Carboxylic acid or carboxylate compound having condensed ring structure, method for producing the same, and use of the compound

Abstract

The present invention provides a compound represented by the following formula, a method for producing the compound, and a use of the compound. 1 and cyclic Ar 2 represents an aromatic ring or a condensed ring thereof represented by a specific formula, R 1 and R 2 represents a specific substituent. v and w are specific integers. 3 and R 4 represents a hydrogen atom or a monovalent substituent. 5 and R 6 represents a hydrogen atom or an alkyl group. 1 and L 2 represents an alkylene group having 1 to 6 carbon atoms, Sp a ~Sp d represents a single bond or a divalent linking group. The fused ring structure in the general formula (A) and (B) does not have a linear symmetric structure. In addition, there is no ring Ar 1 and cyclic Ar 2 The case where one of them is a benzene ring and the other is a quinoline ring.

Description

Technical Field

[0001] The present invention relates to a carboxylic acid or carboxylate compound having a condensed ring structure and a preparation method thereof, and also relates to the use of a carboxylic acid or carboxylate compound having a condensed ring structure. Background Art

[0002] Conventionally, glass materials have been used in optical components of camera modules such as cameras, camcorders, mobile phones with cameras, videophones, and intercoms with cameras. Glass materials have optical properties suitable for optical components of camera modules, can provide desired optical properties, and are also excellent in environmental resistance.

[0003] However, glass materials are not easy to be lightened or miniaturized, and their processability and productivity are also poor. In contrast, cured resins can be mass-produced and have excellent processability. Therefore, in recent years, with the miniaturization of camera modules as the background, cured resins are used as optical components to replace glass materials.

[0004] As camera modules are miniaturized, their optical components are also required to be miniaturized. However, if the optical components are miniaturized, chromatic aberration will occur. Therefore, in optical components using cured resins, studies have been conducted to adjust the Abbe number using monomers or additives of curable compositions to reduce chromatic aberration.

[0005] For example, Patent Document 1 describes a curable resin composition containing a fused ring compound (monomer) in which a (meth)acryloyl group is bonded to a fluorene-type skeleton having four or more rings via a phenylene group, and discloses that a cured product having a low Abbe number (νD) can be obtained by using the resin composition.

[0006] In addition, Patent Document 2 describes a compound (monomer) in which a (meth)acryloyl group is bonded to a fluorene-type skeleton containing a nitrogen atom as a ring atom via a phenylene group, and discloses that a cured product having a low Abbe number (νD) and a high partial dispersion ratio (θg, F value) can be obtained by using a curable composition containing the compound.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2014-208804

[0010] Patent Document 2: International Publication No. 2017 / 115649 Summary of the invention

[0011] Technical issues to be solved by the invention

[0012] In a cured resin used as an optical component, the purity of the raw material compound sometimes affects the light transmittance of the raw material compound or the cured resin. Therefore, it is desirable to use a high-purity raw material compound in the preparation of a cured resin used as an optical component. In order to obtain such a desired high-purity raw material compound, after synthesizing an intermediate of the raw material compound, or after synthesizing the raw material compound from the intermediate, a purification step is required, and certain cumbersomeness cannot be avoided in the preparation of a raw material compound of target purity.

[0013] An object of the present invention is to provide a compound which is suitable as a raw material compound or a synthetic intermediate of an optical component such as a lens, and a method for producing the same.

[0014] Means for solving technical problems

[0015] The above-mentioned problems of the present invention are solved by the following means.

[0016] <1>

[0017] A compound represented by the following general formula (A) or (B).

[0018] [Chemical formula 1]

[0019]

[0020] In the above formula, R 3 and R 4 represents a hydrogen atom or a monovalent substituent. 5 and R 6 represents a hydrogen atom or an alkyl group. 1 and L 2 represents an alkylene group having 1 to 6 carbon atoms, Sp a ~Sp d represents a single bond or a divalent linking group.

[0021] Cyclic Ar 1 represents an aromatic ring represented by the following formula (AR1) or a condensed ring including the aromatic ring as a ring constituting the condensed ring, and the ring Ar 2 It represents an aromatic ring represented by the following formula (AR2) or a condensed ring including the aromatic ring as a ring constituting the condensed ring.

[0022] R 1 Represents ring Ar 1 The substituents possessed by the ring atoms of 2 Represents ring Ar 2 Substituents possessed by the ring-forming atoms.

[0023] v is an integer greater than 0, and the maximum number of v is the ring Ar 1 The maximum number of substituents that a ring-forming atom can take.

[0024] w is an integer greater than 0, and the maximum number of w is the ring Ar 2 The maximum number of substituents that a ring-forming atom can take.

[0025] [Chemical formula 2]

[0026]

[0027] In the above formula, X 11 , Y 11 , X 12 and Y 12 represents an oxygen atom, a sulfur atom, a nitrogen atom or a carbon atom.

[0028] Z 11 For -X 11 -C=CY 11 - an atomic group which together forms a 5- to 7-membered aromatic ring and represents an atomic group consisting of atoms selected from oxygen atoms, sulfur atoms, nitrogen atoms and carbon atoms.

[0029] Z 12 For -X 12 -C=CY 12 - an atomic group which together forms a 5- to 7-membered aromatic ring and represents an atomic group consisting of atoms selected from oxygen atoms, sulfur atoms, nitrogen atoms and carbon atoms.

[0030] * Corresponds to the double bond of the cyclopentadiene ring in the general formula (A) or (B).

[0031] However, in the general formulas (A) and (B), there is no (R 1 ) v -Ar 1 / Cyclopentadiene skeleton / Ar 2 -(R 2 ) w The structure shown is the case of line symmetry. " / " means that the two rings described on the left and right are fused.

[0032] Also, there is no ring Ar 1 and cyclic Ar 2 The case where one of them is a benzene ring and the other is a quinoline ring.

[0033] <2>

[0034] The compound according to <1>, wherein

[0035] The above compound is represented by the above general formula (A).

[0036] <3>

[0037] The compound according to <2>, wherein

[0038] The above compound is represented by the following general formula (A1).

[0039] [Chemical formula 3]

[0040]

[0041] In the above formula, X a and X b It represents a nitrogen atom or CH. The CH at the # position can be replaced by a nitrogen atom.

[0042] R 11 and R 21 represents a substituent, and v1 and w1 are integers of 0-4.

[0043] L 1 , L 2 、Sp a 、Sp b , R 5 and R 6 respectively with L in the above general formula (A) 1 , L 2 、Sp a 、Sp b , R 5 and R 6 Same meaning.

[0044] Among them, when X a and X b When one of the CH atoms is a nitrogen atom, at least one of the CH atoms at the # position is a nitrogen atom. a and X b When all are CH, there is no a The CH bonded to the # position of the same carbon atom and the X b The case where only one of the CH groups at the # position bonded to the same carbon atom is replaced by a nitrogen atom.

[0045] <4>

[0046] A method for producing a compound represented by the general formula (A), comprising the following steps: subjecting a compound represented by the general formula (S) below to an addition reaction of (i) an ethylenically unsaturated carboxylic acid compound, (ii) an ethylenically unsaturated carboxylic acid ester compound, (iii) an ethylenically unsaturated dicarboxylic acid anhydride or (iv) an alkyl carboxylic acid ester compound having a leaving group at the ω position, in the presence of a base, to obtain the compound represented by the general formula (A) below.

[0047] [Chemical formula 4]

[0048]

[0049] In the above formula, R 5and R 6 represents a hydrogen atom or an alkyl group. 1 and L 2 represents an alkylene group having 1 to 6 carbon atoms, Sp a and Sp b represents a single bond or a divalent linking group.

[0050] Cyclic Ar 1 represents an aromatic ring represented by the following formula (AR1) or a condensed ring including the aromatic ring as a ring constituting the condensed ring, and the ring Ar 2 It represents an aromatic ring represented by the following formula (AR2) or a condensed ring including the aromatic ring as a ring constituting the condensed ring.

[0051] R 1 Represents ring Ar 1 The substituents possessed by the ring atoms of 2 Represents ring Ar 2 Substituents possessed by the ring-forming atoms.

[0052] v is an integer greater than 0, and the maximum number of v is the ring Ar 1 The maximum number of substituents that a ring-forming atom can take.

[0053] w is an integer greater than 0, and the maximum number of w is the ring Ar 2 The maximum number of substituents that a ring-forming atom can take.

[0054] [Chemical formula 5]

[0055]

[0056] In the above formula, X 11 , Y 11 , X 12 and Y 12 represents an oxygen atom, a sulfur atom, a nitrogen atom or a carbon atom.

[0057] Z 11 For -X 11 -C=CY 11 - an atomic group which together forms a 5- to 7-membered aromatic ring and represents an atomic group consisting of atoms selected from oxygen atoms, sulfur atoms, nitrogen atoms and carbon atoms.

[0058] Z 12 For -X 12 -C=CY 12 - an atomic group which together forms a 5- to 7-membered aromatic ring and represents an atomic group consisting of atoms selected from oxygen atoms, sulfur atoms, nitrogen atoms and carbon atoms.

[0059] * Corresponds to the double bond of the cyclopentadiene ring in the general formulae (S) and (A).

[0060] However, in the general formula (S) and (A), there is no (R 1 ) v -Ar 1 / Cyclopentadiene skeleton / Ar 2 -(R 2 ) w The structure shown is the case of line symmetry. " / " means that the two rings described on the left and right are fused.

[0061] Also, there is no ring Ar 1 and cyclic Ar 2 The case where one of them is a benzene ring and the other is a quinoline ring.

[0062] <5>

[0063] The method for producing a compound represented by the general formula (A) according to <4>, wherein

[0064] In the above (ii) to (iv), the hydrolysis reaction is carried out after the above addition reaction.

[0065] <6>

[0066] The method for producing a compound represented by the general formula (A) according to <4> or <5>, wherein

[0067] The solvent used in the above addition reaction has an SP value of 21.0 MPa. 1 / 2 The above solvents.

[0068] <7>

[0069] A use of the compound described in any one of <1> to <3> as a synthesis intermediate of a curable monomer.

[0070] <8>

[0071] A use, which is to use the compound described in any one of <1> to <3> as a raw material compound for an optical component or a synthetic intermediate of the raw material compound.

[0072] <9>

[0073] The use according to <8>, wherein

[0074] The above-mentioned optical component is a lens.

[0075] In the present invention, when there are multiple substituents or linking groups represented by specific symbols or formulas (hereinafter referred to as substituents, etc.) or when multiple substituents, etc. are specified at the same time, unless otherwise specified, each substituent, etc. may be the same as or different from each other (regardless of whether there is an expression of "independently", each substituent, etc. may be the same as or different from each other). The same is true for the number of substituents, etc. Furthermore, when multiple substituents, etc. are close (especially, when adjacent), unless otherwise specified, they may be linked to each other to form a ring. Furthermore, unless otherwise specified, rings such as alicyclic rings, aromatic rings, and heterocyclic rings may be further fused to form condensed rings.

[0076] In the present invention, unless otherwise specified, when a double bond exists in a molecule, it may be either E-type or Z-type, and may be a mixture thereof.

[0077] Furthermore, in the present invention, unless otherwise specified, when a compound has one or more asymmetric carbons, the stereochemistry of such asymmetric carbons can be independently either (R) or (S). As a result, the compound may be a mixture of stereoisomers such as optical isomers or diastereomers, or a racemate.

[0078] Furthermore, in the present invention, the compound indicates that a part of the structure may be changed within the range that does not impair the effect of the present invention. Furthermore, for compounds not indicating substitution or unsubstituted, it indicates that the compounds may have any substituent within the range that does not impair the effect of the present invention.

[0079] In the present invention, for a substituent group that is not indicated as substituted or unsubstituted (the same also applies to a linking group and a ring), it means that the group may have any substituent group within the range that does not impair the desired effect. For example, when referred to as "alkyl", it means that both unsubstituted alkyl groups and substituted alkyl groups are included.

[0080] In the present invention, when the number of carbon atoms of a group is specified, unless otherwise specified in the present invention or this specification, the number of carbon atoms refers to the number of carbon atoms of the entire group. That is, when the group further has a substituent, it refers to the number of carbon atoms of the entire group including the substituent. For example, 1 and L 2 The number of carbon atoms in the "straight-chain alkylene group" means the number of carbon atoms in a state without a substituent, as described later.

[0081] In the present invention, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0082] In the present invention, each component may be used alone or in combination of two or more.

[0083] In the present invention, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acryloyl" means either or both of acryloyl and methacryloyl. In the present invention, monomers are distinguished from oligomers and polymers, and refer to compounds with a weight average molecular weight of 1,000 or less.

[0084] In the present invention, "ethylenically unsaturated groups" include groups other than CH 2 In addition to the group represented by =CH-, it also includes CH 2 =CH- is used to mean a group in which three hydrogen atoms in =CH- are replaced by substituents. 2 The substituents replacing the three hydrogen atoms in =CH- are not particularly limited within the range not impairing the effects of the present invention, and examples thereof include alkyl groups, cycloalkyl groups, alkoxy groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, carbamoyl groups, acylamino groups, amino groups, aryl groups, halogen atoms, nitro groups, and cyano groups. Groups in which two or more of these groups are combined can also be used.

[0085] In the present invention, when referred to as an aliphatic hydrocarbon group, it means a group obtained by removing one arbitrary hydrogen atom from a straight or branched alkane, a straight or branched alkene or a straight or branched alkyne. In the present invention, the aliphatic hydrocarbon group is preferably an alkyl group obtained by removing one arbitrary hydrogen atom from a straight or branched alkane. As the alkyl group, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 3-methylbutyl, hexyl, 1-methylpentyl, 4-methylpentyl, heptyl, 1-methylhexyl, 5-methylhexyl, 2-ethylhexyl, octyl, 1-methylheptyl, nonyl, 1-methyloctyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc. can be cited.

[0086] Furthermore, in the present invention, the aliphatic hydrocarbon group (unsubstituted) is preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably a methyl group or an ethyl group.

[0087] In the present invention, when an alkyl group is referred to, it means a straight chain or branched alkyl group. As the alkyl group, the above examples can be cited. The same also applies to the alkyl group in the group containing an alkyl group (alkoxy, alkoxycarbonyl, acyl, acyloxy, acylamino, amino, carbamoyl, etc.).

[0088] Furthermore, in the present invention, examples of the linear alkylene group include groups obtained by removing one hydrogen atom bonded to a terminal carbon atom from the above-mentioned linear alkyl group.

[0089] In the present invention, the alicyclic hydrocarbon ring refers to a saturated hydrocarbon ring (cycloalkane). Examples of the alicyclic hydrocarbon ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane.

[0090] In the present invention, an unsaturated hydrocarbon ring refers to a hydrocarbon ring having a carbon-carbon unsaturated double bond that is not an aromatic ring. Examples of the unsaturated hydrocarbon ring include indene, indane, fluorene, and the like.

[0091] In the present invention, the term "alicyclic hydrocarbon group" refers to a cycloalkyl group obtained by removing one arbitrary hydrogen atom from a cycloalkane. Examples of the alicyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl, and preferably a cycloalkyl group having 3 to 12 carbon atoms.

[0092] In the present invention, a cycloalkylene group represents a divalent group obtained by removing two arbitrary hydrogen atoms from a cycloalkane. Examples of the cycloalkylene group include a cyclohexylene group.

[0093] In the present invention, the term "aromatic ring" refers to either or both of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

[0094] In the present invention, an aromatic hydrocarbon ring refers to an aromatic ring formed by only carbon atoms. The aromatic hydrocarbon ring may be a monocyclic ring or a condensed ring. An aromatic hydrocarbon ring having 6 to 14 carbon atoms is preferred. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like. In the present invention, when an aromatic hydrocarbon ring is bonded to another ring, the aromatic hydrocarbon ring may be substituted on the other ring as a monovalent or divalent aromatic hydrocarbon ring group.

[0095] In the present invention, when a monovalent group is referred to as an aromatic hydrocarbon ring group, it means a monovalent group obtained by removing one arbitrary hydrogen atom from an aromatic hydrocarbon ring. As a monovalent aromatic hydrocarbon ring group, an aromatic hydrocarbon ring group having 6 to 14 carbon atoms is preferred, and examples thereof include phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 3-anthryl, 4-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, etc. Among these, phenyl is preferred.

[0096] In the present invention, when a divalent group is referred to as an aromatic hydrocarbon ring group, it means a divalent group obtained by removing one arbitrary hydrogen atom from the above-mentioned monovalent aromatic hydrocarbon ring group. Examples of divalent aromatic hydrocarbon ring groups include phenylene, naphthylene, phenanthrylene, etc., preferably phenylene, and more preferably 1,4-phenylene.

[0097] In the present invention, an aromatic heterocycle refers to an aromatic ring formed by a carbon atom and a heteroatom. As heteroatoms, oxygen atoms, nitrogen atoms and sulfur atoms can be mentioned. The aromatic heterocycle can be a monocyclic ring or a condensed ring, and the number of atoms constituting the ring is preferably 5 to 20, and more preferably 5 to 14. The number of heteroatoms in the atoms constituting the ring is not particularly limited, but is preferably 1 to 3, and more preferably 1 to 2. As examples of aromatic heterocycles, furan rings, thiophene rings, pyrrole rings, imidazole rings, isothiazole rings, isoxazole rings, pyridine rings, pyrazine rings, quinoline rings, benzofuran rings, benzothiazole rings, benzoxazole rings and examples of nitrogen-containing condensed aromatic rings described later can be mentioned. In the present invention, when an aromatic heterocycle is bonded to other rings, the aromatic heterocycle can be substituted on other rings as a monovalent or divalent aromatic heterocyclic group.

[0098] In the present invention, when a monovalent group is referred to as an aromatic heterocyclic group, it means a monovalent group obtained by removing one arbitrary hydrogen atom from an aromatic heterocyclic ring. Examples of monovalent aromatic heterocyclic groups include furanyl, thienyl, pyrrolyl, imidazolyl, isothiazolyl, isoxazolyl, pyridyl, pyrazinyl, quinolyl, benzofuranyl (preferably 2-benzofuranyl), benzothiazolyl (preferably 2-benzothiazolyl), benzoxazolyl (preferably 2-benzoxazolyl), etc. Among these, furanyl, thienyl, benzofuranyl, benzothiazolyl or benzoxazolyl are preferred, and 2-furanyl or 2-thienyl are more preferred.

[0099] In the present invention, the term "divalent aromatic heterocyclic group" refers to a divalent group obtained by removing two arbitrary hydrogen atoms from an aromatic heterocycle, and examples thereof include a divalent group obtained by removing one arbitrary hydrogen atom from the above-mentioned (monovalent) aromatic heterocyclic group.

[0100] In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0101] Effects of the Invention

[0102] The compound of the present invention can provide a curable monomer that can be used for producing optical parts such as lenses at a high purity by using it as an intermediate, and can improve the light transmittance of the cured product.

[0103] According to the production method of the present invention, the compound of the present invention can be produced with high purity and high yield. DETAILED DESCRIPTION

[0104] The present invention will be described in detail. The description of the constituent elements described below may be based on representative embodiments or specific examples, but the present invention is not limited to these embodiments except as specified in the present invention.

[0105] [Compound]

[0106] The compound of the present invention is a compound represented by the following general formula (A) or (B), and is a carboxylic acid or carboxylate compound having a condensed ring structure.

[0107] [Chemical formula 6]

[0108]

[0109] In the above formula, R 3 and R 4 represents a hydrogen atom or a monovalent substituent. 5 and R 6 represents a hydrogen atom or an alkyl group. 1 and L 2 represents an alkylene group having 1 to 6 carbon atoms, Sp a ~Sp d represents a single bond or a divalent linking group.

[0110] Cyclic Ar 1 represents an aromatic ring represented by the following formula (AR1) or a condensed ring including the aromatic ring as a ring constituting the condensed ring, and the ring Ar 2 It represents an aromatic ring represented by the following formula (AR2) or a condensed ring including the aromatic ring as a ring constituting the condensed ring.

[0111] R 1 Represents ring Ar 1 The substituents possessed by the ring atoms of 2 Represents ring Ar 2 Substituents possessed by the ring-forming atoms.

[0112] v is an integer greater than 0, and the maximum number of v is the ring Ar 1 The maximum number of substituents that a ring-forming atom can take.

[0113] w is an integer greater than 0, and the maximum number of w is the ring Ar 2 The maximum number of substituents that a ring-forming atom can take.

[0114] However, in the general formulas (A) and (B), there is no (R 1 ) v -Ar 1 / Cyclopentadiene skeleton / Ar 2 -(R 2 ) w The structure shown is the case of line symmetry. " / " means that the two rings described on the left and right are fused.

[0115] Also, there is no ring Ar 1 and cyclic Ar 2 The case where one of them is a benzene ring and the other is a quinoline ring.

[0116] In addition, compounds represented by either general formula (A) or (B) are classified as compounds represented by general formula (A).

[0117] One of the characteristic structures of the compound represented by the general formula (A) or (B) of the present invention is, as described above, (R 1 ) v -Ar 1 / Cyclopentadiene skeleton / Ar 2 -(R 2 ) w The condensed ring structure represented does not adopt a linear symmetric structure. Here, " / " represents the cyclopentadiene skeleton and the ring Ar 1 and cyclic Ar 2 Furthermore, the "cyclopentadiene skeleton" refers to a ring structure from which the substituents possessed by cyclopentadiene are removed.

[0118] That is, the above definition in the compound represented by the general formula (A) or (B) means that the substituents R 1 Ring Ar 1 and having w substituents R 2 Ring Ar 2 Different in at least one of the following aspects.

[0119] (i) Ring Ar 1 and cyclic Ar 2 The structure of the parent nucleus;

[0120] (ii) Substituent R 1 and the substituent R 2 the position of the substitution relative to the parent core; and

[0121] (iii) Substituent R 1 and the substituent R 2 structure.

[0122] Among them, it is preferred that they differ in at least the above-mentioned aspect (i).

[0123] The compound of the present invention is preferably used as a synthetic intermediate of a curable monomer, which is a raw material compound of an optical component such as a lens. In a cured product formed by preparing a curable monomer from the compound of the present invention and using the curable monomer, (R 1 ) v -Ar 1 / Cyclopentadiene skeleton / Ar 2 -(R 2 ) w The indicated asymmetric fused ring structure portion greatly contributes to the wavelength dispersion characteristics of the refractive index.

[0124] The curable monomer obtained from the compound of the present invention has the above-mentioned asymmetric fused ring structure part, and the cured product formed using the monomer can achieve a sufficiently low Abbe number νD and show a sufficiently high θ g、F value, preferably used for optical components with chromatic aberration correction function.

[0125] Hereinafter, the substituents, linking groups and symbols in the general formula (A) or (B) will be described in detail.

[0126] (1)L 1 and L 2

[0127] L 1 and L 2 It represents an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. The alkylene group may be linear or branched.

[0128] Forming Link Sp a or Sp b With cyclic Ar 1 and cyclic Ar 2 The number of atoms linking the shortest molecular chain of the condensed 5-membered ring is preferably 1 to 6, more preferably 1 to 4, and even more preferably 2 or 3.

[0129] In addition, L 1 and L 2 To form L 1 and L 2 That is, in the general formula (A), the following Sp a and Sp b The divalent linking group and L 1 or L 2 The bonded portion is not an alkylene group.

[0130] As the above L 1 and L 2 Examples of the substituent that the alkylene group in may have include a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, a carbamoyl group, an acylamino group, an amino group, an aryl group, a halogen atom, a nitro group, a cyano group, and a group represented by -Sp-COOR.

[0131] Sp represents a single bond or a divalent linking group, and Sp described below can be applied. a R represents a hydrogen atom or an alkyl group, and the R described below can be applied. 5 Records of.

[0132] Among them, Sp is preferably a single bond, and R is preferably a hydrogen atom.

[0133] -Sp-COOR is preferably -COOR, more preferably -COOH.

[0134] As the above L 1 and L 2 The substituent that the alkylene group in may have is preferably an aryl group, an alkoxy group or a group represented by -Sp-COOR, more preferably an aryl group or a group represented by -Sp-COOR, and further preferably an aryl group or a group represented by -COOR.

[0135] In the above L 1 and L 2 When the alkylene group in has a substituent, the number of the substituent is not particularly limited, and the alkylene group may have, for example, 1 to 4 substituents, preferably 1 or 2, and more preferably 1.

[0136] The above L 1 and L 2 The alkylene group in the group preferably has no substituent.

[0137] (2)Sp a and Sp b

[0138] Sp a and Sp b represents a single bond or a divalent linking group.

[0139] As a Sp a or Sp b The divalent linking group may be selected from a linear alkylene group, a cycloalkylene group, a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, -O-, -S-, >C(=O) and >NR 201 A divalent linking group formed by bonding one or more groups in

[0140] The above R 201 It represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0141] Among them, can be used as Sp a and Sp b The divalent linking group and L 1 or L 2 The bonded portion is not a straight chain alkylene group or a cycloalkylene group.

[0142] The number of carbon atoms in the linear alkylene group is preferably 1 to 8, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 or 2.

[0143] The cycloalkylene group preferably has 3 to 6 carbon atoms.

[0144] The number of carbon atoms in the above-mentioned "straight-chain alkylene" refers to the number of carbon atoms in the state without a substituent. When the "straight-chain alkylene" has a substituent, an alkyl group can also be used as the substituent. In this case, if it is considered as a whole, it becomes a branched alkylene, but Sp a and Sp b In, it is equivalent to connecting L 1 With COOR 5 or L 2 With COOR 6 The number of atoms linked to the shortest molecular chain portion corresponds to the number of carbon atoms in the above-mentioned "straight chain alkylene group".

[0145] The number of carbon atoms in the above-mentioned "cycloalkylene group" refers to the number of carbon atoms in a state of having no substituent.

[0146] As the above Sp a and Sp b The substituents that the straight-chain alkylene group, cycloalkylene group, divalent aromatic hydrocarbon ring group or divalent aromatic heterocyclic group may have include, for example, alkyl, cycloalkyl, alkoxy, acyl, acyloxy, alkoxycarbonyl, carbamoyl, acylamino, amino, aryl, halogen atom, nitro and cyano groups. Preferably, the alkyl group or aryl group is, more preferably, the alkyl group is, further preferably, the alkyl group having 1 to 3 carbon atoms is, and particularly preferably, the methyl group is.

[0147] The number of substituents is not particularly limited, and for example, the compound may have 1 to 4 substituents.

[0148] Sp as a divalent linking group a and Sp b The above-mentioned straight-chain alkylene group, cycloalkylene group, divalent aromatic hydrocarbon ring group, divalent aromatic heterocyclic group, -O-, -S-, >C(=O) and >NR 201 The number of is preferably 1-6, more preferably 1-3.

[0149] In the case of Sp as a divalent linking group a and Sp b In the case of -O-, -S-, >C(=O) and >NR 201 In the group formed by linking two or more of the above, there are -C(=O)O-, -NR 201 C(=O)-, -SC(=O)-, -OC(=O)O- or -NR 201 C(=O)O-, preferably -C(=O)O-, -NR 201 C(═O)— or —SC(═O)—, more preferably —C(═O)O—.

[0150] The above-mentioned -O-, -S-, >C(=O) and >NR 201The group formed by linking two or more of the above may constitute Sp as a divalent linking group alone or together with at least one of a linear alkylene group and a cycloalkylene group. a and Sp b , preferably together with at least one of a linear alkylene group and a cycloalkylene group, constitutes Sp as a divalent linking group a and Sp b .

[0151] In addition, the above-mentioned -C(=O)O-, -NR 201 C(=O)-、-NR 201 C(=O)O- or -SC(=O-) can be located at L with either the left or right connecting bond. 1 Side or L 2 Side configuration.

[0152] In Sp a or Sp b When Sp is a divalent linking group, a and Sp b In the connection L 1 With COOR 5 or L 2 With COOR 6 The number of atoms connected in the shortest molecular chain can be set to 1 to 20, for example, so as to further increase the number of atoms in the compound containing the cyclopentadiene skeleton and Ar 1 and Ar 2 From the viewpoint of the ratio of the fused structure part, it is preferably 1 to 10, more preferably 1 to 8, further preferably 1 to 6, and particularly preferably 1 to 4. a or Sp b When it is a single bond, it forms a link L 1 With COOR 5 or L 2 With COOR 6 The number of atoms linking the shortest molecular chain is 0, and this form is also preferred from the above viewpoint. 1 With COOR 5 or L 2 With COOR 6 The number of connected atoms in the shortest molecular chain is 8.

[0153] As a Sp a or Sp bThe divalent linking group is preferably a divalent linking group formed by bonding one or more groups selected from the group consisting of straight-chain alkylene, cycloalkylene, -O- and >C(=O), more preferably -C(=O)O-alkylene-, -C(=O)O-cycloalkylene-, -C(=O)O-straight-chain alkylene-OC(=O)-straight-chain alkylene-, -C(=O)O-straight-chain alkylene-OC(=O)-cycloalkylene-, further preferably -C(=O)O-straight-chain alkylene-.

[0154] As Sp a and Sp b , preferably a single bond or a divalent linking group formed by bonding one or more groups selected from linear alkylene, cycloalkylene, -O- and >C(=O), more preferably a single bond, -C(=O)O-linear alkylene-OC(=O)-linear alkylene- or -C(=O)O-linear alkylene-OC(=O)-cycloalkylene-, further preferably a single bond.

[0155] Sp a and Sp b They may be the same or different, but are preferably the same.

[0156] (3)Sp c and Sp d

[0157] Sp c and Sp d represents a single bond or a divalent linking group.

[0158] As a Sp c or Sp d The divalent linking group may be selected from a linear alkylene group, a cycloalkylene group, a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, -O-, -S-, >C(=O) and >NR 201 A divalent linking group formed by bonding one or more groups in

[0159] Sp c and Sp d At least one of the above is preferably the same as CR 3 The linking portion of is a divalent linking group of an alkylene group.

[0160] The above R 201 It represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0161] The number of carbon atoms in the linear alkylene group is preferably 1 to 8, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 or 2.

[0162] The cycloalkylene group preferably has 3 to 6 carbon atoms.

[0163] The number of carbon atoms in the above-mentioned "straight-chain alkylene" refers to the number of carbon atoms in the state without a substituent. When the "straight-chain alkylene" has a substituent, an alkyl group can also be used as the substituent. In this case, if it is considered as a whole, it becomes a branched alkylene, but Sp c and Sp d In, it is equivalent to connecting CR 3 With COOR 5 or CR 3 With COOR 6 The number of atoms linked to the shortest molecular chain portion corresponds to the number of carbon atoms in the above-mentioned "straight chain alkylene group".

[0164] The number of carbon atoms in the above-mentioned "cycloalkylene group" refers to the number of carbon atoms in a state of having no substituent.

[0165] As the above Sp c and Sp d The substituents that the straight-chain alkylene group, cycloalkylene group, divalent aromatic hydrocarbon ring group or divalent aromatic heterocyclic group may have include, for example, alkyl, cycloalkyl, alkoxy, acyl, acyloxy, alkoxycarbonyl, carbamoyl, acylamino, amino, halogen, nitro and cyano groups, preferably alkyl groups, more preferably alkyl groups having 1 to 3 carbon atoms, and further preferably methyl groups.

[0166] The number of substituents is not particularly limited, and for example, the compound may have 1 to 4 substituents.

[0167] Sp as a divalent linking group c and Sp d The above-mentioned straight-chain alkylene group, cycloalkylene group, divalent aromatic hydrocarbon ring group, divalent aromatic heterocyclic group, -O-, -S-, >C(=O) and >NR 201 The number is preferably 1-5, more preferably 1-3.

[0168] In the case of Sp as a divalent linking group c and Sp d In the case of -O-, -S-, >C(=O) and >NR 201 In the group formed by linking two or more of the above, there are -C(=O)O-, -NR 201 C(=O)-, -SC(=O)-, -OC(=O)O- or -NR 201 C(=O)O-, preferably -C(=O)O-, -NR 201 C(═O)— or —SC(═O)—, more preferably —C(═O)O—.

[0169] The above-mentioned -O-, -S-, >C(=O) and >NR 201The group formed by linking two or more of the above may constitute Sp as a divalent linking group alone or together with at least one of a linear alkylene group and a cycloalkylene group. c and Sp d , preferably together with at least one of a linear alkylene group and a cycloalkylene group, constitutes Sp as a divalent linking group c and Sp d .

[0170] In addition, the above-mentioned -C(=O)O-, -NR 201 C(=O)-、-NR 201 C(=O)O- or -SC(=O-) can be located at the CR 3 Side configuration.

[0171] In Sp c or Sp d When Sp is a divalent linking group, c and Sp d In the connection CR 3 With COOR 5 or CR 3 With COOR 6 The number of atoms connected in the shortest molecular chain can be set to 1 to 20, for example, so as to further increase the number of atoms in the compound containing the cyclopentadiene skeleton and Ar 1 and Ar 2 From the viewpoint of the ratio of the fused structure part, it is preferably 1 to 10, more preferably 1 to 8, further preferably 1 to 6, and particularly preferably 1 to 4. c or Sp d In the case of a single bond, it forms a link CR 3 With COOR 5 or CR 3 With COOR 6 The number of atoms linking the shortest molecular chain is 0, and this form is also preferred from the above viewpoint. For example, in the exemplary compound (A1-5) described later, regarding the linking CR 3 With COOR 5 or CR 3 With COOR 6 The number of connected atoms in the shortest molecular chain is 0 for one and 1 for the other.

[0172] As a Sp c or Sp d The divalent linking group is preferably a divalent linking group formed by bonding one or more groups selected from a linear alkylene group, -O- and >C(=O), and more preferably a linear alkylene group.

[0173] As Spc and Sp d , preferably a divalent linking group formed by a single bond or one or more groups selected from a straight-chain alkylene group, -O- and >C(=O), more preferably a single bond or a straight-chain alkylene group.

[0174] Sp c and Sp d It can be the same or different.

[0175] As Sp c and Sp d , preferably Sp c and Sp d One of them is a single bond, and the other is a straight-chain alkylene group.

[0176] (4)R 3 and R 4

[0177] R 3 and R 4 represents a hydrogen atom or a monovalent substituent.

[0178] As can be used as R 3 and R 4 The monovalent substituent of alkyl group may be an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, an acylamino group, an amino group, a halogen atom, a nitro group and a cyano group, and an alkyl group is preferred.

[0179] Can be used as R 3 and R 4 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2.

[0180] As R 3 and R 4 , preferably a hydrogen atom.

[0181] (5)R 5 and R 6

[0182] R 5 and R 6 represents a hydrogen atom or an alkyl group.

[0183] Can be used as R 5 and R 6 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2.

[0184] R 5 and R 6 They may be the same or different, but are preferably the same.

[0185] (6) Cyclic Ar 1and cyclic Ar 2

[0186] Cyclic Ar 1 represents an aromatic ring represented by the following formula (AR1) or a condensed ring including the aromatic ring as a ring constituting the condensed ring, and the ring Ar 2 It represents an aromatic ring represented by the following formula (AR2) or a condensed ring including the aromatic ring as a ring constituting the condensed ring.

[0187] In the ring Ar 1 and cyclic Ar 2 In the case of a condensed ring, the number of ring members of each ring constituting the condensed ring is preferably 5 to 7, more preferably 5 or 6, and even more preferably 6.

[0188] And, in the ring Ar 1 and cyclic Ar 2 In the case of a condensed ring, the number of rings constituting the condensed ring is preferably 2 or 3, more preferably 2. Preferably, the ring Ar 1 and cyclic Ar 2 One of them is a monocyclic ring represented by the following formula (AR1) or (AR2), and the other is a condensed ring. The number of rings constituting the condensed ring is preferably 2.

[0189] Among the ring atoms constituting the fused ring, the ring atoms other than the ring represented by the following formula (AR1) or (AR2) are preferably carbon atoms, oxygen atoms, sulfur atoms or nitrogen atoms, more preferably carbon atoms or nitrogen atoms, and still more preferably carbon atoms.

[0190] As a ring other than the ring represented by the following formula (AR1) or (AR2) constituting the condensed ring, for example, a benzene ring or a pyridine ring is preferable.

[0191] [Chemical formula 7]

[0192]

[0193] In the above formula, X 11 , Y 11 , X 12 and Y 12 represents an oxygen atom, a sulfur atom, a nitrogen atom or a carbon atom,

[0194] Z 11 For -X 11 -C=CY 11 - an atomic group which together forms a 5- to 7-membered aromatic ring and represents an atomic group consisting of atoms selected from oxygen atoms, sulfur atoms, nitrogen atoms and carbon atoms.

[0195] Z 12 For -X 12 -C=CY 12- an atomic group which together forms a 5- to 7-membered aromatic ring and represents an atomic group consisting of atoms selected from oxygen atoms, sulfur atoms, nitrogen atoms and carbon atoms.

[0196] * corresponds to the double bond of the cyclopentadiene ring in the general formula (A) or (B). 1 and cyclic Ar 2 They are fused by sharing the edges indicated by *.

[0197] (X 11 , Y 11 , X 12 and Y 12 )

[0198] The above X 11 , Y 11 , X 12 and Y 12 represents an oxygen atom, a sulfur atom, a nitrogen atom or a carbon atom, and preferably a nitrogen atom or a carbon atom.

[0199] Among them, in the ring Ar described later 1 In the case of a single ring, X 11 and Y 11 Preferably, they are all carbon atoms. 1 In the case of a fused ring, X 11 and Y 11 Preferably, they are all nitrogen atoms or they are all carbon atoms.

[0200] Similarly, in the ring Ar described later 2 In the case of a single ring, X 12 and Y 12 Preferably, they are all carbon atoms. 2 In the case of a fused ring, X 12 and Y 12 Preferably, they are all nitrogen atoms or they are all carbon atoms.

[0201] (Z 11 and Z 12 )

[0202] Z 11 For -X 11 -C=CY 11 - an atomic group that together forms a 5- to 7-membered aromatic ring, preferably an atomic group that forms a 5- or 6-membered aromatic ring, more preferably an atomic group that forms a 6-membered aromatic ring.

[0203] Z 12 For -X 12 -C=CY 12 - an atomic group that together forms a 5- to 7-membered aromatic ring, preferably an atomic group that forms a 5- or 6-membered aromatic ring, more preferably an atomic group that forms a 6-membered aromatic ring.

[0204] Z 11 and Z 12 is an atomic group consisting of atoms selected from oxygen atoms, sulfur atoms, nitrogen atoms and carbon atoms. 11 and Z 12 An atomic group consisting of atoms selected from oxygen atoms, sulfur atoms, nitrogen atoms and carbon atoms and containing at least carbon atoms is preferred, and an atomic group containing carbon atoms is more preferred.

[0205] (7)R 1 and R 2

[0206] R 1 Represents ring Ar 1 The substituents possessed by the ring atoms of 2 Represents ring Ar 2 The substituents possessed by the ring-forming atoms of 1 and R 2 Ring Ar 1 or cyclic Ar 2 The nitrogen atom or carbon atom among the ring-constituting atoms in , which is represented by NH or CH when unsubstituted, may have a substituent.

[0207] As can be used as R 1 and R 2 The substituent of is not particularly limited, but examples thereof include a halogen atom, an alkyl group, an acyl group, a hydroxyl group, an alkoxy group, an aromatic hydrocarbon ring group, and a cyano group.

[0208] Cyclic Ar 1 R 1 Substitution position and ring Ar 2 R 2 The substitution position is not particularly limited.

[0209] Can be used as R 1 and R 2 The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.

[0210] Can be used as R 1 and R 2 The number of carbon atoms in the alkoxy group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.

[0211] Can be used as R 1 and R 2 The aromatic hydrocarbon ring group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.

[0212] As can be used as R 1 and R 2The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a chlorine atom.

[0213] R 1 and R 2 Preferred are halogen atoms, alkyl groups, alkoxy groups, aromatic hydrocarbon ring groups or cyano groups, more preferred are halogen atoms, alkyl groups having 1 to 5 carbon atoms or alkoxy groups having 1 to 5 carbon atoms, and further preferred are halogen atoms, methyl groups or methoxy groups.

[0214] (8) v and w

[0215] v is an integer greater than 0, and the maximum number of v is the ring Ar 1 The maximum number of substituents that a ring-forming atom can take.

[0216] w is an integer greater than 0, and the maximum number of w is the ring Ar 2 The maximum number of substituents that a ring-forming atom can take.

[0217] v and w are preferably integers of 0-4, more preferably integers of 0-2.

[0218] The total of v and w is preferably an integer of 0-4, and more preferably an integer of 0-2.

[0219] The compound of the present invention is preferably a compound represented by the above-mentioned general formula (A), and more preferably a compound represented by the following general formula (A1).

[0220] [Chemical formula 8]

[0221]

[0222] In the above formula, X a and X b It represents a nitrogen atom or CH. The CH at the # position can be replaced by a nitrogen atom.

[0223] R 11 and R 21 represents a substituent, and v1 and w1 are integers of 0-4.

[0224] L 1 , L 2 、Sp a 、Sp b , R 5 and R 6 respectively with L in the above general formula (A) 1 , L 2 、Sp a 、Sp b , R 5 and R 6 Same meaning.

[0225] Among them, when X aand X b When one of the CH atoms is a nitrogen atom, at least one of the CH atoms at the # position is a nitrogen atom. a and X b When both are CH, there is no such situation: a The CH bonded to the # position of the same carbon atom and the X b Only one of the CH at the # position bonded to the same carbon atom is replaced by a nitrogen atom. These #-related annotations refer to the X located on the right side of the cyclopentadiene skeleton. a and X b The condensed ring having ring atoms is not a quinoline ring.

[0226] v1 and w1 are preferably integers of 0-2.

[0227] As can be used as R 11 and R 21 The substituents can be used as the aforementioned R 1 and R 2 The substituents of .

[0228] In addition, R 21 For X a and X b The carbon atoms in CH that can be adopted, and the substituents that the carbon atoms in CH at the # position may have.

[0229] As a 11 or R 21 R 11 or R 21 The substitution position of is not particularly limited, but is preferably at a position represented by the following structure.

[0230] [Chemical formula 9]

[0231]

[0232] X a and X b Preferably, all of them are CH or all of them are nitrogen atoms. a and X b When both are CH, there is no such situation: a The CH bonded to the # position of the same carbon atom and the X b Only one of the CH groups bonded to the # position of the same carbon atom is replaced by a nitrogen atom.

[0233] Furthermore, it is preferred that none of the CH at the # position is replaced by a nitrogen atom.

[0234] That is, the compound represented by the above-mentioned general formula (A1) is preferably a compound represented by the following general formula (A1-1) or (A1-2).

[0235] [Chemical formula 10]

[0236]

[0237] In the above formula, R 11 , R 21 , R 5 , R 6 , L 1 , L 2 、Sp a 、Sp b , v1 and w1 are respectively the same as R in the above general formula (A1) 11 , R 21 , R 5 , R 6 , L 1 , L 2 、Sp a 、Sp b , v1 and w1 have the same meaning.

[0238] When the compound of the present invention is used for an optical material, it is preferably a non-liquid crystal compound. That is, from the viewpoint of use as a lens material, it is preferred that the above Sp a ~Sp d All of them are linking groups without a ring structure.

[0239] Preferred specific examples of the compounds represented by the general formula (A) or (B) are listed below, but the present invention is not limited to these compounds. In the following structural formulas, Me represents a methyl group, and Et represents an ethyl group.

[0240] [Chemical formula 11]

[0241]

[0242] [Chemical formula 12]

[0243]

[0244] [Chemical formula 13]

[0245]

[0246] [Chemical formula 14]

[0247]

[0248] The compound of the present invention has a high reaction rate in its synthesis and can be obtained as a high-purity product even without a purification step. Considering the use as a raw material compound or an intermediate of an optical component, the transmittance of the compound of the present invention is preferably 97.0% or more, more preferably 98.0% or more, and further preferably 99.0% or more.

[0249] The transmittance is the transmittance at 420 nm measured by the method described in Examples below. When preparing a solution of a compound, the compound may be dissolved in a solvent.

[0250] The purity of the compound of the present invention is preferably 89.0% or more, more preferably 90.0% or more, further preferably 93.0% or more, and particularly preferably 95.0% or more.

[0251] The above purity refers to the HPLC purity measured by the method described in the Examples described later.

[0252] [Uses of Compounds]

[0253] The compound of the present invention itself can be used as a novel compound and as a raw material or a synthetic intermediate of various functional materials.

[0254] Furthermore, for example, a polymerizable group such as a (meth)acryloyl group, an epoxy group, or a vinyl group can be introduced via a carboxyl group, and the polyol is also suitable as a synthetic intermediate of a curable monomer.

[0255] As shown in the examples described below, the cured product using the curable monomer derived from the compound represented by the general formula (A) or (B) of the present invention as a raw material can achieve both low Abbe number and high transmittance at a high level, and the partial dispersion ratio θg,F is also high, and the wavelength dispersion characteristics of the refractive index are excellent. Therefore, it can be used as a raw material compound or a synthetic intermediate of an optical component, and as an optical component, it can be preferably used in optical components such as lenses or optical films.

[0256] In the present invention, the Abbe number (νD) and the partial dispersion ratio (θg, F) ​​of the cured product are values ​​measured by the methods described in the examples described later.

[0257] The Abbe number νD of the cured product is preferably 22.0 or less, more preferably 21.0 or less, and further preferably 20.0 or less. The lower limit of the Abbe number of the cured product is not particularly limited, but is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and particularly preferably 7 or more.

[0258] The partial dispersion ratio θg,F of the cured product is not particularly limited, but is preferably 0.65 or more, more preferably 0.70 or more, and further preferably 0.75 or more. From the viewpoint of being particularly preferably used as a lens resin with a high chromatic aberration correction power in the blue region, it is particularly preferably 0.80 or more. Furthermore, the upper limit of the partial dispersion ratio θg,F of the cured product is not particularly limited, but is preferably 2.0 or less, more preferably 1.8 or less, and particularly preferably 1.7 or less.

[0259] In the present invention, the transmittance of the cured product is a transmittance at a wavelength of 420 nm measured by the method described in Examples below, and is a value of external transmittance including surface reflection.

[0260] The transmittance of the cured product is preferably 65.0% or more, more preferably 70.0% or more, and even more preferably 80.0% or more. The upper limit of the transmittance of the cured product is not particularly limited, but is practically 89% or less.

[0261] Compound of the present invention can be obtained as a high-purity and high-transmittance compound simply by the manufacture method described later. And, by using a substance comprising a solvent showing a specific SP value as the solvent used in the reaction, the compound can be further obtained with high yield and high purity. Therefore, by using compound of the present invention, the optical properties of the optical component obtained can be further improved.

[0262] [Method for producing compound]

[0263] In the production method of the present invention, a carboxylic acid or carboxylate compound represented by the general formula (A) or (B) can be produced by subjecting a compound represented by the general formula (S) below to an addition reaction with (i) an ethylenically unsaturated carboxylic acid compound, (ii) an ethylenically unsaturated carboxylic acid ester compound, (iii) an ethylenically unsaturated dicarboxylic acid anhydride or (iv) an alkyl carboxylate compound having a leaving group at the ω position.

[0264] In addition, when 1 equivalent of (i) an ethylenically unsaturated carboxylic acid compound, (ii) an ethylenically unsaturated carboxylic acid ester compound, (iii) an ethylenically unsaturated dicarboxylic acid anhydride or (iv) an alkyl carboxylic acid ester compound having a leaving group at the ω position is introduced to the compound represented by the general formula (S), a compound represented by the general formula (B) can be obtained, and when 2 equivalents are introduced to the compound represented by the general formula (S), a compound represented by the general formula (A) can be obtained.

[0265] Among them, the production method of the present invention is preferably used for the production of the compound represented by the above-mentioned general formula (A).

[0266] [Chemical formula 15]

[0267]

[0268] In the above formula, ring Ar 1 , cyclic Ar 2 , R 1 , R 2 , v and w are respectively the same as the ring Ar in the above general formula (A) and (B) 1 , cyclic Ar 2 , R 1 , R 2 , v and w have the same meaning.

[0269] The reagents, solvents, reaction conditions, etc. used in the above-mentioned addition reaction are described.

[0270] (Compound represented by general formula (S))

[0271] The compound represented by the general formula (S) is preferably a compound represented by the following general formula (SA1), and more preferably a compound represented by the following general formula (SA1-1) or (SA1-2).

[0272] [Chemical formula 16]

[0273]

[0274] In the above formula, R 11 , R 21 , X a , X b , v1, w1 and # are respectively the same as R in the above general formula (A1) 11 , R 21 , X a , X b , v1, w1 and # have the same meaning.

[0275] [Chemical formula 17]

[0276]

[0277] In the above formula, R 11 , R 21 , v1 and w1 are respectively the same as R in the above general formula (A1) 11 , R 21 , v1 and w1 have the same meaning.

[0278] The method for obtaining the compound represented by the above general formula (S) is not particularly limited, and it can be obtained by commercial means or by synthesis. In the case of obtaining by synthesis, the method for manufacturing the compound represented by the general formula (S) (synthesis method) is not particularly limited, and it can be synthesized by conventional methods and by the methods described in the reference examples.

[0279] For example, a carbonyl compound represented by the following general formula (s) is reacted with triethylsilane in the presence of a metal catalyst or a Lewis acid such as a boron trifluoride-diethyl ether complex to reduce the carbonyl group (>C=O) to a methylene group (-CH 2 -), thereby obtaining the compound represented by the above general formula (S). 1 ,Ar 2 , R 1 , R 2 , v and w are respectively the same as Ar in the above general formula (S) 1 ,Ar 2 , R 1 , R 2 , v and w have the same meaning.

[0280] [Chemical formula 18]

[0281]

[0282] (Reactant)

[0283] By reacting the compound represented by the general formula (S) with (i) an ethylenically unsaturated carboxylic acid compound or (iii) an ethylenically unsaturated dicarboxylic acid anhydride, a carboxylic acid compound represented by the general formula (A) or (B) (i.e., R 5 and R 6 Wherein, when (iii) an ethylenically unsaturated dicarboxylic acid anhydride is used, a hydrolysis reaction is carried out after the addition reaction.

[0284] Furthermore, by reacting the compound represented by the general formula (S) with (ii) an ethylenically unsaturated carboxylate compound or (iv) an alkyl carboxylate compound having a leaving group at the ω position, a carboxylate compound represented by the general formula (A) or (B) (i.e., R 5 and R 6 By further performing a hydrolysis reaction after the addition reaction when using (ii) an ethylenically unsaturated carboxylic acid ester compound or (iv) an alkyl carboxylic acid ester compound having a leaving group at the ω position, the corresponding carboxylic acid compound (i.e., the compound represented by the general formula (A) or (B) wherein R 5 and R 6 is a compound containing hydrogen atoms).

[0285] The hydrolysis reactions in (ii) to (iv) above can be carried out according to conventional methods without any particular limitation.

[0286] The number of ethylenically unsaturated groups in each of the above compounds (i) to (iv) is not particularly limited, but is preferably one.

[0287] The above-mentioned (i) ethylenically unsaturated carboxylic acid compound refers to a carboxylic acid compound having an ethylenically unsaturated group.

[0288] The number of carboxyl groups in the above-mentioned (i) ethylenically unsaturated carboxylic acid compound is not particularly limited, and can be, for example, 1 to 4, preferably 1 or 2. In addition, when obtaining a compound represented by general formula (B), the above-mentioned (i) compound is a compound in which at least two of the substituents (a total of 4 substituents) on the two carbon atoms constituting the carbon-carbon double bond in the ethylenically unsaturated group have carboxyl groups.

[0289] Examples of the (i) ethylenically unsaturated carboxylic acid compound include (meth)acrylic acid, maleic acid, itaconic acid, citraconic acid, and cinnamic acid.

[0290] The (ii) ethylenically unsaturated carboxylic acid ester compound is a carboxylic acid ester compound having an ethylenically unsaturated group, and specifically, is a compound having an ethylenically unsaturated group and an alkoxycarbonyl group.

[0291] The number of alkoxycarbonyl groups in the above-mentioned (ii) ethylenically unsaturated carboxylic acid ester compound is not particularly limited, and can be, for example, 1 to 4, preferably 1 or 2. In addition, when obtaining a compound represented by general formula (B), the above-mentioned (ii) compound is a compound in which at least two of the substituents (a total of four substituents) on the two carbon atoms constituting the carbon-carbon double bond in the ethylenically unsaturated group are substituents containing an alkoxycarbonyl group.

[0292] Examples of the (ii) ethylenically unsaturated carboxylic acid ester compound include the alkyl ester compounds of the (i) ethylenically unsaturated carboxylic acid compounds exemplified above.

[0293] The above-mentioned (iii) ethylenically unsaturated dicarboxylic acid anhydride refers to an anhydride of a dicarboxylic acid having an ethylenically unsaturated group.

[0294] The number of dicarboxylic acid anhydride structures in the above-mentioned (iii) ethylenically unsaturated dicarboxylic acid anhydride is not particularly limited, and can be, for example, 1 or 2, preferably 1. The position of the ethylenically unsaturated group in the compound is not particularly limited, and may be present as a 5- or 6-membered ring-forming atomic group containing an anhydride structure (-OC(=O)O-) as a cyclic atomic group, or as a substituent on a 5- or 6-membered ring containing an anhydride structure as a cyclic atomic group.

[0295] Examples of the compound (iii) in the above-mentioned ethylenically unsaturated dicarboxylic anhydride having a carbon-carbon double bond in an ethylenically unsaturated group as a ring-forming atomic group of a 5- or 6-membered ring containing an acid anhydride structure as a ring-forming atomic group include maleic anhydride and citraconic anhydride, and examples of the compound having a carbon-carbon double bond in an ethylenically unsaturated group as a substituent in a 5- or 6-membered ring containing an acid anhydride structure as a ring-forming atomic group include itaconic anhydride.

[0296] The above-mentioned (iv) alkyl carboxylate compound having a leaving group at the ω position refers to an alkyl carboxylate compound having a leaving group such as a halogen atom at the ω position. That is, it has an alkoxycarbonyl group and has a leaving group on the carbonyl side of the ester bond. In addition, when obtaining a compound represented by general formula (B), the above-mentioned (iv) compound is a compound in which the carbon atom at the ω position having a leaving group further contains another alkoxycarbonyl substituent.

[0297] Examples of the leaving group include a halogen atom, a C1-C6 alkylsulfonyloxy group, an arylsulfonyloxy group, and the like. C1-C6 means that the number of carbon atoms is 1 to 6.

[0298] Examples of the (iv) alkyl carboxylate compound having a leaving group at the ω position include ethyl chloroacetate, ethyl bromoacetate, tert-butyl chloroacetate, tert-butyl bromoacetate, ethyl 3-bromopropionate, and ethyl 4-bromobutyrate.

[0299] As a reference example of a method for obtaining a carboxylate compound represented by the general formula (A) or (B) by reacting a compound represented by the general formula (S) with the alkyl carboxylate compound (iv) having a leaving group at the ω position, for example, the synthesis method described in

[0078] and

[0162] of International Publication No. 2014 / 050738 (Japanese Patent No. 5682094) can be cited.

[0300] Furthermore, the above-mentioned (i) ethylenically unsaturated carboxylic acid compound, (ii) ethylenically unsaturated carboxylic acid ester compound, (iii) ethylenically unsaturated dicarboxylic acid anhydride or (iv) alkyl carboxylic acid ester compound having a leaving group at the ω position may have a substituent within a range not affecting the above-mentioned addition reaction.

[0301] When producing the compound represented by the general formula (A), the amount of the (i) ethylenically unsaturated carboxylic acid compound, (ii) ethylenically unsaturated carboxylic acid ester compound, (iii) ethylenically unsaturated dicarboxylic acid anhydride or (iv) alkyl carboxylic acid ester compound having a leaving group at the ω position may be 2 to 10 mol, preferably 2.2 to 6 mol, per 1 mol of the compound represented by the general formula (S).

[0302] When producing the compound represented by the general formula (B), the amount of the (i) ethylenically unsaturated carboxylic acid compound, (ii) ethylenically unsaturated carboxylic acid ester compound, (iii) ethylenically unsaturated dicarboxylic acid anhydride or (iv) alkyl carboxylic acid ester compound having a leaving group at the ω position may be 1 to 10 mol, preferably 1.1 to 6 mol, per 1 mol of the compound represented by the general formula (S).

[0303] (Base)

[0304] Examples of the base used in the above addition reaction include quaternary ammonium salts such as benzyltrimethylammonium hydroxide and benzyltriethylammonium hydroxide, and alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide. Two or more of these may be used in combination.

[0305] The amount of the base used may be 1 to 100 mol%, preferably 5 to 50 mol%, relative to the compound represented by the general formula (S). For example, using 100 mol% of the base means using 1 mol of the base relative to 1 mol of the compound represented by the general formula (S).

[0306] When the quaternary ammonium salt and the alkali metal alkoxide are used in combination, the ratio thereof is preferably 0.1 to 5 mol of the alkali metal alkoxide per 1 mol of the quaternary ammonium salt.

[0307] (Solvent)

[0308] As the solvent used in the above-mentioned addition reaction, an ether solvent, an amide solvent, a nitrile solvent, a sulfoxide solvent or the like can be preferably used.

[0309] In particular, it is preferred to use at least one material having an SP value of 21.0 MPa. 1 / 2 The above solvents. The SP value is 21.0MPa 1 / 2 Examples of the above solvents include N,N-dimethylformamide (SP value: 24.8), N,N-dimethylacetamide (SP value: 22.7), N-methylpyrrolidone (SP value: 22.9), acetonitrile (SP value: 24.6), propionitrile (SP value: 21.7), and dimethyl sulfoxide (SP value: 26.6). The units of the SP values ​​in parentheses are all MPa. 1 / 2 .

[0310] The SP values ​​of the above solvents are from Polymer Handbook 4 th The value recorded in the edition.

[0311] By using SP value of 21.0MPa 1 / 2The above solvents can be used as solvents in the above addition reaction to increase the reaction rate of the addition reaction, and can obtain the target carboxylic acid or carboxylate compound represented by the general formula (A) or (B) at high purity.

[0312] The SP value of the solvent used in the addition reaction is 21.0 MPa. 1 / 2 The proportion of the above solvent is not particularly limited as long as it can improve the reaction rate of the addition reaction, and can be, for example, 10% by mass or more, preferably 25% by mass or more, more preferably 50% by mass or more, and further preferably 75% by mass or more.

[0313] The amount of the solvent used may be 1 to 20 times (v / w), preferably 3 to 17 times (v / w), and more preferably 5 to 15 times (v / w) the amount of the compound represented by the general formula (S).

[0314] v / w refers to the volume of the solvent in milliliters relative to the mass of the compound represented by the above general formula (S) in grams.

[0315] In addition, in addition to the above-mentioned solvents, the reaction system for the addition reaction may contain a solvent such as an alcohol solvent that can be used as a diluent for the reagent. However, when calculating the amount of the above-mentioned solvent used, this solvent is not included in the solvent.

[0316] (Reaction Conditions)

[0317] The reaction conditions of the addition reaction are not particularly limited, but for example, the reaction temperature can be set to 0 to 100° C., preferably 20 to 80° C., and the reaction time can be set to 0.5 to 10 hours, preferably 0.5 to 5 hours.

[0318] After the addition reaction is completed, in the case where the product has a carboxyl group (ie, R 5 and R 6 is a hydrogen atom) and has an alkoxycarbonyl group (ie, R in the general formula (A) or (B) 5 and R 6 In the case of an alkyl group), the treatment method is different.

[0319] In the case of having a carboxyl group, a caustic alkali aqueous solution such as sodium hydroxide is added to the reaction solution and diluted to dissolve the product in the alkaline aqueous solution, and the aqueous solution is washed with an appropriate solvent such as ethyl acetate or toluene. Next, hydrochloric acid is added to the separated aqueous phase to make the aqueous phase acidic, thereby freeing the compound having a carboxyl group. The free compound having a carboxyl group is filtered out, fully washed with distilled water, and then dried to obtain the target compound having a carboxyl group.

[0320] On the other hand, in the case of a compound having an alkoxycarbonyl group, a mineral acid such as hydrochloric acid is added to the reaction solution and neutralized, and the product is extracted into the solvent using an appropriate solvent such as ethyl acetate. The solvent phase is washed with distilled water, and the solvent is removed by distillation to obtain a product having a carboxylate group. As required, the obtained product can be recrystallized from an alcoholic solvent such as methanol or isopropanol to further improve the purity.

[0321] Example

[0322] Below, the present invention is described in further detail according to embodiment.The material, reagent, usage amount and its ratio, processing content and processing step etc. shown in the following embodiment can be appropriately changed without departing from the scope of the gist of the present invention.Therefore, the scope of the present invention is not interpreted restrictively by the specific example shown below.

[0323] [Synthesis example]

[0324] The compound represented by the general formula (A) or (B) was synthesized as follows.

[0325] In the following synthesis routes, THF represents tetrahydrofuran, Et represents ethyl, w / v% refers to the percentage of mass to volume (weight / volume%), and room temperature refers to 25°C.

[0326] In addition, HPLC measurement and transmittance measurement were performed according to the measurement methods shown below.

[0327] (HPLC determination)

[0328] The purity of the compound was measured under the following conditions using a high performance liquid chromatography (trade name: SPD-10AV VP) manufactured by SHIMADZU CORPORATION. In addition, when the compound was solvated, the HPLC purity was calculated after subtracting the peak derived from the solvent.

[0329] Column: TSKgel ODS-100Z 5μm (4.6mmφ×150mm) (manufactured by TOSOH CORPORATION)

[0330] Column temperature: 40℃

[0331] Eluent: acetonitrile: pure water: phosphoric acid (volume ratio) = 700: 300: 1

[0332] Flow rate: 1.0ml / min

[0333] Detection wavelength: 254nm

[0334] Injection volume: 10 μL

[0335] Sample: The compound was dissolved in the eluent so as to have a concentration of 5 mg / 50 ml.

[0336] (Transmittance measurement)

[0337] The transmittance of the compound at a wavelength of 420 nm was measured under the following conditions using a spectrophotometer manufactured by SHIMADZU CORPORATION (trade name: UV-2550). A higher transmittance at 420 nm indicates less coloration.

[0338] Colorimetric cell: angular quartz colorimetric cell (optical path length: 1 cm)

[0339] Sample: The compound was dissolved in THF so as to have a concentration of 50 mg / 5 mL.

[0340] Blank medium: THF (solvent)

[0341] [Synthesis of compounds (SA-1) to (SA-5)]

[0342] <Synthesis of Compound (SA-1)>

[0343] [Chemical formula 19]

[0344]

[0345] 15.0 g of 11H-benzo[b]fluorene-11-one (SM-1) and 60 mL of dichloromethane were added to a 500 mL three-necked flask, and 60 mL of trifluoroacetic acid and 22.8 g of triethylsilane were added while cooling in an ice bath. Next, 18.6 g of boron trifluoride-diethyl ether complex was added dropwise over 30 minutes, and then the reaction was carried out at 40°C for 3 hours. After cooling to room temperature, 180 mL of cyclopentyl methyl ether was added and stirred for further 2 hours. The precipitated solid was recovered by filtration and vacuum dried in a reduced pressure oven, thereby obtaining 10.3 g of compound (SA-1) (yield 73.1%).

[0346] <Synthesis of Compound (SA-2)>

[0347] 7.2 g (yield: 82.0%) of compound (SA-2) was obtained in the same manner as in the synthesis of compound (SA-1) except that compound (SM-1) was replaced by compound (SM-2).

[0348] [Chemical formula 20]

[0349]

[0350] <Synthesis of Compound (SA-3)>

[0351] 6.0 g (yield: 63.8%) of compound (SA-3) was obtained in the same manner as in the synthesis of compound (SA-1) except that compound (SM-1) was replaced with compound (SM-3).

[0352] [Chemical formula 21]

[0353]

[0354] <Synthesis of Compound (SA-4)>

[0355] 6.2 g (yield: 66.0%) of compound (SA-4) was obtained in the same manner as in the synthesis of compound (SA-1) except that compound (SM-1) was replaced with compound (SM-4).

[0356] [Chemical formula 22]

[0357]

[0358] <Synthesis of Compound (SA-5)>

[0359] 8.2 g (yield: 86.5%) of compound (SA-5) was obtained in the same manner as in the synthesis of compound (SA-1) except that compound (SM-1) was replaced with compound (SM-5).

[0360] [Chemical formula 23]

[0361]

[0362] [Synthesis Example 1: Synthesis of Compound (A1-1)]

[0363] [Chemical formula 24]

[0364]

[0365] In a 200 mL three-necked flask, 5.0 g (23 mmol) of compound (SA-1), 6.9 g (69 mmol) of ethyl acrylate and 50 mL of N,N-dimethylacetamide were added and stirred at room temperature for 10 minutes. After adding 2.9 g (0.69 mmol) of a 40% by mass methanol solution of benzyltrimethylammonium hydroxide, the mixture was reacted at 80°C for 1 hour. After confirming the disappearance of the raw material compound (SA-1) by TLC (Thin-Layer Chromatography), 7.5 mL of water and 7.5 mL of a 50 w / v% aqueous sodium hydroxide solution were added and stirred at 80°C for 1 hour to hydrolyze the ethyl ester. After cooling to room temperature, the mixture was neutralized with 6N hydrochloric acid, ethyl acetate was added and a liquid separation operation was performed. After washing the organic layer with 1N hydrochloric acid and saturated brine, the organic layer was dried with magnesium sulfate. After removing magnesium sulfate by filtration, the solvent was concentrated, and the precipitated solid was dispersed and washed with a mixed solvent of ethyl acetate and hexane, thereby obtaining 4.8 g of compound (A1-1) (yield 58%). The area % of compound (A1-1) determined by HPLC was 96.6%, and the area of ​​compound (SA-1) as a raw material was less than 0.1%. In addition, the transmittance of compound (A1-1) at 420 nm was 99.3%.

[0366] Compound (A1-1) 1 H-NMR data (400 MHz, DMSO-d 6 ): δ1.35-1.45ppm (m, 4H), 2.35-2.45ppm (m, 4H), 7.35-7.60ppm (m, 5H), 7.90-8.10ppm (m, 4H), 8.35ppm (s, 1H), 11.9ppm (s, 2H)

[0367] [Synthesis Example 2: Synthesis of Compound (A2-1)]

[0368] [Chemical formula 25]

[0369]

[0370] Except that compound (SA-1) was replaced by compound (SA-2), 4.5 g of compound (A2-1) (yield 59%) was obtained in the same manner as in Synthesis Example 1. The area % of compound (A2-1) determined by HPLC was 96.2%, and the compound (SA-2) as a raw material was less than 0.1%. In addition, the transmittance of compound (A2-1) at 420 nm was 99.0%.

[0371] Compound (A2-1)1 H-NMR data (400 MHz, DMSO-d 6 ): δ1.35-1.45ppm (m, 4H), 2.35-2.45ppm (m, 4H), 3.80ppm (s, 3H), 3.90ppm (s, 3H), 7.15ppm (s, 1H) ), 7.35-7.50ppm (m, 2H), 7.60ppm (s, 1H), 7.85-7.90ppm (m, 3H), 8.20ppm (s, 1H), 11.9ppm (s, 2H)

[0372] [Synthesis Example 3: Synthesis of Compound (A3-1)]

[0373] [Chemical formula 26]

[0374]

[0375] Except that compound (SA-1) was replaced by compound (SA-3), 5.5 g of compound (A3-1) (yield 70%) was obtained in the same manner as in Synthesis Example 1. The area % of compound (A3-1) determined by HPLC was 97.1%, and the compound (SA-3) as a raw material was less than 0.1%. In addition, the transmittance of compound (A3-1) at 420 nm was 99.1%.

[0376] Compound (A3-1) 1 H-NMR data (400 MHz, DMSO-d 6 ): δ1.50-1.75ppm (m, 4H), 2.35-2.55ppm (m, 4H), 7.62ppm (t, 1H), 7.70ppm (t, 1H), 7.75-7.90ppm (m, 3H), 8.15-8.25ppm (m, 3H), 12.0ppm (s, 2H)

[0377] [Synthesis Example 4: Synthesis of Compound (A4-1)]

[0378] [Chemical formula 27]

[0379]

[0380] Except that compound (SA-1) was replaced by compound (SA-4), 6.2 g of compound (A4-1) (yield 78%) was obtained in the same manner as in Synthesis Example 1. The area % of compound (A4-1) determined by HPLC was 97.6%, and the compound (SA-4) as a raw material was less than 0.1%. In addition, the transmittance of compound (A4-1) at 420 nm was 98.9%.

[0381] Compound (A4-1) 1 H-NMR data (400 MHz, DMSO-d 6 ): δ1.50-1.75ppm (m, 4H), 2.35-2.55ppm (m, 10H), 7.55ppm (t, 1H), 7.62ppm (t , 1H), 7.76ppm (d, 1H), 7.90-7.95ppm (m, 2H), 8.10ppm (d, 1H), 12.0ppm (s, 2H)

[0382] [Synthesis Example 5: Synthesis of Compound (A5-1)]

[0383] [Chemical formula 28]

[0384]

[0385] Except that compound (SA-1) was replaced by compound (SA-5), 6.7 g of compound (A5-1) (yield 89%) was obtained in the same manner as in Synthesis Example 1. The area % of compound (A5-1) determined by HPLC was 95.9%, and the compound (SA-5) as a raw material was less than 0.1%. In addition, the transmittance of compound (A5-1) at 420 nm was 98.7%.

[0386] Compound (A5-1) 1 H-NMR data (400 MHz, DMSO-d 6 ): δ1.55-1.80ppm (m, 4H), 2.35-2.55ppm (m, 4H), 7.60ppm (t, 1H), 7.75ppm (t , 1H), 7.80ppm (d, 1H), 8.12ppm (d, 1H), 8.40-8.50ppm (m, 2H), 12.0ppm (s, 2H)

[0387] [Synthesis Example 6: Synthesis of Compound (A1-1)]

[0388] The solvent used in the reaction was changed from N,N-dimethylacetamide (SP value 24.8MPa 1 / 2 ) was replaced with acetonitrile (SP value is 24.6MPa 1 / 2 ), except that 5.2 g of compound (A1-1) (yield 62%) was obtained in the same manner as in Synthesis Example 1. The area % of compound (A1-1) determined by HPLC was 96.1%, and the compound (SA-1) as a raw material was less than 0.1%. In addition, the transmittance of compound (A1-1) at 420 nm was 99.0%.

[0389] [Reference Example 1: Synthesis of Compound (A1-1)]

[0390] The solvent used in the reaction was changed from N,N-dimethylacetamide (SP value 24.8MPa 1 / 2 ) was replaced with 1,4-dioxane (SP value is 20.5 MPa 1 / 2 ), except that 4.1 g of compound (A1-1) (yield 49%) was obtained in the same manner as in Synthesis Example 1. The area % of compound (A1-1) determined by HPLC was 89.7%, and 5.5% of compound (SA-1) as a raw material remained. In addition, the transmittance of compound (A1-1) at 420 nm was 97.9%.

[0391] Furthermore, even when the temperature for the addition reaction is increased, the residual rate of the raw material compound hardly changes.

[0392] As described above, the compound of the present invention has a high transmittance of 97.9% or more at 420 nm and has little coloration.

[0393] Furthermore, in the case of synthesizing compound (A1-1) from compound (SA-1), by using an SP value of 21.0 MPa in the addition reaction, 1 / 2 The above solvents can obtain a compound that shows a transmittance of 99.0% or more and whose coloring is further suppressed (compared to Synthesis Examples 1 and 6 of Reference Example 1).

[0394] [Reference Example 2: Cured product of a curable monomer using the compound of the present invention as a synthetic intermediate]

[0395] [Synthesis of compounds (MA1-1) to (MA5-1)]

[0396] Using the compounds (A1-1) to (A5-1) synthesized in the above-mentioned Synthesis Examples 1 to 5, the following compounds (MA1-1) to (MA5-1) were synthesized as follows, respectively.

[0397] [Reference Example 2-1: Synthesis of compound (MA1-1)]

[0398] [Chemical formula 29]

[0399]

[0400] 4.0 g of compound (A1-1), 20 mL of dichloromethane, 3.3 g of 2-hydroxyethyl methacrylate, 0.1 g of N,N-dimethylaminopyridine and 4.9 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were mixed. After stirring at 40°C for 2 hours, 1N hydrochloric acid was added, and the mixture was washed and separated. Then, a 5% aqueous sodium bicarbonate solution was added, and the mixture was washed and separated. After dehydration with magnesium sulfate, filtration and concentration were performed, the mixture was purified by column chromatography (eluent: a mixture of chloroform and methanol) to obtain 5.4 g of compound (MA1-1) (yield: 83%).

[0401] Compound (MA1-1) 1 H-NMR (400 MHz, CDCl 3 ): δ=1.65-1.85ppm (m, 4H), 1.89ppm (s, 6H), 2.45-2.55ppm (m, 4H), 4.15-4.25ppm (m, 8H), 5.55ppm (s , 2H), 6.05ppm (s, 2H), 7.35-7.55ppm (m, 6H), 7.78ppm (s, 1H), 7.82-7.95ppm (m, 2H), 8.15ppm (s, 1H)

[0402] The absorption spectrum (absorbance) of compound (MA1-1) was measured in the following manner.

[0403] 50 mg of the compound was accurately weighed, diluted with tetrahydrofuran (THF) using a 5 mL volumetric flask, and then further diluted with THF so that the solution concentration became 1 / 500 times to prepare a measurement solution. The measurement was performed using UV-2550 (trade name) manufactured by SHIMADZUCORPORATION.

[0404] First, a square quartz cuvette (cuvette length 10 mm) filled with a reference sample (THF) was placed on both the sample light path and the reference light path, and the absorbance in the wavelength region of 250 to 800 nm was adjusted to zero. Next, the sample in the cuvette on the sample light path side was replaced with the measurement solution of the compound prepared above, and the absorption spectrum of 250 to 800 nm was measured.

[0405] The wavelength λmax of the maximum peak located on the longest wavelength side in the range of 300 to 400 nm obtained from the measurement results was 343 nm.

[0406] [Reference Example 2-2: Synthesis of Compound (MA2-1)]

[0407] [Chemical formula 30]

[0408]

[0409] 4.9 g (yield: 80%) of compound (MA2-1) was obtained in the same manner as in Reference Example 2-1, except that compound (A1-1) was replaced with compound (A2-1).

[0410] Compound (MA2-1) 1 H-NMR (400 MHz, CDCl 3 ): δ=1.65-1.85ppm (m, 4H), 1.89ppm (s, 6H), 2.45-2.55ppm (m, 4H), 3.96ppm (s, 3H), 4.02ppm (s, 3H), 4.15-4.25ppm (m, 8H), 5.55ppm (s , 2H), 6.05ppm (s, 2H), 6.85ppm (s, 1H), 7.35ppm (s, 1H), 7.40-7.55ppm (m, 2H), 7.71ppm (s, 1H), 7.80-7.93ppm (m, 2H), 8.00ppm (s, 1H)

[0411] The wavelength λmax of the maximum peak located on the longest wavelength side in the range of 300 to 400 nm of the compound (MA2-1), measured in the same manner as the compound (MA1-1), was 354 nm.

[0412] [Reference Example 2-3: Synthesis of Compound (MA3-1)]

[0413] [Chemical formula 31]

[0414]

[0415] 5.2 g (yield: 80%) of compound (MA3-1) was obtained in the same manner as in Reference Example 2-1 except that compound (A1-1) was replaced with compound (A3-1).

[0416] Compound (MA3-1) 1 H-NMR data (400 MHz, CDCl 3 ): δ=1.65-1.85ppm (m, 4H), 1.89ppm (s, 6H), 2.38-2.48ppm (m, 2H), 2.68-2.78ppm (m, 2H), 4.15-4.25ppm (m , 8H), 5.55ppm (s, 2H), 6.05ppm (s, 2H), 7.55-7.65ppm (m, 3H), 7.80-7.95ppm (m, 2H), 8.10-8.25ppm (m, 3H)

[0417] The wavelength λmax of the maximum peak located on the longest wavelength side in the range of 300 to 400 nm of the compound (MA3-1), measured in the same manner as the compound (MA1-1), was 360 nm.

[0418] [Reference Example 2-4: Synthesis of Compound (MA4-1)]

[0419] [Chemical formula 32]

[0420]

[0421] 4.4 g (yield: 70%) of compound (MA4-1) was obtained in the same manner as in Reference Example 2-1 except that compound (A1-1) was replaced with compound (A4-1).

[0422] Compound (MA4-1) 1 H-NMR (400 MHz, CDCl 3 ): δ=1.65-1.85ppm (m, 4H), 1.89ppm (s, 6H), 2.35-2.45ppm (m, 2H), 2.50ppm (s, 3H), 2.52ppm (s, 3H), 2.65-2.75ppm (m, 2H), 4. 15-4.25ppm (m, 8H), 5.55ppm (s, 2H), 6.05ppm (s, 2H), 7.55-7.65ppm (m, 3H), 7.88ppm (s, 1H), 7.92ppm (s, 1H), 8.20ppm (d, 2H)

[0423] The wavelength λmax of the maximum peak located on the longest wavelength side in the range of 300 to 400 nm of the compound (MA4-1), measured in the same manner as the compound (MA1-1), was 369 nm.

[0424] [Reference Example 2-5: Synthesis of Compound (MA5-1)]

[0425] [Chemical formula 33]

[0426]

[0427] 5.1 g (yield: 84%) of compound (MA5-1) was obtained in the same manner as in Reference Example 2-1 except that compound (A1-1) was replaced with compound (A5-1).

[0428] Compound (MA5-1) 1 H-NMR (400 MHz, CDCl 3): δ=1.65-1.85ppm (m, 4H), 1.89ppm (s, 6H), 2.35-2.45ppm (m, 2H), 2.65-2.75ppm (m, 2H), 4.15-4.25ppm (m, 8 H), 5.55ppm (s, 2H), 6.05ppm (s, 2H), 7.55-7.65ppm (m, 3H), 8.16ppm (d, 1H), 8.24ppm (s, 1H), 8.28ppm (s, 1H)

[0429] The wavelength λmax of the maximum peak located on the longest wavelength side in the range of 300 to 400 nm of the compound (MA5-1), measured in the same manner as the compound (MA1-1), was 372 nm.

[0430] [Synthesis of comparative compound (CA-3)]

[0431] [Synthesis of Intermediate 4]

[0432] According to the description in paragraph 0133 of WO2017 / 115649, intermediate 4 was synthesized.

[0433] [Chemical formula 34]

[0434]

[0435] 4.8 g of intermediate 4, 6.5 g of mono(2-methacryloyloxyethyl)succinate, 140 mg of N,N-dimethylaminopyridine (DMAP) and 50 mL of dichloromethane were added to a 200 mL three-necked flask and stirred in an ice bath for 10 minutes. 5.8 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDAC·HCl) was added thereto and reacted at room temperature for 4 hours. The reaction solution was diluted with ethyl acetate, washed with water, saturated sodium bicarbonate aqueous solution and saturated saline in that order, and then the organic layer was dried with magnesium sulfate. After removing the magnesium sulfate by filtration, the solution was purified by silica gel column chromatography using hexane / ethyl acetate as a developing solvent to obtain 7.5 g of comparative compound (CA-3).

[0436] The wavelength λmax of the maximum peak located on the longest wavelength side in the range of 300 to 400 nm of the comparative compound (CA-3), measured in the same manner as the compound (MA1-1), was 367 nm.

[0437] [Synthesis of comparative compound (CA-4)]

[0438] [Chemical formula 35]

[0439]

[0440] [Synthesis of Intermediate 1]

[0441] 50 mL of ethanol and 10 mL of acetic acid were added to 25.6 g of 4,5-dimethyl-1,2-phenylenediamine and 35.6 g of ninhydrin, and the mixture was reacted at 70° C. for 3 hours. After the reaction solution was cooled to room temperature, the precipitated crystals were filtered out, washed with ethanol, and dried to obtain 41.1 g of Intermediate 1.

[0442] [Synthesis of Intermediate 2]

[0443] 22 g of intermediate 1 and 32 g of phenol were dissolved in 20 mL of methanesulfonic acid and 20 mL of acetonitrile. The reaction solution was heated and maintained at 90°C, while 0.3 mL of 3-mercaptopropionic acid was added dropwise. After stirring for 3 hours, 200 mL of acetonitrile and 100 mL of water were added, and the reaction solution was stirred in an ice bath for 2 hours. The precipitated crystals were filtered, washed with methanol and dried, thereby obtaining 26 g of intermediate 2.

[0444] [Synthesis of comparative compound (CA-4)]

[0445] A comparative compound (CA-4) was obtained in the same manner as in the synthesis of the above comparative compound (CA-3) except that the intermediate 4 was changed to the intermediate 2.

[0446] The wavelength λmax of the maximum peak located on the longest wavelength side in the range of 300 to 400 nm of the comparative compound (CA-4), measured in the same manner as the compound (MA1-1), was 374 nm.

[0447] [Synthesis of comparative compound (CA-5)]

[0448] [Chemical formula 36]

[0449]

[0450] [Synthesis of Intermediate 5]

[0451] Intermediate 5 was obtained in the same manner as in the synthesis of Intermediate 1 except that 4,5-dimethyl-1,2-phenylenediamine was changed to 4,5-dichloro-1,2-phenylenediamine.

[0452] [Synthesis of Intermediate 6]

[0453] Intermediate 6 was obtained in the same manner as in the synthesis of Intermediate 2 except that Intermediate 1 was changed to Intermediate 5.

[0454] [Synthesis of Comparative Compound (CA-5)]

[0455] A comparative compound (CA-5) was obtained in the same manner as in the synthesis of the above comparative compound (CA-3) except that the intermediate 4 was changed to the intermediate 6.

[0456] The wavelength λmax of the maximum peak located on the longest wavelength side in the range of 300 to 400 nm of the comparative compound (CA-5), measured in the same manner as the compound (MA1-1), was 377 nm.

[0457] [Synthesis of polymers having free radical polymerizable groups in side chains]

[0458] A polymer (G-1) having a radical polymerizable group in a side chain was synthesized by the following method.

[0459] 12.0 g of benzyl methacrylate and 18.0 g of allyl methacrylate were dissolved in 172.3 g of methyl ethyl ketone and heated to 70°C. A solution obtained by dissolving 1.05 g of polymerization initiator V-65 (trade name, manufactured by FUJIFILM Wako Pure Chemical Corporation, oil-soluble azo polymerization initiator) in 12.0 g of methyl ethyl ketone was added dropwise to the solution over 30 minutes. After the addition was completed, the reaction was further carried out at 70°C for 4.5 hours. After the reaction solution was naturally cooled, it was concentrated to a total amount of 107.7 g, and then 42.0 g of methanol was added and stirred until uniform. The reaction solution was added dropwise to 858.0 g of methanol cooled to below 5°C, the precipitated powder was filtered out, and dried. In this way, 20.5 g of polymer (G-1) was obtained. The weight average molecular weight of the obtained polymer was 35,700, and the dispersion degree (Mw / Mn) was 3.3.

[0460] [Chemical formula 37]

[0461]

[0462] The weight average molecular weight and the degree of dispersion of the polymer prepared above are weight average molecular weight and degree of dispersion in terms of standard polystyrene based on gel permeation chromatography (GPC), and are values ​​measured under the following conditions.

[0463] Measuring instrument: HLC-8320GPC (trade name, manufactured by TOSOH CORPORATION)

[0464] Column: TOSOH TSKgel HZM-H (trade name, manufactured by TOSOH CORPORATION), TOSOH TSKgel HZ4000 (trade name, manufactured by TOSOH CORPORATION), and TOSOH TSKgel HZ2000 (trade name, manufactured by TOSOH CORPORATION) were connected.

[0465] Carrier: THF

[0466] Measurement temperature: 40℃

[0467] Carrier flow rate: 0.35ml / min

[0468] Sample concentration: 0.1 mass%

[0469] Detector: RI (refractive index) detector

[0470] [Reference Example 3: Preparation of curable resin composition]

[0471] A curable resin composition was prepared by mixing and stirring a curable monomer or a comparative curable monomer (also referred to as a comparative compound) obtained from a compound represented by the general formula (A) or (B), other monomers, a photopolymerization initiator, a thermal polymerization initiator, and other additives to obtain a composition as shown in Table 1 below.

[0472] [Evaluation 1] Measurement of viscosity of curable resin composition

[0473] A rheometer (trade name: RS600) manufactured by HAAKE was used at 25°C and a shear rate of 10 s -1 The viscosity of the prepared curable resin composition was measured under the conditions of . The results are summarized in Table 1.

[0474] [Reference Example 4: Preparation of Cured Product]

[0475] The obtained curable resin composition was injected into a circular transparent glass mold having a diameter of 20 mm so that the thickness of the cured product would be 1 mm. The glass mold was made of borosilicate glass whose surface was subjected to a hydrophobic treatment with dichlorodimethylsilane.

[0476] Execure 3000 (trade name, manufactured by HOYA CORPORATION) was used as a light source, and 1000 mJ / cm was irradiated from above the transparent glass mold in an atmosphere purged with nitrogen so that the oxygen concentration was 1% or less. 2Then, the obtained photocurable sample was heated at 200° C. for 30 minutes in an atmosphere with an oxygen concentration of 1% or less to produce a cured product in which the curing reaction was completely carried out.

[0477] [Evaluation 2] Evaluation of the refractive index of the cured product

[0478] The refractive index nD of the obtained cured product at a wavelength of 589 nm was measured using an Abbe refractometer (manufactured by ATAGO CO., LTD, trade name: DR-M4) at 25°C. In addition, nF, nC, and ng were also measured, and the Abbe number νD and the partial dispersion ratio θg,F were calculated as the wavelength dispersion characteristics of the refractive index according to the following formula. The results are summarized in Table 1.

[0479] νD=(nD-1) / (nF-nC)

[0480] θg,F=(ng-nF) / (nF-nC)

[0481] Here, nF represents the refractive index at a wavelength of 486 nm, nC represents the refractive index at a wavelength of 656 nm, and ng represents the refractive index at a wavelength of 436 nm.

[0482] [Evaluation 3] Transmittance evaluation of cured product

[0483] The UV-visible transmittance of the obtained cured product was measured at the center (diameter 5 mm) using an UV-visible spectrophotometer UV-2600 (trade name, manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 420 nm was measured.

[0484] [Evaluation 4] Birefringence Δn

[0485] The birefringence at a wavelength of 543 nm within a circle with a diameter of 10 mm including the center of the prepared cured product (cured product sample for optical measurement) was measured using a birefringence evaluation apparatus (WPA-100 (trade name), manufactured by Photonic Lattice, Inc.), and the average value was taken as the birefringence Δn.

[0486] The cured products obtained from curable resin compositions Nos. 101 to 115 all had birefringence Δn as small as 0.0003 to 0.0009, and the image position was not easily shifted and a clear image could be obtained, so they were suitable for optical components of camera modules.

[0487]

[0488]

[0489]

[0490] <Notes on the table>

[0491] The components in the table are as follows: The blending ratio of each component described in the column of each component is based on mass, and "-" means that the component is not contained.

[0492] (Curable Monomer Obtained from the Compound Represented by General Formula (A) or (B))

[0493] [Chemical formula 38]

[0494]

[0495] (Comparative curable monomer)

[0496] [Chemical formula 39]

[0497]

[0498] The comparative compound (CA-1) was synthesized according to the synthesis method described in Example 1 of JP-A-2014-80572.

[0499] The comparative compound (CA-2) was synthesized according to <Synthesis of Compound 2-1> of International Publication No. 2016 / 140245.

[0500] The comparative compound (CA-6) was synthesized according to the synthesis of compound (51) of International Publication No. 2017 / 115649 (Japanese Patent No. 6606195).

[0501] In addition, in the same manner as compound (MA1-1), the wavelength λmax of the maximum peak on the longest wavelength side of comparative compound (CA-1), comparative compound (CA-2) and comparative compound (CA-6) in the range of 300 to 400 nm was measured, and the results were: comparative compound (CA-1) was 347 nm, comparative compound (CA-2) was 359 nm, and comparative compound (CA-6) was 368 nm.

[0502] (Other monomers)

[0503] Each of the compounds shown below is indicated.

[0504] [Chemical formula 40]

[0505]

[0506] (Photopolymerization Initiator)

[0507] Irg819: Irgacure 819 (trade name, manufactured by BASF Japan Ltd.)

[0508] IrgTPO: Irgacure TPO (trade name, manufactured by BASF Japan Ltd.)

[0509] (Thermal polymerization initiator)

[0510] PERHEXYL D: Trade name, manufactured by Nippon Oil and Fats Company, Limited, di-tert-hexyl peroxide

[0511] (Other additives)

[0512] G-1: The polymer prepared above (G-1)

[0513] [Chemical formula 41]

[0514]

[0515] As shown in Table 1, it is known that by using a curable monomer obtained from the compound of the present invention, a cured product having both a low Abbe number and a high transmittance can be obtained at a high level compared to conventional curable monomers in which a phenylene or dimethylphenylene group is bonded to a condensed ring structure.

[0516] Furthermore, the cured product formed using the curable monomer obtained from the compound of the present invention has, in addition to the above-mentioned low Abbe number νD and high transmittance, a partial dispersion ratio θg,F that is sufficiently high to be above 0.67, and also has excellent wavelength dispersion characteristics of the refractive index when used as a chromatic aberration correction lens.

[0517] The present invention has been described together with its embodiments, but unless otherwise indicated, we do not intend our invention to be limited to any of the details described and should be broadly construed without departing from the spirit and scope of the invention as set forth in the appended claims.

[0518] This application claims priority based on Japanese Patent Application No. 2020-140313 filed in Japan on August 21, 2020, the contents of which are incorporated herein by reference as part of the description of this specification.

Claims

1. A compound represented by the following general formula (A1-1), [Chemical formula 1] In the above formula, R 5 and R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L 1 and L 2 represents an alkylene group having 1 to 6 carbon atoms, Spa and Spb represent a single bond or a divalent linking group formed by bonding one or more groups selected from a linear alkylene group, a cycloalkylene group, -O-, and >C(=O), wherein, When Spa is a divalent linking group, the linking group L 1 With COOR 5 The number of atoms in the shortest molecular chain and the number of atoms constituting the linking group L when Spb is a divalent linking group 2 With COOR 6 The number of atoms connected in the shortest molecular chain is 1 to 10. R 11 and R 21 represents a substituent selected from a halogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, an aromatic hydrocarbon ring group having 6 to 14 carbon atoms, and a cyano group, v1 and w1 are integers of 0 to 4, Among them, there is no (R 11 )v1-benzene ring / cyclopentadiene skeleton / naphthalene ring-(R 21 ) The structure represented by w1 is line symmetric, and " / " indicates that the two rings recorded on the left and right are fused.

2. A method for producing a compound represented by the following general formula (A1-1), comprising the following steps: subjecting a compound represented by the following general formula (SA1-1) to an addition reaction in the presence of a base with (i) an ethylenically unsaturated carboxylic acid compound, (ii) an ethylenically unsaturated carboxylic acid ester compound, (iii) an ethylenically unsaturated dicarboxylic acid anhydride or (iv) an alkyl carboxylic acid ester compound having a leaving group at the ω position, to obtain a compound represented by the following general formula (A1-1); [Chemical formula 2] In the above formula, R 5 and R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L 1 and L 2 represents an alkylene group having 1 to 6 carbon atoms, Spa and Spb represent a single bond or a divalent linking group formed by bonding one or more groups selected from a linear alkylene group, a cycloalkylene group, -O-, and >C(=O), wherein, When Spa is a divalent linking group, the linking group L 1 With COOR 5 The number of atoms in the shortest molecular chain and the number of atoms constituting the linking group L when Spb is a divalent linking group 2 With COOR 6 The number of atoms connected in the shortest molecular chain is 1 to 10. R 11 and R 21 represents a substituent selected from a halogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, an aromatic hydrocarbon ring group having 6 to 14 carbon atoms, and a cyano group, v1 and w1 are integers of 0 to 4, However, in the general formulas (SA1-1) and (A1-1), there is no (R 11 )v1-benzene ring / cyclopentadiene skeleton / naphthalene ring-(R 21 ) The structure represented by w1 is line symmetric, and " / " indicates that the two rings recorded on the left and right are fused.

3. The method for producing a compound represented by the general formula (A1-1) according to claim 2, wherein In the above (ii) to (iv), a hydrolysis reaction is performed after the addition reaction. Among them, the R 5 and R 6 A hydrogen atom.

4. The method for producing a compound represented by the general formula (A1-1) according to claim 2 or 3, wherein The solvent used in the addition reaction contains an SP value of 21.0 MPa 1 / 2 The above solvents.

5. Use of the compound according to claim 1 as a synthetic intermediate of a curable monomer.

6. Use of the compound according to claim 1 as a raw material compound for an optical component or as a synthetic intermediate of the raw material compound.

7. The use according to claim 6, wherein The optical component is a lens.

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