JP5458301B2 - Dibenzopyromethene boron chelate compound and method for producing the same, solar cell using the same, photopolymerizable composition, optical storage medium, light emitting element, optical filter, and fluorescent dye for medical diagnosis - Google Patents

Description

  The present invention relates to a novel dibenzopyromethene boron chelate compound having an absorption maximum wavelength on the longer wavelength side, a method for producing the same, and a solar cell, a photopolymerizable composition, an optical storage medium, a light emitting element, and an optical filter using the same. And a fluorescent dye for medical diagnosis.

  A pyromethene compound generally has a maximum absorption wavelength in a wavelength range of 500 to 600 nm, and is a sensitizer for a photopolymerizable composition (Patent Document 1), a dye for optical recording media (Patent Document 2), and an organic electroluminescence display. Widely used as light-emitting element materials (Patent Document 3), dyes for optical filters (Patent Document 4), fluorescent dyes used in the field of medical diagnosis (Patent Document 5), and dyes for solar cells (Non-Patent Document 1) Yes. In addition, pyromethene compounds have been improved for the purpose of increasing the fluorescence wavelength and increasing the intensity (Non-patent Document 2).

JP-A-8-006245 JP-A-11-255774 JP 2003-012676 A JP 2006-0665121 A JP 2008-530063 A

"Organic Letters", Vol. 10, No. 15, 3299-3302, 2008 "Chemical Communications", 1898-1890, 1999

  However, few pyromethene compounds that absorb near infrared rays having a wavelength of 700 nm or more have been known. As compounds that absorb near infrared rays, cyanine compounds, phthalocyanine compounds, diimmonium compounds, and the like are known, but since there are fewer types compared to compounds that absorb visible light, there is little room for selection and practical use. In many cases, inconvenience.

  An object of the present invention is to provide a novel pyromethene compound having a maximum absorption wavelength on the longer wavelength side, and to expand the range of compound selection.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention relates to a dibenzopyromethene boron chelate compound represented by the following general formula (A1).

（式中、Ｒ^１〜Ｒ^１７は各々独立に水素原子、ヒドロキシ基、アミノ基、カルボキシ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、ハロゲノアルキル基、アラルキル基、アリール基、ピロリル基、チエニル基、フラニル基、オキサゾイル基、イソオキサゾイル基、オキサジアゾイル基、イミダゾイル基、ベンゾオキサゾイル基、ベンゾチアゾイル基、ベンゾイミダゾイル基、ベンゾオキサゾイル基、ベンゾチアゾイル基、ベンゾイミダゾイル基、ベンゾフラニル基、インドイル基、アルコキシアルキル基、アルコキシ基、アルコキシアルコキシ基、アリールオキシ基、ジアルキルアミノアルコキシ基、アルキルチオアルコキシ基、アルキルチオ基、アリールチオ基、アルキルカルボニルアミノ基、又はアリールカルボニルアミノ基を表す。）

(Wherein R ^{1 to} R ¹⁷ are each independently a hydrogen atom, a hydroxy group, an amino group, a carboxy group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms. Group, halogenoalkyl group, aralkyl group, aryl group, pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazolyl group, benzoxazoyl group, benzothiazoyl group, benzoimidazoloyl group, benzooxa Zoyl group, benzothiazoyl group, benzoimidazoloyl group, benzofuranyl group, indoyl group, alkoxyalkyl group, alkoxy group, alkoxyalkoxy group, aryloxy group, dialkylaminoalkoxy group, alkylthioalkoxy group, alkylthio group, arylthio group, alkyl Carboni An amino group, or an arylcarbonylamino group.)

  According to the present invention, a pyromethene compound having a maximum absorption wavelength on the longer wavelength side is provided, and the range of dye selection is expanded.

[Dibenzopyromethene Boron Chelate Compound According to the Present Invention]
The dibenzopyromethene boron chelate compound of the present invention is represented by the following general formula (A1).

In the formula (A1), the substituents R ^{1 to} R ¹⁷ may be any substituent. Specific examples of R ^{1 to} R ¹⁷ include a hydrogen atom; a halogen atom of fluorine, chlorine, bromine, and iodine; a nitro group; a cyano group; a hydroxy group; an amino group; a carboxy group;
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2 -Methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-triethylbutyl group, 1,1,2-trie Rubutyl group, 1-ethyl-2-methylpropyl group, cyclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4 -Dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-triethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group N-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1 , 3,5,7-tetramethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, , 6-Diethyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetra A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as a methylhexyl group, a 1-cyclo-pentyl-2,2-dimethylpropyl group, a 1-cyclo-hexyl-2,2-dimethylpropyl group;
Vinyl group, propenyl group, 1-butenyl group, iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2- C2-C20 alkenyl group such as butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxylvinyl group, 2-cyano-2-methylsulfonvinyl group; ethynyl group, 1-propynyl group An alkynyl group having 2 to 20 carbon atoms such as 1-butynyl group;

  Halogenoalkyl groups such as chloromethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, nonafluorobutyl group; benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group , Trimethylbenzyl group, dichlorobenzyl group, methoxybenzyl group, ethoxybenzyl group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, trifluoromethyl Aralkyl groups such as naphthylmethyl group; phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, cyclohexylphenyl group Diisopropylphenyl, dichlorophenyl, methoxyphenyl, ethoxyphenyl, trifluoromethylphenyl, N, N-dimethylaminophenyl, naphthyl, nitronaphthyl, cyanonaphthyl, hydroxynaphthyl, methylnaphthyl, tri Aryl groups such as fluoromethylnaphthyl group; pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazoloyl group, benzoxazoyl group, benzothiazoyl group, benzoimidazoloyl group, benzoxazoyl group, Heteroaryl groups such as benzothiazoyl group, benzimidazolyl group, benzofuranyl group, indoyl group; methoxyethyl group, ethoxyethyl group, iso-propyloxyethyl group, 3-methoxypropyl group, 2 Alkoxyalkyl group such as a methoxy butyl group;

Methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group Alkoxy groups such as n-hexyloxy group and n-dodecyloxy group; alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group, 3-methoxypropyloxy group, and 3- (iso-propyloxy) propyloxy group; phenoxy Group, 2-methylphenoxy group, 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group and other aryloxy groups; 2-dimethylaminoethoxy group, 2- (2-dimethylaminoethoxy) ethoxy group, 4-dimethylamino Toxi group, 1-dimethylaminopropan-2-yloxy group, 3-dimethylaminopropoxy group, 2-dimethylamino-2-methylpropoxy group, 2-diethylaminoethoxy group, 2- (2-diethylaminoethoxy) ethoxy group, 3 -Linear or branched dialkylaminoalkoxy groups such as diethylaminopropoxy group, 1-diethylaminopropoxy group, 2-di-iso-propylaminoethoxy group, 2-di-n-butylaminoethoxy group; 2-methylthioethoxy group, Alkylthioalkoxy groups of 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-iso-propylthioethoxy group, 2-n-butylthioethoxy group, 2-iso-butylthioethoxy group;
Methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, 2-methylbutyl Alkylthio groups such as thio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group, 1,1-dimethylpropylthio group; phenylthio group, 4-methylphenylthio group, 2-methoxy Arylthio groups such as phenylthio group and 4-t-butylphenylthio group; alkylcarbonylamino groups such as acetylamino group, ethylcarbonylamino group and butylcarbonylamino group; phenylcarbonylamino group, 4-ethylphenylcarbonylamino group; 3-butylphenylcarbonylamino Arylcarbonylamino groups such as;

  Formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutyl Acyl groups such as carbonyl group and nitrobenzylcarbonyl group; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group and 2,4-dimethylbutyloxycarbonyl group; phenoxycarbonyl group and 2-methylphenoxycarbonyl group Aryloxycarbonyl groups such as 4-methoxyphenylcarbonyl group and 4-t-butylphenoxycarbonyl group; alkenyloxycarbonyl groups such as allyloxycarbonyl group and 2-butenoxycarbonyl group Aralkyloxycarbonyl groups such as benzyloxycarbonyl group and phenethyloxycarbonyl group; alkoxycarbonylalkoxycarbonyl groups such as methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group, n-propoxycarbonylmethoxycarbonyl group and isopropoxycarbonylmethoxycarbonyl group An alkylcarbonylalkoxycarbonyl group such as a methylcarbonylmethoxycarbonyl group or an ethylcarbonylmethoxycarbonyl group;

Alkylaminocarbonyl groups such as methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, n-hexylaminocarbonyl group; dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n- Dialkylaminocarbonyl groups such as propylaminocarbonyl group, di-n-butylaminocarbyl group, N-methyl-N-cyclohexylaminocarbonyl group; phenylaminocarbonyl group, 4-methylphenylaminocarbonyl group, 2-methoxyphenylamino Arylaminocarbonyl groups such as carbonyl group and 4-n-propylphenylaminocarbonyl group; hydroxyethylaminocarbonyl group, 2-hydroxypropylaminocarbonyl group, 3-hydroxypropylamino group Mono (hydroxyalkyl) aminocarbonyl group such as nocarbonyl group; di (hydroxyalkyl) such as di (hydroxyethyl) aminocarbonyl group, di (2-hydroxypropyl) aminocarbonyl group, di (3-hydroxypropyl) aminocarbonyl group ) Aminocarbonyl group; mono (alkoxyalkyl) aminocarbonyl group such as methoxymethylaminocarbonyl group, methoxyethylaminocarbonyl group, ethoxymethylaminocarbonyl group, ethoxyethylaminocarbonyl group, propoxyethylaminocarbonyl group; di (methoxyethyl) Di (alkoxyalkyl) aminocarbonyl such as aminocarbonyl group, di (ethoxymethyl) aminocarbonyl group, di (ethoxyethyl) aminocarbonyl group, di (propoxyethyl) aminocarbonyl group, etc. Boniru group; and the like.

In the formula (A1), the substituents R ^{1 to} R ¹⁷ may be bonded to each other to form a ring. For example, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , At least one of R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , and R ¹⁷ and R ¹ is They may be bonded together to form a ring structure. Any cyclic structure formed by bonding substituents to each other may be used, for example, an aromatic ring.

  The ultraviolet absorption spectrum analysis of the dibenzopyromethene boron chelate compound according to the present invention preferably has an absorption maximum wavelength of 650 nm or more, more preferably 700 nm or more, and particularly preferably 720 nm or more.

[Synthesis Method of Dibenzopyromethene Boron Chelate Compound According to the Present Invention]
The dibenzopyromethene boron chelate compound represented by the general formula (A1) of the present invention can be synthesized, for example, as follows. That is, the compound represented by the general formula (B1) and the compound represented by the general formula (B2) are reacted in a suitable solvent in the presence of a suitable acid catalyst, and the dipyrromethene represented by the general formula (B5). A system compound is obtained. As a suitable acid catalyst, hydrobromic acid, hydrogen chloride or the like can be used. As a suitable solvent, ethanol, tetrahydrofuran or the like can be used. The dipyrromethene compound represented by the general formula (B5) can also be obtained by reacting the compound represented by the general formula (B3) and the compound represented by the general formula (B4) under the same conditions. Next, the compound represented by the general formula (B5) is reacted with boron trifluoride to obtain the compound represented by the general formula (B6). Finally, the compound represented by the general formula (B6) is reacted with boron tribromide to synthesize the dibenzopyromethene boron chelate compound represented by the general formula (A1).

^R 1 ^{to R 17} in the formula (B1) ~ (B6) shows the same substituents as ^R 1 ^{to R 17} in the formula (A1).

In the dibenzopyromethene boron chelate compound represented by the general formula (A1), R ¹ = R ⁹ , R ² = R ⁸ , R ³ = R ⁷ , R ⁴ = R ⁶ , R ¹⁰ = R ¹⁷ , R ¹¹ A symmetrical dibenzopyromethene boron chelate compound (A2) in which R = R ¹⁶ , R ¹² = R ¹⁵ , and R ¹³ = R ¹⁴ can be synthesized, for example, as follows.

式（Ａ２）中のＲ^１〜Ｒ^４及びＲ^１０〜Ｒ^１３は、式（Ａ１）中のＲ^１〜Ｒ^１７と同様に、どのような置換基であってもよい。具体的には、式（Ａ１）中のＲ^１〜Ｒ^１７に対する例示として上で挙げた置換基が、置換基の例として挙げられる。

R ^{1 to} R ⁴ and R ^{10 to} R ¹³ in the formula (A2) may be any substituents in the same manner as R ^{1 to} R ¹⁷ in the formula (A1). Specifically, the substituents mentioned above as examples for R ^{1 to} R ¹⁷ in formula (A1) are given as examples of substituents.

The compound of the general formula (B7) and the compound of the general formula (B8) are reacted in an appropriate solvent such as alcohol to obtain the compound of the general formula (B9). Subsequently, the compound of the general formula (B9) is treated with lead tetraacetate in an appropriate solvent such as tetrahydrofuran to obtain the compound of the general formula (B10). The dipyrromethene compound of the general formula (B11) in which R ⁵ is a hydrogen atom by dissolving the compound represented by the general formula (B10) in an appropriate alcohol together with acetic acid, adding aqueous ammonia thereto and stirring at room temperature. Get. If necessary, a compound of the general formula (B11) in which R ⁵ is not a hydrogen atom is obtained by reacting this compound with a nucleophile such as R ⁵ MgBr in a suitable solvent such as diethyl ether. You can also. Next, the compound represented by the general formula (B11) is reacted with boron trifluoride to obtain the compound represented by the general formula (B12), and then treated with boron tribromide, the dibenzo represented by the general formula (A2) is obtained. A pyromethene boron chelate compound can be obtained.

R ^{1 to} R ⁵ and R ^{10 to} R ¹³ in the formulas (B7) to (B12) represent the same substituents as R ^{1 to} R ¹⁷ in the formula (A1).

  Specific examples of the dibenzopyromethene boron chelate compound represented by the general formula (A1) include those having substituents shown in Tables 1 to 4.

[Use of dibenzopyromethene boron chelate compound according to the present invention]
The dibenzopyromethene boron chelate compound of the present invention can be used in various applications. For example, as a sensitizer for a photopolymerizable composition, a recording material for an optical recording medium, a light emitting material for an organic electroluminescence display, a dye for an optical filter, a fluorescent dye for medical diagnosis, and a semiconductor material for a solar cell. The dibenzopyromethene boron chelate compound can be used. The photopolymerizable composition using the dibenzopyromethene boron chelate compound of the present invention, an optical storage medium, a light emitting device for an organic electroluminescence display, and an optical filter are known as disclosed in Patent Documents 1 to 4. It can be produced by a method. The solar cell using the dibenzopyromethene boron chelate compound of the present invention will be described in detail in Example 2 below.

[Example 1]

  2-Methoxybenzoylhydrazine (C1) (1.5 g) and 2-hydroxy-4-methoxyacetophenone (C2) (1.5 g) were added to 1-propanol (40 mL), and the mixture was heated to reflux for 27 hours. After completion of the reaction, the precipitated solid was washed with a small amount of 1-propanol and dried under reduced pressure to obtain a yellow solid (C3) (1.30 g).

  Compound (C3) (1.0 g) was dissolved in tetrahydrofuran (60 mL), lead tetraacetate (1.9 g) was added little by little, and the mixture was stirred at room temperature for about 2 hours. After completion of the reaction, the precipitated solid was removed, the filtrate was concentrated, and purified by silica gel column chromatography using chloroform as a developing solvent to obtain a yellow solid (C4) (0.78 g).

  Compound (C4) (9.1 g) was dissolved in 340 mL of methanol while stirring to obtain a uniform solution. After adding acetic acid 160mL and ammonia water 100mL to this solution, it stirred at room temperature for 2 days. After confirming that the reaction did not proceed by thin layer chromatography, stirring was stopped and the precipitated solid was filtered off. The obtained solid was purified by silica gel column chromatography using a hexane-methylene chloride mixed solvent (hexane / methylene chloride volume ratio of 1/4) as a developing solvent to obtain 2.0 g of a dark green solid (C5). It was.

  1 g of the obtained dark green solid (C5) was dissolved in 60 mL of dry toluene under a nitrogen atmosphere, 1 mL of triethylamine was added, and the mixture was heated to 80 ° C. and stirred at 80 ° C. for 30 minutes. Thereto was slowly added 1.4 mL of a diethyl ether complex of trifluoroboron over 5 minutes, followed by stirring for 1 hour. After confirming that the reaction did not proceed by thin layer chromatography, the reaction solution was adjusted to pH 7-8 by adding saturated aqueous sodium hydrogen carbonate solution (100 mL), and extracted and concentrated with ethyl acetate (100 mL). (A liquid). Further, the aqueous layer after extraction with ethyl acetate was extracted again with methylene chloride (100 mL × 3) (solution B). Liquid A and liquid B were combined and washed with water (100 mL × 2), and then sodium sulfate was added to the organic layer for drying. Sodium sulfate was filtered off, and the filtrate was concentrated as much as possible so as not to cause precipitation, and then reprecipitated by adding n-hexane to obtain 0.99 g of a dark blue solid (D1) having the following chemical structure. It was. The compound (D1) is not a dibenzopyromethene boron chelate compound of the present invention, but when subjected to visible ultraviolet spectroscopic analysis for comparison, the absorption maximum wavelength was 654 nm.

Identification data of compound (D1):
¹ H NMR (270 MHz, DMSO-d ₆ ) δ 3.69 (s, 3H), 3.71 (s, 6H), 3.75 (s, 3H), 6.55 (d, J = 1.7 Hz, 2H), 6.99 (t, J = 7.4 Hz, 1H), 7.06 (t, J = 7.4 Hz, 1H), 7.15-7.21 (m, 4H), 7.36-7.50 (m, 4H), 8.02 (dd, J = 8.8, 1.1 Hz, 2H ), 8.44 (s, 1H).
FAB-MASS: 563 [M ⁺ ]
Elemental analysis: Anal. Calcd for C ₃₃ H ₂₇ BF ₂ N ₂ O ₄ · 0.2CH ₂ Cl ₂ · 0.03AcOEt; C, 68.11; H, 4.77; N, 4.80; B. 1.85: Found C, 68.00; H, 4.89; N, 4.92; B, 1.8.
UV-visible spectroscopic analysis data (DMF solution): Absorption maximum wavelength λmax = 654 nm (ε = 1.00 × 10 ⁵ M ^-1 cm ^-1 )

  In a nitrogen atmosphere, compound (D1) (0.7 g) was dissolved in dry methylene chloride (50 mL), the reaction solution was cooled to 0 ° C., and then 1M boron tribromide dichloromethane solution (18 mL) was slowly added over 30 minutes. And dripped. The reaction solution was returned to room temperature and further stirred for 67 hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution (300 mL) was added to adjust to pH 7-8, extraction was performed with ethyl acetate (200 mL × 5), the organic layers were combined and washed with water (500 mL), and then sodium sulfate was added. In addition, it was dried. Thereafter, the filtrate was concentrated as much as possible without causing precipitation, and n-hexane was added to cause reprecipitation to obtain a dark green solid (D2) (0.38 g). When the compound (D2) was subjected to ultraviolet-visible spectroscopic analysis, the absorption maximum wavelength was 760 nm.

Identification data of compound (D2):
¹ H NMR (270 MHz, DMSO-d ₆ ) δ 6.89 (dd, J = 8.2, 0.7 Hz, 2H), 7.18 (dd, J = 8.7, 2.0 Hz, 2H), 7.21 (td, J = 7.5, 1.0 Hz, 2H), 7.36-7.42 (m, 2H), 7.63 (d, J = 1.7 Hz, 2H); 8.06 (d, J = 8.8 Hz, 2H), 8.23 (dd, J = 7.9, 1.3 Hz, 2H ), 8.26 (s, 1H).
FAB-MASS: 467 [M ⁺ ]
Elemental analysis: Anal. Calcd for C ₂₉ H ₁₇ BN ₂ O ₄ · 0.7H ₂ O · 0.6 AcOEt: C, 70.66; H, 4.38; N. 5.25; B. 2.03: Found, C. 70.60; H, 4.07; N, 5.35; B, 1.9.
UV-visible spectroscopic data (DMF solution): Absorption maximum wavelength λmax = 760 nm (ε = 3.80 × 10 ⁴ M ^-1 cm ^-1 )

  Compound (D2) (0.448 g) and sodium iodide (0.661 g) were dissolved in dry N, N-dimethylformamide (10 mL) and heated to 50 ° C. After 10 minutes, when the solution turned yellow, methane iodide (0.5 mL) was added in small portions over 1 minute and then stirred for 36 hours. Thereafter, the reaction solution was added to water (about 20 mL). The precipitated solid was dissolved in chloroform and reprecipitated by adding methanol. In this way, 279.5 mg of the compound (D3) was obtained. When the compound (D3) was subjected to ultraviolet-visible spectroscopic analysis, the absorption maximum wavelength was 747 nm.

  Moreover, the electrochemical measurement was performed about the compound (D3). Compound (D3) was dissolved in an N, N-dimethylformamide solution of tetraethylammonium perchlorate (concentration 0.1 mol / L) to a concentration of 1 mmol / L to prepare an electrolytic solution. The oxidation-reduction potential was measured by cyclic voltammetry at a sweep rate of 100 mV / s with a electrochemical analyzer manufactured by BAS, using glassy carbon as the working electrode, platinum as the counter electrode, and a silver-silver chloride electrode as the reference electrode.

Identification data of compound (D3):
¹ H NMR (270 MHz, DMSO-d6) δ 3.98 (s, 6H), 6.90 (d, J = 8.2 Hz, 2H), 7.23 (t, J = 7.56 Hz, 2H), 7.30 (dd, J = 8.8 , 1.8 Hz, 2H), 7.42 (t, J = 7.6 Hz, 2H), 7.75 (d, J = 1.9 Hz, 2H), 8.12 (d, J = 8.9 Hz, 2H), 8.38 (s, 1H), 8.46 (d, J = 7.7 Hz, 2H).
FAB-MASS: 495 [M ⁺ ]
Elemental Analysis: Anal. Calcd for C ₃₁ H ₂₁ BN ₂ O ₄ · 0.35H ₂ O: C, 74.08; H, 4.35; N. 5.57; B. 2.15: Found, C. 74.08; H, 4.23; N, 5.53 ; B, 2.1.
UV-visible spectroscopic data (DMF solution): Absorption maximum wavelength λmax = 747 nm (ε = 9.90 × 10 ⁴ M ^-1 cm ^-1 )
Electrochemical data (DMF solution, silver-silver chloride reference electrode standard) 1st oxidation peak potential 0.723V, 1st reduction peak potential -0.848V

  In addition to compound (D3), compound (D4) was also synthesized from compound (D2). Compound (D2) (0.453 g) and sodium hydride (0.146 g) were dissolved in dry N, N-dimethylformamide (20 mL) with stirring to obtain a uniform solution. Furthermore, after adding hexyl iodide (1.15 mL) and stirring at room temperature for 2 hours, the reaction solution was added to water (100 mL), and the resulting solid precipitate was obtained by filtration. The obtained precipitate was washed with methanol (100 mL), and chloroform was added until the entire amount was dissolved. The obtained chloroform solution was purified by column chromatography using normal phase silica gel as the filler and a mixed solvent of chloroform and n-hexane (mixing volume ratio 4: 1) as the developing solvent to obtain 240 mg of the compound (D4). It was. For the compound (D4), electrochemical measurement was performed in the same manner as for the compound (D3).

Identification data of compound (D4):
¹ H NMR (500 MHz, CDCl ₃ ) δ 0.930-0.958 (6H, m), 1.37-1.42 (8H, m), 1.51-1.57 (4H, m), 1.88 (4H, quint, J = 7.2 Hz), 4.08 (2H, dt, J = 8.7, 6.6 Hz), 4.13 (2H, dt, J = 8.7, 6.6 Hz), 6.99 (2H, d, J = 8.0 Hz), 7.15 (2H, dd, J = 8.8, 2.0 Hz), 7.18 (2H, t, J = 7.6 Hz), 7.36-7.39 (2H, m), 7.51 (2H, d, J = 1.8 Hz), 7.53 (1H, s), 7.79 (2H, d, J = 8.9 Hz), 8.15 (2H, dd, J = 7.8, 1.3 Hz).
FAB-MASS: 635 [M ⁺ ]
Elemental analysis: Anal. Calcd for C ₄₁ H ₄₁ BN ₂ O ₄ : C, 77.36; H, 6.49; N. 4.40; B. 1.7: Found, C. 77.29; H, 6.48; N, 4.26; B, 1.8.
UV-visible spectroscopic analysis data (DMF solution): Absorption maximum wavelength λmax = 750 nm (ε = 1.02 × 10 ⁵ M ^-1 cm ^-1 )
Electrochemical data (DMF solution, silver-silver chloride reference electrode standard) 1st oxidation peak potential 0.697V, 1st reduction peak potential -0.854V

[Example 2]
A conductive glass with tin oxide film doped with fluorine (manufactured by Nippon Sheet Glass, 13Ω / □) was heated in an aqueous solution of titanium tetrachloride (50 mM) at 70 ° C. for 30 minutes, and then washed with ultrapure water. A titanium oxide dispersion (trade name: PST-18NR, manufactured by Catalyst Chemical Industry Co., Ltd.) was applied to the conductive surface to a thickness of 10 μm by screen printing, and baked at 430 ° C. for 20 minutes. After cooling, the glass was heat-treated at 70 ° C. for 30 minutes in an aqueous titanium tetrachloride solution (50 mM). The glass was washed with ultrapure water, and a titanium oxide dispersion (trade name: PST-400C, manufactured by Catalytic Chemical) was applied on the PST-18NR layer at a thickness of 5 μm by screen printing, and then at 500 ° C. for 30 minutes. Baked. After cooling to 120 ° C., it was immersed in a solution of the above compound (D2) (concentration: 0.0005 mol / liter, solvent: ethanol) for 36 hours. The working electrode of the titania fine particle layer adsorbed with the dye was washed with ethanol and then naturally dried. As the counter electrode, a fluorine-doped conductive glass with tin oxide film (made by Nippon Sheet Glass, 13Ω / □) was used which was obtained by sputtering platinum. Between the working electrode surface and the counter electrode surface, a resin film (hot melt sealant SX1170-25 manufactured by Solaronics) was disposed as a spacer on the edge, and the working electrode surface and the counter electrode surface were faced to each other. 0.05 mol / L iodine, 0.1 mol / L lithium iodide, 0.6 mol / L 1-methyl-3-propylimidazolium iodide and 0 mol in the gap between the working electrode surface and the counter electrode surface An acetonitrile solution containing 0.5 mol / L of 4-t-butylpyridine was injected as an electrolytic solution using a capillary phenomenon, and the gap was sealed with an epoxy resin to produce a photoelectric conversion element. When the measured photoelectric conversion element was irradiated with AM1.5G pseudo-sunlight using a solar simulator manufactured by Spectrometer, the open circuit voltage was 0.31 V, the short-circuit current density was 0.20 mA / cm ² , A fill factor of 0.48 and a conversion efficiency of 0.03% were exhibited.

Claims (12)

A dibenzopyromethene boron chelate compound represented by the following general formula (A1).

(Wherein R ^{1 to} R ¹⁷ are each independently a hydrogen atom, a hydroxy group, an amino group, a carboxy group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms. Group, halogenoalkyl group, aralkyl group, aryl group, pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazolyl group, benzoxazoyl group, benzothiazoyl group, benzoimidazoloyl group, benzooxa Zoyl group, benzothiazoyl group, benzoimidazoloyl group, benzofuranyl group, indoyl group, alkoxyalkyl group, alkoxy group, alkoxyalkoxy group, aryloxy group, dialkylaminoalkoxy group, alkylthioalkoxy group, alkylthio group, arylthio group, alkyl Carboni An amino group, or an arylcarbonylamino group.) The dibenzopyromethene boron chelate compound according to claim 1, which is represented by the following general formula (A2).

Wherein R ^{1 to} R ⁴ and R ^{10 to} R ¹³ are each independently a hydrogen atom, a hydroxy group, an amino group, a carboxy group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon Alkynyl, halogenoalkyl, aralkyl, aryl, pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, imidazolyl, benzoxazoyl, benzothiazoyl, benzoyl Imidazoyl group, benzoxazoyl group, benzothiazoyl group, benzoimidazoloyl group, benzofuranyl group, indoyl group, alkoxyalkyl group, alkoxy group, alkoxyalkoxy group, aryloxy group, dialkylaminoalkoxy group, alkylthioalkoxy group, alkylthio Group, arylthio group Alkylcarbonylamino group, or an arylcarbonylamino group.) The dibenzopyromethene boron chelate compound according to claim 1, which is represented by the following general formula (A3).

(In the formula, R ^{1 to} R ⁴ and R ^{10 to} R ¹³ each independently represent a hydrogen atom, a hydroxy group, or an alkoxy group.)   The dibenzopyromethene boron chelate compound according to claim 1, which is represented by the following general formula (A4).

  (Wherein R ² And R ⁸ Are each independently a hydrogen atom, hydroxy group, amino group, carboxy group, alkoxy group, alkoxyalkoxy group, aryloxy group, dialkylaminoalkoxy group, alkylthioalkoxy group, alkylthio group, arylthio group, alkylcarbonylamino group, or arylcarbonyl Represents an amino group. )   R ² And R ⁸ Each independently represents a hydrogen atom, a hydroxy group, or an alkoxy group, The dibenzopyromethene boron chelate compound of Claim 4 characterized by the above-mentioned. 6. The dibenzopyromethene boron chelate compound according to any one of claims 1 to 5 , wherein the maximum absorption wavelength is 700 nm or more. The solar cell using the dibenzopyromethene boron chelate compound of any one of Claims 1 thru | or 6 as a pigment | dye. A photopolymerizable composition using the dibenzopyromethene boron chelate compound according to any one of claims 1 to 6 as a sensitizer. An optical recording medium containing the dibenzopyromethene boron chelate compound according to any one of claims 1 to 6 in a recording layer. The light emitting element which uses the dibenzopyromethene boron chelate compound of any one of Claims 1 thru | or 6 as a light emitting element material. An optical filter containing the dibenzopyromethene boron chelate compound according to any one of claims 1 to 6 . A fluorescent dye for medical diagnosis containing the dibenzopyromethene boron chelate compound according to any one of claims 1 to 6 .