JP2010106005A - Method for producing amines - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for stably producing amines at a high yield, which are useful as ultraviolet absorbers and the like. <P>SOLUTION: The method for producing specific amines includes an extraction/separation step, in which the specific amines are extracted and separated as an organic layer in the co-presence of at least one of organic solvent (A) having a dielectric constant of not less than 5, at least one of organic solvent (B) having a dielectric constant of less than 5 and water, is carried out at least once after a substitution reaction step illustrated by, for example, reaction formula of the figure, in which step an amine having a specific structure and a compound containing an aminobutadiene compound or the like are used as raw materials. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing amines, and more particularly, to a method for producing specific amines useful as, for example, an ultraviolet absorber stably and with high purity.

  Methods for producing amines have been reported for a long time. For example, formation of a nitrogen-carbon bond by ammonia or alkylation of a primary or secondary amine has been performed using a protective group as necessary. (See Non-Patent Documents 1 and 2 below.) Furthermore, the production of amines by a conjugate addition reaction with an amine is also performed (see Non-Patent Document 3). However, the methods described in Non-Patent Documents 1 and 2 have a problem in that they have low reactivity or must be subjected to intense conditions because of low reactivity. The method described in Non-Patent Document 3 is a conjugate addition reaction having a leaving reaction that is useful as a means for solving the problem. In this method, a large amount of by-products derived from leaving groups are generated as impurities as a by-product with the reaction. It has been a problem that the purity of the resulting amines is reduced.

  Moreover, as an ultraviolet absorber, the thing excellent in safety | security, high solubility, and a high molar extinction coefficient is desired. Conventionally, as UV absorbers, benzotriazole compounds, benzophenone compounds, salicylic acid compounds, triazine compounds, aminobenzoic acid compounds, cinnamic acid compounds, and the like have been used. The solubility and the high molar extinction coefficient were not sufficiently satisfied. A method for producing a merocyanine compound that solves this problem has been developed (see, for example, Patent Documents 1 and 2), but a better production method has been demanded in order to obtain a highly pure merocyanine compound.

The Chemical Society of Japan, “Experimental Chemistry Course”, 5th Edition, Volume 14, Maruzen Co., Ltd., Chapter 5, page 379 The Chemical Society of Japan, “Experimental Chemistry Course”, 1st Edition, Volume 20, Maruzen Co., Ltd., Chapter 8, page 477 The Chemical Society of Japan, “Experimental Chemistry Course”, 5th Edition, Volume 14, Maruzen Co., Ltd., Chapter 5, page 365

JP-A-53-128333 JP 58-181041 A

  An object of the present invention is to provide a method for producing amines useful as an ultraviolet absorber or the like stably and with high purity.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by the following production method, and have completed the present invention. That is, the production method of the present invention is as follows.

[1] A compound represented by the following general formula (II) is reacted with a compound represented by the following general formula (III) to obtain a compound represented by the following general formula (I). In the coexistence of at least one organic solvent (A) having a dielectric constant of 5 or more, at least one organic solvent (B) having a dielectric constant of less than 5, and water after the substitution reaction step represented by A process for producing a compound represented by the following general formula (I), which comprises at least one extraction / separation step of extracting the compound represented by the general formula (I) and separating it as an organic layer.

In the general formulas (I) and (II), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom; ^{11 to} L ¹⁴ each independently represents a single bond or a divalent linking group. —X— represents —O—, —S—, —N—, —C (R ¹⁴ ) —, and R ¹⁴ represents a hydrogen atom or a substituent. n ¹¹ and ^{n 12} are each independently an integer of 0 or more. However, when n ¹¹ and n ¹² are 1 or more at the same time, the arrangement order of the structural units forming the chain structure in [] is arbitrary. n ¹³ is 0 when —X— is —O— or —S—, and is 1 when —N— or —C (R ¹⁴ ) —. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ may be bonded to each other to form a ring.
In the general formula (III), L ^v represents a group containing at least one carbon atom, C ^* denotes a monovalent group containing a carbon atom, the nitrogen atom of the C ^* is in the general formula (II) By substitution, a compound represented by the general formula (I) is formed.
In the general formula (IV), ^{L v} has the same meaning as ^{L v} in the general formula (III).
In the formula (1), one or more compounds represented by the general formula (III) are used, and C ^* in the general formula (I) may be the same or different.

[2] The production method according to [1], wherein the compound represented by the general formula (IV) is a compound represented by the following general formula (IV-a).

In the general formula (IV-a), R ⁴¹ represents —CO—R ⁴²¹ , —SO ₂ —R ⁴²² , —CO—NR ⁴²³ (R ⁴²⁴ ), or —CO—OR ⁴²⁵ , and R ⁴² represents hydrogen. An atom, an aliphatic group, an aromatic group, a heterocyclic group bonded by a carbon atom, or a group having the same meaning as R ⁴¹ , R ⁴²¹ , R ⁴²² , R ⁴²³ , R ⁴²⁴ and R ⁴²⁵ are a hydrogen atom, aliphatic A group, an aromatic group, or a heterocyclic group bonded with a carbon atom. R ⁴¹ and R ⁴² may combine with each other to form a ring.

[3] The production method according to [1] or [2], wherein the compound represented by the general formula (III) is a compound represented by the following general formula (III-a).

In general formula (III-a), R ³¹ and R ³² each independently represent a substituent having a σ _p value of 0.20 or more, and R ³³ , R ³⁴ , and R ³⁵ each independently represent hydrogen. represents atom, an aliphatic group, an aromatic group, a heterocyclic group bonded through a carbon ^{atom, R 41} and ^{R 42} has the same meaning as ^{R 41} and ^{R 42} in the general formula (IV-a).

[4] The production method according to any one of [1] to [3], wherein a weight ratio of the organic solvent (A) having a dielectric constant of 5 or more to a total organic solvent is 15% or more.
[5] The method according to any one of [1] to [4], wherein in the extraction / separation step, the pH value of the aqueous layer after separating the organic layer is in the range of 5 to 9.
[6] The method according to any one of [1] to [5], wherein the temperature in the extraction / separation step is 0 ° C. or higher.

一般式（ＩＩＩ−ｂ）中、Ｒ^３６及びＲ^３７は、各々独立に、脂肪族基、芳香族基又は炭素原子で結合する複素環基を表し、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^４１及びＲ^４２は、前記一般式（ＩＩＩ−ａ）におけるＲ^３３、Ｒ^３４、Ｒ^３５、Ｒ^４１及びＲ^４２と同義である。
［９］ 前記一般式（Ｉ）及び一般式（ＩＩ）において、ｎ^１１が１であり、ｎ^１２が０であり、ｎ^１３が０である［１］から［８］のいずれか１項に記載の製造方法。
［１０］ 前記一般式（Ｉ）で表される化合物が、下記構造式（Ｉ−ａ）で表される化合物である［１］から［９］のいずれか１項に記載の製造方法。

[7] In any one of [1] to [6], in the extraction / separation step, the organic layer / water layer distribution ratio of the compound represented by the general formula (IV) is 3 or less. Manufacturing method.
[8] The production method according to any one of [1] to [7], wherein the compound represented by the general formula (III) is a compound represented by the following general formula (III-b).

In General Formula (III-b), R ³⁶ and R ³⁷ each independently represent an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, and R ³³ , R ³⁴ , R ³⁵ , R ⁴¹ And R ⁴² have the same meanings as R ³³ , R ³⁴ , R ³⁵ , R ⁴¹ and R ^{42 in} formula (III-a).
[9] In any one of [1] to [8], in the general formula (I) and the general formula (II), n ¹¹ is 1, n ¹² is 0, and n ¹³ is 0. The manufacturing method as described.
[10] The production method according to any one of [1] to [9], wherein the compound represented by the general formula (I) is a compound represented by the following structural formula (Ia).

  [11] The production method according to any one of [1] to [10], wherein the compound represented by the general formula (I) is obtained with a purity of 95% by mass or more.

[12] A compound represented by the following general formula (VI) is reacted with a compound represented by the following general formula (III-b) to obtain a compound represented by the following general formula (V): In the coexistence of at least one organic solvent (A) having a dielectric constant of 5 or more, at least one organic solvent (B) having a dielectric constant of less than 5, and water after the substitution reaction step represented by 2) The manufacturing method of the compound represented by the following general formula (V) which has the extraction and liquid separation process which extracts the compound represented by the following general formula (V), and liquid-separates as an organic layer at least once.

In the general formulas (III-b), (IV-a), (V) and (VI), R ²¹ and R ²² are each independently bonded with a hydrogen atom, an aliphatic group, an aromatic group, or a carbon atom. These may be bonded to each other to form a ring. R ³³ , R ³⁴ , and R ³⁵ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom. R ³⁶ and R ³⁷ each independently represents an aliphatic group, an aromatic group or a heterocyclic group bonded via a carbon atom. R ⁴¹ represents —CO—R ⁴²¹ , —SO ₂ —R ⁴²² , —CO—NR ⁴²³ (R ⁴²⁴ ), or —CO—OR ⁴²⁵ , and R ⁴² represents a hydrogen atom, an aliphatic group, or an aromatic group. , A heterocyclic group bonded by a carbon atom, or a group having the same meaning as R ⁴¹ , wherein R ⁴²¹ , R ⁴²² , R ⁴²³ , R ⁴²⁴ and R ⁴²⁵ are a hydrogen atom, an aliphatic group, an aromatic group, or a carbon atom Represents a heterocyclic group bonded with R ⁴¹ and R ⁴² may combine with each other to form a ring.

  ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing amines useful as a ultraviolet absorber etc. stably and with high purity can be provided.

Hereinafter, the production method of the present invention will be described in more detail.
In one embodiment of the present invention, a compound represented by the following general formula (I) is reacted with a compound represented by the following general formula (III) to obtain a compound represented by the following general formula (I). After the substitution reaction step represented by the following formula (1), at least one organic solvent (A) having a dielectric constant of 5 or more, at least one organic solvent (B) having a dielectric constant of less than 5, and water In the presence of the compound represented by the following general formula (I), the compound represented by the following general formula (I) is extracted and separated at least once. It is a manufacturing method.

In the general formulas (I) and (II), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom; ^{11 to} L ¹⁴ each independently represents a single bond or a divalent linking group. —X— represents —O—, —S—, —N—, —C (R ¹⁴ ) —, and R ¹⁴ represents a hydrogen atom or a substituent. n ¹¹ and ^{n 12} are each independently an integer of 0 or more. However, when n ¹¹ and n ¹² are 1 or more at the same time, the arrangement order of the structural units forming the chain structure in [] is arbitrary. n ¹³ is 0 when —X— is —O— or —S—, and is 1 when —N— or —C (R ¹⁴ ) —. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ may be bonded to each other to form a ring.
In the general formula (III), L ^v represents a group containing at least one carbon atom, C ^* denotes a monovalent group containing a carbon atom, the nitrogen atom of the C ^* is in the general formula (II) By substitution, a compound represented by the general formula (I) is formed.
In the general formula (IV), ^{L v} has the same meaning as ^{L v} in the general formula (III).
In the formula (1), one or more compounds represented by the general formula (III) are used, and C ^* in the general formula (I) may be the same or different.

  That is, the method for producing a compound represented by the general formula (I) of the present invention includes performing the extraction / separation step according to the present invention at least once after the substitution reaction step represented by the above formula (1). The by-product containing the leaving group removed in the substitution reaction step is extracted and removed, and the compound represented by the general formula (V) can be produced stably and with high purity.

  Another embodiment of the present invention is represented by the following general formula (V) by reacting a compound represented by the following general formula (VI) with a compound represented by the following general formula (III-b). After the substitution reaction step represented by the following formula (2) to obtain a compound: at least one organic solvent (A) having a dielectric constant of 5 or more and at least one organic solvent (B) having a dielectric constant of less than 5; In the presence of water, the compound represented by the following general formula (V) is extracted and separated at least once by extracting the compound represented by the following general formula (V) and separating it as an organic layer. This is a method for producing the compound.

In the general formulas (III-b), (IV-a), (VI) and (V), R ²¹ and R ²² are each independently bonded with a hydrogen atom, an aliphatic group, an aromatic group, or a carbon atom. These may be bonded to each other to form a ring. R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ⁴¹ and R ⁴² have the same meanings as R ³³ , R ³⁴ , R ³⁵ , R ⁴¹ and R ^{42 in the} general formula (III-a).

  That is, the method for producing the compound represented by the general formula (V) of the present invention includes performing the extraction / separation step according to the present invention at least once after the substitution reaction step represented by the above formula (2). The by-product containing the leaving group removed in the substitution reaction step is extracted and removed, and the compound represented by the general formula (V) can be produced stably and with high purity.

  The compounds represented by the general formula (I) and the general formula (V) obtained by the present invention are amines useful for ultraviolet absorbers and the like and have high purity. For example, a preparation containing the compound is prepared. In preparation, the amines have excellent characteristics such as being able to be formulated without pretreatment such as purification.

  In the following description, the method for producing the compound represented by the general formula (I) of the present invention will be referred to as “the production method (1) of the present invention” as appropriate and represented by the general formula (V) of the present invention. About the manufacturing method of the compound represented, it is called "the manufacturing method (2) of this invention" suitably. Further, the production methods (1) and (2) of the present invention may be collectively referred to as “the production method of the present invention” as appropriate.

Hereafter, each process in the manufacturing method of this invention is demonstrated.
In addition, about each compound represented by the said general formula used as a raw material in the manufacturing method of this invention, and each compound represented by the said general formula produced | generated by the manufacturing method of this invention, the manufacturing method of this invention Will be described in detail after the description of each step.

[Substitution reaction step]
In the production method of the present invention, first, the substitution reaction step represented by the formula (1) or the formula (2) is performed.

That is, in the substitution reaction step in the production method (1) of the present invention, the compound represented by the general formula (II) is reacted with the compound represented by the general formula (III).
Moreover, at the substitution reaction process in the manufacturing method (2) of this invention, the compound represented by general formula (IV) and the compound represented by general formula (III-b) are made to react.

  Examples of the solvent used in the reaction include amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane), sulfoxide solvents ( For example, dimethyl sulfoxide), ureido solvent (for example, tetramethyl urea), alcohol solvent (for example, methanol, ethanol, isopropanol), ether solvent (for example, dioxane, cyclopentyl methyl ether), hydrocarbon solvent (for example, Toluene, xylene, n-decane), halogen solvents (eg, tetrachloroethane, chlorobenzene), pyridine solvents (eg, pyridine, γ-picoline, 2,6-lutidine), nitrile solvents (eg, acetonitrile), esters System solvent ( For example, ethyl acetate), a ketone solvent (for example, acetone, methyl ethyl ketone, cyclohexanone), and an aqueous solvent (which may contain an inorganic compound or a salt if necessary) are used alone or in combination. Can do. Of these solvents, a sulfone solvent, a sulfoxide solvent, an alcohol solvent, an ether solvent, a hydrocarbon solvent, a halogen solvent, and an aqueous solvent are preferable, and an alcohol solvent and an ether solvent are more preferable. , Hydrocarbon solvents, halogen solvents and aqueous solvents, more preferably alcohol solvents, hydrocarbon solvents and aqueous solvents. Most preferably, the reaction is carried out in a mixed solvent of an alcohol solvent and a water solvent.

  The reaction temperature in this step is preferably 0 to 250 ° C, more preferably 20 to 200 ° C, still more preferably 40 to 150 ° C, still more preferably 60 to 130 ° C, still more preferably 70 to 110 ° C.

  In the production method (1) of the present invention, the compound represented by the general formula (I) and the compound represented by the general formula (IV) which is a by-product in the reaction solution obtained in this step. Is included. Moreover, in the manufacturing method (2) of this invention, in the reaction liquid obtained by this process, the compound represented by general formula (V), and general formula (IV-a) which is the by-product The compound represented by these is included.

[Extraction / separation process]
In the production method of the present invention, the extraction / separation step according to the present invention is performed after the substitution reaction step represented by the above formula (1) or formula (2). By passing through this step, the by-product generated in the substitution reaction step is effectively removed.

That is, in the extraction / separation step of the production method (1) of the present invention, at least one organic solvent (A) having a dielectric constant of 5 or more and at least one organic solvent (B) having a dielectric constant of less than 5 are used. In the presence of water, a compound represented by the following general formula (I) is extracted and separated as an organic layer.
In the extraction / separation step of the production method (2) of the present invention, at least one organic solvent (A) having a dielectric constant of 5 or more and at least one organic solvent (B) having a dielectric constant of less than 5 are provided. In the presence of water, a compound represented by the following general formula (V) is extracted and separated as an organic layer.

  The extraction / separation step in the production method of the present invention is performed at least once.

As used herein, the term “organic solvent” refers to an organic compound having at least one carbon atom that is not involved in or derived from subsequent reactions including reaction and decomposition. That is, raw materials, reaction products, reaction by-products, and secondary reaction products derived therefrom do not fall within the category of organic solvents.
In the present invention, among such organic solvents, it is essential in the extraction / separation step to use an organic solvent (A) having a dielectric constant of 5 or more and an organic solvent (B) having a dielectric constant of less than 5. .

The dielectric constant of the organic solvent (A) used in the extraction / separation step is 5 or more, and from the viewpoint of liquid separation, it is preferably 5 to 100, more preferably 10 to 80, and still more preferably 15 to 70. More preferably, it is 15-60, More preferably, it is 15-45. As the organic solvent (A) having such a dielectric constant, methanol (dielectric constant = 32.6, “Maruzen New Experimental Chemistry Lecture 3rd Edition”, particularly preferably inexpensive, widely used industrially and easily available) 14-V Volume 2592 page 12.2 "), ethanol (dielectric constant = 24.3, reference value described in the same document), acetone (dielectric constant = 20.7, described in the same document). Reference value). In addition, acetonitrile (dielectric constant = 37.5, reference value described in the same document), propanol (dielectric constant = 20.8, reference value described in "Maruzen Chemical Handbook Basic Edition 5th Chapter Chapter 14"), butanol (Dielectric constant = 17.8, reference value described in the same document), isopropanol (dielectric constant = 20.2, reference value described in the same document), isopropanol (dielectric constant = 20.2, reference described in the same document) Value), ethylene glycol (dielectric constant = 41.4, reference value described in the same document).
Only 1 type may be used for an organic solvent (A), and 2 or more types may be used together.

The dielectric constant of the organic solvent (B) used in the extraction / separation step is less than 5, preferably from 0.01 to 4.99, more preferably from 1 to 4.5, more preferably from the viewpoint of liquid separation. Preferably it is 1-4.0, More preferably, it is 1.5-4.0. As the organic solvent (B) having such a dielectric constant, toluene (dielectric constant = 2.4, “Maruzen New Experimental Chemistry Lecture 3rd Edition” which is particularly inexpensive, widely used industrially, and easily available is particularly preferable. 14-V Vol. 2592 page 12.2 "), benzene (dielectric constant = 2.2 reference value of the same literature), n-hexane (dielectric constant = 1.9, reference described in the same literature) Value). In addition, decane (dielectric constant = 2.0, reference value described in “Maruzen Chemical Handbook, 5th edition, chapter 14”), nonane (dielectric constant = 2.0, reference value described in the same document), cyclohexane (Dielectric constant = 2.0, reference value described in the same document), octane (dielectric constant = 2.3, reference value described in the same document), ethylbenzene (dielectric constant = 2.4, reference described in the same document) Value), heptane (dielectric constant = 1.9, reference value described in the same document) can also be used.
Only 1 type may be used for an organic solvent (B), and 2 or more types may be used together.

Here, in this specification, the “dielectric constant” is a physical quantity indicating how much atoms in a substance respond when an electric field is applied to the substance. The dielectric constant is generally given by a complex tensor amount. The real part of the complex dielectric constant is an amount representing the ease of polarization, and the imaginary part is an amount representing the degree of dielectric loss. That is, when the real part of the dielectric constant is negative, the light absorption ability is high, and an excellent light absorption ability can be obtained with a small amount of fine particles, and a shielding function can be obtained.
The dielectric constant is the square of the refractive index measured by a refractometer, “Handbook of optical constans”, “Landol-Boernstein Group 3 Volume 15 Subvolume B” or “Maruzen New Experimental Chemistry Course 3rd Edition, Volume 14 page V 2592”. The literature values described in can be used.
In the present invention, the known values in these documents are not limited to a certain solvent, but are included in the same measurement range even if the values are unknown. Of course, as long as it is included.

  The organic solvent (A) used in the extraction / separation step preferably has a weight ratio of 15% or more based on the total organic solvent from the viewpoint of liquid separation. The weight ratio is more preferably 15 to 80%, still more preferably 20 to 60%, still more preferably 25 to 50%.

  From the viewpoint of production suitability, the pH value of the aqueous layer separated by the extraction operation in the extraction / separation step is preferably 5 to 9, more preferably 5 to 8, and more preferably 6 to 8. is there.

  When measuring the pH value, if an organic solvent coexists with water, it becomes a value different from the value derived from the actual acid dissociation equilibrium from the measurement principle. In this specification, the “pH value of the aqueous layer” In addition, after the extraction of the compound represented by the general formula (I) or (V), when the organic layer containing the compound is separated, the aqueous layer is taken out and measured with a commercially available pH meter. . The pH value in the present specification is a value measured using a pH meter (model number HM50G) manufactured by Toa DKK- Co., Ltd.

  The temperature during the extraction operation in the extraction / separation step is preferably 0 ° C. or higher, more preferably 25 ° C. to 70 ° C., more preferably 30 ° C. to 50 ° C. from the viewpoint of liquid separation. is there.

In the production method (1) of the present invention, in the extraction / separation step, the organic layer / water layer distribution ratio of the compound represented by the general formula (IV) is preferably 3 or less.
Here, the distribution ratio of the organic layer / aqueous layer of the compound represented by the general formula (IV) in this specification is not the concentration ratio but the compound represented by the general formula (IV) contained in each layer. The ratio of the total amount (mass) of is shown.

One preferred embodiment of the extraction / separation step in the production method (1) of the present invention is as follows.
First, the organic solvent (B) is added to the reaction liquid after the substitution reaction step represented by the formula (1) is completed and stirred, and then the organic solvent (A) and water are added to perform extraction / separation operation. Do. An organic solvent (A) and water are further added to the separated organic layer to perform extraction / separation operation.

One preferred embodiment of the extraction / separation step in the production method (2) of the present invention is as follows.
First, the organic solvent (B) is added to the reaction liquid after the substitution reaction step represented by the formula (2) is completed and stirred, and then the organic solvent (A) and water are added to perform extraction / separation operation. Do. An organic solvent (A) and water are further added to the separated organic layer to perform extraction / separation operation.

Specifically, the compound represented by general formula (I) can be obtained, for example, by the methods described in Synthesis Examples 1 and 2 described later.
In addition, the compound represented by the general formula (V) can be specifically obtained by, for example, the method described in Synthesis Example 3 described later.

By the production method (1) of the present invention, the compound represented by the general formula (I) can be obtained with a high purity of 95% by mass or more.
By the production method (2) of the present invention, the compound represented by the general formula (V) can be obtained with a high purity of 95% by mass or more.

The compound represented by the general formula (I) and the compound represented by the general formula (V) obtained by the production method of the present invention described above are amines useful as an ultraviolet absorber or the like.
Since these amines obtained by the production method of the present invention are highly pure as described above, it is possible to prepare a preparation without pretreatment when preparing a preparation containing the amine. .

  Conventionally, a material that has been provided with ultraviolet absorptivity by sharing an ultraviolet absorber with various resins has been used. In the case where the compound represented by the general formula (I) and the general formula (V) obtained by the present invention is applied to the use of an ultraviolet absorber, the compound represented by the general formula (I) is more preferable. preferable.

  As an example of the material which gave the ultraviolet absorptivity which can apply the compound represented by general formula (I) and (V) obtained by the manufacturing method of this invention, for example, a glass substitute and its surface coating material Coating materials for window glass, lighting glass and light source protection glass for residences, facilities, transportation equipment, etc., for interior and exterior materials and interior / exterior coating materials for residences, facilities, transportation equipment, etc., for light sources emitting ultraviolet rays such as fluorescent lamps and mercury lamps Materials, precision machinery, materials for electronic and electrical equipment, materials for shielding electromagnetic waves generated from various displays, food or chemicals, containers or packaging materials for chemicals, agricultural or industrial sheets or films, printed matter, dyed matter, pigments Anti-fading agents such as sunscreen cream, shampoo, rinse, hairdressing cosmetics, sportswear, stockings, clothing textiles such as hats, textiles, curtains, carpets, Household interior products such as paper, medical equipment such as plastic lenses, contact lenses, artificial eyes, optical filters, prisms, mirrors, optical supplies such as photographic materials, stationery such as tapes and inks, marking plates, marking devices, etc. A surface coating material etc. can be mentioned.

  Next, in the production methods (1) and (2) of the present invention, the compounds represented by the general formulas will be described in detail.

Each compound in the production method (1) of the present invention will be described.
The compound represented by the general formula (I) is a compound obtained by the production method (1) of the present invention. As described above, the compound represented by the general formula (II) and the general formula (III) It produces | generates by substitution reaction with the compound represented, and the compound represented by general formula (IV) byproduces.

  Hereinafter, the compound represented by the general formula (I) will be described, and then the compound represented by the general formula (II) which is a raw material for obtaining the compound represented by the general formula (I) and The compound represented by formula (III) and the compound represented by formula (IV), which is a by-product, will be described.

<Compound represented by formula (I)>
The compound represented by formula (I) will be described.

In the general formula (I), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, and L ^{11 to} L ¹⁴ Each independently represents a single bond or a divalent linking group. —X— represents —O—, —S—, —N—, —C (R ¹⁴ ) —, and R ¹⁴ represents a hydrogen atom or a substituent. n ¹¹ and ^{n 12} are each independently an integer of 0 or more. However, when n ¹¹ and n ¹² are 1 or more at the same time, the arrangement order of the structural units forming the chain structure in [] is arbitrary. n ¹³ is 0 when —X— is —O— or —S—, and is 1 when —N— or —C (R ¹⁴ ) —. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ may be bonded to each other to form a ring. C ^* represents a monovalent group containing a carbon atom.

In the general formula (I), the aliphatic group represented by R ¹¹ , R ¹² and R ¹³ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, And a substituted aralkyl group.
The alkyl group may have a branch or may form a ring. The number of carbon atoms in the alkyl group is preferably 1-20, and more preferably 1-18.
The alkyl part of the substituted alkyl group is the same as the above alkyl group. The alkenyl group may have a branch or may form a ring. The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group.
The alkynyl group may have a branch or may form a ring. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms.
The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group.
The alkyl part of the aralkyl group and the substituted aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group and the substituted aralkyl group is the same as the following aryl group.

  Examples of the substituent of the alkyl part of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, and the substituted aralkyl group include a halogen atom (eg, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [straight chain, branched Represents a cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ],

Alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 or 6 A monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 30 carbon atoms) Substituted or unsubstituted alkoxy groups such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy),

A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms) Group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, 6 to 30 carbon atoms) A substituted or unsubstituted arylcarbonyloxy group such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted group having 1 to 30 carbon atoms) Place Carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholino carbonyloxy, N, N-di -n- octyl amino carbonyloxy, N-n-octyl carbamoyloxy)

An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (Preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably Is an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, and , N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms) A carbonylamino group such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino),

An aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxy; Carbonylamino), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino),

Alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenyl Sulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably Properly substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, e.g., 2-benzothiazolylthio, 1-phenyl-5-ylthio),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N- Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms) 6 to 30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted groups having 1 to 30 carbon atoms) Replace Alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group having 6 to 30, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- methylphenyl sulfonyl),

Acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon group having 4 to 30 carbon atoms Heterocyclic carbonyl groups bonded to the carbonyl group by an atom, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryl An oxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxy Carbo Group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably having 1 to 30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),

Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms such as phenylazo, p-chlorophenylazo, 5- Ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, For example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphini ), A phosphinyloxy group (preferably A substituted or unsubstituted phosphinyloxy group having 2 to 30 primes, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or An unsubstituted phosphinylamino group such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl, t -Butyldimethylsilyl, phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

  The example of the substituent of the aryl part of a substituted aralkyl group is the same as the example of the substituent which the substituted aryl group which is one aspect | mode of the aromatic group mentioned later has.

In the general formula (I), the aromatic group represented by R ¹¹ , R ¹² , and R ¹³ means an aryl group and a substituted aryl group. These aromatic groups may be condensed with an aliphatic ring, another aromatic ring, or a heterocyclic ring. 6-40 are preferable, as for the carbon atom number of an aromatic group, 6-30 are more preferable, and 6-20 are more preferable. Among them, the aryl group is preferably phenyl or naphthyl, and particularly preferably phenyl.

  The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent that the substituted aryl group has are the same as the examples of the substituent that the alkyl part of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, and the substituted aralkyl group previously have.

In the general formula (I), the heterocyclic group bonded to the carbon atom represented by R ¹¹ , R ¹² , or R ¹³ is preferably a group containing a 5- or 6-membered saturated or unsaturated heterocyclic ring. . Here, the heterocyclic group bonded by a carbon atom means a heterocyclic group bonded by a free valence (monovalent) of a carbon atom contained in the heterocyclic group. The heterocyclic group may be condensed with an aliphatic ring, an aromatic ring, or another heterocyclic ring. Examples of the hetero atom that the heterocyclic ring has include a B atom, an N atom, an O atom, an S atom, a Se atom, and a Te atom. As the hetero atom, an N atom, an O atom and an S atom are preferable. The number of carbon atoms of a preferable heterocyclic group is 1-40, More preferably, it is 1-30, More preferably, it is 1-20. Examples of the saturated heterocyclic ring include a pyrrolidine ring, a morpholine ring, a 2-bora-1,3-dioxolane ring, and a 1,3-thiazolidine ring. Examples of the unsaturated heterocyclic ring include imidazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzotriazole ring, benzoselenazole ring, pyridine ring, pyrimidine ring, and quinoline ring. The heterocyclic group may have a substituent. Examples of the substituent are the same as those described above as examples of the substituent of the alkyl portion of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, and the substituted aralkyl group.

R ¹¹ , R ¹² and R ¹³ in the general formula (I) are preferably a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group or an aryl group, more preferably a hydrogen atom or an alkyl having 1 to 20 carbon atoms. Group, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms and 2 to 10 carbon atoms. An alkenyl group, an aralkyl group having 7 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and 6 carbon atoms. Is an aryl group having 10 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and more preferably an aralkyl group having 7 to 10 carbon atoms. Ri, most preferably benzyl group. It is also preferred that all of R ¹¹ , R ¹² and R ¹³ are the same.

L ¹¹ , L ¹² , L ¹³ and L ¹⁴ in formula (I) are preferably a single bond, alkylene, arylene, a divalent group consisting of a combination of alkylene and arylene, or a divalent group consisting of an alkylene and an oxygen atom. A divalent group consisting of an arylene and an oxygen atom, and a divalent group consisting of an alkylene, an arylene and an oxygen atom, and more preferably a single bond, an alkylene having 1 to 20 carbon atoms, and an alkyl group having 6 to 20 carbon atoms. Arylene, a divalent group consisting of a combination of alkylene and arylene having 7 to 20 carbon atoms, a divalent group consisting of alkylene and oxygen atoms having 1 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms and an oxygen atom A divalent group and a divalent group consisting of an alkylene, arylene and oxygen atom having a total carbon number of 7 to 20, more preferably a single bond, carbon An alkylene having 2 to 10 carbon atoms, an arylene having 6 to 10 carbon atoms, a divalent group comprising a combination of an alkylene and an arylene having 7 to 10 carbon atoms, and a divalent group comprising an alkylene having 2 to 10 carbon atoms and an oxygen atom. A divalent group consisting of an arylene having 7 to 10 carbon atoms and an oxygen atom, and more preferably a single bond, an alkylene having 2 to 10 carbon atoms, an arylene having 6 to 10 carbon atoms, and an alkylene having 2 to 10 carbon atoms. More preferably a single bond, alkylene having 2 to 10 carbon atoms, or a divalent group consisting of alkylene having 2 to 10 carbon atoms and an oxygen atom, most preferably a single bond, Alkylene having 2 to 10 carbon atoms. In addition, the total number of carbon atoms in the linear portion connecting L ¹¹ and L ¹² , the linear portion connecting L ¹¹ and X, and the linear portion connecting L ¹³ and X is 2 or more. It is preferable to become.

When X in the general formula (I) is —C (R ¹⁴ ) —, the preferred range for L ^{14 is the same} as L ¹¹ described above. When X is —N—, L ¹⁴ is preferably alkylene, arylene, a divalent group consisting of a combination of alkylene and arylene, a divalent group consisting of alkylene and an oxygen atom, or a divalent group consisting of arylene and an oxygen atom. And a divalent group consisting of alkylene, substituted or unsubstituted arylene and an oxygen atom, more preferably alkylene having 1 to 20 carbons, arylene having 6 to 20 carbons, and 7 to 20 total carbons. A divalent group consisting of a combination of alkylene and arylene, a divalent group consisting of alkylene having 1 to 20 carbon atoms and an oxygen atom, a divalent group consisting of arylene having 6 to 20 carbon atoms and an oxygen atom, and the total number of carbon atoms A divalent group composed of 7 to 20 alkylene, arylene and oxygen atom, more preferably an alkylene having 2 to 10 carbon atoms and an aliquot having 6 to 10 carbon atoms A divalent group consisting of a combination of alkylene and arylene having a total carbon number of 7 to 10, a divalent group consisting of an alkylene of 2 to 10 carbon atoms and an oxygen atom, an arylene of 7 to 10 carbon atoms and an oxygen atom A divalent group, more preferably an alkylene having 2 to 10 carbon atoms, an arylene having 6 to 10 carbon atoms, an alkylene having 2 to 10 carbon atoms and an oxygen atom, more preferably 2 carbon atoms. -10 alkylene, a divalent group consisting of an alkylene having 2 to 10 carbon atoms and an oxygen atom, most preferably an alkylene having 2 to 10 carbon atoms.

X in the general formula (I) is preferably —N— or —C (R ¹⁴ ) —, more preferably —C (R ¹⁴ ) —.

R ¹⁴ in formula (I) is preferably a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy Group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino Group, mercapto group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbo Nyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, more preferably hydrogen atom, halogen atom, alkyl group, alkenyl Group, aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, amino group, alkylthio group, arylthio group, imide group, silyl group, more preferably hydrogen atom, halogen atom An alkyl group, an aryl group, an alkoxy group, an aryloxy group, a silyloxy group, and an amino group, most preferably a hydrogen atom and an alkyl group. R ¹⁴ is preferably a group represented by the following general formula (VII).

In the general formula (VII), R ¹⁵ has the same meaning as R ¹² described above, and the preferred range is also the same. L ¹⁵ has the same meaning as the aforementioned ^{L 14,} a preferred range is also the same.

N ¹¹ in the general formula (VII) is preferably 0 to 20, more preferably 0 to 10, further preferably 0 to 5, still more preferably 1 to 3, and still more preferably 1 to 1. 2 and most preferably 1.

N ¹² in formula (VII) is preferably 0 to 20, more preferably 0 to 10, further preferably 0 to 5, further preferably 0 to 3, and most preferably 0 to 10. 1.

The monovalent group containing a carbon atom represented by C ^* in the general formula (I) is a group derived from C ^* in the general formula (III) described later, and the preferred range thereof is also the general formula (III). It is the same.

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

(Specific examples of compounds represented by formula (I))

<Compound represented by formula (II)>
The compound represented by formula (II) will be described.

In the general formula (II), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, and L ^{11 to} L ¹⁴ Each independently represents a single bond or a divalent linking group. —X— represents —O—, —S—, —N—, —C (R ¹⁴ ) —, and R ¹⁴ represents a hydrogen atom or a substituent. n ¹¹ and ^{n 12} are each independently an integer of 0 or more. However, when n ¹¹ and n ¹² are 1 or more at the same time, the arrangement order of the structural units forming the chain structure in [] is arbitrary. n ¹³ is 0 when —X— is —O— or —S—, and is 1 when —N— or —C (R ¹⁴ ) —. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ may be bonded to each other to form a ring.

The preferred ranges of R ¹¹ , R ¹² , R ¹³ , L ^{11 to} L ¹⁴ , n ¹¹ , n ¹² , and n ^{13 in} the general formula (II) are R ¹¹ , R ¹² , in the general formula (I), This is the same as R ¹³ , L ^{11 to} L ¹⁴ , n ¹¹ , n ¹² , and n ¹³ .

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

(Specific examples of the compound represented by the general formula (II))

<Compound represented by formula (III)>
The compound represented by formula (III) will be described.

In the general formula (III), L ^v represents a group containing at least one carbon atom, C ^* represents a monovalent group containing a carbon atom. The compound represented by the general formula (I) is formed by replacing C ^* in the general formula (III) with the nitrogen atom in the general formula (II).

The preferred L ^v in formula (III), group bonded to C ^* at the nitrogen atom of 1 to 40 carbon atoms, and a group that binds to C ^* at an oxygen atom, more preferably carbon atom 2 A group represented by —N (R ⁴¹ ) R ⁴² or —O—R ⁴³ of ˜20, and more preferably a group represented by —N (R ⁴¹ ) R ⁴² having 3 to 10 carbon atoms. is there.

R ⁴¹ in the general formula (III) represents —CO—R ⁴²¹ , —SO ₂ —R ⁴²² , —CO—NR ⁴²³ (R ⁴²⁴ ), —CO—OR ⁴²⁵ , and R ⁴²¹ , R ⁴²² , R ⁴²³ , R ⁴²⁴ and R ⁴²⁵ represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, preferably an alkyl group, an alkenyl group, an aralkyl group, or an aryl group, and more preferably An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. , An alkenyl group having 2 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and more preferably an unsubstituted or halogen atom having 1 to 5 carbon atoms. An alkyl group substituted with an alkyl group, an unsubstituted or substituted aralkyl group having 7 to 8 carbon atoms, and an aryl group substituted with an unsubstituted or halogen atom having 6 to 8 carbon atoms, and more preferably 1 carbon atom. Are an unsubstituted or substituted alkyl group having 3 or 3 halogen atoms, and an aryl group having 6 carbon atoms that is unsubstituted or substituted with a halogen atom, and most preferably a methyl group or a phenyl group.

In the general formula (III), among R ⁴¹ represented by —CO—R ⁴²¹ , —SO ₂ —R ⁴²² , —CO—NR ⁴²³ (R ⁴²⁴ ), and —CO—OR ⁴²⁵ , CO-R ⁴²¹ , -SO ₂ -R ⁴²² and -CO-OR ⁴²⁵ are more preferable, -CO-R ⁴²¹ and -SO ₂ -R ⁴²² are most preferable, and -CO-R ⁴²¹ is most preferable.

R ⁴² in the general formula (III) is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group bonded with a carbon atom, or a group having the same meaning as R ^41, and preferably a hydrogen atom, an alkyl group, an alkenyl group Group, an aralkyl group, and an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a 6 to 20 carbon atom. An aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. More preferably, they are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an aryl group having 6 to 8 carbon atoms, more preferably an unsubstituted or substituted alkyl group having 1 to 3 carbon atoms, An aryl group substituted in the fine unsubstituted or halogen atoms carbon atoms 6-7, and most preferably a phenyl group.
R ⁴² is preferably a group having the same meaning as R ^41, and in this case, the preferred range is the same as R ⁴¹ .

In the general formula (III), R ⁴³ represents —CO—R ⁴³¹ , —SO ₂ —R ⁴³² , —CO—NR ⁴³³ (R ⁴³⁴ ), —CO—OR ⁴³⁵ , and R ⁴³¹ , R ⁴³² , R ^433. , R ⁴³⁴ and R ⁴³⁵ have the same meanings as R ⁴²¹ , and the preferred ranges are also the same.

In the general formula (III), among —CO—R ⁴³¹ , —SO ₂ —R ⁴³² , —CO—NR ⁴³³ (R ⁴³⁴ ), and R ⁴³ represented by —CO—OR ⁴³⁵ , preferably —CO -R ⁴²¹ , -SO ₂ -R ⁴²² , and -CO-OR ⁴²⁵ , more preferably -CO-R ⁴²¹ , and -SO ₂ -R ⁴²² , most preferably -SO ₂ -R ⁴²² . .

C ^* in the general formula (III) is preferably a group having 1 to 50 carbon atoms, more preferably a group having 3 to 50 carbon atoms, and still more preferably a group having 5 to 40 carbon atoms. More preferably, it is a group having 8 to 30 carbon atoms, and more preferably a group having 12 to 25 carbon atoms. Further, those having an ethene structure in which the carbon atom serving as the substitution center has a double bond with the adjacent carbon atom, or those having a butadiene structure with four carbon atoms including the carbon atom serving as the substitution center are more preferred. It has a butadiene structure.

Preferred ^{C *} is in the formula (III), in general formula (III-a) shown ^below, it is represented by a butadiene structure replacing with ^{R 41} and ^{R 42} to the nitrogen atom.

  One of the suitable aspects of the compound represented by general formula (III) is a compound represented by the following general formula (III-a).

In addition, regarding an aminobutadiene compound such as a compound represented by the following general formula (III-a), which is a more preferable embodiment of the compound represented by the general formula (III), there are a plurality of stereoisomers. In this specification, for convenience, all isomers are represented by one general formula. That is, the aminobutadiene compound such as the compound represented by the general formula (III-a) shown in the present specification is a specific kind or a mixture of plural kinds among all stereoisomers.
.

In general formula (III-a), R ³¹ and R ³² each independently represent a substituent having a σ _p value of 0.20 or more, and R ³³ , R ³⁴ , and R ³⁵ each independently represent hydrogen. represents atom, an aliphatic group, an aromatic group, a heterocyclic group bonded through a carbon ^{atom, R 41} and ^{R 42} has the same meaning as ^{R 41} and ^{R 42} in the general formula (IV-a).

R ³¹ and R ³² in the general formula (III-a) are preferably a substituent having a σ _p value of 0.30 or more, more preferably an alkane or arylenesulfonyl group, an acyl group, an arylcarbonyl group, a cyano group, An alkoxycarbonyl group and an aryloxycarbonyl group, more preferably an arenesulfonyl group having 6 to 20 carbon atoms (for example, benzenesulfonyl group, p-toluenesulfonyl group, p-chlorobenzenesulfonyl group, naphthalenesulfonyl group), carbon number 1 -20 acyl group (for example, formyl group, acetyl group, propionyl group), arylcarbonyl group having 7 to 20 carbon atoms, nitrile group, alkoxycarbonyl group having 2 to 20 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group) , T-butoxycarbonyl group, octi An oxycarbonyl group, a benzyloxycarbonyl group), an aryloxycarbonyl group having 7 to 20 carbon atoms (for example, a phenoxycarbonyl group or a p-nitrophenoxycarbonyl group), and more preferably an arenesulfonyl group having 6 to 15 carbon atoms, An acyl group having 1 to 10 carbon atoms, an arylcarbonyl group having 7 to 15 carbon atoms, a nitrile group, an alkoxycarbonyl group having 2 to 15 carbon atoms, and an aryloxycarbonyl group having 7 to 15 carbon atoms, more preferably They are a 6-10 arenesulfonyl group, a nitrile group, and a C2-C13 alkoxycarbonyl group, Most preferably, a C6-C8 arenesulfonyl group and a C3-C12 alkoxycarbonyl group.

Here, the σ _p value is L.P. P. A substituent constant proposed by Hammett in 1935, an empirical rule that quantitatively discusses the influence of substituents on the reaction or equilibrium of benzene derivatives. This is widely accepted today. The substituent constants determined by the Hammett rule include sigma _p value and sigma _m value of these values there are described in many general books, for example J. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemical Areas Extra”, 122, 96-103, 1979 (Nan-Edo). In the present invention, the R ³¹ and R ³² are defined by Hammett's substituent constant σ _p value, but it does not mean that they are limited only to substituents having known values described in these documents. Of course, even if the value is unknown, it is included as long as it is included in the range when measured based on Hammett's law.

R ³³ , R ³⁴ and R ³⁵ in general formula (III-a) are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 0 carbon atoms, more preferably a hydrogen atom, It is a C1-C5 alkyl group, More preferably, they are a hydrogen atom, a methyl group, and an ethyl group, Most preferably, it is a hydrogen atom.

General formula (III-a) embodiment was preferred for ^{R 41} and ^{R 42} in is the same as ^{R 41} and ^{R 42} in the general formula (IV-a).

  One preferred embodiment of the compound represented by the general formula (III) is a compound represented by the following general formula (III-b).

In General Formula (III-b), R ³⁶ and R ³⁷ each independently represent an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, and R ³³ , R ³⁴ , R ³⁵ , R ⁴¹ And R ⁴² have the same meanings as R ³³ , R ³⁴ , R ³⁵ , R ⁴¹ and R ^{42 in} formula (III-a).

^R 33 in the general formula ^{(III-b), R 34} , R 35, preferred embodiments of ^{R 41} and ^{R 42,} wherein ^R 33 in the general formula ^{(III-a), R 34} , R 35, R 41 and ^{R 42} It is the same.

R ³⁶ and R ³⁷ in formula (III-b) are preferably a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, preferably a hydrogen atom, an alkyl group, or an alkenyl. Group, an aralkyl group, and an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a 6 to 20 carbon atom. An aryl group, more preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
R ³⁶ is more preferably an alkyl group having 3 to 10 carbon atoms and an aryl group having 6 to 8 carbon atoms, and more preferably an alkyl group having 5 to 10 carbon atoms and an aryl group having 6 to 7 carbon atoms. And most preferably a phenyl group.
R ³⁷ is more preferably an alkyl group having 3 to 10 carbon atoms and an aryl group having 6 to 8 carbon atoms, and more preferably an alkyl group having 5 to 10 carbon atoms and an alkyl group having 6 to 7 carbon atoms. An aryl group, most preferably an octyl group.

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

(Specific examples of the compound represented by the general formula (III))

<Compound represented by formula (IV)>
The compound represented by formula (IV) will be described.

In the general formula (IV), ^{L v} has the same meaning as ^{L v} in formula (III), it is also the preferable range.

Next, each compound in the production method (2) of the present invention will be described.
The compound represented by the general formula (V) is a compound obtained by the production method (2) of the present invention. As described above, the compound represented by the general formula (VI) and the general formula (III-b ) And a by-product of the compound represented by the general formula (IV-a).

  Hereinafter, the compound represented by the general formula (V) will be described, and then the compound represented by the general formula (VI) which is a raw material for obtaining the compound represented by the general formula (V) and The compound represented by the general formula (III-b) and the compound represented by the general formula (IV-a) which is a by-product will be described.

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

(Specific examples of compounds represented by formula (IV))

<Compound represented by formula (V)>
The compound represented by formula (V) will be described.

In the general formula (V), R ²¹ and R ²² each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded by a carbon atom, and these are bonded to each other to form a ring. May be. R ³³ , R ³⁴ , and R ³⁵ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom. R ³⁶ and R ³⁷ each independently represents an aliphatic group, an aromatic group or a heterocyclic group bonded via a carbon atom.

R ²¹ and R ²² in the general formula (V) are more preferably a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, or an aryl group, and more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number. An alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, carbon An aralkyl group having 7 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and an aryl having 6 to 10 carbon atoms. Most preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms.

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

(Specific examples of compounds represented by formula (V))

<Compound represented by formula (III-b)>
The compound represented by the general formula (III-b) in the production method (2) of the present invention is the same as that already described in the description of the production method (1) of the present invention.

<Compound represented by formula (VI-a)>
The compound represented by the general formula (VI-a) in the production method (2) of the present invention is the same as that already described in the description of the production method (1) of the present invention.

<Compound represented by formula (VI)>
The compound represented by the general formula (VI) will be described.

In the general formula (VI), R ²¹ and R ²² each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, and these are bonded to each other to form a ring. May be.

Preferred embodiments of ^{R 21} and ^{R 22} in the general formula (VI) are the same as the ^R 33 in the general formula ^{(V), R 34, R} 35, R 36, and ^{R 37.
R} 33 in the general formula ^{(VI), R 34, R} 35, R 36, and preferred embodiments of ^{R 37,} said ^R 33 in the general formula ^{(III-b), R 34} , R 35, R 36, and R ³⁷ .

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

(Specific examples of compounds represented by formula (VI))

  Hereinafter, the production method of the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[Example 1]
<Synthesis Example of Exemplified Compound (I-1) by Production Method (1) of the Present Invention>
According to the scheme shown in the following formula (3), the compound described above as exemplary compound (I-1) was synthesized.

In a three-necked flask, 24.5 g of the exemplified compound (II-1) shown above, 150 g of the exemplified compound (III-6) shown above, 7.0 g of sodium acetate trihydrate, 500 mL of isopropyl alcohol were added. The mixture was heated and stirred at 85 ° C. for 12 hours.
Thereafter, the internal temperature is set to 35 ° C., 800 mL of toluene as the organic solvent (B) and 260 mL of n-hexane are added and stirred, and further 500 mL of methanol as the organic solvent (A) and 260 mL of water are added thereto for extraction and extraction. Separation operation was performed. (Extraction / separation step according to the present invention, the same shall apply hereinafter) The weight ratio of all organic solvents (organic solvents (A) and (B)) used in the extraction / separation operation is 31:69.
To the obtained organic layer, 500 mL of methanol and 260 mL of water were further added to perform extraction / separation operation. This operation was repeated five more times.
The organic layer thus obtained was crystallized from the residue obtained by concentrating with a rotary evaporator, and crystals were taken out.
As described above, 87.9 g of the target exemplified compound (I-1) was obtained. The obtained exemplary compound (I-1) has a yield of 92%, an HPLC area ratio of 99%, and an HPLC purity of 99.3 wt% obtained from a calibration curve (the column is ODS-80Ts manufactured by Tosoh Corporation, and the eluent is THF). : Pure water = 4: 5 to 5: 4, detection wavelength 254 nm). Moreover, the crystal | crystallization of the obtained compound was pale yellow, and was M ^<+ > ^/ e ⁼ 936.44 as a result of the mass spectrum.

[Example 2]
<Synthesis Example of Exemplified Compound (I-6) by Production Method (1) of the Present Invention>
According to the scheme shown in the following formula (4), the compound described above as exemplary compound (I-6) was synthesized.

In a three-necked flask, 40.2 g of the above-mentioned exemplary compound (II-11), 150 g of the above-described exemplary compound (III-6), 7.0 g of sodium acetate trihydrate, 500 mL of isopropyl alcohol, and an internal temperature of 80 to The mixture was heated and stirred at 85 ° C. for 12 hours. Thereafter, the internal temperature is set to 35 ° C., 800 mL of toluene as the organic solvent (B) and 260 mL of n-hexane are added and stirred, and 500 mL of methanol as the organic solvent (A) and 260 mL of water are further added thereto to perform extraction / separation. The operation was performed. The weight ratio of all organic solvents (organic solvents (A) and (B)) used in the extraction / separation operation is 31:69.
To the obtained organic layer, 500 mL of methanol and 260 mL of water were further added to perform extraction / separation operation. This operation was repeated five more times.
The organic layer thus obtained was concentrated with a rotary evaporator, the resulting residue was stirred under mixed solvent conditions of ethyl acetate, IPA, and n-hexane, and the resulting crystals were suction filtered and dried, 139.6 g of the target exemplified compound (I-6) was obtained.
The obtained exemplary compound (I-6) had a yield of 95%, an HPLC area ratio of 99%, and an HPLC purity determined from a calibration curve of 99.2 wt% (column is ODS-80Ts manufactured by Tosoh Corporation, eluent is THF) : Pure water = 4: 5 to 5: 4, detection wavelength 254 nm). Moreover, the crystal | crystallization of the obtained compound was light yellow, absorption maximum wavelength (lambda) max 375nm (solvent; ethyl acetate), melting | fusing point 75-80 degreeC, and the result of mass spectrum M ^{+ /} e ⁼ 1439.75.

[Example 3]
<The synthesis example of exemplary compound (V-7) by the manufacturing method (2) of this invention>
According to the scheme shown in the following formula (5), the compound described above as the exemplary compound (V-7) was synthesized.

In a three-necked flask, 18.7 g of the above exemplified compound (VI-7), 150 g of the above exemplified compound (III-6), 7.0 g of sodium acetate trihydrate, 500 mL of isopropyl alcohol, and an internal temperature of 80 to The mixture was heated and stirred at 85 ° C. for 12 hours. Thereafter, the internal temperature was set to 35 ° C., 800 mL of toluene as an organic solvent (B) and 260 mL of n-hexane were added and stirred, and 500 mL of methanol as an organic solvent (A) and 260 mL of water were added thereto for extraction and separation. Liquid operation was performed. The weight ratio of all organic solvents (organic solvents (A) and (B)) used in the extraction / separation operation is 31:69.
To the obtained organic layer, 500 mL of methanol and 260 mL of water were further added to perform extraction / separation operations. This operation was repeated five more times.
The organic layer thus obtained was crystallized from the residue obtained by concentrating with a rotary evaporator, and crystals were taken out.
As described above, 53.1 g of the target exemplified compound (V-7) was obtained. The exemplified compound (V-7) obtained had a yield of 98%, an HPLC area ratio of 99%, and an HPLC purity determined from a calibration curve of 99.1 wt% (the column was ODS-80Ts manufactured by Tosoh Corporation, and the eluent was THF). : Pure water = 4: 5 to 5: 4, detection wavelength 254 nm)). Moreover, the obtained crystal | crystallization was pale yellow and it was M ^<+ > ^/ e ⁼ 531.24 as a result of the mass spectrum.

[Example 4]
<Synthesis Example of Exemplified Compound (I-6) by Production Method (1) of the Present Invention>
In Example 2, the organic solvent (A) was replaced with methanol, ethanol, and xylene was used instead of toluene used as the organic solvent (B). The organic solvent used in the first extraction / separation operation ( Compound shown above as exemplary compound (I-6) in the same manner as in Example 2 except that the weight ratio of A) and organic solvent (B) was changed to 40:60 and the extraction temperature was changed to 10 ° C. Was synthesized.
The obtained exemplary compound (I-6) has a yield of 92%, an HPLC area ratio of 98%, and an HPLC purity determined from a calibration curve of 98.9 wt% (column is ODS-80Ts manufactured by Tosoh Corporation, eluent is THF) : Pure water = 4: 5 to 5: 4, detection wavelength 254 nm). The crystals of the obtained compound were pale yellow.

[Example 5]
<Synthesis Example of Exemplified Compound (I-6) by Production Method (1) of the Present Invention>
In Example 2, the organic solvent (A) was replaced with methanol and acetone, the n-hexane was replaced with toluene, and the total amount of the organic solvent (B) was toluene. The organic solvent used for the first extraction / separation operation Exemplified compound (I-6) as described above in Example 2 except that the weight ratio of (A) and organic solvent (B) was changed to 35:65 and the extraction temperature was changed to 25 ° C. The compound was synthesized.
The obtained exemplary compound (I-6) had a yield of 91%, an HPLC area ratio of 98%, and an HPLC purity determined from a calibration curve of 98.7 wt% (column is ODS-80Ts manufactured by Tosoh Corporation, eluent is THF) : Pure water = 4: 5 to 5: 4, detection wavelength 254 nm). The crystals of the obtained compound were pale yellow.

[Example 6]
<Synthesis Example of Exemplified Compound (I-6) by Production Method (1) of the Present Invention>
In Example 2, the organic solvent (A) was changed to acetone instead of acetone, toluene was used instead of n-hexane, and the whole amount of the organic solvent (B) was changed to toluene, which was used for the first extraction / separation operation. Exemplified compound (I-6) was obtained in the same manner as in Example 2 except that the weight ratio of the organic solvent (A) and the organic solvent (B) was changed to 15:85 and the extraction temperature was changed to 35 ° C. The compounds listed above were synthesized.
The obtained exemplary compound (I-6) had a yield of 91%, an HPLC area ratio of 99%, and an HPLC purity determined from a calibration curve of 98.7 wt% (column is ODS-80Ts manufactured by Tosoh Corporation, eluent is THF) : Pure water = 4: 5 to 5: 4, detection wavelength 254 nm). The crystals of the obtained compound were pale yellow.

[Example 7]
<Synthesis Example of Exemplified Compound (I-6) by Production Method (1) of the Present Invention>
In Example 2, 1050 mL of toluene which is an organic solvent (B) and 350 mL of n-hexane were added to the solvent used for the first extraction and stirred, and 160 mL of methanol which is an organic solvent (A) and 260 mL of water were further added thereto. Instead of adding, extraction and liquid separation operations were performed. Thus, the compound shown above as an example compound (I-6) was synthesize | combined like Example 2 except having changed the weight ratio of the organic solvent (A) and the organic solvent (B) into 10:90. .
The obtained exemplary compound (I-6) has a yield of 92%, an HPLC area ratio of 21%, and an HPLC purity determined from a calibration curve of 84.5 wt% (column is ODS-80Ts manufactured by Tosoh Corporation, eluent is THF) : Pure water = 4: 5 to 5: 4, detection wavelength 254 nm). The crystals of the obtained compound were yellow.

[Example 8]
<Synthesis Example of Exemplified Compound (I-6) by Production Method (1) of the Present Invention>
In Example 2, the above-described compound as compound (I-6) was synthesized in the same manner as in Example 2 except that sodium carbonate water was used instead of the water used in the first extraction / separation operation. did.
The obtained exemplary compound (I-6) has a yield of 65%, an HPLC area ratio of 16%, and an HPLC purity determined from a calibration curve of 94.6 wt% (column is ODS-80Ts manufactured by Tosoh Corporation, eluent is THF) : Pure water = 4: 5 to 5: 4, detection wavelength 254 nm). The crystals of the obtained compound were pale yellow.

[Comparative Example 1]
<Synthesis example of exemplary compound (I-6) by a method outside the scope of the production method of the present invention>
Exemplified compound (I-6) as described above in Example 2 except that an “extraction / separation step” different from the “extraction / separation step” in the production method (1) of the present invention was performed. The compound was synthesized as follows.

In a three-necked flask, 40.2 g of the exemplified compound (II-11), 150 g of the exemplified compound (III-6), 7.0 g of sodium acetate trihydrate, and 500 mL of isopropyl alcohol are added, and the internal temperature is 80 to 85 ° C. And stirred for 12 hours. Thereafter, the internal temperature was set to 35 ° C., 800 mL of toluene as the organic solvent (B) and 260 mL of n-hexane were added and stirred, and 760 mL of water was further added thereto to perform extraction / separation operation.
760 mL of water was further added to the obtained organic layer, and extraction / separation operations were performed. This operation was repeated five more times.
The organic layer thus obtained was crystallized from the residue obtained by concentrating with a rotary evaporator, and crystals were taken out. 132 g of the target exemplified compound (I-6) was obtained.
The obtained exemplary compound (I-6) has a yield of 90%, an HPLC area ratio of 19%, and an HPLC purity determined from a calibration curve of 70.3 wt% (column is ODS-80Ts manufactured by Tosoh Corporation, eluent is THF) : Pure water = 4: 5 to 5: 4, detection wavelength 254 nm). The crystals of the obtained compound were yellow.

[Comparative Example 2]
<Synthesis example of exemplary compound (I-6) by a method outside the scope of the production method of the present invention>
Exemplified compound (I-6) as described above in Example 2 except that an “extraction / separation step” different from the “extraction / separation step” in the production method (1) of the present invention was performed. The compound was synthesized as follows.

That is, in Example 2, instead of the organic solvent (B) used in the first extraction / separation operation, ethyl acetate was used, and the weight ratio of methanol and ethyl acetate as the organic solvent (A) was 31: The compound listed above as exemplary compound (I-6) was synthesize | combined like Example 2 except having carried out 69.
The obtained exemplary compound (I-6) has a yield of 94%, an HPLC area ratio of 17%, and an HPLC purity determined from a calibration curve of 76.8 wt% (column is ODS-80Ts manufactured by Tosoh Corporation, eluent is THF) : Pure water = 4: 5 to 5: 4, detection wavelength 254 nm). Moreover, the crystal | crystallization of the obtained exemplary compound was yellow.

  The types of the compounds represented by the general formula (I) or (V) to be synthesized in each of the above Examples and Comparative Examples, the types of the organic solvents (A) and (B) used in the extraction / separation step, The weight ratio A: B), the pH of the aqueous phase, the extraction temperature (° C.), the HPLC purity (area ratio) of the obtained compound and the color of the crystals are summarized in Table 1 below.

  From the above Examples and Comparative Examples, by using the production methods (1) and (2) of the present invention, the compound represented by the general formula (I) and the compound represented by the general formula (V) It can be seen that each can be produced with high purity.

Claims (12)

A compound represented by the following general formula (II) is reacted with a compound represented by the following general formula (III) to obtain a compound represented by the following general formula (I). After the substitution reaction step, in the presence of at least one organic solvent (A) having a dielectric constant of 5 or more, at least one organic solvent (B) having a dielectric constant of less than 5, and water, the following general formula ( A method for producing a compound represented by the following general formula (I), which comprises at least one extraction / separation step of extracting the compound represented by I) and separating it as an organic layer.

In the general formulas (I) and (II), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom; ^{11 to} L ¹⁴ each independently represents a single bond or a divalent linking group. —X— represents —O—, —S—, —N—, —C (R ¹⁴ ) —, and R ¹⁴ represents a hydrogen atom or a substituent. n ¹¹ and ^{n 12} are each independently an integer of 0 or more. However, when n ¹¹ and n ¹² are 1 or more at the same time, the arrangement order of the structural units forming the chain structure in [] is arbitrary. n ¹³ is 0 when —X— is —O— or —S—, and is 1 when —N— or —C (R ¹⁴ ) —. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ may be bonded to each other to form a ring.
In the general formula (III), L ^v represents a group containing at least one carbon atom, C ^* denotes a monovalent group containing a carbon atom, a nitrogen in which the C ^* is situated in general formula (II) By being substituted by an atom, a compound represented by the general formula (I) is formed.
In the general formula (IV), ^{L v} has the same meaning as ^{L v} in the general formula (III).
In the formula (1), one or more compounds represented by the general formula (III) are used, and C ^* in the general formula (I) may be the same or different. The production method according to claim 1, wherein the compound represented by the general formula (IV) is a compound represented by the following general formula (IV-a).

In the general formula (IV-a), R ⁴¹ represents —CO—R ⁴²¹ , —SO ₂ —R ⁴²² , —CO—NR ⁴²³ (R ⁴²⁴ ), or —CO—OR ⁴²⁵ , and R ⁴² represents hydrogen. An atom, an aliphatic group, an aromatic group, a heterocyclic group bonded by a carbon atom, or a group having the same meaning as R ⁴¹ , R ⁴²¹ , R ⁴²² , R ⁴²³ , R ⁴²⁴ and R ⁴²⁵ are a hydrogen atom, aliphatic A group, an aromatic group, or a heterocyclic group bonded with a carbon atom. R ⁴¹ and R ⁴² may combine with each other to form a ring. The manufacturing method according to claim 1 or 2, wherein the compound represented by the general formula (III) is a compound represented by the following general formula (III-a).

In general formula (III-a), R ³¹ and R ³² each independently represent a substituent having a σ _p value of 0.20 or more, and R ³³ , R ³⁴ , and R ³⁵ each independently represent hydrogen. represents atom, an aliphatic group, an aromatic group, a heterocyclic group bonded through a carbon ^{atom, R 41} and ^{R 42} has the same meaning as ^{R 41} and ^{R 42} in the general formula (IV-a).   The manufacturing method according to any one of claims 1 to 3, wherein a weight ratio of the organic solvent (A) having a dielectric constant of 5 or more to a total organic solvent is 15% or more.   The manufacturing method according to any one of claims 1 to 4, wherein in the extraction / separation step, the pH value of the aqueous layer after separating the organic layer is in the range of 5-9.   The manufacturing method according to any one of claims 1 to 5, wherein a temperature in the extraction / separation step is 0 ° C or higher.   The method according to any one of claims 1 to 6, wherein in the extraction / separation step, the organic layer / water layer distribution ratio of the compound represented by the general formula (IV) is 3 or less. . The production method according to any one of claims 1 to 7, wherein the compound represented by the general formula (III) is a compound represented by the following general formula (III-b).

In General Formula (III-b), R ³⁶ and R ³⁷ each independently represent an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, and R ³³ , R ³⁴ , R ³⁵ , R ⁴¹ And R ⁴² have the same meanings as R ³³ , R ³⁴ , R ³⁵ , R ⁴¹ and R ^{42 in} formula (III-a). The production according to any one of claims 1 to 8, wherein in the general formula (I) and the general formula (II), n ¹¹ is 1, n ¹² is 0, and n ¹³ is 0. Method. The production method according to any one of claims 1 to 9, wherein the compound represented by the general formula (I) is a compound represented by the following structural formula (Ia).

  The production method according to any one of claims 1 to 10, wherein the compound represented by the general formula (I) is obtained with a purity of 95% by mass or more. A compound represented by the following general formula (VI) is reacted with a compound represented by the following general formula (III-b) to obtain a compound represented by the following general formula (V). After the substitution reaction step shown, in the presence of at least one organic solvent (A) having a dielectric constant of 5 or more, at least one organic solvent (B) having a dielectric constant of less than 5, and water, The manufacturing method of the compound represented by the following general formula (V) which has the extraction and liquid separation process which extracts the compound represented by Formula (V), and liquid-separates as an organic layer at least once.

In the general formulas (III-b), (IV-a), (V) and (VI), R ²¹ and R ²² are each independently bonded with a hydrogen atom, an aliphatic group, an aromatic group, or a carbon atom. These may be bonded to each other to form a ring. R ³³ , R ³⁴ , and R ³⁵ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom. R ³⁶ and R ³⁷ each independently represents an aliphatic group, an aromatic group or a heterocyclic group bonded via a carbon atom. R ⁴¹ represents —CO—R ⁴²¹ , —SO ₂ —R ⁴²² , —CO—NR ⁴²³ (R ⁴²⁴ ), or —CO—OR ⁴²⁵ , and R ⁴² represents a hydrogen atom, an aliphatic group, or an aromatic group. , A heterocyclic group bonded by a carbon atom, or a group having the same meaning as R ⁴¹ , wherein R ⁴²¹ , R ⁴²² , R ⁴²³ , R ⁴²⁴ and R ⁴²⁵ are a hydrogen atom, an aliphatic group, an aromatic group, or a carbon atom Represents a heterocyclic group bonded with R ⁴¹ and R ⁴² may combine with each other to form a ring.