CN110002967B - Method for producing halide, method for producing potassium salt, and potassium salt - Google Patents
Method for producing halide, method for producing potassium salt, and potassium salt Download PDFInfo
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- CN110002967B CN110002967B CN201811451654.0A CN201811451654A CN110002967B CN 110002967 B CN110002967 B CN 110002967B CN 201811451654 A CN201811451654 A CN 201811451654A CN 110002967 B CN110002967 B CN 110002967B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The purpose of the present invention is to provide a method capable of efficiently producing a halide useful as a precursor of a compound that is generally applicable to, in particular, optical materials. The method for producing the halide comprises: a step of reacting a compound represented by the following general formula (1) with a halogenating agent to produce a halide represented by the following general formula (2),
in the general formula (1), R 1 Represents a linear or branched alkylene group, R 2 Represents an aromatic ring-containing group having a carbon atom constituting an aromatic ring at a bonding site with an oxygen atom represented by the formula, n represents 1 or 2, and in the case where n is 2, 2R' s 1 Each is the same or different;
in the general formula (2), R 1 、R 2 And n and R in the general formula (1) 1 、R 2 And n is the same, X represents a halogen atom, and in the case where n is 2, 2X's are each the same or different.
Description
This application is application No. 201580020214.8 (international application No. PCT/JP 2015/059142), filing date: year 2015, 3, month 25, priority date: a divisional application of chinese invention patent applications (title: a method for producing a halide, a method for producing a potassium salt, and a potassium salt) on 4/17/2014.
Technical Field
The present invention relates to a method for efficiently producing a halide which is useful as a precursor (raw material) of a compound which can be generally and preferably used particularly for an optical material. The present invention also relates to a potassium salt useful as a precursor of the above halide and a method for efficiently producing the potassium salt. This application claims priority based on japanese patent application No. 2014-085214 filed in japan on 4/17/2014 and the contents of which are incorporated herein by reference.
Background
Compounds having an aromatic ring in the molecule, particularly aromatic compounds having a reactive functional group such as an aromatic ring and a polymerizable functional group in the molecule, have been used for various purposes, and are particularly suitable for use as optical materials constituting lenses, optical fibers, optical waveguides, and the like (for example, see patent document 1). Therefore, the precursor of the aromatic compound, which can be converted into such an aromatic compound with high efficiency, is very useful.
As the precursor of the aromatic compound, a halide having a structure in which a reactive functional group in the aromatic compound is replaced with a halogen (halogen atom) is particularly useful. This is because, when such a halide is used as a precursor of the aromatic compound, since the halogen (halide ion) is an excellent leaving group, a reactive functional group can be introduced with high efficiency, and the aromatic compound can be produced with high productivity.
Documents of the prior art
Patent document
Patent document 1: japanese patent application laid-open No. 2010-229263
Disclosure of Invention
Problems to be solved by the invention
The halide can be produced using a phenolic compound such as phenol or naphthol having a hydroxyl group bonded to an aromatic ring as a precursor (starting material). More specifically, for example, a halide (chlorine compound) useful as a precursor of the above aromatic compound can be produced by coupling a phenolic compound and 2-methanesulfonyl chloroethane.
However, the method for producing a halide using a phenolic compound as a precursor as described above has a low yield of the objective halide, and is not considered to be a practical method. In addition, in the case where a halide is produced by synthesizing a phenolic compound and then using the phenolic compound as a precursor, it is necessary to perform a dehydration operation for removing water from an organic layer containing the phenolic compound and a separation and extraction operation for separating and extracting the phenolic compound after the synthesis of the phenolic compound, thereby highly removing water from the phenolic compound, which is troublesome. The reason why such moisture removal is required is that: since the step of synthesizing the phenolic compound includes an operation of quenching the product with water, a large amount of moisture remains in the obtained phenolic compound, and when such moisture is present, the above-described reaction for synthesizing a halide from the phenolic compound cannot proceed thereafter. In this way, the method for producing a halide using a phenolic compound as a precursor has a problem that it is difficult to further improve the production efficiency of the halide.
Accordingly, an object of the present invention is to provide a method capable of efficiently producing a halide useful as a precursor of a compound that can be generally and preferably used for an optical material.
Another object of the present invention is to provide a potassium salt useful as a precursor of the above halide and a method for efficiently producing the potassium salt.
Means for solving the problems
The present inventors have intensively studied to solve the above problems and as a result, have found that a halide corresponding to the above raw material can be efficiently produced by a method comprising a step of using a specific raw material (potassium salt) as a precursor and reacting the precursor with a halogenating agent as essential steps, and have completed the present invention.
That is, the present invention provides a method for producing a halide, comprising: a step of reacting a compound represented by the following general formula (1) with a halogenating agent to produce a halide represented by the following general formula (2),
[ chemical formula 1]
[ in the general formula (1), R 1 Represents a linear or branched alkylene group. R 2 Represents an aromatic ring-containing group having a carbon atom constituting an aromatic ring at a bonding site with an oxygen atom represented by the formula. n represents 1 or 2. In the case where n is 2, 2R 1 Each of which may be the same or different.]
[ chemical formula 2]
[ in the general formula (2), R 1 、R 2 And n and R in the general formula (1) 1 、R 2 And n are the same. X represents a halogen atom. In the case where n is 2, each of 2 xs may be the same or different.]。
Further, there is provided the above method for producing a halide, further comprising, before the above step, a step of reacting a compound represented by the following general formula (3), a compound represented by the following general formula (4), and potassium carbonate to produce a compound represented by the general formula (1),
[ chemical formula 3]
In general formula (3), R 2 And n and R in the general formula (1) 2 And n are the same.]
[ chemical formula 4]
[ in the general formula (4), R 1 And R in the general formula (1) 1 The same is true.]。
Further, the present invention provides a method for producing a potassium salt, comprising: a step of reacting a compound represented by the following general formula (3), a compound represented by the following general formula (4), and potassium carbonate to produce a potassium salt represented by the following general formula (1),
[ chemical formula 5]
In general formula (3), R 2 Represents an aromatic ring-containing group having a carbon atom constituting an aromatic ring at a bonding site to an oxygen atom represented by the formula. n represents 1 or 2.]
[ chemical formula 6]
In general formula (4), R 1 Represents a linear or branched alkylene group.]
[ chemical formula 7]
In general formula (1), R 1 And R in the general formula (4) 1 The same is true. R is 2 And n and R in the general formula (3) 2 And n are the same. In the case where n is 2,2 Rs 1 Each of which may be the same or different.]。
Further, the present invention provides a potassium salt represented by the following general formula (1),
[ chemical formula 8]
In general formula (1), R 1 Represents a linear or branched alkylene group. R 2 Represents an aromatic ring-containing group having a carbon atom constituting an aromatic ring at a bonding site with an oxygen atom represented by the formula. n represents 1 or 2. In the case where n is 2, 2R 1 Each of which may be the same or different.]。
That is, the present invention relates to the following aspects.
A method for producing a [1-1] halide, comprising: a step of reacting a compound represented by formula (1) described later with a halogenating agent to produce a halide represented by formula (2) described later.
[1-2] the method for producing a halide according to [1-1], further comprising a step of reacting a compound represented by the formula (3) described later, a compound represented by the formula (4) described later, and potassium carbonate to produce a compound represented by the formula (1) described later, prior to the step.
[1-3] the method for producing a halide according to [1-1] or [1-2], wherein the compound represented by the formula (1) is a compound represented by the formula (1-1) or the formula (1-2) described later.
[1-4] the method for producing a halide according to any one of [1-1] to [1-3], wherein the compound represented by formula (1) is a compound represented by formula (1-3) to formula (1-20) described below, or a compound represented by formula (1-3) to formula (1-20) described below in which 1 or more hydrogen atoms in the aromatic ring are substituted by a substituent described below.
[1-5] the method for producing a halide according to any one of [1-1] to [1-4], wherein the halogenating agent is at least one selected from the group consisting of: chlorinating agent, brominating agent, iodinating agent, and 1, 3-dialkyl-2-halogenoimidazolinium halides.
[1-6] the method for producing a halide according to any one of [1-1] to [1-5], wherein the compound represented by the formula (1) is reacted with a halogenating agent in an amount of 1 to 10 times by mole the amount of the halogenating agent relative to a potassium alkoxide moiety (-OK) contained in the compound represented by the formula (1).
[1-7] the method for producing a halide according to any one of [1-1] to [1-6], wherein the solvent used in the reaction of the compound represented by the formula (1) with the halogenating agent is at least one selected from the group consisting of: esters, ketones, ethers, glycol monoether monoacylates, and hydrocarbons.
[1-8] the method for producing a halide according to any one of [1-1] to [1-7], wherein the halide represented by the formula (2) is a formula (2-1) or a formula (2-2) described later.
[1-9] the method for producing a halide according to any one of [1-1] to [1-8], wherein the halide represented by formula (2) is a compound represented by formula (2-3) to formula (2-20) described below, or a compound represented by formula (2-3) to formula (2-20) described below, in which 1 or more hydrogen atoms in the aromatic ring are substituted with a substituent described below.
[1-10]According to [1-2]]～[1-9]The method for producing a potassium salt according to any one of the above methods, wherein the compound represented by the formula (3) is a compound obtained by replacing [ -O-R ] in the compound represented by the formula (1) with a hydroxyl group 1 -OK]A compound (phenolic compound) having the structure shown.
[1-11] the method for producing a potassium salt according to any one of [1-2] to [1-10], wherein the compound represented by formula (4) is ethylene carbonate, propylene carbonate, trimethylene carbonate, or 1, 2-butylene carbonate.
[1-12] the method for producing a potassium salt according to any one of [1-2] to [1-11], wherein the solvent used in the reaction of the compound represented by formula (3), the compound represented by formula (4), and potassium carbonate is at least one selected from the group consisting of: esters, ketones, ethers, glycol monoether monoacylates, and hydrocarbons.
[2-1] A method for producing a potassium salt, which comprises: a step of reacting a compound represented by formula (3) described later, a compound represented by formula (4) described later, and potassium carbonate to produce a potassium salt represented by formula (1) described later.
[2-2] the method for producing the potassium salt according to [2-1], wherein the compound represented by the formula (1) is a compound represented by the formula (1-1) or the formula (1-2) described later.
[2-3] the method for producing a potassium salt according to [2-1] or [2-2], wherein the compound represented by formula (1) is a compound represented by formulae (1-3) to (1-20) described later, or a compound represented by formulae (1-3) to (1-20) described later in which 1 or more hydrogen atoms in the aromatic ring are substituted by a substituent described later.
[2-4]According to [2-1]]～[2-3]The method for producing a potassium salt of any one of the above processes, wherein the compound represented by the formula (3) is a compound represented by the formula (1) below, in which a hydroxyl group is substituted for [ -O-R ] 1 -OK]A compound (phenolic compound) having the structure shown.
[2-5] the method for producing a potassium salt according to any one of [2-1] to [2-4], wherein the compound represented by formula (4) is ethylene carbonate, propylene carbonate, trimethylene carbonate, or 1, 2-butylene carbonate.
[2-6] the method for producing a potassium salt according to any one of [2-1] to [2-5], wherein the solvent used in the reaction of the compound represented by formula (3), the compound represented by formula (4), and potassium carbonate is at least one selected from the group consisting of: esters, ketones, ethers, glycol monoether monoacylates, and hydrocarbons.
[3-1] A potassium salt represented by the following formula (1).
[3-2] the potassium salt according to [3-1], wherein the compound represented by the formula (1) is a compound represented by the formula (1-1) or the formula (1-2) described later.
[3-3] the potassium salt according to [3-1] or [3-2], wherein the compound represented by the formula (1) is a compound represented by the formulae (1-3) to (1-20) described later, or a compound represented by the formulae (1-3) to (1-20) described later in which 1 or more hydrogen atoms in the aromatic ring are substituted by the substituents described later.
ADVANTAGEOUS EFFECTS OF INVENTION
The method for producing a halide of the present invention has the above-described configuration, and therefore, according to this method, a halide can be produced efficiently. Specifically, according to the method for producing a halide of the present invention, a halide can be synthesized with a very high yield, and unlike the case where a phenolic compound is used as a precursor, a dehydration operation or a separation and extraction operation for removing water from the phenolic compound is not required, and these operations can be omitted, so that the production efficiency of a halide can be remarkably improved. The potassium salt of the present invention is very useful as a precursor of the above halide. Further, the potassium salt of the present invention can be efficiently produced by the method for producing a potassium salt of the present invention.
Detailed Description
< method for producing halide >
The method for producing a halide of the present invention is a method for producing a halide represented by the general formula (2), and is characterized by comprising a step of reacting a compound represented by the general formula (1) with a halogenating agent to produce the halide (also referred to as a "halogenation step") as an essential step. The present inventors have surprisingly found that a halide represented by the general formula (2) can be produced with very high efficiency by using the method for producing a halide of the present invention, that is, by using a compound represented by the general formula (1) (potassium salt) as a precursor (starting material) in the halogenation step. The method for producing a halide according to the present invention may include any step other than the halogenation step.
[ chemical formula 9]
[ chemical formula 10]
[ halogenation procedure ]
1. A compound represented by the general formula (1)
The compound represented by the general formula (1) used in the halogenation step in the method for producing a halide according to the present invention is a potassium salt having a structure (-OK) in which a hydrogen atom of a hydroxyl group is replaced with a potassium ion. In the general formula (1), R 1 Represents a linear or branched alkylene group. As R 1 Examples thereof include: methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene (propane-1, 3-diyl), and the like. Wherein, as R 1 The alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms. When n is 2,2 Rs 1 Each of which may be the same or different.
In the general formula (1), R 2 Represents an aromatic ring-containing group (monovalent or divalent aromatic ring-containing group; also referred to as "aromatic ring-containing group") having a carbon atom constituting an aromatic ring at a bonding site with an oxygen atom shown in the formula. That is, with R in the general formula (1) 2 Bound oxygen atom and R 2 The carbon atoms constituting the aromatic ring in the (aromatic-ring-containing group) are bonded. The aromatic ring contained in the aromatic ring-containing group may be a monocyclic aromatic ring (e.g., benzene ring) or a polycyclic aromatic ring (e.g., fused polycyclic rings such as pentalene ring, indene ring, naphthalene ring, azulene ring, biphenylene ring (124991250112455911251252431), phenanthrene ring, anthracene ring, fluoranthene ring, etc.. The aromatic ring contained in the aromatic-ring-containing group may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Among them, an aromatic hydrocarbon ring is preferable.
The above aromatic ring-containing group (R) 2 ) The number of aromatic rings contained (in the case of a condensed polycyclic ring composed of m aromatic rings, the number is counted as m aromatic rings) is not particularly limited, but is preferably 1 to 10, more preferably 2 to 8, and further preferably 3 to 6.
When the aromatic ring-containing group is a group containing 2 or more aromatic rings, such a plurality of aromatic rings may be condensed together to form a polycyclic (condensed polycyclic) ring, or may be, for example, a monocyclic aromatic ring or 2 or more of the polycyclic aromatic rings may be bonded together via 1 or more single bonds and/or linking groups (either or both of single bonds and linking groups). Examples of the linking group include: a divalent or higher hydrocarbon group; groups in which 1 or more of these hydrocarbon groups are linked to 1 or more of divalent hetero atom-containing groups; the divalent hetero atom-containing group mentioned above, and the like. Examples of the divalent or higher hydrocarbon group include: a divalent straight, branched, or cyclic aliphatic hydrocarbon group; a trivalent linear, branched, or cyclic aliphatic hydrocarbon group; tetravalent linear, branched, or cyclic aliphatic hydrocarbon groups, and the like. Examples of the divalent linear, branched, or cyclic aliphatic hydrocarbon group include: alkylene [ e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, etc. ], alkenylene [ e.g., alkenylene corresponding to the above alkylene, e.g., vinylene, allylene, etc. ], cycloalkylene [ e.g., cyclopentylene, cyclohexylene, methylcyclohexylene, etc. ], a divalent group in which 2 or more of these groups are bonded [ e.g., methylene-cyclohexylene, etc. ], and the like. Examples of the trivalent linear, branched, or cyclic aliphatic hydrocarbon group include: alkane-triyl [ e.g., methane-triyl, ethane-triyl, propane-triyl, 1-trimethylpropane-triyl, etc. ], cycloalkane-triyl [ e.g., cyclohexane-triyl, methylcyclohexane-triyl, dimethylcyclohexane-triyl, etc. ], and the like. Examples of the tetravalent linear, branched, or cyclic aliphatic hydrocarbon group include: alkane-tetrayl [ e.g., methane-tetrayl, ethane-tetrayl, butane-tetrayl, 2-dimethylpropane-tetrayl, etc. ], cycloalkane-tetrayl [ e.g., cyclohexane-tetrayl, methylcyclohexane-tetrayl, dimethylcyclohexane-tetrayl, etc. ], and the like. Examples of the divalent heteroatom-containing group include: -CO-, -O-CO-O-, -COO-, -O-, -CONH-, -S-, etc.
The aromatic ring-containing group may be a group having a substituent. The substituent may be a substituent on the aromatic ring or a substituent of another moiety (for example, the above-mentioned linking group). Examples of the substituent include: monovalent hydrocarbon groups (for example, straight-chain or branched aliphatic hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, cyclic aliphatic hydrocarbon groups such as cycloalkyl groups, aromatic hydrocarbon groups such as phenyl groups, hydrocarbon groups in which 2 or more of these groups are bonded (for example, benzyl groups), etc.), halogen atoms, oxo groups, hydroxy groups, acyl groups, mercapto groups, acryloyloxy groups, methacryloyloxy groups, substituted oxy groups (for example, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxy groups, substituted oxycarbonyl groups (alkoxycarbonyl groups, aryloxycarbonyl groups, aralkyloxycarbonyl groups, etc.), substituted or unsubstituted carbamoyl groups, cyano groups, nitro groups, substituted or unsubstituted amino groups, sulfo groups, heterocyclic groups, and the like. The hydroxyl group and the carboxyl group may be protected with a protecting group (for example, an acyl group, an alkoxycarbonyl group, an organosilyl group, an alkoxyalkyl group, an oxacycloalkyl group and the like) which is conventionally used in the field of organic synthesis. The number of the substituents of the aromatic ring-containing group is not particularly limited, and is preferably, for example, 0 to 5. In the case of having a plurality of substituents, each of them may be the same or different.
Specifically, examples of the aromatic ring-containing group include: benzene, naphthalene, pentalene, indene, azulene, biphenylene, phenanthrene, anthracene, fluoranthene, biphenyl (e.g., 1 '-biphenyl), binaphthyl (e.g., 1' -binaphthyl), diphenylcyclohexane (e.g., 1-diphenylcyclohexane), tetraphenylmethane, dinaphthylcyclohexane (e.g., 1-dinaphthylcyclohexane), naphthylphenylcyclohexane (e.g., 1-naphthyl-1-phenylcyclohexane), dinaphthyldiphenylmethane, tetranaphthylmethane, triphenylmethane, trinaphthylmethane, 1-diphenylindene, 1-dinaphthyline, 1-diphenylphenalene, 1-dinaphthalene and other aromatic compounds and their derivatives (for example, a monovalent or divalent group corresponding to 1 or more of the hydrogen atoms bonded to carbon atoms in the aromatic compound (particularly, a derivative in which 1 or more of the hydrogen atoms bonded to carbon atoms constituting an aromatic ring are substituted with the substituent) is a monovalent or divalent group (that is, a monovalent or divalent group formed by removing 1 or 2 of the hydrogen atoms bonded to carbon atoms constituting an aromatic ring in the aromatic compound in terms of the structural formula).
In the general formula (1), n represents 1 or 2. That is, the compound represented by the general formula (1) specifically means a compound represented by the general formula (1-1) or the general formula (1-2).
[ chemical formula 11]
R 2 -O-R 1 -OK (1-1)
[ chemical formula 12]
KO-R 1 -O-R 2 -O-R 1 -OK (1-2)
[ general formulae (1-1) and (1-2) wherein R 1 And R 2 And R in the general formula (1) 1 And R 2 The same is true.]
Specific examples of the compound represented by the general formula (1) include: and compounds represented by the following formulae (1-3) to (1-20), compounds represented by the following formulae (1-3) to (1-20) in which 1 or more hydrogen atoms in the aromatic ring are substituted with the above substituent, and the like.
[ chemical formula 13]
[ chemical formula 14]
[ in the above formula, R 1 And n and R in the general formula (1) 1 And n are the same.]
The compound represented by the general formula (1) can be produced by a known or customary method, and the production method is not particularly limited. For example, the compound can be produced by reacting a compound represented by the following general formula (i) with a strong base such as potassium hydroxide or potassium hydride in an aprotic solvent.
[ chemical formula 15]
[ in the general formula (i), R 1 、R 2 And n and R in the general formula (1) 1 、R 2 And n are the same.]
Among these, as the method for producing the compound represented by the general formula (1), a method in which the compound represented by the general formula (3), the compound represented by the general formula (4) (cyclic carbonate) and potassium carbonate are reacted to produce the compound represented by the general formula (1) (potassium salt) is particularly preferable in that the compound represented by the general formula (1) can be efficiently produced in one stage.
[ chemical formula 16]
[ chemical formula 17]
In the general formula (3), R 2 And R in the general formula (1) 2 The same applies to an aromatic ring-containing group having a carbon atom constituting an aromatic ring at a bonding site with an oxygen atom shown in the formula. In addition, n is the same as n in the general formula (1) and represents 1 or 2. Specific examples of the compound represented by the general formula (3) include: the [ -O-R group in the compound represented by the general formula (1) 1 -OK]Compounds (phenolic compounds) in which the structure shown is replaced with a hydroxyl group, and the like.
In the general formula (4), R 1 And R in the general formula (1) 1 The same may be true for the straight-chain or branched alkylene group, and the alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms. The compound represented by the general formula (4) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Examples of the compound represented by the general formula (4) include: ethylene carbonate, propylene carbonate, trimethylene carbonate, 1, 2-butylene carbonate, and the like.
The reaction of the compound represented by the general formula (3), the compound represented by the general formula (4), and potassium carbonate may be carried out in the presence of a solvent or in the absence of a solvent. Among them, the reaction is preferably carried out in the presence of a solvent (in a solvent) from the viewpoint of allowing the reaction to proceed uniformly and producing the compound represented by the general formula (1) in a higher yield. The solvent may be a known or conventional solvent, and may be appropriately selected depending on the kind of the compound represented by the general formula (3) or the compound represented by the general formula (4), and the like, and is not particularly limited, and examples thereof include: esters such as ethyl acetate, butyl acetate, isobutyl acetate, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; glycol monoether monoacylates such as diethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate; and hydrocarbons such as xylene and toluene. Among them, ethers are preferred from the viewpoint of the solubility of the reactants. The solvent may be used alone in 1 kind, or 2 or more kinds may be used in combination (in the form of a mixed solvent).
In the reaction of the compound represented by the general formula (3), the compound represented by the general formula (4) and potassium carbonate, other components may be used in combination in addition to these reactants and the solvent.
The method for reacting the compound represented by the general formula (3), the compound represented by the general formula (4), and potassium carbonate is not particularly limited. Examples thereof include: a method in which a compound represented by the general formula (3), a compound represented by the general formula (4), and potassium carbonate are fed to a reactor at a time to react; a method of charging a part of the compounds into a reactor, and adding the rest of the compounds to the reactor stepwise or continuously to carry out the reaction, etc. In particular, a method of feeding the compound represented by the general formula (3), the compound represented by the general formula (4), and potassium carbonate to a reactor at a time to carry out a reaction is preferable from the viewpoint of ease of operation.
The conditions for carrying out the reaction of the compound represented by the general formula (3), the compound represented by the general formula (4), and potassium carbonate may be appropriately set depending on the kind of the compound represented by the general formula (3), the compound represented by the general formula (4), and the like, and are not particularly limited, and for example, the reaction temperature is preferably 80 to 200 ℃ (more preferably 110 to 180 ℃), and the reaction time is preferably 0.5 to 10 hours (more preferably 1 to 7 hours). In the above reaction, the reaction temperature may be controlled to be constant at all times, or may be controlled to vary stepwise or continuously. The gas atmosphere in which the above reaction is carried out is not particularly limited, and the reaction may be carried out in any gas atmosphere such as the presence of oxygen (for example, in air), an inert gas (for example, in nitrogen or argon), a reducing gas (for example, in hydrogen), and the like. Further, the pressure at which the reaction is carried out is not particularly limited, and may be any of normal pressure, increased pressure and reduced pressure.
The above reaction can be carried out in any reaction form of batch, semi-batch, continuous, etc.
The compound represented by the general formula (1) is produced by the above reaction. The compound represented by the general formula (1) to be produced may be used in the form of being present in the reaction solution obtained by the above reaction (for example, used in the halogenation step), or may be used after being purified (for example, used in the halogenation step). The purification may be carried out by a known or customary method (for example, recrystallization, distillation, adsorption, ion exchange, crystallization, extraction, etc.).
As described above, since the compound represented by the general formula (1) can be produced by a method without using water, unlike the case of using a phenolic compound as a precursor of the halide represented by the general formula (2), the production method of the halide of the present invention does not necessarily require a dehydration operation or a separation and extraction operation of the compound represented by the general formula (1) as a precursor.
2. Halogenating agents
The halogenating agent used in the halogenation step in the process for producing a halide of the present invention functions to convert-OK in the compound represented by the general formula (1) to-X and produce a halide represented by the general formula (2). The halogenating agent may be any known or customary halogenating agent capable of effecting the above-mentioned transformation, and is not particularly limited, and examples thereof include: chlorinating agents such as chlorine molecule, N-chlorosuccinimide, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, sulfuryl chloride, hypochlorite, cyanuric chloride, and 2-chloro-1, 3-dimethylbenzimidazolium chloride; brominating agents such as bromine molecule, N-bromosuccinimide, hypobromite, bis (2, 4, 6-trimethylpyridine) bromonium hexafluorophosphate, etc.; iodinating agents such as molecular iodine and bis (2, 4, 6-trimethylpyridine) iodonium hexafluorophosphate; 1, 3-dialkyl-2-halogenoimidazolinium halides, and the like. The halogenating agent may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
In the halogenation step, 1 kind of halogenating agent may be used alone, or 2 or more kinds may be used in combination. The halogenating agent may be synthesized by a known or customary method, or a commercially available product may be used.
3. Reaction conditions and the like
The conditions for reacting the compound represented by the general formula (1) with the halogenating agent in the halogenation step may be appropriately set according to known or conventional conditions, depending on the type of the halogenating agent used, and the like. The amount of the halogenating agent to be used is not particularly limited, but is usually 1 to 10mol times, more preferably 1.5 to 6mol times, relative to the potassium alkoxide moiety (-OK) contained in the compound represented by the general formula (1).
The reaction of the compound represented by the general formula (1) with the halogenating agent may be carried out in the presence or absence of a solvent. Among them, the above reaction is preferably carried out in the presence of a solvent (in a solvent) from the viewpoint of allowing the reaction to proceed uniformly and producing the halide represented by the general formula (2) in a higher yield. The solvent may be a known or conventional one, and may be appropriately selected depending on the kind of the compound represented by the general formula (1) and the halogenating agent, and the solvent is not particularly limited, and examples thereof include: esters such as ethyl acetate, butyl acetate, isobutyl acetate, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; glycol monoether acetates such as diethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate; hydrocarbons such as xylene and toluene; mixtures thereof and the like. Among them, ethers are preferred from the viewpoint of the solubility of the reactants. The solvent may be used alone in 1 kind, or 2 or more kinds may be used in combination (in the form of a mixed solvent).
In the reaction of the compound represented by the general formula (1) and the halogenating agent, other components (for example, an organic base such as pyridine used for capturing the generated acid) may be used in combination with the above reactants and solvent.
The method for reacting the compound represented by the formula (1) with the halogenating agent is not particularly limited. Examples thereof include: a method of feeding a halogenating agent to a reactor and adding a compound represented by the general formula (1) thereto to conduct a reaction; a method of feeding a compound represented by the general formula (1) to a reactor and adding a halogenating agent thereto to carry out a reaction; a method in which the compound represented by the general formula (1) and a halogenating agent are charged into a reactor at a time to carry out a reaction, and the like. Among them, a method of charging a halogenating agent into a reactor and adding a compound represented by the general formula (1) thereto to carry out a reaction is preferable in that the compound represented by the general formula (1) can be produced with a high conversion and a high selectivity.
The conditions for carrying out the reaction of the compound represented by the general formula (1) and the halogenating agent may be appropriately set depending on the kind of the compound represented by the general formula (1) and the halogenating agent, and are not particularly limited, and for example, the reaction temperature is preferably 40 to 150 ℃ (more preferably 50 to 100 ℃), and the reaction time is preferably 1 to 15 hours (more preferably 2 to 10 hours). In the above reaction, the reaction temperature may be controlled to be constant at all times, or may be controlled to vary stepwise or continuously. The gas atmosphere in which the above reaction is carried out is not particularly limited, and the reaction may be carried out in any gas atmosphere such as the presence of oxygen (for example, in air), an inert gas (for example, in nitrogen or argon), a reducing gas (for example, in hydrogen), and the like. Further, the pressure at which the reaction is carried out is not particularly limited, and may be any of normal pressure, increased pressure and reduced pressure.
The above reaction can be carried out in any reaction form of batch, semi-batch, continuous, etc.
The above reaction produces a halide represented by the general formula (2). The halide represented by the general formula (2) may be used in the form of being present in the reaction solution obtained by the above reaction (for example, a step for replacing X in the general formula (2) with a reactive functional group (for example, a polymerizable functional group such as vinyloxy group, acryloyloxy group, methacryloyloxy group, or the like), or may be used after purification (for example, a step for replacing X in the general formula (2) with a reactive functional group, or the like). The purification may be carried out by a known or customary method (for example, recrystallization, distillation, adsorption, ion exchange, crystallization, extraction, etc.).
4. A halide represented by the general formula (2)
The halide represented by the general formula (2) is a compound produced by the reaction of the compound represented by the general formula (1) with the halogenating agent in the halogenation step. In the general formula (2), R 1 、R 2 And n and R in the general formula (1) 1 、R 2 And n are the same. In the general formula (2), X represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom). In the case where n is 2,2 xs are the same or different. The halide represented by the general formula (2) is represented by the general formula (2-1) when a compound represented by the general formula (1) is used as the compound represented by the general formula (1), and the halide represented by the general formula (2) is represented by the general formula (2-2) when a compound represented by the general formula (1-2) is used as the compound represented by the general formula (1).
[ chemical formula 18]
R 2 -O-R 1 -X (2-1)
[ chemical formula 19]
X-R 1 -O-R 2 -O-R 1 -X (2-2)
[ general formulae (2-1) and (2-2) wherein R 1 、R 2 And X and R in the general formula (2) 1 、R 2 And X are the same.]
Specific examples of the halide represented by the general formula (2) include: and compounds represented by the following formulae (2-3) to (2-20), in which 1 or more hydrogen atoms in the aromatic ring are substituted with the above substituent, and the like.
[ chemical formula 20]
[ chemical formula 21]
[ in the above formula, R 1 N and X with R in the general formula (2) 1 N and X are the same.]
[ other Processes ]
The method for producing a halide according to the present invention may include a step (also referred to as "another step") other than the halogenation step. Examples of the other steps include: a step of purifying the halide represented by the general formula (2) produced after the halogenation step; a step of forming the compound represented by the general formula (1) before the halogenation step. The respective steps in the method for producing a halide of the present invention may be performed continuously or discontinuously.
The step of producing the compound represented by the general formula (1) as another step may be a step using a known or conventional synthesis method, and is not particularly limited, but is preferably a step of producing the compound represented by the general formula (1) by reacting the compound represented by the general formula (3), the compound represented by the general formula (4), and potassium carbonate, from the viewpoint that the compound represented by the general formula (1) can be efficiently produced in one stage. The conditions and the like of this step are as described above.
The method for producing a halide according to the present invention can synthesize a halide represented by the general formula (2) in a very high yield, and unlike the method using a phenolic compound as a precursor, it is not always necessary to perform a dehydration operation or a separation and extraction operation for removing water, and these operations can be omitted, so that the efficiency of producing a halide represented by the general formula (2) can be remarkably improved. The halide represented by the general formula (2) is a compound having a halogen atom capable of easily introducing a functional group in a molecule, and therefore can be preferably used as a precursor of a functional material (a functional compound, a functional resin, or the like) used in various applications in the fields of medicine, agricultural chemicals, optics, electric/electronic fields, and the like. In particular, since the compound has an aromatic ring which exhibits characteristic optical characteristics, the compound is useful as a precursor of a compound which is generally applicable to optical materials such as lenses, optical fibers, and optical waveguides. The compound (potassium salt) represented by the general formula (1) is highly useful as a precursor for obtaining a halide represented by the general formula (2) at a high efficiency (with a high conversion and a high selectivity) in the halogenation step.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
[ production of halide ]
A100 mL reactor was charged with thionyl chloride (19.2 g, 0.161 mol) and tetrahydrofuran (11.2 mL), and a solution of the potassium salt of 2- (p-methoxyphenoxy) ethanol (0.0403 mol), pyridine (7.97 g, 0.101 mol), dipropylene glycol dimethyl ether (33.4 mL) and tetrahydrofuran (56.2 mL) was added dropwise thereto at 60 ℃ over a period of 2 hours. Further, aging was carried out at the same temperature for 3 hours. As a result of HPLC analysis of the aged reaction solution, it was confirmed that the target compound (halide) represented by the following formula was obtained at a conversion of 100% and a selectivity of 98%.
1 H-NMR(CDCl 3 ):δ3.77(s,3H)、3.79(t,2H,J＝4.8Hz)、4.19(t,2H,J＝4.8Hz)、6.83-6.88(m,4H)
[ chemical formula 22]
Example 2
[ production of halide ]
A100 mL reactor was charged with thionyl chloride (16.5 g, 0.139 mol) and tetrahydrofuran (11.2 mL) and a solution of the potassium salt of 2- (2-naphthoxy) ethanol (0.0347 mol), pyridine (6.86 g, 0.0867 mol), dipropylene glycol dimethyl ether (16.7 mL) and tetrahydrofuran (56.2 mL) was added dropwise thereto at 60 ℃ over 2 hours. Further, aging was carried out at the same temperature for 3 hours. As a result of HPLC analysis of the aged reaction solution, it was confirmed that the target compound (halide) represented by the following formula was obtained at a conversion rate of 100% and a selectivity of 98%.
1 H-NMR(CDCl 3 ):δ3.90(t,2H,J＝4.5Hz)、4.37(t,2H,J＝4.5Hz)、7.14-7.80(m,7H)
[ chemical formula 23]
Example 3
[ production of halide ]
A100 mL reactor was charged with thionyl chloride (8.31 g, 0.0699 mol) and tetrahydrofuran (11.2 mL) and a solution of the dipotassium salt of 2,2 '-dihydroxyethoxy-1, 1' -binaphthyl (0.0175 mol), pyridine (3.45 g, 0.0437 mol), dipropylene glycol dimethyl ether (27.9 mL) and tetrahydrofuran (56.2 mL) was added dropwise thereto at 60 ℃ over 2 hours. Further, aging was carried out at the same temperature for 3 hours. As a result of HPLC analysis of the aged reaction solution, it was confirmed that the target compound (halide) represented by the following formula was obtained at a conversion of 100% and a selectivity of 98%.
1 H-NMR(CDCl 3 ):δ4.16(t,4H,J＝5.3Hz)、4.21(t,4H,J＝5.3Hz)、7.16(d,2H,J＝6.8Hz)、7.25(t,2H,J＝6.8Hz)、7.38(t,2H,J＝6.8Hz)、7.45(d,2H,J＝6.8Hz)、7.90(d,2H,J＝6.8Hz)、7.99(d,2H,J＝6.8Hz)
[ chemical formula 24]
Example 4
[ production of halide ]
A100 mL reactor was charged with thionyl chloride (8.86 g, 0.0754 mol) and tetrahydrofuran (11.2 mL) and a solution of the dipotassium salt of 1, 1-bis [4- (hydroxyethoxy) phenyl ] cyclohexane (0.0186 mol), pyridine (3.68 g, 0.0466 mol), dipropylene glycol dimethyl ether (27.9 mL) and tetrahydrofuran (56.2 mL) was added dropwise thereto at 60 ℃ over 2 hours. Further, aging was carried out at the same temperature for 3 hours. As a result of HPLC analysis of the aged reaction solution, it was confirmed that the target compound (halide) represented by the following formula was obtained at a conversion of 99% and a selectivity of 83%.
1 H-NMR(CDCl 3 ):δ1.54(m,4H)、1.95(m,2H)、2.21(m,4H)、3.78(t,4H,J＝5.8Hz)、4.19(t,4H,J＝5.8Hz)、6.81(d,4H,J＝8.8Hz)、7.17(d,4H,J＝8.8Hz)
[ chemical formula 25]
Example 5
[ production of halide ]
A100 mL reactor was charged with thionyl chloride (6.75 g, 0.0567 mol) and tetrahydrofuran (11.2 mL) and a solution of the dipotassium salt of bis [4- (hydroxyethoxy) phenyl ] diphenylmethane (0.0142 mol), pyridine (2.81 g, 0.0355 mol), dipropylene glycol dimethyl ether (27.9 mL) and tetrahydrofuran (56.2 mL) was added dropwise thereto at 60 ℃ over 2 hours. Further, aging was carried out at the same temperature for 3 hours. As a result of HPLC analysis of the aged reaction solution, it was confirmed that the target compound (halide) represented by the following formula was obtained at a conversion of 98% and a selectivity of 79%.
1 H-NMR(CDCl 3 ):δ3.80(t,4H,J＝6.0Hz)、4.21(t,4H,J＝6.0Hz)、6.78-7.25(m,18H)
[ chemical formula 26]
Example 6
[ production of Potassium salt ]
A100 mL reactor was charged with 2-naphthol (5.00 g, 0.0347 mol), ethylene carbonate (6.72 g, 0.0763 mol), potassium carbonate (10.1 g, 0.0728 mol) and dipropylene glycol dimethyl ether (16.7 mL) and aged at 130 ℃ for 5 hours. By HPLC, 1 As a result of H-NMR analysis of the aged reaction solution, it was confirmed that the target compound represented by the following formula was produced with a 2-naphthol conversion of 92% and a selectivity of 100%.
1 H-NMR(CDCl 3 ):δ4.06(t,2H,J＝4.8Hz)、4.24(t,2H,J＝4.8Hz)、7.15-7.80(m,7H)
[ chemical formula 27]
Example 7
[ production of Potassium salt ]
Into a 100mL reactor were charged p-methoxyphenol (5.00 g, 0.0403 mol), ethylene carbonate (7.81 g, 0.0886 mol), potassium carbonate (11.7 g, 0.0846 mol), and dipropylene glycol dimethyl ether (33.4 mL), and the mixture was aged at 130 ℃ for 5 hours. By HPLC, 1 As a result of H-NMR analysis of the aged reaction solution, it was confirmed that the target compound represented by the following formula (potassium salt of 2- (p-methoxyphenoxy) ethanol) was produced with a conversion of p-methoxyphenol of 89% and a selectivity of 100%.
1 H-NMR(CDCl 3 ):δ3.78(s,3H)、3.94(t,2H,J＝4.8Hz)、4.04(t,2H,J＝4.8Hz)、6.81-6.88(m,4H)
[ chemical formula 28]
Example 8
[ production of Potassium salt ]
To a 100mL reactorWhile 2,2 '-dihydroxy-1, 1' -binaphthyl (5.00 g, 0.0175 mol), ethylene carbonate (3.38 g, 0.0384 mol), potassium carbonate (5.07 g, 0.0367 mol) and dipropylene glycol dimethyl ether (27.9 mL) were charged, and the mixture was aged at 130 ℃ for 5 hours. By HPLC, 1 As a result of H-NMR analysis of the aged reaction mixture, it was confirmed that the desired compound represented by the following formula (dipotassium salt of 2,2 '-dihydroxyethoxy-1, 1' -binaphthyl) was produced at a conversion of 93% and a selectivity of 100% for 2,2 '-dihydroxy-1, 1' -binaphthyl.
1 H-NMR(CDCl 3 ):δ4.03(t,4H,J＝5.8Hz)、4.23(t,4H,J＝5.8Hz)、7.13(d,2H,J＝8.0Hz)、7.24(t,2H,J＝8.0Hz)、7.36(t,2H,J＝8.0Hz)、7.45(d,2H,J＝8.0Hz)、7.89(d,2H,J＝8.0Hz)、7.98(d,2H,J＝8.0Hz)
[ chemical formula 29]
Example 9
[ production of Potassium salt ]
A100 mL reactor was charged with 1, 1-bis (4-hydroxyphenyl) cyclohexane (5.00 g, 0.0186 mol), ethylene carbonate (3.61 g, 0.0410 mol), potassium carbonate (5.41 g, 0.0391 mol), and dipropylene glycol dimethyl ether (27.9 mL), and the mixture was aged at 130 ℃ for 5 hours. By HPLC, 1 As a result of H-NMR analysis of the aged reaction solution, it was confirmed that the target compound represented by the following formula (1, 1-bis [4- (hydroxyethoxy) phenyl) cyclohexane) was produced at a conversion rate of 99% and a selectivity of 85%]Dipotassium salt of cyclohexane).
1 H-NMR(CDCl 3 ):δ1.48-2.25(m,10H)、3.92(t,4H,J＝5.0Hz)、4.04(t,4H,J＝5.0Hz)、6.82(d,4H,J＝8.5Hz)、7.16(d,4H,J＝8.5Hz)
[ chemical formula 30]
Example 10
[ production of Potassium salt ]
Bis (4-hydroxyphenyl) diphenylmethane (5.00 g, 0.0142 mol), ethylene carbonate (2.75 g, 0.0312 mol), potassium carbonate (4.12 g, 0.0298 mol) and dipropylene glycol dimethyl ether (27.9 mL) were charged into a 100mL reactor and aged at 130 ℃ for 5 hours. By HPLC, 1 As a result of H-NMR analysis of the aged reaction solution, it was confirmed that the target compound represented by the following formula (bis [4- (hydroxyethoxy) phenyl) was produced with a conversion of bis (4-hydroxyphenyl) diphenylmethane of 98% and a selectivity of 80%]Dipotassium salt of diphenylmethane).
1 H-NMR(CDCl 3 ):δ3.94(t,4H,J＝5.0Hz)、4.06(t,4H,J＝5.0Hz)、6.79-7.25(m,18H)
[ chemical formula 31]
Comparative example 1
A100 mL reactor was charged with 2-naphthol (1.00 g, 0.00693 mol), potassium carbonate (2.11 g, 0.0153 mol) and dipropylene glycol dimethyl ether (4.45 mL), and nitrogen substitution was performed. After a solution of 2-methanesulfonylchloroethane (3.30 g, 0.0208 mol) in dipropylene glycol dimethyl ether (2.23 mL) was added thereto at room temperature, the temperature was raised to 130 ℃ and aging was carried out at the same temperature for 5 hours. As a result of HPLC analysis of the aged reaction solution, it was confirmed that the target compound represented by the following formula was produced at a conversion of 2-naphthol of 33% and a selectivity of 100%.
[ chemical formula 32]
Comparative example 2
Into a 100mL reactor were charged bis (4-hydroxyphenyl) diphenylmethane (5.00 g, 0.0142 mol), ethylene carbonate (2.75 g, 0.0312 mol), sodium carbonate (3.16 g, 0.0298 mol) and dipropylene glycol dimethyl ether (27.9 mL), and the reaction was carried out at 130 ℃Aging was carried out for 5 hours. By HPLC, 1 As a result of H-NMR analysis of the aged reaction solution, it was confirmed that the target compound represented by the following formula (bis [4- (hydroxyethoxy) phenyl) was produced with a conversion of bis (4-hydroxyphenyl) diphenylmethane of 92% and a selectivity of 63%]Disodium salt of diphenylmethane).
[ chemical formula 33]
Comparative example 3
A100 mL reactor was charged with thionyl chloride (6.75 g, 0.0567 mol) and tetrahydrofuran (11.2 mL) and a solution of the disodium salt of bis [4- (hydroxyethoxy) phenyl ] diphenylmethane (0.0142 mol), pyridine (2.81 g, 0.0355 mol), dipropylene glycol dimethyl ether (27.9 mL) and tetrahydrofuran (56.2 mL) was added dropwise thereto at 60 ℃ over 2 hours. Further, aging was carried out at the same temperature for 3 hours. As a result of HPLC analysis of the aged reaction solution, it was confirmed that the target compound (halide) represented by the following formula was obtained at a conversion of 93% and a selectivity of 61%.
1 H-NMR(CDCl 3 ):δ3.80(t,4H,J＝6.0Hz)、4.21(t,4H,J＝6.0Hz)、6.78-7.25(m,18H)
[ chemical formula 34]
Comparative example 4
A100 mL reactor was charged with 1, 1-bis (4-hydroxyphenyl) cyclohexane (5.00 g, 0.0186 mol), ethylene carbonate (3.61 g, 0.0410 mol), sodium carbonate (4.15 g, 0.0391 mol) and dipropylene glycol dimethyl ether (27.9 mL), and the mixture was aged at 130 ℃ for 5 hours. By HPLC, 1 As a result of H-NMR analysis of the aged reaction solution, it was confirmed that the target compound represented by the following formula (1, 1-bis [4- (hydroxyethoxy) phenyl) cyclohexane) was produced at a conversion of 93% and a selectivity of 66%]Bis of cyclohexaneSodium salt).
[ chemical formula 35]
Comparative example 5
A100 mL reactor was charged with thionyl chloride (8.86 g, 0.0754 mol) and tetrahydrofuran (11.2 mL) and a solution of the disodium salt of 1, 1-bis [4- (hydroxyethoxy) phenyl ] cyclohexane (0.0186 mol), pyridine (3.68 g, 0.0466 mol), dipropylene glycol dimethyl ether (27.9 mL) and tetrahydrofuran (56.2 mL) was added dropwise thereto at 60 ℃ over 2 hours. Further, aging was carried out at the same temperature for 3 hours. As a result of HPLC analysis of the aged reaction solution, it was confirmed that the target compound (halide) represented by the following formula was obtained at a conversion of 93% and a selectivity of 64%.
1 H-NMR(CDCl 3 ):δ1.54(m,4H)、1.95(m,2H)、2.21(m,4H)、3.78(t,4H,J＝5.8Hz)、4.19(t,4H,J＝5.8Hz)、6.81(d,4H,J＝8.8Hz)、7.17(d,4H,J＝8.8Hz)
[ chemical formula 36]
Industrial applicability
The method for producing a halide of the present invention has the above-described configuration, and therefore, a halide can be produced efficiently by the method. Specifically, the method for producing a halide according to the present invention can synthesize a halide in a very high yield, and unlike the case of using a phenolic compound as a precursor, it is not necessary to perform a dehydration operation or a separation and extraction operation for removing water from the phenolic compound, and these operations can be omitted, so that the production efficiency of a halide can be remarkably improved. The potassium salt of the present invention is very useful as a precursor of the above halide. Further, the potassium salt of the present invention can be efficiently produced by the method for producing a potassium salt of the present invention.
Claims (3)
1. A method for producing a potassium salt, comprising: a step of reacting a compound represented by the following general formula (3), a compound represented by the following general formula (4), and potassium carbonate to produce a potassium salt selected from any one of compounds represented by the formulae (1-8), (1-10), and (1-14),
in the general formula (3), R 2 Represents binaphthyl, diphenylcyclohexane, or tetraphenylmethane having a carbon atom constituting an aromatic ring at a bonding site with an oxygen atom represented by the formula, and n represents 2;
in the general formula (4) and the formulae (1-8), (1-10) and (1-14), R 1 Represents a linear or branched alkylene group;
in the general formula (1), R 1 And R in the general formula (4) 1 Same, R 2 And n and R in the general formula (3) 2 And n is the same and 2R 1 Each of which may be the same or different.
2. A method for producing a potassium salt, comprising: 2-naphthol or p-methoxyphenol, a compound represented by the following general formula (4), and potassium carbonate are reacted in the presence of an ether as a solvent to produce a potassium salt represented by the following formula,
Or a potassium salt represented by the following formula
The step (2) of (a) is carried out,
in the general formula (4), R 1 Represents an ethylene group.
3. A potassium salt selected from any one of the compounds represented by the following formulae (1-8), (1-10) and (1-14),
wherein R is 1 Represents a linear or branched alkylene group.
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| JP2789693B2 (en) * | 1989-07-20 | 1998-08-20 | 三井化学株式会社 | Method for producing β-hydroxyalkyl aryl ethers |
| JPH0753459A (en) * | 1993-08-20 | 1995-02-28 | Mitsui Toatsu Chem Inc | Production of salicylic acid derivative |
| TW338042B (en) * | 1995-10-31 | 1998-08-11 | Clary Kk | Process for producing all trans-form polyprenols |
| US6080833A (en) * | 1996-07-31 | 2000-06-27 | Mitsui Chemicals, Inc. | Low-birefringent organic optical component and a spirobiindan polymer |
| JPH1171316A (en) * | 1996-07-31 | 1999-03-16 | Mitsui Chem Inc | Organic optical part having low birefringence and spirobiindane-based polymer |
| IL125840A (en) * | 1997-08-22 | 2002-12-01 | Teijin Chemicals Ltd | Bromine compound production method |
| SE9704834D0 (en) * | 1997-12-22 | 1997-12-22 | Astra Ab | New process |
| JP3662761B2 (en) * | 1999-02-10 | 2005-06-22 | アステラス製薬株式会社 | New production method of phenoxyalkyl halide derivatives |
| BRPI0514687A (en) * | 2004-08-26 | 2008-06-17 | Pfizer | amino heteroaryl compounds as protein tyrosine kinase inhibitors |
| GB0525477D0 (en) * | 2005-12-15 | 2006-01-25 | Astrazeneca Ab | Novel compounds |
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| JP5421034B2 (en) * | 2009-09-02 | 2014-02-19 | 帝人株式会社 | Method for producing polyester having plant-derived component |
| CN102617257A (en) * | 2012-02-24 | 2012-08-01 | 常州大学 | Synthetic method of diol phenylate compounds |
| JP2013216582A (en) * | 2012-04-04 | 2013-10-24 | Taoka Chem Co Ltd | Method for producing bis(hydroxyethyl) ether of bisphenol |
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