JP2003119404A - Coupled styrylcyanine coloring matter and method for producing the same - Google Patents
Coupled styrylcyanine coloring matter and method for producing the sameInfo
- Publication number
- JP2003119404A JP2003119404A JP2001346290A JP2001346290A JP2003119404A JP 2003119404 A JP2003119404 A JP 2003119404A JP 2001346290 A JP2001346290 A JP 2001346290A JP 2001346290 A JP2001346290 A JP 2001346290A JP 2003119404 A JP2003119404 A JP 2003119404A
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- JP
- Japan
- Prior art keywords
- dye
- general formula
- chemical
- mmol
- synthesis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/143—Styryl dyes the ethylene chain carrying a COOH or a functionally modified derivative, e.g.-CN, -COR, -COOR, -CON=, C6H5-CH=C-CN
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、一般的な一分子の
色素とは異なり、二分子の色素が共有結合して連結され
ている新規なカップリング色素及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel coupling dye, in which two molecules of dye are covalently linked to each other, unlike a general dye of one molecule, and a method for producing the same.
【０００２】[0002]
【従来の技術】下記一般式で示されている通り、ヒドロ
キシル化合物（開環体、メロシアニン）は熱や可視光に
より右側の一般式の無色化合物（閉環体、スピロピラ
ン）に光変色し、更に紫外線光を照射すると戻される。2. Description of the Related Art As shown by the following general formula, a hydroxyl compound (ring-opened compound, merocyanine) is photo-color-changed to a colorless compound (closed-ring compound, spiropyran) on the right side by heat or visible light, and further UV It is returned when irradiated with light.
【０００３】[0003]
【化６】 [Chemical 6]
【０００４】このような光変色性のため、スピロピラン
化合物を機能性色素として追加記録型記録材料に使用し
ようとする研究が進められ、現在まで化学構造では50種
類で8,500個の化合物が合成された。しかし、メロシア
ニン形態の化合物を利用しようとする場合には、メロシ
アニン形態の化合物の化学構造が熱や可視光により変化
する不安定性のため、却ってこのような光変色性は短所
として作用したりする。このような熱や可視光線に対す
る不安定性を除去する一つの方法は、メロシアニン形態
の化合物のヒドロキシル基を他の官能基で保護すること
である。Due to such photochromic properties, research has been conducted to use spiropyran compounds as functional dyes in additional recording type recording materials, and up to now, 8,500 compounds with 50 kinds of chemical structures have been synthesized. . However, when a merocyanine-type compound is used, the photochromic property rather acts as a disadvantage because the chemical structure of the merocyanine-type compound changes due to heat or visible light. One way to eliminate this heat and visible light instability is to protect the hydroxyl groups of the merocyanine form of the compound with other functional groups.
【０００５】一方、下記一般式のようなスチリルシアニ
ン色素を光記録層の物質として使用する特許が出願され
た（米国特許第6,103,331号）。このような構造の光記
録色素は光変色性を利用せず、使用レーザ波長の吸光に
よる光分解を起こすものである。レーザにより照射され
た部分と照射されていない部分の屈折率及び反射率の変
化を起こすのである。すなわち、このような光分解型記
録色素の必要条件では、使用レーザ（例えば635 nm又は
658 nmの波長）に適当な吸光を示すこと、モル吸光係数
が大きいこと、熱及び光安定性に優れること、熱分解時
に屈折率の変化が大きいこと、溶解性に優れ、スピンキ
ャスティング法により薄膜がよく作られることなどがあ
る。On the other hand, a patent has been filed (US Pat. No. 6,103,331) in which a styryl cyanine dye represented by the following general formula is used as a substance for an optical recording layer. The optical recording dye having such a structure does not utilize the photochromic property and causes photolysis by absorption of the used laser wavelength. This causes a change in the refractive index and the reflectance between the portion irradiated with the laser and the portion not irradiated with the laser. That is, the requirement for such a photo-degradable recording dye is that the laser used (for example, 635 nm or
650 nm wavelength), large molar extinction coefficient, excellent heat and light stability, large change in refractive index during thermal decomposition, excellent solubility, thin film formed by spin casting Are often made.
【０００６】[0006]
【化７】 [Chemical 7]
【０００７】(式中、R1は炭素原子数が1〜18のアルキル
基、アリール基、アリールアルキル基、アルコキシアル
キル基、アシルオキシアルキル基又はヒドロキシアルキ
ル基であるか、又は不飽和結合があるC3-C18置換体であ
り、R2はアルキル基又はアリール基である。アニオンで
あるXはI、Br、ClO4、PF4、SbF4、CH3SO4又はCH3-C6H 4-
SO3-であり、Y1及びY2は共に電子受容基であるか、又は
二つ中の一つが電子供与基であり、他の一つが水素であ
る。Y3は電子供与基である。）(Where R1Is alkyl having 1 to 18 carbon atoms
Group, aryl group, arylalkyl group, alkoxyal
Kill group, acyloxyalkyl group or hydroxyalkyl
C, which is a radical or has an unsaturated bond3-C18Is a substitute
R2Is an alkyl group or an aryl group. With anions
X is I, Br, ClOFour, PFFour, SbFFour, CH3SOFourOr CH3-C6H Four-
SO3-And Y1And Y2Are both electron accepting groups, or
One of the two is an electron donating group and the other is hydrogen.
It Y3Is an electron donating group. )
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、二分
子の色素が共有結合して連結されている構造を有するこ
とにより熱及び光安定性に優れ、高いモル吸光係数を有
する新規な色素及び製造方法を提供することである。DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel dye having a high molar extinction coefficient with excellent heat and photostability by having a structure in which bimolecular dyes are covalently linked. And a manufacturing method.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、熱や可視
光により化学構造が変わらないメロシアニンを合成する
ために二分子の色素を結合した結果、下記一般式で示さ
れている通り、熱や光により異性化が起こらず熱及び光
に安定し、二つの色素分子からなるため高いモル吸光係
数を有する新規な色素を得ることに至った。Means for Solving the Problems As a result of combining two dye molecules to synthesize merocyanine whose chemical structure does not change by heat or visible light, as shown by the following general formula, It has been possible to obtain a novel dye having a high molar extinction coefficient because it is stable to heat and light without isomerization due to heat or light and is composed of two dye molecules.
【００１０】[0010]
【化８】 [Chemical 8]
【００１１】本発明は、下記一般式（1）で示されるカ
ップリング色素に関する。The present invention relates to a coupling dye represented by the following general formula (1).
【００１２】[0012]
【化９】 [Chemical 9]
【００１３】(式中、R1〜R4は互いに同一又は異なって
いてもよく、水素、ハロゲン又はニトロ基であるか、も
しくは一緒にベンゼン環を形成することができる。R5は
C1-C 4のアルキル基である。R6はC3-C6のアルキレンであ
り、R7はC1-C4のアルキル基である。XはOであり、ZはCl
O4、PF6、BF4又はハロゲンである。)(Where R1~ RFourAre the same or different from each other
May be hydrogen, halogen or nitro group,
Or together they can form a benzene ring. RFiveIs
C1-C FourIs an alkyl group. R6Is C3-C6Is an alkylene of
R7Is C1-CFourIs an alkyl group. X is O and Z is Cl
OFour, PF6, BFFourOr halogen. )
【００１４】本発明による色素は、二分子の色素が共有
結合して連結され、一分子となる色素であることを特徴
とする。二つの色素を結合することにより、モル吸光係
数が約２倍増加し、高温で安定し、屈折率も高くて熱分
解時に屈折率の変化が大きいことを特徴とする。更に、
本発明の色素は、合成上電子受容基もしくは電子供与基
を多様に変化させることにより、色素の紫外線-可視光
線吸収スペクトルを長波長あるいは短波長に容易に移動
させることができる。従って、このような光学的及び熱
的特性を利用して色素の吸収スペクトルを光記録波長に
適切に合わせ、光ディスクの記録層物質として使用する
ことができる。1回記録可能な光ディスク媒体としてCD-
R(Compact disc-recordable, 記録容量: 650 MB）とDV
D-R（Digital versatile disc-recordable, 記録容
量: 3.9 GBあるいは4.7 GB）があり、本発明の色素は最
大吸収波長が590-615 nmとしてDVD-Rの記録層物質とし
て使用することができる。The dye according to the present invention is characterized in that two molecules of dye are covalently bonded and linked to form one molecule. By combining two dyes, the molar extinction coefficient increases about twice, is stable at high temperature, has a high refractive index, and has a large change in refractive index during thermal decomposition. Furthermore,
The dye of the present invention can easily shift the ultraviolet-visible absorption spectrum of the dye to a long wavelength or a short wavelength by variously changing the electron accepting group or the electron donating group in terms of synthesis. Therefore, the absorption spectrum of the dye can be appropriately adjusted to the optical recording wavelength by utilizing such optical and thermal characteristics, and the dye can be used as a recording layer material of an optical disc. CD-as a recordable optical disc medium
R (Compact disc-recordable, recording capacity: 650 MB) and DV
There is a DR (Digital versatile disc-recordable, recording capacity: 3.9 GB or 4.7 GB), and the dye of the present invention has a maximum absorption wavelength of 590-615 nm and can be used as a recording layer substance of DVD-R.
【００１５】更に、本発明は、このような二つの分子が
連結された色素の製造方法に関するもので、本発明の色
素の出発材料である一般式（4）のジアルデヒド化合物
を、一般式(2)のアルデヒド化合物と一般式（3）の脂肪
族ジハライドとを溶媒に溶解し、塩基を使用して加熱縮
合反応して合成する。この際、溶媒としてはジメチルホ
ルムアミド(DMF)、テトラヒドロフラン(THF)、アセトン
などが適し、塩基としてはK2CO3、KOH、NaOHなどが適し
ている。ジアルデヒドは水に沈殿させると濾過で分離し
易く、再結晶により精製することも容易である。その
後、合成されたジアルデヒド化合物と一般式（5）で示
された種々のインドリウム塩化合物を溶媒で還流、脱水
反応させ、本発明の色素を合成することができる。反応
溶媒としてはメタノール、エタノール、酢酸などが適
し、反応速度及び反応収率を向上させるために触媒とし
てピリジンが適している。合成された化合物は反応溶媒
に直ぐ沈殿されるため、反応後、濾過して容易に分離で
きる。このような反応を反応式で示せば、反応式1の通
りである。一般式（5）のインドリウム塩化合物は、下
記反応式2のように合成して使用した。Furthermore, the present invention relates to a method for producing a dye in which two molecules are linked as described above, wherein the dialdehyde compound of the general formula (4), which is the starting material for the dye of the present invention, is prepared by The aldehyde compound of 2) and the aliphatic dihalide of the general formula (3) are dissolved in a solvent, and a heat condensation reaction is performed using a base to synthesize the compound. At this time, dimethylformamide (DMF), tetrahydrofuran (THF), acetone and the like are suitable as the solvent, and K 2 CO 3 , KOH, NaOH and the like are suitable as the base. When dialdehyde is precipitated in water, it is easily separated by filtration, and can be easily purified by recrystallization. Then, the synthesized dialdehyde compound and various indolium salt compounds represented by the general formula (5) are refluxed and dehydrated in a solvent to synthesize the dye of the present invention. Methanol, ethanol, acetic acid, etc. are suitable as the reaction solvent, and pyridine is suitable as the catalyst in order to improve the reaction rate and reaction yield. Since the synthesized compound is immediately precipitated in the reaction solvent, it can be easily separated by filtration after the reaction. The reaction formula 1 shows such a reaction. The indolium salt compound represented by the general formula (5) was synthesized according to the following reaction formula 2 and used.
【００１６】[0016]
【化１０】 [Chemical 10]
【００１７】[0017]
【化１１】 [Chemical 11]
【００１８】[0018]
【化１２】 [Chemical 12]
【００１９】[0019]
【化１３】 [Chemical 13]
【００２０】[0020]
【化１４】 [Chemical 14]
【００２１】[0021]
【化１５】 [Chemical 15]
【００２２】(式中、halはCl、Br又はIであり、nは3,
4, 5又は6である。R1〜R5、R7、X及びZは上記一般式1と
同様である。)(Wherein hal is Cl, Br or I, and n is 3,
4, 5 or 6. R 1 to R 5 , R 7 , X and Z are the same as in the above general formula 1. )
【００２３】[0023]
【実施例】以下、本発明を下記合成実施例をあげて詳細
に説明するが、本発明は下記実施例に限定されるもので
はない。The present invention will be described in detail below with reference to the following synthetic examples, but the present invention is not limited to the following examples.
【００２４】<実施例>合成例1
nが３、Xが０であり、R7がC2H5である一般式（4）の出
発材料（A3）（Mw 426.53）の合成:力学攪拌機、コンデ
ンサ付きの２Ｌ三つ口フラスコに４-(ジエチルアミノ)
サリチルアルデヒド 75 g（0.388 mol, Mw 193.24，東
京化成）、ジブロモプロパン39 g（0.194 mol, Mw 201.
89, Acros社）を入れ 、ジメチルホルムアミド（DMF）6
00 mLに溶解した。これにK2CO3 53.6 g（0.388 mol）を
入れ、反応槽温度100 ℃で24時間攪拌した。反応物を冷
却した後、3Lの冷却水に注ぎ、生成物を沈殿させた。生
成物を濾過した後、乾燥した。得られた固体粉末をエチ
ルアセテートで再結晶し、濃黄色の結晶、A3を得た。
収率 77 g（94％）、1H-NMR(DMSO-d6）: 1.11（t, 12H,
NCH2 CH3 ), 2.27 (m,2H, CH2), 3.44 (q, 8H, NCH2),
4.29 (t, 4H, OCH2), 6.17 (s, 2H, ArH), 6.33 (d, 2
H, ArH), 7.49 (d, 2H, ArH), 10.03 (s, 2H, CHO)Examples Synthesis Example 1 Synthesis of starting material (A3) (Mw 426.53) of general formula (4) wherein n is 3, X is 0 and R 7 is C 2 H 5 : mechanical stirrer, 4- (diethylamino) in a 2L three-necked flask with a condenser
Salicylaldehyde 75 g (0.388 mol, Mw 193.24, Tokyo Kasei), dibromopropane 39 g (0.194 mol, Mw 201.
89, Acros), and dimethylformamide (DMF) 6
It was dissolved in 00 mL. 53.6 g (0.388 mol) of K 2 CO 3 was added to this, and the mixture was stirred at a reaction tank temperature of 100 ° C. for 24 hours. After cooling the reaction, it was poured into 3 L of cold water to precipitate the product. The product was filtered and dried. The obtained solid powder was recrystallized from ethyl acetate to obtain dark yellow crystals, A3. Yield 77 g (94%), 1 H-NMR (DMSO-d 6 ): 1.11 (t, 12H,
NCH 2 CH 3 ), 2.27 (m, 2H, CH 2 ), 3.44 (q, 8H, NCH 2 ),
4.29 (t, 4H, OCH 2 ), 6.17 (s, 2H, ArH), 6.33 (d, 2
H, ArH), 7.49 (d, 2H, ArH), 10.03 (s, 2H, CHO)
【００２５】合成例２
nが４、Xが０であり、R7がC2H5である一般式（4）の出
発材料（A4）(Mw 440.58）の合成:力学攪拌機、コンデ
ンサ付きの２Ｌ三つ口フラスコに４-(ジエチルアミノ)
サリチルアルデヒド 75 g (0.388 mol, Mw 193.24，東
京化成)、ジブロモブタン42g (0.194 mol, Mw 215.92,
Acros社)を入れ、テトラヒドロフラン（THF）1500mLに
溶解した。これにK2CO3 53.6 g（0.388 mol）を入れ、
還流しながら24時間攪拌した。生成されたKBｒを濾過し
た後、反応溶媒を蒸留して濃縮し、これを3Lの水に注
ぎ、生成物を沈殿させた。生成物を濾過した後、乾燥し
た。得られた固体粉末をエチルアセテートで再結晶し、
薄黄色の結晶、A4を得た。収率 79 g（93％）、1H-NMR
(CDCl3）: 1.22（t, 12H, NCH2 CH3 ）, 2.01 (m, 4H, CH
2CH2), 3.43 (q, 8H, NCH2), 4.14 (t, 4H, OCH2), 6.0
4 (s, 2H, ArH), 6.31 (d, 2H, ArH), 7.72 (d, 2H, Ar
H), 10.18 (s, 2H, CHO) Synthesis Example 2 Synthesis of starting material (A4) (Mw 440.58) of the general formula (4) in which n is 4, X is 0 and R 7 is C 2 H 5 : 2 L with mechanical stirrer and condenser 4- (diethylamino) in a three-necked flask
Salicylaldehyde 75 g (0.388 mol, Mw 193.24, Tokyo Kasei), dibromobutane 42 g (0.194 mol, Mw 215.92,
Acros) was added and dissolved in 1500 mL of tetrahydrofuran (THF). Add K 2 CO 3 53.6 g (0.388 mol) to it,
The mixture was stirred under reflux for 24 hours. After the produced KBr was filtered, the reaction solvent was distilled and concentrated, and this was poured into 3 L of water to precipitate the product. The product was filtered and dried. The obtained solid powder is recrystallized with ethyl acetate,
A pale yellow crystal, A4, was obtained. Yield 79 g (93%), 1 H-NMR
(CDCl 3 ): 1.22 (t, 12H, NCH 2 CH 3 ), 2.01 (m, 4H, CH
2 CH 2 ), 3.43 (q, 8H, NCH 2 ), 4.14 (t, 4H, OCH 2 ), 6.0
4 (s, 2H, ArH), 6.31 (d, 2H, ArH), 7.72 (d, 2H, ArH
H), 10.18 (s, 2H, CHO)
【００２６】合成例３
nが５、Xが０であり、R7がC2H5である一般式（4）の出
発材料（A5）（Mw 454.61）の合成:力学攪拌機、コンデ
ンサ付きの２Ｌ三つ口フラスコに４-(ジエチルアミノ)
サリチルアルデヒド 75 g（0.388 mol, Mw 193.24，東
京化成）、ジブロモペンタン45 g（0.194 mol, Mw 229.
94, Acros社）を入れ、ジメチルホルムアミド（DMF）50
0 mLに溶解した。これにK2CO3 53.6 g（0.388 mol）を
入れ、100 ℃で24時間攪拌した。反応物を冷却した後、
3Lの水に注ぎ、生成物を沈殿させた。生成物を濾過した
後、乾燥した。得られた固体粉末をエチルアセテートで
再結晶し、薄黄色の結晶、A5を得た。
収率 84 g (95％）、1H-NMR(CDCl3）: 1.22（t, 12H, N
CH2 CH3 ）, 1.73 (m, 2H, OCH2CH2 CH2 ), 1.94 (m, 4H, O
CH2 CH2 ), 3.43 (q, 8H, NCH2), 4.07 (t, 4H,OCH2), 6.
03 (s, 2H, ArH), 6.28 (d, 2H, ArH), 7.72 (d, 2H, A
rH), 10.18 (s, 2H, CHO) Synthesis Example 3 Synthesis of starting material (A5) (Mw 454.61) of the general formula (4) in which n is 5, X is 0 and R 7 is C 2 H 5 : 2 L with mechanical stirrer and condenser 4- (diethylamino) in a three-necked flask
75 g of salicylaldehyde (0.388 mol, Mw 193.24, Tokyo Kasei), 45 g of dibromopentane (0.194 mol, Mw 229.
94, Acros) and put in dimethylformamide (DMF) 50
It was dissolved in 0 mL. 53.6 g (0.388 mol) of K 2 CO 3 was added to this, and the mixture was stirred at 100 ° C. for 24 hours. After cooling the reaction,
Poured into 3 L of water to precipitate the product. The product was filtered and dried. The obtained solid powder was recrystallized from ethyl acetate to obtain a pale yellow crystal, A5. Yield 84 g (95%), 1 H-NMR (CDCl 3 ): 1.22 (t, 12H, N
CH 2 CH 3 ), 1.73 (m, 2H, OCH 2 CH 2 CH 2 ), 1.94 (m, 4H, O
CH 2 CH 2 ), 3.43 (q, 8H, NCH 2 ), 4.07 (t, 4H, OCH 2 ), 6.
03 (s, 2H, ArH), 6.28 (d, 2H, ArH), 7.72 (d, 2H, A
rH), 10.18 (s, 2H, CHO)
【００２７】合成例４
nが６、Xが０であり、R7がC2H5である一般式（4）の出
発材料（A6）(Mw 468.63）の合成:力学攪拌機、コンデ
ンサ付きの２Ｌ三つ口フラスコに４-(ジエチルアミノ)
サリチルアルデヒド 75 g（0.388 mol, 東京化成）、ジ
ブロモヘキサン47 g（0.194 mol, Acros社）を入れ、テ
トラヒドロフラン1500 mLに溶解した。これにKOH 65.3
g (1.16 mol)を入れ、還流しながら３日攪拌した。反応
物を冷却した後、生成されたKBrを濾過して反応物を濃
縮し、これを3Lの水に注ぎ、生成物を沈殿させた。生成
物を濾過した後、乾燥した。得られた固体粉末をクロロ
ホルムで再結晶し、薄黄色の微細結晶、A6を得た。
収率 86 g(94％）、1H-NMR(CDCl3）: 1.22（t, 12H, NC
H2 CH3 ）, 1.58 (m, 4H, OCH2CH2 CH2 ), 1.86 (m, 4H, OC
H2 CH2 ), 3.43 (q, 8H, NCH2), 4.06 (t, 4H, OCH2), 6.
02 (s, 2H, ArH), 6.28 (d, 2H, ArH), 7.72 (d, 2H, A
rH), 10.19 (s,2H, CHO) Synthesis Example 4 Synthesis of starting material (A6) (Mw 468.63) of the general formula (4) in which n is 6, X is 0 and R 7 is C 2 H 5 : 2 L with mechanical stirrer and condenser 4- (diethylamino) in a three-necked flask
75 g (0.388 mol, Tokyo Kasei) of salicylaldehyde and 47 g (0.194 mol, Acros) of dibromohexane were added and dissolved in 1500 mL of tetrahydrofuran. To this KOH 65.3
g (1.16 mol) was added, and the mixture was stirred under reflux for 3 days. After cooling the reaction, the formed KBr was filtered to concentrate the reaction, which was poured into 3 L of water to precipitate the product. The product was filtered and dried. The obtained solid powder was recrystallized from chloroform to obtain light yellow fine crystals, A6. Yield 86 g (94%), 1 H-NMR (CDCl 3 ): 1.22 (t, 12H, NC
H 2 CH 3 ), 1.58 (m, 4H, OCH 2 CH 2 CH 2 ), 1.86 (m, 4H, OC
H 2 CH 2 ), 3.43 (q, 8H, NCH 2 ), 4.06 (t, 4H, OCH 2 ), 6.
02 (s, 2H, ArH), 6.28 (d, 2H, ArH), 7.72 (d, 2H, A
rH), 10.19 (s, 2H, CHO)
【００２８】合成例５
本発明で使用したインドリウム塩の合成（反応式3）:5-
クロロ-2-メチレン-1,3,3-トリメチルインドリン11.4 g
(0.055 mol, Mw 207.7, Aldrich社)をジエチルエーテ
ルに溶解した後、70重量％過塩素酸15.79 g (0.11 mol,
Mw 100.46, Aldrich社)を滴下し、白色の固体を析出し
た。これを濾過して乾燥した。 Synthesis Example 5 Synthesis of indolium salt used in the present invention (Scheme 3): 5-
Chloro-2-methylene-1,3,3-trimethylindoline 11.4 g
(0.055 mol, Mw 207.7, Aldrich) was dissolved in diethyl ether, and then 70 wt% perchloric acid 15.79 g (0.11 mol,
Mw 100.46, Aldrich) was added dropwise to deposit a white solid. It was filtered and dried.
【００２９】[0029]
【化１６】 [Chemical 16]
【００３０】合成例６
本発明で使用したインドリウム塩の合成（反応式4）:1,
1,2,3-テトラメチル-1H-ベンズ[e]インドリウムアイオ
ダイド19.3 g (0.055mol, Mw 351.23, Aldrich社)をメ
タノール300 mlに入れ、全て溶解した。NaOH40 gを蒸
留水500 mlに溶解した塩基水溶液を上記反応液に徐々に
滴下し、２時間攪拌した。この混合物をジエチルエーテ
ルを使用して抽出した。抽出した溶液に60重量％ヘキサ
フルオロ燐酸26.7 g (0.11 mol, Aldrich社)を徐々に滴
下し、白色の固体を析出した。これを濾過して乾燥し
た。 Synthesis Example 6 Synthesis of indolium salt used in the present invention (Scheme 4): 1,
1,2,3-Tetramethyl-1H-benz [e] indolium iodide (19.3 g, 0.055 mol, Mw 351.23, Aldrich) was added to 300 ml of methanol and dissolved. An aqueous base solution in which 40 g of NaOH was dissolved in 500 ml of distilled water was gradually added dropwise to the above reaction solution and stirred for 2 hours. The mixture was extracted using diethyl ether. 26.7 g (0.11 mol, Aldrich) of 60 wt% hexafluorophosphoric acid was gradually added dropwise to the extracted solution to deposit a white solid. It was filtered and dried.
【００３１】[0031]
【化１７】 [Chemical 17]
【００３２】合成例７
本発明の色素（D1）（Mw 1020.97）の合成:500 mL一つ
口フラスコにA5 0.45 g (1 mmol)、1,2,3,3-テトラメチ
ル-3H-インドリウムアイオダイド0.909 g (3 mmol)、エ
タノール200 mLを入れ、2日間還流した。沈殿された生
成物を濾過した後、更に100 mLエタノールに入れ、2時
間還流した。濾過した固体をアセトニトリルで低温で再
結晶し、下記一般式（6）の色素、D1を得た。
収率 0.38 g (37％)、1H-NMR(DMSO-d6): 1.14 (t, 12
H), 1.64 (s, 12H, (CH 3)2), 1.76 (m, 2H), 1.91 (m,
4H), 3.58 (q, 8H), 3.84 (s, 6H, N+-CH3), 4.20 (t,
4H), 6.15 (s, 2H), 6.25 (d, 2H), 6.58 (d, 2H), 7.1
8 (d, 2H), 7.43(d, 2H), 7.63 (s, 2H), 8.03 (d, 2
H), 8.44 (d, 2H)[0032]Synthesis example 7
Synthesis of dye (D1) of the present invention (Mw 1020.97): 500 mL each
In a neck flask, 0.45 g (1 mmol) of A5, 1,2,3,3-tetramethyi
Le-3H-indolium iodide 0.909 g (3 mmol), d
200 mL of tanol was added and refluxed for 2 days. Precipitated raw
After filtering the product, add it to 100 mL ethanol for 2 hours.
It was refluxed for a while. Recycle the filtered solid with acetonitrile at low temperature.
Crystallization was performed to obtain a dye of the following general formula (6), D1.
Yield 0.38 g (37%),1H-NMR (DMSO-d6): 1.14 (t, 12
H), 1.64 (s, 12H, (CH 3)2), 1.76 (m, 2H), 1.91 (m,
4H), 3.58 (q, 8H), 3.84 (s, 6H, N+-CH3), 4.20 (t,
4H), 6.15 (s, 2H), 6.25 (d, 2H), 6.58 (d, 2H), 7.1
8 (d, 2H), 7.43 (d, 2H), 7.63 (s, 2H), 8.03 (d, 2
H), 8.44 (d, 2H)
【００３３】[0033]
【化１８】 [Chemical 18]
【００３４】合成例８
本発明の色素（D2）（Mw 1006.90）の合成:500 mL一つ
口フラスコにA3 0.43 g (1 mmol)、合成例5で得られた
インドリウム塩化合物0.93 g (3 mmol)、エタノール200
mLを入れ、3日間還流した。沈殿された生成物を濾過し
た後、アセトニトリルで低温で再結晶し、一般式（7）
の色素、D2を得た。
収率0.89 g (88％)、1H-NMR(DMSO-d6): 1.14 (t, 12H),
1.64 (s, 12H, (CH3) 2), 2.07 (m, 2H), 3.55 (q, 8
H), 3.78 (s, 6H, N+-CH3), 4.45 (t, 4H), 6.27(s, 2
H), 6.60 (d, 2H), 7.12 (d, 2H), 7.57 (d, 2H), 7.59
(d, 2H), 7.79 (s, 2H), 8.04 (d, 2H), 8.39 (d, 2H)[0034]Synthesis example 8
Synthesis of dye (D2) (Mw 1006.90) of the present invention: 500 mL each
A3 0.43 g (1 mmol) in a necked flask, obtained in Synthesis Example 5
Indolium salt compound 0.93 g (3 mmol), ethanol 200
mL was added and refluxed for 3 days. The precipitated product is filtered
And then recrystallized in acetonitrile at low temperature to give the general formula (7)
To obtain D2.
Yield 0.89 g (88%),1H-NMR (DMSO-d6): 1.14 (t, 12H),
1.64 (s, 12H, (CH3) 2), 2.07 (m, 2H), 3.55 (q, 8
H), 3.78 (s, 6H, N+-CH3), 4.45 (t, 4H), 6.27 (s, 2
H), 6.60 (d, 2H), 7.12 (d, 2H), 7.57 (d, 2H), 7.59
(d, 2H), 7.79 (s, 2H), 8.04 (d, 2H), 8.39 (d, 2H)
【００３５】[0035]
【化１９】 [Chemical 19]
【００３６】合成例９
本発明の色素（D3）（Mw 1020.93）の合成:500 mL一つ
口フラスコにA4 0.44 g (１mmol)、合成例5で得られた
インドリウム塩化合物0.93 g (3 mmol)、エタノール300
mLを入れ、3日間還流した。沈殿された生成物を濾過し
た後、更に100 mLエタノールに入れ、2時間還流した。
濾過した固体をアセトニトリルで低温で再結晶し、一般
式（7）の色素、D3を得た。
収率0.37 g (36％)、1H-NMR(DMSO-d6): 1.16 (t, 12H),
1.63 (s, 12H, (CH3) 2), 2.01 (m, 4H), 3.57 (q, 8
H), 3.78 (s, 6H, N+-CH3), 4.27 (t, 4H), 6.26(s, 2
H), 6.58 (d, 2H), 7.11 (d, 2H), 7.58-7.60 (m, 4H),
7.74 (s, 2H), 8.02 (d, 2H), 8.39 (d, 2H)[0036]Synthesis example 9
Synthesis of dye (D3) of the present invention (Mw 1020.93): 500 mL each
A4 0.44 g (1 mmol) in a necked flask, obtained in Synthesis Example 5
Indolium salt compound 0.93 g (3 mmol), ethanol 300
mL was added and refluxed for 3 days. The precipitated product is filtered
Then, the mixture was further put into 100 mL ethanol and refluxed for 2 hours.
The filtered solid was recrystallized from acetonitrile at low temperature,
A dye of formula (7), D3, was obtained.
Yield 0.37 g (36%),1H-NMR (DMSO-d6): 1.16 (t, 12H),
1.63 (s, 12H, (CH3) 2), 2.01 (m, 4H), 3.57 (q, 8
H), 3.78 (s, 6H, N+-CH3), 4.27 (t, 4H), 6.26 (s, 2
H), 6.58 (d, 2H), 7.11 (d, 2H), 7.58-7.60 (m, 4H),
7.74 (s, 2H), 8.02 (d, 2H), 8.39 (d, 2H)
【００３７】合成例１０
本発明の色素（D4）（Mw 1034.96）の合成:500 mL一つ
口フラスコにA5 0.45 g (1 mmol)、合成例5で得られた
インドリウム塩化合物0.93 g (3 mmol)、エタノール200
mLを入れ、3日間還流した。沈殿された生成物を濾過し
た後、アセトニトリルで低温で再結晶し、一般式（7）
の色素、D4を得た。
収率0.87 g (84％)、1H-NMR(DMSO-d6): 1.17 (t, 12H),
1.65 (s, 12H, (CH3) 2), 1.86 (m, 2H), 2.01 (m, 4
H), 3.59 (q, 8H), 3.80 (s, 6H, N+-CH3), 4.29(t, 4
H), 6.28 (s, 2H), 6.60 (d, 2H), 7.17 (d, 2H), 7.60
-7.63 (m, 4H), 7.76 (s, 2H), 8.03 (d, 2H), 8.41
(d, 2H)[0037]Synthesis example 10
Synthesis of dye (D4) of the present invention (Mw 1034.96): 500 mL each
A5 0.45 g (1 mmol) in a necked flask, obtained in Synthesis Example 5
Indolium salt compound 0.93 g (3 mmol), ethanol 200
mL was added and refluxed for 3 days. The precipitated product is filtered
And then recrystallized in acetonitrile at low temperature to give the general formula (7)
D4 was obtained.
Yield 0.87 g (84%),1H-NMR (DMSO-d6): 1.17 (t, 12H),
1.65 (s, 12H, (CH3) 2), 1.86 (m, 2H), 2.01 (m, 4
H), 3.59 (q, 8H), 3.80 (s, 6H, N+-CH3), 4.29 (t, 4
H), 6.28 (s, 2H), 6.60 (d, 2H), 7.17 (d, 2H), 7.60
-7.63 (m, 4H), 7.76 (s, 2H), 8.03 (d, 2H), 8.41
(d, 2H)
【００３８】合成例１１
本発明の色素（D5）（Mw 1048.98）の合成:500 mL一つ
口フラスコにA6 0.47 g (1 mmol)、合成例5で得られた
インドリウム塩化合物0.93 g (3 mmol)、エタノール200
mLを入れ、3日間還流した。沈殿された生成物を濾過し
た後、アセトニトリルで低温で再結晶し、一般式（7）
の色素、D5を得た。
収率0.96 g (91％)、1H-NMR(DMSO-d6): 1.13 (t, 12H),
1.63 (s, 12H, (CH3) 2), 1.70 (m, 4H), 1.92 (m, 4
H), 3.53 (q, 8H), 3.78 (s, 6H, N+-CH3), 4.22(t, 4
H), 6.20 (s, 2H), 6.53 (d, 2H), 7.10 (d, 2H), 7.57
(d, 2H), 7.63 (s, 2H), 7.80 (s, 2H), 8.00 (d, 2
H), 8.41 (d, 2H)[0038]Synthesis Example 11
Synthesis of dye (D5) (Mw 1048.98) of the present invention: 500 mL each
0.47 g (1 mmol) of A6 in a neck flask, obtained in Synthesis Example 5
Indolium salt compound 0.93 g (3 mmol), ethanol 200
mL was added and refluxed for 3 days. The precipitated product is filtered
And then recrystallized in acetonitrile at low temperature to give the general formula (7)
To obtain D5.
Yield 0.96 g (91%),1H-NMR (DMSO-d6): 1.13 (t, 12H),
1.63 (s, 12H, (CH3) 2), 1.70 (m, 4H), 1.92 (m, 4
H), 3.53 (q, 8H), 3.78 (s, 6H, N+-CH3), 4.22 (t, 4
H), 6.20 (s, 2H), 6.53 (d, 2H), 7.10 (d, 2H), 7.57
(d, 2H), 7.63 (s, 2H), 7.80 (s, 2H), 8.00 (d, 2
H), 8.41 (d, 2H)
【００３９】合成例１２
本発明の色素（D6）（Mw 1075.79）の合成:500 mL一つ
口フラスコにA3 0.43 g (1 mmol)、反応式2により製造
した該当インドリウム塩化合物1.03 g (3 mmol)、エタ
ノール200 mLを入れ、3日間還流した。沈殿された生成
物を濾過した後、アセトニトリルで低温で再結晶し、一
般式（8）の色素、D6を得た。
収率0.58 g (54％)、1H-NMR(DMSO-d6): 1.17 (t, 12H),
1.66 (s, 12H, (CH3) 2), 2.06 (m, 2H), 3.61 (q, 8
H), 3.74 (s, 6H, N+-CH3), 4.47 (t, 4H), 6.34(s, 2
H), 6.66 (d, 2H), 7.05 (d, 2H), 7.51 (s, 2H), 7.76
(s, 2H), 8.09 (d, 2H), 8.44 (d, 2H)[0039]Synthesis Example 12
Synthesis of dye (D6) (Mw 1075.79) of the present invention: 500 mL each
0.43 g (1 mmol) of A3 in a necked flask, prepared by reaction formula 2
Corresponding indolium salt compound 1.03 g (3 mmol),
200 mL of knoll was added and refluxed for 3 days. Precipitated production
The product was filtered and then recrystallized from acetonitrile at low temperature.
D6, a dye of general formula (8), was obtained.
Yield 0.58 g (54%),1H-NMR (DMSO-d6): 1.17 (t, 12H),
1.66 (s, 12H, (CH3) 2), 2.06 (m, 2H), 3.61 (q, 8
H), 3.74 (s, 6H, N+-CH3), 4.47 (t, 4H), 6.34 (s, 2
H), 6.66 (d, 2H), 7.05 (d, 2H), 7.51 (s, 2H), 7.76
(s, 2H), 8.09 (d, 2H), 8.44 (d, 2H)
【００４０】[0040]
【化２０】 [Chemical 20]
【００４１】合成例１３
本発明の色素（D7）（Mw 1090.24）の合成:500 mL一つ
口フラスコにA4 0.44 g (1 mmol)、反応式2により製造
した該当インドリウム塩化合物1.03 g (3 mmol)、エタ
ノール200 mLを入れ、3日間還流した。沈殿された生成
物を濾過した後、アセトニトリルで低温で再結晶し、一
般式（8）の色素、D7を得た。
収率0.77 g (70％)、1H-NMR(DMSO-d6): 1.21 (t, 12H),
1.73 (s, 12H, (CH3) 2), 2.18 (m, 4H), 3.65 (q, 8
H), 3.76 (s, 6H, N+-CH3), 4.36 (t, 4H), 6.33(s, 2
H), 6.67 (d, 2H), 7.07 (d, 2H), 7.53 (s, 2H), 7.80
(s, 2H), 8.12 (d, 2H), 8.49 (d, 2H)[0041]Synthesis Example 13
Synthesis of dye (D7) of the present invention (Mw 1090.24): 500 mL each
A4 0.44 g (1 mmol) in a necked flask, prepared by reaction formula 2
Corresponding indolium salt compound 1.03 g (3 mmol),
200 mL of knoll was added and refluxed for 3 days. Precipitated production
The product was filtered and then recrystallized from acetonitrile at low temperature.
D7, a dye of general formula (8), was obtained.
Yield 0.77 g (70%),1H-NMR (DMSO-d6): 1.21 (t, 12H),
1.73 (s, 12H, (CH3) 2), 2.18 (m, 4H), 3.65 (q, 8
H), 3.76 (s, 6H, N+-CH3), 4.36 (t, 4H), 6.33 (s, 2
H), 6.67 (d, 2H), 7.07 (d, 2H), 7.53 (s, 2H), 7.80
(s, 2H), 8.12 (d, 2H), 8.49 (d, 2H)
【００４２】合成例１４
本発明の色素（D8）（Mw 1111.85）の合成:500 mL一つ
口フラスコにA4 0.45 g (1 mmol)、反応式2により製造
した該当インドリウム塩化合物1.03 g (3 mmol, Mw 35
3.67)、エタノール200 mLを入れ、3日間還流した。沈殿
された生成物を濾過した後、アセトニトリルで低温で再
結晶し、下記一般式（9）の色素、D8を得た。
収率1.03 g (93％)、1H-NMR(DMSO-d6): 1.17 (t, 12H),
1.63 (s, 12H, (CH3) 2), 2.12 (m, 4H), 3.58 (q, 8
H), 3.78 (s, 6H, N+-CH3), 4.31 (t, 4H), 6.27(s, 2
H), 6.60 (d, 2H), 7.12 (d, 2H), 7.55-7.57 (m, 4H),
7.77 (s, 2H), 8.04 (d, 2H), 8.36 (d, 2H)[0042]Synthesis Example 14
Synthesis of dye (D8) of the present invention (Mw 1111.85): 500 mL each
0.45 g (1 mmol) of A4 in a necked flask, prepared according to reaction formula 2.
Corresponding Indolium salt compound 1.03 g (3 mmol, Mw 35
3.67) and 200 mL of ethanol were added, and the mixture was refluxed for 3 days. Precipitation
The filtered product is filtered and then re-cooled with acetonitrile at low temperature.
Crystallization gave D8, a dye of the following general formula (9).
Yield 1.03 g (93%),1H-NMR (DMSO-d6): 1.17 (t, 12H),
1.63 (s, 12H, (CH3) 2), 2.12 (m, 4H), 3.58 (q, 8
H), 3.78 (s, 6H, N+-CH3), 4.31 (t, 4H), 6.27 (s, 2
H), 6.60 (d, 2H), 7.12 (d, 2H), 7.55-7.57 (m, 4H),
7.77 (s, 2H), 8.04 (d, 2H), 8.36 (d, 2H)
【００４３】[0043]
【化２１】 [Chemical 21]
【００４４】合成例１５
本発明の色素（D9）（Mw 1119.01）の合成:500 mL一つ
口フラスコにA3 0.43 g (1 mmol)、反応式2により製造
した該当インドリウム塩化合物1.09 g (3 mmol, Mw 36
4.22)、エタノール200 mLを入れ、3日間還流した。沈殿
された生成物を濾過した後、アセトニトリルで低温で再
結晶し、下記一般式（10）の色素、D9を得た。
収率1.0 g (89％)、1H-NMR(DMSO-d6): 1.19 (t, 12H),
1.73 (s, 12H, (CH3)2), 2.06 (m, 2H), 3.66 (q, 8H),
3.82 (s, 6H, N+-CH3), 4.52 (t, 4H), 6.34(s, 2H),
6.75 (d, 2H), 7.25 (d, 2H), 7.74 (d, 2H), 7.77 (d,
2H), 8.17 (s, 2H), 8.44 (d, 2H), 8.56 (d, 2H) Synthesis Example 15 Synthesis of dye (D9) (Mw 1119.01) of the present invention: 0.43 g (1 mmol) of A3 in a 500 mL one-necked flask, 1.09 g (3 mmol, Mw 36
4.22) and 200 mL of ethanol were added and refluxed for 3 days. The precipitated product was filtered and then recrystallized from acetonitrile at a low temperature to obtain a dye of the following general formula (10), D9. Yield 1.0 g (89%), 1 H-NMR (DMSO-d 6 ): 1.19 (t, 12H),
1.73 (s, 12H, (CH 3 ) 2 ), 2.06 (m, 2H), 3.66 (q, 8H),
3.82 (s, 6H, N + -CH 3 ), 4.52 (t, 4H), 6.34 (s, 2H),
6.75 (d, 2H), 7.25 (d, 2H), 7.74 (d, 2H), 7.77 (d,
2H), 8.17 (s, 2H), 8.44 (d, 2H), 8.56 (d, 2H)
【００４５】[0045]
【化２２】 [Chemical formula 22]
【００４６】合成例１６
本発明の色素（D10）（Mw 1129.13）の合成:500 mL一つ
口フラスコにA3 0.43 g (1 mmol)、合成例6で得られた
インドリウム塩化合物1.11 g (3 mmol, Mw 369.29)、エ
タノール200 mLを入れ、5日間還流した。沈殿された生
成物を濾過した後、アセトニトリルで低温で再結晶し、
一般式(11)の色素、D10を得た。
収率0.55 g (49％)、1H-NMR(DMSO-d6): 1.15 (t, 12H),
1.85 (s, 12H, (CH3) 2), 2.62 (m, 2H), 3.59 (q, 8
H), 3.98 (s, 6H, N+-CH3), 4.59 (t, 4H), 6.43(s, 2
H), 6.66 (d, 2H), 7.26 (d, 2H), 7.60 (t, 2H), 7.70
(t, 2H), 7.90 (d, 2H), 8.10-8.21 (m, 8H), 8.60
(d, 2H)[0046]Synthesis Example 16
Synthesis of dye (D10) (Mw 1129.13) of the present invention: 500 mL each
A3 0.43 g (1 mmol) in a necked flask, obtained in Synthesis Example 6
Indolium salt compound 1.11 g (3 mmol, Mw 369.29),
200 mL of tanol was added and refluxed for 5 days. Precipitated raw
The product was filtered and then recrystallized from acetonitrile at low temperature.
A dye of the general formula (11), D10, was obtained.
Yield 0.55 g (49%),1H-NMR (DMSO-d6): 1.15 (t, 12H),
1.85 (s, 12H, (CH3) 2), 2.62 (m, 2H), 3.59 (q, 8
H), 3.98 (s, 6H, N+-CH3), 4.59 (t, 4H), 6.43 (s, 2
H), 6.66 (d, 2H), 7.26 (d, 2H), 7.60 (t, 2H), 7.70
(t, 2H), 7.90 (d, 2H), 8.10-8.21 (m, 8H), 8.60
(d, 2H)
【００４７】[0047]
【化２３】 [Chemical formula 23]
【００４８】合成例１７
本発明の色素（D11）（Mw 1143.158）の合成:500 mL一
つ口フラスコにA4 0.44 g (1 mmol)、合成例6で得られ
たインドリウム塩化合物1.10 g (3 mmol)、エタノール2
00 mLを入れ、5日間還流した。沈殿された生成物を濾過
した後、アセトニトリルで低温で再結晶し、一般式（1
1）の色素、D11を得た。
収率0.65 g (57％)、1H-NMR(DMSO-d6): 1.21 (t, 12H),
1.89 (s, 12H, (CH3) 2), 2.26 (m, 4H), 3.62 (q, 8
H), 3.96 (s, 6H, N+-CH3), 4.43 (t, 4H), 6.38(s, 2
H), 6.65 (d, 2H), 7.22 (d, 2H), 7.55-7.58 (m, 4H),
7.87 (d, 2H), 8.09-8.18 (m, 8H), 8.61 (d, 2H)[0048]Synthesis Example 17
Synthesis of dye (D11) (Mw 1143.158) of the present invention: 500 mL
A4 0.44 g (1 mmol) in a two-necked flask, obtained in Synthesis Example 6
Indolinium salt compound 1.10 g (3 mmol), ethanol 2
00 mL was added and refluxed for 5 days. Filter the precipitated product
After that, it was recrystallized from acetonitrile at a low temperature, and the general formula (1
The dye of 1), D11, was obtained.
Yield 0.65 g (57%),1H-NMR (DMSO-d6): 1.21 (t, 12H),
1.89 (s, 12H, (CH3) 2), 2.26 (m, 4H), 3.62 (q, 8
H), 3.96 (s, 6H, N+-CH3), 4.43 (t, 4H), 6.38 (s, 2
H), 6.65 (d, 2H), 7.22 (d, 2H), 7.55-7.58 (m, 4H),
7.87 (d, 2H), 8.09-8.18 (m, 8H), 8.61 (d, 2H)
【００４９】合成例１８
本発明の色素（D12）（Mw 1157.19）の合成:500 mL一つ
口フラスコにA5 0.45 g (1 mmol)、合成例6で得られた
インドリウム塩化合物1.10 g (3 mmol)、エタノール200
mLを入れ、5日間還流した。沈殿された生成物を濾過し
た後、アセトニトリルで低温で再結晶し、一般式（11）
の色素、D12を得た。
収率0.65 g (56％)、1H-NMR(DMSO-d6): 1.14 (t, 12H),
1.89 (s, 12H, (CH3) 2), 1.98 (m, 2H), 2.12 (m, 4
H), 3.51 (q, 8H), 3.97 (s, 6H, N+-CH3), 4.41(t, 4
H), 6.36 (s, 2H), 6.53 (d, 2H), 7.20 (d, 2H), 7.58
-7.62 (m, 4H), 7.90 (d, 2H), 8.07-8.21 (m, 8H), 8.
56 (d, 2H)[0049]Synthesis Example 18
Synthesis of dye (D12) of the present invention (Mw 1157.19): 500 mL each
A5 0.45 g (1 mmol) in a necked flask, obtained in Synthesis Example 6
Indolium salt compound 1.10 g (3 mmol), ethanol 200
mL was added and refluxed for 5 days. The precipitated product is filtered
And then recrystallized in acetonitrile at low temperature to give the general formula (11)
To obtain D12.
Yield 0.65 g (56%),1H-NMR (DMSO-d6): 1.14 (t, 12H),
1.89 (s, 12H, (CH3) 2), 1.98 (m, 2H), 2.12 (m, 4
H), 3.51 (q, 8H), 3.97 (s, 6H, N+-CH3), 4.41 (t, 4
H), 6.36 (s, 2H), 6.53 (d, 2H), 7.20 (d, 2H), 7.58
-7.62 (m, 4H), 7.90 (d, 2H), 8.07-8.21 (m, 8H), 8.
56 (d, 2H)
【００５０】合成例１９
本発明の色素（D13）（Mw 1038.10）の合成:500 mL一つ
口フラスコにA3 0.43 g (1 mmol)、反応式2により製造
した該当インドリウム塩化合物1.30 g (4 mmol, Mw 32
3.77)、エタノール200 mLを入れ、5日間還流した。沈殿
された生成物を濾過した後、アセトニトリルで低温で再
結晶し、一般式（12）の色素、D13を得た。
収率0.79 g (76％)、1H-NMR(DMSO-d6): 1.15 (t, 12H),
1.85 (s, 12H, (CH3) 2), 2.61 (m, 2H), 3.59 (q, 8
H), 3.98 (s, 6H, N+-CH3), 4.58 (t, 4H), 6.43(s, 2
H), 6.66 (d, 2H), 7.26 (d, 2H), 7.60 (t, 2H), 7.70
(t, 2H), 7.90 (d, 2H), 8.10-8.21 (m, 8H), 8.60
(d, 2H)[0050]Synthesis Example 19
Synthesis of dye (D13) of the present invention (Mw 1038.10): 500 mL each
0.43 g (1 mmol) of A3 in a necked flask, prepared by reaction formula 2
Corresponding Indolium salt compound 1.30 g (4 mmol, Mw 32
3.77) and 200 mL of ethanol were added, and the mixture was refluxed for 5 days. Precipitation
The filtered product is filtered and then re-cooled with acetonitrile at low temperature.
Crystallization gave D13, a dye of general formula (12).
Yield 0.79 g (76%),1H-NMR (DMSO-d6): 1.15 (t, 12H),
1.85 (s, 12H, (CH3) 2), 2.61 (m, 2H), 3.59 (q, 8
H), 3.98 (s, 6H, N+-CH3), 4.58 (t, 4H), 6.43 (s, 2
H), 6.66 (d, 2H), 7.26 (d, 2H), 7.60 (t, 2H), 7.70
(t, 2H), 7.90 (d, 2H), 8.10-8.21 (m, 8H), 8.60
(d, 2H)
【００５１】[0051]
【化２４】 [Chemical formula 24]
【００５２】合成例２０
本発明の色素（D14）（Mw 1052.13）の合成:500 mL一つ
口フラスコにA4 0.44 g (1 mmol)、反応式2により製造
した該当インドリウム塩化合物1.30 g (4 mmol)、エタ
ノール200 mLを入れ、5日間還流した。沈殿された生成
物を濾過した後、アセトニトリルで低温で再結晶し、一
般式（12）の色素、D14を得た。
収率0.93 g (88％)、1H-NMR(DMSO-d6): 1.21 (t, 12H),
1.89 (s, 12H, (CH3) 2), 2.26 (m, 4H), 3.63 (q, 8
H), 3.96 (s, 6H, N+-CH3), 4.44 (t, 4H), 6.40(s, 2
H), 6.65 (d, 2H), 7.22 (d, 2H), 7.57-7.60 (m, 4H),
7.88 (d, 2H), 8.11-8.19 (m, 8H), 8.60 (d, 2H)[0052]Synthesis example 20
Synthesis of dye (D14) (Mw 1052.13) of the present invention: 500 mL each
A4 0.44 g (1 mmol) in a necked flask, prepared by reaction formula 2
Corresponding indolium salt compound 1.30 g (4 mmol),
200 mL of knoll was added and refluxed for 5 days. Precipitated production
The product was filtered and then recrystallized from acetonitrile at low temperature.
D14, a dye of general formula (12), was obtained.
Yield 0.93 g (88%),1H-NMR (DMSO-d6): 1.21 (t, 12H),
1.89 (s, 12H, (CH3) 2), 2.26 (m, 4H), 3.63 (q, 8
H), 3.96 (s, 6H, N+-CH3), 4.44 (t, 4H), 6.40 (s, 2
H), 6.65 (d, 2H), 7.22 (d, 2H), 7.57-7.60 (m, 4H),
7.88 (d, 2H), 8.11-8.19 (m, 8H), 8.60 (d, 2H)
【００５３】合成例２１
本発明の色素（D15）（Mw 1066.16）の合成:500 mL一つ
口フラスコにA4 0.45 g (1 mmol)、反応式2により製造
した該当インドリウム塩化合物0.97 g (3 mmol)、エタ
ノール200 mLを入れ、5日間還流した。沈殿された生成
物を濾過した後、アセトニトリルで低温で再結晶し、一
般式（12）の色素、D15を得た。
収率0.29 g (27％)、1H-NMR(DMSO-d6): 1.12 (t, 12H),
1.88 (s, 12H, (CH3) 2), 1.95 (m, 2H), 2.10 (m, 4
H), 3.52 (q, 8H), 3.96 (s, 6H, N+-CH3), 4.36(t, 4
H), 6.32 (s, 2H), 6.51 (d, 2H), 7.19 (d, 2H), 7.58
-7.62 (m, 4H), 7.91 (d, 2H), 8.06-8.20 (m, 8H), 8.
52 (d, 2H)[0053]Synthesis Example 21
Synthesis of dye (D15) (Mw 1066.16) of the present invention: 500 mL each
0.45 g (1 mmol) of A4 in a necked flask, prepared according to reaction formula 2.
Corresponding indolium salt compound 0.97 g (3 mmol),
200 mL of knoll was added and refluxed for 5 days. Precipitated production
The product was filtered and then recrystallized from acetonitrile at low temperature.
D15, a dye of general formula (12), was obtained.
Yield 0.29 g (27%),1H-NMR (DMSO-d6): 1.12 (t, 12H),
1.88 (s, 12H, (CH3) 2), 1.95 (m, 2H), 2.10 (m, 4
H), 3.52 (q, 8H), 3.96 (s, 6H, N+-CH3), 4.36 (t, 4
H), 6.32 (s, 2H), 6.51 (d, 2H), 7.19 (d, 2H), 7.58
-7.62 (m, 4H), 7.91 (d, 2H), 8.06-8.20 (m, 8H), 8.
52 (d, 2H)
【００５４】合成例２２
本発明の色素（D16）（Mw 1068）の合成:500 mL一つ口
フラスコにA4 0.45 g (1 mmol)、反応式2により製造し
た該当インドリウム塩化合物1 g (3 mmol)、エタノール
200 mLを入れ、5日間還流した。沈殿された生成物を濾
過した後、アセトニトリルで低温で再結晶し、一般式
（13）の色素、D16を得た。
収率0.74 g (70％)、1H-NMR(DMSO-d6): 1.21 (t, 12H),
1.37 (t, N+-CH2 CH3 ,3H), 1.89 (s, 12H, (CH3)2), 1.
95 (m, 2H), 2.10 (m, 4H), 3.52 (q, 8H), 4.36 (t, 4
H), 4.51 (q, N+-CH2, 4H), 6.32 (s, 2H), 6.51 (d, 2
H), 7.19 (d,2H), 7.58-7.62 (m, 4H), 7.91 (d, 2H),
8.06-8.20 (m, 8H), 8.52 (d, 2H) Synthesis Example 22 Synthesis of dye (D16) (Mw 1068) of the present invention: 0.45 g (1 mmol) of A4 in a 500 mL one-necked flask, 1 g (3 g) of the corresponding indium salt compound prepared by the reaction scheme 2. mmol), ethanol
200 mL was added and refluxed for 5 days. The precipitated product was filtered and then recrystallized from acetonitrile at a low temperature to obtain a dye of the general formula (13), D16. Yield 0.74 g (70%), 1 H-NMR (DMSO-d 6 ): 1.21 (t, 12H),
1.37 (t, N + -CH 2 CH 3 , 3H), 1.89 (s, 12H, (CH 3 ) 2 ), 1.
95 (m, 2H), 2.10 (m, 4H), 3.52 (q, 8H), 4.36 (t, 4
H), 4.51 (q, N + -CH 2 , 4H), 6.32 (s, 2H), 6.51 (d, 2
H), 7.19 (d, 2H), 7.58-7.62 (m, 4H), 7.91 (d, 2H),
8.06-8.20 (m, 8H), 8.52 (d, 2H)
【００５５】[0055]
【化２５】 [Chemical 25]
【００５６】<色素の物性評価>表1に上記合成例で製造
した色素の最大吸収波長（ポリカルボネート基板上及び
テトラフルオロプロパノール溶媒内)、モル吸光係数、
分解温度を表した。各色素の最大吸収波長は590〜615 n
mであり（紫外線-可視光線分光器）、モル吸光係数は17
0,000〜280,000であった。分解温度は221〜293 ℃ （DT
Aで10 ℃/min.の速度で窒素雰囲気で測定）であった。
ベンゼンを含有したインドリウム塩から合成された色素
（D1〜D9）は、ナフタレンを含有したインドリウム塩か
ら合成された色素(D10〜D16）より最大吸収波長が低
く、モル吸光係数は高く、分解温度は低かった。<Evaluation of Physical Properties of Dye> In Table 1, the maximum absorption wavelength (on a polycarbonate substrate and in a tetrafluoropropanol solvent) of the dye produced in the above Synthesis Example, the molar extinction coefficient,
The decomposition temperature was expressed. The maximum absorption wavelength of each dye is 590 to 615 n
m (UV-visible spectrometer), molar extinction coefficient 17
It was between 0,000 and 280,000. Decomposition temperature is 221-293 ° C (DT
A was measured in a nitrogen atmosphere at a rate of 10 ° C / min.).
Dyes synthesized from benzene-containing indolium salts (D1 to D9) have lower maximum absorption wavelength, higher molar absorption coefficient, and decomposition than dyes synthesized from indolium salts containing naphthalene (D10 to D16). The temperature was low.
【００５７】[0057]
【表１】 [Table 1]
【００５８】[0058]
【発明の効果】本発明により製造された色素は、合成上
電子受容基又は電子供与基を多様に変化させることによ
り、色素の紫外線-可視光線吸収スペクトルを長波長又
は短波長に移動させることが容易である。従って、この
ような光学的及び熱的特性を利用して色素の吸収スペク
トルを光記録波長に適切に合せ、光ディスクの記録層物
質として使用することができる。INDUSTRIAL APPLICABILITY The dyes produced according to the present invention can shift the ultraviolet-visible absorption spectrum of the dyes to long wavelength or short wavelength by variously changing the electron accepting group or the electron donating group in terms of synthesis. It's easy. Therefore, the absorption spectrum of the dye can be appropriately adjusted to the optical recording wavelength by utilizing such optical and thermal characteristics, and the dye can be used as a recording layer material of an optical disc.
フロントページの続き (72)発明者 李 哲周 大韓民国ソウル特別市東大門区清涼里１洞 美宙アパート４−1411 (72)発明者 白 賢真 大韓民国ソウル特別市江北区水踰５洞430 −６ (72)発明者 宋 東▲ヒョン▼ 大韓民国ソウル特別市冠岳区新林９洞344 −102 Ｆターム(参考） 4C204 AB01 BB09 DB15 EB10 FB03 GB01 GB24 GB32 4H056 CA02 CA05 CB03 CC02 CE03 CE06 DD02 DD03 Continued front page (72) Inventor, Tetsu Zhou 1 Cheongryeo-ri, Dongdaemun-gu, Seoul, South Korea Misora Apartment 4-1411 (72) Inventor Ken Shiro 430, Suede 5-gil, Gangbuk-gu, Seoul, Republic of Korea -6 (72) Inventor Song Dong ▲ Hyun ▼ 344, Shinlin 9-dong, Gwanak-gu, Seoul, South Korea −102 F-term (reference) 4C204 AB01 BB09 DB15 EB10 FB03 GB01 GB24 GB32 4H056 CA02 CA05 CB03 CC02 CE03 CE06 DD02 DD03
Claims (2)
水素、ハロゲン又はニトロ基であるか、もしくは一緒に
ベンゼン環を形成することができる。R5はC1-C 4のアル
キル基である。R6はC3-C6のアルキレンであり、R7はC1-
C4のアルキル基である。XはOであり、ZはClO4、PF6、BF
4又はハロゲンである。）1. A dye of the following general formula (1). [Chemical 1] (In the formula, R1~ RFourMay be the same or different from each other,
Hydrogen, a halogen or a nitro group, or together
A benzene ring can be formed. RFiveIs C1-C FourThe al
It is a kill group. R6Is C3-C6Is an alkylene of R7Is C1-
CFourIs an alkyl group. X is O and Z is ClOFour, PF6, BF
FourOr halogen. )
下記一般式（3）の脂肪族ジハライドを溶媒に溶解し、
塩基を使用して加熱縮合反応し、下記一般式（4）のジ
アルデヒド化合物を製造する段階、及び得られたジアル
デヒド化合物を下記一般式（5）のインドリウム塩化合
物をエタノールで還流、脱水反応させる段階を含むこと
を特徴とする請求項１記載の色素の製造方法。 【化２】 【化３】 【化４】 【化５】 (式中、halはCl、Br又はIであり、nは3, 4, 5又は6であ
る。R1〜R5、R7、X及びZは上記一般式（1）と同様であ
る。)2. An aldehyde compound represented by the following general formula (2) and an aliphatic dihalide represented by the following general formula (3) are dissolved in a solvent,
A step of producing a dialdehyde compound of the following general formula (4) by a heat condensation reaction using a base, and refluxing the obtained dialdehyde compound with an indolium salt compound of the following general formula (5) with ethanol. The method for producing a dye according to claim 1, comprising a step of reacting. [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] (In the formula, hal is Cl, Br or I, and n is 3, 4, 5 or 6. R 1 to R 5 , R 7 , X and Z are the same as those in the general formula (1). )
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2001-0060900A KR100406460B1 (en) | 2001-09-29 | 2001-09-29 | Coupled Styrylcyanine Dyes and Their Synthesis |
| KR2001-60900 | 2001-09-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003119404A true JP2003119404A (en) | 2003-04-23 |
| JP3652637B2 JP3652637B2 (en) | 2005-05-25 |
Family
ID=36083897
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001346290A Expired - Fee Related JP3652637B2 (en) | 2001-09-29 | 2001-11-12 | Coupled styryl cyanine dye and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3652637B2 (en) |
| KR (1) | KR100406460B1 (en) |
| TW (1) | TWI230183B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101577491B1 (en) | 2012-12-17 | 2015-12-15 | 주식회사 엘지화학 | Styryl-based compound and dye comprising the compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH597311A5 (en) * | 1974-05-14 | 1978-03-31 | Sandoz Ag | |
| US4463076A (en) * | 1983-02-22 | 1984-07-31 | Eastman Kodak Company | Merocyanine-cyanine-merocyanine (MCM) electrically photosensitive colorants for photoelectrophoretic imaging |
| JPH07119367B2 (en) * | 1987-11-24 | 1995-12-20 | 株式会社日本化学工業所 | Cationic dye |
| EP0825927B1 (en) * | 1996-04-23 | 1999-08-11 | Kodak Polychrome Graphics Company Ltd. | Lithographic printing form precursor and its use by heat imaging |
| JP2000345062A (en) * | 1999-04-02 | 2000-12-12 | Oji Kagaku Kenkyusho:Kk | Production of indolenine cyanine color or indolenine styryl color |
| DE19917713A1 (en) * | 1999-04-09 | 2000-10-19 | Diagnostikforschung Inst | Short-chain peptide-dye conjugates as contrast agents for optical diagnostics |
| JP2002206061A (en) * | 2000-07-05 | 2002-07-26 | Hayashibara Biochem Lab Inc | Styryl dye |
-
2001
- 2001-09-29 KR KR10-2001-0060900A patent/KR100406460B1/en not_active IP Right Cessation
- 2001-11-12 JP JP2001346290A patent/JP3652637B2/en not_active Expired - Fee Related
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2002
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101577491B1 (en) | 2012-12-17 | 2015-12-15 | 주식회사 엘지화학 | Styryl-based compound and dye comprising the compound |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030027559A (en) | 2003-04-07 |
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| KR100406460B1 (en) | 2003-11-19 |
| JP3652637B2 (en) | 2005-05-25 |
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