Compound, nonlinear optically active polymer compound, composition, nonlinear optical element, and optical modulator

Abstract

The purpose of the present invention is to provide a compound that, even in a state of being dispersed in or bonded to a medium such as a polymer material at a high concentration, has an improved EO coefficient in accordance with the concentration, and to provide a composition containing the compound, a nonlinear optical element formed using the composition, and an optical modulator that includes the nonlinear optical element and operates on the basis of the electro-optic effect. The present invention relates to a compound represented by formula (I) below. (The definitions of the groups in formula (1) are as described in the specification.)

Description

Compound, nonlinear optically active polymer compound, composition, nonlinear optical element and optical modulator

[0001] The present invention relates to a compound, a nonlinear optically active polymer compound, a composition, a nonlinear optical element, and an optical modulator.

[0002] In recent years, development of various optoelectronic devices using nonlinear optical materials has been progressing in fields such as optical information processing and optical communications. Nonlinear optical materials are materials that exhibit a polarization response proportional to the square, cube, or higher order terms of the magnitude of the electric field of light, and those that produce the first-order electro-optic effect (Pockels effect), which is a second-order nonlinear optical effect, are being considered for applications such as optical switches and optical modulation.

[0003] Lithium niobate and potassium dihydrogen phosphate have been commercialized and widely used as inorganic nonlinear optical materials. However, in recent years, organic nonlinear optical materials have attracted attention because of their advantages over these inorganic materials, such as high nonlinear optical performance, low material costs, and high mass productivity, and active research and development is being conducted toward their practical application.

[0004] Organic nonlinear optical materials are generally obtained by dispersing or bonding a compound (dye) with nonlinear optical activity in a polymer compound such as polymethyl methacrylate (PMMA). Nonlinear optical properties are expressed by the electro-optic coefficient (hereinafter also referred to as the "EO coefficient"), also denoted as r33. To exhibit the electro-optic effect, nonlinear optical materials require the alignment of the compound with nonlinear optical activity. The alignment of the compound with nonlinear optical activity can be achieved by a poling process, in which an electric field is applied at a temperature near the glass transition temperature (Tg) of the electro-optic polymer, and then the temperature is cooled to room temperature while the electric field is still applied, and then the electric field is released. Known nonlinear optical compounds include so-called push-pull π-conjugated compounds, which have an electron-donating group and an electron-accepting group at each end of the molecular structure, and a π-conjugated chain connecting them. Nonlinear optical materials are desired to have a high EO coefficient, high heat resistance, and low absorption loss at wavelengths used in optical communications (Patent Documents 1 to 4).

[0005] One known method for improving the EO coefficient is to increase the concentration of a compound having nonlinear optical activity added to a polymeric material. It is known that the EO coefficient and the concentration of a compound having nonlinear optical activity added to a polymeric material are correlated (Patent Documents 5 and 6, and Non-Patent Document 1).

[0006] International Publication No. 2019 / 151318 Japanese Patent Application Laid-Open No. 2010-066325 International Publication No. 2011 / 024774 Japanese Patent Application Laid-Open No. 2015-178544 International Publication No. 2013 / 172342 Japanese Patent Application Laid-Open No. 2014-130196

[0007] Journal of Polymer Science Part A: Polymer Chemistry, 2010, Vol. 49, Issue 1, p. 47-54.

[0008] However, compounds with nonlinear optical activity have large dipole moments, which result in large intermolecular interactions and poor dispersibility in media. For this reason, it is known that when the concentration of a compound with nonlinear optical activity is increased in a polymeric material such as PMMA, which is commonly used as a medium, the EO coefficient does not improve once the concentration exceeds a certain level. It is also known that a similar phenomenon is observed when a compound with nonlinear optical activity is bonded to a polymeric compound.

[0009] In view of the above problems, the present invention aims to provide a compound that exhibits an improved EO coefficient in accordance with its concentration, even when dispersed or bonded at a high concentration in a medium such as a polymer material. Another object of the present invention is to provide a composition containing the compound, a nonlinear optical element using the composition, and an optical modulator that includes the nonlinear optical element and operates based on the electro-optic effect.

[0010] As a result of intensive research, the present inventors have found that a compound having a predetermined chemical structure can reduce intermolecular interactions and improve dispersibility in a medium. As a result of further research, the present inventors have found that a compound having a predetermined chemical structure can be dispersed at a high concentration in a medium such as a polymer material, and that even when the addition concentration is increased, the EO coefficient increases in proportion to the addition concentration, thereby completing the present invention.

[0011] That is, the present invention provides the following.

[0012] Aspect 1 of the present invention relates to a compound represented by the following formula (1):

[0013]

[0014] [In formula (1), Z １１ is a group represented by the following formula (2): １２ is an aromatic group which may have a substituent, or a branched, linear or cyclic hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, and the hydrocarbon group may be saturated or unsaturated, and a part of the hydrocarbon chain constituting the hydrocarbon group may be substituted with at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms. １３ is a divalent aromatic group which may have a substituent. １１ is a divalent π-conjugated group. １１ is a group represented by the following formula (6) or formula (7): １２ and Z １３ may be linked to each other to form a cyclic structure.

[0015]

[0016] [In formula (2), R ２１is a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted amino group, a halogen atom, an optionally substituted aralkyloxy group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aralkylthio group, and an optionally substituted silyl group. ２１ is a group selected from the group consisting of an aromatic group, a hydrocarbon ring group, and a heterocyclic group, and R ２１ * indicates the bonding position to N in formula (1).

[0017]

[0018] [In formula (6), * represents L in formula (1)] １１ This is the bonding position with R ６１ and R ６２ are each independently a group selected from the group consisting of an alkyl group which may have a substituent, an aromatic group which may have a substituent, a halogen atom, an alkylsulfonyl group which may have a substituent, and an aralkyl group which may have a substituent. ６１ is O or S.

[0019]

[0020] [In formula (7), * represents L in formula (1)] １１ This is the bonding position with R ７３ is a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted acyl group, an optionally substituted alkyloxycarbonyl group, and an optionally substituted aralkyl group.

[0021] Aspect 2 of the present invention relates to the compound of Aspect 1, wherein the formula (2) is represented by the following formula (3):

[0022]

[0023] [In formula (3), R ３１ and R３２ are each independently R in formula (2). ２１ Ar is a group having the same meaning as ３３ is a group selected from the group consisting of an aromatic group, a hydrocarbon ring group, and a heterocyclic group, and R ３１ and R ３２ * indicates the bonding position to N in formula (1).

[0024] Aspect 3 of the present invention is a compound according to aspect 1 or 2, wherein Z in formula (1) １２ is an optionally substituted alkyl group or an optionally substituted aromatic group.

[0025] A fourth aspect of the present invention is a compound of any one of the first to third aspects, wherein Z in the formula (1) is １３ is a divalent aromatic hydrocarbon group which may have a substituent.

[0026] Aspect 5 of the present invention is a compound of any one of aspects 1 to 4, wherein L in formula (1) １１ is a group represented by the following formula (4) or formula (5):

[0027]

[0028] [In formula (4), R ４ａ are each independently a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted amino group, a halogen atom, an optionally substituted alkyloxycarbonyl group, an optionally substituted alkylsulfonyl group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and an optionally substituted aralkylthio group. ４ｂ R are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, and an aromatic group which may have a substituent. ４ｃare each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic group which may have a substituent. ４ａ , R ４ｂ and R ４ｃ may be bonded to each other to form a ring, l is an integer of 0 to 5, n is an integer of 0 to 5, m is an integer of 0 to 5, and l+n+m>0.

[0029]

[0030] [In formula (5), Ar ５ R each independently represents a divalent aromatic group which may have a substituent. ５ａ are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic group which may have a substituent. ５ has a substituent, the substituent and R ５ａ and may be bonded to each other to form a ring, e is an integer of 0 to 4, f is an integer of 0 to 5, and e+f>0.

[0031] A sixth aspect of the present invention relates to a nonlinear optically active polymer compound, which comprises a group obtained by removing at least one hydrogen atom from the compound of any one of the first to fifth aspects and which is bonded to a repeating unit in the polymer compound.

[0032] A seventh aspect of the present invention relates to the nonlinear optically active polymer compound of the sixth aspect, wherein the polymer compound is selected from the group consisting of poly(meth)acrylic acid ester, polyvinyl chloride, polystyrene, polyimide, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, polycarbonate, and copolymers thereof.

[0033] Aspect 8 of the present invention relates to a composition containing at least one compound according to any one of Aspects 1 to 5, a polymeric material, and a solvent; at least one nonlinear optically active polymeric compound according to Aspect 6 or 7, and a solvent; or at least one compound according to any one of Aspects 1 to 5, at least one nonlinear optically active polymeric compound according to Aspect 6 or 7, and a solvent.

[0034] A ninth aspect of the present invention relates to the composition of the eighth aspect, wherein the polymer material is selected from the group consisting of poly(meth)acrylic acid ester, polyvinyl chloride, polystyrene, polyimide, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, polycarbonate, and copolymers thereof.

[0035] A tenth aspect of the present invention relates to a nonlinear optical element comprising the composition of the eighth or ninth aspect.

[0036] An eleventh aspect of the present invention relates to the nonlinear optical element of the tenth aspect, which operates based on the electro-optic effect.

[0037] A twelfth aspect of the present invention relates to an optical modulator comprising the nonlinear optical element according to the tenth or eleventh aspect.

[0038] According to the present invention, it is possible to provide a compound whose EO coefficient improves in accordance with its concentration even when dispersed or bound at a high concentration in a medium such as a polymer material.

[0039] The following describes in detail the embodiments of the present invention, but the present invention is not limited to the following description and can be modified as desired without departing from the spirit of the present invention. In this specification, when an expression using "~" is used with a numerical value or physical property value before and after it, the value before and after it is used as including the values ​​before and after it.

[0040] (Explanation of Terms) The terms used in this embodiment will be explained.

[0041] <Substituents> Unless otherwise specified, the substituents are any groups, but are preferably those in the following substituent group G. １The substituents that may be possessed are selected from the group of substituents G １ The substituents selected from or optionally having are selected from the substituent group G １ In the case where it is stated that the substituent is preferably selected from the following substituent group G, the preferred substituents are also selected from the following substituent group G １ As stated in the

[0042] Substituent group G １ is a group consisting of a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aromatic oxy group, an alkyloxycarbonyl group, an acyloxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyl group, a halogen atom, a haloalkyl group, an alkylthio group, an aromatic thio group, a silyl group, a siloxy group, a cyano group, an aralkyl group, and an aromatic group. These substituents may have any of a linear, branched, and cyclic structure.

[0043] A linear, branched, or cyclic alkyl group having 1 or more carbon atoms and usually 24 or less, preferably 12 or less, more preferably 8 or less, and even more preferably 6 or less. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, a dodecyl group, and an adamantyl group. A linear, branched, or cyclic alkenyl group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less, and more preferably 6 or less. Specific examples include a vinyl group.

[0044] A linear or branched alkynyl group having a carbon number of usually 2 or more and usually 24 or less, preferably 12 or less, more preferably 6 or less. A specific example is an ethynyl group.

[0045] A linear, branched, or cyclic alkoxy group having 1 or more carbon atoms and usually 24 or less, preferably 12 or less, and more preferably 6 or less. Specific examples include a methoxy group and an ethoxy group.

[0046] An aromatic oxy group having 4 or more, preferably 5 or more, carbon atoms, and usually 36 or less, preferably 24 or less, more preferably 10 or less. Specific examples include a phenoxy group, a naphthoxy group, and a thiophenyloxy group.

[0047] An alkyloxycarbonyl group having at least 2 carbon atoms and usually at most 24, preferably at most 12, and more preferably at most 7. Specific examples include a methoxycarbonyl group and an ethoxycarbonyl group.

[0048] An acyloxy group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less, and more preferably 7 or less. Specific examples include an acetyloxy group, a propionyloxy group, and a benzoyloxy group. A dialkylamino group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less, and more preferably 6 or less. Specific examples include a dimethylamino group, a diethylamino group, an ethylmethylamino group, and an isopropylamino group.

[0049] An aromatic amino group having 10 or more, preferably 12 or more, and usually 36 or less, preferably 24 or less, more preferably 14 or less carbon atoms. Specific examples include a diphenylamino group, a ditolylamino group, and an N-carbazolyl group.

[0050] An aromatic alkylamino group, which is an aromatic amino group having 7 or more carbon atoms and usually 36 or less, preferably 24 or less, more preferably 8 or less carbon atoms. A specific example is a phenylmethylamino group.

[0051] An acyl group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less, and more preferably 7 or less carbon atoms. Specific examples include an acetyl group and a benzoyl group.

[0052] Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Preferably, it is a fluorine atom.

[0053] A haloalkyl group having at least 1 carbon atom and usually at most 12, preferably at most 6. Specific examples include a trifluoromethyl group.

[0054] an alkylthio group having at least 1 carbon atom and usually at most 24, preferably at most 12, more preferably at most 6. Specific examples include a methylthio group and an ethylthio group.

[0055] An aromatic thio group having 4 or more, preferably 5 or more, carbon atoms, and usually 36 or less, preferably 24 or less, more preferably 10 or less. Specific examples include a phenylthio group and a naphthylthio group.

[0056] A silyl group having a carbon number of usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less, more preferably 18 or less. Specific examples include a trimethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, and a triphenylsilyl group.

[0057] A siloxy group having 2 or more, preferably 3 or more, carbon atoms, and usually 36 or less, preferably 24 or less, and more preferably 18 or less. Specific examples include a trimethylsiloxy group, a tert-butyldimethylsiloxy group, a tert-butyldiphenylsiloxy group, and a triphenylsiloxy group.

[0058] An aralkyl group having a carbon number of usually 7 or more, preferably 9 or more, and usually 30 or less, preferably 18 or less, more preferably 10 or less. Specific examples include a benzyl group, a 2-phenylethyl group, a 2-phenylpropyl-2-yl group, a 2-phenylbutyl-2-yl group, a 3-phenylpentyl-3-yl group, a 3-phenyl-1-propyl group, a 4-phenyl-1-butyl group, a 5-phenyl-1-pentyl group, a 6-phenyl-1-hexyl group, a 7-phenyl-1-heptyl group, and an 8-phenyl-1-octyl group.

[0059] An aromatic group having 6 or more carbon atoms and usually 36 or less, preferably 24 or less. Specific examples include a phenyl group, a naphthyl group, a group in which multiple phenyl groups are linked together, a thienyl group, a furanyl group, and a pyridyl group.

[0060] The substituents may have any of a linear, branched, or cyclic structure. When the substituents are adjacent to each other, the adjacent substituents may be bonded to each other to form a ring. The preferred ring size is a 4-membered ring, a 5-membered ring, or a 6-membered ring, and specific examples include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0061] <Alkyl Group> The alkyl group may have a substituent, and may be linear, branched, or cyclic. The number of carbon atoms is not usually limited, but preferably has 1 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 30 or less, and even more preferably 10 or less. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, a dodecyl group, an adamantyl group, and the like. The substituents that these groups may have are those in the substituent group G. １ is selected from.

[0062] <Aromatic Group> The aromatic group represents an aromatic hydrocarbon group or an aromatic heterocyclic group, which may have a substituent, and refers to a monovalent, divalent, or trivalent or higher valent structure depending on the bonding state in the structure of a compound to be described later.

[0063] In the structure of the aromatic hydrocarbon group, the number of carbon atoms is not usually limited, but is preferably 6 to 60, with the upper limit of the carbon number being more preferably 48 or less, and even more preferably 30 or less. Specific examples include 6-membered monocyclic rings or fused ring groups containing 2 to 5 rings, such as phenyl rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings, or structures in which multiple groups selected from these are linked. When multiple aromatic hydrocarbon groups are linked, typically, structures in which 2 to 10 groups are linked are exemplified, with structures in which 2 to 5 groups are linked being preferred. When multiple aromatic hydrocarbon groups are linked, the linked groups may be the same structure or different structures.

[0064] In the structure of the aromatic heterocyclic group, the number of carbon atoms is usually not limited, but is preferably 3 to 50, and the upper limit of the number of carbon atoms is more preferably 45 or less, and even more preferably 30 or less. Specific examples thereof include a 5- or 6-membered single ring or a fused ring group containing 2 to 4 rings, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, or a quinazolinone ring, or a group in which a plurality of these rings are linked together. When a plurality of aromatic heterocyclic groups are linked, the same structures may be linked or different structures may be linked. When a plurality of aromatic heterocyclic groups are linked, usually, a structure in which 2 to 10 groups are linked can be mentioned, and a structure in which 2 to 5 groups are linked is preferred.

[0065] The substituents which these groups may have are listed in the substituent group G １ is selected from.

[0066] <Amino Group> The amino group may have a substituent and is preferably a secondary or tertiary amino group, more preferably a tertiary amino group. The substituent on the amino group is preferably an alkyl group, a cycloalkyl group, or an aromatic group, and these groups may have a substituent. In the case of a dialkylamino group, the number of carbon atoms is 2 or more and usually 24 or less, preferably 12 or less, and more preferably 6 or less. Specific examples include a dimethylamino group, a diethylamino group, an ethylmethylamino group, an n-propylmethylamino group, a di-n-butylamino group, a di-n-hexylamino group, and a di-isopropylamino group.

[0067] In the case of an aromatic amino group, the number of carbon atoms is 10 or more, preferably 12 or more, and usually 36 or less, preferably 24 or less, more preferably 14 or less. Specific examples include a diphenylamino group, a ditolylamino group, and an N-carbazolyl group.

[0068] In the case of an aromatic alkylamino group, the aromatic amino group has 7 or more carbon atoms and usually 36 or less, preferably 24 or less, more preferably 8 or less. A specific example is a phenylmethylamino group. When the amino group has a plurality of substituents, they may be the same or different and may be bonded to each other to form a ring together with the nitrogen atom to which each is bonded. The substituents that these groups may have are those in the substituent group G. １ is selected from.

[0069] <Halogen Atom> Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0070] <Alkyloxycarbonyl Group> The alkyloxycarbonyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an iso-propoxycarbonyl group, an n-butoxycarbonyl group, an iso-butoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a dodecyloxycarbonyl group. The substituents that these groups may have are those in the substituent group G. １ is selected from.

[0071] <Acyl group> The acyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 24 or less, and even more preferably 12 or less. Specific examples include a benzoyl group and an acetyl group. The substituents that these groups may have are those listed in the substituent group G １ is selected from.

[0072] <Alkylsulfonyl Group> The alkylsulfonyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an iso-propylsulfonyl group, an n-butylsulfonyl group, an iso-butylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonyl group, an n-hexylsulfonyl group, a cyclohexylsulfonyl group, and a dodecylsulfonyl group. The substituents that these groups may have are those listed in the substituent group G １ is selected from.

[0073] <Aralkyl Group> The aralkyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 4 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzyl group, a tolylmethyl group, a thiophenylmethyl group, a 2-phenylethyl group, a 2-phenylpropyl-2-yl group, a 2-phenylbutyl-2-yl group, a 3-phenylpentyl-3-yl group, a 3-phenyl-1-propyl group, a 4-phenyl-1-butyl group, a 5-phenyl-1-pentyl group, a 6-phenyl-1-hexyl group, a 7-phenyl-1-heptyl group, and an 8-phenyl-1-octyl group. The substituents that these groups may have are those listed in the substituent group G. １ is selected from.

[0074] <Aromatic Oxy Group> The aromatic oxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 30 or less, and even more preferably 20 or less. Specific examples include a naphthoxy group and a thiophenyloxy group. The substituents that these groups may have are those listed in the substituent group G. １ is selected from.

[0075] <Aralkyloxy Group> The aralkyloxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 4 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzyloxy group, a tolylmethoxy group, a thiophenylmethoxy group, a 2-phenylethyloxy group, a 2-phenylpropyl-2-yloxy group, a 2-phenylbutyl-2-yloxy group, a 3-phenylpentyl-3-yloxy group, a 3-phenyl-1-propyloxy group, a 4-phenyl-1-butyloxy group, a 5-phenyl-1-pentyloxy group, a 6-phenyl-1-hexyloxy group, a 7-phenyl-1-heptyloxy group, and an 8-phenyl-1-octyloxy group. The substituents that these groups may have are those listed in the substituent group G. １ is selected from.

[0076] <Alkoxy Group> The alkoxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 1 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, and a dodecyloxy group. The substituents that these groups may have are those in the substituent group G. １ is selected from.

[0077] <Alkylthio Group> The alkylthio group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 1 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, an n-hexylthio group, a cyclohexylthio group, and a dodecylthio group. The substituents that these groups may have are those in the substituent group G. １ is selected from.

[0078] <Aromatic Thio Group> The aromatic thio group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzylthio group, a tolylthio group, and a thiophenylthio group. The substituents that these groups may have are those listed in the substituent group G １ is selected from.

[0079] <Aralkylthio Group> The aralkyloxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 4 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzylthio group, a tolylmethylthio group, a 2-phenylethylthio group, a 2-phenylpropyl-2-ylthio group, a 2-phenylbutyl-2-ylthio group, a 3-phenylpentyl-3-ylthio group, a 3-phenyl-1-propylthio group, a 4-phenyl-1-butylthio group, a 5-phenyl-1-pentylthio group, a 6-phenyl-1-hexylthio group, a 7-phenyl-1-heptylthio group, and an 8-phenyl-1-octylthio group. The substituents that these groups may have are those listed in Substituent Group G １ is selected from.

[0080] <Silyl Group> The silyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a trimethylsilyl group, a triethylsilyl group, a propyldimethylsilyl group, a tert-butyldimethylsilyl group, and a tert-butyldiphenylsilyl group. The substituents that these groups may have are those in the substituent group G １ is selected from.

[0081] <Hydrocarbon Ring Group> The hydrocarbon ring group is a cyclic hydrocarbon group, which may have a substituent, and is generally not limited in the number of carbon atoms, but preferably has 3 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a group in which a plurality of these groups are linked together. The substituents that these groups may have are those listed in the substituent group G １ is selected from.

[0082] <Heterocyclic Group> The heterocyclic group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a thiane group, a 1,4-dithiane group, a tetrahydrofuran group, a tetrahydropyran group, a pyran group, a 1,4-dioxane group, or a group in which a plurality of these groups are linked together. The substituents that these groups may have are those in the substituent group G. １ is selected from.

[0083] <Branched, linear, or cyclic saturated or unsaturated hydrocarbon chain, some of whose carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms> A branched, linear, or cyclic saturated or unsaturated hydrocarbon chain, some of whose carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, is a group in which a carbon chain consisting of a branched, linear, or cyclic alkyl group, alkenyl group, or alkynyl group having 1 to 20 carbon atoms may be partially substituted with oxygen atoms, sulfur atoms, and / or silicon atoms. These groups may have a substituent.

[0084] Specific examples include the following groups. Specific examples of unsubstituted groups include hydrocarbon chains of 1 to 20 carbon atoms, more specific examples include methyl, ethyl, 1-butyl, tert-butyl, cyclopentyl, 4-ethyl-1-cyclohexyl, 2-penten-1-yl, 1-octyl, and 1-decyl groups, with methyl, ethyl, and 1-butyl groups being preferred. Specific examples of substituted oxygen atoms include 2-ethoxyethyl, 2-(2-ethoxyethoxy)ethyl, 2-hydroxyethyl, and tetrahydropyranyloxypropyl groups, with 2-ethoxyethyl and 2-hydroxyethyl groups being preferred, and 2-hydroxyethyl groups being particularly preferred. Specific examples of substituted sulfur atoms include 2-ethylthioethyl, tetrahydrothienyl, and 2-(2-ethylthioethylthio)ethyl groups. Specific examples of the silicon atom substituted include a trimethylsilyl group and a tert-butyldimethylsilyl group.

[0085] These may also be substituted with an oxygen atom or a silicon atom at the same time, and specific examples thereof include a 2-(trimethylsilyloxy)ethyl group, a 2-(tert-butyldimethylsilyloxy)ethyl group, a 4-(tert-butyldimethylsilyloxy)butyl group, a 2-(tert-butyldiphenylsilyloxy)ethyl group, and a 2-(tert-butyldimethylsilyloxy)hexyl group, and preferably a 2-(tert-butyldimethylsilyloxy)ethyl group and a 4-(tert-butyldimethylsilyloxy)butyl group. The substituents that these groups may have are those in the substituent group G １ is selected from.

[0086] <π-conjugated group> The π-conjugated group is a group consisting of alternately connected single bonds and multiple bonds and having delocalized electrons (π electrons). The π-conjugated group may have a substituent, and the number of carbon atoms is usually not limited, but preferably has 2 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 30 or less, and even more preferably 20 or less. In addition, the substituents of multiple π-conjugated groups may be bonded to form a cyclic structure. Specific examples include vinylene, thiophene, furan, and pyrrole. The substituents that these groups may have are listed in the substituent group G １ is selected from.

[0087] <Blocked Isocyanate Group> A blocked isocyanate group represents a group in which an isocyanate group is protected with a blocking agent. It is characterized by remaining stable under normal conditions and by dissociating the blocking agent upon heat treatment, resulting in the regeneration of the isocyanate group. The group selected as the blocking agent is not particularly limited, but may have 1 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. In addition, the substituents of multiple π-conjugated groups may be bonded to form a cyclic structure. Specific examples include a methylethyloxime group, a 3,5-dimethylpyrazolyl group, and an ε-caprolactam group. A dimethylpyrazole group is preferred.

[0088] The heat treatment temperature required for dissociating the blocking agent is not particularly limited as it differs depending on the catalyst and reaction conditions, but is generally 20° C. to 250° C. The lower limit is preferably 40° C. or higher, more preferably 60° C. or higher, and most preferably 100° C. or higher, and the upper limit is preferably 250° C. or lower, more preferably 200° C. or lower.

[0089] <π-Conjugated Electron-Withdrawing Group> The π-conjugated electron-withdrawing group is a group consisting of alternately connected single bonds and multiple bonds, having delocalized electrons (π electrons), and having one or more electron-withdrawing groups as substituents. Generally, the number of carbon atoms is not limited, but is preferably 2 to 30 carbon atoms, with the upper limit of the carbon number being more preferably 10 or less, and even more preferably 6 or less. Furthermore, the substituents of multiple π-conjugated groups may be bonded to form a cyclic structure, which provides high amorphousness and high chemical stability, and is therefore more preferably an electron-withdrawing π-conjugated group having a cyclic structure. Specific examples of the electron-withdrawing group include a nitro group, a cyano group, an alkylcarbonyl group, or an alkyloxycarbonyl group, and more preferably a cyano group.

[0090] <Polymer Compound> In this specification, the polymer compound refers to a compound having a molecular weight of 2000 or more and containing four or more identical repeating units in the molecule. The polymer compound is not particularly limited, but is preferably a polymer, and may be any of a homopolymer, a block copolymer, a random copolymer, an alternating copolymer, or a graft copolymer, or may be in other forms.

[0091] <Dendron> In this specification, dendron refers to a compound having a structure regularly branched from the center, preferably having 6 to 84 carbon atoms, with the lower limit being more preferably 8 or more and the upper limit being more preferably 57 or less, even more preferably 49 or less, and particularly preferably 25 or less. In this specification, dendron does not include compounds that fall under the above-mentioned polymer compounds. Specific preferred examples of dendrons in this specification include compounds represented by the following general formula A or B:

[0092]

[0093] (In the above general formula A and general formula B, * indicates the bonding position with the compound represented by formula (1). D １ ~D １０ Each independently represents a divalent linking group which may have a substituent, and may be bonded to any position on the benzene ring. １ ~E ４２ each independently represents a monovalent group and may be bonded to any position on the benzene ring.

[0094] D １ ~D １０ are preferably each independently an alkylene group having 1 to 5 carbon atoms, an ester group, an ether group, or an alkyl ether group having 1 to 3 carbon atoms, and from the viewpoint of compound stability, are more preferably an alkylene group having 1 to 2 carbon atoms, an ester group, or an ether group having 1 carbon atom.

[0095] E １ ~E ４２ Preferably, each independently represents a group selected from the group consisting of a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted alkoxy group, an optionally substituted aromatic oxy group, an optionally substituted alkyloxycarbonyl group, an optionally substituted acyloxy group, an optionally substituted dialkylamino group, an optionally substituted aromatic amino group, an optionally substituted aromatic alkylamino group, an optionally substituted acyl group, a halogen atom, an optionally substituted alkylthio group, an optionally substituted aromatic thio group, an optionally substituted silyl group, an optionally substituted siloxy group, a cyano group, an optionally substituted aralkyl group, and an optionally substituted aromatic group, more preferably an optionally substituted acyl group, an optionally substituted aralkyl group, a hydrogen atom, or a fluorine atom, and even more preferably a hydrogen atom or a fluorine atom. The optionally substituted substituent is preferably an alkyl group having 1 to 5 carbon atoms or a fluorine atom.

[0096] <Compound Represented by Formula (1)> The compound according to the present embodiment is represented by the following formula (1).

[0097]

[0098] [In formula (1), Z １１ is a group represented by the following formula (2): １２ is an aromatic group which may have a substituent, or a branched, linear or cyclic hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, and the hydrocarbon group may be saturated or unsaturated, and a part of the hydrocarbon chain constituting the hydrocarbon group may be substituted with at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms. １３ is a divalent aromatic group which may have a substituent. １１ is a divalent π-conjugated group. １１ is a group represented by the following formula (6) or formula (7): １２ and Z １３ may be linked to each other to form a cyclic structure.

[0099]

[0100] [In formula (2), R ２１ is a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted amino group, a halogen atom, an optionally substituted aralkyloxy group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aralkylthio group, and an optionally substituted silyl group. ２１ is a group selected from the group consisting of an aromatic group, a hydrocarbon ring group, and a heterocyclic group, and R ２１ * indicates the bonding position to N in formula (1).

[0101] [Z １１ ] Z １１ is a group represented by the formula (2). １１is a group in which R, which will be described later, is attached to the position adjacent to the "*" which indicates the bonding position with N in formula (1). ２１ The compound represented by formula (1) has Z １１ is R ２１ By having Z １１ and Z １３ The compounds are not on the same plane, and the molecular structure is bulky, which suppresses aggregation of the compounds. This is thought to enable the compound represented by formula (1) to be dispersed or bonded at a high concentration in a medium such as a polymer material, and to achieve a high EO coefficient even when dispersed or bonded at a high concentration.

[0102] (R ２１ ) R ２１ is a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted amino group, a halogen atom, an optionally substituted aralkyloxy group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aralkylthio group, and an optionally substituted silyl group.

[0103] R ２１ Among the groups selected as , from the viewpoint of enhancing the nonlinear optical effect, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aralkyloxy group which may have a substituent, an aralkyl group which may have a substituent, an alkylthio group which may have a substituent, an aralkylthio group which may have a substituent, an aromatic group which may have a substituent, or a silyl group which may have a substituent is preferred, and further, from the viewpoint of the stability of the compound, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent is more preferred, and an alkyl group which may have a substituent is most preferred.

[0104] More preferred specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, and a dodecyl group, and more preferred examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-hexyl group, and most preferred examples include a methyl group and an ethyl group.

[0105] More preferred examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, and a dodecyloxy group, and most preferred examples are a methoxy group, an ethoxy group, an iso-propoxy group, and an n-hexyloxy group.

[0106] R ２１ The substituents which may be contained in the １ From the viewpoint of compound stability, more preferred specific examples include a hydroxy group, an alkoxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a halogen atom, a silyl group, and a siloxy group, further preferably a halogen atom, a hydroxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a silyl group, and a siloxy group, and most preferably a hydroxy group or a siloxy group.

[0107] (Ar ２１ ) Ar ２１ is a group selected from the group consisting of an aromatic group, a hydrocarbon ring group, and a heterocyclic group, and R ２１ Among these, an aromatic group or a hydrocarbon ring group is more preferred, and an aromatic group is most preferred.

[0108] Ar ２１ Preferred specific examples of the aromatic group selected as Ar include a phenyl ring, a furan ring, and a thiophene ring, more preferably a phenyl ring and a thiophene ring, and most preferably a phenyl ring. ２１Preferred specific examples of the hydrocarbon ring group selected as include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and preferably a cyclohexyl group.

[0109] Ar ２１ The substituents which may be contained in the alkyl group may be substituted, an aromatic group which may be substituted, an amino group which may be substituted, a halogen atom, an aralkyloxy group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, or an aralkylthio group which may be substituted. From the viewpoint that the higher the electron donating property, the more preferable are an alkyl group which may be substituted, an amino group which may be substituted, an aralkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, an aralkylthio group which may be substituted, or an aralkyloxy group, more preferable are an aralkyloxy group which may be substituted, an alkyl group which may be substituted, an amino group which may be substituted, or an alkoxy group which may be substituted, and most preferable are an alkyl group, an amino group, or an alkoxy group.

[0110] More preferred examples of the amino group include dimethylamino, diethylamino, ethylmethylamino, n-propylmethylamino, di-isopropylamino, di-n-butylamino, and di-n-hexylamino, and more preferred examples include ethylmethylamino, di-n-butylamino, methylphenylamino, ethylphenylamino, butylphenylamino, hexylphenylamino, diphenylamino, 2,6-dimethylphenylphenylamino, and 2,4,6-trimethylphenylphenylamino. More preferred examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, and dodecyloxy, and most preferred examples include methoxy, ethoxy, isopropoxy, and n-hexyloxy.

[0111] Ar ２１ When the substituent that may be possessed by １ From the viewpoint of compound stability, more preferred specific examples include a hydroxy group, an alkoxy group, an acyloxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a halogen atom, a silyl group, and a siloxy group, further preferred are a halogen atom, a hydroxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a silyl group, and a siloxy group, and most preferred are a hydroxy group, an acyloxy group, and a siloxy group.

[0112] Since aggregation of the compounds represented by formula (1) is further suppressed, formula (2) is more preferably represented by the following formula (3).

[0113]

[0114] [In formula (3), R ３１ and R ３２ are each independently R in formula (2). ２１ Ar is a group having the same meaning as ３３is a group selected from the group consisting of an aromatic group, a hydrocarbon ring group, and a heterocyclic group, and R ３１ and R ３２ * indicates the bonding position to N in formula (1).

[0115] (R ３１ , R ３２ ) R ３１ and R ３２ are each independently R in formula (2). ２１ R ３１ and R ３２ A preferred embodiment of the formula (2) is ２１ The range is the same as that described above.

[0116] (Ar ３３ ) Ar ３３ is a group selected from the group consisting of an aromatic group, a hydrocarbon ring group, and a heterocyclic group, and R ３１ and R ３２ Ar may have a group other than ３３ A preferred embodiment of the formula (2) is Ar ２１ The range is the same as that described above.

[0117] [Z １２ ] Z １２ is an aromatic group which may have a substituent, or a branched, linear or cyclic hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, and the hydrocarbon group may be saturated or unsaturated, and a part of the hydrocarbon chain constituting the hydrocarbon group may be substituted with at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms. １２ From the viewpoint of compound stability, is preferably an alkyl group which may have a substituent or an aromatic group which may have a substituent, and more preferably an aromatic group which may have a substituent.

[0118] Z １２ In the above formula, a part of the hydrocarbon chain constituting the hydrocarbon group may be substituted with at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms. １２In the above, when a portion of the hydrocarbon chain constituting the hydrocarbon group is substituted, it is preferably substituted with at least one atom selected from an oxygen atom, a sulfur atom, and a silicon atom. Here, "a portion of the hydrocarbon chain" refers to at least one methylene group, a methine group, or a carbon atom contained in the hydrocarbon chain. For example, a methylene group contained in the hydrocarbon chain may be substituted with an oxygen atom or a sulfur atom to form -O- or -S-, a methine group contained in the hydrocarbon chain may be substituted with a nitrogen atom to form -NH-, or a carbon atom contained in the hydrocarbon chain may be substituted with a silicon atom to form -SiH ２ - may also be the case.

[0119] Z １２ More preferred examples of the aromatic group selected as Z include a phenyl ring, a biphenyl ring, a furan ring, and a thiophene ring, more preferably a phenyl ring, a biphenyl ring, and a thiophene ring, and most preferably a phenyl ring. １２ More preferred specific examples of the branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, thiane, 1,4-dithiane, tetrahydrofuran, tetrahydropyran, pyran, and 1,4-dioxane.

[0120] Z １２The substituents which may be possessed by the group include an alkyl group which may have a substituent, an aromatic group which may have a substituent, an amino group which may have a substituent, a halogen atom, an alkyloxycarbonyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aralkylthio group which may have a substituent, and an acyl group which may have a substituent. From the viewpoint that the higher the electron tolerance, the more improved the EO coefficient, the more preferred are an alkyl group which may have a substituent, an amino group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and an aralkylthio group which may have a substituent, even more preferred are an alkyl group which may have a substituent, an amino group which may have a substituent, and an alkoxy group which may have a substituent, and most preferred are an amino group which may have a substituent, and an alkoxy group which may have a substituent.

[0121] More preferred specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, and a dodecyl group, more preferably a methyl group, an ethyl group, an n-propyl group, and an n-hexyloxy group, and most preferably a methyl group and an ethyl group. More preferred specific examples of the amino group include a dimethylamino group, a diethylamino group, an ethylmethylamino group, an n-propylmethylamino group, a di-isopropylamino group, a di-n-butylamino group, and a di-n-hexylamino group, and more preferred examples include an ethylmethylamino group, a di-n-butylamino group, a methylphenylamino group, an ethylphenylamino group, a butylphenylamino group, a hexylphenylamino group, a diphenylamino group, a 2,6-dimethylphenylphenylamino group, and a 2,4,6,trimethylphenylphenylamino group, and particularly preferred examples include a methylphenylamino group, an ethylphenylamino group, a butylphenylamino group, a hexylphenylamino group, a diphenylamino group, a 2,6-dimethylphenylphenylamino group, and a 2,4,6,trimethylphenylphenylamino group, and most preferred examples are a methylphenylamino group, an ethylphenylamino group, a butylphenylamino group, and a hexylphenylamino group. More preferred examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, and a dodecyloxy group, and most preferred examples are a methoxy group, an ethoxy group, an iso-propoxy group, and an n-hexyloxy group.

[0122] Z １２ When the substituent that may be possessed by １From the viewpoint of compound stability, more preferred specific examples include a hydroxy group, an alkoxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a halogen atom, a silyl group, a siloxy group, and an acyloxy group, more preferred examples include a halogen atom, a hydroxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a silyl group, and a siloxy group, and most preferred examples include a hydroxy group, an acyloxy group, and a siloxy group.

[0123] [Z １３ ] Z １３ represents a divalent aromatic group which may have a substituent. １３ is more preferably a divalent aromatic hydrocarbon group which may have a substituent. １２ and Z １３ and may be linked to each other to form a cyclic structure. １３ Among the aromatic groups selected as the aromatic ring, more preferred specific examples include a phenyl ring, a naphthalene ring, an anthracene ring, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, and a thienothiophene ring, more preferred examples include a phenyl ring and a thiophene ring, and most preferred examples include a phenyl ring.

[0124] Z １３ The substituents which may be possessed by the group are preferably an alkyl group which may have a substituent, an aromatic group which may have a substituent, an amino group which may have a substituent, a halogen atom, an alkyloxycarbonyl group which may have a substituent, an acyloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aralkyloxy group which may have a substituent. From the viewpoint of compound stability, an alkyl group which may have a substituent, a halogen atom which may have a substituent, an alkoxy group which may have a substituent, or an aralkyloxy group which may have a substituent is more preferred, and an alkoxy group which may have a substituent, or an aralkyloxy group which may have a substituent is most preferred.

[0125] More preferred examples of the alkoxy group include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, and dodecyloxy, and most preferred are methoxy, ethoxy, iso-propoxy, and n-hexyloxy. More preferred examples of the aralkyloxy group include benzyloxy, tolylmethoxy, 2-phenylethyloxy, 2-phenylpropyl-2-yloxy, 2-phenylbutyl-2-yloxy, 3-phenylpentyl-3-yloxy, 3-phenyl-1-propyloxy, 4-phenyl-1-butyloxy, 5-phenyl-1-pentyoxy, and 6-phenyl-1-hexyloxy, and most preferred is benzyl.

[0126] Z １３ When the substituent that may be possessed by １ From the viewpoint of compound stability, more preferred specific examples include a hydroxy group, an alkoxy group, an acyloxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a halogen atom, a silyl group, a siloxy group, and an aromatic group. More preferred examples include a halogen atom, a hydroxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a silyl group, and a siloxy group. Most preferred examples include a hydroxy group, an acyloxy group, and a siloxy group.

[0127] [L １１ ] L １１ is a divalent π-conjugated group. More preferred is a group represented by the following formula (4) or formula (5).

[0128]

[0129] [In formula (4), R ４ａare each independently a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted amino group, a halogen atom, an optionally substituted alkyloxycarbonyl group, an optionally substituted alkylsulfonyl group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and an optionally substituted aralkylthio group. ４ｂ R are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, and an aromatic group which may have a substituent. ４ｃ are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic group which may have a substituent. ４ａ , R ４ｂ and R ４ｃ may be bonded to each other to form a ring, l is an integer of 0 to 5, n is an integer of 0 to 5, m is an integer of 0 to 5, and l+n+m>0.

[0130] l is an integer of 0 to 5, n is an integer of 0 to 5, m is an integer of 0 to 5, and l+n+m>0. l is preferably 0 or more and 3 or less, more preferably 1 or more and 2 or less, and most preferably 1. n is preferably 0 or more and 3 or less, more preferably 1 or more and 2 or less, and most preferably 1. m is preferably 0 or more and 3 or less, more preferably 1 or more and 2 or less, and most preferably 1.

[0131] (R ４ａ ) R ４ａare each independently a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted amino group, a halogen atom, an optionally substituted alkyloxycarbonyl group, an optionally substituted alkylsulfonyl group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and an optionally substituted aralkylthio group. ４ａ Of the groups that can be selected as , from the viewpoint of compound stability and suppression of aggregation, more preferred are optionally substituted alkyl groups, optionally substituted aromatic groups, halogen atoms, optionally substituted aralkyl groups, optionally substituted alkoxy groups, optionally substituted alkylthio groups, and optionally substituted aralkylthio groups, more preferred are optionally substituted alkyl groups, optionally substituted aralkyl groups, optionally substituted alkoxy groups, optionally substituted alkylthio groups, and optionally substituted aralkylthio groups, and most preferred are optionally substituted alkoxy groups and optionally substituted alkylthio groups.

[0132] More preferred specific examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, n-butylthio group, isobutylthio group, and n-hexylthio group, and most preferred are methylthio group, ethylthio group, n-propylthio group, n-butylthio group, and n-hexylthio group. More preferred specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, isobutoxy group, and n-hexyloxy group, and most preferred are methoxy group, ethoxy group, isopropoxy group, and n-hexyloxy group.

[0133] (R ４ｂ ) R ４ｂ R are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, and an aromatic group which may have a substituent. ４ｂAmong the groups that can be selected as , more preferred are a hydrogen atom and an alkyl group which may have a substituent, and most preferred is an alkyl group which may have a substituent.

[0134] More preferred specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, and a dodecyl group, and more preferred examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-hexyl group, and most preferred examples include a methyl group, an ethyl group, an n-propyl group, and an n-hexyl group.

[0135] (R ４ｃ ) R ４ｃ R are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic group which may have a substituent. ４ｃ Among the groups selected as , an alkyl group which may have a substituent, a hydrogen atom, or an alkoxy group which may have a substituent is more preferred, and a hydrogen atom is most preferred.

[0136] These R ４ａ , R ４ｂ , R ４ｃ The substituents which may be contained in the １ From the viewpoint of the stability of the compound, more preferred specific examples of the substituent are a hydroxy group, an alkoxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a halogen atom, a silyl group, and a siloxy group, further preferred are a halogen atom, a hydroxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a silyl group, and a siloxy group, and most preferred are a hydroxy group, an acyloxy group, and a siloxy group.

[0137] Also, R ４ａ , R ４ｂ and R ４ｃmay be bonded to each other to form a ring. The ring size is preferably a 5-membered or 6-membered ring, and specific examples include a cyclopentane ring and a cyclohexane ring.

[0138]

[0139] [In formula (5), Ar ５ R each independently represents a divalent aromatic group which may have a substituent. ５ａ are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic group which may have a substituent. ５ has a substituent, the substituent and R ５ａ and may be bonded to each other to form a ring, e is an integer of 0 to 4, f is an integer of 0 to 5, and e+f>0.

[0140] e is an integer of 0 to 4, f is an integer of 0 to 5, and e+f>0. e is preferably 0 or more and 3 or less, more preferably 1 or more and 2 or less, and most preferably 1. f is preferably 1 or more and 3 or less, and the upper limit is more preferably 2 or less, and most preferably 1.

[0141] (Ar ５ ) Ar ５ each independently represents a divalent aromatic group which may have a substituent. ５ The preferred ring size in the formula (I) is a 5-membered or 6-membered ring, and specific examples include a phenyl ring and a thiophene ring.

[0142] Ar ５ Specific examples of the aromatic group selected as Ar include preferably a phenyl ring, a naphthalene ring, an anthracene ring, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, and a structure in which 2 to 5 of these aromatic groups are linked together, more preferably a phenyl ring or a thiophene ring, and most preferably a thiophene ring. ５ The substituents of ５ａand may be bonded to each other to form a ring. The ring size is preferably a 5-membered or 6-membered ring, and specific examples of the ring include a cyclopentane ring and a cyclohexane ring.

[0143] Ar ５ The aromatic group selected as １ From the viewpoint of the stability of the compound, more preferred substituents are a hydroxy group, an alkoxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a halogen atom, a silyl group, and a siloxy group, still more preferred are a halogen atom, a hydroxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a silyl group, and a siloxy group, and particularly preferred are a hydroxy group, an acyloxy group, and a siloxy group.

[0144] (R ５ａ ) R ５ａ R are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic group which may have a substituent. ５ａ A preferred embodiment of the formula (4) is ４ｃ The range is the same as that described for Ar. ５ has a substituent, the substituent and R ５ａ may be bonded to each other to form a ring.

[0145] [A １１ ] A １１ is a group represented by the following formula (6) or formula (7): １１ From the viewpoint of improving the EO coefficient by having stronger electron-withdrawing properties, it is preferable that the compound has an electron-withdrawing group as a substituent, more preferably has two or more cyano groups as substituents, further preferably has two, three or four cyano groups as substituents, and particularly preferably has two or three cyano groups as substituents.

[0146]

[0147] [In formula (6), * represents L in formula (1)]１１ This is the bonding position with R ６１ and R ６２ are each independently a group selected from the group consisting of an alkyl group which may have a substituent, an aromatic group which may have a substituent, a halogen atom, an alkylsulfonyl group which may have a substituent, and an aralkyl group which may have a substituent. ６１ is O or S.

[0148] (R ６１ , R ６２ ) R ６１ and R ６２ R are each independently a group selected from the group consisting of an alkyl group which may have a substituent, an aromatic group which may have a substituent, a halogen atom, an alkylsulfonyl group which may have a substituent, and an aralkyl group which may have a substituent. ６１ and R ６２ Among the groups selected as , the most preferred are alkyl groups which may have a substituent and aromatic groups which may have a substituent.

[0149] More preferred specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, and a dodecyl group, and more preferably a methyl group and an ethyl group, and most preferably a methyl group.

[0150] More preferred examples of the aromatic group include a phenyl ring, a naphthalene ring, and a thiophene ring, and even more preferred examples include a phenyl ring and a thiophene ring, and most preferred examples include a phenyl ring.

[0151] R ６１ and R ６２ When has a substituent, the optional substituent is a substituent group G １ From the viewpoint of compound stability, more preferred specific examples are an acyloxy group, an acyl group, a halogen atom, a silyl group, and a siloxy group, further preferred are a halogen atom and a siloxy group, and most preferred are a hydroxy group, an acyloxy group, and a siloxy group.

[0152] [X ６１ ] X ６１ is O or S. From the viewpoint of enhancing the electro-optical effect, O is more preferable.

[0153]

[0154] [In formula (7), * represents L in formula (1)] １１ This is the bonding position with R ７３ is a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted acyl group, an optionally substituted alkyloxycarbonyl group, and an optionally substituted aralkyl group.

[0155] (R ７３ ) R ７３ R is a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, an aromatic group which may have a substituent, an acyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, and an aralkyl group which may have a substituent. ７３ Among the groups selected as , a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted acyl group, an optionally substituted alkyloxycarbonyl group, or an optionally substituted aralkyl group is more preferred, an optionally substituted alkyl group, an optionally substituted acyl group, an optionally substituted alkyloxycarbonyl group, or an optionally substituted aralkyl group is more preferred, and from the viewpoint of compound stability, an optionally substituted acyl group or an optionally substituted aralkyl group is most preferred.

[0156] More preferred examples of the acyl group include a benzoyl group and an acetyl group, and the most preferred is a benzoyl group.

[0157] R ７３ When has a substituent, the optional substituent is a substituent group G １From the viewpoint of preventing aggregation of the compounds, more preferred specific examples are a hydroxy group, an alkoxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a halogen atom, a silyl group, and a siloxy group, further preferred are a halogen atom, a hydroxy group, a dialkylamino group, an aromatic amino group, an aromatic alkylamino group, an acyloxy group, an acyl group, a silyl group, and a siloxy group, and most preferred are a hydroxy group, an acyloxy group, and a siloxy group.

[0158] (X ６１ ) X ６１ is either O or S. From the viewpoint of increasing electron-withdrawing property, X ６１ is preferably O.

[0159] The compound represented by formula (1) in this embodiment may have the above-mentioned dendron bonded thereto. From the viewpoint of improving nonlinear optical activity, the dendron is preferably one represented by the general formula A or the general formula B. In the compound represented by formula (1), the bonding position with the dendron is not particularly limited. However, from the viewpoint of compound stability, Z １２ , Z １３ , L １１ , or A １１ is preferred, and Z １２ , or L １１ is more preferred.

[0160] [Specific examples of the compound represented by formula (1)] Specific examples of the compound represented by formula (1) in this embodiment are shown below, but the present invention is not limited thereto.

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259] (In the formula, OTBS represents a tert-butyldimethylsiloxy group, and Ph represents a phenyl group.)

[0260] <Nonlinear Optically Active Polymer Compound> The nonlinear optically active polymer compound of this embodiment is formed by bonding a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) described above (hereinafter also referred to as a "group derived from the compound represented by formula (1)") to a repeating unit in the polymer compound. In the nonlinear optically active polymer compound of this embodiment, the group derived from the compound represented by formula (1) may be present as part of the main chain of the repeating unit in the polymer compound, or a group derived from the compound represented by formula (1) may be bonded as part of a side chain. Furthermore, the group derived from the compound represented by formula (1) may be bonded to the dendron described above.

[0261] The polymer compound is not particularly limited, and specific examples include poly(meth)acrylic acid esters (for example, polymethyl methacrylate (PMMA), polydicyclopentanyl methacrylate (poly DCPMA), polyadamantyl methacrylate (poly AdMA), poly(DCPMA-co-MMA), poly(AdMA-co-MMA), polycarbonylaminoethyl methacrylate, etc.), polyamides, polyimides, maleimide-styrene copolymers, maleimide-olefin copolymers, maleimide-methyl methacrylate copolymers, polycarbonates, polystyrenes, polyethylenes, polymethylpentenes, polypropylenes, polyvinyl alcohols (PVA), polyethylene terephthalates, polysulfones, polyether sulfones, polyesters, polyolefins, polyphenylene sulfide, aromatic polyamines, polyamines, polyureas, silicone-based resins, epoxy-based resins, polyvinyl chloride, fluoropolymers, and copolymers thereof. The term "(meth)acrylic" refers to at least one selected from the group consisting of acrylic and methacrylic. The same applies to (meth)acrylates, etc.

[0262] In particular, from the viewpoint of general excellence as an optical material, it is more preferable to select from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimide, maleimide-styrene copolymers, maleimide-olefin copolymers, maleimide-methyl methacrylate copolymers, polycarbonates, and copolymers thereof, and from the viewpoint of compound stability, polystyrene, polymethacrylic acid esters, maleimide-styrene copolymers, and maleimide-methyl methacrylate copolymers are most preferable. Preferred examples of polymethacrylic acid esters include polyadamantyl methacrylate (polyAdMA), polyalkyloxycarbonylaminoethyl methacrylate, polymethyl methacrylate (PMMA), and poly(cyclic or linear) alkyl methacrylates.

[0263] The bonding form between the group derived from the compound represented by formula (1) and the polymer compound is not particularly limited, and may be, for example, a (thio)urethane bond, a (thio)urea bond, a (thio)amide bond, a carbon-carbon bond, a (thio)ester bond, a (thio)ether bond, or the like. (Thio)urethane means at least one selected from the group consisting of urethane and thiourethane, and the same applies to (thio)urea, (thio)ester, (thio)ether, and (thio)amide. In particular, from the viewpoint of compound stability, a urethane bond, a carbon-carbon bond, an ester bond, or an ether bond is preferred, and a urethane bond is most preferred.

[0264] The number of bonds to the polymer compound per group derived from the compound represented by formula (1) is preferably 1 to 3, more preferably 1 to 2. That is, in one embodiment, the nonlinear optically active polymer compound can be obtained by bonding to the polymer compound a group obtained by removing preferably 1 to 3, more preferably 1 to 2, hydrogen atoms from the compound represented by formula (1). The site having the removed hydrogen atom in the group derived from the compound represented by formula (1) is not particularly limited as long as it is a group having a hydrogen atom, but it can be any of the following: Z in formula (1) １１ , Z １２ , Z １３ and / or L １１is preferably a hydrogen atom possessed by Z １２ , Z １１ or L １１ is more preferably a hydrogen atom possessed by Z １２ It is most preferable that the hydrogen atom is a hydrogen atom possessed by

[0265] The nonlinear optically active polymer compound in this embodiment may have a crosslinking group. By having a crosslinking group, crosslinking can be performed after poling treatment, improving the durability of the compound. Examples of the crosslinking group include a vinyl group, an acryloyl group, a methacryloyl group, an allyl group, a thiol group, a polyamine, a polyol, an isocyanate group, a cyanoacryloyl group, a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylidene acetyl group, an α-methylcinnamylidene group, an α-methylcinnamylidene acetyl group, an α,γ-dimethylcinnamylidene group, an α,γ-dimethylcinnamylidene acetyl group, an α-phenylcinnamylidene group, an α-phenylcinnamylidene acetyl group, an α-phenoxycinnamylidene group, an α-phenoxycinnamylidene acetyl group, an α-cyanocinnamylidene group, an α-cyano Examples of the alkyl group include a cinnamylideneacetyl group, a chalcone residue, an oxetane group, an epoxy group, an isocoumarin residue, a 2,5-dimethoxystilbene residue, a thymine residue, a stilpyridinium residue, a maleimide residue, an α-phenylmaleimide residue, an anthracene residue, a 2-pyrone residue, a vinyl ether group, a trifluorovinyl ether group, a benzocyclobutene group, and derivatives thereof, and preferably an acryloyl group, a methacryloyl group, a thiol group, an isocyanate group, a blocked isocyanate group, a cinnamoyl group, a cinnamylidene group, an α-cyanocinnamylidene group, an anthracene residue, and a maleimide residue. From the viewpoint of compound stability, an isocyanate group or a blocked isocyanate group is preferred, and a blocked isocyanate group is most preferred.

[0266] [Specific Examples of Nonlinear Optically Active Polymer Compounds] Specific examples of repeating units that may be contained in the nonlinear optically active polymer compound of this embodiment are shown below, but the present invention is not limited thereto.

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280] (In the formula, Ph represents a phenyl group, and s, n, m, o, p, r, s, t, u, and v represent the molar percentage of the repeating units contained in the nonlinear optically active polymer compound, and are greater than 0 and less than 1. The repeating units contained in the nonlinear optically active polymer compound may be in any order.)

[0281] As described above, the repeating units of the nonlinear optically active polymer compound may be in any order; that is, the nonlinear optically active polymer compound may be a nonlinear optically active polymer compound that is a block copolymer, or may be a nonlinear optically active polymer compound that is a random copolymer.

[0282] <Nonlinear Optical Material> The nonlinear optical material in this embodiment is made of at least one selected from the group consisting of nonlinear optically active compounds and nonlinear optically active polymer compounds.

[0283] [Nonlinear Optically Active Compound] In one aspect of the nonlinear optical material in this embodiment, the nonlinear optically active compound described above is used. The nonlinear optically active compound is a compound represented by the above formula (1). The definitions of each group in the nonlinear optically active compound and their preferred aspects are as described above for formula (1). The nonlinear optically active compound can be used by being dispersed in a polymer material described below.

[0284] [Nonlinear Optically Active Polymer Compound] In one aspect of the nonlinear optical material in this embodiment, the nonlinear optically active polymer compound described above is used. The nonlinear optically active polymer compound is formed by bonding a group obtained by removing at least one hydrogen atom from the compound represented by the above formula (1) to the polymer compound. The definitions of each group in the nonlinear optically active polymer compound and their preferred aspects are as described above.

[0285] The content of the group derived from the compound represented by formula (1) in the nonlinear optically active polymeric compound can be expressed as the ratio of the mass of the entire nonlinear optically active polymeric compound to the mass of the group derived from the compound represented by formula (1), or can be expressed as the molar percentage of the compound derived from the compound represented by formula (1) to the sum of the repeating units of the nonlinear optically active polymeric compound. When expressed as a mass ratio, there are no particular restrictions on the content of the group derived from the compound represented by formula (1) in the nonlinear optically active polymeric compound, but from the viewpoint of the balance between the electro-optical effect and solubility, when the mass of the entire nonlinear optically active polymeric compound is taken as 100, the lower limit of the mass of the group derived from the compound represented by formula (1) is preferably 1 or more, more preferably 10 or more, and even more preferably 20 or more, and the upper limit is preferably 80 or less, more preferably 60 or less, and even more preferably 50 or less. When expressed as a molar percentage, there are no particular limitations, but from the viewpoint of the balance between the electro-optical effect and solubility, the molar percentage of the group derived from the compound represented by formula (1) relative to the total of all repeating units of the nonlinear optically active polymer compound is preferably 0.1 mol% or more as a lower limit, more preferably 1 mol% or more, and even more preferably 2 mol% or more as an upper limit, and is preferably 60 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less as an upper limit.

[0286] The content of the group derived from the compound represented by formula (1) in the nonlinear optically active polymer compound is １ It is calculated by H-NMR, absorbance measurement, gel permeation chromatography (GPC) or the like, but preferably, １ H-NMR, absorbance measurement, most preferably １ Calculated by H-NMR.

[0287] １ ​A specific method for calculating the content of groups derived from the compound represented by formula (1) in a nonlinear optically active polymer compound by H-NMR is to use the spectral integral value derived from specific hydrogen atoms of the compound represented by formula (1) as a reference and calculate the ratio of the spectral integral value derived from specific hydrogen atoms of groups possessed by each repeating unit of the nonlinear optically active polymer compound, thereby calculating the molar ratio of the compound represented by formula (1) to each repeating unit of the nonlinear optically active polymer compound. From this molar ratio, the apparent mass ratio can be calculated, and the content of groups derived from the compound represented by formula (1) in the nonlinear optically active polymer compound can be calculated.

[0288] A specific method for calculating the content of groups derived from the compound represented by formula (1) in a nonlinear optically active polymer compound by absorbance measurement is to calculate the ratio of the maximum absorbance measured using a solution in which the compound represented by formula (1) is dissolved at a predetermined concentration to the concentration, and then the ratio is calculated. The absorbance is measured using an ultraviolet-visible-near-infrared spectrophotometer.

[0289] The weight-average molecular weight of the nonlinear optically active polymer compound is not particularly limited, but is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 30,000 or more in order to improve durability. In addition, in order to improve solubility, it is preferably 500,000 or less, more preferably 400,000 or less, and even more preferably 300,000 or less. The weight-average molecular weight of the nonlinear optically active polymer compound is confirmed by measuring the weight-average molecular weight using polystyrene as a standard by GPC.

[0290] There are no particular restrictions on the molecular weight distribution of the nonlinear optically active polymer compound, but it is preferably 3 or less, more preferably 2.8 or less, and even more preferably 2.5 or less. From the viewpoint of improving performance, it is preferable that the molecular weight distribution of the nonlinear optically active polymer compound is 3 or less. The molecular weight distribution of the nonlinear optically active polymer compound is confirmed by measuring the ratio of the number average molecular weight to the weight average molecular weight using GPC when polystyrene is used as a standard.

[0291] The glass transition temperature (Tg) of the nonlinear optically active polymer compound is not particularly limited, but is generally 40°C to 400°C. To improve heat resistance, the Tg is preferably 45°C or higher, more preferably 50°C or higher, and even more preferably 80°C or higher. From the viewpoint of the poling process, the Tg is preferably 330°C or lower, more preferably 300°C or lower, even more preferably 280°C or lower, and particularly preferably 250°C or lower. The Tg of the nonlinear optically active polymer compound is confirmed by measuring the temperature corresponding to the intersection of the slope of the rising part of the endothermic process and the baseline of the baseline shift of the DSC curve accompanying the glass transition using a differential scanning calorimeter (DSC).

[0292] The decomposition temperature (Td) of the nonlinear optically active polymer compound is not particularly limited, but is preferably 0°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. It is also preferably 500°C or lower, more preferably 400°C or lower, even more preferably 350°C or lower, and particularly preferably 300°C or lower. The Td of the nonlinear optically active polymer compound is confirmed by measuring the temperature at which the mass decreases by 5% using a thermogravimetric differential thermal analyzer (TG-DTA).

[0293] [Uses of Nonlinear Optical Materials] There are no particular limitations on the uses of nonlinear optical materials, and examples thereof include nonlinear optical elements, electric field sensors, etc. Particularly preferred is nonlinear optical elements.

[0294] <Composition> The composition of this embodiment is a mixture containing the nonlinear optical material and a solvent. When the composition contains at least one compound represented by formula (1) above as the nonlinear optical material, it can further contain a polymeric material. The composition can also contain a compound exhibiting nonlinear optical activity other than the nonlinear optical material described above. The composition of this embodiment is, for example, a composition containing at least one compound represented by formula (1) above, a polymeric material, and a solvent; a composition containing at least one nonlinear optically active polymeric compound formed by bonding a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) to a repeating unit in the polymeric compound, and a solvent; or a composition containing at least one compound represented by formula (1) above, at least one nonlinear optically active polymeric compound, and a solvent.

[0295] [Nonlinear Optical Material] The nonlinear optical material in the composition is at least one selected from the group consisting of the nonlinear optically active compounds and nonlinear optically active polymeric compounds described above. The definitions and preferred embodiments of each group in the nonlinear optically active compounds and nonlinear optically active polymeric compounds are as described above.

[0296] [Solid content] The solid content refers to the amount of components other than the solvent contained in the composition. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the solid content.

[0297] Although there are no particular restrictions on the content of the nonlinear optical material in the composition, the content of the component exhibiting nonlinear optical activity is preferably 1 to 100 parts by mass, more preferably 5 to 100 parts by mass, and even more preferably 10 to 100 parts by mass, per 100 parts by mass of the solid content.

[0298] [Polymer Material] When the nonlinear optical material is a nonlinear optically active compound, it is preferable that a polymer material be used in the composition.

[0299] The polymer material is not particularly limited as long as it can disperse a nonlinear optically active compound, but a transparent polymer that does not scatter light is preferred for use as an optical material, and examples thereof include (meth)acrylate polymers (e.g., polymethyl methacrylate (PMMA)), polyamide, polyimide, polycarbonate, polydicyclopentanyl methacrylate (poly DCPMA), polyadamantyl methacrylate (poly AdMA), poly(DCPMA-co-MMA), poly(AdMA-co-MMA)), cycloolefin polymers, cycloolefin copolymers, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyester, polyolefin, polyphenylene sulfide, polyurea, silicone resins, epoxy resins, polyvinyl chloride, and fluororesins. Of these, from the viewpoint of molecular orientation, it is preferable to select from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimide, maleimide-styrene copolymers, maleimide-olefin copolymers, maleimide-methyl methacrylate copolymers, polycarbonates, and copolymers thereof, and it is more preferable to select from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimides, and polycarbonates. Furthermore, polymethyl(meth)acrylate is preferred as the poly(meth)acrylic acid ester. The above organic polymers may be used alone or in combination of two or more types.

[0300] There are no particular restrictions on the content of the polymer material in the composition, but from the viewpoint of coatability, it is preferably 0 to 99 parts by mass, more preferably 0 to 95 parts by mass, and even more preferably 0 to 90 parts by mass, per 100 parts by mass of solid content.

[0301] [Solvent] The solvent that can be used in the composition according to this embodiment is not particularly limited as long as it can dissolve the nonlinear optically active compound and the polymer material, or the nonlinear optically active polymer compound. However, preferred are organic solvents, for example, aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, and styrene; aliphatic hydrocarbons such as n-hexane and n-heptane; chlorobenzene, orthodichlorobenzene, chloroform, dichloromethane, dibromomethane, 1,2-dichloroethane, trifluoromethylbenzene, and 3-methoxybenzothiazolinone. halogenated hydrocarbons such as acetone, ethyl methyl ketone, isopropyl methyl ketone, isobutyl methyl ketone, butyl methyl ketone, diacetone alcohol, diethyl ketone, cyclopentanone, cyclohexanone, and the like; ethyl acetate, propyl acetate, phenyl acetate, 2-methoxyethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethyl lactate, γ-butyrolactone, ethyl benzoate, methyl benzoate, benzoyl benzoate, 2-ethylhexyl benzoate, 4-methylbenzoate, esters such as ethyl benzoate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; methanol, ethanol, propanol, 2-propanol, allyl alcohol, butanol, isobutyl alcohol, tert-butyl alcohol, pentanol, 2-methylbutanol, 2-methyl-2-butanol, cyclohexanol, 2-methylpentanol, octanol, 2-ethylhexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofuran, tetramethylpropanol, tetrahydrofuran ... Alcohols such as dihydrofurfuryl alcohol; glycols such as ethylene glycol, propylene glycol, hexylene glycol, trimethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether;Examples of suitable organic solvents include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; and anisole. These organic solvents may be used alone or in combination of two or more.

[0302] Of the above solvents, from the viewpoint of coatability, chlorobenzene, orthodichlorobenzene, 1,2-dichloroethane, trifluoromethylbenzene, 3-methoxybenzotrifluoride, 3-methoxybenzotrifluoride, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are more preferable, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are even more preferable, and cyclopentanone, cyclohexanone, toluene, anisole, and dibromomethane are particularly preferable.

[0303] The content of the solvent in the composition is not particularly limited, but from the viewpoint of film uniformity, it is preferably 80 to 99 parts by mass relative to 100 parts by mass of the composition, and from the viewpoint of ensuring the stability of the composition, it is more preferably 85 to 99 parts by mass, and even more preferably 85 to 98 parts by mass.

[0304] [Other Components] In addition to the nonlinear optical material, polymer material, and solvent, other components may be used in the composition.

[0305] There are no particular restrictions on the other components as long as they do not impair the purpose of using the composition. However, as long as the effects of the present invention are not impaired, the composition may contain, as necessary, antioxidants such as hydroquinone, ultraviolet absorbers such as benzophenone, rheology modifiers such as silicone oil and surfactants, adhesion aids such as silane coupling agents, crosslinkers for the polymer matrix, compatibilizers, curing agents, pigments, storage stabilizers, antifoaming agents, and the like.

[0306] The content of other components in the composition is not particularly limited, but from the viewpoint of film uniformity, the content is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the composition.

[0307] [Method for producing a composition] There are no particular limitations on the method for producing a composition, as long as it includes a step of dissolving the nonlinear optical material described above in the solvent described above. One embodiment includes a method for producing a composition that includes a step of mixing the polymer material described above with the solvent described above, and heating and stirring to dissolve, a step of mixing the solution with the nonlinear optically active compound described above, and stirring to dissolve, and a step of filtering the solution. Another embodiment includes a method for producing a composition that includes a step of mixing the nonlinear optically active polymer compound described above with the solvent described above, and stirring to dissolve, and a step of filtering the solution.

[0308] [Uses of the composition] There are no particular limitations on the uses of the composition, but it is generally used to form a nonlinear optical material into a film or thin film. The nonlinear optical material formed into a film or thin film can be used in a nonlinear optical element. That is, the composition can be used as an ink for forming a nonlinear optical element.

[0309] The method for forming a film or thin film from the composition is not particularly limited, and examples thereof include known techniques such as injection molding, press molding, soft lithography, and wet coating. Among these, wet coating methods such as spin coating, blade coating, dip coating, and inkjet coating are preferred from the viewpoints of ease of use of the production equipment, mass productivity, and film quality (uniformity of film thickness, few defects such as bubbles, etc.). One example is a method in which a composition in which the above-mentioned nonlinear optically active compound and the above-mentioned polymer material are dissolved in the above-mentioned solvent is coated on a substrate and dried. Here, "drying" refers to, for example, a process in which the substrate is placed on a heating device such as a hot plate and heated to dry, or a process in which the coated substrate is placed in a chamber and dried under vacuum, or a combination of both processes. Another example is a method in which a composition in which the above-mentioned nonlinear optically active polymer compound is dissolved in the above-mentioned solvent is coated on a substrate and dried under vacuum by heating.

[0310] <Nonlinear Optical Element> The nonlinear optical element in this embodiment is made using the nonlinear optical material described above. For example, the nonlinear optical element in this embodiment can be made using the composition described above. The nonlinear optical element is not particularly limited as long as it uses the nonlinear optical material described above and operates based on the nonlinear optical effect, and examples include wavelength conversion elements, photorefractive elements, and electro-optical elements. Of these, nonlinear optical elements that operate based on the electro-optic effect are preferred, and more specifically, electro-optical elements such as optical switches, optical modulators, and phase shifters are preferred. In one aspect, the nonlinear optical element can be an optical modulator equipped with the nonlinear optical element described above.

[0311] The electro-optical element is preferably an element having a structure in which a film containing a nonlinear optical material is formed on a substrate and sandwiched between a pair of electrodes for inputting electrical signals.

[0312] Examples of materials that can be used to form such substrates include metals such as aluminum, gold, iron, nickel, chromium, and titanium; semiconductors such as silicon, titanium oxide, zinc oxide, and gallium arsenide; glass; and plastics such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polysulfone, polyether ketone, and polyimide.

[0313] A conductive film may be formed on the surface of the substrate. Examples of materials for such a conductive film include metals such as aluminum, gold, nickel, chromium, and titanium; conductive oxides such as tin oxide, indium oxide, ITO (tin oxide-indium oxide composite oxide), and IZO (indium oxide-zinc oxide composite oxide); and conductive polymers such as polythiophene, polyaniline, polyparaphenylene vinylene, and polyacetylene. The conductive film is formed using a known dry film formation method such as vapor deposition or sputtering, or a known wet film formation method such as dip coating or electrolytic deposition, and may be patterned as needed. The conductive substrate, or the conductive film formed on the substrate as described above, is used as an electrode (hereinafter also referred to as the "lower electrode") during poling or during operation as a device.

[0314] On the surface of the substrate, if necessary, an adhesive layer for improving the adhesion between the film formed thereon and the substrate, a leveling layer for smoothing the unevenness of the substrate surface, or some intermediate layer that provides these functions all at once may be formed.The material for forming such a film is not particularly limited, and known materials such as acrylic resin, methacrylic resin, amide resin, vinyl chloride resin, vinyl acetate resin, phenolic resin, urethane resin, vinyl alcohol resin, acetal resin, etc. and their copolymers; zirconium chelate compound, titanium chelate compound, crosslinked material of silane coupling agent, etc. and their co-crosslinked material can be used.

[0315] The electro-optical element is preferably formed to include a waveguide structure, and it is particularly preferable that the above-mentioned nonlinear optical material is contained in the core layer of the waveguide.

[0316] A cladding layer (hereinafter also referred to as a "lower cladding layer") may be formed between the substrate and the core layer containing the nonlinear optical material. This lower cladding layer may be any material as long as it has a lower refractive index than the core layer and is not affected during the formation of the core layer. Preferred materials for forming the lower cladding layer include, for example, UV-curable or thermosetting resins such as acrylic, epoxy, oxetane, styrene, and silicone; polyimide; and glass.

[0317] After forming the core layer using the nonlinear optical material described above, a clad layer (hereinafter also referred to as an "upper clad layer") may be formed on top of it in the same manner as the lower clad layer, thereby forming a slab waveguide having a structure of substrate / lower clad layer / core layer / upper clad layer.

[0318] After forming the core layer, the core layer can be patterned by a known method using semiconductor process technology such as reactive ion etching (RIE), photolithography, electron beam lithography, etc. to form a channel waveguide or a ridge waveguide. Alternatively, a channel waveguide can be formed by patterning and irradiating part of the core layer with UV light, electron beam, etc., to change the refractive index of the irradiated part.

[0319] A basic electro-optical element can be formed by forming an electrode (hereinafter also referred to as "upper electrode") for applying an input electrical signal to the surface of the upper clad layer in a desired region of the upper clad layer.

[0320] When a channel waveguide or a ridge waveguide is formed as described above, the core layer pattern can be configured to have a known device structure such as a linear type, a Y-branch type, a directional coupler type, or a Mach-Zehnder type, and can be applied to known optical information communication devices such as optical switches, optical modulators, phase shifters, etc. One example of the application to an optical information communication device is an optical modulator equipped with a nonlinear optical element that operates based on the above-mentioned electro-optic effect.

[0321] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples, and the present invention can be practiced with any modifications within the scope of the present invention.

[0322] [ １ H-NMR and １３ C-NMR Measurement] Nuclear magnetic resonance spectrum ( １ H-NMR and １３ C-NMR) was measured using a JNM-ECZ400S manufactured by JEOL Ltd., and CDCl ３ was used as a solvent, and the chemical shift value δ from the internal standard tetramethylsilane is shown in ppm. The symbols used have the following meanings: s: singlet, d: doublet, dd: double doublet, t: triplet, m: multiplet, b: broad, J: coupling constant

[0323] Compound EOD-001 was synthesized by the following method.

[0324] Synthesis of Compound 2

[0325]

[0326] In a 1 L four-neck flask, compound 1 (25.3 g, 0.117 mol) was dissolved in N,N-dimethylformamide (ultra-dehydrated, 253 mL) with stirring at room temperature under a nitrogen stream, and imidazole (15.9 g, 2.0 eq.) was added. After cooling to an internal temperature of -6 ° C, tert-butyldimethylchlorosilane (TBDMSCl) (19.3 g, 1.1 eq.) was added in portions over 6 minutes at an internal temperature of 3 ° C or less, and the mixture was stirred for 1.5 hours while the internal temperature was returned to 26 ° C. The mixture was again cooled to an internal temperature of -2 ° C and quenched with purified water (250 mL). Toluene (500 L) was added and stirred for a while, then the mixture was allowed to stand to separate the oil and water, and the aqueous layer was extracted with toluene (250 mL). The two toluene layers were combined, washed sequentially with saturated aqueous sodium bicarbonate (250 mL), purified water (250 mL), and saturated saline (100 mL), and then dried over sodium sulfate. The desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a pale yellow, transparent liquid crude product 2 (46.5 g). This crude product was purified by silica gel column chromatography (Kanto Chemical Co., Inc., silica gel 60N, spherical neutral, 63-210 μm, 600 g, eluted with dichloromethane / hexane = 1 / 4) to obtain compound 2 (36.7 g, colorless, transparent liquid).

[0327] Synthesis of Compound 4

[0328]

[0329] Compound 3 (20.0 g, 53.9 mmol), toluene (270 mL, ca. 0.2 M), and 2-ethylaniline (9.79 g, 1.5 eq.) were charged into a 1 L four-neck flask at room temperature under an argon stream. After argon bubbling at room temperature for 20 minutes, tert-BuONa (12.9 g, 2.5 eq.) was added and argon bubbling was continued at room temperature for an additional 10 minutes. Palladium acetate (242 mg, 2 mol%) and (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (Binap) (1.34 g, 4 mol%) were added simultaneously in one go, and the mixture was heated and stirred at an internal temperature of 90-100°C for 5 hours. After standing overnight at room temperature, the mixture was stirred at an internal temperature of 4°C and quenched by pouring purified water (150 mL). After stirring for a while, the mixture was allowed to stand to separate the oil and water, and the aqueous layer was extracted with ethyl acetate (250 mL). The two organic layers were combined and washed successively with purified water (200 mL) and saturated brine (100 mL), and then dried over anhydrous sodium sulfate. The desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a dark brown oily crude product (36.9 g). This crude product was purified by silica gel column chromatography (Kanto Chemical Co., Inc., silica gel 60N, spherical neutral, 63-210 μm, 1.11 kg, eluted with ethyl acetate / hexane = 1 / 19) to obtain compound 4 (20.9 g, yield 90.3%, yellow transparent viscous product).

[0330] Synthesis of Compound 5

[0331]

[0332] Compound 4 (11.7 g, net weight 27.2 mmol), toluene (136 mL, ca. 0.2 M), and compound 2 (10.8 g, 1.2 eq.) were placed in a 500 mL four-neck flask at room temperature under an argon stream, and argon was bubbled through the flask for 20 minutes at room temperature. Then, tert-BuONa (6.53 g, 2.5 eq.) was added, and argon was bubbled through the flask for an additional 14 minutes at room temperature. Tris(dibenzylideneacetone)dipalladium(0) (Pd ２ (dba) ３) (498 mg, 2 mol%) and tri-tert-butylphosphonium tetrafluoroborate (631 mg, 8 mol%) were added all at once, the temperature was raised, and the mixture was stirred at an internal temperature of 90-100°C for 6.5 hours. After standing overnight at room temperature, the mixture was stirred at an internal temperature of 0°C, and purified water (150 mL) was poured in to quench the mixture. After stirring for a while, the mixture was allowed to stand to separate the oil and water, and the aqueous layer was extracted with ethyl acetate (200 mL). The two organic layers were combined and washed successively with purified water (100 mL) and saturated brine (100 mL), and then dried over anhydrous sodium sulfate. The desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a dark brown crude oil (29.1 g). This crude product was purified by silica gel column chromatography (Kanto Chemical Co., Inc., silica gel 60N, spherical neutral, 40-50 μm, 720 g, eluted with ethyl acetate / hexane=1 / 49 to 1 / 29) to obtain Compound 5 (14.1 g, yield 78.5%, yellow transparent viscous liquid).

[0333] Synthesis of Compound 6

[0334]

[0335] In a 500 mL four-neck flask, compound 5 (14.1 g, 21.3 mmol) was dissolved in tetrahydrofuran (ultra-dehydrated, 141 mL) with stirring under an argon atmosphere at room temperature. The mixture was then cooled to an internal temperature of -74°C, and a 1.6 M n-BuLi / n-hexane solution (14.6 mL, 1.1 eq.) was added dropwise over 8 minutes at an internal temperature of -65°C or lower. After stirring at an internal temperature of -68 to -74°C for 1 hour, a solution of N,N-dimethylformamide (6.23 g, 4.0 eq.) in THF (6.2 mL) was added dropwise over 4 minutes at an internal temperature of -66°C or lower. The mixture was stirred for 1 hour and 36 minutes while the internal temperature was returned to 0°C, and then cooled again to an internal temperature of -24°C. The reaction mixture was quenched by dropwise addition of purified water (44 mL) and extracted twice with ethyl acetate (140 mL). The two organic layers were combined, washed sequentially with purified water (140 mL) and saturated brine (140 mL), and dried over anhydrous sodium sulfate. The desiccant was filtered off, and the filtrate was concentrated under reduced pressure to give a crude orange viscous product (17.0 g). This crude product was purified by silica gel column chromatography (Kanto Chemical Co., Inc., silica gel 60N, spherical neutral, 40-50 μm, 600 g, eluted with dichloromethane / hexane = 1 / 1 to 2 / 1) to give Compound 6 (11.4 g, yield 76.7%, reddish-orange viscous oil).

[0336] Synthesis of compound EOD-001

[0337]

[0338] Compound 6 (4.40 g, net weight 6.38 mmol), tetrahydrofuran (ultra-anhydrous, 11 mL), ethanol (ultra-anhydrous, 22 mL), and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (3.61 g, 1.8 eq.) were charged into a 200 mL three-neck flask at room temperature under a nitrogen stream and stirred at room temperature for 20 hours. The mixture was then heated to 40°C and stirred for 4 hours. The solution was concentrated under reduced pressure and purified by medium-pressure flash column chromatography (Yamazen Corporation, Universal Column 2 L size, eluted with ethyl acetate / hexane = 1 / 4 to 2 / 1) to obtain compound EOD-001 (3.82 g, yield 60.7%, dark green solid).

[0339] The NMR measurement results of the compound EOD-001 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.77 (d, J=15.1Hz, 1H), 7.52 (d, J=28.4Hz, 6H), 7.33-7.08 (m, 12H), 6.99-6.95 (m, 3H), 6.81 (d, J=8.7Hz, 2H), 6.60 (d, J=15.6H) z, 1H), 6.31 (d, J=14.6Hz, 2H), 4.95 (s, 2H), 4.03-4.01 (m, 2H), 3 98-3.95 (m, 2H), 2.36 (q, J=7.5Hz, 2H), 0.91 (s, 9H), 0.11 (s, 6H)

[0340] Compound EOD-002 was synthesized by the following method.

[0341] Synthesis of Compound 7

[0342] The following compound 7 was synthesized in the same manner as compound 10b described in Journal of Polymer Science Part A: Polymer Chemistry, 2010, 49, 47-54.

[0343]

[0344] Synthesis of compound EOD-002

[0345]

[0346] Compound 7 (3.11 g, net weight 6.13 mmol), tetrahydrofuran (ultra-anhydrous, 100 mL), ethanol (ultra-anhydrous, 220 mL), and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (2.86 g, eq. 1.486) were charged into a 500 mL three-neck flask at room temperature under a nitrogen stream and stirred at room temperature for 6 hours. The mixture was then heated to 35°C and stirred for 4 hours. The solution was concentrated under reduced pressure and purified by medium-pressure flash column chromatography (Yamazen Corporation, Universal Column 2L size, eluted with dichloromethane / hexane / ethyl acetate = 2 / 1 / 0.1) to obtain compound EOD-002 (2.59 g, yield 52.5%, dark green solid).

[0347] The NMR measurement results of the compound EOD-002 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.79 (d, J = 15.1Hz, 1H), 7.46 (m, 12H), 7.29 (t, J = 4.6Hz, 1H), 7.15 (d , J=15.6Hz, 1H), 6.93(d, J=4.1Hz, 1H), 6.56(d, J=15.1Hz, 1H), 6.34(d d, J=9.1, 2.3Hz, 1H), 6.19 (d, J=2.3Hz, 1H), 5.18 (s, 2H), 3.73 (t, J=5. 7Hz, 2H), 3.50 (t, J=5.7Hz, 2H), 3.04 (s, 3H), 0.87 (s, 9H), 0.07 (s, 6H)

[0348] An organic compound represented by structural formula (A) described in Japanese Patent No. 4453383 was used as compound EOD-003.

[0349]

[0350] Compound EOD-004 was synthesized by the following method.

[0351] Synthesis of Compound 8

[0352]

[0353] Under a nitrogen stream, 4-bromosalicylaldehyde (20.1 g, 0.10 mol), potassium carbonate (27.6 g, 0.20 mol), and DMF (200 mL) were added to a 500 mL three-neck flask and stirred. After cooling to 0°C in an ice bath, benzyl bromide (20.5 g, 0.12 mol) was added dropwise and stirred at 0°C for 2 hours. After the reaction, the temperature was raised to room temperature, and the reaction solution was poured into water (400 mL) and extracted with ethyl acetate (400 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 8 (7.60 g, yield 77.6%).

[0354] Synthesis of Compound 9

[0355]

[0356] Under a nitrogen stream, compound 8 (16.3 g, 56.1 mmol), diethyl-2-thienylmethylphosphonate (15.8 g, 67.3 mmol), and THF (163 mL) were mixed in a 500 mL three-neck flask and cooled to 0°C in an ice bath. Potassium tert-butoxide (6.92 g, 61.7 mmol) was slowly added to the reaction solution, and the mixture was then warmed to room temperature and stirred for 4 hours. After the reaction, the reaction solution was poured into water (100 mL) and extracted with ethyl acetate (400 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 9 (17.4 g, yield 83.7%).

[0357] Synthesis of Compound 10

[0358]

[0359] Under a nitrogen stream, a 500 mL three-neck flask was charged with a solution of compound 9 (17.0 g, 45.8 mmol) and 2,4,6-trimethylaniline (9.30 g, 68.7 mmol) in toluene (229 mL), and sodium tert-butoxide (11.0 g, 114.5 mmol), palladium acetate (103 mg, 0.46 mmol), and 2-2'bis(diphenylphosphino-1-1')-binaphthyl (570 mg, 0.92 mmol) were added, followed by stirring at 100°C for 10 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 10 (13.7 g, yield 70.3%).

[0360] Synthesis of Compound 11

[0361]

[0362] In a 1 L flask, 2-(N-methylanilino)ethanol (80.0 g, 0.53 mol), pyridine (400 mL), and 1,4-dioxane (400 mL) were mixed and cooled to 0°C, and then iodine (201 g, 0.80 mol) was added. The reaction solution was then heated to 35°C and stirred for 7 hours. After completion of the reaction, the reaction solution was diluted with DCM (800 mL) and washed with a saturated aqueous solution of sodium thiosulfate. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 11 (74.0 g, yield 50.4%).

[0363] Synthesis of Compound 12

[0364]

[0365] Under a nitrogen stream, a solution of compound 11 (20.0 g, 72.2 mmol) in DMF (200 mL) in a 500 mL flask was cooled to 0°C, and then tert-butyldimethylchlorosilane (11.90 g, 79.4 mmol) was added. The reaction solution was then heated to 25°C and stirred for 2 hours. After the reaction, the reaction solution was poured into water (200 mL) and extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 12 (22.9 g, yield 81.1%).

[0366] Synthesis of Compound 13

[0367]

[0368] In a 500 mL three-neck flask, a solution of compound 10 (11.9 g, 28.0 mmol) and compound 12 (13.1 g, 33.6 mmol) in toluene (186 mL) was added with sodium tert-butoxide (6.72 g, 69.9 mmol), Pd ２ (dba) ３ (512 mg, 0.56 mmol) and tri-tert-butylphosphonium tetrafluoroborate (649 mg, 2.24 mmol) were added, and the mixture was stirred at 100°C for 6.5 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 13 (12.1 g, yield 62.9%).

[0369] Synthesis of Compound 14

[0370]

[0371] Under a nitrogen stream, a solution of compound 13 (12.0 g, 17.4 mmol) in THF (120 mL) in a 500 mL three-neck flask was cooled to -78 °C, and n-BuLi (1.6 M in hexane, 12 mL) was added. After stirring at -78 °C for 1 hour, DMF (5.4 mL) diluted with THF (5.0 mL) was added, and the mixture was heated to 0 °C and stirred for 3 hours. After the reaction, water (50 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 14 (9.09 g, yield 72.8%).

[0372] Synthesis of EOD-004

[0373]

[0374] In a 300 mL three-neck flask, under a nitrogen stream, ethanol (40 mL) was added to a solution of compound 14 (0.50 g, 0.83 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (0.34 g, 10.8 mmol) in tetrahydrofuran (20 mL), and the mixture was stirred at room temperature for 10 hours. After completion of the reaction, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain EOD-004 (390 mg, yield 52.2%).

[0375] The NMR measurement results of the compound EOD-004 are shown below. １ H-NMR (400MHz, CHLOROFORM-D) δ7.77 (d, J = 15.1Hz, 1H), 7.57-7.48 (m, H), 7.35-7.33 (m, 3H), 7.28 (d, J = 4.6Hz, 2H), 7.15 (d, J = 16.0Hz, 1H), 6.95-6.89 (m, 5H), 6.59-6.56 ( m, 3H), 6.36-6.29 (m, 2H), 4.97 (s, 2H), 3.76 (t, J = 6.2Hz, 2H), 3.44 (t, J = 5.9Hz, 2H), 2 96 (s, 3H), 2.34 (s, 3H), 1.95 (t, J=14.9Hz, 6H), 0.92-0.83 (m, 9H), 0.07-0.01 (m, 6H)

[0376] Compound EOD-005 was synthesized by the following method.

[0377] Synthesis of Compound 1-2

[0378]

[0379] In a 1 L flask, a solution of 2-(N-methylanilino)ethanol (151 g, 1.00 mol) in N,N-dimethylformamide (1.51 L) was cooled to 0°C, and then a solution of N-bromosuccinimide (NBS) (187 g) in N,N-dimethylformamide (560 mL) was added. The reaction solution was then stirred at room temperature for 7 hours. After completion of the reaction, the reaction solution was diluted with DCM (800 mL) and washed with saturated aqueous sodium thiosulfate. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 1-2 (214 g, yield 93.2%).

[0380] Synthesis of Compound 1-3

[0381]

[0382] Under a nitrogen stream, a solution of compound 1-2 (25.3 g, 11.7 mmol) and imidazole (15.9 g) in DMF (253 mL) was cooled to 0°C in a 500 mL flask, and then tert-butyldimethylchlorosilane (19.3 g) was added. The reaction solution was then heated to 25°C and stirred for 1.5 hours. After the reaction, the reaction solution was poured into water (200 mL) and extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 1-3 (22.9 g).

[0383] Synthesis of Compound 1-4

[0384]

[0385] In a 500 mL three-neck flask, under a nitrogen atmosphere, a solution of compound 1-3 (6.10 g, 20.0 mmol) and 2,4,6-trimethylaniline (6.9 g, 20.0 mmol) in toluene (100 mL) was added with sodium tert-butoxide (4.8 g), Pd ２ (dba) ３(45 mg) and tri-tert-butylphosphonium tetrafluoroborate (250 mg) were added, and the mixture was stirred at 100°C for 16 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 1-4 (8.6 g).

[0386] Synthesis of Compound 1-5

[0387]

[0388] Under a nitrogen stream, a solution of isophorane oxide (50.9 g, 0.330 mol) in methanol (330 mL) was cooled to -13°C in a 500 mL three-neck flask, and 100 mL of a 28% by mass sodium methoxide methanol solution was added, followed by heating under reflux with stirring for 5 hours. After the reaction, water (200 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (200 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 1-5 (41.2 g).

[0389] Synthesis of Compound 1-6

[0390]

[0391] Under a nitrogen stream, in a 500 mL three-neck flask, compound 8 (26.2 g) and 77.8 mL of a 28% by mass aqueous solution of sodium hydroxide were added to a solution of compound 1-5 (41.2 g) in ethanol (142 mL), and the mixture was then heated under reflux with stirring for 5 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 1-6 (52.90 g).

[0392] Synthesis of Compounds 1-7

[0393]

[0394] Under a nitrogen stream, 6.23 g of sodium hydride (concentration 60% by mass in liquid paraffin) was added to a solution of compound 1-6 (52.9 g) in tetrahydrofuran (120 mL) in a 500 mL three-neck flask. The mixture was then cooled to -4°C, and a solution of diethyl cyanomethylphosphonate (27.60 g) in tetrahydrofuran (120 mL) was slowly added dropwise with stirring. The mixture was then stirred at room temperature for 1 hour. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 1-7 (39.7 g, yield 71%).

[0395] Synthesis of Compound 1-8

[0396]

[0397] In a 500 mL three-neck flask, a solution of compound 1-4 (32.0 g, 68.9 mmol) and compound 1-7 (27.67 g) in toluene (689 mL) was added with sodium tert-butoxide (16.56 g), Pd ２ (dba) ３ (1.26g), tert-Bu ３ PHBF ４ (1.60 g) was added, and the mixture was stirred at 100°C for 5 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 1-8 (42.7 g, yield 78.3%).

[0398] Synthesis of Compounds 1-9

[0399]

[0400] Under a nitrogen stream, a solution of compound 1-8 (5.35 g, 6.84 mmol) in toluene (137 mL) was cooled to -76°C in a 500 mL three-neck flask, and a 1 M diisobutylaluminum hydride n-hexane solution (8.5 mL) was slowly added dropwise to the solution, followed by stirring at a temperature range of -68 to -62°C for 4.5 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 1-9 (2.40 g, yield 44.8%).

[0401] Synthesis of EOD-005

[0402]

[0403] In a 300 mL three-neck flask, under a nitrogen stream, ethanol (40 mL) was added to a solution of compound 1-9 (2.20 g, 2.80 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (1.15 g) in tetrahydrofuran (20 mL), and the mixture was stirred at room temperature for 10 hours. After completion of the reaction, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain EOD-005 (1.30 g, yield 42.9%).

[0404] The NMR measurement results of the compound EOD-005 are shown below. １ H-NMR (400MHz, CHLOROFORM-D) δ7.58-7.30 (m, 14H), 6.91 (t, 3H), 6.72 (d, J=4.6Hz, 1H), 6.55 (m, 2H), 6.29-6.41 (m, 3H), 4 91 (s, 2H), 3.76 (t, J=6.2Hz, 2H), 3.49-3.41 (m, 5H), 2.44 (s, 2H), 2.31 (s, 3H), 1.95 (s, 6H), 1.51 (s, 2H), 0.92-0.83 (m, 6H), 0.07-0.01 (m, 6H)

[0405] Compound EOD-006 was synthesized by the following method.

[0406] Synthesis of Compound 2-0

[0407]

[0408] Under a nitrogen atmosphere, a 500 mL three-necked flask was charged with a solution of 1-benzyloxy-3-bromobenzene (120 g, 456 mmol) and 2,4,6-trimethylaniline (92.49 g) in toluene (2.28 L), sodium tert-butoxide (4.8 g), Pd ２ (dba) ３ (8.35 g) and tri-tert-butylphosphonium tetrafluoroborate (10.59 g) were added, and the mixture was stirred at 90°C for 8 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2-0 (77.33 g, yield 53.4%).

[0409] Synthesis of Compound 2-1

[0410]

[0411] Under a nitrogen stream, in a 500 mL three-neck flask, 14.6 g of sodium hydride (concentration 60% by mass in liquid paraffin) was added to a solution of compound 2-0 (77.0 g, 0.243 mol) in N,N-dimethylformamide (770 mL), and the mixture was cooled to 0 ° C. While stirring, a solution of (2-bromoethoxy)-tert-butyldimethylsilane (69.6 g) in DMF (70 mL) was slowly added dropwise, then the temperature was raised to 70 ° C. and the mixture was stirred for 1.5 hours, and then stirred at 70 ° C. for 8 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2-1 (24.4 g, yield 27.8%).

[0412] Synthesis of Compound 2-2

[0413]

[0414] In a 500 mL three-neck flask, a solution of compound 2-1 (58.0 g, 0.122 mol) in N,N-dimethylformamide (580 mL) was cooled to 0°C, and N-bromosuccinimide (21.7 g) was slowly added thereto. The mixture was then cooled to 0°C and stirred at room temperature for 3.5 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2-2 (55.9 g, yield 81.0%).

[0415] Synthesis of Compound 2-3

[0416]

[0417] In a 500 mL three-neck flask, a solution of compound 2-2 (50.0 g, 90.2 mmol) in tetrahydrofuran (500 mL) was cooled to -74°C, then cooled to -78°C, and 1.6 M n-butyllithium hexane solution (62.0 mL) was slowly added dropwise and stirred for 30 minutes. N,N-dimethylformamide (27.9 mL) was then slowly added dropwise, and the mixture was stirred for 30 minutes, followed by stirring at room temperature for 3.5 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2-3 (30.8 g, yield 65.1%).

[0418] Synthesis of Compound 2-4

[0419]

[0420] Under a nitrogen stream, a solution of isophorane oxide (19.2 g, 0.125 mol) in ethylene glycol (376 mL) was cooled to 0°C in a 500 mL three-neck flask, and 7.48 g of sodium hydride (concentration 60% by mass in liquid paraffin) was added, followed by stirring at room temperature for 1 hour. After the reaction, cooled water (200 mL) was added to the reaction solution, and the mixture was extracted with normal hexane / ethyl acetate = 1 / 1 (v / v) (200 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2-4 (11.5 g, yield 46.6%).

[0421] Synthesis of Compound 2-5

[0422]

[0423] Under a nitrogen stream, compound 2-4 (12.1 g) and piperidine (54.8 mL) were added to a solution of compound 2-3 (27.9 g) in ethanol (142 mL) in a 500 mL three-neck flask, and the mixture was heated to reflux at 78°C for 16 hours with stirring. After the reaction, water (200 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (200 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2-5 (27.8 g, yield 73.5%).

[0424] Synthesis of Compound 2-6

[0425]

[0426] Under a nitrogen stream, diethyl cyanomethylphosphonate (10.9 g) was added to a solution of compound 2-5 (21.0 g, 30.70 mmol) in tetrahydrofuran (307 mL) in a 500 mL three-neck flask, and the mixture was then cooled to -19°C. Sodium tert-butoxide (5.90 g) was added with stirring, and the mixture was then stirred at 40°C for 12 hours. After the reaction, water (300 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (300 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2-6 (15.8 g, yield 72.0%).

[0427] Synthesis of Compound 2-7

[0428]

[0429] Under a nitrogen stream, a 500 mL three-neck flask was charged with a solution of compound 2-6 (12.6 g, 17.8 mmol) in toluene (360 mL) and cooled to -75°C. A 1 M diisobutylaluminum hydride solution in n-hexane (40.0 mL) was slowly added dropwise to the solution, followed by stirring at -75°C for 2 hours and then at -40°C for 1 hour. The solution was cooled to -75°C, and a 1 M diisobutylaluminum hydride solution in n-hexane (19.6 mL) was slowly added dropwise to the solution, followed by stirring at -40°C for 2 hours. After the reaction, ethyl acetate (200 mL) was added to the reaction solution, which was then washed with water (400 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2-7 (8.09 g, yield 58.4%).

[0430] Synthesis of EOD-006

[0431]

[0432] Under a nitrogen stream, ethanol (20 mL) was added to a solution of compound 2-7 (1.15 g, 0.70 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (0.24 g) in tetrahydrofuran (10 mL) in a 300 mL three-neck flask, and the mixture was stirred at room temperature for 10 hours. After completion of the reaction, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain EOD-006 (700 mg, yield 98.7%).

[0433] The NMR measurement results of the compound EOD-006 are shown below. １ H-NMR (400MHz, CHLOROFORM-D) δ7.85-8.14 (s, 1H), 7.27-7.65 (m, 14H), 6.82-7.00 (m, 3H), 6.62-6.80 (m, 1H) , 6.24-6.49 (m, 1H), 3.36-4.08 (m, 8H), 2.17-2.65 (m, 7H), 1.75-2.17 (m, 9H), 0.73-1.15 (m, 14H), 0.22 (s, 6H)

[0434] Compound EOD-007 was synthesized by the following method.

[0435]

[0436] In a 200 mL three-neck flask, a solution of EOD-006 (0.70 g, 0.986 mmol) in tetrahydrofuran (45 mL) was ice-cooled, and 1 M hydrochloric acid (9.86 mL) was slowly added under ice-cooling, followed by stirring at room temperature for 4 hours. After completion of the reaction, saturated brine (50 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (50 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain EOD-007 (0.42 g, yield 86.7%).

[0437] The NMR measurement results of the compound EOD-007 are shown below. １ H-NMR (400MHz, CHLOROFORM-D) δ7.97 (s, 1H), 7.67-7.25 (m, 15H), 6.93 (s, 2H), 6.74 (d, J = 12.3Hz, 1H), 6.37 (d, J = 14.2H) z, 1H), 5.08 (d, J=57.2Hz, 2H), 3.87-3.67 (m, 8H), 2.45-2.17 (m, 7H), 2.06-1.79 (m, 9H), 1.55 (s, 1H), 1.09-0.84 (m, 6H)

[0438] Compound EOD-008 was synthesized by the following method.

[0439] The following compound 5-1 was synthesized in the same manner as compound RH described in MATERIALS CHEMISTRY FRONTIERS, 2018, 2, 901-909.

[0440]

[0441] Synthesis of Compound 5-2

[0442]

[0443] In a 200 mL three-neck flask, a solution of compound 2-7 (0.88 g, 1.25 mmol), compound 5-1 (0.661 g, 1.50 mmol), and 4-dimethylaminopyridine (DMAP) (15.2 mg) in chloroform (35 mL) was ice-cooled under a nitrogen stream, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCl.HCl) (6.21 g) was slowly added under ice-cooling, followed by stirring for 4 hours at 65° C. After completion of the reaction, the mixture was concentrated under reduced pressure and purified by silica gel chromatography to obtain compound 5-2 (0.48 g, yield 34.0%).

[0444] Synthesis of EOD-008

[0445]

[0446] Under a nitrogen atmosphere, ethanol (2 mL) was added to a solution of compound 5-2 (215 mg, 0.19 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (0.066 g) in tetrahydrofuran (2 mL) in a 200 mL three-neck flask, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain EOD-008 (180 mg, yield 66.3%).

[0447] The NMR measurement results of the compound EOD-008 are shown below. １ H-NMR (400MHz, CHLOROFORM-D) δ7.84 (s, 1H), 7.53-7.25 (m, 21H), 7 .00-6.97 (m, 4H), 6.90 (s, 2H), 6.68 (d, J=12.8Hz, 2H), 6.26 (d, J=14 .2Hz, 1H), 4.91 (s, 6H), 4.52 (s, 2H), 3.98 (s, 2H), 3.70 (s, 2H), 3.56 (s, 2H), 2.38 (d, J=48.9Hz, 6H), 0.96 (d, J=28.4Hz, 5H), 0.84 (s, 9H)

[0448] Compound EOD-009 was synthesized by the following method.

[0449] Synthesis of Compound 3-1

[0450]

[0451] In a three-neck flask, 2-(methylamino)ethanol (179.4 g) was dissolved in dichloromethane (3.0 L), and imidazole (271.0 g) was added, followed by cooling to -9°C. While stirring at -9°C, tert-butyldimethylsilyl chloride (300.0 g) was slowly added, and the mixture was stirred at a temperature ranging from -9 to 5°C for 15 hours. After adding 3 L of water, the organic layer was separated and concentrated under reduced pressure to obtain compound 3-1 (350.8 g).

[0452] Synthesis of Compound 3-2

[0453]

[0454] In a three-necked flask, under an argon stream, compound 3-1 (64.77 g) and B2307 (75.00 g) were dissolved in toluene (750 mL), sodium tert-butoxide (60.26 g) was added, and the mixture was heated to 60 °C to prepare solution A. In a separate container, under an argon stream, tris(dibenzylideneacetone)dipalladium (2.61 g) and (4-dimethylaminophenyl)di-tert-butylphosphine (Amphos) (3.03 g) were dissolved in toluene (75 mL), and the mixture was stirred at 60 °C for 25 minutes. The solution was then slowly added dropwise to solution A and stirred at 100 °C for 5 hours and 30 minutes. The reaction solution was then purified by silica gel column chromatography to obtain compound 3-2 (87.61 g).

[0455] Synthesis of Compound 3-3

[0456]

[0457] In a three-neck flask, compound 3-2 (87.55 g) was dissolved in N,N-dimethylformamide (876 mL) and cooled to −10° C., and then N-bromosuccinimide (271.0 g) was slowly added with stirring, followed by stirring for 3 hours at a temperature between 0° C. and 10° C. The reaction solution was then purified by silica gel column chromatography to obtain compound 3-3 (95.69 g).

[0458] Synthesis of Compound 3-4

[0459]

[0460] In a three-neck flask, under a nitrogen stream, compound 3-3 (90.00 g) was dissolved in THF (900 mL). After cooling to -74°C, 1.6 M n-butyllithium hexane solution (137.4 mL) was slowly added with stirring, and the mixture was stirred at -78°C for 30 minutes. Thereafter, a mixed solution of DMF (62 mL) and THF (60 mL) was slowly added dropwise to the reaction solution. 500 mL of water was added to the reaction solution, and the organic layer was separated. After washing with saturated saline (300 mL), the organic layer was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain compound 3-4 (60.03 g).

[0461] Synthesis of Compound 3-5

[0462]

[0463] Under a nitrogen stream, compound 2-4 (5.12 g) and piperidine (8.50 mL) were added to a solution of compound 3-4 (8.60 g) in ethanol (20 mL) in a 100 mL three-neck flask, and the mixture was heated to reflux at 78°C for 6 hours with stirring. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with dichloromethane (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 3-5 (6.87 g, yield 44.5%).

[0464] Synthesis of Compound 3-6

[0465]

[0466] Under a nitrogen stream, diethyl cyanomethylphosphonate (3.8 g) was added to a solution of compound 3-5 (8.3 g) in tetrahydrofuran (83 mL) in a 200 mL three-neck flask, and the mixture was then cooled to -75°C. A 1.6 M n-butyllithium hexane solution (10.1 mL) was slowly added while stirring, and the mixture was then stirred at 40°C for 2 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 3-6 (15.0 g, yield 57.9%).

[0467] Synthesis of Compound 3-7

[0468]

[0469] Under a nitrogen stream, a solution of compound 3-6 (4.55 g, 7.55 mmol) in toluene (89 mL) was cooled to -78°C in a 500 mL three-neck flask, and a 1 M diisobutylaluminum hydride n-hexane solution (9.43 mL) was slowly added dropwise to the solution, followed by stirring at -78°C for 2 hours and then at -40°C for 1 hour. After the reaction, ethyl acetate (100 mL) was added to the reaction solution, and the mixture was washed with water (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 3-7 (3.20 g, yield 70.0%).

[0470] Synthesis of Compound 3-8

[0471]

[0472] In a 200 mL three-neck flask, a solution of compound 3-7 (0.70 g, 0.986 mmol) in tetrahydrofuran (45 mL) was ice-cooled, and 1 M hydrochloric acid (9.86 mL) was slowly added under ice-cooling, followed by stirring at room temperature for 4 hours. After completion of the reaction, saturated brine (50 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (50 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 3-8 (0.42 g, yield 86.7%).

[0473] Synthesis of EOD-009

[0474]

[0475] In a 300 mL three-neck flask, under a nitrogen stream, ethanol (5 mL) was added to a solution of compound 3-8 (0.70 g, 0.9 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (0.264 g) in tetrahydrofuran (2 mL), and the mixture was stirred at room temperature for 10 hours. After completion of the reaction, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain EOD-009 (230 mg, yield 34.1%).

[0476] The NMR measurement results of the compound EOD-009 are shown below.１ H-NMR (400MHz, CHLOROFORM-D) δ7.92 (d, J = 16.5Hz, 1H), 7.57-7.30 (m, 13H), 6.71 (d, J = 18.3Hz, 1H), 6.40-6.32 (m, 2H), 5.29 ( s, 3H), 5.21-5.13 (m, 2H), 3.92-3.85 (m, 2H), 3.82-3.74 (m, 4H), 3.51-3.48 (m, 2H), 2.44 (t, J=10.3Hz, 2H), 1.03-0.80 (m, 10H)

[0477] Compound EOP-001 was synthesized by the following method.

[0478] Synthesis of Compound 4-1

[0479]

[0480] In a 300 mL three-neck flask, a solution of EOD-001 (2.50 g, 3.62 mmol) in tetrahydrofuran (100 mL) was ice-cooled, and 1 M hydrochloric acid (36.2 mL) was slowly added under ice-cooling, followed by stirring at room temperature for 4 hours. After completion of the reaction, saturated brine (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 4-1 (2.0 g, yield 95.6%).

[0481] Synthesis of base polymer 1

[0482]

[0483] Methyl methacrylate (MMA) (12.8 g, 127.8 mmol), 1-adamantyl methacrylate (28.2 g, 128.0 mmol), and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (16.1 g, 64.1 mmol) were dissolved in deoxygenated toluene (110 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (171 mg, 0.69 mmol) was added. The reaction solution was then heated to 60°C and stirred for 6 hours, then heated to 70°C and stirred for an additional 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to hexane (120 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with hexane (120 mL) and dried in vacuo to obtain base polymer 1 (35.0 g, yield 61%).

[0484] The molecular weight of the obtained base polymer 1 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mmID×150 mmL, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.). The weight average molecular weight Mw was 114,000 and the number average molecular weight Mn was 34,000.

[0485] Synthesis of base polymer 2

[0486]

[0487] Styrene (3.00 g, 25.4 mmol) and N-ethylmaleimide (3.18 g, 25.4 mmol) were dissolved in anhydrous DMF (78 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (67 mg, 0.20 mmol) was added. The reaction solution was then heated to 60°C and stirred for 6 hours, then heated to 70°C and stirred for an additional 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to hexane (120 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with hexane (120 mL) and dried in vacuo to obtain base polymer 2 (3.2 g, yield 52%).

[0488] The molecular weight of the obtained base polymer 2 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mmID×150 mmL, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.), and two peaks were observed. The first peak had a weight average molecular weight Mw of 114,000 and a number average molecular weight Mn of 34,000, and the second peak had a weight average molecular weight Mw of 501,000.

[0489] Synthesis of EOP-001

[0490]

[0491] Base polymer 1 (0.573 g) and compound 4-1 (300 mg) were dissolved in anhydrous 1,4-dioxane (32.7 mL) under a nitrogen stream, and dibutyltin dilaurate (DBTDL) (8 μL) was added. The mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, anhydrous methanol (0.17 mL) was added, and the mixture was stirred in an oil bath at 110°C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (150 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 60°C to obtain EOP-001 (0.42 g). The content of the group in EOP-001 in which one hydrogen atom has been removed from compound 4-1 was calculated from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and the content of the group in which one hydrogen atom has been removed from compound 4-1 was 38% by mass.

[0492] Compound EOP-002 was synthesized by the following method.

[0493]

[0494] Under a nitrogen stream, base polymer 1 (0.141 g) and compound 4-1 (100 mg) were dissolved in anhydrous 1,4-dioxane (6.0 mL), dibutyltin dilaurate (DBTDL) (7 μL) was added, and the mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, anhydrous methanol (0.11 mL) was added, and the mixture was stirred in an oil bath at 110°C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (50 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 60°C to obtain EOP-002 (0.42 g). The content of the group in which one hydrogen atom has been removed from compound 4-1 contained in EOP-002 was calculated from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and the content of the group in which one hydrogen atom has been removed from compound 4-1 was 47% by mass.

[0495] The following equipment was used in the evaluations below.・Spin coater: MS-A150 manufactured by Mikasa Corporation ・Hot plate: HP-1SA manufactured by AS ONE Corporation ・Oven: Small high-temperature chamber STH-120 manufactured by ESPEC Corporation ・Film thickness measurement: Optical interferometer VertScan manufactured by Hitachi High-Tech Corporation ・Gold evaporation: EX-400-C08 manufactured by ULVAC, Inc. ・Vacuum constant temperature dryer: DP-23 manufactured by Yamato Scientific Co., Ltd. ・Temperature controller: Model 3060 manufactured by Lake Shore Cryotronics ・Voltage application device: 2470 Source Meter manufactured by KEITHLEY ・Laser light source: TSL-570 manufactured by santec Corporation ・Function generator: T3AFG10 manufactured by Teledyne LeCroy ・Lock-in amplifier: Digital lock-in amplifier LI5600 manufactured by NF Corporation

[0496] [Evaluation of Example 1] (Cleaning of ITO Substrate) A thin-film ITO substrate manufactured by EHC Corporation (having a 9 nm thick ITO film on one side of a 0.7 mm thick glass plate; sheet resistance of the ITO film side: 519 to 578 Ω / □) was cleaned in ultrapure water using an ultrasonic cleaner to obtain an ITO substrate to be used for coating the intermediate layer composition. Here, the glass plate included in the ITO substrate corresponds to the carrier, and the ITO film corresponds to the electrode.

[0497] (Preparation of Substrate with Intermediate Layer Film) A compound represented by the following structural formula (hereinafter also referred to as "Material 1") was dissolved in cyclohexanone to a concentration of 3 mass %, and the solution was filtered through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.22 μm to obtain Intermediate Layer Composition A. Using a spin coater, Intermediate Layer Composition A was applied to the surface of the ITO substrate on which the ITO film was provided.

[0498]

[0499] The ITO substrate coated with intermediate layer composition A was prebaked on a hot plate at 60°C for 1 minute, and then heat-treated in an oven at 230°C for 30 minutes to harden intermediate layer composition A, thereby obtaining a substrate with an intermediate layer film formed on the ITO substrate. The film thickness of the obtained film was measured and found to be 0.17 µm.

[0500] Example 1 (Preparation of Film 1) A mixture of compound EOD-001 and polymer material PMMA was dissolved in cyclohexanone at a mass ratio of 30:70 to a total solids concentration of 13 mass%, and the solution was filtered through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.22 μm to obtain composition 1. Using a spin coater, composition 1 was applied onto the surface of a substrate with an intermediate layer film on the side where the intermediate layer was provided.

[0501] The substrate with the intermediate layer film coated with the composition 1 was prebaked on a hot plate at 60°C for 1 minute, and then subjected to a thermal drying treatment at 85°C for 15 hours in a vacuum constant temperature dryer to remove the solvent, thereby obtaining a substrate with a film (film 1) containing 30% by mass of nonlinear optical material formed on the substrate with the intermediate layer film (substrate 1). The film thickness of film 1 was measured and found to be 1.36 μm. The obtained film 1 had a sufficient thickness to exhibit electro-optical effects in devices such as optical modulators and optical switches.

[0502] (Preparation of Film 2) A substrate with a film containing a nonlinear optical material (Substrate 2) was obtained in the same manner as in preparation of Film 1, except that the mixing ratio of EOD-001 and the polymer material PMMA was 40:60 (mass ratio). The film thickness of the obtained film (Film 2) was measured and found to be 1.24 μm.

[0503] (Preparation of Film 3) A substrate with a film containing a nonlinear optical material (Substrate 3) was obtained in the same manner as in preparation of Film 1, except that the mixing ratio of EOD-001 and the polymer material PMMA was 50:50 (mass ratio). The film thickness of the obtained film (Film 3) was measured and found to be 1.11 μm.

[0504] (Preparation of Substrates with Electrodes) The surface of the film containing the nonlinear optical material on each of the prepared substrates 1 to 3 was coated with a film having a thickness of 50 nm and an area of ​​30 mm. ２ Gold electrodes were formed by vapor deposition to form a circular shape, yielding electrode-attached substrates 1 to 3. Electrode-attached substrates 1 to 3 have the following layer structure and were used to evaluate the electro-optical effect. Layer structure: ITO substrate (glass substrate + ITO film) / intermediate layer film / film containing nonlinear optical material / gold electrode

[0505] [Poling Treatment] The prepared electrode-attached substrates 1 to 3 were heated to 116°C using a temperature controller, and then cooled to room temperature with liquid nitrogen while applying a voltage of 100 V / μm using a voltage application device, thereby obtaining poled substrates 1 to 3 in which the nonlinear optical material in the electrode-attached substrates 1 to 3 was electrically oriented.

[0506] [Electro-optical Effect Measurement] The electro-optical coefficients of the poled substrates 1 to 3 were measured at a wavelength of 1.31 μm using a method similar to that disclosed in C. C. Teng et al., Appl. Phys. Lett., 56, p. 1734 (1990) and Y. Shuto et al., J. Appl. Phys., 77, p. 4632 (1995). From the measurement results, the increase in the electro-optical coefficient of substrate 2 relative to that of substrate 1 ("30% to 40% increase in the electro-optical coefficient") [times], and the increase in the electro-optical coefficient of substrate 3 relative to that of substrate 2 ("40% to 50% increase in the electro-optical coefficient") [times] were calculated. The results are shown in Table 1. (30% to 40% increase in electro-optic coefficient) = electro-optic coefficient of substrate 2 / electro-optic coefficient of substrate 1 (40% to 50% increase in electro-optic coefficient) = electro-optic coefficient of substrate 3 / electro-optic coefficient of substrate 2

[0507] Example 2 A substrate was prepared and the electro-optical effect was measured in the same manner as in Example 1, except that compound EOD-004 was used instead of compound EOD-001. The results are shown in Table 1.

[0508] [Example 7] A substrate was prepared and the electro-optical effect was measured in the same manner as in Example 2, except that polymer base polymer 2 was used instead of the polymer PMMA, an ITO substrate was used instead of the substrate with an intermediate layer film, and a poling treatment was performed at 50 V / μm. The results are shown in Table 1.

[0509] Comparative Example 1 Except for using compound EOD-002 instead of compound EOD-001, a substrate was prepared and the electro-optical effect was measured in the same manner as in Example 1. The results are shown in Table 1.

[0510] Comparative Example 2 A substrate was prepared and the electro-optical effect was measured in the same manner as in Example 1, except that compound EOD-003 was used instead of compound EOD-001. The results are shown in Table 1.

[0511]

[0512] As is clear from Table 1, in Examples 1, 2, and 7, even when the concentration of the nonlinear optical material increased, the increase in the electro-optic coefficient was greater than 1, indicating that the electro-optic coefficient continued to improve even when the concentration of the nonlinear optical material became high. On the other hand, in Comparative Examples 1 and 2, the increase in the electro-optic coefficient from 40% by mass to 50% by mass was 1.0, indicating that the electro-optic coefficient no longer improved when the concentration of the nonlinear optical material became high.

[0513] Example 3 A composition using EOP-001 instead of the mixture of compound EOD-001 and polymer material PMMA, and a composition using EOP-002 instead of the mixture of compound EOD-001 and polymer material PMMA were each obtained in the same manner as in Example 1. Substrates were prepared and electro-optical effects were measured using the obtained compositions in the same manner as in Example 1. The results are shown in Table 2.

[0514]

[0515] As is clear from Table 2, even when the concentration of the group obtained by removing one hydrogen atom from the compound represented by formula (1), i.e., the nonlinear optically active compound, increases from 38% by mass to 47% by mass, the increase in the electro-optic coefficient is greater than 1, indicating that the electro-optic coefficient continues to improve even when the concentration of the group obtained by removing one hydrogen atom from the nonlinear optically active compound increases. On the other hand, in Non-Patent Document 1, when the concentration of the group obtained by removing one hydrogen atom from the compound exhibiting nonlinear optical activity increases from 36% by mass to 42% by mass, the increase in the electro-optic coefficient is clearly less than 1.0, indicating that the electro-optic coefficient no longer improves when the concentration of the group obtained by removing one hydrogen atom from the compound exhibiting nonlinear optical activity increases.

[0516] Example 4 Compound EOD-005 was used instead of compound EOD-001, and compositions in which the mixing ratio of EOD-005 to polymer material PMMA was 10:90 (mass ratio), 20:80 (mass ratio), and 30:70 (mass ratio) were obtained in the same manner as in Example 1. Substrates were prepared using the obtained compositions, and the electro-optical effects were measured in the same manner as in Example 1. The results are shown in Table 3.

[0517] Example 5 A substrate was prepared and the electro-optical effect was measured in the same manner as in Example 4, except that compound EOD-006 was used instead of compound EOD-005. The results are shown in Table 3.

[0518] Example 6 A substrate was prepared and the electro-optical effect was measured in the same manner as in Example 4, except that compound EOD-007 was used instead of compound EOD-005, an ITO substrate was used instead of a substrate with an intermediate layer film, and a poling treatment was performed at 25 V / μm. The results are shown in Table 3.

[0519] Comparative Example 3 A substrate was prepared and the electro-optical effect was measured in the same manner as in Example 4, except that compound EOD-009 was used instead of compound EOD-005. The results are shown in Table 3.

[0520]

[0521] As is clear from Table 3, in Examples 4 to 6, even when the concentration of the nonlinear optical material increased, the increase in the electro-optic coefficient was greater than 1, indicating that the electro-optic coefficient continued to improve even when the concentration of the nonlinear optical material became high. On the other hand, in Comparative Example 3, the increase in the electro-optic coefficient from 20% by mass to 30% by mass was less than 1.0 (0.6), indicating that the electro-optic coefficient no longer improved when the concentration of the nonlinear optical material became high.

[0522] Although various embodiments have been described above, it goes without saying that the present invention is not limited to such examples. It is clear that a person skilled in the art can conceive of various modifications or alterations within the scope of the claims, and it is understood that these also naturally fall within the technical scope of the present invention. Furthermore, the components of the above embodiments may be combined in any manner as long as they do not deviate from the spirit of the invention.

[0523] This application is based on a Japanese patent application (Patent Application No. 2024-30022) filed on February 29, 2024, the contents of which are incorporated herein by reference.

[0524] The compound of the present invention can be used in nonlinear optical elements, electric field sensors, and the like.

Claims

1. A compound represented by the following formula (1): [In formula (1), Z １１ is a group represented by the following formula (2): １２ is an aromatic group which may have a substituent, or a branched, linear or cyclic hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, and the hydrocarbon group may be saturated or unsaturated, and a part of the hydrocarbon chain constituting the hydrocarbon group may be substituted with at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms. １３ is a divalent aromatic group which may have a substituent. １１ is a divalent π-conjugated group. １１ is a group represented by the following formula (6) or formula (7): １２ and Z １３ may be linked to each other to form a cyclic structure. [In formula (2), R ２１ is a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted amino group, a halogen atom, an optionally substituted aralkyloxy group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aralkylthio group, and an optionally substituted silyl group. ２１ is a group selected from the group consisting of an aromatic group, a hydrocarbon ring group, and a heterocyclic group, and R ２１ * indicates the bonding position to N in formula (1). [In formula (6), * represents L in formula (1)] １１ This is the bonding position with R ６１ and R ６２ are each independently a group selected from the group consisting of an alkyl group which may have a substituent, an aromatic group which may have a substituent, a halogen atom, an alkylsulfonyl group which may have a substituent, and an aralkyl group which may have a substituent. ６１ is O or S. [In formula (7), * represents L in formula (1)] １１ This is the bonding position with R ７３ is a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted acyl group, an optionally substituted alkyloxycarbonyl group, and an optionally substituted aralkyl group.

2. The compound according to claim 1, wherein the formula (2) is represented by the following formula (3): [In formula (3), R ３１ and R ３２ are each independently R in formula (2). ２１ Ar is a group having the same meaning as ３３ is a group selected from the group consisting of an aromatic group, a hydrocarbon ring group, and a heterocyclic group, and R ３１ and R ３２ * indicates the bonding position to N in formula (1).

3. Z in the formula (1) １２ The compound according to claim 1 , wherein is an optionally substituted alkyl group or an optionally substituted aromatic group.

4. Z in the formula (1) １３ The compound according to claim 1 , wherein is an optionally substituted divalent aromatic hydrocarbon group.

5. L in the formula (1) １１ The compound according to claim 1, wherein is a group represented by the following formula (4) or formula (5): [In formula (4), R ４ａ are each independently a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted amino group, a halogen atom, an optionally substituted alkyloxycarbonyl group, an optionally substituted alkylsulfonyl group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and an optionally substituted aralkylthio group. ４ｂ R are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, and an aromatic group which may have a substituent. ４ｃ are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic group which may have a substituent. ４ａ , R ４ｂ and R ４ｃ may be bonded to each other to form a ring, l is an integer of 0 to 5, n is an integer of 0 to 5, m is an integer of 0 to 5, and l+n+m>0. [In formula (5), Ar ５ R each independently represents a divalent aromatic group which may have a substituent. ５ａ are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic group which may have a substituent. ５ has a substituent, the substituent and R ５ａ and may be bonded to each other to form a ring, e is an integer of 0 to 4, f is an integer of 0 to 5, and e+f>0.

6. A nonlinear optically active polymer compound in which a group obtained by removing at least one hydrogen atom from the compound according to claim 1 is bonded to a repeating unit in the polymer compound.

7. The nonlinear optically active polymer compound according to claim 6, wherein the polymer compound is selected from the group consisting of poly(meth)acrylic acid ester, polyvinyl chloride, polystyrene, polyimide, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, polycarbonate, and copolymers thereof.

8. A composition comprising at least one compound according to any one of claims 1 to 5, a polymer material, and a solvent, or at least one nonlinear optically active polymer compound according to claim 6, and a solvent, or at least one compound according to any one of claims 1 to 5, at least one nonlinear optically active polymer compound according to claim 6, and a solvent.

9. The composition of claim 8, wherein the polymeric material is selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimides, maleimide-styrene copolymers, maleimide-olefin copolymers, maleimide-methyl methacrylate copolymers, polycarbonates, and copolymers thereof.

10. A nonlinear optical element comprising the composition according to claim 8.

11. The nonlinear optical element according to claim 10, which operates based on the electro-optic effect.

12. An optical modulator comprising the nonlinear optical element according to claim 10.

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