ 0.88 (t, J = 7 Hz, 3 H), 1.20-1.40 (m, 18 H), 1.79-1.92 (m, 2 H), 2.90 ( s, 3 H), 4.17 (t, J = 7.5 Hz, 2 H), 5.75 (s, 2 H), 7.36 (br s, 1 H), 7.41 (br s, 1 H), 7.51 (d, J = 6 Hz, 1 H), 7.75 (d, J = 9 Hz, 1 H).

[Example 20] 1-cetyl 2-methyl-3- (2,5-dichloro) benzylimidazolium iodide Same as Example 1 except that 2,5-difluorobenzyl bromide was used instead of benzyl bromide By the method, 1-cetyl 2-methyl-3- (2,5-difluoro) benzylimidazolium iodide (Compound 20) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.08 Hz), 1.20-1.35 (22 H), 1.58 (4 H), 1.88 (2 H, m), 2.92 (3 H), 4.17 (2 H, t, J = 7.08 Hz), 5.59 (2 H, s), 7.31 (1 H, d, J = 2.1 Hz), 7.39-7.40 (3 H), 7.58 (1 H, d, J = 2.1 Hz).

[Example 21] 1-tetradecyl-2-methyl-3- (2,6-dichloro) benzylimidazolium iodide
Example 1 except that 1-tetradecyl-2-methylimidazole was used instead of 1-hexadecyl-2-methylimidazole and 2,6-dichlorobenzylbromide was used instead of benzylbromide. By the method, 1-tetradecyl-2-methyl-3- (2,6-dichloro) benzylimidazolium iodide (Compound 21) was obtained.

[Example 22] 1-cetyl 2-methyl-3- (3-bromo) benzylimidazolium iodide Iodine was prepared in the same manner as in Example 1 except that 3-bromobenzyl bromide was used instead of benzyl bromide. 1-cetyl 2-methyl-3- (3-bromo) benzylimidazolium (compound 22) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 6.76 Hz), 1.25 (28 H, m), 1.60 (2 H, s), 2.83 (3 H, s), 4.15 (2 H , t, J = 7.69 Hz), 7.32-7.56 (6 H, m)

[Example 23] 1-cetyl 2-methyl-3- (3-chloro) benzylimidazolium iodide In the same manner as in Example 1 except that 3-chlorobenzyl bromide was used instead of benzyl bromide, iodine 1-cetyl 2-methyl-3- (3-chloro) benzylimidazolium (compound 23) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 6.96 Hz), 1.15-1.40 (26 H, m), 1.65 (2 H, m), 1.83 (2 H, m), 2.83 ( 3 H, s), 4.14 (2 H, t, J = 7.63 Hz), 5.61 (2 H, s), 7.35 (2 H, d, J = 2.08 Hz), 7.39 (2 H, q, J = 9.60 Hz), 7.55 (2 H, d, J = 2.20 Hz)

[Example 24] 1-cetyl 2-methyl-3- (2,5-dichloro) benzylimidazolium iodide Same as Example 1 except that 2,5-dichlorobenzyl bromide was used instead of benzyl bromide By the method, 1-cetyl 2-methyl-3- (2,5-dichloro) benzylimidazolium iodide (Compound 24) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.08 Hz), 1.20-1.35 (22 H, m), 1.58 (4 H, m), 1.88 (2 H, m), 2.92 ( 3 H, s), 4.17 (2 H, t, J = 7.08 Hz), 5.59 (2 H, s), 7.31 (1 H, d, J = 2.1 Hz), 7.39-7.40 (3 H), 7.39- 7.40 (3 H), 7.58 (1 H, d, J = 2.1 Hz)

[Example 25] 1-cetyl iodide 1-cetyl iodide in the same manner as in Example 1 except that pentafluorobenzyl bromide was used instead of benzyl bromide. 2-Methyl-3-pentafluorobenzylimidazolium (Compound 25) was obtained.
¹ H NMR (CDCl ₃ ): δ0.88 (3 H, t, J = 7.08 Hz), 1.25-1.36 (24 H), 1.61 (2 H), 1.87 (2 H, m), 2.96 (3 H) , 4.18 (2 H, t, J = 7.08 Hz), 5.65 (2 H, s), 7.27-7.40 (2 H, m) 19 F NMR (CDCl 3):. δ 3.1 (m), 12.7 (m) , 21.4 (m) ppm from ext C 6 F 6 13 C NMR (CDCl 3):.. δ 13.13, 14.13, 22.20, 25.90, 28.17, 28.59, 28.88, 29.22, 30.20, 31.43, 40,91, 49.11, 106.68 , 121.62 (dd, J = 119.1, 32.0 Hz), 137.43 (d, J = 246.1 Hz), 140.62, 143.85, 146.24.

Example 26 1-cetyl 2-methyl iodide 1-cetyl 2-methyl iodide In the same manner as in Example 1 except that propargyl bromide was used instead of benzyl bromide. -3-Propargyrimidazolium (Compound 26) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.08 Hz), 1.25-1.37 (26 H), 1.87 (2 H, m), 2.91 (3 H), 4.17 (2 H, t , J = 7.08 Hz), 5.30 (2 H, m), 7.41 (1 H, d, J = 2.20 Hz), 7.69 (1 H, t, J = 2.08 Hz).

[Example 27] 1-dodecyl-2-methyl-3-propargylimidazolium bromide In a flask, 1-dodecyl-2-methylimidazole (50 mg, 0.2 mmol), propargyl bromide (19.5 μl, 0.26 mmol) and chloride were added. After adding methylene (1 ml) and heating under reflux for 20 hours, the solvent was distilled off to obtain 1-dodecyl-2-methyl-3-propargylimidazolium bromide (Compound 27) in a yield of 76%.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.88 (t, J = 7 Hz, 3 H), 1.20-1.38 (m, 18 H), 1.76-1.91 (m, 2 H), 2.75 (d, J = 2 Hz, 1 H), 2.91 (s, 3 H), 4.23 (t, J = 7.5 Hz, 2 H), 5.44 (d, J = 2 Hz, 2 H), 7.58 (s, 1 H), 7.89 (s, 1 H).

[Example 28] 1-dodecyl-2-methyl-3- (3-pentyl) propargylimidazolium bromide As in Example 27, except that (3-pentyl) propargyl bromide was used instead of propargyl bromide In this manner, 1-dodecyl-2-methyl-3- (3-pentyl) propargylimidazolium bromide (Compound 28) was obtained.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.88 (t, J = 7 Hz, 3 H), 0.90 (t, J = 7 Hz, 3 H), 1.22-1.38 (m, 22 H), 1.45-1.63 (m, 2 H), 1.78-1.90 (m, 2 H), 2.21 (tt, J = 7, 2 Hz, 2 H), 2.88 (s, 3 H), 4.25 (t, J = 7.5 Hz, 2 H), 5.23 (t, J = 2 Hz, 2 H), 7.59 (d, J = 2 Hz, 1 H), 7.72 (d, J = 2 Hz, 1 H).

Example 29 1-cetyl 2-methyl-3-benzylimidazolium tetrafluoroborate 1-cetyl 2-methyl-3-benzylimidazolium iodide (5 mmol) and ammonium tetrafluoroborate (6 mmol) were added to tetrahydrofuran ( After the solution dissolved in 30 ml) was reacted at room temperature for 24 hours, the solvent was distilled off. The product was purified by a column using a mixed solution of chloroform and methanol to obtain 1-cetyl 2-methyl-3-benzylimidazolium tetrafluoroborate (Compound 29).
¹ H NMR (CDCl ₃ ): δ0.88 (3 H, t, J = 7.08 Hz), 1.20-1.32 (28 H, m), 1.79-1.82 (2 H, m), 2.64 (3 H, s) , 4.08 (2 H, q), 5.32 (2 H, s), 7.20-7.40

[Example 30] 1-cetyl 2-methyl-3-benzylimidazolium hexafluorophosphate 1-cetyl 2-methyl-3-benzylimidazolium iodide (0.262 g, 0.5 mmol) and KPF ₆ (0.10 g) in a flask After adding tetrahydrofuran (10 ml), the mixture was stirred at room temperature for 24 hours. After the solvent was distilled off under reduced pressure, 1-cetyl 2-methyl-3-benzylimidazolium hexafluorophosphate (Compound 30) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.08 Hz), 1.25-1.33 (24 H), 1.59 (2 H), 1.82 (2 H, m), 2.67 (3 H), 4.09 (2 H, t, J = 7.08 Hz), 5.33 (2 H, m), 7.06-7.43 (7 H, m) 19 F NMR (CDCl 3):. δ 98.4 (d, J FP = 712.6 Hz) ppm from ext. C ₆ F ₆ .

[Example 31] 1-cetyl 3-benzylimidazolium iodide In Example 1, instead of benzylimidazolium, cetylimidazolium, benzyl bromide, and potassium iodide were used for the reaction under the same conditions. 1-cetyl 3-benzylimidazolium (compound 31) was obtained.

[Example 32] 1-tetradecyl-3-benzylimidazolium iodide In Example 1, instead of benzylimidazolium, tetradecylimidazolium, benzyl bromide, and potassium iodide were used for the reaction under the same conditions. 1-cetyl 3-benzylimidazolium iodide (compound 32) was obtained.
¹ H NMR (CDCl ₃ ): δ0.88 (3 H, t, J = 7.08 Hz), 1.20-1.32 (22 H, m), 1.89-1.94 (2 H, m), 4.29 (2 H, q) , 5.61 (2 H, s), 7.27-7.32

[Example 33] 1-dodecyl-2-methyl-3- (3-pentyl) propargylimidazolium iodide In Example 1, instead of benzylimidazolium, 1-dodecyl-2-methylimidazolium and bromide ( The reaction was carried out under the same conditions using 3-pentyl) propargyl and potassium iodide to obtain 1-dodecyl-2-methyl-3- (3-pentyl) propargylimidazolium iodide (Compound 33).
¹ H NMR (CDCl ₃ ): δ0.88 (3 H, t, J = 7.08 Hz), 1.24-1.32 (18 H, m), 1.91-1.94 (2 H, m), 4.30 (2 H, q) , 5.62 (2 H, s), 7.28-7.53, 10.3 (1 H, s)

[Example 34] 1-dodecyl-2-methyl-3- (3-pentyl) propargylimidazolium trifluoromethyl trifluoroborate Iodine 1-dodecyl-2-methyl-3- (3-pentyl) propargylimidazo After adding lithium (1 mmol), potassium trifluoromethyl trifluoroborate (0.35 g, 2 mmol) and tetrahydrofuran (10 ml), the inside of the flask was replaced with argon. After the mixture was reacted at room temperature for 28 hours, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using a mixed solvent (chloroform: methanol = 5: 1) to give 1-dodecyl-2-methyl- 3- (3-Pentyl) propargylimidazolium trifluoromethyl trifluoroborate (Compound 34) was obtained.

[Example 35] 1-dodecyl-3- (2-fluoro) benzylimidazolium iodide In Example 1, instead of benzylimidazolium, dodecylimidazolium, (2-fluoro) benzyl bromide, and potassium iodide were used. And 1-dodecyl-3- (2-fluoro) benzylimidazolium iodide (Compound 35) was obtained by carrying out the reaction under the same conditions.

[Example 36] 1-decyl-3- (2-fluoro) benzylimidazolium iodide In Example 1, instead of benzylimidazolium, decylimidazolium, (2-fluoro) benzyl bromide, and potassium iodide were used. And 1-decyl-3- (2-fluoro) benzylimidazolium iodide (Compound 36) was obtained by carrying out the reaction under the same conditions.

Example 37 1-dodecyl-3- (3-pentyl) propargylimidazolium bromide Dodecylimidazolium (5 mmol) and 1-bromo-2-octyne (6 mmol) were dissolved in chloroform (50 ml), After heating at reflux for 12 hours at 80 ° C., the solvent was distilled off to obtain 1-dodecyl-3- (3-pentyl) propargylimidazolium bromide (Compound 37).

Example 38 1- (4-Trimethylsilyl) butyl-3- (3-pentyl) propargylimidazolium iodide 1- (4-trimethylsilyl) butylimidazole (0.78 g, 4 mmol), 1-promo-2 in a flask -After adding octyne (1.13 g, 6 mmol), potassium iodide (4,98 g, 30 mmol) and chloroform (50 ml), the inside of the flask was replaced with argon. After the mixture was reacted at 80 ° C. for 8 hours, the solvent was distilled off under reduced pressure to obtain 1- (4-trimethylsilyl) butyl-3- (3-pentyl) -propargylimidazolium iodide (Compound 38) in a yield. Obtained at 70%.
¹ H NMR (CDCl ₃ ): δ0.00 (9 H, m), 0.55-0.59 (2 H, m), 0.90-0.93 (3 H, m), 1.33-1.44 (6 H, m), 1.52- 1.58 (2 H, m), 2.00 (2 H, quint, J = 7.57 Hz), 2.26-2.30 (2 H, m), 4.37 (2 H, t, J = 7.82 Hz), 5.28-5.29 (2 H , m), 7.55 (1 H , m), 7.64 (1 H, m), 10.10 (1 H, d, J = 1.47 Hz) 13 C NMR (CDCl 3):. δ-1.92, 13.69, 15.93, 18.57 , 20.59, 21.88, 27.60, 30.83, 33.58, 40.72, 50.00, 69.75, 90.83, 121.60, 122.08, 135.80.

Example 39 1- (4-Trimethylsilyl) butyl-3- (3-pentyl) propargylimidazolium trifluoromethyl trifluoroborate 1- (4-Trimethylsilyl) butyl-3- (3-pentyl) iodide in a flask -After adding propargyl imidazolium (0.56 g, 1.3 mmol), potassium trifluoromethyltrifluoroborate (0.35 g, 2 mmol) and tetrahydrofuran (10 ml), the inside of the flask was replaced with argon. After the mixture was reacted at room temperature for 28 hours, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using a mixed solvent (chloroform: methanol = 5: 1) to give 1- (4-trimethylsilyl) butyl. -3- (3-pentyl) -propargylimidazolium trifluoromethyl trifluoroborate (Compound 39) was obtained in a yield of 70%.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.54-0.57 (2 H, m), 0.91-0.93 (3 H, m), 1.32-1.42 (6 H, m), 1.51-1.61 (2 H, m), 1.94 (2 H, quint, J = 7.57 Hz), 2.25-2.29 (2 H, m), 4.23 (2 H, t, J = 7.81 Hz), 5.06-5.07 (2 H, . m), 7.25-7.26 (1 H , m), 7.47-7.48 (1 H, m), 9.12 (1 H, s) 19 F NMR (CDCl 3): δ 5.67 (BF 3, J = 82.39, 41.2 _{. Hz), 85.4 (CF 3} , J = 67.14, 32.04 Hz) 13 C NMR (CDCl 3): δ -1.96, 13.75, 15.88, 18.49, 20.58, 21.95, 27.65, 30.91, 33.46, 40.27, 49.99, 69.58, 90.96, 121.72, 122.09, 135.26.

Example 40 1- (5-Trimethylsilyl) pentyl-3- (3-pentyl) propargylimidazolium iodide
Except that 1- (5-trimethylsilyl) pentylimidazole was used instead of 1- (4-trimethylsilyl) butylimidazole, 1- (5-trimethylsilyl) pentyl-3- (iodide iodide) was prepared in the same manner as in Example 38. 3-Pentyl) propargylimidazolium (compound 40) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.49-0.53 (2 H, m), 0.92-0.95 (3 H, m), 1.35-1.43 (8 H, m), 1.54-1.60 (2 H, m), 1.98 (2 H, quint, J = 7.57 Hz), 2.27-2.31 (2 H, m), 4.36 (2 H, t, J = 7.57 Hz), 5.29-5.30 (2 H, . m), 7.31-7.32 (1 H , m), 7.53-7.54 (1 H, m), 10.34 (1 H, s) 13 C NMR (CDCl 3): δ -1.85, 13.75, 16.40, 18.62, 21.94 , 13.30, 27.67, 29.79, 29.93, 30.89, 40.82, 50.47, 69.76, 90.95, 121.51, 121.83, 136.06

Example 41 1- (4-Trimethylsilyl) butyl-2-methyl-3- (3-pentyl) propargylimidazolium iodide
Except that 1- (4-trimethylsilyl) butyl-2-methylimidazole was used instead of (4-trimethylsilyl) butylimidazole, 1- (4-trimethylsilyl) butyl-2iodide was prepared in the same manner as in Example 40. -Methyl-3- (3-pentyl) propargylimidazolium (compound 41) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.55-0.59 (2 H, m), 0.90-0.93 (3 H, m), 1.33-1.44 (6 H, m), 1.52-1.58 (2 H, m), 2.00 (2 H, quint, J = 7.57 Hz), 2.26-2.30 (2 H, m), 4.37 (2 H, t, J = 7.82 Hz), 5.28-5.29 (2 H, m), 7.55-7.64 (2 H, m), 10.10 (1 H, d, J = 1.47 Hz) 13 C NMR (CDCl 3):. δ -1.92, 13.69, 15.93, 18.57, 20.59, 21.88, 27.60, 30.83, 33.58, 40.72, 50.00, 69.75, 90.83, 121.60, 122.08, 135.80

[Example 42] 1-methyl-1- (3-pentyl) propargylpyrrolidinium iodide 1-methylpyrrolidine (5 mmol), 1-promo-2-octyne (1.13 g, 6 mmol), iodide in a flask After potassium (4,98 g, 30 mmol) and chloroform (50 ml) were added, the inside of the flask was replaced with argon. After the mixture was reacted at 80 ° C. for 8 hours, the solvent was distilled off under reduced pressure to obtain 1-methyl-1- (3-pentyl) propargylpyrrolidinium iodide (Compound 42) in a yield of 78%. .
¹ H NMR (CDCl ₃ ): δ0.91 (3 H, t, J = 7.08 Hz), 1.33-1.36 (4 H, m), 1.51-1.57 (2 H, m), 2.25-2.35 (6 H, m), 3.48 (3 H, s), 3.86-3.91 (2 H, m), 3.98-4.02 (2 H, m), 4.59 (2 H, t, J = 2.19 Hz).

Example 43 1-methyl-1- (3-pentyl) propargylpiperidinium iodide 1-methylpiperidinium (5 mmol), 1-promo-2-octyne (1.13 g, 6 mmol) in a flask, After potassium iodide (4,98 g, 30 mmol) and chloroform (50 ml) were added, the inside of the flask was replaced with argon. After the mixture was reacted at 80 ° C. for 8 hours, the solvent was distilled off under reduced pressure to obtain 1-methyl-1- (3-pentyl) propargylpiperidinium iodide (Compound 43) in a yield of 89%. .
¹ H NMR (CDCl ₃ ): δ 0.91 (3 H, t, J = 7.33 Hz), 1.33-1.35 (4 H, m), 1.52-1.57 (2 H, m), 1.80-1.98 (6 H, m ), 2.26-2.89 (2 H, m), 3.42 (3 H, s), 3.83-3.84 (4 H, m), 4.65 (2 H, m).

Example 44 1-hexyl-3- (3-pentyl) propargylimidazolium iodide Hexylimidazole (5 mmol), 1-promo-2-octyne (1.13 g, 6 mmol), potassium iodide (4 , 98 g, 30 mmol) and chloroform (50 ml) were added, and the inside of the flask was replaced with argon. After the mixture was reacted at 80 ° C. for 8 hours, the solvent was distilled off under reduced pressure to obtain 1-hexyl-3- (3-pentyl) propargylimidazolium iodide (Compound 44) in a yield of 65%.
¹ H NMR (CDCl ₃ ): δ 0.86-0.92 (6 H, m), 1.33 (8 H), 1.51-1.57 (2 H, m), 1.91-1.98 (2 H, m), 2.25-2.28 (2 H, m), 4.33-4.36 (2 H, m), 5.26-5.27 (2 H, m), 7.35 (1 H, m), 7.53 (1 H, m), 10.3 (1 H, s)

Example 45 1- (5-Trimethylsilyl) pentyl-2-methylimidazole (5 mmol) 1- (5-trimethylsilyl) pentyl-2-methyl-3- (3-pentyl) propargylimidazolium iodide in a flask 1-Promo-2-octyne (1.13 g, 6 mmol), potassium iodide (4,98 g, 30 mmol) and chloroform (50 ml) were added, and the flask was purged with argon. After the mixture was reacted at 80 ° C. for 8 hours, the solvent was distilled off under reduced pressure to obtain 1- (5-trimethylsilyl) pentyl-2-methyl-3- (3-pentyl) propargylimidazolium iodide (Compound 45). Was obtained in 77% yield.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.49-0.53 (2 H, m), 0.91-0.94 (3 H, m), 1.34-1.37 (8 H, m), 1.51-1.57 (2 H, m), 1.88 (2 H, quint, J = 7.67 Hz), 2.22-2.26 (2 H, m), 2.91 (3 H, s), 4.24 (2 H, t, J = 7.57 Hz) , 5.23-5.24 (2 H, m), 7.50 (1 H, m), 7.69 (1 H, m).

Example 46 1- (4-Trimethylsilyl) butyl-3-benzylimidazolium iodide 1- (4-trimethylsilyl) butylimidazole (0.77 g, 3.9 mmol), benzyl bromide (1.03 g, 6 mmol) in a flask, After potassium iodide (4,98 g, 30 mmol) and chloroform (50 ml) were added, the inside of the flask was replaced with argon. After the mixture was reacted at 80 ° C. for 18 hours, the solvent was distilled off under reduced pressure to obtain 1- (4-trimethylsilyl) butyl-3-benzylimidazolium iodide (Compound 46) in a yield of 88%.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.54-0.58 (2 H, m), 1.35-1.42 (2 H, m),
1.99 (2 H, quint, J = 7.57 Hz), 4.15 (2 H, quint., J = 7.08 Hz), 5.65 (2 H, s), 7.29-7.30 (1 H, m), 7.43-7.44 (1 H, m), 10.37 (1 H, m)
¹³ C NMR (CDCl ₃ ): δ -1.91, 15.92, 20.61, 33.50, 49.88, 53.23, 121.94, 121.98, 128.97, 129.32, 129.41, 132.65, 136.17,

Example 47 1- (3-pentyl) propargyl-3-benzylimidazolium trifluoromethyl trifluoroborate 1- (3-pentyl) propargyl-3-benzylimidazolium iodide (2 mmol) and trifluoromethyl trifluoro After reacting roborate potassium (3 mmol) with tetrahydrofuran (10 ml) at room temperature for 24 hours, the solvent was distilled off and 1- (3-pentyl) propargyl-3-benzylimidazolium trifluoromethyltrifluoroborate (compound) 47) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.08 Hz), 0.9 (3 H, t, J = 6.59 Hz), 1.25 to 1.38 (22 H, m), 1.51-1.64 (2 H, m), 1.86-1.92 (2 H, m), 4.19 (2 H, q), 5.00 (2 H, m), 7.25-7.26 (Ar-H), 7.45 (1H, m)

Example 48 1-dodecyl-3-benzylimidazolium trifluoromethyltrifluoroborate 1-dodecyl-3-benzylimidazolium iodide (2 mmol) and potassium trifluoromethyltrifluoroborate (3 mmol) were added to tetrahydrofuran (3 mmol). 10 ml) was reacted at room temperature for 24 hours, and then the solvent was distilled off to obtain 1-dodecyl-3-benzylimidazolium trifluoromethyltrifluoroborate (Compound 48).
¹ H NMR (CDCl ₃ ): δ 0.88 (3 H, t, J = 7.32 Hz), 1.19 to 1.31 (18H, m), 1.85 to 1.86 (2 H, m), 420 (2H, q), 5.38 ( 2H, S), 7.21-7.24 (Ar-H), 9.26 (1H, S), 19F NMR (CDCl ₃ ): 8, 6.23 (3F, m), 85.7 (3F, m),

Example 49 1- (5-Trimethylsilylpentyl) -1- (3-pentyl) propargylpyrrolidinium iodide 1- (3-pentyl) propargylpyrrolidine (5 mmol), 5-trimethylsilylpentyl bromide (5 mmol) 6 mmol), potassium iodide (4,98 g, 30 mmol) and chloroform (50 ml) were added, and the flask was replaced with argon. After the mixture was reacted at 80 ° C. for 8 hours, the solvent was distilled off under reduced pressure to obtain 1- (5-trimethylsilylpentyl) -1- (3-pentyl) propargylpyrrolidinium iodide (Compound 49). .
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.50-0.53 (2 H, m), 0.93 (3 H, t, J = 7.08 Hz), 1.35-1.58 (10 H, m), 1.79-1.80 (2 H, m), 2.27-2.39 (6 H, m), 3.62-3.65 (2 H, m), 3.85-3.90 (2 H, m), 3.95-3.99 (2 H, m), 4.33 (2 H, m)

Example 50 1- (4-Pentyl) benzyl-3- (4-trimethylsilyl) butylimidazolium iodide
(4-Trimethylsilyl) butylimidazole (5 mmol), (4-pentyl) benzyl bromide (6 mmol) and chloroform (30 ml) were heated to reflux for 10 hours. Pentyl) benzyl-3- (4-trimethylsilyl) butylimidazolium (Compound 50) was obtained in 88% yield.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.54-0.57 (2 H, m), 0.92 (3 H, t, J = 7.02 Hz), 1.32-1.40 (10 H, m), 1.60-1.67 (2 H, m), 1.69-2.00 (2 H, m), 2.61-2.64 (2 H, m), 7.19-7.24 (4 H, m), 7.30 (1 H, s), 7.40- 7.41 (2 H, m).

Example 51 1- (4-Trimethylsilyl) hexyl-2-methyl-3- (3-pentyl) propargylimidazolium iodide in a flask with 1- (4-trimethylsilyl) hexyl-2-methylimidazole (5 mmol), 1-Promo-2-octyne (1.13 g, 6 mmol), potassium iodide (4,98 g, 30 mmol) and chloroform (50 ml) were added, and the flask was purged with argon. After the mixture was reacted at 80 ° C. for 8 hours, the solvent was distilled off under reduced pressure to give 1- (4-trimethylsilyl) hexyl-2-methyl-3- (3-pentyl) propargylimidazolium iodide (Compound 51) Was obtained in a yield of 52%.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.48-0.51 (2 H, m), 0.93 (3 H, t, J = 7.08 Hz), 1.31-1.41 (10 H, m), 1.51-1.65 (2 H, m), 1.87-1.90 (2 H, m), 2.23-2.26 (2 H, m), 4.19-4.22 (2 H, m), 5.16-5.17 (2 H, s), 7.38 (1 H, d, J = 2.20 Hz), 7.57 (1 H, d, J = 2.20 Hz).

Example 52 1- (4-Trimethylsilyl) heptyl-2-methyl-3- (3-pentyl) propargylimidazolium iodide
The reaction was conducted in the same manner as in Example 51 using 1- (4-trimethylsilyl) heptyl-2-methylimidazole instead of 1- (4-trimethylsilyl) hexyl-2-methylimidazole, and 1- (4-trimethylsilyl) hexyl-2-methylimidazole Trimethylsilyl) heptyl-2-methyl-3- (3-pentyl) propargylimidazolium (Compound 52) was obtained in a yield of 78%.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.48-0.51 (2 H, m), 0.92 (3 H, t, J = 7.08 Hz), 1.33-1.38 (14 H, m), 1.53-1.56 (2 H, m), 1.87-1.89 (2 H, m), 2.23-2.26 (2 H, m), 2.91 (3 H, s), 4.23-4.26 (2 H, m), 5.24 ( 2 H, s), 7.31 (1 H, s), 7.50 (1 H, d, J = 1.96 Hz), 7.69 (1 H, d, J = 1.96 Hz).

Example 53 1- (4-Trimethylsilyl) nonyl-2-methyl-3- (3-pentyl) propargylimidazolium iodide
The reaction was carried out in the same manner as in Example 51 using 1- (4-trimethylsilyl) nonyl-2-methylimidazole instead of 1- (4-trimethylsilyl) hexyl-2-methylimidazole, and 1- (4-trimethylsilyl) hexyl-2-methylimidazole Trimethylsilyl) nonyl-2-methyl-3- (3-pentyl) propargylimidazolium (compound 53) was obtained in a yield of 52%.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.48-0.51 (2 H, m), 0.93 (3 H, t, J = 7.08 Hz), 1.31-1.41 (10 H, m), 1.51-1.65 (2 H, m), 1.87-1.90 (2 H, m), 2.23-2.26 (2 H, m), 4.19-4.22 (2 H, m), 5.16-5.17 (2 H, s), 7.38 (1 H, d, J = 2.20 Hz), 7.57 (1 H, d, J = 2.20 Hz).

Example 54 1- (4-Trimethylsilyl) undecanyl-2-methyl-3- (3-pentyl) propargylimidazolium iodide
The reaction was carried out in the same manner as in Example 51 using 1- (4-trimethylsilyl) undecanyl-2-methylimidazole instead of 1- (4-trimethylsilyl) hexyl-2-methylimidazole, and 1- (4-trimethylsilyl) hexyl-2-methylimidazole Trimethylsilyl) undecanyl-2-methyl-3- (3-pentyl) propargylimidazolium (compound 54) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.03 (9 H, m), 0.47-0.49 (2 H, m), 0.88-0.91 (4 H, m), 1.25-1.37 (24 H, m), 1.49-1.52 (2 H, m), 1.83-1.86 (2 H, m), 2.88 (3 H, s), 4.20-4.23 (2 H, m), 5.22 (2 H, m), 7.50 (1 H, d, J = 2.20 Hz), 7.68 (1 H, d, J = 2.20 Hz).

Example 55 1- (5,5,5-Trimethyl) pentyl-3- (3-pentyl) propargylimidazolium iodide
The reaction was carried out in the same manner as in Example 51 using 1- (5,5,5-trimethyl) pentylimidazole instead of 1- (4-trimethylsilyl) hexyl-2-methylimidazole, and 1- (5, 5,5-Trimethyl) pentyl-3- (3-pentyl) propargylimidazolium (Compound 55) was obtained in a yield of 70%.
¹ H NMR (CDCl ₃ ): δ 0.87 (9 H), 0.91 (3 H, t, J = 7.08 Hz), 1.22-1.25 (2 H, m), 1.32-1.36 (6 H, m), 1.51- 1.57 (2 H, m), 1.90-1.96 (4 H, m), 2.25-2.28 (2 H, m), 4.33-4.64 (2 H, m), 5.26-5.27 (2 H, m), 7.41 ( 1 H, m), 7.57 (1 H, m), 10.1 (1 H, s) Y. 70%

Example 56 1- (4- (2-Ethylsilyl) benzyl-3- (4-trimethylsilyl) butylimidazolium iodide
The reaction was carried out in the same manner as in Example 51 using 1- (4-trimethylsilyl) butylimidazole and 4- (2-ethylsilyl) benzyl bromide instead of 1- (4-trimethylsilyl) hexyl-2-methylimidazole, 1- (4- (2-Ethylsilyl) benzyl-3- (4-trimethylsilyl) butylimidazolium iodide (Compound 56) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.51-0.55 (2 H, m), 0.82-0.84 (2 H, m), 1.35-1.38 (2 H, m), 1.94-1.97 (2 H, m), 2.60-2.64 (2 H, m), 4.29-4.32 (2 H, m), 5.55 (2 H, s), 7.12-7.38 (Ar-H + 2 H), 10.82 (1 H, s)

[Example 57] 1-biphenylmethyl-3- (4-trimethylsilyl) butylimidazolium iodide
The reaction was performed in the same manner as in Example 51 using 1- (4-trimethylsilyl) butylimidazole and biphenylmethane bromide instead of 1- (4-trimethylsilyl) hexyl-2-methylimidazole, and 1-biphenylmethyl iodide was obtained. -3- (4-Trimethylsilyl) butylimidazolium (Compound 57) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.55-0.58 (2 H, m), 1.38-1.41 (2 H, m), 1.99-2.02 (2 H, m), 4.31-4.34 (2 H, m), 5.70 (2 H, s), 7.26-7.66 (Ar-H + 2 H), 10.46 (1 H, s)

Example 58 1-methyl-1- (3-pentyl) propargylpyrrolidinium trifluorotrifluoroborate
After reacting a solution of 2-1-methyl-1- (3-pentyl) propargylpyrrolidinium (4 mmol) and CF ₃ BF ₃ K (4.1 mmol) in THF (20 ml) at room temperature for 20 hours, the solvent was removed. Distilled off. Purification by chromatography yielded 1-methyl-1- (3-pentyl) propargylpyrrolidinium iodide tetrafluoroborate (compound 58) in 78% yield.
¹ H NMR (CDCl ₃ ): δ 0.91 (3 H, t, J = 7.08 Hz), 1.33-1.36 (4 H, m), 1.51-1.57 (2 H, m), 2.25-2.35 (6 H, m ), 3.48 (3 H, s), 3.86-3.91 (2 H, m), 3.98-4.02 (2 H, m), 4.59 (2 H, t, J = 2.19 Hz). ¹⁹ F NMR (CDCl ₃ ) : δ 6.03-6.30 (BF ₃ , m), 85.55-85.76 (CF ₃ , m)

[Example 59] 1-methyl-1- (4-trimethylsilylbutyl) propargylpyrrolidinium iodide methylpyrrolidinium (0.34 g, 4 mmol), 4-trimethylsilylbutyl bromide (1.09 g, 4.5 mmol), iodide Potassium (4.98 g, 30 mmol) was dissolved in chloroform (50 ml). After the mixture was heated to reflux, the solvent was distilled off under reduced pressure. By purification by chromatography, 1-methyl-1- (4-trimethylsilylbutyl) propargylpyrrolidinium iodide (Compound 59) was obtained in a yield of 46%.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H), 0.55-0.59 (2 H, m), 1.41-1.45 (2 H, m), 1.91-1.85 (2 H, m), 2.34 (4 H, m), 3.31 (3 H, s), 3.59-3.63 (2 H, m), 3.81-3.89 (4 H, m)

[Example 60] 1-Methyl-1- (4,4,4-trifluorobutyl) piperidinium iodide Methylpiperidinium (5 mmol), 4,4,4-trifluorobutyl bromide (6 mmol), potassium iodide (4,98 g, 30 mmol) and chloroform (50 ml) were added, and the flask was purged with argon. After the mixture was reacted at 80 ° C. for 8 hours, the solvent was distilled off under reduced pressure to obtain 1-methyl-1- (4,4,4-trifluorobutyl) piperidinium iodide (Compound 60) in a yield. Obtained at 35%.
¹ H NMR (CDCl ₃ ): δ 1.71-1.90 (2 H, m), 1.94-2.02 (4 H, m), 2.06-2.13 (2 H, m), 2.39-2.44 (2 H, m), 3.38 (3 H, s), 3.70-3.72 (4 H, m), 3.94-3.97 (2 H, m)
¹⁹ NMR NMR (CDCl ₃ ): δ96.0 (t, J = 10.7 Hz).

Example 61 1-methyl-1- (4,4,4-trifluorobutyl) pyrrolidinium iodide Methylpyrrolidinium (5 mmol), 4,4,4-trifluorobutyl bromide (6 mmol) in a flask ), Potassium iodide (4,98 g, 30 mmol) and chloroform (50 ml) were added, and the flask was purged with argon. After the mixture was reacted at 80 ° C. for 8 hours, the solvent was distilled off under reduced pressure to obtain 1-methyl-1- (4,4,4-trifluorobutyl) pyrrolidinium iodide (Compound 61) in a yield of 62%. I got it.
¹ H NMR (CDCl ₃ ): δ 2.11-2.17 (2 H, m), 2.30-2.43 (6 H, m), 3.32 (3 H, s), 3.81--3.98 (6 H, m)
¹⁹ F NMR NMR (CDCl ₃ ): δ95.6 (t, J = 10.7 Hz).

Example 62 1-methyl-1- (4,4,4-trifluorobutyl) pyrrolidinium trifluoromethyl trifluoroborate 1-methyl-1- (4,4,4-trifluorobutyl) pyrrolidinium iodide ( 2 mmol) and potassium trifluoromethyltrifluoroborate (3 mmol) were reacted with tetrahydrofuran (10 ml) at room temperature for 24 hours, and then the solvent was distilled off to give 1-methyl-1- (4,4,4-trimethyl). Fluorobutyl) pyrrolidinium trifluoromethyl trifluoroborate (Compound 62) was obtained.
¹ H NMR (CDCl ₃ ): δ 1.91-1.99 (2 H, m), 2.32-2.38 (2 H, m), 2.50-2.51 (2 H, m), 3.01 (3 H, s), 3.34-3.53 (8 H, m). ¹⁹ F NMR NMR (CDCl ₃ ): δ8.50 (BF ₃ , m), 88.4 (CF ₃ , m).

Example 63 1- (4- (2-Ethylsilyl) benzyl-3- (5-trimethylsilyl) pentylimidazolium iodide
The reaction was conducted in the same manner as in Example 51 using 1- (5-trimethylsilyl) pentylimidazole and 4- (2-ethylsilyl) benzyl bromide instead of 1- (4-trimethylsilyl) hexyl-2-methylimidazole, 1- (4- (2-Ethylsilyl) benzyl-3- (5-trimethylsilyl) pentylimidazolium iodide (Compound 63) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.45-0.48 (2 H, m), 0.82-0.85 (2 H, m), 1.33-1.37 (4 H, m), 1.91-1.94 (2 H, m), 2.60-2.64 (2 H, m), 4.28-4.31 (2 H, m), 5.54 (2 H, s), 7.24-7.27 (1 H, m), 7.27-7.40 (1 H, m), 10.43 (1 H, s)

Example 64 1- (4- (2-Ethylsilyl) benzyl-3- (6-trimethylsilyl) hexylimidazolium iodide
The reaction was carried out in the same manner as in Example 51 using 1- (6-trimethylsilyl) hexylimidazole and 4- (2-ethylsilyl) benzyl bromide instead of 1- (4-trimethylsilyl) hexyl-2-methylimidazole, 1- (4- (2-ethylsilyl) benzyl-3- (6-trimethylsilyl) hexylimidazolium iodide (Compound 64) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.43-0.47 (2 H, m), 0.82-0.85 (2 H, m), 1.27-1.37 (6 H, m), 1.92 (2 H, m), 2.60-2.64 (2 H, m), 4.29-4.32 (2 H, m), 5.54 (2 H, s), 7.24-7.27 (1 H, m), 7.38-7.39 (1 H, m), 10.42 (1 H, s)

Example 65 1- (4- (2-Ethylsilyl) benzyl-3- (7-trimethylsilyl) heptylimidazolium iodide
A reaction was carried out in the same manner as in Example 51 using 1- (7-trimethylsilyl) heptylimidazole and 4- (2-ethylsilyl) benzyl bromide instead of 1- (4-trimethylsilyl) hexyl-2-methylimidazole, 1- (4- (2-Ethylsilyl) benzyl-3- (7-trimethylsilyl) heptylimidazolium iodide (Compound 65) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.47-0.50 (2 H, m), 0.85-0.88 (2 H, m), 1.31-1.36 (8 H, m), 1.91-1.95 (2 H, m), 2.63-2.67 (2 H, m), 4.32-4.35 (2 H, m), 5.56 (2 H, s), 7.23-7.43 (Ar-H + 2 H), 10.78 (1 H, s)

Example 66 1- (4- (2-Ethylsilyl) benzyl-3- (9-trimethylsilyl) nonylimidazolium iodide
The reaction was conducted in the same manner as in Example 51 using 1- (9-trimethylsilyl) nonylimidazole and 4- (2-ethylsilyl) benzyl bromide instead of 1- (4-trimethylsilyl) hexyl-2-methylimidazole, 1- (4- (2-Ethylsilyl) benzyl-3- (9-trimethylsilyl) nonylimidazolium iodide (Compound 66) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.00 (9 H, m), 0.50 (2 H, m), 0.85-0.88 (2 H, m), 1.28-1.36 (10 H, m), 1.94-1.96 (2 H, m), 2.63-2.67 (2 H, m), 4.31-4.34 (2 H, m), 5.58 (2 H, s), 7.24-7.44 (Ar-H + 2 H), 10.39 (1 H, s)

[Test Example 1] Measurement of melting point The melting points of Compound 1 to Compound 37 were measured. The results are shown in Table 1.

表１から以下のことが示唆される。

Table 1 suggests the following.

(1) When the number of carbon atoms in the 1-position alkyl group of imidazole decreases, the melting point decreases. For example, among Compound 1, Compound 2, and Compound 3 in which the 2-position and 3-position of imidazole have the same structure, Compound 3 having a dodecyl group has the lowest melting point, and Compound 1 having a cetyl group has the highest melting point.

(2) Comparing compounds having a halogen substituent on the phenyl group, the compound having a fluorine substituent has a lower melting point than compounds having other halogen substituents. For example, when Compound 6, Compound 22, and Compound 23 having the same structure other than the type of halogen are compared, Compound 6 having a fluorine substituent has the lowest melting point.

  As for the position of the substituent, a compound having a substituent at the 3-position of the phenyl group has a lower melting point than other compounds. For example, when the melting points of Compound 4, Compound 6, and Compound 7 are compared, Compound 6 having a fluorine substituent at the 3-position has the lowest melting point.

(3) When a compound having a benzyl group and a compound having a propargyl group are compared at the 3-position of imidazole, the compound having a propargyl group has a lower melting point. For example, comparing Compound 1 and Compound 26 in which the 1-position and 2-position of imidazole have the same structure, Compound 1 having a benzyl group has a melting point of 98 ° C., whereas Compound 26 having a propargyl group is at room temperature. It is liquid.

(4) When comparing a compound introduced with a methyl group at the 2-position of imidazole with a compound not introduced with a methyl group, the compound having no methyl group introduced has a lower melting point. For example, when comparing Compound 1 and Compound 31 in which the 1-position and 3-position of imidazole have the same structure, the melting point of Compound 1 having a methyl group is 98 ° C., whereas the melting point of Compound 31 having no methyl group is Is 47 ° C.

[Test Example 2] Measurement of antibacterial activity (1) Experimental method The antibacterial activity of each compound was examined by the agar plate dilution method based on the standard method of the Japanese Chemotherapy Society.

(1-1) Medium and test strain
A mixture of Mueller Hinton Broth (DIFICO) with Agar Powder (WAKO) added to 1.5% was sterilized with an autoclave (TOMY BS325) and then dispensed into a petri dish. After solidifying at room temperature, it was dried for about 1 hour with a thermostatic device (AS-ONE DO-450A) set at 45 ° C. Thereafter, the test bacteria were inoculated into the petri dish and cultured for 16-20 hours in a thermostat at 30 ° C. The test strains used are as follows.

Escherichia coli MG 1655 strain (Gram-negative bacteria)
Bacillus subtilis 168 strain (Gram positive bacteria)
Pseudomonas putida NBRC 14164 (Gram-negative bacteria)
Staphylococcus aureus subsp aureus NRBC 15035 (Gram-positive bacteria)
Salmonella typhimurium NBRC 13245 strain (Gram-negative bacteria)
Corynebacterium glutamicum ATCC 31831 strain (gram positive bacteria)
(1-2) Preparation of Bacteria Single colonies of the inoculated bacteria were collected and cultured in LB Broth (DIFCO) with shaking at 30 ° C. for 16-20 hours.

(1-3) Production of activity-agar plate First, 0.63 g of Mueller Hinton Broth and 30 ml of pure water were added to a Falcon tube containing 0.45 g of Agar Powder, and the mixture was stirred and sterilized by an autoclave. Next, the compound synthesized in Example was dissolved in methanol so as to be 10 mg / ml, and stored in ice. Each compound was put into the medium in each Falcon tube after sterilization kept at 60 ° C. or lower, mixed and dispensed onto a Petri dish. After solidification, the surface of the flat plate was dried for 2 hours with a thermostat at 45 ° C.

(1-4) Preparation of inoculum
Each cultured bacterium was serially diluted 10 ^-1 to 10 ^-6 times. For dilution, physiological saline (0.85%) was used.

(1-5) Determination of activity 10 μl of each prepared bacterial cell of each concentration was spotted on the prepared agar plate. Then, it culture | cultivated for 16-20 hours with a 30 degreeC thermostat, and the presence or absence of activity was determined. The presence / absence of activity was determined based on the presence or absence of growth of bacteria by visual observation at a spot with a concentration of 10 ⁶ cells / ml, and the minimum concentration of a compound in which no growth was observed was defined as the minimum growth inhibitory concentration.

(2) Experimental results Table 2 shows the minimum inhibitory concentration of each compound against the test strain.

表２から以下のことが示唆される。

Table 2 suggests the following.

(1) Comparing compounds having a halogen substituent on the phenyl group, the compounds having a fluorine substituent have higher antibacterial activity than compounds having other halogen substituents. For example, when Compound 6, Compound 22, and Compound 23 having the same structure other than the type of halogen are compared, Compound 6 having a fluorine substituent has the lowest minimum inhibitory concentration.

(2) When comparing a compound introduced with a methyl group at the 2-position of imidazole with a compound not introduced with a methyl group, the compound introduced with a methyl group has a higher antibacterial activity against Gram-positive bacteria. For example, comparing Compound 1 and Compound 31 in which the 1-position and 3-position of imidazole have the same structure, Compound 1 having a methyl group is more B.sutilis and S.aureus than Compound 31 having no methyl group. The minimum inhibitory concentration against is low.

(3) Regarding the counter anion, CF ₃ BF ₃ ⁻ shows higher antibacterial activity than other anions. For example, when comparing the compounds 38 and 39 having the same structure except for the counter anion and the compounds 48 and 49, the compound having CF ₃ BF ₃ ^— has a lower minimum inhibitory concentration.

Claims (10)

The following general formula (I)

[Wherein, R ¹ is a linear or branched alkyl group having 4 to 20 carbon atoms which may be substituted with one or more substituents selected from the following substituent group A, or the following substitution Represents a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted by one or more substituents selected from the group A, and R ² represents a hydrogen atom or a carbon number 1 to 1 3 represents a linear or branched alkyl group, and R ³ represents a phenyl group which may be substituted with one or more substituents selected from the following substituent group A or from the following substituent group A. Represents a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted with one or more selected substituents, and Xa ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , I ^{−. _{, BF 4 -, PF 6 -}} , CF 3 BF 3 - C ₂ F ₅ BF ₃ ^-, or _{(CF 3 SO 3) 2 N} - represents the, substituent group A is a group consisting of a halogen atom, a trimethylsilyl group, ethylsilyl group and a phenyl group. ]
A compound represented by The compound according to claim 1, wherein R ¹ in the general formula (I) is a linear alkyl group having 10 to 12 carbon atoms. The compound according to claim 1 or 2, wherein R ² in the general formula (I) is a methyl group. The compound according to claim 1 or 2, wherein R ² in the general formula (I) is a hydrogen atom. The compound according to any one of claims 1 to 4, wherein R ³ in the general formula (I) is a phenyl group substituted by a fluorine atom. The compound according to any one of claims 1 to 4, wherein R ³ in the general formula (I) is an ethynyl group. Xa in the general formula (I) is, _{CF 3} BF 3 ^- A compound according to any one of claims 1 to 6 is. Below, general formula (II)

[Wherein, R ⁴ represents a linear or branched alkyl group having 1 to 5 carbon atoms which may be substituted by a hydrogen atom or one or more substituents selected from the following substituent group B. R ⁵ represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with one or more substituents selected from the following substituent group B, or the following substituent group Represents a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted by one or more substituents selected from B, Xb ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , Represents I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ BF ₃ ⁻ , C ₂ F ₅ BF ₃ ⁻ , or (CF ₃ SO ₃ ) ₂ N ⁻ , and the substituent group B includes a halogen atom and a trimethylsilyl group. It is a group. ]
A compound represented by Below, general formula (III)

[In the formula, R ⁶ represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms which may be substituted with one or more substituents selected from the following substituent group C. R ⁷ represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with one or more substituents selected from the following substituent group C, or the following substituent group Represents a linear or branched alkynyl group having 2 to 20 carbon atoms which may be substituted by one or more substituents selected from C, Xc ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ BF ₃ ⁻ , C ₂ F ₅ BF ₃ ⁻ , or (CF ₃ SO ₃ ) ₂ N ⁻ , and the substituent group C is a halogen atom and a trimethylsilyl group. It is a group. ]
A compound represented by   An antibacterial agent comprising the compound according to any one of claims 1 to 9.