JPH0679125B2 - Non-linear optical material - Google Patents
Non-linear optical materialInfo
- Publication number
- JPH0679125B2 JPH0679125B2 JP5346286A JP5346286A JPH0679125B2 JP H0679125 B2 JPH0679125 B2 JP H0679125B2 JP 5346286 A JP5346286 A JP 5346286A JP 5346286 A JP5346286 A JP 5346286A JP H0679125 B2 JPH0679125 B2 JP H0679125B2
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3611—Organic materials containing Nitrogen
- G02F1/3612—Heterocycles having N as heteroatom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
-
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
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- C—CHEMISTRY; METALLURGY
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- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/08—Radicals containing only hydrogen and carbon atoms
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D—HETEROCYCLIC COMPOUNDS
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- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- Optics & Photonics (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、波長変換素子等の非線形光学効果を利用する
各種素子に用いるに適した非線形光学材料に関する。TECHNICAL FIELD The present invention relates to a non-linear optical material suitable for use in various elements such as wavelength conversion elements that utilize non-linear optical effects.
（従来の技術） 近年、非線形光学効果−強いレーザー光を物質に入射し
た時、その相互作用によつて入射光と異なつた成分を持
つ出射光が得られる現象−を有した材料が注目を集めて
いる。かかる材料は、一般に非線形光学材料として知ら
れており、例えば次のものなどに詳しく記載されている
“Nonliner Optical Properties of Organic and Polym
eric Materials"ACS SYMPOSIUM SERIES 233、David J.W
ulliams編（American Chemical Society、1983年刊）、
「有機非線形光学材料」加藤政雄、中西八郎監修（シー
・エム・シー社、1985年刊）。(Prior Art) In recent years, materials having a non-linear optical effect-a phenomenon in which, when a strong laser beam is incident on a substance, an emitted light having a component different from the incident light is obtained due to the interaction-has attracted attention. ing. Such materials are generally known as nonlinear optical materials, and are described in detail in, for example, “Nonliner Optical Properties of Organic and Polym
eric Materials "ACS SYMPOSIUM SERIES 233, David JW
ulliams (American Chemical Society, 1983),
"Organic nonlinear optical materials" edited by Masao Kato and Hachiro Nakanishi (CMC, 1985).
非線形光学材料の用途の１つに、２次の非線形効果に基
いた第２高調波発生（SHG）および和周波、差周波を用
いた波長変換デバイスがある。これまで実用上用いられ
ているものは、ニオブ酸リチウムに代表される無機質の
ペロブスカイト類である。しかし近年になり、電子共与
基および電子吸引基を有するπ電子共役系有機化合物は
前述の無機質を大きく上回る、非線形光学材料としての
諸性能を有していることが知られるようになつた。しか
しながら、高いSHGを示すことで知られているｐ−ニト
ロアニリンの誘導体、例えば、２−メチル−４−ニトロ
アニリン（MNA）や２−N,N−ジメチルアミノ−５−ニト
ロアセトアニリド（DAN）などでは、強く黄色に着色し
ているために、青色光に対する透過率が低く問題となつ
ている。従つて青色光に対する透過率の高い非線形光学
材料の出現が望まれている。従来、ニトロアニリンのベ
ンゼン核の炭素原子を窒素原子などで置き換えることが
検討されて来たが必ずしも満足のいく結果は得られてい
ない。One of the applications of the nonlinear optical material is a second harmonic generation (SHG) based on the second-order nonlinear effect and a wavelength conversion device using a sum frequency and a difference frequency. So far, those which have been practically used are inorganic perovskites represented by lithium niobate. However, in recent years, it has become known that a π-electron conjugated organic compound having an electron-donating group and an electron-withdrawing group has various performances as a nonlinear optical material, which greatly exceeds the above-mentioned inorganic substances. However, derivatives of p-nitroaniline known to show high SHG, such as 2-methyl-4-nitroaniline (MNA) and 2-N, N-dimethylamino-5-nitroacetanilide (DAN), etc. However, since it is strongly colored yellow, the transmittance for blue light is low, which is a problem. Therefore, the advent of a nonlinear optical material having a high transmittance for blue light is desired. Conventionally, replacement of carbon atoms in the benzene nucleus of nitroaniline with nitrogen atoms has been studied, but satisfactory results have not necessarily been obtained.
（発明が解決しようとする問題点） 従つて、本発明の目的は青色光に対する透過率の高く、
且つ高い非線形光学効果を示す新規な有機化合物を提供
することにある。(Problems to be Solved by the Invention) Accordingly, an object of the present invention is to have a high transmittance for blue light,
Another object of the present invention is to provide a novel organic compound exhibiting a high nonlinear optical effect.
（問題点を解決するための手段） 本発明者らは前記の目的を、従来の方法とは異り、ニト
ロアニリン骨格を保持したままで達成できることを見出
し、本発明を成すに至つた。本発明の目的は下記一般式
（Ｉ）またはその酸付加物で示される化合物を用いるこ
とにより達成することができる。(Means for Solving the Problems) The present inventors have found that, unlike the conventional methods, the above-mentioned object can be achieved while retaining the nitroaniline skeleton, and have completed the present invention. The object of the present invention can be achieved by using a compound represented by the following general formula (I) or an acid addition product thereof.
一般式（Ｉ） 式中、Z1およびZ2は同一でも異つていてもよくＮ原子ま
たは、CR2基を表わし、但し、Z1およびZ2のうち少なく
とも一方はＮ原子である。Ｘはアルキル基、アリール
基、ハロゲン原子、アルコキシ基、アリールオキシ基、
アシルアミノ基、カルバモイル基、スルフアモイル基、
アシルオキシ基、アルキルオキシカルボニル基、アリー
ルオキシカルボニル基、アルキルオキシスルホニル基、
アリールオキシスルホニル基、アルキルチオ基、アリー
ルチオ基、ヒドロキシ基、チオール基、カルボキシ基、
ウレイド基、シアノ基、アルキルスルホニル基、アリー
ルスルホニル基、アルキルスルフイニル基、アリールス
ルフイニル基、ニトロ基を表わす。ｎは０ないし３の整
数を表わす。R1は水素原子、アルキル基、アリール基、
アシル基を表わし、R2は水素原子、アルキル基、または
アリール基を表わす。General formula (I) In the formula, Z 1 and Z 2 may be the same or different and each represents an N atom or a CR 2 group, provided that at least one of Z 1 and Z 2 is an N atom. X is an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group,
Acylamino group, carbamoyl group, sulfamoyl group,
Acyloxy group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyloxysulfonyl group,
Aryloxysulfonyl group, alkylthio group, arylthio group, hydroxy group, thiol group, carboxy group,
It represents an ureido group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, and a nitro group. n represents an integer of 0 to 3. R 1 is a hydrogen atom, an alkyl group, an aryl group,
It represents an acyl group, and R 2 represents a hydrogen atom, an alkyl group, or an aryl group.
後述の実施例より明らかなように、上記一般式（Ｉ）で
表わされる本発明の非線形光学材料は波長変換素子用の
材料として特に有用なものである。しかしながら本発明
の非線形光学材料の用途は波長変換素子に限られるもの
ではなく、非線形光学効果を利用するものであればいか
なる素子にも使用可能である。本発明の非線形光学材料
が用いられうる素子の具体例として、波長変換素子以外
に、光双安定素子（光記憶素子、光パルス波形制御素
子、光リミター、微分増幅素子、光トランジスター、A/
D変換素子、光論理素子、光マルチバイブレーター、光
フリツプフロツプ回路等）、光変調素子および位相共役
光学素子等が挙げられる。As will be apparent from Examples described later, the nonlinear optical material of the present invention represented by the above general formula (I) is particularly useful as a material for a wavelength conversion element. However, the application of the non-linear optical material of the present invention is not limited to the wavelength conversion element, and can be used for any element as long as it utilizes the non-linear optical effect. As specific examples of the element in which the nonlinear optical material of the present invention can be used, in addition to the wavelength conversion element, an optical bistable element (optical storage element, optical pulse waveform control element, optical limiter, differential amplification element, optical transistor, A /
D conversion elements, optical logic elements, optical multivibrators, optical flip-flop circuits, etc.), optical modulators and phase conjugate optical elements.
本発明の一般式（Ｉ）について更に説明する。アルキル
基としては、例えばメチル基、エチル基、イソプロピル
基、ブチル基、ｔ−ブチル基、オクチル基、ｔ−オクチ
ル基、デシル基、ヘキサデシル基、ドコシル基、２−ヒ
ドロキシエチル基、カルボキシメチル基、シアノメチル
基、２−メトキシエチル基、ベンジル基、２−フエニル
エチル基、トリフルオロメチル基、３−（２−ベンゾイ
ミダゾリル）プロピル基などが挙げられる。前記アリー
ル基としてはフエニル基、４−メチルフエニル基、３−
メトキシフエニル基、、４−クロロフエニル基などが挙
げられる。前記ハロゲン原子としてはフツ素原子、塩素
原子、臭素原子、沃素原子が挙げられる。アルコキシ基
としては、例えばメトキシ基、ブトキシ基、２−メトキ
シエトキシ基、ベンジルオキシ基、２−フエニルエトキ
シ基などが挙げられる。アリールオキシ基としては、例
えばフエノキシ基、４−ｔ−ブチルフエノキシ基、４−
クロロフエノキシ基などが挙げられる。アシルアミノ基
としては例えばアセチルアミノ基、メタンスルホニルア
ミノ基、ベンゾイルアミノ基、４−メチルベンゼンスル
ホニルアミノ基などが挙げられる。カルバモイル基とし
ては例えば、カルバモイル基、Ｎ−メチルカルバモイル
基、Ｎ−エチルカルバモイル基、Ｎ−フエニルカルバモ
イル基などが挙げられる。スルフアモイル基としては例
えばスルフアモイル基、Ｎ−メチルスルフアモイル基、
Ｎ−フエニルスルフアモイル基などが挙げられる。アシ
ルオキシ基としては例えばアセチルオキシ基、ピバロイ
ルオキシ基、ベンゾイルオキシ基、ベンゼンスルホニル
オキシ基などが挙げられる。ウレイド基としては例えば
メチルウレイド、エチルウレイド、フエニルウレイドな
どが挙げられる。The general formula (I) of the present invention will be further described. As the alkyl group, for example, methyl group, ethyl group, isopropyl group, butyl group, t-butyl group, octyl group, t-octyl group, decyl group, hexadecyl group, docosyl group, 2-hydroxyethyl group, carboxymethyl group, Examples thereof include a cyanomethyl group, a 2-methoxyethyl group, a benzyl group, a 2-phenylethyl group, a trifluoromethyl group and a 3- (2-benzimidazolyl) propyl group. The aryl group is a phenyl group, a 4-methylphenyl group, 3-
Examples thereof include a methoxyphenyl group and a 4-chlorophenyl group. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the alkoxy group include a methoxy group, a butoxy group, a 2-methoxyethoxy group, a benzyloxy group and a 2-phenylethoxy group. Examples of the aryloxy group include a phenoxy group, 4-t-butylphenoxy group, 4-
Examples thereof include a chlorophenoxy group. Examples of the acylamino group include an acetylamino group, a methanesulfonylamino group, a benzoylamino group and a 4-methylbenzenesulfonylamino group. Examples of the carbamoyl group include a carbamoyl group, an N-methylcarbamoyl group, an N-ethylcarbamoyl group and an N-phenylcarbamoyl group. Examples of the sulfamoyl group include a sulfamoyl group, an N-methylsulfamoyl group,
Examples thereof include N-phenylsulfamoyl group. Examples of the acyloxy group include an acetyloxy group, a pivaloyloxy group, a benzoyloxy group and a benzenesulfonyloxy group. Examples of the ureido group include methylureido, ethylureido, phenylureido and the like.
また、一般式（Ｉ）の中で好ましいものとしては、下記
の一般式（II）またはその酸付加物があげられる。Further, among the general formula (I), preferred are the following general formula (II) and acid addition products thereof.
一般式（II） 式中、Z3およびZ4はZ1およびZ2と同義であり、R3はR1と
同義である。General formula (II) In the formula, Z 3 and Z 4 have the same meanings as Z 1 and Z 2 , and R 3 has the same meaning as R 1 .
次に、一般式（II）の中で好ましいものとしては下記の
一般式（III）もしくは（IV）またはこれらの酸付加物
があげられる。Next, among the general formula (II), the following general formulas (III) and (IV) or acid addition products thereof are preferable.
一般式（III） 式中、R4はR1と同義でありR5はR2と同義である。またNO
2基は５位または６位に置換されている。General formula (III) In the formula, R 4 has the same meaning as R 1 and R 5 has the same meaning as R 2 . Also NO
The two groups are substituted at the 5 or 6 positions.
一般式（IV） 式中、R6はR1と同義であり、R7はR2と同義である。また
NO2基は５位または６位に置換されている。General formula (IV) In the formula, R 6 has the same meaning as R 1 , and R 7 has the same meaning as R 2 . Also
The NO 2 group is substituted at the 5 or 6 position.
上記の酸付加物とは、一般式（Ｉ）または（II）、（II
I）の化合物に有機酸（例えば、カルボン酸、スルホン
酸など）、または無機酸（例えば、硫酸、塩酸、硝酸、
リン酸など）が付加（通常１分子）したものである。The above-mentioned acid addition product is represented by the general formula (I) or (II), (II
Organic compounds (for example, carboxylic acids, sulfonic acids, etc.) or inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, etc.)
Phosphoric acid, etc.) is added (usually one molecule).
以下に、本発明に用いられる化合物の具体例を示すが、
本発明の範囲はこれらのみに限定されるものではない。The specific examples of the compounds used in the present invention are shown below,
The scope of the present invention is not limited to these.
化合物例 次に本発明の化合物の合成について記述する。Compound example Next, the synthesis of the compound of the present invention will be described.
一般式（Ｉ）で示される化合物のうち大部分は、既知化
合物であり、それらの合成に関しては例えばRobert C.E
lderfield著Hetero−cyclic Compounds volume5およびv
olume7（John Wiley ＆ Sons,Inc.New York.London）に
記載されている方法で合成することが可能であり、また
一般に市販されている試薬（例えば和光純薬、東京化
成、Aldrich等）としても入手可能である。Most of the compounds represented by the general formula (I) are known compounds, and their synthesis is described in, for example, Robert CE.
Hetero-cyclic Compounds volume 5 and v by lderfield
It can be synthesized by the method described in olume7 (John Wiley & Sons, Inc. New York.London), and also as a commercially available reagent (eg Wako Pure Chemical, Tokyo Kasei, Aldrich, etc.). It is available.
次に代表的な化合物についての具体的合成法を以下に示
す。Next, specific synthetic methods for representative compounds are shown below.
合成例−１（化合物２の合成） ３−ニトロ−1,2−ジアミノベンゼン15gを無水酢酸80ml
中に加え次いで濃塩酸1mlを注意深く滴下し３時間撹拌
下にて加熱還流させる。Synthesis Example-1 (Synthesis of Compound 2) 15 g of 3-nitro-1,2-diaminobenzene was mixed with 80 ml of acetic anhydride.
Then, 1 ml of concentrated hydrochloric acid is carefully added dropwise, and the mixture is heated to reflux with stirring for 3 hours.
反応溶液を室温まで冷却し得られる結晶を減圧下にて濾
過し濾取した結晶を10％苛性ソーダ水溶液中に加え、１
時間70℃にて撹拌する。反応溶液を氷冷下に濃塩酸にに
て中和する。得られる結晶を減圧下にて濾取し、メタノ
ールより再結晶すると無色板状結晶の化合物２を6.5g得
る。融点223℃ 合成例−２（化合物５の合成） オルトフエニレンジアミン22gと吉草酸30gを混合し、２
時間加熱還流させた後、エタノール中に注ぎ、苛性カリ
水溶液にて中和する。得られた結晶を濾取し、エタノー
ルと水の混合溶媒にて再結晶すると針状結晶14gが得ら
れる。この結晶10gを濃硫酸60ml中に加え、氷冷撹拌下
にて硝酸6.5mlを徐々に滴下する。滴下終了後、氷冷下
にて２時間撹拌後、氷水中に注ぎアンモニア水にて中和
し、得られる結晶をエタノールと水の混合溶媒にて中和
すると、融点139℃の化合物５の白色結晶4.5gを得る。The reaction solution was cooled to room temperature, the resulting crystals were filtered under reduced pressure, and the crystals collected by filtration were added to a 10% aqueous solution of caustic soda.
Stir at 70 ° C for hours. The reaction solution is neutralized with concentrated hydrochloric acid under ice cooling. The obtained crystals are collected by filtration under reduced pressure and recrystallized from methanol to obtain 6.5 g of compound 2 as colorless plate crystals. Melting point 223 ° C. Synthesis example-2 (Synthesis of compound 5) 22 g of orthophenylenediamine and 30 g of valeric acid were mixed, and 2
After heating under reflux for an hour, it is poured into ethanol and neutralized with an aqueous solution of potassium hydroxide. The obtained crystals are collected by filtration and recrystallized with a mixed solvent of ethanol and water to obtain 14 g of needle crystals. 10 g of the crystals are added to 60 ml of concentrated sulfuric acid, and 6.5 ml of nitric acid is gradually added dropwise while stirring with ice cooling. After the dropwise addition, the mixture was stirred for 2 hours under ice cooling, poured into ice water and neutralized with aqueous ammonia, and the obtained crystals were neutralized with a mixed solvent of ethanol and water to give compound 5 as white with a melting point of 139 ° C. 4.5 g of crystals are obtained.
他の化合物も上記の合成方法に準じて容易に行なうこと
ができる。Other compounds can be easily prepared according to the above synthetic method.
本発明の化合物は、例えば粉末の形、宿主格子（ポリマ
ー、包接化合物、固溶体、液晶）中の分子の包有物の
形、支持体上に沈積した薄層の形（ラングミーア・ブロ
ジエツト膜など）、単結晶の形、溶液の形等、種々の形
で非線形光学材料として用いることができる。The compounds according to the invention are, for example, in the form of powders, inclusions of molecules in the host lattice (polymers, clathrates, solid solutions, liquid crystals), in the form of thin layers deposited on supports (Langmere Brodgett's membranes, etc.). ), A single crystal form, a solution form, and the like, and can be used as a nonlinear optical material in various forms.
また本発明の化合物をペンダントの形でポリマー、ポリ
ジアセチレンなどに結合させて用いることもできる。Also, the compound of the present invention can be used in the form of a pendant linked to a polymer, polydiacetylene or the like.
これらの方法について詳しくは前述のD.J.Williams編の
著作などに記載されている。Details of these methods are described in the above-mentioned book edited by DJ Williams.
（実施例） 次に、本発明を実施例に基づいて詳しく説明する。(Example) Next, the present invention will be described in detail based on an example.
実施例1. 第２高調波発生の測定をエス・ケー・クルツ（S.K.Kurt
z）、テイー・テイー・ペリー（T.T.Perry）著、ジヤー
ナル オブ アプライド フイジツクス（J.Appl.Phy
s.）39巻 3798頁（1968年刊）中に記載されている方法
に準じて、本発明の化合物の粉末に対して行なつた。Example 1. SK Kurt measurement of the second harmonic generation
z) by TTPerry, Journal of Applied Physics (J.Appl.Phy)
s.) Vol. 39, page 3798 (published in 1968) according to the method described in the powder of the compound of the present invention.
線源としてNd:YAGレーザー（20mWパルス）の1,064μ線
を使用し、ガラスセル中に充填した粉末のサンプルに照
射し、緑色光の発生を観測した。結果を表１に示す。Using a 1,064μ line of an Nd: YAG laser (20mW pulse) as a radiation source, a powder sample filled in a glass cell was irradiated and the generation of green light was observed. The results are shown in Table 1.
実施例2. 実施例１と同様の線源およびサンプルを用い、発生した
緑色光をフイルターおよびモノクロメーター（532nm）
で分光し、光電子増倍管で検知した。結果を表２に示
す。 Example 2. Using the same radiation source and sample as in Example 1, the generated green light was filtered by a filter and a monochromator (532 nm).
It was analyzed by a photomultiplier tube and detected. The results are shown in Table 2.
実施例3. 線源としてNd:YAGレーザーの第２高調波で励起させた色
素レーザー〔色素:DTTC（イーストマンコダツク社
製）、溶媒：ジメチルスルオキシド〕の870nm線（50mJ/
パルス）を使用し、実施例２と同様にして435nmの青色
光の強度を測定した。 Example 3. Dye laser excited by the second harmonic of Nd: YAG laser as a radiation source [dye: DTTC (manufactured by Eastman Kodak Co., solvent: dimethylsulfoxide), 870 nm line (50 mJ /
Pulse) was used and the intensity of blue light at 435 nm was measured in the same manner as in Example 2.
結果を表３に示した。The results are shown in Table 3.
ここでMNAとは を示す。 What is MNA here Indicates.
実施例１〜３から明らかなように本発明の化合物は優れ
た非線形光学材料となり得た。As is clear from Examples 1 to 3, the compound of the present invention could be an excellent nonlinear optical material.
実施例4. 青色光の透過性を調べるため、下記の化合物の４×10-4
モル／のエタノール溶液の波長に対する透過率を測定
した。結果を図１に示した。図中の〜は各々下記の
ものを示す。Example 4. To investigate blue light transmission, 4 × 10 −4 of the following compound was used.
The transmittance of the mol / ethanol solution with respect to the wavelength was measured. The results are shown in Fig. 1. In the figure, -indicate the following.
ここでPNP、MNA、PANは各々下記のものを表わす。 Here, PNP, MNA, and PAN represent the following, respectively.
MNA PAN PNP 第１図から明らかなように本発明の化合物は青色光の透
過性において優れたものであつた。MNA PAN PNP As is clear from FIG. 1, the compound of the present invention was excellent in blue light transmittance.
次に、好ましい実施態様を以下に示す。Next, a preferred embodiment will be described below.
（１） 下記一般式（II）で表わされる化合物、あるい
は（II）の酸付加物を用いた非線形光学材料 一般式（II） 式中Z3およびZ4はZ1およびZ2と同義であり、R3はR1と同
義である。(1) Nonlinear optical material using a compound represented by the following general formula (II) or an acid adduct of (II) General formula (II) In the formula, Z 3 and Z 4 have the same meanings as Z 1 and Z 2 , and R 3 has the same meaning as R 1 .
（２） 下記一般式（III）で表わされる化合物、ある
いは（III）の酸付加物を用いた非線形光学材料 一般式（III） 式中、R4はR1と同義であり、R5はR2と同義である。また
NO2基は５位または６位に置換されている。(2) Nonlinear optical material using the compound represented by the following general formula (III) or the acid addition product of (III) General formula (III) In the formula, R 4 has the same meaning as R 1 and R 5 has the same meaning as R 2 . Also
The NO 2 group is substituted at the 5 or 6 position.
（３） 下記一般式（IV）で表わされる化合物、あるい
は（IV）の酸付加物を用いた非線形光学材料 一般式（IV） 式中、R6はR1と同義であり、R7はR2と同義である。また
NO2基は５位または６位に置換されている。(3) Nonlinear optical material using a compound represented by the following general formula (IV) or an acid adduct of (IV) General formula (IV) In the formula, R 6 has the same meaning as R 1 , and R 7 has the same meaning as R 2 . Also
The NO 2 group is substituted at the 5 or 6 position.
第１図は、実施例４における各化合物のエタノール溶液
中における分光透過率を示した。 図中〜は各々化合物10、２、比較化合物PNP、MNP、
PANを示す。 なお、縦軸は透過率（Ｔ％）を、横軸は波長（nm）を表
わす。FIG. 1 shows the spectral transmittance of each compound in Example 4 in an ethanol solution. In the figure, ~ are compounds 10 and 2, comparative compounds PNP, MNP,
Indicates PAN. The vertical axis represents the transmittance (T%) and the horizontal axis represents the wavelength (nm).
Claims (1)
いはその酸付加物からなることを特徴とする非線形光学
材料。 一般式（Ｉ） （式中Z1およびZ2は同一でも異つていてもよくＮ原子ま
たはCR2基を表わす。但し、Z1およびZ2のうち少くとも
一方はＮ原子を表わす。Ｘはアルキル基、アリール基、
ハロゲン原子、アルコキシ基、アリールオキシ基、アシ
ルアミノ基、カルバモイル基、スルフアモイル基、アシ
ルオキシ基、アルコキシカルボニル基、アリールオキシ
カルボニル基、アルコキシスルホニル基、アリールオキ
シスルホニル基、アルキルチオ基、アリールチオ基、ヒ
ドロキシ基、チオール基、カルボキシ基、ウレイド基、
シアノ基、アルキルスルホニル基、アリールスルホニル
基、アルキルスルフイニル基、アリールスルフイニル基
またはニトロ基を表わす。ｎは０ないし３の整数を表わ
す。R1は水素原子、アルキル基、アリール基またはアシ
ル基を表わし、R2は水素原子、アルキル基またはアリー
ル基を表わす。なお、Ｘ、R1、R2に含まれるアルキル基
およびアリール基は置換されていてもよい。）1. A nonlinear optical material comprising a compound represented by the following general formula (I) or an acid addition product thereof. General formula (I) (In the formula, Z 1 and Z 2 may be the same or different and each represents an N atom or a CR 2 group, provided that at least one of Z 1 and Z 2 represents an N atom. X is an alkyl group or aryl. Base,
Halogen atom, alkoxy group, aryloxy group, acylamino group, carbamoyl group, sulfamoyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, alkylthio group, arylthio group, hydroxy group, thiol Group, carboxy group, ureido group,
It represents a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group or a nitro group. n represents an integer of 0 to 3. R 1 represents a hydrogen atom, an alkyl group, an aryl group or an acyl group, and R 2 represents a hydrogen atom, an alkyl group or an aryl group. The alkyl group and aryl group contained in X, R 1 and R 2 may be substituted. )
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5346286A JPH0679125B2 (en) | 1986-03-11 | 1986-03-11 | Non-linear optical material |
| DE19873707835 DE3707835A1 (en) | 1986-03-11 | 1987-03-11 | NON-LINEAR OPTICAL MATERIAL |
| US07/263,977 US4982112A (en) | 1986-03-11 | 1988-10-26 | Nonlinear optical material |
| US07/598,514 US5115337A (en) | 1986-03-11 | 1990-10-16 | Nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5346286A JPH0679125B2 (en) | 1986-03-11 | 1986-03-11 | Non-linear optical material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62210430A JPS62210430A (en) | 1987-09-16 |
| JPH0679125B2 true JPH0679125B2 (en) | 1994-10-05 |
Family
ID=12943523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5346286A Expired - Lifetime JPH0679125B2 (en) | 1986-03-11 | 1986-03-11 | Non-linear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0679125B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07122724B2 (en) * | 1987-01-16 | 1995-12-25 | 日本電信電話株式会社 | Organic nonlinear optical material |
| JPH01188831A (en) * | 1988-01-22 | 1989-07-28 | Matsushita Electric Ind Co Ltd | Liquid crystal display device |
-
1986
- 1986-03-11 JP JP5346286A patent/JPH0679125B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62210430A (en) | 1987-09-16 |
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