JP2010070478A - Method for producing benzodithiol compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a benzodithiol compound easily in high yield, using inexpensive materials, which is useful as one of various functional materials including organic electronic materials, ultraviolet light absorbers, coloring materials and optical materials and as an intermediate for synthesizing these functional materials. <P>SOLUTION: The method for producing a compound of general formula (IV) includes conducting a reaction between a compound of general formula (III) and an oxidizing agent in the presence of water at 1 eq. or more based on the compound of general formula (III). In general formulas (III) and (IV), R<SP>1</SP>and R<SP>2</SP>are each independently H, alkyl, aryl or a heterocyclic group, wherein the R<SP>1</SP>and R<SP>2</SP>may be the same as or different from each other or may be bound to each other to form a ring; R<SP>3</SP>and R<SP>4</SP>are each independently H, alkyl, aryl or a heterocyclic group, wherein the R<SP>3</SP>and R<SP>4</SP>may be the same as or different from each other or may be bound to each other to form a ring. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

A compound having a structure in which a dithiol ring is condensed at the 2- and 3-positions of hydroquinone and further substituted with various substituents at the 2-position of the dithiol ring via an exomethylene group is known. Further, compounds having a structure in which an imino group is substituted on the carbon atom at the 2-position of the dithiol ring are known. These compounds are useful as organic electronic materials such as organic semiconductors and synthetic intermediates thereof. Among these compounds, compounds in which an imino group is substituted on the carbon atom at the 2-position of the dithiol ring are particularly useful as intermediates for the synthesis of tetrathiafulvalene derivatives, and therefore, a search for a simple synthesis method has recently been carried out (for example, non-conversion). (See Patent Document 1).
So far known compounds in which a dialkylimino group is substituted on the carbon atom at the 2-position of the dithiol ring have been synthesized from the corresponding dialkyldithiocarbamic acid and benzoquinone. Dialkyldithiocarbamic acid is used by dissolving in an arbitrary organic solvent, and the reaction has been carried out in a non-aqueous system containing no water (for example, see Patent Document 1 and Non-Patent Documents 1 and 2).
By the way, dialkyldithiocarbamic acid is prepared by reacting dialkylamine and carbon disulfide in alkaline water. Therefore, in the conventional synthesis method, in order to perform the reaction in a non-aqueous system, it was necessary to bother to isolate and use dithiocarbamic acid prepared in a hydrous system.
On the other hand, there is an example in which a reaction between dithiocarbamic acid and benzoquinone is performed in a hydrous system (see, for example, Non-Patent Document 3). However, in this example, only the step of obtaining an intermediate by reacting dialkyldithiocarbamic acid and benzoquinone is carried out in a water-containing system, and after the intermediate is isolated, the next step is carried out in a non-aqueous system. It was not performed, and it had the trouble of isolating the intermediate.

JP 2008-107767 Journal of Organic Chemistry, 2004, 69, 2164 Journal of Chemical Crystallography, 1997, 27, 515 Australian Journal of Chemistry, 1974, 27, 1309

  An object of the present invention is to provide a simple method for producing various functional materials such as organic electronic materials, ultraviolet absorbers, coloring materials and the like and benzodithiol compounds useful as synthetic intermediates thereof.

  As a result of detailed examination of conditions for synthesizing a benzodithiol compound by oxidizing an intermediate obtained from dithiocarbamic acid and benzoquinones, the present inventor has advantageously performed a reaction in the presence of water, which has not been conventionally performed. It has been found that the oxidant can be used as an aqueous solution. Furthermore, it discovered that the target object was obtained by oxidizing without isolating the intermediate body prepared with the water-containing system, and came to complete this invention.

  The object of the present invention has been achieved by the following method.

［一般式(III)中、Ｒ¹及びＲ²は、互いに独立して水素原子、アルキル基、アリール基またはヘテロ環基を表し、Ｒ¹及びＲ²は同一でも異なっていてもよく、互いに結合して環を形成していてもよい。Ｒ³及びＲ⁴は、互いに独立して水素原子、アルキル基、アリール基またはヘテロ環基を表し、Ｒ³及びＲ⁴は同一でも異なっていてもよく、互いに結合して環を形成していてもよい。］

［一般式(IV)中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は、それぞれ一般式(III)におけるＲ¹、Ｒ²、Ｒ³及びＲ⁴と同義である。Ｘは電荷の調整に必要なイオンを表す。ｍは０以上の数を表す。］
＜２＞前記一般式(III)で表される化合物が、下記一般式(I)で表される化合物と下記一般式(II)で表される化合物とを用い、下記一般式(I)で表される化合物に対して５当量以上１００００当量以下の水の存在下で反応を行って製造されたものであることを特徴とする、＜１＞項に記載の方法。

［一般式(I)中、Ｒ¹及びＲ²は、互いに独立して水素原子、アルキル基、アリール基またはヘテロ環基を表し、Ｒ¹及びＲ²は同一でも異なっていてもよく、互いに結合して環を形成していてもよい。Ｍは水素原子、金属原子または塩基の共役酸を表す。ｐは１ないし４の整数を表し、ｑは１ないし４の整数を表す。］

［一般式(II)中、Ｒ³及びＲ⁴は、互いに独立して水素原子、アルキル基、アリール基、ヘテロ環基、ハロゲン原子、アミノ基、アルコキシ基、アルキルチオ基、又はカルバモイル基を表し、Ｒ³及びＲ⁴は同一でも異なっていてもよく、互いに結合して環を形成していてもよい。］
＜３＞アルコール系溶剤の存在下で反応を行うことを特徴とする、＜１＞又は＜２＞項に記載の方法。
＜４＞前記一般式(I)で表される化合物と酸とが共存した状態で反応させることを特徴とする、＜２＞又は＜３＞項に記載の方法。
＜５＞前記の製造された一般式(III)で表される化合物を単離することなく前記酸化剤と反応させることを特徴とする、＜２＞〜＜４＞のいずれか１項に記載の方法。
＜６＞前記酸化剤を水溶液として使用することを特徴とする、＜１＞〜＜５＞のいずれか１項に記載の方法。
＜７＞前記酸化剤がペルオキソ二硫酸塩であることを特徴とする、＜１＞〜＜６＞のいずれか１項に記載の方法。 <1> A compound represented by the following general formula (III) is reacted with an oxidizing agent in the presence of 1 equivalent or more of water with respect to the compound represented by the following general formula (III). The manufacturing method of the compound represented by the following general formula (IV).

[In the general formula (III), R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹ and R ² may be the same or different and are bonded to each other. To form a ring. R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ³ and R ⁴ may be the same or different and are bonded to each other to form a ring. Also good. ]

[In the general formula (IV), R ^1, R ^2, R ³ and R ⁴ are the same meanings as R ^1, R ^2, R ³ and R ⁴ in the general formula (III). X represents an ion required for charge adjustment. m represents a number of 0 or more. ]
<2> The compound represented by the general formula (III) is a compound represented by the following general formula (I) and a compound represented by the following general formula (II). The method according to <1>, wherein the compound is produced by performing a reaction in the presence of 5 to 10,000 equivalents of water with respect to the compound represented.

[In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹ and R ² may be the same or different and are bonded to each other. To form a ring. M represents a hydrogen atom, a metal atom or a base conjugate acid. p represents an integer of 1 to 4, and q represents an integer of 1 to 4. ]

[In general formula (II), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an amino group, an alkoxy group, an alkylthio group, or a carbamoyl group, R ³ and R ⁴ may be the same or different and may be bonded to each other to form a ring. ]
<3> The method according to <1> or <2>, wherein the reaction is performed in the presence of an alcohol solvent.
<4> The method according to <2> or <3>, wherein the reaction is performed in a state where the compound represented by the general formula (I) and an acid coexist.
<5> The compound according to any one of <2> to <4>, wherein the produced compound represented by the general formula (III) is reacted with the oxidizing agent without isolation. the method of.
<6> The method according to any one of <1> to <5>, wherein the oxidizing agent is used as an aqueous solution.
<7> The method according to any one of <1> to <6>, wherein the oxidizing agent is peroxodisulfate.

  According to the method of the present invention, various functional materials such as organic electronic materials, ultraviolet absorbers, coloring materials, optical materials, and benzodithiol compounds useful as synthetic intermediates can be easily collected using inexpensive raw materials. It can be manufactured efficiently.

Hereinafter, the present invention will be described in detail.
The present invention is characterized in that the compound represented by the general formula (III) is reacted with an oxidizing agent in the presence of 1 equivalent or more of water relative to the compound represented by the general formula (III). To do. First, the compound represented by the general formula (III) will be described.

In the general formula (III), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10) (for example, methyl, ethyl, propyl, butyl, isobutyl), An aryl group having 6 to 20 (preferably 6 to 10) carbon atoms (for example, phenyl or naphthyl) or a 4- to 7-membered (preferably 5 to 6-membered) heterocyclic group (for example, pyridyl or morpholino) is represented. R ¹ and R ² may further have a substituent at an arbitrary position.

  Examples of the monovalent substituent (hereinafter sometimes referred to as “substituent in the present invention”) include, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carbon number of 1 to 20 (preferably 1 To 10) linear or branched alkyl groups (for example, methyl, ethyl), aryl groups having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, phenyl, naphthyl), cyano groups, carboxyl groups, 1 to carbon atoms. 20 (preferably 1-10) alkoxycarbonyl group (for example, methoxycarbonyl), C6-C20 (preferably 6-10) aryloxycarbonyl group (for example, phenoxycarbonyl), C1-C20 (preferably 1) To 10) substituted or unsubstituted carbamoyl group (eg carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), carbon 1-20 (preferably 1-10) alkylcarbonyl group (eg acetyl), C6-C20 (preferably 6-10) arylcarbonyl group (eg benzoyl), nitro group, C0-20 (preferably Is a substituted or unsubstituted amino group (for example, amino, dimethylamino, anilino) having 1 to 10 carbon atoms, an acylamino group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, acetamide, ethoxycarbonylamino), 0 carbon atoms -20 (preferably 0-10) sulfonamide group (for example, methanesulfonamide), C2-C20 (preferably 2-10) imide group (for example, succinimide, phthalimide), C1-C20 (preferably 1-10) imino group (for example, benzylideneamino), hydroxy group, carbon number 1-20 (preferably 1 0) an alkoxy group (for example, methoxy), an aryloxy group having 6 to 20 (preferably 6 to 10) carbon atoms (for example, phenoxy), an acyloxy group having 1 to 20 (preferably 1 to 10) carbon atoms (for example, acetoxy) A C 1-20 (preferably 1-10) alkylsulfonyloxy group (eg methanesulfonyloxy), a C6-C20 (preferably 6-10) arylsulfonyloxy group (eg benzenesulfonyloxy), sulfo Group, a substituted or unsubstituted sulfamoyl group having 0 to 20 carbon atoms (preferably 0 to 10 carbon atoms (preferably sulfamoyl, N-phenylsulfamoyl)), an alkylthio group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) ( For example, methylthio), an arylthio group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, phenylthio) An alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methanesulfonyl), an arylsulfonyl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, benzenesulfonyl), and a 4 to 7-membered ring (Preferably a 5- to 6-membered ring) heterocyclic group (for example, pyridyl, morpholino) and the like can be mentioned.

Examples of the divalent substituent include a carbon atom having a divalent substituent bonded thereto, C = CR ₂ , C═O, C═S, C═NR, C═N ⁺ R ₂ , and a sulfur atom having 2 P = O, P = S, P = NR, etc., where S = O in a form in which a valent substituent is bonded, and in a form in which a divalent substituent is bonded to a phosphorus atom (R is a hydrogen atom, a carbon number of 1 to 20 represents a linear or branched alkyl group having 20 (preferably 1 to 10) and an aryl group having 6 to 20 carbon atoms (preferably 6 to 10).
The substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. A substituent may be bonded to each other to form a ring.

R ¹ and R ² may be the same or different. R ¹ and R ² may be bonded to each other to form a ring. Examples of the ring formed including a nitrogen atom to which R ¹ and R ² are bonded include a pyrrolidine ring, a piperidine ring, a perhydroazepine ring, a morpholine ring, and a piperazine ring. These may further have a substituent (for example, a pipecoline ring in which a methyl group is substituted at the 2-position of the piperidine ring).

R ¹ and R ² are preferably an alkyl group or an aryl group. More preferably, it is an alkyl group.
Specifically, R ¹ and R ² are preferably methyl, ethyl, propyl, isopropyl, butyl, benzyl, phenyl, 2-hydroxyethyl, 2-ethylhexyl, and bonded to each other. A pyrrolidine ring, a piperidine ring, and a pipecoline ring. More preferably, from the viewpoint of availability of the compound represented by the general formula (I) described later, a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, a 2-ethylhexyl group, The formed pyrrolidine ring and piperidine ring. More preferred are a methyl group, an ethyl group, a butyl group, a pyrrolidine ring formed by bonding to each other, and a piperidine ring from the viewpoint of easy preparation of the compound represented by the general formula (III). Most preferred are a methyl group and an ethyl group from the viewpoint of easy handling of the compound represented by the general formula (IV). Most preferably, from the viewpoint of solubility of the compound represented by the general formula (III), R ¹ and R ² are both ethyl groups.
When R ¹ and R ² have a substituent, the substituent is preferably a halogen atom, alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, carbamoyl group, alkylcarbonyl group, arylcarbonyl group, amino group, hydroxy group Group, alkoxy group, aryloxy group, sulfo group, cyano group, and heterocyclic ring. More preferably, they are an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group, a hydroxy group, an alkoxy group, and a cyano group from the viewpoint of availability of the compound represented by the general formula (I). More preferable are an alkyl group, an alkoxycarbonyl group, a hydroxy group, and an alkoxy group from the viewpoint of easy preparation of the compound represented by the general formula (I) described later. Most preferably, they are an alkyl group, a hydroxy group, and an alkoxy group from the viewpoint of the solubility of the compound represented by the general formula (III).

In the general formula (III), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10) (for example, methyl, ethyl, propyl, butyl, isobutyl), An aryl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, phenyl or naphthyl), a 4- to 7-membered ring (preferably 5 to 6-membered ring) heterocyclic group (for example, pyridyl or morpholino), a halogen atom, C1-C20 (preferably 0-10) amino group (for example, amino, dimethylamino, arylamino), C1-C20 (preferably 1-10) alkoxy group (for example, methoxy), C1-C1 20 (preferably 1 to 10) alkylthio group (for example, methylthio), C 1-20 (preferably 1 to 10) carbamoyl group (for example, carbamoyl, alkylcarbamoyl) Represent. Of these, a hydrogen atom, an alkyl group, an aryl group, a halogen atom, and an alkoxy group are preferable from the viewpoint of availability of the compound represented by the general formula (II) described later. More preferably, they are a hydrogen atom and an alkyl group from the viewpoint of suppressing side reactions in the reaction. More preferably, it is a hydrogen atom from the viewpoint of the solubility of the compound represented by the general formula (II).

R ³ and R ⁴ may further have a substituent at an arbitrary position. Examples of the substituent include the above-mentioned “substituent in the present invention”.
When R ³ and R ⁴ have a substituent, the substituent is preferably a halogen atom, alkyl group, aryl group, carboxyl group, alkoxycarbonyl group, carbamoyl group, alkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group. Carboxy group, amino group, hydroxy group, alkoxy group, aryloxy group, sulfo group, cyano group and heterocyclic ring. More preferably, they are an alkyl group, an aryl group, an alkoxycarbonyl group, a hydroxy group, an alkoxy group, and a cyano group from the viewpoint of availability of the compound represented by the general formula (II) described later. More preferred are an alkyl group, an aryl group, an alkoxycarbonyl group, and an alkoxy group from the viewpoint of easy preparation of the compound represented by the general formula (II) described later. Most preferably, it is an alkyl group from the viewpoint of the solubility of the compound represented by the general formula (II).

When there are a plurality of substituents, they may be the same or different. R ³ and R ⁴ may be the same or different. R ³ and R ⁴ may be bonded to each other to form a ring. Examples of the ring to be formed include a benzene ring and an imidazoline ring. These may be further substituted with the substituent described above.

  The compound represented by the general formula (III) is more preferably represented by the following general formula (III ′) from the viewpoint of availability of raw materials and solubility.

In the general formula (III ′), R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 5 or less carbon atoms.

  Specific examples of the compound represented by the general formula (III) are shown below, but the present invention is not limited thereto.

  The compound represented by the general formula (III) can be produced using the compound represented by the general formula (I) and the compound represented by the general formula (II). Hereinafter, the compound represented by the general formula (I) and the compound represented by the general formula (II) as raw materials will be described.

In the general formula (I), R ¹ and R ² are the same as R ¹ and R ² in each of the formula (III), and preferred ranges are also the same.
M represents a hydrogen atom, a metal atom or a base conjugate acid. Preferred metal atoms include K, Na, Li, Be, Ca, Mg, Al, Mn, Fe, Ni, Cu, B, Zn, and Te, and more preferably represented by the general formula (I). From the viewpoint of easy handling of the compound, K, Na, Ca, and Al are most preferable, and K and Na are most preferable from the viewpoint of easy preparation of the compound represented by the general formula (I). Examples of the base conjugate acid include ammonium, dimethylammonium, diethylammonium, pyrrolidinium, piperidinium, and pyridinium.
p represents an integer of 1 to 4, q represents an integer of 1 to 4, and p = q.

  The compound represented by the general formula (I) is more preferably represented by the following general formula (I ′) from the viewpoint of availability or ease of preparation.

In the general formula (I ′), R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms. M represents Na or K.

  Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

As the compound represented by the general formula (I), not only commercially available chemicals but also those prepared by an arbitrary method can be used. For example, “Synthesis”, 1996, Vol. 10, p. 1193-1195, in the literature, the experimental section from page 1194, 4th line on the left, “Journal of the Chemical Society Dalton Transactions”, 1992, vol. 9, p. 1477-1484 It is obtained by using the synthesis method described in the experimental section from page 33 on the left, page 1483, 2000, volume 4, pages 605-610, the experimental section from page 15 on the left, page 606. Can be used.
For example, exemplary compound (1-1) can be prepared by adding carbon disulfide and an aqueous sodium hydroxide solution to a methanol solution of dimethylamine hydrochloride to cause a reaction. Illustrative compound (1-39) can be prepared by adding diethylamine to an aqueous solution of potassium hydroxide and carbon disulfide and reacting them. Exemplary compound (1-43) can be prepared by reacting carbon disulfide with piperidine.

  The compound represented by the general formula (I) may be isolated and used, or the compound represented by the general formula (I) is synthesized in the presence of a solvent and is not isolated and may be used as a solution or dispersion. It may be used as it is. It is more preferable to prepare the compound represented by the general formula (I) in the presence of a solvent and use it as a solution, and it is particularly preferable to prepare it using an aqueous solution and use it as an aqueous solution.

In the general formula (II), R ³ and R ⁴ are respectively synonymous with R ³ and R ⁴ in the general formula (III), and preferred ranges are also the same.
The compound represented by the general formula (II) is more preferably represented by the following general formula (II ′) from the viewpoint of availability and solubility.

In the general formula (II ′), R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 5 or less carbon atoms.

  Specific examples of the compound represented by the general formula (II) are shown below, but the present invention is not limited thereto.

  As the compound represented by the general formula (II), not only commercially available chemicals but also those prepared by an arbitrary method can be used. For example, “Organic Synthesis Collective”, Volume 1, page 482, volume 2, page 553, volume 4, page 15, volume 4, page 148, volume 4, page 698, volume 6, page 890, etc. What was prepared using the synthesis method described in 1 can be used. For example, what was prepared by oxidation of hydroquinone can be used for exemplary compound (2-1).

The method for producing the compound represented by the general formula (III) using the compound represented by the general formula (I) and the compound represented by the general formula (II) in the present invention will be described.
The production method of the present invention is characterized in that the reaction is carried out in the presence of water. The compound represented by the general formula (I) generally has a property of being easily dissolved in a polar solvent, and the solubility is improved by containing water. Therefore, the number of solvent types that can be used in combination with the compound represented by the general formula (I) increases, and the operational convenience such as isolation, purification, and handling is improved. In addition, since the compound represented by the general formula (I) is prepared by an aqueous reaction as described above, the compound represented by the general formula (I) can be easily obtained. In order to perform the reaction under anhydrous conditions, it is necessary to isolate and dry the prepared raw material, but in the present invention, the prepared raw material can be subjected to the reaction without the need to isolate and dry.

The amount of water present is 5 equivalents or more and 10,000 equivalents or less with respect to the compound represented by the general formula (I). More preferably, they are 10 equivalents or more and 1000 equivalents or less, More preferably, they are 20 equivalents or more and 1000 equivalents or less. If there is too little water, it may be contained in the solid as hydration water when isolating the compound represented by the general formula (I), and the effect of improving the solubility in the present invention is reduced. Water should just be 5 equivalent or more, and it is preferable to use the quantity which can melt | dissolve or disperse | distribute the compound represented with the said general formula (I). On the other hand, if the amount of water is too large, the compound represented by the general formula (I) or (II) may precipitate and become unable to participate in the reaction, and the effect of the present invention will be impaired.
The mass of water used is preferably 0.1 to 100 times, more preferably 0.2 to 10 times, and even more preferably 0.5 to 5 times the mass of the compound represented by the general formula (I). .

  The molar ratio of the compound represented by the general formula (I) and the compound represented by the general formula (II) is preferably in the range of 3: 1 to 1: 2. When an excessive amount of the compound represented by the general formula (I) or the general formula (II) is used, it is advantageous for promoting the reaction, but a portion not used in the reaction remains, and a side reaction occurs. This is undesirable in terms of progress, purity and adverse effects on the next process. In particular, since the compound represented by the general formula (II) functions as an oxidizing agent, it is desirable to use only a necessary amount in order to suppress side reactions. The molar ratio of the compound represented by the general formula (I) and the compound represented by the general formula (II) is more preferably in the range of 3: 1 to 1: 1.5, and 2: 1 to 1: A range of 1.2 is more preferred, a range of 1.5: 1 to 1: 1.1 is particularly preferred, and a range of 1.2: 1 to 1: 1 is most preferred.

  The order in which the compound represented by the general formula (I) and the compound represented by the general formula (II) are reacted is the same as that in the system containing the compound represented by the general formula (I). Or a compound represented by the general formula (I) may be added to a system containing the compound represented by the general formula (II). Further, both may be added simultaneously so that the abundance ratio between the compound represented by the general formula (I) and the compound represented by the general formula (II) is kept constant. The method of adding the other to the system containing one is preferable in terms of easy operation. More preferred is a method of adding the compound represented by the general formula (II) to a system containing the compound represented by the general formula (I).

The compound represented by the general formula (I) may be used for the reaction alone, but is preferably used by dissolving or dispersing in an arbitrary medium. It is more preferable to use it dissolved or dispersed in water or the above-mentioned organic solvent. More preferably, it is used in a state dissolved or dispersed in a mixed solution of water and an organic solvent. It is particularly preferable to use it in a state dissolved or dispersed in water and a mixed liquid of an organic solvent mixed with water. Most preferably, it is used in a state dissolved in a mixed solution of water and methanol. The mixing ratio of the mixture of water and organic solvent may be any ratio, but the ratio of water: organic solvent is preferably in the range of 50: 1 to 1:50 (the ratio in this case is the volume ratio before mixing). ). From the viewpoint of solubility of the compound represented by the general formula (I), a range of 10: 1 to 1:30 is more preferable, and from a viewpoint of reducing the amount of organic solvent used, a range of 10: 1 to 1:10 is preferable. Further preferred.
The concentration of the compound represented by the general formula (I) when dissolved or dispersed in an arbitrary medium may be any concentration, but the compound represented by the general formula (I): medium Is preferably in the range of 10: 1 to 1:50 (the ratio in this case is defined by the mass ratio). The range of 2: 1 to 1:30 is more preferable from the viewpoint of handling the solution or dispersion, and the range of 2: 1 to 10: 1 is more preferable from the viewpoint of reducing the amount of medium used.

The compound represented by the general formula (II) may be used for the reaction alone, but is preferably used by dissolving or dispersing in any medium. It is more preferable to use it dissolved or dispersed in water or the above-mentioned organic solvent. It is more preferable to use it dissolved or dispersed in an organic solvent mixed with water. It is particularly preferable to use it dissolved or dispersed in methanol, ethanol, isopropanol, acetone, 2-butanone, N, N-dimethylacetamide or N-methylpyrrolidone. Most preferably, it is used by dissolving in methanol.
The concentration when the compound represented by the general formula (II) is dissolved or dispersed in any medium may be any concentration, but the compound represented by the general formula (II): medium Is preferably in the range of 10: 1 to 1:50 (the ratio in this case is defined by the mass ratio). The range of 2: 1 to 1:30 is more preferable from the viewpoint of handling the solution or dispersion, and the range of 2: 1 to 10: 1 is more preferable from the viewpoint of reducing the amount of medium used.

  When reacting the compound represented by the general formula (I) and the compound represented by the general formula (II), such as acceleration of reaction, suppression of side reactions, improvement of selectivity, adjustment of solubility, etc. Additives may be used for the purpose. For example, acids (for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butanoic acid, succinic acid, oxalic acid, tartaric acid, benzoic acid, salicylic acid, phthalic acid, methanesulfonic acid, ethanesulfonic acid, benzene Bronsted acids such as sulfonic acid, p-toluenesulfonic acid, boric acid and phenol, Lewis acids such as aluminum chloride, trimethyl borate, titanium tetrachloride, titanium tetraisopropoxide and zinc chloride), base ( For example, inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium acetate, potassium acetate, potassium carbonate, cesium carbonate, sodium methoxide, potassium t-butoxide, ammonia, triethylamine, diisopropylethylamine, diazabicyclo [2.2. 0] Undesen (DBU), Pyrigi Organic bases such as, etc.), organic substances (eg, N, N-dimethylaminopyridine, proline, triphenylphosphine), inorganic substances (eg, iron, copper, zinc, palladium, gold, silver, sulfur, etc.) And salts such as sodium chloride, sodium sulfate, ammonium sulfate, magnesium sulfate, sodium phosphate, potassium phosphate, iron chloride, iron sulfide, copper chloride, palladium acetate, and metal oxides such as iron oxide and titanium oxide) And others (for example, activated carbon, celite, silica gel, alumina, activated clay, molecular sieves, zeolite, montmorillonite, ion exchange resin, etc.). A plurality of them may be used.

  From the viewpoint of promoting the reaction and suppressing side reactions, the additive is preferably an acid or a base. The reaction for obtaining the compound represented by the general formula (III) from the compound represented by the general formula (I) and the compound represented by the general formula (II) in the present invention is represented by the general formula (I). A mechanism is conceivable in which the compound represented by the general formula (II) is conjugated to the represented compound. Since the conjugate addition reaction is an addition reaction involving a carbonyl group, it is more preferable to add an acid from the viewpoint of activating the carbonyl group. Additives include hydrochloric acid, sulfuric acid, carboxylic acids (eg formic acid, acetic acid, propionic acid, butanoic acid, succinic acid, oxalic acid, tartaric acid, benzoic acid, salicylic acid, phthalic acid) or sulfonic acids (eg methanesulfonic acid, ethanesulfone) Acid, benzenesulfonic acid, and p-toluenesulfonic acid) are more preferable. A carboxylic acid or a sulfonic acid is particularly preferable from the viewpoint of obtaining an appropriate reaction promoting effect, and a carboxylic acid is most preferable. It is even more preferred that acetic acid is the additive.

  The usage-amount of an additive can be arbitrarily set with the objective and effect. It is preferable to add the compound represented by the general formula (I) at a molar ratio of 0.01 to 100 times, more preferably 0.1 to 50 times, and 0.5 to 10 times. More preferably, it is used. The case of using 1 to 5 times is particularly preferable. In addition, when the molecular weight or formula weight of an additive cannot be calculated | required correctly, it can also define by mass ratio. It is preferable to add the compound represented by the general formula (I) at a mass ratio of 0.01 to 100 times, more preferably 0.1 to 50 times, and 0.5 to 10 times. More preferably, it is used.

  The method for using the additive may be present from the beginning of the reaction or may be added during the reaction. Further, it may be present together with the compound represented by the general formula (I) or may be present together with the compound represented by the general formula (II). Preferably, it is a case where it is present together with the compound represented by the general formula (II). More preferably, the compound represented by the general formula (II) and an acid coexist. More preferably, the compound represented by the general formula (II) and a carboxylic acid are allowed to coexist. Particularly preferred is the case where acetic acid is allowed to coexist with the compound represented by the general formula (II).

  Although reaction temperature is suitably selected according to a substrate, Preferably it is -10-80 degreeC, More preferably, it is 0-60 degreeC, More preferably, it is 0-40 degreeC, Most preferably, it is 0-35 degreeC. The temperature may be changed during the mixing and reaction of the compound represented by the general formula (I) and the compound represented by the general formula (II).

While the reaction time is appropriately adjusted depending on the substrate, it is preferably 1 second to 5 hours, more preferably 1 minute to 2 hours, still more preferably 3 minutes to 1 hour, and most preferably 5 minutes to 30 minutes.
In the present invention, the time period from the completion of the mixing of the compound represented by the general formula (I) and the compound represented by the general group (II) to the start of the operation to be performed after the reaction is completed. The reaction time is defined, and the time during which the compound represented by the general formula (I) and the compound represented by the general formula (II) are mixed is not included. In order to suppress reaction runaway and to improve the yield, purity and selectivity by adjusting the mixing speed and temperature, the compound represented by the general formula (I) and the general formula (II) The operation of mixing the compound is desirably performed while controlling the temperature and time. Control of temperature and time depends on the scale at which the reaction is carried out, the size and shape of the container, the stirring efficiency, the cooling and heating efficiency, and the mixing speed also affects the selectivity of the reaction, but it cannot be specified unconditionally. It is preferable to mix in a short time while maintaining the temperature below a certain temperature. The mixing temperature is preferably lower than the above reaction temperature, more preferably −10 to 60 ° C., further preferably −5 to 40 ° C., and particularly preferably 0 to 30 ° C. The mixing time is preferably 1 second to 5 hours, more preferably 1 minute to 3 hours, further preferably 5 minutes to 2 hours, and particularly preferably 10 minutes to 1 hour.

  The compound represented by the general formula (III) may be isolated by removing a solvent or a by-product, or may be used as it is for the next purpose without isolation. In the case of isolation, it may be purified by a combination of distillation, recrystallization, column chromatography, etc., but it is isolated according to the nature of the compound represented by the general formula (III) and the isolation method. If the quality suitable for the purpose is obtained even if only the operation is performed, the purification operation may not be performed. From the viewpoint of simplification of the production process, it is preferable to perform only the isolation operation or to use it as it is without isolation, and more preferable to use it as it is without isolation.

  Next, a method for producing the compound represented by the general formula (IV) by reacting the compound represented by the general formula (III) with an oxidizing agent will be described.

The compound represented by the general formula (IV) will be described.
In the general formula (IV), R ^1, R ^2, R ³ and R ⁴ have the same meaning as R ^1, R ^2, R ³ and R ⁴ in each of the general formula (III). The same applies to the preferred case. And R ^1, R ^2, R ³ and R ⁴ in the general formula (III), R ^1, R ^2, R ³ and R ⁴ in the general formula (IV) may be represent the same thing, the During the reaction of the invention, a functional group conversion reaction (for example, a hydrolysis reaction, a transesterification reaction, an oxidation reaction, etc.) may be subjected to different ones. It is more preferable to represent the same thing.

  X represents an ion necessary for charge adjustment. Typical cations are hydrogen ions, inorganic ammonium ions, organic ammonium ions having 1 to 50 (preferably 1 to 20) carbon atoms (for example, trialkylammonium ions, tetraalkylammonium ions, pyridinium ions, imidazolinium ions, Guanidinium ions), alkali metal ions (eg, sodium ions, potassium ions), and alkaline earth metal ions (eg, calcium ions). On the other hand, the anion may specifically be either an inorganic anion or an organic anion, for example, a halide ion (for example, chloride ion, bromide ion, iodide ion, fluoride ion), carbon number 1 -30 (preferably 1-20) alkyl sulfonate ion (for example, methane sulfonic acid, trifluoromethane sulfonic acid), C6-C30 (preferably 6-20) aryl sulfonate ion (for example, p-toluene) Sulfonate ion, p-chlorobenzenesulfonate ion), aryl disulfonate ion having 6 to 30 carbon atoms (preferably 6 to 10) (for example, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), hydroxide ion, alcohol having 1 to 30 carbon atoms (preferably 1 to 10) Xy ion (for example, methoxy ion, ethoxy ion, t-butoxy ion), aryloxy ion having 6 to 30 carbon atoms (preferably 6 to 20) (for example, phenoxy ion, hydroquinone monoanion, catechol monoanion), carbon number 1 To 30 (preferably 1 to 20) alkyl carboxylate ion (for example, acetate ion, trifluoroacetate ion, tartrate ion), aryl carboxylate ion (for example, benzoate) having 6 to 30 carbon atoms (preferably 6 to 20) Acid ions, salicylate ions), alkyl sulfate ions having 1 to 30 carbon atoms (preferably 1 to 20 carbon atoms) (for example, methyl sulfate ions), sulfate ions, thiocyanate ions, perchlorate ions, tetrafluoroborate ions, and the like. Can be mentioned.

When X is a cation, a hydrogen ion, an inorganic ammonium ion, an organic ammonium ion, or an alkali metal ion is preferable. More preferred are hydrogen ion, organic ammonium ion, and alkali metal ion. More preferred are hydrogen ions and alkali metal ions. Particularly preferred is hydrogen ion.
When X is an anion, a halide ion, an alkyl sulfonate ion, an aryl sulfonate ion, a hydroxide ion, an alkoxy ion, an aryloxy ion, an alkyl carboxylate ion, and an aryl carboxylate ion are preferable. More preferred are halide ions, alkoxy ions, aryloxy ions, alkylcarboxylate ions, and arylcarboxylate ions. More preferred are chloride ion, bromide ion, iodide ion, methoxy ion, ethoxy ion, t-butoxy ion, phenoxy ion, hydroquinone monoanion, acetate ion and benzoate ion. Particularly preferred are chloride ion, methoxy ion, ethoxy ion, hydroquinone monoanion and acetate ion. Most preferred are chloride ion, hydroquinone monoanion, and acetate ion. From the viewpoint of the solubility of the compound represented by the general formula (IV), acetate ion is particularly preferable.
X is more preferably an anion.

  m represents a number of 0 or more required for charge adjustment. Depending on the combination of X and the structure other than X in the compound represented by the general formula (IV), values other than integers such as 1/2 and 2/3 can be taken. The value of m is preferably 0 or 1.

In the compound represented by the general formula (IV), the structure excluding X has an iminium cation as a partial structure. However, the structure represented by the general formula (IV) excluding X is actually positive. Whether it is an ion, an anion, or a net ionic charge depends on the structure of the general formula (IV). Preferably, it is a cation or has no net ionic charge.
In the compound represented by the general formula (IV), when the structure excluding X is a cation, X is the preferred anion described above.
When there is no net ionic charge, an anion may be present in the substituents represented by R ¹ , R ² , R ³ and R ⁴ , and the following general formula (IV-a) It may be a zwitterionic structure in which the phenolic hydroxyl group represented is dissociated.

  The compound represented by the general formula (IV) is more preferably represented by the following general formula (IV ′) or (IV-a ′) from the viewpoint of easy isolation and easy handling.

In the general formulas (IV ′) and (IV-a ′), R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 5 or less carbon atoms. X represents a chloride ion and an acetate ion.

  Specific examples of the compound represented by the general formula (IV) are shown below, but the present invention is not limited thereto.

  A method for producing the compound represented by the general formula (IV) by reacting the compound represented by the general formula (III) with an oxidizing agent in the present invention will be described.

Any oxidizing agent may be used in the present invention. For example, M.M. Examples include oxidants described in Hudlicky, “Oxidations in Organic Chemistry” (ACS Monograph, 1990). Specifically, oxygen (for example, oxygen (O ₂ ; including air), ozone (O ₃ )), peroxide (for example, hydrogen peroxide (H ₂ O ₂ ), sodium peroxide (Na ₂ O ₂₎ ), Potassium peroxide (K ₂ O ₂ ), sodium perborate, sodium peroxodisulfate (Na ₂ S ₂ O ₈ ), potassium peroxodisulfate (K ₂ S ₂ O ₈ ), ammonium peroxodisulfate ((NH ₄ ) ₂ S ₂ O ₈ ), persulfuric acid (H ₂ SO ₅ ), potassium peroxomonosulfate (KHSO ₅ ), Oxone (registered trademark; 2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ ), dioxirane (for example, dimethyldioxirane) ), Organic peracids (eg t-butyl hydroperoxide ( ^t BuCOOH), benzoyl peroxide ((PhCOO) ₂ O), p-nitrobenzoyl peroxide ((p-NO ₂ -C ₆ H ₄ COO) ₂ O), diisopropyl peroxydicarbonate _{^{((i PrOCOO) 2),}} t- butyl peroxy A Tate ^(t BuCOOCOCH _3), t- butyl peroxybenzoate ^(t BuCOOCOPh), bis (trimethylsilyl) peroxide (Me ₃ SiOOSiMe _3)), performic acid (HCOOOH), peracetic acid (CH ₃ COOOH), peracetic trifluoroacetic acid ( CF ₃ COOOH), perbenzoic acid (PhCOOOH), m-chloroperbenzoic acid (m-Cl-C ₆ H ₄ COOOH), p-nitroperbenzoic acid (p-NO ₂ -C ₆ H ₄ COOOH), peroxy Phthalic acid (oC ₆ H ₄ (CO ₂ H) COOOH), permaleic acid (cis-HOOCH = CHCOOOH), perdichloromaleic acid (cis-HOOCCl = CClCOOOH), perpropionic acid (C ₂ H ₅ COOOH), Lauric acid (C ₁₁ H ₂₃ COOOH), perpentafluorobenzoic acid (C ₆ F ₅ COOOH), metal (eg, copper, copper chloride (CuCl), copper oxide (CuO), copper sulfate (CuSO ₄ ), chromic acid Copper (CuCr ₂ O ₄ ), Copper acetate (Cu (OAc) ₂ ), Basic copper carbonate (CuCO ₃ · Cu (OH) ₂ ), Silver, Silver oxide (Ag ₂ O), Silver nitrate (AgNO ₃ ), Carbonic acid Silver (Ag ₂ CO ₃ ), bromide Mercury (HgBr ₂ ), mercury oxide (HgO), mercury acetate (Hg (OAc) ₂ ), mercury trifluoroacetate (HgOCOCF ₃ , Hg (OCOCF ₃ ) ₂ ), aluminum chloride (AlCl ₃ ), thallium nitrate (Tl ( NO ₃ ) ₃ ), thallium monoacetate (TlOAc), thallium triacetate (Tl (OAc) ₃ ), ammonium cerium nitrate ((NH ₄ ) ₂ Ce (NO ₃ ) ₆ ), ammonium cerium sulfate ((NH ₄ ) ₂ Ce ( SO ₄ ) ₄・ 2 (NH ₄ ) ₂ SO ₄ ), lead oxide (PbO ₂ , Pb ₃ O ₄ ), lead acetate (Pb (OAc) ₄ ), lead trifluoroacetate (Pb (OCOCF ₃ ) ₄ ), Dinitrogen trioxide (N ₂ O ₃ ), nitrous acid (HNO ₂ ), alkyl nitrites (eg ethyl nitrite (C ₂ H ₅ ONO), butyl nitrite (C ₄ H ₉ ONO), pentyl nitrite (C ₅ H ₁₁ ONO)), dinitrogen tetroxide (N ₂ O ₄ ), nitric acid (HNO ₃ ), ammonium nitrate (NH ₄ NO ₃ ), lead nitrate (Pb (NO ₃ ) ₂ ), vanadium oxide (V ₂ O ₅ ), Vanadyl acetylacetonate (VO (aca c) ₂ ), bismuth oxide (Bi ₂ O ₃ ), sodium bismuth trioxide (NaBiO ₃ ), dipotassium nitrosodisulfonate (Fremy salt; ON (SO ₃ K) ₂ ), sulfur, sulfuric acid (H ₂ SO ₄ ), Selenium oxide (SeO ₂ ), molybdenum hexafluoride (MoF ₆ ), molybdenum oxychloride (MoOCl ₃ ), molybdenum oxide (MoO ₃ ), chromium oxide (CrO ₃ ), chromium oxide-pyridine complex (Collins reagent; CrO ₃ · 2C ₅ H ₅ N), pyridinium chlorochromate (PCC; C ₅ H ₅ N · HCl · CrO ₃ ), potassium chromate (K ₂ CrO ₄ ), silver chromate (Ag ₂ CrO ₄ ), heavy chromium Potassium (K ₂ Cr ₂ O ₇ ), pyridinium dichromate (PDC; (C ₅ H ₅ N) ₂ Cr ₂ O ₇ ), chromyl chloride (Cr ₂ O ₂ Cl ₂ ), t-butyl chromate (( ^t BuO) ₂ CrO _4), chromium acetate _{((AcO) 2 CrO 4)} , chlorine, sodium hypochlorite (NaOCl), potassium hypochlorite (KOCl), hypochlorite Cal Um (Ca (OCl) _2), hypochlorous acid t- butyl ^(t BuOCl), sodium chlorite (NaClO _2), potassium chlorite (KClO _2), sodium chlorate (NaClO _3), potassium chlorate (KClO ₃ ), silver chlorate (AgClO ₃ ), barium chlorate (Ba (ClO ₃ ) ₂ ), N-chlorosuccinimide (NCS), 1,3-dichloro-5,5-dimethylhydantoin, isocyanuric chloride, Sodium N-chloro-p-toluenesulfonamide (Chloramine-T), bromine, sodium hypobromite (NaOBr), potassium hypobromite (KOBr), sodium bromite (NaBrO ₂ ), potassium bromite ( KBrO ₂ ), sodium bromate (NaBrO ₃ ), potassium bromate (KBrO ₃ ), N-bromosuccinimide (NBS), 1,3-dibromo-5,5-dimethylhydantoin, N-bromoacetamide (CH ₃ CONHBr), pyridinium bromide perbromide (C ₅ H ₅ NHBr ₃ ), iodine, hypochlorous Sodium iodate (NaOI), potassium hypoiodite (KOI), sodium iodate (NaIO ₃ ), periodic acid (HIO ₄ ), orthoperiodic acid (H ₅ IO ₆ ), sodium periodate (NaIO ₄ ), Potassium periodate (KIO ₅ ), tetrabutylammonium periodate ((C ₄ H ₉ ) ₄ NIO ₄ ), iodosobenzene (PhIO), iodobenzene diacetate (PhI (OAc) ₂ ), iodoxy Benzene (PhIO ₂ ), manganese sulfate (Mn ₂ (SO ₄ ) ₃ ), manganese acetate (Mn (OAc) ₃ ), manganese dioxide (MnO ₂ ), potassium manganate (K ₂ MnO ₄ ), potassium permanganate ( KMnO ₄ ), copper permanganate (Co (MnO ₄ ) ₂ ), magnesium permanganate (Mg (MnO ₄ ) ₂ ), zinc permanganate (Zn (MnO ₄ ) ₂ ), iron chloride (FeCl ₃ ), Iron sulfate (Fe ₂ (SO ₄ ) ₃ ), potassium ferrate (K ₂ FeO ₄ ), Raney nickel, ruthenium tetroxide (RuO ₄₎ ), Osmium tetroxide (OsO ₄ ), hexamine (C ₆ H ₁₂ N ₄ ), chloral (CCl ₃ CHO), chloranil (C ₆ Cl ₄ O ₂ ), 2,3-dichloro-5,6-dicyano-p -Benzoquinone (DDQ), diethyl azodicarboxylate (EtOOCN = NCOOEt), nitrosobenzene (PhNO), 2-nitropropane (CH ₃ CHNO ₂ CH ₃ ), trimethylamine oxide (Me ₃ NO), N-methylmorpholine oxide (O (CH ₂ CH ₂ ) ₂ NMeO), pyridine oxide (C ₅ H ₄ NO), 1-oxo-2,2,6,6-tetramethylpiperidinium chloride, triphenylphosphine oxide, dimethyl sulfoxide, phenyl Examples include selenyl chloride. These oxidizing agents may function as oxidizing agents for the compound represented by the general formula (III), or may be co-oxidized to oxidize the true oxidizing agent of the compound represented by the general formula (III). It may function as an agent.

  From the viewpoint of ease of handling and availability of oxidizing agent, silver oxide, cerium ammonium sulfate, lead oxide, lead acetate, dinitrogen tetroxide, sodium dichromate, sodium peroxodisulfate, potassium peroxodisulfate, peroxodisulfate Ammonium sulfate, sodium chlorate, potassium chlorate, ammonium chlorate, sodium chlorite, potassium chlorite, ammonium chlorite, sodium hypochlorite, potassium hypochlorite, ammonium hypochlorite, sodium iodate , Potassium permanganate, iron chloride, iron sulfate, hydrogen peroxide, N-chlorosuccinimide, N-bromosuccinimide, isocyanuric chloride, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo- 5,5-dimethylhydantoin.

  From the standpoint of high selectivity to the target oxidation reaction and preventing unwanted oxidation reaction, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, sodium chlorate, potassium chlorate, ammonium chlorate, Sodium chlorite, potassium chlorite, ammonium chlorite, sodium hypochlorite, potassium hypochlorite, ammonium hypochlorite, sodium iodate, iron chloride, iron sulfate, hydrogen peroxide, N-chlorosucci Acid imide, N-bromosuccinimide, isocyanuric chloride, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin.

  From the viewpoint that the oxidizing agent itself and the treated product after the reaction have less influence on the environment, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, sodium chlorate, potassium chlorate, ammonium chlorate, Sodium chlorate, potassium chlorite, ammonium chlorite, sodium hypochlorite, potassium hypochlorite, ammonium hypochlorite, iron chloride, iron sulfate, hydrogen peroxide, N-chlorosuccinimide, isocyanuric chloride 1,3-dichloro-5,5-dimethylhydantoin.

  Particularly preferred from the viewpoint of easy handling as an aqueous solution are sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, and hydrogen peroxide, and ammonium peroxodisulfate is even more preferred.

  In the reaction of synthesizing the compound represented by the general formula (IV) with the compound represented by the general formula (III) and the oxidizing agent, the oxidizing agent oxidizes two electrons. When the equivalent of the oxidizing agent is expressed with the equivalent of the oxidizing ability of two electrons, the amount of the oxidizing agent used in the present invention is preferably 1 equivalent or more and 10 equivalents or less. From the viewpoint of facilitating the post-treatment of an excess oxidizing agent, it is more preferably 1 to 5 equivalents. From the viewpoint of suppressing unwanted side reactions, it is more preferably 1 to 2 equivalents. From the viewpoint of suppressing further oxidation of the compound represented by the general formula (IV) as a product, the amount is particularly preferably 1 to 1.2 equivalents.

  The order of reacting the compound represented by the general formula (III) and the oxidizing agent may be that the oxidizing agent may be added to the system containing the compound represented by the general formula (III) or the oxidizing agent is included. A compound represented by the general formula (III) may be added to the system. Further, both of them may be added simultaneously so as to keep the abundance ratio of the compound represented by the general formula (III) and the oxidizing agent constant. The method of adding the other to the system containing one is preferable in terms of easy operation. More preferred is a method of adding an oxidizing agent to a system containing the compound represented by the general formula (III).

  The production method of the present invention is characterized in that the reaction is carried out in the presence of water. Since water is present, the oxidizing agent can be used as an aqueous solution, and there are advantages such as the use of an inorganic inexpensive oxidizing agent and the control of the reaction by the selection of the oxidizing agent. In addition, the compound represented by the general formula (III) generally has a property of being easily dissolved in a polar solvent, and the solubility is changed by containing water. The operational convenience is improved. Further, when the compound represented by the general formula (III) is prepared by an aqueous reaction as described above, the compound represented by the general formula (III) can be used as it is without being isolated. Become.

  The amount of water present is 1 equivalent or more with respect to the compound represented by the general formula (III). Below this, the effect of using water together in the present invention is reduced. Water should be 1 equivalent or more, but it is preferable to use an amount that can dissolve or disperse the oxidizing agent to be used. The mass of water to be used is preferably 0.1 to 100 times the mass of the oxidant to be used, more preferably 0.2 to 10 times from the viewpoint of superiority in equipment that can reduce the volume of the entire reaction solution. 5 to 5 times is more preferable.

In this reaction, the compound represented by the general formula (III) may be prepared by any method, but the compound represented by the general formula (I) and the general formula (II) It is preferable to use what was prepared by reacting with the compound represented by). In particular, it is prepared by reacting with the compound represented by the general formula (II) in the presence of 5 equivalents or more and 10,000 equivalents or less of water with respect to the compound represented by the general formula (I). Is more preferable. In addition, it is more preferable that the reaction be carried out in the presence of an alcohol solvent.
The compound represented by the general formula (III) prepared by reacting the compound represented by the general formula (I) and the compound represented by the general formula (II) may be isolated and used. The solution or dispersion may be used as it is without isolation. It is more preferable to synthesize the compound represented by the general formula (III) in the presence of a solvent and use it as a solution or dispersion from the viewpoint of easy operation by omitting the isolation operation and shortening the time required for production. It is particularly preferable to use a solution or dispersion as synthesized by using a solvent containing water.

  This reaction may be performed using only the compound represented by the general formula (III) and the oxidizing agent, but may be performed using any solvent. Even if the solvent is completely dissolved, a part or the whole of the solvent may not be dissolved.

  In this reaction, an organic solvent may be used in combination with water. The organic solvent may be either a polar solvent or a non-polar solvent. In the case of a polar solvent, either a protic solvent or an aprotic solvent may be used. For example, hydrocarbon type (for example, hexane, octane, cyclohexane, toluene, xylene) alcohol type (for example, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol), glycol ether type (for example, ethylene glycol monomethyl ether, ethylene glycol) Monoethyl ether), ketones (eg, acetone, 2-butanone, cyclohexanone), ethers (eg, diethyl ether, diisopropyl ether, cyclopentyl methyl ether, dimethoxyethane), carboxylic acids (eg, acetic acid, propionic acid), Sulfonic acid (for example, methanesulfonic acid), nitrile (for example, acetonitrile, propionitrile, benzonitrile), halogen (for example, dichloromethane) , Chloroform, 1,2-dichloroethane), amide systems (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone), sulfoxide systems (eg, dimethyl sulfoxide), heterocyclic systems (eg, , Tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, sulfolane, pyridine), ester systems (eg, methyl acetate, ethyl acetate, butyl acetate), urea systems (eg, tetramethylurea, 1,3-dimethyl- 2-Imidazolidinone). These solvents can be used alone or in combination of two or more in consideration of the solubility of the compound. When using an organic solvent that is easily mixed with water, the reaction can be carried out in a homogeneous system, and when using an organic solvent that is not mixed with water, the reaction should be carried out in a two-phase system consisting of an aqueous phase and an organic phase. Can do. These can be arbitrarily selected from the viewpoints of the structure and properties of raw materials and products, and reaction control. Moreover, an ionic liquid may be used as a solvent, a fluorous solvent may be used, and a supercritical fluid or a subcritical fluid may be used as a solvent.

  The organic solvent that can be used is preferably an alcohol type, a ketone type, an ether type, an amide type, a heterocyclic type, a hydrocarbon type, or an ester type, and more preferably an alcohol type solvent. Among these, methanol, ethanol, isopropanol, 1-butanol, 2-butanol, acetone, 2-butanone, diisopropyl ether, cyclopentyl methyl ether, N, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, toluene, xylene, ethyl acetate It is. More preferred are methanol, ethanol, isopropanol, acetone, N, N-dimethylacetamide, N-methylpyrrolidone, toluene, xylene and ethyl acetate. From the viewpoint of ease of dissolution of the compound represented by the general formula (I), (II) or (III), methanol, ethanol, acetone, N, N-dimethylacetamide, N-methylpyrrolidone is particularly preferable. is there. Most preferred are methanol, ethanol and isopropanol, with methanol being particularly preferred.

  Most preferably, it is the same as that used when the compound represented by the general formula (III) is synthesized from the compound represented by the general formula (I) and the compound represented by the general formula (II). This is the case with a solvent. More preferably, it is a case where a new solvent is not used by carrying out the reaction for synthesizing the general formula (IV) as it is without isolating the compound represented by the general formula (III).

  The concentration of the compound represented by the general formula (III) when dissolved or dispersed in an arbitrary medium may be any concentration, but the compound represented by the general formula (III): medium Is preferably in the range of 10: 1 to 1:50 (the ratio in this case is defined by the mass ratio). The range of 2: 1 to 1:30 is more preferable from the viewpoint of handling the solution or dispersion, and the range of 2: 1 to 10: 1 is more preferable from the viewpoint of reducing the amount of medium used.

  In the present invention, the oxidizing agent may be used as it is, but it is preferable to use it dissolved or dispersed in an arbitrary medium. Examples of the medium include water and the above organic solvents. The media that can be used is limited by the oxidant used because the medium is oxidized or forms undesirable oxides, but combinable oxidants and media can be used. Among these, use of water is preferable from the viewpoint of solubility of the oxidizing agent.

  The concentration when the oxidant is dissolved or dispersed in an arbitrary medium may be any concentration, but the oxidant: medium ratio is preferably in the range of 10: 1 to 1:50 (in this case Ratio is defined by mass ratio). The range of 2: 1 to 1:30 is more preferable from the viewpoint of handling the solution or dispersion, and the range of 2: 1 to 10: 1 is more preferable from the viewpoint of reducing the amount of medium used.

  When reacting the compound represented by the general formula (III) with an oxidizing agent, an additive may be used for the purpose of accelerating the reaction, suppressing side reactions, improving the selectivity, and adjusting the solubility. good. Examples of the additive include those described above.

  From the viewpoint of promoting the reaction and suppressing side reactions, the additive is preferably an acid or a base. Although the mechanism of the reaction from the compound represented by the general formula (III) in the present invention to the compound represented by the general formula (IV) is not clear, the compound represented by the general formula (III) is oxidized. Thus, a mechanism may be considered in which a benzoquinone intermediate is formed and the resulting compound is represented by the general formula (IV) by the subsequent intramolecular addition reaction. In the reaction in which the compound represented by the general formula (III) is oxidized to form a benzoquinone intermediate, it is preferable to add a base because the basicity is accelerated, and the benzoquinone intermediate is added by intramolecular addition reaction. In the reaction to be the compound represented by the general formula (IV), it is preferable to add an acid from the viewpoint of activating the carbonyl group, and the obtained compound represented by the general formula (IV) is further oxidized. In order to suppress the reaction that becomes a benzoquinone byproduct, it is preferable to add an acid. In addition, the additive corresponds to X in the compound represented by the general formula (IV), so that the reaction can be controlled by utilizing the change in solubility, and the product can be easily isolated and purified. Is also preferable. In order to control these, a plurality of additives may be used in combination, or may be added separately.

  Additives include hydrochloric acid, sulfuric acid, carboxylic acid (eg, formic acid, acetic acid, propionic acid, butanoic acid, succinic acid, oxalic acid, tartaric acid, benzoic acid, salicylic acid, phthalic acid), sulfonic acid (eg, methanesulfonic acid, ethanesulfone) Acid, benzenesulfonic acid, p-toluenesulfonic acid) and a base (for example, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, sodium methoxide) are more preferable. From the viewpoint of suppressing side reactions, hydrochloric acid, carboxylic acid, sulfonic acid, and base are particularly preferable, and from the viewpoint of promoting reaction, carboxylic acid and base are most preferable.

  The usage-amount of an additive can be arbitrarily set with the objective and effect. The case where it is added at a molar ratio of 0.01 to 100 times with respect to the compound represented by the general formula (III) is preferable, the case where it is added at a rate of 0.1 to 50 times is more preferable, and the ratio is 0.5 to 10 times. More preferably, it is used. The case of using 1 to 5 times is particularly preferable. In addition, when the molecular weight or formula weight of an additive cannot be calculated | required correctly, it can also define by mass ratio. It is preferable to add the compound represented by the general formula (III) at a mass ratio of 0.01 to 100 times, more preferably 0.1 to 50 times, and 0.5 to 10 times. More preferably, it is used.

  The method for using the additive may be present from the beginning of the reaction or may be added during the reaction. Further, it may be present together with the compound represented by the general formula (III) or may be present together with an oxidizing agent. Preferably, it is a case where it is added after the mixing of the general formula (III) and the oxidizing agent is completed. More preferably, the acid is added after completion of mixing.

  The reaction temperature is appropriately selected depending on the substrate, but is preferably −10 to 100 ° C., more preferably 0 to 80 ° C. from the viewpoint of easy temperature control, and further preferably 10 to 60 ° C. from the viewpoint of promoting the reaction. Most preferably, it is 20-50 degreeC from a viewpoint of side reaction suppression. The temperature may be changed during the mixing of the compound represented by the general formula (III) and the oxidizing agent and during the reaction.

Although reaction time is suitably adjusted with a substrate, Preferably it is 1 second-24 hours, More preferably, it is 1 minute-10 hours from a viewpoint of manufacturing efficiency improvement, More preferably, 5 minutes-8 hours from the viewpoint of fully progressing reaction From the viewpoint of suppressing side reactions, it is most preferably 10 minutes to 5 hours.
In the present invention, the time from the completion of the mixing of the compound represented by the general formula (III) and the oxidizing agent to the start of the operation performed after the reaction is defined as the reaction time. The time during which the compound represented by III) and the oxidizing agent are mixed is not included in this. In order to suppress reaction runaway and to improve the yield, purity and selectivity by adjusting the mixing speed and temperature, the operation of mixing the compound represented by the general formula (III) with the oxidizing agent is carried out with the temperature and It is desirable to control the time. Control of temperature and time depends on the scale at which the reaction is carried out, the size and shape of the container, the stirring efficiency, the cooling and heating efficiency, and the mixing speed also affects the selectivity of the reaction, but it cannot be specified unconditionally. It is preferable to mix in a short time while maintaining the temperature below a certain temperature. The mixing temperature is preferably lower than the above reaction temperature, more preferably −10 to 60 ° C., further preferably −5 to 40 ° C., and particularly preferably 0 to 30 ° C. from the viewpoint of ease of temperature management. . The mixing time is preferably 1 second to 5 hours, more preferably 1 minute to 3 hours, further preferably 5 minutes to 2 hours, and particularly preferably 10 minutes to 1 hour from the viewpoint of production efficiency.

  The compound represented by the general formula (IV) may be isolated by removing the solvent and by-products, or may be used as it is for the next purpose without isolation. In the case of isolation, it may be purified by a combination of distillation, recrystallization, column chromatography, etc., but it is isolated depending on the nature of the compound represented by the general formula (IV) and the isolation method. If the quality suitable for the purpose is obtained even if only the operation is performed, the purification operation may not be performed. From the viewpoint of simplification of the production process, it is preferable to perform only the isolation operation or to use it as it is without isolation, and more preferable to use it as it is without isolation.

In the present invention, the compound represented by any one of the general formulas (I), (II), (III) or (IV) is an isotope (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O , ¹⁸ O, etc.).

  The compound represented by any one of the general formulas (I), (II), (III) and (IV) in the present invention can take a tautomer depending on the structure and the environment in which it is placed. In the present specification, it is described in one of the representative forms, but tautomers different from those described in the present specification are also used in the general formulas (I), (II), (III) used in the present invention. Or it is contained in the compound represented by either (IV).

  The compound represented by the general formula (II) or (III) in the present invention can be a cation or an anion with an appropriate counter ion depending on the structure and the environment in which the compound is placed. In the present specification, it is described as a representative counter ion. However, a compound having a counter ion other than these is also included in the compound represented by the general formula (II) or (III) used in the present invention. One type of counter ion may be used, or a plurality of types having an arbitrary ratio may be used.

  The compound represented by the general formula (IV) obtained in the present invention is “Journal of Organic Chemistry”, 2004, 69, 2146, “Angewandte Chemie International Edition”, 2003, 42, 2765. , "Organic Letters", 2002, 4, 961, "Tetrahedron Letters", 1977, 2223, JP 2008-107767, JP 2007-304287, etc. It can be induced to various functional materials.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this.

Example 1
<Preparation of Exemplified Compound 4-2>
22.5 g (0.1 mol) of sodium diethyldithiocarbamate (Exemplary Compound 1-2) trihydrate was dissolved in 15 ml of water and 100 ml of methanol. The solution was cooled under a nitrogen stream, and a solution of 10.8 g (0.1 mol) of benzoquinone (Exemplary Compound 2-1) and 5.7 ml (0.1 mol) of acetic acid and 50 ml of methanol was added dropwise while keeping the internal temperature at 20 ° C. or lower. The reaction was allowed to proceed for 30 minutes at room temperature. The reaction solution was analyzed by thin layer chromatography (TLC), and Exemplified Compound 1-2 and Exemplified Compound 2-1 disappeared to produce a new product. This product was analyzed by mass spectrometry from m / z = 257. Therefore, the production of Exemplified Compound 3-2 was identified. A solution of 22.8 g (0.1 mol) of ammonium peroxodisulfate and 50 ml of water was added to this reaction solution while keeping the internal temperature at 25 ° C. or lower. The resulting reaction mixture was reacted at room temperature for 2 hours. The resulting solid was filtered, washed with 20 ml of water and 50 ml of methanol, and dried to obtain 23.8 g of Exemplified Compound 4-2. Yield 93%.
¹³ C NMR (CF ₃ COOD) δ 9.35, 54.33, 116.18, 120.56, 145.73, 187.51.
¹ H NMR (CF ₃ COOD) δ 1.38 (t, 6H), 3.93 (q, 4H), 6.92 (s, 2H), 10.65-10.80 (br, 2H)
MS m / z 256

Examples 2-9
Exemplified Compound 4-2 was prepared by reacting in the same manner as in Example 1 except that the type of the solvent or additive was changed as shown in Table 1 below. In addition, it was identified that the product in each Example was Exemplified Compound 4-2 as in Example 1. Table 1 shows the yield in each example.

Comparative Example 1
As a solvent, 15 ml of water and 100 ml of methanol were used instead of 100 ml of methanol, and 22.8 g (0.1 mol) of ammonium peroxodisulfate remained as a solid instead of a solution of 22.8 g (0.1 mol) of ammonium peroxodisulfate and 50 ml of water. Except having added, it reacted like Example 1 and prepared Exemplified Compound 4-2. In addition, it was identified that the product in Comparative Example 1 was Exemplified Compound 4-2 as in Example 1. The yield in Comparative Example 1 is shown in Table 1.

Comparative Example 2
Exemplified compound 4-2 was prepared in the same manner as in Comparative Example 1 except that the solvent was changed to 100 ml of acetone instead of 100 ml of methanol. The product in Comparative Example 2 was identified as Exemplified Compound 4-2 as in Comparative Example 1. The yield in Comparative Example 2 is shown in Table 1.

As is clear from the results in Table 1, the yield was low under conditions where no water was used (Comparative Examples 1 and 2). This is considered to be because the oxidizing agent was not sufficiently dissolved in the reaction solution. On the other hand, in Examples 1 to 9 where the reaction was performed in the presence of water, the target compound could be prepared in a high yield.
In Examples 1 to 9, the compound represented by the general formula (IV) could be obtained in high yield without isolating the compound represented by the general formula (III).
As a solvent used in combination with Example 1, it was found from the comparison between Example 1 and Example 2 that the yield was high when an alcohol, particularly methanol was used.
As the oxidizing agent, it was found that the yield generally increased when persulfate was used (Examples 1 to 4).

Example 10
<Preparation of Exemplary Compound 4-2 Alternative Method-1>
18.7 g (0.1 mol) of an aqueous solution of potassium diethyldithiocarbamate (Exemplary Compound 1-39) (> 50% aqueous solution; manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 50 ml of methanol were mixed. The mixture was ice-cooled under a nitrogen stream, and a solution of benzoquinone (Exemplary Compound 2-1) 5.4 g (0.05 mol) and acetic acid 9.0 g (0.15 mol) and methanol 50 ml was added dropwise while maintaining the internal temperature at 10 ° C. or lower. After reacting for 30 minutes at an internal temperature of 4 ° C., a solution of 11.4 g (0.05 mol) of ammonium peroxodisulfate and 25 ml of water was added while keeping the internal temperature at 10 ° C. or lower. The resulting reaction mixture was reacted at room temperature for 2 hours. The resulting solid was filtered, washed with 20 ml of water and 50 ml of methanol, and dried to obtain 23.8 g of Exemplified Compound 4-2. Yield 93%

Example 11
<Preparation of Exemplary Compound 4-2 Alternative Method-2>
Hydroquinone 5.5 g (50 mmol) was dissolved in 50 ml of methanol. The solution was cooled under a nitrogen stream, and a solution of ammonium peroxodisulfate 11.4 g (50 mmol) and water 50 ml was added while keeping the internal temperature at 10 ° C. or lower. Acetic acid (25 ml) was added to the resulting reaction mixture, and a solution of sodium diethyldithiocarbamate (Exemplary Compound 1-2) trihydrate (11.3 g, 50 mmol) and water (27.5 ml) was added while maintaining the internal temperature at 10 ° C. or lower. . After stirring for 30 minutes while cooling with ice, 20 ml of methanol was added, and a solution of 11.4 g (50 mmol) of ammonium peroxodisulfate and 50 ml of water was added while keeping the internal temperature at 10 ° C. or lower. The resulting reaction mixture was stirred at room temperature. The parent ion peak corresponding to the exemplary compound 4-2 was confirmed by mass spectrometry of the crude product obtained by filtration.

Example 12
<Preparation of Exemplified Compound 4-8>
2.46 g (10 mmol) of piperidine pentamethylenedithiocarbamate (Exemplary Compound 1-43) was dissolved in 10 ml of methanol. The mixture was ice-cooled under a nitrogen stream, and a solution of 1.08 g (10 mmol) of benzoquinone (Exemplary Compound 2-1) and 0.57 ml (10 mmol) of acetic acid and 10 ml of methanol was added dropwise while keeping the internal temperature at 10 ° C. or lower. After reacting at an internal temperature of 4 ° C. for 15 minutes, a solution of 2.28 g (10 mmol) of ammonium peroxodisulfate and 10 ml of water was added while keeping the internal temperature at 10 ° C. or lower. The resulting reaction mixture was reacted at room temperature for 2 hours. 10 ml of methanol was added, the solid was filtered, washed with 10 ml of water and 10 ml of methanol and dried to obtain 1.85 g of Exemplified Compound 4-8. Yield 69%
1H NMR (CF ₃ COOD) δ 2.10-2.45 (6H), 7.34 (2H).
MS m / z 268

Example 13
<Preparation of Exemplified Compound 4-1>
9.0 g (50 mmol) of sodium dimethyldithiocarbamate (Exemplary Compound 1-1) dihydrate was dissolved in 5.3 ml of water and 50 ml of methanol. The solution was cooled under a nitrogen stream, and a solution of 5.4 g (50 mmol) of benzoquinone (Exemplary Compound 2-1) and 8.58 ml (150 mmol) of acetic acid and 25 ml of methanol was added dropwise while maintaining the internal temperature at 10 ° C. or lower. After reacting for 30 minutes under ice cooling, a solution of ammonium peroxodisulfate (11.4 g, 50 mmol) and water (25 ml) was added while keeping the internal temperature at 10 ° C or lower. The resulting reaction mixture was reacted on a 50 ° C. water bath for 1 hour. The resulting solid was filtered, washed with 50 ml of water and 50 ml of methanol, and dried to obtain 10.4 g of Exemplified Compound 4-1. Yield 91%
¹ H NMR (CF ₃ COOD) δ 3.92 (6H), 7.27 (2H).
MS m / z 228

Example 14
<Preparation of Exemplified Compound 4-21>
2.25 g (10 mmol) of sodium diethyldithiocarbamate (Exemplary Compound 1-2) trihydrate was dissolved in 1 ml of water and 10 ml of methanol. Cool under a nitrogen stream and keep 1.22 g (10 mmol) of 2-methyl-1,4-benzoquinone (Exemplary Compound 2-2) and 1.7 ml (30 mmol) of acetic acid and 5 ml of methanol at an internal temperature of 10 ° C. or lower. While dripping. After reacting for 30 minutes under ice cooling, a solution of 2.28 g (10 mmol) of ammonium peroxodisulfate and 5 ml of water was added while keeping the internal temperature at 10 ° C. or lower. The resulting reaction mixture was reacted at 50 ° C. for 2 hours. The resulting solid was filtered, washed with 10 ml of water and 10 ml of methanol, and dried to obtain 1.74 g of Exemplified Compound 4-21. Yield 76%
¹ H NMR (CF ₃ COOD) δ 3.93 (6H), 7.28 (2H).
MS m / z 228

  Further, other exemplary compounds could be prepared by reacting in the same manner. Specifically, preparation of exemplary compound 4-4 from exemplary compound 3-4 (prepared from exemplary compound 1-4 and exemplary compound 2-1), exemplary compound 3-5 (exemplary compound 1-11 and exemplary compound) Preparation of Exemplified Compound 4-5 from Exemplified Compound 4-23, Prepared from Exemplified Compound 3-22 (Prepared from Exemplified Compound 1-2 and Exemplified Compound 2-3), Exemplified Compound 4-23 3-4 (prepared from exemplary compound 1-2 and exemplary compound 2-10) to prepare exemplary compound 4-23, exemplary compound 3-28 (prepared from exemplary compound 1-2 and exemplary compound 2-37) ), Example Compound 4-28, Example Compound 3-33 (prepared from Example Compound 1-55 and Example Compound 2-1), Example Compound 4-33, Example Compound 3-47 (Example Compound 1) -59 and Exemplified Compound 2-3 The preparation was conducted in the exemplified compound 4-47 from prepared) and a, each exemplified compounds could be prepared in good yield.

Claims (7)

A compound represented by the following general formula (III) is reacted with an oxidizing agent in the presence of 1 equivalent or more of water with respect to the compound represented by the following general formula (III). A method for producing a compound represented by formula (IV).

[In the general formula (III), R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹ and R ² may be the same or different and are bonded to each other. To form a ring. R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ³ and R ⁴ may be the same or different and are bonded to each other to form a ring. Also good. ]

[In the general formula (IV), R ^1, R ^2, R ³ and R ⁴ are the same meanings as R ^1, R ^2, R ³ and R ⁴ in the general formula (III). X represents an ion required for charge adjustment. m represents a number of 0 or more. ] The compound represented by the general formula (III) is represented by the following general formula (I) using a compound represented by the following general formula (I) and a compound represented by the following general formula (II). The method according to claim 1, wherein the compound is produced by performing a reaction in the presence of 5 to 10,000 equivalents of water with respect to the compound.

[In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹ and R ² may be the same or different and are bonded to each other. To form a ring. M represents a hydrogen atom, a metal atom or a base conjugate acid. p represents an integer of 1 to 4, and q represents an integer of 1 to 4. ]

[In general formula (II), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an amino group, an alkoxy group, an alkylthio group, or a carbamoyl group, R ³ and R ⁴ may be the same or different and may be bonded to each other to form a ring. ]   The method according to claim 1 or 2, wherein the reaction is carried out in the presence of an alcohol solvent. The method according to claim 2 or 3, wherein the reaction is carried out in the state where the compound represented by the general formula (I) and an acid coexist.
  The method according to any one of claims 2 to 4, wherein the produced compound represented by the general formula (III) is reacted with the oxidizing agent without isolation.   The method according to claim 1, wherein the oxidizing agent is used as an aqueous solution.   The method according to claim 1, wherein the oxidizing agent is peroxodisulfate.