WO2005028446A1

WO2005028446A1 - Ionic liquid and method of reaction using the same

Info

Publication number: WO2005028446A1
Application number: PCT/JP2004/013467
Authority: WO
Inventors: Chiaki Yokoyama; Kun Qiao
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2003-09-18
Filing date: 2004-09-15
Publication date: 2005-03-31
Also published as: JPWO2005028446A1; CN1852898B; CN1852898A; TW200517375A; DE112004001729T5

Abstract

A novel acidic ionic liquid which is useful as a catalyst for alkylation, nitration, Beckmann rearrangement, etc. and is stable to air and water. It is an ionic liquid represented by the following formula (1): (1) wherein X represents halogeno or hydroxy; Y- represents CF3SO3-, BF4-, PF6-, CH3COO-, CF3COO-, (CF3SO2)2N-, (CF3SO2)3C-, F-, Cl-, Br-, or I-; n is an integer of 2 to 16; and R represents methyl, allyl, or vinyl. This ionic liquid not only functions as a BrDnsted acid or a Lewis acid but is a liquid insoluble in many organic solvents. The liquid is hence useful as a catalyst or solvent for Friedel-Crafts reaction, nitration, and Beckmann rearrangement. It can be easily separated from the reaction mixture and reused.

Description

Specification

Ionic liquid and reaction method using the same

Technical field

The present invention relates to a novel ionic liquid, a reaction method using the same, and a method for producing a compound using the reaction method. Reactions using this ionic liquid include alkylation, nitration, and Beckmann rearrangement.

Background art

[0002] In recent years, ionic liquids have been recognized as promising solvents in the field of synthetic chemistry, and include Aldall reaction, Diels-Alder reaction, Claisen rearrangement reaction, Heck reaction, Beckman reaction, Friedel's Kraft reaction, It is expected that it can be used for many chemical reactions such as the Vils'Hillman reaction, nitration reaction, and asymmetric synthesis reaction.

[0003] An ionic liquid is an organic salt composed of an aion and an organic cation, and is numbered over one hundred. It has a melting point below C, has almost no vapor pressure, has low viscosity instead of being ionic, is heat resistant and has a wide liquid temperature range, has high ionic conductivity, can be made water-insoluble, and has acidity. A new group of substances that have the characteristics of being stable, stable, etc., and have the potential to fundamentally reform existing materials and systems as reusable solvents, catalysts or electrolytes. It is academically in the spotlight and highly expected from the industrial world (see Modern Chemistry, March 2001, p.56-62).

[0004] The most important feature of ionic liquids is that the chemical and physical properties can be precisely optimized by careful selection of cations and aions, and furthermore, This means that the cations and aions can be modified by the functional groups. It is known that various compounds can be used as the ionic liquid. However, it is required that the ionic liquid has a function as a catalyst and a solvent and is not decomposed in a reaction system and can be used repeatedly. Have been. J. Am. Chem. Soc, 2002, 124, p5962-5963, reported that a Bronsted acidic ionic liquid functionalized with a kind of sulfonic acid group is suitable as a catalyst for esterification and ethereal reaction. ing.

However, 1-n-butyl-3-methylimidazolium-tetrafluoroborate (BMImBF ) And 1-n-butyl-3-methylimidazolyme-hexafluorophosphate (BMImPF)

Well-known ionic liquids, such as 46, are stable to air and water, but are generally considered neutral and can only be used as solvents in most cases. The chloroaluminate ionic liquid also functions as an acidic catalyst, but is reactive to air and water, which is a major obstacle to practical use.

[0006] As for the Friedel-Crafts-Alkylation reaction of aromatic hydrocarbons using alkenes, J. Mol. Catal. A, 2001, reports that the reaction proceeds in a chloroaluminate ionic liquid. , 171, p81-84. Also, Chem. Comnun. 2000

, pl695-1696, the cation moiety is linked to the n-Bu group and CH-SOH is linked to the N atom of imidazole.

4 8 3

An ionic liquid (la) having a combined structure and the aion part is CF SO, and a cation part

3 3

Is P (Ph) C H SO H and the anionic part is p-CH-CH-SO (2a)

3 3 6 3 3 6 4 3

And you have done some reactions. This reaction is said to be superior to the ionic liquid (2a) which is an esterification reaction, a dehydration dimerization reaction of alcohol, a pinacol rearrangement reaction or the like.

[0007] The alkylidation reaction of an aromatic hydrocarbon with an alkene using the Friedel-Crafts reaction is one of the most important reactions in the chemical industry. The most typical example is the production of 1-phenyl-1-xylylethane (PXE) by alkylation of xylene with styrene. PXE is a colorless synthetic oil widely used as a solvent for pressure-sensitive recording materials, plasticizers, heat transfer media, and electrical insulating oils.

[0008] Polycyclic aromatic hydrocarbons obtained by the alkyl reaction of alkylbenzene and styrenes have excellent compatibility, heat resistance, lubricity, and electrical properties, and include plasticizers, high-boiling solvents, Provides synthetic oils suitable for a wide range of applications, such as media, electrical insulating oils, hydraulic oils, and lubricants. This synthetic oil has excellent performance for these uses, and since styrene, which is a raw material, which is a preferable raw material, has an extremely easy property to polymerize, the use of a conventional alkylation catalyst is not sufficient. Cannot be obtained in good yield.

[0009] Anciently, this reaction was performed in the presence of sulfuric acid. JP-A-47-29351 discloses that a sulfuric acid having a concentration of 70-95% is used as a catalyst, the concentration of styrene in a reaction system is kept at 5% by weight or less, and the concentration of a product is kept at 50% by weight or less. At a temperature below 30 ° C A method of reacting styrene with xylene or toluene under stirring is proposed. In this method, when removing the catalyst after the reaction is completed, Na SO is by-produced to neutralize the acid with NaOH,

2 4 It is necessary to spend a great deal of money on post-processing of the neutralized water washing, and it is necessary to prevent corrosion of the equipment and environmental pollution by wastewater.

[0010] In order to overcome these problems, a method for synthesizing PXE by alkylating xylene with styrene using a solid acid catalyst such as silica'alumina zeolite has been developed. JP-A-53-135959 discloses a method of alkylating a side chain alkyl group having 14 carbon atoms with at least one type of styrene such as styrene, butyltoluene and α-methylstyrene. A method for alkylidene alkylbenzene by continuously supplying alkylbenzene and styrenes in a liquid phase at a temperature of 100 to 200 ° C to a silica 'alumina solid acid catalyst layer having a controlled pore size and specific area, You. This method does not have the post-treatment problems of the concentrated sulfuric acid catalyst method, but the styrene oligomerization product blocks the active site of the catalyst, causing rapid catalyst deactivation. Is required.

[0011] Chem. Comnun. 2000, p695-1696 describes a method of alkylating an aromatic compound using an ionic liquid and scandium triflate as a catalyst. Here, as the ionic liquid, [emim] [SbF]

6, [emim] [BF]] [OTf] or [PF]

4, [emim [bmim]

6 are used and may decompose to generate acids such as HF. This makes it difficult to reuse the ionic liquid, and corrosion by the generated acid becomes a problem. Furthermore, in this reaction, the ionic liquid functions as a solvent instead of a catalyst, and a large amount of the ionic liquid is required for processing. Here, [emim] + represents 1-ethyl-3-methylimidazolium cation, and [bmim] + represents 1-butyl-3-methylimidazolidine cation.

The alkylation reaction of an aromatic compound with an alkene utilizing the Friedel-Crafts reaction is one of the most important reactions in the chemical industry. The most typical example is the production of alkylated aromatic hydrocarbons such as ethylbenzene and octylbenzene by reacting benzene with an aliphatic olefin having 2 or more carbon atoms. These alkylated aromatic hydrocarbons are useful as raw materials for styrene and surfactants. [0013] The alkylation reaction of an aromatic compound with an alkene utilizing the Friedel-Crafts reaction is usually carried out using a solid acid such as a protonic acid such as a mineral acid, a Lewis acid such as A: i or BF, or zeolite.

3 3

Often done using an acid catalyst. However, unless a solid acid catalyst is used, there is a problem that a large amount of waste such as waste acid is generated. On the other hand, the method using a solid acid catalyst often has problems with the reaction yield and catalyst life, particularly when the molecular weight of the alkene is large.

[0014] Also, Japanese Patent Application Laid-Open No. 8-508754 discloses that, when an aromatic hydrocarbon is reacted with an olefin in the presence of an ionic liquid to carry out alkylation, a) a formula R MX (R Haa

n 3-n alkyl group, M is A1 or Ga, X is halogen, n is 0-2 compound, and b) hydrocarbyl-substituted imidazolym halide, hydrocarbyl-substituted pyridinium halide is proposed. There is only teaching the production of ethylbenzene.

[0015] In JP-A-11-199525, Sc (OTl)

A method for alkylating an aromatic compound using a triflate conjugate of a rare earth element as a catalyst is described, and teaches that the triflate conjugate is effective as a Friedel-Crafts reaction catalyst. Special table

2001-509134 describes a method for alkylating aromatic compounds using a catalyst in which a Lewis acid such as aluminum chloride is dissolved in an ionic liquid. Here, examples of the ionic liquid include a quaternary ammonium salt, an imidazoline salt, a pyridinium salt, a sulfodium salt, and a phosphonium salt.

On the other hand, a nitrated aromatic compound represented by nitrobenzene is obtained by reacting concentrated nitric acid with an aromatic compound in the presence of a catalyst such as sulfuric acid. However, such a reaction generates a large amount of waste acid, and causes environmental problems. As the catalyst, besides sulfuric acid, boron trifluoride, which is a Lewis acid, and a solid acid catalyst are known, but there is a problem in treating a waste catalyst.

[0017] As a reusable catalyst, Chem. Comnun. 1996, p469-470 describes a nitration method using acetic anhydride and zeolite, but there is a problem in the treatment of acetic anhydride and the like. is there . Chem. Comnun. 1997, p 613-614, describes a nitration method using a lanthanide (III) triflate catalyst. It is necessary to use harmful solvents such as force S and dichloromethane. is there. [0018] By the way, in J. Org. Chem. 2001, 66, p35-40, [emim] [X] (where emim indicates 1-ethyl-3-methylimidazolym as an ionic liquid) , X is CF COO, NO, AlxCly, BF

3 3 4

, PF, OTf) are disclosed.

6

In addition to the use of Lewis acids as catalysts, nitrates or salts are used as nitrating agents.

Next, the Beckmann rearrangement reaction is performed by treating ketoxime or aldoxime with a strong acid such as sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, hydrogen fluoride, polyphosphoric acid, phosphorus pentachloride and similar substances. For example, when sulfuric acid or fuming sulfuric acid is used, a sulfated amide complex is obtained after the rearrangement reaction, in which case the desired amide can be removed by neutralizing the reaction mixture with ordinary ammonia, and this step is carried out. A large amount of ammonium sulfate is by-produced.

[0020] An example of an industrial application using the Beckmann rearrangement reaction is a method for producing a ratatum such as ketoximeca such as cyclohexanone oxime and a mopro I prolatatam. Ratatams such as ε-caprolactam are raw materials for nylon and are industrially important materials. _ε- Caprolactam is industrially produced by the Beckmann rearrangement of cyclohexanone oxime using fuming sulfuric acid, and a large amount of ammonium sulfate is produced as a by-product.

[0021] In Japanese Patent Application Laid-Open No. 09-3041, a gas phase reaction is carried out using a metal oxide catalyst in the presence of ammonia, hydrogen, and water vapor using ε-force prolataton or the like as a starting material.

In JP-A 09-241236, cyclohexanone oxime is used as a starting material and in contact with zeolite / 3 in the gas phase in a gas phase. By producing Beckmann rearrangement, ammonium sulfate is not produced as a by-product! We have proposed a process.However, since it is a gas phase reaction at a high temperature and also requires energy to regenerate a solid acid catalyst, a lower temperature reaction is required. It is desirable to develop a process that is possible and easy to recycle.

[0022] In Tetrahedron lett. 2001, 42, p403-405, in the Beckmann rearrangement reaction of ketoxime, the ionic liquid n-butylpyridin-dimethyl-tetrafluoroborate and PC1 were touched.

5 It has been reported that ε-force prolatatam can be synthesized quantitatively by using Yes. HC1 is a by-product during post-treatment with water, and PC1 is used as a co-catalyst.

5 Because of the need for addition and the difficulty in regenerating the catalyst system, it cannot be said that it is sufficiently satisfactory from an industrial point of view.

[0023] In J. Am. Chem. Soc, 2002, 124, p5962-5963, the cation moiety has an n-Bu group and C H

4 8

-SO H has a structure bonded to the N atom of imidazole, and the ion is CF SO

3 3 3 An acid catalyzed reaction such as an esterification reaction or a dehydration dimerization reaction of alcohol is described using ionic liquids, etc., but in these Bronsted acidic ionic liquids, the Beckmann rearrangement reaction of ketoxime is described. Does not progress.

Disclosure of the invention

Problems to be solved by the invention

[0024] An object of the present invention is to provide a novel ionic liquid useful as a catalyst for the Friedel-Crafts reaction and the like. Another object is to provide a method for the Alkylic reaction of aromatic compounds by the Friedel's Clough reaction using an ionic liquid. Another object is to provide a nitration reaction method using an ionic liquid of an aromatic compound. Still another object is to provide a method for Beckmann rearrangement of ketoximes using an ionic liquid or a carrier thereof. Another object is to provide a novel method for producing alkyl-substituted aromatic compounds, nitro-substituted aromatic compounds and ratatams.

Means for solving the problem

[0025] The inventors have studied diligently and, when reacted with the above Bronsted acidic ionic liquid and further with thionyl chloride, a kind of Lewis acidic ionic liquid that is stable to air and water. I thought that it could be converted to. Since the above-described Brentstead acidic ionic liquid and the Lewis acidic ionic liquid thus obtained have the characteristics of being stable to air and water and being acidic at the same time, they have been used in synthetic chemistry. It was expected to be a promising catalyst as an acidic catalyst.

[0026] Accordingly, the present inventors have conducted intensive studies on using the ionic liquid thus obtained as a catalyst for the Friedel 'Crafts' alkylation reaction, nitration reaction, and Beckmann rearrangement reaction. , Both have excellent reactivity and are reusable As a result, the present invention was completed.

[0027] For example, in the case of alkylene xylene using styrene, it reacts effectively even at 70 ° C, which is much lower than the reaction temperature of 100-200 ° C when using a solid acid catalyst, and can be reused. Was found to be a suitable catalyst. Since both the reaction raw material and the product are immiscible with the ionic liquid, the reaction proceeds in a two-liquid phase system, and has an advantage that the product can be easily separated after the reaction. To the inventors' knowledge, this is the first example of an Friedel-Crafts alkylation reaction of an aromatic compound with an alkene using an air- and water-stable ionic liquid as a catalyst. However, when using only this ionic liquid as a catalyst, it was found that the reaction did not proceed depending on the type of the olefins, and various studies were conducted to improve this. It has been found that it is effective to use a toy dagger in combination.

[0028] In addition, even in the nitration reaction, good toro-formation is performed, and both the reaction raw material and the product are immiscible with the ionic liquid. This has the advantage that the product can be easily separated after the reaction. To the best of the present inventors' knowledge, this is the first example of an aromatic compound toro conversion reaction with nitric acid using an ionic liquid stable in air and water as a catalyst. Further, regarding the Beckmann rearrangement reaction of various ketoximes, a favorable rearrangement reaction proceeds to generate ratatams. To the inventor's knowledge, this is the first example of a Beckmann rearrangement reaction of ketoximes that does not require a cocatalyst using an ionic liquid stable in air and water as a catalyst.

[0029] The present invention provides an ionic liquid represented by the following formula (1).

[Chemical 1]

(X represents a halogen atom or a hydroxyl group, Υ represents CF SO, BF

3 3 4, PF

6, CH CO 3

O—, CF COO—, (CF SO) N—, (CF SO) C—, F—, CI—, Br—, or I—, where n is 2

3 3 2 2 3 2 3

Represents an integer of 16 and R represents a methyl group, an aryl group or a vinyl group) In the present invention, a preferable ionic liquid is represented by the following formula (2).

[Formula 2]

(X represents a halogen atom or a hydroxyl group, and n represents an integer of 3 or 4.) Further, the present invention is characterized in that an aromatic compound is reacted with an olefin in the presence of the ionic liquid. To provide a method for alkylating aromatic compounds.

In addition, the present invention relates to the ionic liquid and M (OTf)

(M represents a divalent or trivalent metal atom, Tf represents SOCF, and m represents an integer of 2 or 3.

twenty three

You)

A method of reacting an aromatic compound with olefins in the presence of a triflate compound represented by the formula:

The present invention also provides a method for producing an alkyl-substituted aromatic compound, which comprises a step of reacting an aromatic compound with olefins in the presence of the ionic liquid.

Further, the present invention provides the ionic liquid and

M (OTf)

twenty three

You)

A process for producing an alkyl-substituted aromatic compound, comprising the step of reacting an aromatic compound with olefins in the presence of a triflate compound represented by the formula: Further, the present invention provides a method for converting an aromatic compound into nitrogen, which comprises reacting an aromatic compound with nitric acid in the presence of the ionic liquid.

Further, the present invention is a method for producing a nitro-substituted aromatic compound, which comprises a step of reacting an aromatic compound with nitric acid in the presence of the ionic liquid. Following the step of reacting this aromatic compound with nitric acid, the resulting reaction mixture Phase separating a phase containing an ionic liquid and a phase containing an aromatic compound from the compound, a step of recovering a nitro-substituted aromatic compound from a phase containing a aromatic compound, and a process containing an ionic liquid Provided is a method for producing a nitro-substituted aromatic compound, which comprises a step of reusing a phase in a reaction between an aromatic compound and nitric acid after adjusting a nitric acid concentration as necessary.

Further, the present invention provides a Beckmann rearrangement reaction method, which comprises subjecting oximes to Beckmann rearrangement in the presence of the ionic liquid.

Further, the present invention relates to a method for producing ratatams, which comprises a step of subjecting ketoximes to Beckmann rearrangement in the presence of the ionic liquid. Following the rearrangement step, the reaction mixture is

(2) A method for producing ratatams comprising a step of subjecting to supercritical extraction, a step of recovering ratatams from the extract, and a step of reusing the remaining ionic liquid without extraction for the Beckmann rearrangement reaction of ketoximes. provide.

Hereinafter, the ionic liquid of the present invention will be described.

The ionic liquid of the present invention is represented by the above formula (1). In the formula (1), X is a halogen atom or a hydroxyl group, preferably a chlorine atom. Y— is CF SO—, BF—, PF—,

3 3 4 6

CH COO—, CF COO—, (CF SO) N—, (CF SO) C—, F—, CI—, Br—, or Γ

3 3 3 2 2 3 2 3

The force is preferably CF SO—, PF—, C1—, and more preferably CF SO—. n is 2—

3 3 6 3 3

Although it is an integer of 16, it is preferably an integer of 3-8, and more preferably an integer of 3 or 4.

Among them, ionic liquids include the following 3a, 4a, 3b and 4b. In the above formula (2), n and X are as follows.

3a: n = 3, X = OH

4a: n = 4, X = OH

3b: n = 3, X = Cl (melting point: 219.8K ± 1.3K)

4b: n = 4, X = Cl (melting point: 211.8K ± 2.4K)

3a and 4a have properties as Bronsted acids, and 3b and 4b have properties as Lewis acids.

Similarly preferred ionic liquids include the following 2A and 2B, which are represented by the above formula ( In 1), R is a methyl group, and n, X and Y— are as follows. These 2A and 2B have properties as Lewis acids.

2A: n = 2, X = C1, Y— = C1—

2B: n = 2, X = C1, Y— = PF—

6

Further, similarly preferred ionic liquids include the following 3C, wherein in the formula (1), R is an aryl group, and n, X and Y— are as follows. Note that this 3C has the property of Louis acid.

3C: n = 3, X = C1, Y— = CF SO—

3 3

The ionic liquid of the present invention can be obtained by applying a reaction known in Chem. Comnun. 2000, pl695-1696 and the like.

For example, N-methylimidazole is first reacted with 1,3-propane sultone or 1,4-butane sultone to obtain a zwitterionic compound in which (CH 2) n-SO— is bonded to the imidazole ring structure N.

twenty three

Combine. Note that n is 3 or 4. Next, an equimolar amount of CF SO

3 3

Reaction with H and the cation with (CH 2) n-SO H bonded to the imidazole ring and CF SO—

2 3 3 3 It is the ionic liquid of 3a or 4a above, which also has the aeon and power. The ionic liquid of the above 3b or 4b is obtained by reacting the ionic liquid with the salt of the salt. In addition, the ionic liquid of 3a or 4a becomes a force equilibrium reaction also obtained by hydrolyzing the ionic liquid of 3b or 4b. Ionic liquids having other aions can be obtained in the same manner as described above by changing the aion source.

[0034] Further, when (CH 2) n-SO— bonded to imidazole ring structure N is n = 2 and 5-16,

twenty three

For example, by reacting N-methylimidazole with Cn; CH) n-SOCI

twenty two

Obtainable. Further, by using N-arylimidazole ゃ N-bulimidazole instead of N-methylimidazole in the above, an ionic liquid in which R in the above formula (1) is an aryl group or a bullet group can be obtained. .

The obtained ionic liquid can be identified by NMR measurement or the like.

[0035] This ionic liquid is an acidic ionic liquid that is stable to air and water, and is a kind of ionic liquid having a stable function. Examples of applications include an alkylation reaction catalyst and a nitration reaction. Limited to catalysts and Beckmann rearrangement catalysts or their reaction solvents It can be used for many other reaction catalysts and reaction solvents.

Next, a method for alkylating an aromatic compound using the ionic liquid of the present invention and a method for producing an alkyl-substituted aromatic compound will be described. In addition, alkylation is used in a sense including aralkylation. The alkylation reaction of the present invention includes a method using an ionic liquid as a catalyst and a method using a triflate compound together with an ionic liquid. First, the former method will be described.

[0037] In the alkylation reaction method using an ionic liquid as a catalyst, the aromatic compound to be alkylated is benzene, alkylbenzene or the like having a certain power, preferably methylbenzenes having one or two methyl groups, More preferably, it is xylene.

Examples of the olefins that serve as the alkylating agent include aromatic olefins, and are preferably aromatic butyl compounds such as benzene or alkyl-substituted butylbenzene, and more preferably one or two styrene or methyl groups. And more preferably styrene.

[0038] The compound formed by this alkylation reaction has a large number of compounds represented by [Ar-CH (CH)] -Ατ '

3a

A ring compound that varies depending on the molar ratio between the reacting aromatic compound and the olefins such as aromatic vinyl compounds.One to thirteen aromatic compounds such as aromatic vinyl conjugates are substituted for one aromatic compound. This is often a compound, and is often obtained as a mixture of compounds having different substitution numbers a. In the above formula, Ar is an aromatic group obtained by removing a bullet group from an aromatic vinyl conjugate, and Ar ′ is an aromatic group obtained by removing a hydrogen from an aromatic hydrocarbon. If α-methylstyrene is used as the aromatic vinyl compound, this formula varies depending on the raw materials used so that the above CH (CH 2) <C (CH 2).

3 3 2

Is easily understood.

[0039] Alkylation reaction conditions vary depending on the type of the target product and the like, and are not constant. The molar ratio of the aromatic compound to the olefins is in the range of about 10: 1 to 1: 2, preferably about 5: 1 to 1: 1. When the amount of the olefins is excessive, a homopolymer of the olefins such as an aromatic vinyl conjugate is easily formed. Since the ionic liquid of the present invention acts as a catalyst, it is not necessary to use a separate catalyst, but it may be used if desired. The amount of ionic liquid used is the raw material of the reaction It is 0.5 to 20 times (by weight), preferably about 110 times the total amount of the aromatic compound and the olefins. In this reaction, the ionic liquids 3a, 4a, 3b, and 4b all act as excellent catalysts, but the ionic liquids 3a and 4a seem to exhibit more excellent functions.

Next, an alkylation reaction using a triflate compound together with an ionic liquid will be described. Preferred ionic liquids include the above 3a, 4a, 3b and 4b, more preferably 3b and 4b.

[0041] The triflate conjugate used together with the above ionic liquid is represented by Μ (公知) and is a compound known in the literature and the like, and is conventionally known as an alkyl sulfide catalyst or Friedel's Crafts catalyst. If they are, they can be used. In the above formula, M represents a divalent or trivalent metal atom, preferably a rare earth metal, and more preferably scandium. m corresponds to the valence of the metal atom M. Tf is SO CF.

twenty three

[0042] The ratio of the ionic liquid and the triflate conjugate used varies depending on the type of the olefin compound as the reaction raw material, and the like. The range of the degree is good.

[0043] The aromatic compound and the olefins used as raw materials for this reaction will be described.

The aromatic compound used as a raw material is preferably benzene, naphthalene, azulene, anthracene, phenanthrene, pyrene, fluorene or a substituted product thereof, particularly an alkyl substituted product thereof. Further, the aromatic compound may be a heterocyclic compound such as pyridine and quinoline, or a substituted product thereof. More preferred are benzene such as benzene, toluene, xylene, and ethylbenzene, and lower alkyl-substituted benzenes having 1 to 2 carbon atoms substituted with 1 to 2 lower alkyls.

[0044] Olefins used as the alkylating agent are preferably aliphatic olefins having 2 to 20 carbon atoms such as ethylene, butene, otaten, and dodecene, and more preferably aliphatic monoolefins having 415 carbon atoms. is there. The olefins may be aromatic olefins such as benzene or alkyl-substituted benzene. Further, it is also preferable to be an aliphatic cyclic olefin.

[0045] The compound formed by this alkylation reaction is an alkyl-substituted aromatic compound, and the main component is a monoalkyl-substituted aromatic compound depending on the reaction conditions. But the reaction By adjusting the conditions, a polyalkyl-substituted aromatic hydrocarbon or an aromatic compound such as a dialkyl-substituted aromatic hydrocarbon can be obtained. When a monoalkyl-substituted aromatic compound is intended, the aromatic compound is preferably used in excess with respect to the olefins.

The alkylidation reaction conditions are not constant because they vary depending on the type of the target product and the like, but the reaction temperature is preferably 30 to 100 ° C. and the reaction time is about 0.2 to 10 hours. The molar ratio of the aromatic compound to the olefins is in the range of about 10: 1 to 1: 2, preferably about 5: 1 to 1: 1. The amount of the ionic liquid used is about 0.01 to 1 times, preferably about 0.02 to 0.2 times the mol of the olefins as the reaction raw materials, and the amount of the triflate conjugate used is preferably within the range.

Next, a nitration reaction method and a method for producing a -toro-substituted aromatic compound will be described.

The ionic liquid used in the present invention is represented by the above formula (1), preferably by the formula (2). X is preferably a hydroxyl group, and Y— is preferably CF SO—

3 3, PF-

6, C1—, more preferably CF SO—, and n is preferably 3-8, more preferably 3 or 4. Concrete

3 3

Specifically, there are 3a and 4a described above.

[0048] The ionic liquid acts as a catalyst and a solvent for the nitration reaction. The raw materials for the nitration reaction are aromatic compounds and nitric acid. By using the above-mentioned ionic liquid alone as a catalyst or a solvent for the nitration reaction, it can be easily reused. However, if necessary, other catalysts or solvents may be used.

[0049] As an aromatic compound as a raw material for the nitration reaction, a compound having a hydrogen that can be substituted for an aromatic ring-constituting carbon at a nitratable position is used. Preferably, unsubstituted one- to three-ring aromatic hydrocarbons such as benzene, naphthalene and anthracene, and two- to three-ring aromatic hydrocarbons such as biphenyl, terphenyl and diphenylmethane, diphenyl ketone, Examples thereof include a 2- to 3-ring aromatic compound such as diphenyl sulfone and diphenyl ether, and a substituted aromatic compound obtained by substituting these with an alkyl group, halogen, or the like. More preferably, it is benzene, monoalkylbenzene or monohalogenobenzene. Here, the alkyl group is preferably a lower alkyl having 6 or less carbon atoms.

However, as described above, the present invention is characterized by the ionic liquid used in the It is widely applicable to known aromatic compounds as a raw material for torrefaction.

[0050] The nitric acid used as the nitrating agent is preferably concentrated nitric acid of 50 wt% or more, but the reaction proceeds even at about 30 wt%. From the viewpoint of ease of handling and reactivity, it is advantageous to use nitric acid of about 35 to 70 wt%. In the case of polynitration over dinitration or more, it is natural that a higher concentration of nitric acid is preferably used.

[0051] The amount of the ionic liquid used is 2 to 30 mol%, preferably about 415 mol%, based on the aromatic compound. The amount of nitric acid used is about 115 times mol, preferably about 113 times mol% of the aromatic compound.

[0052] The nitration reaction conditions vary depending on the reaction raw materials, but when benzene or monoalkylbenzene is subjected to mono-toro-formation, the boiling point of the aromatic compound is set at 50 to 120 ° C, preferably 60 to 100 ° C or lower. It is advantageous. The reaction time varies depending on the conditions such as the reaction raw materials and the reaction temperature, but it is suitably about 110 hr, preferably about 2-20 hr.

For the purpose of poly-nitrolation beyond dinitration, it is preferable to use a higher concentration of nitric acid, use a larger amount of nitric acid, and adopt a higher reaction temperature or a longer reaction time. become.

[0053] At the beginning of the reaction, there are two phases, an ionic liquid phase containing nitric acid and an aromatic compound phase, and these are stirred to progress the reaction. As the reaction proceeds, a nitrated aromatic compound is generated and present in the aromatic compound phase, and water is by-produced to lower the nitric acid concentration in the ionic liquid phase. After the completion of the reaction, the stirring is stopped to separate into two liquid layers of an ionic liquid phase and an aromatic compound phase. Therefore, both can be easily separated by layer separation. If necessary, a solvent or the like for facilitating layer separation can be added.

[0054] Since the aromatic compound phase separated by layer separation or the like contains a nitro-substituted aromatic compound, it is separated or purified to recover the nitro-substituted aromatic compound. When the conversion of the raw material aromatic compound is less than 100%, unreacted raw material aromatic compounds are included, and can be reused. The reaction rate of the starting aromatic compound is preferably about 50 to 95% when a mono-toro-substituted aromatic compound is intended.

[0055] On the other hand, the separated ionic liquid phase contains the ionic liquid and nitric acid at a reduced concentration. Since the ionic liquid has almost no denaturation or loss, it is reused. Even if the concentration of nitric acid is reduced, the separated ionic liquid phase can be reused if it is still usable. If the nitric acid concentration falls below a certain level, add concentrated nitric acid, concentrate and regenerate.

Next, the Beckmann rearrangement reaction will be described.

The ionic liquid used in the present invention is represented by the above formula (1), preferably (2). In the formula (1), X is preferably a halogen atom, more preferably a chlorine atom, and n is preferably 3 or 4. Specific preferred examples of the ionic liquid include the above 3b and 4b.

[0057] The ionic liquid used in the present invention can be used as it is, with the force ionic liquid supported on a carrier. In the case of supporting or binding to a carrier, it can be obtained, for example, by dissolving an ionic liquid in a low-boiling solvent such as THF, and immersing the carrier in a relatively large specific surface area. In this case, a drying step for removing the low-boiling-point solvent can be provided if necessary, but the need for the solvent used in the rearrangement reaction is small. In the case of binding to a carrier, for example, as described in Tetrahedron Lett. 26, 3361 (1985), there is a method in which the surface of the carrier is modified beforehand and chemically bonded to an ionic liquid. As the carrier, there are an acidic carrier such as a solid acidic catalyst and a porous carrier, and any porous solid can be used. The specific surface area is preferably 10 m ² / g or more. Specific examples include zeolite, silica, alumina, silica alumina, zeolite, clay minerals (such as smectite), and supported heteropolyacid catalysts. Also, a solid acid catalyst such as silica'alumina or a solid basic catalyst can be used. In the case of a solid acid catalyst, a synergistic effect of the acid catalyst effect of the ionic liquid can be expected. A supported catalyst in which an ionic liquid is supported or bound to such a solid support has advantages such as easy separation from the product. The loading amount of the ionic liquid is preferably in the range of 1 to 70 wt%, preferably 5 to 30 wt%.

[0058] The oximes used as a raw material include saturated and unsaturated, substituted or unsubstituted aliphatic ketoximes having 2 to 12 carbon atoms, aldoximes or cyclic ketoximes, and preferably cyclic ketoximes. Examples of oximes include acetone oxime, acetoaldoxime, benzaldoxime, propanal oxime, butanal Oxime, butanone oxime, buten-1-oxoxime, cyclopropanone oxime, cyclohexanone oxime, cycloquatanone oxime, cyclododecanone oxime, cyclopentanone oxime, cyclododecenone oxime, 2-phenylcyclo Powers such as hexanone oxime, cyclohexenone oxime, 2-methyl-2-pentanone oxime, etc. Cyclohexanone oxime is preferred.

[0059] In the Beckmann rearrangement reaction of the present invention, when a cyclic ketoxime is used which produces an acid amide corresponding to the starting oxime, cyclic ratatams are produced. In particular, an industrially useful ratatum is ε-force prolatatum.

[0060] The Beckmann rearrangement reaction conditions are not constant because they vary depending on the ketoxime used, the type of the target product, and the like, but the reaction temperature is 0 to 100 ° C, more preferably 10 to 80 ° C. Preferably it is 10-50 ° C. If the temperature is lower than 0 ° C., it takes time to obtain a desired conversion. If the temperature is higher than 100 ° C, the ionic liquid or the carrier may take part in the reaction and the product may be complicated. The reaction time varies depending on the raw materials and the reaction temperature, and can be set so as to obtain a desired conversion. Usually, lmin-24hr is good. When ε-caprolatatam is used as the target product, the reaction temperature is preferably 0 to 50 ° C and the reaction time is preferably about 0.1 to 10 hours. If the reaction temperature is too high, the reaction solution turns black and the generation of by-products increases.

[0061] The amount of the ionic liquid to be used varies depending on other conditions. Even if the amount of ionic liquid used is near the equimolar amount, which is the stoichiometric amount (0.5 to 2 times mol), or even sufficiently less! The reaction proceeds well. The ionic liquid acts as a reaction catalyst. However, if the ionic liquid is used in a molar amount of about 0.1 times or more, the ionic liquid also functions as a solvent, so that no special reaction solvent is required. However, when the ionic liquid is used as a solid carrier or when the amount of the ionic liquid is small and the reaction temperature is low and the raw material or the target substance or both are not dissolved, it is preferable to use a reaction solvent. . The reaction solvent is selected so as to dissolve the oxime and the target acid amide. Examples of such a solvent include benzene and the like, and supercritical CO can also be used. Supercritical

2

CO can be used to separate the reaction mixture as described below, so use a carrier

2

Then, depending on the conditions, it will be an IJ. [0062] After completion of the reaction, the reaction mixture is recovered as a solution in which the target substance is dissolved when the ionic liquid is used as it is. In some cases, unreacted raw materials and by-products may be contained. Then, the target acid amide is recovered by an operation such as extraction of the reaction mixture. When the ionic liquid is used by being supported or chemically bonded, the target acid amide can be recovered by operations such as filtration and distillation.

[0063] Desirably, the ionic liquid in which the target substance is dissolved is collected and reused. Advantageously, the ionic liquid in which

Perform supercritical extraction using 2. In this case, the target substance such as ε-force prolatatum is extracted, and the ionic liquid remains without being extracted. However, since the ionic liquid in which the target substance is dissolved often has a high viscosity, the more advantageous

2 together with an auxiliary extraction solvent to lower the viscosity. Examples of such an auxiliary extraction solvent include solvents such as water, ethanol, black-mouthed form, and tetrahydrocarbon, and the like. Preferred is that since chloroform has the least decrease in the activity of the recovered ionic liquid. Use CO

When performing supercritical extraction using 2, the ionic liquid may be itself or may be a carrier. The extraction conditions were 3 hours at 50 ° C and 125 MPa, the amount of CO used was 25 ° C, and 10-100 L at 0.1 MPa,

2

It is preferably about 24-82 L.

By performing a powerful supercritical extraction operation, the target substance and the ionic liquid are recovered, and the ionic liquid can be reused.

When synthesizing ε-force prolatatam from cyclohexanone oxime, Beckman is reacted at 10 to 50 ° C. in the presence of 0.1 to 2 moles of an ionic liquid per mole of cyclohexanone oxime. It is desirable that 98% or more be reacted by rearrangement. The reaction mixture thus obtained is used together with CO together with an auxiliary extraction solvent to reduce the viscosity.

2

It is desirable to extract ε-force prolatatam by supercritical extraction, and to reuse the ionic liquid left unextracted. The number of reuses depends on the reaction conditions, but if the generation of by-products is suppressed as much as possible, it can be reused 5 times or more, preferably 10 times or more.

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1

1-Methylimidazole and 1,4-butanesultone were mixed with stirring at a molar ratio of 1: 1 and reacted at room temperature with stirring for 24 hours. At this time, white crystals were obtained with a yield of 100%. Then After crushing the white crystals, washing them several times with ethyl ether, the washed crystals and CF

Three

SO H was mixed at a molar ratio of 1: 1 and reacted at 60 ° C. for 24 hours. In the formula (2), n = 4 and X = 〇H

Three

Was obtained as the ionic liquid 4a. Next, this ionic liquid 4a is added in a refluxing state (approximately 80 ° C.) with little addition of thiol chloride to cause a reaction, thereby obtaining an ionic liquid 4b in which n = 4 and X = C1 in the formula (2). Was.

[0066] A more advantageous method of obtaining the ionic liquid 4b from the ionic liquid 4a will be described below.

0.12 mol of thiol chloride was placed in a 50 ml two-necked flask, and refluxed while stirring with a magnetic stirrer. Under reflux conditions, 0.1 mol of the ionic liquid 4a was slowly added dropwise, and stirring was continued for another 8 hours. After the completion of the reaction, unreacted salty diol was removed by distillation to obtain a liquid as a crude product. After cooling the liquid, it was washed twice with distilled water to remove trace amounts of residual thiochloride. Next, this product was evaporated at 50 ° C. for 2 hours to obtain a purified ionic liquid 4b.

Example 2

Ionic liquids 3a, 4a, 3b and 4b were used. For comparison, the well-known ionic liquids BMImBF and BMImPF were also examined at the same time. In experiments, ionic liquids and p-

4 6

Silene (30 mmol) and styrene were charged into a 10 ml test tube equipped with a magnetic stirrer and reacted at 70 ° C. for 15 hours. The molar ratio of styrene to ionic liquid was set to 10, and the molar ratio of aromatic hydrocarbon to styrene was set to 9: 1 to 13: 1. After the completion of the reaction, the upper organic layer was separated and analyzed by FID gas chromatography (Shimadzu GC-14A, ULBON HR-52 capillary single column 25 mm x 0.32 mm).

Table 1 shows the results of the Friedel 'Crafts' alkylation reaction of p-xylene with styrene under various reaction conditions. In all these cases, two main products were detected, namely monostyrenated and distyrenated. These are both industrially desirable substances. When p-xylene and styrene were reacted using the Lewis acidic ionic liquid 3b or 4b (Experiment No. 16), the reaction between P-xylene and styrene proceeded well, and an effective catalyst was used. It turns out that it is. However, Lewis acidic ionic liquid 4b, which has a long side chain, has a decrease in styrene conversion and clearly affects the product distribution. On the other hand, when treated with the Bronsted acidic ionic liquid 3a or 4a (Experiment Nos. 715), sufficient styration was achieved after the reaction at 70 ° C. for 5 hours. This is due to the presence of active sites such as sulfuric acid in these ionic liquid molecules.

When the reaction is carried out in a well-known neutral ionic liquid (Experiment No. 16-17), these ionic liquids have an acid point necessary for the alkylidation reaction. Naturally, no reaction was observed.

The reaction results are shown in Table 1. Experiment numbers 116 and 715 are examples.

[¾1]

Reaction time and the molar ratio of P-xylene to styrene are two important factors that affect styrene conversion and distribution of reactant products. Regarding the effect of reaction time on the alkylation reaction, it can be seen that most of the reaction between P-xylene and styrene was completed within 2 hours. Also, the product distribution does not change significantly in any of the reactions. Regarding the effect of P-xylene Z-styrene molar ratio, as the molar ratio increases, the styrene conversion Gradually decreases, but the selectivity of the monostyrene form greatly increases. This is probably because the dilute solution of P-xylene and styrene reduces the chance of the reaction between the monostyrene product and styrene.

[0071] After the reaction, the product in the upper layer can be easily separated from the ionic liquid by decantation. Then, the remaining ionic liquid can be reused. For example, the ionic liquid 4a retained the catalytic performance even after being used 5 times under the same conditions (Experiment No. 15). This means that the ionic liquid has reusability in the alkylation reaction of P-xylene with styrene. This reusability shows the advantage of the ionic liquid of the present invention as an industrial catalyst!

Example 3

The alkylidation reaction was carried out in the same manner as in Example 1 by using the ionic liquid 4a as a catalyst and changing the types of the aromatic hydrocarbon and the alkene. Table 2 shows the types of aromatic hydrocarbons and alkenes and the reaction times together with the results. Other conditions are: reaction temperature 70 ° C, aromatic hydrocarbon 30 mmol, aromatic hydrocarbon / alkene = 3 (molar ratio), alkene / ionic liquid = 10 (molar ratio). Table 2 shows the reaction conditions and results.

[Table 2]

[0074] It can be seen that the ionic liquid of the present invention is an effective catalyst for the alkylation of benzene and toluene with styrene. Under the same conditions, it can be inferred that benzene can be formed relatively easily with toluene or p-xylene. However, very interestingly, even when the acidic ionic liquid catalyst 4a was applied to the alkylation reaction of benzene with a long-chain alkene such as hexenedodecene, the reaction did not occur. Although the reason is unknown, the reaction proceeds in a two-phase direction, and the reason for the change in the activity of styrene and long-chain alkenes is related to the reduced solubility of long-chain alkenes in ionic liquids. I guess I don't!

Example 4

To a 10 ml test tube were added 5.2 mmol of benzene, 2.6 mmol of olefin, an ionic liquid (an amount corresponding to 5 mol% of the olefin) and a triflate conjugate (an amount corresponding to 5 mol% of the olefin). However, in Experiment No. 24, P-xylene was used instead of benzene as the aromatic compound, and the amounts of the ionic liquid and the triflate compound used were each equivalent to 10% mol of the olefin. There is no limitation on the order of addition. The reaction solution was reacted at 70 ° C. while stirring. The reaction proceeded in a two-phase system consisting of a hydrocarbon phase (upper layer) and an ionic liquid phase (lower layer). After completion of the reaction, the upper layer was separated and composition analysis was performed. Table 3 shows the reaction conditions and results.

In addition, the metal element symbol in the column of triflate in Table 3 indicates that the metal is a Trifle M ligated compound.

[Table 3]

Example 5

In the same experiment as in Example 4, the triflate conjugate was Sc triflate, Y triflate, La triflate or Zn triflate.

When an experiment was carried out under the same conditions as in Experiment No. 23 when using in combination with ionic liquid 4b, Sc triflate showed the best results as an alkylidani catalyst, and Y triflate was about 4%. La triflate and Zn triflate showed no activity. Only However, it is expected that the activity will be exhibited by changing the type of olefin and the reaction conditions.And, by using Sc triflate in combination with an ionic liquid, aromatic compounds and olefins, especially long-chain olefins or cycloolefins, can be used. It has excellent catalytic action to promote the reaction.

Example 6

The aromatic compound was subjected to the toro conversion using the ionic liquid 3a or 4a. As the aromatic compound used as a raw material, benzene or mono-substituted benzene represented by R-Ar (where Ar represents a phenyl group and R represents H or a substituent) was used. As nitric acid, 62% nitric acid was used. Typically, 5-15 mol% of the ionic liquid relative to the aromatic compound was used, and 20 mmol of the aromatic compound and 20-60 mmol of 62% nitric acid were placed in a 50 ml round bottom flask equipped with a magnetic stirrer. At this time, it was separated into two layers: an aromatic compound phase and an ionic liquid phase containing nitric acid. Next, the temperature was adjusted to 80 ° C., and the reaction was performed with stirring for 12 to 22 hours. During the reaction, the organic phase turned yellow. After completion of the reaction, the organic phase was separated by a separating funnel and analyzed by a GC device equipped with an FID detector.

[0079] Table 4 shows the reaction conditions and the reaction results. In Table 4, R means R of the above R-Ar,

% Indicates the used amount (mol%) of the ionic liquid, the aromatic compound Z nitric acid indicates the molar ratio, and the conversion indicates the conversion of the aromatic compound.

[0080] [Table 4]

[0081] From Table 4, it can be seen that the ionic liquid is more excellent in the directional deformation ratio of 4a than 3a. In addition, it can be seen that the conversion of the ionic liquid is superior in the order of 5%, 10%, and 15%. It can be seen that the molar ratio of the aromatic compound nitric acid is superior in the order of 1/3, 1/2 and 1/1 in the order of transfer. Regarding the reaction time, it can be seen that the conversion is better for 22 hours than for 12 hours. When a substituted aromatic compound is used as the aromatic compound, the same reaction occurs in many cases, and it can be seen that the conversion ratio differs depending on the type of the force substituent obtained with the ortho- and para-forms as main components.

Example 7

An experiment was conducted to reuse the ionic liquid. The first reaction was performed under the same conditions as in Experiment No. 31 of Example 6. After the completion of the reaction, the ionic liquid phase containing nitric acid was separated into layers. The amount of ionic liquid separated was almost the same as that used in the first reaction, but the nitric acid concentration was lower. The whole amount was used as it was in the second reaction, but the molar ratio of the aromatic compound Z nitric acid was kept at 1Z2. This was repeated five times, and the change in the transfer ratio was measured.

Table 5 shows the results.

[Table 5] Number of aromatic compounds Z nitric acid Nitric acid concentration% Conversion rate%

1 1/2 62 70. 1

2 1/2 52 58. 3

3 1/2 46 54. 1

4 1/2 41 52. 3

5 1/2 35 47. 3

[0084] From Table 5, it is found that the separated ionic liquid phase is used as it is without treatment not only in the second and subsequent nitration reactions but also repeatedly in the fifth or subsequent nitrification reaction. It is expected that a practically sufficient conversion rate can be obtained by slightly changing the reaction conditions, which is not enough to obtain a good conversion rate. This can be said to indicate that when the reaction is repeated, the amount of waste greatly decreases, and operations such as catalyst regeneration greatly decrease.

Example 8

JRC-SIO-9, a reference catalyst of the Catalysis Society of Japan, was immersed in a THF solution of an ionic liquid as a carrier, immersed for lhr, then the THF solvent was removed and dried to obtain an ionic liquid carrier . The composition and properties of JRC-SIO-9 are as follows.

SiO: 99.9%, Al: 2.3 ppm, Ti: 0.1 ppm or less, Ca: 0.5 ppm, Fe: 3.9 ppm, Na: 60 ppm, Mg

2

: 0.1 ppm. Packing density: 0.49 g / cm ³ , pore volume: 0.654 cm ³ / g, average pore diameter: 11.0 nm, specific surface area: 336 mVgo The ionic liquid carrying amount is 20 wt%.

[0086] Ionic liquids 3b and 4b, and using carrier 4b ²⁾ of the ionic liquid supported on the supported material ionic liquids 4b as described above. In addition to the well-known ionic liquids BMImBF and BMImPF for comparison, the Bronsted acidic ionic liquids 4a and 3a are the same.

4 6

Sometimes considered. In the experiment, the ionic liquid and ketoxime were charged into a 10 ml test tube equipped with a magnetic stirrer, stirred for 3 minutes, and reacted at 20-80 ° C for 5 minutes-120 minutes. The molar ratio of ketoxime to ionic liquid was set at 115.

[0087] Further, the reaction mixture (viscous liquid) after the reaction is completed is mixed with CO and chlorophos as an auxiliary extraction solvent.

2

Lum was used for supercritical extraction with CO. Extract ε-caprolatatam from the extract

2

The ionic liquid collected and left unextracted was recovered and reused in the next reaction. ε-force Prolatatam was almost completely (> 95%) extracted. Reuse the recovered ionic liquid The molar ratio of ketoxime to ionic liquid was 1, and the reaction was carried out at 40 ° C for 60 minutes. The conversion ratio of the ketoxime and the selectivity of the ratatam were analyzed by FID gas chromatography (Shimadzu GC-14A, ULBON HR-52 cantilever ram 25 mx 0.32 mm). The supercritical extraction conditions were achieved by flowing 15 MPa of CO at 60 ° C for 3 hours to the raw materials of oximes lg.

2

I got it. The CO used for the extraction is about 24-82 L under the conditions of 25 ° C and 0.1Mpa.

2

[0088] Table 6 shows the results of the Beckmann rearrangement reaction of ketoxime under various reaction conditions. In all of these cases, when the reaction was carried out using the Lewis acidic ionic liquid 3b or 4b (Experiment Nos. 42-47), the reaction proceeded favorably, and the transfer rate was 99% or more. This shows that the selectivity is around 99%. In the case of using the ionic liquid 4b ¹ ) recovered by supercritical extraction and reused (Experiment No. 48), the conversion was slightly reduced, but the selectivity was good and the ionic liquid was recycled. It can be seen that use is possible. The reaction using the ionic liquid 4 obtained by supercritical extraction of the reaction mixture of Experiment No. 48 and the reaction using the ionic liquid recovered from the reaction were sequentially repeated and reused. The reaction was repeated under the same conditions as above, but the result was almost the same as that of Experiment No. 48 even when it was reused four times. Furthermore, when the carrier 4b ²⁾ of the ionic liquid 4b was used (Experiment No. 49), it was found that the reaction proceeded favorably and exhibited a transfer rate of 99% or more.

[0089] However, when the Bronsted acidic ionic liquids 3a and 4a were used, or when the well-known neutral ionic liquids of BMImBF and BMImPF were used (Experiment No. 50-

4 6

In 53), no reaction was observed since it did not have the activity required for the Beckmann rearrangement reaction.

Table 6 shows the reaction conditions and reaction results. In the table, the molar ratio indicates the molar ratio of the ketoxime Z ionic liquid, and the selectivity indicates the ratatum selectivity. Also, CHOX indicates cyclohexanone oxime, and TOX indicates tetralone oxime.

[0090] [Table 6] Experiment Reaction conditions Reaction result

No. Ionic liquid Ketoxime Molar ratio Temperature Time Conversion Selectivity

Body ° C min%%

42 3b CHOX 1 20 15 99.6> 99

43 4b TOX 1 20 15 99. 2> 99

44 4b CHOX 1 20 15 99.4〉 99

45 4b CHOX 3 40 60> 99 98.8

46 4b CHOX 5 40 120> 99 98.2

47 4b CHOX 5 80 5> 99〉 99

48 4b ^l! CHOX 1 40 60 71.3 95.6

49 4b ²⁾ CHOX 5 40 120> 99 96.8

50 BMIinBF ₄ CHOX 3 40 60 <1 0

51 BMImPF ₆ CHOX 3 40 60 <1 0

52 3a CHOX 3 40 60 <1 0

53 4a CHOX 3 40 60 <1 0

[0091] Example 9

When 5 mmol of chain oxime was used as a raw material and reacted in 4 mmol of Lewis acidic ionic liquid under the conditions shown in Table 7, the results shown in Table 7 were obtained.

[0092] [Table 7]

It can be seen that the ionic liquid represented by the general formula (1) or a supported substance thereof is an effective catalyst also for a ratatum synthesis reaction by a Beckmann rearrangement reaction of various ketoximes. The reason for the slight decrease in conversion when using a reused ionic liquid is unknown, but it is thought to be due to the contamination of impurities, and by optimizing the reaction conditions, recovery of the ionic liquid, and purification conditions, It is thought that the conversion rate can be prevented from lowering and the number of reuses can be increased. available.

[0094] Example 10

1-methylimidazole and CH CH CH -SO CI are mixed at a molar ratio of 2: 1 while stirring,

2 2 2

The reaction was performed for 6 hours under ice cooling. Unreacted 1-methylimidazole was removed by extraction with ethyl ether, and further washed several times with ethyl ether to obtain a black viscous liquid. This viscous liquid is referred to as ionic liquid 2A. In the ionic liquid 2A, the component corresponding to Y— in the above formula (1) is C1—.

Next, the obtained black viscous liquid and HPF were mixed at a molar ratio of 1: 2, and reacted at 60 ° C for 24 hours.

6

I responded. After removing unreacted HPF and C1 root by washing with water (about 10 times),

6

Extract with ethyl ether until As a result of drying the obtained crystal with a vacuum dryer, a brown slurry crystal was obtained at room temperature. This crystal is called an ionic liquid 2B. The crystal was a liquid at room temperature with a force of 110 ° C.

[0095] The ionic liquid 2A and cyclohexanone oxime were charged into a 10 ml test tube equipped with a magnetic stirrer, stirred for 3 minutes, and subjected to a Beckmann rearrangement reaction at 110 ° C for 5 hours. Here, the molar ratio of cyclohexanoxoxime to ionic liquid was set to 5.

After completion of the reaction, the reaction mixture was dissolved in ethanol and analyzed by FID gas chromatography (Shimadzu GC-14A, ULBON HR-52 Capillary One-Ram 25m x 0.32mm). The reaction rate of cyclohexanone oxime and _ε The selectivity to force prolatatam is as follows.

Reaction rate 20.1%

Selectivity 28.1%

[0096] The reaction of Beckmann rearrangement was carried out in the same manner as described above except that 2% of the ionic liquid was used instead of 2% of the ionic liquid. The conversion of cyclohexanone oxime and the selectivity to ε-proprotamata were as follows.

Reaction rate 39.1%

Selectivity 9.2%

[0097] Example 11

In Example 1, 1-aryl imidazole was used instead of 1-methyl imidazole. In addition, an ionic liquid 3C was obtained in the same manner except that 1,3-propane sultone was used instead of 1,4-butane sultone.

On the other hand, using silica gel-60 (70-230mesh; manufactured by Merck) and 3-mercaptopropyltrimethoxysilane (MPS), an MPS-modified silica gel was obtained by the method described in Tetrahedron Lett. 26, 3361 (1985).

Specifically, silica gel-60 (4.8 g) and MPS (21 ml) were added to a mixture of pyridine and toluene (mixing ratio: pyridine: toluene = 1: 1) (20 ml), and the mixture was added at 90 ° C. Allowed to react for hours. After filtration, the product was washed with toluene and dried under vacuum to obtain a solid (1). The S content in the obtained individual was 1.01 mmol / g.

To acetonitrile, ionic liquid 3C (3.2 g), solid (1) (4.8 g), a, a, a-azoisobuty-tolyl (AIBN) (164 mg) were added, and the reaction was carried out under reflux conditions for 30 hours. . After completion of the reaction, the solid was filtered, washed with methanol, and dried. The obtained solid is referred to as an ionic liquid immobilization catalyst (1).

[0098] The ionic liquid-immobilized catalyst (1) (0.02 g) and cyclohexanone oxime (0.018 g) were added to toluene (1.48 g), and reacted at 100 ° C for 7 hours. After the reaction was completed, the reaction mixture was analyzed by FID gas chromatography (Shimadzu GC-14A, ULBON HR-52 Capillary Ram 25m x 0.32mm). The selection rates are as follows.

Reaction rate 35.5%

Selectivity 73.9%

[0099] Separately, instead of using the above silica gel-60, a silica gel solid (2) was prepared in the same manner as described above except that pellet silica gel (manufactured by Nikki Chemical Co., Ltd .: Silicate Reference Catalyst JRC-SIO-9) was used. Thus, an ionic liquid fixed catalyst (2) was prepared from the ionic liquid 3C and the solid (2). The ionic liquid-immobilized catalyst (2) (0.92 g) and cyclohexanone oxime (0.10 g) were added to toluene (1.48 g) and reacted at 110 ° C. for 7 hours. After the reaction was completed, the reaction mixture was analyzed by FID gas chromatography (Shimadzu GC-14A, ULBON HR-52 Capillary Ram 25m x 0.32mm). The selection rates are as follows. Reaction rate 69.1%

Selectivity 48.2%

Industrial applicability

The acidic ionic liquid of the present invention, which is stable to air and water, is a kind of ionic liquid having a stable function, and is useful as a catalyst or a solvent for a reaction using an acidic catalyst. According to the alkylation reaction, the nitration reaction, and the Beckmann rearrangement reaction using the acidic ionic liquid, the reaction can be performed under relatively mild conditions, the separation is easy, and the catalyst can be reused. According to the present invention, industrially useful alkyl-substituted aromatic compounds, nitro-substituted aromatic compounds, _ε- force prolatatam, and the like can be obtained with high yield and high selectivity. Further, since the ionic liquid serving as a catalyst is a Lewis acid, which can be reused, generation of waste is suppressed and problems such as corrosion of the apparatus are reduced.

Claims

Claims [1] An ionic liquid represented by the following formula (1).

[Chemical 1]

(X represents a halogen atom or a hydroxyl group, Y represents CF SO, BF

3 3 4, PF

6, CH CO 3

3 3 2 2 3 2 3

One represents an integer of 16, and R represents a methyl group, an aryl group or a vinyl group. )

[2] The ionic liquid according to claim 1, which is an R-force methyl group.

3. The ionic liquid according to claim 1, wherein the ionic liquid is Y—force SCF SO—.

3 3

[4] The ionic liquid according to any one of claims 13 to 13, wherein n is 3 or 4.

[5] The ionic liquid according to any one of claims 14 to 14, wherein X is a chlorine atom.

[6] A method for alkylating an aromatic compound, comprising reacting an aromatic compound with an olefin in the presence of the ionic liquid according to any one of [15] to [15].

[7] The ionic liquid according to any one of claims 1-15 and

M (OTf)

twenty three

You)

A method for alkylating an aromatic compound, comprising reacting an aromatic compound with olefins in the presence of a triflate compound represented by the formula:

[8] The method for alkylating an aromatic compound according to claim 7, wherein M is Sc and m is 3.

[9] The method of alkylation of an aromatic compound according to any one of claims 6 to 8, which is an aromatic olefin.

[10] The method for alkylating an aromatic compound according to claim 9, wherein the aromatic olefins are aromatic vinyl compounds.

[11] Aromatic beading compound strength Styrene or methylstyrene having one or two methyl groups 11. The method for alkylating an aromatic compound according to claim 10, which is a compound.

[12] The method of alkylating an aromatic compound according to any one of claims 6 to 8, which is an aliphatic olefin.

[13] The claim 6-1, wherein the aromatic compound is a methylbenzene having one or two methyl groups.

3. The method for alkylating an aromatic compound according to any one of 2.

[14] A method for producing an alkyl-substituted aromatic compound, comprising a step of reacting an aromatic compound with an olefin in the presence of the ionic liquid according to any one of [15] to [15]. .

[15] The ionic liquid according to any one of claims 1-15 and

M (OTf)

twenty three

You)

A process for producing an alkyl-substituted aromatic compound, which comprises the step of reacting an aromatic compound with olefins in the presence of a triflate conjugate represented by the formula:

[16] The claim 14 or 1 wherein the aromatic compound is a methylbenzene having one or two methyl groups, and the olefin is styrene or a methylstyrene having one or two methyl groups.

6. The method for producing an alkyl-substituted aromatic compound according to 5.

[17] A method for nitrating an aromatic compound, comprising reacting an aromatic compound with nitric acid in the presence of the ionic liquid according to claim 15.

[18] The method for nitrating an aromatic compound according to claim 17, wherein the aromatic compound is benzene, monoalkylbenzene or monohalogenobenzene.

[19] The method for nitrating an aromatic compound according to claim 17 or 18, wherein the reaction is performed in the absence of a catalyst other than the ionic liquid.

[20] A method for producing a nitro-substituted aromatic compound, comprising a step of reacting an aromatic compound with nitric acid in the presence of the ionic liquid according to any one of claims 15 to 15.

[21] the aromatic compound is benzene, monoalkylbenzene or monohalogenobenzene;

21. The method for producing a toro-substituted aromatic compound according to claim 20, wherein the nitro-substituted aromatic compound is one of these mono-toro compounds.

22. The method for producing a nitro-substituted aromatic compound according to claim 20, wherein the reaction is performed in the absence of a catalyst other than the ionic liquid.

[23] Subsequent to the step of reacting the aromatic compound with nitric acid, a step of phase-separating the phase containing the ionic liquid and the phase containing the aromatic compound from the obtained reaction mixture, 21. A method comprising the steps of: recovering a toro-substituted aromatic compound from a tobacco; and reusing the phase containing the ionic liquid for the reaction between the aromatic compound and nitric acid after adjusting the concentration of nitric acid as necessary. — The method for producing a -toro-substituted aromatic compound according to any of 22.

[24] A Beckmann rearrangement reaction method comprising subjecting an oxime compound to Beckmann rearrangement in the presence of the ionic liquid according to claim 15.

25. The Beckmann rearrangement reaction method according to claim 24, wherein the ionic liquid is used by being supported on or bonded to a carrier.

26. The method according to claim 24 or 25, wherein the oximes are ketoximes.

[27] The method according to claim 26, wherein the ketoxime is cyclohexanone oxime.

[28] A method for producing ratatams, comprising a step of performing Beckmann rearrangement of ketoximes in the presence of the ionic liquid according to any one of claims 115.

29. The method for producing a ratatum according to claim 28, wherein the ionic liquid is used by being carried on or bonded to a carrier.

[30] The method for producing ratatams according to claim 28 or 29, wherein the ketoxime is cyclohexanone oxime and the ratatams are ε-force prolatatam.

[31] The method according to any one of claims 28 to 30, wherein the ionic liquid is used in an amount of 0.05 to 2 mol per 1 mol of cyclohexanone oxime.

[32] The method for producing ratatams according to claim 31, wherein the ionic liquid is used in an amount of 0.1 to 2 mol per 1 mol of cyclohexanone oxime.

[33] The step of performing the Beckmann rearrangement of ketoximes in a temperature range of 10 to 80 ° C.

32. The method for producing a ratatum according to any one of 8 to 31. Following the Beckmann rearrangement of ketoxime, the reaction mixture was

2. The method according to claim 28, further comprising a step of subjecting to a critical extraction, a step of recovering ratatams from the extract, and a step of reusing an ionic liquid remaining without extraction for the Beckmann rearrangement reaction of ketoximes. A method for producing a ratatum according to any one of the above.