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WO2005113547A1 - Composé couronne supportant un liquide ionique - Google Patents

Composé couronne supportant un liquide ionique Download PDF

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Publication number
WO2005113547A1
WO2005113547A1 PCT/JP2005/009365 JP2005009365W WO2005113547A1 WO 2005113547 A1 WO2005113547 A1 WO 2005113547A1 JP 2005009365 W JP2005009365 W JP 2005009365W WO 2005113547 A1 WO2005113547 A1 WO 2005113547A1
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group
general formula
represented
alkyl group
formula
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Japanese (ja)
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Atsunori Sano
Keiji Oono
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Fujifilm Wako Pure Chemical Corp
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Wako Pure Chemical Industries Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0204—Ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions

Definitions

  • the present invention relates to a novel ionic liquid-carrying crown compound that enables recovery and reuse.
  • Ionic liquids are also referred to as room temperature molten salts, and have properties such as heat resistance, a wide liquid temperature range, non-volatility with almost no vapor pressure, low viscosity, and high ionic conductivity. Have.
  • Ionic liquids having such properties are expected to be applied to a wide range of fields, for example, as environmentally friendly reaction solvents for green chemistry, electrolyte solutions in the field of electrochemical devices, and the like. Is expected.
  • organic solvents that are commonly used as reaction solvents for various synthesis reactions are volatile, and their gases are harmful to the human body, and cause pollution and fire. Furthermore, these organic solvents have a problem that they are difficult to reuse after the reaction and are discarded, thereby causing environmental pollution.
  • ionic liquids are non-volatile with almost no vapor pressure, they are easy to handle because they are not flammable or flammable, and they have the property of being hardly soluble in water or low-polarity organic solvents. Utilizing this property, if various reactions are carried out using an ionic liquid as a reaction solvent, the ionic liquid is extracted from the reaction system by, for example, extracting products and by-products with water or an organic solvent. Collection and reuse becomes possible.
  • crown ethers such as 18-crown-6 are widely used as phase transfer catalysts in various reactions such as nucleophilic substitution reactions. These crown ethers are expensive catalysts. Further, even if it is used as a reaction catalyst, it is difficult to recover it, so that there is a problem that it is costly to carry out the reaction using these crown ethers as a catalyst. [0007] Under such circumstances, it has been desired to develop a new catalyst which has a catalytic action of crown ether and can be recovered and reused after performing various reactions.
  • the present invention relates to a novel ionic liquid-supported crowned conjugate that can be used as a recoverable and reusable catalyst.
  • the present invention has been made for the purpose of solving the above problems, and has a general formula [1]
  • R 1 is a group derived from a crowny conjugate
  • R 2 is a group derived from an ionic liquid
  • T is an alkylene chain having 1 to 8 carbon atoms.
  • the ionic liquid-carrying crowny conjugate of the present invention contains an ionic liquid and a crown compound in the molecule. Therefore, the present invention has been found to have a catalytic activity such as a crown ether such as 18-crown-6 and to facilitate the recovery from the reaction system, regeneration of the catalytic activity, and further reuse. Was completed.
  • the ionic liquid-carrying crown compound of the present invention is used as a catalyst, for example, a crown conjugate such as 18-crown-6 is recovered from a reaction system despite an expensive catalyst and is reused. Since it has an ionic liquid and a crown compound in a molecule that does not have the problem of being difficult to perform, it has a catalytic action like crown ether, can be efficiently recovered like an ionic liquid, and Since the recovered catalyst can easily regenerate its catalytic activity, it can be reused repeatedly.
  • the group derived from the crown conjugate represented by R 1 is, for example, a group derived from a macrocyclic polyether containing a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.
  • a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.
  • examples include groups derived from crown compounds having a 12-crown-4 skeleton, a 15-crown-5 skeleton, an 18-crown-6 skeleton, a 21-crown-7 skeleton, and a 24-crown-8 skeleton.
  • R 3 to R 8 , m R 9 s, and m R 1G are each independently a bond bonded to T in the general formula [1], a hydrogen atom, an alkyl group ,
  • R 11 represents a hydroxy group, an alkoxy group, an aralkyloxy group or an acyloxy group.
  • R 12 and R 13 each independently represent a hydrogen atom, a hydroxy group, an alkoxy group or an acyloxy group, except that both R 12 and R 13 are hydrogen atoms ) Or a general formula [5]
  • R 14 represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or an aryloxy group which may have an alkyl group as a substituent, or a general formula [6]
  • a to A and m A are each independently an oxygen atom, a sulfur atom or
  • R 17 has a bond bonded to the general formula [1], a hydrogen atom, an alkyl group, an alkylsulfur group, or an alkyl group as a substituent. Represents a aryl group, a benzenesulfol group, or a heterocyclic group).
  • any of R 3 to R 8 , m R 9 , m R 1G , and A to A and m A are represented by the general formula [7].
  • R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , and R 9 are each independently a cyclohexane ring together with carbons adjacent to each other.
  • a benzene ring or a naphthalene ring may be formed.
  • the cyclohexane ring, benzene ring and naphthalene ring each independently represent an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbyl group, a morpholmethyl group or a decahydronaphthyl group. It may have a group. ⁇ .
  • any one of 1 34 is a group represented by the general formula [7]
  • only one is a bond that bonds to T in the general formula [1]. That is, in general formula [1], there is only one bond to be bonded to T in general formula [2], and the bond is derived from a crown compound represented by general formula [2].
  • the groups when present in R 3 to R 8 , m R 9 s and m R 1G , or R 17 represented by the general formula [7], and the group containing R 17 is A to A And one of m A
  • crowny daggers include, for example, general formulas
  • R to R, n R and n R are each independently a hydrogen atom, an alkyl group ,
  • R 11 represents a hydroxy group, an alkoxy group, an aralkyloxy group or an acyloxy group
  • R 12 and R 13 each independently represent a hydrogen atom, a hydroxy group, an alkoxy group, or an acyloxy group, provided that R 12 and R 13 are not both hydrogen atoms ) Or a general formula [5]
  • R 14 represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or an aryloxy group which may have an alkyl group as a substituent, or a general formula [6] ]
  • R 15 represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or an aryloxy group which may have an alkyl group as a substituent, or a general formula [6] ]
  • a to A and n A are each independently an oxygen atom, a sulfur atom or
  • R 25 represents a hydrogen atom, an alkyl group, an alkylsulfol group, an aryl group or a benzenesulfol group which may have an alkyl group as a substituent, or a heterocyclic group
  • n represents an integer of 1 to 5.
  • R 18 and R 19, R 21 and R 22, and R 2 3 and R 24 are each independently together with the carbon adjacent to each other, hexane ring, may form a benzene ring or a naphthalene ring cyclohexylene .
  • the cyclohexane ring, benzene ring and naphthalene ring each independently represent an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbyl group, a morpholmethyl group or a decahydronaphthyl group. It may have a group. ⁇ Or a general formula [10]
  • R b to R dl , p and p R dd each independently represent a hydrogen atom, an alkyl group
  • R 11 represents a hydroxy group, an alkoxy group, an aralkyloxy group or an acyloxy group
  • R 12 and R 13 each independently represent a hydrogen atom, a hydroxy group, an alkoxy group, or an acyloxy group, provided that R 12 and R 13 are not both hydrogen atoms ) Or a general formula [5]
  • R 14 represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or an aryloxy group which may have an alkyl group as a substituent, or a general formula [6]
  • A, A and p of A are each independently an oxygen atom, a sulfur atom or
  • R 25 represents a hydrogen atom, an alkyl group, an alkylsulfol group, an aryl group or a benzenesulfol group which may have an alkyl group as a substituent, or a heterocyclic group. You. ), And p represents an integer of 1 to 5.
  • R 26 and R 27 , R 28 and R 29 , R 3G and R 31 , and R 32 and R 33 each independently form a cyclohexane ring, a benzene ring or a naphthalene ring together with adjacent carbons. It may be.
  • the cyclohexane ring, benzene ring and naphthalene ring each independently represent an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbyl group, a morpholmethyl group or a decahydronaphthyl. It may have a group. ⁇ .
  • the group derived from the ionic liquid represented by R 2 includes a group represented by the general formula [11]
  • R 34q + represents a q-valent quaternary ammonium ion or a quaternary phospho-pium ion
  • q X— represents a counter-one
  • q represents 1 or 2.
  • the alkylene chain having 1 to 8 carbon atoms represented by T generally has 1 carbon atom.
  • linear alkyl groups preferably 1 to 4, linear alkyl groups.
  • Specific examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and otatamethylene. And a methylene group and an ethylene group.
  • Examples thereof include those having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, which may be linear, branched or cyclic, and specifically, for example, a methyl group, an ethyl group, n -Propyl, isopropyl, n-butyl, isobutyl, sec-butynole, tert-butynole, n-pentynole, isopentynole, sec-pentynole, tert-pentyl, neopentyl, n-hexyl Group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, cyclopropyl group, cyclobutyl group,
  • the alkoxy group represented by R n to R ′′ may be any of linear, branched or cyclic, usually having 1 to 6 carbon atoms. Preferred are those having 1-3, specifically, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group , N-pentyloxy group , Isopentyloxy, sec-pentyloxy, tert-pentyloxy, neopentyloxy, n-hexyloxy, isohexyloxy, sec-hexyloxy, tert-hexyloxy, neohexyloxy, cyclo Examples include a propoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
  • the Ararukiruokishi group represented by R 11 includes generally one carbon number 7-11, specifically, for example, base Njiruokishi group, Fuenechiruokishi group, naphthylmethoxy And the like.
  • examples of the acyloxy group represented by R n to R 13 include those derived from a carboxylic acid having usually 2 to 20 carbon atoms.
  • Decanoyloxy dodecanoyloxy, tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy, hexadecanyloxy, heptadecanoyloxy, octadecanoyloxy, nonadecanyloxy Groups, icosanoyloxy group
  • the alkyl group represented by R 14 to R 17 in the general formulas [5] to [7] and R 25 in the general formula [9] includes a linear, branched or cyclic alkyl group. Any one of which usually has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n -butyl group, isobutyl group Group, sec -butyl group, tert-butyl group, n-pentynole group, isopentynole group, sec-pentynole group, tert-pentynole group, neopentynole group, n-hexyl group, isohexyl group, sec-hexyl group Tert-hexyl group, neohexyl group, cyclopropyl group, cyclobutyl group, cycl
  • examples of the aryl group of the aryl group include those having 6 to L0 carbon atoms, and specific examples include a phenyl group and a naphthyl group.
  • examples of the alkyl group as the substituent include those having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • aryl group having an alkyl group as a substituent include, for example, a tolyl group, a xylyl group, and a tamenyl group.
  • examples of the aryloxy group of the aryloxy group which may have an alkyl group as the substituent represented by R 14 include those having 6 to 10 carbon atoms. Specific examples include a phenoxy group and a naphthoxy group.
  • alkyl group as the substituent examples include those having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • Preferred specific examples of the aryloxy group having an alkyl group as a substituent include, for example, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,4-dimethylphenyl, and 3,5-dimethylphenyl.
  • Examples thereof include an enoxy group and the like, and among them, for example, a 4-methylphenoxy group, a 2,4-dimethylphenoxy group and the like are preferable.
  • the OH group in the sulfonic acid group is an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group include R 3 to R 1G in the general formula [2], R 18 to R 24 in the general formula [8], and R 18 to R 24 in the general formula [8]. Examples are the same as the examples of the alkyl group represented by R 26 to R 33 in the formula [10].
  • [0068] have the general formula [7] in R 17 and the formula [9] as a substituent represented by at R 25 an alkyl group, even I, benzenesulfonyl - The group, Examples of the benzenesulfonyl group include those in which 1 to 5, preferably 1 to 2 hydrogen atoms of an aromatic ring have been replaced by an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl groups represented by ⁇ 1 ° in the general formula [2], R 18 to R 24 in the general formula [8] and R 26 to R 33 in the general formula [10] The same thing is mentioned.
  • nitrogen atom a sulfur atom
  • those having preferably 1 to 3 are mentioned, and may be monocyclic or polycyclic.
  • Specific examples include chenyl group, quinolyl group, isoquinolyl group, pyridyl group, thiazolyl group, furfuryl group, imidazolyl group and the like. No.
  • n in the general formula [8] and p in the general formula [10] are usually integers of 1 to 5, preferably 1 to 3, more preferably 3
  • the cyclohexane ring, benzene ring and naphthalene ring may further have a substituent.
  • substituents include an alkyl group, an alkenyl group, an acyl group, an acyloxy group and an alkoxycarbonyl group. Morphonylmethyl group, decahydronaphthyl group and the like.
  • alkyl group mentioned as the substituent examples include those having a carbon number of usually 1 to 6, preferably 1 to 3, which may be linear, branched or cyclic.
  • R 3 to R 1C> in the above general formula [2], R 18 to R 24 in the above general formula [8], and R 26 to R 33 in the above general formula [10] And the same as those exemplified for the alkyl group.
  • alkenyl group as the substituent examples include those having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, which may be linear, branched or cyclic. Is, for example, vinyl, aryl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylaryl, 2-methylaryl, 1-methyl -Topoyl, 2-methyl-1-propyl, 1-pentyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl 1-butenyl group, 2-methyl-1-butyl group, 3-methyl-1-butyl group, 1,1-dimethyl-1-propyl group, 1-hexyl group, 2-hexyl -Le group, 3-hexyl group, 4-hexyl group, 5-hexyl group, 3-methyl-3-pentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, And a
  • acyl group as the substituent examples include those derived from a carboxylic acid having usually 2 to 20 carbon atoms. Specific examples include an acetyl group, a propioyl group, a butyryl group, an isobutyryl group, Valeryl group, isovaleryl group, bivaloyl group, hexanoyl group, heptanyl group, otatanyl group, nonanoyl group, decanoyl group, dodecanoyl group, tridecanoyl group, tetradecanol group, pentadecanol group, hexanodecanol group, hexdecanoyl group, hexdecanoyl group Icosanoyl group, benzoyl group, naphthoyl group and the like.
  • Examples of the acyloxy group as the substituent include those derived from a carboxylic acid having 2 to 20 carbon atoms.
  • R n in the above general formulas [3] and [4] ⁇ are the same as those of the exemplary Ashiruokishi groups represented by R 13.
  • Examples of the alkoxycarboyl group as the substituent include those in which a hydrogen atom of a carboxylic acid is substituted with an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group is represented by the general formula [2] ] in R 3 to R 1C to>, similar to the example of the alkyl group represented by in R 18 to R 24 and the one general formula [10] to at R 26 to R 33 in the general formula [8] Of those
  • R 18 to R 22, n pieces of R 23 and n number of R 24 is is preferred that all hydrogen atoms.
  • a to A and n A's are preferably all oxygen atoms.
  • R 26 to R 31 , p R 32, and p R 33 are preferably all hydrogen atoms.
  • A, A, and p A's are preferably all oxygen atoms.
  • Preferred specific examples of the group derived from the crowny conjugate represented by the general formula [8] include, for example, the general formula [12]
  • a group represented by the following formula (corresponding to the general formula [13], wherein A to A and two A's are oxygen atoms);
  • a group represented by the formula [20] (corresponding to a group in which A to A and three A's are oxygen atoms in the general formula [14]);
  • a and one A are nitrogen atoms, and A, A and two A Corresponds to what is an oxygen atom.
  • the group represented by the formula [19] is more preferable.
  • the q-valent quaternary ammonium ion represented by R 34q + includes, for example, the general formula [31]
  • R 35 to R 37 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, or an alkenyl group, provided that R 35 to R 37 are not hydrogen atoms.
  • R 41 represents. An alkyl group
  • divalent quaternary Anmoniumuio emissions such as the group represented by.
  • R 35 to R 37 are the same as described above.
  • a monovalent quaternary phospho-pium ion such as a group represented by the following formula: Etc.
  • the alkyl group represented by R 35 to R 41 a linear, Yogu usually 1 to 6 carbon atoms either branched or cyclic, Preferred are those having 1 to 3, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n_pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl, Examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • the aralkyl group represented by R 35 to R 38 is usually an aralkyl group having 7 or more carbon atoms: L 1.
  • L 1 Are, for example, benzyl, phenyl, 1-phenyl, 2-phenylpropyl, 3-phenylpropyl, phenylphenyl, 1-methyl-3-phenylpropyl, naphthylmethyl And the like.
  • the alkenyl group represented by R 35 to R 37 may be any of linear, branched or cyclic and usually has 2 to 20 carbon atoms. And specifically include, for example, a butyl group, an aryl group, a 1-propyl group, an isopropyl group, a 1-butyl group, a 2-butyl group, a 3-butyl group, and a 1-methylaryl group.
  • k is an integer of usually 1 to 5, preferably 1 to 2.
  • R 44 represents a fluorine atom, a phenyl group or a cyano group which may have a haloalkyl group as a substituent, and a boric acid represented by the general formula [39]
  • R 45 represents an alkyl group, a haloalkyl group, or an alkyl group or a halogen atom as a substituent, and may also represent a phenyl group).
  • R 46 has an alkyl group, a haloalkyl group, or an alkyl group or a halogen atom as a substituent, and may be a phenyl group.
  • Examples of the halogen atom exemplified as the counter-on represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the haloalkyl group represented by R 42 , R 43 , R 45, and R 46 is a straight-chain or branched-chain haloalkyl group.
  • part or all of the hydrogen atoms of the alkyl group having 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms, which may be any of cyclic ones, are halogen atoms (eg, fluorine, chlorine, bromine, iodine, etc.). Examples thereof include substituted ones.
  • Specific examples include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an odomethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a trimethylmethyl group, and a trifluoromethyl group.
  • the haloalkyl group exemplified as these substituents may be a straight-chain, branched or cyclic, usually having 1 to 20, preferably 1 to 10 carbon atoms, part of a hydrogen atom of an alkyl group. Or those in which all are substituted with halogen atoms (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), and specifically, for example, those represented by the above general formulas [36], [37], [39] And the same haloalkyl groups as R 42 , R 43 , R 45 and R 46 in [40].
  • halogen atoms for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
  • the alkyl group represented by R 45 and R 46 may be any of linear, branched or cyclic, and usually has 1 to 20 carbon atoms. Preferred are 1 to: L0, and specifically, for example, R 3 to R 1C> in the above general formula [2], R 18 to R 24 in the above general formula [8] and the above The same as the examples of the alkyl group represented by R 26 to R 33 in the general formula [10], n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, neoheptyl Group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, n-nor group, isonol group, sec-nor group, tert-nor group, Neononyl group, n
  • examples of the phenyl group which may have an alkyl group or a halogen atom as a substituent represented by R 45 and R 46 include phenyl. Examples thereof include those in which 1 to 5, preferably 1 to 3, hydrogen atoms of a group or a ball group are substituted with an alkyl group or a halogen atom.
  • alkyl group mentioned as the substituent examples include those having a carbon number of usually from 1 to 20, preferably from 1 to L0, which may be any of linear, branched or cyclic. Examples thereof include those similar to the examples of the alkyl group represented by R 45 and R 46 in the general formulas [39] and [40].
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • the group derived from the ionic liquid represented by R 34q + represented by the general formula [11] includes, for example, a group derived from an imidazolium cation represented by the general formula [32], and a group represented by the general formula [33] Among these groups, groups derived from an imidazole cation represented by the general formula [32] are more preferable.
  • Preferable specific examples of the group derived from the quaternary ammonium cation represented by the general formula [31] include, for example, triethyl ammonium ion, tri-n-propyl ammonium ion, and tri-n-butyl ammonium ion.
  • Tri-n-pentylammonium-ammion tri-n-hexylammonium-ammonium, tri-n-heptylammonium-ammonium, tri-n-octylammonium-ammonium, tri-n-nor-ammonium-ammonium, tri-n-ammonium n-decylammonium-ammonium, tri-n-pentadecylammonium-pam ion, trilauryl (dodecyl) ammonium ion, tri-n-tridecylammonium-pam ion, trimyristyl (tetradecyl) ammonium-pam ion, tri-n-pentantadecylammonium-pam ion, tri-ion Cetyl ammonium-pium ion, tri-n-heptadecylammo-pium ion, dioctadecy Me
  • Preferred specific examples of the group represented by the general formula [32] include, for example, 3-methylimidazolym Ion, 3-ethinoreimidazolium ion, 3-butinoreimidazolium ion, 3-pentinoreimidazolium ion, 3-hexinoreimidazolium ion, 3-otachinoreimidazolium ion, 3-decylimidazolidium ion, 3- Groups derived from alkyl-substituted imidazolium cations such as dodecyl imidazolium ion, 3-tetradecyl imidazolium ion, 3-hexadecyl imidazolium ion, and 3-octadecyl imidazolium ion; for example, 3-benzyl imidazolium ion; Groups derived from aralkyl-substituted imidazolym cations such as 3-pheny
  • Preferable specific examples of the group represented by the general formula [33] include, for example, pyridium-ion, 3-methylpyridin-ion, 3-ethylpyridin-ion, 4-methylpyridin-ion, 4-ethylpyridin-ion, and 3 And groups derived from a pyridium-cation such as 1,4-dimethylpyridin-dumion and 3,5-dimethylpyridin-dumion.
  • Preferable specific examples of the group represented by the general formula [34] include, for example, N-methyl-4,4'-bipyridium-dumion, N-ethyl-4,4'-bipyridi-dumion, N-propyl -4,4'-bipyridi-dumion, N-butyl-4,4'-bipyridy-dumion, N-pentyl-4,4'-vipyridy-dumion, N-hexyl-4,4'-dibirid- Pemion, N-heptyl-4,4'-bividium-ion, N-octyl-4,4'-bividium-ion, N-nor-4,4'-Vividium-ion, N-decyl-4 4'-Viviridi-ammion, N-Pindecyl-4,4'-Vibilidi-aluminum, N-do
  • Preferable specific examples of the group represented by the general formula [35] include, for example, trimethylphospho-pam ion, triethylphospho-pam ion, tripropylphospho-pam ion, tributylphospho-pam ion, tripentylphospho-pam ion, and tripentylphospho-pam ion.
  • imido acid represented by the general formula [36] include, for example, bis (trifluoromethylsulfol) imidic acid, bis (pentafluoroethylsulfol) imidic acid, and bis (heptafluroic acid).
  • carbon acid represented by the general formula [37] include, for example, tris (trifluoromethylsulfol) carbon acid, tris (pentafluoroethylsulfol) carbon acid, and tris (nonafluoro).
  • tris (trifluoromethylsulfol) carbonic acid and tris (pentafluorophenol) Tylsulfonyl) carbonic acid, tris (perfluorooctylsulfonyl) carbonic acid and the like are preferred, .
  • Preferred specific examples of the boric acid represented by the general formula [38] include, for example, tetrafluoroboric acid, tetrachloroboric acid, tetrabromoboric acid, tetraiodoboric acid, tetracyanoboric acid, tetraphenylboric acid, Tetrakis ⁇ bis (triphenylmethyl) phenyl ⁇ boric acid; and the like, among which tetrafluoroboric acid is preferable.
  • sulfonic acid represented by the general formula [39] include, for example, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and propanesulfonic acid, for example, trifluoromethanesulfonic acid, pentafluoroethane and the like.
  • Preferred specific examples of the carboxylic acid represented by the general formula [40] include alkyl carboxylic acids such as acetic acid, propionic acid, butyric acid, and isobutyric acid, for example, perfluoroacetic acid, perfluoropropionic acid, and perfluorobutane. Acid, perfluorooctanoic acid, chloroacetic acid, chloroacetic acid, perchloropropionic acid, perchlorobutanoic acid, chlorooctanoic acid, perbromoacetic acid, perbromopropionic acid, perbromobutanoic acid, perbromobutanoic acid And the like.
  • alkyl carboxylic acids such as acetic acid, propionic acid, butyric acid, and isobutyric acid, for example, perfluoroacetic acid, perfluoropropionic acid, and perfluorobutane.
  • Examples of the ionic liquid-supported crown conjugate represented by the general formula [1] include those represented by the following general formulas [41] to [90].
  • ionic liquid-carrying crown compound represented by the general formula [1] include, for example, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dium chloride, 1- (Methyl-18-crown-6) -3-methyl-3H-imidazole-1-dim bromide, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimoxide , 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimhexafluorophosphate, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole 1-dimethyl tetrafluoroborate, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimethyl trifluoromethanesulfo Acid salt, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dium t
  • the ionic liquid-carrying crowned conjugate represented by the general formula [1] can be produced, for example, as follows.
  • C is explained as follows, taking as an example those represented by general formulas [52] and [77].
  • X represents a halogen atom, and A to A, T, R 38 , R 39 and X are the same as described above.
  • the halogen atom represented by X is, for example, fluorine.
  • a halogenating agent for example, triphenylphosphine and carbon tetrachloride, pel, POC1, PC1
  • a halogen salt of the ionic liquid-carrying crowny conjugate according to the present invention represented by the general formula [94].
  • the desired HX is reacted therewith to carry out an anion exchange reaction to obtain the ionic liquid-carrying crowned conjugate of the present invention having the desired counter-on (X).
  • hydroxy compound represented by the general formula [91] a commercially available hydroxy compound or a compound appropriately synthesized according to a conventional method may be used.
  • the halogen atom represented by X is, for example, fluorine. Elemental atoms, iodine atoms, bromine atoms, iodine atoms and the like.
  • a halogenating agent for example, triphenylphosphine and carbon tetrachloride, PC1, POC1, PC1, etc.
  • a halogenated product represented by the general formula [97] This is dissolved without solvent or in a suitable solvent (for example, aromatic hydrocarbons such as toluene, xylene, and benzene, and ethers such as tetrahydrofuran and dioxane, for example).
  • a suitable solvent for example, aromatic hydrocarbons such as toluene, xylene, and benzene, and ethers such as tetrahydrofuran and dioxane, for example.
  • 1.5 mol of the imidazole compound represented by the general formula [93] is stirred and reacted at 20 to 140 ° C. for 0.5 to 24 hours, and the ionic liquid carrier of the present invention represented by the general formula [98] is supported.
  • a halogen salt of the crowned ridge is obtained.
  • the desired HX is reacted therewith to effect an aion exchange reaction to obtain the ionic liquid-carrying crowned conjugate of the present invention
  • amino compound represented by the general formula [95] a commercially available amino compound or a compound appropriately synthesized according to a conventional method may be used.
  • the ionic liquid-supported crown conjugate represented by the general formula [1] of the present invention can be used as a catalyst for various synthetic reactions using a crown ether such as 18-crown-6 as a phase transfer catalyst.
  • a crown ether such as 18-crown-6
  • various syntheses such as an acylylation reaction, a halogen substitution reaction, an ether synthesis reaction, a dehydrogenation, a hydrogenation reaction, a benzene sulfide formation reaction, a nucleophilic substitution reaction such as an ester synthesis reaction, an olefin isomerization reaction, and a reduction reaction.
  • a reaction catalyst for various synthetic reactions using a crown ether such as 18-crown-6 as a phase transfer catalyst.
  • various syntheses such as an acylylation reaction, a halogen substitution reaction, an ether synthesis reaction, a dehydrogenation, a hydrogenation reaction, a benzene sulfide formation reaction, a nucleophil
  • reaction catalyst 1 equivalent of the IL catalyst is dissolved in a reaction solvent, and a lithium salt, a sodium salt, Addition of 1.5 equivalents of a nucleophilic reagent which also has metal salt power such as potassium salt and cesium salt and 0.2 equivalents of a reaction substrate can be allowed to react to produce a desired reaction product.
  • a nucleophilic reagent which also has metal salt power such as potassium salt and cesium salt
  • 0.2 equivalents of a reaction substrate can be allowed to react to produce a desired reaction product.
  • the obtained reaction product is, for example, getyl. Extract with organic solvents such as ether, ethyl acetate and toluene. It is obtained by doing.
  • the reaction solvent to be used is not particularly limited as long as it is usually used as a reaction solvent, but for the purpose of reuse, an ionic liquid is preferable.
  • the ionic liquid is not particularly limited as long as it is usually used as an ionic liquid. Examples thereof include 1-ethyl-3-methylimidazolym methanesulfonate ([emim] [CH SO]), 1 -Ethyl-3-
  • reaction solvent containing the IL catalyst into which the metal ion has been taken in after the reaction is completed is washed with water, whereby the metal ion taken into the IL catalyst can be easily removed. That is, since the activity of the IL catalyst is regenerated in this manner, the same reaction can be repeatedly performed by reusing the reaction solvent containing the IL catalyst.
  • This recycling step is shown below.
  • examples of the ionic liquid-supported crown compound according to the present invention include 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimethylhexafluorophosphate. . ⁇ .
  • the ionic liquid-carrying crown conjugate of the present invention has the same properties as the conventional crown terrier conjugates such as 18-crown-6, but also in the reaction system despite expensive catalysts. It has a catalytic action similar to crown ether, which has the problem that it is difficult to recover and reuse it, and efficiently recovers the ionic liquid-carrying crown compound from the reaction system to regenerate the catalytic activity And can be reused.
  • the IL catalyst according to the present application was used more than when the fluorination reaction was performed using 18-crown-6 as the catalyst (Comparative Example 3).
  • the other factor was that the yield was high even after several uses.
  • 18-crown-6 is used as a catalyst, the captured potassium ions cannot be removed, so that the yield decreases with each passing.
  • the ionic liquid-carrying crown compound of the present invention is used, the captured potassium ions can be easily removed by washing with water. Obtained in yield.

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  • Engineering & Computer Science (AREA)
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Abstract

Un nouveau composé couronne supportant un liquide ionique qui peut être utilisé en tant que catalyseur susceptible d’être recouvert et réutilisé. Il s’agit d’un composé couronne supportant un liquide ionique représenté par la formule générale [1] (où R1 est un groupe dérivé d’un composé couronne ; R2 est un groupe dérivé d’un liquide ionique ; et T1 est une chaîne alkylène en C1 à C8).
PCT/JP2005/009365 2004-05-24 2005-05-23 Composé couronne supportant un liquide ionique Ceased WO2005113547A1 (fr)

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Cited By (5)

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US9029421B2 (en) 2008-06-02 2015-05-12 Cipla Limited Process for the synthesis of arformoterol
CN108554448A (zh) * 2018-05-17 2018-09-21 扬州工业职业技术学院 一种用于催化甘油制备甘油磷酸酯的新型催化剂及其制备方法
CN110396082A (zh) * 2019-08-08 2019-11-01 山西大学 一种氮杂冠醚功能化离子液体的合成方法
US20200030716A1 (en) * 2018-07-25 2020-01-30 Massachusetts Institute Of Technology Task specific chelating ionic liquids for removal of metal ions from aqueous solution via liquid/liquid extraction and electrochemistry
CN115947880A (zh) * 2023-03-10 2023-04-11 南京聚隆科技股份有限公司 一种离子液体-钌/铑系膦化物催化氢化的sebs的制备方法

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JP2001067931A (ja) * 1999-08-25 2001-03-16 Fuji Photo Film Co Ltd 電解質組成物、光電変換素子および光電気化学電池
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JPH01168645A (ja) * 1987-12-24 1989-07-04 Nippon Soda Co Ltd ４−クロル−２−フルオロニトロベンゼンの製造法
JP2001067931A (ja) * 1999-08-25 2001-03-16 Fuji Photo Film Co Ltd 電解質組成物、光電変換素子および光電気化学電池
JP2002255941A (ja) * 2001-03-02 2002-09-11 Koei Chem Co Ltd イミダゾール化合物の製造法
JP2003154275A (ja) * 2001-11-22 2003-05-27 Univ Nihon 逆相間移動酸触媒

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9029421B2 (en) 2008-06-02 2015-05-12 Cipla Limited Process for the synthesis of arformoterol
CN108554448A (zh) * 2018-05-17 2018-09-21 扬州工业职业技术学院 一种用于催化甘油制备甘油磷酸酯的新型催化剂及其制备方法
CN108554448B (zh) * 2018-05-17 2021-05-18 扬州工业职业技术学院 一种用于催化甘油制备甘油磷酸酯的催化剂及其制备方法
US20200030716A1 (en) * 2018-07-25 2020-01-30 Massachusetts Institute Of Technology Task specific chelating ionic liquids for removal of metal ions from aqueous solution via liquid/liquid extraction and electrochemistry
CN110396082A (zh) * 2019-08-08 2019-11-01 山西大学 一种氮杂冠醚功能化离子液体的合成方法
CN115947880A (zh) * 2023-03-10 2023-04-11 南京聚隆科技股份有限公司 一种离子液体-钌/铑系膦化物催化氢化的sebs的制备方法

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