JPH01287175A - Naphthalocyanine compound - Google Patents
Naphthalocyanine compoundInfo
- Publication number
- JPH01287175A JPH01287175A JP63114737A JP11473788A JPH01287175A JP H01287175 A JPH01287175 A JP H01287175A JP 63114737 A JP63114737 A JP 63114737A JP 11473788 A JP11473788 A JP 11473788A JP H01287175 A JPH01287175 A JP H01287175A
- Authority
- JP
- Japan
- Prior art keywords
- tert
- amylthio
- product
- purified
- elemental analysis
- 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.)
- Pending
Links
- -1 Naphthalocyanine compound Chemical class 0.000 title claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 4
- 150000005309 metal halides Chemical class 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 16
- 239000012043 crude product Substances 0.000 abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 12
- 239000004202 carbamide Substances 0.000 abstract description 12
- 238000004440 column chromatography Methods 0.000 abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 125000005287 vanadyl group Chemical group 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 4
- XPDVJLMQJNOQMN-UHFFFAOYSA-N 6-(2-methylbutan-2-ylsulfanyl)naphthalene-2,3-dicarbonitrile Chemical compound C1=C(C#N)C(C#N)=CC2=CC(SC(C)(C)CC)=CC=C21 XPDVJLMQJNOQMN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 238000000921 elemental analysis Methods 0.000 description 22
- 239000000843 powder Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 230000008033 biological extinction Effects 0.000 description 11
- 239000012264 purified product Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical class N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000012015 optical character recognition Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000011011 black crystal Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- KNBYJRSSFXTESR-UHFFFAOYSA-N naphthalene-2,3-dicarbonitrile Chemical compound C1=CC=C2C=C(C#N)C(C#N)=CC2=C1 KNBYJRSSFXTESR-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 102200074327 rs587783521 Human genes 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Optical Record Carriers And Manufacture Thereof (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規なナフタロシアニン化合物に関し、詳しく
は近赤外吸収性色素として有用な新規なナフタロシアニ
ン化合物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel naphthalocyanine compound, and more particularly to a novel naphthalocyanine compound useful as a near-infrared absorbing dye.
近年、コンパクトディスク、ビデオディスク、液晶表示
装置、光学文字読取り機等における書込みあるいは読取
りの為に、半導体レーザ光を利用することが実用化され
ている。半導体レーザ光による書込み又は読取りの為に
は、半導体レーザ光即ち近赤外を吸収する物質が不可欠
である。In recent years, the use of semiconductor laser light has been put into practical use for writing or reading in compact discs, video discs, liquid crystal display devices, optical character readers, and the like. For writing or reading using semiconductor laser light, a substance that absorbs semiconductor laser light, that is, near-infrared light, is essential.
近赤外光を吸収する有機色素としては従来、シアニン色
素がよく知られている。しかしシアニン色素は反面、耐
光堅牢度が極めて低いので、これを使用する場合には多
くの制約を受けざるを得ない。また、オキシムやチオー
ルの金属錯体もその能力は低いが近赤外光を吸収する有
機色素として知られている。しかし、これはある種の媒
体中では錯体から金属が脱離して近赤外光の吸収能力が
消失する欠点がある。Cyanine dyes are well known as organic dyes that absorb near-infrared light. However, cyanine dyes, on the other hand, have extremely low light fastness, so their use must be subject to many restrictions. Metal complexes of oximes and thiols are also known as organic dyes that absorb near-infrared light, although their ability is low. However, this has the disadvantage that in certain media, the metal is desorbed from the complex and the ability to absorb near-infrared light is lost.
本発明者らは、近赤外吸収性色素における前記の諸問題
を解決する為にナフタロシアニン化合物に着１」シ、こ
れを形成するナフタレン環にアルキルチオ基、無置換も
しくはアルキル基、ハロゲン原子等の置換基を有するア
リールチオ基を導入することにより近赤外光を吸収する
能力に著しく優れるのみならず、種々の有機媒体への溶
解性にも優れる新規なナフタロシアニン化合物を得るこ
とが出来ることを見出して、木発明に至ったものである
。従って本発明は近赤外光を吸収する能力に優れると共
に種々の有機媒体への溶解性にも優れる新規なナフタロ
シアニン化合物を提供することを目的とする。In order to solve the above-mentioned problems in near-infrared absorbing dyes, the present inventors have developed a naphthalocyanine compound with an alkylthio group, an unsubstituted or alkyl group, a halogen atom, etc. in the naphthalene ring forming the compound. By introducing an arylthio group having a substituent of This discovery led to the invention of wood. Therefore, an object of the present invention is to provide a novel naphthalocyanine compound that has an excellent ability to absorb near-infrared light and also has excellent solubility in various organic media.
木発明によるナフタロシアニン化合物は−・般式（式中
Ｒ＋ 、Ｒ：ｚ、Ｒ３ｔ Ｒ４はそれぞれアルキル基、
置換基を有してもよいフェニル基または置換基を有して
もよいナフチル基を示し、ｎｌ、ｎ７ 、ｎ３、ｎ４は
それぞれ１〜４の整数を示し、Ｍは水素２原子、金属、
金属酸化物または金属ハロゲン化物を示す。）で表され
る。The naphthalocyanine compound according to the wood invention has the general formula (where R+, R:z, R3t and R4 are each an alkyl group,
It represents a phenyl group that may have a substituent or a naphthyl group that may have a substituent, nl, n7, n3, and n4 each represent an integer of 1 to 4, and M represents two hydrogen atoms, a metal,
Indicates a metal oxide or metal halide. ).
一般式（Ｉ）においてＲ＋ 、Ｒ２、Ｒ３、Ｒ４のアル
キル基は好ましくは炭素数１〜１８のアルキル基であり
、フェニル基およびナフチル基の置換基は炭素数Ｉ〜１
８のアルキルおよびハロゲン原子である。Ｒ，Ｓ、Ｒ２
Ｓ、Ｒ３Ｓ、Ｒ４Ｓの結合位置はそれぞれナフタレン環
のいずれの位置であっても良い。またＭの金属、金属酸
化物、金属ハロゲン化物の好ましい具体例としてＣｕ、
Ｎｉ、Ｍｇ、Ｐｂ、Ｐｄ、Ｖ、Ｃｏ、Ｎｂ、Ａ１．Ｓｎ
、Ｉｎ、Ｆｅ、Ｇｅおよびこれらの耐化物、塩化物等を
挙げることが出来るが、これに制限されるものでない。In the general formula (I), the alkyl groups of R+, R2, R3, and R4 are preferably alkyl groups having 1 to 18 carbon atoms, and the substituents of the phenyl group and naphthyl group have 1 to 1 carbon atoms.
8 alkyl and halogen atoms. R, S, R2
The bonding positions of S, R3S, and R4S may be any position on the naphthalene ring. Preferred specific examples of metals, metal oxides, and metal halides of M include Cu,
Ni, Mg, Pb, Pd, V, Co, Nb, A1. Sn
, In, Fe, Ge, and their resistant substances, chlorides, etc., but are not limited thereto.
本発明の一般式（Ｉ）で示されるナフタロシアニン化合
物は、７５０〜９００ｎｍの近赤外光を吸収する能力に
優れる緑色又は黒色の結晶又は粉末であり、耐光性、耐
熱性、耐酸性、耐アルカリ性に優れ、しかも種々の有機
溶剤、液晶、樹脂等の有機媒体によく溶解し近赤外吸収
色素として有用である。The naphthalocyanine compound represented by the general formula (I) of the present invention is a green or black crystal or powder that has an excellent ability to absorb near-infrared light of 750 to 900 nm, and has light resistance, heat resistance, acid resistance, and resistance to light. It has excellent alkalinity and dissolves well in various organic solvents, liquid crystals, resins, and other organic media, making it useful as a near-infrared absorbing dye.
本発明のナフタロシアニン化合物はメルカプト置換−２
，３−ジシアノナフタレンから公知の方法で得ることが
出来る。The naphthalocyanine compounds of the present invention have mercapto-substituted -2
, 3-dicyanonaphthalene by a known method.
以下に実施例を挙げて本発明を具体的に説明するが本発
明はこれらの実施例に限定されるものでない。The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.
実施例１
テトう（ｔｅｒｔ−アミルチオ）ナフタロシアニンバナ
ジルの製造
６−ｔｅｒｔ−アミルチオ−２，３−ジシアノナフタレ
ン４ｇ、三塩化バナジル０．８ｇ及び尿素２０ｇを １
８５〜２００°Ｃで３時間反応した。冷却後、固化した
反応生成物を粗砕し、５％塩酸３００ｍ文と８０°Ｃで
３０分間攪拌した。次いで濾取したケーキを１０％水酸
化ナトリウム水溶液３００ｍＪＬと８０°Ｃにて３０分
間撹拌した後、固形物を濾取した。再度１０％水酸化ナ
トリウム水溶液３００ｍＭで同様の処理後湯洗した。こ
のケーキをメタノール３００ｍＪｌｊと還流した後、固
形物を濾取し乾燥して粗製物３．５ｇを得た。この粗製
物をトルエン１５０ｍＭに溶解し不溶物を濾別した後、
カラムクロマトグラフィーにて精製し、精製物１ｇを緑
色粉末として得た。元素分析値より目的物であることを
確認した（金属の分析には原子吸光光度法を用いた）。Example 1 Production of tert-amylthio-naphthalocyanine vanadyl 4 g of 6-tert-amylthio-2,3-dicyanonaphthalene, 0.8 g of vanadyl trichloride and 20 g of urea were mixed into 1
The reaction was carried out at 85-200°C for 3 hours. After cooling, the solidified reaction product was crushed and stirred with 300 m of 5% hydrochloric acid at 80°C for 30 minutes. Next, the cake collected by filtration was stirred with 300 mJL of 10% aqueous sodium hydroxide solution at 80°C for 30 minutes, and the solid matter was collected by filtration. The sample was treated in the same manner again with 300 mM of 10% aqueous sodium hydroxide solution, and then washed with hot water. After refluxing this cake with 300 mJlj of methanol, the solid matter was filtered and dried to obtain 3.5 g of a crude product. After dissolving this crude product in 150mM toluene and filtering off insoluble matter,
It was purified by column chromatography to obtain 1 g of purified product as a green powder. It was confirmed that it was the desired product based on elemental analysis values (atomic absorption spectrometry was used for metal analysis).
元素分析値
理論値ｍ Ｃ；Ｈ，７１Ｈ，５，４４Ｎ 、Ｌ４３Ｓ
；１０．７９ Ｖ 、４．２８
４１１１定値（χ） Ｃ；６Ｂ、５３ Ｈ，５，４
７Ｎ 、９．３２Ｓ 、ＩＯ，３８Ｖ ：４．１５
この物のトルエン溶液は８１２ｎｍに極大吸収を７１く
し、分子吸光係数は２．８７Ｘ １０５１ ／ｍｏ１．
ｃｍ であった。Elemental analysis value theoretical value m C; H, 71H, 5, 44N, L43S
;10.79 V, 4.28 4111 constant value (χ) C; 6B, 53 H, 5,4
7N, 9.32S, IO, 38V: 4.15 A toluene solution of this substance has a maximum absorption of 71 at 812 nm, and a molecular extinction coefficient of 2.87X 1051/mo1.
It was cm.
実施例２
テトラ（フェニルチオ）ナフタロシアニンバナジルの製
造
６−フェニルチオ−２，３−ジシアノナフタレン１０．
９ｇ、三塩化バナジル３．６ｇ及び尿素５０ｇを １９
５〜２００ ”Ｃで３時間反応した。次いで実施例１と
同様に処理して粗精物６．５ｇを得た。これをトルエン
で再結晶して精製物１，９ｇを緑色粉末として得た。元
素分析値より目的物であることを確認した。Example 2 Preparation of tetra(phenylthio)naphthalocyanine vanadyl 6-phenylthio-2,3-dicyanonaphthalene 10.
9g, vanadyl trichloride 3.6g and urea 50g 19
The reaction was carried out at 5-200"C for 3 hours. Then, it was treated in the same manner as in Example 1 to obtain 6.5 g of a crude product. This was recrystallized from toluene to obtain 1.9 g of a purified product as a green powder. .It was confirmed to be the desired product based on elemental analysis values.
元素分析値
理論値（駕） Ｃ，７１，３０Ｈ，３，３３Ｎ 、９
．２４Ｓ 、ｔｏ、ｅｏ Ｖ 、４．２０
測定値（Ｘ） Ｃ；７１．１３ Ｈ；３．０８
Ｎ ；９．４３Ｓ 、１０．３［ｆ Ｖ 、４．１３
この物のトルエン溶液は８２４ｎｍに極大吸収を示し、
分子吸光係数は３．１４Ｘ １０’ ｌ ＃ｎｏ１．ｃ
ｍであった。Elemental analysis value theoretical value (parallel) C, 71, 30H, 3, 33N, 9
．． 24S, to, eo V, 4.20 Measured value (X) C; 71.13 H; 3.08
N; 9.43S, 10.3[fV, 4.13
A toluene solution of this substance shows maximum absorption at 824 nm,
The molecular extinction coefficient is 3.14X 10' l #no1. c.
It was m.
実施例３
テトラ（ｔｅｒｔ−アミルチオ）ナフタロシアニンニッ
ケルクロリドの製造
６−ｔｅｒｔ−アミルチオ−２，３−ジシアノナフタレ
ン８．０ｇ、塩化ニッケル（ＩＩ）１．７ｇ、尿素３０
ｇ、モリフテン酸アンモニウム０．１ｇヲ１９０〜２０
０℃で３時間反応した。次いで実施例１と同様に処理し
て粗精物８．５ｇを得た。これをカラムクロマトグラフ
ィーにて精製し精製物４．７ｇを暗緑色粉末として得た
。元素分析値より目的物であることを確認した。Example 3 Production of tetra(tert-amylthio)naphthalocyanine nickel chloride 6-tert-amylthio-2,3-dicyanonaphthalene 8.0 g, nickel(II) chloride 1.7 g, urea 30
g, ammonium molyftenate 0.1g 190-20
The reaction was carried out at 0°C for 3 hours. The mixture was then treated in the same manner as in Example 1 to obtain 8.5 g of crude product. This was purified by column chromatography to obtain 4.7 g of purified product as a dark green powder. The elemental analysis value confirmed that it was the desired product.
元素分析値
理論値ｍ Ｃ，６７，１７Ｈ，５，３２Ｎ 、９．２
２Ｓ ；１０．５５ Ｎｉ；４．８３
実測値（χ） ０．６７．２１ ８ ：５．４６
Ｎ 、９．３８Ｓ ；１０．８８ Ｎｉ；４．８８
この物のトルエン溶液は？８７ｎｍに極大吸収を示し、
分子吸光係数は１．６８Ｘ １０’ ｌ ／ｍｏ１．ｃ
ｍであった。Elemental analysis value theoretical value m C, 67, 17H, 5, 32N, 9.2
2S; 10.55 Ni; 4.83 Actual value (χ) 0.67.21 8:5.46
N, 9.38S; 10.88 Ni; 4.88 What is the toluene solution of this product? Shows maximum absorption at 87 nm,
The molecular extinction coefficient is 1.68X 10'l/mo1. c.
It was m.
実施例４
オクタ（ｔｅｒｔ−アミルチオ）ナフタロシアニンバナ
ジルの製造
６．７−シーｔｅｒｔ−アミルチオ−２，３−ジシアノ
ナフタレン２ｇ、三塩化バナジル０．４ｇ、尿素１０ｇ
をＩＨ〜２００ ’Ｏで３時間反応した。次いで実施例
１と同様に処理して粗精物１．７ｇを得た。これをカラ
ムクロマトグラフィーにて精製し精製物０６ｇを暗緑色
粉末として得た。元素分析値より目的物であることを確
認した。Example 4 Production of octa(tert-amylthio)naphthalocyanine vanadyl 6.2 g of 7-tert-amylthio-2,3-dicyanonaphthalene, 0.4 g of vanadyl trichloride, 10 g of urea
was reacted at IH~200'O for 3 hours. The mixture was then treated in the same manner as in Example 1 to obtain 1.7 g of crude product. This was purified by column chromatography to obtain 06 g of purified product as a dark green powder. The elemental analysis value confirmed that it was the desired product.
元素分析値
理論値（＄） 、ｃ ；ＢＢ、Ｉｅ Ｈ，６，５８Ｎ
、７．０２Ｓ ；１ｅ、ｏｅ Ｖ 、３．１９
実測値（駕） Ｃ；６Ｂ、２３ ）１．８．５２
Ｎ 、８．９８Ｓ ；１Ｂ、１２ Ｖ 、３．３０
この物のトルエン溶液は８２５ｎｍに極大吸収を示し、
分子吸光係数は３．１８Ｘ １０５１ ／ｍｏ１．ｃｍ
であった。Elemental analysis value theoretical value ($), c; BB, Ie H, 6,58N
, 7.02S; 1e, oe V, 3.19 Actual value (parallel) C; 6B, 23) 1.8.52
N, 8.98S; 1B, 12V, 3.30 A toluene solution of this product shows maximum absorption at 825 nm,
The molecular extinction coefficient is 3.18X 1051 /mo1. cm
Met.
実施例５
オクタ（ｔｅｒｔ−アミルチオ）ナフタロシアニンニッ
ケルクロリドの製造
６．７−シーｔｅｒｔ−アミルチオ−２，３−ジシアノ
ナフタレン５．７ｇ、塩化ニッケル（ＩＩ）０．７ｇ、
尿素２０ｇ、モリブデン酸アンモニウム０．１ｇを１９
０〜２００ ’０で３時間反応した。次いで実施例１と
同様に処理して粗精物３．７ｇを得た。これをカラムク
ロマトグラフィーにて精製し、精製物０．７ｇを暗緑色
粉末として得た。元素分析値より目的物であることを確
認した。Example 5 Production of octa(tert-amylthio)naphthalocyanine nickel chloride 6.7-tert-amylthio-2,3-dicyanonaphthalene 5.7 g, nickel(II chloride) 0.7 g,
20g of urea, 0.1g of ammonium molybdate at 19
The reaction was carried out at 0 to 200'0 for 3 hours. The mixture was then treated in the same manner as in Example 1 to obtain 3.7 g of crude product. This was purified by column chromatography to obtain 0.7 g of purified product as a dark green powder. The elemental analysis value confirmed that it was the desired product.
元素分析値
理論値（Ｘ） Ｃ；８５．０５ Ｈ，８，４７Ｎ
、８．９０Ｓ ；１５．７８Ｎｉ；３．６１
実測値（Ｘ）Ｃ，８５，０７Ｈ，８，７４Ｎ 、８．７
８Ｓ ；１５．５３ Ｎｉ；３．３Ｂ
この物のトルエン溶液は８２Ｂｎｍに極大吸収を示し、
分子吸光係数は１．４８Ｘ １０４文／ｍｏ１．ｃｍで
あった。Elemental analysis value theoretical value (X) C; 85.05 H, 8,47N
, 8.90S; 15.78Ni; 3.61 Actual value (X)C, 85,07H, 8,74N, 8.7
8S; 15.53 Ni; 3.3B A toluene solution of this substance shows maximum absorption at 82Bnm,
The molecular extinction coefficient is 1.48X 104 sentences/mo1. It was cm.
実施例６
テトラ（ｔｅｒｔ−アミルチ＃）ナフタロシアニン銅の
製造
８−ｔｅｒｔ−アミルチオ−２，３−ジシアノナフタレ
ン５．８ｇ、塩化銅（Ｉ）０．８ｇ、尿素２０ｇ、モリ
ブデン酸アンモニウム０．１ｇを１９０〜２００℃で３
時間反応した。次いで実施例１と同様に処理して粗精物
３．８ｇを得た。これをカラムクロマトグラフィーにて
精製し、精製物２．６ｇを暗緑色粉末として得た。元素
分析値より目的物であることを確認した。Example 6 Production of copper tetra(tert-amylthi#) naphthalocyanine 5.8 g of 8-tert-amylthio-2,3-dicyanonaphthalene, 0.8 g of copper(I) chloride, 20 g of urea, and 0.1 g of ammonium molybdate were added. 3 at 190-200℃
Time reacted. The mixture was then treated in the same manner as in Example 1 to obtain 3.8 g of crude product. This was purified by column chromatography to obtain 2.6 g of purified product as a dark green powder. The elemental analysis value confirmed that it was the desired product.
元素分析値
理論値（％） Ｃ；ｅｓ、ｓｔ Ｈ，５，４５Ｎ
、９．４６Ｓ ；１０．８２ Ｃｕ；５．３６
実測値（Ｘ） Ｃ；Ｂ８．８８ ）１ ；５．４１
Ｎ ；９．３２Ｓ ；１０．５２ Ｃｕ；５．１
１
この物のトルエン溶液は？７３ｎｍに極大吸収を示し、
分子吸光係数は２．２３Ｘ １０’ ｎ ／ｍｏ１．ｃ
ｆｆｉであった。Elemental analysis value theoretical value (%) C; es, st H, 5,45N
, 9.46S; 10.82 Cu; 5.36 Actual value (X) C; B8.88) 1; 5.41
N; 9.32S; 10.52 Cu; 5.1
1 What is the toluene solution of this thing? Shows maximum absorption at 73 nm,
The molecular extinction coefficient is 2.23X 10' n /mo1. c.
It was ffi.
実施例７
テトラ（ｔｅｒｔ−アミルチオ）ナフタロシアニンイン
ジウムクロリドの製造
８−ｔｅｒｔ−アミルチオ−２，３−ジシアノナフタレ
ン５、Ｅｉｇ、塩化インジウム（ｍ） １．８ｇ、尿素
２０ｇ、モリブデン酸アンモニウム０．１ｇを１９０〜
２００℃で３時間反応した。次いで実施例１と同様に処
理して粗精物４．８ｇを得た。これをカラムクロマトグ
ラフィーにて精製して、精製物１．３ｇを暗緑色粉末と
して得た。元素分析値より目的物であることを確認した
。Example 7 Production of tetra(tert-amylthio)naphthalocyanine indium chloride 8-tert-amylthio-2,3-dicyanonaphthalene 5, Eig, 1.8 g of indium chloride (m), 20 g of urea, and 0.1 g of ammonium molybdate. 190～
The reaction was carried out at 200°C for 3 hours. The mixture was then treated in the same manner as in Example 1 to obtain 4.8 g of crude product. This was purified by column chromatography to obtain 1.3 g of purified product as a dark green powder. The elemental analysis value confirmed that it was the desired product.
元素分析値
理論値（Ｘ） Ｃ；Ｉ（４，２１Ｈ；５．０８ Ｎ
、８．８１Ｓ ；１０．０８ Ｉｎ；９．０３
実測値ｍ Ｃ；８４．１２ Ｈ；４．９９ Ｎ
；８．Ｂ２Ｓ ；１０．２０ Ｉｎ；９．１１
この物のトルエン溶液は８０８ｒ＋ｍに極大吸収を示し
、分子吸光係数は１．３５Ｘ １０５１ ／ｍｏ！、ｃ
ｍ テあった。Elemental analysis value theoretical value (X) C; I (4,21H; 5.08 N
, 8.81S; 10.08 In; 9.03 Actual value m C; 84.12 H; 4.99 N
;8. B2S;10.20 In;9.11 A toluene solution of this substance shows maximum absorption at 808r+m, and the molecular extinction coefficient is 1.35X 1051 /mo! ,c
There was m.
実施例８
テトラ（ｔｅｒｔ−アミルチオ）ナフタロシアニンコバ
ルトの製造
Ｂ−ｔｅｒｔ−アミルチオ−２，３−ジシアノナフタレ
ン５．６ｇ、塩化コバルト（ＩＩ）１．１ｇ、尿素２０
ｇ、モリブデン酸アンモニウム０．１ｇを１８０〜２０
０°Ｃで３時間反応した。次いで実施例１と同様に処理
して粗精物３．９ｇを得た。これをカラムクロマトグラ
フィーにて精製し、精製物２．１ｇを暗緑色粉末として
得た。元素分析値より目的物であることを確認した。Example 8 Production of cobalt tetra(tert-amylthio)naphthalocyanine B-tert-amylthio-2,3-dicyanonaphthalene 5.6 g, cobalt(II) chloride 1.1 g, urea 20
g, ammonium molybdate 0.1g 180-20
The reaction was carried out at 0°C for 3 hours. The mixture was then treated in the same manner as in Example 1 to obtain 3.9 g of crude product. This was purified by column chromatography to obtain 2.1 g of purified product as a dark green powder. The elemental analysis value confirmed that it was the desired product.
元素分析値
理論値（Ｘ） Ｃ；１３９．１８ Ｈ，５，４８Ｎ
；９．４９Ｓ ；１０．８［ｆ Ｃｏ；４．９９実
測値（Ｘ） Ｃ；Ｂ９．０８Ｈ；５．３１ Ｎ ；
９．３７Ｓ ；１０．Ｂ？ Ｃｏ；４．７９
この物のトルエン溶液は７５！３ｎｍに極大吸収を示し
、分子吸光係数は１．２４Ｘ １０５１ ／ｍｏ１．ｃ
ｍ テあった。Elemental analysis value theoretical value (X) C; 139.18 H, 5,48N
; 9.49S; 10.8 [f Co; 4.99 actual value (X) C; B9.08H; 5.31 N;
9.37S;10. B? Co; 4.79 A toluene solution of this substance shows maximum absorption at 75!3 nm, and the molecular extinction coefficient is 1.24X 1051 /mo1. c.
There was m.
実施例９
テトラ（ｔｅｒｔ−アミルチオ）ナフタロシアニンアル
ミニウムクロリドの製造
８−ｔｅｒｔ−アミルチオ−２，３−ジシアノナフタレ
ン５．６ｇ、塩化アルミニウム１．１ｇ、尿素２０ｇ、
モリフテン酸アンモニウム０．１ｇヲ１９０〜２００℃
で３時間反応した。次いで実施例１と同様に処理して粗
精物５．１ｇを得た。これをカラムクロマトグラフィー
にて精製し、精製物１．８ｇを暗緑色粉末として得た。Example 9 Production of tetra(tert-amylthio)naphthalocyanine aluminum chloride 8-tert-amylthio-2,3-dicyanonaphthalene 5.6 g, aluminum chloride 1.1 g, urea 20 g,
Ammonium molyftate 0.1g 190-200℃
It reacted for 3 hours. The mixture was then treated in the same manner as in Example 1 to obtain 5.1 g of crude product. This was purified by column chromatography to obtain 1.8 g of purified product as a dark green powder.
元素分析値より目的物であることを確認した。The elemental analysis value confirmed that it was the desired product.
元素分析値
理論値（駕） Ｃ、ｆ（８，９７Ｈ，５，４１３Ｎ
、９．４７Ｓ 、１０．８３ Ａ１．２．２８
実測値（％） Ｃ，８８，７３Ｍ 、５．４９ Ｎ
；９．３３Ｓ 、１０．８７ Ａ１．２．１０
この物のトルエン溶液は８０７ｒ＋ｍに極大吸収を示し
、分子吸光係数は１．２８Ｘ １０５１ ／ｍｏ１．ｃ
ｍであった。Elemental analysis value theoretical value (parallel) C, f (8,97H, 5,413N
, 9.47S, 10.83 A1.2.28 Actual value (%) C, 88,73M, 5.49 N
;9.33S, 10.87 A1.2.10 A toluene solution of this substance shows maximum absorption at 807r+m, and the molecular extinction coefficient is 1.28X 1051 /mo1. c.
It was m.
実施例１０
テトラ（ｎ−ラウリルチオ）ナフタロシアニンバナジル
の製造
８−ｎ−ラウリルチオ−２，３−ジシアノナフタレン７
゜６ｇ、三塩化バナジル１．４ｇ。尿素２０ｇを １９
０〜２００°Ｃで３時間反応した。次いで実施例１と同
様に処理して粗精物５．７ｇを得た。これをカラムクロ
マトグラフィーにて精製して、精製物２．１ｇを暗緑色
粉末として得た。元素分析値より目的物であることを確
認した。Example 10 Production of tetra(n-laurylthio)naphthalocyanine vanadyl 8-n-Laurylthio-2,3-dicyanonaphthalene 7
゜6g, vanadyl trichloride 1.4g. 20g of urea 19
The reaction was carried out at 0 to 200°C for 3 hours. The mixture was then treated in the same manner as in Example 1 to obtain 5.7 g of crude product. This was purified by column chromatography to obtain 2.1 g of purified product as a dark green powder. The elemental analysis value confirmed that it was the desired product.
元素分析値
理論値（＄） Ｃ；７２．９２ Ｈニア、８８
Ｎ ；７．０９Ｓ ；ｅ、ｉｏ Ｖ 、３．２２
実測値（％） Ｃ；７２．８３ Ｈ；’７．ｅｅ
Ｎ ；７．０５Ｓ 、８．０３ Ｖ 、３．０９
この物のトルエン溶液は８１４ｎｍに極大吸収を示し、
分子吸光係数は２．１７Ｘ １０５ｎ ／ｍｏ１．ｃｍ
であった。Elemental analysis value theoretical value ($) C; 72.92 H near, 88
N; 7.09S; e, io V, 3.22 Actual value (%) C; 72.83 H; '7. ee
N; 7.05S, 8.03V, 3.09 A toluene solution of this product shows maximum absorption at 814nm,
The molecular extinction coefficient is 2.17X 105n/mo1. cm
Met.
実施例１１
オクタ（フェニルチオ）ナフタロシアニンバナジルの製
造
８．７−シフエニルチオー２．３−ジシアノナフタレン
７．９ｇ、三塩化バナジル１．４ｇ、尿素２０ｇを １
９０〜２００°Ｃで３時間反応した。次いで実施例１と
同様に処理して粗精物６．３ｇを得た。これをカラムク
ロマトグラフィーにて精製し、精製物１．８ｇを暗緑色
粉末として得た。元素分析値より目的物であることを確
認した。Example 11 Production of octa(phenylthio)naphthalocyanine vanadyl 8.7-cyphenylthio 2,3-dicyanonaphthalene 7.9 g, vanadyl trichloride 1.4 g, urea 20 g 1
The reaction was carried out at 90-200°C for 3 hours. The mixture was then treated in the same manner as in Example 1 to obtain 6.3 g of crude product. This was purified by column chromatography to obtain 1.8 g of purified product as a dark green powder. The elemental analysis value confirmed that it was the desired product.
元素分析値
理論値ｍ Ｃニア０．０８ Ｈ：３．４４ Ｎ
；ｅ、ｓ＋Ｓ 、１５．５９ Ｖ 、３．１０
実測値（χ） Ｃ，７０，０１）１．３．３３ Ｎ
、８．８５Ｓ 、１５．２３ Ｖ 、３．２２
１この物のトルエン溶液は８３４ｎｍに極大吸収を示し
、分子吸光係数は１．８９Ｘ １０５１ ／ｍｏ１．ｃ
ｍであった。Elemental analysis value theoretical value m C near 0.08 H: 3.44 N
;e, s+S, 15.59 V, 3.10 Actual value (χ) C, 70,01) 1.3.33 N
, 8.85S, 15.23V, 3.22
1. A toluene solution of this product shows maximum absorption at 834 nm, and the molecular extinction coefficient is 1.89X 1051 /mo1. c.
It was m.
本発明による新規なナフタロシアニン化合物は、これを
形成するナフタレン環にアルキルチオ基、無置換もしく
はアルキル基、ハロゲン原子等の置換基を有するアリー
ルチオ基を導入することにより、近赤外光吸収能力に優
れると共に種々の有機媒体への溶解性に優れ、しかも耐
光性、耐熱性、耐酸性、耐アルカリ性等にも優れるので
、光記録媒体、液晶表示装置、ＯＣＲ用ボールペン。The novel naphthalocyanine compound of the present invention has excellent near-infrared light absorption ability by introducing an alkylthio group, an unsubstituted or alkyl group, an arylthio group having a substituent such as a halogen atom into the naphthalene ring forming the compound. It also has excellent solubility in various organic media, and also has excellent light resistance, heat resistance, acid resistance, alkali resistance, etc., so it is suitable for optical recording media, liquid crystal display devices, and OCR ballpoint pens.
光学フィルターのほか樹脂の着色及び染色、インキや塗
料の着色に好適に用いることが出来る。In addition to optical filters, it can be suitably used for coloring and dyeing resins, and for coloring inks and paints.
Claims (1)
キル基、置換基を有しても良いフェニル基または置換基
を有しても良いナフチル基を示し、ｎ＿１、ｎ＿２、ｎ
＿３、ｎ＿４はそれぞれ１〜４の整数を示し、Ｍは水素
２原子、金属、金属酸化物または金属ハロゲン化物を示
す。）[Claims] A naphthalocyanine compound represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1, R_2, R_3, and R_4 each represent an alkyl group, a phenyl group that may have a substituent, or a naphthyl group that may have a substituent. , n_1, n_2, n
_3 and n_4 each represent an integer of 1 to 4, and M represents two hydrogen atoms, a metal, a metal oxide, or a metal halide. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63114737A JPH01287175A (en) | 1988-05-13 | 1988-05-13 | Naphthalocyanine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63114737A JPH01287175A (en) | 1988-05-13 | 1988-05-13 | Naphthalocyanine compound |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4040633A Division JPH0586300A (en) | 1992-01-31 | 1992-01-31 | Production of naphthalocyanine compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01287175A true JPH01287175A (en) | 1989-11-17 |
Family
ID=14645381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63114737A Pending JPH01287175A (en) | 1988-05-13 | 1988-05-13 | Naphthalocyanine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01287175A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007002980A1 (en) * | 2005-07-05 | 2007-01-11 | Silverbrook Research Pty Ltd | Red-shifted water-dispersible naphthalocyanine dyes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01105788A (en) * | 1987-07-27 | 1989-04-24 | Toyo Ink Mfg Co Ltd | Optical recording medium |
-
1988
- 1988-05-13 JP JP63114737A patent/JPH01287175A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01105788A (en) * | 1987-07-27 | 1989-04-24 | Toyo Ink Mfg Co Ltd | Optical recording medium |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007002980A1 (en) * | 2005-07-05 | 2007-01-11 | Silverbrook Research Pty Ltd | Red-shifted water-dispersible naphthalocyanine dyes |
| US7470315B2 (en) | 2005-07-05 | 2008-12-30 | Silverbrook Research Pty Ltd | Red-shifted water dispersible napthalocyanine dyes |
| JP2009500460A (en) * | 2005-07-05 | 2009-01-08 | シルバーブルック リサーチ ピーティワイ リミテッド | Red-shifted water dispersible naphthalocyanine dye |
| US7579064B2 (en) | 2005-07-05 | 2009-08-25 | Silverbrook Research Pty Ltd | Substrate having IR-absorbing dye disposed thereon |
| JP4750849B2 (en) * | 2005-07-05 | 2011-08-17 | シルバーブルック リサーチ ピーティワイ リミテッド | Red-shifted water dispersible naphthalocyanine dye |
| US8346024B2 (en) | 2005-07-05 | 2013-01-01 | Silverbrook Research Pty Ltd | Method of initiating requested action via substrate printed with naphthalocyanine dye |
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