JP6086526B2 - Bis-boron dipyrromethene dye and its precursor - Google Patents

Description

  The present invention relates to a bis-boron dipyrromethene dye having excellent stability and a precursor thereof.

Conventionally, in applications such as an infrared cut filter, a near-infrared absorbing film, and a security ink, there is a high demand for a pigment having invisibility that is invisible and having a sharp absorption in the near-infrared region.
As dyes having absorption in the near infrared region, azo dyes, cyanine dyes, styryl dyes and the like are known. However, since these dyes all have a flexible molecular skeleton, the absorption wavelength changes due to isomerization, reaction with nucleophiles, decomposition due to heat or oxygen easily occurs, and the durability is poor. In addition, phthalocyanine dyes and naphthalocyanine dyes are also known. However, these dyes have a large absorption in the visible region, and the invisibility is insufficient.
Therefore, a pyrrolopyrrole dye (see Patent Document 1 (Compound D-30) and Non-Patent Document 1) having pyrrolopyrrole as the main skeleton as a dye having invisibility and absorption in the near infrared region. Proposed. Such a pyrrolopyrrole pigment is prepared using a diketopyrrolopyrrole compound, but it is necessary to introduce a bulky substituent in order to increase the solubility of the compound. In each of the pyrrolopyrrole dyes described in Patent Document 1 and Non-Patent Document 1, a cyano group is introduced at the meso position, but these are introduced only to facilitate the synthesis of the dye. .
Non-Patent Document 2 describes bis-boron dipyrromethene dyes.

JP 2009-263614 A

George M. Fischer, 3 others, “Near-Infrared Dyes and Fluorophores Based on Diketopyrrolopyrroles”, Angelevante Chemie International Edition (Angewandte Chemie International Edition), (Germany), Wiley-VCH, 2007, 46th edition, p.3750-3753 Hidemitsu Uno and three others, “Efficient Synthesis of Highly π-Expanded Heterocycles Based on the Pericyclic Cycloreversion”, 23rd International Heterocyclic Chemistry Conference (July 31 – August 4, 2011, Glasgow, UK) Proceedings, p.68

The bis-boron dipyrromethene dye described in Non-Patent Document 2 has little absorption in the visible region and has absorption characteristics in the near infrared region. However, near-infrared absorbing dyes with expanded π conjugation tend to accelerate the decomposition and deterioration of the dyes by oxygen, for example, in a solution state dissolved in an organic solvent. Therefore, the conventional bis-boron dipyrromethene dye has room for improvement from the viewpoint of stability.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a bis-boron dipyrromethene dye having excellent stability. Another object of the present invention is to provide a precursor of a bis-boron dipyrromethene dye useful for obtaining such a bis-boron dipyrromethene dye.

According to the study by the present inventors, in the case of a bis-boron dipyrromethene dye compound, when the molecular HOMO (Highest Occupied Molecular Orbital) level is high (threshold is about −5 eV) by DFT (Density Functional Theory) calculation. It was found that the molecule is easily oxidized and decomposes. Therefore, as a result of research on bis-boron dipyrromethene dyes, it was found that the stability to oxygen can be improved by lowering the HOMO level of the molecule, and the present invention was completed.
The bis-boron dipyrromethene dye of the present invention that has solved the above-mentioned problems is represented by the formula (1) or (2).

[In Formula (1), at least one of R ^{1 to} R ¹⁴ is an electron withdrawing group, and the rest is hydrogen or an organic substituent.
In formula (2), at least one of R ^{15 to} R ²⁸ is an electron withdrawing group, and the rest is hydrogen or an organic substituent. ]

  The precursor of the bis-boron dipyrromethene dye of the present invention is represented by the formulas (13) to (16).

[In formula (13), RingA is any one cyclic structure selected from the following formulas Ia to IIa (in formulas Ia to IIa, a1 to a4 represent carbon numbers).

In formula (14), RingB is any one cyclic structure selected from the following formulas Ib to IIb (in formulas Ib to IIb, b1 to b4 represent carbon numbers).

In formula (15), RingC is any one cyclic structure selected from the following formulas Ic to IIc (in formulas Ic to IIc, c1 to c4 represent carbon numbers),

RingD is any one cyclic structure selected from the following formulas Id to IIId (in formulas Id to IIId, d1 to d4 represent carbon numbers),

RingE is any one cyclic structure selected from the following formulas Ie to IIIe (in formulas Ie to IIIe, e1 to e4 represent carbon numbers).

In the formula (16), RingF is any one cyclic structure selected from the following formulas If to IIf (in the formulas If to IIf, f1 to f4 represent carbon numbers),

RingG is any one cyclic structure selected from the following formulas Ig to IIIg (in formulas Ig to IIIg, g1 to g4 represent carbon numbers),

RingH is any one cyclic structure selected from the following formulas Ih to IIIh (in formulas Ih to IIIh, h1 to h4 represent carbon numbers).

In formulas (13) and (15), at least one of R ^{39 to} R ⁵² is an electron withdrawing group, and the rest is hydrogen or an organic substituent.
In formulas (14) and (16), at least one of R ^{53 to} R ⁶⁶ is an electron withdrawing group, and the rest is hydrogen or an organic substituent.
In the formulas, L ¹ ~L ⁸ are each _{independently, * - CH 2 -CH 2 -} *, * - C (= O) - *, * - C (= O) -C (= O) - * Indicates. * Indicates a bond. ]

  In addition, the precursor of the bis-boron dipyrromethene dye of the present invention is desirably a compound represented by the formulas (3) to (6).

[In Formulas (3) and (5), at least one of R ^{1 to} R ¹⁴ is an electron withdrawing group, and the rest is hydrogen or an organic substituent.
In formulas (4) and (6), at least one of R ^{15 to} R ²⁸ is an electron withdrawing group, and the remainder is hydrogen or an organic substituent.
In the formulas, L ¹ ~L ⁸ are each _{independently, * - CH 2 -CH 2 -} *, * - C (= O) - *, * - C (= O) -C (= O) - * Indicates. * Indicates a bond. ]

  The precursor of the bis-boron dipyrromethene dye and the precursor of the bis-boron dipyrromethene dye is a group in which the electron withdrawing group is a halogen, a cyano group, a nitro group, a sulfo group, an alkyloxycarbonyl group, or an acyl group It is preferable that it is at least 1 type selected from.

Since the bis-boron dipyrromethene dye of the present invention has an electron withdrawing group as a substituent, the molecule has a low HOMO level. Therefore, decomposition by oxygen is suppressed and stability is excellent. Furthermore, in the bis-boron dipyrromethene dye of the present invention, the precursor has excellent solubility as described later. Therefore, for example, a dye precursor is added to a polymerizable composition or a polymer solution, and heat treatment is performed to convert the material into an invisible material.
In addition, as a precursor of the bis-boron dipyrromethene dye of the present invention, a compound having a bicyclo structure, a cyclohexane structure, or a cyclohexene structure is used for a part or all of a portion that becomes a benzene ring structure in the final dye. It can be used for excellent versatility. In particular, a compound in which a part or all of the portion having a benzene ring structure in the final dye has a bicyclo structure has high solubility in an organic solvent and is easy to handle. In addition, since the bicyclo structure can be converted into a benzene ring structure and can be easily converted into a bis-boron dipyrromethene dye only by heat treatment of the precursor, a dye-containing film or the like can be easily produced.

It is an absorption spectrum in the chloroform solution of the compound (2-2) produced by the synthesis example 3. It is the absorption spectrum which confirmed the time-dependent change at the time of dissolving the compound (2-2) produced in the synthesis example 3 in the solvent. It is the absorption spectrum which confirmed the time-dependent change at the time of dissolving a compound (Z) in a solvent.

1. Bis-boron dipyrromethene dye The bis-boron dipyrromethene dye of the present invention has two boron dipyrromethenes (4,4-difluoro-3H-4-bora (IV) -3a, 4a-diaza-s-indacene). These boron dipyrromethenes are bonded to each other through one pyrrole ring via a benzene ring, and the other pyrrole ring of each boron dipyrromethene has a structure in which a benzene ring is bonded. The main skeleton. The bis-boron dipyrromethene dye has at least one electron withdrawing group as a substituent bonded to the main skeleton.
By having an electron withdrawing group, in the bis-boron dipyrromethene dye (high conjugated compound), the electron energy level can be controlled, the HOMO level of the molecule can be lowered, and the stability to oxygen is improved. .

  The bis-boron dipyrromethene dye of the present invention is represented by the formula (1) or (2). The compound represented by the formula (1) or (2) has structural isomerism depending on which of the two adjacent nitrogen atoms (N) is covalently bonded to which of the boron atoms (B). There is a body. These structural isomers are also included in the present invention.

[In Formula (1), at least one of R ^{1 to} R ¹⁴ is an electron withdrawing group, and the rest is hydrogen or an organic substituent.
In formula (2), at least one of R ^{15 to} R ²⁸ is an electron withdrawing group, and the rest is hydrogen or an organic substituent. ]

  The electron withdrawing group is not particularly limited as long as it can be introduced by an electrophilic substitution reaction. In the electron withdrawing group, the Hammett's rule substituent constant σ is known as an electron withdrawing index, and a functional group having a positive Hammett's substituent constant σ is used as the electron withdrawing group. Can be mentioned. Examples of the electron withdrawing group include halogen, cyano group, nitro group, thiocyanate group, trifluoromethyl group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group. Group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like.

In Formula (1), two or more of R ^{1 to} R ¹⁴ are preferably electron withdrawing groups, more preferably 4 or more, and still more preferably 6 or more.
In the formula (2), two or more of R ^{15 to} R ²⁸ are preferably electron withdrawing groups, more preferably 4 or more, and still more preferably 6 or more.
The position at which the electron withdrawing group is introduced is not particularly limited, but from the viewpoint of the effect of improving the stability of the bis-boron dipyrromethene dye, the alpha position (R ^{11 to} R ¹⁴ in formula (1), formula (2) R ^{25 to} R ²⁸ ) or the meso position (R ⁹ and R ^{10 in} the formula (1), R ²³ and R ^{24 in} the formula (2)) are preferably introduced. In the pyromethene skeleton, the alpha position and the meso position are the most reactive portions, and the reaction site can be crushed by introducing an electron withdrawing group into this portion.

  Examples of the halogen include fluorine, chlorine, bromine and iodine. Among these, fluorine is preferable.

  Examples of the acyl group include acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, trifluoroacetyl, benzoyl, 1-naphthoyl, 2- A naphthoyl group etc. are mentioned. Among these, a C1-C15 acyl group is preferable and a C1-C10 thing is more preferable.

  Examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, and a decyloxycarbonyl group. , Octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group and the like.

  Examples of the aryloxycarbonyl group include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, and 2-chlorophenyloxycarbonyl. Group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, and 4-methoxyphenyloxycarbonyl Group, and the like.

  Examples of the carbamoyl group include a carbamoyl group, an N-ethylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-dibutylcarbamoyl group, and an N- (2-dodecyloxyethyl) carbamoyl group.

  Examples of the alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a hexylsulfinyl group, a cyclohexylsulfinyl group, a 2-ethylhexylsulfinyl group, an octylsulfinyl group, and a cyanomethylsulfinyl group. Group, methoxymethylsulfinyl group and the like.

  Examples of the arylsulfinyl group include phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, and 2-butoxyphenylsulfinyl group. Group, 2-fluorophenylsulfinyl group, 3-methylphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-methylphenylsulfinyl group Group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group, etc. It is below.

  Examples of the alkylsulfonyl group include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, octylsulfonyl group, and cyanomethylsulfonyl. Group, methoxymethylsulfonyl group, trifluoromethylsulfonyl group and the like.

  Examples of the arylsulfonyl group include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, a 2-methoxyphenylsulfonyl group, and 2-butoxyphenylsulfonyl. Group, 2-fluorophenylsulfonyl group, 3-methylphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 3-fluorophenylsulfonyl Group, 4-methylphenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group and the like. It is.

  Examples of the sulfamoyl group include a sulfamoyl group, an N-methylsulfamoyl group, an N-ethylsulfamoyl group, an N-propylsulfamoyl group, an N-butylsulfamoyl group, and an N-hexylsulfamoyl group. N-cyclohexylsulfamoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-phenylsulfamoyl group, N-2-methylphenylsulfuryl group Famoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3 -Nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-metho Siphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfur Examples include a famoyl group, an N-methyl-N-phenylsulfamoyl group, an N, N-dimethylsulfamoyl group, an N, N-dibutylsulfamoyl group, and an N, N-diphenylsulfamoyl group.

Further, as an electron withdrawing group, an alkyl group or an aryl group having a halogen, a cyano group, a nitro group, an acyl group, a sulfo group, a trifluoromethyl group, or the like can also be used.
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Examples include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like. Among these, a C1-C20 alkyl group is preferable and a C1-C10 thing is more preferable.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group, an azulenyl group, a fluorenyl group, a terphenyl group, a quarterphenyl group, a pentarenyl group, a heptaenyl group, and a biphenylenyl group. Group, indacenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, phenanthryl group and the like. Among these, an aryl group having 1 to 25 carbon atoms is preferable, and an aryl group having 1 to 15 carbon atoms is more preferable.

  Examples of the organic substituent include an alkyl group, an alkoxy group, a thioalkoxy group, an aryl group, an aryloxy group, and an arylthiooxy group.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Examples include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like. Among these, a C1-C20 alkyl group is preferable and a C1-C10 thing is more preferable.
The alkyl group may have a substituent. Examples of the substituent that the alkyl group has include a halogen and an alkyloxy group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. A tridecyloxy group, a tetradecyloxy group, a pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a nonadecyloxy group, an icosyloxy group, and the like. Among these, a C1-C20 alkoxy group is preferable and a C1-C10 thing is more preferable.

  Examples of the thioalkoxy group include a methylthiooxy group, an ethylthiooxy group, a propylthiooxy group, a butylthiooxy group, a pentylthiooxy group, a hexylthiooxy group, a heptylthiooxy group, an octylthiooxy group, and a nonylthio group. Oxy, decylthiooxy, undecylthiooxy, dodecylthiooxy, tridecylthiooxy, tetradecylthiooxy, pentadecylthiooxy, hexadecylthiooxy, heptadecylthiooxy, octadecyl A thiooxy group, a nonadecyl thiooxy group, an icosyl thiooxy group, etc. are mentioned. Among these, a C1-C20 thioalkoxy group is preferable and a C1-C10 thing is more preferable.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group, an azulenyl group, a fluorenyl group, a terphenyl group, a quarterphenyl group, a pentarenyl group, a heptaenyl group, and a biphenylenyl group. Group, indacenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, phenanthryl group and the like. Among these, an aryl group having 1 to 30 carbon atoms is preferable, and an aryl group having 1 to 15 carbon atoms is more preferable.
The aryl group may have a substituent. Examples of the substituent of the aryl group include an alkyl group, an alkyloxy group, a halogen, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, and an alkylsulfinyl group. , Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group.

  The aryloxy group, for example, phenyloxy group, biphenyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, pyrenyloxy group, indenyloxy group, azulenyloxy group, fluorenyloxy group, terphenyloxy Group, quarterphenyloxy group, pentarenyloxy group, heptaenyloxy group, biphenylenyloxy group, indacenyloxy group, acenaphthylenyloxy group, phenalenyloxy group, fluorenyloxy group, A phenanthryloxy group and the like can be mentioned. Among these, an aryloxy group having 1 to 25 carbon atoms is preferable, and an aryloxy group having 1 to 15 carbon atoms is more preferable.

  Examples of the arylthiooxy group include phenylthiooxy group, biphenylthiooxy group, naphthylthiooxy group, anthrylthiooxy group, phenanthrylthiooxy group, pyrenylthiooxy group, indenylthiooxy group, azene Renylthiooxy group, fluorenylthiooxy group, terphenylthiooxy group, quarterphenylthiooxy group, pentarenylthiooxy group, heptalenylthiooxy group, biphenylenylthiooxy group, indacenylthiooxy group, acenaphthyleni Examples include a ruthiooxy group, a phenalenylthiooxy group, a fluorenylthiooxy group, and a phenanthrylthiooxy group. Among these, an arylthiooxy group having 1 to 25 carbon atoms is preferable, and an arylthiooxy group having 1 to 15 carbon atoms is more preferable.

R ^{1 to} R ⁸ are preferably hydrogen, halogen, cyano group, nitro group, acyl group, sulfo group, alkyl group, alkyloxy group, or aryloxy group, and more preferably hydrogen or halogen.
R ⁹ or R ¹⁰ is preferably hydrogen, halogen, cyano group, nitro group, acyl group, sulfo group, or optionally substituted aryl group, more preferably hydrogen, cyano group, or optionally substituted aryl group. preferable.
R ^{11 to} R ¹⁴ are preferably hydrogen, halogen, cyano group, nitro group, acyl group, alkyloxycarbonyl group, sulfo group, or optionally substituted aryl group, and may be hydrogen, cyano group or substituted. A good aryl group is more preferred.

R ^{15 to} R ²² are preferably hydrogen, halogen, cyano group, nitro group, acyl group, sulfo group, alkyl group, alkyloxy group, or aryloxy group, and more preferably hydrogen or halogen.
R ²³ or R ²⁴ is preferably hydrogen, halogen, cyano group, nitro group, acyl group, sulfo group, or optionally substituted aryl group, more preferably hydrogen, cyano group, or optionally substituted aryl group. preferable.
R ^{25 to} R ²⁸ are preferably hydrogen, halogen, cyano group, nitro group, acyl group, alkyloxycarbonyl group, sulfo group or optionally substituted aryl group, and may be hydrogen, cyano group or substituted. A good aryl group is more preferred.

As the compound represented by the formula (1), at least one of R ^{1 to} R ⁸ is an electron withdrawing group (embodiment 1-1); at least one of R ^{11 to} R ¹⁴ is an electron withdrawing group Embodiment (embodiment 1-2); Embodiment in which at least one of R ⁹ or R ¹⁰ is an electron withdrawing group (embodiment 1-3); At least one of R ^{1 to} R ⁸ is an electron withdrawing group And the aspect (embodiment 1-4) whose at least one of R < ¹¹ > -R < ¹⁴ > is an electron withdrawing group is mentioned.
As the compound represented by the formula (2), at least one of R ^{15 to} R ²² is an electron withdrawing group (embodiment 2-1); at least one of R ^{25 to} R ²⁸ is an electron withdrawing group. Embodiment (Embodiment 2-2) in which at least one of R ²³ or R ²⁴ is an electron withdrawing group (Embodiment 2-3); At least one of R ^{15 to} R ²² is an electron withdrawing group And an embodiment (embodiment 2-4) in which at least one of R ^{25 to} R ²⁸ is an electron-withdrawing group.

In the aspect (1-1) or (2-1), it is preferable that all of R ^{1 to} R ⁸ or all of R ^{15 to} R ²² are electron withdrawing groups.
In the aspect (1-2) or (2-2), it is preferable that all of R ^{11 to} R ¹⁴ or all of R ^{25 to} R ²⁸ are electron withdrawing groups.

The compound represented by the formula (1) preferably has a bulky organic substituent in at least one of R ^{1 to} R ¹⁴ . The compound represented by the formula (2) preferably has a bulky organic substituent in at least one of R ^{15 to} R ²⁸ . By having a bulky substituent, solubility in a solvent is further improved. Examples of the bulky organic substituent include an alkyl group which may have a substituent having 1 to 30 carbon atoms and an aryl group which may have a substituent having 3 to 15 carbon atoms (preferably t- Butylphenyl group).

  The precursor of the bis-boron dipyrromethene dye of the present invention is an optical filter for a semiconductor light receiving element having a function of absorbing and cutting near infrared rays as a near infrared absorbing dye; a near infrared absorbing film that blocks heat rays for energy saving Near-infrared absorbing plate; Information display material as security ink and invisible barcode ink; Dye for solar cell using near-infrared light; Infrared cut filter for plasma display panel (PDP) and CCD; Photothermal for laser welding It can be used for conversion material use;

2. Precursor of bis-boron dipyrromethene dye The bis-boron dipyrromethene dye precursor of the present invention has a benzene ring structure in the final dye as represented by formulas (13) to (16). A compound having a bicyclo structure, a cyclohexane structure, or a cyclohexene structure can be used for some or all of the moieties.

  In the formula (13), RingA is any one cyclic structure selected from the following formulas Ia to IIa (in the formulas Ia to IIa, a1 to a4 mean carbon numbers).

In formula (14), RingB is any one cyclic structure selected from the following formulas Ib to IIb (in formulas Ib to IIb, b1 to b4 represent carbon numbers).

In formula (15), RingC is any one cyclic structure selected from the following formulas Ic to IIc (in formulas Ic to IIc, c1 to c4 represent carbon numbers),

RingD is any one cyclic structure selected from the following formulas Id to IIId (in formulas Id to IIId, d1 to d4 represent carbon numbers),

RingE is any one cyclic structure selected from the following formulas Ie to IIIe (in formulas Ie to IIIe, e1 to e4 represent carbon numbers).

In the formula (16), RingF is any one cyclic structure selected from the following formulas If to IIf (in the formulas If to IIf, f1 to f4 represent carbon numbers),

RingG is any one cyclic structure selected from the following formulas Ig to IIIg (in formulas Ig to IIIg, g1 to g4 represent carbon numbers),

RingH is any one cyclic structure selected from the following formulas Ih to IIIh (in formulas Ih to IIIh, h1 to h4 represent carbon numbers).

In formulas (13) and (15), at least one of R ^{39 to} R ⁵² is an electron withdrawing group, and the rest is hydrogen or an organic substituent.
In formulas (14) and (16), at least one of R ^{53 to} R ⁶⁶ is an electron withdrawing group, and the rest is hydrogen or an organic substituent.
In the formulas, L ¹ ~L ⁸ are each _{independently, * - CH 2 -CH 2 -} *, * - C (= O) - *, * - C (= O) -C (= O) - * Indicates. * Indicates a bond.

R ^{39 to} R ⁵² and R ^{53 to} R ⁶⁶ have the same meanings as R ^{1 to} R ¹⁴ and R ^{15 to} R ^{28 in} formula (1) or (2) described above, and preferred ones are also the same.

2-1. Precursor of bis-boron dipyrromethene dye having a bicyclo structure A precursor of a bis-boron dipyrromethene dye having a bicyclo structure in part or all of the portion that becomes a benzene ring structure in the final dye is represented by the following formula ( 3) to (6). That is, the precursor having a bicyclo structure is a compound having the cyclic structure Ia in the compound (13); a compound having the cyclic structure Ib in the compound (14); and having the cyclic structures Ic, Id, and Ie in the compound (15). Compound: Compound (16) having a cyclic structure If, Ig and Ih.
The compounds represented by formulas (3) to (6) have structural isomerism depending on which of the two adjacent nitrogen atoms (N) is covalently bonded to which of the boron atoms (B). There is a body. These structural isomers are also included in the present invention.

  This precursor can convert a bicyclo structure into a benzene ring structure only by heat treatment, and can easily convert it into a bis-boron dipyrromethene dye, so that a dye-containing film or the like can be easily produced. Further, since the precursor has a bicyclo structure, it has high solubility in an organic solvent. Therefore, purification using a solvent can be performed, and a bis-boron dipyrromethene dye having higher purity can be easily obtained.

[In Formulas (3) and (5), at least one of R ^{1 to} R ¹⁴ is an electron withdrawing group, and the rest is hydrogen or an organic substituent.
In formulas (4) and (6), at least one of R ^{15 to} R ²⁸ is an electron withdrawing group, and the remainder is hydrogen or an organic substituent.
In the formulas, L ¹ ~L ⁸ are each _{independently, * - CH 2 -CH 2 -} *, * - C (= O) - *, * - C (= O) -C (= O) - * Indicates. * Indicates a bond. ]

R < ¹ > -R < ¹⁴ > and R < ¹⁵ > -R < ²⁸ > are synonymous with Formula (1) or (2) mentioned above, and a preferable thing is also the same.

L ^{1 to} L ⁸ each independently represent * —CH ₂ —CH ₂ — *, * —C (═O) — *, * —C (═O) —C (═O) — *. When L ^{1 to} L ⁸ in the bicyclo structure are any of these, the precursor is heated, irradiated with light, or simultaneously treated with light and heat, thereby causing a reverse Diels-alder reaction and easily causing a benzene ring. Can be changed to structure. Among these, as the ^{L 1 ~L 8, * - CH} 2 -CH 2 - * ( ethylene group).

As a compound represented by Formula (3) or (5), at least one of R ^{1 to} R ⁸ is an electron withdrawing group ((Aspect 3-1) or (Aspect 5-1)); R ¹¹ at least one of an electron withdrawing group aspect of to R ¹⁴ ((embodiment 3-2) or (embodiment 5-2)); aspect at least one of R ⁹ or R ¹⁰ is an electron-attracting group ( (Aspect 3-3) or (Aspect 5-3)); at least one of R ^{1 to} R ⁸ is an electron withdrawing group, and at least one of R ^{11 to} R ¹⁴ is an electron withdrawing group. Aspect ((Aspect 3-4) or (Aspect 5-4)).
As the compound represented by formula (4) or (6), an embodiment ((embodiment 4-1) or (embodiment 6-1)) in which at least one of R ^{15 to} R ²² is an electron withdrawing group; R Embodiment in which at least one of ^{25 to} R ²⁸ is an electron withdrawing group ((embodiment 4-2) or (embodiment 6-2)); an embodiment in which at least one of R ²³ or R ²⁴ is an electron withdrawing group ( (Aspect 4-3) or (Aspect 6-3)); at least one of R ^{15 to} R ²² is an electron withdrawing group, and at least one of R ^{25 to} R ²⁸ is an electron withdrawing group. Aspect ((Aspect 4-4) or (Aspect 6-4)).

In the embodiment (3-1), (4-1), (5-1) or (6-1), all of R ^{1 to} R ⁸ or all of R ^{15 to} R ²² are electron withdrawing groups. It is preferable.
In the embodiment (3-2), (4-2), (5-2) or (6-2), all of R ^{11 to} R ¹⁴ or all of R ^{25 to} R ²⁸ are electron withdrawing groups. It is preferable.

Examples of the compound in which L ^{1 to} L ⁸ are * —CH ₂ —CH ₂ — * include the following.

Examples of the compound in which L ^{1 to} L ⁸ are * —C (═O) — * include the following.

Examples of the compound in which L ^{1 to} L ⁸ are * —C (═O) —C (═O) — * include the following.

2-2. Precursor of bis-boron dipyrromethene dye having cyclohexane structure and / or cyclohexene structure A compound having a cyclohexane structure and / or a cyclohexene structure in which a part or all of the portion that becomes a benzene ring structure in the final dye is a cyclohexane structure and / or a cyclohexene structure, It can be used as a precursor of a bis-boron dipyrromethene dye.

  Examples of the precursor of a bis-boron dipyrromethene dye having a cyclohexane structure and / or a cyclohexene structure include a compound having a cyclic structure IIa as RingA in formula (13); and a cyclic structure IIb as RingB in formula (14) A compound having the cyclic structure IIc as RingC, any of IId or IIId as RingD, and any of the cyclic structures IIe or IIIe as RingE; in the formula (15); And a compound having either IIg or IIIg as RingG and any of cyclic structures IIh or IIIh as RingH.

  In the precursor of the bis-boron dipyrromethene dye having a cyclohexane structure and / or a cyclohexene structure, two nitrogen atoms adjacent to each other with the boron atom (B) are present, as in the compounds represented by the formulas (3) to (6). There are structural isomers depending on which of the atoms (N) is covalently bonded. The present invention includes these structural isomers.

2-3. Bicyclo structure and precursor of bis-boron dipyrromethene dye having cyclohexane structure and / or cyclohexene structure In the final dye, a part having a benzene structure has a bicyclo structure, and a part other than the bicyclo structure A compound having a cyclohexane structure and / or a cyclohexene structure can also be used as a precursor of a bis-boron dipyrromethene dye. That is, the precursor includes (i) a precursor having a bicyclo structure as a part of a portion that becomes a benzene structure in the final dye, and a portion other than the bicyclo structure having a cyclohexane structure. In a typical dye, a precursor having a bicyclo structure as a part of a part that becomes a benzene structure and a part other than the bicyclo structure being a cyclohexene structure, (iii) One of the parts that become a benzene structure in the final dye A precursor having a bicyclo structure as a part and having both a cyclohexane structure and a cyclohexene structure in a part other than the bicyclo structure is included.

  A bicyclo structure and a precursor of a bis-boron dipyrromethene dye having a cyclohexane structure and / or a cyclohexene structure are cyclic structures Ic as RingC, IId or IIId as RingD, and cyclic as RingE in Formula (15) Compound having either structure IIe or IIIe, RingC as cyclic structure IIc, RingD and RingE at least one is bicyclostructure (RingD is cyclic structure Id or RingE is cyclic structure Ie, or cyclic A compound having both structure Id and cyclic structure Ie; in formula (16), a compound having either cyclic structure If as RingF, either IIg or IIIg as RingG, and either cyclic structure IIh or IIIh as RingH, Ri At least one of cyclic structures IIf and RingG and RingH as gF is a bicyclo structure (RingG is cyclic structure Ig or RingH is cyclic structure Ih, or both cyclic structure Ig and cyclic structure Ih) A compound.

  Also in the precursor of the bis-boron dipyrromethene dye having a bicyclo structure and a cyclohexane structure and / or a cyclohexene structure, a boron atom (B) is adjacent to the precursor represented by the formulas (3) to (6). There are structural isomers depending on which of the two nitrogen atoms (N) to be bonded covalently. The present invention includes these structural isomers.

3. Synthesis Method of Bis-Boron Dipyromethene Dye Hereinafter, an example of a synthesis method of the bis-boron dipyrromethene dye of the present invention will be described.

  As a method for synthesizing the bis-boron dipyrromethene dye of the present invention, it can be produced by synthesizing the compounds represented by the formulas (13) to (16) and then heat-treating them. In the case of a precursor having a structure, for example, a method of synthesizing a compound represented by formula (3) or (4) and then heat-treating the compound (production method 1); represented by formula (5) or (6) After synthesizing the compound, a method of heat-treating the compound to obtain a compound represented by the formula (3) or (4) and heat-treating the compound (Production Method 2) may be mentioned.

  Further, in the case of a precursor having a cyclohexane structure and / or a cyclohexene structure in a compound, examples of the method for synthesizing a bis-boron dipyrromethene dye include bis-boron dipyrroyl having a cyclohexane structure and / or a cyclohexene structure described above. An example is a method of producing a precursor of a methene dye and then oxidizing the precursor (Production Method 3).

  In the case of a precursor having a bicyclo structure and a cyclohexane structure and / or a cyclohexene structure in a compound, as a synthesis method of a bis-boron dipyrromethene dye, for example, a bicyclo unit is first thermally decomposed, and thereafter A method of converting a cyclohexane structure and a cyclohexene structure existing in a compound by oxidation (production method 4); a method of oxidizing a cyclohexane structure and a cyclohexene structure in a compound first and then thermally decomposing a bicyclo unit (production method 5); .

In both production method 1 and production method 2, as a starting material, a compound represented by formula (7) (hereinafter, “compound represented by formula (7)” is abbreviated as “compound (7)”). In addition, compounds represented by other chemical formulas may be abbreviated in the same manner.) Or a compound represented by (8) can be used.
These compounds are described in, for example, “Hidemitsu Uno et al., Synthesis and structures of pyrroles fused with rigid bicyclic ring systems at β-positions, J. Chem. Soc., Perkin Trans. 1, 2000, p.4347- 4355 ”,“ Yoko Yamada et al., Photochemical Synthesis of Pentacene and its Derivatives, Chem. Eur. J. 2005, 11, p. 6212-6220 ”, described in US Patent Application Publication No. 2009/0226634. It can be synthesized with reference to the above method.

Expression (7), (8) in, L ⁹ and L ¹⁰ are each _{independently, * - CH 2 -CH 2 -} *, * - C (= O) - *, * - C (= O) -C (= O)-* is shown. * Indicates a bond. ]

  In addition, you may use a compound (7), (8), after changing a substituent like the compound represented by Formula (9) or (10).

Expression (9), (10) in, L ⁹ and L ¹⁰ are each _{independently, * - CH 2 -CH 2 -} *, * - C (= O) - *, * - C (= O) -C (= O)-* is shown. * Indicates a bond. R ^{31 to} R ³⁴ each represents an electron withdrawing group, hydrogen, or an organic substituent. ]

  Examples of the compounds (7) to (10) include the following.

  And in the manufacturing method 1, compound (3) or (4) is made by making the compound represented by Formula (11) and boron trifluoride diethyl ether complex react with either of said compounds (7)-(10). ) Is obtained. In production method 2, compound (5) or (6) is prepared by reacting any one of compounds (7) to (10) with the compound represented by formula (12) and boron trifluoride diethyl ether complex. ) Is obtained.

[In the formulas (11) and (12), R ^{35 to} R ³⁸ each represent an electron withdrawing group, hydrogen, or an organic substituent. X represents an aldehyde group or an ethoxycarbonyl group. Y represents an optionally substituted methyl group.
In the formula (12), L ¹¹ represents * —CH ₂ —CH ₂ — *, * —C (═O) — *, * —C (═O) —C (═O) — *. * Indicates a bond. ]

  Examples of the substituent of the optionally substituted methyl group include an electron withdrawing group, an alkoxy group, a thioalkoxy group, an optionally substituted aryl group, and an optionally substituted alkyl group.

  Next, in Production Method 3, a precursor having a cyclohexane structure and / or a cyclohexene structure can be used as the precursor. As a starting material for the precursor, a compound represented by the formula (17) or a compound represented by the formula (18) can be used.

  In the production method 3, cyclohexane is reacted with either the compound (17) or (18) by a compound represented by the formula (11), (19) or (20) and a boron trifluoride diethyl ether complex. A precursor having a structure and / or a cyclohexene structure can be obtained.

[In formulas (11), (19), and (20), R ^{43 to} R ⁴⁶ each represent an electron-withdrawing group, hydrogen, or an organic substituent. X represents an aldehyde group or an ethoxycarbonyl group. Y represents an optionally substituted methyl group. ]

  Next, production methods 4 and 5 will be described. In any of production methods 4 and 5, a precursor having a bicyclo structure, a cyclohexane structure and / or a cyclohexene structure can be used. As the starting material of the precursor, compounds represented by the formulas (7) to (10) can be used.

  In addition, as a compound represented by Formula (7)-(10), the same thing as the compound explained in full detail in the column of the manufacturing method 1 and 2 can be used.

  Then, by reacting any of the compounds (7) to (10) with the compound represented by the formula (11), (19) or (20) and a boron trifluoride diethyl ether complex, A precursor having a cyclohexane structure and / or a cyclohexene structure can be obtained.

[In formulas (11), (19), and (20), R ^{43 to} R ⁴⁶ each represent an electron-withdrawing group, hydrogen, or an organic substituent. X represents an aldehyde group or an ethoxycarbonyl group. Y represents an optionally substituted methyl group. ]

  Moreover, the precursor which has a bicyclo structure, a cyclohexane structure, and / or a cyclohexene structure uses the compound represented by Formula (17) or Formula (18) mentioned above as a starting material of this precursor, Either of the compounds (12) is essential and can be produced by reacting with boron trifluoride diethyl ether complex in a reaction system containing the compounds (11), (19), and (20) as necessary. .

  The method for purifying the precursor is not particularly limited, and silica gel chromatography, alumina column chromatography, sublimation purification, recrystallization, crystallization, and the like can be used. From the viewpoint of simplicity of work, recrystallization, crystallization, silica gel chromatography, and alumina column chromatography are preferable.

Next, in production method 2, compound (5) or (6) is subjected to a heat treatment to convert the bicyclo structure at both ends of the molecule into a benzene ring structure to obtain compound (3) or (4).
In this case, the heat treatment temperature is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, preferably 190 ° C. or lower, more preferably 180 ° C. or lower. The heat treatment time is preferably 0.2 hours or longer, more preferably 0.5 hours or longer, 4 hours or shorter, more preferably 3 hours or shorter.

Then, in both production method 1 and production method 2, compound (3) or (4) is subjected to a heat treatment to convert the bicyclo structure at the center of the molecule into a benzene ring structure to obtain compound (1) or (2).
In this case, the heat treatment temperature is preferably 200 ° C. or higher, more preferably 210 ° C. or higher, preferably 280 ° C. or lower, more preferably 270 ° C. or lower. The heat treatment time is preferably 0.2 hours or longer, more preferably 0.5 hours or longer, 4 hours or shorter, more preferably 3 hours or shorter.

  In addition, in the production methods 3 to 5, the cyclohexane structure and / or cyclohexene structure in the compound is, for example, “Cai Chenxin et al., 3 authors, Fasile synthesis of 4,9-dihydro-2H-benz [f] -and 4,11- dihydro-2H-naphth [2,3-f] -isoindoles and their utility for porphyrin synthesis, Heterocycles, vol. 84, No.2, 2012, p.829-841 `` Scheme 1 vii) Converts the cyclohexane structure described in “Timsy Uppal et al., Synthesis, Computational Modeling, and Properties of Benzo-Appended BODIPYs, Chem. Eur. J., vol. 18, 2012, p.3893-3905” to a benzene ring. Referring to each scheme, these may be oxidized and converted to a benzene ring. By such a method, a bis-boron dipyrromethene dye (compound (1) or (2)) can be synthesized.

  The obtained bis-boron dipyrromethene dye (compound (1) or (2)) may be purified as necessary. Examples of the purification method include the same method as that for the precursor.

  In addition, the manufacturing method of the compound (17) used as a raw material of the manufacturing method 3 and a compound (18) uses the 7,4-cyclohexadiene as a raw material, for example, the following scheme I and 7 of the Example of this-application specification. It may be synthesized by referring to the method described in the column.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention.

In addition, the following apparatus was used for the analysis about the compound synthesize | combined.
Melting point: Model “EXSTAR6000 / TG / DTA6200” manufactured by Seiko Instruments
Ultraviolet-visible absorption spectrum: model “U-2810” manufactured by Hitachi High-Technologies Corporation, model “v-570 model” manufactured by JASCO Corporation
Infrared absorption spectrum: HORIBA, Ltd. Model “FT-720”
NMR spectrum: “JNM-AL400” manufactured by JEOL Ltd., “JNM-EX400” manufactured by JEOL Ltd., “Mercury 2000” manufactured by Varian Technologies, Inc.
Mass spectrum: manufactured by JEOL Ltd. Model “JMS-MS 700”
(MALDI-TOF) mass spectrum; manufactured by Applied Biosystems, model “Voyager-DE ^™ -PRO”

1. Synthesis Example 1 (syn 4-tBu-phenyl tetrafluoroisoindole benzo bisBODIPY)
1-1. syn diiodo dipyrrole
In a reaction vessel, 520 mg (1.59 mmol) of compound (7-1), 1.20 g (3.45 mmol) of benzyltrimethylammonium dichloroiodate (BTMA · ICl ₂ ), 500 mg (5 mmol) of CaCO ₃ , 33 ml of CH ₂ Cl ₂ , 13 ml of MeOH was added and refluxed for 4 hours. After completion of the reaction, the temperature was returned to room temperature, and the reaction solution was washed with a saturated aqueous sodium sulfite solution, water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Furthermore, by trituration with a hexane / methanol (volume ratio 9: 1) solution, the compound represented by the formula (3-1-1) 500 mg (0.86 mmol, yield from the compound (7-1) 54 mol%) was obtained.

The analytical data of the obtained compound (3-1-1) are as follows.
Mol. Form: C ₁₈ H ₁₈ I ₂ N ₂ O ₄ (Exact Mass: 599.9356, MW: 580.1555)
Appearance: white powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.40 (t, 3H), 1.71 (m, 4H), 3.82 (m, 1H), 4.34 (q, 4H), 5. 23 (m, 1H), 8.50 (br, 1H).
mp: 271 ° C
HRMS calcd for C ₁₈ H ₁₈ I ₂ N ₂ O ₄ : 580.9434, found 580.9432
MS (FAB) m / z 580M ⁺

1-2. syn 4-tBu phenyl dipyrrole bis ester
Compound (3-1-1) 100 mg (0.172 mmol), 4-t-Bu-phenylboronic acid 68 mg (0.38 mmol), tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ) 10 mg in a reaction vessel (0.009 mmol) was added and replaced with argon. Next, 5 ml of dry-toluene was added and freeze deaeration was performed. Then, 10 wt% Na ₂ CO ₃ aqueous solution (Na ₂ CO ₃ 56mg / water 0.56 ml) was added and stirred for 16 hours at 90 ° C.. After completion of the reaction, the mixture was filtered through Celite, and the reaction solution was washed with water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Furthermore, by trituration with a hexane / methanol (volume ratio 9: 1) solution, 53 mg (0.089 mmol of the compound represented by the formula (3-1-2), from the compound (3-1-1) Yield 50 mol%).

The analytical data of the obtained compound (3-1-2) are as follows.
Mol. Form: C ₃₈ H ₄₄ N ₂ O ₄ (Exact Mass: 592.3301, MW: 592.7670)
Appearance: white powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.36 (s, 18H), 1.44 (t, 6H, J = 7 Hz), 1.76-1.85 (m, 4H), 4.37 (Q, 4H, J = 7.0 Hz), 4.86 (m, 1H), 5.35 (m, 1H), 7.45 (m, 8H), 8.44 (br, 2H).
MS (MALDI-TOF) m / z = 592 (M ⁺ )

1-3. syn 4-tBu phenyl dipyrrole
The reaction vessel was charged with 50 mg (0.084 mmol) of the compound (3-1-2) and purged with nitrogen. After adding 4 ml of ethylene glycol and shielding from light, 90 mg (2.25 mmol) of sodium hydroxide was added and stirred at 160 ° C. for 2 hours. After completion of the reaction, the mixture was returned to room temperature, quenched with water, and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Furthermore, by washing with hexane, 53 mg of a crude product of the compound represented by the formula (3-1-3) was obtained. It was used for the next reaction without further purification.

Analytical data of the obtained compound (3-1-3) are as follows.
Mol. Form: C ₃₂ H ₃₆ N ₂ (Exact Mass: 448.2878, MW: 448.6416)
Appearance: white solid
MS (MALDI-TOF) m / z = 448 (M ⁺ )

1-4. syn 4-tBu-phenyl tetrafluoroisoindole BCOD bisBODIPY
The reaction vessel was charged with 90 mg of the crude product of the compound (3-1-3) and 70 mg (0.32 mmol) of 4,5,6,7-tetrafluorobenzo [c] pyrrole-1carbaldehyde, and the atmosphere was replaced with nitrogen. After 20 ml of dry-toluene was added and protected from light, 0.1 ml (1 mmol) of phosphoryl chloride (POCl ₃ ) was added dropwise and stirred at 80 ° C. for 12 hours. The temperature was returned to room temperature, 0.2 ml (1.1 mmol) of N, N-diisopropylethylamine (DIPEA) was added, and the mixture was stirred at 80 ° C. for 1 hour. After returning to room temperature again, 0.14 ml (1.1 mmol) of boron trifluoride diethyl ether complex (BF ₃ .Et ₂ O) was added, followed by stirring at 80 ° C. for 5 hours. After completion of the reaction, the reaction solution was returned to room temperature, quenched with water, and unnecessary substances were removed by Celite filtration. The mixture was extracted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate, water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Furthermore, 29 mg (0.03 mmol) of the compound represented by Formula (3-1) was obtained by purification by column chromatography.

The analytical data of the obtained compound (3-1) are as follows.
Mol. Form: C ₅₀ H ₃₆ B ₂ F ₁₂ N ₄ (Exact Mass: 942.2934, MW: 942.4505)
Appearance: purple solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.38 (s, 18H), 2.0-2.1 (m, 4H), 3.73 (m, 1H), 4.35 (m, 1H) ), 7.45 (m, 8H), 7.80 (s, 2H), 8.32 (s, 2H).
mp: 250 ° C. (dcmp)
MS (MALDI-TOF) m / z = 942 (M ⁺ ), 914 (M-28)
UV-vis (CHCl ₃ ): λ = 590 nm
FL (CHCl ₃ ): λ = 624 nm

1-5. syn 4-tBu-phenyl tetrafluoroisoindole benzo bisBODIPY
The compound (3-1) was placed in a microtube and heated at 250 ° C. for 2 hours in a vacuum. After returning to room temperature, the compound represented by Formula (1-1) was obtained.

The analytical data of the obtained compound (1-1) are as follows.
Mol. Form: C ₄₈ H ₃₂ B ₂ F ₁₂ N ₄ (Exact Mass: 914.2621, MW: 914.3939)
Appearance: black solid
_{HRMS calcd for C 48 H 32 B} 2 F 12 N 4: 915.2700, found 915.2710
MS (MALDI-TOF) m / z = 914 (M ⁺ )
UV-vis (CHCl ₃ ): λ = 748 nm
FL (CHCl ₃ ): λ = 755 nm

2. Synthesis example 2 (anti 4-tBu-phenyl tetrafluoroisoindole benzo bisBODIPY)
2-1. anti diiodo dipyrrole
In a reaction vessel, 456 mg (1.39 mmol) of the compound represented by the formula (8-1), 1.053 g (3.03 mmol) of BTMA · ICl ₂ , 439 mg (4.39 mmol) of CaCO _3, 29 ml of CH ₂ Cl ₂ , 11 ml of MeOH was added and refluxed for 4 hours. After completion of the reaction, the temperature was returned to room temperature, and the reaction solution was washed with a saturated aqueous sodium sulfite solution, water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Furthermore, by trituration with a hexane / methanol (volume ratio 9: 1) solution, the compound represented by the formula (4-1-1) 737 mg (1.27 mmol, yield from the compound (8-1)) 91 mol%) was obtained.

Analytical data of the obtained compound (4-1-1) are as follows.
Mol. Form: C ₁₈ H ₁₈ I ₂ N ₂ O ₄ (Exact Mass: 580.9434, MW: 580.9438)
Appearance: white powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.42 (t, 6H, J = 7.0 Hz), 1.70-1.73 (m, 4H), 4.24-4.44 (m, 4H), 4.54 (m, 2H), 8.35 (br, 2H).
mp: 277 ° C
_{HRMS calcd for C 18 H 18 I} 2 N 2 O 4,: 579.9356, found 579.9438
MS (FAB) m / z 580M ⁺ ,

2-2. anti 4-tBu phenyl dipyrrole bis ester
To the reaction vessel, 764 mg (1.32 mmol) of the compound (4-1-1), 474 mg (2.65 mmol) of 4-t-butylphenylboronic acid, 76.4 mg (0.066 mmol) of Pd (PPh ₃ ) ₄ were added, Argon substitution was performed. Next, 21 ml of dry-toluene was added and freeze deaeration was performed. Thereafter, Na ₂ CO ₃ aqueous solution (Na ₂ CO ₃ 430mg / water 4.3 ml) was added and stirred for 16 hours at 90 ° C.. After completion of the reaction, the mixture was filtered through Celite, and the reaction solution was washed with water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Furthermore, by triturating with a hexane / methanol (volume ratio 9: 1) solution, 513 mg (0.86 mmol of the compound represented by the formula (4-1-2), from the compound (4-1-1) Yield 66 mol%) was obtained.

The analytical data of the obtained compound (4-1-2) are as follows.
Mol. Form: C ₃₈ H ₄₄ N ₂ O ₄ (Exact Mass: 593.3379, MW: 593.3372)
Appearance: white powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.36 (s, 18H), 1.44 (t, 6H, J = 7 Hz), 1.76-1.79 (m, 4H), 4.43 -4.45 (m, 4H), 5.15 (m, 2H), 7.45-7.55 (m, 8H), 8.42 (br, 2H).
mp: 318 ° C
_{HRMS calcd for C 38 H 44 N} 2 O 4,: 593.3379, found 593.3372
MS (MALDI-TOF) m / z = 592 (M ⁺ )

2-3. anti 4-tBu phenyl dipyrrole
The reaction vessel was charged with 140 mg (0.24 mmol) of the compound (4-1-2) and purged with nitrogen. After 11 ml of ethylene glycol was added and protected from light, 250 mg (6.25 mmol) of sodium hydroxide was added and stirred at 160 ° C. for 2 hours. After completion of the reaction, the reaction solution was returned to room temperature, quenched with water, and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Furthermore, by washing with hexane, 80 mg of a crude product of the compound represented by the formula (4-1-3) was obtained. It was used for the next reaction without further purification.

The analytical data of the obtained compound (4-1-3) are as follows.
Mol. Form: C ₃₂ H ₃₆ N ₂ (Exact Mass: 448.2878, MW: 448.6416)
Appearance: white solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.35 (s, 18H), 1.82 (m, 4H), 4.56 (m, 2H), 6.55 (m, 2H), 7. 41 (m, 8H), 7.59 (br, 2H).
MS (MALDI-TOF) m / z = 448 (M ⁺ )

2-4. anti 4-tBu-phenyl tetrafluoroisoindole BCOD bisBODIPY
The reaction vessel was charged with 200 mg of the crude product of compound (4-1-3) and 200 mg (0.92 mmol) of 4,5,6,7-tetrafluorobenzo [c] pyrrole-1 carbaldehyde, and the atmosphere was replaced with nitrogen. After 40 ml of dry-toluene was added and protected from light, 0.3 ml (3 mmol) of POCl ₃ was added dropwise and stirred at 80 ° C. for 12 hours. The temperature was returned to room temperature, 0.6 ml (3.3 mmol) of DIPEA was added, and the mixture was stirred at 80 ° C. for 1 hour. After returning to room temperature again, 0.42 ml (1.1 mmol) of BF ₃ .Et ₂ O was added, followed by stirring at 80 ° C. for 5 hours. After completion of the reaction, the reaction solution was returned to room temperature, quenched with water, and unnecessary substances were removed by Celite filtration. The mixture was extracted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate, water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Furthermore, 75 mg (0.08 mmol) of the compound represented by Formula (4-1) was obtained by purification by column chromatography.

The analytical data of the obtained compound (4-1) are as follows.
Mol. Form: C ₅₀ H ₃₆ B ₂ F ₁₂ N ₄ (Exact Mass: 942.2934, MW: 942.4505)
Appearance: purple solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.37-1.42 (m, 4H), 1.42-1.45 (s, 18H), 4, 25 (m, 2H), 7.51 (S, 2H), 7.61 (m, 4H), 7.68 (s, 2H), 7.74 (m, 4H).
mp: 250 ° C. (dcmp)
MS (MALDI-TOF) m / z = 592 (M ⁺ )
MS (MALDI-TOF) m / z = 942 (M ⁺ ), 914 (M-28)
UV-vis (CHCl ₃ ): λ = 600 nm
FL (CHCl ₃ ): λ = 609 nm

2-5. anti 4-tBu-phenyl tetrafluoroisoindole benzo bisBODIPY
The compound (4-1) was placed in a microtube, and heated at 250 ° C. for 2 hours in a vacuum. After returning to room temperature, the compound represented by Formula (2-1) was obtained.

The analytical data of the obtained compound (2-1) are as follows.
Mol. Form: C ₄₈ H ₃₂ B ₂ F ₁₂ N ₄ (Exact Mass: 914.2621, MW: 914.3939)
Appearance: black solid
_{HRMS calcd for C 48 H 32 B} 2 F 12 N 4: 915.2700, found 915.2711
MS (MALDI-TOF) m / z = 914 (M ⁺ )
UV-vis (CHCl ₃ ): λ = 811 nm
FL (CHCl ₃ ): λ = 819 nm

3. Synthesis example 3
3-1. Compound (6-1-1)
The reaction vessel was charged with 3.69 g (20.7 mmol) of 4-t-butylbenzoic acid and replaced with Ar. To this vessel was added 2.9 ml (20.7 mmol) of trifluoroacetic anhydride and stirred for 15 minutes. 2.7 ml (35.3 mmol) of trifluoroacetic acid was added and stirred for 5 minutes. The reaction vessel was shielded from light, and 1.50 g (6.90 mmol) of ethyl 4,7-dihydro-4β, 7β-ethano-2H-isoindole-1-carboxylate was added and stirred at room temperature for 3 days. Saturated aqueous sodium hydrogen carbonate was added to quench the reaction, extraction was performed with chloroform, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine. The extract is dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (Si, CHCl ₃ , Rf = 0.29) to obtain 1.509 g of a compound represented by the formula (6-1-1). (4.00 mmol, yield 58 mol%) was obtained.

The analytical data of the obtained compound (6-1-1) are as follows.
Mol. Form. : C ₂₄ H ₂₇ NO ₃ (Exact Mass: 377.1991, Mol. Wt .: 377.4761)
Appearance: White solid
m. p. 138 ° C
¹ H NMR (CDCl ₃ , 400 MHz): δ = 9.20 (brs, 1H), 7.74 (dd, J = 8.4 Hz, 2H), 7.52 (dd, J = 8) .4 Hz, 2H), 6.54 (m, 1H), 6.43 (m, 1H), 4.45 (m, 1H), 4.37 (q, J = 7.1 Hz, 2H), 3. 84 (m, 1H), 1.64-1.44 (m, 4H), 1.41 (t, J = 7.1 Hz, 3H), 1.39 (s, 9H)
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 186.01, 161.21, 156.40, 136.54, 137.09, 136.37, 136.09, 135.23, 129.32, 125. 57, 125.02, 118.24, 61.07, 35.55, 34.87, 33.93, 31.60, 26.58, 26.55, 14.87
MS (MALDI-TOF): m / z: 378.50 [M + H ⁺ ], 349.46 [M-C ₂ H ₄ ] ⁺
Anal. _{Calcd for C 24 H 27 NO 3} : C, 76.36; H, 7.21; N, 3.71
Found: C, 76.13; H, 7.20; N, 3.76

3-2. Compound (6-1-2)
The reaction vessel was charged with 1.12 g (2.98 mmol) of compound (6-1-1) and substituted with Ar. To this reaction vessel, 30 ml of dry-THF and 10 ml of dry-MeOH were added, and 0.375 g (9.91 mmol) of NaBH ₄ was added in an ice bath. Then, it returned to room temperature and stirred for 2 hours. Water was added, extraction was performed with ethyl acetate, and the organic layer was washed with water and saturated brine. After drying over anhydrous sodium sulfate and concentrating under reduced pressure, a mixture of the compound represented by formula (6-1-2a) and the compound represented by formula (6-1-2b) (compound (6-1) -2)) 1.084 g (2.86 mmol, 95 mol% yield from compound (6-1-1)) was obtained.

Analytical data of the obtained compound (6-1-2) are as follows.
Mol. Form. : C ₂₄ H ₂₉ NO ₃ (Exact Mass: 379.2147, Mol. Wt .: 379.4920)
Appearance: White solid
m. p. : 170 ° C decomp
¹ H NMR (CDCl ₃ , 400 MHz): δ = 8.67-8.34 (m, 1H), 7.35 (m, 2H), 7.31 (m, 2H), 6.50-6.33 (M, 2H), 5.88 (m, 1H), 4.32 (m, 1H), 4.27 (m, 2H), 3.54 (m, 1H), 2.49-2.19 ( m, 1H), 1.55-1.37 (m, 4H), 1.34 (m, 3H), 1.31 (m, 9H).
Anal. _{Calcd for C 24 H 29 NO 3} (M + 1 / 6CHCl 3): C, 72.68; H, 7.36; N, 3.51
Found: C, 72.66; H, 7.16; N, 3.60

3-3. Compound (6-1-3)
The reaction vessel was charged with 0.759 g (2.00 mmol) of the compound (6-1-2) and 0.0375 g (0.307 mmol) of N, N-dimethyl-4-aminopyridine, and substituted with Ar. To the reaction vessel, 28 ml of dry-CH ₂ Cl _{2 and} 1.9 ml (20.1 mmol) of acetic anhydride were added and stirred at room temperature for 30 minutes. The reaction solution was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. By purification by column chromatography (Si, 40% ethyl acetate / hexane, Rf = 0.61), the compound represented by formula (6-1-3a) and the formula (6-1-3b) are represented. 0.8400 g (1.99 mmol, yield 99.6 mol% from compound (6-1-2)) was obtained as a mixture with the above compound (compound (6-1-3)).

The analytical data of the obtained compound (6-1-3) are as follows.
Mol. Form. : C ₂₆ H ₃₁ NO ₄ (Exact Mass: 421.2253, Mol. Wt .: 421.5286)
Appearance: White solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 8.28 (m, 1H), 7.38 (m, 2H), 7.27 (m, 2H), 6.93 (m, 1H), 6. 43 (m, 2H), 4.30 (m, 3H), 3.57 (s, 1H), 2.14 (s, 3H), 1.55-1.37 (m, 4H), 1.35 (M, 3H), 1.32 (s, H)
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 170.09, 170.02, 161.61, 151.35, 151.30, 136.71, 135.81, 135.69, 135.31, 135. 28, 135.14, 134.79, 130.25, 129.93, 126.43, 126.25, 125.50, 124.68, 124.66, 113.78, 113.69, 69.88, 69.53, 59.90, 34.53, 33.59, 33.56, 32.47, 32.44, 31.23, 26.48, 26.43, 26.22, 26.15, 21. 14, 14.47
Anal. Calcd for C ₂₆ H ₃₁ NO ₄ + (1 / 3H ₂ O): C, 73.04; H, 7.47; N, 3.28
Found: C, 72.89; H, 7.42; N, 3.32.
HRMS (FAB): Calcd for C ₂₆ H ₃₂ NO ₄ [M + H], 422.2231
Found: 422.2322

3-4. Compound (6-1-4)
The reaction vessel was charged with 0.847 g (2.01 mmol) of compound (6-1-3) and 0.329 g (1.00 mmol) of compound (8-1) and substituted with Ar. To this reaction vessel, 26 ml of acetic acid was added and protected from light. 0.10 g (0.53 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at room temperature for 3 hours. Water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by column chromatography (Si, 40% ethyl acetate / hexane, Rf = 0.52), a compound represented by formula (6-1-4a) and a compound represented by formula (6-1-4b) And a compound represented by formula (6-1-4c) (compound (6-1-4)) 1.040 g (0.99 mmol, 99 mol% yield from the compound (8-1)) were obtained. It was.

The analytical data of the obtained compound (6-1-4) are as follows.
Mol. Form. : C ₆₆ H ₇₄ N ₄ O ₈ (Exact Mass: 1050.5507, Mol. Wt .: 1051.3158)
Appearance: White powder
m. p. : 170 ° C decomp
¹ H NMR (CDCl ₃ , 400 MHz): δ = 8.04 (m, 4H), 7.36-7.27 (m, 4H), 7.15-7.01 (m, 4H), 6.49 -5.99 (m, 4H), 5.56-5.16 (m, 2H), 4.45-4.03 (m, 12H), 3.10 (m, 2H), 1.56-1 .10 (m, 42H)
MS (MALDI-TOF): m / z: 1022 [M- (H + C 2 H 4)] +, 978 [M + H- (C 2 H 4) 2] +
Anal. _{Calcd for C 66 H 74 N 4} O 8: C, 75.40; H, 7.09; N, 5.33
Found: C, 75.30; H, 7.09; N, 5.42

3-5. Compound (6-1-5)
Ar was substituted with 0.526 g (0.500 mmol) of the compound (6-1-4), 0.32 g (8.00 mmol) of sodium hydroxide, and 10 ml of ethylene glycol in the reaction vessel. The reaction vessel was shielded from light and stirred at 170 ° C. for 3 hours. The mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine. After drying over anhydrous sodium sulfate, concentrating under reduced pressure and purifying by column chromatography (Si, 40% ethyl acetate / hexane, Rf = 0.74), compound represented by formula (6-1-5) 0.341 g (0.447 mmol, 89 mol% yield from compound (6-1-4)) was obtained.

Analytical data of the obtained compound (6-1-5) are as follows.
Mol. Form. : C ₅₄ H ₅₈ N ₄ (Exact Mass: 762.44661, Mol. Wt .: 763.0651)
Appearance: Black oil
¹ H NMR (CD ₂ Cl ₂ , 400 MHz): δ = 7.33-6.89 (m, 12H), 6.38-6.06 (m, 8H), 5.34 (m, 2H), 3.65 (s, 2H), 3.27 (m, 2H), 2.99 (s, 2H), 1.50-1.34 (m, 12H), 1.23 (m, 18H)

3-6. Compound (6-1-6)
The reaction vessel was charged with 0.341 g (0.447 mmol) of the compound (6-1-5) and substituted with Ar. To this reaction vessel, 11 ml of dry-DMF and 4.5 ml of dry-CH ₃ CN were added. The prepared chlorosulfonyl isocyanate (CSI) solution (CSI 0.17 ml (1.97 mmol), CH ₃ CN 2 ml) was added dropwise at −50 ° C., and the mixture was stirred at that temperature for 1 hour 30 minutes. The temperature was slowly raised to room temperature and stirred overnight. Water was added, the mixture was extracted with ethyl acetate, and washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine. After drying over anhydrous sodium sulfate, concentrating under reduced pressure and purifying by column chromatography (Si, 40% ethyl acetate / hexane, Rf = 0.46), compound represented by formula (6-1-6) 0.342 g (0.396 mmol, 88 mol% from compound (6-1-5)) was obtained.

The analytical data of the obtained compound (6-1-6) are as follows.
Mol. Form. : C ₅₈ H ₅₄ N ₈ (Exact Mass: 862.4471, Mol. Wt .: 863.10.30)
Appearance: Brown oil
¹ H NMR (CDCl ₃ , 400 MHz): δ = 8.16-7.77 (m, 4H), 7.41 (m, 4H), 7.05 (m, 4H), 6.53-6.20 (M, 4H), 5.51 (m, 2H), 4.01 (s, 2H), 3.86-3.70 (m, 2H), 3.34-2.93 (m, 2H), 1.64-1.41 (m, 12H), 1.34 (m, 18H)

3-7. Compound (6-1)
The reaction vessel was charged with 0.342 g (0.396 mmol) of the compound (6-1-6) and substituted with Ar. To this reaction vessel, 15 ml of dry-toluene was added and protected from light. 0.181 g (0.797 mmol) of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) was added, and the mixture was stirred at room temperature for 1 hour. 2.0 ml (14.3 mmol) of dry-triethylamine was added, and the mixture was stirred at room temperature for 10 minutes, BF ₃ · OEt ₂ was added, and the mixture was stirred at 80 ° C. overnight. The mixture was cooled to room temperature, water was added, the mixture was extracted with ethyl acetate, and washed with saturated aqueous sodium hydrogen carbonate, water, and saturated brine. After drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure, purified by column chromatography (Si, CH ₂ Cl ₂ , Rf = 0.33), and recrystallized (chloroform / hexane) to obtain the formula (6-1a) A mixture of the compound represented by formula (6-1b) and the compound represented by formula (6-1c) (compound (6-1)) 0.1039 g (0.109 mmol, compound ( 6-1-6) yield 28 mol%).

The analytical data of the obtained compound (6-1) are as follows.
Mol. Form. : C ₅₈ H ₄₈ B ₂ F ₄ N ₈ (Exact Mass: 954.4124, Mol. Wt .: 954.6709)
Appearance: Red powder
m. p. : 170 ° C decomp
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.90 (brs, 2H), 7.68 (brs, 2H), 7.36 (dd, J = 8.3 Hz, 4H), 6.45 (M, J = 5.6 Hz, 2H), 6.16 (t-tm, 2H), 4.14 (d, J = 5.6 Hz, 2H), 3.17 (d, J = 12.4 Hz, 2H), 2.98 (s, 2H), 1.48 (s, 18H), 1.47-1.15 (m, 12H)
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 156.73, 156.56, 1
56.22, 156.17, 150.45, 150.30, 146.25, 146.05, 142.19, 135.25, 134.99, 133.72, 133.37, 131.85, 130. 85, 128.52, 128.48, 128.27, 128.00, 127.70, 127.43, 125.80, 120.49, 116.57, 111.09, 110.77, 110.70, 36.13, 36.03, 35.42, 33.36, 33.31, 32.53, 32.45, 31.59, 31.24, 26.87, 25.69, 25.57, 22. 66, 14.13
FL (CHCl ₃ ): λ _max (φ) = 571 nm (0.014)
HRMS (FAB): Calcd for C 58 H 49 B 2 F 4 N 8 [M + H], 955.4202
Found: 955.4201

3-8. Compound (4-2)
The reaction vessel (microtube) was charged with 4.8 mg (5.03 μmol) of the compound (6-1) and substituted with Ar. This was heated under reduced pressure at 170 ° C. for 2 hours and cooled to room temperature, whereby 3.8 mg of the compound represented by formula (4-2) (4.23 μmol, yield from compound (6-1) 84 mol) %).

The analytical data of the obtained compound (4-2) are as follows.
Mol. Form. : C ₅₄ H ₄₀ B ₂ F ₄ N ₈ (Exact Mass: 898.3498, Mol. Wt .: 898.5646)
Appearance: Black solid
m. p. : 260 ° C decomp
¹ H NMR (CD ₂ Cl ₂ , 400 MHz): δ = 7.87 (t, J = 7.8 Hz, 4H), 7.67 (d, J = 7.8 Hz, 2H), 7.45 (t, J = 7.8 Hz, 2H), 7.40-7.31 (m, 6H), 6.60 (d, J = 8.3 Hz, 2H), 2.93 (s, 2H), 1.44 ( s, 18H), 1.36 (brs, 4H)
¹³ C NMR (CD ₂ Cl ₂ , 100 MHz): δ = 155.62, 147.50, 145.38, 142.40, 135.94, 133.71, 132.95, 130.59, 129.44, 129.10, 128.19, 127.92, 127.67, 126.82, 123.58, 123.18, 112.36, 111.69, 110.67, 35.63, 32.38, 31. 45, 27.18
FL (CHCl ₃ ): λ _max (φ) = 608 nm (0.88)
HRMS (FAB): Calcd for C 54 H 41 B 2 F 4 N 8 [M + H], 899.3576
Found: 899.3571

3-9. Compound (2-2)
The compound (4-2) was placed in a reaction vessel (microtube) and replaced with Ar. This was heated under reduced pressure at 260 ° C. for 2 hours and cooled to room temperature, whereby a compound represented by the formula (2-2) was obtained.

The analytical data of the obtained compound (2-2) are as follows.
Mol. Form. : C ₅₂ H ₃₆ B ₂ F ₄ N ₈ (Exact Mass: 870.3185, Mol. Wt .: 870.5115)
Appearance: Black powder
HRMS (FAB): Calcd for C 52 H 37 B 2 F 4 N 8 [M + H], 871.3263
Found: 871.3273
Further, 0.1 mg of the obtained compound (2-2) was dissolved in 25 ml of chloroform to prepare a chloroform solution, and the absorption spectrum of this solution is shown in FIG.

4). Synthesis example 4
4-1. Compound (6-2) (Alpha-CO ₂ Et-meso-4-tert-Butylphenyl-BCOD-bisBODIPY)

In a reaction vessel, 0.402 g (0.382 mmol) of the compound (6-1-4) obtained in Step 3-4 of Synthesis Example 3 was added and stirred, and then the inside of the vessel was replaced with Ar. CH ₂ Cl ₂ (4 ml) was added and protected from light. DDQ (0.176 g, 0.775 mmol) was added and stirred at room temperature for 3 hours. Diisopropylethylamine (0.95 ml, 5.59 mmol) was added, and the mixture was stirred at room temperature for 10 minutes. BF ₃ · OEt ₂ (0.7 ml, 5.67 mmol) was added, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was quenched by adding water and extracted with chloroform. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate, water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by column chromatography (Si, 40% ethyl acetate / hexane, Rf = 0.47) and recrystallization (chloroform / hexane) gave 0.267 g (0) of the compound represented by the formula (6-2). 234 mmol, 61 mol% yield from compound (6-1-4)).

The analytical data of the obtained compound (6-2) are as follows.
Mol. Form. : C ₆₆ H ₆₈ B ₂ F ₄ N ₂ O ₈ (Exact Mass: 1142.5159, Mol. Wt .: 1142.88837)
Appearance: Orange solid
¹ H NMR (solvent, 400 MHz): δ = 7.61 (m, 4H), 7,29 (m, 4H), 6.39 (m, 2H), 6.05 (m, 2H), 4. 49-4.32 (m, 8H), 4.30 (m, 2H), 3.51 (s, 2H), 2.51 (s, 2H), 1.48 (s, 18H), 1.45 -1.40 (m, 12H), 1.40-1.05 (m, 12H)
¹³ C NMR (solvent, 100 MHz): δ = 160.93, 160.91, 160.76, 160.72, 154.05, 153.81, 151.49, 149.21, 142.57, 139. 89, 138.68, 138.48, 135.88, 135.81, 133.65, 130.83, 130.43, 129.76, 128.47, 128.08, 127.64, 126.05, 125.89, 125.21, 61.56, 61.50, 35.46, 35.06, 34.08, 34.03, 32.76, 31.33, 27.05, 25.79, 25. 74, 25.65, 25.57, 14.11, 14.06
IR (KBr) ν _max / cm ⁻¹ : 2962, 1701, 1558, 1111
UV / Vis / NIR (solvent): λ _max (log ε) = 553 (5.06), 448 (4.43) nm
Anal. _{Calcd for C 66 H 68 B 2} F 4 N 4 O 8 +1/2 CHCl 3: C, 66.42; H, 5.74; N, 4.66Found: C, 66.25; H, 5.68; N, 4.54
HRMS (FAB): Calcd for C ₆₆ H ₆₈ B ₂ F ₄ N ₄ O ₈ + H, 1143.5238
Found: 1143.5247

4-2. Compound (2-2) (Alpha-CO ₂ Et-meso-4-tert-Butylphenyl-All retro-bisBODIPY)

22.9 mg (20.04 μmol) of the compound (6-2) obtained in the above step was put in a reaction vessel, and the inside of the vessel was substituted with N ₂ . Under reduced pressure, heated at 175 ° C. for 1 hour, 240 ° C. for 30 minutes, 250 ° C. for 30 minutes, and cooled to room temperature, whereby 21.0 mg (19.8 μmol of compound represented by formula (2-2) 99% yield from (6-2).

The analytical data of the obtained compound (2-2) are as follows.
Mol. Form. : C ₆₀ H ₅₆ B ₂ F ₄ N ₄ O ₈ (Exact Mass: 10588.420, Mol. Wt .: 10588.7243)
Appearance: Black solid
m. p. : 333 ° C decomp
¹ H NMR (CDCl ₃ , 400 MHz): δ = 8.13 (d, J = Hz, 2H), 7.76 (d, J = Hz, 4H), 7.44 (d, J = Hz, 4H) ), 7.20 (s, 2H), 7.04 (t, J = Hz, 2H), 6.13 (d, J = Hz, 2H), 4.57 (q, J = Hz, 4H), 4.47 (q, J = Hz, 4H), 1.57 (s, 18H), 1.54 (m, 12H)
UV / Vis / NIR (CHCl ₃ ): λ _max (log ε) = 884 (***), 796 (***), 418 nm
HRMS (FAB): Calcd for C 60 H 56 B 2 F 4 N 4 O 8 + H, 1059.4299
Found: 1059.4301

5. Calculation of HOMO and LUMO HOMO and LUMO of each compound were carried out at the B3LYP / 6-31G (d) level according to Density Functional Theory (DFT). The energy level was calculated using a general-purpose quantum chemistry calculation program (Gaussian (registered trademark) 03W, manufactured by Gaussian). In addition, a calculation result visualization program (“GaussView (registered trademark) 4.1” manufactured by Gaussian Co., Ltd.) was used for drawing a trajectory map and confirming numerical values of energy levels. The results are shown in Table 1.

  As shown in Table 1, No. 1 having an electron withdrawing group as a substituent bonded to the main skeleton. The compounds 1 to 9 all have a HOMO level deeper than −5 eV. Therefore, No. which does not have an electron withdrawing group. It can be seen that the HOMO level is lower than that of the compound of No. 10.

6). Compound stability test The stability of the compound (2-2) obtained in Synthesis Example 3 and the following compound (Z) in a solution state was evaluated. Compound (Z) was synthesized based on the description in Non-Patent Document 2. Evaluation was performed as follows.
6-1. Compound (2-2)
0.1 mg of the compound (2-2) was dissolved in 25 ml of chloroform to prepare a chloroform solution. FIG. 2 shows the change over time of this solution, which was confirmed by measuring the absorption spectrum.
6-2. Compound (Z)
Compound (Z) 0.27 mg was dissolved in chloroform 50 ml to prepare a chloroform solution. The change over time of this solution was confirmed by measuring the absorption spectrum and is shown in FIG.

As shown in FIG. 2, in the compound (2-2), after being dissolved in the chloroform solution, the absorption spectrum after 12 hours (12h) and after 19 hours (19h) is the absorption spectrum immediately after dissolution (0 min). And substantially the same waveform. This shows that the compound (2-2) having an electron withdrawing group bonded to the main skeleton is very stable when dissolved in a solvent.
On the other hand, as shown in FIG. 3, the compound (Z) has a large peak at about 840 nm immediately after dissolution in the chloroform solution (0 min), and the peak appearing at about 610 nm is very small. However, after dissolution in the chloroform solution, the peak at about 840 nm decreases and the peak at about 610 nm increases with time. And after dissolving in the chloroform solution, the peak at about 610 nm is larger than the peak at about 840 nm after 2 hours (2 h), and about 4 hours (4 h) after about 4 hours (4 h). The peak at 840 nm almost disappears, and a very large peak is shown at about 610 nm (visible region).
That is, it can be seen that the compound (Z) having no electron-withdrawing group in the main skeleton is very unstable when dissolved in a solvent and loses invisibility in a short time.

7). Synthesis Example 7-1. Compound (17-2)
The reaction vessel was purged with nitrogen, and dry-CH ₂ Cl ₂ (50 ml) was added. 1,4-cyclohexadiene (5 ml, 53 mmol) was added, the reaction vessel was cooled to −78 ° C., and sulfenyl chloride (6 ml, 53 mmol) was added dropwise. After returning to room temperature and stirring for 1 hour, the reaction solution was washed with saturated aqueous sodium hydrogen carbonate, water and brine, and anhydrous sodium sulfate was added to the organic phase, followed by filtration with a cotton plug. Further, the filtrate was concentrated under reduced pressure to obtain 10.26 g (1.16 mmol, yield 86% from compound (17-1)) of the compound represented by formula (17-2).

The analytical data of the obtained compound (17-2) are as follows.
Mol. Form: C ₁₂ H ₁₃ ClS (Exact Mass: 224.0426, MW: 224.7696)
Appearance: color oil
¹ H NMR (CDCl ₃ , 400 MHz): δ = 2.25 (m, 1H), 2.38 (m, 1H), 2.84 (m, 1H), 2.98 (m, 1H), 2. 59 (m, 1H), 4.18 (m, 1H), 5.60 (m, 1H), 5.68 (m, 1H), 7.30 (m, 3H), 7.45 (m, 2H) )
¹³ C NMR (100 MHz, CDCl ₃ ): d = 133.56, 132.09, 128.95, 127.38, 123.60, 122.27, 56.95, 47.43, 31.14 27.80
mp: --- (oil compound)
_{HRMS calcd for C 12 H 13 ClS} ,: 225.0505, found 225.0485
MS (FAB) m / z 225 M ⁺
Anal. _{Calcd for C 38 H 44 N 2} O 4: C, 64.13; H, 5.83.
Found: C, 63.92; H, 5.93; N, 0.09.

7-2. Compound (17-3)
A compound represented by the formula (17-2) (10.26 g, 46 mmol) was placed in a reaction vessel, and dichloromethane (500 ml) was added. The reaction vessel was cooled to 0 ° C., mCPBA (24.1 g, 92 mmol) having a purity of 69 to 75% was added, and the mixture was returned to room temperature and stirred for 16 hours. After completion of the reaction, insoluble matters were removed by Celite filtration, the filtrate was washed with saturated aqueous sodium hydrogen carbonate, water and brine, and the organic phase was dried over anhydrous sodium sulfate. Furthermore, 7.55 g (29.4 mmol, yield 64% from the compound (17-2)) represented by the formula (17-3) was obtained by concentrating under reduced pressure.

The analytical data of the obtained compound (17-3) are as follows.
Mol. Form: C ₁₂ H ₁₃ ClSO ₂ (Exact Mass: 256.0325, MW: 256.7484)
Appearance: color oil
¹ H NMR (CDCl ₃ , 400 MHz): δ = 2.45 (m, 1H), 2.55 (m, 1H) 2.65 (m, 1H), 2.94 (m, 1H), 3.57 (M, 1H), 4.63 (m, 1H), 5.67 (m, 2H), 7.58 (m, 2H), 7.68 (m, 1H), 7.92 (m, 2H)
¹³ C NMR (100 MHz, CDCl ₃ ): d = 138.22, 133.90, 129.19, 128.57, 122.81, 122.23, 63.69, 51.48, 32.44, 22. 08.
mp: −−− (oil compound)
HRMS calcd for C ₁₂ H ₁₃ ClSO ₂ : 257.0403, found 257.0408
MS (FAB) m / z 257M ⁺ ,

7-3. Compound (17-4)
The compound (3.87 g, 15.1 mmol) represented by the formula (17-3) was placed in a reaction vessel, and the atmosphere was replaced with nitrogen, and dry-dichloromethane (56 ml) was added. The reaction vessel was cooled to 0 ° C. and DBU (2.24 ml, 15.1 mmol) was added dropwise. After returning to room temperature and stirring for 3 hours, 1M hydrochloric acid was added to quench the reaction, and the reaction solution was washed with saturated aqueous sodium hydrogen carbonate, water and brine. Silica gel and anhydrous sodium sulfate were added to the organic phase, and the filtrate was concentrated under reduced pressure to give 2.06 g (9.35 mmol, compound (3) of compounds represented by formulas (17-4a) and (17-4b). Yield 62%).

Analytical data of the obtained compounds (17-4a) and (17-4b) are as follows. Each data is measured in a state where the compounds (17-4a) and (17-4b) are mixed.
Mol. Form: C ₁₂ H ₁₃ SO ₂ (Exact Mass: 220.0558, MW: 220.2875)
Appearance: colorless oil
¹ H NMR (CDCl ₃ , 400 MHz): δ = 2.82 (m, 4H), 2.95 (m, 2H) 3.88 (m, 1H), 5.54 (m, 2H), 5.67 (M, 2H), 5.79 (m, 1H), 6.08 (m, 1H), 7.05 (m, 1H), 7.45-7.59 (m, 4H), 7.62 ( m, 2H), 7.87 (m, 4H)
mp: −−− (oil compound)

7-4. Compound (17-5)
A compound (1.08 g, 4.9 mmol) represented by the formulas (17-4a) and (17-4b) was placed in the reaction vessel, and the atmosphere was purged with nitrogen. Then, dry-THF (40 ml) was added. After adding ethyl isocyanoacetate (0.65 ml, 6 mmol), the reaction vessel was cooled to 0 ° C., and 1M t-BuOK / dry-THF solution (1.36 g, 12 mmol, 12 ml) was added dropwise. After returning to room temperature and stirring for 12 hours, 1M hydrochloric acid was added to quench the reaction, and the mixture was extracted with ethyl acetate. The reaction solution was washed with saturated aqueous sodium hydrogen carbonate, water, and brine, and anhydrous sodium sulfate was added to the organic phase, followed by filtration with a cotton plug. Furthermore, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform). Then, the solid obtained by concentrating the solution is washed with hexane, whereby 500 mg (2.61 mmol of the compound represented by the formula (17-5), a mixture of the compounds (17-4a) and (17-4b) is obtained. Yield of 53%).

The analytical data of the obtained compound (17-5) are as follows.
Mol. Form: C ₁₁ H ₁₃ NO ₂ (Exact Mass: 191.0946, MW: 191.2264)
Appearance: white solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.35 (t, 3H, J = 7 Hz), 3.22 (m, 2H), 3.44 (m, 2H), 4.30 (q, 4H) , J = 7.0 Hz), 5.88 (m, 2H), 6.71 (m, 1H), 8.88 (br, 1H)
¹³ C NMR (100 MHz, CDCl ₃ ): d = 161.55, 124.79, 124.31, 123.72, 118.83, 118.44, 117.42, 59.88, 24.14, 22. 44, 14.63.
IR v _max (KBr) / cm ⁻¹ : 3288, 1685, 1675, 1323, 1250, 1154
mp: 94 ° C
_{HRMS calcd for C 11 H 13 NO} 2,: 192.1025, found 192.1014
MS (FAB) m / z 192M ⁺ ,
Anal. Calcd for C ₁₁ H ₁₃ NO ₂ : C, 69.09; H, 6.85 N, 7.32
Found: C, 68.92; H, 7.03; N, 7.42.

7-5. Compound (17-6)
The reaction vessel was charged with the compound represented by the formula (17-5) (3.35 g, 17.5 mmol), purged with nitrogen, and dry-dichloromethane (150 ml) was added. The reaction vessel was cooled to −78 ° C. and sulfenyl chloride (1.99 ml, 17 mmol) was added dropwise. After returning to room temperature and stirring for 1 hour, the reaction solution was washed with saturated aqueous sodium hydrogen carbonate, water and brine, and the organic phase was dried over anhydrous sodium sulfate. Furthermore, 4.95 g (14.7 mmol, 84% yield from the compound (17-5)) represented by the formulas (17-6a) and (17-6b) was obtained by concentration under reduced pressure. .

Analytical data of the obtained compounds (17-6a) and (17-6b) are as follows. Each data is measured in a state where the compounds (17-6a) and (17-6b) are mixed.
Mol. Form: C ₁₇ H ₁₈ ClNO ₂ S (Exact Mass: 335.0407, MW: 335.8484)
Appearance: pale yellow solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.32-1.38 (m, 6H, J = 7 Hz), 2.98-2.34 (m, 4H), 3.35-3.67 ( m, 4H), 3.73 (m, 2H), 4.30 (m, 4H), 4.88-5.10 (m, 2H), 6.74 (m, 2H), 7.28-7 .36 (m, 6H), 7.45-7.51 (m, 4H), 8.90 (br, 2H)
¹³ C NMR (100 MHz, CDCl ₃ ): d = 161.39, 161.33, 133.66, 133.63, 132.27, 132.14, 129.19, 129.18, 127.64, 127. 60, 122.66, 121.91, 119.42, 119.25, 118.57, 118.34, 116.85, 116.17, 60.02, 60.00, 57.51, 57.43, 47.94, 47.80, 28.81, 27.31, 25.07, 23.54, 14.49, 14.45.
mp: 110 ° C
_{HRMS calcd for C 17 H 18 ClNO} 2 S,: 336.0825, found 336.0824
MS (FAB) m / z 336M ⁺ ,
Anal. Calcd for C ₁₇ H ₁₈ ClNO ₂ S: C, 60.80; H, 5.40 N, 4.17
Found: C, 61.10; H, 5.67; N, 3.84.

7-6. Compound (17-7)
A compound (4.95 g, 14.7 mmol) represented by the formulas (17-6a) and (17-6b) was placed in a reaction vessel, and dichloromethane (179 ml) was added. The reaction vessel was cooled to 0 ° C., mCPBA (7.05 g, 29.4 mmol) having a purity of 69 to 75% was added, and the mixture was returned to room temperature and stirred for 16 hours. After completion of the reaction, insoluble matters were removed by Celite filtration, the filtrate was washed with saturated aqueous sodium hydrogen carbonate, water and brine, and the organic phase was dried over anhydrous sodium sulfate. Further, by concentrating under reduced pressure, from a mixture of compounds 5.4 g (14.7 mmol, compounds (17-6a) and (17-6b) represented by formulas (17-7a) and (17-7b) Yield 99%).

Analytical data of the obtained compounds (17-7a) and (17-7b) are as follows. Each data is measured in a state where the compounds (17-7a) and (17-7b) are mixed.
Mol. Form: C ₁₇ H ₁₈ ClNO ₄ S (Exact Mass: 367.0645, MW: 367.8471)
Appearance: pale yellow solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.28-1.40 (m, 6H), 3.01-3.64 (m, 8H), 3.73 (m, 2H), 4.30 (M, 4H), 4.88-5.12 (m, 2H), 6.73 (m, 2H), 7.45-7.78 (m, 6H), 7.82-8.01 (m , 4H), 9.08 (br, 2H)
mp: 80 ° C
_{HRMS calcd for C 17 H 18 ClNO} 4 S,: 368.0723, found 368.0688
MS (FAB) m / z 368M ⁺ ,

7-7. Compound (17-8)
A compound (1.12 g, 3.05 mmol) represented by the formulas (17-7a) and (17-7b) was placed in a reaction vessel, purged with nitrogen, and dry-THF (30 ml) was added. The reaction vessel was cooled to 0 ° C., 1M t-BuOK / THF solution (340 mg, 3.04 mmol, 3.04 ml) was added, and the mixture was returned to room temperature and stirred for 4 hours. After completion of the reaction, the reaction mixture was quenched with 1M hydrochloric acid and extracted with ethyl acetate. The reaction solution was washed with saturated aqueous sodium hydrogen carbonate, water, and brine. Anhydrous sodium sulfate was added to the organic phase, and the filtrate was concentrated under reduced pressure. And by refine | purifying with silica gel column chromatography (chloroform), 770 mg (2.32 mmol, compound (17-7a) of a compound (17-7a) and (17-7b) of a formula (17-8a) and (17-8b) is represented. A yield of 76% from the mixture) was obtained.

Analytical data of the obtained compounds (17-8a) and (17-8b) are as follows. Each data is measured in a state where the compounds (17-8a) and (17-8b) are mixed.
Mol. Form: C ₁₇ H ₁₇ NO ₄ S (Exact Mass: 331.0878, MW: 331.3862)
Appearance: pale yellow solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.26-1.39 (m, 6H), 3.36-3.78 (m, 8H), 4.30 (m, 4H), 6.72 (M, 2H), 7.49-7.63 (m, 6H), 7.87-7.97 (m, 4H), 8.95 (br, 2H)

7-8. Compound (17)

A compound (680 mg, 2.05 mmol) represented by the formulas (17-8a) and (17-8b) was added to the reaction vessel, and the atmosphere was replaced with nitrogen. Then, dry-THF (20 ml) was added. After adding ethyl isocyanoacetate (0.27 ml, 2.5 mmol), the reaction vessel was cooled to 0 ° C., and 1M t-BuOK / THF solution (570 mg, 5.09 mmol, 5.1 ml) was added dropwise. After returning to room temperature and stirring for 12 hours, 1M hydrochloric acid was added to quench the reaction, and the mixture was extracted with ethyl acetate. The reaction solution was washed with saturated aqueous sodium hydrogen carbonate, water and brine, anhydrous sodium sulfate was added, and the filtrate was concentrated under reduced pressure. And it refine | purified by silica gel column chromatography (chloroform). Further, the solid obtained by concentrating the solution was washed with hexane, whereby the compound represented by the formula (17) from a mixture of 70 mg (0.232 mmol, compounds (17-8a) and (17-8b) was obtained. Yield 11%).

The analytical data of the obtained compound (17) are as follows.
Mol. Form: C ₁₆ H ₁₈ N ₂ O ₄ (Exact Mass: 302.1267, MW: 302.3251)
Appearance: pale brown powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.40 (m, 6H), 3.99 (m, 4H), 4.37 (m, 4H), 6.86 (m, 2H), 8. 95 (br, 2H)
_{HRMS calcd for C 16 H 18 N} 2 O 4,: 303.1345, found 303.1348
MS (FAB) m / z 303M ⁺

  The bis-boron dipyrromethene dye of the present invention is an optical filter for a semiconductor light-receiving element having a function of absorbing and cutting near infrared rays as a near infrared absorbing dye; a near infrared absorbing film and a near infrared ray for blocking heat rays for energy saving Absorber plate; Information display material as security ink and invisible barcode ink; Solar cell dye using near infrared light; Infrared cut filter for plasma display panel (PDP) and CCD; Heat conversion material using laser light As near-infrared absorbing materials for laser plate making, thermal transfer recording, rewritable heat sensitivity, laser welding, and thermosetting resin; materials for protective glasses such as sunglasses;

Claims (5)

A bis-boron dipyrromethene dye represented by the formula (1) or (2).
[In Formula (1), at least one of R ^{1 to} R ¹⁴ is an electron-attracting group having a positive Hammett's substituent constant σ , and the remainder is hydrogen or an organic substituent.
In formula (2), at least one of R ^{15 to} R ²⁸ is an electron-attracting group having a positive Hammett's substituent constant σ , and the remainder is hydrogen or an organic substituent. ]   The bis-boron dipyrromethene group according to claim 1, wherein the electron withdrawing group is at least one selected from the group consisting of halogen, cyano group, nitro group, sulfo group, alkyloxycarbonyl group and acyl group. Pigment. A precursor of a bis-boron dipyrromethene dye represented by formulas (13) to (16).
[In formula (13), RingA is any one cyclic structure selected from the following formulas Ia to IIa (in formulas Ia to IIa, a1 to a4 represent carbon numbers).
In formula (14), RingB is any one cyclic structure selected from the following formulas Ib to IIb (in formulas Ib to IIb, b1 to b4 represent carbon numbers).
In formula (15), RingC is any one cyclic structure selected from the following formulas Ic to IIc (in formulas Ic to IIc, c1 to c4 represent carbon numbers),
RingD is any one cyclic structure selected from the following formulas Id to IIId (in formulas Id to IIId, d1 to d4 represent carbon numbers),
RingE is any one cyclic structure selected from the following formulas Ie to IIIe (in formulas Ie to IIIe, e1 to e4 represent carbon numbers).
In the formula (16), RingF is any one cyclic structure selected from the following formulas If to IIf (in the formulas If to IIf, f1 to f4 represent carbon numbers),
RingG is any one cyclic structure selected from the following formulas Ig to IIIg (in formulas Ig to IIIg, g1 to g4 represent carbon numbers),
RingH is any one cyclic structure selected from the following formulas Ih to IIIh (in formulas Ih to IIIh, h1 to h4 represent carbon numbers).
In formulas (13) and (15), at least one of R ^{39 to} R ⁵² is an electron-attracting group having a positive Hammett's substituent constant σ , and the remainder is hydrogen or an organic substituent.
In formulas (14) and (16), at least one of R ^{53 to} R ⁶⁶ is an electron-attracting group having a positive Hammett's substituent constant σ , and the remainder is hydrogen or an organic substituent.
In the formulas, L ¹ ~L ⁸ are each _{independently, * - CH 2 -CH 2 -} *, * - C (= O) - *, * - C (= O) -C (= O) - * Indicates. * Indicates a bond. ] The precursor of the bis-boron dipyrromethene dye according to claim 3, which is represented by formulas (3) to (6).
[In Formulas (3) and (5), at least one of R ^{1 to} R ¹⁴ is an electron-attracting group having a positive Hammett's substituent constant σ , and the remainder is hydrogen or an organic substituent. .
In formulas (4) and (6), at least one of R ^{15 to} R ²⁸ is an electron-attracting group having a positive Hammett's substituent constant σ , and the remainder is hydrogen or an organic substituent.
In the formulas, L ¹ ~L ⁸ are each _{independently, * - CH 2 -CH 2 -} *, * - C (= O) - *, * - C (= O) -C (= O) - * Indicates. * Indicates a bond. ]   The bis-boron dipyro of claim 3 or 4, wherein the electron withdrawing group is at least one selected from the group consisting of halogen, cyano group, nitro group, sulfo group, alkyloxycarbonyl group and acyl group. Methenic pigment precursor.