TW201800401A - Production method for thiocarbonyl compound - Google Patents

Abstract

Provided is a method with which it is possible to produce a high-purity thiocarbonyl compound via an industrially practicable production method by removing a sulfurizing agent-derived byproduct via a simple post-reaction purification method. This production method for a thiocarbonyl compound (B) includes, in the following order: a step (1), in which a carbonyl compound (A), a diphosphetane-disulfide compound (C), and a solvent (X) are heated, yielding a mixture; and a step (2), in which the mixture is alkali-treated with an alkali aqueous solution having a concentration of at most 25 wt%.

Description

Method for producing thiocarbonyl compound

The present invention relates to a method for producing a thiocarbonyl compound.

As a method for producing a thiocarbonyl compound from a carbonyl compound, for example, production of a thiocarbonyl compound using phosphorus pentoxide (P ₄ S ₁₀ ) has been disclosed (Non-Patent Document 1). The use of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphocyclobutane-2,4-disulfide (commonly known as Lawson's reagent. Hereinafter, unless otherwise defined, it is described as Lawson's reagent.) A method for producing a thiocarbonyl compound as a vulcanizing agent (Patent Document 1, and Non-Patent Documents 2, 3).

[Prior technical literature] [Patent Literature]

[Patent Document 1] WO2001 / 046180

[Non-patent literature]

[Non-Patent Document 1] Lecture on New Experimental Chemistry 14 Synthesis and Reaction of Organic Compounds [III] 1817-1821 (1978 Maruzen Co., Ltd.)

[Non-Patent Document 2] J. Am. Chem. Soc. 2015, 137, 9273.

[Non-Patent Document 3] J. Org. Chem. 2002, 67, 6461.

Since the method disclosed in Non-Patent Document 1 uses hydrogen sulfide or sulfur dioxide as a vulcanizing agent, implementation on an industrial scale may cause various problems. On the other hand, when phosphorous pentasulfide is used in the vulcanizing agent system, although phosphorus pentasulfide is solid, it is highly hygroscopic. It decomposes during moisture absorption to generate hydrogen sulfide. Many by-products are generated, which requires purification work. .

As disclosed in Patent Document 1 and Non-Patent Documents 2 and 3, when using Lawson's reagent as a vulcanizing agent, there is no problem as when using the aforementioned vulcanizing agent, and it has been widely used in recent years as a very excellent vulcanizing agent. However, Lawson's reagent must produce thiophosphone compounds after the reaction. Therefore, in order to take out the target compound with high purity, it is generally necessary to supply it to column chromatography in a purification step, and it is difficult to implement it on an industrial scale. In particular, Non-Patent Document 3 clearly describes the problems caused by the use of Lawson's reagent.

As a result of examining the manufacturing method capable of solving the above-mentioned problems, the inventors discovered that a high-purity thiocarbonyl compound can be obtained by using a diphosphocyclobutane disulfide containing a Lawson reagent as a vulcanizing agent.

That is, the present invention provides the following [1] to [6].

(式(I-1)中，A表示-C-、-O-、-S-、或-NR₁-之任一者，R₁表示氫原子或碳數1~10之烷基。)

(化合物(C)中，R₂及R₃係各自獨立表示氫原子、羥基、鹵素原子、碳數1~6之烷基、碳數1~6之烷氧基、碳數1~6之烷硫基、或-O-Ar，Ar表示碳數6~10之芳基，A₁及A₂係各自獨立表示碳數1~6之烷基、鹵素原子，n₁及n₂係各自獨立表示0~4之整數。)

(式(I-3)中，A與(I-1)中相同。) [1] A method for producing a compound (B) containing a structural unit (I-3), which sequentially includes: heating a compound (A) containing a structural unit (I-1), a compound (C), and a solvent (X ) And step (1) of obtaining the mixture, and step (2) of subjecting the obtained mixture to alkali treatment using an aqueous alkali solution having a concentration of 25% by weight or less.

(In formula (I-1), A represents any of -C-, -O-, -S-, or -NR _1- , and R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

(In compound (C), R ₂ and R ₃ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkane having 1 to 6 carbon atoms. Sulfur, or -O-Ar, Ar represents an aryl group having 6 to 10 carbon atoms, A ₁ and A ₂ each independently represent an alkyl group or halogen atom having 1 to 6 carbon atoms, and n ₁ and n ₂ each independently represent An integer from 0 to 4.)

(In formula (I-3), A is the same as in (I-1).)

[2] The production method according to [1], which uses an alkaline aqueous solution having a concentration of 10 to 25% by weight to perform alkali treatment.

[3] The manufacturing method according to [1] or [2], wherein the alkali is sodium hydroxide, potassium hydroxide, or a mixture thereof.

[4] The production method according to any one of [1] to [3], wherein the alkali treatment is performed at 60 ° C or higher and 90 ° C or lower.

[5] The method according to any one of [1] to [4], wherein the solvent (X) is a hydrocarbon solvent.

[6] The manufacturing method according to any one of [1] to [5], which is performed while mixing and heating.

According to the present invention, it is possible to obtain a high-purity sulfur carbonyl compound by a simple and convenient purification method after the reaction by removing byproducts derived from the sulfurizing agent.

Hereinafter, the present invention will be described in detail.

The present invention sequentially includes: heating the compound (A), the compound (C), and the solvent (X) containing the structural unit (I-1), preferably, step (1) of mixing and simultaneously heating to obtain a mixture, And right The obtained mixture is subjected to step (2) of alkali treatment. Hereinafter, step (1) will be described in detail.

The compound (A) used in step (1) includes a structural unit represented by the following formula (I-1).

In Formula (I-1), A represents any of -C-, -O-, -S-, or -NR _1- , and R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. From the viewpoint of reducing side reactions to -C -, - O-, or -NR ₁ - preferably, in particular based -O -, - NR ₁ - is good good. R ₁ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

The compound (A) is preferably a compound represented by the following formula (I-2).

In the formula (I-2), M ₁ and M ₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an alkoxy group, an aromatic hydrocarbon group, or a heterocyclic group, and may be a combination of these. The structure may have a substituent, and M ₁ and M ₂ may be connected to form a cyclic structure. When M ₁ and M ₂ have at least one methylene group, the methylene group may also be -O-, -S-, -CO-, -CS-, -COO-, CONR _4- , and -NR ₅ CO -Replaced by any one of them. Here, R ₄ and R ₅ each independently represent an alkyl group having 1 to 10 carbon atoms, and may be connected to M ₁ and M ₂ to form a cyclic structure. When M ₁ and M ₂ have a ring structure, the ring structure may be a constricted ring structure. A represents the same meaning as A in formula (I-1).

The carbon number of M ₁ and M ₂ is not particularly limited, and the carbon number is preferably 0 to 50, more preferably 1 to 40, more preferably 2 to 30, and most preferably 3 to 20. When the number of carbons of M ₁ and M ₂ is within the above range, the solubility to the solvent (X) described later is good, and the reactivity with the compound (C) is good, so it is preferable.

Specific examples of the aliphatic hydrocarbon group include methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, and 1-butenyl. , 2-butenyl and the like.

Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a tolyl group, a stubyl group, and a mesityl group.

The heterocyclic group refers to a group in which a heterocyclic structure is connected to a structural unit represented by formula (I-1) through a linking group. Specific examples of the heterocyclic structure include a pyrrolidine ring, a pyrroline ring, a pyrrole ring, a piperidine ring, a piperazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrazine ring, and a triazine ring. Oxolane ring, oxane ring, oxane ring, dioxane ring, furan ring, thiolane ring, thiophene ring, oxazole ring, thiazole ring, morpholine ring, indene An indole ring, a benzimidazole ring, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, a carbazole ring, a porphyrin ring, and the like.

Examples of structures in which M ₁ and M ₂ are combined with any of an aliphatic hydrocarbon group, an alkoxy group, an aromatic hydrocarbon group, or a heterocyclic group include the following structures.

(＊表示結合處。)

(* Indicates a junction.)

Specific examples of the substituent which M ₁ and M ₂ may have include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a sulfhydryl group, a sulfonic acid group, an acryl group, a vinyl group, an amine group, an azo group, and a methyl group.醯 基 et al.

M ₁ and M _{2 are} preferably any of an aliphatic hydrocarbon group, an alkoxy group, an aromatic hydroxyl group, and a heterocyclic group, and more preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. . Further, as the substituents M ₁ and M ₂ have, a halogen atom, a mercapto group, and an amine group are preferred. This is due to the viewpoint that the side reactions in step (1) are small, and the compound (B) containing the structural unit (I-3) obtained in step (1) is included in the structural unit ( I-3) The compound (B) is preferred from the viewpoint of alkali resistance.

Examples of the compound (A) include the following compounds.

In the step (1), the compound (C) is used as a vulcanizing agent for the compound (A). The compound (C) is represented by the following formula (II). The compound (C) is a diphosphocyclobutane disulfide compound such as a Lawson's reagent.

In the compound (C), R ₂ and R ₃ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl sulfur having 1 to 6 carbon atoms. Or -O-Ar, Ar represents an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include phenyl (hereinafter abbreviated as Ph), tolyl, stubyl, naphthyl, and the like. R ₂ and R ₃ may be appropriately selected according to the solubility of the compound (C) in the solvent (X) used in the reaction, but from the viewpoint of production of the compound (C), R ₂ and R _{3 have} the same structure. It is preferably a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or -O-Ph, and a methoxy group is most preferred.

A ₁ and A ₂ each independently represent an alkyl group having 1 to 6 carbon atoms or a halogen atom, and n ₁ and n ₂ each independently represent an integer of 0 to 4. A ₁ and A ₂ may be appropriately selected according to the solubility of the compound (C) in the solvent (X) used in the reaction, but from the viewpoint of production of the compound (C), A ₁ and A _{2 have} the same structure. It is preferably a hydrogen atom or a halogen atom, and n ₁ = n ₂ = 0 or 1 is more preferable.

Examples of the compound (C) include the following compounds.

The method for producing the compound (C) can be produced from phosphorus pentoxide and a benzene derivative. A method for producing Lawson's reagent is described in, for example, a non-patent literature (Organic Syntheses, Coll. Vol. 7, P372, 1990). Specifically, Lawson's reagent can be produced by refluxing the phosphorus pentoxide in anisole, cooling it, and filtering the precipitated crystals.

The amount of the compound (C) used in step (1) is 1 mole relative to the compound (A) used, usually 0.50 × Z ~ 5.0 × Z mole, and 0.50 × Z ~ 2.0 × Z mole as The range is preferably 0.50 × Z to 1.0 × Z mole. Here, Z represents the number of carbonyl groups that the compound (A) has in one molecule. If the amount of compound (C) used is within the above range, It is preferable from a viewpoint of suppressing the side reaction by compound (C), and the ease of a purification process. The compounds (C) may be used individually or in a plural form.

As long as the solvent (X) used in step (1) is not compatible with the compound (A) and compound (C) used, and the compound (B) produced by the reaction and the by-product caused by the compound (C) There is no particular limitation on who reacts.

Specific examples of the solvent (X) include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; aromatic hydrocarbon solvents such as benzene, toluene, stub, and mesitylene; and anisole (anisole), benzyl sulfide (thioanisole) and other aromatic solvents with heteroatoms in the molecule; aromatic heterocyclic solvents such as pyridine and pyrazine; diethyl ether, tetrahydrofuran, dimethoxyethane Ether solvents such as 1,4-dioxane; and chlorinated hydrocarbon solvents such as dichloromethane, chloroform, chlorobenzene, bromobenzene, etc. From the viewpoints of the solubility of the compound (A) and the compound (C) and the operability during the alkali treatment in the step (2) described later, toluene, stubble, mesitylene, and chlorobenzene are preferred. The solvent (X) can be used in combination of plural solvents.

The temperature for implementing step (1) is preferably in the range of 30 ° C to 160 ° C, more preferably in the range of 50 ° C to 130 ° C, and most preferably 60 to 120 ° C. If the temperature at which the step (1) is carried out is within the above range, it is preferable from the viewpoints of the solubility of the compound (A) and the compound (C) and suppression of side reactions.

The pressure in the reaction vessel in which step (1) is performed is usually atmospheric pressure. However, from the viewpoint of the solubility of compound (A) or compound (C) When using a solvent having a boiling point of 80 ° C. or lower as the solvent (X), it may be performed under pressure. The pressure in the reaction vessel at this time is usually in the range of 2 kPa to 1 MPa.

In step (1), a compound (B) containing a structural unit represented by the following formula (I-3) can be obtained by reacting the compound (A) with the compound (C). A in the formula (I-3) represents the same meaning as A in the formula (I-1).

When the compound (A) is a compound represented by the formula (I-2), the compound (B) obtained in step (1) is a compound represented by the following formula (I-4). A, M ₁ and M _{2 in the} formula (I-4) have the same meanings as A, M ₁ and M ₂ in the formula (I-2).

Examples of the compound (B) include the following compounds.

The present invention includes a step (2) of subjecting the obtained mixture to an alkali treatment. Hereinafter, step (2) will be described. In step (1), the compound (C) is converted into a compound represented by the following formula (III-1) and formula (III-2). R ₂ , R ₃ , A ₁ , A ₂ , n ₁ and n _{2 in} formula (III-1) and formula (III-2) have the same meanings as in formula (II), respectively.

Compounds represented by formula (III-1) and formula (III-2) General system is oxidizing. For example, in the case where the compound (B) obtained in step (1) is successively provided to the reaction, if the compounds represented by formula (III-1) and formula (III-2) are mixed into compound (B), there will be a formula The compounds represented by (III-1) and formula (III-2) cause anxiety about side reactions. In particular, in the oxidation reaction, it is considered that the compounds represented by the formula (III-1) and the formula (III-2) react with the oxidizing agent to cause a reaction that hinders the purpose. Therefore, it is preferable to isolate the compound (B) from the compound represented by the formula (III-1) and the formula (III-2).

Step (2) included in the present invention is to convert the compounds represented by formula (III-1) and formula (III-2) into compounds represented by the following formula (IV-1) and formula (IV-2), In addition, it can be easily removed as a water-soluble compound. R ₂ , R ₃ , A ₁ , A ₂ , n ₁ , and n _{2 in the} formula (IV-1) and the formula (IV-2) have the same meanings as in the formula (II).

The alkali treatment performed in step (2) means that the compounds represented by formula (III-1) and formula (III-2) are converted into compounds represented by formula (IV-1) and formula (IV-2) using a basic compound. Represented compounds.

The basic compound used in the alkali treatment may be a base of an organic compound (hereinafter referred to as an organic base), or a base of an inorganic compound (hereinafter referred to as an inorganic base). Specific examples of the organic base include triethylamine, pyridine, piperidine, imidazole, ethylenediamine, N, N-dimethyl-4-aminopyridine, 1,8-diazine bicyclic [5.4 .0] -7-undecene, 1,5-diazepine Ring [4.3.0] -5-nonene, 1,4-diazinebicyclo [2.2.2] octane, etc. Specific examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, and barium hydroxide. The basic compound used is preferably an inorganic base, and more preferably sodium hydroxide or potassium hydroxide. It is preferable from the viewpoint of not reacting with the compound (B) obtained in step (1), and from the viewpoint of economy. The basic compounds can be used individually or in combination.

When the basic compound used is an inorganic base, an inorganic base can be used directly, but it is preferable to use an aqueous solution with a predetermined concentration. When an inorganic base is used as an aqueous solution, the compounds represented by the formula (IV-1) and the formula (IV-2) produced by the alkali treatment can be extracted in the aqueous solution, and it is easy to obtain the compound obtained in step (1). Compound (B) is preferably isolated.

When an alkaline compound is used as an inorganic alkali aqueous solution of a predetermined concentration, the concentration of the inorganic alkali is preferably in a range of 10 to 25% by weight, more preferably in a range of 15 to 23% by weight, and in a range of 18 to 22% by weight. For the best. When the concentration of the inorganic base is within the range, the compounds represented by the formulae (III-1) and (III-2) can be efficiently converted into those represented by the formulae (IV-1) and (IV-2). It is preferred that the compound is a compound which prevents deterioration of material properties. The substance referred to herein means a liquid composition composed of the compound (A), the compound (B), the compound (C), the solvent (X), and the basic compound obtained in the step (1). Deterioration of material properties means that, for example, the compounds represented by formula (III-1) and formula (III-2) and / or formula (IV-1) and formula (IV-2) become a blocky, highly viscous state, and become Non-uniform nature.

As the basic compound, an inorganic alkaline aqueous solution having a predetermined concentration is used, and the compound (B) obtained in step (1) is separated from the compound represented by formula (IV-1) and formula (IV-2) by a liquid separation operation. In some cases, in order to improve the liquid separation property, a liquid separation improver may be used. Liquid-separating improver refers to a compound that has a small specific gravity difference between the organic layer and the water layer during the liquid-separating operation, or eliminates the emulsion or precipitation effect of low-solubility components or amphiphilic components when mixed. Specific examples of the liquid-separation improver include inorganic chlorine compounds such as lithium chloride, sodium chloride, potassium chloride, calcium chloride, and barium chloride; methanol, ethanol, 2-propanol, tetrahydrofuran, 1 , 4-dioxane, acetonitrile, acetone, 2-butanone and other amphiphilic solvents. These liquid-separating improvers are used in combination in plural.

In the case where the compound (B) obtained in step (1) is precipitated as a crystal, a solvent may be added in order to dissolve the compound (B). Examples of solvents that can be used at this time include the solvents (X) as described above, and examples thereof include methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, Alcohol solvents such as propylene glycol, ethylene glycol monomethyl ether, and diacetone alcohol; ketone solvents such as acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ethyl acetate, butyl acetate Ester solvents such as esters, propylene glycol monomethyl ether, ethyl lactate, γ-butyrolactone; N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methyl Aprotic polar solvents such as 2-pyrrolidone and dimethylarsin. These solvents may be used in combination.

The amount of the basic compound used in the alkali treatment is 1 mole per mole of the compound (C) used in step (1), usually 2.0 / E ~ 20 / E mole, and 2.2 / E ~ 10 / E mole. More preferably, 2.5 / E ~ 5 / E moles are preferred. Here, E represents the valence of a basic compound. If the amount of the basic compound is within this range, the total amount of the compounds represented by formula (III-1) and formula (III-2) can be converted into formula (IV-1) and formula (IV) stoichiometrically. -2) is preferred. In addition, in the case where an inorganic alkaline aqueous solution is used as the basic compound, if the amount of the basic compound is within the above range, the compounds represented by the formulae (IV-1) and (IV-2) can be efficiently extracted to This aqueous solution is preferred.

When an inorganic alkaline aqueous solution is used as the basic compound, the pH of the aqueous solution is preferably in the range of 12.0 to 13.9, and more preferably in the range of 13.0 to 13.9. If the pH of the aqueous solution is within the above range, the compounds represented by the formula (III-1) and the formula (III-2) can be efficiently converted into the compounds represented by the formula (IV), so it is preferable.

The temperature at which the alkali treatment is performed is usually in the range of 40 to 90 ° C, preferably 50 to 85 ° C, and more preferably 60 to 83 ° C. If the temperature is within this temperature range, the compound represented by the formula (III) can be efficiently converted into the compounds represented by the formula (IV-1) and the formula (IV-2), so it is preferable.

[Example]

Hereinafter, the present invention will be described in more detail based on examples. "%" And "part" in the example are weight% and weight part unless it is specifically defined.

(Example 1)

A 300 mL four-necked flask equipped with a stirrer, a Dairy condenser, and a thermometer was used as a nitrogen environment, and 10 g of Compound 1 powder synthesized by reference patent document (Japanese Patent Application Laid-Open No. 2011-207765) and Lawson reagent (Tokyo Kasei) 6.46 g (manufactured by Industrial Co., Ltd.) and 111 g of toluene, and stirring was started at room temperature. The oil bath was heated to an internal temperature of 110 ° C, and the temperature was maintained at the internal temperature of 110 ° C for 2 hours. After the reaction was completed, the internal temperature was cooled to 80 ° C., and 40 g of a 20% caustic soda aqueous solution was dropped into the system using a dropping funnel for more than 30 minutes, and then kept at an internal temperature of 80 ° C. for more than 12 hours.

In addition, a 500-mL detachable flask with a jacket with a two-way stopcock was prepared in the lower part, and a stirrer, a Daiichi condenser, and a thermometer were set. A 60 ° C heat medium was circulated in the jacket using a constant temperature circulation device, and the internal temperature was adjusted to 60 ° C. The liquid separation solution was transferred to the separable flask, and the lower liquid separation layer (aqueous layer) was removed by a lower two-way stopcock at an internal temperature of 60 ° C. 50 g of pure water was added to the remaining toluene container, and the mixture was stirred at an internal temperature of 60 ° C for 30 minutes. Thereafter, the lower layer (aqueous layer) was removed by standing. Separation washing with pure water was performed a total of 3 times until the drainage pH became <9. The organic layer after liquid separation was concentrated under reduced pressure, the concentration of Compound 2 was adjusted to 25%, and cooled to 25 ° C. The precipitated crystals were filtered using a Buchner funnel, and the obtained wet crystals were washed with 10 g of methanol, and then dried at 60 ° C. using a reduced-pressure dryer to obtain 9.44 g of dried crystals of Compound 2. The yield was 90%.

Using ICP luminescence analyzer ICPS-7510 ((share) island (Manufactured by Tsu Seisakusho), and the amount of residual phosphorus in the dried crystals of Compound 2 obtained was quantified, and the result was 5 ppm.

(Example 2)

A nitrogen atmosphere was placed in a 300 mL four-necked flask equipped with a stirrer, a Dairy condenser, and a thermometer, and 10 g of p-benzanisidide (manufactured by Tokyo Chemical Industry Co., Ltd.) and Lawson's reagent ( 9.25 g of Tokyo Chemical Industry Co., Ltd. and 111 g of toluene, and stirring was started at room temperature. It was heated to an internal temperature of 110 ° C using an oil bath, and the temperature was maintained at the internal temperature of 110 ° C for 2 hours. After the reaction was completed, the internal temperature was cooled to 80 ° C., and 57 g of a 20% caustic soda aqueous solution was dropped into the system using a dropping funnel for 30 minutes or more, and then kept at an internal temperature of 80 ° C. for more than 12 hours.

In addition, a 500-mL detachable flask with a jacket with a two-way stopcock was prepared in the lower part, and a stirrer, a Daiichi condenser, and a thermometer were set. A 60 ° C heat medium was circulated in the jacket using a constant temperature circulation device, and the internal temperature was adjusted to 60 ° C. The liquid separation solution was transferred to the separable flask, and the lower liquid separation layer (aqueous layer) was removed by a lower two-way stopcock at an internal temperature of 60 ° C. 50 g of pure water was added to the remaining toluene container, and the mixture was stirred at an internal temperature of 60 ° C for 30 minutes. Thereafter, the lower layer (aqueous layer) was removed by standing. Separation washing with pure water was performed a total of 3 times until the drainage pH became <9. The organic layer after liquid separation was concentrated under reduced pressure, the concentration of Compound 3 was adjusted to 25%, and cooled to 25 ° C. Make The precipitated crystals were filtered through a Buchner funnel, and the wet crystals obtained were washed with 10 g of methanol, and then dried at 60 ° C. using a reduced-pressure dryer to obtain 8.89 g of dried crystals of Compound 3. The yield was 83%.

The amount of residual phosphorus in the dry crystal of the obtained compound 3 was quantified using an ICP emission analysis device ICPS-7510 (manufactured by Shimadzu Corporation), and the result was 8 ppm.

(Example 3)

All operations were performed in the same manner as in Example 1 except that the internal temperature was maintained at 70 ° C. after being held in a 20% caustic soda aqueous solution for more than 12 hours after the reaction. The amount of residual phosphorus in the dried crystal of Compound 2 obtained was quantitatively measured using an ICP emission analysis device ICPS-7510 (manufactured by Shimadzu Corporation), and the result was 88 ppm.

(Example 4)

All operations were performed in the same manner as in Example 1 except that the internal temperature was maintained at 60 ° C. after being held in a 20% caustic soda aqueous solution for more than 12 hours after the reaction. The amount of residual phosphorus in the dry crystal of the obtained compound 2 was quantified using an ICP emission analysis device ICPS-7510 (manufactured by Shimadzu Corporation), and the result was 1300 ppm.

(Example 5)

All operations were performed in the same manner as in Example 1 except that the caustic soda aqueous solution used after the reaction was changed to 100 g of an 8% aqueous solution. use The ICP emission analysis device ICPS-7510 (manufactured by Shimadzu Corporation) quantified the amount of residual phosphorus in the dry crystal of Compound 2 obtained, and the result was 2900 ppm.

(Comparative example 1)

When the caustic soda aqueous solution used after the reaction was changed to 27 g of a 30% aqueous solution, brown insoluble matter was generated during dropping, and it became difficult to stir uniformly.

Claims (6)

A manufacturing method of a compound (B) containing a structural unit (I-3), which comprises sequentially: heating and obtaining the compound (A), a compound (C), and a solvent (X) containing a structural unit (I-1) Step (1) of the mixture, and step (2) of subjecting the obtained mixture to alkali treatment using an aqueous alkali solution having a concentration of 25% by weight or less;

In formula (I-1), A represents any one of -C-, -O-, -S-, or -NR _1- , and R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

In the compound (C), R ₂ and R ₃ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl sulfur having 1 to 6 carbon atoms. Or -O-Ar, Ar represents an aryl group having 6 to 10 carbon atoms, A ₁ and A ₂ each independently represent an alkyl group having 1 to 6 carbon atoms, a halogen atom, and n ₁ and n ₂ each independently represent 0 An integer of ~ 4;

In formula (I-3), A is the same as that in (I-1). The manufacturing method according to claim 1, wherein the alkali treatment is performed using an alkali aqueous solution having a concentration of 10 to 25% by weight. The method of claim 1 or 2, wherein the alkali is sodium hydroxide, potassium hydroxide, or a mixture thereof. The manufacturing method according to any one of claims 1 to 3, wherein the alkali treatment is performed at 60 ° C to 90 ° C. The manufacturing method according to any one of claims 1 to 4, wherein the solvent (X) is a hydrocarbon solvent. The manufacturing method according to any one of claims 1 to 5, which involves mixing and heating at the same time.