TWI720410B - Method for manufacturing potash and potash - Google Patents

Abstract

The present invention provides a method for producing a halogen compound with high efficiency, and the halogen compound is suitable as a compound precursor that can be suitably used in the entire optical system material. The method for producing a halogen compound is characterized by comprising: making the following general formula (1) [in the general formula (1), R ¹ represents a linear or branched alkylene group; R ² represents an aromatic ring-containing group, It has a carbon atom constituting an aromatic ring at the bonding site with the oxygen atom shown in the formula; n represents 1 or 2; when n is 2, the two R ^1s may be the same or different.] The compound shown in and halogenated The agent reacts to produce the following general formula (2) [In the general formula (2), R ¹ , R ² and n are the same as those in the general formula (1); X represents a halogen atom; when n is 2, 2 Each of X may be the same or different from the step of the halogen compound shown in].

Description

Method for manufacturing potash and potash

The present invention relates to a method for producing a halogen compound with high efficiency, and the halogen compound is suitable as a compound precursor (raw material) that can be suitably used in the entire optical system material. In addition, the present invention relates to a potassium salt suitable as a precursor of the above-mentioned halogen compound, and a method for producing the potassium salt with high efficiency. This application claims the priority of Japanese Patent Application No. 2014-085214 filed in Japan on April 17, 2014, and its content is used here.

Compounds having an aromatic ring in the molecule, especially aromatic compounds having reactive functional groups such as an aromatic ring and a polymerizable functional group in the molecule, are used in a variety of applications and are particularly suitable for use as lenses, optical fibers, Optical system materials constituting optical waveguides and the like (for example, refer to Patent Document 1). Therefore, if such an aromatic compound precursor can be converted to the aromatic compound with high efficiency, the usefulness is very high.

As the precursor of the above-mentioned aromatic compound, a halogen compound system having a structure in which the reactive functional group in the above-mentioned aromatic compound is substituted with a halogen (halogen atom) is particularly useful. This is because when such a halogen compound is used as the precursor of the above-mentioned aromatic compound, since the halogen (halogen ion) is an excellent leaving group, it can be introduced into the reaction with high efficiency. The sexual functional group can produce the above-mentioned aromatic compound with high productivity.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2010-229263 A

The above-mentioned halogen compound is produced using a phenolic compound such as phenol or naphthol having a hydroxyl group bonded to an aromatic ring as a precursor (starting material). In more detail, for example, by coupling a phenolic compound with 2-methanesulfonyl chloroethane, a halogen compound (chlorine compound) suitable as a precursor of the above-mentioned aromatic compound can be produced.

However, the method of producing a halogen compound using the above-mentioned phenolic compound as a precursor has a low yield of the target halogen compound and cannot be said to be a practical method. In addition, when synthesizing a phenolic compound and then using this as a precursor to produce a halogen compound, after synthesizing the phenolic compound, it is necessary to perform a dehydration operation for removing water from the organic layer containing the phenolic compound or for isolating the phenol The isolation operation of sexual compounds removes water from phenolic compounds to a high degree, which is complicated. Such water removal is necessary because the step of synthesizing the phenolic compound involves the operation of quenching the product with water, so a considerable amount of water remains in the obtained phenolic compound, but if such water exists, it will be followed The above reaction system of synthesizing halogen compounds from phenolic compounds does not proceed. As such, the method of producing a halogen compound using a phenolic compound as a precursor has a problem that it is difficult to further improve the production efficiency of the halogen compound.

Therefore, the object of the present invention is to provide a method for producing a halogen compound with high efficiency, and the halogen compound is suitable as a compound precursor that can be preferably used in the entire optical system material.

In addition, another object of the present invention is to provide a potassium salt suitable as the precursor of the above-mentioned halogen compound, and a method for producing the potassium salt with high efficiency.

In order to solve the above-mentioned problems, the inventors have studied intensively. As a result, they have found that a method including the step of using a specific raw material (potassium salt) as a precursor and reacting this with a halogenating agent as a necessary step can achieve high The halogen compound corresponding to the above-mentioned raw materials was efficiently produced, and the present invention was completed.

That is, the present invention provides a method for producing a halogen compound, which is characterized by comprising a step of reacting a compound represented by the following general formula (1) with a halogenating agent to produce a halogen compound 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, which has an aromatic ring at the bonding site to the oxygen atom shown in the formula Carbon atom; n represents 1 or 2; when n is 2, the two R1s may be the same or different

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

Furthermore, there is provided a method for producing a halogen compound as described above, which comprises reacting a compound represented by the following general formula (3) and a compound represented by the following general formula (4) with potassium carbonate before the aforementioned step. Step of the compound represented by general 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 potassium salt, which is characterized by comprising reacting a compound represented by the following general formula (3), a compound represented by the following general formula (4), and potassium carbonate to produce the following general formula (1) The steps of the potassium salt shown;

[In the general formula (3), R ² represents an aromatic ring-containing group, which has a carbon atom constituting the aromatic ring at the bonding site with the oxygen atom shown in the formula; n represents 1 or 2];

[In the general formula (4), R ¹ represents a linear or branched alkylene group];

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

In addition, the present invention provides a potassium salt represented by the following general formula (1),

[In the general formula (1), R ¹ represents a linear or branched alkylene group; R ² represents an aromatic ring-containing group, which has an aromatic ring at the bonding site with the oxygen atom shown in the formula Carbon atom; n represents 1 or 2; when n is 2, the two 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, characterized by comprising a step of reacting a compound represented by the formula (1) described below with a halogenating agent to produce a halogen compound represented by the formula (2) described below.

[1-2] The method for producing a halogen compound as described in [1-1], which further comprises, before the aforementioned step, a compound represented by the general formula (3) described later, and a compound represented by the general formula (4) described later The step of reacting the compound with potassium carbonate to produce the compound represented by the general formula (1) described later;

[1-3] The method for producing a halogen compound as described in [1-1] or [1-2], wherein the compound represented by the formula (1) is the formula (1-1) or formula (1-2) described later The compound shown.

[1-4] The method for producing a halogen compound according to any one of [1-1] to [1-3], wherein the compound represented by formula (1) is the following formula (1-3) to formula ( One or more of the hydrogen atoms on the aromatic ring in the compound represented by 1-20), or the compound represented by formula (1-3) to formula (1-20) described later, is substituted by the following The compound substituted by the group.

[1-5] The method for producing a halogen compound as described in any one of [1-1] to [1-4], wherein the halogenating agent is selected from the group consisting of chlorinating agents, brominating agents, iodinating agents, and 1,3 -At least one member of the group consisting of 1,3-dialkyl-2-halogenoimidazolinium halides (1,3-dialkyl-2-halogenoimidazolinium halides).

[1-6] The method for producing a halogen compound as described in any one of [1-1] to [1-5], wherein when the compound represented by formula (1) is reacted with a halogenating agent, the The usage amount is 1 to 10 times mol relative to the potassium alkoxide part (-OK) of the compound represented by formula (1).

[1-7] The method for producing a halogen compound according to any one of [1-1] to [1-6], wherein the solvent used in the reaction between the compound represented by formula (1) and the halogenating agent is At least 1 selected from the group consisting of esters, ketones, ethers, glycol monoether monoacylates, and hydrocarbons.

[1-8] The method for producing a halogen compound according to any one of [1-1] to [1-7], wherein the halogen compound represented by the formula (2) is the following formula (2-1) or formula (2-2).

[1-9] The method for producing a halogen compound as described in any one of [1-1] to [1-8], wherein the halogen compound represented by formula (2) is the following formula (2-3) to formula The compound represented by (2-20), or the compound represented by the following formula (2-3) to formula (2-20), one or more of the hydrogen atoms on the aromatic ring is substituted with the substituent described later Compound.

[1-10] The method for producing potassium salt according to any one of [1-2] to [1-9], wherein the compound represented by formula (3) is substituted with a hydroxyl group for the compound represented by formula (1) The compound (phenolic compound) of the structure shown in [-OR ^{1 -OK].}

[1-11] The method for producing potassium salt according to any one of [1-2] to [1-10], wherein the compound represented by formula (4) is ethylene carbonate, propylene carbonate, and carbonic acid 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 compound represented by formula (3) and the compound represented by formula (4) and potassium carbonate The solvent used in the reaction is at least one selected from the group consisting of esters, ketones, ethers, glycol monoether monohydrides and hydrocarbons.

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

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

[2-3] The method for producing a potassium salt as described in [2-1] or [2-2], wherein the compound represented by formula (1) is the following formula (1-3) to formula (1-20) Compounds in which one or more of the hydrogen atoms on the aromatic ring in the compounds shown or the compounds represented by the formulas (1-3) to (1-20) described below are substituted with the substituents described below.

[2-4] The method for producing a potassium salt as described in any one of [2-1] to [2-3], wherein the compound represented by formula (3) is represented by the following formula (1) substituted with a hydroxyl group Among the compounds, a compound (phenolic compound) of the structure shown by [-OR ^{1 -OK].}

[2-5] The method for producing potassium salt according to any one of [2-1] to [2-4], wherein the compound represented by formula (4) is ethylene carbonate and 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 compound represented by formula (3) and the compound represented by formula (4) and potassium carbonate The solvent used in the reaction is at least one selected from the group consisting of esters, ketones, ethers, glycol monoether monohydrides and hydrocarbons.

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

[3-2] The potassium salt according to [3-1], wherein the compound represented by formula (1) is a compound represented by formula (1-1) or formula (1-2) described later.

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

Since the method for producing a halogen compound of the present invention has the above-mentioned structure, the method can produce a halogen compound with high efficiency. In detail, the method for producing a halogen compound of the present invention can synthesize a halogen compound with a very high yield, and unlike the case where a phenolic compound is used as a precursor, it is not necessary to remove water from the phenolic compound. Since the dehydration operation or single ionization operation can be omitted, the production efficiency of halogen compounds can be significantly improved. In addition, the potassium salt of the present invention is very suitable as the precursor of the above-mentioned halogen compound. Furthermore, by the method for producing the potassium salt of the present invention, the potassium salt of the present invention can be produced with high efficiency.

[The form of implementing the invention]

<Manufacturing method of halogen compound>

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

[Halogenation step]

1. The 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 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 by a potassium ion. In the general formula (1), R ¹ represents a linear or branched alkylene group. Examples of R ¹ include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene (propane-1,3-diyl), and the like. Among them, R ^{1 is} preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms. Furthermore, when n is 2, the two R ¹ may be the same or different.

In the general formula (1), R ² represents an aromatic ring-containing group (a monovalent or divalent aromatic ring-containing group having a carbon atom constituting the aromatic ring at the bonding site with the oxygen atom shown in the formula; also Only called "group 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, pentalene ring, indene ring, Condensed polycyclic rings such as naphthalene ring, azulene ring, biphenylene ring, phenanthrene ring, anthracene ring, flouranthene ring, etc.). The aromatic ring system 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 preferred.

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

When the above-mentioned aromatic ring-containing group is a group containing two or more aromatic rings, these plural aromatic rings may also be condensed in order to form a polycyclic ring (condensed polycyclic ring), and for example, a monocyclic aromatic ring and a polycyclic ring Two or more rings may be bonded via one or more single bonds and/or linking groups (either or both of single bonds and linking groups). Examples of the above-mentioned linking group include, for example, a bivalent or higher hydrocarbon group; a group in which one or more of these hydrocarbon groups are connected to one or more of a divalent heteroatom-containing group; the above-mentioned divalent heteroatom-containing group, etc. . Examples of the bivalent or higher hydrocarbon group include divalent linear, branched or cyclic aliphatic hydrocarbon groups; trivalent linear, branched or cyclic aliphatic hydrocarbons Group; tetravalent linear, branched or cyclic aliphatic hydrocarbon groups, etc. As the above-mentioned divalent linear, branched or cyclic aliphatic hydrocarbon group, for example, alkylene [for example, methylene, ethylene, propylene, butylene, pentylene, hexylene Etc.], alkenylene [alkenylene corresponding to the above-mentioned alkylene, such as vinylene, arylene group, etc.], cycloalkylene [for example, cyclopentylene, cyclohexylene, methyl Cyclohexylene, etc.], cycloalkylene [e.g., cyclopentylene, cyclohexylene, methylcyclohexylene, etc.], a divalent group formed by bonding two or more of these groups [e.g., Methylene-cyclohexylene, etc.] and so on. As the trivalent linear, branched or cyclic aliphatic hydrocarbon group, for example, an alkane-triyl group [e.g., methane-triyl, ethane-triyl, propane-triyl, 1,1,1 -Trimethylpropane-triyl, etc.], cycloalkane-triyl [for example, cyclohexane-triyl, methylcyclohexane-triyl, dimethylcyclohexane-triyl, etc.] and the like. As the above-mentioned tetravalent linear, branched or cyclic aliphatic hydrocarbon group, for example, alkane-tetrayl [e.g., methane-tetrayl, ethane-tetrayl, butane-tetrayl, 2,2- Dimethylpropane-tetrayl, etc.], cycloalkane-tetrayl [for example, 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-, and the like.

The above-mentioned aromatic ring-containing group may have a substituent. The substituent system may be a substituent on the aromatic ring, or may be a substituent in another part (for example, the above-mentioned linking group, etc.). Examples of the substituent include monovalent hydrocarbon groups (for example, linear or branched aliphatic hydrocarbon groups such as alkyl, alkenyl, and alkynyl groups, cyclic aliphatic hydrocarbon groups such as cycloalkyl groups, and phenyl groups. Aromatic hydrocarbon groups such as these, hydrocarbon groups formed by connecting two or more of these (for example, benzyl, etc.), halogen atoms, pendant oxygen groups, hydroxyl groups , Acyl, mercapto, acryloxy, methacryloxy, substituted oxy (e.g., alkoxy, aryloxy, aralkoxy, acoxy, etc.), carboxyl, substituted oxycarbonyl ( Alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, etc.), substituted or unsubstituted aminoformyl, cyano, nitro, substituted or unsubstituted amine, sulfo, heterocyclic group, etc. The above-mentioned hydroxyl or carboxyl group may also be protected by a protective group commonly used in the field of organic synthesis (for example, an acyl group, an alkoxycarbonyl group, an organosilyl group, an alkoxyalkyl group, an oxacycloalkyl group, etc.). The number of substituents that the aromatic ring-containing group has is not particularly limited, but it is preferably 0 to 5, for example. In addition, when it has plural substituents, these systems may be the same or different.

Specifically, as the above-mentioned aromatic ring-containing group, for example, those corresponding to benzene, naphthalene, pentacyclopentadiene, indene, azulene, biphenylene, phenanthrene, anthracene, fluoranthene, biphenyl (for example, 1,1 '-Biphenyl), binaphthyl (for example, 1,1'-binaphthyl), diphenylcyclohexane (for example, 1,1-diphenylcyclohexane), tetraphenylmethane, dinaphthyl ring Hexane (for example, 1,1-dinaphthyl cyclohexane), naphthyl phenyl cyclohexane (for example, 1-naphthyl-1-phenyl cyclohexane), dinaphthyl diphenyl methane, tetra Naphthylmethane, triphenylmethane, trinaphthylmethane, 1,1-diphenylindene, 1,1-dinaphthylindene, 1,1-diphenyl phenalene (1,1-diphenyl phenalene), 1 , 1-Dinaphthyl and other aromatic compounds and their derivatives (for example, the hydrogen atoms bonded to the carbon atoms in the above-mentioned aromatic compounds (especially the hydrogen atoms bonded to the carbon atoms constituting the aromatic ring) ) One or more of the above-mentioned substituents substituted by the above-mentioned substituents, etc.) of the monovalent or divalent group (that is, in the structural formula, remove the hydrogen atom bonded to the carbon atom constituting the aromatic ring in the above-mentioned aromatic compound 1 or 2 and form a monovalent or divalent base).

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

R ² -OR ¹ -OK (1-1)

KO-R ¹ -OR ² -OR ¹ -OK (1-2)

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

As a specific example of the compound represented by the general formula (1), for example, a compound represented by the following formula (1-3) to formula (1-20), or the following formula (1-3) to formula ( 1-20) Compounds in which one or more of the hydrogen atoms on the aromatic ring in the compound shown are substituted with the above-mentioned substituents.

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

The compound represented by the general formula (1) can be produced by a well-known or commonly used method, and the production method is not particularly limited. For example, it 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.

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

Among them, as a method for producing the compound represented by the general formula (1), it is particularly preferred that the compound represented by the general formula (3) can be produced at a high efficiency in one stage. A method of reacting the compound represented by the general formula (4) (cyclic carbonate) and potassium carbonate to produce the compound represented by the general formula (1) (potassium salt).

In the general formula (3), R ² is the same as in the general formula (1), and represents an aromatic ring-containing group having carbon atoms constituting the aromatic ring at the bonding site with the oxygen atom shown in the formula. In addition, the n system is the same as that in the general formula (1), and represents 1 or 2. As a specific example of the compound represented by the general formula (3), for example, a compound having a structure represented by ^{[-OR 1 -OK] in the compound represented by the general formula (1) substituted with a hydroxyl group (phenolic compound)} )Wait.

In the general formula (4), R ¹ is the same as in the general 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 groups. In addition, the compound system represented by general formula (4) may be used individually by 1 type, and may be used in combination of 2 or more types. 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 system 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 (solvent) or in the absence of a solvent. Among them, from the viewpoint of uniformly performing the reaction to produce the compound represented by the general formula (1) in a higher yield, the above-mentioned reaction is preferably performed in the presence of a solvent (in a solvent). As the solvent, a well-known or customary solvent can be used, and it can be appropriately selected according to the type of the compound represented by the general formula (3) or the compound represented by the general formula (4), etc., and is not particularly limited, but can be exemplified 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, Dipropylene glycol monomethyl ether and other ethers; diethylene glycol monobutyl Glycol monoether monoacetate such as base ether acetate and propylene glycol monomethyl ether acetate; hydrocarbons such as xylene and toluene. Among them, from the viewpoint of the solubility of the reactant, ethers are preferred. In addition, the solvent system may be used individually by 1 type, and may be used in combination of 2 or more types (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, in addition to these reactants and solvents, other components may be used in combination.

The method of reacting the compound represented by the general formula (3) with the compound represented by the general formula (4) and potassium carbonate is not particularly limited. For example, a method of adding the compound represented by the general formula (3), the compound represented by the general formula (4), and potassium carbonate to the reactor to react; adding a part of the compound to the reactor, and the remaining The compound is added to the reactor successively or continuously to make the reaction method and so on. Particularly, in terms of ease of operation, a method of adding the compound represented by the general formula (3), the compound represented by the general formula (4), and potassium carbonate to the reactor to react is preferred.

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 in accordance with the compound represented by the general formula (3) or the compound represented by the general formula (4) The kind, etc. are appropriately set, and there is no particular limitation. For example, the reaction temperature is preferably 80-200°C (more preferably 110-180°C), and the reaction time is preferably 0.5-10 hours (more preferably 1-7 hour). Furthermore, in the above reaction, the reaction temperature can be controlled to be constantly fixed, or can be controlled to vary gradually or continuously. In addition, the gas environment for performing the above reaction is not particularly limited, and it may be in the presence of oxygen (for example, in air), in an inert gas (for example, in nitrogen, argon), or in a reducing gas (for example, in hydrogen). The reaction is carried out in any gas environment. In addition, the pressure during the reaction is not particularly limited, and may be any of normal pressure, increased pressure, and reduced pressure.

The above-mentioned reaction system can be carried out in any reaction format such as a batch type, a semi-batch type, and a continuous type.

Through the above reaction, the compound represented by the general formula (1) is produced. The resulting compound represented by the general formula (1) may also be used in the form of being present in the reaction solution obtained through the above reaction (for example, performing a halogenation step), or may be used after purification (for example, performing a halogenation step). Furthermore, the purification system can be implemented by a well-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 that does not use water, the method for producing the halogen compound of the present invention is the same as before using a phenolic compound as the halogen compound represented by the general formula (2) The situation of flooding is different, and it is not necessary to perform the dehydration operation or the isolation operation of the compound represented by the general formula (1) of the precursor.

2. Halogenating agent

The halogenating agent used in the halogenation step in the method for producing the halogen compound of the present invention is capable of converting -OK in the compound represented by the general formula (1) to -X to generate the halogen represented by the general formula (2) The task of the compound. As the halogenating agent, a well-known or customary halogenating agent capable of performing the above conversion can be used, and it is not particularly limited, but examples include chlorine molecules, N-chlorosuccinimide, phosphorus pentachloride, and phosphorus chloride. Phosphoryl chloride, phosphorous oxychloride, thionyl chloride, sulphur chloride, hypochlorite, cyanuric chloride, 2-chloro-1,3-dimethylbenzimidazolium- Chlorinating agent such as chloride; bromine molecule, N-bromosuccinimide, hypobromous acid Bromination agents such as salt, bis(2,4,6-trimethylpyridinium) bromide hexafluorophosphate, etc.; iodine molecule, bis(2,4,6-trimethylpyridinium) iodonium hexafluorophosphate, etc. The iodinating agent; 1,3-dialkyl-2-haloimidazolinium halides, etc. In addition, the halogenating agent system may be used individually by 1 type, and may be used in combination of 2 or more types.

In addition, the halogenating agent system in the said halogenation process may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, the halogenating agent can be synthesized by a well-known or commonly used 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 general formula (1) with the halogenating agent in the above halogenation step can be appropriately set based on known or customary conditions according to the type of halogenating agent used, etc. The amount of halogenating agent used is not particularly limited, but it is usually 1 to 10 times mol, more preferably 1.5 relative to the potassium alkoxide moiety (-OK) of the compound represented by the general formula (1). ~6 times mole.

The reaction between the compound represented by the general formula (1) and the halogenating agent can be carried out in the presence of a solvent or in the absence of a solvent. Among them, from the viewpoint of making the reaction proceed uniformly to produce the halogen compound represented by the general 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 well-known or customary solvent can be used, and it can be appropriately selected according to the type of the compound represented by the general formula (1) or the halogenating agent, etc., and is not particularly limited, but for example, ethyl acetate, butyl acetate Ester, isobutyl acetate, etc.; 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 two Alcohol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, etc.; diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, etc. glycol monoether acetic acid Esters; hydrocarbons such as xylene and toluene; mixtures of these, etc. Among them, from the viewpoint of the solubility of the reactant, ethers are preferred. In addition, the solvent system can be used individually by 1 type, and can also be used in combination of 2 or more types (in the form of a mixed solvent).

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

The method of reacting the compound represented by the general formula (1) with the halogenating agent is not particularly limited. For example, a method of adding a halogenating agent to the reactor and adding the compound represented by the general formula (1) to react; adding the compound represented by the general formula (1) to the reactor and adding the halogenation A method of reacting with an agent; a method of adding the compound represented by the general formula (1) and a halogenating agent to the reactor to react. Among them, at the point that the compound represented by the general formula (1) can be produced at a high conversion rate and a high selectivity, it is preferable to add a halogenating agent to the reactor and add the compound represented by the general formula (1) to it. The way to make the reaction.

The conditions for carrying out the reaction between the compound represented by the general formula (1) and the halogenating agent can be appropriately set according to the compound represented by the general formula (1) or the type of the halogenating agent, etc., and are not particularly limited, but for example, the reaction temperature It is preferably 40 to 150°C (more preferably 50 to 100°C), and the reaction time is preferably 1 to 15 hours (more preferably 2 to 10 hours). Furthermore, in the above reaction, the reaction temperature can be controlled to be constantly fixed, or can be controlled to vary gradually or continuously. Furthermore, the gas environment in which the above-mentioned reaction is carried out is not particularly limited. The reaction may also be carried out in any gas environment in the presence of oxygen (for example, in air), inert gas (for example, in nitrogen, argon), and in reducing gas (for example, in hydrogen). In addition, the pressure during the reaction is not particularly limited, and may be any of normal pressure, increased pressure, and reduced pressure.

The above-mentioned reaction system can be carried out in any reaction format such as a batch type, a semi-batch type, and a continuous type.

Through the above reaction, a halogen compound represented by the general formula (2) is produced. The halogen compound represented by the general formula (2) can be used in the form of being present in the reaction solution obtained through the above reaction (for example, the substitution of X in the general formula (2) with a reactive functional group (for example, vinyl oxide) Polymerizable functional groups such as oxy group, acryloxy group, methacryloxy group, etc.), etc.), can also be used after purification (for example, substituting X in the general formula (2) with a reactive functional group) Basic steps, etc.). Furthermore, the purification system can be implemented by a well-known or customary method (for example, recrystallization, distillation, adsorption, ion exchange, crystallization, extraction, etc.).

4. The halogen compound represented by the general formula (2)

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

R ² -OR ¹ -X (2-1)

XR ¹ -OR ² -OR ¹ -X (2-2)

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

As a specific example of the halogen compound represented by the general formula (2), for example, a compound represented by the following formula (2-3) to formula (2-20), or the following formula (2-3) to formula (2-20) Compounds in which one or more of the hydrogen atoms on the aromatic ring in the compound shown in (2-20) are substituted with the above-mentioned substituents, etc.

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

[Other steps]

The method for producing the halogen compound of the present invention may also include steps other than the above-mentioned halogenation step (also referred to as "other steps"). As other steps, for example, after the halogenation step, the step of refining the halogen compound represented by the general formula (2); before the halogenation step, the step of producing the compound represented by the general formula (1) Wait. Furthermore, each step in the method for producing a halogen compound of the present invention may be performed continuously or discontinuously.

As for the steps of producing the compound represented by the general formula (1) as other steps, there can be exemplified steps using well-known or customary synthetic methods, and there is no particular limitation, but it can be efficiently produced in one step. For the compound represented by formula (1), it is preferable to react the compound represented by general formula (3), the compound represented by general formula (4), and potassium carbonate to produce the compound represented by general formula (1) Compound steps. The conditions for this step are as described above.

With the method for producing the halogen compound of the present invention, the halogen compound represented by the general formula (2) can be synthesized in a very high yield, and unlike the method using a phenolic compound as a precursor, it is not necessary to remove water. The dehydration operation or single ionization operation can be omitted, so the production efficiency of the halogen compound represented by the general formula (2) can be significantly improved. The halogen compound represented by the general formula (2) is a compound that has a functional group in the molecule that can be easily introduced as a halogen atom, so it can be suitably used for various applications in the fields of medicine, agrochemicals, optics, electricity, and electronics. Functional materials (functional compounds or functional resins) Etc.) Precursors. In particular, since it is a compound having an aromatic ring that exhibits characteristic optical properties, it can be suitably used as a precursor of a compound that is preferably used in all optical system materials such as lenses, optical fibers, and optical waveguides. In addition, as a precursor for the halogen compound represented by the general formula (2) with high efficiency (high conversion rate and high selectivity) through the above-mentioned halogenation step, the compound represented by the general formula (1) (potassium salt) The usefulness of the system is high.

[Example]

Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited by these examples.

Example 1

[Manufacturing of Halogen Compounds]

In a 100 mL reactor, sulfite chloride (19.2 g, 0.161 mol) and tetrahydrofuran (11.2 mL) were added, and the potassium salt of 2-(p-methoxyphenoxy) ethanol ( 0.0403mol), pyridine (7.97g, 0.101mol), dipropylene glycol dimethyl ether (33.4mL) and a solution of tetrahydrofuran (56.2mL). Furthermore, the maturation was carried out at the same temperature for 3 hours. The aging reaction liquid was analyzed by HPLC. As a result, it was confirmed that the desired compound (halogen compound) represented by the following formula was obtained with a conversion rate 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)

Example 2

[Manufacturing of Halogen Compounds]

In a 100mL reactor, sulfite chloride (16.5g, 0.139mol) and tetrahydrofuran (11.2mL) were added, and the potassium salt of 2-(2-naphthyloxy)ethanol (0.0347mol) was dropped at 60°C for 2 hours. ), pyridine (6.86g, 0.0867mol), dipropylene glycol dimethyl ether (16.7mL) and tetrahydrofuran (56.2mL) solution. Furthermore, the maturation was carried out at the same temperature for 3 hours. The aging reaction liquid was analyzed by HPLC. As a result, it was confirmed that the desired compound (halogen compound) represented by the following formula was obtained with 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)

Example 3

[Manufacturing of Halogen Compounds]

In a 100mL reactor, add sulfite chloride (8.31g, 0.0699mol) and tetrahydrofuran (11.2mL), and drop 2,2'-dihydroxyethoxy-1,1'- at 60°C for 2 hours. A solution of the 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, the maturation was carried out at the same temperature for 3 hours. The aging reaction liquid was analyzed by HPLC. As a result, it was confirmed that the desired compound (halogen compound) represented by the following formula was obtained with a conversion rate 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)

Example 4

[Manufacturing of Halogen Compounds]

In a 100mL reactor, add sulfite chloride (8.86g, 0.0754mol) and tetrahydrofuran (11.2mL), and drop 1,1-bis[4-(hydroxyethoxy)phenyl at 60℃ for 2 hours. ] A solution of the 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, the maturation was carried out at the same temperature for 3 hours. The aging reaction liquid was analyzed by HPLC. As a result, it was confirmed that the desired compound (halogen compound) represented by the following formula was obtained with a conversion rate 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)

Example 5

[Manufacturing of Halogen Compounds]

In a 100mL reactor, add sulfite chloride (6.75g, 0.0567mol) and tetrahydrofuran (11.2mL), and drop bis[4-(hydroxyethoxy)phenyl]diphenyl at 60℃ for 2 hours. Dipotassium salt of methane (0.0142mol), pyridine (2.81g, 0.0355mol), dipropylene glycol dimethyl ether (27.9mL) and tetrahydrofuran (56.2mL) solution. Furthermore, the maturation was carried out at the same temperature for 3 hours. The aging reaction solution was analyzed by HPLC. As a result, it was confirmed that the desired compound (halogen compound) represented by the following formula was obtained with a conversion rate 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)

Example 6

[Manufacture of Potash]

In a 100mL reactor, add 2-naphthol (5.00g, 0.0347mol), ethylene carbonate (6.72g, 0.0763mol), potassium carbonate (10.1g, 0.0728mol) and dipropylene glycol dimethyl ether (16.7mL ), matured at 130°C for 5 hours. The aging reaction liquid was analyzed by HPLC and ¹ H-NMR. As a result, it was confirmed that the desired compound represented by the following formula was produced with a conversion rate of 2-naphthol 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)

Example 7

[Manufacture of Potash]

In a 100mL reactor, add p-methoxyphenol (5.00g, 0.0403mol), ethylene carbonate (7.81g, 0.0886mol), potassium carbonate (11.7g, 0.0846mol) and dipropylene glycol dimethyl ether (33.4 mL), matured at 130°C for 5 hours. The aging reaction solution was analyzed by HPLC and ¹ H-NMR. As a result, it was confirmed that the conversion rate of p-methoxyphenol was 89%, and the selectivity was 100%. The target compound represented by the following formula (2-(p-methoxy Phenoxy) the potassium salt of ethanol).

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)

Example 8

[Manufacture of Potash]

In a 100mL reactor, add 2,2'-dihydroxy-1,1'-binaphthyl (5.00g, 0.0175mol), ethylene carbonate (3.38g, 0.0384mol), potassium carbonate (5.07g, 0.0367mol) ) And dipropylene glycol dimethyl ether (27.9 mL), aged at 130°C for 5 hours. The matured reaction solution was analyzed by HPLC and ¹ H-NMR, and it was confirmed that the conversion rate of 2,2'-dihydroxy-1,1'-binaphthyl was 93% and the selectivity was 100%. The compound (the dipotassium salt of 2,2'-dihydroxyethoxy-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)

Example 9

[Manufacture of Potash]

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

Example 10

[Manufacture of Potash]

In a 100mL reactor, add bis(4-hydroxyphenyl)diphenylmethane (5.00g, 0.0142mol), ethylene carbonate (2.75g, 0.0312mol), potassium carbonate (4.12g, 0.0298mol) and two Propylene glycol dimethyl ether (27.9 mL) was matured at 130°C for 5 hours. The aging reaction solution was analyzed by HPLC and ¹ H-NMR. As a result, it was confirmed that the conversion rate of bis(4-hydroxyphenyl)diphenylmethane was 98% and the selectivity was 80%. The target compound represented by the following formula ( The dipotassium salt of bis[4-(hydroxyethoxy)phenyl]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)

Comparative example 1

In a 100 mL reactor, add 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 perform nitrogen replacement. After adding 2-methanesulfonyl chloroethane (3.30g, 0.0208mol) in dipropylene glycol dimethyl ether (2.23mL) solution at room temperature, the temperature was raised to 130°C and matured at the same temperature for 5 hours . The aging reaction liquid was analyzed by HPLC. As a result, it was confirmed that the desired compound represented by the following formula was produced with a conversion rate of 33% of 2-naphthol and a selectivity of 100%.

Comparative example 2

In a 100mL reactor, add bis(4-hydroxyphenyl)diphenylmethane (5.00g, 0.0142mol), ethylene carbonate (2.75g, 0.0312mol), sodium carbonate (3.16g, 0.0298mol) and two Propylene glycol dimethyl ether (27.9 mL) was matured at 130°C for 5 hours. The matured reaction solution was analyzed by HPLC and ¹ H-NMR. As a result, it was confirmed that the conversion rate of bis(4-hydroxyphenyl)diphenylmethane was 92% and the selectivity was 63%. The target compound represented by the following formula ( Disodium salt of bis[4-(hydroxyethoxy)phenyl]diphenylmethane).

Comparative example 3

In a 100mL reactor, add sulfite chloride (6.75g, 0.0567mol) and tetrahydrofuran (11.2mL), and drop bis[4-(hydroxyethoxy)phenyl]diphenyl at 60℃ for 2 hours. A solution of methane disodium salt (0.0142 mol), pyridine (2.81 g, 0.0355 mol), dipropylene glycol dimethyl ether (27.9 mL) and tetrahydrofuran (56.2 mL). Furthermore, the maturation was carried out at the same temperature for 3 hours. The aging reaction solution was analyzed by HPLC. As a result, it was confirmed that the desired compound (halogen compound) represented by the following formula was obtained with a conversion rate 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)

Comparative example 4

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

Comparative example 5

In a 100mL reactor, add sulfite chloride (8.86g, 0.0754mol) and tetrahydrofuran (11.2mL), and drop 1,1-bis[4-(hydroxyethoxy)phenyl at 60℃ 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, the maturation was carried out at the same temperature for 3 hours. The aging reaction liquid was analyzed by HPLC. As a result, it was confirmed that the desired compound (halogen compound) represented by the following formula was obtained with a conversion rate 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)

[Industrial availability]

Since the method for producing a halogen compound of the present invention has the above-mentioned constitution, the method can produce a halogen compound with high efficiency. In detail, the method for producing a halogen compound of the present invention can synthesize a halogen compound with a very high yield, and unlike the case where a phenolic compound is used as a precursor, it does not need to be used to remove water from the phenolic compound. Since the dehydration operation or single ionization operation can be omitted, the production efficiency of halogen compounds can be significantly improved. In addition, the potassium salt system of the present invention is very suitable as a precursor of the above-mentioned halogen compound. Furthermore, by the method for producing the potassium salt of the present invention, the potassium salt of the present invention can be produced with high efficiency.

Claims (4)

A method for producing potassium salt, characterized by comprising 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 following general formula (1) The step of potassium salt, the reaction temperature of this step is 110~200℃;

In the general formula (3), R ² represents corresponding to indene, azulene, biphenyl, phenanthrene, anthracene, fluoranthene, biphenyl, binaphthyl, diphenylcyclohexane, tetraphenylmethane, dinaphthylcyclohexane Alkyl, naphthylphenylcyclohexane, dinaphthyldiphenylmethane, tetranaphthylmethane, triphenylmethane, trinaphthylmethane, 1,1-diphenylindene, 1,1-dinaphthylindene , 1,1-diphenyl acetylene, 1,1-dinaphthyl acetylene, or one or more of the hydrogen atoms bonded to carbon atoms in these aromatic compounds are substituted by substituents or A divalent group, which has a carbon atom constituting an aromatic ring at the bonding site with the oxygen atom shown in the formula; n represents 1 or 2;

In the general formula (4), R ¹ represents a linear or branched alkylene group;

In general formula (1), R ¹ is the same as in general formula (4); R ² and n are the same as in general formula (3); when n is 2, two R ^1s may be the same or different . The method for producing a potassium salt according to claim 1, wherein the potassium salt represented by the general formula (1) is selected from the group consisting of compounds represented by the following formulas (1-5) to (1-20) Either,

In the above general formula, R ¹ and n are the same as those in the general formula (1). A method for producing potassium salt, characterized by comprising a step of reacting p-methoxyphenol, a compound represented by the following general formula (4) with potassium carbonate to produce a potassium salt represented by the following formula, and the reaction of this step The temperature is 110~200℃;

In the general formula (4), R ¹ represents an ethylene group;

A potassium salt represented by the following general formula,

In the formula, R ¹ represents a linear or branched alkylene group.