TW201546037A - Method for producing halogen compound, method for producing potassium salt, and potassium salt - Google Patents

Abstract

Provided is a method which is capable of efficiently producing a halogen compound that is useful as a precursor for a compound which is favorably used particularly in optical materials in general. A method for producing a halogen compound, which is characterized by comprising a step for producing a halogen compound represented by general formula (2) by reacting a compound represented by general formula (1) with a halogenation agent. (In general formula (1), R1 represents a linear or branched alkylene group; R2 represents an aromatic ring-containing group that has a carbon atom constituting the aromatic ring in the binding site with the oxygen atom expressed in the formula; and n represents 1 or 2, and in cases where n is 2, the two R1 moieties may be the same as or different from each other.) (In general formula (2), R1, R2 and n are as defined in general formula (1); and X represents a halogen atom, and in cases where n is 2, the two X moieties may be the same as or different from each other.).

Description

Method for producing halogen compound, method for producing potassium salt, and potassium salt

The invention relates to a method for manufacturing halogen compounds with high efficiency The halogen compound is suitable as a precursor (raw material) of a compound which can be preferably used in the entire optical material. Further, the present invention relates to a potassium salt which is suitable as a precursor of the above halogen compound, and a method which can produce the potassium salt with high efficiency. The present application claims priority to Japanese Patent Application No. 2014-085214, filed on Jan.

a compound having an aromatic ring in the molecule, especially in An aromatic compound having a reactive functional group such as an aromatic ring and a polymerizable functional group in the sub-group is used for various applications, and an optical material such as a lens, an optical fiber, or an optical waveguide is preferably used (for example, Patent Document 1). Therefore, such an aromatic compound precursor can be converted to the aromatic compound with high efficiency, and the usefulness is very high.

As the precursor of the above aromatic compound, having A halogen compound having a structure in which a reactive functional group in an aromatic compound is substituted with a halogen (halogen atom) is particularly useful. When such a halogen compound is used as the precursor of the above aromatic compound, since the halogen (halogen ion) is an excellent leaving group, the reaction can be introduced with high efficiency. The functional group can produce the above aromatic compound with high productivity.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-229263

The halogen compound is produced by using a phenolic compound such as phenol or naphthol to which a hydroxyl group is bonded to an aromatic ring as a precursor (starting material). More specifically, for example, by coupling a phenolic compound with 2-methanesulfonylchloroethane, a halogen compound (chlorine compound) suitable as a precursor of the above aromatic compound can be produced.

However, a method of producing a halogen compound using a phenolic compound as described above as a precursor has a low yield of a halogen compound, and cannot be said to be a practical method. Further, when a phenolic compound is synthesized and then a halogen compound is produced as a precursor, after the synthesis of the phenolic compound, it is necessary to carry out a dehydration operation for removing moisture from the organic layer containing the phenolic compound or for the separation of phenol. The single-off operation of a compound, which removes moisture from a phenolic compound, is complicated. Such water removal is necessary because the step of synthesizing the phenolic compound involves the operation of quenching the product by water, so that a considerable amount of water remains in the obtained phenolic compound, but if the moisture is present, then The above reaction system for synthesizing a halogen compound from a phenolic compound does not proceed. As described above, a method of producing a halogen compound using a phenolic compound as a precursor is a problem in that it is difficult to further improve the production efficiency of the halogen compound.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a process for producing a halogen compound which is suitable for use as a precursor of a compound which is preferably used in the entire optical material.

Further, another object of the present invention is to provide a potassium salt which is suitable as a precursor of the above halogen compound, and a method which can produce the potassium salt with high efficiency.

The present inventors have intensively studied in order to solve the above problems, and as a result, it has been found that by a method comprising a specific raw material (potassium salt) as a precursor, the step of reacting the halogenating agent as a necessary step can be high. The present invention has been completed by efficiently producing a halogen compound corresponding to the above raw materials.

In other words, the present invention provides a method for producing a halogen compound, which comprises the step of reacting a compound represented by the following formula (1) with a halogenating agent to form a halogen compound represented by the following formula (2);

[In the formula (1), R ¹ represents a linear or branched alkylene group; and R ² represents an aromatic ring-containing group which has an aromatic ring at a bonding site with an oxygen atom represented by the formula. Carbon atom; n means 1 or 2; when n is 2, 2 R1 can be the same or different

In the formula (2), R ¹ , R ² and n are the same as those in the formula (1); X represents a halogen atom; and when n is 2, two X's may be the same or different each].

Furthermore, the method for producing a halogen compound as described above, which comprises reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) with potassium carbonate before the step a step of the compound represented by the formula (1);

[In the general formula (3), R ² and n are the same as those in the general formula (1)];

In the general formula (4), R ¹ is the same as in the general formula (1).

Furthermore, the present invention provides a method for producing a potassium salt, which comprises reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) with potassium carbonate to form a general formula (1) the step of the potassium salt shown;

[In the formula (3), R ² represents an aromatic ring-containing group which has 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 formula (4), R ¹ represents a linear or branched alkylene group];

[In the formula (1), R ¹ is the same as in the formula (4); R ² and n are the same as those in the formula (3); when n is 2, each of the two R ¹ may be the same or a phase different].

Further, the present invention provides a potassium salt represented by the following formula (1),

[In the formula (1), R ¹ represents a linear or branched alkylene group; and R ² represents an aromatic ring-containing group which has an aromatic ring at a bonding site with an oxygen atom represented by the formula. Carbon atom; n represents 1 or 2; when n is 2, each of R ¹ may be the same or different].

That is, the present invention relates to the following.

[1-1] A method for producing a halogen compound, which comprises the step of reacting a compound represented by the formula (1) to be described later with a halogenating agent to form a halogen compound represented by the formula (2) to be described later.

[1-2] The method for producing a halogen compound according to [1-1], which further comprises a compound represented by the formula (3) to be described later and a formula (4) to be described later. a step of reacting a compound with potassium carbonate to form a compound represented by the formula (1) described later;

[1-3] The method for producing a halogen compound according to [1-1] or [1-2], wherein the compound represented by the formula (1) is a formula (1-1) or a formula (1-2) which will be described later. The compound shown.

The method for producing a halogen compound according to any one of the above aspects, wherein the compound represented by the formula (1) is a formula (1-3) to a formula (hereinafter) (hereinafter). One or more of the hydrogen compounds on the aromatic ring in the compound represented by 1-20) or the compound represented by the formula (1-3) to the formula (1-20) described later are substituted as described later. A compound substituted by a group.

The method for producing a halogen compound according to any one of [1] to [1-4] wherein the halogenating agent is selected from the group consisting of a chlorinating agent, a brominating agent, an iodinating agent, and 1,3 At least one of the group consisting of 1,3-dialkyl-2-halogenoimidazolinium halides.

The method for producing a halogen compound according to any one of the above [1], wherein, when the compound represented by the formula (1) is reacted with a halogenating agent, the halogenating agent is The amount used is 1 to 10 moles per mole of the potassium alkoxide moiety (-OK) which the compound represented by the formula (1) has.

The method for producing a halogen compound according to any one of the above [1], wherein the solvent used in the reaction of the compound represented by the formula (1) with a halogenating agent is a solvent. At least one selected from the group consisting of esters, ketones, ethers, glycol monoether monoterpenes, and hydrocarbons is selected.

The method for producing a halogen compound according to any one of the above aspects, wherein the halogen compound represented by the formula (2) is a formula (2-1) or a formula described later. (2-2).

The method for producing a halogen compound according to any one of the above aspects, wherein the halogen compound represented by the formula (2) is a formula (2-3) to be described later. One or more of the hydrogen atoms on the aromatic ring in the compound represented by the formula (2-20) or the compound represented by the following formula (2-3) to the formula (2-20) are substituted by a substituent described later. Compound.

The method for producing a potassium salt according to any one of the above [1], wherein the compound represented by the formula (3) is a compound represented by the formula (1) by a hydroxyl group. A compound (phenolic compound) of the structure shown by [-OR ¹ -OK].

The method for producing a potassium salt according to any one of the above [1], wherein the compound represented by the formula (4) is ethyl carbonate, propyl carbonate, or carbonic acid. Trimethylene carbonate or 1,2-butylene carbonate.

The method for producing a potassium salt according to any one of [1] to [1], wherein the compound represented by the formula (3) and the compound represented by the formula (4) and potassium carbonate are used. The solvent used in the reaction is at least one selected from the group consisting of esters, ketones, ethers, glycol monoether monoterpenes, and hydrocarbons.

[2-1] A method for producing a potassium salt, which comprises reacting a compound represented by the formula (3) to be described later with a compound represented by the formula (4) described later and potassium carbonate to form a formula (1) to be described later. The steps of the potassium salt shown.

[2-2] The method for producing a potassium salt according to the above [2-1], wherein the compound represented by the formula (1) is a compound represented by the formula (1-1) or the formula (1-2) which will be described later.

[2-3] The method for producing a potassium salt according to [2-1] or [2-2], wherein the compound represented by the formula (1) is a formula (1-3) to a formula (1-20) which will be described later. One or more compounds of the above-mentioned compounds or a hydrogen atom on the aromatic ring in the compound represented by the formula (1-3) to the formula (1-20), which are described later, are substituted with a substituent described later.

The method for producing a potassium salt according to any one of the above aspects, wherein the compound represented by the formula (3) is substituted with a hydroxyl group and is represented by the formula (1) described later. A compound (phenolic compound) having a structure represented by [-OR ¹ -OK] in the compound.

The method for producing a potassium salt according to any one of the above aspects, wherein the compound represented by the formula (4) is ethyl carbonate or propyl carbonate. , Trimethyl carbonate or 1,2-butyl butyl carbonate.

The method for producing a potassium salt according to any one of the above aspects, wherein the compound represented by the formula (3) and the compound represented by the formula (4) and potassium carbonate are used. The solvent used in the reaction is at least one selected from the group consisting of esters, ketones, ethers, glycol monoether monoterpenes, and hydrocarbons.

[3-1] A potassium salt represented by the formula (1) to be described later.

[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) which will be described later.

[3-3] The potassium salt according to [3-1] or [3-2], wherein the compound represented by the formula (1) is represented by the formula (1-3) to the formula (1-20) described later. The compound or a compound in which one or more hydrogen atoms on the aromatic ring in the compound represented by the formula (1-3) to the formula (1-20) described below are substituted with a substituent described later.

Since the method for producing a halogen compound of the present invention has the above configuration, the halogen compound can be produced with high efficiency by this method. In detail, by the method for producing a halogen compound of the present invention, a halogen compound can be synthesized in a very high yield, and unlike the case where a phenolic compound is used as a precursor, it is not necessary to remove water for phenolic compound. The dehydration operation or the single-off operation can significantly improve the production efficiency of the halogen compound since the operations can be omitted. Further, the potassium salt of the present invention is very suitable as the precursor of the above halogen compound. Further, the potassium salt of the present invention can be produced with high efficiency by the method for producing a potassium salt of the present invention.

[Formation of the Invention] <Method for Producing Halogen Compound>

The method for producing a halogen compound of the present invention is a method for producing a halogen compound represented by the formula (2), which comprises the step of reacting a compound represented by the formula (1) with a halogenating agent to form the halogen compound (also This is called the "halogenation step" as a necessary step. The present inventors have found that by using the method for producing a halogen compound of the present invention, a compound (potassium salt) represented by the formula (1) is used as a precursor (starting material) in the above halogenation step. Surprisingly, the halogen compound represented by the formula (2) can be produced with very high efficiency. Further, the method for producing a halogen compound of the present invention may include any step other than the above halogenation step.

[halogenation step] 1. A compound represented by the formula (1)

The compound represented by the formula (1) used in the halogenation step in the method for producing a halogen compound of the present invention is a potassium salt having a structure (-OK) in which a hydrogen atom of a hydroxyl group is substituted with potassium ions. In the formula (1), R ¹ represents a linear or branched alkylene group. Examples of R ¹ include a methylene group, a methylmethylene group, a dimethylmethylene group, an exoethyl group, a propyl group, and a trimerylene group (propane-1,3-diyl group). Among them, R ^{1 is} preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms. Furthermore, when n is 2, each of the two R ^{1 's} may be the same or different.

In the formula (1), R ² represents an aromatic ring-containing group (monovalent or divalent aromatic ring-containing group) having a carbon atom constituting an aromatic ring at a bonding site to an oxygen atom represented by the formula; It is only called "base containing aromatic ring"). I.e., bonded to the carbon atom constituting the aromatic ring (aromatic ring-containing group) of the general formula (1) with R ² an oxygen atom bonded to R ² lines. The aromatic ring contained in the aromatic ring-containing group may be a monocyclic aromatic ring (for example, a benzene ring) or a polycyclic aromatic ring (for example, a pentalene ring or an anthracene ring). A naphthalene ring, an azulene ring, a biphenylene ring, a phenanthrene ring, an anthracene ring, a fused polycyclic ring such as a flouranthene ring. The aromatic ring system contained in the aromatic ring-containing group may be an aromatic hydrocarbon ring or an aromatic hetero ring. Among them, an aromatic hydrocarbon ring is preferred.

The number of the aromatic rings contained in the aromatic ring-containing group (R ² ) (counting for the fused polycyclic ring composed of m aromatic rings as m aromatic rings) is not particularly limited, but is preferably 1~10, more preferably 2~8, especially 3~6.

When the above aromatic ring-containing group contains two or more aromatic In the case of a ring group, the plural aromatic rings may be condensed in order to form a polycyclic ring (fused polycyclic ring), and for example, a single ring aromatic ring or a polycyclic ring may be passed through one or more single bonds. And/or a linking group (either one or both of a single bond and a linking group) is bonded. Examples of the above-mentioned linking group include a divalent or higher hydrocarbon group; one or more of these hydrocarbon groups and one or more of a divalent hetero atom-containing group; and the above-mentioned divalent hetero atom-containing group. . The divalent or higher hydrocarbon group may, for example, be a divalent linear, branched or cyclic aliphatic hydrocarbon group; a trivalent linear, branched or cyclic aliphatic hydrocarbon; a tetravalent linear, branched or cyclic aliphatic hydrocarbon group or the like. The divalent linear, branched or cyclic aliphatic hydrocarbon group may, for example, be an alkylene group [e.g., methylene, ethyl, propyl, butyl, pentyl, hexyl). Et.], an alkenyl group [corresponding to an extended alkenyl group of the above alkyl group, such as a vinyl group, an arylene group, etc.], a cycloalkyl group [e.g., a cyclopentyl group, a cyclohexyl group, a a cyclopentylene group or the like], a cycloalkylene group (for example, a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group or the like), or a divalent group formed by bonding two or more of these groups [for example, Methylene-cyclohexylene, etc.]. The trivalent linear, branched or cyclic aliphatic hydrocarbon group may, for example, be an alkane-triyl group (for example, methane-triyl, ethane-triyl, propane-triyl, 1,1,1). - trimethylpropane-triyl or the like], cycloalkane-triyl [for example, cyclohexane-triyl, methylcyclohexane-triyl, dimethylcyclohexane-triyl, etc.] and the like. The tetravalent linear, branched or cyclic aliphatic hydrocarbon group may, for example, be an alkane-tetrayl group (for example, methane-tetrayl, ethane-tetrayl, butane-tetrayl, 2,2- Dimethylpropane-tetrayl or the like], cycloalkane-tetrayl [e.g., cyclohexane-tetrayl, methylcyclohexane-tetrayl, dimethylcyclohexane-tetrayl, etc.] and the like. Examples of the divalent hetero atom-containing group include -CO-, -O-CO-O-, -COO-, -O-, -CONH-, -S-, and the like.

The above aromatic ring-containing group may have a substituent. Replace The base may be a substituent on the aromatic ring, or may be a substituent in another moiety (for example, the above-mentioned linking group). The substituent may, for example, be a monovalent hydrocarbon group (for example, a linear or branched aliphatic hydrocarbon group such as an alkyl group, an alkenyl group or an alkynyl group; a cyclic aliphatic hydrocarbon group such as a cycloalkyl group; or a phenyl group; An aromatic hydrocarbon group or the like, a hydrocarbon group (for example, a benzyl group or the like) formed by linking two or more of these, a halogen atom, a sideoxy group, or a hydroxyl group , mercapto, fluorenyl, acryloxy, methacryloxy, substituted oxygen a group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, a decyloxy group, etc.), a carboxyl group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), a substitution or Unsubstituted aminemethanyl, cyano, nitro, substituted or unsubstituted amine, sulfo, heterocyclic, and the like. The above hydroxyl group or carboxyl group may also be protected by a protecting group conventionally used in the field of organic synthesis (for example, mercapto group, alkoxycarbonyl group, organodecyl group, alkoxyalkyl group, oxacycloalkyl group, etc.). The number of the substituents of the aromatic ring-containing group is not particularly limited, and is preferably, for example, 0 to 5. Further, when there are a plurality of substituents, each of these may be the same or different.

Specifically, examples of the aromatic ring-containing group include For example, corresponding to benzene, naphthalene, cyclopentadiene, anthracene, anthracene, a diphenyl, a phenanthrene, an anthracene, a fluorene, a biphenyl group (for example, 1,1'-biphenyl), a binaphthyl group (for example) , 1,1 '-binaphthyl), diphenylcyclohexane (for example, 1,1-diphenylcyclohexane), tetraphenylmethane, dinaphthylcyclohexane (for example, 1,1- Dinaphthylcyclohexane), naphthylphenylcyclohexane (eg, 1-naphthyl-1-phenylcyclohexane), dinaphthyldiphenylmethane, tetraphthylmethane, triphenylmethane, Trinaphthylmethane, 1,1-diphenylanthracene, 1,1-dinaphthyl anthracene, 1,1-diphenylpheneene, 1,1-dinaphthyl anthracene, etc. The aromatic compound and the derivative thereof (for example, one or more of the above-mentioned substitutions of a hydrogen atom bonded to a carbon atom in the aromatic compound (particularly a hydrogen atom bonded to a carbon atom constituting the aromatic ring) a monovalent or divalent group of a substituent, etc., that is, a one formed by removing one or two hydrogen atoms bonded to a carbon atom constituting an aromatic ring in the aromatic compound The basis of price or price.)

In the formula (1), n represents 1 or 2. That is, the formula (1) is shown The compound is specifically a compound represented by the formula (1-1) or the formula (1-2).

R ² -OR ¹ -OK (1-1)

KO-R ¹ -OR ² -OR ¹ -OK (1-2)

In the general formulae (1-1) and (1-2), R ¹ and R ² are the same as those in the general formula (1).

Specific examples of the compound represented by the formula (1) include, for example, a compound represented by the following formula (1-3) to formula (1-20) or a formula (1-3) to the following formula (1-3). 1-20) A compound in which one or more hydrogen atoms on the aromatic ring in the compound shown are substituted with the above substituents.

[In the above formula, R ¹ and n are the same as those in the formula (1)].

The compound represented by the formula (1) can be known or It is manufactured by a conventional method, and the manufacturing method thereof is not particularly limited. For example, it can be produced by reacting a compound represented by the following formula (i) with a strong base such as potassium hydroxide or potassium hydride in an aprotic solvent.

[In the formula (i), R ¹ , R ² and n are the same as those in the formula (1)].

Among them, the manufacturer of the compound represented by the formula (1) In view of the fact that the compound represented by the formula (1) can be produced with high efficiency in one stage, it is particularly preferable to use a compound represented by the formula (3) and a compound represented by the formula (4) (ring). A method in which a carbonate (carbonate) is reacted with potassium carbonate to form a compound (potassium salt) represented by the formula (1).

In the formula (3), R ² is the same as in the formula (1), and 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. Further, n is the same as in the formula (1), and represents 1 or 2. Specific examples of the compound represented by the formula (3) include a compound having a structure represented by [-OR ¹ -OK] in the compound represented by the formula (1) by a hydroxyl group (phenolic compound) )Wait.

In the formula (4), R ¹ is the same as in the formula (1), and represents a linear or branched alkylene group, preferably an alkylene group having 1 to 4 carbon atoms, more preferably a carbon number. 2~4 alkylene. In addition, the compound represented by the formula (4) may be used alone or in combination of two or more. The compound represented by the formula (4) may, for example, be an ethyl carbonate, a propyl carbonate, a trimethylene carbonate or a 1,2-butylene carbonate.

a compound represented by the formula (3) and a compound represented by the formula (4) The reaction of the substance with potassium carbonate can be carried out in the presence of a solvent (solvent) or in the absence of a solvent. Among them, in the viewpoint of uniformly conducting the reaction and producing the compound represented by the formula (1) in a higher yield, the above reaction is preferably carried out in the presence of a solvent (in a solvent). As the solvent, a solvent which is well-known or conventionally used can be used, and it can be suitably selected according to the compound represented by the formula (3) or the compound represented by the formula (4), and is not particularly limited, but may be mentioned. For example, esters of ethyl acetate, butyl acetate, isobutyl acetate, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.; 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, Ether of dipropylene glycol monomethyl ether; diethylene glycol monobutyl A glycol monoether monoterpene such as a phenyl ether acetate or a propylene glycol monomethyl ether acetate; a hydrocarbon such as xylene or toluene; and the like. Among them, from the viewpoint of the solubility of the reactant, an ether is preferred. Further, the solvent may be used singly or in combination of two or more kinds (in the form of a mixed solvent).

The compound represented by the formula (3) and the compound represented by the formula (4) In the reaction of the compound with potassium carbonate, in addition to these reactants and solvents, other components may be used in combination.

The compound represented by the formula (3) and the compound represented by the formula (4) The method of reacting the compound with potassium carbonate is not particularly limited. For example, a method in which a compound represented by the formula (3), a compound represented by the formula (4), and potassium carbonate are added to a reactor to cause a reaction; a part of the compound is added to the reactor, and the remainder is added. The compound is added to the reactor sequentially or continuously to make the reaction method or the like. In particular, in the case of ease of handling, a method in which a compound represented by the formula (3) and a compound represented by the formula (4) are added to a reactor together with potassium carbonate is preferred.

The compound represented by the formula (3) and the formula (4) are The reaction conditions of the compound and the potassium carbonate are appropriately set according to the compound represented by the formula (3) or the compound represented by the formula (4), and are not particularly limited, but for example, the reaction temperature is preferably The reaction time is preferably from 0.5 to 10 hours (more preferably from 1 to 7 hours) at 80 to 200 ° C (more preferably from 110 to 180 ° C). Further, in the above reaction, the reaction temperature can be controlled to be constantly fixed, or can be controlled to vary sequentially or continuously. Further, the gas atmosphere in which the above reaction is carried out is not particularly limited, and may be in the presence of oxygen (for example, in air), in an inert gas (for example, in nitrogen, in argon), or in a reducing gas (for example, in hydrogen). The reaction is carried out in any of the gaseous environments. Further, the pressure at the time of the reaction is not particularly limited, and may be any of normal pressure, pressure, and reduced pressure.

The above reaction system can be batch, semi-batch, continuous Any reaction form of the formula or the like is carried out.

By the above reaction, a compound represented by the formula (1) is produced. . The compound represented by the formula (1) which is produced may be used in the form of the reaction solution obtained by the above reaction (for example, a halogenation step), or may be used after purification (for example, a halogenation step). Further, the purification can be carried out by a well-known or conventional method (for example, recrystallization, distillation, adsorption, ion exchange, crystallization, extraction, etc.).

As described above, since the compound represented by the formula (1) can be used Since the method for producing a halogen compound of the present invention is different from the case of using a phenolic compound as a precursor of a halogen compound represented by the formula (2), it is not necessary to carry out the formula of the precursor ( 1) Dehydration operation or single operation of the compound shown.

2. Halogenating agent

The halogenating agent used in the halogenation step in the method for producing a halogen compound of the present invention is obtained by converting -OK in the compound represented by the formula (1) to -X to form a halogen represented by the formula (2). The task of the compound. As the halogenating agent, a well-known or conventional halogenating agent capable of performing the above-described conversion can be used, and is not particularly limited, and examples thereof include chlorine molecules, N-chlorosuccinimide, phosphorus pentachloride, and phosphorus chloride. Phosphoryl chloride, phosphorus oxychloride, thionyl chloride, thioindigo chloride, hypochlorite, cyanuric chloride, 2-chloro-1,3-dimethylbenzimidazole Chlorinating agent such as chloride; bromine molecule, N-bromosinium imine, hypobromous acid a brominating agent such as salt, bis(2,4,6-trimethylpyridine) bromine hexafluorophosphate; iodine molecule, bis(2,4,6-trimethylpyridine) iodonium hexafluorophosphate, etc. An iodinating agent; a 1,3-dialkyl-2-halazolimidazolium halide or the like. In addition, the halogenating agent may be used alone or in combination of two or more.

Furthermore, the halogenating agent in the above halogenation step can be separately used One type may be used, or two or more types may be used in combination. Further, the halogenating agent can be synthesized by a known or customary method, and a commercially available product can also be used.

3. Reaction conditions, etc.

The conditions for the reaction of the compound represented by the formula (1) with the halogenating agent in the above-mentioned halogenation step can be appropriately set according to the type of the halogenating agent to be used, etc., based on known or customary conditions. The amount of the halogenating agent to be used is not particularly limited, but is usually 1 to 10 moles, more preferably 1.5, based on the potassium alkoxide moiety (-OK) of the compound represented by the formula (1). ~6 times Moule.

Reaction of a compound represented by the formula (1) with a halogenating agent It can be carried out in the presence of a solvent or in the absence of a solvent. In the viewpoint of uniformly reacting the reaction to form a halogen compound represented by the formula (2) in a higher yield, the above reaction is preferably carried out in the presence of a solvent (in a solvent). As the solvent, a solvent which is known or conventionally used, and which can be appropriately selected according to the type of the compound represented by the formula (1) or the halogenating agent, and the like are not particularly limited, and examples thereof include ethyl acetate and butyl acetate. Esters of esters, isobutyl acetate, etc.; ketones of acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.; tetrahydrofuran, ethylene glycol dimethyl ether, diethyl Glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol An ether such as alcohol monomethyl ether, propylene glycol monomethyl ether or dipropylene glycol monomethyl ether; glycol monoether acetic acid such as diethylene glycol monobutyl ether acetate or propylene glycol monomethyl ether acetate Ester; a hydrocarbon such as xylene or toluene; a mixture of these, and the like. Among them, from the viewpoint of the solubility of the reactant, an ether is preferred. Further, the solvent may be used singly or in combination of two or more kinds (in the form of a mixed solvent).

In the reaction of the compound represented by the formula (1) with a halogenating agent In addition to these reactants and solvents, other components (for example, an organic base such as pyridine used to capture the generated acid) may be used in combination.

A method of reacting a compound represented by the formula (1) with a halogenating agent The law is not particularly limited. For example, a method in which a halogenating agent is introduced into a reactor, a compound represented by the formula (1) is added thereto to cause a reaction, and a compound represented by the formula (1) is added to a reactor, and a halogenation is added thereto. A method of reacting a reagent; a method of adding a compound represented by the formula (1) together with a halogenating agent to a reactor, and a reaction method. Among them, in order to produce a compound represented by the formula (1) at a high conversion ratio and a high selectivity, it is preferred to add a halogenating agent to the reactor, and to add a compound represented by the formula (1) thereto. The method of making the reaction.

The reaction of the compound represented by the formula (1) with a halogenating agent is carried out. The conditions are not particularly limited, and the reaction temperature is preferably from 40 to 150 ° C (more preferably from 50 to 100 ° C). The reaction time is preferably from 1 to 15 hours (more preferably from 2 to 10 hours). Further, in the above reaction, the reaction temperature can be controlled to be constantly fixed, or can be controlled to vary sequentially or continuously. Further, the gas atmosphere in which the above reaction is carried out is not particularly limited. The reaction can also be carried out in the presence of oxygen (for example, in air), in an inert gas (for example, in nitrogen, in argon), or in a reducing gas (for example, in hydrogen). Further, the pressure at the time of the reaction is not particularly limited, and may be any of normal pressure, pressure, and reduced pressure.

The above reaction system can be batch, semi-batch, continuous Any reaction form of the formula or the like is carried out.

By the above reaction, halogenation represented by the general formula (2) is produced. Compound. The halogen compound represented by the formula (2) may be used in the form of the reaction solution obtained by the above reaction (for example, the substitution of X in the formula (2) into a reactive functional group (for example, vinyl oxygen) The step of a polymerizable functional group such as a acryloxy group or a methacryloxy group, etc.) may be used after purification (for example, substitution of X in the general formula (2) to a reactive functional group) Basic steps, etc.). Further, the purification can be carried out by a well-known or conventional method (for example, recrystallization, distillation, adsorption, ion exchange, crystallization, extraction, etc.).

4. A halogen compound represented by the formula (2)

The halogen compound represented by the formula (2) is a compound produced by a reaction of a compound represented by the formula (1) and a halogenating agent in the above halogenation step. In the formula (2), R ¹ , R ² and n are the same as those in the formula (1). In the formula (2), X represents a halogen atom (for example, a chlorine atom, a bromine atom, or an iodine atom). When n is 2, each of the two X's may be the same or different. When the compound represented by the formula (1-1) is used as the compound represented by the formula (1), the halogen compound represented by the formula (1) is represented by the formula (2-1). The compound represented by (1-2) is represented by the formula (2-2).

R ² -OR ¹ -X (2-1)

XR ¹ -OR ² -OR ¹ -X (2-2)

In the general formulae (2-1) and (2-2), R ¹ , R ² and X are the same as those in the general formula (2).

Specific examples of the halogen compound represented by the formula (2), For example, a compound represented by the following formula (2-3) to formula (2-20) or an aromatic ring of a compound represented by the following formula (2-3) to formula (2-20); One or more hydrogen atoms are substituted with the above substituents.

[In the above formula, R ¹ , n and X are the same as those in the formula (2)].

[other steps]

The method for producing a halogen compound of the present invention may further comprise a step other than the above halogenation step (also referred to as "other steps"). As another step, for example, a step of purifying the halogen compound represented by the formula (2) after the halogenation step; and a step of producing a compound represented by the formula (1) before the halogenation step Wait. Further, each step in the method for producing a halogen compound of the present invention may be carried out continuously or discontinuously.

The compound shown in the general formula (1) is produced as another step. The step of the method of the present invention is not particularly limited, but a step of efficiently producing a compound represented by the formula (1) in one stage is preferred. The step of reacting the compound represented by the above formula (3), the compound represented by the formula (4), and potassium carbonate to form a compound represented by the formula (1). The conditions of this step and the like are as described above.

By the method for producing a halogen compound of the present invention, The halogen compound represented by the general formula (2) is synthesized in a very high yield, and unlike the method of using a phenolic compound as a precursor, since it is not necessary to carry out a dehydration operation or a single operation for removing moisture, it may be omitted. By such an operation, the production efficiency of the halogen compound represented by the general formula (2) can be remarkably improved. Since the halogen compound represented by the formula (2) is a compound having a functional group and having a halogen atom introduced therein, it can be preferably used in various applications such as medicines, agricultural chemicals, optical, electrical, and electronic fields. Functional material (functional compound or functional resin) Etc.) before the drive. In particular, since it is a compound having an aromatic ring which exhibits optical characteristics of a feature, a compound precursor which is preferably used as a whole of an optical material such as a lens, an optical fiber, or an optical waveguide can be applied. In addition, as a precursor for a halogen compound represented by the formula (2), a compound represented by the formula (1) (potassium salt) is obtained by high-efficiency (high conversion ratio and high selectivity) by the above halogenation step. It is highly useful.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples.

Example 1 [Manufacture of halogen compounds]

In a 100 mL reactor, sulfinium chloride (19.2 g, 0.161 mol) and tetrahydrofuran (11.2 mL) were added, and a potassium salt of 2-(p-methoxyphenoxy)ethanol was added thereto at 60 ° C for 2 hours. A solution of 0.0403 mol), pyridine (7.97 g, 0.101 mol), dipropylene glycol dimethyl ether (33.4 mL) and tetrahydrofuran (56.2 mL). Furthermore, it was aged at the same temperature for 3 hours. The reaction liquid after the aging was analyzed by HPLC, and it was confirmed that the compound (halogen compound) represented by the following formula was obtained at a conversion ratio of 100% and a selectivity of 98%.

¹ H-NMR (CDCl ₃ ): δ 3.77 (s, 3H), 3.79 (t, 2H, J = 4.8 Hz), 4.19 (t, 2H, J = 4.8 Hz), 6.83-6.88 (m, 4H)

Example 2 [Manufacture of halogen compounds]

In a 100 mL reactor, sulfite chloride (16.5 g, 0.139 mol) and tetrahydrofuran (11.2 mL) were added, and a potassium salt of 2-(2-naphthalenyloxy)ethanol (0.0347 mol) was added thereto at 60 ° C for 2 hours. A solution of pyridine (6.86 g, 0.0867 mol), dipropylene glycol dimethyl ether (16.7 mL) and tetrahydrofuran (56.2 mL). Furthermore, it was aged at the same temperature for 3 hours. The reaction liquid after the aging was analyzed by HPLC, and it was confirmed that the compound (halogen compound) represented by the following formula was obtained at a conversion ratio of 100% and a selectivity of 98%.

¹ H-NMR (CDCl ₃ ): δ 3.90 (t, 2H, J = 4.5 Hz), 4.37 (t, 2H, J = 4.5 Hz), 7.14 - 7.80 (m, 7H)

Example 3 [Manufacture of halogen compounds]

In a 100 mL reactor, sulfinium chloride (8.31 g, 0.0699 mol) and tetrahydrofuran (11.2 mL) were added, and 2,2'-dihydroxyethoxy-1,1'- was added dropwise at 60 ° C for 2 hours. A solution of dipotassium salt of binaphthyl (0.0175 mol), pyridine (3.45 g, 0.0437 mol), dipropylene glycol dimethyl ether (27.9 mL) and tetrahydrofuran (56.2 mL). Furthermore, it was aged at the same temperature for 3 hours. The reaction liquid after the aging was analyzed by HPLC, and it was confirmed that the compound (halogen compound) represented by the following formula was obtained at a conversion ratio of 100% and a selectivity of 98%.

¹ H-NMR (CDCl ₃ ): δ 4.16 (t, 4H, J = 5.3 Hz), 4.21 (t, 4H, J = 5.3 Hz), 7.16 (d, 2H, J = 6.8 Hz), 7.25 (t , 2H, J = 6.8 Hz), 7.38 (t, 2H, J = 6.8 Hz), 7.45 (d, 2H, J = 6.8 Hz), 7.90 (d, 2H, J = 6.8 Hz), 7.99 (d, 2H) , J=6.8Hz)

Example 4 [Manufacture of halogen compounds]

In a 100 mL reactor, sulfinium chloride (8.86 g, 0.0754 mol) and tetrahydrofuran (11.2 mL) were added, and 1,1-bis[4-(hydroxyethoxy)phenyl group was added dropwise at 60 ° C for 2 hours. A solution of dipotassium salt of cyclohexane (0.0186 mol), pyridine (3.68 g, 0.0466 mol), dipropylene glycol dimethyl ether (27.9 mL) and tetrahydrofuran (56.2 mL). Furthermore, it was aged at the same temperature for 3 hours. The reaction liquid after the aging was analyzed by HPLC, and it was confirmed that the compound (halogen compound) represented by the following formula was obtained at a conversion rate of 99% and a selectivity of 83%.

¹ H-NMR (CDCl ₃ ): δ 1.54 (m, 4H), 1.95 (m, 2H), 2.21 (m, 4H), 3.78 (t, 4H, J = 5.8 Hz), 4.19 (t, 4H, J = 5.8 Hz), 6.81 (d, 4H, J = 8.8 Hz), 7.17 (d, 4H, J = 8.8 Hz)

Example 5 [Manufacture of halogen compounds]

In a 100 mL reactor, sulfinium chloride (6.75 g, 0.0567 mol) and tetrahydrofuran (11.2 mL) were added, and bis[4-(hydroxyethoxy)phenyl]diphenyl was added dropwise at 60 ° C for 2 hours. Dipotassium salt of methane A solution of (0.0142 mol), pyridine (2.81 g, 0.0355 mol), dipropylene glycol dimethyl ether (27.9 mL) and tetrahydrofuran (56.2 mL). Furthermore, it was aged at the same temperature for 3 hours. The reaction liquid after the aging was analyzed by HPLC, and it was confirmed that the compound (halogen compound) represented by the following formula was obtained at a conversion rate of 98% and a selectivity of 79%.

¹ H-NMR (CDCl ₃ ): δ 3.80 (t, 4H, J = 6.0 Hz), 4.21 (t, 4H, J = 6.0 Hz), 6.78-7.25 (m, 18H)

Example 6 [Manufacture of Potassium Salt]

2-naphthol (5.00 g, 0.0347 mol), ethyl carbonate (6.72 g, 0.0763 mol), potassium carbonate (10.1 g, 0.0728 mol) and dipropylene glycol dimethyl ether (16.7 mL) were added to a 100 mL reactor. ), cooked at 130 ° C for 5 hours. The reaction liquid after the aging was analyzed by HPLC and ¹ H-NMR, and it was confirmed that the compound represented by the following formula was produced by the conversion of 2-naphthol of 92% and the selectivity of 100%.

¹ H-NMR (CDCl ₃ ): δ 4.06 (t, 2H, J = 4.8 Hz), 4.24 (t, 2H, J = 4.8 Hz), 7.15 - 7.80 (m, 7H)

Example 7 [Manufacture of Potassium Salt]

In a 100 mL reactor, p-methoxyphenol (5.00 g, 0.0403 mol), ethyl carbonate (7.81 g, 0.0886 mol), potassium carbonate (11.7 g, 0.0846 mol) and dipropylene glycol dimethyl ether (33.4) were added. mL), cooked at 130 ° C for 5 hours. The reaction liquid after the ripening was analyzed by HPLC and ¹ H-NMR, and the compound represented by the following formula (2-(p-methoxy) which was obtained by the conversion of p-methoxyphenol of 89% and the selectivity of 100% was confirmed. Potassium salt of phenoxy)ethanol).

¹ H-NMR (CDCl ₃ ): δ 3.78 (s, 3H), 3.94 (t, 2H, J = 4.8 Hz), 4.04 (t, 2H, J = 4.8 Hz), 6.81-6.88 (m, 4H)

Example 8 [Manufacture of Potassium Salt]

In a 100 mL reactor, 2,2'-dihydroxy-1,1'-binaphthyl (5.00 g, 0.0175 mol), ethyl carbonate (3.38 g, 0.0384 mol), potassium carbonate (5.07 g, 0.0367 mol) were added. And dipropylene glycol dimethyl ether (27.9 mL), which was aged at 130 ° C for 5 hours. The reaction liquid after the ripening was analyzed by HPLC and ¹ H-NMR, and it was confirmed that the conversion ratio of the 2,2'-dihydroxy-1,1'-binaphthalene was 93%, and the selectivity was 100%. Compound (dipotassium salt of 2,2'-dihydroxyethoxy-1,1'-binaphthyl).

¹ H-NMR (CDCl ₃ ): δ 4.03 (t, 4H, J = 5.8 Hz), 4.23 (t, 4H, J = 5.8 Hz), 7.13 (d, 2H, J = 8.0 Hz), 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)

Example 9 [Manufacture of Potassium Salt]

In a 100 mL reactor, 1,1-bis(4-hydroxyphenyl)cyclohexane (5.00 g, 0.0186 mol), ethyl carbonate (3.61 g, 0.0410 mol), potassium carbonate (5.41 g, 0.0391 mol) were added. And dipropylene glycol dimethyl ether (27.9 mL), which was aged at 130 ° C for 5 hours. The reaction liquid after the ripening was analyzed by HPLC and ¹ H-NMR, and it was confirmed that the conversion ratio of 1,1-bis(4-hydroxyphenyl)cyclohexane was 99%, and the selectivity was 85%. Compound (dipotassium salt of 1,1-bis[4-(hydroxyethoxy)phenyl]cyclohexane).

¹ H-NMR (CDCl ₃ ): δ 1.48-2.25 (m, 10H), 3.92 (t, 4H, J = 5.0 Hz), 4.04 (t, 4H, J = 5.0 Hz), 6.82 (d, 4H, J=8.5Hz), 7.16 (d, 4H, J=8.5Hz)

Example 10 [Manufacture of Potassium Salt]

In a 100 mL reactor, bis(4-hydroxyphenyl)diphenylmethane (5.00 g, 0.0142 mol), ethyl carbonate (2.75 g, 0.0312 mol), potassium carbonate (4.12 g, 0.0298 mol) and two were added. Propylene glycol dimethyl ether (27.9 mL) was aged at 130 ° C for 5 hours. The reaction liquid after the aging was analyzed by HPLC and ¹ H-NMR, and it was confirmed that the compound represented by the following formula was produced by the conversion of 98% of bis(4-hydroxyphenyl)diphenylmethane and the selectivity of 80%. Dipotassium salt of bis[4-(hydroxyethoxy)phenyl]diphenylmethane).

¹ H-NMR (CDCl ₃ ): δ 3.94 (t, 4H, J = 5.0 Hz), 4.06 (t, 4H, J = 5.0 Hz), 6.79 - 7.25 (m, 18H)

Comparative example 1

2-naphthol (1.00 g, 0.00693 mol), potassium carbonate (2.11 g, 0.0153 mol) and dipropylene glycol dimethyl ether (4.45 mL) were placed in a 100 mL reactor, and nitrogen substitution was carried out. After adding a solution of 2-methanesulfonylchloroethane (3.30 g, 0.0208 mol) in dipropylene glycol dimethyl ether (2.23 mL) at room temperature, the temperature was raised to 130 ° C, and the mixture was aged at the same temperature for 5 hours. . The reaction liquid after the aging was analyzed by HPLC, and it was confirmed that the compound represented by the following formula was produced by the conversion of 2-naphthol of 33% and the selectivity of 100%.

Comparative example 2

In a 100 mL reactor, bis(4-hydroxyphenyl)diphenylmethane (5.00 g, 0.0142 mol), ethyl carbonate (2.75 g, 0.0312 mol), sodium carbonate (3.16 g, 0.0298 mol) and two were added. Propylene glycol dimethyl ether (27.9 mL) was aged at 130 ° C for 5 hours. The reaction liquid after the aging was analyzed by HPLC and ¹ H-NMR, and it was confirmed that the compound represented by the following formula was produced by the conversion of bis(4-hydroxyphenyl)diphenylmethane of 92% and the selectivity of 63%. Bisodium salt of bis[4-(hydroxyethoxy)phenyl]diphenylmethane).

Comparative example 3

In a 100 mL reactor, sulfinium chloride (6.75 g, 0.0567 mol) and tetrahydrofuran (11.2 mL) were added, and bis[4-(hydroxyethoxy)phenyl]diphenyl was added dropwise at 60 ° C for 2 hours. A solution of the disodium salt of methane (0.0142 mol), pyridine (2.81 g, 0.0355 mol), dipropylene glycol dimethyl ether (27.9 mL), and tetrahydrofuran (56.2 mL). Furthermore, it was aged at the same temperature for 3 hours. The reaction liquid after the aging was analyzed by HPLC, and it was confirmed that the compound (halogen compound) represented by the following formula was obtained at a conversion rate of 93% and a selectivity of 61%.

¹ H-NMR (CDCl ₃ ): δ 3.80 (t, 4H, J = 6.0 Hz), 4.21 (t, 4H, J = 6.0 Hz), 6.78-7.25 (m, 18H)

Comparative example 4

In a 100 mL reactor, 1,1-bis(4-hydroxyphenyl)cyclohexane (5.00 g, 0.0186 mol), ethyl carbonate (3.61 g, 0.0410 mol), sodium carbonate (4.15 g, 0.0391 mol) were added. And dipropylene glycol dimethyl ether (27.9 mL), which was aged at 130 ° C for 5 hours. The reaction liquid after the ripening was analyzed by HPLC and ¹ H-NMR, and it was confirmed that the conversion ratio of the 1,1-bis(4-hydroxyphenyl)cyclohexane was 93%, and the selectivity was 66%. The compound (disodium salt of 1,1-bis[4-(hydroxyethoxy)phenyl]cyclohexane).

Comparative Example 5

In a 100 mL reactor, sulfinium chloride (8.86 g, 0.0754 mol) and tetrahydrofuran (11.2 mL) were added, and 1,1-bis[4-(hydroxyethoxy)phenyl group was added dropwise at 60 ° C for 2 hours. A solution of the disodium salt of cyclohexane (0.0186 mol), pyridine (3.68 g, 0.0466 mol), dipropylene glycol dimethyl ether (27.9 mL) and tetrahydrofuran (56.2 mL). Furthermore, it was aged at the same temperature for 3 hours. The reaction liquid after the aging was analyzed by HPLC, and it was confirmed that the compound (halogen compound) represented by the following formula was obtained at a conversion rate of 93% and a selectivity of 64%.

¹ H-NMR (CDCl ₃ ): δ 1.54 (m, 4H), 1.95 (m, 2H), 2.21 (m, 4H), 3.78 (t, 4H, J = 5.8 Hz), 4.19 (t, 4H, J = 5.8 Hz), 6.81 (d, 4H, J = 8.8 Hz), 7.17 (d, 4H, J = 8.8 Hz)

[Industrial availability]

Since the method for producing a halogen compound of the present invention has the above configuration, the halogen compound can be produced with high efficiency by this method. In detail, by the method for producing a halogen compound of the present invention, a halogen compound can be synthesized in a very high yield, and unlike the case where a phenolic compound is used as a precursor, it is not necessary to remove water for phenolic compound. The dehydration operation or the single-off operation can significantly improve the production efficiency of the halogen compound since the operation can be omitted. Further, the potassium salt of the present invention is very suitable as the precursor of the above halogen compound. Further, the potassium salt of the present invention can be produced with high efficiency by the method for producing a potassium salt of the present invention.

Claims (4)

A method for producing a halogen compound, comprising the step of reacting a compound represented by the following formula (1) with a halogenating agent to form a halogen compound represented by the following formula (2); In the formula (1), R ¹ represents a linear or branched alkylene group; and R ² represents an aromatic ring-containing group which has a carbon constituting an aromatic ring at a bonding site with an oxygen atom represented by the formula. An atom; n represents 1 or 2; when n is 2, each of R ¹ may be the same or different; In the formula (2), R ¹ , R ² and n are the same as those in the formula (1); X represents a halogen atom; and when n is 2, each of the two X groups may be the same or different. The method for producing a halogen compound according to claim 1, which further comprises reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) with potassium carbonate to form a pass. a step of the compound represented by the formula (1); In the formula (3), R ² and n are the same as those in the formula (1); In the formula (4), R ¹ is the same as in the formula (1). A method for producing a potassium salt, which comprises reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) with potassium carbonate to form a compound represented by the following formula (1): Step of potassium salt; In the formula (3), R ² represents an aromatic ring-containing group, which has 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 formula (4), R ¹ represents a linear or branched alkylene group; In the formula (1), R ¹ is the same as in the formula (4); R ² and n are the same as those in the formula (3); when n is 2, two R ^{1 's} may be the same or different . a potassium salt represented by the following formula (1), In the formula (1), R ¹ represents a linear or branched alkylene group; and R ² represents an aromatic ring-containing group which has a carbon constituting an aromatic ring at a bonding site with an oxygen atom represented by the formula. An atom; n represents 1 or 2; when n is 2, each of R ¹ may be the same or different.