JP2009139911A - Optical filter containing squarylium compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical filter that absorbs long wavelength ultraviolet radiation, has high transparency to visible light and is stable to light. <P>SOLUTION: The optical filter contains a squarylium compound represented by general formula (I), wherein R<SP>1a</SP>, R<SP>1b</SP>, R<SP>2a</SP>and R<SP>2b</SP>are the same or different from each other, and represent an alkyl group that may have a substituent, an alkanoyl group that may have a substituent, an aralkyl group that may have a substituent, a heterocyclic alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent; and at least either of R<SP>1a</SP>and R<SP>2a</SP>and of R<SP>1b</SP>and R<SP>2b</SP>represents an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, or R<SP>1a</SP>and R<SP>2a</SP>, or R<SP>1b</SP>and R<SP>2b</SP>may be combined with an adjacent nitrogen atom to form a heterocycle that may have a substituent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an optical filter containing a squarylium compound.

A compound that absorbs light having a wavelength in the ultraviolet region (320 to 400 nm) is used for display materials and the like. As a compound that absorbs light having a wavelength in the ultraviolet region, a compound having excellent ultraviolet absorption performance of 380 nm or less is preferable in order to prevent deterioration of liquid crystal or decomposition of a near-infrared absorbing dye of a plasma display, and it is used for display materials. For this purpose, those having high transparency to visible light are preferred. However, such general-purpose compounds are extremely limited.
As a filter using a squarylium compound, a filter that shields light with a wavelength of 380 to 450 nm is known (see Patent Document 1). A method of synthesizing a squarylium compound by reacting squaric acid with a secondary aromatic amine is known (see Non-Patent Document 1 and Non-Patent Document 2). Further, a plastic stabilizer using a squarylium compound (see Patent Document 2) and an optical recording material (see Patent Document 3) are known.
Tetrahedron Letters, (36), 3509-3515 (1967) Tetrahedron Letters, (11), pages 1339 to 1343 (1968) International Publication No. 2006/011514 Pamphlet Japanese Patent Publication No.54-41618 Japanese Patent Laid-Open No. 11-110815

An object of the present invention is to provide an optical filter that absorbs long-wavelength ultraviolet light, has high transparency to visible light, and is stable to light.

  The present invention provides the following [1] to [14].

[1] General formula (I)

(Wherein R ^1a , R ^1b , R ^2a , and R ^2b are the same or different and each represents an alkyl group that may have a substituent, an alkanoyl group that may have a substituent, or a substituent. An aralkyl group which may have, a heterocyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent , R ^1a and R ^2a , and at least one of R ^1b and R ^2b each represents an optionally substituted aryl group, or an optionally substituted heterocyclic group, or R ^1a and R ^2a , or R ^1b and R ^2b together with the adjacent nitrogen atom may form a heterocyclic ring which may have a substituent, respectively) filter.

[2] The squarylium compound has the general formula (II)

(In the formula, R ³ and R ¹⁴ are the same or different and each represents an optionally substituted alkyl group or an optionally substituted aryl group; R ⁴ , R ⁵ , R ^6; , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same or different and are a hydrogen atom, hydroxyl group, carboxyl group, halogen atom, nitro group, cyano group, triphenylmethyl A group, an alkyl-substituted or unsubstituted amino group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent; A heterocyclic alkyl group which may have, an aryl group which may have a substituent, an aryloxy group which may have a substituent, or a heterocyclic group which may have a substituent; Represent) A Aririumu compound [1] optical filter according.

[3] The optical filter according to [2], wherein R ³ and R ¹⁴ are the same or different and are an alkyl group which may have a substituent.
[4] R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same or different and are a hydrogen atom, a halogen atom, a cyano group, a substitution The optical filter according to [3], which is an alkyl group which may have a group or an alkoxyl group which may have a substituent.
[5] At least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl The optical filter according to [3], which is a group.

[6] At least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group, and R ⁹ , R ¹⁰ , R ¹¹ , R ¹² And at least one of R ¹³ is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group.
[7] R ³ and R ¹⁴ are the same or different and are a fluorine-substituted alkyl group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and The optical filter according to [2], wherein R ¹³ is the same or different and is a hydrogen atom or a cyano group.
[8] R ³ and R ¹⁴ are the same or different and are an aryl group which may have a substituent, and at least one of R ⁴ , R ⁸ , R ⁹ and R ¹³ is an alkyl group or an alkoxyl group. An optical filter according to [2].

[9] The optical filter according to [8], wherein at least one of R ⁴ and R ⁸ is an alkyl group or an alkoxyl group, and at least one of R ⁹ and R ¹³ is an alkyl group or an alkoxyl group.

[10] General formula (IIa)

(Wherein R ^3a and R ^14a are the same or different and represent an alkyl group which may have a substituent, and R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a , R ^11a , R ^12a , and R ^13a are the same or different and each represents a hydrogen atom, a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group, but R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a , R ^11a , R ^12a , and R ^13a is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group).

[11] At least one of R ^4a , R ^5a , R ^6a , R ^7a , and R ^8a is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group, and R ^9a , R ^10a , R ^11a , R ^12a And at least one of R ^13a is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group.

[12] General formula (IIb)

(Wherein R ^3b and R ^14b are the same or different and each represents a fluorine-substituted alkyl group, and R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b , R ^10b , R ^11b , R ^12b , And R ^13b are the same or different and each represents a hydrogen atom or a cyano group).

[13] General formula (IIc)

(R ^3c and R ^14c are the same or different and each represents an aryl group which may have a substituent, and R ^4c , R ^5c , R ^6c , R ^7c , R ^8c , R ^9c , R ^10c , R ^11c , R ^12c , and R ^13c are the same or different and each represents a hydrogen atom, an alkyl group, or an alkoxyl group, but at least one of R ^4c , R ^8c , R ^9c, and R ^13c represents an alkyl group or an alkoxyl group. A squarylium compound represented by:
[14] The squarylium compound according to [13], wherein at least one of R ^4c and R ^8c is an alkyl group or an alkoxyl group, and at least one of R ^9c and R ^13c is an alkyl group or an alkoxyl group.

According to the present invention, it is possible to provide an optical filter that absorbs long-wavelength ultraviolet light, has high transparency to visible light, and is stable to light.

Hereinafter, the compound represented by formula (I) is referred to as compound (I). The same applies to compounds with other formula numbers.
In the definition of each group in the general formula, examples of the alkyl group, the alkyl part in the alkoxyl group, and the alkyl part of the alkanoyl group include, for example, a linear or branched alkyl group having 1 to 8 carbon atoms or a group having 3 to 8 carbon atoms. And a cyclic alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 2-methylbutyl group. Tert-pentyl group, hexyl group, octyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like.
The alkyl part of the fluorine-substituted alkyl group and the fluorine-substituted alkoxyl group has the same meaning as the above alkyl group. Examples of the fluorine-substituted alkyl group include an alkyl group containing 1 to 3 fluorine atoms. Specific examples of the fluorine-substituted alkyl group include a trifluoromethyl group, a trifluoroethyl group, a trifluorobutyl group, a difluoroethyl group, a monofluoroethyl group, a trifluoropropyl group, and the like. A 4,4-trifluorobutyl group is preferred. Examples of the fluorine-substituted alkoxyl group include an alkoxyl group containing 1 to 3 fluorine atoms. Specific examples include a trifluoromethoxy group, a trifluoroethoxy group, a trifluorobutoxy group, a difluoroethoxy group, a monofluoroethoxy group, a trifluoropropoxy group, and the like, and a trifluoromethoxy group is preferable.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the aralkyl group include an aralkyl group having 7 to 15 carbon atoms, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.
Examples of the aryl group and the aryl moiety of the aryloxy group include a phenyl group, a naphthyl group, and an anthryl group, and a phenyl group is preferable.
Examples of the heterocyclic group and the heterocyclic moiety of the heterocyclic alkyl group include an aromatic heterocyclic group and an alicyclic heterocyclic group.
The alkylene portion of the heterocyclic alkyl group has the same meaning as that obtained by removing one hydrogen atom from the alkyl group.

  As the aromatic heterocyclic group, for example, a 5- or 6-membered monocyclic aromatic heterocyclic group containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and a 3- to 8-membered ring are condensed. A bicyclic or tricyclic fused ring aromatic heterocyclic group containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more specifically, a pyridyl group, a pyrazinyl group, Pyrimidinyl, pyridazinyl, quinolyl, isoquinolyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, cinnolinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thienyl, furyl, thiazolyl , Oxazolyl group, indolyl group, isoindolyl group, indazolyl group, benzimidazolyl group, ben Triazolyl, benzothiazolyl, benzoxazolyl, purinyl, carbazolyl group and the like.

Examples of the alicyclic heterocyclic group include a 5-membered or 6-membered monocyclic alicyclic heterocyclic group containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and a 3- to 8-membered ring. And a condensed alicyclic heterocyclic group containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more specifically a pyrrolidinyl group, Piperidyl group, piperazinyl group, morpholinyl group, thiomorpholinyl group, homopiperidyl group, homopiperazinyl group, tetrahydropyridyl group, tetrahydroquinolyl group, tetrahydroisoquinolyl group, tetrahydrofuryl group, tetrahydropyranyl group, dihydrobenzofuranyl group, tetrahydro Examples thereof include a carbazolyl group and a phthalimide group.
Examples of the heterocyclic ring formed by combining R ^1a and R ^2a , or R ^1b and R ^2b with the adjacent nitrogen atom include a bicyclic ring in which a 3- to 8-membered ring containing at least one nitrogen atom is condensed. Or a tricyclic heterocyclic ring etc. are mention | raise | lifted, More specifically, a 1,2,3,4-tetrahydroquinoline ring, an indoline ring, a 1,2,3,4-tetrahydroquinoxaline ring etc. are mention | raise | lifted.

Examples of the substituent of the alkyl group, the alkoxyl group, and the alkanoyl group include the same or different 1 to 3 substituents, specifically, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxyl group, an alkoxyalkoxyl group, And fluorine-substituted alkoxyl groups. Here, the alkoxyl group, the halogen atom, and the fluorine-substituted alkoxyl group have the same meanings as described above. The alkyl part of the alkoxyalkoxyl group has the same meaning as described above, and the alkylene part of the alkoxyalkoxyl group has the same meaning as that obtained by removing one hydrogen atom from the alkyl group.

Examples of the substituent of the aralkyl group, aryloxy group, heterocyclic group, and heterocyclic alkyl group are the same or different and are 1 to 5 substituents, specifically, a hydroxyl group, a carboxyl group, a halogen atom, Examples thereof include an alkyl group, an alkoxyl group, a nitro group, a cyano group, an alkyl-substituted or unsubstituted amino group, a fluorine-substituted alkyl group, and a fluorine-substituted alkoxyl group. Here, the halogen atom, alkyl group, alkoxyl group, fluorine-substituted alkyl group, and fluorine-substituted alkoxyl group have the same meanings as described above. The alkyl part of the alkyl-substituted amino group has the same meaning as the alkyl group. When the alkyl-substituted amino group is an amino group substituted with two alkyl groups, the two alkyl groups may be the same or different.
Examples of the substituent for the aryl group when R ^{3 to} R ¹⁴ , R ^3c or R ^14c is an aryl group having a substituent include, for example, an aralkyl group, an aryloxy group, a heterocyclic group, and a heterocyclic alkyl group Examples of the substituent include the same functional groups exemplified above.

When R ^1a , R ^1b , R ^2a , or R ^2b is an aryl group having a substituent, the aryl group, and R ^1a and R ^2a , or R ^1b and R ^2b are combined with the adjacent nitrogen atom Examples of the substituents of the heterocyclic ring formed are, for example, the same or different 1 to 5 substituents, specifically, a hydroxyl group, a carboxyl group, a halogen atom, a nitro group, a cyano group, a triphenylmethyl group. An alkyl-substituted or unsubstituted amino group, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, an alkanoyl group that may have a substituent, and a substituent. An aralkyl group which may have a substituent, a heterocyclic alkyl group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent An optionally substituted heterocyclic group, and the like also. Here, a halogen atom, an alkyl-substituted or unsubstituted amino group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an alkanoyl group which may have a substituent , An aralkyl group which may have a substituent, a heterocyclic alkyl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. The heterocyclic group is as defined above, and the aryl group that may have a substituent is an aryl group in which R ^{3 to} R ¹⁴ , R ^3c, or R ^14c may have a substituent. It is synonymous with it.
In the squarylium compound provided in [10], at least one of R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a , R ^11a , R ^12a , and R ^13a is a fluorine atom. Preferably, at least four of R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a , R ^11a , R ^12a , and R ^13a are fluorine atoms.

Next, the production method of compound (I) will be described with examples.
Compound (Ia) can be produced according to Reaction Scheme 1.
Reaction formula 1

(Wherein, R ^1a and R ^2a are as defined above)

Compound (Ia) is a compound in which R ^1a and R ^1b are the same and R ^2a and R ^2b are the same in compound (I).

Reaction formula 1
Compound (Ia) is obtained by reacting compound (III) with 2 to 5 moles of compound (IV) in a solvent at 25 to 150 ° C. for 1 to 100 hours, and then collecting the precipitate by filtration. It is obtained by subjecting to purification such as washing with the solvent used and drying.
Examples of the solvent include alcohol solvents such as ethanol, propanol, 2-propanol, butanol, and octanol, or a mixed solvent of the alcohol solvent (50% by volume or more) and benzene, toluene, or xylene. After the reaction, if necessary, the target compound may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).
Compound (Ib) can then be produced according to Reaction Scheme 2.

(Wherein, R ^1a and R ^2a have the same ^{meanings as} above, R ^1bb has the same meaning as R ^1b , and R ^2bb has the same ^meaning as R ^2b , but the combination of R ^1bb and R ^2bb is R Not the same as the combination of ^1a and R ^2a )
Reaction formula 2
The same as in Reaction Scheme 1, except that compound (Ia) is used instead of compound (III), and 1-2 times moles of compound (V) is used instead of compound (IV) with respect to compound (Ia). To react. After the reaction, if necessary, the target compound may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).
Compound (Ib) can also be produced according to Reaction Schemes 3 to 5.
Reaction formula 3

Reaction formula 4

Reaction formula 5

(Wherein, R ^1a and R ^2a have the same meanings as described above, and W represents a chlorine atom or a bromine atom)

Reaction formula 3
Compound (VII) is obtained by reacting Compound (VI) with 1 to 2 moles of Compound (IV) in a solvent at 0 to 40 ° C. for 1 to 20 hours in the presence of 0 to 2 moles of a base. Is obtained.
Examples of the solvent include halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane, ethers such as diethyl ether and tert-butyl methyl ether, aromatic hydrocarbons such as toluene and benzene, methanol and ethanol. And alcohols such as propanol, tetrahydrofuran, ethyl acetate, dimethylformamide, dimethyl sulfoxide (DMSO) and the like.
Examples of the base include organic bases such as quinoline, triethylamine and pyridine, or potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide and the like.

Reaction formula 4
Compound (VIII) is prepared by treating Compound (VII) in 50 to 90% by volume of acetic acid aqueous solution at 90 to 120 ° C. for 0.1 to 7 hours, or in 50 to 99% by weight of trifluoroacetic acid aqueous solution. It is obtained by treating at 45-50 ° C. for 0.1-3 hours.
Reaction formula 5
Compound (Ib) was obtained by reacting Compound (VIII) with 1 to 2.5 moles of Compound (V) in a solvent at 25 to 150 ° C. for 1 to 100 hours, and then collecting the precipitate by filtration. It can be obtained by purification such as washing with the solvent used in the reaction and drying.
Examples of the solvent include alcohol solvents such as ethanol, propanol, 2-propanol, butanol, and octanol, or a mixed solvent of the alcohol solvent (50% by volume or more) and benzene, toluene, or xylene. After the reaction, if necessary, the compound (Ib) may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).

Compound (II) is compound (IX) instead of compound (IV)

(Wherein R ^{3 to} R ⁸ are as defined above)
In place of compound (V)

(Wherein R ^{9 to} R ¹⁴ are as defined above)
It can be produced by the same method as the production method of compound (I) except that is used. Compounds (IIa), (IIb), and (IIc) can be produced in the same manner as in the method of compound (II).
Compounds (IV), (V), (IX) and (X) are obtained as commercially available products or from known methods such as halides described in the 4th edition, Experimental Chemistry Course 1992, Volume 20, Chapter 6. Or a reductive amination reaction or J. Org. Chem. It can be synthesized according to the method described in 1997, 62, 1568.

Specific examples of preferred compounds (I) and (II) are shown below. In the formula, Me represents a methyl group.

  The compound (I) used in the filter of the present invention is compatible with ultraviolet absorbers, ultraviolet absorbers for electronic display device filters, two-photon absorbing dyes as three-dimensional recording materials, and short wavelength lasers (eg, blue lasers). It can be used as a sensitizing dye. Compound (I) absorbs long-wavelength ultraviolet rays, has high transparency to visible light, and is stable to light, and therefore is particularly suitable as an ultraviolet absorber for electronic display device filters.

Among the compounds (I) used in the filter of the present invention, those having an absorption maximum wavelength in a chloroform solution in the region of 320 to 410 nm are preferred, and those in the region of 330 to 410 nm are more preferred. The molar extinction coefficient at the absorption maximum wavelength is preferably 10,000 or more, and more preferably 30000 or more.
Compound (I) has high solubility in organic solvents, and is suitable for a method for producing a filter using a coating liquid described later.

Examples of the filter of the present invention include a laminate of a binder containing compound (I) and a transparent substrate. The filter of this invention can be manufactured by apply | coating the coating liquid containing compound (I) to a transparent substrate, and drying, for example.
The coating liquid may be prepared by, for example, dissolving compound (I) and a binder in an organic solvent. If necessary, an antioxidant, a light stabilizer, a processing stabilizer, an anti-aging agent and the like may be added.
Examples of the organic solvent include ethers such as dimethoxyethane, methoxyethoxyethane, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and aromatic hydrocarbons such as benzene, toluene, xylene and monochlorobenzene. These may be used, and these may be used alone or in admixture of two or more. The organic solvent is preferably used in an amount of 10 to 3000 times (by weight) based on the compound (I).
Examples of the binder include a polyester resin, a polycarbonate resin, an acrylic resin, a polystyrene resin, a polyvinyl chloride resin, a polyvinyl acetate resin, and the like. It is preferable to use up to 500 times (weight).

The transparent substrate is not particularly limited as long as it is transparent and is a resin or glass that absorbs and scatters little, but examples of the resin include polyester resins, polycarbonate resins, acrylic resins, polystyrene resins, and polyester resins. Examples thereof include vinyl chloride resins and polyvinyl acetate resins.
As a method for applying the coating liquid containing the compound (I) to the transparent substrate, a known coating method such as a bar coating method, a spray method, a roll coating method, or a dipping method can be used (US Pat. No. 2,681,294, etc.).
The maximum absorption wavelength of the filter of the present invention is preferably in the region of 320 to 410 nm, and more preferably in the region of 330 to 410 nm in order to absorb long wavelength ultraviolet rays.
The half width of the absorption peak in the region of 320 to 410 nm of the filter of the present invention is preferably 100 nm or less and more preferably 80 nm or less in order to have high transparency to visible light.
Applications of the filter of the present invention include, for example, window covers, showcases, foreheads, photo stands, portable game machines, transparent covers such as watches, light source members, coating materials for light source protection glass, containers for food and pharmaceuticals, etc. Examples thereof include medical devices such as goggles, eyeglass lenses, and contact lenses, and materials for blocking electromagnetic waves generated from various electronic displays.
Examples of the electronic display include a liquid crystal display, a plasma display, an organic electroluminescence display, a field emission display, and the like. Among these, a plasma display is preferable.

Hereinafter, the present invention will be described more specifically with reference to Examples, Test Examples, and Reference Examples.
Reference example 1

(Production of Compound 1)
1.40 g of 3,4-dihydroxycyclobutene-1,2-dione and 4.87 g of Nn-butylaniline are added to a mixed solvent of butanol 8.0 ml and toluene 8.0 ml and reacted at 130 ° C. for 30 hours. It was. Thereafter, the precipitated yellowish white solid was collected by filtration to obtain Compound 1 (1.64 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.82 (6H, s (broad)), 1.28 (4H, s (broad)), 1.47 (4H, s (broad)) ), 4.31 (4H, s (broad)), 7.29-7.41 (10H, m).
Absorption maximum wavelength (CHCl ₃ ): 369.0 nm
Molar extinction coefficient (CHCl ₃ ): 36400 (mol / l) ⁻¹ · cm ⁻¹
Reference example 2

(Production of Compound 2)
2.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 6.81 g of N-sec-butylaniline are added to a mixed solvent of butanol 8.0 ml and toluene 8.0 ml and reacted at 130 ° C. for 30 hours. It was. Thereafter, the precipitated yellowish white solid was collected by filtration to obtain Compound 2 (1.50 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.92 (6H, t, J = 7.2 Hz), 1.23 (6H, m), 1.51-1.71 (4H, m), 4.66 (2H, s (broad)), 7.23-7.38 (10H, m).
Absorption maximum wavelength (CHCl ₃ ): 348.0 nm
Molar extinction coefficient (CHCl ₃ ): 33400 (mol / l) ⁻¹ · cm ⁻¹
Reference example 3

(Production of Compound 3)
2.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 9.62 g of N-benzylaniline were added to a mixed solvent of butanol 8.0 ml and toluene 8.0 ml, and reacted at 130 ° C. for 14 hours. Thereafter, the precipitated yellowish white solid was collected by filtration to obtain Compound 3 (7.13 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 5.60 (4H, s), 7.25-7.34 (20H, m).
Absorption maximum wavelength (CHCl ₃ ): 369.0 nm
Molar extinction coefficient (CHCl ₃ ): 37100 (mol / l) ⁻¹ · cm ⁻¹
Reference example 4

(Production of Compound 4)
2.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 6.99 g of 1,2,3,4-tetrahydroquinoline are added to a mixed solvent of 8.0 ml of butanol and 8.0 ml of toluene at 130 ° C. The reaction was carried out for 14 hours. Thereafter, the precipitated orange solid was collected by filtration to obtain Compound 4 (5.73 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 2.05 (4H, t, J = 5.6 Hz), 2.89 (4H, t, J = 6.6 Hz), 4.34 ( 4H, t, J = 5.6 Hz), 7.12-7.23 (6H, m), 7.47 (2H, d, J = 8.1 Hz).
Absorption maximum wavelength (CHCl ₃ ): 403.0 nm
Molar extinction coefficient (CHCl ₃ ): 47000 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 5

(Production of Compound 5)
2.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 9.20 g of N-cyclohexylaniline were added to a mixed solvent of 8.0 ml of butanol and 8.0 ml of toluene and reacted at 130 ° C. for 20 hours. Thereafter, the precipitated white solid was collected by filtration to obtain Compound 5 (5.16 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.95-1.91 (20H, m), 4.44 (2H, m), 7.23-7.35 (10H, m) .
Absorption maximum wavelength (CHCl ₃ ): 346.5 nm
Molar extinction coefficient (CHCl ₃ ): 32400 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 6

(Production of Compound 6)
2.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 7.89 g of N-ethyl-m-toluidine are added to a mixed solvent of butanol 8.0 ml and toluene 8.0 ml and reacted at 130 ° C. for 20 hours. I let you. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 6 (1.94 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.15 (6H, t, J = 7.1 Hz), 2.32 (6H, s), 4.29 (4H, q, J = 7.1 Hz), 7.10-7.30 (8H, m).
Absorption maximum wavelength (CHCl ₃ ): 369.5 nm
Molar extinction coefficient (CHCl ₃ ): 33000 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 7)
The raw material N-isopropyl-3-fluoroaniline was synthesized by the following procedure. 8.00 g of 3-fluoroaniline, 22.04 g of isopropyl iodide and 9.95 g of potassium carbonate were added to 15 ml of N, N-dimethylformamide, reacted at 90 ° C. for 13 hours, allowed to cool to room temperature, and the organic layer was separated. The mixture was extracted with diethyl ether, washed with water, dried over magnesium sulfate, and the solvent was distilled off to obtain N-isopropyl-3-fluoroaniline (9.53 g, colorless transparent liquid).
2.0 g of 3,4-dihydroxycyclobutene-1,2-dione and 6.19 g of N-isopropyl-3-fluoroaniline were added to a mixed solvent of 7.0 ml of butanol and 7.0 ml of toluene, and the mixture was stirred at 130 ° C. for 35 hours. Reacted. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 7 (1.57 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.27 (12H, d, J = 6.6 Hz), 4.87 (2H, m), 7.13-7.43 (8H, m).
Absorption maximum wavelength (CHCl ₃ ): 349.0 nm
Molar extinction coefficient (CHCl ₃ ): 31400 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 7

(Production of Compound 8)
The raw material N-isopropyl-1-naphthylamine was synthesized by the following procedure. 12.00 g of 1-naphthylamine, 36.00 g of isopropyl iodide and 29.30 g of potassium carbonate were added to 15 ml of N, N-dimethylformamide, reacted at 90 ° C. for 3 hours, and then allowed to cool to room temperature. After extraction with ether, washing with water and drying over magnesium sulfate, the solvent was distilled off and distilled under reduced pressure to obtain N-isopropyl-1-naphthylamine (11.71 g, colorless transparent liquid).
2.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 9.73 g of N-isopropyl-1-naphthylamine are added to a mixed solvent of 7.5 ml of butanol and 7.5 ml of toluene and reacted at 130 ° C. for 68 hours. I let you. Thereafter, the precipitated yellow solid was recrystallized from methanol to obtain Compound 8 (2.71 g, pale pink solid).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.10-1.40 (12H, m), 4.69 (1H, m), 5.00 (1H, m), 7.39 −8.04 (14H, m).
Absorption maximum wavelength (CHCl ₃ ): 350.5 nm
Molar extinction coefficient (CHCl ₃ ): 33600 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 9)
The raw material N-isopropyl-3-trifluoromethylaniline was synthesized by the following procedure. 15.00 g of 3-aminobenzotrifluoride, 47.78 g of isopropyl iodide and 38.60 g of potassium carbonate were added to 15 ml of N, N-dimethylformamide, reacted at 90 ° C. for 6 hours, allowed to cool to room temperature, and organic The layer was extracted with diethyl ether, washed with water, dried over magnesium sulfate, and the solvent was distilled off to obtain N-isopropyl-3-trifluoromethylaniline (17.24 g, colorless transparent liquid).
Add 2.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 16.67 g of N-isopropyl-3-trifluoromethylaniline to a mixed solvent of 8.0 ml of butanol and 8.0 ml of toluene, and The reaction was performed for 20 hours. Thereafter, the precipitated white solid was collected by filtration to obtain Compound 9 (1.20 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.12-1.35 (12H, m), 4.87 (2H, m), 7.62-7.74 (8H, m) .
Absorption maximum wavelength (CHCl ₃ ): 333.5 nm
Molar extinction coefficient (CHCl ₃ ): 52700 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 10)
The starting material 2-isopropyldiphenylamine is described in J.A. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. 16.72 g of bromobenzene, 15.00 g of o-isopropylaniline, 13.31 g of tert-butoxy sodium, bis (dibenzylideneacetone) palladium (0) [hereinafter referred to as Pd (dba) ₂ ] 642 mg (J. Organomet. Chem. 1974) , 65, 253) and 1,1-diphenylphosphinoferrocene 892 mg was added to 40 ml of toluene, reacted at 110 ° C. for 1 hour, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -Isopropyl-diphenylamine (21.30 g, red liquid) was obtained.
3,4-Dihydroxycyclobutene-1,2-dione (3.00 g) and 2-isopropyl-diphenylamine (13.89 g) were added to a mixed solvent of butanol (4.0 ml) and toluene (4.0 ml) and reacted at 130 ° C. for 20 hours. . Thereafter, the precipitated orange solid was collected by filtration to obtain Compound 10 (10.33 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.83-1.13 (12H, m), 2.91 (2H, m), 7.12-7.44 (18H, m) .
Absorption maximum wavelength (CHCl ₃ ): 404.5 nm
Molar extinction coefficient (CHCl ₃ ): 43100 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 11)
The starting material 2-isopropyl-3′-trifluoromethyldiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. 3-Iodobenzotrifluoride 15.45 g, o-isopropylaniline 8.00 g, tert-butoxy sodium 7.10 g, Pd (dba) ₂ 343 mg (according to the method described in J. Organomet. Chem. 1974, 65, 253) Synthesis), and 410 mg of 1,1-diphenylphosphinoferrocene were added to 20 ml of toluene, reacted at 110 ° C. for 4 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -Isopropyl-3'-trifluoromethyldiphenylamine (13.95 g, orange liquid) was obtained.
800 mg of 3,4-dihydroxycyclobutene-1,2-dione and 4.90 g of 2-isopropyl-3′-trifluoromethyldiphenylamine are added to a mixed solvent of 1.5 ml of butanol and 1.5 ml of toluene, and the mixture is heated at 130 ° C. for 20 minutes. Reacted for hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 11 (3.97 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.84-1.17 (12H, m), 2.89-2.93 (2H, m), 7.32-7.65 ( 16H, m).
Absorption maximum wavelength (CHCl ₃ ): 407.0 nm
Molar extinction coefficient (CHCl ₃ ): 43500 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 12)
The raw material N-isopropyl-3,5-bis (trifluoromethyl) aniline was synthesized by the following procedure. 3,5-bis (trifluoromethyl) aniline (15.00 g), isopropyl iodide (50.09 g) and potassium carbonate (40.73 g) were added to N, N-dimethylformamide (20 ml), reacted at 90 ° C. for 7 hours, and then to room temperature. The mixture was allowed to cool, and the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent toluene / n-hexane = 1/3). Purification gave N-isopropyl-3,5-bis (trifluoromethyl) aniline (12.85 g, light yellow liquid).
2.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 9.73 g of N-isopropyl-3,5-bis (trifluoromethyl) aniline were mixed in a mixed solvent of 7.5 ml of butanol and 7.5 ml of toluene. In addition, it was reacted at 130 ° C. for 68 hours. Thereafter, the precipitated pale yellow solid was collected by filtration to obtain Compound 12 (2.71 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.38 (12H, d, J = 6.6 Hz), 4.78 (2H, septet, J = 6.6 Hz), 8.03 ( 4H, s), 8.13 (2H, s).
Absorption maximum wavelength (CHCl ₃ ): 364.5 nm
Molar extinction coefficient (CHCl ₃ ): 32800 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 13)
The raw material N-isopropyl-4-trifluoromethoxyaniline was synthesized by the following procedure. 4-trifluoromethoxyaniline (15.00 g), isopropyl iodide (43.19 g) and potassium carbonate (35.11 g) were added to N, N-dimethylformamide (25 ml), reacted at 90 ° C. for 8 hours, allowed to cool to room temperature, organic The layer was extracted with ethyl acetate, washed with water, the solvent was distilled off, dried over magnesium sulfate, and isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -Isopropyl-4-trifluoromethoxyaniline (10.05 g, colorless transparent liquid) was obtained.
1.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 4.80 g of N-isopropyl-4-trifluoromethoxyaniline are added to a mixed solvent of 3.0 ml of butanol and 3.0 ml of toluene at 130 ° C. The reaction was carried out for 14 hours. Thereafter, the precipitated white solid was collected by filtration to obtain Compound 13 (3.03 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.26 (12H, d, J = 6.8 Hz), 4.87 (2H, m), 7.39 (4H, m).
Absorption maximum wavelength (CHCl ₃ ): 349.0 nm
Molar extinction coefficient (CHCl ₃ ): 34600 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 8

(Production of Compound 14)
The starting material N-benzyl-4-trifluoromethoxyaniline was synthesized by the following procedure. 10.00 g of 4-trifluoromethoxyaniline, 7.89 g of benzyl bromide and 8.08 g of potassium carbonate were added to 10 ml of N, N-dimethylformamide, reacted at 90 ° C. for 8 hours, allowed to cool to room temperature, and organic The layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -Benzyl-4-trifluoromethoxyaniline (3.56 g, yellow liquid) was obtained.
589 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.45 g of N-benzyl-4-trifluoromethoxyaniline were added to a mixed solvent of 2.0 ml of butanol and 2.0 ml of toluene, and the mixture was stirred at 130 ° C. for 21 hours. Reacted. Thereafter, the precipitated yellowish white solid was collected by filtration to obtain Compound 14 (2.56 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 5.60 (4H, s), 7.27-7.51 (18H, m).
Absorption maximum wavelength (CHCl ₃ ): 371.5 nm
Molar extinction coefficient (CHCl ₃ ): 39300 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 15)
The raw material Nn-butyl-3-trifluoromethylaniline was synthesized by the following procedure. 10.00 g of 3-aminobenzotrifluoride, 34.90 g of n-butyl bromide and 25.35 g of potassium carbonate were added to 10 ml of N, N-dimethylformamide, reacted at 90 ° C. for 6 hours, and then allowed to cool to room temperature. The organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). n-Butyl-3-trifluoromethylaniline (14.74 g, pale yellow liquid) was obtained.
1.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 5.71 g of Nn-butyl-3-trifluoromethylaniline are added to a mixed solvent of 4.0 ml of butanol and 4.0 ml of toluene. The reaction was carried out at 43 ° C. for 43 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 15 (460 mg).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.84 (6H, m), 1.27 (4H, m), 1.48 (4H, m), 4.37 (4H, m ), 7.66-7.77 (8H, m).
Absorption maximum wavelength (CHCl ₃ ): 376.5 nm
Molar extinction coefficient (CHCl ₃ ): 31700 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 16)
The raw material Nn-butyl-3,5-bis (trifluoromethyl) aniline was synthesized by the following procedure. After adding 10.00 g of 3,5-bis (trifluoromethyl) aniline, 24.84 g of n-butyl bromide and 18.10 g of potassium carbonate to 10 ml of N, N-dimethylformamide and reacting at 90 ° C. for 6 hours, The mixture was allowed to cool to room temperature, and the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). After separation and purification, Nn-butyl-3,5-bis (trifluoromethyl) aniline (3.30 g, colorless transparent liquid) was obtained.
480 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of Nn-butyl-3,5-bis (trifluoromethyl) aniline are mixed in a mixed solvent of 2.0 ml of butanol and 2.0 ml of toluene. In addition, the mixture was reacted at 130 ° C. for 28 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 16 (1.18 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.85 (6H, m), 1.31 (4H, m), 1.52 (4H, m), 4.46 (4H, m ), 8.03 (2H, s), 8.15 (4H, s).
Absorption maximum wavelength (CHCl ₃ ): 386.0 nm
Molar extinction coefficient (CHCl ₃ ): 40000 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 9

(Production of Compound 17)
The starting material N-isopropyl-3-nitroaniline was synthesized by the following procedure. 3-Nitroaniline (12.00 g), isopropyl iodide (14.77 g) and potassium carbonate (12.01 g) were added to N, N-dimethylformamide (15 ml), reacted at 90 ° C. for 6 hours, and allowed to cool to room temperature. Extraction with ethyl acetate, washing with water, drying over magnesium sulfate, and after distilling off the solvent, N-isopropyl was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -3-Nitroaniline (7.64 g, red liquid) was obtained.
1.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 3.95 g of N-isopropyl-3-nitroaniline are added to a mixed solvent of 2.0 ml of butanol and 2.0 ml of toluene, and the mixture is kept at 130 ° C. for 27 hours. Reacted. Thereafter, the precipitated orange solid was collected by filtration to obtain Compound 17 (1.65 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.32 (12H, m), 4.88 (2H, m), 7.68-8.25 (8H, m).
Absorption maximum wavelength (CHCl ₃ ): 352.5 nm
Molar extinction coefficient (CHCl ₃ ): 27600 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 10

(Production of Compound 18)
The starting material N-benzyl-3,5-bis (trifluoromethyl) aniline was synthesized by the following procedure. After adding 10.00 g of 3,5-bis (trifluoromethyl) aniline, 6.10 g of benzyl bromide and 6.03 g of potassium carbonate to 10 ml of N, N-dimethylformamide, the mixture was reacted at 90 ° C. for 4 hours, and then allowed to reach room temperature. The mixture was allowed to cool, and the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent toluene / n-hexane = 1/3). Purification gave N-benzyl-3,5-bis (trifluoromethyl) aniline (9.15 g, light yellow liquid).
1.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 7.00 g of N-benzyl-3,5-bis (trifluoromethyl) aniline were mixed in a mixed solvent of 2.0 ml of butanol and 2.0 ml of toluene. In addition, the mixture was reacted at 130 ° C. for 17 hours. Thereafter, the precipitated yellowish white solid was collected by filtration to obtain Compound 18 (4.30 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 5.80 (4H, s), 7.26-7.41 (10H, m), 7.94 (2H, s), 8.18 (4H, s).
Absorption maximum wavelength (CHCl ₃ ): 385.0 nm
Molar extinction coefficient (CHCl ₃ ): 39800 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 11

(Production of Compound 19)
The starting material N-isopropyl-2-chloro-5-trifluoromethylaniline was synthesized by the following procedure. 2-chloro-5-trifluoromethylaniline (15.00 g), isopropyl iodide (39.11 g) and potassium carbonate (31.93 g) were added to N, N-dimethylformamide (25 ml), reacted at 90 ° C. for 16 hours, and then released to room temperature. After cooling, the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent: toluene / n-hexane = 1/3). As a result, N-isopropyl-2-chloro-5-trifluoromethylaniline (1.27 g, colorless transparent liquid) was obtained.
230 mg of 3,4-dihydroxycyclobutene-1,2-dione and 1.20 g of N-isopropyl-2-chloro-5-trifluoromethylaniline were added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, and 130 The reaction was carried out at 29 ° C. for 29 hours. Thereafter, the precipitated white solid was collected by filtration to obtain Compound 19 (147 mg).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.22-1.48 (12H, m), 4.54-4.77 (2H, m), 7.79-8.01 ( 6H, m).
Absorption maximum wavelength (CHCl ₃ ): 352.5 nm
Molar extinction coefficient (CHCl ₃ ): 35000 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 12

(Production of Compound 20)
The starting material N-isopropyl-3-methoxyaniline was synthesized by the following procedure. 10.00 g of m-anisidine, 13.80 g of isopropyl iodide and 11.22 g of potassium carbonate were added to 10 ml of N, N-dimethylformamide, reacted at 90 ° C. for 6 hours, allowed to cool to room temperature, and the organic layer was acetic acid. Extraction with ethyl, washing with water, drying over magnesium sulfate, evaporation of the solvent, isolation and purification by silica gel column chromatography (eluent toluene / n-hexane = 1/3), N-isopropyl- 3-Methoxyaniline (6.13 g, yellow liquid) was obtained.
1.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 3.62 g of N-isopropyl-3-methoxyaniline are added to a mixed solvent of 2.0 ml of butanol and 2.0 ml of toluene, and the mixture is heated at 130 ° C. for 58 hours. Reacted. Thereafter, the precipitated light white pink solid was collected by filtration to obtain Compound 20 (940 mg).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.25 (12H, d, J = 6.6 Hz), 3.75 (6H, s), 4.88 (2H, m), 6 .80 (2H, s), 6.82 (2H, d, J = 8.3 Hz), 6.94 (2H, d, J = 8.3 Hz), 7.28 (2H, t, J = 7. 9 Hz).
Absorption maximum wavelength (CHCl ₃ ): 346.5 nm
Molar absorption coefficient (CHCl ₃ ): 34100 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 13

(Production of Compound 21)
The starting material N-isopropyl-4- (2,6-diisopropylphenoxy) aniline was synthesized by the following procedure. 17.60 g of 1-chloro-4-nitrobenzene, 23.90 g of 2,6-diisopropylphenol and 5.60 g of potassium hydroxide were added to 150 ml of dimethyl sulfoxide, reacted at 90 ° C. for 5 hours, and then allowed to cool to room temperature. The resultant solid was poured into an aqueous hydrochloric acid solution and the resulting solid was recrystallized from ethanol to obtain 2,6-diisopropyl-4′-nitrodiphenyl ether (27.17 g, yellow solid). 23.88 g of this 2,6-diisopropyl-4′-nitrodiphenyl ether and 0.50 g of 10% Pd / C were added to 300 ml of methanol / 20 ml of water and brought to 60 ° C., and then a 40 ml aqueous solution of 6.00 g of NaBH ₄ was added. The mixture was allowed to cool to room temperature, ethyl acetate was added to precipitate the target product, and this was washed with water to give 4- (2,6-diisopropylphenoxy) aniline (19.8 g, white solid).
5.00 g of 4- (2,6-diisopropylphenoxy) aniline, 3.16 g of isopropyl iodide and 2.57 g of potassium carbonate are added to 10 ml of N, N-dimethylformamide, reacted at 90 ° C. for 6 hours, and then brought to room temperature. The mixture was allowed to cool, and the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent toluene / n-hexane = 1/3) Purification gave N-isopropyl-4- (2,6-diisopropylphenoxy) aniline (4.29 g, tan liquid).
586 mg of 3,4-dihydroxycyclobutene-1,2-dione and 4.00 g of N-isopropyl-4- (2,6-diisopropylphenoxy) aniline are added to a mixed solvent of 1.5 ml of butanol and 1.5 ml of toluene, The reaction was carried out at 130 ° C. for 27 hours. Thereafter, the precipitated yellowish white solid was collected by filtration to obtain Compound 21 (2.25 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.07 (24H, d, J = 6.6 Hz), 1.15 (12H, m), 3.01 (4H, m), 4 .90 (4H, m), 6.73-7.27 (14H, m).
Absorption maximum wavelength (CHCl ₃ ): 347.0 nm
Molar extinction coefficient (CHCl ₃ ): 37500 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 22)
The starting material 2-isopropyl-4′-trifluoromethoxydiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. 10.00 g of 1-bromo-4-trifluoromethoxybenzene, 5.79 g of o-isopropylaniline, 5.13 g of tert-butoxy sodium, 246 mg of Pd (dba) ₂ (described in J. Organomet. Chem. 1974, 65, 253) Synthesis according to the method), and 341 mg of 1,1-diphenylphosphinoferrocene were added to 30 ml of toluene, reacted at 110 ° C. for 3 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -Isopropyl-4'-trifluoromethoxydiphenylamine (9.33 g, orange liquid) was obtained.
1.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 6.47 g of 2-isopropyl-4′-trifluoromethoxydiphenylamine were added to a mixed solvent of 4.0 ml of butanol and 4.0 ml of toluene, For 18 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 22 (4.84 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.80-1.15 (12H, m), 2.87 (2H, m), 7.09-7.63 (16H, m) .
Absorption maximum wavelength (CHCl ₃ ): 405.5 nm
Molar extinction coefficient (CHCl ₃ ): 37500 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 14

(Production of Compound 23)
The raw material N- (4-trifluoromethylbenzyl) -3-trifluoromethylaniline was synthesized by the following procedure. To a mixed solution of 5.00 g of 3-aminobenzotrifluoride and 1 ml of methanol, a mixed solution of 5.40 g of 4-trifluoromethylbenzaldehyde and 1 ml of methanol was added and reacted at room temperature for 3 hours. Then, 20 ml of dehydrated tetrahydrofuran and 3.52 g of NaBH ₄ were added to the yellow reaction liquid from which the generated water had been removed, and reacted at room temperature for 8 hours. Hydrated with water, the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). Separation and purification gave N- (4-trifluoromethylbenzyl) -3-trifluoromethylaniline (5.39 g, white solid).
To a mixed solvent of 1.5 ml of butanol and 1.5 ml of toluene, 715 mg of 3,4-dihydroxycyclobutene-1,2-dione and 5.00 g of N- (4-trifluoromethylbenzyl) -3-trifluoromethylaniline were added. In addition, the mixture was reacted at 130 ° C. for 25 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 23 (4.30 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 5.89 (4H, s), 7.65-8.22 (16H, m).
Absorption maximum wavelength (CHCl ₃ ): 385.0 nm
Molar extinction coefficient (CHCl ₃ ): 33600 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 15

(Production of Compound 24)
The starting material N- (4-trifluoromethylbenzyl) -3,5-bis (trifluoromethyl) aniline was synthesized by the following procedure. To a mixed solution of 5.00 g of 3,5-bis (trifluoromethyl) aniline and 1 ml of methanol, a mixed solution of 3.80 g of 4-trifluoromethylbenzaldehyde and 1 ml of methanol was added and reacted at room temperature for 3 hours. Thereafter, 20 ml of dehydrated tetrahydrofuran and 2.48 g of NaBH ₄ were added to the yellow reaction liquid from which the generated water had been removed, and reacted at room temperature for 8 hours. Hydrated with water, the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). After separation and purification, N- (4-trifluoromethylbenzyl) -3,5-bis (trifluoromethyl) aniline (6.89 g, yellow liquid) was obtained.
766 mg of 3,4-dihydroxycyclobutene-1,2-dione, 6.50 g of N- (4-trifluoromethylbenzyl) -3,5-bis (trifluoromethyl) aniline, 1.5 ml of butanol and 1. The mixture was added to 5 ml of the mixed solvent and reacted at 130 ° C. for 25 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 24 (3.69 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 5.79 (4H, s), 7.60-7.69 (8H, m), 7.71 (2H, s), 7.86 (4H, s).
Absorption maximum wavelength (CHCl ₃ ): 376.0 nm
Molar extinction coefficient (CHCl ₃ ): 44200 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 16

(Production of Compound 25)
The raw material N- (4-trifluoromethylbenzyl) -4-trifluoromethoxyaniline was synthesized by the following procedure. To a mixed solution of 5.00 g of 4-trifluoromethoxyaniline and 1 ml of methanol, a mixed solution of 4.92 g of 4-trifluoromethylbenzaldehyde and 1 ml of methanol was added and reacted at room temperature for 3 hours. Then, 20 ml of dehydrated tetrahydrofuran and 3.20 g of NaBH ₄ were added to the yellow reaction liquid from which the generated water was removed, and reacted at room temperature for 8 hours. Hydrated with water, the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). Separation and purification gave N- (4-trifluoromethylbenzyl) -4-trifluoromethoxyaniline (7.56 g, colorless transparent liquid).
1.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 6.16 g of N- (4-trifluoromethylbenzyl) -4-trifluoromethoxyaniline were mixed with 1.5 ml of butanol and 1.5 ml of toluene. In addition to the solvent, the mixture was reacted at 130 ° C. for 25 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 25 (5.25 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 5.70 (4H, s), 7.36-7.70 (16H, m).
Absorption maximum wavelength (CHCl ₃ ): 373.5 nm
Molar extinction coefficient (CHCl ₃ ): 37800 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 17

(Production of Compound 26)
The starting material N- (4-trifluoromethylbenzyl) -4-isopropylaniline was synthesized by the following procedure. To a mixed solution of 5.00 g of 4-isopropylaniline and 5 ml of methanol, a mixed solution of 6.44 g of 4-trifluoromethylbenzaldehyde and 1 ml of methanol was added, and the resulting brown solid was collected by filtration. To this brown solid, 20 ml of dehydrated tetrahydrofuran and 4.20 g of NaBH ₄ were added and reacted at 70 ° C. for 19 hours. Hydrated with water, the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and the solvent was distilled off to remove N- (4-trifluoromethylbenzyl) -4-isopropylaniline (8.10 g). A brown solid).
467 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of N- (4-trifluoromethylbenzyl) -4-isopropylaniline were added to a mixed solvent of 2.0 ml of butanol and 2.0 ml of toluene, The reaction was carried out at 130 ° C. for 38 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 26 (1.78 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.15 (12H, d, J = 7.1 Hz), 2.85 (2H, seppet, J = 6.8 Hz), 5.67 ( 4H, s), 7.22 (4H, m), 7.29 (4H, m), 7.56 (4H, m), 7.69 (2H, m).
Absorption maximum wavelength (CHCl ₃ ): 375.0 nm
Molar extinction coefficient (CHCl ₃ ): 37800 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 18

(Production of Compound 27)
The starting material N- (4-trifluoromethylbenzyl) -2-methoxyaniline was synthesized by the following procedure. A mixed solution of 7.00 g of 4-trifluoromethylbenzaldehyde and 1 ml of methanol was added to a mixed solution of 5.00 g of o-anisidine and 1 ml of methanol, and the produced yellow solid was collected by filtration. To this yellow solid, 20 ml of dehydrated tetrahydrofuran and 4.56 g of NaBH ₄ were added and reacted at 70 ° C. for 13 hours. Hydrated with water, the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and the solvent was distilled off to remove N- (4-trifluoromethylbenzyl) -2-methoxyaniline (10.31 g). Light yellow liquid).
Add 811 mg of 3,4-dihydroxycyclobutene-1,2-dione and 5.00 g of N- (4-trifluoromethylbenzyl) -2-methoxyaniline to a mixed solvent of 2.0 ml of butanol and 2.0 ml of toluene, The reaction was carried out at 130 ° C. for 33 hours. Thereafter, the precipitated brown solid was collected by filtration to obtain Compound 27 (2.76 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 3.68 (3H, s), 3.74 (3H, s), 5.35 (2H, s), 5.45 (2H, s ), 6.83-7.69 (16H, m).
Absorption maximum wavelength (CHCl ₃ ): 356.5 nm
Molar extinction coefficient (CHCl ₃ ): 41000 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 19

(Production of Compound 28)
The raw material N-isopropyl-4-triphenylmethylaniline was synthesized by the following procedure. 26.20 g of aniline hydrochloride and 25.00 g of triphenylmethanol were added to 60 ml of acetic acid and reacted at 120 ° C. for 3 hours. After allowing to cool to room temperature, an aqueous sodium hydroxide solution (50.00 g of sodium hydroxide / 500 ml of water) was added to the reaction solution and heated to 120 ° C. After allowing to cool to room temperature, the precipitate was recrystallized from toluene to give 4-triphenylmethylaniline (17.63 g, white solid).
7.00 g of 4-triphenylmethylaniline, 3.55 g of isopropyl iodide and 2.88 g of potassium carbonate were added to 25 ml of N, N-dimethylformamide, reacted at 90 ° C. for 6 hours, and then allowed to cool to room temperature. The layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was evaporated, and the residue was isolated and purified by silica gel column chromatography (eluent chloroform) to give N-isopropyl-4-triphenylmethyl. Aniline (3.86 g, white solid) was obtained.
302 mg of 3,4-dihydroxycyclobutene-1,2-dione and 2.50 g of N-isopropyl-4-triphenylmethylaniline were added to a mixed solvent of 3.5 ml of butanol and 3.5 ml of toluene, and the mixture was heated at 130 ° C. for 60 hours. Reacted. Thereafter, the precipitated yellowish white solid was collected by filtration to obtain Compound 28 (1.66 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 1.25 (12H, d, J = 6.1 Hz), 4.70 (2H, m), 7.10-7.34 (38H, m).
Absorption maximum wavelength (CHCl ₃ ): 350.0 nm
Molar extinction coefficient (CHCl ₃ ): 36800 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 29)
The starting material 2-methoxy-2′-methyldiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. o-bromotoluene 6.00 g, o-anisidine 4.32 g, tert-butoxy sodium 4.38 g, Pd (dba) ₂ 100 mg (synthesized according to the method described in J. Organomet. Chem. 1974, 65, 253), Then, 146 mg of 1,1-diphenylphosphinoferrocene was added to 20 ml of toluene, reacted at 110 ° C. for 2 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -Methoxy-2'-methyldiphenylamine (5.77 g, pale yellow liquid) was obtained.
642 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 2-methoxy-2′-methyldiphenylamine were added to a mixed solvent of 1.5 ml of butanol and 1.5 ml of toluene, and the reaction was carried out at 130 ° C. for 28 hours. I let you. Thereafter, the precipitated orange solid was collected by filtration to obtain Compound 29 (425 mg).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 2.33 (6H, s), 3.77 (6H, s), 7.03-7.32 (16H, m).
Absorption maximum wavelength (CHCl ₃ ): 383.5 nm
Molar extinction coefficient (CHCl ₃ ): 39600 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 30)
The raw material 2,2′-dimethoxydiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. 2-bromoanisole 8.00 g, o-anisidine 5.32 g, tert-butoxy sodium 5.34 g, Pd (dba) ₂ 122 mg (synthesized according to the method described in J. Organomet. Chem. 1974, 65, 253), Then, 178 mg of 1,1-diphenylphosphinoferrocene was added to 20 ml of toluene, reacted at 110 ° C. for 90 minutes, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). , 2′-dimethoxydiphenylamine (5.34 g, pale yellow liquid) was obtained.
597 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 2,2′-dimethoxydiphenylamine were added to a mixed solvent of 1.5 ml of butanol and 1.5 ml of toluene and reacted at 130 ° C. for 28 hours. . Thereafter, the precipitated brown solid was collected by filtration to obtain Compound 30 (675 mg).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 3.78 (12H, s), 6.88 (4H, m), 7.03 (4H, m), 7.10 (4H, m ), 7.28 (4H, m).
Absorption maximum wavelength (CHCl ₃ ): 378.0 nm
Molar extinction coefficient (CHCl ₃ ): 30500 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 20

(Production of Compound 31)
600 mg of 3,4-dihydroxycyclobutene-1,2-dione and 2.36 g of N-phenyl-1-naphthylamine were added to a mixed solvent of 5.0 ml of butanol and 5.0 ml of toluene and reacted at 110 ° C. for 10 hours. . Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 31 (1.23 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 7.13-7.90 (24H, m).
Absorption maximum wavelength (CHCl ₃ ): 407.0 nm
Molar extinction coefficient (CHCl ₃ ): 40600 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 32)
The starting material 2-methoxy-2 ′, 5-dimethyldiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. o-bromotoluene (6.00 g), 2-methoxy-5-methylaniline (4.91 g), tert-butoxynatriu (4.38 g), Pd (dba) ₂ 100 mg (in the method described in J. Organomet. Chem. 1974, 65, 253) 146 mg of 1,1-diphenylphosphinoferrocene added to 20 ml of toluene, reacted at 110 ° C. for 4 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -Methoxy-2 ', 5-dimethyldiphenylamine (6.39 g, pale yellow liquid) was obtained.
602 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 2-methoxy-2 ′, 5-dimethyldiphenylamine were added to a mixed solvent of 1.0 ml of butanol and 1.0 ml of toluene, Reacted for hours. Thereafter, the precipitated pink solid was collected by filtration to obtain Compound 32 (424 mg).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 2.17 (6H, d, J = 4.9 Hz), 2.21 (6H, d, J = 5.1 Hz), 3.75 ( 6H, s), 6.84 (2H, m), 7.01-7.26 (12H, m).
Absorption maximum wavelength (CHCl ₃ ): 384.5 nm
Molar extinction coefficient (CHCl ₃ ): 36200 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 33)
The starting material 2-methoxy-2 ′, 4′-dimethyldiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. 2-bromoanisole 8.00 g, 2,4-dimethylaniline 5.29 g, tert-butoxy sodium 5.34 g, Pd (dba) ₂ 122 mg (according to the method described in J. Organomet. Chem. 1974, 65, 253) Synthesis), and 178 mg of 1,1-diphenylphosphinoferrocene were added to 20 ml of toluene, reacted at 110 ° C. for 4 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -Methoxy-2 ', 4'-dimethyldiphenylamine (6.93 g, orange liquid) was obtained.
602 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 2-methoxy-2 ′, 4′-dimethyldiphenylamine were added to a mixed solvent of 1.0 ml of butanol and 1.0 ml of toluene at 130 ° C. The reaction was allowed to proceed for 45 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 33 (750 mg).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 2.16 (6H, s), 2.26 (6H, s), 3.77 (6H, s), 6.88-7.31 (14H, m).
Absorption maximum wavelength (CHCl ₃ ): 384.5 nm
Molar extinction coefficient (CHCl ₃ ): 32700 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 34)
The raw material 2,4′-dimethoxy-2′-methyldiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. 2-bromoanisole 8.00 g, 4-methoxy-2-methylaniline 5.87 g, tert-butoxy sodium 5.34 g, Pd (dba) ₂ 122 mg (according to the method described in J. Organomet. Chem. 1974, 65, 253) And 178 mg of 1,1-diphenylphosphinoferrocene was added to 20 ml of toluene, reacted at 110 ° C. for 2 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). , 4′-Dimethoxy-2′-methyldiphenylamine (6.65 g, yellowish white solid) was obtained.
563 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 2,4′-dimethoxy-2′-methyldiphenylamine were added to a mixed solvent of 1.0 ml of butanol and 1.0 ml of toluene at 130 ° C. The reaction was allowed to proceed for 45 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 34 (435 mg).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 2.18 (6H, s), 3.74 (6H, s), 3.77 (6H, s), 6.73 (2H, m ), 6.82 (2H, s), 6.90 (2H, m), 7.00-7.05 (4H, m), 7.11 (2H, m), 7.28 (2H, m) .
Absorption maximum wavelength (CHCl ₃ ): 386.5 nm
Molar extinction coefficient (CHCl ₃ ): 36400 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 35)
The starting material 2-methoxy-2 ′, 5′-dimethyldiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. 2-bromoanisole 7.00 g, 2,5-dimethylaniline 4.54 g, tert-butoxy sodium 4.68 g, Pd (dba) ₂ 107 mg (according to the method described in J. Organomet. Chem. 1974, 65, 253) Synthesis) and 156 mg of 1,1-diphenylphosphinoferrocene were added to 20 ml of toluene, reacted at 110 ° C. for 4 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -Methoxy-2 ', 5'-dimethyldiphenylamine (7.36 g, white solid) was obtained.
602 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 2-methoxy-2 ′, 5′-dimethyldiphenylamine were added to a mixed solvent of 1.0 ml of butanol and 1.0 ml of toluene at 130 ° C. The reaction was performed for 30 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 35 (432 mg).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 2.14 (3H, s), 2.17 (3H, s), 2.20 (3H, s), 2.21 (3H, s ), 3.78 (3H, s), 3.80 (3H, s), 6.89-7.32 (14H, m).
Absorption maximum wavelength (CHCl ₃ ): 384.0 nm
Molar extinction coefficient (CHC ₃ ): 36900 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 36)
The raw material 2,2 ′, 4-trimethyldiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. o-bromotoluene 5.00 g, 2,4-dimethylaniline 3.54 g, t-butoxy sodium 3.65 g, Pd (dba) ₂ 86 mg (according to the method described in J. Organomet. Chem. 1974, 65, 253) Synthesis) 244 mg of 1,1-diphenylphosphinoferrocene was added to 20 ml of toluene, reacted at 110 ° C. for 2 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/4). , 2 ′, 4-trimethyldiphenylamine (5.58 g, brown liquid) was obtained.
648 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 2,2 ′, 4-trimethyldiphenylamine are added to a mixed solvent of 1.0 ml of butanol and 1.0 ml of toluene and reacted at 130 ° C. for 70 hours. I let you. Thereafter, the precipitate was recrystallized from methanol to obtain Compound 36 (557 mg, yellow solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 2.26 (6H, s), 2.27 (6H, s), 2.31 (6H, s), 6.90-7.22 (14H , M).
Absorption maximum wavelength (CHCl ₃ ): 389.0 nm
Molar extinction coefficient (CHCl ₃ ): 22400 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 37)
The starting material N-isopropyl-3,4-difluoroaniline was synthesized by the following procedure. 5.00 g of 3,4-difluoroaniline, 13.16 g of isopropyl iodide and 5.89 g of potassium carbonate were added to 20 ml of N, N-dimethylformamide, reacted at 110 ° C. for 9 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/3). -Isopropyl-3,4-difluoroaniline (3.86 g, clear liquid) was obtained.
798 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of N-isopropyl-3,4-difluoroaniline are added to a mixed solvent of 1.0 ml of butanol and 1.0 ml of toluene, and the mixture is kept at 130 ° C. for 38 hours. Reacted. Thereafter, the precipitated white solid was collected by filtration to obtain Compound 37 (2.39 g).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 1.33 (12H, m), 4.98 (1H, m), 5.12 (1H, m), 6.91-7.00 (6H , M).
Absorption maximum wavelength (CHCl ₃ ): 347.0 nm
Molar extinction coefficient (CHCl ₃ ): 38100 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 38)
The raw material Nn-butyl-3,4-difluoroaniline was synthesized by the following procedure. 5.00 g of 3,4-difluoroaniline, 7.12 g of butyl iodide and 5.89 g of potassium carbonate were added to 20 ml of N, N-dimethylformamide, reacted at 110 ° C. for 5 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 0.5 / 9.5). By purification, Nn-butyl-3,4-difluoroaniline (3.54 g, transparent liquid) was obtained.
Add 741 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of Nn-butyl-3,4-difluoroaniline to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, and The reaction was performed for 6 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 38 (2.60 g).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.86-0.95 (6H, m), 1.33-1.44 (4H, m), 1.54-1.61 (4H, m), 4.22-4.30 (4H, m), 7.00-7.23 (6H, m).
Absorption maximum wavelength (CHCl ₃ ): 369.5 nm
Molar extinction coefficient (CHCl ₃ ): 38600 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 39)
The starting material N-isopropyl-2,4-difluoroaniline was synthesized by the following procedure. 5.00 g of 2,4-difluoroaniline, 6.58 g of isopropyl iodide and 5.89 g of potassium carbonate were added to 20 ml of N, N-dimethylformamide, reacted at 110 ° C. for 23 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 0.5 / 9.5). By purification, N-isopropyl-2,4-difluoroaniline (3.55 g, transparent liquid) was obtained.
798 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of N-isopropyl-2,4-difluoroaniline are added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, and the mixture is kept at 130 ° C. for 12 hours. Reacted. Thereafter, the precipitated white solid was collected by filtration to obtain Compound 39 (2.25 g).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 1.27-1.32 (12H, m), 4.92 (1H, septet, J = 6.8 Hz), 5.10 (1H, septet, J = 6.8 Hz), 6.83-7.27 (6H, m).
Absorption maximum wavelength (CHCl ₃ ): 343.0 nm
Molar extinction coefficient (CHCl ₃ ): 38000 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 40)
The raw material Nn-butyl-2,3,4-trifluoroaniline was synthesized by the following procedure. 2.00 g of 2,3,4-trifluoroaniline, 6.26 g of butyl iodide and 5.17 g of potassium carbonate were added to 20 ml of N, N-dimethylformamide, reacted at 110 ° C. for 12 hours, and then allowed to cool to room temperature. did. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 0.5 / 9.5). By purification, Nn-butyl-2,3,4-trifluoroaniline (2.68 g, transparent liquid) was obtained.
561 mg of 3,4-dihydroxycyclobutene-1,2-dione and 2.50 g of Nn-butyl-2,3,4-trifluoroaniline are added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, The reaction was carried out at 130 ° C. for 6 hours. Thereafter, the precipitated white solid was collected by filtration to obtain Compound 40 (2.02 g).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.86 (3H, t, J = 7.3 Hz), 0.94 (3H, t, J = 7.3 Hz), 1.33 (2H, hexet, J = 7.3 Hz), 1.40 (2H, hexet, J = 7.3 Hz), 1.51-1.61 (4H, m), 4.11 (2H, t, J = 7.3 Hz) ), 4.19 (2H, t, J = 7.3 Hz), 6.96-7.07 (4H, m).
Absorption maximum wavelength (CHCl ₃ ): 354.0 nm
Molar extinction coefficient (CHCl ₃ ): 37500 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 21

(Production of Compound 41)
The raw material N- (2-anilinoethyl) phthalimide was synthesized by the following procedure. 4.00 g of N- (2-aminoethyl) aniline and 4.35 g of phthalic anhydride were added to 40 ml of acetic acid and reacted at 110 ° C. for 5 hours. Acetic acid was distilled off, and the residue was neutralized with aqueous ammonia, washed with methanol, and collected by filtration to obtain N- (2-anilinoethyl) phthalimide (6.03 g, yellow solid).
270 mg of 3,4-dihydroxycyclobutene-1,2-dione and 1.41 g of N- (2-anilinoethyl) phthalimide were added to a mixed solvent of 2.0 ml of butanol and 2.0 ml of toluene and reacted at 110 ° C. for 5 hours. It was. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 41 (1.37 g).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 3.93 (4H, m), 4.50 (4H, m), 6.95-7.90 (18H, m).
Absorption maximum wavelength (CHCl ₃ ): 373.0 nm
Molar extinction coefficient (CHCl ₃ ): 34000 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 22

(Production of Compound 42)
The starting material 3- (N-butylamino) benzonitrile was synthesized by the following procedure. 10.00 g of m-aminobenzonitrile, 15.56 g of butyl iodide and 12.86 g of potassium carbonate were added to 20 ml of N, N-dimethylformamide, reacted at 110 ° C. for 3 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 0.5 / 9.5). Purification gave 3- (N-butylamino) benzonitrile (8.01 g, brown liquid).
787 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 3- (N-butylamino) benzonitrile are added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, and the mixture is kept at 130 ° C. for 7 hours. Reacted. Thereafter, the precipitate was recrystallized from methanol to obtain Compound 42 (2.36 g, yellow solid).
¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.84 (6H, m), 1.26 (4H, m), 1.48 (4H, m), 4.35 (4H, m ), 7.63-7.94 (8H, m).
Absorption maximum wavelength (CHCl ₃ ): 381.0 nm
Molar extinction coefficient (CHCl ₃ ): 39800 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 43)
The raw material Nn-butyl-2,4-difluoroaniline was synthesized by the following procedure. After adding 10.00 g of 2,4-difluoroaniline, 14.26 g of butyl iodide and 11.79 g of potassium carbonate to 20 ml of N, N-dimethylformamide, the mixture was reacted at 90 ° C. for 16 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 0.5 / 9.5). By purification, Nn-butyl-2,4-difluoroaniline (8.31 g, purple liquid) was obtained.
Add 741 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of Nn-butyl-2,4-difluoroaniline to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, and The reaction was performed for 24 hours. Thereafter, the precipitated white solid was collected by filtration to obtain Compound 43 (2.10 g).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.86 (3H, t, J = 7.3 Hz), 0.93 (3H, t, J = 7.3 Hz), 1.32 (2H, hexet, J = 7.3 Hz), 1.39 (2H, hexet, J = 7.3 Hz), 1.45-1.62 (4H, m), 4.10 (2H, t, J = 7.3 Hz) ), 4.19 (2H, t, J = 7.3 Hz), 6.84-7.30 (6H, m).
Absorption maximum wavelength (CHCl ₃ ): 353.0 nm
Molar extinction coefficient (CHCl ₃ ): 42700 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 44)
The starting material 2,4-difluoro-2′-methyldiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. o-bromotoluene 10.00 g, 2,4-difluoroaniline 7.55 g, t-butoxy sodium 7.31 g, Pd (dba) ₂ 165 mg (according to the method described in J. Organomet. Chem. 1974, 65, 253) Synthesis) and 487 mg of 1,1-diphenylphosphinoferrocene were added to 40 ml of toluene, reacted at 110 ° C. for 2 hours, and then allowed to cool to room temperature. The organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent n-hexane) to give 2,4-difluoro- 2'-methyldiphenylamine (11.51 g, orange liquid) was obtained.
627 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 2,4-difluoro-2′-methyldiphenylamine were added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, Reacted for hours. Thereafter, the precipitate was recrystallized from methanol to obtain Compound 44 (1.62 g, yellow solid).
^{1 H-NMR, 400MHz, δ} (CDCl 3) ppm: 2.24 (3H, s), 2.27 (3H, s), 6.81-7.28 (14H, m).
Absorption maximum wavelength (CHCl ₃ ): 383.5 nm
Molar extinction coefficient (CHCl ₃ ): 44000 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 45)
The starting material 3,4-difluoro-2′-methyldiphenylamine is described in J. Org. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. o-bromotoluene 5.00 g, 3,4-difluoroaniline 3.77 g, t-butoxy sodium 3.65 g, Pd (dba) ₂ 86 mg (according to the method described in J. Organomet. Chem. 1974, 65, 253) Synthesis) and 244 mg of 1,1-diphenylphosphinoferrocene were added to 20 ml of toluene, reacted at 110 ° C. for 1 hour, and then allowed to cool to room temperature. The organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent toluene / n-hexane = 1/4). 3,4-Difluoro-2′-methyldiphenylamine (5.48 g, brown liquid) was obtained.
627 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 3,4-difluoro-2′-methyldiphenylamine were added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, Reacted for hours. Thereafter, the precipitate was recrystallized from methanol to obtain Compound 45 (1.91 g, yellow solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 2.17 (6H, s), 7.00-7.33 (14H, m).
Absorption maximum wavelength (CHCl ₃ ): 404.0 nm
Molar extinction coefficient (CHCl ₃ ): 39300 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 46)
The starting material N- (4,4,4-trifluorobutyl) aniline was synthesized by the following procedure. 1.96 g of aniline, 5.00 g of 1,1,1-trifluoro-4-iodobutane and 3.19 g of potassium carbonate were added to 20 ml of N, N-dimethylformamide, reacted at 90 ° C. for 1 hour, and then released to room temperature. Chilled. The organic layer is extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent is distilled off, and the residue is isolated and purified by silica gel column chromatography (eluent ethyl acetate / n-hexane = 1/9). Gave N- (4,4,4-trifluorobutyl) aniline (1.74 g, clear liquid).
336 mg of 3,4-dihydroxycyclobutene-1,2-dione and 1.50 g of N- (4,4,4-trifluorobutyl) aniline were added to a mixed solvent of 0.3 ml of butanol and 0.3 ml of toluene, and 130 The reaction was carried out at 6 ° C. for 6 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 46 (1.17 g).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 1.87-1.89 (4H, m), 2.12-2.16 (4H, m), 4.36-4.42 (4H, m), 7.22-7.49 (10H, m).
Absorption maximum wavelength (CHCl ₃ ): 369.0 nm
Molar extinction coefficient (CHCl ₃ ): 32800 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 47)
The raw material 3- [N- (4,4,4-trifluorobutyl) amino] benzonitrile was synthesized by the following procedure. After adding 5.00 g of m-aminobenzonitrile, 10.07 g of 1,1,1-trifluoro-4-iodobutane and 6.43 g of potassium carbonate to 20 ml of N, N-dimethylformamide and reacting at 60 ° C. for 9 hours. And allowed to cool to room temperature. The organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1.5 / 8.5). By purification, 3- [N- (4,4,4-trifluorobutyl) amino] benzonitrile (6.34 g, transparent liquid) was obtained.
593 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 3- [N- (4,4,4-trifluorobutyl) amino] benzonitrile were mixed with 0.5 ml of butanol and 0.5 ml of toluene. In addition to the mixed solvent, the mixture was reacted at 130 ° C. for 18 hours. Thereafter, the precipitate was recrystallized from methanol to obtain Compound 47 (2.29 g, yellow solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 1.90-1.94 (4H, m), 2.19 (4H, m), 4.40-4.42 (4H, m), 7 .50-7.66 (8H, m).
Absorption maximum wavelength (CHCl ₃ ): 379.0 nm
Molar extinction coefficient (CHCl ₃ ): 39000 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 23

(Production of Compound 48)
The raw material N-isopropyl-N ′, N′-dimethyl-1,4-benzenediamine was synthesized by the following procedure. N, N-dimethyl-1,4-benzenediamine (5.00 g), isopropyl iodide (6.13 g) and potassium carbonate (5.58 g) were added to N, N-dimethylformamide (20 ml) and reacted at 60 ° C. for 7 hours. It was left to cool. The organic layer is extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent is distilled off, and the residue is isolated and purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 3/7). Gave N-isopropyl-N ′, N′-dimethyl-1,4-benzenediamine (4.38 g, brown liquid).
A mixed solvent of 0.54 butanol and 0.5 ml of toluene containing 764 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of N-isopropyl-N ′, N′-dimethyl-1,4-benzenediamine And reacted at 130 ° C. for 21 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 48 (530 mg).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 1.22 (6H, d, J = 6.6 Hz), 1.28 (6H, d, J = 6.6 Hz), 2.89 (6H, s), 2.97 (6H, s), 5.04 (1H, septet, J = 6.6 Hz), 5.15 (1H, septet, J = 6.6 Hz), 6.57 (2H, d, J = 8.8 Hz), 6.69 (2H, d, J = 8.8 Hz), 6.97 (2H, d, J = 8.5 Hz), 7.06 (2H, d, J = 8.8 Hz) ).
Absorption maximum wavelength (CHCl ₃ ): 350.0 nm
Molar extinction coefficient (CHCl ₃ ): 34600 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 24

(Production of Compound 49)
The raw material Nn-octyl-3-nitroaniline was synthesized by the following procedure. 5.00 g of m-nitroaniline, 8.69 g of octyl iodide and 5.50 g of potassium carbonate were added to 20 ml of N, N-dimethylformamide, reacted at 60 ° C. for 10 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 0.5 / 9.5). Purification gave Nn-octyl-3-nitroaniline (1.61 g, yellow liquid).
274 mg of 3,4-dihydroxycyclobutene-1,2-dione and 1.50 g of Nn-octyl-3-nitroaniline were added to a mixed solvent of 0.2 ml of butanol and 0.2 ml of toluene, and the mixture was kept at 130 ° C. for 33 hours. Reacted. Thereafter, the precipitate was recrystallized from methanol to obtain Compound 49 (691 mg, yellow solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.84 (6H, m), 1.24 (20H, m), 1.65 (4H, m), 4.36 (4H, m), 7.58-7.63 (4H, m), 8.17 (4H, m).
Absorption maximum wavelength (CHCl ₃ ): 381.0 nm
Molar extinction coefficient (CHCl ₃ ): 31500 (mol / l) ⁻¹ · cm ⁻¹

(Production of Compound 50)
The raw material 2,4,4′-trifluoro-2′-methyldiphenylamine is * J. Org. Chem. It was synthesized according to the method described in 1997, 62, 1568. 2-bromo-5-fluorotoluene 10.00 g, 2,4-difluoroaniline 6.83 g, t-butoxy sodium 6.61 g, Pd (dba) ₂ 148 mg (described in J. Organomet. Chem. 1974, 65, 253) And 432 mg of 1,1-diphenylphosphinoferrocene was added to 40 ml of toluene, reacted at 110 ° C. for 3 hours, and then allowed to cool to room temperature. The organic layer was extracted with ethyl acetate, washed with water, the solvent was distilled off, and the residue was isolated and purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 0.5 / 9.5). 4,4′-Trifluoro-2′-methyldiphenylamine (8.50 g, brown liquid) was obtained.
570 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 2,4,4′-trifluoro-2′-methyldiphenylamine were added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, The reaction was carried out at 130 ° C. for 31 hours. Thereafter, the precipitate was recrystallized from methanol to obtain Compound 50 (1.40 g, yellow solid).
^{1 H-NMR, 400MHz, δ} (CDCl 3) ppm: 2.25 (3H, s), 2.27 (3H, s), 6.87-7.19 (12H, m).
Absorption maximum wavelength (CHCl ₃ ): 382.5 nm
Molar extinction coefficient (CHCl ₃ ): 44200 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 25

(Production of Compound 51)
The raw material Nn-octyl-4-nitroaniline was synthesized by the following procedure. 5.00 g of p-nitroaniline, 8.69 g of octyl iodide and 5.50 g of potassium carbonate were added to 20 ml of N, N-dimethylformamide, reacted at 90 ° C. for 12 hours, and then allowed to cool to room temperature. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the residue was isolated by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1.5 / 8.5). By purification, Nn-octyl-4-nitroaniline (1.98 g, yellow crystals) was obtained.
342 mg of 3,4-dihydroxycyclobutene-1,2-dione and 1.90 g of Nn-octyl-4-nitroaniline are added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, and the mixture is kept at 130 ° C. for 22 hours. Reacted. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 51 (1.15 g).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.84-0.87 (6H, m), 1.23 (20H, m), 1.67 (4H, m), 4.41 (4H M), 7.42-7.44 (4H, m), 8.30 (4H, m).
Absorption maximum wavelength (CHCl ₃ ): 438.5 nm
Molar extinction coefficient (CHCl ₃ ): 42800 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 26

(Production of Compound 52)
4- (N-butylamino) benzonitrile as a raw material was synthesized by the following operation. p-Aminobenzonitrile (5.00 g), n-butyraldehyde (3.05 g) and sodium triacetoxyborohydride (14.35 g) were added to 1,2-dichloroethane (100 ml), reacted at room temperature for 24 hours, and then neutralized with saturated aqueous sodium bicarbonate. The organic layer is extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and then evaporated and purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 2/8). This gave 4- (N-butylamino) benzonitrile (3.72 g, white crystals).
787 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of 4- (N-butylamino) benzonitrile were added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, and the mixture was stirred at 130 ° C. for 21 hours. Reacted. Thereafter, the precipitate was recrystallized from methanol to obtain Compound 52 (2.35 g, yellow solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.92 (6H, m), 1.37 (4H, m), 1.63 (4H, m), 4.38 (4H, m), 7.37 (4H, m), 7.72 (4H, m).
Absorption maximum wavelength (CHCl ₃ ): 403.5 nm
Molar extinction coefficient (CHCl ₃ ): 49400 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 27

(Production of Compound 53)
The starting material N- (2-thienylmethyl) aniline was synthesized by the following procedure. 4.15 g of aniline, 5.00 g of 2-thiophenaldehyde and 15.13 g of sodium triacetoxyborohydride were added to 100 ml of 1,2-dichloroethane, and reacted at room temperature for 20 minutes. The mixture was neutralized with saturated aqueous sodium hydrogen carbonate, and the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and silica gel column chromatography (eluent ethyl acetate / n-hexane = 1/9). ) To obtain N- (2-thienylmethyl) aniline (7.48 g, yellow liquid).
719 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of N- (2-thienylmethyl) aniline are added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene and reacted at 130 ° C. for 3 hours. I let you. Thereafter, the precipitate was recrystallized from methanol to obtain Compound 53 (1.21 g, yellow solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 5.64 (2H, s), 5.70 (2H, s), 6.87-7.41 (16H, m).
Absorption maximum wavelength (CHCl ₃ ): 371.0 nm
Molar extinction coefficient (CHCl ₃ ): 32800 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 28

(Production of Compound 54)
The starting material N- (2-thienylmethyl) -3,5-bis (trifluoromethyl) aniline was synthesized by the following procedure. 10.21 g of 3,5-bis (trifluoromethyl) aniline, 5.00 g of 2-thiophene aldehyde and 15.13 g of sodium triacetoxyborohydride were added to 100 ml of 1,2-dichloroethane and reacted at room temperature for 23 hours. The mixture was neutralized with saturated aqueous sodium hydrogen carbonate, and the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and silica gel column chromatography (eluent ethyl acetate / n-hexane = 1/9). ) To obtain N- (2-thienylmethyl) -3,5-bis (trifluoromethyl) aniline (11.00 g, orange liquid).
421 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of N- (2-thienylmethyl) -3,5-bis (trifluoromethyl) aniline were mixed with 0.5 ml of butanol and 0.5 ml of toluene. In addition to the mixed solvent, the mixture was reacted at 130 ° C. for 42 hours. Thereafter, the precipitate was recrystallized from isopropyl alcohol to obtain Compound 54 (562 mg, yellow solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 5.74-5.78 (4H, m), 6.93-7.07 (4H, m), 7.26 (2H, m), 7 .67-7.82 (6H, m).
Absorption maximum wavelength (CHCl ₃ ): 386.0 nm
Molar extinction coefficient (CHCl ₃ ): 37400 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 29

(Production of Compound 55)
The raw material N-furfurylaniline was synthesized by the following procedure. 4.84 g of aniline, 5.00 g of furfural and 17.63 g of sodium triacetoxyborohydride were added to 100 ml of 1,2-dichloroethane and reacted at room temperature for 1 hour. The mixture was neutralized with saturated aqueous sodium hydrogen carbonate, and the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was evaporated, and silica gel column chromatography (eluent ethyl acetate / n-hexane = 1/9). ) To obtain N-furfurylaniline (8.50 g, orange liquid).
787 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of N-furfurylaniline were added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene and reacted at 130 ° C. for 8 hours. Thereafter, the precipitate was recrystallized from methanol to obtain Compound 55 (1.30 g, white solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 5.45 (2H, s), 5.50 (2H, s), 6.27-6.31 (4H, m), 7.23-7 .40 (12H, m).
Absorption maximum wavelength (CHCl ₃ ): 372.0 nm
Molar extinction coefficient (CHCl ₃ ): 32600 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 30

(Production of Compound 56)
The starting material N- (2-thienylmethyl) -4- (trifluoromethoxy) aniline was synthesized by the following procedure. 7.00 g of 4- (trifluoromethoxy) aniline, 4.43 g of 2-thiophenaldehyde and 13.39 g of sodium triacetoxyborohydride were added to 100 ml of 1,2-dichloroethane and reacted at room temperature for 17 hours. The mixture was neutralized with saturated aqueous sodium hydrogen carbonate, and the organic layer was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off, and silica gel column chromatography (eluent ethyl acetate / n-hexane = 1/9). ) To obtain N- (2-thienylmethyl) -4- (trifluoromethoxy) aniline (9.47 g, brown liquid).
In a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene, 502 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of N- (2-thienylmethyl) -4- (trifluoromethoxy) aniline were added. In addition, the mixture was reacted at 130 ° C. for 14 hours. Thereafter, the precipitate was recrystallized from isopropyl alcohol to obtain Compound 56 (2.33 g, yellow solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 5.63 (2H, s), 5.67 (2H, s), 6.90-7.01 (4H, m), 7.16-7 .31 (10H, m).
Absorption maximum wavelength (CHCl ₃ ): 370.5 nm
Molar extinction coefficient (CHCl ₃ ): 39100 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 31

(Production of Compound 57)
The raw material N-furfuryl-4- (trifluoromethoxy) aniline was synthesized by the following procedure. 7.00 g of 4- (trifluoromethoxy) aniline, 3.80 g of furfural and 13.39 g of sodium triacetoxyborohydride were added to 100 ml of 1,2-dichloroethane and reacted at room temperature for 2 hours. The organic layer was extracted with toluene, washed with water, dried over magnesium sulfate, the solvent was distilled off, and the precipitated solid was recrystallized from hexane to give N-furfuryl-4- (Trifluoromethoxy) aniline (9.47 g, white crystals) was obtained.
536 mg of 3,4-dihydroxycyclobutene-1,2-dione and 3.00 g of N-furfuryl-4- (trifluoromethoxy) aniline are added to a mixed solvent of 0.5 ml of butanol and 0.5 ml of toluene at 130 ° C. The reaction was allowed for 8 hours. Thereafter, the precipitate was recrystallized from isopropyl alcohol to obtain Compound 57 (2.22 g, yellow solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 5.43 (2H, s), 5.47 (2H, s), 6.30-6.40 (4H, m), 7.16-7 .40 (10H, m).
Absorption maximum wavelength (CHCl ₃ ): 374.0 nm
Molar extinction coefficient (CHCl ₃ ): 39700 (mol / l) ⁻¹ · cm ⁻¹
Reference Example 32
(Production of Compound 58)
2.00 g of 3,4-dihydroxycyclobutene-1,2-dione and 8.89 g of diphenylamine were added to a mixed solvent of 8.0 ml of butanol and 8.0 ml of toluene and reacted at 130 ° C. for 25 hours. Thereafter, the precipitated orange solid was collected by filtration to obtain Compound 58 (5.48 g, orange solid).
¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 7.23-7.25 (8H, m), 7.32-7.36 (2H, m), 7.41-7.45 (8H, m).
Absorption maximum wavelength (CHCl ₃ ): 410.5 nm
Molar extinction coefficient (CHCl ₃ ): 41000 (mol / l) ⁻¹ · cm ⁻¹

[Test Example 1]
Each of a 0.6% by weight tetrahydrofuran solution of a squarilim compound (compound described in Table 1) and a 20% by weight dimethoxyethane solution of an acrylic resin [Dianal BR-70 (manufactured by Mitsubishi Rayon Co., Ltd.)]: The mixture was mixed at a ratio of 2, applied onto a glass substrate with a spin coater, and then dried to prepare a filter. Using a U-4000 type self-recording spectrophotometer [manufactured by Hitachi, Ltd.], the UV-visible absorption spectra of these filters were measured (800 to 300 nm). Table 1 shows the absorption maximum wavelength and the half-value width of the absorption peak of these filters.

From Table 1, it can be seen that the filter of the present invention absorbs long-wavelength ultraviolet rays and has high transparency to visible light because of its narrow half-value width.
[Test Example 2]
A filter was produced in the same manner as in Test Example 1 except that the compounds listed in Table 2 were used instead of the compounds listed in Table 1. Using the Dew panel light control weather meter [DPWL-5R manufactured by Suga Test Instruments Co., Ltd.], the produced filter was exposed (irradiance 15 W / m ² , test tank temperature 45 ° C., exposure for 32 hours). Using a U-4000 self-recording spectrophotometer [manufactured by Hitachi, Ltd.], the absorbance at the absorption maximum wavelength of the filter was measured before and after exposure to determine the residual ratio of the dye. The results are shown in Table 2.

Table 2 Results of photostability test for filters containing squarylium compounds

  Table 2 shows that the optical filter of the present invention is stable to light.

According to the present invention, it is possible to provide an optical filter that absorbs long-wavelength ultraviolet light, has high transparency to visible light, and is stable to light.

Claims (14)

Formula (I)

(Wherein R ^1a , R ^1b , R ^2a , and R ^2b are the same or different and each represents an alkyl group that may have a substituent, an alkanoyl group that may have a substituent, or a substituent. An aralkyl group which may have, a heterocyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent , R ^1a and R ^2a , and at least one of R ^1b and R ^2b each represents an optionally substituted aryl group, or an optionally substituted heterocyclic group, or R ^1a and R ^2a , or R ^1b and R ^2b together with the adjacent nitrogen atom may form a heterocyclic ring which may have a substituent, respectively) filter. The squarylium compound has the general formula (II)

(In the formula, R ³ and R ¹⁴ are the same or different and each represents an optionally substituted alkyl group or an optionally substituted aryl group; R ⁴ , R ⁵ , R ^6; , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same or different and are a hydrogen atom, hydroxyl group, carboxyl group, halogen atom, nitro group, cyano group, triphenylmethyl A group, an alkyl-substituted or unsubstituted amino group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent; A heterocyclic alkyl group which may have, an aryl group which may have a substituent, an aryloxy group which may have a substituent, or a heterocyclic group which may have a substituent; Represent) The optical filter of claim 1 wherein the Aririumu compound. The optical filter according to claim 2, wherein R ³ and R ¹⁴ are the same or different and are alkyl groups which may have a substituent. R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same or different and have a hydrogen atom, a halogen atom, a cyano group, or a substituent. The optical filter according to claim 3, which is an alkyl group which may be substituted, or an alkoxyl group which may have a substituent. At least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group. The optical filter according to claim 3. At least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group, and R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R The optical filter according to claim 3, wherein at least one of ¹³ is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group. R ³ and R ¹⁴ are the same or different and are a fluorine-substituted alkyl group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are The optical filter according to claim 2, which is the same or different and is a hydrogen atom or a cyano group. R ³ and R ¹⁴ are the same or different and are aryl groups which may have a substituent, and at least one of R ⁴ , R ⁸ , R ⁹ and R ¹³ is an alkyl group or an alkoxyl group. 2. The optical filter according to 2. The optical filter according to claim ⁸ , wherein at least one of R ⁴ and R ⁸ is an alkyl group or an alkoxyl group, and at least one of R ⁹ and R ¹³ is an alkyl group or an alkoxyl group. Formula (IIa)

(Wherein R ^3a and R ^14a are the same or different and represent an alkyl group which may have a substituent, and R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a , R ^11a , R ^12a , and R ^13a are the same or different and each represents a hydrogen atom, a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group, but R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a , R ^11a , R ^12a , and R ^13a is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group). At least one of R ^4a , R ^5a , R ^6a , R ^7a , and R ^8a is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group, and R ^9a , R ^10a , R ^11a , R ^12a , and R The squarylium compound according to claim 10, wherein at least one of ^13a is a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxyl group. Formula (IIb)

(Wherein R ^3b and R ^14b are the same or different and each represents a fluorine-substituted alkyl group, and R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b , R ^10b , R ^11b , R ^12b , And R ^13b are the same or different and each represents a hydrogen atom or a cyano group). Formula (IIc)

(R ^3c and R ^14c are the same or different and each represents an aryl group which may have a substituent, and R ^4c , R ^5c , R ^6c , R ^7c , R ^8c , R ^9c , R ^10c , R ^11c , R ^12c , and R ^13c are the same or different and each represents a hydrogen atom, an alkyl group, or an alkoxyl group, but at least one of R ^4c , R ^8c , R ^9c, and R ^13c represents an alkyl group or an alkoxyl group. A squarylium compound represented by: The squarylium compound according to claim 13, wherein at least one of R ^4c and R ^8c is an alkyl group or an alkoxyl group, and at least one of R ^9c and R ^13c is an alkyl group or an alkoxyl group.