JPS63185984A - Spironaphthopyran compound - Google Patents
Spironaphthopyran compoundInfo
- Publication number
- JPS63185984A JPS63185984A JP1623287A JP1623287A JPS63185984A JP S63185984 A JPS63185984 A JP S63185984A JP 1623287 A JP1623287 A JP 1623287A JP 1623287 A JP1623287 A JP 1623287A JP S63185984 A JPS63185984 A JP S63185984A
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- groups
- compound
- formula
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 25
- 125000002252 acyl group Chemical group 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 125000003277 amino group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- -1 2-methylenebenzoxazoline compound Chemical class 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 238000004040 coloring Methods 0.000 abstract description 2
- 239000007793 ph indicator Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000906 photoactive agent Substances 0.000 description 3
- ACNUVXZPCIABEX-UHFFFAOYSA-N 3',6'-diaminospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical class O1C(=O)C2=CC=CC=C2C21C1=CC=C(N)C=C1OC1=CC(N)=CC=C21 ACNUVXZPCIABEX-UHFFFAOYSA-N 0.000 description 2
- UYMBCDOGDVGEFA-UHFFFAOYSA-N 3-(1h-indol-2-yl)-3h-2-benzofuran-1-one Chemical class C12=CC=CC=C2C(=O)OC1C1=CC2=CC=CC=C2N1 UYMBCDOGDVGEFA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMKZIDQTQXLDP-UHFFFAOYSA-N C1=CC=C(C=C1)S(=O)(C2=CC=CC=C2)(C3=CC=C(C=C3)SC4=CC=C(C=C4)S(=O)(C5=CC=CC=C5)(C6=CC=CC=C6)O)O Chemical compound C1=CC=C(C=C1)S(=O)(C2=CC=CC=C2)(C3=CC=C(C=C3)SC4=CC=C(C=C4)S(=O)(C5=CC=CC=C5)(C6=CC=CC=C6)O)O ZAMKZIDQTQXLDP-UHFFFAOYSA-N 0.000 description 2
- ATJXMQHAMYVHRX-CPCISQLKSA-N Ellagic acid Natural products OC1=C(O)[C@H]2OC(=O)c3cc(O)c(O)c4OC(=O)C(=C1)[C@H]2c34 ATJXMQHAMYVHRX-CPCISQLKSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LDKDGDIWEUUXSH-UHFFFAOYSA-N Thymophthalein Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3C(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C LDKDGDIWEUUXSH-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- VHNFAQLOVBWGGB-UHFFFAOYSA-N benzhydrylbenzene;3h-2-benzofuran-1-one Chemical class C1=CC=C2C(=O)OCC2=C1.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 VHNFAQLOVBWGGB-UHFFFAOYSA-N 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 2
- 125000003387 indolinyl group Chemical class N1(CCC2=CC=CC=C12)* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 2
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- MEMWNTAFSYIKSU-UHFFFAOYSA-N pyran Chemical compound O1C=CC=C=C1 MEMWNTAFSYIKSU-UHFFFAOYSA-N 0.000 description 2
- ZHFPEICFUVWJIS-UHFFFAOYSA-M sodium 2-hydroxy-5-[(3-nitrophenyl)diazenyl]benzoate Chemical compound [Na+].Oc1ccc(cc1C([O-])=O)N=Nc1cccc(c1)[N+]([O-])=O ZHFPEICFUVWJIS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 150000004961 triphenylmethanes Chemical class 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- CCIAVEMREXZXAK-UHFFFAOYSA-M 4-(dimethylamino)benzenediazonium;chloride Chemical compound [Cl-].CN(C)C1=CC=C([N+]#N)C=C1 CCIAVEMREXZXAK-UHFFFAOYSA-M 0.000 description 1
- NQBCOOUVQLBMAC-UHFFFAOYSA-M 4-ethoxybenzenediazonium;chloride Chemical compound [Cl-].CCOC1=CC=C([N+]#N)C=C1 NQBCOOUVQLBMAC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical class C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規物質に関し、とくに、ＤＨ指示薬用、感光
材料用電子供与性呈色性化合物として使用可能な新規ス
ピロピラン化合物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a new substance, and particularly to a new spiropyran compound that can be used as an electron-donating color-forming compound for DH indicators and photosensitive materials.
（従来技術） ′
電子供与性呈色性有機化合物としてアリザリンイエロー
Ｒ１メタニルイエロー、コンゴーレッド、ニトロフェノ
ール類、チモールフタレイン、メチルレッドなどがｐＨ
指示薬として利用されている（Ｓｃｈｕｌｚ著Ｉ Ｆａ
ｒｂｓｔｏｆｆ ｔａｂｅｌ ｆｅｎ 第１巻」）。(Prior art) ' Electron-donating color-forming organic compounds such as alizarin yellow R1 methanyl yellow, Congo red, nitrophenols, thymol phthalein, and methyl red are
It is used as an indicator (I Fa by Schulz).
rbstoff tabel fen vol. 1).
また、トリフェニルメタンフタリド化合物、フルオラン
化合物、フェノチアジン化合物、インドリルフタリド化
合物、ロイコオーラミン化合物、ローダミンラクタム化
合物、ローダミンラクトン化合物、インドリン化合物、
トリフェニルメタン化合物、アザフタリド化合物などが
、染料便覧（丸首、有機合成化学協会編）に記載されて
おり、特公昭４５−３０８８５号公報、特公昭４９−５
２１号公報、特開昭６１−２０７４８２号公報に開示さ
れている。In addition, triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leucoauramine compounds, rhodamine lactam compounds, rhodamine lactone compounds, indoline compounds,
Triphenylmethane compounds, azaphthalide compounds, etc. are listed in the Dye Handbook (Marukubi, edited by the Organic Synthetic Chemistry Association), and are published in Japanese Patent Publications No. 30885-1985 and Japanese Patent Publication No. 49-5
This method is disclosed in Japanese Patent Laid-Open No. 21-207482.
（発明が解決しようとする問題点）
アリザリンイエローＲ１メタニルイエロー、コンゴーレ
ッド、平トロフェノール類、チモールフタレイン、メチ
ルレッドなどのｐＨ指示薬として使われている電子供与
性呈色性有機化合物はいずれも着色状態からの変色であ
った。またトリフェニルメタンフタリド化合物、フルオ
ラン化合物、フェノチアジン化合物、インドリルフタリ
ド化合物、ロイコオーラミン化合物、ローダミンラクタ
ム化合物、ローダミンラクトン化合物、インドリン化合
物、トリフェニルメタン化合物、アザフタリド化合物は
無色または淡色からの着色であるが、いずれも赤色〜緑
色であり、無色から黄色の着色を呈するものは存在しな
かった。無色または淡色から赤〜緑色への着色では、溶
液が有色である場合、色調の変化が小さく判別が困難で
必るという問題があった。また着色状態から黄色への変
色では、感圧材料または感光月利の構造要素として用い
ることができないという問題があった。このように無色
から黄色に着色する電子供与性呈色性化合物が待望され
ていた。(Problems to be Solved by the Invention) Which electron-donating color-forming organic compounds are used as pH indicators, such as Alizarin Yellow R1 metanyl yellow, Congo red, platotrophenols, thymolphthalein, and methyl red? The color also changed from the colored state. In addition, triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leuco auramine compounds, rhodamine lactam compounds, rhodamine lactone compounds, indoline compounds, triphenylmethane compounds, and azaphthalide compounds are colorless or light colored. However, all of them were red to green in color, and none showed coloration ranging from colorless to yellow. When coloring from colorless or light color to red to green, there is a problem in that when the solution is colored, the change in color tone is small and difficult to distinguish. Further, if the color changes from a colored state to yellow, there is a problem that it cannot be used as a pressure-sensitive material or a structural element of a photosensitive material. Thus, an electron-donating color-forming compound that changes color from colorless to yellow has been long-awaited.
本発明はかかる無色から黄色に着色する電子供与性呈色
性化合物を提供する。The present invention provides such an electron-donating color-forming compound that changes color from colorless to yellow.
［問題点を解決するための手段］
本発明は前期問題点を解決するための新規スピロピラン
化合物に関するものである。すなわち本発明により提供
される新規化合物とは、一般式（Ａ＞で表されるベンゾ
オキサゾリノスピロナフトピラン化合物である。[Means for Solving the Problems] The present invention relates to a novel spiropyran compound for solving the above problems. That is, the novel compound provided by the present invention is a benzoxazolinospironaphthopyran compound represented by the general formula (A>).
（式中、Ｒ１、Ｒ３、Ｒ４、Ｒ５はヒドロキシ基、アミ
ノ基、有機置換アミノ基、炭素数１〜６のアルコキシ基
、炭素数７〜１５のアラルコキシ基、炭素数６〜１４の
アリーロキシ基、炭素数１〜２０のアルキル基、炭素数
７〜１５のアラルキル基、炭素数６〜１４のアリール基
、ハロゲン基、カルボキシ基、炭素数２〜１０のアルコ
キシカルボニル基、炭素数２〜１０のアシル基、ニトロ
基から選ばれた置換基を表し、Ｒ２はヒドロキシ基、ア
ミン基、有機置換アミン基、炭素数１〜６のアルコキシ
基、炭素数７〜１５のアラルコキシ基、炭素数６〜１４
のアリーロキシ基、炭素数７・〜１５のアラルキル基、
炭素数６〜１４のアリール基、ハロゲン基、カルボキシ
基、炭素数２〜１０のアルコキシカルボニル基、炭素数
２〜１０のアシル基、二１・口塞から選ばれた置換基を
表し、０およびｎはＯ〜４の整数、ｍは０〜２の整数で
あり、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５はそれぞれ同種で
あっても異種であってもよい。〉
かかる式（Ａ＞におＣプる置換基Ｒ１、Ｒ２、Ｒ３、Ｒ
４、Ｒ５の具体例としては、ヒドロキシ基；アミノ基：
メチルアミノ基、ジエチルアミノ基などの有Ｉａ置換ア
ミン基；メトキシ基、エトキシ基、ｔｅｒｔ−ブトキシ
基などの炭素数１〜６のアルコキシ基：ベンジロキシ基
などの炭素数７〜１５のアラルコキシ基；フェノキシ基
などの炭素数６〜１４のアリーロキシ基；ベンジル基、
２，４゜６−トリメチルベンジル基、（２−ナフチル）
エチル基などの炭素数７〜１５のアラルキル基；フェニ
ル基、４−ニトロフェニル基、１−ナフチル基などの炭
素数６是１４のアリール基；フルオロ基、クロロ基など
のハロゲン基：カルポキシ基：エトキシカルボニル基な
どの炭素数２〜１ｏのアルコキシカルボニル基ニアセチ
ル基、ベンゾイル基などの炭素数２〜１ｏのアシル基：
ニトロ基などが挙げられ、ざらにＲ１、Ｒ２、Ｒ３、Ｒ
４、Ｒ５は、メチル基、エチル基、オクタデシル基、３
−メチルペンチル基、トリフルオロメチル基などの炭素
数′１〜２０のアルキル基の具体例として挙げることが
できる。(In the formula, R1, R3, R4, R5 are a hydroxy group, an amino group, an organic substituted amino group, an alkoxy group having 1 to 6 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, Alkyl group having 1 to 20 carbon atoms, aralkyl group having 7 to 15 carbon atoms, aryl group having 6 to 14 carbon atoms, halogen group, carboxy group, alkoxycarbonyl group having 2 to 10 carbon atoms, acyl having 2 to 10 carbon atoms R2 represents a substituent selected from a group, a nitro group, a hydroxy group, an amine group, an organically substituted amine group, an alkoxy group having 1 to 6 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, and a substituent having 6 to 14 carbon atoms.
aryloxy group, aralkyl group having 7 to 15 carbon atoms,
Represents a substituent selected from an aryl group having 6 to 14 carbon atoms, a halogen group, a carboxy group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, and 21. n is an integer of 0 to 4, m is an integer of 0 to 2, and R1, R2, R3, R4, and R5 may be the same or different. 〉 Substituents R1, R2, R3, R
4. Specific examples of R5 include hydroxy group; amino group:
Ia-substituted amine groups such as methylamino and diethylamino groups; alkoxy groups with 1 to 6 carbon atoms such as methoxy, ethoxy, and tert-butoxy groups; aralkoxy groups with 7 to 15 carbon atoms such as benzyloxy; phenoxy groups Aryloxy group having 6 to 14 carbon atoms such as; benzyl group,
2,4゜6-trimethylbenzyl group, (2-naphthyl)
Aralkyl groups with 7 to 15 carbon atoms such as ethyl groups; aryl groups with 6 to 14 carbon atoms such as phenyl groups, 4-nitrophenyl groups, and 1-naphthyl groups; halogen groups such as fluoro groups and chloro groups; carpoxy groups: Alkoxycarbonyl group having 2 to 1 carbon atoms such as ethoxycarbonyl group Niacetyl group, acyl group having 2 to 1 carbon atoms such as benzoyl group:
Examples include nitro groups, and roughly R1, R2, R3, R
4, R5 is a methyl group, an ethyl group, an octadecyl group, 3
Specific examples of alkyl groups having 1 to 20 carbon atoms include -methylpentyl group and trifluoromethyl group.
前述のとおりＲ１、Ｒ２、Ｒ３、Ｒ，４、Ｒ５はそれぞ
れ同種であっても異種でおってもよい。As described above, R1, R2, R3, R, 4, and R5 may be of the same type or different types.
かかる式（Ａ）の化合物は、酸性物質の存在により無色
→黄色という呈色を示す性質を有している。ざらには置
換基の選択、あるいは適当な媒体との組み合わせなどに
よってフォトクロミック性を発現させることも可能であ
る。The compound of formula (A) has the property of changing color from colorless to yellow in the presence of an acidic substance. In addition, it is also possible to develop photochromic properties by selecting substituents or by combining with a suitable medium.
かかる式（Ａ）で表される化合物の代表的な具体例とし
ては、スピロ［ベンゾオキサゾリン−２゜３’−［３Ｈ
］−ナフト［２，１−ｂコピラン］の３．２′−ジメチ
ル誘導体、３，２′−ジメチル−６−クロロ誘導体、３
，２′−ジメチル−６−メトキシ誘導体、３−エチル−
２′−メ１〜キシ＝８−ブロモ誘導体、３−シクロへキ
シル−２′−フェノキシ−９−メトキシ誘導体、３−ベ
ンジル−２′−フェニル誘導体、３−（２−メチル−４
−二トロベンジル）−２′−フェニル誘導体、３−フェ
ニルエチル−２’−（４−タロロフェニル〉−５，６−
ジクロロ誘導体、３，２′−ジフェニル−５−トリフル
オロメチル−６′−ヒドロギシ誘導体などが挙げられる
。A typical example of the compound represented by formula (A) is spiro[benzoxazoline-2゜3'-[3H
]-3,2'-dimethyl derivative of naphtho[2,1-b copyran], 3,2'-dimethyl-6-chloro derivative, 3
, 2'-dimethyl-6-methoxy derivative, 3-ethyl-
2'-Me1-xy-8-bromo derivative, 3-cyclohexyl-2'-phenoxy-9-methoxy derivative, 3-benzyl-2'-phenyl derivative, 3-(2-methyl-4
-nitrobenzyl)-2'-phenyl derivative, 3-phenylethyl-2'-(4-talolophenyl>-5,6-
Examples include dichloro derivatives, 3,2'-diphenyl-5-trifluoromethyl-6'-hydroxy derivatives, and the like.
式（Ａ＞または（Ｂ）によって表される本発明の新規ス
ピロピラン化合物は、酸の存在により無色から黄色に着
色する電子供与性呈色性有機化合物である。The novel spiropyran compound of the present invention represented by formula (A> or (B)) is an electron-donating color-forming organic compound that changes color from colorless to yellow in the presence of an acid.
本発明のかかる式（Ａ＞の化合物は、例えば次の製造方
法に従って製造される。The compound of formula (A>) of the present invention is produced, for example, according to the following production method.
一般式（Ｉ＞
で表される２−メチレンベンゾオキサゾリン化合物と、
一般式（Ｉｔ）
１４ｍ
で表されるヒドロキシナフトアルデヒド化合物を反応さ
せて式（Ａ＞の化合物を製造する。A 2-methylenebenzoxazoline compound represented by the general formula (I>),
A hydroxynaphthaldehyde compound represented by the general formula (It) 14m is reacted to produce a compound represented by the formula (A>).
本発明の式（Ａ＞の化合物の他の製造法の例としては、
一般式（ＩＩＩ）
で表されるベンゾオキサゾール化合物、四級化剤Ｒ’
−Ｘ （Ｘはアニオン性脱離基）、塩基および一般式（
ＩＩ）の化合物を任意の順で加え反応させる方法も挙げ
ることができる。Examples of other methods for producing the compound of formula (A>) of the present invention include:
Benzoxazole compound represented by general formula (III), quaternizing agent R'
-X (X is an anionic leaving group), base and general formula (
A method of adding the compounds II) in any order and reacting can also be mentioned.
また製造段階における精製方法としては各種溶剤による
再結晶法、シワ力力ラムなどによるカラムクロマト分離
あるいは活性炭処理などが好適な例として挙げることが
できる。Preferred examples of purification methods in the manufacturing stage include recrystallization using various solvents, column chromatography using a wrinkle ram, and treatment with activated carbon.
本発明の新規スピロピラン化合物の使用例としては、ｐ
Ｈ指示薬として使用可能であるばかりか、光活性剤と絹
み合わせることにより感光材料としても使用可能である
。かかる光活性剤とは、光照射により遊離基を発生する
物質である。具体例としては、四臭化炭素、α、α、α
−トリブロモアセ１〜フェノン、ω、ω、ω−トリブ凸
七キナルジン、１．３−ベンゼンスルフォニルクロライ
ド、ヘキサプロ［ジメチルスルフォン、４−エトキシベ
ンゼンジアゾニウムクロライド、４−ジアゾ−２，５−
ジメトキシ−ジフェニル、４−ジメチルアミノベンゼン
ジアゾニウムクロライド、４−ジェトキシアミノベンゼ
ンジアゾニウムクロライド１−ジアゾ−２，５−ジクロ
ル−４−ベンジルアミノベンピン、１−ジアゾ−４−メ
チルベンジルアミノ−２，５−ｊエトキシベンゼン、１
−ジアゾ−２，５−ジェトキシベンゾイルアミノベンピ
ン、１−ジアゾ−４−トリルメルカプト−２，５−ジェ
トキシベンゼン、ビス［４−（ジフェニルスルフィノ〉
フェニル］スルフィドφビスーヘキリーフルオロホスフ
エート、ビス［４−（ジフェニルスルフィノ）フェニル
］スルフィド・ビス−へキサフルオロアセテート、ビス
［４−（ジフェニルスルフィン）フェニルコスルフイド
・ビスーヘキサフルオロアンチモネート、ビス［４−（
ジフェニルスルフィノ〉フェニル］スルフィド・ビス−
バークロレート、ビス［４−（ジフェニルスルフィノ）
フェニル］スルフィド・ビス−ヘキサフルオロホスフェ
ートなどが挙げられる。Examples of the use of the novel spiropyran compound of the present invention include p
Not only can it be used as an H indicator, but it can also be used as a photosensitive material by combining it with a photoactive agent. Such a photoactive agent is a substance that generates free radicals when irradiated with light. Specific examples include carbon tetrabromide, α, α, α
-tribromoace1-phenone, ω, ω, ω-tribconvex hepquinaldine, 1,3-benzenesulfonyl chloride, hexapro[dimethylsulfone, 4-ethoxybenzenediazonium chloride, 4-diazo-2,5-
Dimethoxy-diphenyl, 4-dimethylaminobenzenediazonium chloride, 4-jethoxyaminobenzenediazonium chloride 1-diazo-2,5-dichloro-4-benzylaminobenpine, 1-diazo-4-methylbenzylamino-2,5 -j ethoxybenzene, 1
-Diazo-2,5-jethoxybenzoylaminobenpine, 1-diazo-4-tolylmercapto-2,5-jethoxybenzene, bis[4-(diphenylsulfino)
phenyl] sulfide φ bis-hekylyfluorophosphate, bis[4-(diphenylsulfino)phenyl] sulfide bis-hexafluoroacetate, bis[4-(diphenylsulfine) phenylcosulfide bis-hexafluoroantimonate, Bis[4-(
diphenylsulfino〉phenyl]sulfide bis-
Barchlorate, bis[4-(diphenylsulfino)
[phenyl] sulfide bis-hexafluorophosphate and the like.
感光材料として用いる際、本発明の化合物は光活性剤に
対して０．１〜５０倍用いられるのが好ましい。When used as a photosensitive material, the compound of the present invention is preferably used in an amount of 0.1 to 50 times the amount of the photoactive agent.
また、酸性物質を含むマイクロカプセルと組み合わせる
ことににり感圧材料として使用することも可能である。It can also be used as a pressure-sensitive material in combination with microcapsules containing acidic substances.
（実施例）
実施例１
■ ３−メチル−２′−フェニルスピロ［ベンゾオキサ
ゾリン−２，３’ −［３Ｈ］−ナフト［２゜１−ｂ］
ピラン］の合成
３−メチル−２−ベンジリデンベンゾオキサゾリン５ｇ
および２−ヒドロキシ−１−ナフトアルデヒド５３を１
００１７ｆのエタノールに溶解し、窒素気流中５時間還
流する。反応後冷却すると結晶が析出してくる。これに
少量のエタノールを加え濾取し、得られた粗結品をエタ
ノールに溶解した溶液を５０〜６０℃まで加熱した後、
活性炭 １０ｇを加え十分に攪拌する。その後濾過し、
ろ液を濃縮して１１られた淡黄色固体をプロパツールか
ら再結晶し、３−メチル−２′−フエニルスピロ［ベン
ゾオキサゾリン−２，３’ −［３Ｈ］−ナフト［２，
１−ｂ］ピラン］の白色結晶を得た。(Example) Example 1 ■ 3-Methyl-2'-phenylspiro[benzoxazoline-2,3'-[3H]-naphtho[2°1-b]
pyran] Synthesis of 3-methyl-2-benzylidenebenzoxazoline 5g
and 2-hydroxy-1-naphthaldehyde 53 to 1
0017f in ethanol and refluxed in a nitrogen stream for 5 hours. When cooled after the reaction, crystals begin to precipitate. A small amount of ethanol was added to this and collected by filtration, and a solution of the obtained crude product dissolved in ethanol was heated to 50 to 60 ° C.
Add 10g of activated carbon and stir thoroughly. Then filter,
The pale yellow solid obtained by concentrating the filtrate was recrystallized from propatool to give 3-methyl-2'-phenylspiro[benzoxazoline-2,3'-[3H]-naphtho[2,
1-b]pyran] were obtained.
■ 分析結果
（元素分析値） 実測値（％） 計算値（％）Ｃ８３
，４８２，８
Ｈ４，８５，Ｏ
Ｎ ３．６ ３．７
■ 応用例
本化合物をアセトン中の０．１重Ｈ％の濃度で溶解させ
た溶液に、１Ｎ−塩酸を滴下すると無色から黄色に着色
した。次に、１Ｎ−水酸化ナトリウム水溶液を滴下して
いくと、黄色から無色になった。■ Analysis result (elemental analysis value) Actual value (%) Calculated value (%) C83
,482,8 H4,85,O N 3.6 3.7 ■ Application example When 1N hydrochloric acid is added dropwise to a solution of this compound dissolved in acetone at a concentration of 0.1% by weight, the color changes from colorless to yellow. Colored. Next, when a 1N aqueous sodium hydroxide solution was added dropwise, the color changed from yellow to colorless.
実施例２
実施例１と同様にして合成した３−（３−メチルベンジ
ル）−２’−（４−メチルフェニル）−５−メチルスピ
ロ［ベンゾオキサゾリン−２゜３’−［３１−１］−ナ
フト［２，１−ｂ］ピラン］をメチルエチルケトン中に
０．２重量％のｍ度で溶解させた溶液に、０．１Ｎ−硝
酸水溶液を滴下すると無色から黄色に着色した。次に、
１Ｎ−水酸化カリウム水溶液を滴下していくと、黄色か
ら無色になった。Example 2 3-(3-methylbenzyl)-2'-(4-methylphenyl)-5-methylspiro[benzoxazoline-2°3'-[31-1]-naphtho synthesized in the same manner as in Example 1 When a 0.1N aqueous nitric acid solution was added dropwise to a solution of [2,1-b]pyran] dissolved in methyl ethyl ketone at a concentration of 0.2% by weight, the solution changed from colorless to yellow. next,
When a 1N aqueous potassium hydroxide solution was added dropwise, the color changed from yellow to colorless.
（発明の効果）
本発明の化合物は、溶媒、マトリックスポリマーの種類
によらず一般的な状態では無色であるが、酸性物質の存
在により黄色に着色する電子供与性呈色性有機化合物で
ある。(Effects of the Invention) The compound of the present invention is an electron-donating color-forming organic compound that is colorless in a general state regardless of the type of solvent or matrix polymer, but is colored yellow in the presence of an acidic substance.
Claims (1)
ロナフトピラン化合物。 ▲数式、化学式、表等があります▼（Ａ） （式中、Ｒ＾１、Ｒ＾３、Ｒ＾４、Ｒ＾５はヒドロキシ
基、アミノ基、有機置換アミノ基、炭素数１〜６のアル
コキシ基、炭素数７〜１５のアラルコキシ基、炭素数６
〜１４のアリーロキシ基、炭素数１〜２０のアルキル基
、炭素数７〜１５のアラルキル基、炭素数６〜１４のア
リール基、ハロゲン基、カルボキシ基、炭素数２〜１０
のアルコキシカルボニル基、炭素数２〜１０のアシル基
、ニトロ基から選ばれた置換基を表し、Ｒ＾２はヒドロ
キシ基、アミノ基、有機置換アミノ基、炭素数１〜６の
アルコキシ基、炭素数７〜１５のアラルコキシ基、炭素
数６〜１４のアリーロキシ基、炭素数７〜１５のアラル
キル基、炭素数６〜１４のアリール基、ハロゲン基、カ
ルボキシ基、炭素数２〜１０のアルコキシカルボニル基
、炭素数２〜１０のアシル基、ニトロ基から選ばれた置
換基を表し、ｌおよびｎは０〜４の整数、ｍは０〜２の
整数であり、Ｒ＾１、Ｒ＾２、Ｒ＾３、Ｒ＾４、Ｒ＾５
はそれぞれ同種であつても異種であつてもよい。）(1) A benzoxazolinospironaphthopyran compound represented by general formula (A). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) (In the formula, R^1, R^3, R^4, and R^5 are hydroxy groups, amino groups, organic substituted amino groups, and groups with 1 to 6 carbon atoms. Alkoxy group, aralkoxy group having 7 to 15 carbon atoms, 6 carbon atoms
-14 aryloxy group, C1-20 alkyl group, C7-15 aralkyl group, C6-14 aryl group, halogen group, carboxy group, C2-10
represents a substituent selected from an alkoxycarbonyl group, an acyl group having 2 to 10 carbon atoms, and a nitro group, and R^2 is a hydroxy group, an amino group, an organically substituted amino group, an alkoxy group having 1 to 6 carbon atoms, and a carbon Aralkoxy group having 7 to 15 carbon atoms, aryloxy group having 6 to 14 carbon atoms, aralkyl group having 7 to 15 carbon atoms, aryl group having 6 to 14 carbon atoms, halogen group, carboxy group, alkoxycarbonyl group having 2 to 10 carbon atoms , represents a substituent selected from an acyl group having 2 to 10 carbon atoms, and a nitro group, l and n are integers of 0 to 4, m is an integer of 0 to 2, R^1, R^2, R ^3, R^4, R^5
may be of the same type or different types. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1623287A JPS63185984A (en) | 1987-01-28 | 1987-01-28 | Spironaphthopyran compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1623287A JPS63185984A (en) | 1987-01-28 | 1987-01-28 | Spironaphthopyran compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63185984A true JPS63185984A (en) | 1988-08-01 |
Family
ID=11910807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1623287A Pending JPS63185984A (en) | 1987-01-28 | 1987-01-28 | Spironaphthopyran compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63185984A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012163484A (en) * | 2011-02-08 | 2012-08-30 | Tokyo Denki Univ | COPOLYMER FOR pH INDICATION, AND pH MONITORING DEVICE AND pH MEASUREMENT METHOD USING THE SAME |
-
1987
- 1987-01-28 JP JP1623287A patent/JPS63185984A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012163484A (en) * | 2011-02-08 | 2012-08-30 | Tokyo Denki Univ | COPOLYMER FOR pH INDICATION, AND pH MONITORING DEVICE AND pH MEASUREMENT METHOD USING THE SAME |
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