JP6436878B2 - Compound production method and mixed crystal - Google Patents

Description

  The present invention relates to a method for producing a compound and a mixed crystal.

  Conventionally, a glass material has been used for an optical member of an imaging module such as a camera, a video camera, a camera-equipped mobile phone, a videophone, or a camera door phone. Glass materials have been used preferably because they have various optical properties and are excellent in environmental resistance. However, they have the disadvantages that weight reduction and size reduction are not easy, and workability and productivity are poor. On the other hand, the cured resin can be mass-produced and is excellent in workability, and has recently been used for various optical members.

  As the monomer used in the curable composition for forming the resin cured product, a compound having a fluorene skeleton may be used. For example, Patent Document 1 discloses a method for producing 9,9-bis (4-hydroxyphenyl) fluorene, which includes a step of forming an inclusion compound composed of a specific solvent and a compound having a fluorene skeleton. Here, alcohol water such as methanol, ketones such as acetone, and ethers such as diisopropyl ether are listed as solvents used in the step of crystallizing the clathrate compound. Patent Document 2 discloses a method for producing a fluorene-based diol compound. The fluorene-based diol compound produced here has a hydroxy group at the 2-position of two phenyl groups bonded to the 9-position of the fluorene ring. In Patent Document 2, a general organic solvent such as toluene is cited as a solvent used in the reaction step and the crystallization step.

JP 2008-115139 A JP 2014-114387 A

  However, in the conventional production method as described above, since the yield of the compound having a fluorene skeleton is poor, development of a method capable of producing the compound more efficiently has been demanded. In addition, the compound having a fluorene skeleton produced by a conventional production method may contain impurities, and in such a case, the crystal may be yellowish, which has been a problem.

  Therefore, in order to solve the problems of the prior art, the present inventors are a method for producing a compound having a predetermined structure with high yield and high purity, and producing a compound in which coloring is suppressed. The study proceeded with the aim of providing a method.

As a result of intensive studies to solve the above problems, the present inventors have found that a carbonate ester-based solvent is used as a solvent used in the condensation step or crystallization step when synthesizing a predetermined compound used in the curable composition. It has been found that crystals can be obtained with high yield and purity by using a solvent. The present inventors have found that crystals obtained by such a production method are less colored and are preferably used for forming an optical member, and have completed the present invention.
Specifically, the present invention has the following configuration.

一般式（Ａ）〜（Ｃ）中、Ａｒ^１及びＡｒ^２は、それぞれ独立に置換基を有してもよい単環又は置換基を有してもよい縮合環を表し、Ａｒ^３は、置換基を有してもよいアリーレン基又は置換基を有してもよいヘテロアリーレン基を表す。
［２］一般式（Ａ）で表される化合物が下記一般式（Ａ−１）で表される化合物であり、一般式（Ｂ）で表される化合物が下記一般式（Ｂ−１）で表される化合物であり、一般式（Ｃ）で表される化合物が下記一般式（Ｃ−１）で表される化合物である［１］に記載の製造方法；

一般式（Ａ−１）〜（Ｃ−１）中、Ａｒ^１１〜Ａｒ^１３は、それぞれ独立に破線で囲まれたベンゼン環を含む単環又は破線で囲まれたベンゼン環を含む縮合環を表し、Ｒ^１〜Ｒ^３はそれぞれ独立に置換基を表し、ａ〜ｃはそれぞれ独立に０又は、破線で囲まれたベンゼン環を含む単環又は破線で囲まれたベンゼン環を含む縮合環に置換可能な最大置換数を上限とする整数を表す；Ａｒ^１１〜Ａｒ^１３がそれぞれ独立に破線で囲まれたベンゼン環を含む縮合環である場合は、Ｒ^１〜Ｒ^３はそれぞれ独立に破線で囲まれたベンゼン環に置換していても、破線で囲まれたベンゼン環以外の環に置換していてもよい。
［３］一般式（Ａ−１）〜（Ｃ−１）において、Ａｒ^１１〜Ａｒ^１３のうち少なくとも１つは破線で囲まれたベンゼン環を縮合環のひとつとして含む芳香族縮合環である［２］に記載の製造方法。
［４］一般式（Ａ−１）および（Ｃ−１）において、Ａｒ^１１又はＡｒ^１２は破線で囲まれたベンゼン環を縮合環のひとつとして含む芳香族縮合環である［２］又は［３］に記載の製造方法。
［５］一般式（Ｂ）で表される化合物が下記一般式（Ｂ−３）で表される化合物である［１］〜［４］のいずれかに記載の製造方法；

一般式（Ｂ−３）中、Ｒ^３は置換基を表し、ｃは０〜４の整数を表す。
［６］一般式（Ｂ）で表される化合物がフェノールである［１］〜［５］のいずれかに記載の製造方法。
［７］一般式（Ａ）で表される化合物が下記一般式（Ａ−３）で表される化合物であり、一般式（Ｂ）で表される化合物がフェノールであり、一般式（Ｃ）で表される化合物が下記一般式（Ｃ−３）で表される化合物である［１］〜［６］のいずれかに記載の製造方法；

一般式（Ａ−３）および（Ｃ−３）中、Ｒ^１及びＲ^２はそれぞれ独立に置換基を表し、ａは０〜４の整数を表し、ｂは０〜６の整数を表す。
［８］一般式（Ａ−３）および（Ｃ−３）において、ａは０であり、ｂは０である［７］記載の製造方法。
［９］炭酸エステル系溶媒の使用量は、一般式（Ａ）で表される化合物１００モル％に対して、１５モル％以上である［１］〜［８］のいずれかに記載の製造方法。
［１０］炭酸エステル系溶媒が、炭酸ジメチル、炭酸ジエチル及び炭酸プロピレンから選択される少なくともいずれかである［１］〜［９］のいずれかに記載の製造方法。
［１１］炭酸エステル系溶媒が炭酸ジメチルである［１］〜［１０］のいずれかに記載の製造方法。
［１２］下記一般式（Ｃ）で表される化合物と、炭酸エステルとを含む混晶；

一般式（Ｃ）中、Ａｒ^１及びＡｒ^２は、それぞれ独立に置換基を有してもよい単環又は置換基を有してもよい縮合環を表し、Ａｒ^３は、置換基を有してもよいアリーレン基又は置換基を有してもよいヘテロアリーレン基を表す。
［１３］一般式（Ｃ）で表される化合物が１１，１１−ビス（４−ヒドロキシフェニル）−１１Ｈ−ベンゾ［ｂ］フルオレンであり、炭酸エステルが炭酸ジメチルである［１２］に記載の混晶。
［１４］混晶における、炭酸ジメチルの割合は、１１，１１−ビス（４−ヒドロキシフェニル）−１１Ｈ−ベンゾ［ｂ］フルオレン１００モル％に対して、１５〜２５モル％である［１３］に記載の混晶。 [1] It is represented by the general formula (C) including a step of condensing the compound represented by the general formula (A) and the compound represented by the general formula (B) in a solvent containing an acid catalyst and a thiol compound. In the step of condensing, using a carbonate ester solvent as a solvent in the step of condensing, a step of obtaining a crystal containing the compound represented by formula (C), and a step of condensing after the step of condensing A method for producing a compound comprising at least one of the steps of obtaining a crystal containing a compound represented by the general formula (C) using a carbonate ester solvent as:

In General Formulas (A) to (C), Ar ¹ and Ar ² each independently represent a monocyclic ring that may have a substituent or a condensed ring that may have a substituent, and Ar ³ represents a substituted group. Represents an arylene group which may have a group or a heteroarylene group which may have a substituent.
[2] The compound represented by the general formula (A) is a compound represented by the following general formula (A-1), and the compound represented by the general formula (B) is represented by the following general formula (B-1). The production method according to [1], wherein the compound represented by the general formula (C) is a compound represented by the following general formula (C-1):

In general formulas (A-1) to (C-1), Ar ^{11 to} Ar ¹³ each independently represent a single ring containing a benzene ring surrounded by a broken line or a condensed ring containing a benzene ring surrounded by a broken line. , R ^{1 to} R ³ each independently represents a substituent, and a to c are each independently 0 or substituted with a single ring containing a benzene ring surrounded by a broken line or a condensed ring containing a benzene ring surrounded by a broken line Represents an integer with an upper limit of the maximum possible number of substitution; when Ar ^{11 to} Ar ¹³ are each independently a condensed ring containing a benzene ring surrounded by a broken line, R ^{1 to} R ³ are each independently surrounded by a broken line The benzene ring may be substituted, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
[3] In the general formulas (A-1) to (C-1), at least one of Ar ^{11 to} Ar ¹³ is an aromatic condensed ring including a benzene ring surrounded by a broken line as one of condensed rings [ 2].
[4] In the general formulas (A-1) and (C-1), Ar ¹¹ or Ar ¹² is an aromatic condensed ring containing a benzene ring surrounded by a broken line as one of the condensed rings [2] or [3 ] The manufacturing method of description.
[5] The production method according to any one of [1] to [4], wherein the compound represented by the general formula (B) is a compound represented by the following general formula (B-3);

In General Formula (B-3), R ³ represents a substituent, and c represents an integer of 0 to 4.
[6] The production method according to any one of [1] to [5], wherein the compound represented by the general formula (B) is phenol.
[7] The compound represented by the general formula (A) is a compound represented by the following general formula (A-3), the compound represented by the general formula (B) is phenol, and the general formula (C) The method represented by any one of [1] to [6], wherein the compound represented by formula (C-3) is a compound represented by the following formula;

In general formulas (A-3) and (C-3), R ¹ and R ² each independently represent a substituent, a represents an integer of 0 to 4, and b represents an integer of 0 to 6.
[8] The production method according to [7], wherein in general formulas (A-3) and (C-3), a is 0 and b is 0.
[9] The production method according to any one of [1] to [8], wherein the amount of the carbonate ester solvent used is 15 mol% or more with respect to 100 mol% of the compound represented by the general formula (A). .
[10] The production method according to any one of [1] to [9], wherein the carbonate solvent is at least one selected from dimethyl carbonate, diethyl carbonate, and propylene carbonate.
[11] The production method according to any one of [1] to [10], wherein the carbonate solvent is dimethyl carbonate.
[12] A mixed crystal containing a compound represented by the following general formula (C) and a carbonate ester;

In General Formula (C), Ar ¹ and Ar ² each independently represent a monocyclic ring that may have a substituent or a condensed ring that may have a substituent, and Ar ³ has a substituent. An arylene group which may be substituted or a heteroarylene group which may have a substituent.
[13] The mixture according to [12], wherein the compound represented by the general formula (C) is 11,11-bis (4-hydroxyphenyl) -11H-benzo [b] fluorene, and the carbonate is dimethyl carbonate. Akira.
[14] The ratio of dimethyl carbonate in the mixed crystal is 15 to 25 mol% with respect to 100 mol% of 11,11-bis (4-hydroxyphenyl) -11H-benzo [b] fluorene. The mixed crystal described.

  According to the production method of the present invention, crystals can be produced with high yield and high purity. In addition, crystals produced using the production method of the present invention are less colored and are preferably used as a material for a curable composition for producing an optical member.

  Hereinafter, the present invention will be described in detail. The constituent elements described below may be described based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  In the notation of groups in this specification, the notation which does not describe substitution and non-substitution includes those having a substituent as well as those not having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

(Method for producing compound)
<Compounds represented by formulas (A) to (C)>
This invention is represented by general formula (C) including the process of condensing the compound represented by general formula (A), and the compound represented by general formula (B) in the solvent containing an acid catalyst and a thiol compound. The present invention relates to a method for producing a compound. The production method of the present invention includes a step of obtaining a crystal containing a compound represented by the general formula (C) using a carbonate ester solvent as a solvent in the step of condensation, and a step of carbonation as a crystallization solvent after the step of condensation. It includes at least one of a step of obtaining a crystal containing the compound represented by the general formula (C) using an ester solvent.

In General Formulas (A) to (C), Ar ¹ and Ar ² each independently represent a monocyclic ring that may have a substituent or a condensed ring that may have a substituent, and Ar ³ represents a substituted group. Represents an arylene group which may have a group or a heteroarylene group which may have a substituent.

The monocyclic ring which may have a substituent represented by Ar ¹ and Ar ² or the condensed ring which may have a substituent is preferably a monocyclic or condensed ring having 6 to 18 ring skeleton atoms. More preferably, it is a monocyclic or condensed ring having 6 to 14 ring skeleton atoms, and more preferably a monocyclic or condensed ring having 6 to 10 ring skeleton atoms.
The monocycle includes a hydrocarbon ring and a heterocycle, and the condensed ring is a ring obtained by condensing these monocycles. The hydrocarbon ring is preferably an aromatic hydrocarbon ring, and the heterocyclic ring is preferably an aromatic heterocyclic ring. Among these, Ar ¹ and Ar ² are each preferably an aromatic hydrocarbon ring that may have a substituent, and the aromatic hydrocarbon ring is more preferably a benzene ring or a naphthalene ring.
In addition, as a hetero atom which comprises a heterocyclic ring, a nitrogen atom, an oxygen atom, and a sulfur atom can be mentioned.

In addition, at least one selected from Ar ¹ and Ar ² is preferably an aromatic condensed ring which may have a substituent, and Ar ¹ or Ar ² may have an aromatic condensed which may have a substituent. A ring is preferred. Here, the aromatic condensed ring is preferably a polycyclic aromatic hydrocarbon or polycyclic aromatic heterocycle having 9 to 14 ring skeleton atoms. Among these, the aromatic condensed ring is preferably a polycyclic aromatic hydrocarbon, and particularly preferably a naphthalene ring.

Ar ³ represents an arylene group which may have a substituent or a heteroarylene group which may have a substituent. Ar ³ is preferably an arylene group or heteroarylene group having 6 to 18 ring skeleton atoms, more preferably an arylene group or heteroarylene group having 6 to 14 ring skeleton atoms, More preferably, it is an arylene group or heteroarylene group having 6 to 10 skeleton atoms. Among these, Ar ³ is preferably an arylene group, more preferably a phenylene group or a naphthylene group, and even more preferably a phenylene group.

Examples of the substituent that Ar ¹ and Ar ² may have include a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, an acyl group, an alkoxy group, an aryl group, a heteroaryl group, an alicyclic group, and an amino group. Can be mentioned. Among them, the substituent that Ar ¹ and Ar ² may have is preferably an electron donating group, such as a cyclopropyl group, an amino group, a dimethylamino group, a benzoylamino group, a methoxy group, an ethoxy group, or a propoxy group. Etc.

Examples of the substituent that Ar ³ may have include a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, an acyl group, an alkoxy group, an aryl group, a heteroaryl group, an alicyclic group, and an amino group. Can do.

The substitution position of the hydroxy group in Ar ³ is not particularly limited, and when Ar ³ is a phenylene group, any of 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene may be used. . In particular, when Ar ³ is a phenylene group, Ar ³ is preferably 1,4-phenylene. That is, it is preferable to have a hydroxy group at the 4-position with respect to the ring skeleton bonding site of the phenylene group. When Ar ³ is 1,4-phenylene, the synthesis of the compound represented by the general formula (C) can be facilitated, and the yield can be increased.

  Moreover, it is preferable that the compound represented by general formula (A) is a compound represented by the following general formula (A-1), and the compound represented by general formula (B) is the following general formula (B-1). ), And the compound represented by the general formula (C) is preferably a compound represented by the following general formula (C-1).

In general formulas (A-1) to (C-1), Ar ^{11 to} Ar ¹³ each independently represent a single ring containing a benzene ring surrounded by a broken line or a condensed ring containing a benzene ring surrounded by a broken line. , R ^{1 to} R ³ each independently represents a substituent, and a to c are each independently 0 or substituted with a single ring containing a benzene ring surrounded by a broken line or a condensed ring containing a benzene ring surrounded by a broken line Represents an integer up to the maximum possible number of substitutions. When Ar ^{11 to} Ar ¹³ are each independently a condensed ring containing a benzene ring surrounded by a broken line, R ^{1 to} R ³ are each independently substituted with a benzene ring surrounded by a broken line. It may be substituted with a ring other than the enclosed benzene ring.

The monocyclic or condensed ring containing a benzene ring surrounded by a broken line represented by Ar ^{11 to} Ar ¹³ is preferably a monocyclic or condensed ring having 6 to 18 ring skeleton atoms, and the number of atoms constituting the ring skeleton is A monocyclic or condensed ring having 6 to 14 is more preferable, and a monocyclic or condensed ring having 6 to 10 ring skeleton atoms is more preferable. The number of atoms constituting the ring skeleton includes the number of carbon atoms of the benzene ring surrounded by a broken line.

The monocycle includes a hydrocarbon ring and a heterocycle, and the condensed ring is a ring obtained by condensing these monocycles. The hydrocarbon ring is preferably an aromatic hydrocarbon ring, and the heterocyclic ring is preferably an aromatic heterocyclic ring. Among these, Ar ^{11 to} Ar ¹³ are preferably each independently an aromatic hydrocarbon ring containing a benzene ring surrounded by a broken line, more preferably a benzene ring surrounded by a broken line or a naphthalene ring. preferable.

In General Formulas (A-1) to (C-1), at least one of Ar ^{11 to} Ar ¹³ is preferably an aromatic condensed ring including a benzene ring surrounded by a broken line as one of the condensed rings. Among them, at least one selected from Ar ¹¹ and Ar ¹² is preferably an aromatic condensed ring including a benzene ring surrounded by a broken line as one of the condensed rings, and Ar ¹¹ or Ar ¹² is a benzene surrounded by a broken line. An aromatic condensed ring containing a ring as one of the condensed rings is preferable. Here, the aromatic condensed ring is preferably a polycyclic aromatic hydrocarbon or polycyclic aromatic heterocycle having 9 to 14 ring skeleton atoms. Among these, the aromatic condensed ring is preferably a polycyclic aromatic hydrocarbon, and particularly preferably a naphthalene ring.

Ar ¹³ is preferably an aromatic hydrocarbon ring including a benzene ring surrounded by a broken line, and the aromatic hydrocarbon ring is more preferably a benzene ring or a naphthalene ring. Ar ¹³ may be a condensed ring including a benzene ring surrounded by a broken line, but is preferably a single ring composed of a benzene ring surrounded by a broken line.

R ^{1 to} R ³ each independently represents a substituent. The substituent represented by R ^{1 to} R ³ is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, alkoxy groups, aryl groups, heteroaryl groups, alicyclic groups, An amino group etc. can be mentioned. Among them, R ¹ and R ² are preferably each independently an electron donating group, and examples thereof include a cyclopropyl group, an amino group, a dimethylamino group, a benzoylamino group, a methoxy group, an ethoxy group, and a propoxy group. Can do.
In addition, when Ar ^{11 to} Ar ¹³ are each independently a condensed ring containing a benzene ring surrounded by a broken line, R ^{1 to} R ³ may be independently substituted by a benzene ring surrounded by a broken line, It may be substituted with a ring other than the benzene ring surrounded by a broken line.

  a to c each independently represent 0 or an integer up to the maximum number of substitutions that can be substituted with a single ring including a benzene ring surrounded by a broken line or a condensed ring including a benzene ring surrounded by a broken line. a to c are each independently preferably an integer of 0 to 4, more preferably an integer of 0 to 3, further preferably 0 or 1, and particularly preferably 0.

  Moreover, it is preferable that the compound represented by general formula (B) is a compound represented by the following general formula (B-3).

In General Formula (B-3), R ³ represents a substituent, and c represents an integer of 0 to 4.

^{R 3} in general formula (B-3) is the same as ^{R 3} in the general formula (B-1), and preferred ranges are also the same.

  c is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, further preferably 0 or 1, and particularly preferably 0. In general formula (B-3), c is preferably 0, that is, the compound represented by general formula (B) is preferably phenol.

  Furthermore, the compound represented by the general formula (A) is a compound represented by the following general formula (A-3), the compound represented by the general formula (B) is phenol, and the general formula (C) It is preferable that the represented compound is a compound represented by the following general formula (C-3).

In general formulas (A-3) and (C-3), R ¹ and R ² each independently represent a substituent, a represents an integer of 0 to 4, and b represents an integer of 0 to 6.

^{R 1} and ^{R 2} in general formula (A-3) and (C-3), the general formula (A-1) and (C-1) are each same as ^{R 1} and ^{R 2} in the preferred range is also respectively It is the same.

a is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, further preferably 0 or 1, and particularly preferably 0. Further, b is preferably an integer of 0 to 6, more preferably an integer of 0 to 4, more preferably 0 or 1, and particularly preferably 0.
That is, a is preferably 0 and b is preferably 0.

Specific examples of the compound represented by the general formula (A) preferably used in the present invention are listed below, but the compound represented by the general formula (A) is not limited to the following compounds.
Me represents a methyl group.

  Specific examples of the compound represented by the general formula (B) preferably used in the present invention are listed below, but the compound represented by the general formula (B) is not limited to the following compounds. Me represents a methyl group.

  Specific examples of the compound represented by the general formula (C) preferably used in the present invention are listed below, but the compound represented by the general formula (C) is not limited to the following compounds. Me represents a methyl group.

  Among the above, the compound represented by the general formula (A) is preferably the compound (a4), (a7) or (a10), and particularly preferably the compound (a4). Moreover, it is preferable that the compound represented by general formula (B) is a compound (b1). The compound represented by the general formula (C) is preferably the compound (c4), (c7) or (c10), and particularly preferably the compound (c4). That is, the compound represented by the general formula (C) is particularly preferably 11,11-bis (4-hydroxyphenyl) -11H-benzo [b] fluorene.

<Carbonate solvent>
The production method of the present invention includes a step of obtaining a crystal containing a compound represented by the general formula (C) using a carbonate ester solvent as a solvent in the step of condensation, and a step of carbonation as a crystallization solvent after the step of condensation. It includes at least one of a step of obtaining a crystal containing the compound represented by the general formula (C) using an ester solvent. In the present invention, it is considered that a mixed crystal of the compound represented by the general formula (C) and the carbonate ester is obtained by using a carbonate ester solvent in at least one of the above steps. In the present invention, such a mixed crystal can be obtained in a high yield, and further, the purity is high and coloring is suppressed.

  Examples of the carbonate ester solvent used in the present invention include dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl methyl carbonate, 1,2-butylene carbonate, and the like. Among these, the carbonate ester solvent is preferably at least one selected from dimethyl carbonate, diethyl carbonate, and propylene carbonate, and more preferably dimethyl carbonate. By using the carbonate ester solvent, highly stable crystals can be obtained.

  The amount of the carbonate ester solvent used is preferably 15 mol% or more, more preferably 20 mol% or more, relative to 100 mol% of the compound represented by the general formula (A). By setting the use amount of the carbonate ester solvent in the above range, as described later, the content of the carbonate ester in the mixed crystal containing the compound represented by the general formula (C) and the carbonate ester is within the desired range. It can be. Moreover, by making the usage-amount of a carbonate ester solvent into the said range, it becomes easy to obtain a crystal | crystallization with high purity and a high yield. Furthermore, the structural stability of the mixed crystal can be enhanced.

<Acid catalyst and thiol compound>
The condensation reaction of the compound represented by the general formula (A) and the compound represented by the general formula (B) is performed in a solvent containing an acid catalyst and a thiol compound. Here, examples of the acid catalyst include p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, concentrated sulfuric acid, and the like. Among these, the acid catalyst is preferably methanesulfonic acid. As the thiol compound, alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, and n-lauryl mercaptan, and mercaptocarboxylic acids such as mercaptopropionic acid, thioglycolic acid, and mercaptobenzoic acid can be used. Of these, the thiol compound is preferably mercaptopropionic acid.
In the present invention, the target compound can be efficiently obtained by conducting the condensation reaction of the compound represented by the general formula (A) and the compound represented by the general formula (B) in the presence of an acid catalyst and a thiol compound. it can.

<Manufacturing process>
In this invention, since the crystal | crystallization containing a compound is manufactured using the compound, solvent, catalyst, etc. which were mentioned above, the target compound (crystal) can be obtained with a high yield and high purity. Further, in the crystal obtained in the present invention, coloring is suppressed. That is, the production method of the present invention is a method capable of efficiently obtaining a high-quality curable composition material, and produces a crystal suitable as a curable composition material used for production of an optical member such as a lens. Is the method.

  The production method of the present invention includes a step of condensing the compound represented by the general formula (A) and the compound represented by the general formula (B) in a solvent containing an acid catalyst and a thiol compound. Further, in the present invention, the step of obtaining a crystal containing a compound represented by the general formula (C) using a carbonate ester solvent as a solvent in the step of condensing, and the step of condensing the ester carbonate as a crystallization solvent. It includes at least one of a step of obtaining a crystal containing the compound represented by the compound (C) using a system solvent. The carbonic acid ester solvent may be used in any of the above steps, but is preferably used in the step of condensation. That is, the production method of the present invention preferably includes a step of obtaining crystals containing the compound represented by the general formula (C) using a carbonate ester solvent as a solvent in the step of condensing. Thereby, the number of reaction steps can be reduced, and the production efficiency of the compound can be increased.

  In the production method of the present invention, a known condensation method can be employed in the step of condensing the compound represented by the general formula (A) and the compound represented by the general formula (B). A known crystallization method can also be employed in the step of obtaining crystals using a crystallization solvent.

  By using the production method of the present invention, the yield of crystals obtained can be increased. Specifically, the yield of crystals can be 50% or more, can be 60% or more, and can be 70% or more. As described above, in the production method of the present invention, crystals can be obtained with a high yield, so that the production cost of the material used for the curable composition can be suppressed, and consequently the production cost of the cured product can be suppressed. it can. Further, the crystal obtained by the production method of the present invention has high purity and is excellent in quality.

(Mixed crystal)
The present invention also relates to a mixed crystal containing a compound represented by the following general formula (C) and a carbonate.

In General Formula (C), Ar ¹ and Ar ² each independently represent a monocyclic ring that may have a substituent or a condensed ring that may have a substituent, and Ar ³ has a substituent. An arylene group which may be substituted or a heteroarylene group which may have a substituent.

^Ar 1 to Ar ³ in the general formula (C) are respectively similar to the ^Ar 1 to Ar ³ in formula (C), the same preferable range, respectively. As described above, the compound represented by the general formula (C) is preferably a compound represented by the general formula (C-1), and is preferably a compound represented by the general formula (C-3). More preferred.
Among them, the compound represented by the general formula (C) is particularly preferably 11,11-bis (4-hydroxyphenyl) -11H-benzo [b] fluorene.

  Examples of the carbonate ester include dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl methyl carbonate, 1,2-butylene carbonate, and the like. Among them, the carbonate ester is preferably at least one selected from dimethyl carbonate, diethyl carbonate, and propylene carbonate, and more preferably dimethyl carbonate.

  When the mixed crystal is a mixed crystal of 11,11-bis (4-hydroxyphenyl) -11H-benzo [b] fluorene and dimethyl carbonate, the ratio of dimethyl carbonate contained in the mixed crystal is 11,11-bis (4 -Hydroxyphenyl) -11H-benzo [b] fluorene is preferably 15 to 30 mol%, more preferably 15 to 25 mol%, and more preferably 20 to 25 mol% with respect to 100 mol%. Is more preferable. By setting the content ratio in the mixed crystal within the above range, coloring can be suppressed and a mixed crystal having excellent stability can be obtained.

  The melting point of the mixed crystal of the present invention is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 160 ° C. or higher. The melting point of the mixed crystal in the present specification is measured by a DSC (Differential Scanning Calorimetry) measurement method. A mixed crystal having a high melting point has high crystal stability and is preferably used as a material for the curable composition.

  In the mixed crystal of the present invention, yellowish coloring is suppressed, and the mixed crystal is preferably a white crystal. Specifically, when the mixed crystal is dissolved in a THF (tetrahydrofuran) solution so as to be 0.1 w / v% (weight / volume%) and the transmission spectrum of the solution is measured, the transmittance at a wavelength of 400 nm is It is preferably 90% or more. The transmission spectrum of the solution is measured using a spectrophotometer (UV-2550) manufactured by Shimadzu Corporation. In this case, a square quartz cell (optical path length: 1 cm) is used for the cell, and a THF solution is used for the blank.

(Curable composition)
The crystal (mixed crystal) obtained by the production method of the present invention is used as a monomer constituting the curable composition after being mixed with a compound having a polymerizable group. Examples of the polymerizable group include a polymerizable group capable of radical polymerization or cationic polymerization.
Examples of the radical polymerizable group include generally known radical polymerizable groups. Preferable examples include a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization, and specific examples include a vinyl group and a (meth) acryloyloxy group. Among these, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
Examples of the cationically polymerizable group include generally known cationically polymerizable groups, and specifically include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiro orthoester groups, A vinyloxy group etc. can be mentioned. Of these, alicyclic ether groups and vinyloxy groups are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are preferable.
Among the above-mentioned, the polymerizable group is preferably a (meth) acryloyloxy group, and is preferably an acryloyloxy group.

  When mixed with a compound having a polymerizable group, the polymerizable group is substituted for the compound represented by the general formula (C) to form a polymerizable group-containing compound. In the present invention, an increase in the liquid viscosity of the curable composition containing the polymerizable group-containing compound can be suppressed by obtaining the compound represented by the general formula (C) under the conditions described above. Thereby, the mold followability and moldability of the hardened | cured material formed from a curable composition can be improved. Moreover, in this invention, coloring of a curable composition or hardened | cured material can also be suppressed by obtaining the compound represented by general formula (C) on conditions as mentioned above.

As described above, the curable composition preferably contains a polymerizable group-containing compound. The curable composition preferably contains a (meth) acrylate monomer, a non-conjugated vinylidene group-containing compound, a photo radical polymerization initiator, a thermal radical polymerization initiator, and the like. Furthermore, the curable composition may contain additives such as a polymer, other monomers, a dispersant, a plasticizer, a heat stabilizer, and a release agent.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate. The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a weight average molecular weight of 1,000 or less.

  As the (meth) acrylate monomer contained in the curable composition, those described in paragraphs 0094 to 0096 of JP-A-2014-080572 can be used. Moreover, as a nonconjugated vinylidene group containing compound, the thing of Paragraphs 0068-0083 of Unexamined-Japanese-Patent No. 2014-080572 can be used. As a radical photopolymerization initiator and a thermal radical polymerization initiator, those described in paragraphs 0084 to 0093 of JP-A-2014-080572 can be used. As other additives, those described in paragraphs 0097 to 0102 of JP-A No. 2014-080572 can be used.

(Method for producing cured product)
When manufacturing hardened | cured material using the curable composition mentioned above, it is preferable to include the process of first semi-hardening a curable composition and also hardening a semi-hardened material. Here, the “semi-cured product” is a product obtained by polymerizing a curable composition, which is not completely solid and has a certain degree of fluidity. For example, a light and / or heat polymer of a curable composition, and a cured product having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz is a semi-cured product. In the present specification, the upper limit of the complex viscosity at 25 ° C. and a frequency of 10 Hz is referred to as a semi-cured product up to 1.0 × 10 ⁹ mPa · s. On the other hand, the “cured product” is a product obtained by further curing the semi-cured product and is in a completely solid state.

  Paragraphs 0103 to 0118 of JP-A-2014-080572 can be referred to for the method for producing the semi-cured product and the method for producing the cured product. Further, the physical properties of the cured product are also preferably within the range described in paragraphs 0120 to 0122 of JP-A No. 2014-080572.

(Optical member)
It is preferable that the hardened | cured material formed from the curable composition mentioned above is used as an optical member. In particular, a cured product formed from the above-described curable composition is excellent in optical characteristics, and thus can be suitably used as an optical member that transmits light (a so-called passive optical member). Examples of the optical functional device including such an optical member include various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP (Overhead Projector), liquid crystal projector, etc.), optical fiber communication devices (optical waveguide, And an imaging device such as a camera or a video.

  Moreover, as a passive optical member used for an optical function apparatus, a lens, a prism, a prism sheet, a panel (plate-shaped molded object), a film, an optical waveguide (film shape, fiber shape, etc.), an optical disk, LED (Light Emitting), for example. Diode) sealant and the like are exemplified. The passive optical member absorbs light with an undesired wavelength that causes deterioration of any coating layer, for example, a protective layer that prevents mechanical damage to the coated surface due to friction or wear, and inorganic particles and substrates, as necessary. Multi-layered with optional additional function layers such as light absorbing layer, transmission blocking layer that suppresses or prevents the transmission of reactive low molecules such as moisture and oxygen gas, antiglare layer, antireflection layer, low refractive index layer, etc. It is good also as a structure. Specific examples of such an optional coating layer include a transparent conductive film and gas barrier film made of an inorganic oxide coating layer, a gas barrier film made of an organic coating layer, a hard coat, and the like. A known coating method such as a CVD (Chemical Vapor Deposition) method, a sputtering method, a dip coating method, or a spin coating method can be used.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

(Example 4)
In a three-necked flask equipped with a stirrer, a condenser and a thermometer, 24.0 g of 2,3-benzofluorenone and 49.1 g of phenol were weighed, and 20 ml of dimethyl carbonate was added and dissolved at 40 ° C. After adding 0.4 g of 3-mercaptopropionic acid to the solution in the three-necked flask, 13.5 g of methanesulfonic acid was added dropwise over 30 minutes and stirred at 60 ° C. for 1 hour. As a result, white crystals were precipitated. . After cooling the solution in the three-necked flask to room temperature, 300 ml of toluene was added and stirred for 1 hour, and white crystals were separated by filtration. It was dried in a vacuum oven to obtain 38.4 g of white crystals (yield 92%, HPLC (High Performance Liquid Chromatography) purity 98.2%).
The obtained crystal was dissolved in dimethyl sulfoxide-d6, and ¹ H-NMR (Nuclear Magnetic Resonance) measurement was performed using AVANCE-300 manufactured by BRUKER. As a result, 4.2 mol of compound (c4) was contained in the crystal. 1 mol of dimethyl carbonate was contained. The melting point of the crystal as measured by DSC was 180 ° C. Moreover, when the transmission spectrum of the THF solution of the crystal prepared to 0.1 w / v% was measured, the transmittance | permeability in wavelength 400nm was 99.3%.
The HLPC purity, appearance (coloring), transmission spectrum and melting point were measured by the methods shown below.

(Examples 1-3 and 5-18)
Crystals were obtained in the same manner as in Example 4 except that the materials shown in Table 1 were used. All were white crystals without coloring.

(Example 19)
For Example 19, 28.8 g of white crystals were obtained in the same manner as in Example 4 except that the amount of dimethyl carbonate used in the reaction was 5 ml (yield 69%, HPLC purity 97.4%). The obtained crystals were dissolved in dimethyl sulfoxide-d6 and subjected to ¹ H-NMR measurement using AVANCE-300 manufactured by BRUKER. The crystals contained 1 mol with respect to 5.2 mol of compound (c4). Of dimethyl carbonate.

(Example 20)
In a three-necked flask equipped with a stirrer, a condenser and a thermometer, 24.0 g of 2,3-benzofluorenone and 49.1 g of phenol were weighed and 20 ml of toluene was added and dissolved at 40 ° C. After adding 0.4 g of 3-mercaptopropionic acid to the solution in the three-necked flask, 13.5 g of methanesulfonic acid was added dropwise over 30 minutes, and the mixture was stirred at 60 ° C. for 1 hour. To a three-necked flask, 200 ml of toluene and 100 ml of water were added for liquid separation, and the organic layer was washed three times with saturated saline. When 20 ml of dimethyl carbonate was added to the obtained toluene layer, the temperature was raised to 80 ° C., and the mixture was gradually cooled to room temperature, whereby white crystals were precipitated. After stirring at room temperature for 1 hour and separating the white crystals by filtration, the crystals were dried in a vacuum oven to obtain 35.5 g of white crystals (yield 85%, HPLC purity 98.1%).
The obtained crystals were dissolved in dimethyl sulfoxide-d6 and subjected to ¹ H-NMR measurement using AVANCE-300 manufactured by BRUKER. The crystals contained 1 mol with respect to 4.9 mol of compound (c4). Of dimethyl carbonate. The melting point of the crystal as measured by DSC was 180 ° C. Moreover, when the transmission spectrum of the THF solution of the crystal prepared to 0.1 w / v% was measured, the transmittance | permeability in wavelength 400nm was 99.1%.

(Comparative Example 1)
In a three-necked flask equipped with a stirrer, a condenser and a thermometer, 24.0 g of 2,3-benzofluorenone and 49.1 g of phenol were weighed and 20 ml of toluene was added and dissolved at 40 ° C. After adding 0.4 g of 3-mercaptopropionic acid to the solution in the three-necked flask, 10.2 g of sulfuric acid was added dropwise over 30 minutes, and the mixture was stirred at 60 ° C. for 1 hour. To a three-necked flask, 200 ml of toluene and 100 ml of water were added for liquid separation, and the organic layer was washed three times with saturated saline. The obtained toluene layer was stirred at 5 ° C. for 5 hours, and the precipitated crystals were separated by filtration, and then washed with toluene at 5 ° C. three times. Drying in a vacuum oven gave 20.0 g of yellowish crystals (yield 48%, HPLC purity 96.2%).
The melting point of the crystal as measured by DSC was 130 ° C. Moreover, when the transmission spectrum of the THF solution of the crystal prepared to 0.1 w / v% was measured, the transmittance | permeability in wavelength 400nm was 96.9%.
The obtained crystal was dissolved in dimethyl sulfoxide-d6 and subjected to ¹ H-NMR measurement using AVANCE-300 manufactured by BRUKER. As a result, 1 mol of toluene was contained in 12% of compound (c4) in the crystal. Was included.

(Measuring method)
<HPLC purity>
The purity of the crystals was measured under the following conditions using high performance liquid chromatography (SPD-10AV VP) manufactured by Shimadzu Corporation.
Column: TSKgel ODS-100Z 5 μm (4.6 mmφ × 150 mm) (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent:
Acetonitrile: Pure water: Triethylamine: Phosphoric acid (volume ratio)
= 700: 300: 1: 1
Flow rate: 1.0 ml / min
Detection wavelength: 254 nm
Injection volume: 10 μL
Sample concentration: 5mg / 50ml diluted with eluent

<Appearance (coloring)>
About 3 g of the crystals obtained in Examples and Comparative Examples were collected in a colorless and transparent vial, and the presence or absence of coloring and color were visually confirmed under a daylight fluorescent lamp.

<Transmission spectrum>
Using a spectrophotometer (UV-2550) manufactured by Shimadzu Corporation, the transmittance of the crystal at a wavelength of 400 nm was measured under the following conditions. The higher the transmittance at 400 nm, the less yellow the crystals are colored.
Cell: Square quartz cell (optical path length: 1 cm)
Sample concentration: 50.0 mg / 50 mL of crystals diluted with THF solution Blank: THF solution

<Melting point>
Using a differential scanning calorimeter (DSC 6200) manufactured by SII Nano Technology Co., Ltd., the melting point of the crystal was measured within the range of room temperature (25 ° C.) to 300 ° C. at a temperature rising rate of 10 ° C./min. It was.

  In Examples 1-20, it turns out that the target crystal | crystallization is obtained with high yield and high purity. Moreover, the obtained crystal | crystallization is white and yellowish coloring is suppressed. On the other hand, in Comparative Example 1, the yield of the target crystal is poor and the purity is slightly inferior. Moreover, the obtained crystal | crystallization is yellowish.

Claims (14)

The compound represented by the general formula (C) includes a step of condensing the compound represented by the general formula (A) and the compound represented by the general formula (B) in a solvent containing an acid catalyst and a thiol compound. A manufacturing method comprising:
A step of obtaining a crystal containing a compound represented by the general formula (C) using a carbonate ester solvent as the solvent in the step of condensing, or
After the step of condensing, a step of obtaining a crystal containing a compound represented by formula (C) using a carbonate ester solvent as a crystallization solvent;

In General Formulas (A) to (C), Ar ¹ and Ar ² each independently represent a monocyclic ring that may have a substituent or a condensed ring that may have a substituent, and Ar ³ represents a substituted group. Represents an arylene group which may have a group or a heteroarylene group which may have a substituent. The compound represented by the general formula (A) is a compound represented by the following general formula (A-1), and the compound represented by the general formula (B) is represented by the following general formula (B-1). The production method according to claim 1, wherein the compound represented by the general formula (C) is a compound represented by the following general formula (C-1);

In general formulas (A-1) to (C-1), Ar ^{11 to} Ar ¹³ each independently represents a single ring containing a benzene ring surrounded by a broken line or a condensed ring containing a benzene ring surrounded by a broken line. , R ^{1 to} R ³ each independently represents a substituent, and a to c are each independently 0 or substituted with a single ring containing a benzene ring surrounded by a broken line or a condensed ring containing a benzene ring surrounded by a broken line Represents an integer with the maximum number of possible substitutions as the upper limit; when Ar ^{11 to} Ar ¹³ are each independently a condensed ring containing a benzene ring surrounded by a broken line, R ^{1 to} R ³ are each independently surrounded by a broken line The benzene ring may be substituted, or may be substituted with a ring other than the benzene ring surrounded by a broken line. In the general formulas (A-1) to (C-1), at least one of Ar ^{11 to} Ar ¹³ is an aromatic condensed ring including a benzene ring surrounded by a broken line as one of the condensed rings. The manufacturing method as described. In general formula (A-1) and (C-1), Ar < ¹¹ > or Ar < ¹² > is an aromatic condensed ring which contains the benzene ring enclosed by the broken line as one of the condensed rings. Method. The production method according to any one of claims 1 to 4, wherein the compound represented by the general formula (B) is a compound represented by the following general formula (B-3).

In General Formula (B-3), R ³ represents a substituent, and c represents an integer of 0 to 4.   The production method according to claim 1, wherein the compound represented by the general formula (B) is phenol. The compound represented by the general formula (A) is a compound represented by the following general formula (A-3), the compound represented by the general formula (B) is phenol, and the general formula (C) The compound represented by general formula (C-3) is a compound represented by any one of Claims 1-6;

In general formulas (A-3) and (C-3), R ¹ and R ² each independently represent a substituent, a represents an integer of 0 to 4, and b represents an integer of 0 to 6.   In the general formulas (A-3) and (C-3), a is 0 and b is 0.   The production method according to any one of claims 1 to 8, wherein an amount of the carbonate ester solvent used is 15 mol% or more with respect to 100 mol% of the compound represented by the general formula (A).   The production method according to any one of claims 1 to 9, wherein the carbonate solvent is at least one selected from dimethyl carbonate, diethyl carbonate, and propylene carbonate.   The manufacturing method according to any one of claims 1 to 10, wherein the carbonate solvent is dimethyl carbonate. A mixed crystal containing a compound represented by the following general formula (C) and a carbonate ,
A mixed crystal having a transmittance of 90% or more at a wavelength of 400 nm when the mixed crystal is dissolved in a tetrahydrofuran solution so as to be 0.1 w / v% ;

In general formula (C), Ar ¹ and Ar ² each independently represent a monocyclic ring that may have a substituent or a condensed ring that may have a substituent, and Ar ³ has a substituent. An arylene group which may be substituted or a heteroarylene group which may have a substituent.   The mixed crystal according to claim 12, wherein the compound represented by the general formula (C) is 11,11-bis (4-hydroxyphenyl) -11H-benzo [b] fluorene, and the carbonate is dimethyl carbonate.   The ratio of the dimethyl carbonate in the mixed crystal is 15 to 25 mol% with respect to 100 mol% of the 11,11-bis (4-hydroxyphenyl) -11H-benzo [b] fluorene. The mixed crystal described.