JPH0262879A - Photochromic compound and production thereof - Google Patents
Photochromic compound and production thereofInfo
- Publication number
- JPH0262879A JPH0262879A JP21282788A JP21282788A JPH0262879A JP H0262879 A JPH0262879 A JP H0262879A JP 21282788 A JP21282788 A JP 21282788A JP 21282788 A JP21282788 A JP 21282788A JP H0262879 A JPH0262879 A JP H0262879A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- expressed
- films
- formulas
- 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 27
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 trimethylammoniomethyl Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 10
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000000693 micelle Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001600 hydrophobic polymer Polymers 0.000 description 3
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920005553 polystyrene-acrylate Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- ZTUKGBOUHWYFGC-UHFFFAOYSA-N 1,3,3-trimethyl-2-methylideneindole Chemical compound C1=CC=C2N(C)C(=C)C(C)(C)C2=C1 ZTUKGBOUHWYFGC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001481824 Indri Species 0.000 description 1
- 239000000232 Lipid Bilayer Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 1
- IMNRJGSQCGFPHL-UHFFFAOYSA-N benzene;oxolane Chemical compound C1CCOC1.C1=CC=CC=C1 IMNRJGSQCGFPHL-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は多種の高分子材料あるいは二分子膜、ミセル
、ＬＢフィルムといった分子集合体中に良好な溶解性を
示し、例えば表示素子や光記録素子として用いられるフ
ォトクロミック材料の製造に有用な新規インドリノスピ
ロベンゾピラン誘導体に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention exhibits good solubility in various polymeric materials or molecular aggregates such as bilayer films, micelles, and LB films, and can be used as display elements and optical recording elements, for example. The present invention relates to novel indolinospilobenzopyran derivatives that are useful in the production of photochromic materials used.
従来の技術
一般式（Ｉ）
一方、この種の化合物に置換基を導入する方法としては
、例えば、インドリン１位の窒素に置換基を導入する方
法が一般的であるが、その他の位置、特にインドリン環
ベンゼン核に多種の置換基を導入するのは非常に困難で
あった。Prior Art General Formula (I) On the other hand, as a method for introducing a substituent into this type of compound, for example, a method of introducing a substituent into the nitrogen at the 1st position of indoline is common, but it is also possible to introduce a substituent into the nitrogen at the 1st position of indoline. It was extremely difficult to introduce various substituents into the benzene nucleus of the indoline ring.
（式中Ｒ３はおもにメチル基としたアルキル基、Ｒ２は
水素原子またはメトキシ基）で表されるインドリノスピ
ロベンゾビラン誘導体は、フォトクロミズムを示す化合
物として知られている。これらは通常プラスチック中に
配合して用いられるが、このプラスチックはポリスチレ
ンやポリメチルメタクリレート等の疎水性のものに限ら
れていた。The indolinospilobenzobilane derivative represented by the formula (wherein R3 is an alkyl group mainly a methyl group, and R2 is a hydrogen atom or a methoxy group) is known as a compound exhibiting photochromism. These are usually mixed into plastics, but these plastics have been limited to hydrophobic ones such as polystyrene and polymethyl methacrylate.
（例えば、クリスツエフスキーらの文献（Ｍ、 Ｋｒｙ
ｓｚｅｗｓｋｉ、 Ｄ、Ｌａｐｉｅｎｉｓ、 Ｂ、 Ｎ
ａｄｏｌｓｋｉ、 Ｊ、 Ｐｏｌｙｍ。(For example, Kryszewski et al. (M, Kry
szewski, D., Lapienis, B.N.
adolski, J., Polym.
Ｓｃｉ、、 Ｐｏ１ｙａ＋、Ｃｈｅｗ。Ｅｄ、、
１１．２４２３（１９７３）など）。Sci,, Po1ya+, Chew. Ed...
11.2423 (1973), etc.).
発明が解決しようとする課題
この発明の目的は水溶性プラスチックを含めた多種の高
分子材料あるいはＬＢ膜、二分子膜、ミセル等の分子集
合体など広範な材料にドープしつるインドリノスピロベ
ンゾピラン誘導体を提供することである。Problems to be Solved by the Invention The purpose of this invention is to provide indolinospilobenzopyran that can be doped into a wide range of materials, including various polymeric materials including water-soluble plastics, and molecular aggregates such as LB films, bilayer films, and micelles. The object of the present invention is to provide derivatives.
課題を解決するための手段
本発明者は多種の有機材料との相容性が高く、容易に得
られるインドリノスピロベンゾビラン誘導体を開発する
ために鋭意研究を重ねた結果、インドリン環の５位にア
ミノ基を導入した後アシル化をすることで得られる誘導
体がこの目的に適合することをＪ！Ｊ、）だし、この発
明を成すに至った。Means for Solving the Problems The present inventor conducted extensive research to develop an easily obtainable indolinospirobenzobilane derivative that has high compatibility with a variety of organic materials. J! showed that a derivative obtained by introducing an amino group into and then acylating it is suitable for this purpose. J.), and was able to make this invention.
すなわち、この発明は一般式
に各種−数式
（式中のＲは炭素数１〜１８の直鎮あるいは分岐したア
ルキル基あるいはトリノチルアンモニオメチル基（（Ｃ
Ｈ３）３ Ｎ” ＣＨｚ ）である）で表される
インドリノスピロベンゾビラン誘導体を提供するもので
ある。That is, this invention provides a general formula with various formulas (R in the formula is a straight or branched alkyl group having 1 to 18 carbon atoms or a trinotylammoniomethyl group ((C
H3) 3 N''CHz)) is provided.
この発明の化合物はいずれも文献未載の新規化合物テア
リ、ゲールらの方法（Ｄ、 Ｊ、 Ｇａ１ｅ、 Ｊ、Ｐ
Ｋ、に１ｌｓｈｉｒｅ、 Ｊ、Ｓａｃ、 Ｄｙｅｒ、
Ｃｏ１ｏｒ、、且７４．９７）により合成した５−アミ
ノフイシャー塩基Ｌ
１ｌｓ
（Ｒは式（ＩＩ）のＲに対応する）
で表される酸クロリドと等モルあるいは酸クロリド過剰
で反応させることによって５位の一級アミンをアシル化
し、次いでこれを５−二トロサリチルアルデヒドと縮合
させて目的化合物を得ることができる。The compounds of this invention are all novel compounds that have not been described in literature.
K, Nishire, J, Sac, Dyer,
By reacting with the acid chloride represented by 5-aminofischer base L 1ls (R corresponds to R in formula (II)) synthesized by Co1or, , and 74.97) in an equimolar amount or in excess of the acid chloride. The target compound can be obtained by acylating the primary amine at position 5 and then condensing it with 5-nitrosalicylaldehyde.
５−アミノフィシャー塩基と一般式（ＩＩＩ）との反応
はベンゼン、クロロホルム、テトラヒドロフラン等の溶
媒中で室温２〜２０時間程度で完了する。The reaction between the 5-aminoFischer base and the general formula (III) is completed in a solvent such as benzene, chloroform, tetrahydrofuran or the like at room temperature for about 2 to 20 hours.
フィシャー塩基自身、三級アミンを有しているので系に
トリエチルアミン等の塩基を加えなくても反応は進行す
る。アシル化物の精製はヘキサンや塩化メチレン−ヘキ
サン混合溶媒からの再結晶による。Since Fischer's base itself has a tertiary amine, the reaction proceeds without adding a base such as triethylamine to the system. The acylated product is purified by recrystallization from hexane or a mixed solvent of methylene chloride and hexane.
得られたアシル化物を５−二トロサリチルアルデヒドと
エタノール中で２時間還流することにより目的化合物を
得るが、Ｒの炭素数が小さい場合はエタノールより再結
晶を、炭素数が大きい場合はベンゼン−酢酸エチル混合
溶媒を展開液としたシリカゲルを充填剤としだカラムク
ロマトグラフィーにより精製する。The target compound is obtained by refluxing the obtained acylated product with 5-nitrosalicylaldehyde in ethanol for 2 hours. If the number of carbon atoms in R is small, recrystallization is performed from ethanol, and when the number of carbon atoms in R is large, it is recrystallized from benzene. It is purified by column chromatography using silica gel as a packing material and a mixed solvent of ethyl acetate as a developing solution.
水溶性を持たせるためのトリメチルアンモニオ基の導入
は式（ＩＩＩ）の化合物としてクロロアセチルクロリド
を用い、５−ニトロサリチルアルデヒドとの縮合の後に
過剰のトリメチルアミンガスを吹き込むことにより得ら
れる。これはエタノールからの再結晶により精製する。Introduction of a trimethylammonio group to impart water solubility can be achieved by using chloroacetyl chloride as the compound of formula (III) and bubbling in excess trimethylamine gas after condensation with 5-nitrosalicylaldehyde. This is purified by recrystallization from ethanol.
この発明化合物はＩＨ−Ｎ Ｍ Ｒスペクトルにおける
アミドのピーク（ＣＤＣＩ、中、δ＝９．７〜１１．１
ｐｐ’ｍ）、導入されたアルキル基のピーク（同δ＝０
．９〜１，４ｐｐｍ）あるいはトリメチルアンモニオ基
（ＤＭＳＯ−ｄ。The compound of this invention has an amide peak in the IH-NMR spectrum (CDCI, middle, δ=9.7-11.1).
pp'm), the peak of the introduced alkyl group (δ=0
．． 9-1.4 ppm) or trimethylammonio group (DMSO-d.
中、δ＝３．３ｐｐｍ＞ により同定できる。It can be identified by δ=3.3ppm>.
発明の効果
この発明化合物において四級化アンモニウムを持つもの
は水溶性であり、水溶性高分子と混合してフィルムを得
ることができる。また、長鎖アルキル基を導入したもの
については、多種の疎水性高分子との混合が可能である
ばかりではなく、ＬＢ膜や二分子膜などの分子集合体と
の相溶が可能であり、フォトクロミズムを示す広範な有
機材料を提供することができる。Effects of the Invention Among the compounds of this invention, those having quaternized ammonium are water-soluble and can be mixed with water-soluble polymers to obtain a film. In addition, products with long-chain alkyl groups can not only be mixed with various types of hydrophobic polymers, but also be compatible with molecular aggregates such as LB films and bilayer films. A wide range of organic materials exhibiting photochromism can be provided.
実 施 例
次に、実施例及び参考例によってこの発明をさらに詳細
に説明する。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples and Reference Examples.
実施例１
５−アミノフ４シャー塩基１．２ｇを２９ｍ１のベンゼ
ンに溶かし、水冷下ステアロイルクロリド２，３ｇを溶
かしたベンゼン溶液１−Ｑｍｌを滴下する。室温にて２
０時間撹拌させた後、反応溶媒を減圧留去して得た残渣
をクロロホルムに溶解して１％アンモニア水で洗浄、ク
ロロホルム溶液を無水硫酸す）ＩＪウムで乾燥、溶媒留
去した後、ヘキサンから再結晶して、２．５ｇの５−ス
テアロイルアミノ−１，３３−トリメチル−２−インド
レニンを得る。Example 1 1.2 g of 5-aminof-4-Shar base is dissolved in 29 ml of benzene, and 1-Q ml of a benzene solution in which 2.3 g of stearoyl chloride is dissolved is added dropwise under water cooling. 2 at room temperature
After stirring for 0 hours, the reaction solvent was distilled off under reduced pressure, the resulting residue was dissolved in chloroform and washed with 1% aqueous ammonia, the chloroform solution was dried over anhydrous sulfuric acid, and the solvent was distilled off, followed by hexane. Recrystallization from 2.5 g of 5-stearoylamino-1,33-trimethyl-2-indolenine is obtained.
さらにこの化合物１ｇを溶かしたエタノール溶液ＩＱｍ
ｌを５−ニトロサリチルアルデヒド０．４４ｇ を溶か
したエタノール中へ滴下し、４時間還流させる。反応後
エタノールを留去し、残渣をベンゼン−酢酸エチルを展
開溶液としたシリカゲルカラムクロマトグラフィーによ
り精製し、目的物である５−ステアロイルアミノ−１，
３，３−）ツメチル−６′−二トロスピロロインドリン
−２，２’２Ｈ″−ベンゾビラン］ ０．８ｇを得る。Furthermore, an ethanol solution IQm in which 1 g of this compound was dissolved
1 was added dropwise to ethanol in which 0.44 g of 5-nitrosalicylaldehyde was dissolved, and the mixture was refluxed for 4 hours. After the reaction, ethanol was distilled off, and the residue was purified by silica gel column chromatography using benzene-ethyl acetate as a developing solution to obtain the target product, 5-stearoylamino-1,
3,3-)tumethyl-6'-nitrospiroloindoline-2,2'2H''-benzobilane] 0.8 g is obtained.
ｍｐ、 １１６ 〜１１８ ℃
元素分析値（Ｃ３ＪｓａＮ４０．として）ＨＮ
計 算 値 （％） ７３．２２ ９．０９
６．８５実 測 値 （％） ７３．００
８．９０ ６．７９このものの’Ｈ−ＮＭＲスペ
クトルを第１図に示す。mp, 116 - 118 ℃ Elemental analysis value (as C3JsaN40.) HN calculation value (%) 73.22 9.09
6.85 Actual measurement value (%) 73.00
8.90 6.79 The 'H-NMR spectrum of this product is shown in Figure 1.
実施例２
実施例１におけるステアロイルクロリドの代わりにクロ
ロアセチルクロリド２．４ｇ、１ｇの５−アミノフィシ
ャー塩基と実施例１と同様の操作で反応時間２時間、塩
化メチレン−ヘキサン混合溶媒から再結晶することによ
り、５−クロロアセチルアミノ−１，３，３−）ジメチ
ル−２−インドレニン０．９５ｇを得る。この０．５ｇ
を５−二トロサリチルアルデヒド０．３８ｇ と共にエ
タノール９４時間還流させ冷却して生じた固体をエタノ
ールより再結晶して０．６ｇの５−クロロアセチルアミ
／−１，３゜３−ト’Ｊメチル−６゛ −ニトロスピ
ロ［インドリ：／−２，２°−２Ｈ′−ベンゾビランコ
を得る。Example 2 In place of stearoyl chloride in Example 1, 2.4 g of chloroacetyl chloride and 1 g of 5-aminoFischer base were used and recrystallized from a methylene chloride-hexane mixed solvent in the same manner as in Example 1 for 2 hours. This gives 0.95 g of 5-chloroacetylamino-1,3,3-)dimethyl-2-indolenine. This 0.5g
was refluxed with 0.38 g of 5-nitrosalicylaldehyde in ethanol for 94 hours, cooled, and the resulting solid was recrystallized from ethanol to yield 0.6 g of 5-chloroacetylamide/-1,3°3-t'J methyl. -6゛-Nitrospiro[indri:/-2,2°-2H'-benzoviranco is obtained.
この化合物０．５４ｇをテトラヒドロフラン−ベンゼン
混合溶媒２０ｍ１に溶かし、トリメチルアミンガスを大
過剰吹き込む。室温にて４時間撹拌して生じた固体をエ
タノールより再結晶することにより目的とする水溶性化
合物、５−トリメチルアンモニオアセチルアミノ−１，
３，３−）ダメチル−６゛−二トロスピロ［インドリン
−２，２°−２Ｈ゛−ベンゾビランコクロリド−永和物
０．４８ｇを得る。0.54 g of this compound is dissolved in 20 ml of a tetrahydrofuran-benzene mixed solvent, and a large excess of trimethylamine gas is blown into the solution. The desired water-soluble compound, 5-trimethylammonioacetylamino-1, was obtained by stirring at room temperature for 4 hours and recrystallizing the resulting solid from ethanol.
0.48 g of 3,3-)damethyl-6'-nitrospiro[indoline-2,2'-2H'-benzobylancochloride] is obtained.
ｍｐ、 ２５０ 〜２５２ ℃
元素分析値（Ｃ２ａＨｚｓＮａＯｎ・Ｈ２Ｏとして）Ｈ
Ｎ
計 算 値 （％） ５８．７１ ６．３６
１１．４１実 測 値 （％） ５８．２
８ ６゜３６ １１．４にのものの’）Ｉ−ＮＭＲ
スペクトルを第２図に示す。mp, 250 ~ 252 ℃ Elemental analysis value (as C2aHzsNaOn・H2O) H
N Calculated value (%) 58.71 6.36
11.41 Actual measurement value (%) 58.2
8 6゜36 11.4') I-NMR
The spectrum is shown in FIG.
参 考 例
これらの発明化合・物は一般式（Ｉ）の公知化合物と同
様にフォトクロミズムを示す。すなわち、エタノール、
クロロホルム、酢酸エチル等の有機溶媒中にて３６０ｎ
ｍ以下の紫外光を照射することにより、無色から紫ある
いは青色の発色種となり、４４０ｎｍ以上の可視光照射
あるいは熱で元の無色体に戻る。発色種の可視吸収スペ
クトルのピークはエタノール中で５４５〜５５０ｎｍ
（公知化合物（Ｉ）では５３５〜５８８ｎｍ （公知化
合物（１）では５７８〜５８６ｎｍ）であり、２〜ｌＱ
ｒ＋＋ｎ長波長に存在する。四級化アンモニウム基を有
する発明化合物は水中での吸収スペクトルを測定するこ
とができ、５０５ｎｍ Ｉこ吸収極大が存在する。また
、各種有機溶媒中での発色種から無色種への２５℃での
熱退色速度は公知化合物（Ｉ）と同程度である。四級化
アンモニウムを有する発明化合物を水に溶かし、水溶性
高分子であるポリビニルアルコールと水中で混合する。Reference Examples These invented compounds/products exhibit photochromism like the known compounds of general formula (I). That is, ethanol,
360n in an organic solvent such as chloroform or ethyl acetate
By irradiating with ultraviolet light of 440 nm or less, the material changes from colorless to purple or blue, and returns to its original colorless state by irradiation with visible light of 440 nm or more or heat. The peak of the visible absorption spectrum of the colored species is 545-550 nm in ethanol.
(535-588 nm for known compound (I) (578-586 nm for known compound (1)), 2-1Q
Exists at r++n long wavelengths. The absorption spectrum of the compound of the invention having a quaternized ammonium group in water can be measured, and there is an absorption maximum at 505 nm. Further, the thermal fading rate at 25° C. from a colored species to a colorless species in various organic solvents is comparable to that of the known compound (I). The invention compound having quaternized ammonium is dissolved in water and mixed with polyvinyl alcohol, which is a water-soluble polymer, in water.
これをキャスト法あるいはスピンコード法により透明フ
ィルムが得られるが、このフィルムは赤色＝無色という
フォトクロミズムを示す。A transparent film can be obtained by casting or spin-coding this film, and this film exhibits photochromism of red = colorless.
長鎖アルキル基（炭素数１８など）を有する発明化合物
は、水中に分散させた脂質二分子膜中によく取り込まれ
、この膜中において、紫＝無色の７オトクロミズムを示
す。またこの化合物はポリスチレンやポリメチルメタク
リレート等の多くの疎水性高分子フィルム中に分子状分
散させることができ、透明フィルムが容易に得られる。The compound of the invention having a long-chain alkyl group (such as 18 carbon atoms) is well incorporated into a lipid bilayer membrane dispersed in water, and exhibits purple=colorless 7-otochromism in this membrane. Moreover, this compound can be molecularly dispersed in many hydrophobic polymer films such as polystyrene and polymethyl methacrylate, and transparent films can be easily obtained.
疎水性高分子フィルム中では青＝無色のフォトクロミズ
ムを示す。In a hydrophobic polymer film, blue = colorless photochromism is exhibited.
このように本発明による化合物は広範な存機材料へ分子
分散させることができ、それらの材料にフォトクロミッ
ク機能を付与することができる。In this manner, the compounds according to the present invention can be molecularly dispersed into a wide variety of existing materials and can impart photochromic functionality to those materials.
第１図はこの発明化合物（実施例１）の３６０ＭＨｚ’
）Ｉ−ＮＭＲスペクトル図、第２図は別の例（実施例２
）の３６０ＭＨ２’Ｈ−ＮＭＲスペクトル図である。Figure 1 shows the 360MHz' of this invention compound (Example 1).
) I-NMR spectrum diagram, Figure 2 is another example (Example 2).
) is a 360MH2'H-NMR spectrum diagram.
Claims (2)
ルキル基、またはトリメチルアンモニオメチル基である
）で表される５−置換インドリノスピロベンゾピラン化
合物。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R in the formula is a straight chain or branched alkyl group having 1 to 18 carbon atoms, or a trimethylammoniomethyl group) 5-substituted indolinospirobenzopyran compounds.
ルデヒドと縮合させることを特徴とする一般式 ▲数式、化学式、表等があります▼ で表される５−置換インドリノスピロベンゾピランの製
造方法。(2) A general formula characterized by reacting with an acid chloride represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A method for producing 5-substituted indolinospilobenzopyran.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21282788A JPH0262879A (en) | 1988-08-26 | 1988-08-26 | Photochromic compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21282788A JPH0262879A (en) | 1988-08-26 | 1988-08-26 | Photochromic compound and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0262879A true JPH0262879A (en) | 1990-03-02 |
Family
ID=16629018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21282788A Pending JPH0262879A (en) | 1988-08-26 | 1988-08-26 | Photochromic compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0262879A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59148098A (en) * | 1983-02-14 | 1984-08-24 | 三洋電機株式会社 | Voice recognition equipment |
| JPH06214595A (en) * | 1993-01-20 | 1994-08-05 | Asahi Chem Ind Co Ltd | Voice recognition method |
| WO1994020502A1 (en) * | 1993-03-11 | 1994-09-15 | Otsuka Kagaku Kabushiki Kaisha | Spiropyran compound, optically active spiropyran compound, and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945229A (en) * | 1972-07-20 | 1974-04-30 | ||
| JPS60166686A (en) * | 1983-10-10 | 1985-08-29 | イエダ リサ−チ アンド デベロツプメント カンパニ− リミテツド | Compound suitable for producing quasi-liquid crystal |
-
1988
- 1988-08-26 JP JP21282788A patent/JPH0262879A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945229A (en) * | 1972-07-20 | 1974-04-30 | ||
| JPS60166686A (en) * | 1983-10-10 | 1985-08-29 | イエダ リサ−チ アンド デベロツプメント カンパニ− リミテツド | Compound suitable for producing quasi-liquid crystal |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59148098A (en) * | 1983-02-14 | 1984-08-24 | 三洋電機株式会社 | Voice recognition equipment |
| JPH041918B2 (en) * | 1983-02-14 | 1992-01-14 | Sanyo Electric Co | |
| JPH06214595A (en) * | 1993-01-20 | 1994-08-05 | Asahi Chem Ind Co Ltd | Voice recognition method |
| WO1994020502A1 (en) * | 1993-03-11 | 1994-09-15 | Otsuka Kagaku Kabushiki Kaisha | Spiropyran compound, optically active spiropyran compound, and use thereof |
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