JPS62195076A - Novel spironaphthopyran compound - Google Patents
Novel spironaphthopyran compoundInfo
- Publication number
- JPS62195076A JPS62195076A JP3532286A JP3532286A JPS62195076A JP S62195076 A JPS62195076 A JP S62195076A JP 3532286 A JP3532286 A JP 3532286A JP 3532286 A JP3532286 A JP 3532286A JP S62195076 A JPS62195076 A JP S62195076A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- carbon atoms
- substituted
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- UCIRJYREYJDVKS-UHFFFAOYSA-N 2-methylidene-3h-1,3-benzothiazole Chemical compound C1=CC=C2SC(=C)NC2=C1 UCIRJYREYJDVKS-UHFFFAOYSA-N 0.000 abstract 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- -1 cyclodecyl groups Chemical group 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 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 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 241000894007 species Species 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 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
- WOHLSTOWRAOMSG-UHFFFAOYSA-N 2,3-dihydro-1,3-benzothiazole Chemical compound C1=CC=C2SCNC2=C1 WOHLSTOWRAOMSG-UHFFFAOYSA-N 0.000 description 1
- 125000003163 2-(2-naphthyl)ethyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(C([H])=C([H])C2=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- BFNOSDJDOFMYPB-UHFFFAOYSA-N 2-ethoxy-3-methyl-2H-1,3-benzothiazole Chemical compound C1=CC=C2N(C)C(OCC)SC2=C1 BFNOSDJDOFMYPB-UHFFFAOYSA-N 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
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- PUBTWNNLKLYGSY-UHFFFAOYSA-N 3-methyl-2-(phenoxymethylidene)-1,3-benzothiazole Chemical compound S1C2=CC=CC=C2N(C)C1=COC1=CC=CC=C1 PUBTWNNLKLYGSY-UHFFFAOYSA-N 0.000 description 1
- WIFWCSTVYGGLAE-UHFFFAOYSA-N 4ah-benzo[f]chromene Chemical compound C1=CC=C2C3=CC=COC3C=CC2=C1 WIFWCSTVYGGLAE-UHFFFAOYSA-N 0.000 description 1
- 241001553014 Myrsine salicina Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])[H] 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
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 230000000007 visual effect 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】
本発明は印写用フォトクロミック材料、光学機器用フォ
トクロミック材料、記録材料用フォトクロミック材料ま
たは衣料、装飾品用フォトクロミック材料として有用な
新規なフォトクロミック化合物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photochromic compound useful as a photochromic material for printing, a photochromic material for optical instruments, a photochromic material for recording materials, or a photochromic material for clothing and ornaments.
［従来技術］
フォトクロミック化合物の代表的なものに、スピロベン
ゾピラン化合物があり、多くの化合物が知られている（
ジーエイチ・ブラウン著“フォトクロミズム″、ウィリ
ーインター１）−イエンス社、ニューヨーク＞（Ｇ、Ｈ
，Ｂｒｏｗｎ、−”ｐｈ。[Prior art] A typical photochromic compound is a spirobenzopyran compound, and many compounds are known (
“Photochromism” by G. H. Brown, Wiley Inter 1) - Jens Publishing, New York > (G, H
, Brown, -”ph.
ｔＯｃｈｒｏｍｉ Ｓｍ、Ｗｉ ｌ ｅＶ、Ｉ ｎｔｅ
ｒｓｃ ｉ ｅｎｃｅ、Ｎｅｗ Ｙｏｒｋ （１９７
１））。tOchromi Sm, WilleV, Inte
rsc i ence, New York (197
1)).
またスピロナフトピラン化合物としては特公昭４６−１
００７５号公報、特公昭４７−７７０４号公報、特公昭
４７−７７０６号公報、特開昭４９−１４５２４号公報
、Ｇｅｒ ０ｆｆｅｎ ＤＥ １，９６１，９２
１号明細書（１９７０，８゜２７）に開示されており、
また日本化学学会誌−９第１３２９〜１３３５頁（１９
８３）、Ｔｅｔｒ ａ ｈ、ｅ ｄ ｒ ｏ’ｎ第２７
巻、−９第１６９９〜１７１３頁（１９７１）、Ｂｕ
ｌ １．Ｓｏｃ、Ｃｈｉｍ、Ｆｒ、［８］第３１９０〜
３２ｏｏ頁（１９６８）、Ｂｕ ｌ １．Ｓｏｃ、Ｃｈ
ｉｍ、Ｆｒ。In addition, as a spironaphthopyran compound,
0075 Publication, Japanese Patent Publication No. 47-7704, Japanese Patent Publication No. 47-7706, Japanese Patent Publication No. 49-14524, Ger Offen DE 1,961,92
It is disclosed in Specification No. 1 (1970, 8°27),
Also, Journal of the Chemical Society of Japan-9, pages 1329-1335 (19
83), Tetr ah, ed r o'n No. 27
Volume, -9, pp. 1699-1713 (1971), Bu
l 1. Soc, Chim, Fr, [8] No. 3190~
32oo pages (1968), Bu l 1. Soc, Ch.
im, Fr.
［５］第２０１６〜２０７４頁（１９６８）Ｉｚｖ、３
ｅｖ−１（ａｖｋ、Ｎａｕｃｈｎ、Ｔｓｅｎｔｙａ
Ｖｙｓｓｈ、Ｓｈｋ、、Ｅｓｔｅｓｔｖ。[5] pp. 2016-2074 (1968) Izv, 3
ev-1 (avk, Nauchn, Tsentya
Vyssh, Shk,,Estestv.
Ｎａ ｕｋｉ ［１］第６８〜６９頁（１９８３＞に
記載されている。Nauki [1] pages 68-69 (1983).
［発明が解決しようとする問題点］
スピロベンゾピラン化合物は光発消色め繰り返し使用に
おける耐疲労性に問題があった。また公知のスピロナフ
トピラン化合物は耐疲労性は前記化合物に比べ向上して
いるものの、室温付近における発色性が不十分であり、
ざらには黄色に発色するものはなかった。[Problems to be Solved by the Invention] The spirobenzopyran compound has a problem in fatigue resistance during repeated use due to photo-decolorization. Furthermore, although known spironaphthopyran compounds have improved fatigue resistance compared to the above-mentioned compounds, their color development near room temperature is insufficient;
There was no yellow color in the grains.
［問題点を解決するための手段］
本発明は前記問題点を解決するための新規スピロナフト
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、下記一般式（Ａ＞で表わ
されるものである。[Means for Solving the Problems] The present invention relates to a novel spironaphthopyran compound for solving the above problems. That is, the novel compound provided by the present invention is represented by the following general formula (A>).
（式中、Ｒ１およびＲ２は炭素数１〜２０の無置換また
は置換アルキル基、炭素数３〜１０の無置換または置換
シクロアルキル基、炭素数７〜２０の無置換または置換
アラキル基、炭素数６〜１４の無置換または置換アリー
ル基から選ばれた置換基を表わし、Ｒ３，Ｒ４およびＲ
５は炭素数１〜４のアルキル基、炭素数１または２のハ
ロゲン置換アルキル基、炭素数１〜４のアルコキシ基、
ハロゲン基、ニトロ基から選ばれた置換基を表わし、Ｕ
はＯ〜２の整数２ｍおよびｎはＯ〜４の整数であり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＞における置換基Ｒ１およびＲ２の具体例
としては、メチル基、エチル基、プロピル基、ブチル基
、オクチル基、ヘキザデシル基、エイコシル基などの炭
素数１〜２ｏの鎖状アルキル基；イソ−プロピル基、ｔ
ｅｒｔ−ブチル基、４゜４−ジメチルヘキシル基、５，
７−ジニチルヘキサデシル基などの炭素数３〜２０の分
枝状アルキル基；シクロプロピル基、シクロヘキシル基
、シクロオクチル基、シクロデシル基などの炭素数３〜
１０のシクロアルキル基；ベンジル基、２−）工二ルエ
チル基、（１−ナフチル）メチル基、２−（１−ナフチ
ル）エチル基、（２−ナフチル）メチル基、２−（２−
ナフチル）エチル基、１９−アントラシル）メチル基、
（９−フエナントリル）メチル基、２−（５−ナツタシ
ル）エチル基などの炭素数７〜２０のアラルキル基；フ
ェニル基、１−ナフチル基、２−ナフチル基、９−アン
トラシル基などの炭素数７〜２ｏのアリール基が挙げら
れる。かかるＲ１およびＲ２が非環状アルキル基である
場合、その置換基誘導体に含まれる置換基の具体例とし
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機置換アミノ基；メトキシ基、エ
トキシ基、ｔｅｒｔ−ブトキシ基などの炭素数１〜４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、１−ナフトキシ基など
の炭素数６〜１４のアリーロキシ基；フルオロ基、クロ
ロ基、ブロモ基などのハロゲン基；シアノ基；カルボキ
シ基；エトキシカルボニル基などの炭素数２〜１０のア
ルコキシカルボニル基；アセチル基、ベンゾイル基など
の炭素数２〜１０のアシル基；二１〜ロ基などが挙げら
れる。(In the formula, R1 and R2 are an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, a carbon number Represents a substituent selected from 6 to 14 unsubstituted or substituted aryl groups, R3, R4 and R
5 is an alkyl group having 1 to 4 carbon atoms, a halogen-substituted alkyl group having 1 or 2 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
Represents a substituent selected from a halogen group and a nitro group, and U
is an integer of O~2 2m and n is an integer of O~4 and R3
, R4, and R5 may be the same or different. ) Specific examples of the substituents R1 and R2 in the formula (A>) include a chain alkyl group having 1 to 2 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a hexadecyl group, and an eicosyl group. ;iso-propyl group, t
ert-butyl group, 4゜4-dimethylhexyl group, 5,
Branched alkyl groups having 3 to 20 carbon atoms, such as 7-dinitylhexadecyl; 3 to 20 carbon atoms, such as cyclopropyl, cyclohexyl, cyclooctyl, and cyclodecyl groups;
10 cycloalkyl groups; benzyl group, 2-)engineered ethyl group, (1-naphthyl)methyl group, 2-(1-naphthyl)ethyl group, (2-naphthyl)methyl group, 2-(2-
naphthyl)ethyl group, 19-anthracyl)methyl group,
Aralkyl groups having 7 to 20 carbon atoms such as (9-phenanthryl)methyl group and 2-(5-natutasyl)ethyl group; 7-carbon atoms such as phenyl group, 1-naphthyl group, 2-naphthyl group, and 9-anthracil group -2o aryl groups are mentioned. When R1 and R2 are acyclic alkyl groups, specific examples of substituents included in the substituent derivative include hydroxy group; amino group; organic substituted amino groups such as methylamino group and diethylamino group; methoxy group; Alkoxy groups with 1 to 4 carbon atoms such as ethoxy group and tert-butoxy group; aralkoxy groups with 7 to 15 carbon atoms such as benzyloxy group; aryloxy groups with 6 to 14 carbon atoms such as phenoxy group and 1-naphthoxy group; fluoro a halogen group such as a chloro group, a bromo group; a cyano group; a carboxy group; an alkoxycarbonyl group having 2 to 10 carbon atoms such as an ethoxycarbonyl group; an acyl group having 2 to 10 carbon atoms such as an acetyl group or a benzoyl group; Examples include 1 to 2 groups.
ざらにかかるＲ１およびＲ２がシクロアルキル基、アラ
ルキル基またはアリール基である場合、シクロアルキル
基、アラルキル基の７リ一ル部およびアリール基の置換
基誘導体に含まれる置換基の具体例としては、ヒドロキ
シ基；メチルアミノ基、ジエチルアミノ基などの有機置
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１〜４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、１−ナフトキシ基などの炭素数６〜１４のアリー
ロキシ基；メチル基、エチル基、ｔｅｒｔ−ブチル基な
どの炭素数１〜４の低級アルキル基；フルオロ基、クロ
ロ基、ブロモ基などのハロゲン基；シアノ基；カルボキ
シ基：エトキシカルボニル基などの炭素数２〜１０のフ
ルコキシ力ルボニル基；アセチル基、ベンゾイル基など
の炭素数２〜１０のアシル基；トリフルオロメチル基な
どの炭素数１または２のハロゲン置換アルキル基：二ト
ロ基などが挙げられる。また、これらの置換基は１置換
体として含まれるもののみならず、２置換以上の複数個
の置換基を有する多置換体として含まれてもよい。ざら
には、多置換体における置換基は同種であっても、異種
であっても何ら支障はない。また置換基の位置について
は、目的あるいは用途に応じて変えられるべきである。When R1 and R2 are a cycloalkyl group, an aralkyl group, or an aryl group, specific examples of substituents included in the cycloalkyl group, the 7lyl moiety of the aralkyl group, and the substituent derivative of the aryl group include: Hydroxy group; organic substituted amine groups such as methylamino group and diethylamino group; alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, and tert-butoxy group; aralkoxy groups having 7 to 15 carbon atoms such as benzyloxy group; Aryloxy groups having 6 to 14 carbon atoms such as phenoxy group and 1-naphthoxy group; Lower alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group and tert-butyl group; fluoro group, chloro group, bromo group, etc. Halogen group; Cyano group; Carboxy group: Flukoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl group; Acyl group having 2 to 10 carbon atoms such as acetyl group and benzoyl group; 1 carbon number such as trifluoromethyl group or a halogen-substituted alkyl group of 2: a nitro group, and the like. Furthermore, these substituents are not only included as monosubstituted products, but may also be included as polysubstituted products having two or more substituents. In general, there is no problem whether the substituents in the polysubstituted product are the same or different. Furthermore, the positions of substituents should be changed depending on the purpose or use.
次に一般式（Ａ＞におけるＲ３．Ｒ４およびＲ５は前述
のとおりであるが、それぞれが同種であっても異種であ
ってもよい。Next, R3, R4 and R5 in the general formula (A> are as described above, but each may be the same or different.
かかる式（Ａ）の化合物は、従来知られているベンゾチ
アゾリン環を構成要素とするスピロナフトピラン化合物
が２′位にメチル基が導入されているのに対し、より電
子供与性の強い置換基が導入されているため、発色種の
安定性が向上している。そのため室温でも紫外光照射に
より変色しかつ発色種が安定なフォトクロミック化合物
である。The compound of formula (A) has a methyl group introduced at the 2' position of the conventionally known spironaphthopyran compound having a benzothiazoline ring as a constituent element, whereas the compound of formula (A) has a substituent with a stronger electron donating property. is introduced, the stability of the coloring species is improved. Therefore, it is a photochromic compound that changes color even at room temperature when irradiated with ultraviolet light, and the coloring species are stable.
かかる式（Ａ＞で表わされる化合物の具体的な代表例と
しては、スピロ［ベンゾチアゾリン−２゜３”−［３Ｈ
］−ナフト［２，１−ｂ］ピランの３−メチル−２−−
フェノキシ誘導体
３−へキシル−２−−フェノキシ−６−クロロ誘導体
３−（３−プロモオクデシタル）−２′−フェノキシ−
６−トリフルオロメチル誘導体
３−（１Ｑ−フェニルエイコシル）−２′−フェノキシ
−６−メトキシ誘導体
３−イソプロピル−２′−フェノキシ−６−メチル誘導
体
３− ｔｅｒｔ−ブチル−２′−ベンジロキシ−５′−
力ルボキシ誘導体
３−（４−クロロシクロヘキシル）−２−−ベンジロキ
シ−８−ｍ：トロ誘導体
３−（３−アミノシクロオクチル）−２′−フエネチロ
キシー８−−ブロモ誘導体
３−ベンジル−２−’−（２−ナフチル）メトキシ−９
′−フルオロ誘導体
３−（３−メチルベンジル）−２−−シクロプロポキシ
−７′−エトキシ誘導体
３−（４−アセチルベンジル）−２−−シクロヘキシロ
キシ−６−エトキシ−８−−ブチル誘導体３−（３，５
−ビストリフルオロメチルベンジル）−２−−メトキシ
−６−クロロ誘導イキ３−（２，３，４，５，６−ペン
タフルオロベンジル）−２−−メトキシ−６−１〜リフ
ルオロメチル誘導体
３−（２−ナフチル）メチル−２−一エトキシー６−メ
トキシ誘導体
３−（３−メトキシ−２−ナフチル）メチル−２−一エ
トキシー９′−メチル誘導体
３−（５’−ｔｅｒｔ−ブチル−１−ナフチル）エチル
−２−一エトキシー５′−力ルボキシ誘導体３−（９−
アントラシル）メチル−２−−イソプロポキシ−８′−
二トロ誘導体
３−（９−フエナントリル）メチル−２′−ブトキシ−
８′−ブロモ誘導体
３−フェニル−２−−オクタデシロキシ−９′−フルオ
ロ誘導体
３−（４−ニトロフェニル）−２′−エイコシロキシー
７−−エトキシ誘導体
３− （２，４，ｆ３−１−リメチルフェニル）−２′
−フェノキシ−６−ニトキシー８−−ブチル誘導体
３−（１−ナフチル〉−２′−フェノキシ−５−クロロ
誘導体
３−（４−ブロモ−２−ナフチル）−２−一フエノキシ
ー６−１〜リフルオロメチル誘導体３−（９−シアノ−
１−アントラシル）−２”−エトキシ−５−メトキシ誘
導体などが挙げられる。A specific representative example of the compound represented by the formula (A>) is spiro[benzothiazoline-2゜3''-[3H
]-3-methyl-2-- of naphtho[2,1-b]pyran
Phenoxy derivative 3-hexyl-2-phenoxy-6-chloro derivative 3-(3-promoocdecital)-2'-phenoxy-
6-trifluoromethyl derivative 3-(1Q-phenyleicosyl)-2'-phenoxy-6-methoxy derivative 3-isopropyl-2'-phenoxy-6-methyl derivative 3-tert-butyl-2'-benzyloxy-5 ′−
Ruboxy derivative 3-(4-chlorocyclohexyl)-2-benzyloxy-8-m: Toro derivative 3-(3-aminocyclooctyl)-2'-phenethyloxy 8--bromo derivative 3-benzyl-2-'- (2-naphthyl)methoxy-9
'-Fluoro derivative 3-(3-methylbenzyl)-2-cyclopropoxy-7'-ethoxy derivative 3-(4-acetylbenzyl)-2--cyclohexyloxy-6-ethoxy-8-butyl derivative 3- (3,5
-bistrifluoromethylbenzyl)-2--methoxy-6-chloro derivative 3-(2,3,4,5,6-pentafluorobenzyl)-2--methoxy-6-1~lifluoromethyl derivative 3- (2-naphthyl)methyl-2-1ethoxy-6-methoxy derivative 3-(3-methoxy-2-naphthyl)methyl-2-1ethoxy9'-methyl derivative 3-(5'-tert-butyl-1-naphthyl ) Ethyl-2-monoethoxy 5'-carboxy derivative 3-(9-
anthracyl)methyl-2--isopropoxy-8'-
Nitro derivative 3-(9-phenanthryl)methyl-2'-butoxy-
8'-bromo derivative 3-phenyl-2-octadecyloxy-9'-fluoro derivative 3-(4-nitrophenyl)-2'-eicosyloxy 7--ethoxy derivative 3- (2,4,f3- 1-limethylphenyl)-2'
-phenoxy-6-nitoxy-8-butyl derivative 3-(1-naphthyl)-2'-phenoxy-5-chloro derivative 3-(4-bromo-2-naphthyl)-2-monophenoxy 6-1-refluoro Methyl derivative 3-(9-cyano-
Examples include 1-anthracil)-2''-ethoxy-5-methoxy derivatives.
式（Ａ＞によって表わされる本発明の新規スピロオキサ
ジン化合物は光による発消色の耐疲労性に優れかつ発色
性の良いフォトクロミック化合物である。The novel spirooxazine compound of the present invention represented by the formula (A>) is a photochromic compound that has excellent fatigue resistance to color development and fading due to light and good color development.
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（Ｂ）
で表わされる２−メチレンベンゾチアゾリン化合物と、
一般式（Ｃ）
３ ｎ
で表わ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-methylenebenzothiazoline compound represented by general formula (B);
A compound of formula (A) is produced by reacting a hydroxynaphthaldehyde compound represented by general formula (C) 3 n .
１１一
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（Ｄ）
で表わされるベンゾチアゾール化合物、四級化剤Ｒ１−
Ｘ （Ｘはアニオン性脱離基）、塩基および一般式（Ｃ
）の化合物を任意の順序で加え反応させる方法も挙げる
ことができる。11 - Examples of other methods for producing the compound of formula (A>) of the present invention include:
Benzothiazole compound represented by general formula (D), quaternizing agent R1-
X (X is an anionic leaving group), a base and the general formula (C
) may also be added in any order and reacted.
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、シリカカ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 production stage include recrystallization using various solvents, column chromatography using a silica column, and treatment with activated carbon.
本発明フォトクロミック化合物は光学的に透明な樹脂類
、たとえばジエチレングリコールビスアリルカーボネー
トポリマー、ポリメタアクリレートおよびその共重合体
、セルロース類、ポリ酢酸ビニル、ポリビニルアルコー
ル、ポリビニルブチラール、ポリエステル樹脂、ポリカ
ーボネート、ポリスチレンおよびその共重合体、エポキ
シ樹脂、（ハロゲン化）ビスフェノールＡのジ（メタ）
アクリレートポリマーおよびその共重合体、（ハロゲン
化）ビスフェノールＡのウレタン変性ジ（メタ〉アクリ
レートポリマーおよびその共重合体、ナイロン樹脂、ポ
リウレタンなどに配合して好ましく使用される。配合さ
れた樹脂類は光による変色性を有する光学素子として使
用することが可能である。光学素子としてはサングラス
レンズ、スキー用ゴーグル、保護メガネレンズ、さらに
はカーテン、衣服、玩具等が好適な例として挙げられる
。The photochromic compound of the present invention can be applied to optically transparent resins such as diethylene glycol bisallyl carbonate polymer, polymethacrylate and its copolymers, celluloses, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyester resin, polycarbonate, polystyrene and its copolymers. Copolymer, epoxy resin, di(meth) of (halogenated) bisphenol A
Acrylate polymers and copolymers thereof, urethane-modified di(meth)acrylate polymers of (halogenated) bisphenol A and copolymers thereof, nylon resins, polyurethanes, etc. are preferably used by blending them. Suitable examples of optical elements include sunglass lenses, ski goggles, safety glasses lenses, curtains, clothes, toys, etc.
樹脂類への本発明フォトクロミック化合物の配合方法と
しては、染色方法、キャスティング法、配合されたポリ
マー溶液のコーティング法などを各種の方法が適用でき
る。Various methods can be used for blending the photochromic compound of the present invention into resins, including dyeing, casting, and coating a blended polymer solution.
また樹脂中への配合量としては目的および使用方法など
によって決められるべきものであるが、視覚に対する感
度という観点からは０．０１〜２０重最％の添加量が好
ましい。The amount added to the resin should be determined depending on the purpose and method of use, but from the viewpoint of visual sensitivity, the amount added is preferably 0.01 to 20% by weight.
実施例１
■ ３−メチル−２−−フェノキシスピロ［ベンゾチア
ゾリン−２，３−−［３Ｈ］−ナフト［２゜１−ｂ］ピ
ラン］の合成
３−メチル−２−フェノキシメチレンベンゾチアゾリン
５ｑおよび２−ヒドロキシ−１−ナフトアルデヒド５ｑ
を１００ｒｌのエタノールに溶解し、窒素気流中５時間
速流する。反応後冷却すると結晶が析出して来る。これ
に少量のエタノールを加え戸数し、得られた粗結晶をエ
タノールに溶解した溶液を５０〜６０℃まで加熱した後
、活性炭１０Ｑを加え十分に攪拌する。その後濾過し、
３液を濃縮して得られた緑白色固体をプロパツールから
再結晶し、３−メチル−２′−フェノキシスピロ［ベン
ゾチアゾリン−２，３−−［３Ｈ］−ナフ１〜［２，１
−ｂ］ピランコの緑白色結晶を得た。Example 1 ■ Synthesis of 3-methyl-2-phenoxyspiro[benzothiazoline-2,3--[3H]-naphtho[2゜1-b]pyran] 3-methyl-2-phenoxymethylenebenzothiazoline 5q and 2-hydroxy-1-naphthaldehyde 5q
was dissolved in 100 ml of ethanol, and the mixture was rapidly flowed in a nitrogen stream for 5 hours. When cooled after the reaction, crystals begin to precipitate. A small amount of ethanol is added to this, and a solution of the obtained crude crystals dissolved in ethanol is heated to 50 to 60°C, and then activated carbon 10Q is added and thoroughly stirred. Then filter,
The greenish-white solid obtained by concentrating the three liquids was recrystallized from propatool to give 3-methyl-2'-phenoxyspiro[benzothiazoline-2,3--[3H]-naf1-[2,1
-b] Green-white crystals of Piranco were obtained.
■ 分析結果
（融点） １７１°Ｃ
（元素分析値） 実測値（％） 計算値（％）Ｃ７６，
３７６，３
Ｈ４，５４，６
Ｎ ３．５ ３．４■ 応用
例
本化合物をアセトン中に０．１重量％の濃度で溶解させ
た。溶液にケミカルランプを使用して紫外線を照射させ
た。溶液は直ちに黄色に変化した。■ Analysis result (melting point) 171°C (Elemental analysis value) Actual value (%) Calculated value (%) C76,
376,3 H4,54,6 N 3.5 3.4■ Application example The present compound was dissolved in acetone at a concentration of 0.1% by weight. The solution was irradiated with ultraviolet light using a chemical lamp. The solution immediately turned yellow.
また、このものは光照射を除いて放置しておくともとの
無色に戻った。このような発色および消色テストは繰り
返して行なうことができた。Moreover, when this material was left without light irradiation, it returned to its original colorless color. Such coloring and decoloring tests could be repeated.
実施例２
■ ３−メチル−２−一エトキシスピロ［ベンゾチアゾ
リン−２，３”−［３Ｈ］−ナツト［２゜１−ｂ］ピラ
ンコの合成
３−メチル−２−フェノキシメチレンベンゾチアゾリン
の代りに３−メチル−２−エトキシベンゾチアゾリンを
５０用いる他は実施例１とまったく同様にして行なった
。Example 2 ■ Synthesis of 3-methyl-2-monoethoxyspiro[benzothiazoline-2,3''-[3H]-natu[2゜1-b]piranco 3-methyl-2-phenoxymethylene instead of benzothiazoline Example 1 was carried out in exactly the same manner as in Example 1, except that 50% of 3-methyl-2-ethoxybenzothiazoline was used.
■ 分析結果
（融点） １８０℃
（元素分析値） 実測値（％） 計算値（％）Ｃ７２，
６７３，１
Ｈ５，１５，３
Ｎ ４．０ ３．９■ 応用
例
本化合物をアセトンに０．５重量％の濃度で溶解した溶
液は紫外線の照射を受けると黄色になった。■ Analysis result (melting point) 180℃ (Elemental analysis value) Actual value (%) Calculated value (%) C72,
673,1 H5,15,3 N 4.0 3.9■ Application example A solution of the present compound dissolved in acetone at a concentration of 0.5% by weight turned yellow when irradiated with ultraviolet light.
［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、紫外線の照射
を受けると直ちに可視光領域に吸収波長を有する化合物
に変化する。ざらに発色種が熱的に安定で、室温１日放
置しても発色時の光学濃度の９０％以上を保持している
フォトクロミック化合物である。[Effects of the Invention] The compound of the present invention is generally colorless regardless of the type of solvent or matrix polymer, but upon irradiation with ultraviolet light, it immediately changes into a compound having an absorption wavelength in the visible light region. It is a photochromic compound whose color-forming species is thermally stable and retains 90% or more of its optical density at the time of color development even after being left at room temperature for one day.
Claims (1)
または置換アルキル基、炭素数３〜１０の無置換または
置換シクロアルキル基、炭素数７〜２０の無置換または
置換アラルキル基、炭素数６〜１４の無置換または置換
アリール基から選ばれた置換基を表わし、Ｒ＾３、Ｒ＾
４およびＲ＾５は炭素数１〜４のアルキル基、炭素数１
または２のハロゲン置換アルキル基、炭素数１〜４のア
ルコキシ基、ハロゲン基、ニトロ基から選ばれた置換基
を表わし、ｌは０〜２の整数、ｍおよびｎは０〜４の整
数でありＲ＾３、Ｒ＾４、Ｒ＾５はそれぞれ同種であっ
ても異種であってもよい。）[Claims] A spironaphthopyran compound represented by general formula (A). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) (In the formula, R^1 and R^2 are unsubstituted or substituted alkyl groups having 1 to 20 carbon atoms, unsubstituted or substituted cycloalkyl having 3 to 10 carbon atoms. R^3, R^
4 and R^5 are alkyl groups having 1 to 4 carbon atoms, and 1 carbon number
or 2 represents a substituent selected from a halogen-substituted alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen group, and a nitro group, l is an integer of 0 to 2, and m and n are integers of 0 to 4. R^3, R^4, and R^5 may be of the same type or different types. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3532286A JPH0725770B2 (en) | 1986-02-21 | 1986-02-21 | Novel spironaphthopyran compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3532286A JPH0725770B2 (en) | 1986-02-21 | 1986-02-21 | Novel spironaphthopyran compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62195076A true JPS62195076A (en) | 1987-08-27 |
| JPH0725770B2 JPH0725770B2 (en) | 1995-03-22 |
Family
ID=12438576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3532286A Expired - Lifetime JPH0725770B2 (en) | 1986-02-21 | 1986-02-21 | Novel spironaphthopyran compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725770B2 (en) |
-
1986
- 1986-02-21 JP JP3532286A patent/JPH0725770B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0725770B2 (en) | 1995-03-22 |
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