TWI824040B - Crystallization of a compound having a fluorine skeleton and its production method - Google Patents

Abstract

The present invention is a crystal of a compound having a fentanyl skeleton represented by the following formula (1), which has at least one endothermic peak obtained by differential scanning calorimetry in the range of 110 to 190°C. The crystallization of this compound is operated by It is easy to use the crystallization of this compound in the resin obtained from the raw material to reduce the quality variation. (In the formula, ring Z represents (the same or different) aromatic group, R ¹ and R ² independently represent a hydrogen atom, a halogen atom or a hydrocarbon group that may contain an aromatic group with 1 to 12 carbon atoms, Ar ¹ and Ar ² represents an aromatic group which may have a substituent having a carbon number of 6 to 10, L ¹ and L ² represent an alkylene group, and m and n each independently represent an integer of 0 to 5).

Description

Crystallization of a compound having a fluorine skeleton and its production method

The present invention relates to the crystallization of a compound having a novel fluorine skeleton that is suitable as a monomer for forming resins (optical resins) constituting optical components represented by optical lenses and optical films and has excellent processability and productivity, and a method for producing the same.

In recent years, polycarbonates, polyesters, polyester carbonates, etc., which use alcohols having a fluorine skeleton represented by 9,9-bis(4-(2-hydroxyethoxy)phenyl)quinone (BPEF) as raw materials Thermoplastic resin materials are attracting attention as optical components such as optical lenses and optical sheets due to their excellent optical properties, heat resistance, formability, etc.

As a method for producing 9,9-bis(4-(2-hydroxyethoxy)phenyl)quinone (BPEF), it is disclosed that sulfuric acid and mercaptans are used as catalysts to dehydrate quinone and phenoxyethanol. Condensation method (Non-Patent Document 1). In addition, it is disclosed that 9,9-bis(4-(4-hydroxyphenyloxy)phenyl)quinone (OPBPEF) uses a metallic acid catalyst such as zinc chloride in addition to sulfuric acid to combine quinone with Method for dehydration and condensation of p-phenoxyphenol (Patent Document 1). However, with either method, sulfur components or metal components derived from catalysts are mixed into the product, causing problems such as coloration of the product, a decrease in stability, and a decrease in purity. Furthermore, in order to obtain high-purity products such as optical resin materials, it is necessary to repeat the purification operation to remove sulfur or metal components, which cannot be said to be an industrially advantageous method.

Furthermore, it is disclosed that 9,9-bis(4-(4-hydroxyphenyloxy)phenyl)benzoate (OPBPEF) has polycrystals derived from alcohol compounds, and is formed by reaction or removal operation after reaction (crystallization operation) ) and have crystals with different melting points (Patent Document 2). In this way, the alcohol compound in the fluorine skeleton changes in the form of the product, so it becomes difficult to provide a thermoplastic resin material with stable quality. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2015-182970 [Patent Document 2] Japanese Patent Application Publication No. 2018-48086 [Non-patent literature]

[Non-patent document 1] Chemistry Letters, 1998, pages 1055-1056

[Problem to be solved by the invention]

In the present invention, although the method for producing the compound of the following formula (1) through molecular design consists of two steps, it includes various forms such as crystalline or glassy, and the operability with a certain quality cannot be obtained. Excellent compounds.

In addition, when the amount of catalyst used in step 1 is large, or when activated carbon treatment or other metal removal treatment is not sufficient, the crystals of the compound represented by the following formula (1) are mixed with the catalyst derived from step 1. The black particles of the palladium catalyst used in the reaction cause the color of the alcohol compound to deteriorate.

Accordingly, an object of the present invention is to provide a crystallization of a compound having a fluorine skeleton that is easy to handle and a method for producing the same.

Furthermore, as another object, it is to provide a crystalline compound with a low content of specific metals such as palladium content in the raw material, and a resin using the raw material that is excellent in hue or various properties (optical properties, heat resistance, formability, etc.) with novel properties. Crystallization of skeleton compounds and methods for their production. [Means used to solve problems]

The inventors of the present invention have made efforts and research in order to solve the above-mentioned problems of the conventional technology. As a result, they have found that the crystallization operation of a compound with a fluorine skeleton having a specific endothermic peak is easy, and the quality variation of the resin obtained by using the crystallization of this compound as a raw material has been found. become less.

Furthermore, it was discovered that a crystal of a compound having a fluorine skeleton and a sufficiently low palladium content is excellent in hue and various properties (optical properties, heat resistance, moldability, etc.) of a resin obtained by using the crystal of this compound as a raw material.

That is, according to the present invention, the subject of the invention is achieved as follows.

1. A crystal of a compound having a fluorine skeleton represented by the following formula (1), which has at least one endothermic peak in the range of 110 to 190°C as measured by differential scanning calorimetry.

(In the formula, ring Z represents (the same or different) aromatic group, R ¹ and R ² independently represent a hydrogen atom, a halogen atom or a hydrocarbon group that may contain an aromatic group with 1 to 12 carbon atoms, Ar ¹ and Ar ² represents an aromatic group which may have a substituent having a carbon number of 6 to 10, L ¹ and L ² represent an alkylene group, and m and n each independently represent an integer of 0 to 5). 2. The crystal of the compound having a fluorine skeleton as described in the preceding paragraph 1, which contains 95% by weight or more of the fluorine derivative represented by the above formula (1).

3. The crystal of the compound having a fluorine skeleton as described in the preceding item 1, wherein the palladium element content satisfies the following formula (2).

4. A method for producing a crystal as described in the preceding paragraph 1, which includes the following steps 1, 2 and a crystal production step. Step 1: A step of reacting a quinone represented by the following formula (3) and a boric acid represented by the following formula (4) in a reaction solvent in the presence of an alkali and a catalyst,

(X ¹ and X ² represent halogen atoms).

(Y represents an aromatic group, and R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group or a halogen atom) Step 2: The reactant represented by the following formula (5) produced in step 1 is mixed with the following formula ( 6) The step of reacting the alcohol compound represented in the reaction solvent using an acid catalyst,

(Ar ¹ and Ar ² are the same as formula (1)).

(Ring Z is the same as formula (1); R ⁴ represents a hydrogen atom, a halogen atom or a hydrocarbon group that may contain an aromatic group with 1 to 12 carbon atoms, L ³ represents an alkylene group, and l represents an integer of 0 to 5). Crystallization production step: use a solvent to dissolve the compound obtained in step 2, perform a recrystallization operation, and take out the crystallization step. [Effects of the invention]

According to the present invention, it is possible to obtain a crystal of a compound that is easy to handle and has a fluorine skeleton, and has the effect of reducing the variation in the quality of a resin obtained by using the crystal of this compound as a raw material. In addition, it is possible to obtain crystals of a compound having a fluorine skeleton with a small palladium content, and the resin obtained by using the crystal of this compound as a raw material has the effect of being excellent in hue and various properties (optical properties, heat resistance, moldability, etc.).

Although the present invention has been described in detail, the descriptions of the constituent elements described below are representative examples of embodiments of the present invention and are not limited thereto. (Crystal of a compound with a fluorine skeleton) The crystal of a compound having a fluorine skeleton of the present invention is a crystal of a compound having a fluorine skeleton represented by the following formula (1), which has at least one temperature in the range of 110 to 190°C as determined by differential scanning calorimetry. Endothermic peak.

(In the formula, ring Z represents (the same or different) aromatic group, R ¹ and R ² independently represent a hydrogen atom, a halogen atom or a hydrocarbon group that may contain an aromatic group with 1 to 12 carbon atoms, Ar ¹ and Ar ² represents an aromatic group which may have a substituent having a carbon number of 6 to 10, L ¹ and L ² represent an alkylene group, and m and n each independently represent an integer of 0 to 5). The crystal of the compound having a fluorine skeleton preferably has at least one endothermic peak obtained by differential scanning calorimetry in the range of 115 to 185°C, and more preferably has at least one endothermic peak in the range of 120 to 180°C. Note that the endothermic peak represents the melting point (Tm) of the crystal of a compound having a fluorine skeleton.

The crystallization of the compound having a fluorine skeleton is easy to handle, and has the effect of reducing the quality variation of the resin obtained by using the crystallization of the compound as a raw material.

Furthermore, the crystal of the compound containing the fentanyl derivative represented by the above formula (1) is preferably 95 wt% or more, more preferably 96 wt% or more of the compound, and still more preferably 97 wt% or more of the compound. The crystal is preferably a crystal containing 98% by weight or more of the compound, and most preferably a crystal containing 99% by weight or more of the compound. Purity was determined from HPLC purity. In addition to the fluorine derivative component represented by the above formula (1), raw materials or solvents used in the reaction and by-products generated in the reaction may be included.

Furthermore, the crystal of the compound having a fluorine skeleton represented by the above formula (1) is preferably such that the palladium element content satisfies the following formula (2).

It is preferable to satisfy the following formula (2-1).

More preferably, it satisfies the following formula (2-2).

More preferably, it satisfies the following formula (2-3).

Particularly preferably, it satisfies the following formula (2-4).

It is optimal to satisfy the following formula (2-5).

When the upper limit of the above range is exceeded, the hue of the resin using the compound represented by the aforementioned formula (1) or the optical member using the resin may be adversely affected.

In the above formula (1), examples of the aromatic group represented by ring Z include, in addition to a benzene ring, condensed polycyclic aromatic hydrocarbons having at least a benzene ring skeleton. For example, preferred are condensed bicyclic hydrocarbons and condensed tricyclic hydrocarbons. Condensation of cyclic hydrocarbons, etc. Two to four cyclic hydrocarbon rings, etc.

The condensed bicyclic hydrocarbon ring is preferably a condensed bicyclic hydrocarbon ring having 8 to 20 carbon atoms (hereinafter sometimes expressed as C8-20) such as an indene ring or a naphthalene ring, and more preferably a condensed bicyclic hydrocarbon ring of C10-16. Moreover, as the condensed tricyclic hydrocarbon ring, an onion ring, a phenanthrene ring, etc. are preferable.

Among ring Z, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.

In the above formula (1), as a specific example of the aromatic hydrocarbon ring represented by ring Z, a 1,4-phenylene group, a 1,4-naphthylenediyl group or a 2,6-naphthylenediyl group is preferable, and a more preferable one is 1,4-phenylene.

Furthermore, the two rings Z replacing the 9-position of the fluorine ring may be the same as each other or may be different from each other, and more preferably, they are the same ring. Incidentally, the substituent substituting ring Z at position 9 of the fluorine skeleton is not particularly limited. For example, when ring Z is naphthalene, the group of ring Z corresponding to the 9-position substituted fluorine ring can be 1-naphthyl, 2-naphthyl, etc.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms, and is preferably a hydrogen atom, a methyl group or a phenyl group.

In the above formula (1), examples of the hydrocarbon group represented by R ¹ and R ² include an alkyl group, a cycloalkyl group, an aryl group, a naphthyl group, an aralkyl group, and the like. Specific examples of the alkyl group are preferably C1-6 alkyl groups, C1-4 alkyl groups, C1-3 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, etc. More preferably, it is a C1-3 alkyl group, and even more preferably, it is a methyl or ethyl group.

Moreover, as a specific example of a cycloalkyl group, a C5-8 cycloalkyl group, a C5-6 cycloalkyl group, etc. such as a cyclopentyl group, a cyclohexyl group, etc. are preferable, and a C5-6 cycloalkyl group is more preferable.

Moreover, as a specific example of an aryl group, a phenyl group, an alkylphenyl group (mono or dimethylphenyl, tolyl, 2-methylphenyl, xylyl, etc.) etc. are preferable, and a phenyl group is more preferable. .

Further, as specific examples of the aralkyl group, preferably C6-10 aryl-C1-4 alkyl groups such as benzyl group and phenethyl group can be exemplified.

Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are preferable.

In the above formula (1), the substitution numbers of the substituents R ¹ and R ² can be appropriately selected according to the number of condensed rings of the condensed hydrocarbon, etc., and are not particularly limited. It is preferable that they independently represent an integer of 0 or more, and more preferably 1 or more. . Moreover, an integer of 6 or less is preferable, and an integer of 4 or less is more preferable. However, the number of substitutions in ring Z can be the same or different, and usually the same is the case.

In the above formula (1), L ¹ and L ² each independently represent a divalent linking group, preferably an alkylene group having 1 to 12 carbon atoms, more preferably an ethylene group. Usually, L ¹ and L ² are in the same ring Z and can be the same alkylene group. In addition, L ¹ and L ² may be the same or different from each other in different rings Z, and usually they may be the same.

The numbers of the oxyalkylene groups (OL ¹ ) and (OL ² ) (addition molar number) m and n can be selected from the range of 0 to 5 respectively. The lower limit is preferably 0 or more, and the upper limit is preferably 4 or less, more preferably The best value is 3 or less, and even better is 2 or less. Excellent is 0 or 1, best is 1. Shang, m and n can be integers or average values, and they can be the same or different in different rings Z.

In the above formula (1), Ar ¹ and Ar ² each independently represent an aromatic group having 6 to 10 carbon atoms, preferably a phenyl group or a naphthyl group. Although the groups Ar ¹ and Ar ² may be different from each other or the same as each other, they are usually the same. In addition, the respective bonding positions of Ar ¹ and Ar ² are preferably the 1st and 8th positions, the 2nd and 7th positions, the 3rd and 6th positions, or the 4th and 5th positions of the skeleton, and more preferably the 2nd and 7th positions. digits, 3 digits and 6 digits, or 4 digits and 5 digits, preferably 2 digits and 7 digits.

Although representative examples of the compounds represented by the aforementioned formula (1) are shown below, the compounds used in the present invention by the aforementioned formula (1) are not limited thereto.

Preferable examples of diphenyl fluoride include 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-diphenyl fluoride and 9,9-bis(4-(2 -Hydroxyethoxy)-3-methylphenyl)-1,8-diphenylbenzene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1 ,8-diphenyl fluoride, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-1,8-diphenyl fluoride, 9,9-bis(6-(2 -Hydroxyethoxy)-2-naphthyl)-1,8-diphenyl fluoride, 9,9-bis(4-hydroxyphenyl)-1,8-diphenyl fluoride, 9,9-bis( 4-Hydroxy-3-methylphenyl)-1,8-diphenyl fluoride, 9,9-bis(4-hydroxy-3-phenylphenyl)-1,8-diphenyl fluoride, 9, 9-bis(4-hydroxy-1-naphthyl)-1,8-diphenyl fluoride, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-diphenyl fluoride, 9, 9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluoride, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl )-2,7-diphenyl fluoride, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-diphenyl fluoride, 9,9-bis (4-(2-hydroxyethoxy)-1-naphthyl)-2,7-diphenylfluoride, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)- 2,7-diphenyl fluoride, 9,9-bis(4-hydroxyphenyl)-2,7-diphenyl fluoride, 9,9-bis(4-hydroxy-3-methylphenyl)-2 ,7-Diphenyl fluoride, 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-diphenyl fluoride, 9,9-bis(4-hydroxy-1-naphthyl) -2,7-diphenyl fluoride, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenyl fluoride, 9,9-bis(4-(2-hydroxyethoxy) )phenyl)-3,6-diphenyl fluoride, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-3,6-diphenyl fluoride, 9, 9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-3,6-diphenylfluoride, 9,9-bis(4-(2-hydroxyethoxy)-1 -Naphthyl)-3,6-diphenyl fluoride, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-3,6-diphenyl fluoride, 9,9- Bis(4-hydroxyphenyl)-3,6-diphenyl fluoride, 9,9-bis(4-hydroxyphenyl)-3,6-diphenyl fluoride, 9,9-bis(4-hydroxyphenyl)-3,6-diphenyl fluoride (4-Hydroxy-3-phenylphenyl)-3,6-diphenyl fluoride, 9,9-bis(4-hydroxy-1-naphthyl)-3,6-diphenyl fluoride, 9,9 -Bis(6-hydroxy-2-naphthyl)-3,6-diphenyl fluoride, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-4,5-diphenyl fluoride , 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-4,5-diphenylfluoride, 9,9-bis(4-(2-hydroxyethoxy) )-3-phenylphenyl)-4,5-diphenylbenzene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-4,5-diphenylbenzene , 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-4,5-diphenylfluoride, 9,9-bis(4-hydroxyphenyl)-4,5- Diphenyl fluoride, 9,9-bis(4-hydroxy-3-methylphenyl)-4,5-diphenyl fluoride, 9,9-bis(4-hydroxy-3-phenylphenyl)- 4,5-diphenyl fluoride, 9,9-bis(4-hydroxy-1-naphthyl)-4,5-diphenyl fluoride, 9,9-bis(6-hydroxy-2-naphthyl)- 4,5-diphenylbenzoate, etc.

Among them, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-diphenylfluoride and 9,9-bis(4-(2-hydroxyethoxy)phenyl) Phenyl)-2,7-diphenyl fluoride, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-3,6-diphenyl fluoride, 9,9-bis(4- (2-Hydroxyethoxy)phenyl)-4,5-diphenyl fluoride, 9,9-bis(4-hydroxyphenyl)-1,8-diphenyl fluoride, 9,9-bis(4 -Hydroxyphenyl)-2,7-diphenyl fluoride, 9,9-bis(4-hydroxyphenyl)-3,6-diphenyl fluoride, 9,9-bis(4-hydroxyphenyl)- 4,5-diphenyl fluoride, particularly preferably 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenyl fluoride, 9,9-bis(4-hydroxy Phenyl)-2,7-diphenyl fluoride.

Preferable dinaphthyl fluoride types include 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-dinaphthyl fluoride and 9,9-bis(4-(2 -Hydroxyethoxy)-3-methylphenyl)-1,8-dinaphthylfluoride, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1 ,8-dinaphthyl fluoride, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-1,8-dinaphthyl fluoride, 9,9-bis(6-(2 -Hydroxyethoxy)-2-naphthyl)-1,8-dinaphthylfluoride, 9,9-bis(4-hydroxyphenyl)-1,8-dinaphthylfluoride, 9,9-bis( 4-Hydroxy-3-methylphenyl)-1,8-dinaphthyl fluoride, 9,9-bis(4-hydroxy-3-phenylphenyl)-1,8-dinaphthyl fluoride, 9, 9-bis(4-hydroxy-1-naphthyl)-1,8-dinaphthyl fluoride, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-dinaphthyl fluoride, 9, 9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluoride, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl )-2,7-dinaphthyl fluorine, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-dinaphthyl fluorine, 9,9-bis (4-(2-hydroxyethoxy)-1-naphthyl)-2,7-dinaphthylfluoride, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)- 2,7-dinaphthyl fluoride, 9,9-bis(4-hydroxyphenyl)-2,7-dinaphthyl fluoride, 9,9-bis(4-hydroxy-3-methylphenyl)-2 ,7-dinaphthyl fluoride, 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-dinaphthyl fluoride, 9,9-bis(4-hydroxy-1-naphthyl) -2,7-dinaphthylfluoride, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-dinaphthylfluoride, 9,9-bis(4-(2-hydroxyethoxy) )phenyl)-3,6-dinaphthylfluoride, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-3,6-dinaphthylfluoride, 9, 9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-3,6-dinaphthylfluoride, 9,9-bis(4-(2-hydroxyethoxy)-1 -naphthyl)-3,6-dinaphthylfluoride, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-3,6-dinaphthylfluoride, 9,9- Bis(4-hydroxyphenyl)-3,6-dinaphthyl fluoride, 9,9-bis(4-hydroxy-3-methylphenyl)-3,6-dinaphthyl fluoride, 9,9-bis(4-hydroxyphenyl)-3,6-dinaphthyl fluoride (4-Hydroxy-3-phenylphenyl)-3,6-dinaphthyl fluoride, 9,9-bis(4-hydroxy-1-naphthyl)-3,6-dinaphthyl fluoride, 9,9 -Bis(6-hydroxy-2-naphthyl)-3,6-dinaphthyl fluoride, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-4,5-dinaphthyl fluoride , 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-4,5-dinaphthylfluoride, 9,9-bis(4-(2-hydroxyethoxy) )-3-phenylphenyl)-4,5-dinaphthylfluoride, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-4,5-dinaphthylfluoride , 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-4,5-dinaphthylfluoride, 9,9-bis(4-hydroxyphenyl)-4,5- Dinaphthyl fluoride, 9,9-bis(4-hydroxy-3-methylphenyl)-4,5-dinaphthyl fluoride, 9,9-bis(4-hydroxy-3-phenylphenyl)- 4,5-dinaphthylfluoride, 9,9-bis(4-hydroxy-1-naphthyl)-4,5-dinaphthylfluoride, 9,9-bis(6-hydroxy-2-naphthyl)- 4,5-dinaphthylfluoride, etc.

Among them, more preferred are 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-dinaphthylfluoride and 9,9-bis(4-(2-hydroxyethoxy) Phenyl)-2,7-dinaphthyl fluoride, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-3,6-dinaphthyl fluoride, 9,9-bis(4- (2-Hydroxyethoxy)phenyl)-4,5-dinaphthylfluoride, 9,9-bis(4-hydroxyphenyl)-1,8-dinaphthylfluoride, 9,9-bis(4 -Hydroxyphenyl)-2,7-dinaphthyl fluoride, 9,9-bis(4-hydroxyphenyl)-3,6-dinaphthyl fluoride, 9,9-bis(4-hydroxyphenyl)- 4,5-dinaphthyl fluoride, particularly preferably 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthyl fluoride, 9,9-bis(4-hydroxyl) Phenyl)-2,7-dinaphthylfluoride. (Method for producing crystals of compounds having fluorine skeleton) The crystallization of the compound represented by the above formula (1) of the present invention is preferably a process including the following steps 1, 2 and The method of crystallization manufacturing steps is manufactured. By producing a crystal of the compound represented by the above formula (1) in the following method, a crystal of the compound having the above characteristics can be obtained. Step 1: A step of reacting a quinone represented by the following formula (3) and a boric acid represented by the following formula (4) in a reaction solvent in the presence of an alkali and a catalyst,

(X ¹ and X ² represent halogen atoms).

(Y represents an aromatic group, and R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group or a halogen atom). Step 2: A step of reacting the reactant represented by the following formula (5) produced in step 1 and the alcohol compound represented by the following formula (6) in a reaction solvent using an acid catalyst,

(Ar ¹ and Ar ² are the same as formula (1)).

(Ring Z is the same as formula (1); R ⁴ represents a hydrogen atom, a halogen atom or a hydrocarbon group that may contain an aromatic group with 1 to 12 carbon atoms, L ³ represents an alkylene group, and l represents an integer of 0 to 5). Crystallization production step: use a solvent that dissolves the compound obtained in step 2, perform a recrystallization operation, and take out the crystallization step. Describe the details of the following individual steps (step 1). Step 1 is to combine the quinones represented by the above formula (3) with The step of reacting boric acid represented by the above formula (4) in a reaction solvent in the presence of a base and a catalyst.

The compound represented by the above formula (3) is a quinone compound corresponding to the quinone skeleton in the aforementioned formula ( ¹ ), X ¹ is a substituent at the 1-position, 2-position, 3-position or 4-position, and , the substituent at position 7 or 8 represents a halogen atom.

Although representative examples of the quinone compounds represented by the above-mentioned formula (3) are shown below, the raw materials used in the above-mentioned formula (1) of the present invention are not limited by these.

Specific examples of the quinone compound include preferably 1,8-difluorofonone, 2,7-difluorofonone, 3,6-difluorofonone, 4,5-difluorofonone, and 1, 8-dichlorofluorinone, 2,7-dichlorofluorinone, 3,6-dichlorofluorinone, 4,5-dichlorofluorinone, 1,8-diiodofluorinone, 2,7-diiodofluorinone Ketone, 3,6-diiodoquinone, 4,5-diiodoquinone, 1,8-dibromoquinone, 2,7-dibromoquinone, 3,6-dibromoquinone, 4,5 -Dibromoquinone, etc. Among them, 1,8-dibromoquinone, 2,7-dibromoquinone, 3,6-dibromoquinone, and 4,5-dibromoquinone are preferred, and 2,7-dibromoquinone is particularly preferred. Filone.

These can be used alone, or two or more types can be mixed, and can be selected arbitrarily depending on the purpose. In the present invention, 2,7-dibromoquinone is preferred.

The purity of the quinones represented by the aforementioned formula (3) is not particularly limited, but is generally preferably 95% or more, and more preferably 99% or more. However, commercially available quinones can also be used, or synthetic ones can be used.

The ring Y of the compound represented by the above formula (4) corresponds to the groups Ar ¹ and Ar ² of the above formula (1). In addition, in the aforementioned formula (4), the preferred aspect of the group R ³ is the same as the preferred aspect of the aforementioned R ¹ and R ² .

Although the purity of the boric acids represented by the above formula (4) is not particularly limited, it is generally preferably 95% or more, and more preferably 99% or more. However, commercially available boric acids can be used, or synthetic ones can be used.

The boric acid used in the present invention includes alkylboronic acid, alkenylboronic acid, arylboronic acid, heteroarylboronic acid and anhydride thereof represented by the aforementioned formula (4). Examples of alkylboronic acid include butylboronic acid, cyclohexylboronic acid, cyclohexylboronic acid, cyclohexylboronic acid, and anhydride. Pentylboronic acid, 2-ethylboronic acid, 4-ethylboronic acid, hexylboronic acid, isobutylboronic acid, isopropylboronic acid, methylboronic acid, n-octylboronic acid, propylboronic acid, amylboronic acid, 2-benzene Ethylboronic acid or these anhydrides, as alkenylboronic acid, including 1-cyclopentenylboronic acid, ferroceneboronic acid, 1,1'-ferrocene diboronic acid or these anhydrides, as arylboronic acid, Contains 2-onium boric acid, 9-ononium boric acid, benzylboric acid, 2-biphenylboric acid, 3-biphenylboric acid, 4-biphenylboric acid, 2,3-dimethylphenylboronic acid, 2,4-dimethyl phenylboronic acid, 2,5-dimethylphenylboronic acid, 2,6-dimethylphenylboronic acid, 3,4-dimethylphenylboronic acid, 3,5-dimethylphenylboronic acid, 2 -Ethoxyphenylboronic acid, 3-ethoxyphenylboronic acid, 4-ethoxyphenylboronic acid, 6-methoxy-2-naphthaleneboronic acid, 2-methylphenylboronic acid, 3-methylbenzene boronic acid, 4-methylphenylboronic acid, 1-naphthaleneboronic acid, 2-naphthylboronic acid, 9-phenanthreneboronic acid, 10-phenyl-9-onionboronic acid, phenylboronic acid, phenylethaneboronic acid, 4-phenylboronic acid (Naphthalen-1-yl)boronic acid, 3-propoxyphenylboronic acid, 3-iso-propoxyphenylboronic acid, 4-iso-propoxyphenylboronic acid, 4-propylphenylboronic acid, 4- Iso-propylphenylboronic acid, 10-(naphthyl-1-yl)-9-allium boronic acid, 10-(naphth-2-yl)-9-allium boronic acid or anhydrides thereof, as heteroarylboronic acids, include Benzofuran-2-boric acid, dibenzofuran-4-boric acid, 5-formyl-2-furanboric acid, 5-formylthiophene-2-boric acid, furan-2-boric acid, furan-3-boric acid , pyridine-3-boric acid, pyridine-4-boric acid, quinoline-2-boric acid, quinoline-3-boric acid, quinoline-4-boric acid, quinoline-5-boric acid, quinoline-6-boric acid, quinoline -8-boronic acid, iso-quinoline-4-boronic acid, 2-thiopheneboronic acid, 3-thiopheneboronic acid, 5-pyrimidineboronic acid or anhydrides of these.

These can be used alone, or two or more types can be mixed, and can be selected arbitrarily depending on the purpose. In the present invention, phenylboronic acid or anhydride thereof is preferred.

The usage ratio of the compound represented by the aforementioned formula (4) when used as a raw material is preferably 2.0 to 5.0 moles, more preferably 2.0 to 1 mole of the compound represented by the aforementioned formula (3) (halogenated quinone compound). 3.0 moles, preferably 2.05~2.5 moles. When the boric acid content is less than 2.0 mol, the yield of the product represented by the aforementioned formula (6) may decrease. Moreover, when it exceeds 5.0 mol, although the reaction rate becomes faster and the yield improves, the manufacturing cost of the compound which has this fluorine skeleton may increase.

The reaction (dehalogenation reaction) of the compound represented by the aforementioned formula (3) and the aforementioned formula (4) in step 1 can be carried out in the reaction solvent in the presence of a base and a catalyst.

Examples of the base used in the reaction in step 1 include hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), and cesium carbonate (Cs ₂ CO ₃ ) Inorganic salts such as carbonates, acetates such as sodium acetate and potassium acetate, phosphates such as sodium phosphate (Na ₃ PO ₄ ), potassium phosphate (K ₃ PO ₄ ), etc., triethylamines, pyridine , organic salts of ammonium salts such as morpholine, quinoline, piperidine, anilines, tetra-n-butylammonium acetate, etc. Among them, carbonates are preferably used, and potassium carbonate and/or sodium carbonate are preferred. Such bases may be used alone, or two or more types may be used in combination.

In addition, in the reaction of step 1, the usage amount of the above-mentioned base is not particularly limited, but it is preferably 1 to 30 equivalents, and more preferably 1 to 10 equivalents per mole of boric acid.

As the catalyst used in the reaction in step 1, the palladium compound used in the Suzuki coupling is preferably (Diphenylideneacetone)dipalladium, bis(diphenylideneacetone)palladium, bis[4-(N, N-dimethylamino)phenyl]di-tert-butylphosphine palladium dichloride, Bis(di-tert-butylisoprenylphosphine)palladium dichloride, bis(di-tert-crotylphosphine)palladium dichloride. Or a catalyst that fixes palladium on metal is also preferable. Examples include palladium supported on silica (PL catalyst), Pd/C (palladium supported on carbon), and the like. Among them, quaternary (triphenylphosphine) palladium and/or PL catalyst are preferred. Such catalysts can be used alone, or two or more types can be used in combination.

In the reaction of step 1, the usage amount of the above-mentioned catalyst is not particularly limited, but it is preferably 0.005 to 0.5 mmol in terms of palladium metal atoms relative to 1 mole of the quinone compound represented by the aforementioned formula (3). , more preferably 0.1～0.3 mmol. When the usage amount of the palladium catalyst is less than 0.005 mmol in terms of palladium metal atoms, the reaction may not be completed. In addition, when the usage amount of the palladium catalyst exceeds 5 millimoles in terms of palladium metal atoms, although the reaction is completed, it becomes difficult to set the palladium element content in the compound having the fluorine skeleton within the range of formula (2), and there is a problem. The possibility of using this compound to worsen the hue of the manufactured thermoplastic resin.

As the reaction solvent used in step 1, for example, aromatic hydrocarbon solvents such as toluene and xylene can be used alone or in combination with alcohols such as methanol, ethanol, isopropyl alcohol, and n-butanol. Aromatic hydrocarbon-based solvents are high-boiling-point solvents and can be used to increase the set reaction temperature. Furthermore, by using alcohol, they have good affinity with water and have good reactivity, so they can be suitably used. Such solvents can be used alone, or two or more types can be used in combination. Furthermore, aprotic solvents such as N,N-dimethylformamide or N,N-dimethylacetamide, and halobenzenes such as o-dichlorobenzene can also be used. Such solvents can be used alone, or two or more types can be used in combination. In the present invention, it is more preferred to use a mixed solvent of toluene and ethanol or toluene.

The usage amount of the reaction solvent (in the case of the present invention, preferably a mixed solvent of toluene and ethanol or toluene) is not particularly limited. However, toluene is preferably 0.1 wt. times or more, preferably 0.5 to 100 times by weight, still more preferably 1 to 50 times by weight. When the amount of toluene used is less than 0.1 times by weight, the precipitated product may become difficult to stir. In addition, when the usage amount of toluene exceeds 100 times by weight, there is no effect commensurate with the usage amount, and the volumetric efficiency is also deteriorated, which may increase the production cost of the compound having the fluorine skeleton. In addition, the usage amount of ethanol is not particularly limited, but it is preferably 0.1 to 50 times by weight, and more preferably 1 to 20 times by weight relative to the quinones represented by the aforementioned formula (3). When the amount of ethanol used is less than 0.1 times by weight, the reaction rate may be slowed down and the yield may be reduced. In addition, when the usage amount of ethanol exceeds 50 times by weight, there is no effect commensurate with the usage amount like toluene, and the volumetric efficiency is also deteriorated, which may increase the production cost of the compound having this fluorine skeleton.

Although the reaction temperature varies depending on the types of raw materials and solvents used, it is preferably 50 to 150°C, more preferably 60 to 130°C, and still more preferably 70 to 120°C. The reaction can be followed by analytical means such as liquid chromatography.

The reaction mixture after the reaction usually contains, in addition to the compound represented by the aforementioned formula (5), unreacted quinones, unreacted boric acids, bases, catalysts, side reaction products, etc. Therefore, it can be separated by conventional methods, such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or very similar metal removal treatment, column chromatography, etc., or a combination of these separation means for separation and purification. For example, boric acid can be removed by conventional methods (methods such as adding alkali aqueous solution to form a water-soluble complex, etc.), activated carbon treatment or metal removal treatment that is very similar to it can be performed by removing the palladium compound and then adding recrystallization. The solvent is cooled to recrystallize, and then filtered and separated for purification. (step 2) Step 2 is a step in which the reactant represented by the above formula (5) produced in step 1 and the alcohol compound represented by the above formula (6) are reacted in a reaction solvent using an acid catalyst.

In the above formula (6), ring Z corresponds to ring Z in the above formula (1), L ³ corresponds to L ¹ and L ² , l corresponds to m and n, R ⁴ corresponds to R ¹ and R ² , and benzene exemplified above can be exemplified. ring or naphthalene ring.

The alkylene group represented by L ³ is not particularly limited, but examples thereof include ethylene, propylene, trimethylene, tetramethylene, hexamethylene, and the like. An alkylene group having 1 to 6 carbon atoms is preferred, and an alkylene group having 2 to 3 carbon atoms is more preferred. The replacement position of L ³ is not particularly limited. The number of substituents l is 0 or 1 or more, and may be the same or different. Preferably it is 0-15, More preferably, it is 0-5. Furthermore, when l is 2 or more, the polyalkoxy group may be composed of the same alkoxy group, and may be mixed with different types of alkoxy groups (such as ethoxy group and propyleneoxy group), but it is usually composed of The same alkoxy group composition.

R ⁴ represents a hydrogen atom, a halogen atom or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms, and is preferably a hydrogen atom, a methyl group or a phenyl group.

Examples of the hydrocarbon group represented by R ⁴ include an alkyl group, a cycloalkyl group, an aryl group, a naphthyl group, an aralkyl group, and the like. Specific examples of the alkyl group are preferably C1-6 alkyl groups, C1-4 alkyl groups, C1-3 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, etc. More preferably, it is a C1-3 alkyl group, and even more preferably, it is a methyl or ethyl group. Specific examples of the cycloalkyl group are preferably C5-8 cycloalkyl groups such as cyclopentyl and cyclohexyl groups, C5-6 cycloalkyl groups, etc., and more preferably C5-6 cycloalkyl groups. Specific examples of the aryl group are preferably phenyl, alkylphenyl (mono- or dimethylphenyl, tolyl, 2-methylphenyl, xylyl, etc.), and more preferably phenyl. Specific examples of the aralkyl group include preferably C6-10 aryl-C1-4 alkyl groups such as benzyl and phenethyl groups. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are preferred.

The number of substitutions of the substituent R ⁴ can be appropriately selected according to the number of condensed rings of the condensed hydrocarbon, etc., and is not particularly limited. It is preferably an integer of 0 or more, more preferably 1 or more. Moreover, an integer of 6 or less is preferable, and an integer of 4 or less is more preferable.

Specific examples of the compound represented by the formula (6) include alkylphenols such as phenol, 2-methylphenol, and 3-methylphenol; 2,3-xylenol; Dialkylphenols such as 2,6-xylenol and 3,5-xylenol, alkoxyphenols such as 2-methoxyphenol and 2-ethoxyphenol, 2-phenylphenol, 3- Phenylphenol, etc. Phenylphenol, etc. Examples of compounds in which l=1 include phenoxyalkyl alcohols such as phenoxyethanol, phenoxypropanol, and phenoxybutanol, (2-methyl-phenoxy)ethanol, (3-methyl (3-ethyl-phenoxy)ethanol, (3-ethyl-phenoxy)ethanol, (3-butyl-phenoxy)ethanol, (2-methyl-phenoxy)propanol, (3-methyl Alkylphenoxyalkyl alcohols such as -phenoxy) propanol, (2,3-dimethylphenoxy)ethanol, (2,5-dimethylphenoxy)ethanol, (2,6 - Dimethylphenoxy)ethanol, (2,6-dibutylphenoxy)ethanol, dialkylphenoxyalkyl alcohol, (2-methoxyphenoxy)ethanol, etc. alkoxy cycloalkylphenoxyalkyl alcohols such as (2-cyclohexylphenoxy)ethanol, etc., arylphenoxyalkyl alcohols such as biphenyloxyethanol, etc. Examples of compounds in which l is 2 or more include polyoxyalkylene phenyl ethers corresponding to these phenoxyalkyl alcohols. Preferably it is phenoxy C2-6 alkyl alcohol or C1-4 alkyl phenoxy C2-6 alkyl alcohol, particularly preferably phenoxyethanol.

Although the usage amount of the compound represented by the aforementioned formula (6) is not particularly limited, from the viewpoint of side reaction suppression and economical efficiency, relative to 1 mole of the quinones, which are the reactants represented by the aforementioned formula (5), It is preferably 2 to 50 moles, more preferably 2.5 to 20 moles, and still more preferably 3 to 10 moles. Moreover, these compounds can also be used as a reaction solvent.

These compounds represented by the aforementioned formula (6) may be commercially available or may be synthesized.

The purity of the compound represented by the formula (6) used as a raw material is not particularly limited, but is usually 95% or more, preferably 99% or more.

The reaction in step 2 can usually be carried out in the presence of an acid catalyst. Examples of the acid catalyst include sulfuric acid, mercaptanic acid, montmorillonite, heteropoly acid, etc. Among these, impurities derived from the acid catalyst are particularly small, and it is easy to obtain the scaffold having the present invention. compounds, so heteropolyacids are preferred.

The so-called heteropoly acid preferably used in the present invention generally refers to the general name of compounds generated by condensation of two or more different inorganic oxyacids, by condensing the central oxyacid with other types of oxyacids around it. Combinations with various heteropolyacids are possible. The elements that form a smaller number of oxyacids in the center are called heteroelements, and the elements that form the oxyacids condensed around them are called polyelements. A poly element can be a single type of element or a plurality of types of elements.

Although the heteroelement constituting the oxyacid of the heteropoly acid is not particularly limited, examples thereof include copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, thorium, nitrogen, phosphorus, and arsenic. , antimony, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, iridium, platinum. Preferred are phosphorus (phosphoric acid) or silicon (silicic acid). In addition, the poly element constituting the oxyacid of the heteropoly acid is not particularly limited, but examples thereof include vanadium, molybdenum, tungsten, niobium, and tantalum. Preferably, it is at least one element selected from the group consisting of vanadium, molybdenum and tungsten.

As the heteropolyacid anion constituting the heteropolyacid skeleton, those having various compositions can be used. Examples include XM ₁₂ O ₄₀ , XM ₁₂ O ₄₂ , XM ₁₈ O ₆₂ , XM ₆ O ₂₄ , and the like. Preferably, the composition of the heteropoly acid anion is XM ₁₂ O ₄₀ . In each formula, X is a hetero element and M is a poly element. Specific examples of the heteropoly acid having such a composition include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, phosphovanadium molybdic acid, and the like.

The heteropolyacid may be a free heteropolyacid, or a part or all of the protons may be replaced with other cations to be used as a salt of the heteropolyacid. Accordingly, the so-called heteropolyacid in the present invention also includes the salts of these heteropolyacids. Examples of cations that can be substituted by protons include ammonium, alkali metals, alkaline earth metals, and the like.

The heteropolyacid may be an anhydride or a substance containing crystal water, but the anhydride is preferred because it reacts faster and suppresses the formation of by-products. In the case of a substance containing crystal water, the same effect as anhydride can be obtained by performing dehydration treatment in advance such as drying under reduced pressure or azeotropic dehydration with a solvent. Heteropoly acids can be used in the form of being supported on a carrier such as activated carbon, alumina, silica-alumina, diatomaceous earth, or the like. These heteropolyacids can be used alone or in combination of two or more kinds. Moreover, if necessary, a catalyst other than heteropolyacid may be used together within the scope which does not impair the object of the present invention.

Although the usage amount of the heteropoly acid is not particularly limited, in order to obtain a sufficient reaction rate, it is preferably 0.0001 times or more by weight, more preferably 0.001 to 30 times by weight, and still more preferably 0.01 to 5 times the weight of the quinone. times the weight.

Although the method of carrying out the reaction in step 2 is not particularly limited, it can usually be achieved by placing the reactant represented by the aforementioned formula (5), the compound represented by the aforementioned formula (6), and the heteropoly acid in a reaction device in the air. Or it can be performed with heating and stirring in an inert gas environment such as nitrogen or argon, or in the presence or absence of an inert solvent such as toluene or xylene. At this time, by performing the reaction under dehydration conditions in which the water in the reaction system such as catalyst-containing water or reaction product water is removed, the reaction proceeds faster than when dehydration is not performed, suppresses the generation of by-products, and obtains the product with a higher yield. target object. Although the dehydration method is not particularly limited, examples thereof include dehydration by addition of a dehydrating agent, dehydration by reduced pressure, dehydration by azeotropy with a solvent under normal pressure or reduced pressure, and the like.

The azeotropic dehydration solvent is not particularly limited, but may include aromatic hydrocarbon solvents such as toluene and xylene, halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene, pentane, hexane, and heptane. Aliphatic hydrocarbon solvents such as methylene chloride, 1,2-dichloroethane and other halogenated aliphatic hydrocarbon solvents, diethyl ether, di-iso-propyl ether, methyl-t-butyl ether, Aliphatic and cyclic ether solvents such as diphenyl ether, tetrahydrofuran, dioxane, etc., ester solvents such as ethyl acetate, butyl acetate, etc., nitrile solvents such as acetonitrile, propionitrile, butyronitrile, benzonitrile, etc., N, Amide solvents such as N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, etc. Preferred are aromatic hydrocarbon solvents and halogenated aromatic hydrocarbon solvents, more preferred are toluene, xylene, chlorobenzene, and dichlorobenzene, and even more preferred are toluene. Although the usage amount is not particularly limited, from an economical point of view, it is preferably 0.1 times by weight or more, and more preferably 0.5 to 100 times by weight relative to the reactant represented by the above formula (5), i.e., quinone. , and preferably 1 to 20 times the weight.

Although the reaction temperature varies depending on the types of raw materials and solvents used, it is preferably 50 to 300°C, more preferably 80 to 250°C, and still more preferably 120 to 180°C. The reaction can be followed by analytical means such as liquid chromatography.

The reaction mixture after the reaction is completed usually contains, in addition to the compound represented by the aforementioned formula (1), unreacted hydrochloric acid, unreacted boric acid, unreacted alcohol compounds, alkali, catalyst, and by-products. Reaction products, etc. Therefore, it can be separated by conventional methods, such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or very similar metal removal treatment, column chromatography, etc., or a combination of these separation means for separation and purification. For example, boric acid can be removed by conventional methods (methods such as adding alkali aqueous solution to form a water-soluble complex, etc.), activated carbon treatment or metal removal treatment that is very similar to it can be performed by removing the palladium compound and then adding recrystallization. The solvent is cooled to recrystallize, and then filtered and separated for purification. (Crystal manufacturing method) The compound represented by the above formula (1) produced by steps 1 and 2 is preferably produced by the following crystallization production steps (i), (ii) and (iii).

(i) A step of preparing a solution (crystallization solution) of the compound represented by the above formula (1) (hereinafter, may also be referred to as a crystallization solution preparation step).

(ii) A step of precipitating the crystallization of the compound represented by the aforementioned formula (1) from the crystallization solution obtained in step (i) at a temperature above 0°C, and isolating the precipitated crystals (hereinafter also referred to as crystallization) steps).

(iii) A step in which the crystal obtained in step (ii) is heated to 80°C or above (hereinafter, it may also be called a drying step).

Below, the above steps (i), (ii) and (iii) are described in detail.

<(i) Crystallization solution adjustment step> Examples of solvents that can be used in the crystallization solution preparation step include aromatic hydrocarbon solvents such as toluene and xylene, halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene, methylene chloride, and 1,2-dichloroethane. Halogenated aliphatic hydrocarbon solvents such as alkanes, aliphatic and cyclic ethers such as diethyl ether, di-iso-propyl ether, methyl-t-butyl ether, diphenyl ether, tetrahydrofuran, dioxane, etc. Solvents, ester solvents such as ethyl acetate and butyl acetate, nitrile solvents such as acetonitrile, propionitrile, butyronitrile, benzonitrile, etc., N,N-dimethylformamide, N,N-dimethylacetyl Amine, 1-methyl-2-pyrrolidinone, etc. amide solvent. Among them, chloroform, ethyl acetate, and toluene having good solubility and appropriate boiling points of the above formula (1) are preferably used.

The crystallization solvent may contain other solvents in addition to the above. Examples include solvents used in step 1 or step 2 of the above reaction. When other solvents are included, the solvent amount is usually 0.5 weight times or less, preferably 0.3 weight times or less relative to the crystallization solution.

The total amount of solvent contained in the crystallization solution is usually 0.5 to 20 times by weight, preferably 1 to 10 times by weight relative to the weight times of the compound of formula (1) contained in the crystallization solution.

Although it depends on the content of impurities contained in the crystallization solution, depending on the amount of water in the crystallization solution, a crystalline compound represented by the formula (1) may not be obtained. Furthermore, even when a crystalline compound represented by the above formula (1) is obtained, the purity or hue may not be sufficiently improved, so the water content in the crystallization solution is preferably 5% by weight or less, more preferably 5% by weight or less. Set it to 1% by weight or less.

<(ii) Crystallization step> Next, the crystallization steps are described in detail. The crystallization solution prepared by the method (i) above depends on the boiling point of the solvent used, but it is preferably heated to 40°C or above, and more preferably heated to a temperature just below the boiling point of the crystallization solution. , the crystals are completely dissolved and then cooled, preferably above 0°C, more preferably in the temperature range of 0 to 40°C to precipitate the crystals. Although it depends on the solvent used, when the crystal is precipitated at a temperature higher than 40° C., it is close to the boiling point of the solvent, so it is difficult to precipitate the crystal, and this may cause safety issues. Examples of methods for precipitating crystals in the aforementioned temperature range include a method of maintaining the temperature of the crystallization solution so as to fall within the aforementioned temperature range until the crystals are precipitated, a method of inoculating seed crystals in the aforementioned temperature range, and the addition of hard-to-dissolve crystals. Methods to reduce the solubility of solvents, etc. In addition, after the crystals are precipitated, an operation of keeping the same temperature for a certain period of time to grow the crystals can be performed. After the crystals are precipitated, if necessary, further cooling can be performed to separate the precipitated crystals.

When using a solvent that is difficult to dissolve the above-mentioned crystals and reducing the solubility, examples of the solvent include aliphatic hydrocarbon solvents such as pentane, hexane, and heptane. The usage amount of this solvent is preferably 0.5 to 50 times by weight, more preferably 10 to 30 times by weight relative to the total amount of solvents contained in the crystallization solution.

<(iii) Heating step> Although the heating step depends on the solvent used, it can be implemented by heating the obtained crystal to a temperature of preferably from 60°C or higher to below the melting point of the crystal, more preferably 100°C or lower. Furthermore, the temperature of crystallization in the present invention refers to the temperature observed when a thermometer is inserted inside the device used for drying and the thermometer comes into contact with the crystallization. The crystals used in the heating step may include the solvent used in the crystallization step. When the heating step is performed, the solvent included in the crystals may also be removed at the same time. When performing the heating step, the solvent used in the crystallization step included in the crystallization is removed at the same time. By setting the heating step under reduced pressure, the solvent used in the crystallization step can be efficiently removed from the crystallization, so it is more efficient. good.

The crystal of the present invention thus obtained can be subjected to ordinary purification operations such as adsorption, steam distillation, recrystallization, etc. if necessary. However, even if such operations are not performed, it is sufficiently high-purity and therefore can be suitably used as Resin materials such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy are used. [Example]

The present invention will be described in detail below using examples, etc., but the present invention is not limited to the examples. Furthermore, in the examples, various measurements were carried out by the following methods. In addition, the production rate (residual rate) and purity of each component described in the following examples and comparative examples are the area percentage values of HPLC measured under the following conditions (corrected area percentage of the peak of the organic compound after removing the solvent in the reaction solution). value).

(1) HPLC Purity The compounds obtained in the Examples and Comparative Examples were measured with the following equipment and the HPLC purity was calculated. Device: Hitachi Co., Ltd. Column: Nomura Chemical Develosil ODS-MG-5 Mobile phase: acetonitrile, 0.1 trifluoroacetic acid, ultrapure water flow rate: 1.0ml/min, column temperature: 40°C, detection wavelength: UV253nm (2 )ICP measurement The Pd content of the compounds obtained in Examples and Comparative Examples was measured using the following equipment. Machine used: Agilent Technologies Equipment: Agilent5100 ICP-OES (3) Melting point (Tm) measurement Using 5 mg of the resin obtained in the example, the endothermic peak (melting point) by differential scanning calorimetry was measured under the following equipment and conditions. Apparatus: (Co., Ltd.) DSC-60A manufactured by Shimadzu Corporation Conditions: Temperature rise rate 20°C/min [Example 1] <Step 1> Using a 3L three-necked flask equipped with a stirrer, a cooler, and a thermometer, 2,7- Dibromoquinone (hereinafter sometimes referred to as DBFN) 25.25g (74.7 mmol), 19.13g phenylboronic acid (156.9 mmol) dissolved in toluene/ethanol mixed solvent (mixing ratio = 4/1) 920mL, Furthermore, after adding 0.15 g (0.13 mmol) of quaternary (triphenylphosphine) palladium and 85 mL of a 2M potassium carbonate aqueous solution, the mixture was stirred at 80° C. for 4 hours to react. The progress of the reaction was confirmed by HPLC, and the remaining amount of DBFN was confirmed to be 0.1% by weight or less, and the reaction was completed. The reaction solution obtained was concentrated under reduced pressure, and toluene/ethanol was removed. Then, a 1M sodium hydroxide aqueous solution was added to the residue, and the mixture was extracted with chloroform. The chloroform layer is treated with activated carbon to remove the palladium catalyst, remove the remaining palladium catalyst in the system, and then concentrate. Stop the concentration at the time when yellow crystals precipitate and directly recrystallize. By filtering out the precipitated yellow crystals and drying them at 85° C. for 24 hours, 20 g of white crystals of the target 2,7-diphenylquinone (hereinafter sometimes referred to as DPFN) were obtained with a yield of 81%. <Step 2> In a 1L three-necked flask equipped with a stirrer, a cooler, a water separator, and a thermometer, 340 g of toluene and 12 tungsten (VI) phosphoric acid n-hydrate (H ₃ [PW ₁₂ O ₄₀ ] are placed as the solvent ･nH ₂ O) 2.94g, azeotropic dehydration under toluene reflux for 30 minutes. After cooling the contents, add 99.72g (0.3 mol) of DPFN synthesized in step 1, 165.80g (1.2 mol) of 2-phenoxyethanol, and 50g of toluene. The toluene is refluxed and the generated water is reacted outside the system. Discharge and stir for 12 hours. The progress of the reaction was appropriately confirmed by HPLC, and the time point when the remaining amount of DPFN became 0.1% by weight or less was regarded as the end point of the reaction. The obtained reaction liquid was adjusted to 70°C, and washed three times with 200 g of water. The obtained organic layer was concentrated under reduced pressure to remove toluene and excess 2-phenoxyethanol. The obtained mixture was dissolved in 500 g of toluene and decolorized with activated carbon. When the treatment liquid was concentrated, crystals began to precipitate, so the concentration was stopped and recrystallization was performed directly. The precipitated white crystals were filtered out, and the crystals were dried to obtain 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylphosphonium. 140 g of white crystals of the crude purified product (hereinafter sometimes referred to as BPDP) (yield 70%, purity 95.2%). When the remaining metal content was measured by ICP, Pd was 0.4 ppm. <Crystalization Production Step> Place 10 g (0.016 mol) of the white crystals of BPDP obtained in step 2 and 100 g of chloroform into a flask, and dissolve BPDP at 50° C. (crystallization solution preparation step). After BPDP is completely dissolved, 30 g of hexane is added, and then cooled to 0°C (crystallization step). The precipitated crystals were filtered and dried at 80° C. to obtain 5.5 g of white crystals of BPDP (yield 55%, purity 99.5%) (drying step). When the melting point was measured by DSC, the melting points were 137°C and 178°C (see Figure 1). [Example 2] The procedure was carried out in the same manner as Example 1, except that the solvent in the crystallization production step was changed from chloroform to ethyl acetate, and 2.6 g of white crystals of BPDP were obtained (yield 26%, purity 99.5%). The melting point measured by DSC was 168°C (see Figure 2). [Example 3] The same procedure as in Example 1 was carried out except that the dissolution temperature was set to 40°C in the crystallization production step, and 3.1 g of white crystals of BPDP were obtained (yield 31%, purity 97.5%). The melting points determined by DSC were 131°C and 175°C. [Example 4] 10 g of the crude BPDP biomass (95.2%, Pd content: 0.4 ppm) obtained by the same operation as step 2 and 100 g of toluene were placed in a flask and dissolved at 70°C. After BPDP was completely dissolved, the solution was cooled to 25°C, the precipitated crystals were filtered, and the crystals were dried at 80°C to obtain 3.2 g of BPDP white crystals (yield 32%, purity 96.2%). When measuring DSC, the melting point was 161°C. [Example 5] The white crystals of BPDP obtained in Example 4 were dried at 100°C and then cooled to 25°C. When DSC was measured again, the melting point was 166°C. [Example 6] The same procedure was carried out except that the phenylboronic acid in step 1 was changed to 26.99g (156.9 mmol) of 2-naphthylboronic acid, and 2,7-dinaphthylquinone was obtained with a yield of 75%. (hereinafter sometimes referred to as DNFN) crystal 24 g. Except that the DPFN in step 2 was changed to DNFN 129.75g (0.3 mol), the others were carried out in the same manner to obtain 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-bis The crude product of naphthyl fluoride (hereinafter sometimes referred to as BPDN2) was 124 g of white crystals (yield 60%, purity 94.0%). When the remaining metal content was measured by ICP, Pd was 1.0 ppm.

The crystallization production step is to put 10g (0.014 mol) of white crystals of BPDN2 and 100g of ethyl acetate into a flask, and dissolve BPDN2 at 75°C (crystallization solution adjustment step). After BPDN2 is completely dissolved, add 30g of hexane and then cool to 40°C (crystallization step). The precipitated crystals were filtered and dried at 80°C to obtain 5.9 g of white crystals of BPDN2 (yield 59%, purity 98.7%) (drying step). When DSC was measured, the melting points were 123°C and 175°C (see Figure 3). [Example 7] The crystallization solution adjustment step of Example 6 was carried out in the same manner except that the ethyl acetate was changed to chloroform and dissolved at 50°C, and 4.0 g of white crystals of BPDN2 were obtained (yield 40%, purity 97.3%). When DSC was measured, the melting point was 165°C (see Figure 4). [Comparative example 1] The BPDP white crystals obtained in Example 4 were dried at 170°C and then cooled to 25°C. When DSC was measured again, no melting point was observed. [Comparative example 2] Step 1 is carried out in the same manner as in Example 1. Then, in a 1L three-necked flask equipped with a stirrer, a cooler, a water separator, and a thermometer, 340g of toluene as a solvent, 2.94g of 12tungsten (VI) phosphoric acid n-hydrate (H3[PW12O40]･nH2O), and toluene were placed Azeotropic dehydration under reflux for 30 minutes. After cooling the contents, add 99.72g (0.3 mole) of DPFN synthesized in step 1, 165.80g (1.2 mole) of 2-phenoxyethanol, and 50g of toluene. The toluene is refluxed and the water generated by the reaction is discharged to the outside of the system. Discharge and stir for 12 hours. The progress of the reaction was appropriately confirmed by HPLC, and the time point when the remaining amount of DPFN became 0.1% by weight or less was regarded as the end point of the reaction. The obtained reaction liquid was adjusted to 70°C and washed three times with 200 g of water. The obtained organic layer was concentrated under reduced pressure, and toluene and excess 2-phenoxyethanol were removed to obtain 186 g of crudely purified BPDP (yield 90%, purity 91%).

10 g (0.016 mol) of the obtained yellow crystals of BPDP and 100 g of chloroform were placed in a flask, and BPDP was dissolved at 50°C. After BPDP is completely dissolved, add 30 g of hexane and then cool to 0°C. The precipitated crystals were filtered and dried at 80°C to obtain 5.5 g of white crystals of BPDP (yield 55%, purity 99.5%). The obtained BPDP was dissolved in toluene, decolorized with activated carbon, and the treatment liquid was concentrated to obtain 5.3 g of a white solid of BPDP (purity 99.5%, Pd 3.0 ppm). No crystallization manufacturing step was performed. When measuring DSC, no melting point was observed.

[Industrial availability]

A resin in which a crystal of a compound having a fluorine skeleton of the present invention is used as a raw material (monomer) is used, for example, in films, lenses, prisms, optical discs, transparent conductive substrates, optical cards, sheets, optical fibers, optics It is extremely useful for optical components such as membranes, optical filters, and hard coating films, especially lenses.

[Fig. 1] DSC chart of the compound having a fluorine skeleton obtained in Example 1. [Fig. 2] DSC chart of the compound having a fluorine skeleton obtained in Example 2. [Fig. 3] DSC chart of the compound having a fluorine skeleton obtained in Example 6. [Fig. 4] DSC chart of the compound having a fluorine skeleton obtained in Example 7.

Claims (4)

A crystal of a compound having a fluorine skeleton represented by formula (1), which is used as a raw material for resin used in lenses and has at least one endothermic peak in the range of 110 to 190°C as determined by differential scanning calorimetry,

(In the formula, Ring Z represents the same or different aromatic group, R ¹ and R ² independently represent a hydrogen atom, a halogen atom or a hydrocarbon group that may contain an aromatic group with 1 to 12 carbon atoms, Ar ¹ and Ar ² It represents an aromatic group which may have a substituent having 6 to 10 carbon atoms, L ¹ and L ² represent an alkylene group, and m and n each independently represent 1). For example, the crystal of the compound having the fentanyl skeleton represented by the formula (1) as described in claim 1 contains more than 95% by weight of the fentanyl derivative represented by the formula (1). A crystal of a compound having a quinilium skeleton represented by formula (1) as described in claim 1, wherein the palladium element content satisfies the following formula (2), 0≦Pd≦50ppm (2). A method for producing crystals of a compound having a fentanyl skeleton represented by formula (1) as described in claim 1, which includes the following steps 1, 2 and crystallization production steps: Step 1: Make the following formula (3) The step of reacting the quinones represented by the formula (4) with the boric acid represented by the following formula (4) in a reaction solvent in the presence of an alkali and a catalyst,

(X ¹ and X ² represent halogen atoms)

(Y represents an aromatic group, and R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group or a halogen atom) Step 2: The reactant represented by the following formula (5) produced in step 1 is mixed with the following formula ( 6) The step of reacting the alcohol compound represented in the reaction solvent using an acid catalyst,

(Ar ¹ and Ar ² are the same as formula (1))

(Ring Z is the same as formula (1); R ⁴ represents a hydrogen atom, a halogen atom or a hydrocarbon group that may contain an aromatic group with 1 to 12 carbon atoms, L ³ represents an alkylene group, and l represents 1) Crystallization manufacturing steps: use Dissolve the compound obtained in step 2 in a solvent, perform a recrystallization operation, and take out the crystallization step.

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