JPH04145190A - Production of photochromic material - Google Patents
Production of photochromic materialInfo
- Publication number
- JPH04145190A JPH04145190A JP26911690A JP26911690A JPH04145190A JP H04145190 A JPH04145190 A JP H04145190A JP 26911690 A JP26911690 A JP 26911690A JP 26911690 A JP26911690 A JP 26911690A JP H04145190 A JPH04145190 A JP H04145190A
- Authority
- JP
- Japan
- Prior art keywords
- photochromic material
- groups
- compound
- producing
- nitrating agent
- 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
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 230000000802 nitrating effect Effects 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000005042 acyloxymethyl group Chemical group 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000006396 nitration reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 239000012528 membrane Substances 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 5
- 150000001350 alkyl halides Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- NEFKBMGPCLMTKR-UHFFFAOYSA-N 3,3-dimethyl-2-methylidene-1-octadecylindole Chemical compound C1=CC=C2N(CCCCCCCCCCCCCCCCCC)C(=C)C(C)(C)C2=C1 NEFKBMGPCLMTKR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- ZNJOCVLVYVOUGB-UHFFFAOYSA-N 1-iodooctadecane Chemical compound CCCCCCCCCCCCCCCCCCI ZNJOCVLVYVOUGB-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ONJRTQUWKRDCTA-UHFFFAOYSA-N 2h-thiochromene Chemical group C1=CC=C2C=CCSC2=C1 ONJRTQUWKRDCTA-UHFFFAOYSA-N 0.000 description 1
- -1 3 -Nitro-5-methoxythiosalicylaldehyde Chemical compound 0.000 description 1
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical group C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- DJZIQJRNFAJVSV-UHFFFAOYSA-E [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] DJZIQJRNFAJVSV-UHFFFAOYSA-E 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- QJNOTGALJMOAGN-UHFFFAOYSA-N octadecane hydroiodide Chemical compound I.CCCCCCCCCCCCCCCCCC QJNOTGALJMOAGN-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 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
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000000772 tip-enhanced Raman spectroscopy Methods 0.000 description 1
Landscapes
- 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
本発明はフォトクロミック材料の製造法に関す従来の技
術
従来 可逆的な色の変化を生ずる材料として、フォトク
ロミック材料が知られている。このフォトクロミック材
料のうち玄 最もよく検討されているものにスピロピラ
ンが挙げられる。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing photochromic materials.Background Art Photochromic materials are known as materials that produce a reversible color change. Among these photochromic materials, spiropyran is the most widely studied material.
現在までに数多くのスピロピランが発表されていも 例
えば下記に示すスピロピランに紫外光を照射すると、メ
ロシアニンに変化し赤色を呈する。Although many spiropyrans have been published to date, for example, when the spiropyran shown below is irradiated with ultraviolet light, it changes to merocyanine and exhibits a red color.
このメロシアニンは可視光を照射すると、元のスピロピ
ランに戻も
（以下余白）
Ｈ３
（Ａ）
フォトクロミック材料のこのような性質を用いて、光学
記録媒体を作成することができも光学記録装置を小型化
するために（戴 記録光源に半導体レーザーを用いるこ
とが望ましい力丈 従来のスピロピランは半導体レーザ
ー発振領域に感度がなｔ〜 そのために例えばケミスト
リイ レターズ１９８５年板第１８０５頁（Ｓ、Ａｒａ
ｋａｗａ ｅｔ ａｌ、、Ｃｈｅｍｉｓｔｒｙ Ｌｅｔ
ｔｅｒｓ １８０５（１９８５））に記載されているよ
う圏 スピロピランの代わりは ベンゾピラン環をベン
ゾチオピラン環に変えたスピロチオビラン系（たとえば
下記構造）を用いることにより、記録感度を長波長域に
移動させることが行なわれていも
しかしより出力が大きく、安価な半導体レーザーを記録
に用いるために１よ このスピロチオビランの着色体の
感度をさらに長波長域に移動させることが望まれも そ
のためには例えばケミストリイ レターズ１９８５年版
第１８０５頁（Ｓ、Ａｒａｋａｖａ ｅｔ ａｌ７．Ｃ
ｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ １８０５（１９８
５））に記載されているよう圏 インドリン環側に５°
位にニトロ基を導入することが知られていも一方、高い
記録感度と安定性を得るため番へ 均一な超薄膜の記
録媒体を得ることが望まれる。When this merocyanine is irradiated with visible light, it reverts to its original spiropyran (see the margin below). H3 (A) Using these properties of photochromic materials, optical recording media can be created and optical recording devices can be miniaturized. In order to achieve this, it is desirable to use a semiconductor laser as a recording light source. Conventional spiropyran has no sensitivity in the semiconductor laser oscillation region.
Kawa et al, Chemistry Let
TERS 1805 (1985)), instead of spiropyran, a spirothiopyran system (for example, the structure below) in which a benzopyran ring is replaced with a benzothiopyran ring is used to move the recording sensitivity to a longer wavelength region. However, in order to use a semiconductor laser with higher output and lower cost for recording, it is desirable to move the sensitivity of this spirothiobilane colored substance to an even longer wavelength range. Page (S, Arakava et al7.C
hemistry Letters 1805 (198
As described in 5)), the circle is 5° to the indoline ring side.
Although it is known that a nitro group can be introduced into a position, it is desirable to obtain a recording medium with a uniform ultra-thin film in order to obtain high recording sensitivity and stability.
このような超薄膜を穏和な条件で得るために１よラング
ミュアブロジェット法（以下ＬＢ法と略すも ）が最も
優れていも
ＬＢ法で薄膜化するために（友 分子内に親木部と疎水
部をバランス良く有することが必須であａしかしながら
スピロチオピランの骨格は疎水性が低く、単独ではＬＢ
膜を形成しな（℃したがって、スピロチオピランをＬＢ
法で薄膜化するためにζ戴 多くの場合インドリン環の
Ｎ位にアルキル長鎖を導入し 親疎水性のバランスを持
たせる必要があも
発明が解決しようとする課題
Ｎ位に長鎖を有するニトロスピロチオビランの合成には
ニトロ基を有するインドリン環のＮ位に長鎖を導入す
る次式に示すようなインドレニンと、ハロゲン化アルキ
ル（ＲＸ）のカップリング反応を行なう反応が一般的で
ある。In order to obtain such ultra-thin films under mild conditions, the Langmuir-Blodgett method (hereinafter referred to as the LB method) is the best method. However, the skeleton of spirothiopyran has low hydrophobicity, and when used alone, LB
does not form a film (°C, therefore, spirothiopyran is LB
In many cases, it is necessary to introduce a long alkyl chain at the N-position of the indoline ring to create a thin film using the indoline method to balance the hydrophilic and hydrophobic properties. The general synthesis of spirothiobilane involves a coupling reaction between indolenine and an alkyl halide (RX) as shown in the following formula, which introduces a long chain into the N-position of an indoline ring having a nitro group. .
Ｒ
ところがアルキル鎖が長いハロゲン化アルキルは反応性
が低いた八 ニトロ基のないインドレニン（Ｙ ＝ Ｈ
）に関しては上式は進行する力（ニトロインドレニン（
Ｙ＝ＮＯａ）では上式はまったく進行しない力＼ 進行
しても非常に過酷な条件が必要であった
これはニトロ基の電子吸引性によって、インドレニン環
の活性が下がるためであム
以上のように従来の方法で（上 長鎖を有するニトロス
ピロチオビランの製造は不可能であっちしたがって、ニ
トロスピロチオピランをＬＢ法によって薄膜化すること
ができなかっ九そこで本発明はＬＢＨ化が可能で、長波
長に感度を有するフォトクロミック材料を、容易に製造
する方法を提供することを目的とすム
課題を解決するための手段
上記課題を解決するために 本発明は下記一般式で示さ
れるフォトクロミック材料に対しニトロ化剤を直接作用
させて、下記一般式のニトロ化フォトクロミック材料の
製造方法を提供するものであａ
（以下余白）
ただＬＲはアルキルＪｉＲ＋、Ｒ２はケトアルキル展
アルコキシ基 ニトロ基 ハロゲン基 アルカノイルオ
キシメチル基のうちのいずれかとする。R However, alkyl halides with long alkyl chains have low reactivity.
), the above equation is the advancing force (nitroindolenine (
In the case of Y=NOa), the above formula does not proceed at all\Even if it does proceed, very harsh conditions are required.This is because the activity of the indolenine ring is reduced due to the electron-withdrawing property of the nitro group. Therefore, it is impossible to produce nitrospirothiopyran with a long chain using the conventional method (see above).Therefore, it is not possible to make nitrospirothiopyran into a thin film by the LB method. It is an object of the present invention to provide a method for easily producing a photochromic material having sensitivity to long wavelengths. The present invention provides a method for producing a nitrated photochromic material of the following general formula by directly acting a nitrating agent on
An alkoxy group, a nitro group, a halogen group, or an alkanoyloxymethyl group.
作用
先に長鎖を導入し スピロチオピラン骨格を完成させて
からニトロ基を導入する上記フォトクロミック材料の製
造法（よ 最初にニトロ基を導入する従来の製造法とは
まったく異なる製造法で、これにより、ニトロ化インド
リン環と長鎖を同時に有するスピロチオビランを、穏和
な条件で得ることができ、従ってスピロピランの他の官
能基に悪影響を及ぼさなＩ、％
実施例
本製法を用いて製造したフォトクロミック材料の一例と
して、下記化学構造式のスピロピラン（以下ＴＰ−Ｂと
称する。）を例にとり、以下具体的実施例を挙げて説明
すも
具体的実施例
合成法は以下に示す４ステツプに大別され このステッ
プ順で行なった力交 本発明の特徴はステップ４にあム
（ステップ１）
２、３．３− トリメチルインドレニン（±） ４２．
３ｇ（２６６ｍｍｏｌ）とヨードオクタデカン（り１０
１．１ｇ （２６６ｍｍｏｌ）とを２−ブタノン２００
＋ｎｌに溶解り、、４０時間加熱還流した
２−ブタノンを留去後、残った固体を１０１００Ｏのエ
タノールから再結晶し 赤白色の固恢 １−オクタデシ
ル−２，３，３−トリメチルインドレニウムのヨウ素塩
（，１） ９１．５ｇ （１９７ｍｍｏｌ、収率６３
．９％）を得九
（ステップ２）
上記１−オクタデシル−２，３，３−）リンチルインド
レニウムのヨウ素塩（２） ９１．５ｇ （１９７ｍ
ｍｏｌ）を１００ｍ１のジエチルエーテルに分散し こ
れを３．８Ｎ水酸化ナトリウム水溶液４００ｍ１に分散
し九
３．５時間撹はんした徽 油層をジエチルエーテルで抽
出し九
水酸化ナトリウムで１昼夜乾燥した後、ジエチルエーテ
ルを留去して、黄色液体の１−オクタデシル−２−メチ
レン−３，３−ジメチルインドリン（ｉ）６５．６ｇ
（１，５９ｍｍｏｌ、収率８０．７％）を得九（ステッ
プ３）
１−オクタデシル−２−メチレン−３，３−ジメチルイ
ンドリン （ｉ）２ｇ（４，９ｍ辺ｏ１） と、 ３
−ニトロ−５−メトキシチオサリチルアルデヒド（Ｍ）
０．８ｇ（４、１ｍｍｏｌ）とを２０ｍ１のエタノール
中で１時間加熱還流し九
濃緑色の反応溶液を冷却して、析出した沈澱を８０ｍ１
のエタノールから３回再結晶して、スピロチオビラン（
１）（黄褐色結晶）１．６ｇ（２，７ｍｍ＋ｏｌ、収率
６５．９％）を得た
（以下余白）
このようにして得たスピロチオピランに 次のステップ
４に示す方法により、ニトロ化を行なった
（ステップ４）
酢酸中に発煙硝酸（ｄ＝ １．５２、９９％）０．２５
ｍｌ （６、０ｍｍｏｌ）を加え撹拌する。The manufacturing method of the photochromic material described above involves introducing a long chain into the acting target, completing the spirothiopyran skeleton, and then introducing a nitro group. Spirothiobilane having a nitrated indoline ring and a long chain at the same time can be obtained under mild conditions, and therefore has no adverse effect on other functional groups of spiropyran.Example An example of a photochromic material produced using the present production method The synthesis method of the specific example is roughly divided into the following four steps. Force exchange performed in order The feature of the present invention is step 4 (step 1) 2, 3. 3-trimethylindolenine (±) 42.
3g (266mmol) and iodooctadecane (ri10
1.1g (266mmol) and 2-butanone 200
After distilling off the 2-butanone, the remaining solid was recrystallized from 10100O ethanol to form a red-white solid.Iodine of 1-octadecyl-2,3,3-trimethylindolenium Salt (,1) 91.5g (197mmol, yield 63
．． 9%) (Step 2) 91.5 g (197 m
mol) was dispersed in 100 ml of diethyl ether, which was then dispersed in 400 ml of 3.8N aqueous sodium hydroxide solution and stirred for 93.5 hours.The oil layer was extracted with diethyl ether and dried over sodium nonahydroxide for 1 day and night. , diethyl ether was distilled off to obtain 65.6 g of yellow liquid 1-octadecyl-2-methylene-3,3-dimethylindoline (i).
(1,59 mmol, yield 80.7%) was obtained (Step 3) 1-octadecyl-2-methylene-3,3-dimethylindoline (i) 2 g (4,9 m side o1) and 3
-Nitro-5-methoxythiosalicylaldehyde (M)
0.8 g (4.1 mmol) was heated under reflux in 20 ml of ethanol for 1 hour, the dark green reaction solution was cooled, and the precipitate was dissolved in 80 ml of ethanol.
It was recrystallized three times from ethanol of
1) 1.6 g (2.7 mm + ol, yield 65.9%) of (yellow brown crystals) was obtained (blank below) The spirothiopyran thus obtained was nitrated by the method shown in step 4 below. (Step 4) Fuming nitric acid (d = 1.52, 99%) 0.25 in acetic acid
ml (6.0 mmol) and stir.
そこへスピロピラン１６−） １．６ｇ （２，７ｍ
ｍｏｌ）の酢酸溶液を、 ３０分かけて滴下した１時間
徴 ヘキサンと水酸化ナトリウムの混合物にあけて、ヘ
キサンで抽出し九
有機層を乾燥濃縮後、カラムクロマトグラフィーで精製
し さらにエタノールから２回再結晶して、ニトロ化ス
ピロピランＴＰ−Ｂを３００ｍｇ得た
（以下余白）
このＴＰ−Ｂは親水性と疎水性のバランスがよいたム
以下の条件でラングミュアブロジェット法による薄膜化
を行なうことができな
圧縮速度： １０ ｍｍ／ｍｉｎ
累積速度： １０ｍｍ／ｍｉｎ
累積圧：２０ｍＮ／ｍ
この薄膜１上 膜厚が２．５ｎｍと非常に薄く、顕微鏡
観察を行なっても膜面の均一性はきわめて高かった
この薄膜に紫外線を照射すると、 λｍａｘ＝ ７５０
ｎｍの吸収ピークが現われた この吸収ピークは波長７
５０ｎｍの半導体レーザーを照射することにより速やか
に消失し このサイクルは可逆であっ九な耘 本実施例
においてヨウ化オクタデカンの代わりへ 炭素数１から
３２のヨウ化物を用いても合成及び物性に変化はみられ
なかっ旭 ただしＬＢ法で製膜を行なうためには炭素数
が６から３２が最も好ましｌ、Ｘ。There, spiropyran 16-) 1.6g (2.7m
1 mol) of acetic acid solution was added dropwise over 30 minutes, poured into a mixture of hexane and sodium hydroxide, extracted with hexane, dried and concentrated the organic layer, purified by column chromatography, and purified with ethanol twice. After recrystallization, 300 mg of nitrated spiropyran TP-B was obtained (white space below).
Compression speed that allows thinning by Langmuir-Blodgett method under the following conditions: 10 mm/min Cumulative speed: 10 mm/min Cumulative pressure: 20 mN/m On this thin film 1 The film thickness is very thin at 2.5 nm. When this thin film was irradiated with ultraviolet light, the uniformity of the film surface was extremely high even when observed under a microscope, λmax = 750
nm absorption peak appeared This absorption peak has a wavelength of 7
It disappears quickly by irradiation with a 50 nm semiconductor laser, and this cycle is reversible. In this example, even if an iodide with a carbon number of 1 to 32 is used instead of octadecane iodide, there is no change in the synthesis or physical properties. Not seen Asahi However, in order to form a film by the LB method, the carbon number is most preferably 6 to 32.
比較例
ニトロインドレニンとヨードオクタデカンとを２−フタ
ノンに溶解Ｌ ４０時間加熱還流した力（まったく反
応は進行せず、原料が回収され池（以下余白）
この反応は炭素数６以上のハロゲン化アルキルで耘 同
様に反応はまったく進行しなかっ九炭素数５以下のハロ
ゲン化アルキルでは反応はわずかに進行する力（生成物
の収率は低１．％従って本製造法は効果を発挿すも
なお実施例で（よ ビラン環側のベンゼン環の置換基が
メトキシ基とニトロ基 インドリン環のＮ位の置換基が
オクタデシル基のスピロチオビランに関して説明した力
丈 他の置換基でも同様に利用することが可能であっ九
以下の第１
表に他の置換基の例と吸収極大を示
す。Comparative Example Nitroindolenine and iodooctadecane were dissolved in 2-phthanone L. The power of heating and refluxing for 40 hours (the reaction did not proceed at all, and the raw materials were collected (blank below)). Similarly, the reaction did not proceed at all, but with alkyl halides having less than 5 carbon atoms, the reaction proceeded only slightly (the yield of the product was low, 1.%).Therefore, although this production method has some effects, it is still difficult to implement. In the example, the substituent on the benzene ring on the biran ring side is a methoxy group and a nitro group.The substituent on the N-position of the indoline ring is an octadecyl group.It can be used in the same way with other substituents. Table 1 below shows examples of other substituents and absorption maxima.
第１表 な抵 ニトロ化に関してＣよ 発煙硝酸が最も好 ましい力丈 他のニ トロ化剤たとえば 硝酸ナ ト リ ラムや、 硝酸−硫酸系の反応剤でも同様に進行した。Table 1 resistance Regarding nitration, C. Fuming nitric acid is the most preferred great strength other ni For example, a thickening agent Sodium nitrate to Li Ram, The reaction proceeded in the same manner with a nitric acid-sulfuric acid-based reactant.
発明の効果
本発明（よ
下記一般式で示される化合物に対し
く以下余白）
ニトロ化剤を直接作用させて下記一般式の化合物を得る
フォトクロミック材料の製造方法であるた取 ラングミ
ュアブロジェット膜で薄膜化可能で、かつインドリン環
にニトロ基を有するスピロピラン系フォトクロミック材
料を大量に製造することが可能であり、長波長に感度を
有するフォトクロミック材料が提供でき、その波及効果
は犬である。Effects of the Invention The present invention (see the blanks below for the compound represented by the general formula below) is a method for producing a photochromic material that obtains the compound of the general formula below by directly reacting with a nitrating agent. It is possible to produce a spiropyran-based photochromic material in large quantities that can be converted into a nitro group and has a nitro group on the indoline ring, and a photochromic material that is sensitive to long wavelengths can be provided, and its ripple effects are significant.
Claims (3)
学式、表等があります▼ ニトロ化剤を直接作用させて下記一般式の化合物を得る
ことを特徴とするフォトクロミック材料の製造方法。 ▲数式、化学式、表等があります▼ （ただし、Ｒはアルキル基、Ｒ＿１、Ｒ＿２はケトアル
キル基 アルコキシ基、ニトロ基 ハロゲン基、アルカ
ノイルオキシメチル基のうちのいずれかである。）(1) A method for producing a photochromic material, which is characterized in that a compound represented by the general formula below is directly treated with a nitrating agent to obtain a compound represented by the general formula below. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R is an alkyl group, and R_1 and R_2 are ketoalkyl groups, alkoxy groups, nitro groups, halogen groups, and alkanoyloxymethyl groups.)
する、 請求項１記載のフォトクロミック 材料の製造方法。(2) The method for producing a photochromic material according to claim 1, characterized in that fuming nitric acid is used as the nitration agent.
とを特徴とする、請求項１記載のフォトクロミック材料
の製造方法。(3) The method for producing a photochromic material according to claim 1, wherein R is a hydrocarbon chain having 6 to 32 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2269116A JP3064377B2 (en) | 1990-10-05 | 1990-10-05 | Method for producing photochromic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2269116A JP3064377B2 (en) | 1990-10-05 | 1990-10-05 | Method for producing photochromic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04145190A true JPH04145190A (en) | 1992-05-19 |
| JP3064377B2 JP3064377B2 (en) | 2000-07-12 |
Family
ID=17467901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2269116A Expired - Fee Related JP3064377B2 (en) | 1990-10-05 | 1990-10-05 | Method for producing photochromic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3064377B2 (en) |
-
1990
- 1990-10-05 JP JP2269116A patent/JP3064377B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3064377B2 (en) | 2000-07-12 |
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