阅读说明：本技术 溶剂化物及溶剂化物的制造方法 (Solvate and method for producing solvate ) 是由 师冈直之 中山贵文 于 2020-03-12 设计创作，主要内容包括：作为能够制造透光率高的透镜等光学部件的材料,本发明提供一种溶剂化物,其为由通式1表示的化合物的溶剂化物,其中,溶剂包含分子量为200以下的含氮原子有机化合物,将含氮原子有机化合物中的碳原子数除以氮原子数与氧原子数之和而得的值为5以下；式中,X和Y分别独立地为杂原子或碳原子,其中,X和Y中的至少一者为氮原子,Z是与X-C＝C-Y一起形成5～7元环的原子团,且表示含有选自碳原子和杂原子中的至少1种的原子团,R～(3)～R～(6)表示取代基,q和r为0～4的整数,v为0～4的整数,w为0以上的整数。(The present invention provides a solvate of a compound represented by general formula 1, wherein the solvent contains a nitrogen atom-containing organic compound having a molecular weight of 200 or less, and a value obtained by dividing the number of carbon atoms in the nitrogen atom-containing organic compound by the sum of the number of nitrogen atoms and the number of oxygen atoms is 5 or less; wherein X and Y are each independently a heteroatom or a carbon atom, wherein at least one of X and Y is a nitrogen atom, Z is an atomic group which forms a 5-to 7-membered ring together with X-C ═ C-Y and represents an atomic group containing at least 1 selected from a carbon atom and a heteroatom, and R is a hydrogen atom 3 ～R 6 Represents a substituent group, q and r are 0 to 4V is an integer of 0 to 4, and w is an integer of 0 or more.)

1. A solvate of a compound represented by formula 1, wherein,

the solvent constituting the solvate contains an organic compound containing a nitrogen atom,

the nitrogen atom-containing organic compound may contain an oxygen atom,

a value obtained by dividing the number of carbon atoms in the nitrogen atom-containing organic compound by the sum of the number of nitrogen atoms and the number of oxygen atoms is 5 or less,

the molecular weight of the nitrogen atom-containing organic compound is 200 or less;

[ chemical formula 1]

In the general formula 1, X and Y are respectively and independently an oxygen atom, a sulfur atom, a nitrogen atom or a carbon atom, wherein at least one of X and Y is a nitrogen atom;

z represents an atomic group which forms a 5-7 membered ring together with X-C ═ C-Y and contains at least 1 selected from carbon atoms and hetero atoms;

R³～R⁶each independently represents a substituent;

q and r are each independently an integer of 0 to 4;

v is an integer of 0 to 4, w is an integer of 0 or more, and the maximum number of w is the maximum number of substituents that can be substituted on the ring formed by X-C ═ C-Y and Z;

when q is an integer of 2 to 4, 2 or more R³May be the same or different, 2 or more R³May be bonded to each other to form a ring;

when R is an integer of 2 to 4, 2 or more R⁴May be the same or different, 2 or more R⁴May be bonded to each other to form a ring;

when v is an integer of 2 to 4, 2 or more R⁵May be the same or different, 2 or more R⁵Are not connected with each other to form a ring;

when w is an integer of 2 to 5, 2 or more R⁶May be the same or different, 2 or more R⁶May be bonded to each other to form a ring.

2. The solvate according to claim 1, wherein,

the compound represented by formula 1 is a compound represented by formula 2;

[ chemical formula 2]

In the general formula 2, R³、R⁴、R⁵、R⁷Each independently represents a substituent;

q and r are each independently an integer of 0 to 4;

v is an integer of 0 to 4, and s is an integer of 0 to 2;

when q is an integer of 2 to 4, 2 or more R³May be the same or different, 2 or more R³May be bonded to each other to form a ring;

when R is an integer of 2 to 4, 2 or more R⁴May be the same or different, 2 or more R⁴May be bonded to each other to form a ring;

when v is an integer of 2 to 4, 2 or more R⁵May be the same or different, 2 or more R⁵Are not connected with each other to form a ring;

when s is 2, 2R⁷May be the same or different, 2R⁷May be bonded to each other to form a ring.

3. The solvate according to claim 1 or 2, wherein,

the compound represented by formula 1 is a compound represented by formula 3;

[ chemical formula 3]

In the general formula 3, R³、R⁴、R⁵、R⁸Each independently represents a substituent;

q and r are each independently an integer of 0 to 4;

v is an integer of 0 to 4, and t is an integer of 0 to 4;

when q is an integer of 2 to 4, 2 or more R³May be the same or different, 2 or more R³May be bonded to each other to form a ring;

when R is an integer of 2 to 4, 2 or more R⁴May be the same or different, 2 or more R⁴May be bonded to each other to form a ring;

when v is an integer of 2 to 4, 2 or more R⁵May be the same or different, 2 or more R⁵Are not connected with each other to form a ring;

when t is an integer of 2-4, more than 2R⁸May be the same or different.

4. The solvate according to any one of claims 1 to 3, wherein,

the nitrogen atom-containing organic compound is any 1 or more selected from the group consisting of pyridine, pyrimidine, pyrazine, a compound represented by the general formula B, and a compound represented by the general formula C;

[ chemical formula 4]

In the general formula B, R^e、R^f、R^gEach independently represents a hydrogen atom or a hydrocarbon group which may have a substituent,

R^eand R^gOr R^eAnd R^fMay be bonded to each other to form a ring structure,

in the general formula C, R^hIs a hydrogen atom or a hydrocarbon group which may have a substituent.

5. The solvate according to any one of claims 1 to 4, wherein,

the value obtained by dividing the number of carbon atoms in the nitrogen atom-containing organic compound by the sum of the number of nitrogen atoms and the number of oxygen atoms is less than 5.

6. The solvate according to any one of claims 1 to 5, wherein,

the nitrogen atom-containing organic compound is any 1 or more selected from the group consisting of N, N' -dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone.

7. The solvate according to any one of claims 1 to 6, wherein,

the content of the nitrogen atom-containing organic compound is 10 to 200 mol% relative to 100 mol% of the compound represented by formula 1.

8. A production method of producing the solvate according to any one of claims 1 to 7,

the method comprises the following steps: crystallizing the compound represented by the general formula 1 using the nitrogen atom-containing organic compound as a solvent.

9. The manufacturing method according to claim 8,

the method comprises the following steps: after dissolving the compound represented by general formula 1 in the solvent composed of the organic compound containing a nitrogen atom, a solvent containing 1 or more kinds of organic solvents selected from the group consisting of methyl acetate, ethyl acetate, and butyl acetate is added to precipitate the solvate.

Technical Field

The present invention relates to a solvate and a method for producing the solvate.

Background

Glass materials have been used for optical parts of camera modules such as cameras, video cameras, mobile phones with cameras, video phones, and video intercoms. Glass materials have various optical properties and are excellent in environmental resistance, and therefore, they are preferably used, but they have disadvantages that they are not easy to be reduced in weight and size and that they are poor in processability and productivity. On the contrary, resin cured products are used for various optical components because of mass production and excellent processability.

In recent years, along with the miniaturization of image pickup modules, miniaturization of optical components used in the image pickup modules is demanded, but if the optical components are miniaturized, a problem of chromatic aberration arises. Therefore, in an optical component using a cured resin, it has been studied to correct chromatic aberration by adjusting abbe number with a raw material monomer or an additive of a curable composition.

For example, patent document 1 discloses the following: a cured product having a low Abbe number can be molded from a curable composition containing a compound having a heteroatom-containing skeleton similar to a diphenylfluorene skeleton.

Prior art documents

Patent document

Patent document 1: WO2017/115649

Disclosure of Invention

Technical problem to be solved by the invention

In the production of a cured product or the like described in patent document 1, if the purity of the raw material compound is high, the transmittance of the cured product is high, and it is more preferable as an optical component such as a lens.

The present invention addresses the problem of providing a material that can improve the light transmittance of a product, as a material that can be used for manufacturing optical components such as lenses.

Means for solving the technical problem

The present inventors have made intensive studies in order to solve the above problems, and as a result, have found that the purity of a phenol compound having a hetero atom-containing skeleton similar to a diphenylfluorene skeleton as described in patent document 1 can be easily improved by forming a solvate with a specific solvent. Further, it has been found that a curable monomer having a high purity can be produced using such a phenol compound as an intermediate. Further, it has been found that the solvate has high solubility in a solvent such as tetrahydrofuran, and a product having high purity can be obtained by forming a reaction system into a homogeneous system. The present invention has been completed based on this finding.

Namely, the present invention provides the following < 1 > to < 9 >.

< 1 > a solvate, which is a solvate of the compound represented by formula 1, wherein,

the solvent constituting the above solvate contains an organic compound containing a nitrogen atom,

the nitrogen atom-containing organic compound may contain an oxygen atom,

a value obtained by dividing the number of carbon atoms in the nitrogen atom-containing organic compound by the sum of the number of nitrogen atoms and the number of oxygen atoms is 5 or less,

the molecular weight of the nitrogen atom-containing organic compound is 200 or less;

[ chemical formula 1]

In the general formula 1, X and Y are respectively and independently an oxygen atom, a sulfur atom, a nitrogen atom or a carbon atom, wherein at least one of X and Y is a nitrogen atom;

z represents an atomic group which forms a 5-7 membered ring together with X-C ═ C-Y and contains at least 1 selected from carbon atoms and hetero atoms;

R³～R⁶each independently represents a substituent;

q and r are each independently an integer of 0 to 4;

v is an integer of 0 to 4, w is an integer of 0 or more, and the maximum number of w is the maximum number of substituents that can be substituted on the ring formed by X-C ═ C-Y and Z;

when q is an integer of 2 to 4, 2 or more R³May be the same or different, 2 or more R³May be bonded to each other to form a ring;

when R is an integer of 2 to 4, 2 or more R⁴May be the same or different, 2 or more R⁴May be bonded to each other to form a ring;

when v is an integer of 2 to 4, 2 or more R⁵May be the same or different, 2 or more R⁵Are not connected with each other to form a ring;

when w is an integer of 2 to 5, 2 or more R⁶May be the same or different, 2 or more R⁶May be bonded to each other to form a ring.

< 2 > the solvate according to < 1 > wherein the compound represented by formula 1 is a compound represented by formula 2;

[ chemical formula 2]

In the general formula 2, R³、R⁴、R⁵、R⁷Each independently represents a substituent;

q and r are each independently an integer of 0 to 4;

v is an integer of 0 to 4, and s is an integer of 0 to 2;

when q is an integer of 2 to 4, 2 or more R³May be the same or different, 2 or more R³May be bonded to each other to form a ring;

when R is an integer of 2 to 4, 2 or more R⁴May be the same or different, 2 or more R⁴May be bonded to each other to form a ring;

when v is an integer of 2 to 4, 2 or more R⁵May be the same or different, 2 or moreUpper R⁵Are not connected with each other to form a ring;

when s is 2, 2R⁷May be the same or different, 2R⁷May be bonded to each other to form a ring.

< 3 > the solvate according to < 1 > or < 2 >, wherein the compound represented by formula 1 is a compound represented by formula 3;

[ chemical formula 3]

In the general formula 3, R³、R⁴、R⁵、R⁸Each independently represents a substituent;

q and r are each independently an integer of 0 to 4;

v is an integer of 0 to 4, and t is an integer of 0 to 4;

when q is an integer of 2 to 4, 2 or more R³May be the same or different, 2 or more R³May be bonded to each other to form a ring;

when R is an integer of 2 to 4, 2 or more R⁴May be the same or different, 2 or more R⁴May be bonded to each other to form a ring;

when v is an integer of 2 to 4, 2 or more R⁵May be the same or different, 2 or more R⁵Are not connected with each other to form a ring;

when t is an integer of 2-4, more than 2R⁸May be the same or different.

< 4 > the solvate according to any one of < 1 > to < 3 >, wherein the organic compound containing a nitrogen atom is any 1 or more selected from the group consisting of pyridine, pyrimidine, pyrazine, compound represented by the general formula B and compound represented by the general formula C.

[ chemical formula 4]

In the general formula B, R^e、R^f、R^gEach independently represents a hydrogen atom or a hydrocarbon group which may have a substituent,

R^eand R^gOr R^eAnd R^fMay be bonded to each other to form a ring structure,

in the general formula C, R^hIs a hydrogen atom or a hydrocarbon group which may have a substituent.

< 5 > the solvate according to any one of < 1 > to < 4 >, wherein the value obtained by dividing the number of carbon atoms in the above-mentioned nitrogen atom-containing organic compound by the sum of the number of nitrogen atoms and the number of oxygen atoms is less than 5.

< 6 > the solvate according to any one of < 1 > to < 5 >, wherein the organic compound containing a nitrogen atom is at least one selected from the group consisting of N, N' -dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and N-ethylpyrrolidone.

< 7 > the solvate according to any one of < 1 > to < 6 >, wherein the content of the nitrogen atom-containing organic compound is 10 to 200 mol% relative to 100 mol% of the compound represented by formula 1.

< 8 > a production method for producing the solvate according to any one of < 1 > to < 7 >, wherein,

comprises crystallizing a compound represented by the general formula 1 using the nitrogen atom-containing organic compound as a solvent.

< 9 > the production method according to < 8 >, wherein the method comprises dissolving the compound represented by the general formula 1 in a solvent comprising the nitrogen atom-containing organic compound, and then adding 1 or more kinds of solvents selected from the group consisting of methyl acetate, ethyl acetate and butyl acetate to precipitate the solvate.

Effects of the invention

The present invention provides a solvate of a compound represented by general formula 1 that can be used for producing an optical component such as a lens with high purity, and a method for producing the solvate. The solvate of the present invention can be used as a raw material for forming a cured product that can be used for an optical component or the like, or as an intermediate for producing a curable monomer for forming the cured product. The solvate of the present invention has high solubility in a solvent such as tetrahydrofuran, and therefore, when used as a production intermediate, can be reacted in a homogeneous system, and thus a curable monomer can be produced with high purity and high yield.

Drawings

FIG. 1 is a graph showing the results of powder X-ray diffraction measurement of Compound c 3.

FIG. 2 is a graph showing the results of powder X-ray diffraction measurement of solvate crystals solvated in c3 of N, N-dimethylacetamide in example 1.

FIG. 3 is a graph showing the results of powder X-ray diffraction measurements of solvate crystals solvated in c3 with N-ethylpyrrolidone of example 3.

FIG. 4 is a graph showing the results of powder X-ray diffraction measurement of solvate crystals solvated in c3 of N, N-dimethylacetamide in example 10.

FIG. 5 is a graph showing the results of powder X-ray diffraction measurement of the crystal of comparative example 1.

Detailed Description

The present invention will be described in detail below. The constituent elements described below will be described based on a representative embodiment or specific example, but the present invention is not limited to this embodiment.

In the present specification, the numerical range represented by "to" means a range in which the numerical values before and after "to" are included as the lower limit value and the upper limit value. The monomer in the present invention is a compound having a weight average molecular weight of 1000 or less, which is distinguished from an oligomer and a polymer.

< solvate >

The solvate of the present invention is a solvate of a compound (phenol compound) represented by formula 1, and is prepared from the compound represented by formula 1 and a solvent. In the solvate of the present invention, the number of the compounds represented by formula 1 may be 1, or 2 or more, but is usually 1. In the solvate of the present invention, the number of the solvents may be 1,2 or more, and preferably 1.

The present inventors have found that a compound represented by the general formula 1 can be obtained with high purity by forming a solvate with a specific solvent described below. Typically, the solvate can be isolated as a crystal with high purity, but it may be amorphous, and the state or shape of the solvate of the present invention is not particularly limited. The solvate of the present invention is preferably crystalline.

[ solvent ]

In the solvate of the present invention, the solvent constituting the solvate contains an organic compound containing a nitrogen atom and having a molecular weight of 200 or less. The nitrogen atom-containing organic compound is a compound having a structural formula containing a carbon atom, a hydrogen atom and a nitrogen atom (N). The nitrogen atom-containing organic compound may further contain an oxygen atom. The value obtained by dividing the number of carbon atoms in the nitrogen atom-containing organic compound by the sum of the number of nitrogen atoms and the number of oxygen atoms is 5 or less. That is, the solvent constituting the solvate of the present invention includes a compound represented by the following formula.

[ chemical formula 5]

C_aN_bO_cH_d

In the molecular formula, a, b and d are integers more than 1, c is an integer more than 0, and a/(b + c) is less than or equal to 5.

The molecular weight of the nitrogen atom-containing organic compound is 200 or less, preferably 180 or less, and more preferably 160 or less. The value obtained by dividing the number of carbon atoms in the nitrogen atom-containing organic compound by the sum of the number of nitrogen atoms and the number of oxygen atoms is preferably less than 5. That is, in the above formula, a/(b + c) < 5 is preferable.

Examples of the nitrogen atom-containing organic compound include pyridine, pyrimidine, pyrazine, compounds represented by the general formula B, and compounds represented by the general formula C.

[ chemical formula 6]

In the general formula B, R^e、R^f、R^gEach independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R^eAnd R^gOr R^eAnd R^fMay be bonded to each other to form a ring structure. R^e、R^fPreferred is a hydrocarbon group which may have a substituent, and further preferred is R^eAnd R^gBonded to each other to form a ring structure. In the general formula C, R^hIs a hydrogen atom or a hydrocarbon group which may have a substituent.

Examples of the substituent include an alkyl group such as a methyl group and an ethyl group. As the hydrocarbon group which may have a substituent in the general formula B and the general formula C, an unsubstituted hydrocarbon group is preferable. Examples of the hydrocarbon group include a branched or straight-chain alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 1 to 6 carbon atoms, a phenyl group, or a combination thereof, preferably a branched or straight-chain alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. In the general formula B, as R^eAnd R^gExamples of the ring structure formed by bonding to each other include a pyrrolidone ring and the like. And as R^eAnd R^fExamples of the ring structure formed by bonding to each other include a pyrrolidine ring, a piperazine ring, and a morpholine ring. R^eAnd R^fPreferably one and the same group.

Examples of the nitrogen atom-containing organic compound include N, N-dimethylformamide (1.5), N-dimethylacetamide (2), N-dimethylpropionamide (2.5), N-diethylpropionamide (3.5), 2-pyrrolidone (2), N-methylpyrrolidone (2.5), N-ethylpyrrolidone (3), morpholine (2), N-methylmorpholine (2.5), pyridine (5), pyrimidine (2), pyrazine (2), and the like having the following structures. The value in parentheses is a value (a/(b + c)) obtained by dividing the number of carbon atoms in the compound by the sum of the number of nitrogen atoms and the number of oxygen atoms.

[ chemical formula 7]

Among them, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone are preferable, and N, N-dimethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone are more preferable.

The content of the nitrogen atom-containing organic compound in the solvate of the present invention is not particularly limited, and may be 300 mol% or less, preferably 10 to 200 mol%, based on 100 mol% of the compound represented by the general formula 1, depending on the types of the compound represented by the general formula 1 and the nitrogen atom-containing organic compound.

The solvent in the solvate of the present invention preferably does not contain an organic compound having a nitrogen atom other than the above-described organic compound having a nitrogen atom. The solvent in the solvate of the present invention may contain an organic compound having no nitrogen atom. The organic compound having no nitrogen atom is not particularly limited, and examples thereof include organic compounds that are liquid at room temperature and are generally used as solvents. Specific examples thereof include methyl acetate, ethyl acetate and butyl acetate.

[ Compound represented by the formula 1]

[ chemical formula 8]

In formula 1, X and Y are each independently an oxygen atom, a sulfur atom, a nitrogen atom, or a carbon atom, wherein at least one of X and Y is a nitrogen atom. In X and Y, R is not bonded⁶The carbon atom(s) of (2) may be bonded to a hydrogen atom to form CH.

Z represents an atomic group which forms a 5-7 membered ring together with X-C ═ C-Y and contains at least 1 selected from carbon atoms and hetero atoms. In Z, R is not bonded⁶The carbon atom(s) of (2) may be bonded to a hydrogen atom to form CH.

R³～R⁶Each independently represents a substituent. q and r are each independently an integer of 0 to 4. v is an integer of 0 to 4, w is an integer of 0 or more, and the maximum number of w is the maximum number of substituents that can be substituted on the ring formed by X-C ═ C-Y and Z;

when q is an integer of 2 to 4, 2 or more R³Can be combined withAnd also may be different, 2 or more R³May be bonded to each other to form a ring;

when R is an integer of 2 to 4, 2 or more R⁴May be the same or different, 2 or more R⁴May be bonded to each other to form a ring;

when v is an integer of 2 to 4, 2 or more R⁵May be the same or different, 2 or more R⁵Are not connected with each other to form a ring;

when w is an integer of 2 to 5, 2 or more R⁶May be the same or different, 2 or more R⁶May be bonded to each other to form a ring.

In formula 1, X and Y are each independently preferably a nitrogen atom or a carbon atom. And, more preferably, both X and Y are nitrogen atoms.

In formula 1, Z is preferably an atomic group forming a 5-or 6-membered ring together with X-C ═ C-Y, and more preferably an atomic group forming a 6-membered ring. Z is an atomic group containing at least 1 kind selected from a carbon atom and a hetero atom, and is preferably an atomic group containing a carbon atom, and more preferably an atomic group consisting of a carbon atomic group.

In the general formula 1, as R³～R⁶The substituent is not particularly limited, and examples thereof include a halogen atom, a haloalkyl group, an alkyl group, an alkenyl group, an acyl group, an alkoxycarbonyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, an aryl group, a heteroaryl group, a cycloalkyl group, and a cyano group.

In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the present specification, an alkyl group means a linear or branched alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a 1-methylbutyl group, a 3-methylbutyl group, a hexyl group, a 1-methylpentyl group, a 4-methylpentyl group, a heptyl group, a 1-methylhexyl group, a 5-methylhexyl group, a 2-ethylhexyl group, an octyl group, a 1-methylheptyl group, a nonyl group, a 1-methyloctyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. The same applies to the alkyl group in the alkyl group-containing group (halogenated alkyl group, alkoxy group, alkoxycarbonyl group, acyl group, etc.). As the alkyl group, a methyl group or an ethyl group is preferable.

In the present specification, examples of the alkenyl group include a vinyl group and an allyl group.

In the present specification, an aryl group represents a 1-valent group obtained by removing 1 arbitrary hydrogen atom from an aromatic hydrocarbon ring. As the aryl group, preferred is an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 3-anthryl group, a 4-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group. Among them, phenyl is preferable.

In the present specification, heteroaryl represents a 1-valent group obtained by removing 1 arbitrary hydrogen atom from an aromatic heterocycle. Examples of heteroaryl groups include furyl, thienyl, pyrrolyl, imidazolyl, isothiazolyl, isoxazolyl, pyridyl, pyrazinyl, quinolyl, benzofuryl (preferably 2-benzofuryl), benzothiazolyl (preferably 2-benzothiazolyl), benzoxazolyl (preferably 2-benzoxazolyl), and the like.

In the present specification, cycloalkyl represents a 1-valent group obtained by removing 1 arbitrary hydrogen atom from cycloalkane. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

R³～R⁶The substituent represented by the formula (I) is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group or a cyano group, more preferably a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group or a cyano group, and particularly preferably a halogen atom, a methyl group, a methoxy group, a phenyl group or a cyano group.

Wherein R is³And R⁴Each independently is preferably methyl or methoxy. In addition, a plurality of R³Or a plurality of R⁴May form a ring, respectively, and in this case, a condensed ring may be formed with the substituted ring. R⁵Preferably a halogen atom, a methyl group or a methoxy group. R⁶Preferably a halogen atom, a methyl group, a methoxy group or a cyano group. And, a plurality ofR is⁶More preferably a group forming a condensed ring with the substituted ring.

R³～R⁶The substituent represented is preferably not a polymerizable group.

In the general formula 1, q and r are each independently preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and further preferably 0. v is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and further preferably 0. w is preferably an integer of 0 to 3, more preferably an integer of 0 to 2.

When q is an integer of 2 to 4, 2 or more R³May be the same or different. Plural R³May be bonded to each other to form a ring, but a plurality of R' s³Preferably, the ring is formed without bonding to each other. When R is an integer of 2 to 4, 2 or more R⁴May be the same or different. Plural R⁴May be bonded to each other to form a ring, but a plurality of R' s⁴Preferably, the ring is formed without bonding to each other.

When v is an integer of 2 to 4, 2 or more R⁵May be the same or different. And a plurality of R⁵Are not interconnected to form a ring.

When w is an integer of 2 to 5, 2 or more R⁶May be the same or different, 2 or more R⁶May be bonded to each other to form a ring. Wherein when w is an integer of 2 to 5, 2 or more R⁶Groups that are bonded to each other to form a fused ring with the substituted ring are preferred. The condensed ring may have a substituent, and in this case, the substituent may be represented by R⁶The substituents mentioned are preferred as the substituents.

When a plurality of R⁶In the case of a group which forms a condensed ring with a substituted ring in order to bond with each other, the number of rings forming the condensed ring is preferably 4 or less, more preferably 3 or less, and still more preferably 2. When the number of rings forming a condensed ring is within the above range, coloring of a cured product containing the compound can be easily suppressed.

The compound represented by formula 1 is preferably a compound represented by formula 2.

[ chemical formula 9]

R in the general formula 2³～R⁵Are as defined and preferred with R in formula 1, respectively³～R⁵The definitions and preferred ranges of (a) are the same.

The definitions and preferred ranges of q, r and v in formula 2 are the same as those of q, r and v in formula 1, respectively.

In the general formula 2, R⁷Represents a substituent. Examples of the substituent include the above-mentioned R³～R⁶The substituents are exemplified by the substituents shown. In the general formula 2, s represents an integer of 0 to 2, preferably 2. When s is 2, 2R⁷May be the same or different. And, 2R⁷May be connected to each other to form a ring. R⁷Preferably a cyano group, a phenyl group, a halogen atom, a methyl group or a methoxy group, more preferably a cyano group or a phenyl group.

The compound represented by formula 1 is more preferably a compound represented by the following formula 3.

[ chemical formula 10]

R in the general formula 3³～R⁵Are as defined and preferred with R in formula 1, respectively³～R⁵The definitions and preferred ranges of (a) are the same.

The definitions and preferred ranges of q, r and v in formula 3 are the same as those of q, r and v in formula 1, respectively.

In the general formula 3, R⁸Represents a substituent. Examples of the substituent include the above-mentioned R³～R⁶The substituents are exemplified by the substituents shown. In the general formula 3, t is an integer of 0 to 4. When t is an integer of 2-4, more than 2R⁸May be the same or different. Here, a plurality of R⁸Are not interconnected to form a ring.

R⁸Preferably a halogen atom,A methoxycarbonyl group, a methyl group or a methoxy group, more preferably a halogen atom or a methyl group, and still more preferably a methyl group.

t is preferably 0 to 2. Also, in formula 3, v is more preferably 0, and t is 1 or 2, further preferably v is 0, and t is 2. R when t is 1⁸Is preferably the 6-or 7-position of the quinoxaline ring formed, R when t is 2⁸The substitution positions of (b) are preferably the 6-and 7-positions of the quinoxaline ring formed.

Specific examples of the compound represented by the general formula 1 preferably used in the present invention will be described below, but the present invention is not limited to the following compounds. In the following compounds, Me represents a methyl group.

[ chemical formula 11]

The above-mentioned compounds c2, c8, c10 are mixtures of compounds in which a substituent is bonded to the 6-or 7-position of the quinoxaline ring.

The compound represented by the general formula 1 can be produced, for example, by the method described in WO 2017/115649. That is, the compound represented by the general formula 4 can be produced by condensing the compound represented by the general formula 5 and/or the general formula 6. The above condensation reaction is preferably carried out in a solvent comprising an acid catalyst and a thiol compound.

[ chemical formula 12]

X, Y, Z, R in the general formula 4, the general formula 5 or the general formula 6³～R⁶Q, r, v, w are each as defined in formula 1.

[ Synthesis method of solvate ]

The solvate of the present invention can be produced by dissolving the compound represented by formula 1 in a solvent containing the above nitrogen atom-containing organic compound having a molecular weight of 200 or less (preferably, a solvent composed of a nitrogen atom-containing organic compound) and crystallizing the resulting solution. In general, the solvate of the present invention can be precipitated by dissolving the compound represented by formula 1 in a solvent composed of an organic compound containing a nitrogen atom, and then adding a poor solvent. Examples of the poor solvent include methyl acetate, ethyl acetate, and butyl acetate. As the compound represented by the general formula 1 used for producing the solvate of the present invention, for example, a crude crystal of a product obtained by the production method of the compound represented by the general formula 1 can be used as it is.

[ use of solvates ]

The compound represented by the general formula 1 can be derived from a hydroxyl group in the structure thereof to a compound having a side chain having a polymerizable group, and can be used as an intermediate for producing a curable monomer. As also described in WO2017/115649, a cured product of a composition containing a curable monomer derived from a compound represented by formula 1 can be preferably used for optical members such as lenses. The compound represented by formula 1 can be used as it is as one component of a curable composition for producing an optical component such as a lens. As described above, the compound represented by the general formula 1 can be isolated as a solvate with a solvent containing the above-mentioned nitrogen atom-containing organic compound to obtain a crystal with high purity. Furthermore, the solvate obtained as a crystal has high solubility in a solvent such as tetrahydrofuran, and when it is used as an intermediate for production, it can be reacted in a homogeneous system, and a curable monomer can be produced with high purity and high yield. Therefore, an optical member such as a lens having high light transmittance can be easily produced using the solvate of the present invention.

Examples

The features of the present invention will be described in more detail below with reference to examples and comparative examples. The materials, the amounts used, the ratios, the contents of the processes, the steps of the processes, and the like described 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 to the specific examples shown below.

< synthetic example >

Synthesis example 1 (compound c 3):

to 26.6g of 4, 5-dimethyl-1, 2-phenylenediamine and 35.6g of ninhydrin were added 150mL of toluene, 125mL of ethanol and 100mL of acetic acid, and the mixture was reacted at 70 ℃ for 3 hours. After the reaction solution was cooled to room temperature, the precipitated crystals were collected by filtration, washed with ethanol, and dried to obtain 47g of intermediate c 2A.

¹H-NMR(300MHz,CDCl₃)：δ2.49ppm(s,3H)、2.51ppm(s,3H)、7.52-7.58ppm(t,1H)、7.71-7.76ppm(t,1H)、7.85-7.95ppm(m,3H)、8.02-8.08ppm(d,1H)

22g of intermediate c2A and 32g of phenol were dissolved in 20mL of methanesulfonic acid and 20mL of acetonitrile. The reaction solution was heated, and 0.3mL of 3-mercaptopropionic acid was added dropwise while maintaining 90 ℃. After stirring for 3 hours, 200mL of acetonitrile and 100mL of water were added, and the reaction solution was stirred at 40 ℃ for 2 hours. The precipitated crystals were collected by filtration, washed with 200mL of a mixed solution of acetonitrile and water (1 v:1 v), and dried to obtain 22g of compound c 3.

¹H-NMR(300MHz,DMSO-d₆)：δ2.47ppm(s,3H)、2.49ppm(s,3H)、6.61-6.67ppm(d,4H)、6.95-7.01ppm(d,4H)、7.52-7.62ppm(m,3H)、7.84ppm(s,1H)、7.93ppm(s,1H)、8.12-8.14ppm(d,1H)、9.40ppm(bs,2H)

Synthesis example 2 (compound c 1):

28g of Compound c1 was obtained in the same manner as in the synthesis of Compound c3, except that 4, 5-dimethyl-1, 2-phenylenediamine was replaced with o-phenylenediamine.

¹H-NMR(300MHz,DMSO-d₆)：δ6.61-6.68ppm(d,4H)、6.95-7.01ppm(d,4H)、7.50-7.70ppm(m,3H)、7.72-7.90ppm(m,2H)、8.00-8.08ppm(d,1H)、8.12-8.25ppm(m,2H)、9.41ppm(bs,2H)

Synthesis example 3 (compound c 2):

26g of Compound c2 was obtained in the same manner as in the synthesis of Compound c3, except that 4, 5-dimethyl-1, 2-phenylenediamine was changed to 3, 4-diaminotoluene.

¹H-NMR(300MHz,DMSO-d₆)：δ2.50ppm(s,3H)、6.61-6.67ppm(d,4H)、6.95-7.01ppm(d,4H)、7.52-7.64ppm(m,4H)、7.84-8.14ppm(m,2H)、8.14-8.20ppm(d,1H)、9.40ppm(bs,2H)

Synthesis example 4 (compound c 9):

21g of Compound c9 was obtained in the same manner as in the synthesis of Compound c3, except that 4, 5-dimethyl-1, 2-phenylenediamine was changed to 4, 5-dichloro-1, 2-phenylenediamine.

¹H-NMR(300MHz,DMSO-d₆)：δ6.61-6.68ppm(d,4H)、6.95-7.01ppm(d,4H)、7.52-7.70ppm(m,3H)、8.14-8.20ppm(d,1H)、8.39ppm(s,1H)、8.45ppm(s,1H)、9.44ppm(bs,2H)

Synthesis example 2 (compound c 10):

21g of Compound c10 was obtained in the same manner as in the synthesis of Compound c3, except that 4, 5-dimethyl-1, 2-phenylenediamine was changed to methyl 3, 4-diaminobenzoate.

¹H-NMR(300MHz,DMSO-d₆)：δ3.94ppm(s,3H)、6.61-6.67ppm(d,4H)、6.95-7.01ppm(d,4H)、7.50-7.75ppm(m,3H)、8.19-8.30ppm(m,3H)、8.52-8.60ppm(m,1H)、9.43ppm(bs,2H)

Example 1

To 2g of compound c3, 4mL of N, N-dimethylacetamide was added, and the mixture was stirred at 60 ℃ for 1 hour, thereby dissolving compound c 3. Subsequently, 8mL of ethyl acetate and 8mL of n-hexane were added, and the mixture was stirred at 50 ℃ for 2 hours and then at 25 ℃ for 1 hour. The precipitate was collected by filtration, washed with 10mL of a mixture of ethyl acetate and N-hexane ═ 1:1, and dried at 60 ℃. By carrying out the solvation¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, when the compound c3 was assumed to be 100 mol%, N-dimethylacetamide was assumed to be 100 mol%.

Example 2

N-methylpyrrolidone was obtained in the same manner as in example 1 except that N, N-dimethylacetamide was changed to N-methylpyrrolidoneA solvate solvated in compound c 3. By carrying out the solvation¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, when the compound c3 was assumed to be 100 mol%, N-methylpyrrolidone was 140 mol%.

Example 3

A solvate of N-methylpyrrolidone solvated in compound c3 was obtained in the same manner as in example 1, except that N, N-dimethylacetamide was changed to N-ethylpyrrolidone. By carrying out the solvation¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, when the compound c3 was assumed to be 100 mol%, N-ethylpyrrolidone was 17.5 mol%.

Example 4

A solvate of pyridine and ethyl acetate solvated in compound c3 was obtained in the same manner as in example 1, except that pyridine was used instead of N, N-dimethylacetamide. By carrying out the solvation¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, when compound c3 was assumed to be 100 mol%, pyridine was 26.5 mol% and ethyl acetate was 6.8 mol%.

Example 5

A solvate of morpholine and ethyl acetate solvated in compound c3 was obtained in the same manner as in example 1, except that N, N-dimethylacetamide was changed to morpholine. By carrying out the solvation¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, assuming that compound c3 was 100 mol%, morpholine was 100 mol% and ethyl acetate was 90 mol%.

Example 6

A solvate of N, N-dimethylacetamide solvated in compound c9 was obtained in the same manner as in example 1, except that compound c3 was changed to compound c 9. By carrying out the solvation¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, when the compound c9 was assumed to be 100 mol%, N-dimethylacetamide was assumed to be 100 mol%.

Example 7

Obtained in the same manner as in example 1 except that the compound c3 in example 1 was changed to the compound c2To solvates of N, N-dimethylacetamide solvated in compound c 2. By carrying out the solvation¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, when the compound c2 was assumed to be 100 mol%, N-dimethylacetamide was assumed to be 100 mol%.

Example 8

A solvate of N, N-dimethylacetamide solvated in compound c10 was obtained in the same manner as in example 1, except that compound c3 was changed to compound c 10. By carrying out the solvation¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, when the compound c10 was assumed to be 100 mol%, N-dimethylacetamide was 185 mol%.

Example 9

A solvate of N, N-dimethylacetamide solvated in compound c1 was obtained in the same manner as in example 1, except that compound c3 was changed to compound c 1. By carrying out the solvation¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, when the compound c1 was assumed to be 100 mol%, N-dimethylacetamide was assumed to be 100 mol%.

Example 10

To 2g of compound c3, 4mL of N, N-dimethylacetamide was added, and the mixture was stirred at 60 ℃ for 1 hour, thereby dissolving compound c 3. Then, 16mL of water was added, and the mixture was stirred at 50 ℃ for 2 hours and then at 25 ℃ for 1 hour. The precipitate was collected by filtration, washed with 10mL of water, and dried at 60 ℃ to obtain a solvate of N, N-dimethylacetamide solvated in compound c 3. By carrying out the solvation¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, when compound c3 was assumed to be 100 mol%, N-dimethylacetamide was 6.8 mol%.

Comparative example 1

To 2g of compound c3, 4mL of methanesulfonic acid was added, and the mixture was stirred at 60 ℃ for 1 hour, whereby compound c3 was dissolved. Subsequently, 6mL of water and 10mL of acetonitrile were added, and the mixture was stirred at 50 ℃ for 2 hours and then at 25 ℃ for 1 hour. The precipitate was collected by filtration, washed with 10mL of a mixture of water and acetonitrile 1:1, and dried at 60 ℃. Go on to¹H-NMR measurement (300MHz, DMSO-d)₆) As a result, assuming that the compound c3 was 100 mol%, the methanesulfonic acid was 0 mol%.

Comparative example 2

To 2g of compound c3 was added 4mL of N, N, N ', N' -tetraethylmalonamide and stirred at 60 ℃ for 1 hour, but compound c3 was not dissolved in N, N, N ', N' -tetraethylmalonamide. Subsequently, 8mL of ethyl acetate and 8mL of n-hexane were added, and the mixture was stirred at 50 ℃ for 2 hours and then at 25 ℃ for 1 hour. The stirred insoluble matter was collected by filtration, washed with 10mL of a mixed solution of ethyl acetate and n-hexane 1:1, and dried at 60 ℃ to obtain a collected filtrate, and the collected filtrate was subjected to filtration¹H-NMR measurement (300MHz, DMSO-d)₆) However, no N, N, N ', N' -tetraethylmalonamide was observed.

Comparative example 3

The filtered collection obtained in the same manner as in comparative example 2 was subjected to the same procedure except that N, N, N ', N' -tetraethylmalonamide was changed to N, N-dimethyldecanamide¹H-NMR measurement (300MHz, DMSO-d)₆) However, no N, N-dimethyldecanamide was observed.

Comparative example 4

A filtered collection was obtained in the same manner as in comparative example 2 except that N, N, N ', N' -tetraethylmalonamide was changed to 1-methylpiperidine, and the filtered collection was subjected to the same procedure as in comparative example 2¹H-NMR measurement (300MHz, DMSO-d)₆) However, 1-methylpiperidine was not observed.

Comparative example 5

A filtration collection was obtained in the same manner as in comparative example 2 except that N, N, N ', N' -tetraethylmalonamide was changed to triethylamine, and the filtration collection was subjected to the same procedure as described above¹H-NMR measurement (300MHz, DMSO-d)₆) But no triethylamine was observed.

Comparative example 6

The compound c3 obtained in synthesis example 1 was used as it was.

(evaluation 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. In addition, in the case of crystal solvation, the HPLC purity was calculated by subtracting the peak value derived from the solvent.

Column: TSKgel ODS-100Z 5 μm (4.6 mm. phi. times.150 mm) (manufactured by Tosoh Corporation)

Column temperature: 40 deg.C

Eluent:

acetonitrile, pure water, phosphoric acid (volume ratio)

＝700:300:1

Flow rate: 1.0ml/min

Detection wavelength: 254nm

Injection amount: 10 μ L

Sample concentration: diluting with eluent to 5mg/50ml

Transmittance measurement

The transmittance of the crystal at a wavelength of 450nm was measured under the following conditions using a spectrophotometer (UV-2550) manufactured by SHIMADZU CORPORATION. The higher the transmittance at 450nm, the less yellow coloration of the crystal is indicated.

Pool: square quartz cuvette (optical path length: 1cm)

Sample concentration: the crystals were diluted to 50.0mg/50mL with N, N-dimethylacetamide solution

Blank medium: n, N-dimethylacetamide solution

Tetrahydrofuran solubility:

tetrahydrofuran was mixed with 50mg of the crystals of examples 1 to 10 and comparative examples 1 to 6 to evaluate the solubility of the crystals at room temperature. When a value obtained by subtracting the amount of solvent contained in the crystal is W (unit: mg),

a: complete dissolution in less than 25mL of tetrahydrofuran relative to W.

B: w is not completely dissolved in less than 25mL of tetrahydrofuran, but is dissolved in 25mL or more and less than 50mL of tetrahydrofuran.

C: relative to W, it was not dissolved in 50mL of tetrahydrofuran.

[ Table 1]

< measurement of XRD >

Powder X-ray diffraction (XRD) measurements were performed on the crystals obtained in examples and comparative examples using an X-ray diffraction apparatus (SmartLab) manufactured by Rigaku Corporation.

Tube ball: CuKa

And (3) outputting: 40kV30mA

Measurement range: 2 theta is 3 to 80 DEG

Sampling interval: 0.02 degree

Measuring speed: 5 °/min

XRD measurement results of unsolvated compound c3 and solvated compound c3 of example 1, example 3, example 10 and comparative example 1 are shown in fig. 1 to 5. Fig. 1 to 5 each show a range up to 21 ° in which a characteristic peak can be observed.

As can be seen by comparing fig. 1 and fig. 2 (example 1), the powder X-ray diffraction measurements of compound c3 showed different profiles and different crystal forms than the unsolvated compound. Even when fig. 1 and fig. 3 (example 3) are compared, it is found that the peak near 3.5 ° 2 θ disappears and a different crystal form is obtained, as compared with the result of the powder X-ray diffraction measurement of unsolvated compound c 3. When fig. 1 and fig. 4 (example 10) are compared, it is found that the X-ray diffraction measurement results of unsolvated compound c3 show that the peak intensity ratio is different and the crystal form is different although the diffraction peak positions are the same as each other. If fig. 1 and fig. 5 (comparative example 1) are compared, it is found that the compound shows the same profile and the same crystal form as those of unsolvated compound c3 as measured by powder X-ray diffraction.