WO2005028446A1 - Liquide ionique et procede de reaction utilisant ce liquide - Google Patents

Liquide ionique et procede de reaction utilisant ce liquide Download PDF

Info

Publication number
WO2005028446A1
WO2005028446A1 PCT/JP2004/013467 JP2004013467W WO2005028446A1 WO 2005028446 A1 WO2005028446 A1 WO 2005028446A1 JP 2004013467 W JP2004013467 W JP 2004013467W WO 2005028446 A1 WO2005028446 A1 WO 2005028446A1
Authority
WO
WIPO (PCT)
Prior art keywords
ionic liquid
aromatic compound
reaction
producing
catalyst
Prior art date
Application number
PCT/JP2004/013467
Other languages
English (en)
Japanese (ja)
Inventor
Chiaki Yokoyama
Kun Qiao
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to JP2005514045A priority Critical patent/JPWO2005028446A1/ja
Priority to CN2004800269737A priority patent/CN1852898B/zh
Priority to DE112004001729T priority patent/DE112004001729T5/de
Publication of WO2005028446A1 publication Critical patent/WO2005028446A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/025—Sulfonic acids

Definitions

  • 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.
  • 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.
  • 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).
  • ionic liquids 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.
  • BMImBF 1-n-butyl-3-methylimidazolium-tetrafluoroborate
  • BMImPF 1-n-butyl-3-methylimidazolyme-hexafluorophosphate
  • ionic liquids such as 46
  • 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.
  • the cation moiety is linked to the n-Bu group and CH-SOH is linked to the N atom of imidazole.
  • An ionic liquid (la) having a combined structure and the aion part is CF SO, and a cation part
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • 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 ⁇ -methylstyrene.
  • 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.
  • Chem. Comnun. 2000, p695-1696 describes a method of alkylating an aromatic compound using an ionic liquid and scandium triflate as a catalyst.
  • ionic liquid [emim] [SbF]
  • [emim] + represents 1-ethyl-3-methylimidazolium cation
  • [bmim] + represents 1-butyl-3-methylimidazolidine cation.
  • 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.
  • alkylated aromatic hydrocarbons are useful as raw materials for styrene and surfactants.
  • 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.
  • a solid acid such as a protonic acid such as a mineral acid, a Lewis acid such as A: i or BF, or zeolite.
  • 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
  • hydrocarbyl-substituted imidazolym halide, hydrocarbyl-substituted pyridinium halide is proposed.
  • 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.
  • 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.
  • a Lewis acid such as aluminum chloride
  • examples of the ionic liquid include a quaternary ammonium salt, an imidazoline salt, a pyridinium salt, a sulfodium salt, and a phosphonium salt.
  • 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.
  • a catalyst such as sulfuric acid.
  • 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.
  • 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.
  • nitrates or salts are used as nitrating agents.
  • 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.
  • a strong acid such as sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, hydrogen fluoride, polyphosphoric acid, phosphorus pentachloride and similar substances.
  • a strong acid such as sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, hydrogen fluoride, polyphosphoric acid, phosphorus pentachloride and similar substances.
  • a strong acid such as sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, hydrogen fluoride, polyphosphoric acid, phosphorus pentachloride and similar substances.
  • 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 ⁇ -caprolactam are raw materials for nylon and are industrially important materials.
  • ⁇ - 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.
  • 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.
  • ammonium sulfate is not produced as a by-product!
  • HC1 is a by-product during post-treatment with water
  • PC1 is used as a co-catalyst.
  • -SO H has a structure bonded to the N atom of imidazole, and the ion is CF SO
  • 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.
  • 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.
  • the present invention provides an ionic liquid represented by the following formula (1).
  • a preferable ionic liquid is represented by the following formula (2).
  • the present invention is characterized in that an aromatic compound is reacted with an olefin in the presence of the ionic liquid.
  • the present invention relates to the ionic liquid and M (OTf)
  • M represents a divalent or trivalent metal atom
  • Tf represents SOCF
  • m represents an integer of 2 or 3.
  • 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.
  • the present invention provides the ionic liquid and
  • M represents a divalent or trivalent metal atom
  • Tf represents SOCF
  • m represents an integer of 2 or 3.
  • 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.
  • 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.
  • 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.
  • the present invention provides a Beckmann rearrangement reaction method, which comprises subjecting oximes to Beckmann rearrangement in the presence of the ionic liquid.
  • 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
  • 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.
  • the ionic liquid of the present invention is represented by the above formula (1).
  • X is a halogen atom or a hydroxyl group, preferably a chlorine atom.
  • Y— is CF SO—, BF—, PF—,
  • the force is preferably CF SO—, PF—, C1—, and more preferably CF SO—.
  • n is 2—
  • ionic liquids include the following 3a, 4a, 3b and 4b.
  • n and X are as follows.
  • 3a and 4a have properties as Bronsted acids, and 3b and 4b have properties as Lewis acids.
  • 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.
  • 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.
  • the ionic liquid of the present invention can be obtained by applying a reaction known in Chem. Comnun. 2000, pl695-1696 and the like.
  • 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.
  • 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.
  • 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.
  • the obtained ionic liquid can be identified by NMR measurement or the like.
  • 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.
  • 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.
  • 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.
  • 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.
  • Ar is an aromatic group obtained by removing a bullet group from an aromatic vinyl conjugate
  • Ar ′ is an aromatic group obtained by removing a hydrogen from an aromatic hydrocarbon. If ⁇ -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).
  • 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.
  • the amount of the olefins is excessive, a homopolymer of the olefins such as an aromatic vinyl conjugate is easily formed.
  • 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.
  • Preferred ionic liquids include the above 3a, 4a, 3b and 4b, more preferably 3b and 4b.
  • the triflate conjugate used together with the above ionic liquid is represented by ⁇ ( ⁇ ⁇ ) 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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—
  • n is preferably 3-8, more preferably 3 or 4.
  • 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.
  • 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.
  • 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.
  • the alkyl group is preferably a lower alkyl having 6 or less carbon atoms.
  • 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.
  • 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.
  • 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.
  • 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.
  • nitric acid 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.
  • an ionic liquid phase containing nitric acid and an aromatic compound phase there are two phases, an ionic liquid phase containing nitric acid and an aromatic compound phase, and these are stirred to progress the reaction.
  • 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.
  • 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.
  • 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.
  • the reaction rate of the starting aromatic compound is preferably about 50 to 95% when a mono-toro-substituted aromatic compound is intended.
  • 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.
  • the ionic liquid used in the present invention is represented by the above formula (1), preferably (2).
  • 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.
  • the ionic liquid used in the present invention can be used as it is, with the force ionic liquid supported on a carrier.
  • 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.
  • a low-boiling solvent such as THF
  • the surface of the carrier is modified beforehand and chemically bonded to an ionic liquid.
  • 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.
  • a solid acid catalyst such as silica'alumina or a solid basic catalyst can be used.
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a 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
  • CO can be used to separate the reaction mixture as described below, so use a carrier
  • 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.
  • the ionic liquid in which the target substance is dissolved is collected and reused.
  • the ionic liquid in which the target substance is dissolved is collected and reused.
  • the target substance such as ⁇ -force prolatatum is extracted, and the ionic liquid remains without being extracted.
  • the ionic liquid in which the target substance is dissolved often has a high viscosity, the more advantageous
  • auxiliary extraction solvent examples 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.
  • the ionic liquid 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,
  • It is preferably about 24-82 L.
  • the target substance and the ionic liquid are recovered, and the ionic liquid can be reused.
  • Ionic liquids 3a, 4a, 3b and 4b were used.
  • the well-known ionic liquids BMImBF and BMImPF were also examined at the same time.
  • 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.
  • 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.
  • Lewis acidic ionic liquid 4b which has a long side chain, has a decrease in styrene conversion and clearly affects the product distribution.
  • Reaction time and the molar ratio of P-xylene to styrene are two important factors that affect styrene conversion and distribution of reactant products.
  • 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.
  • 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.
  • the product in the upper layer can be easily separated from the ionic liquid by decantation. Then, the remaining ionic liquid can be reused.
  • 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!
  • 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.
  • 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.
  • the metal element symbol in the column of triflate in Table 3 indicates that the metal is a Trifle M ligated compound.
  • the triflate conjugate was Sc triflate, Y triflate, La triflate or Zn triflate.
  • the aromatic compound was subjected to the toro conversion using the ionic liquid 3a or 4a.
  • 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.
  • R-Ar mono-substituted benzene represented by R-Ar (where Ar represents a phenyl group and R represents H or a substituent) was used.
  • nitric acid 62% nitric acid was used.
  • 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.
  • Table 4 shows the reaction conditions and the reaction results.
  • 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.
  • the ionic liquid is more excellent in the directional deformation ratio of 4a than 3a.
  • the conversion of the ionic liquid is superior in the order of 5%, 10%, and 15%.
  • 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.
  • the reaction time it can be seen that the conversion is better for 22 hours than for 12 hours.
  • 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.
  • the Bronsted acidic ionic liquids 4a and 3a are the same.
  • 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.
  • reaction mixture viscous liquid
  • CO and chlorophos as an auxiliary extraction solvent
  • Lum was used for supercritical extraction with CO. Extract ⁇ -caprolatatam from the extract
  • the ionic liquid collected and left unextracted was recovered and reused in the next reaction. ⁇ -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.
  • the CO used for the extraction is about 24-82 L under the conditions of 25 ° C and 0.1Mpa.
  • 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.
  • Table 6 shows the reaction conditions and reaction results.
  • the molar ratio indicates the molar ratio of the ketoxime Z ionic liquid
  • the selectivity indicates the ratatum selectivity.
  • CHOX indicates cyclohexanone oxime
  • TOX indicates tetralone oxime.
  • 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.
  • ionic liquid 2A This viscous liquid is referred to as ionic liquid 2A.
  • the component corresponding to Y— in the above formula (1) is C1—.
  • 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.
  • the molar ratio of cyclohexanoxoxime to ionic liquid was set to 5.
  • 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).
  • FID gas chromatography Shiadzu GC-14A, ULBON HR-52 Capillary One-Ram 25m x 0.32mm.
  • the reaction rate of cyclohexanone oxime and ⁇ The selectivity to force prolatatam is as follows.
  • Example 1 1-aryl imidazole was used instead of 1-methyl imidazole.
  • an ionic liquid 3C was obtained in the same manner except that 1,3-propane sultone was used instead of 1,4-butane sultone.
  • silica gel-60 70-230mesh; manufactured by Merck
  • MPS 3-mercaptopropyltrimethoxysilane
  • 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).
  • 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.
  • 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.
  • 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%
  • 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.
  • the reaction can be performed under relatively mild conditions, the separation is easy, and the catalyst can be reused.
  • industrially useful alkyl-substituted aromatic compounds, nitro-substituted aromatic compounds, ⁇ - force prolatatam, and the like can be obtained with high yield and high selectivity.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)

Abstract

Cette invention se rapporte à un nouveau liquide ionique acide, qui peut servir de catalyseur pour des alkylations, des nitratations, et des agencements de Beckmann, notamment, et qui est stable à l'air et à l'eau. Ce liquide ionique est représenté par la formule (1), dans laquelle X représente halogéno ou hydroxy; Y- représente CF3SO3-, BF4-, PF6-, CH3COO-, CF3COO-, (CF3SO2)2N-, (CF3SO2)3C-, F-, Cl-, Br-, ou I-; n est égal à un nombre entier compris entre 2 et 16; et R représente méthyle, allyle ou vinyle. Non seulement ce liquide ionique fonctionne comme acide de Brζnsted ou comme acide de Lewis mais il constitue également un liquide insoluble dans de nombreux solvants organiques. Ce liquide est par conséquent utile comme catalyseur ou comme solvant pour des réactions de Friedel-Crafts, pour des nitratations et pour des réagencements de Beckmann. Il peut facilement être séparé du mélange de réaction et réutilisé.
PCT/JP2004/013467 2003-09-18 2004-09-15 Liquide ionique et procede de reaction utilisant ce liquide WO2005028446A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2005514045A JPWO2005028446A1 (ja) 2003-09-18 2004-09-15 イオン性液体及びそれを使用する反応方法
CN2004800269737A CN1852898B (zh) 2003-09-18 2004-09-15 离子性液体及使用离子性液体的反应方法
DE112004001729T DE112004001729T5 (de) 2003-09-18 2004-09-15 Ionische Flüssigkeit und Reaktionsverfahren, das dieselbe einsetzt

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2003-325590 2003-09-18
JP2003325590 2003-09-18
JP2003-374512 2003-11-04
JP2003374512 2003-11-04
JP2004029219 2004-02-05
JP2004-029219 2004-02-05
JP2004036947 2004-02-13
JP2004-036947 2004-02-13

Publications (1)

Publication Number Publication Date
WO2005028446A1 true WO2005028446A1 (fr) 2005-03-31

Family

ID=34382099

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/013467 WO2005028446A1 (fr) 2003-09-18 2004-09-15 Liquide ionique et procede de reaction utilisant ce liquide

Country Status (5)

Country Link
JP (1) JPWO2005028446A1 (fr)
CN (1) CN1852898B (fr)
DE (1) DE112004001729T5 (fr)
TW (1) TW200517375A (fr)
WO (1) WO2005028446A1 (fr)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007237117A (ja) * 2006-03-10 2007-09-20 Japan Science & Technology Agency イオン性液体で被覆された固定化ルイス酸触媒、及びその使用
CN100374410C (zh) * 2005-08-26 2008-03-12 中国科学院兰州化学物理研究所 一种酮肟经贝克曼重排反应制备酰胺的方法
WO2008145312A1 (fr) 2007-05-25 2008-12-04 Dsm Ip Assets B.V. Procédé de préparation d'un lactame dans un liquide ionique
JP2009502990A (ja) * 2005-08-03 2009-01-29 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング アルケンまたはエーテルを得るためのアルコールの脱水
JP2009534181A (ja) * 2006-04-26 2009-09-24 ズード−ケミー アーゲー イオン液体で被覆される多孔質不均一系担持金属触媒、生成プロセス、及び触媒使用方法
JP2009275022A (ja) * 2008-05-19 2009-11-26 Sumitomo Chemical Co Ltd イミダゾリウム塩およびそれが固定化された粒子状酸化物
WO2009154144A1 (fr) * 2008-06-17 2009-12-23 日本ポリウレタン工業株式会社 Procédé de production de polyamine aromatique
WO2010004818A1 (fr) * 2008-07-09 2010-01-14 日本ポリウレタン工業株式会社 Procédé de production de polyisocyanate
US20100063274A1 (en) * 2008-09-11 2010-03-11 CHINA PETROCHEMICAL DEVELOPMENT CORPORATION, Taipei(Taiwan) Method for preparing amide
CN101973940A (zh) * 2010-09-28 2011-02-16 盐城师范学院 磺酸烷基离子液体的连续合成方法
JP2011072991A (ja) * 2009-09-30 2011-04-14 Chinese Petrochemical Dev Corp アミドの製造に用いられる触媒組成物及びアミドの製造方法
US20110105793A1 (en) * 2009-10-30 2011-05-05 China Petrochemical Development Corporation Method for separating amide from amino acid ionic liquid
JP2013503733A (ja) * 2009-09-03 2013-02-04 テクニカル・ユニヴァーシティ・オブ・デンマーク 双性イオンおよび／または酸官能化イオン性液体を含むパラジウム触媒系
JP2013043176A (ja) * 2011-08-26 2013-03-04 Chinese Petrochemical Dev Corp アミドを製造するための触媒組成物、及びアミドの製造方法
CN103073405A (zh) * 2013-02-04 2013-05-01 河北工业大学 一种在酸性离子液中催化环己酮肟水解反应的方法
CN103265435A (zh) * 2013-06-20 2013-08-28 江苏大华化学工业有限公司 一种4-氯-3-硝基三氟甲苯的清洁制备方法
US8802596B2 (en) 2005-10-07 2014-08-12 Board Of Trustees Of The University Of Alabama Multi-functional ionic liquid compositions for overcoming polymorphism and imparting improved properties for active pharmaceutical, biological, nutritional, and energetic ingredients
CN104030925A (zh) * 2014-06-26 2014-09-10 扬州大学 一种催化合成单硝基氯苯的方法
CN105289746A (zh) * 2015-11-04 2016-02-03 常州大学 一种用于Beckmann重排反应的改性氧化石墨烯催化剂及其制备方法
US9278134B2 (en) 2008-12-29 2016-03-08 The Board Of Trustees Of The University Of Alabama Dual functioning ionic liquids and salts thereof
JP2019534278A (ja) * 2016-10-21 2019-11-28 華南理工大学 リグニンの触媒選択的酸化によるマレイン酸エステルの製造方法
JP7001861B1 (ja) 2021-03-31 2022-01-20 第一工業製薬株式会社 フッ素系イオン性液体およびその製造方法
WO2022046537A1 (fr) * 2020-08-24 2022-03-03 University Of Kansas Processus de préparation d'alkylbenzènes

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1970582B (zh) * 2006-12-04 2010-07-14 南京大学 聚(n-乙烯基-n′-烷基-咪唑)离子液体结构材料及其制备方法
EP2072530A1 (fr) * 2007-12-21 2009-06-24 Dow Wolff Cellulosics GmbH Procédé de fabrication de dérivés de cellulose contenant des groupements amino dans un liquide ionique
CN101250160B (zh) * 2008-03-21 2011-05-25 西北师范大学 氯化1,3-二(2-羟基乙基)咪唑离子液体及其合成方法
CN101602673B (zh) * 2009-07-14 2013-05-08 西安近代化学研究所 在离子液体中制备硝基苯的方法
CN102249927B (zh) * 2010-05-20 2014-02-12 江苏大华化学工业有限公司 降解型功能化离子液体催化对氯三氟甲苯清洁硝化反应
CN101838175B (zh) * 2010-05-21 2013-08-21 哈尔滨师范大学 离子液体的应用及离子液体催化脱肟的方法
CN102229569A (zh) * 2011-04-11 2011-11-02 新疆大学 一种基于苯并咪唑阳离子的Brφnsted酸性离子液体的制备方法
CN102250026A (zh) * 2011-05-23 2011-11-23 浙江常山科润化学有限公司 一种2,4,6-三（2,4-二羟基苯基）-1,3,5-三嗪的合成方法
CN102295614B (zh) * 2011-07-01 2013-12-25 安徽中天化工有限公司 一种2-甲基-4-甲氨基-6-甲氧基-1，3，5-三嗪的合成方法
CN103288735B (zh) * 2012-02-29 2015-03-04 北京安耐吉能源工程技术有限公司 一种用于贝克曼重排的催化剂体系以及制备己内酰胺的方法
CN102633929B (zh) * 2012-03-27 2013-11-06 绍兴文理学院 一种酸性离子液体介孔聚合材料的制备方法
CN103420747B (zh) * 2012-05-14 2016-07-06 苏州奥索特新材料有限公司 烯烃类化合物的合成方法
CN103553925B (zh) * 2013-10-28 2015-05-06 河北工业大学 一种液相硝化合成硝基环己烷的工艺
US9416071B2 (en) 2014-05-06 2016-08-16 Uop Llc Hydrocarbon conversion processes using lactamium-based ionic liquids
CN106380418B (zh) * 2016-09-07 2018-07-31 上饶师范学院 一种用N-甲基吡咯烷酮/SOCl2高效实现酮肟Beckmann重排的方法
CN109721462B (zh) * 2017-10-30 2022-03-11 中国石油化工股份有限公司 一种制备长链烷基苯的方法
CN108911999B (zh) * 2018-08-06 2021-05-04 朱晓萍 一种1-氨基蒽醌的合成方法
WO2021097200A1 (fr) * 2019-11-15 2021-05-20 University Of Kansas Composition de catalyseur d'alkylation et procédés associés
CN111690004B (zh) * 2020-07-17 2022-11-29 山东药石药业有限公司 一种离子液体改性硅胶负载氯化铝催化剂

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002003478A (ja) * 2000-06-20 2002-01-09 Japan Science & Technology Corp Ｎ−アルコキシアルキルイミダゾリウム塩、該イミダゾリウム塩からなるイオン性液体ならびにイオン性ゲル
JP2002025610A (ja) * 2000-06-09 2002-01-25 Merck Patent Gmbh イオン性流動体
WO2003086605A2 (fr) * 2002-04-05 2003-10-23 University Of South Alabama Liquides ioniques fonctionnalises et leurs procedes d'utilisation
JP2003313171A (ja) * 2002-04-23 2003-11-06 Kuraray Co Ltd Ｎ−アルキル−ｎ’−アルキルイミダゾリウム塩の製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9402569D0 (en) * 1994-02-10 1994-04-06 Bp Chem Int Ltd Alkylation process
US5824832A (en) * 1996-07-22 1998-10-20 Akzo Nobel Nv Linear alxylbenzene formation using low temperature ionic liquid
JPH11199525A (ja) * 1997-12-27 1999-07-27 Teikoku Chem Ind Corp Ltd アルキル化方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002025610A (ja) * 2000-06-09 2002-01-25 Merck Patent Gmbh イオン性流動体
JP2002003478A (ja) * 2000-06-20 2002-01-09 Japan Science & Technology Corp Ｎ−アルコキシアルキルイミダゾリウム塩、該イミダゾリウム塩からなるイオン性液体ならびにイオン性ゲル
WO2003086605A2 (fr) * 2002-04-05 2003-10-23 University Of South Alabama Liquides ioniques fonctionnalises et leurs procedes d'utilisation
JP2003313171A (ja) * 2002-04-23 2003-11-06 Kuraray Co Ltd Ｎ−アルキル−ｎ’−アルキルイミダゾリウム塩の製造方法

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009502990A (ja) * 2005-08-03 2009-01-29 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング アルケンまたはエーテルを得るためのアルコールの脱水
CN100374410C (zh) * 2005-08-26 2008-03-12 中国科学院兰州化学物理研究所 一种酮肟经贝克曼重排反应制备酰胺的方法
US8802596B2 (en) 2005-10-07 2014-08-12 Board Of Trustees Of The University Of Alabama Multi-functional ionic liquid compositions for overcoming polymorphism and imparting improved properties for active pharmaceutical, biological, nutritional, and energetic ingredients
WO2007105668A1 (fr) * 2006-03-10 2007-09-20 Japan Science And Technology Agency Catalyseurs acide de lewis immobilises enduits de liquides ioniques et leur utilisation
US8871668B2 (en) 2006-03-10 2014-10-28 Japan Science And Technology Agency Immobilized lewis acid catalysts coated with ionic liquids and use thereof
JP2007237117A (ja) * 2006-03-10 2007-09-20 Japan Science & Technology Agency イオン性液体で被覆された固定化ルイス酸触媒、及びその使用
JP2009534181A (ja) * 2006-04-26 2009-09-24 ズード−ケミー アーゲー イオン液体で被覆される多孔質不均一系担持金属触媒、生成プロセス、及び触媒使用方法
JP2010527950A (ja) * 2007-05-25 2010-08-19 ディーエスエム アイピー アセッツ ビー．ブイ． イオン性液体中でラクタムを製造する方法
WO2008145312A1 (fr) 2007-05-25 2008-12-04 Dsm Ip Assets B.V. Procédé de préparation d'un lactame dans un liquide ionique
JP2009275022A (ja) * 2008-05-19 2009-11-26 Sumitomo Chemical Co Ltd イミダゾリウム塩およびそれが固定化された粒子状酸化物
JP2009298755A (ja) * 2008-06-17 2009-12-24 Nippon Polyurethane Ind Co Ltd 芳香族ポリアミンの製造方法
WO2009154144A1 (fr) * 2008-06-17 2009-12-23 日本ポリウレタン工業株式会社 Procédé de production de polyamine aromatique
WO2010004818A1 (fr) * 2008-07-09 2010-01-14 日本ポリウレタン工業株式会社 Procédé de production de polyisocyanate
US8524895B2 (en) * 2008-09-11 2013-09-03 China Petrochemical Development Corporation Method for preparing amide
US20100063274A1 (en) * 2008-09-11 2010-03-11 CHINA PETROCHEMICAL DEVELOPMENT CORPORATION, Taipei(Taiwan) Method for preparing amide
US9278134B2 (en) 2008-12-29 2016-03-08 The Board Of Trustees Of The University Of Alabama Dual functioning ionic liquids and salts thereof
JP2013503733A (ja) * 2009-09-03 2013-02-04 テクニカル・ユニヴァーシティ・オブ・デンマーク 双性イオンおよび／または酸官能化イオン性液体を含むパラジウム触媒系
JP2011072991A (ja) * 2009-09-30 2011-04-14 Chinese Petrochemical Dev Corp アミドの製造に用いられる触媒組成物及びアミドの製造方法
US8552180B2 (en) * 2009-10-30 2013-10-08 China Petrochemical Development Corporation Method for separating amide from amino acid ionic liquid
US20110105793A1 (en) * 2009-10-30 2011-05-05 China Petrochemical Development Corporation Method for separating amide from amino acid ionic liquid
JP2011093905A (ja) * 2009-10-30 2011-05-12 Chinese Petrochemical Dev Corp アミノ酸型イオン液体からアミド生成物を分離する方法
CN101973940A (zh) * 2010-09-28 2011-02-16 盐城师范学院 磺酸烷基离子液体的连续合成方法
JP2013043176A (ja) * 2011-08-26 2013-03-04 Chinese Petrochemical Dev Corp アミドを製造するための触媒組成物、及びアミドの製造方法
CN103073405B (zh) * 2013-02-04 2015-08-19 河北工业大学 一种在酸性离子液中催化环己酮肟水解反应的方法
CN103073405A (zh) * 2013-02-04 2013-05-01 河北工业大学 一种在酸性离子液中催化环己酮肟水解反应的方法
CN103265435A (zh) * 2013-06-20 2013-08-28 江苏大华化学工业有限公司 一种4-氯-3-硝基三氟甲苯的清洁制备方法
CN104030925A (zh) * 2014-06-26 2014-09-10 扬州大学 一种催化合成单硝基氯苯的方法
CN105289746A (zh) * 2015-11-04 2016-02-03 常州大学 一种用于Beckmann重排反应的改性氧化石墨烯催化剂及其制备方法
JP2019534278A (ja) * 2016-10-21 2019-11-28 華南理工大学 リグニンの触媒選択的酸化によるマレイン酸エステルの製造方法
WO2022046537A1 (fr) * 2020-08-24 2022-03-03 University Of Kansas Processus de préparation d'alkylbenzènes
JP7001861B1 (ja) 2021-03-31 2022-01-20 第一工業製薬株式会社 フッ素系イオン性液体およびその製造方法
WO2022209538A1 (fr) * 2021-03-31 2022-10-06 第一工業製薬株式会社 Liquide ionique à base de fluor et son procédé de production
JP2022157468A (ja) * 2021-03-31 2022-10-14 第一工業製薬株式会社 フッ素系イオン性液体およびその製造方法

Also Published As

Publication number Publication date
CN1852898B (zh) 2010-04-28
TW200517375A (en) 2005-06-01
JPWO2005028446A1 (ja) 2007-11-15
DE112004001729T5 (de) 2006-10-19
CN1852898A (zh) 2006-10-25

Similar Documents

Publication Publication Date Title
WO2005028446A1 (fr) Liquide ionique et procede de reaction utilisant ce liquide
Corma et al. Lewis acids: from conventional homogeneous to green homogeneous and heterogeneous catalysis
AU774373B2 (en) Immobilised ionic liquids
US7285698B2 (en) Method for manufacturing alkylate oil with composite ionic liquid used as catalyst
FI64135C (fi) Foerfarande foer framstaellning av alkylaromatiska kolvaeten
DE68925081T2 (de) Katalytisches Verfahren zur Alkylierung von aromatischen Kohlenwasserstoffen in einem Fest-Bett
US6998497B2 (en) Metal bis-triflimide compounds and methods for synthesis of metal bis-triflimide compounds
Bui et al. Alkylation of isobutane with 2-butene using ionic liquids as catalyst
FI79831C (fi) Transalkylerings- eller dealkylerings foerfarande foer alkylaromatiska kolvaeten.
AU2002241085A1 (en) Processes using metal bis-triflimide compounds
KR101872798B1 (ko) 이온성 액체-용매 복합체, 이의 제조와 용도
Bhatt et al. Supported 12-tungstophosphoricacid: A recoverable solid acid catalyst for liquid phase Friedel–Crafts alkylation of phenol
US9321046B2 (en) Recovery method and recycling method for boron trifluoride complex
AU2013357218B2 (en) Process for preparing alkylate comprising an improved solids removal step
Castro et al. On the acylation reactions of anisole using α, β-unsaturated organic acids as acylating agents and solid acids as catalysts: a mechanistic overview
WO2015171291A2 (fr) Procédé de conversion d'hydrocarbures comprenant la régénération du catalyseur
RU2182896C2 (ru) Способ получения диарилметана или его производных
EP0671213A1 (fr) Procédé de récupération de catalyseur d'alkylation
JP3537483B2 (ja) 芳香族化合物のアルキル化方法
WO1996036587A1 (fr) Nitruration catalytique
Békássy et al. Selectivity of C-versus O-acylation of diphenols by clay catalysts. I. Acylation of resorcinol with phenylacetyl chloride
JPS6141593A (ja) 感圧紙染料用溶剤
JPH07268364A (ja) ガソリン留分中の芳香族化合物の低減方法
JPH0583529B2 (fr)
Sood The role of strongly acidic media on the formylation of toluene

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200480026973.7

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BW BY BZ CA CH CN CO CR CU CZ DK DM DZ EC EE EG ES FI GB GD GE GM HR HU ID IL IN IS JP KE KG KP KZ LC LK LR LS LT LU LV MA MD MK MN MW MX MZ NA NI NO NZ PG PH PL PT RO RU SC SD SE SG SK SY TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SZ TZ UG ZM ZW AM AZ BY KG MD RU TJ TM AT BE BG CH CY DE DK EE ES FI FR GB GR HU IE IT MC NL PL PT RO SE SI SK TR BF CF CG CI CM GA GN GQ GW ML MR SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2005514045

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 1120040017297

Country of ref document: DE

122 Ep: pct application non-entry in european phase