JP2022188858A - New compound - Google Patents

Abstract

To provide a squarylium compound excellent in chemical stability.SOLUTION: The compound is represented by formula (I) in the figure. (In formula (I), X is one of -OCH3, -SCH3, and -N(C2H5)2; and An- is one selected from a group of monovalent anions.)SELECTED DRAWING: None

Description

The present invention relates to novel compounds consisting of cationic squarylium units.

Since near-infrared region absorbing dyes have poor stability against heat and light due to the narrow HOMO-LUMO gap, how to impart stability can be said to be an issue in molecular design. Many ionic compounds generally have higher chemical stability than non-ionic compounds because ionic interactions work between anions and cations.

式中、Q¹およびQ²は各々イミダゾール、ベンズイミダゾール、チアゾール、ベンズチアゾール、オキサゾール、ベンズオキサゾール、２－ピリジニウム、４－ピリジニウム、２－キノリニウム、４－キノリニウム、インドリニウム、ピリリウム、チオピリリウム、セレノピリリウム、ベンズピリリウム、ベンズチオピリリウムまたはベンズセレノピリリウム核であり、しかも式Q¹CH₂R¹およびQ²CH₂R²の化合物において、メチレン水素は活性水素であり、R¹およびR²は各々独立して水素原子、脂肪族基または環式脂肪族基であり、そしてΩは式－NR³R⁴または式－CR⁵R⁶R⁷など（R³～R⁷は各々独立して、水素原子、アシル基、脂肪族基、環式脂肪族基、芳香族基または複素環式基など）を示す。 As such a composition for an optical film excellent in near-infrared absorption stability, Patent Document 1 (International Publication No. 2018/100834) discloses a composition containing two types of structurally defined cationic squarylium or squarylium (croconium). things are disclosed.
Further, Patent Document 2 (Japanese Patent No. 2633086) discloses a squarylium dye represented by the following formula.

wherein Q ¹ and Q ² are imidazole, benzimidazole, thiazole, benzthiazole, oxazole, benzoxazole, 2-pyridinium, 4-pyridinium, 2-quinolinium, 4-quinolinium, indolinium, pyrylium, thiopyrylium, selenopyryl , ^benzpyrylium , _{benzthiopyrylium} or ^{benzselenopyrylium} nucleus, and in compounds of the formulas ^Q1CH2R1 and _Q2CH2R2 , methylene hydrogen is the active hydrogen, ^R1 and ^{R 2} is each independently a hydrogen atom, an aliphatic group or a cycloaliphatic group ^, and Ω is of the formula -NR ³ R ⁴ or ^{-CR 5} R ⁶ R ⁷ etc. a hydrogen atom, an acyl group, an aliphatic group, a cycloaliphatic group, an aromatic group, a heterocyclic group, etc.).

WO2018/100834 Japanese Patent No. 2633086

Squarylium, which is widely used as a near-infrared absorption dye, has excellent spectral characteristics suitable for applications such as optical filters, but many of them have chemical stability problems. In view of such problems, the present invention develops novel compounds having excellent spectral properties and chemical stability.

The present invention is a compound represented by the following formula (I), which achieves the above objects of the present invention.

（式（Ｉ）中、Ｘは－ＯＣＨ₃、－ＳＣＨ₃、－Ｎ（Ｃ₂Ｈ₅）₂のいずれかであり、Ａｎ^-は下記式（ＩＩ）で表される一価のアニオン群から選ばれる１種である。）

(In formula (I), X is any one of —OCH ₃ , —SCH ₃ and —N(C ₂ H ₅ ) ₂ , and An ⁻ is selected from the group of monovalent anions represented by formula (II) below. It is the one selected.)

INDUSTRIAL APPLICABILITY According to the present invention, novel squarylium compounds having excellent chemical stability and absorption in the near-infrared region can be provided.

Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be arbitrarily modified within the scope of the invention.

The compound of the present invention is represented by the following formula (I).

（式（Ｉ）中、Ｘは－ＯＣＨ₃、－ＳＣＨ₃、－Ｎ（Ｃ₂Ｈ₅）₂のいずれかであり、Ａｎ^-は下記式（ＩＩ）で表される一価のアニオン群から選ばれる１種である。）

(In formula (I), X is any one of —OCH ₃ , —SCH ₃ and —N(C ₂ H ₅ ) ₂ , and An ⁻ is selected from the group of monovalent anions represented by formula (II) below. It is the one selected.)

The compound of the present invention is suitably used, for example, as an organic dye compounded in an optical filter used in an imaging device or the like.
Such a compound is prepared, for example, by reacting a compound represented by the following formula (A) with squaric acid or a derivative thereof to synthesize a squarylium compound of the following formula (1). It can then be reacted with a compound that constitutes An ⁻ to produce a compound of the present invention.

スクアリン酸誘導体としては、スクアリン酸エステル、スクアリン酸アミド、スクアリン酸塩等を用いることができる。

As the squaric acid derivative, squaric acid ester, squaric acid amide, squaric acid salt and the like can be used.

The amount of squaric acid used is preferably 0.3 mol or more, more preferably 0.4 mol or more, still more preferably 0.45 mol or more, or 1.0 mol, per 1 mol of the compound of formula (A). The following is preferable, 0.8 mol or less is more preferable, and 0.7 mol or less is even more preferable.

The reaction of the compound of formula (A) with squaric acid is preferably carried out in a solvent. Solvents that can be used include aliphatic hydrocarbons such as hexane, toluene, heptane, octane, decane, cyclohexane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; dichloromethane, chloroform, and 1,2-dichloroethane. Ethers such as diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, diisopropyl ether and methyl tertiary butyl ether; Alcohols such as methanol, ethanol, propanol and butanol. These solvents may be used alone or in combination of two or more. The reaction temperature may be appropriately set according to the reaction conditions, for example, it may be appropriately set between 50°C and 180°C. The reaction is preferably carried out under reflux. The reaction time is not particularly limited, and may be appropriately set according to the progress of the reaction. For example, it is preferably 0.5 hours or longer, more preferably 1 hour or longer, preferably 24 hours or shorter, and more preferably 12 hours or shorter. . The reaction is preferably carried out in an inert gas (for example, nitrogen gas or argon gas) atmosphere.

When CF ₃ SO ₃ Me (Me is methyl) is used as the compound constituting An ⁻ , the squarylium compound of formula (1) is dissolved in anhydrous dichloromethane or the like, CF ₃ SO ₃ Me is added dropwise, and the temperature is maintained at 0° C. to At a temperature of 30° C., the reaction is effected by stirring. After completion of the reaction, the product can be dried and purified as necessary to obtain compound (11). Further, by substituting the base of compound (11) with lithium tetrakis(pentafluorophenyl)borate, compound (12) can be obtained, and by substituting with sodium tetrakisphenylborate, compound (13) can be obtained. Substitution with lithium hexafluorophosphate can give compound (14), and substitution with sodium pentacyanocyclopentadienide can give compound (15). Alternatively, compound (12) is dissolved in anhydrous dichloromethane or the like, diethylamine is added dropwise, and the mixture is reacted by stirring at a temperature of 0° C. to 30° C. After completion of the reaction, the product is dried and purified as necessary. By doing so, compound (16) can be obtained. Alternatively, the squarylium compound of formula (1) is dissolved in anhydrous toluene or the like, Lawesson's reagent is added, and the reaction mixture is stirred at a temperature of 80° C. to 120° C. to dissolve the resulting product in anhydrous dichloromethane or the like. , and CF ₃ SO ₃ Me are added dropwise and stirred at a temperature of 0° C. to 30° C. to react. After completion of the reaction, the product is dried and, if necessary, purified to give compound (17). Obtainable.

EXAMPLES The present invention will be specifically described below with reference to examples.

In the following, the molecular structure and physical properties of the products obtained in the examples were measured using a nuclear magnetic resonance instrument ECA-600 (JEOL Ltd.) and a mass spectrometer Shimadzu Axima-CFRplus (Shimadzu Corporation). .

[Example 1]
2-tert-Butyl-4-((Z)-(3-(((E)-2-tert-butyl-6-methoxy-4H-thiochromen-4-ylidene)methyl)-2-methoxy-4-oxocyclobut Synthesis of -2-en-1-ylidene)methyl)-6-methoxy-thiochromenylium triflate (compound 11)

（式中、「Ｍｅ」はメチル基である。以下同様。）

(Wherein, "Me" is a methyl group. Same below.)

Compound 1(Z)-2-(((E)-2-tert-butyl-6-methoxy-4H-thiochromen-4-ylidene)methyl)-4-((2-tert-butyl- 6-methylthiochromenylium-4-yl)methylene)-3-oxocyclobut-1-en-1-olate, 152.2 mg, 0.266 mmol) was dissolved in anhydrous dichloromethane (33 ml) and CF ₃ SO ₃ Me (117 μl, 1 .06 mmol) was added dropwise and stirred at room temperature for 5 hours. After completion of the reaction, 5% aqueous NaHCO ₃ solution was added, and the organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (Wakogel C-300; developing solvent 3% MeOH/CH ₂ Cl ₂ ) and recrystallized from CH ₂ Cl ₂ /Et ₂ O to give the target compound 11 (yield 105 mg). (brown powder) was obtained.

The results of decomposition temperature, ¹ H-NMR, ¹³ C-NMR, IR, mass spectrometry, and elemental analysis of Compound 11 obtained are shown below.
Decomposition temperature: 250°C
¹ H-NMR (CDCl ₃ , 600 MHz) 7.70 (d, J = 9.0 Hz, 2H, Ar-H), 7.34 (dd, J = 9.0 and 2.4 Hz, 2H, Ar—H), 7.00 (s, 2H, CH ₂ ), 4.84 (s, 3H, OCH ₃ ), 4.06 (s, 6H, OCH ₃ ), 1.57 (s, 18H, C ( _CH3 ) ₃ )
¹⁹ F-NMR (CDCl ₃ , 564 MHz) - 81.446 (s, 3F)
MS (MALDI) m/z (%) 585.2 (100), 586.2 (37), 587.2 (13) [M ⁺ ].
MS (MALDI) m/z (%) 149.0 (100), 149.3 (7) [M- ^] .
Anal. calcd for _{C35H37O4S2 + (} [M ⁺ ]) ^: _583.21 , _{CF3SO3- (} [M] ^- ) ^: 149.0

[Example 2]
2-tert-Butyl-4-((Z)-(3-(((E)-2-tert-butyl-6-methoxy-4H-thiochromen-4-ylidene)methyl)-2-methoxy-4-oxocyclobut -2-en-1-ylidene)methyl)-6-methoxy-thiochromenylium tetrakis(perfluorophenyl)-borate (compound (12))

Compound (11) (83.8 mg, 114 μmol) and lithium tetrakis (perfluorophenyl) borate (LiFABA, 149.8 mg, 218 μmol) were stirred in a 100 ml eggplant flask in dichloromethane (140 ml) at room temperature for 1 hour. Thereafter, the reaction solution was washed with water, the solvent was removed under reduced pressure, and recrystallization was performed with CH ₂ Cl ₂ /MeOH to obtain 86 mg of target compound (12) (red powder).

The results of decomposition temperature, ¹ H-NMR, ¹³ C-NMR, IR, mass spectrometry, and elemental analysis of Compound 12 obtained are shown below.
Decomposition temperature: 270°C
¹ H-NMR (CDCl ₃ , 600 MHz) 9.19 (s, 2H, Ar-H), 7.76 (d, J = 9.0 Hz, 2H, Ar-H), 7.60 (d, J = 2.4 Hz, 2H, Ar-H), 7.38 (dd, J = 9.0 and 2.4 Hz, 2H, Ar-H), 6.78 (s, 2H, CH ₂ ), 4.57 (s, _3H , OCH3), 3.96 (s, 6H, OCH3), 1.59 (s, 18H, C _{( CH3} ) ₃ )
¹⁹ F-NMR (CDCl ₃ , 564 MHz) -135.84 (d, J = 8.5 Hz, 8F, Ar-F), -166.37 (t, J = 21.7 Hz, 4F, Ar- F), -170.10 (t, J = 17.2 Hz, 8F, Ar-F)
MS (MALDI) (pos) m/z (%) 585.2 (100), 586.2 (39), 587.2 (17).
MS (MALDI) (neg) m/z (%) 679.0 (100), 680.0 (27), 681.0 (7).
Anal. _calcd for _{C35H37O4S2 +} ([M] ⁺ ): _585.21 , B( _C6F5 ⁾ _4- ([M] ^- ) ^: ( _678.98 )

[Example 3]
2-tert-Butyl-4-((Z)-(3-(((E)-2-tert-butyl-6-methoxy-4H-thiochromen-4-ylidene)methyl)-2-methoxy-4-oxocyclobut Synthesis of -2-en-1-ylidene)methyl)-6-methoxy-thiochromenylium tetrakisphenyl-borate (compound (13))

Compound (11) (10.0 mg, 14 μmol) and sodium tetrakisphenylborate (NaFABA, 26.2 mg, 77 μmol) were stirred in acetonitrile (9 ml) in a 100 ml eggplant flask at room temperature for 1 hour. After that, water was added to the reaction solution and the precipitated solid was collected to obtain 7.7 mg of target compound (13) (dark brown powder).

The decomposition temperature, ¹ H-NMR, and mass spectrometry results of Compound 13 obtained are shown below.
Decomposition temperature: 270°C
¹ H-NMR (CDCl ₃ , 600 MHz) 9.13 (s, 2H, Ar-H), 7.68 (d, J = 9.0 Hz, 2H, Ar-H), 7.55 (broad, 2H, Ar-H), 7.43 (broad, 8H, Ph-H), 7.31 (dd, J = 9.0 and 2.4 Hz, 2H, Ph-H), 7.01 (t, J = 7.8 Hz, 2H, Ph-H), 6.84 (t, J = 7.2 Hz, 4H, Ph-H), 6.69 (s, 2H, CH ₂ ), 4.11 ( s, _3H , OCH3), 3.88 (s, 6H, OCH3), 1.58 (s, 18H, C _{( CH3} ) ₃ )
MS (MALDI) (pos) m/z (%) 585.2 (100), 586.2 (32), 587.2 (10).
MS (MALDI) (neg) m/z (%) 318.2 (5), 319.2 (100), 320.2 (20), 321.2 (13).
Anal. _calcd for _{C35H37O4S2 +} ([M] ⁺ ): _585.21 , B( _C6H5 ⁾ _4- ([M] ^- ) ^: _319.17 .

[Example 4]
2-tert-Butyl-4-((Z)-(3-(((E)-2-tert-butyl-6-methoxy-4H-thiochromen-4-ylidene)methyl)-2-methoxy-4-oxocyclobut Synthesis of -2-en-1-ylidene)methyl)-6-methoxy-thiochromenylium hexafluorophosphate (compound (14))

Compound (11) (33.5 mg, 45.6 μmol) and lithium hexafluorophosphate (LiPF ₆ , 140 mg, 0.92 mmol) were stirred in dichloromethane (60 ml) at room temperature for 1 hour in a 100 ml eggplant flask. Thereafter, the reaction solution was washed with water, the solvent was removed under reduced pressure, and recrystallization was performed with acetone/H ₂ O to obtain 20 mg of target compound (14) (brown powder).

The results of ¹ H-NMR and mass spectrometry of the obtained compound 14 are shown below.
¹ H-NMR (CD ₂ Cl ₂ , 600 MHz) 9.20 (s, 2H, Ar-H), 7.83 (d, J = 9.0 Hz, 2H, Ar-H), 7.67 ( d, J = 2.4 Hz, 2H, Ar-H), 7.41 (dd, J = 9.0 and 2.4 Hz, 2H, Ar-H), 6.84 (s, 2H, CH ₂ ), 4.68 (s, _3H , OCH3), 4.00 (s, 6H, OCH3), 1.59 (s, 18H, C _{( CH3} ) ₃ )
¹⁹ F-NMR (CD ₂ Cl ₂ , 564 MHz) - 75.9 (d, J = 710 Hz, 6F).
MS (MALDI) (pos) m/z (%) 585.2 (100), 586.2 (37), 587.2 (10).
MS (MALDI) (neg) m/z (%) 145.0 (100).
Anal. calcd for _{C35H37O4S2 + (} [M] ⁺ ): _585.21 , _PF6- ⁽ [M] ^- ) ^: 144.96.

[Example 5]
2-tert-Butyl-4-((Z)-(3-(((E)-2-tert-butyl-6-methoxy-4H-thiochromen-4-ylidene)methyl)-2-methoxy-4-oxocyclobut Synthesis of -2-en-1-ylidene)methyl)-6-methoxy-thiochromenylium pentacyanocyclopentadienide (compound (15))

Compound (11) (18.8 mg, 25.6 μmol) and sodium pentacyanocyclopentadienide (10.4 mg, 48.8 μmol) were stirred in acetonitrile (200 ml) at room temperature for 5 hours in a 100 ml eggplant flask. After that, water was added to the reaction solution and the precipitated solid was collected to obtain 15.3 mg of target compound (15) (dark brown powder).

The results of ¹ H-NMR and mass spectrometry of the obtained compound 15 are shown below.
¹ H-NMR (CDCl ₃ , 600 MHz) 9.18 (s, 2H, Ar-H), 7.75 (d, J = 9.0 Hz, 2H, Ar-H), 7.63 (d, J = 1.8 Hz, 2H, Ar-H), 7.38 (dd, J = 9.0 and 2.4 Hz, 2H, Ar-H), 6.81 (s, 2H, CH ₂ ), 4.75 (s, _3H , OCH3), 4.02 (s, 6H, OCH3), 1.60 (s, 18H, C _{( CH3} ) ₃ )
MS (MALDI) (pos) m/z (%) 585.2 (100), 586.2 (35), 587.2 (16).
MS (MALDI) (neg) m/z (%) 190.0 (100), 191.0 (7).
Anal. _calcd for _{C35H37O4S2 + (} ^[ M] ⁺ ): _585.21 , _C10N5- ([M] ^- ) ^: 190.02.

[Example 6]
2-tert-Butyl-4-((Z)-(3-(((E)-2-tert-butyl-6-methoxy-4H-thiochromen-4-ylidene)methyl)-2-dimethylamino-4-oxocyclobut Synthesis of -2-en-1-ylidene)methyl)-6-methoxy-thiochromenylium pentacyanocyclopentadienide (Compound (16))

Compound 12 (14.7 mg, 11.6 µmol) was dissolved in anhydrous dichloromethane (10 ml) in a 100 ml eggplant flask, (C ₂ H ₅ ) ₂ NH (17 µl, 0.17 mmol) was added dropwise, and the mixture was stirred at room temperature for 3 hours. did. After completion of the reaction, the mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (Wakogel C-300; developing solvent 1% MeOH/CH ₂ Cl ₂ ) and recrystallized from CH ₂ Cl ₂ /hexane to give the target compound 16 (yield 3.0 mg). (purple powder) was obtained.

The results of decomposition temperature, ¹ H-NMR, ¹³ C-NMR, IR, mass spectrometry, and elemental analysis of Compound 16 obtained are shown below.
¹ H-NMR (CD ₂ Cl ₂ , 600 MHz) 9.31 (s, 2H, Ar-H), 7.75 (d, J = 9.0 Hz, 2H, Ar-H), 7.50 ( d, J = 2.4 Hz, 2H, Ar-H), 7.34 (dd, J = 9.0 and 2.4 Hz, 2H, Ar-H), 6.81 (s, 2H, CH ₂ ), 3.96 (s, 6H _, OCH3), 3.85 (q, J = 7.2 Hz, 4H, _CH2 ), 1.60 ((t, J = 7.2 Hz, 6H, CH ₃ ), 1.55 (s, 18H, C( _CH3 ) ₃ )
¹³ C-NMR (CD ₂ Cl ₂ , 151 MHz) 176.79, 167.45, 166.55, 161.02, 158.04, 149.33, 148.12, 147.74, 139.44, 137 .82, 137.50, 135.86, 130.70, 130.68, 129.86, 125.43, 124.24, 120.89, 108.44, 108.29, 56.00, 47.72 , 40.67, 30.83, 15.05.
¹⁹ F-NMR (CDCl ₃ , 564 MHz) -135.48 (s, 8F, Ar-F), -166.08 (t, J = 19.5 Hz, 4F, Ar-F), -169.92 (t, J = 17.2Hz, 8F, Ar-F)
MS (MALDI) (pos) m/z (%) 626.3 (100), 627.3 (47), 628.3 (21), 629.3 (6).
MS (MALDI) (neg) m/z (%) 679.0 (100), 680.0 (33), 681.0 (4).
Anal. _calcd for _{C38H44NO3S2 + (} [M] ⁺ ): _626.28 , B( _C6F5 ⁾ _4- ([M] ^- ) ^: (678.98)

Compound 11 (197.16 mg, 0.345 mmol) was dissolved in anhydrous toluene (50 ml) in a 100 ml eggplant flask, Lawesson's reagent (58.0 mg, 0.143 mmol) was added dropwise, and the mixture was stirred at 100° C. for 2 hours. After completion of the reaction, it was concentrated under reduced pressure, and the crude product was purified by alumina column chromatography (developing solvent: 1% MeOH/CH ₂ Cl ₂ ), silica gel column chromatography (Wakogel C-300; developing solvent 5% MeOH). /CH ₂ Cl ₂ ) and recrystallized with CH ₂ Cl ₂ /hexane to give a purple powder, yield 85.8 mg. The obtained purple powder was dissolved in anhydrous dichloromethane (45 ml) in a 100 ml eggplant flask, CF ₃ SO ₃ Me (52.4 μl, 0.48 mmol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 5% aqueous NaHCO ₃ solution was added, and the organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (Wakogel C-300; developing solvent 5% MeOH/CH ₂ Cl ₂ ) and recrystallized from CH ₂ Cl ₂ /hexane to give the target compound 17 (yield 85.8 mg). (brown powder) was obtained.

The results of decomposition temperature, ¹ H-NMR, ¹³ C-NMR, IR, mass spectrometry, and elemental analysis of Compound 17 obtained are shown below.
¹ H-NMR (CDCl ₃ , 600 MHz) 9.14 (s, 2H, Ar-H), 7.77 (dd, J = 9.0 and 2.4 Hz, 2H, Ar-H), 7. 71 (d, J = 2.4 Hz, 2H, Ar-H), 7.39 (dd, J = 9.0 and 2.4 Hz, 2H, Ar-H), 6.88 (s, 2H, _CH2 ), 4.05 (s, 6H, OCH3), 3.24 (s, _3H , _SCH3 ), 1.58 (s, 18H, C( _CH3 ) ₃ )
¹⁹ F-NMR (CDCl ₃ , 564 MHz) - 81.35 (s, 3F)
MS (MALDI) m/z (%) 601.2 (100), 602.2 (39), 603.2 (22), 604.2 (4) [M ⁺ ].
MS (MALDI) m/z (%) 149.0 (100) [M- ^] .
Anal. calcd for _{C35H37O4S2 + (} [M ⁺ ]) ^: _601.19 , _{CF3SO3- (} [M] ^- ) ^: 149.0

Claims (1)

A compound represented by the following formula (I).

(In formula (I), X is any one of —OCH ₃ , —SCH ₃ and —N(C ₂ H ₅ ) ₂ , and An ⁻ is selected from the group of monovalent anions represented by formula (II) below. It is the one selected.)