Method for producing a compound and compound

Abstract

To provide a method for producing a compound in which the group adjacent to the electron-withdrawing tricyanofuran (TCF) ring is a divalent aromatic group rather than a vinylene group, and in which the structure of the π-conjugated chain other than the aromatic group is not limited to a viareylene or triarylene structure, and to provide a compound that can be used as a synthetic intermediate in the said production method. [Solution] For example, the target pigment 1 is synthesized from compound 1 and compound 20 as shown in the following formula. TIFF2026169002000079.tif31164

Description

[Technical Field]

[0001] This invention relates to a method for producing compounds and to compounds themselves. [Background technology]

[0002] In recent years, the development of various optoelectronic devices using nonlinear optical materials has been progressing in fields such as optical information processing and optical communication. 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. Those that produce a second-order nonlinear optical effect, such as the first-order electro-optic effect (Pockels effect), are being considered for applications such as optical switches and optical modulation.

[0003] Nonlinear optical materials, particularly organic nonlinear optical materials, are generally obtained by mixing or bonding compounds (dyes) having nonlinear optical activity to polymer materials such as polymethyl methacrylate (PMMA). Nonlinear optical properties are expressed by the electro-optic coefficient (hereinafter also referred to as the "EO coefficient" in this specification), and are also denoted as r33. As dyes, so-called push-pull type π-conjugated compounds are known, which have electron-donating groups and electron-withdrawing groups located at both ends of the molecular structure, and a π-conjugated chain connecting them. Among such π-conjugated compounds, dyes having an amino group as the electron-donating group and a heterocyclic group having a cyano group such as a tricyanofuran (TCF) ring as the electron-withdrawing group have attracted attention as dyes that exhibit particularly high nonlinear optical properties, and progress is being made in the design of dye molecules and the development of synthesis methods aimed at further improving these properties (Patent Documents 1-4).

[0004] One of the most common methods for synthesizing dyes is the Knoevenagel condensation reaction, which involves condensing a compound containing an aldehyde group with an electron-withdrawing group such as a TCF ring or malononitrile, as shown in the following formula (Non-Patent Literature 1). However, the dyes synthesized by this method are limited to those in which the group adjacent to the electron-withdrawing group is a vinylene group. Therefore, from the perspective of dye development, there is a need to develop alternative synthesis methods.

[0005] [ka]

[0006] Patent Document 5 discloses that a dye in which a phenylene group is adjacent to the electron-withdrawing TCF ring is synthesized by a reaction in which a nucleophilic amine compound and a compound having an aryl halide structure are reacted in the presence of a base, known as an aromatic nucleophilic substitution reaction, and that a nonlinear optical material exhibiting low absorption loss can be obtained using this dye. However, since the absorption wavelength of the dye is short and the electro-optic effect is not sufficiently obtained, a method for synthesizing a dye in which the absorption wavelength is controlled by further extending the π-conjugated chain is needed.

[0007] [ka]

[0008] Non-patent document 2 discloses a method for synthesizing dyes in which the π-conjugated chain connecting the electron-withdrawing group and the electron-donating group has a biaryl or triaryl structure, as shown by the following formula. Compared to the dyes described in Patent Document 5, a longer absorption wavelength due to the elongation of the π-conjugated chain has been observed. On the other hand, reported examples of dyes synthesized by this method are limited to those with a viarelen or triarylene structure in the π-conjugated chain. From the viewpoint of improving the efficiency and saving energy of nonlinear optical elements, there is a need for a general-purpose dye synthesis method that can further improve the electro-optic effect of materials while maintaining low absorption loss.

[0009] [ka] [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] International Publication No. 2019 / 151318 [Patent Document 2] Japanese Patent Publication No. 2010-066325 [Patent Document 3] International Publication No. 2011 / 024774 [Patent Document 4] Japanese Patent Publication No. 2015-178544 [Patent Document 5] International Publication No. 2023 / 021921 [Non-patent literature]

[0011] [Non-Patent Document 1] Prog.Polym.,2008,33,1013-1058 [Non-Patent Document 2] Chem.Mater.,2009,21,297-810 [Overview of the Initiative] [Problems that the invention aims to solve]

[0012] The object of the present invention is to provide a method for producing a compound in which the group adjacent to the electron-withdrawing tricyanofuran (TCF) ring is a divalent aromatic group rather than a vinylene group, and in which the structure of the π-conjugated chain other than the aromatic group is not limited to a viareylene structure or a triarylene structure. Another object of the present invention is to provide a compound that can be used as a synthetic intermediate in the said production method. [Means for solving the problem]

[0013] In view of the above problems, the present inventors conducted extensive research and found that by using a phosphorus compound having a structure in which a divalent aromatic group is directly bonded to an electron-withdrawing group such as a tricyanofuran (TCF) ring as a synthetic intermediate, and reacting it with an aldehyde compound containing an electron-donating group and a π-conjugated chain, in a so-called Wittig reaction, it is possible to synthesize a compound in which a divalent aromatic group is directly bonded to an electron-withdrawing group such as a tricyanofuran (TCF) ring, and an amine, which is an electron-donating group, is bonded to a structure in which a π-conjugated chain is extended from the aromatic group, thus completing the present invention.

[0014] The gist of the present invention is as follows.

[0015] Aspect 1 of the present invention relates to a method for producing a compound represented by the following formula (3), comprising a step of reacting a compound represented by the following formula (1) with a base, and a step of reacting the product of the aforementioned step with a compound represented by the following formula (2).

[0016]

Chemical Formula

[0017] [In formula (1), Ar 11 is a divalent aromatic group which may have a substituent, R 11 and R 12 are each independently a group selected from the following hydrocarbon group group A which may have a substituent, or an aromatic group which may have a substituent; R 11 and R 12 may be bonded to form a ring, or R 11 and R 12 may form a carbonyl group together with R 11 , R 12 and the carbon atom to which they are bonded, R 13 and R 14 are each independently a cyano group, an alkyloxycarbonyl group having 2 to 30 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 30 carbon atoms which may have a substituent, X 11 is an oxygen atom, a sulfur atom or N-Q 11 , Q 11 is a hydrogen atom, a group selected from the following hydrocarbon group group A which may have a substituent, or an aralkyl group which may have a substituent, V 11 is a group represented by the following formula (1a) or the following formula (1b).]

[0018] ​​ [ka]

[0019] [In formula (1a), *J 1a1 This is the Ar in formula (1) above. 11 This is the bonding position with, R 1a1 , R 1a2 , and R 1a3 Each of these is independently a group selected from the following hydrocarbon group A which may have substituents, or an aromatic group which may have substituents. P is a phosphorus atom, X - It is a monovalent anion.

[0020] [ka]

[0021] [In formula (1b), *J 1b1 This is the Ar in formula (1) above. 11 This is the bonding position with, R 1b1 and R 1b2 Each of these is independently a group selected from the following hydrocarbon group A which may have substituents, or an aromatic group which may have substituents. P represents a phosphorus atom. <Hydrogen Group A> A branched, linear, or cyclic alkyl group having 1 to 30 carbon atoms, a branched, linear, or cyclic alkenyl group having 2 to 30 carbon atoms, or a branched, linear, or cyclic alkynyl group having 2 to 30 carbon atoms, wherein part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group, and / or a silicon atom.

[0022] [ka]

[0023] [In formula (2), Ar 21 Each of these is independently a divalent aromatic group which may have substituents, R 21 and R 23 Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A which may have substituents, or a divalent aromatic group which may have substituents. R 22 and R 24 Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom. Y 21 Each is independently a divalent π-conjugated linkage group which may have substituents, where Y 21 At least one of them is a vinylene group which may have substituents, Z 21 is an aldehyde group, or -C(O)-R 25 And, R 25 This is a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, m 21 Each of these is an integer between 0 and 5, independently of the others. m 22 These are integers from 1 to 5, m 23 These are integers from 0 to 5, n 21 [This is an integer between 1 and 15.]

[0024] [ka]

[0025] [In formula (3), Ar 21 , R 21 , R 22 , R 23 , R 24 , Y21 , m 21 , m 22 , m 23 , and n 21 This is equivalent to that in formula (2) above. Z 31 This is the group represented by the following formula (1c).

[0026] [ka]

[0027] [In formula (1c), Ar 11 , R 11 , R 12 , R 13 , R 14 , and X 11 This is as defined in formula (1) above. *J 1c1 Y in equation (3) above 21 This is the bonding position.

[0028] Aspect 2 of the present invention is the manufacturing method of Aspect 1, In equations (2) and (3) above, Y 21 At least one of them is independently represented by the following formula (7), where n in formulas (2) and (3) is 21 If it is 2 or more, then R in equation (7) below 31 and R 32 is, other Y 21 R included 31 or R 32 The present invention relates to a manufacturing method which may be linked together to form a ring.

[0029] [ka]

[0030] [In formula (7), R 31 and R 32each independently represent a hydrogen atom, a group selected from the aforementioned hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom, or a boryl group which may have a substituent, and R 31 and R 32 may be bonded to each other to form a ring.]

[0031] Aspect 3 of the present invention is the production method according to Aspect 1 or 2, wherein Y in the aforementioned formula (2) and formula (3) 21 each independently are represented by the following formula (4), the following formula (5), or the following formula (6), Y 21 at least one of which is represented by the following formula (4), when n in the aforementioned formula (2) and formula (3) 21 is 2 or more, the Y 21 R in 41 , R 42 , R 51 , R 52 , and R 61 ~R 67 may be linked with R contained in the other Y 21 41 , R 42 , R 51 , R 52 , or R 61 ~R 67 to form a ring. The present invention relates to the production method.

[0032]

Chemical formula

[0033] [In formula (4), R 41 and R 42 each independently represent a hydrogen atom, a group selected from the aforementioned hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom, or a boryl group which may have a substituent, and R 41 and R 42 ​may be bonded to form a ring.]

[0034]

Chemical Formula

[0035] [In formula (5), R 51 and R 52 are each independently a hydrogen atom, a group selected from the aforementioned hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom, or a boryl group which may have a substituent, and R 51 and R 52 may be bonded to form a ring, X 51 is an oxygen atom, a sulfur atom or N-Q 51 , Q 51 is a hydrogen atom, a group selected from the aforementioned hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom, or a boryl group which may have a substituent.]

[0036]

Chemical Formula

[0037] [In formula (6), R 61 ~R 67 are each independently a hydrogen atom, a group selected from the aforementioned hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom, or a boryl group which may have a substituent, and at least two of R 61 ~R 67 may be bonded to form a ring.]

[0038] Aspect 4 of the present invention is a manufacturing method according to any one of aspects 1 to 3, n in equations (2) and (3) 21 This concerns a manufacturing method where the value is an integer between 2 and 5.

[0039] Aspect 5 of the present invention is a manufacturing method according to any one of aspects 1 to 4, The present invention relates to a method for producing a base in which the base is a carbonate, a metal hydroxide, a metal alkoxide, an alkyl metal, or a metal hydride.

[0040] Aspect 6 of the present invention is, This relates to a compound represented by the following formula (1).

[0041] [ka]

[0042] [In formula (1), Ar 11 is a divalent aromatic group which may have substituents, R 11 and R 12 Each of these is independently a group selected from the following hydrocarbon group A which may have substituents, or an aromatic group which may have substituents, and R 11 and R 12 They may be bonded together to form a ring, or R 11 and R 12 R 11 and R 12 These may also form a carbonyl group together with the carbon atom to which they are bonded. R 13 and R 14 Each of these is independently a cyano group, an alkyloxycarbonyl group having 2 to 30 carbon atoms which may have substituents, or an alkylsulfonyl group having 1 to 30 carbon atoms which may have substituents. X 11 is an oxygen atom, a sulfur atom, or NQ 11 And, Q 11This is a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. V 11 This is a group represented by the following formula (1a) or formula (1b).

[0043] [ka]

[0044] [In formula (1a), *J 1a1 This is the Ar in formula (1) above. 11 This is the bonding position with, R 1a1 , R 1a2 , and R 1a3 Each of these is independently a group selected from the following hydrocarbon group A which may have substituents, or an aromatic group which may have substituents. P is a phosphorus atom, X - It is a monovalent anion.

[0045] [ka]

[0046] [In formula (1b), *J 1b1 This is the Ar in formula (1) above. 11 This is the bonding position with, R 1b1 and R 1b2 Each of these is independently a group selected from the following hydrocarbon group A which may have substituents, or an aromatic group which may have substituents. P represents a phosphorus atom. <Hydrogen Group A> A branched, linear, or cyclic alkyl group having 1 to 30 carbon atoms, a branched, linear, or cyclic alkenyl group having 2 to 30 carbon atoms, or a branched, linear, or cyclic alkynyl group having 2 to 30 carbon atoms, wherein part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group, and / or a silicon atom. [Effects of the Invention]

[0047] The present invention provides a method for producing compounds in which the group adjacent to the electron-withdrawing tricyanofuran (TCF) ring is a divalent aromatic group rather than a vinylene group, and the structure of the π-conjugated chain other than the aromatic group is not limited to a viareylene or triarylene structure. Furthermore, the present invention provides compounds that can be used as synthetic intermediates in the said production method. [Modes for carrying out the invention]

[0048] Explanation of terms The following is an explanation of the terms used in this specification.

[0049] <Substituent> Unless otherwise specified, a substituent is any group, but preferably the substituent group W described below. 1 The group is selected from the substituent group W. The substituents that may be present are also the substituent group W. 1 If it is stated that selection from is preferable, the preferred substituents are also the substituent group W below. 1 As stated therein.

[0050] <Substituent group W 1 > Substituent group W 1 This group consists of hydroxyl groups, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aromatic oxy groups, aralkyloxy groups, alkylthio groups, aromatic thio groups, aralkylthio groups, alkyloxycarbonyl groups, dialkylamino groups, diarylamino groups, arylalkylamino groups, acyl groups, halogen atoms, haloalkyl groups, alkylthio groups, arylthio groups, silyl groups, siloxy groups, cyano groups, aralkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups. These substituents may include linear, branched, or cyclic structures. Substituent group W 1Among these, from the viewpoint of improving solubility, the group consisting of alkyl groups, alkoxy groups, aralkyloxy groups, alkylthio groups, aralkylthio groups, haloalkyl groups, silyl groups, and aralkyl groups is preferred, and the group consisting of alkyl groups, alkoxy groups, haloalkyl groups, and silyl groups is particularly preferred. Substituent group W 1 More specifically, the following structures are examples, from the alkyl group to the bond of adjacent substituents.

[0051] [Alkyl group] Alkyl groups are linear, branched, or cyclic, and have one or more carbon atoms, preferably four or more, usually 24 or fewer, preferably 12 or fewer, more preferably 8 or fewer, and even more preferably 6 or fewer. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group, adamantyl group, and the like.

[0052] [Alkenyl group] Alkenyl groups are linear, branched, or cyclic, and typically have two or more carbon atoms, usually 24 or fewer, preferably 12 or fewer. Specific examples include vinyl groups.

[0053] [Alkynyl group] The alkynyl group is linear or branched, usually has two or more carbon atoms, usually 24 or fewer, preferably 12 or fewer. Specific examples include the ethynyl group.

[0054] [Alkyloxy group] Alkyloxy groups are linear, branched, or cyclic, have one or more carbon atoms, and usually have 24 or fewer carbon atoms, preferably 12 or fewer. Specific examples include methoxy groups, ethoxy groups, n-propoxy groups, iso-propoxy groups, n-butoxy groups, iso-butoxy groups, sec-butoxy groups, tert-butoxy groups, n-hexyloxy groups, cyclohexyloxy groups, dodecyloxy groups, adamantyloxy groups, and the like.

[0055] [Aromatic oxy group] Aromatic oxy groups have 4 or more carbon atoms, preferably 5 or more, and usually 36 or fewer, preferably 24 or fewer. Specific examples include phenoxy groups, naphthoxy groups, and pyridyloxy groups.

[0056] [Aralkyloxy group] The aralkyloxy group has 4 or more carbon atoms, preferably 5 or more, and is usually 50 or less, preferably 30 or less. Specific examples include the benzyloxy group, tolylmethoxy group, thiophenylmethoxy group, 2-phenylethyloxy group, 2-phenylpropyl-2-yloxy group, 2-phenylbutyl-2-yloxy group, 3-phenylpentyl-3-yloxy group, 3-phenyl-1-propyloxy group, 4-phenyl-1-butyloxy group, 5-phenyl-1-pentioxyl group, 6-phenyl-1-hexyloxy group, 7-phenyl-1-heptyloxy group, and 8-phenyl-1-octyloxy group.

[0057] [Alkylthio group] Alkylthio groups have one or more carbon atoms, usually 24 or fewer, preferably 12 or fewer. Specific examples include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, tert-butylthio group, n-hexylthio group, cyclohexylthio group, dodecylthio group, adamantylthio group, and the like.

[0058] [Aromatic thio group] Aromatic thio groups have 3 or more carbon atoms, preferably 4 or more, and usually 50 or fewer, preferably 30 or fewer. Specifically, examples include phenylthio groups, naphthylthio groups, and pyridylthio groups.

[0059] [Aralkylthio group] The aralkylthio group has four or more carbon atoms, usually 50 or less, preferably 30 or less. Specific examples include the benzylthio group, tolylmethylthio group, 2-phenylethylthio group, 2-phenylpropyl-2-ylthio group, 2-phenylbutyl-2-ylthio group, 3-phenylpentyl-3-ylthio group, 3-phenyl-1-propylthio group, 4-phenyl-1-butylthio group, 5-phenyl-1-pentylthio group, 6-phenyl-1-hexylthio group, 7-phenyl-1-heptylthio group, and 8-phenyl-1-octylthio group.

[0060] [Alkyloxycarbonyl group] Alkyloxycarbonyl groups have two or more carbon atoms, usually 24 or fewer, and preferably 12 or fewer. Specific examples include methoxycarbonyl groups and ethoxycarbonyl groups.

[0061] [Dialkylamino group] A dialkylamino group has two or more carbon atoms, usually 24 or fewer, and preferably 12 or fewer. Specific examples include dimethylamino group and diethylamino group.

[0062] [Amino group] The amino group may have substituents, preferably a secondary amino group, a tertiary amino group, and more preferably a tertiary amino group. Preferred substituents on the amino group are alkyl groups, cycloalkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups, and these groups may also have substituents. Furthermore, if there are multiple substituents on the amino group, they may be the same or different, and they may bond to each other to form a ring with the nitrogen atom to which each is bonded. Specific examples include dimethylamino group, diethylamino group, ethylmethylamino group, n-propylmethylamino group, di-iso-propylamino group, di-n-butylamino group, di-n-hexylamino group, di-n-butylamino group, methylphenylamino group, ethylphenylamino group, butylphenylamino group, hexylphenylamino group, diphenylamino group, 2,6-dimethylphenylphenylamino group, and 2,4,6-trimethylphenylphenylamino group.

[0063] [Halogen atom] Halogen atoms are typically fluorine, chlorine, bromine, or iodine atoms. More preferably, they are fluorine atoms.

[0064] [haloalkyl group] The haloalkyl group has one or more carbon atoms, usually 12 or fewer, and preferably 6 or fewer. Specific examples include the trifluoromethyl group and the chloromethyl group, with the trifluoromethyl group being more preferred.

[0065] [Silicone group] The silyl group typically has 2 or more carbon atoms, preferably 3 or more, and typically 36 or fewer carbon atoms, preferably 24 or fewer. Specific examples include the trimethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, and triphenylsilyl group.

[0066] [Siloxy group] The siloxy group has 2 or more carbon atoms, preferably 3 or more, and is usually 36 or less, preferably 24 or less, and more preferably 18 or less. Specific examples include the trimethylsiloxy group, tert-butyldimethylsiloxy group, tert-butyldiphenylsiloxy group, and triphenylsiloxy group.

[0067] [Aralkyl group] The aralkyl group typically has 7 or more carbon atoms, preferably 9 or more, typically 30 or less, preferably 18 or less, and more preferably 10 or less. Specific examples include the benzyl group, 2-phenylethyl group, 2-phenylpropyl-2-yl group, 2-phenylbutyl-2-yl group, 3-phenylpentyl-3-yl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, 7-phenyl-1-heptyl group, and 8-phenyl-1-octyl group.

[0068] [Aromatic hydrocarbon group] Aromatic hydrocarbon groups have 6 or more carbon atoms, usually 36 or fewer, and preferably 24 or fewer. Specific examples include phenyl groups, naphthyl groups, and groups formed by linking multiple phenyl groups.

[0069] [Aromatic heterocyclic groups] Aromatic heterocyclic groups have 3 or more carbon atoms, preferably 4 or more, and typically 36 or fewer, preferably 24 or fewer. Specific examples include thienyl groups and pyridyl groups.

[0070] [Shape of substituent] The substituents may include linear, branched, or cyclic structures.

[0071] [Bonding of adjacent substituents] When the above substituents are adjacent, adjacent substituents may bond to each other to form a ring. Preferred ring sizes are 4-membered, 5-membered, and 6-membered rings, with specific examples including cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0072] <Alkyl group> Alkyl groups may have substituents, and can be linear, branched, or cyclic. While the number of carbon atoms is generally not limited, it is preferably between 1 and 30 carbon atoms, more preferably 20 or fewer carbon atoms, and even more preferably 10 or fewer carbon atoms. Specific examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, dodecyl, and adamantyl groups. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0073] <Aromatic hydrocarbon group> Aromatic hydrocarbon groups refer to monovalent, divalent, or trivalent or more structures of a hydrocarbon aromatic ring structure, depending on the bonding state within the structure of the compounds described below. The number of carbon atoms in an aromatic hydrocarbon group is not usually limited, but it is preferably 6 to 60 carbon atoms, more preferably 48 carbon atoms or less, and even more preferably 30 carbon atoms or less. Specifically, examples include monocyclic rings with 6 members or fused ring groups containing 2 to 5 rings, such as benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluorantene rings, and fluorene rings, or structures in which multiple groups selected from these are linked together. When multiple aromatic hydrocarbon groups are linked together, typically 2 to 10 linked groups are used, and 2 to 5 linked groups are preferred. When multiple aromatic hydrocarbon groups are linked together, the same structure may be linked, or different structures may be linked. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0074] <Aromatic heterocyclic group> Aromatic heterocyclic groups refer to heteroaromatic ring structures that are monovalent, divalent, or trivalent or more, depending on their bonding state within the structure of the compounds described below. While the number of carbon atoms in an aromatic heterocyclic group is not usually limited, it is preferably between 3 and 50 carbon atoms, more preferably 45 carbon atoms or less, and even more preferably 30 carbon atoms or less. Specifically, examples include monocyclic rings with 5 to 6 members or fused ring groups containing 2 to 4 rings, such as furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienopyrrole rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinnoline rings, quinoxaline rings, phenanthridine rings, perimidine rings, quinazoline rings, and quinazolinone rings, or groups in which multiple such groups are linked. When multiple aromatic heterocyclic groups are linked, the same structure may be linked, or different structures may be linked. When multiple aromatic heterocyclic groups are linked together, typically a structure with 2 to 10 linked groups is common, and a structure with 2 to 5 linked groups is preferred. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0075] <Aromatic group> The aromatic group may have substituents and represents the aforementioned aromatic hydrocarbon group or aromatic heterocyclic group, and refers to a monovalent, divalent, or trivalent or more structure depending on the bonding state within the structure of the compound that is the subject of the explanation below. The aromatic group may be a group in which multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together. When multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together, the same structure may be linked, or different structures may be linked together. When multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together, a structure in which 2 to 10 groups are usually shown, and a structure in which 2 to 5 groups are preferred. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0076] <amino group> The amino group may have substituents, preferably a secondary amino group, a tertiary amino group, and more preferably a tertiary amino group. Preferred substituents on the amino group are groups selected from hydrocarbon group A, or aromatic groups, and these groups may also have substituents. Furthermore, if there are multiple substituents on the amino group, they may be the same or different, and they may bond to each other to form a ring with the nitrogen atom to which each is bonded. Specific examples include dimethylamino group, diethylamino group, ethylmethylamino group, n-propylmethylamino group, di-iso-propylamino group, di-n-butylamino group, di-n-hexylamino group, di-n-butylamino group, methylphenylamino group, ethylphenylamino group, butylphenylamino group, hexylphenylamino group, diphenylamino group, 2,6-dimethylphenylphenylamino group, and 2,4,6-trimethylphenylphenylamino group. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0077] <Halogen atom> Halogen atoms are typically fluorine, chlorine, bromine, or iodine atoms. More preferably, they are fluorine atoms.

[0078] <Alkyloxycarbonyl group> The alkyloxycarbonyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 to 30 carbon atoms, more preferably 20 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 10 carbon atoms or less. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, and the like. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0079] <Alkyl sulfonyl group> The alkylsulfonyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 1 to 30 carbon atoms, more preferably 20 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 10 carbon atoms or less. Specific examples include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, dodecylsulfonyl group, and the like. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0080] <aralkyl group> The aralkyl group may have a substituent, and the number of carbon atoms is usually not limited, but it is preferably 2 or more and 50 or less, more preferably 30 or less, and still more preferably 20 or less as the upper limit of the number of carbon atoms. Specific examples include benzyl group, 2-phenylethyl group, 2-phenylpropan-2-yl group, 2-phenylbutan-2-yl group, 3-phenylpentan-3-yl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, 7-phenyl-1-heptyl group, 8-phenyl-1-octyl group and the like. The substituent that these groups may have is the aforementioned substituent group W 1 is preferably selected from.

[0081] <Boryl group> The boryl group may have a substituent, preferably a secondary boryl group or a tertiary boryl group, and more preferably a tertiary boryl group. As the substituent that the boryl group has, a hydroxy group, an alkyloxycarbonyl group, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group are preferred, and these groups may have a substituent. When a plurality of substituents are present on the boryl group, they may be the same or different, and may be bonded to each other to form a ring together with the boron atom to which each is bonded. The substituent that these groups may have is the aforementioned substituent group W 1 is preferably selected from.

[0082] <Acyl group> The acyl group may have a substituent, and the number of carbon atoms is usually not limited, but it is preferably 2 or more and 50 or less, more preferably 24 or less, and still more preferably 12 or less as the upper limit of the number of carbon atoms. Specific examples include benzoyl group, acetyl group and the like. The substituent that these groups may have is the aforementioned substituent group W 1 is preferably selected from.

[0083] <Aromatic oxy group> Aromatic oxy groups may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 3 to 50 carbon atoms, more preferably 30 carbon atoms or less, and even more preferably 20 carbon atoms or less. Specific examples include naphthoxy groups and phenyloxy groups. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0084] <Aralkyloxy group> The aralkyloxy group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 4 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 20 carbon atoms or less. Specific examples include benzyloxy group, tolylmethoxy group, thiophenylmethoxy group, 2-phenylethyloxy group, 2-phenylpropyl-2-yloxy group, 2-phenylbutyl-2-yloxy group, 3-phenylpentyl-3-yloxy group, 3-phenyl-1-propyloxy group, 4-phenyl-1-butyloxy group, 5-phenyl-1-pentioxyl group, 6-phenyl-1-hexyloxy group, 7-phenyl-1-heptyloxy group, and 8-phenyl-1-octyloxy group. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0085] <Aromatic thio group> Aromatic thio groups may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 3 to 50 carbon atoms, more preferably 30 carbon atoms or less, and even more preferably 20 carbon atoms or less. Specific examples include naphthylthio groups, tolthio groups, and phenylthio groups. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0086] <Aralkylthio group> The aralkylthio group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 4 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit, and even more preferably 20 carbon atoms or less. Specific examples include benzylthio group, tolylmethylthio group, 2-phenylethylthio group, 2-phenylpropyl-2-ylthio group, 2-phenylbutyl-2-ylthio group, 3-phenylpentyl-3-ylthio group, 3-phenyl-1-propylthio group, 4-phenyl-1-butylthio group, 5-phenyl-1-pentylthio group, 6-phenyl-1-hexylthio group, 7-phenyl-1-heptylthio group, and 8-phenyl-1-octylthio group. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0087] <Hydrogen ring group> A hydrocarbon ring group is a cyclic hydrocarbon group that may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 3 to 50 carbon atoms, more preferably 20 carbon atoms or less, and even more preferably 10 carbon atoms or less. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a group formed by linking multiple such groups. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0088] <Hydrogen Group A> Hydrocarbon group A refers to branched, linear, or cyclic alkyl groups having 1 to 30 carbon atoms, branched, linear, or cyclic alkenyl groups having 2 to 30 carbon atoms, or branched, linear, or cyclic alkynyl groups having 2 to 30 carbon atoms, where part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group, and / or a silicon atom. Specifically, the following points can be cited.

[0089] Specific examples of unsubstituted hydrocarbon group A are hydrocarbon chains having 1 to 15 carbon atoms, more specifically, methyl group, ethyl group, 1-butyl group, tert-butyl group, cyclopentyl group, 4-ethyl-1-cyclohexyl group, 2-penten-1-yl group, 1-octyl group, 1-decyl group, etc., with methyl group, ethyl group, and 1-butyl group being preferred.

[0090] Specific examples of hydrocarbon group A, in which part of the carbon chain is substituted with an oxygen atom, include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyloxy group, dodecyloxy group, 2-ethoxyethyl group, 2-(2-ethoxyethoxy)ethyl group, 2-hydroxyethyl group, tetrahydropyranyloxypropyl group, and the like, with 2-ethoxyethyl group and 2-hydroxyethyl group being preferred, and 2-hydroxyethyl group being particularly preferred.

[0091] Specific examples of hydrocarbon group A, in which part of the carbon chain is substituted with a sulfur atom, include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, tert-butylthio group, n-hexylthio group, cyclohexylthio group, dodecylthio group, 2-ethylthioethyl group, tetrahydrothienyl group, and 2-(2-ethylthioethylthio)ethyl group.

[0092] Specific examples of cases where part of the carbon chain is substituted with an aromatic hydrocarbon group include the benzyl group, phenylethyl group, phenylhexyl group, 4-phenylcyclohexylmethyl group, and 4-methylbenzyl group.

[0093] Specific examples of hydrocarbon group A, in which part of the carbon chain is substituted with a silicon atom, include trimethylsilyl group, triethylsilyl group, propyldimethylsilyl group, tert-butyldimethylsilyl group, and tert-butyldiphenylsilyl group.

[0094] Furthermore, a portion of the carbon chain may be simultaneously substituted with an oxygen atom and a silicon atom. Specific examples of such hydrocarbon group A include 2-(trimethylsilyloxy)ethyl group, 2-(tert-butyldimethylsilyloxy)ethyl group, 4-(tert-butyldimethylsilyloxy)butyl group, 2-(tert-butyldiphenylsilyloxy)ethyl group, 2-(tert-butyldimethylsilyloxy)hexyl group, and 2-(tert-butyldiphenylsilyloxy)ethyl group. Preferably, the group is 2-(tert-butyldimethylsilyloxy)ethyl group, 4-(tert-butyldimethylsilyloxy)butyl group, or 2-(tert-butyldiphenylsilyloxy)ethyl group.

[0095] The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0096] <Heterocyclic group> The heterocyclic group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 3 to 50 carbon atoms, more preferably 20 carbon atoms or less as the upper limit, and even more preferably 10 carbon atoms or less. Specific examples include thiane group, 1,4-dithiane group, tetrahydrofuran group, tetrahydropyran group, pyran group, 1,4-dioxane group, or groups formed by linking multiple of these groups. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0097] <π-conjugated linking group> The π-conjugated linking group refers to a divalent group in the structure of a compound to be described later, which is composed of alternating single bonds and multiple bonds and has delocalized electrons (π electrons). The π-conjugated linking group may have a substituent, and the number of carbon atoms is not particularly limited, but is preferably 2 or more and 50 or less, more preferably 30 or less, and still more preferably 20 or less as the upper limit of the number of carbon atoms. Further, the substituents possessed by a plurality of π-conjugated linking groups may be bonded to form a cyclic structure. Specific examples thereof include a vinylene group, a phenylene group, a divalent group composed of a thiophene ring, a furan ring or a pyrrole ring, and a group in which a plurality of these groups are linked. The substituent that these groups may have is preferably selected from the aforementioned substituent group W 1 .

[0098] <Description of Formula (1)>

[0099]

Chemical Formula

[0100] [In Formula (1), Ar 11 is a divalent aromatic group which may have a substituent, R 11 and R 12 are each independently a group selected from the aforementioned hydrocarbon group group A which may have a substituent, or an aromatic group which may have a substituent; R 11 and R 12 may be bonded to each other to form a ring, or R 11 and R 12 may form a carbonyl group together with R 11 and R 12 and the carbon atom to which they are bonded, R 13 and R 14 are each independently a cyano group, an optionally substituted alkyloxycarbonyl group having 2 to 30 carbon atoms, or an optionally substituted alkylsulfonyl group having 1 to 30 carbon atoms, X 11is an oxygen atom, a sulfur atom, or NQ 11 And, Q 11 This is a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. V 11 This is a group represented by the following formula (1a) or formula (1b).

[0101] (Ar 11 ) Ar 11 This is a divalent aromatic group which may have substituents. A divalent aromatic group that may have substituents is defined in the same way as described in the explanation of the terms above. Ar 11 The group is preferably a divalent group consisting of a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, a thiophene ring, or a biphenyl ring, and more preferably a divalent group consisting of a benzene ring, a pyridine ring, or a pyrimidine ring, and these groups may have substituents.

[0102] (R 11 and R 12 ) R 11 and R 12 Each of these is independently a group selected from the hydrocarbon group A which may have substituents, and an aromatic group which may have substituents, and R 11 and R 12 They may be bonded together to form a ring, or R 11 and R 12 R 11 and R 12 These may also form a carbonyl group together with the carbon atom to which they are bonded. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above.

[0103] From the viewpoint of film formation properties, R 11 and R 12Each of these groups is preferably a C1-C20 group selected from the hydrocarbon group A which may have substituents, or an aromatic hydrocarbon group which may be substituted with a C6-C30 group; more preferably a branched, linear, or cyclic alkyl group which may have substituents, or an aromatic hydrocarbon group which may be substituted with a C6-C30 group; particularly preferably a methyl group, an ethyl group, a linear or branched propyl group, a phenyl group, or a naphthyl group; and most preferably a methyl group or a phenyl group. These R 11 and R 12 The substituents that may be present are the substituent group W 1 Preferably selected from the following, more preferably an alkyl group or halogen atom, and most preferably a fluorine atom.

[0104] (R 13 and R 14 ) R 13 and R 14 Each of these is independently a cyano group, an alkyloxycarbonyl group having 2 to 30 carbon atoms which may have substituents, or an alkylsulfonyl group having 1 to 30 carbon atoms which may have substituents. A C2-C30 alkyloxycarbonyl group, which may have substituents, is synonymous with the description given in the explanation of the terms above. A C1-C30 alkylsulfonyl group, which may have substituents, is defined in the same way as described in the explanation of the terms above.

[0105] From the perspective of improving nonlinear optical properties, R 13 and R 14 Each of these is preferably a cyano group, an alkyloxycarbonyl group having 2 to 10 carbon atoms which may have substituents, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have substituents, with the cyano group being more preferred.

[0106] (X 11 ) X 11 is an oxygen atom, a sulfur atom, or NQ 11 That is the case. X11 As such, oxygen atoms are preferred.

[0107] (Q 11 ) Q 11 This is a hydrogen atom, a group selected from the optionally substituted hydrocarbon group A, or an optionally substituted aralkyl group. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aralkyl group which may have substituents" is synonymous with the description given in the explanation of the terms above.

[0108] From the perspective of film formation, Q 11 The group is preferably a C1-C20 group selected from the hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents, more preferably an aralkyl group which may have substituents, and particularly preferably an aralkyl group which may have substituents.

[0109] (substituent) These Ar 11 , R 11 ~R 14 Q 11 Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group as described in the explanations of the terms above.

[0110] (V 11 ) V 11 This is a group represented by the following formula (1a) or formula (1b).

[0111] <Explanation of equation (1a)>

[0112] [ka]

[0113] [In formula (1a), *J 1a1 In equation (1), Ar 11 This is the bonding position with, R 1a1 , R 1a2 , and R 1a3 Each of these is independently a group selected from the hydrocarbon group A which may have substituents, or an aromatic group which may have substituents. P is a phosphorus atom, X - It is a monovalent anion.

[0114] (*J 1a1 ) *J 1a1 In equation (1), Ar 11 This is the connection point.

[0115] (R 1a1 , R 1a2 and R 1a3 ) R 1a1 , R 1a2 , and R 1a3 Each of these is independently a group selected from the hydrocarbon group A which may have substituents, or an aromatic group which may have substituents. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above.

[0116] From the perspective of reactivity, R 1a1 , R 1a2 , and R 1a3 Each of these groups is preferably a C1-C20 group selected from the hydrocarbon group A which may have substituents, or an aromatic group which may have substituents, more preferably an aromatic group which may have substituents, and even more preferably a phenyl group.

[0117] (substituent) These R 1a1 , R 1a2 , and R 1a3 Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group as described in the explanations of the terms above.

[0118] (X - ) X - It is a monovalent anion. From the standpoint of compound stability, X - The ion is preferably a chloride ion, a bromide ion, or an iodide ion, with chloride ions being more preferred.

[0119] <Explanation of equation (1b)>

[0120] [ka]

[0121] [In formula (1b), *J 1b1 In equation (1), Ar 11 This is the bonding position with, R 1b1 and R 1b2 Each of these is independently a group selected from the hydrocarbon group A which may have substituents, or an aromatic group which may have substituents. P represents a phosphorus atom.

[0122] (*J 1b1 ) *J 1b1 In equation (1), Ar 11 This is the connection point.

[0123] (R 1b1 and R 1b2 ) R 1b1 and R 1b2 Each of these is independently a group selected from the hydrocarbon group A which may have substituents, or an aromatic group which may have substituents. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above.

[0124] From the perspective of reactivity, R1b1 and R 1b2 Each of these groups is preferably independently selected from the hydrocarbon group A which may have substituents, more preferably an alkyl group which may have substituents, even more preferably a branched, chain, or cyclic alkyl group having 1 to 20 carbon atoms which may have substituents, and particularly preferably a methyl group, an ethyl group, or a 1-butyl group.

[0125] (substituent) These R 1b1 , and R 1b2 Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group as described in the explanations of the terms above.

[0126] <Explanation of equation (2)>

[0127] [ka]

[0128] [In formula (2), Ar 21 Each of these is independently a divalent aromatic group which may have substituents, R 21 and R 23 Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A which may have substituents, or a divalent aromatic group which may have substituents. R 22 and R 24 Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom. Y 21 Each is independently a divalent π-conjugated linkage group which may have substituents, where Y 21 At least one of them is a vinylene group which may have substituents, Z 21 is an aldehyde group, or -C(O)-R 25 And, R 25 This is a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, m 21 Each of these is an integer between 0 and 5, independently of the others. m 22 These are integers from 1 to 5, m 23 These are integers from 0 to 5, n 21 [This is an integer between 1 and 15.]

[0129] (Ar 21 ) Ar 21 Each of these is independently a divalent aromatic group which may have substituents. A divalent aromatic group that may have substituents is defined in the same way as described in the explanation of the terms above.

[0130] Ar 21 Each of these groups is preferably a divalent group consisting of a benzene ring, a naphthalene ring, a 9,9-dialkylfluorene ring, a thiophene ring, or a biphenyl ring, and more preferably a divalent group consisting of a benzene ring, and these groups may have substituents.

[0131] (R 21 and R 23 ) R 21 and R 23 Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A which may have substituents, or a divalent aromatic group which may have substituents. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above. The term "amino group which may have substituents" is synonymous with the description given in the explanation of the terms above. The term "halogen atom" is synonymous with the description given in the explanation of the terms above.

[0132] From the perspective of improving nonlinear optical properties, R 22 and R 24 Each of these groups is independently preferably a group selected from the hydrocarbon group A which may have substituents, or an amino group which may have substituents; more preferably a group having 1 to 20 carbon atoms selected from the hydrocarbon group A which may have substituents, or an amino group which may have substituents; and particularly preferably an ethoxy group which may have substituents, or an tertiary amino group which may have substituents.

[0133] (R 22 and R 24 ) R 22 and R 24 Each of these is independently a hydrogen atom, a group selected from the optionally substituted hydrocarbon group A, an optionally substituted aromatic group, an optionally substituted amino group, a hydroxyl group, or a halogen atom. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above. The term "amino group which may have substituents" is synonymous with the description given in the explanation of the terms above. The term "halogen atom" is synonymous with the description given in the explanation of the terms above.

[0134] From the perspective of improving nonlinear optical properties, R 22 and R 24 Each of these groups is independently preferably a group selected from the hydrocarbon group A which may have substituents, preferably an amino group which may have substituents, more preferably a group having 1 to 20 carbon atoms selected from the hydrocarbon group A which may have substituents, preferably an amino group which may have substituents, and particularly preferably an ethoxy group which may have substituents, or a tertiary amino group which may have substituents.

[0135] (Y 21 ) Y 21Each is independently a divalent π-conjugated linkage group which may have substituents, where Y 21 At least one of these is a vinylene group which may have substituents. Y 21 If there are multiple Y 21 The structures may be the same or different. Also, Y 21 Multiple substituents on the compound may form bonds to create a cyclic structure. The term π-conjugated linkage is synonymous with the description given in the explanation of the terms above.

[0136] (Z 21 ) Z 21 is an aldehyde group, or -C(O)-R 25 That is the case.

[0137] (R 25 ) R 25 This is a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom which may have substituents.

[0138] From the perspective of reactivity, R 25 The group is preferably a group selected from the hydrocarbon group A which may have substituents, or an aromatic group which may have substituents, more preferably an alkyl group, and even more preferably a methyl group, an ethyl group, or a 1-butyl group.

[0139] (substituent) These Ar 21 , R 21 ~R 25 , and Y 21 Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group as described in the explanations of the terms above.

[0140] (subscript m 21 , m 22 , m 23 , n 21 ) m 21Each of these is an integer between 0 and 5, independently of the others. m 22 These are integers from 1 to 5, m 23 These are integers from 0 to 5, n 21 This is an integer between 1 and 15.

[0141] From the viewpoint of improving the nonlinear optical properties of dyes, 21 is preferably an integer between 0 and 4, more preferably an integer between 0 and 3, and even more preferably an integer between 0 and 2. From the viewpoint of improving the nonlinear optical properties of dyes, 22 m is preferably an integer between 1 and 4, and more preferably an integer between 1 and 3. 23 is preferably an integer between 0 and 4, more preferably an integer between 0 and 3, and even more preferably an integer between 0 and 2. From the viewpoint of improving the nonlinear optical properties of dyes, n 21 Preferably, it is 1 or more, more preferably 2 or more, even more preferably 3 or more, and from the viewpoint of reducing absorption loss, it is preferably 14 or less, more preferably 13 or less, even more preferably 10 or less, and particularly preferably 5 or less. As one aspect, n 21 n can be an integer between 2 and 5. That is, in one aspect, n in equation (2) and equation (3) described later. 21 It can be an integer between 2 and 5.

[0142] <Explanation of equation (3)>

[0143] [ka]

[0144] [In formula (3), Ar 21 , R 21 , R 22 , R 23 , R 24 , Y 21 , m 21 , m 22 , m 23 , and n21 This is equivalent to that in formula (2) above. Z 31 This is the group represented by formula (1c).

[0145] (Z 31 ) Z 31 This is the group represented by equation (1c), which will be described later.

[0146] <Explanation of formula (1c)>

[0147] [ka]

[0148] [In formula (1c), Ar 11 , R 11 , R 12 , R 13 , R 14 , and X 11 This is defined in equation (1) above. *J 1c1 Y in equation (3) above 21 This is the bonding position.

[0149] (*J 1c1 ) *J 1c1 Y in equation (3) above 21 This is the connection point.

[0150] (Example structure) Examples of compounds represented by formula (3) include, but are not limited to, those represented by formulas (3)-1 to (3)-32. Furthermore, these compounds may have substituents.

[0151] [ka]

[0152] [ka]

[0153] [ka]

[0154] [ka]

[0155] [ka]

[0156] [ka]

[0157] [ka]

[0158] [ka]

[0159] <Explanation of equation (4)>

[0160] [ka]

[0161] [In formula (4), R 41 and R 42 Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 41 and R 42 They may be joined together to form a ring.

[0162] (R 41 and R 42 ) R 41 and R 42 Each of these is independently a hydrogen atom, a group selected from optionally substituted hydrocarbon group A, an optionally substituted aromatic group, a hydroxyl group, an optionally substituted amino group, a thiol group, a cyano group, a halogen atom, or an optionally substituted boryl group. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above. The term "amino group which may have substituents" is synonymous with the description given in the explanation of the terms above. The term "halogen atom" is synonymous with the description given in the explanation of the terms above. A boryl group that may have substituents is defined in the same way as described in the explanation of the terms above. Also, R 41 and R 42 They may be bonded together to form a ring. 41 and R 42 When R is bonded to form a ring, 41 and R 42 Either of them may be a single bond. R 41 and R 42 The relationship can be either cis-form or trans-form.

[0163] From the viewpoint of improving nonlinear optical effects, R 41 , R 42 Each of these is independently preferably a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, more preferably a hydrogen atom, or an alkyl group, and particularly preferably a hydrogen atom.

[0164] (substituent) These R 41 and R 42Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the above-mentioned explanations, and preferably the substituent group W 1 It is a base selected from among them.

[0165] <Explanation of equation (5)>

[0166] [ka]

[0167] [In formula (5), R 51 and R 52 Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 51 and R 52 They may be bonded together to form a ring. X 51 is an oxygen atom, a sulfur atom, or NQ 51 And, Q 51 This is a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, or a boryl group which may have substituents.

[0168] (R 51 and R 52 ) R 51 and R 52 R in equation (4) 41 and R 42 It is synonymous with [the above].

[0169] From the viewpoint of improving nonlinear optical effects, R 51 , R 52Each of these is independently preferably a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, more preferably a hydrogen atom, or an alkyl group, and most preferably a hydrogen atom.

[0170] (X 51 ) X 51 is an oxygen atom, a sulfur atom, or NQ 51 That is the case.

[0171] From the perspective of improving nonlinear optical effects, X 51 It is preferable that it be a sulfur atom.

[0172] (Q 51 ) Q 51 This is a hydrogen atom, a group selected from optionally substituted hydrocarbon groups A, an optionally substituted aromatic group, a hydroxyl group, an optionally substituted amino group, a thiol group, a cyano group, a halogen atom, or an optionally substituted boryl group. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above.

[0173] From the viewpoint of film formation, groups selected from hydrocarbon groups A having 1 to 20 carbon atoms, which may have substituents, and aromatic hydrocarbon groups having 6 to 60 carbon atoms are preferred; groups selected from hydrocarbon groups A having 1 to 20 carbon atoms, which may have substituents, and aromatic hydrocarbon groups having 6 to 30 carbon atoms are more preferred; and groups selected from hydrocarbon groups A having 1 to 10 carbon atoms, which may have substituents, and aromatic hydrocarbon groups having 6 to 20 carbon atoms are particularly preferred.

[0174] (substituent) Q 51 Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the above-mentioned explanations, and preferably the substituent group W 1It is a base selected from among them.

[0175] <Explanation of equation (6)>

[0176] [ka]

[0177] [In formula (6), R 61 ~R 67 Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 61 ~R 67 At least two of them may be joined together to form a ring.

[0178] (R 61 ~R 67 ) R 61 ~R 67 R in equation (4) 41 and R 42 This is synonymous with R. 61 ~R 67 In the case of R 61 ~R 67 At least two of them may be joined together to form a ring.

[0179] From the viewpoint of improving the nonlinear optical effect, preferably, R 61 R is a hydrogen atom, a group selected from the optionally substituted hydrocarbon group A, or an optionally substituted aromatic group, 62 ~R 67 Each is independently a hydrogen atom, or a group selected from the hydrocarbon group A which may have substituents. More preferably, R 61 R is a hydrogen atom or a group selected from hydrocarbon group A which may have substituents, 62 , R 63 , R 66 , R 67R is a hydrogen atom, 64 , R 65 Each is independently a hydrogen atom or a group selected from the hydrocarbon group A which may have substituents. Most preferably, R 71 R is a hydrogen atom or a group selected from hydrocarbon group A which may have substituents, 62 , R 63 , R 66 , R 67 R is a hydrogen atom, 64 , R 65 Each of these is independently either a hydrogen atom or an alkyl group.

[0180] (substituent) These R 61 ~R 67 Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the above explanation, and preferably the substituent group W 1 It is a base selected from among them.

[0181] From the viewpoint of improving the nonlinear optical effect, Y in equations (2) and (3) 21 However, each can be expressed independently by equation (4), equation (5), or equation (6), Y 21 At least one of them is expressed by equation (4), and n in equations (2) and (3) 21 If it is 2 or more, Y 21 R inside 41 , R 42 , R 51 , R 52 , and R 61 ~R 67 is, other Y 21 R included 41 , R 42 , R 51 , R 52 , or R 61 ~R 67 It is preferable that they be connected to form a ring.

[0182] <Explanation of equation (7)>

[0183] [ka]

[0184] [In formula (7), R 31 and R 32 Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 31 and R 32 They may be joined together to form a ring.

[0185] (R 31 and R 32 ) R 31 and R 32 R in equation (4) 41 and R 42 It is synonymous with [the above].

[0186] From the viewpoint of improving the nonlinear optical effect, Y in equations (2) and (3) 21 At least one of them is expressed independently by equation (7), where n in equations (2) and (3) 21 If it is 2 or more, then R in equation (7) 31 and R 32 is, other Y 21 R included 31 or R 32 It is preferable that they be connected to form a ring.

[0187] <Method for producing the compound represented by formula (3)> In embodiments of the present invention, a method for producing a compound represented by formula (3) includes a step of reacting a compound represented by formula (1) with a base (hereinafter also referred to as "step A") and a step of reacting the product of step A with a compound represented by formula (2) (hereinafter also referred to as "step B").

[0188] The method for producing the compound represented by formula (3) is not particularly limited as long as it includes steps A and B described above. A method for producing the compound represented by formula (3) is preferably one in which the phosphorus atom and Ar contained in the compound represented by formula (1) are 11 This reaction involves a reaction in which one hydrogen atom bonded to the carbon atom between the two atoms is abstracted by a base (step A), followed by a reaction with the compound represented by formula (2) to obtain the compound represented by formula (3) (step B).

[0189] An example of a procedure for mixing each compound used in the method for producing the compound represented by formula (3) is a procedure in which the compound represented by formula (1) and a solvent are mixed under an inert gas atmosphere such as nitrogen gas, and then the base and the compound represented by formula (2) are mixed in that order and reacted. The reason for using an inert gas atmosphere here is to suppress the deactivation of bases, which are often sensitive to oxygen and moisture, and the compounds produced in step A.

[0190] The reaction temperature in step A is not particularly limited, but -100°C to 100°C is preferred, -78°C to 60°C is more preferred, and -78°C to 30°C is even more preferred in terms of obtaining a better product yield. The reaction time for step A is not particularly limited, but it is preferably 0.1 hours to 7 days, more preferably 0.1 hours to 24 hours, and even more preferably 0.1 hours to 12 hours, in terms of obtaining a better yield of the product.

[0191] The reaction temperature in step B is not particularly limited, but -100°C to 200°C is preferred, -78°C to 160°C is more preferred, and 0°C to 100°C is even more preferred in terms of obtaining a better product yield. The reaction time for step B is not particularly limited, but it is preferably 0.1 hours to 7 days, more preferably 1 hour to 5 days, and even more preferably 2 hours to 48 hours, in terms of obtaining a better yield of the product.

[0192] The compound represented by formula (3) can be separated and purified by separation methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and sublimation, or by a combination of these methods.

[0193] One embodiment of the present invention is a manufacturing method comprising, in this manner, a step A in which a compound represented by formula (1) is reacted with a base, and a step B in which the product of the first step is reacted with a compound represented by formula (2) to obtain a compound represented by formula (3).

[0194] Furthermore, as another positional aspect of the manufacturing method according to the embodiment of the present invention, a method is obtained by further modifying the compound represented by formula (3) to obtain another compound represented by formula (3). As a step of further modifying the compound represented by formula (3), for example, R 22 Ya R 24 The process of converting to another substituent, R 11 Ya R 12 The process of converting to another substituent, Q 11 Examples include the process of converting one substituent to another.

[0195] (base) The base (hereinafter also referred to as a basic compound) can be any chemical species that accepts a proton or donates a base pair, and can be used by dissolving or suspending it in a solvent; it is not particularly limited. From the viewpoint of improving reactivity, the base is preferably a carbonate, metal hydroxide, metal alkoxide, alkyl metal, or metal hydride.

[0196] Preferred basic compounds include alkali metal and alkaline earth metal carbonates such as sodium carbonate and potassium carbonate; metal hydroxides such as alkali metals and alkaline earth metals such as sodium hydroxide and barium hydroxide; metal alkoxides such as sodium ethoxide and sodium t-butoxide; and alkali metals such as n-butyllithium, tert-butyllithium, and phenyllithium. Particularly preferred are metal alkoxides such as sodium ethoxide and sodium t-butoxide, and alkali metals such as n-butyllithium, tert-butyllithium, and phenyllithium. These basic compounds may be used individually or in combination of two or more. stomach.

[0197] The amount of base used is preferably 0.1 to 10 molar equivalents, more preferably 0.5 to 1.2 molar equivalents, relative to the compound represented by formula (1), in order to reduce side reactions and improve the reaction yield.

[0198] (solvent) The steps of reacting the compound represented by formula (1) with a base, and further reacting the product of the first step with the compound represented by formula (2) to obtain the compound represented by formula (3), are preferably carried out in the presence of a solvent.

[0199] Preferred solvents include hydrocarbon solvents, aromatic solvents, ether solvents, amide solvents, amine solvents, halogen solvents, sulfoxide solvents, and the like. Of these, aromatic solvents, ether solvents, amide solvents, amine solvents, and sulfoxide solvents are particularly preferred due to their high stability under reaction conditions.

[0200] Examples of hydrocarbon solvents include hexane, heptane, and octane. Examples of aromatic solvents include benzene, toluene, and xylene. Examples of alcoholic solvents include methanol, ethanol, and butanol. Examples of ether-based solvents include tetrahydrofuran, anisole, and ethylene glycol. Examples include dimethyl ether.

[0201] Examples of amide solvents include N,N-dimethylformamide, N,N-diethylformamide, and N,N-dimethylacetamide. Examples of ketone solvents include acetone, methyl ethyl ketone, and acetophenone. Examples of amine solvents include triethylamine and N,N-diethylaniline.

[0202] Examples of halogenated solvents include trifluoromethylbenzene. Examples of sulfoxide solvents include dimethyl sulfoxide.

[0203] These solvents may be used individually or as a mixture of two or more. When using a mixture of two or more solvents, they may be miscible or miscible.

[0204] The solvent should be used in an amount sufficient to form a homogeneous reaction system without making the reaction system excessive, preferably in an amount of 0.01 to 1000 times the weight of the compound represented by formula (1), and more preferably in an amount of 1 to 500 times.

[0205] Furthermore, in order to efficiently react the basic compounds, a surfactant may be added to the reaction system in any ratio relative to the solvent, or the surfactant itself may be used as the solvent.

[0206] <Compound represented by formula (1)> As described above, the manufacturing method according to the embodiment of the present invention may preferably use the compound represented by formula (1) as a synthetic intermediate. The present invention also relates to the compound represented by formula (1). [Examples]

[0207] 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 can be modified and implemented as such without departing from the paper format.

[0208] [ 1 [Measurement of H-NMR] Nuclear magnetic resonance spectrum ( 1 ¹H-NMR was measured using a JEOL Ltd. JNM-ECZ400S, with CDCl3 as the solvent, and the chemical shift value δ from the internal standard tetramethylsilane is expressed in ppm. The symbols used have the following meanings. s: singlet, d: doublet, dd: double doublet, t: triplet, m: multiplet

[0209] <Synthesis of Compound 1> Compound 1, described below, was synthesized by the same method as compound 10b described in Non-Patent Document 1.

[0210] [ka]

[0211] <Synthesis of Compound 2>

[0212] [ka]

[0213] Under a nitrogen stream, 4-bromosalicylicaldehyde (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-necked flask and stirred. After cooling to 0°C in an ice bath, benzyl bromide (20.5 g, 0.12 mol) was added dropwise, and the mixture was stirred at 0°C for 2 hours. After the reaction, the mixture was heated to room temperature, 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 2 (7.60 g, yield 77.6%).

[0214] <Synthesis of Compound 3>

[0215] [ka]

[0216] Under a nitrogen atmosphere, compound 2 (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-necked 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 heated 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 3 (17.4 g, yield 83.7%).

[0217] <Synthesis of Compound 4>

[0218] [ka]

[0219] Under a nitrogen atmosphere, in a 500 mL three-necked flask, a solution of compound 3 (17.0 g, 45.8 mmol) and 2,4,6-trimethylaniline (9.30 g, 68.7 mmol) in toluene (229 mL) was added. Sodium tert-butoxide (11.0 g, 114.5 mmol), palladium acetate (103 mg, 0.46 mmol), and 2,2'-bis(diphenylphosphin-1-1')-binaphthyl (BINAP) (570 mg, 0.92 mmol) were then added, and the mixture was stirred 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 4 (13.7 g, yield 70.3%).

[0220] <Synthesis of Compound 5>

[0221] [ka]

[0222] 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. Iodine (201 g, 0.80 mol) was then added. The reaction solution was then heated to 35°C and stirred for 7 hours. After the reaction was complete, the reaction solution was diluted with DCM (800 mL) and washed with saturated sodium thiosulfate aqueous solution. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 5 (74.0 g, yield 50.4%).

[0223] <Synthesis of Compound 6>

[0224] [ka]

[0225] Under a nitrogen atmosphere, a solution of compound 5 (20.0 g, 72.2 mmol) in DMF (200 mL) was cooled to 0°C in a 500 mL flask, and then tert-butyldimethylchlorosilane (TBDMSCl) (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 6 (22.9 g, yield 81.1%).

[0226] <Synthesis of Compound 7>

[0227] [ka]

[0228] Under a nitrogen atmosphere, in a 500 mL three-necked flask, a solution of compound 4 (11.9 g, 28.0 mmol) and compound 6 (13.1 g, 33.6 mmol) in toluene (186 mL) was added to sodium tert-butoxide (6.72 g, 69.9 mmol), Pd2(dba)3 (512 mg, 0.56 mmol), and tert-Bu3PHBF4 (649 mg, 2.24 mmol). The mixture was then 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 7 (12.1 g, yield 62.9%).

[0229] <Synthesis of Compound 8>

[0230] [ka]

[0231] Under a nitrogen stream, a solution of compound 7 (12.0 g, 17.4 mmol) in THF (120 mL) was cooled to -78°C in a 500 mL three-necked flask, 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 it 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 8 (9.09 g, yield 72.8%).

[0232] <Synthesis of Compound 9>

[0233] [ka]

[0234] Under a nitrogen stream, potassium hydroxide (17.8 g, 0.28 mol) was slowly added to a DMSO (540 mL) solution of dihexylamine (25.0 g, 0.14 mol) in a 500 mL three-necked flask. The mixture was stirred at room temperature for 30 minutes, and then 1-bromo-3,5-dimethylbenzene (50.0 g, 0.28 mol) was added dropwise. After the addition was complete, the temperature was raised to 50°C and the mixture was stirred for 9 hours. After the reaction, the reaction solution was poured into water (500 mL) and extracted with ethyl acetate (800 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 9 (25.2 g, yield 64.4%).

[0235] <Synthesis of Compound 10>

[0236] [ka]

[0237] Under a nitrogen atmosphere, compound 9 (22.2 g, 76.7 mmol) and 4 M aqueous hydrogen chloride solution (114 mL) were mixed in a 500 mL three-necked flask. After cooling to -5°C, sodium nitrite solution (5.82 g, 84.4 mmol) aqueous solution (3 mL) was added dropwise while stirring. After addition, the mixture was stirred at -5°C to 0°C for 1 hour. Then, 8 M aqueous hydrogen chloride solution (205 mL) was added to the reaction solution, and zinc powder (22.1 g, 337 mmol) was slowly added at 0°C. The reaction solution was heated to 25°C and stirred for 4 hours. After stirring, it was neutralized with sodium hydroxide 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 10 (15.1 g, yield 64.5%).

[0238] <Synthesis of Compound 11>

[0239] [ka]

[0240] Under a nitrogen atmosphere, in a 500 mL three-necked flask, a solution of compound 3 (19.3 g, 51.9 mmol) and compound 10 (15.8 g, 51.9 mmol) in toluene (259 mL) was prepared. Sodium tert-butoxide (12.5 g, 130 mmol), palladium acetate (116 mg, 0.52 mmol), and 2,2'-bis(diphenylphosphin-1-1')-binaphthyl (BINAP) (646 mg, 1.04 mmol) were added, and the mixture was stirred at 100 °C for 6 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 11 (24.0 g, yield 73.1%).

[0241] <Synthesis of Compound 12>

[0242] [ka]

[0243] Under a nitrogen atmosphere, in a 100 mL three-necked flask, a solution of compound 11 (595 mg, 1.0 mmol) and compound 6 (470 mg, 1.2 mmol) in toluene (6.70 mL) was added. Sodium tert-butoxide (240 g, 2.5 mmol), Pd2(dba)3 (18.0 mg, 0.02 mmol), and tert-Bu3PHBF4 (23 mg, 0.039 mmol) were then added, and the mixture was stirred at 100 °C for 8 hours. After the reaction, water (10 mL) was added to the reaction solution, and it was extracted with ethyl acetate (20 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 12 (586 mg, yield 63.6%).

[0244] <Synthesis of Compound 13>

[0245] [ka]

[0246] Under a nitrogen stream, a solution of compound 12 (2.10 g, 2.4 mmol) in THF (21 mL) in a 100 mL three-necked flask was cooled to -78 °C, and n-BuLi (1.6 M in hexane, 1.70 mL) was added. After stirring at -78 °C for 1 hour, DMF (0.74 mL) diluted with THF (0.8 mL) was added, and the temperature was raised to 0 °C and stirred for 3 hours. After the reaction, water (50 mL) was added to the reaction solution and 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 13 (1.56 g, yield 73.1%).

[0247] <Synthesis of Compound 14>

[0248] [ka]

[0249] Under a nitrogen stream, triethylamine (55.9 mL, 0.40 mol) was added to a solution of 4-bromobenzyl alcohol (50.0 g, 0.27 mol) in DMF (835 mL) in a 2 L flask, and the reaction solution was cooled to 0°C. While stirring, tert-butylchlorodiphenylsilane (83.0 g, 0.30 mol) was added dropwise to the reaction solution, and the temperature was raised to room temperature, after which stirring was continued for 4 hours. After the reaction, water (1.0 L) was added to the reaction solution, and it was extracted with ethyl acetate (2.0 L). The organic layer was washed with water (250 mL x 2), dried over magnesium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 14 (100.9 g, yield 88.7%).

[0250] <Synthesis of Compound 15>

[0251] [ka]

[0252] Under a nitrogen atmosphere, a solution of acetone cyanohydrin (19.4 g, 0.23 mol) in pyridine (18.1 mL) was cooled to -10°C in a 200 mL three-necked flask, and chlorotrimethylsilane (25.0 mL, 0.20 mol) was added while stirring. After stirring at -10°C for 20 minutes, the temperature was raised to room temperature and stirred for a further 14 hours. After the reaction, water (100 mL) was added to the reaction solution and extracted with ethyl acetate (200 mL). The organic layer was washed with water (100 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. Compound 15 (22.1 g, yield 71.1%) was obtained by vacuum distillation of the resulting crude product.

[0253] <Synthesis of Compound 16>

[0254] [ka]

[0255] Under a nitrogen stream, a solution of compound 14 (44.5 g, 104.5 mmol) in THF (615 mL) was cooled to -72°C in a 2 L three-necked flask, and n-BuLi hexane solution (1.6 mol / L, 71.8 mL, 115 mmol) was added dropwise over 25 minutes. After the addition was complete, the mixture was stirred at -72°C for 40 minutes. Then, at -72°C, a solution of compound 15 (19.7 g, 125.4 mmol) in THF (197 mL) was added dropwise to the reaction solution over 15 minutes. After addition, the mixture was stirred at 0°C for 1.5 hours, and then stirred at room temperature for 2 hours. Then, aqueous hydrogen chloride solution (2.0 mol / L, 261 mL) was added at room temperature, and the mixture was stirred for 30 minutes. The product was extracted with ethyl acetate (1000 mL), the organic layer was washed with water (250 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel chromatography to obtain compound 16 (31.8 g, yield 70.1%).

[0256] <Synthesis of Compound 17>

[0257] [ka]

[0258] Under a nitrogen atmosphere, compound 16 (18.0 g, 41.6 mmol) and malononitrile (8.25 g, 125 mmol) were dissolved in anhydrous pyridine (90 mL) in a 300 mL three-necked flask. Molecular sieves 3A (18 g) were added to the solution, followed by the addition of acetic acid (150 mg, 2.5 mmol), and the mixture was stirred at room temperature for 96 hours. After removing the molecular sieves by filtration, the filtrate was flushed with water (500 mL), and the resulting precipitate was collected by filtration. The filtered material was washed with water and dried. The resulting crude compound was purified by silica gel column chromatography to obtain compound 17 (9.6 g, yield 43.6%).

[0259] <Synthesis of Compound 18>

[0260] [ka]

[0261] Under a nitrogen atmosphere, compound 17 (20.0 g, 37.8 mmol) was dissolved in anhydrous THF (160 mL) in a 300 mL three-necked flask and stirred at room temperature. To the solution, a THF solution of tetra-n-butylammonium fluoride (TBAF) (1 mol / L, 56.6 mL, 56.6 mmol) was added and stirred at room temperature for 24 hours. After the reaction, water (100 mL) was added to the reaction solution and extracted with dichloromethane (100 mL x 3). The organic layer was washed with water (100 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 18 (6.2 g, yield 56.4%).

[0262] <Synthesis of Compound 19>

[0263] [ka]

[0264] Under a nitrogen atmosphere, compound 18 (6.2 g, 21.3 mmol) was dissolved in anhydrous DCM (50 mL) in a 200 mL three-necked flask and stirred at room temperature. Thionyl chloride (5.06 g, 42.6 mmol) was added to the solution and stirred at room temperature for 24 hours. The organic layer was washed with water (50 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 19 (4.0 g, yield 60.7%).

[0265] <Synthesis of Compound 20>

[0266] [ka]

[0267] Under a nitrogen atmosphere, compound 19 (4.0 g, 12.9 mmol) and triphenylphosphine (16.9 g, 64.6 mmol) were dissolved in anhydrous toluene (40 mL) in a 200 mL three-necked flask and stirred for 8 hours while heating to reflux temperature. After the reaction, the resulting white solid was collected by filtration, washed with toluene (50 mL), and dried under reduced pressure to obtain compound 20 (5.8 g, yield 78.5%).

[0268] The results of the NMR measurement of compound 20 are shown below. 1 H-NMR(400MHz,CDCl3)δ7.77-7.82(m,9H),7.68-7.63(m,6H),7.49(dd,2H),7.41(dd,2H),5.82(d,2H),1.70(s,6H)

[0269] <Synthesis of Compound 21>

[0270] [ka]

[0271] Under a nitrogen stream, a solution of 4-bromobenzyloxy-tert-butyldimethylsilane (50.0 g, 166 mmol) in THF (1.0 L) was cooled to -72°C in a 2 L three-necked flask, and n-BuLi hexane solution (1.6 mol / L, 114 mL, 182.6 mmol) was added dropwise over 25 minutes. After the addition was complete, the mixture was stirred at -72°C for 40 minutes. Then, at -72°C, a solution of dimethylformamide (DMF) (25.7 mL, 332 mmol) diluted with THF (25 mL) was added dropwise to the reaction solution over 15 minutes. After addition, the mixture was stirred at 0°C for 2 hours, and then stirred at room temperature for another 2 hours. Then, water (500 mL) was added to the reaction solution at room temperature, and the mixture was stirred for 30 minutes. The product was extracted with ethyl acetate (1000 mL), the organic layer was washed with water (250 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel chromatography to obtain compound 21 (31.7 g, yield 76.4%).

[0272] <Synthesis of Compound 22>

[0273] [ka]

[0274] Under a nitrogen stream, in a 1 L three-necked flask, a solution of compound 21 (20.8 g, 83.1 mmol) and 2,2,2-trifluoro-1-phenylethane-1-one (28.9 g, 166.2 mmol) in THF (250 mL) was added to a solution of diazaabicycloundecene (DBU) (2.5 mL, 16.6 mmol) and 2-phenyl-6,7-dihydro-5H-pyrrole[2,1-c][1,2,4]2-triazolium chloride (1.84 g, 8.31 mmol) in THF (9 mL). The mixture was stirred at room temperature for 24 hours. Water (200 mL) was added to the reaction solution, and it was extracted with dichloromethane (100 mL x 3). The organic layer was washed with water (50 mL x 3), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 22 (22.4 g, yield 62.3%).

[0275] <Synthesis of Compound 23>

[0276] [ka]

[0277] Under a nitrogen atmosphere, compound 22 (0.90 g, 2.12 mmol) and malononitrile (0.70 g, 10.6 mmol) were dissolved in anhydrous THF (10 mL) in a 30 mL Schlenk flask and stirred at room temperature. Then, piperidine (0.63 mL, 6.4 mmol) and ethoxylithium (110 mg, 2.12 mmol) were added, and the mixture was stirred for 8 hours while heating to reflux temperature. After cooling to room temperature, precipitates were removed by filtration, and the collected filtrate was concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 23 (400 mg, yield 36.2%).

[0278] <Synthesis of Compound 24>

[0279] [ka]

[0280] Under a nitrogen atmosphere, compound 23 (3.80 g, 8.04 mmol) and malononitrile (2.66 g, 40.2 mmol) were dissolved in anhydrous pyridine (20 mL) in a 100 mL three-necked flask. Molecular sieves 3A (5 g) were added to the solution, followed by the addition of acetic acid (230 mg, 4.02 mmol), and the mixture was stirred at room temperature for 96 hours. After removing the molecular sieves by filtration, the filtrate was flushed into water (200 mL) and extracted with dichloromethane (50 mL x 2). The organic layer was washed with water (20 mL x 3), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 24 (1.8 g, yield 42.9%).

[0281] <Synthesis of Compound 25>

[0282] [ka]

[0283] Under a nitrogen atmosphere, compound 24 (1.80 g, 3.45 mmol) was dissolved in anhydrous THF (100 mL) in a 300 mL three-necked flask and cooled to 0°C. A THF solution of tetra-n-butylammonium fluoride (TBAF) (1 mol / L, 3.80 mL, 3.80 mmol) was added to the solution, and the mixture was stirred at 0°C for 2 hours, followed by stirring at room temperature for 2 hours. After the reaction, saturated ammonium chloride solution (100 mL) was added to the reaction solution, and the mixture was extracted with dichloromethane (100 mL x 3). The organic layer was washed with water (100 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 25 (500 mg, yield 35.6%).

[0284] <Synthesis of Compound 26>

[0285] [ka]

[0286] Under a nitrogen atmosphere, compound 25 (500 mg, 1.23 mmol) was dissolved in anhydrous DCM (30 mL) in a 100 mL three-necked flask and stirred at room temperature. Thionyl chloride (292 mg, 2.45 mmol) was added to the solution and stirred at room temperature for 12 hours. The organic layer was washed with water (50 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 26 (420 mg, yield 82.3%).

[0287] <Synthesis of Compound 27>

[0288] [ka]

[0289] Under a nitrogen atmosphere, compound 26 (200 mg, 4.70 mmol) and triphenylphosphine (616 mg, 2.35 mmol) were dissolved in anhydrous toluene (20 mL) in a 200 mL three-necked flask and stirred for 9 hours while heating to reflux temperature. After the reaction, the resulting white solid was collected by filtration, washed with toluene (20 mL), and dried under reduced pressure to obtain compound 27 (250 mg, yield 81.6%).

[0290] The results of the NMR measurement of compound 27 are shown below. 1 H-NMR(400MHz,CDCl3)δ7.78-7.73(m,9H),7.64-7.58(m,7H),7.52(t,2H),7.33(t,2H),7.01(d,2H),5.82(dt,2H)

[0291] [Example 1] <Synthesis of pigment 1>

[0292] [ka]

[0293] Under a nitrogen stream, compound 20 (1.50 g, 2.62 mmol) was dissolved in anhydrous THF (10 mL) in a 30 mL Schlenk flask. The solution was then cooled to -78°C, and n-BuLi hexane solution (1.6 mol / L, 1.47 mL, 2.36 mmol) was added dropwise. After the addition was complete, the mixture was stirred at -78°C for 15 minutes, and compound 1 (1.33 g, 2.62 mmol) was added. After the addition, the mixture was raised to room temperature and stirred for 30 minutes. Further stirring was carried out at reflux temperature for 24 hours. After the reaction, methanol (1.5 mL) was added, and the reaction solution was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain dye 1 (300 mg, yield 15.0%).

[0294] The results of the NMR measurement of dye 1 are shown below. 1H-NMR(400MHz,CDCl3)δ7.88(d,2H),7.60(d,2H),7.30-7.51(m,8H),7.11(d,1H),7.04(d,1H),6.84(d,1H),6.81(d,1H) ),6.33(dd,1H),6.23(d,1H),5.17(s,2H),3.73(t,2H),3.47(t,2H),3.01(s,3H),1.85(s,6H),0.88(s,9H),0.01(s,6H)

[0295] [Example 2] <Synthesis of pigment 2>

[0296] [ka]

[0297] Under a nitrogen stream, compound 20 (600 mg, 1.05 mmol) was dissolved in anhydrous THF (10 mL) in a 30 mL Schlenk flask. The solution was then cooled to -78°C, and n-BuLi hexane solution (1.6 mol / L, 0.59 mL, 0.94 mmol) was added dropwise. After the addition was complete, the mixture was stirred at -78°C for 15 minutes, and compound 8 (753 mg, 1.05 mmol) was added. After the addition, the mixture was raised to room temperature and stirred for 30 minutes. Further stirring was carried out at reflux temperature for 24 hours. After the reaction, methanol (0.6 mL) was added, and the reaction solution was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain dye 2 (210 mg, yield 20.5%).

[0298] The results of the NMR measurement of dye 2 are shown below. 1H-NMR(400MHz,CDCl3)δ7.89(d,2H),7.61(d,2H),7.22-7.41(m,12H),7.05(d ,1H),6.81-6.90(m,5H),6.57(s,1H),6.36(s,1H),4.97(s,2H),3.77(t,2H), 3.77(t,2H),6.23(d,1H),5.17(s,2H),3.77(t,2H),3.45(s,2H),2.96(s,2H) ,2.34(s,3H),1.96(s,6H),1.86(s,6H),1.55(s,4H),0.88(s,9H),0.04(s,6H)

[0299] [Example 3] <Synthesis of pigment 3>

[0300] [ka]

[0301] Under a nitrogen stream, compound 20 (600 mg, 1.05 mmol) was dissolved in anhydrous THF (10 mL) in a 30 mL Schlenk flask. The solution was then cooled to -78°C, and n-BuLi hexane solution (1.6 mol / L, 0.59 mL, 0.94 mmol) was added dropwise. After the addition was complete, the mixture was stirred at -78°C for 15 minutes, and compound 13 (930 mg, 1.05 mmol) was added. After the addition, the mixture was raised to room temperature and stirred for 30 minutes. Further stirring was carried out at reflux temperature for 24 hours. After the reaction, methanol (0.6 mL) was added, and the reaction solution was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain dye 3 (180 mg, yield 15.4%).

[0302] The results of the NMR measurement of dye 3 are shown below. 1H-NMR(400MHz,CDCl3)δ7.90(d,2H),7.60(d,2H),7.28-7.40(m,8H),7.11(d,1H), 7.07(d,1H),6.95(d,2H),6.85(d,1H),6.83(d,1H),6.70(d,2H),6.47(t,1H),6.40 (dd,1H),6.35(s,2H),5.00(s,2H),3.81(t,2H),3.41(t,2H),3.26(t,4H),2.91(s, 3H),1.95(s,6H),1.86(s,6H),1.34(s,12H),0.91(t,6H),0.88(s,9H),0.02(s,6H)

[0303] [Example 4] <Synthesis of pigment 4>

[0304] [ka]

[0305] Under a nitrogen atmosphere, compound 27 (175 mg, 0.203 mmol) was dissolved in anhydrous THF (3 mL) in a 10 mL Schlenk flask. The solution was then cooled to -78°C, and n-BuLi hexane solution (1.6 mol / L, 0.11 mL, 0.18 mmol) was added. The mixture was then stirred at -78°C for 15 minutes, and compound 13 (140 mg, 1.05 mmol) was added. After the addition, the mixture was raised to room temperature and stirred for 30 minutes. Further stirring was carried out at reflux temperature for 24 hours. After the reaction, methanol (0.2 mL) was added, and the reaction solution was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain dye 4 (45 mg, yield 25.1%).

[0306] The results of the NMR measurement of dye 4 are shown below. 1H-NMR(400MHz,CDCl3)δ8.10(d,2H),7.80(d,2H),7.28-7.40(m,13H),7.13(d,1H), 7.09(d,1H),6.96(d,2H),6.87(d,1H),6.85(d,1H),6.73(d,2H),6.48(t,1H),6.40 (dd,1H),6.35(s,2H),5.00(s,2H),3.81(t,2H),3.41(t,2H),3.26(t,4H),2.91(s, 3H),1.95(s,6H),1.86(s,6H),1.34(s,12H),0.91(t,6H),0.87(s,9H),0.01(s,6H)

[0307] Examples 1-4 demonstrate that by using a phosphorus compound having a structure in which an aryl group is directly bonded to an electron-withdrawing group such as a tricyanofuran (TCF) ring as a synthetic intermediate, and reacting it with an aldehyde compound containing an electron-donating group and a π-conjugated chain (a so-called Wittig reaction), it is possible to synthesize novel compounds (dyes 1-4) in which an aryl group is directly bonded to an electron-withdrawing group such as a tricyanofuran (TCF) ring, and an amine, which is an electron-donating group, is bonded to a structure in which a π-conjugated chain is extended from the aryl group. [Industrial applicability]

[0308] The present invention provides a method for producing a compound, which includes the step of reacting a compound represented by formula (1) with a base, and then reacting the product of the first step with a compound represented by formula (2) to obtain a compound represented by formula (3). This method can be used as an industrially advantageous method for obtaining novel compounds in which an aryl group is directly bonded to an electron-withdrawing group such as a tricyanofuran (TCF) ring, and an electron-donating amine group is bonded to a structure in which a π-conjugated chain extends from the aryl group. Furthermore, the obtained compound represented by formula (3) can be used, for example, as a nonlinear optical material.

Claims

1. A step of reacting a compound represented by the following formula (1) with a base, The process includes a step of reacting the product of the above step with a compound represented by the following formula (2). A method for producing the compound represented by the following formula (3). 【Chemistry 1】 [In formula (1), Ar １１ is a divalent aromatic group which may have substituents, R １１ and R １２ are each independently a group selected from the following hydrocarbon group group A which may have a substituent, or an aromatic group which may have a substituent, and R １１ and R １２ may be bonded to each other to form a ring, or R １１ and R １２ may form a carbonyl group together with R １１ and R １２ and the carbon atom to which they are bonded, R １３ and R １４ Each of these is independently a cyano group, a C2-C30 alkyloxycarbonyl group which may have substituents, or a C1-C30 alkylsulfonyl group which may have substituents. X １１ is an oxygen atom, a sulfur atom, or N-Q １１ And, Q １１ This is a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. V １１ This is a group represented by the following formula (1a) or formula (1b). 【Chemistry 2】 [In formula (1a), *J １ａ１ This is Ar in formula (1) above. １１ This is the bonding position with, R １ａ１ , R １ａ２ , and R １ａ３ Each of these is independently a group selected from the following hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents. P is a phosphorus atom, X － It is a monovalent anion. 【Transformation 3】 [In formula (1b), *J １ｂ１ This is Ar in formula (1) above. １１ This is the bonding position with, R １ｂ１ and R １ｂ２ Each of these is independently a group selected from the following hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents. P represents a phosphorus atom. <Hydroxide Group A> A branched, linear, or cyclic alkyl group having 1 to 30 carbon atoms, a branched, linear, or cyclic alkenyl group having 2 to 30 carbon atoms, or a branched, linear, or cyclic alkynyl group having 2 to 30 carbon atoms, wherein part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group, and / or a silicon atom. 【Chemistry 4】 [In formula (2), Ar ２１ Each of these is independently a divalent aromatic group which may have substituents, R ２１ and R ２３ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A which may have substituents, or a divalent aromatic group which may have substituents. R ２２ and R ２４ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom. Y ２１ Each is independently a divalent π-conjugated linkage group which may have substituents, where Y ２１ At least one of them is a vinylene group which may have substituents, Z ２１ is an aldehyde group, or -C(O)-R ２５ And, R ２５ This is a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, I understand ２１ Each of these is an integer between 0 and 5, independently of the others. I understand ２２ These are integers from 1 to 5, I understand ２３ is an integer from 0 to 5, n ２１ [This is an integer between 1 and 15.] 【Transformation 5】 [In formula (3), Ar ２１ , R ２１ , R ２２ , R ２３ , R ２４ , Y ２１ , m ２１ , m ２２ , m ２３ , and n ２１ This is equivalent to that in formula (2) above. Z ３１ This is the group represented by the following formula (1c). 【Transformation 6】 [In formula (1c), Ar １１ , R １１ , R １２ , R １３ , R １４ , and X １１ This is as defined in formula (1) above. *J １ｃ１ Y in equation (3) above ２１ This is the bonding position.

2. Y in equations (2) and (3) ２１ At least one of them is independently represented by the following formula (7), where n in formulas (2) and (3) is ２１ If it is 2 or more, then R in formula (7) below ３１ and R ３２ is, other Y ２１ R included ３１ or R ３２ The manufacturing method according to claim 1, which may be connected to form a ring. 【Transformation 7】 [In formula (7), R ３１ and R ３２ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R ３１ and R ３２ They may be joined together to form a ring.

3. Y in equations (2) and (3) ２１ However, each can be expressed independently by the following equations (4), (5), or (6): Y ２１ At least one of them is expressed by the following equation (4), n in formulas (2) and (3) ２１ If the number is 2 or more, the Y ２１ R inside ４１ , R ４２ , R ５１ , R ５２ , and R ６１ ~R ６７ is, other Y ２１ R included ４１ , R ４２ , R ５１ , R ５２ , or R ６１ ~R ６７ The manufacturing method according to claim 1 or 2, which may be connected to form a ring. 【Transformation 8】 [In formula (4), R ４１ and R ４２ each independently represent a hydrogen atom, a group selected from the aforementioned hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom, or a boryl group which may have a substituent, and R ４１ and R ４２ may be bonded to each other to form a ring.] 【Chemistry 9】 [In formula (5), R ５１ and R ５２ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R ５１ and R ５２ They may be bonded together to form a ring. X ５１ is an oxygen atom, a sulfur atom, or N-Q ５１ And, Q ５１ is a hydrogen atom, a group selected from the aforementioned hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom, or a boryl group which may have a substituent.] 【Chemistry 10】 [In formula (6), R ６１ ~R ６７ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R ６１ ~R ６７ At least two of them may be joined together to form a ring.

4. n in formulas (2) and (3) ２１ The manufacturing method according to claim 1 or 2, wherein is an integer from 2 to 5.

5. The manufacturing method according to claim 1 or 2, wherein the base is a carbonate, a metal hydroxide, a metal alkoxide, an alkyl metal, or a metal hydride.

6. A compound represented by the following formula (1). 【Chemistry 11】 [In formula (1), Ar １１ is a divalent aromatic group which may have substituents, R １１ and R １２ Each of these is independently a group selected from the following hydrocarbon group A which may have substituents, or an aromatic group which may have substituents, and R １１ and R １２ They may be bonded together to form a ring, or R １１ and R １２ R １１ and R １２ These may also form a carbonyl group together with the carbon atom to which they are bonded. R １３ and R １４ Each of these is independently a cyano group, a C2-C30 alkyloxycarbonyl group which may have substituents, or a C1-C30 alkylsulfonyl group which may have substituents. X １１ is an oxygen atom, a sulfur atom, or N-Q １１ And, Q １１ This is a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. V １１ This is a group represented by the following formula (1a) or formula (1b). 【Chemistry 12】 [In formula (1a), *J １ａ１ This is Ar in formula (1) above. １１ This is the bonding position with, R １ａ１ , R １ａ２ , and R １ａ３ Each of these is independently a group selected from the following hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents. P is a phosphorus atom, X － It is a monovalent anion. 【Chemistry 13】 [In formula (1b), *J １ｂ１ This is Ar in formula (1) above. １１ This is the bonding position with, R １ｂ１ and R １ｂ２ Each of these is independently a group selected from the following hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents. P represents a phosphorus atom. <Hydroxide Group A> A branched, linear, or cyclic alkyl group having 1 to 30 carbon atoms, a branched, linear, or cyclic alkenyl group having 2 to 30 carbon atoms, or a branched, linear, or cyclic alkynyl group having 2 to 30 carbon atoms, wherein part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group, and / or a silicon atom.

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