JP4465236B2 - Quinophthalone compounds - Google Patents
Quinophthalone compounds Download PDFInfo
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- JP4465236B2 JP4465236B2 JP2004195249A JP2004195249A JP4465236B2 JP 4465236 B2 JP4465236 B2 JP 4465236B2 JP 2004195249 A JP2004195249 A JP 2004195249A JP 2004195249 A JP2004195249 A JP 2004195249A JP 4465236 B2 JP4465236 B2 JP 4465236B2
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- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical class C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 title description 3
- -1 quinophthalone compound Chemical class 0.000 claims description 72
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 52
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 7
- 229940116333 ethyl lactate Drugs 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000000434 field desorption mass spectrometry Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229940057867 methyl lactate Drugs 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000001052 yellow pigment Substances 0.000 description 4
- YZBBUYKPTHDZHF-KNVGNIICSA-N (3R)-7,2'-dihydroxy-4'-methoxyisoflavanol Chemical compound OC1=CC(OC)=CC=C1[C@H]1C(O)C2=CC=C(O)C=C2OC1 YZBBUYKPTHDZHF-KNVGNIICSA-N 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- 0 *c1c(C(C(C2=O)c3nc(cccc4)c4cc3O)=O)c2c(*)c(*)c1* Chemical compound *c1c(C(C(C2=O)c3nc(cccc4)c4cc3O)=O)c2c(*)c(*)c1* 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- MMYKTRPLXXWLBC-UHFFFAOYSA-N 1-bromo-2-ethoxyethane Chemical compound CCOCCBr MMYKTRPLXXWLBC-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005948 methanesulfonyloxy group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000612 phthaloyl group Chemical group C(C=1C(C(=O)*)=CC=CC1)(=O)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
- Quinoline Compounds (AREA)
Description
本発明は、高分子材料の着色等に用いられ、有機溶媒に対する溶解性に優れる鮮明な黄色の色素である新規なキノフタロン化合物に関する。 The present invention relates to a novel quinophthalone compound that is used for coloring a polymer material and the like and is a bright yellow pigment having excellent solubility in an organic solvent.
近年、高分子材料の着色剤として、作業環境及び安全性に優れる有機溶媒、例えば、乳酸メチル、乳酸エチルに対する溶解性に優れた鮮明な黄色の色素が要望されている。
キノフタロン化合物は、黄色色素として種々の用途に使用されている。例えば、特開２００１−３１１０１６号公報ではインクジェット用の黄色染料として開示されている。また、特開昭４９−１３４７３９号公報の７頁の実施例４３に下記構造式（Ｉ）のキノフタロン化合物が、合成樹脂および合成繊維材料の黄色染料として開示されている。
In recent years, as a colorant for a polymer material, there has been a demand for a clear yellow pigment having excellent solubility in an organic solvent excellent in work environment and safety, for example, methyl lactate and ethyl lactate.
The quinophthalone compound is used for various uses as a yellow pigment. For example, JP-A-2001-311016 discloses it as a yellow dye for inkjet. Further, in Example 43 on page 7 of JP-A-49-134739, a quinophthalone compound of the following structural formula (I) is disclosed as a yellow dye for synthetic resins and synthetic fiber materials.
本発明の課題は、高分子材料の着色剤として、作業環境及び安全性に優れる有機溶媒である乳酸メチル、乳酸エチルや、樹脂に対する溶解性の優れた鮮明な黄色のキノフタロン化合物を提供することである。 An object of the present invention is to provide methyl lactate and ethyl lactate, which are organic solvents excellent in working environment and safety, as a colorant for a polymer material, and a clear yellow quinophthalone compound having excellent solubility in a resin. is there.
本発明者等は、前記の課題を解決するために鋭意検討した結果、特定の構造のキノフタロン化合物が前述の問題点を解決し、鮮明な黄色で、乳酸メチル、乳酸エチルや樹脂への溶解性が高いことを発見するに至った。すなわち、本発明は下記一般式（１） As a result of intensive studies to solve the above-mentioned problems, the present inventors have solved the above-mentioned problems with quinophthalone compounds having a specific structure. It came to discover that there is high. That is, the present invention provides the following general formula (1)
で表されるキノフタロン化合物を提供するものである。さらに、式(１)中、Ｒ５が酸素原子をエーテル結合の形で１〜６個含む総炭素数２〜１６のアルキル基であるキノフタロン化合物が好ましく、Ｒ２及びＲ３が−Ｓ−Ｒ５であり、Ｒ１及びＲ４が水素原子またはハロゲン原子であるのが好ましい。
なお、本発明キノフタロン化合物の構造上の特徴のひとつは、フタロイル側のベンゼン環にエーテル結合を有するアルキル基を少なくとも１つ有する点にある。
The quinophthalone compound represented by these is provided. Further, in formula (1), a quinophthalone compound in which R 5 is an alkyl group having 2 to 16 carbon atoms in total containing 1 to 6 oxygen atoms in the form of an ether bond is preferred, and R 2 and R 3 are —S—R 5 and R 1 and R 4 are preferably a hydrogen atom or a halogen atom.
One of the structural features of the quinophthalone compound of the present invention is that it has at least one alkyl group having an ether bond in the benzene ring on the phthaloyl side.
前記一般式（１）において、Ｒ１〜Ｒ４がハロゲン原子であるものとしては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、好ましくは、塩素原子および臭素原子である。
Ｒ１〜Ｒ４が−Ｓ−Ｒ５である場合において、Ｒ５としては酸素原子をエーテル結合の形で1〜６個含む総炭素数２〜１６個のアルキル基が好ましく、特に酸素原子をエーテル結合の形で２〜４個含む総炭素数２〜１２個のアルキル基が好ましい。ここでアルキル基は直鎖又は分岐鎖であってもよく、環を形成した部分を有していてもよい。
Ｒ５の例としては、２−メトキシエチル基、２−エトキシエチル基、２−ブトキシエチル基、メトキシエトキシエチル基、エトキシエトキシエチル基、３−エトキシプロピル基、２−エトキシ−１−メチルプロピル基、３−プロポキシプロピル基、２−メトキシプロピル基、２−エトキシプロピル基、４−メトキシブチル基、４−プロポキシブチル基、６−メトキシヘキシル基、６−エトキシヘキシル基、２，３−ジメトキシプロピル基、２，３−ジエトキシプロピル基、２，３−ジプロポキシプロピル基、２，３−ジイソプロポキシプロピル基、２，３−ジブトキシプロピル基、２，３−ジシクロヘキシルプロピル基、２，３−ジ（２−エトキシエトキシ）プロピル基、２，３−ジ（２−エトキシエトキシエトキシ）プロピル基、２−（２−エトキシエトキシ）−３−（２−エトキシエトキシエトキシ）プロピル基、２−（２−エトキシエトキシエトキシ）−３−（２−プロポキシエトキシエトキシ）プロピル基、２，３−ジ（１，３−ジオキソラン−２−イル−エトキシ）プロピル基、（２，２−ジメチル−１，３−ジオキソラン−４−イル）メチル基、（２−エチル−２−メチル−１，３−ジオキソラン−４−イル）メチル基、（２，２−ジエチル−１，３−ジオキソラン−４−イル）メチル基、（２−プロピル−１，３−ジオキソラン−４−イル）メチル基、（２，２−ジプロピル−１，３−ジオキソラン−４−イル）メチル基、（２−プロピル−１，３−ジオキソラン−４−イル）メチル基、（２−ペンチル−１，３−ジオキソラン−４−イル）メチル基、２−（テトラハイドロフルフリルオキシ）エチル基、２−（１，３−ジオキソラン−２−イルメチルオキシ）エチル基、２−（１，３−ジオキソラン−２−イルエチルオキシ）エチル基、２−（１，３−ジオキソラン−２−イルメチルオキシ）プロピル基、２−（テトラハイドロピラン−２−メチルオキシ）エチル基、２−（１，３−ジオキサン−２−イルエチルオキシ）エチル基、２−（１，３−ジオキサン−２−イルエチルオキシ）プロピル基、ヒドロキシエトキシエチル基、ヒドロキシエトキシエトキシエチル基、２−（ヒドロキシエトキシ）プロピル基、２−ヒドロキシ−３−メトキシプロピル基、２−ヒドロキシ−３−エトキシプロピル基、２−ヒドロキシ−３−ブトキシプロピル基、２−ヒドロキシ−３−（エトキシエトキシ）プロピル基が挙げられる。
In Formula (1), as R 1 to R 4 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, preferably a chlorine atom and a bromine atom.
In the case where R 1 to R 4 are —S—R 5 , R 5 is preferably an alkyl group having 2 to 16 carbon atoms in total containing 1 to 6 oxygen atoms in the form of an ether bond. Alkyl groups having 2 to 12 carbon atoms in total in the form of 2 to 4 ether bonds are preferred. Here, the alkyl group may be linear or branched, and may have a ring-forming portion.
Examples of R 5 include 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, 3-ethoxypropyl group, 2-ethoxy-1-methylpropyl group 3-propoxypropyl group, 2-methoxypropyl group, 2-ethoxypropyl group, 4-methoxybutyl group, 4-propoxybutyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 2,3-dimethoxypropyl group 2,3-diethoxypropyl group, 2,3-dipropoxypropyl group, 2,3-diisopropoxypropyl group, 2,3-dibutoxypropyl group, 2,3-dicyclohexylpropyl group, 2,3- Di (2-ethoxyethoxy) propyl group, 2,3-di (2-ethoxyethoxyethoxy) propyl group, 2- (2 -Ethoxyethoxy) -3- (2-ethoxyethoxyethoxy) propyl group, 2- (2-ethoxyethoxyethoxy) -3- (2-propoxyethoxyethoxy) propyl group, 2,3-di (1,3-dioxolane) -2-yl-ethoxy) propyl group, (2,2-dimethyl-1,3-dioxolan-4-yl) methyl group, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl Group, (2,2-diethyl-1,3-dioxolan-4-yl) methyl group, (2-propyl-1,3-dioxolan-4-yl) methyl group, (2,2-dipropyl-1,3) -Dioxolan-4-yl) methyl group, (2-propyl-1,3-dioxolan-4-yl) methyl group, (2-pentyl-1,3-dioxolan-4-yl) methyl group, 2- (tetra Idrofurfuryloxy) ethyl group, 2- (1,3-dioxolan-2-ylmethyloxy) ethyl group, 2- (1,3-dioxolan-2-ylethyloxy) ethyl group, 2- (1,3 -Dioxolan-2-ylmethyloxy) propyl group, 2- (tetrahydropyran-2-methyloxy) ethyl group, 2- (1,3-dioxan-2-ylethyloxy) ethyl group, 2- (1, 3-dioxane-2-ylethyloxy) propyl group, hydroxyethoxyethyl group, hydroxyethoxyethoxyethyl group, 2- (hydroxyethoxy) propyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy-3-ethoxy Propyl group, 2-hydroxy-3-butoxypropyl group, 2-hydroxy-3- (ethoxyethoxy) propyl group It is below.
Ｒ１〜Ｒ４が−Ｓ−Ｒ６である場合において、Ｒ６としてはヒドロキシ基を1〜４個含む総炭素数２〜１２個のアルキル基が好ましく、色素の光学濃度の点から、ヒドロキシ基を1〜３個含む総炭素数２〜８個のアルキル基が特に好ましい。
Ｒ６の例としては、２−ヒドロキシエチル基、３−ヒドロキシプロピル基、２−ヒドロキシプロピル基、２，３−ジヒドロキシプロピル基、２−ヒドロキシ−１−メチルプロピル基、４−ヒドロキシブチル基、２，３，４−トリヒドロキシブチル基、２，３，４，５−テトラヒドロキペンチル基、６−ヒドロキシヘキシル基、１１−ヒドロキシウンデカニル基、１２−ヒドロキシドデカニル基が挙げられる。
一般式（１）の化合物においては、Ｒ１〜Ｒ４に含まれるエーテル結合としての酸素原子の総数は、１〜１６個であるものが好ましく、溶解性および色素の光学濃度の点から、２〜１２個であるのが特に好ましい。
また、ヒドロキシ基を含めたＲ１〜Ｒ４の酸素原子の総数は、２〜２４個であるのが好ましく、３〜１６個であるのが特に好ましい。
また、色素の吸収特性の点から、Ｒ２および／またはＲ３に−Ｓ−Ｒ５が導入された構造のものが好ましい。
なお、一般式（１）の化合物は下記一般式（１′）および（１″）等の構造の互変異性体が存在するが、これらの互変異性体についても本発明の権利範囲内のものである。
In the case where R 1 to R 4 are —S—R 6 , R 6 is preferably an alkyl group having 1 to 4 hydroxy groups and 2 to 12 carbon atoms in total, from the viewpoint of the optical density of the dye. An alkyl group having 2 to 8 carbon atoms and containing 1 to 3 groups is particularly preferred.
Examples of R 6 include 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-1-methylpropyl group, 4-hydroxybutyl group, 2 , 3,4-trihydroxybutyl group, 2,3,4,5-tetrahydropentyl group, 6-hydroxyhexyl group, 11-hydroxyundecanyl group, 12-hydroxydodecanyl group.
In the compound of the general formula (1), the total number of oxygen atoms as ether bonds contained in R 1 to R 4 is preferably 1 to 16, from the viewpoint of solubility and optical density of the dye, 2 It is particularly preferable that the number is -12.
Moreover, the total number of oxygen atoms of R 1 to R 4 including the hydroxy group is preferably 2 to 24, and particularly preferably 3 to 16.
Further, from the viewpoint of dye absorption characteristics, those having a structure in which —S—R 5 is introduced into R 2 and / or R 3 are preferred.
The compound of the general formula (1) has tautomers having the structures of the following general formulas (1 ′) and (1 ″), and these tautomers also fall within the scope of the present invention. Is.
（キノフタロン化合物の製造方法）
本発明の前記一般式(１)で表されるキノフタロン化合物の製造方法を以下に説明する。代表的な製造方法の概略は、次のとおりである。
第一の製造方法としては、下記式の化合物（Ａ）
の１モル量に対して、有機溶媒中、アルカリ化合物を１〜１６モル量用い、下記式の化合物（Ｂ）
ＨＳ−Ｒ５ （Ｂ）
（式（Ｂ）中、Ｒ５は、前記一般式（１）におけるものと同じ。）
を１〜８モル量を用いて、２０〜２００℃で１〜８時間反応する。有機溶媒としては、Ｎ−メチルピロリドン、ＤＭＩ、スルホラン、ＤＭＦ，ＤＭＡＣ、トルエンおよび酢酸エチル等が使用され、アルカリ化合物としては、炭酸カリウム、炭酸カルシウム、水酸化ナトリウムおよび水酸化カリウム等が使用される。反応後、水に排出、酢酸エチル等の有機溶媒で抽出、水洗、濃縮後、必要に応じてカラムクロマトグラフィーにて精製することにより、目的とする一般式（１）のキノフタロン化合物を得ることができる。
(Method for producing quinophthalone compound)
The method for producing the quinophthalone compound represented by the general formula (1) of the present invention will be described below. The outline of a typical manufacturing method is as follows.
As a 1st manufacturing method, the following formula (A)
In an organic solvent, 1 to 16 moles of an alkali compound is used with respect to 1 mole of the compound (B).
HS-R 5 (B)
(In the formula (B), R 5 is the same as that in the general formula (1).)
Is reacted at 20-200 ° C. for 1-8 hours. As the organic solvent, N-methylpyrrolidone, DMI, sulfolane, DMF, DMAC, toluene, ethyl acetate and the like are used, and as the alkali compound, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like are used. . After the reaction, it is discharged into water, extracted with an organic solvent such as ethyl acetate, washed with water, concentrated, and then purified by column chromatography as necessary to obtain the target quinophthalone compound of the general formula (1). it can.
第二の製造方法としては、前記化合物（Ａ）１モル量に対して、有機溶媒中、アルカリ化合物を１〜１６モル量用いて、下記式の化合物（Ｃ）
ＨＳ−Ｒ６ （Ｃ）
（式（Ｃ）中、Ｒ６は一般式（１）におけるものと同じものを表す。）
の１〜８モル量と２０〜２００℃で１〜２４時間反応し、水に排出、希塩酸あるいは酢酸等で中和し、濾取、水洗し、下記式の化合物（Ｄ）
を得る。有機溶媒としては、Ｎ−メチルピロリドン、ＤＭＩ、スルホラン、ＤＭＦ，ＤＭＡＣ、トルエンおよび酢酸エチル等が使用され、アルカリ化合物としては、炭酸カリウム、炭酸カルシウム、水酸化ナトリウムおよび水酸化カリウム等が使用される。
次に、化合物（Ｄ）を有機溶媒中、アルカリ化合物を１〜２４モル量用いて、下記化合物（Ｅ）
Ｚ−Ｒ９ （Ｅ）
（式（Ｅ）中、Ｚはハロゲン原子、トルエンスルホニルオキシ基あるいはメタンスルホニルオキシ基を表し、Ｒ９は、酸素原子をエーテル結合の形、あるいはヒドロキシ基の形で含んでもよいアルキル基を表す。）
の１〜２４モル量と２０〜２００℃で１〜２４時間反応させることにより、目的とする一般式（１）のキノフタロン化合物が得られる。有機溶媒およびアルカリ化合物としては、前記第一の製造方法で用いたものと同様のものが使用される。
As a 2nd manufacturing method, 1-16 mol amount of alkali compounds are used in an organic solvent with respect to 1 mol amount of said compound (A), and compound (C) of a following formula is used.
HS-R 6 (C)
(In formula (C), R 6 represents the same as in general formula (1).)
Of 1 to 8 mol of the compound at 20 to 200 ° C. for 1 to 24 hours, discharged into water, neutralized with dilute hydrochloric acid or acetic acid, collected by filtration, washed with water, and compound (D) of the following formula
Get. As the organic solvent, N-methylpyrrolidone, DMI, sulfolane, DMF, DMAC, toluene, ethyl acetate and the like are used, and as the alkali compound, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like are used. .
Next, using the compound (D) in an organic solvent in an amount of 1 to 24 moles of an alkali compound, the following compound (E)
ZR 9 (E)
(In formula (E), Z represents a halogen atom, a toluenesulfonyloxy group or a methanesulfonyloxy group, and R 9 represents an alkyl group which may contain an oxygen atom in the form of an ether bond or in the form of a hydroxy group. )
The intended quinophthalone compound of the general formula (1) is obtained by reacting at 1 to 24 mol of the compound at 20 to 200 ° C. for 1 to 24 hours. As the organic solvent and the alkali compound, the same ones as those used in the first production method are used.
または、前記化合物（Ｄ）と前記化合物（Ｅ）を有機溶媒中、相間移動触媒とアルカリ水溶液を用いた２相系で反応させても同様に一般式（１）の化合物を製造することができる。反応に用いる有機溶媒としては、Ｎ−メチルピロリドン、ＤＭＩ、スルホラン、ＤＭＦ，ＤＭＡＣ、トルエンおよび酢酸エチル等であり、アルカリ水溶液としては、水酸化ナトリウム水溶液および水酸化カリウム水溶液等であり、相間移動触媒としては、テトラブチルアンモニウムブロマイド、テトラメチルアンモニウムクロライド、ベンジルトリエチルアンモニウムクロリド、テトラブチルアンモニウム硫酸水素塩等である。
また、前記化合物（Ｄ）のＲ６がα，β−ジヒドロキシ基を有するアルキル基である場合、有機溶媒中、下記化合物（Ｆ）
When R 6 of the compound (D) is an alkyl group having an α, β-dihydroxy group, the following compound (F) in an organic solvent:
以下に、実施例により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はない。
なお、本願において、キノフタロン化合物の置換基の位置は、下記の命名法に従って記載している。
In addition, in this application, the position of the substituent of a quinophthalone compound is described according to the following nomenclature.
［実施例１］
（前記具体例番号３９の化合物の合成）
５−ブロモ−３’−ヒドロキシ−キノフタロン５．０ｇ、ＤＭＩ５０ｍｌ、炭酸カリウム８．２６ｇおよびα−チオグリセロール２．４３ｇを１０４〜１０６℃で２．０時間反応した後、昇温し、１１４〜１１６℃で５．０時間反応した。反応液を３０℃まで冷却し、水３００ｍｌ排出し、１５分間攪拌後、濾取し、濾取物を水２００ｍｌにて２回洗浄後、メタノール１００ｍｌと水１００ｍｌとともに３０分間攪拌後、濾取し、濾取物を水２５０ｍｌにて洗浄、乾燥し、橙色の粉末４．７ｇの中間体（ア）を得た。
得られた中間体（ア）４．０ｇ、ＤＭＩ５０ｍｌ、ｎ−テトラブチルアンモニウム硫酸水素塩０．１７ｇおよびヨウ化エチル４．７ｇを３５℃で攪拌下、２５％水酸化ナトリウム水溶液７．２ｇを３０分間で滴下し、昇温し、５０〜５５℃で２．０時間攪拌した。反応液を２５℃まで冷却し、水１５０ｍｌに排出し、酢酸を添加してｐＨ６とした後、酢酸エチル１５０ｍｌにて抽出し、水１００ｍｌにて３回洗浄し、濾過、濃縮した後、カラムクロマトグラフィーで精製し、褐色粘性樹脂２．３ｇを得た。
下記分析結果により、目的の具体例番号３９の化合物であることを確認した。このもののアセトン溶液での極大吸収波長は４５０ｎｍ、４２８ｎｍであった。
ＦＤ−ＭＳ分析：ｍ／ｚ ４５１
元素分析値（Ｃ２５２Ｈ２５ＮＯ５Ｓ１）：
Ｃ Ｈ Ｎ
計算値（％） ６６．５０ ５．５８ ３．１０
実測値（％） ６６．４８ ５．５５ ３．０９
[Example 1]
(Synthesis of the compound of the specific example No. 39)
After reacting 5.0 g of 5-bromo-3′-hydroxy-quinophthalone, 50 ml of DMI, 8.26 g of potassium carbonate and 2.43 g of α-thioglycerol at 104 to 106 ° C. for 2.0 hours, the temperature was raised, and 114 to 116 The reaction was carried out at ° C for 5.0 hours. The reaction solution is cooled to 30 ° C., discharged with 300 ml of water, stirred for 15 minutes and then filtered. The filtered product was washed with 200 ml of water twice, stirred with 100 ml of methanol and 100 ml of water for 30 minutes, and then filtered. The filtered product was washed with 250 ml of water and dried to obtain 4.7 g of an intermediate powder (a) as an orange powder.
The obtained intermediate (a) 4.0 g, DMI 50 ml, n-tetrabutylammonium hydrogen sulfate 0.17 g and ethyl iodide 4.7 g were stirred at 35 ° C., and 25% sodium hydroxide aqueous solution 7.2 g 30 The mixture was added dropwise over a period of minutes, the temperature was raised, and the mixture was stirred at 50 to 55 ° C for 2.0 hours. The reaction solution is cooled to 25 ° C., discharged into 150 ml of water, acetic acid is added to adjust the pH to 6, followed by extraction with 150 ml of ethyl acetate, washing with 100 ml of water, filtration and concentration, and column chromatography. Purification by chromatography gave 2.3 g of a brown viscous resin.
The following analysis results confirmed that the compound was the target compound of specific example number 39. The maximum absorption wavelength of this in an acetone solution was 450 nm and 428 nm.
FD-MS analysis: m / z 451
Elemental analysis value (C 252 H 25 NO 5 S 1 ):
C H N
Calculated value (%) 66.50 5.58 3.10
Actual value (%) 66.48 5.55 3.09
［実施例２］
（前記具体例番号９１の化合物の合成）
５，６−ジクロロ−３’−ヒドロキシ−キノフタロン１５．０ｇ、ＤＭＩ１６０ｍｌ、炭酸カリウム２０．３ｇおよびα−チオグリセロール１１．３ｇを１００〜１０３℃で２．５時間反応した後、昇温し、１１０〜１１３℃で２．０時間反応した。反応液を３０℃まで冷却し、水５００ｍｌに排出し、３０分間攪拌後、濾取し、濾取物を水５００ｍｌにて２回洗浄後、乾燥し、茶色の固形物２０．０ｇの中間体（イ）を得た。
得られた中間体（イ）１０．０ｇ、ＤＭＩ１５０ｍｌ、ｎ−テトラブチルアンモニウム硫酸水素塩０．６８ｇおよびヨウ化エチル２０．３ｇを３５℃で攪拌下、２５％水酸化ナトリウム水溶液２８．７ｇを３０分間で滴下し、昇温し、６０〜６５℃で２．０時間攪拌した。反応液を２５℃まで冷却し、水５００ｍｌに排出し、酢酸にて排出液をｐＨ６とした後、酢酸エチル３００ｍｌにて抽出し、水２００ｍｌにて４回洗浄し、濾過、濃縮した後、カラムクロマトグラフィーで精製し、褐色粘性樹脂２．５ｇを得た。
下記分析結果により、目的の具体例番号９１の化合物であることを確認した。このもののアセトン溶液での最大吸収波長は４５６ｎｍであった。
ＦＤ−ＭＳ分析：ｍ／ｚ ６１３
元素分析値（Ｃ３２Ｈ３９ＮＯ７Ｓ２）：
Ｃ Ｈ Ｎ
計算値（％） ６２．６２ ６．４０ ２．２８
実測値（％） ６２．５９ ６．３８ ２．２５
[Example 2]
(Synthesis of the compound of the specific example number 91)
After reacting 15.0 g of 5,6-dichloro-3′-hydroxy-quinophthalone, 160 ml of DMI, 20.3 g of potassium carbonate and 11.3 g of α-thioglycerol at 100 to 103 ° C. for 2.5 hours, the temperature was raised, The reaction was carried out at ~ 113 ° C for 2.0 hours. The reaction solution was cooled to 30 ° C., discharged into 500 ml of water, stirred for 30 minutes, and then collected by filtration. The filtered product was washed twice with 500 ml of water, dried, and an intermediate of 20.0 g of a brown solid. (I) was obtained.
The resulting intermediate (I) 10.0 g, DMI 150 ml, n-tetrabutylammonium hydrogen sulfate 0.68 g and ethyl iodide 20.3 g were stirred at 35 ° C., and 25% aqueous sodium hydroxide solution 28.7 g was added 30 The solution was added dropwise over a period of minutes, the temperature was raised, and the mixture was stirred at 60 to 65 ° C. for 2.0 hours. The reaction solution is cooled to 25 ° C., discharged into 500 ml of water, and the discharged solution is adjusted to pH 6 with acetic acid, extracted with 300 ml of ethyl acetate, washed four times with 200 ml of water, filtered and concentrated, and then column. Purification by chromatography gave 2.5 g of a brown viscous resin.
From the following analysis results, it was confirmed that the compound was the target compound of specific example number 91. The maximum absorption wavelength of this in an acetone solution was 456 nm.
FD-MS analysis: m / z 613
Elemental analysis (C 32 H 39 NO 7 S 2):
C H N
Calculated value (%) 62.62 6.40 2.28
Actual value (%) 62.59 6.38 2.25
［実施例３］
（前記具体例番号９４の化合物の合成）
前記実施例２で合成した中間体（イ）１．０ｇ、ＤＭＩ２０ｍｌ、ｎ−テトラブチルアンモニウム硫酸水素塩０．０６８ｇおよび２−ブロモエチルエチルエーテル２．２８ｇを２５℃で攪拌下、２５％水酸化ナトリウム水溶液２．４ｇを３分間で滴下し、昇温し、９０℃で２．０時間攪拌した。反応液を２５℃まで冷却し、水１００ｍｌに排出し、酢酸にて排出液をｐＨ６とした後、酢酸エチル１００ｍｌにて抽出、水１００ｍｌにて３回洗浄し、濾過、濃縮した後、カラムクロマトグラフィーで精製し、褐色粘性樹脂０．２４ｇを得た。
下記分析結果により、目的の具体例番号９４の化合物であることを確認した。このもののアセトン溶液での最大吸収波長は４５７ｎｍ、４３５ｎｍであった。
ＦＤ−ＭＳ分析：ｍ／ｚ ７８９
元素分析値（Ｃ４０Ｈ５５ＮＯ１１Ｓ２）：
Ｃ Ｈ Ｎ
計算値（％） ６０．８１ ７．０２ １．７７
実測値（％） ６０．８３ ７．０１ １．７５
[Example 3]
(Synthesis of the compound of the specific example No. 94)
The intermediate (a) synthesized in Example 2 (1.0 g), DMI (20 ml), n-tetrabutylammonium hydrogen sulfate 0.068 g and 2-bromoethyl ethyl ether (2.28 g) were stirred at 25 ° C. under 25% hydroxylation. Sodium aqueous solution 2.4g was dripped in 3 minutes, and it heated up, and stirred at 90 degreeC for 2.0 hours. The reaction solution is cooled to 25 ° C., discharged into 100 ml of water, adjusted to pH 6 with acetic acid, extracted with 100 ml of ethyl acetate, washed three times with 100 ml of water, filtered and concentrated, and then column chromatography. Purification by chromatography gave 0.24 g of a brown viscous resin.
The following analysis results confirmed that the compound was the target compound of specific example number 94. The maximum absorption wavelength of this in an acetone solution was 457 nm and 435 nm.
FD-MS analysis: m / z 789
Elemental analysis (C 40 H 55 NO 11 S 2):
C H N
Calculated value (%) 60.81 7.02 1.77
Actual value (%) 60.83 7.01 1.75
［実施例４］
（前記具体例番号９６の化合物の合成）
前記実施例２で合成した中間体（イ）４．０ｇ、ＤＭＩ４０ｍｌ、トルエン１６０ｍｌ、ｐ−トルエンスルホン酸０．２ｇおよび２−ブタノン０．８６ｇを、１１２〜１２１℃にて１６時間脱水還流した後、２５℃まで冷却した。その後、反応液より減圧下にトルエンを留去し、水１６０ｍｌに排出、１時間攪拌後、析出物を濾取し、乾燥した後、カラムクロマトグラフィーで精製し、橙色の粉末１．８ｇを得た。
下記分析結果により、目的の具体例番号９６の化合物であることを確認した。このもののアセトン溶液での最大吸収波長は４５３ｎｍであった。
ＦＤ−ＭＳ分析：ｍ／ｚ ５５５
元素分析値（Ｃ２８Ｈ２９ＮＯ７Ｓ２）：
Ｃ Ｈ Ｎ
計算値（％） ６０．５２ ５．２６ ２．５２
実測値（％） ６０．５０ ５．２４ ２．５３
[Example 4]
(Synthesis of Compound of Specific Example No. 96)
After dehydrating and refluxing 4.0 g of intermediate (a) synthesized in Example 2 above, 40 ml of DMI, 160 ml of toluene, 0.2 g of p-toluenesulfonic acid and 0.86 g of 2-butanone at 112 to 121 ° C. for 16 hours. And cooled to 25 ° C. Thereafter, toluene was distilled off from the reaction solution under reduced pressure, discharged into 160 ml of water, stirred for 1 hour, the precipitate was collected by filtration, dried and purified by column chromatography to obtain 1.8 g of an orange powder. It was.
The following analysis results confirmed that the compound was the target compound of specific example number 96. The maximum absorption wavelength of this in an acetone solution was 453 nm.
FD-MS analysis: m / z 555
Elemental analysis (C 28 H 29 NO 7 S 2):
C H N
Calculated value (%) 60.52 5.26 2.52
Actual value (%) 60.50 5.24 2.53
［実施例５］
（前記具体例番号９７の化合物の合成）
前記実施例２で合成した中間体（イ）４．０ｇ、ＤＭＩ４０ｍｌ、トルエン１６０ｍｌ、ｐ−トルエンスルホン酸０．２ｇおよび２−ブタノン２．１６ｇを、１１２〜１１８℃にて１時間脱水還流した後、２−ブタノン２．１６ｇを追加し、１１８〜１２１℃にて１６時間脱水還流した。さらに、ｐ−トルエンスルホン酸０．１ｇと２−ブタノン２．１６ｇを追加し、１１８〜１２１℃にて１８時間脱水還流した後、２５℃まで冷却し、反応液を減圧下でトルエンを留去し、水１６０ｍｌに排出、１時間攪拌後、析出物を濾取し、乾燥した。得られた粗製物をカラムクロマトグラフィーで精製し、橙色の粉末２．９ｇを得た。
下記分析結果により、目的の具体例番号９７の化合物であることを確認した。このもののアセトン溶液での最大吸収波長は４５３ｎｍであった。
ＦＤ−ＭＳ分析：ｍ／ｚ ６０９
元素分析値（Ｃ３２Ｈ３５ＮＯ７Ｓ２）：
Ｃ Ｈ Ｎ
計算値（％） ６３．０３ ５．７９ ２．３０
実測値（％） ６３．００ ５．７５ ２．３３
[Example 5]
(Synthesis of the compound of the specific example No. 97)
After dehydrating and refluxing 4.0 g of the intermediate (i) synthesized in Example 2 above, 40 ml of DMI, 160 ml of toluene, 0.2 g of p-toluenesulfonic acid and 2.16 g of 2-butanone at 112 to 118 ° C. for 1 hour. 2-butanone (2.16 g) was added, and the mixture was dehydrated and refluxed at 118 to 121 ° C. for 16 hours. Further, 0.1 g of p-toluenesulfonic acid and 2.16 g of 2-butanone were added, dehydrated and refluxed at 118 to 121 ° C. for 18 hours, then cooled to 25 ° C., and toluene was distilled off under reduced pressure. After discharging into 160 ml of water and stirring for 1 hour, the precipitate was collected by filtration and dried. The obtained crude product was purified by column chromatography to obtain 2.9 g of orange powder.
The following analysis results confirmed that the compound was the target compound of specific example No. 97. The maximum absorption wavelength of this in an acetone solution was 453 nm.
FD-MS analysis: m / z 609
Elemental analysis (C 32 H 35 NO 7 S 2):
C H N
Calculated value (%) 63.03 5.79 2.30
Actual value (%) 63.00 5.75 2.33
［実施例６］
（前記具体例番号９２の化合物の合成）
４，５，６，７−テトラクロロ−３’−ヒドロキシ−キノフタロン５．０ｇ、ＤＭＩ８０ｍｌ、炭酸カリウム６．５ｇおよびα−チオグリセロール２．５ｇを８０〜８３℃で２．０時間反応した。反応液を３０℃まで冷却し、水２００ｍｌに排出し、酢酸にてｐＨ６とし、３０分間攪拌後、濾取し、濾取物を水１５０ｍｌにて２回洗浄後、乾燥し、こげ茶色の固形物５．３ｇの中間体（ウ）を得た。
得られた中間体（ウ）５．０ｇ、ＤＭＩ５０ｍｌ、ｎ−テトラブチルアンモニウム硫酸水素塩０．１５ｇおよびヨウ化エチル２．７ｇを添加し、２５℃にて攪拌下、２５％水酸化ナトリウム水溶液４．２ｇを５分間で滴下し、昇温し、６０〜６２℃で３０分間攪拌した。反応液を２５℃まで冷却し、１ｗｔ％酢酸水溶液２００ｇに排出し、１時間攪拌後、濾取、水２００ｍｌにて２回洗浄し、乾燥した後、カラムクロマトグラフィーで精製し、褐色粘性樹脂２．３ｇを得た。
下記分析結果により、目的の具体例番号９２の化合物であることを確認した。このもののアセトン溶液での最大吸収波長は４４８ｎｍであった。
ＦＤ−ＭＳ分析：ｍ／ｚ ６８１
元素分析値（Ｃ３２Ｈ３７Ｃｌ２ＮＯ７Ｓ２）：
Ｃ Ｈ Ｎ
計算値（％） ５６．３０ ５．４６ ２．０５
実測値（％） ５６．３２ ５．４８ ２．０３
[Example 6]
(Synthesis of the compound of the specific example number 92)
4,5,6,7-Tetrachloro-3′-hydroxy-quinophthalone 5.0 g, DMI 80 ml, potassium carbonate 6.5 g and α-thioglycerol 2.5 g were reacted at 80 to 83 ° C. for 2.0 hours. The reaction solution is cooled to 30 ° C., discharged into 200 ml of water, adjusted to pH 6 with acetic acid, stirred for 30 minutes, collected by filtration, washed with 150 ml of water twice, dried and dark brown solid. An intermediate (U) of 5.3 g of product was obtained.
5.0 g of the obtained intermediate (c), 50 ml of DMI, 0.15 g of n-tetrabutylammonium hydrogen sulfate and 2.7 g of ethyl iodide were added, and 25% aqueous sodium hydroxide solution 4 was stirred at 25 ° C. .2 g was added dropwise over 5 minutes, the temperature was raised, and the mixture was stirred at 60 to 62 ° C. for 30 minutes. The reaction solution is cooled to 25 ° C., discharged into 200 g of 1 wt% acetic acid aqueous solution, stirred for 1 hour, filtered, washed twice with 200 ml of water, dried, purified by column chromatography, brown viscous resin 2 .3 g was obtained.
The following analysis results confirmed that the compound was the target compound of specific example number 92. The maximum absorption wavelength of this in an acetone solution was 448 nm.
FD-MS analysis: m / z 681
Elemental analysis (C 32 H 37 Cl 2 NO 7 S 2):
C H N
Calculated value (%) 56.30 5.46 2.05
Actual value (%) 56.32 5.48 2.03
［比較化合物１］
実施例２で合成した下記構造式の中間体（イ）
Intermediate (a) of the following structural formula synthesized in Example 2
［比較化合物２］
特開昭４９−１３４７３９号公報７頁の実施例４３の操作法に従って合成した、前記構造式（Ｉ）の化合物
[Comparative Compound 2]
Compound of the above structural formula (I) synthesized according to the procedure of Example 43 on page 7 of JP-A-49-13439
［溶解度測定］
実施例１〜６で合成した各キノフタロン化合物および比較化合物１〜２の乳酸メチル及び乳酸エチルに対する溶解度を測定した。結果を表２に示す。
[Solubility measurement]
The solubility of each quinophthalone compound synthesized in Examples 1 to 6 and
［スペクトル測定］
実施例１〜６で合成した各キノフタロン化合物のスペクトルの測定を行った。
樹脂（ＰＭＭＡ）／色素（実施例１〜６の化合物、比較化合物１〜２の各キノフタロン化合物）／乳酸エチル＝４ｇ／０．４ｇ／１６ｇの割合で混合溶解した溶液を、ガラス板（５ｃｍ×５ｃｍ）にスピンコーター（１０００ｒｐｍ ３０秒間）を用いて塗布し、６０℃で１時間乾燥して、着色試料を作成し、島津製作所のＵＶ−１６００ＰＣを使用して、吸収スペクトルを測定した。各スペクトルの測定結果を図１〜６に示す。
比較化合物１、２については、色素が溶解しなかったため、スペクトルを測定することができなかった。
[Spectrum measurement]
The spectrum of each quinophthalone compound synthesized in Examples 1 to 6 was measured.
Resin (PMMA) / pigment (compounds of Examples 1-6, each quinophthalone compound of Comparative Compounds 1-2) / ethyl lactate = 4 g / 0.4 g / 16 g mixed and dissolved in a glass plate (5 cm × 5 cm) was applied using a spin coater (1000 rpm for 30 seconds), dried at 60 ° C. for 1 hour to prepare a colored sample, and an absorption spectrum was measured using UV-1600PC manufactured by Shimadzu Corporation. The measurement results of each spectrum are shown in FIGS.
For Comparative Compounds 1 and 2, the spectrum could not be measured because the dye did not dissolve.
［産業上の利用可能性］
本発明のキノフタロン化合物は、作業環境及び安全性に優れた乳酸メチル、乳酸エチルおよび樹脂に対する溶解性に優れた鮮明な黄色の色素で、高分子材料の着色材として好適である。
[Industrial applicability]
The quinophthalone compound of the present invention is a bright yellow pigment excellent in solubility in methyl lactate, ethyl lactate and resin excellent in working environment and safety, and is suitable as a colorant for a polymer material.
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| JP4793209B2 (en) * | 2006-09-29 | 2011-10-12 | 大日本印刷株式会社 | Sublimation type thermal transfer sheet |
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| KR20170063633A (en) * | 2014-09-30 | 2017-06-08 | 꽁빠니 제네날 드 에따블리세망 미쉘린 | Sulphur-containing aromatic polyol compound |
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