JPH0267527A - Organic nonlinear optical material - Google Patents
Organic nonlinear optical materialInfo
- Publication number
- JPH0267527A JPH0267527A JP21966988A JP21966988A JPH0267527A JP H0267527 A JPH0267527 A JP H0267527A JP 21966988 A JP21966988 A JP 21966988A JP 21966988 A JP21966988 A JP 21966988A JP H0267527 A JPH0267527 A JP H0267527A
- Authority
- JP
- Japan
- Prior art keywords
- nitroaniline
- methoxymethyl
- nonlinear optical
- optical material
- single crystal
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/56—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
Description
【発明の詳細な説明】
く〈産業上の利用分野〉〉
本発明は、有機非線形光学材料、詳しくは、Ｎメトキシ
メチル−４−ニトロアニリンからなる有機非線形光学効
果を有する化合物に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an organic nonlinear optical material, and more particularly to a compound having an organic nonlinear optical effect composed of N-methoxymethyl-4-nitroaniline.
〈〈従来の技術〉〉
非線形光学材料は、レーザー光の強電界下で２次以上の
非線形応答を示す材料であり、現象的には波長変換、増
幅、変調、短パルス化、スイッチング、メモリー自己制
御など数多くの素子機能をもたらすことから、オプトエ
レクトロニクスや光コンピュータの基幹素材として注目
されている。<<Prior art>> Nonlinear optical materials are materials that exhibit a nonlinear response of second order or higher under the strong electric field of laser light, and their phenomena include wavelength conversion, amplification, modulation, shortening of pulses, switching, and memory self-response. Because it provides many element functions such as control, it is attracting attention as a core material for optoelectronics and optical computers.
リン酸２水素カリウム、ニオブ酸リチウム等の無機誘電
体や半導体を中心に研究開発されてきた。Research and development has focused on inorganic dielectrics and semiconductors such as potassium dihydrogen phosphate and lithium niobate.
最近、尿素、２−メチル−４−ニトロアニリン、メチル
−（２，４−ジニトロフェニル）−アミノプロパネート
、３−メチル−４−二トロピリジン−１−オキサイド等
の有機化合物が、従来の無機材料を遥かに上回る非線形
応答を示すことが判り、有機非線形光学材料の研究開発
が注目されている。Recently, organic compounds such as urea, 2-methyl-4-nitroaniline, methyl-(2,4-dinitrophenyl)-aminopropanate, and 3-methyl-4-nitropyridine-1-oxide have been used to replace conventional inorganic materials. It has been found that organic nonlinear optical materials exhibit a nonlinear response that far exceeds that of organic nonlinear optical materials, and research and development of organic nonlinear optical materials is attracting attention.
有機結晶の中には無機結晶に比べ、第２次非線形光学効
果が紫外から近赤外域において１０００倍程度０性能指
数７ （１：ｄ２／ｎ” ｄ：ＮＬＯ定数、ｎ：屈折ｆ
Ｘ）を有するものがある。光応答速度もフェムト秒程度
と格子振動が関与しないため無機結晶に比べ遥かに速く
、また光損傷に対する閾値も大きいことが認められてい
る。Some organic crystals have a second-order nonlinear optical effect in the ultraviolet to near-infrared region that is about 1000 times higher than that of inorganic crystals. Figure of merit 7 (1: d2/n" d: NLO constant, n: refraction f
Some have X). The photoresponse speed is on the order of femtoseconds, which is much faster than inorganic crystals because lattice vibrations are not involved, and it is also recognized that the threshold for photodamage is large.
しかし、
（１）第２次高調波発生（以下ＳＨＧという）は、偶数
次の特徴として対称中心を持つ結晶では発現しないこと
、
（２）非線形光学効果向上を計るため２次の超分子分極
率βを大きく設計すると、吸収が長波長域にまで及び実
用には不向きであること、また中心対称性の結晶を生成
し易いこと、
（３）あるいは、大きな単結晶を得にくいものが多いこ
と、
などが大きな問題点となっている。However, (1) second-order harmonic generation (hereinafter referred to as SHG) does not occur in crystals that have a center of symmetry as an even-order feature; (2) second-order supramolecular polarization is required to improve the nonlinear optical effect. If β is designed to be large, the absorption will extend to a long wavelength region, making it unsuitable for practical use.Also, centrally symmetrical crystals are likely to be produced.(3) Or, in many cases, it is difficult to obtain large single crystals. etc. are a major problem.
〈〈発明の目的〉〉
本発明の目的とするところは、対称中心を持たない単結
晶であることによってＳＨＧ活性が大きく、しかも室温
で安定であり、さらには、吸収が短波長域に存在し、大
きな単結晶が得られ、より安価に合成されるＮ−メトキ
シメチル−４−ニトロアニリンからなる有機非線形光学
材料を提供することにある。<<Object of the Invention>> The object of the present invention is to have a single crystal with no center of symmetry, which has high SHG activity, is stable at room temperature, and has absorption in a short wavelength region. An object of the present invention is to provide an organic nonlinear optical material made of N-methoxymethyl-4-nitroaniline, which can be synthesized at a lower cost and has a large single crystal.
〈〈発明の構成〉〉
本発明は、Ｎ−メトキシメチル−４−ニトロアニリンか
らなる有機非線形光学材料である。<<Structure of the Invention>> The present invention is an organic nonlinear optical material made of N-methoxymethyl-4-nitroaniline.
本発明によるＮ−メトキシメチル−４−ニトロアニリン
の合成法は種々あるが、その−例を述べる。There are various methods for synthesizing N-methoxymethyl-4-nitroaniline according to the present invention, and examples thereof will be described below.
Ｎ−メトキシメチル−４−ニトロアニリンは、４−ニト
ロアニリン、ホルムアルデヒド、メタノールをアルカリ
触媒存在下で反応させることにより、淡黄色透明針状結
晶として得られる。N-methoxymethyl-4-nitroaniline is obtained as pale yellow transparent needle-shaped crystals by reacting 4-nitroaniline, formaldehyde, and methanol in the presence of an alkali catalyst.
本発明によるＮ−メトキシメチル−４−ニトロアニリン
は、粉末法測定におけるＮｄ ： ＹＡＧレーザ−（波
長１１０６４ｎ ）の照射により第２次高調波を発生し
、入射光の１７２波長（５３２ｎｍ ）の緑色光を発現
する。N-methoxymethyl-4-nitroaniline according to the present invention generates a second harmonic by irradiation with a Nd: YAG laser (wavelength 11064 nm) in powder method measurement, and green light with a wavelength of 172 (532 nm) of the incident light. Express.
これは、本発明によるＮ−メトキシメチル−４−ニトロ
アニリンが対称中心を持たない単結晶であることによっ
てＳＨＧ活性を示したものである。しかも熱的に安定で
あり、また、容易に大きな単結晶に成長させることがで
きる。This shows that N-methoxymethyl-4-nitroaniline according to the present invention exhibits SHG activity because it is a single crystal without a center of symmetry. Moreover, it is thermally stable and can be easily grown into a large single crystal.
〈〈発明の効果〉〉
本発明によるＮ−メトキシメチル−４−ニトロアニリン
からなる有機非線形光学材料は、ＳＨＧが尿素の５０倍
と大きく、熱的に安定であり、さらに、容易に大きな単
結晶に成長させることができる。<<Effects of the Invention>> The organic nonlinear optical material made of N-methoxymethyl-4-nitroaniline according to the present invention has SHG as large as 50 times that of urea, is thermally stable, and can be easily formed into a large single crystal. can be grown to.
したがって、非線形光学応答を利用した波長変換素子、
光スィッチ等、光制御デバイス、非線形光学デバイス等
の素材用材料として有効である。Therefore, a wavelength conversion element using nonlinear optical response,
It is effective as a material for optical switches, optical control devices, nonlinear optical devices, etc.
以下実施例で本発明を更に詳しく説明する。The present invention will be explained in more detail with reference to Examples below.
実施例１
メタノール４００１に、水酸化ナトリウム３２０ｍｇを
溶解し、ホルムアルデヒド（３７％）水溶液２０ｇを加
え、室温で３０分間攪拌反応させた。その溶液中に、４
−ニトロアニリン１３．８ｇを加え、更に、室温で６時
間攪拌反応させた０反応終了後、低温減圧下メタノール
等を留去し、反応物にジエ″チルエーテル２００１を加
え溶解した。その溶液に水２００１ずつを加え、水洗操
作を３回繰り返した。有機層より得られた反応物をメタ
ノール飽和溶液とし、再結晶させることにより、淡黄色
透明針状結晶のＮ−メトキシメチル−４−ニトロアニリ
ン１２．７ｇ （収率７０％、純度９９．５％以上）
を得た。Example 1 320 mg of sodium hydroxide was dissolved in methanol 4001, 20 g of formaldehyde (37%) aqueous solution was added, and the mixture was stirred and reacted at room temperature for 30 minutes. In the solution, 4
- Added 13.8 g of nitroaniline and further stirred the reaction at room temperature for 6 hours. After the reaction was completed, methanol etc. were distilled off under reduced pressure at a low temperature, and diethyl ether 2001 was added to the reaction product and dissolved. The reaction product obtained from the organic layer was made into a methanol saturated solution and recrystallized to give N-methoxymethyl-4-nitroaniline 12 as pale yellow transparent needle crystals. .7g (yield 70%, purity 99.5% or more)
I got it.
このものは、融点１１５℃（ＤＳＣ測定）１分子量１８
２（ＦＤ−ＭＳ測定）である、さらに詳しい分析結果は
、下記の通りである。This product has a melting point of 115°C (DSC measurement) and a molecular weight of 18
The more detailed analysis results of No. 2 (FD-MS measurement) are as follows.
’Ｈ−ＮＭＲ測定（溶媒重アセトン）
δ８．０２，２１（、二重線、Ａｒ−Ｈ１δ７．２１．
１８．−重線、Ｎ−Ｈδ６．８５，２１１．二重線、Ａ
ｒ−Ｈ，δ４．６７．２Ｈ，二重線、Ｃ］δ３．２１．
３Ｈ，二重線、Ｃ−Ｈ。'H-NMR measurement (solvent deuterated acetone) δ8.02,21 (, doublet, Ar-H1δ7.21.
18. -Double line, N-Hδ6.85,211. double line, A
r-H, δ4.67.2H, doublet, C] δ3.21.
3H, doublet, C-H.
ＩＲ測測定ＫＢｒ錠剤法）
３４５０、１５５０ 、１２９０ｃｍ−’ 、Ａｒ−Ｎ
Ｈ−Ｒ，１０７０，９４０ｃｏ＋−’ 、Ｃ−０−Ｃ，
２９４０ｃｍ”” 、 Ｃ−１１３等の出現、１６２０
ｃｍ、Ｎ）１２の消失等ＳＨＧの測定は、Ｎ−メトキシ
メチル−４−ニトロアニリンを直径６０〜１００＃１１
に粒状化してスライドガラスに挟み、この試料に、Ｑス
イッチ付きＮｄ：ＹＡＧレーザ−（１０６４ｎｍ）によ
る１０ｎｓｅｃのパルスを照射、試料よりのＳＨＧを検
知した。標準試料には、同様に粒状化した尿素を用い、
尿素の３８０強度を１としたときの試料の３８０強度を
求めることにより行った。IR measurement KBr tablet method) 3450, 1550, 1290 cm-', Ar-N
H-R, 1070,940co+-', C-0-C,
2940cm"", appearance of C-113 etc., 1620
cm, N) Measurement of SHG such as disappearance of 12 is performed using N-methoxymethyl-4-nitroaniline with a diameter of 60 to 100 #11
The sample was granulated and sandwiched between slide glasses, and the sample was irradiated with a 10 nsec pulse from a Q-switched Nd:YAG laser (1064 nm) to detect SHG from the sample. For the standard sample, similarly granulated urea was used,
This was done by determining the 380 intensity of the sample when the 380 intensity of urea was set as 1.
上記方法により前記試料の３８０強度を測定したところ
、尿素に対して５０倍のＳＨＧを確認することができた
。When the 380 intensity of the sample was measured using the above method, it was confirmed that SHG was 50 times as strong as urea.
参考例Ｉ
Ｎ−メトキシメチル−４−ニトロアニリン２ｇをテトラ
ヒドロフラン飽和溶液とし、これを室温で静置した。１
日ないし２日間で容易に２ｍｍＸ ２１１！１Ｘ２０ｍ
ｍ程度の単結晶を得な。Reference Example I 2 g of N-methoxymethyl-4-nitroaniline was made into a saturated solution in tetrahydrofuran, and the solution was allowed to stand at room temperature. 1
2mmX 211!1X20m easily in a day or two days
Obtain a single crystal of about m.
比較例１
実施例１と同様にして、４−ニトロアニリンについてＳ
ＨＧ強度を測定したところ、ＳＨＧを確認することがで
きなかった。Comparative Example 1 In the same manner as in Example 1, S
When the HG intensity was measured, no SHG could be confirmed.
Claims (1)
らなる有機非線形光学材料。[Claims] An organic nonlinear optical material consisting of N-methoxymethyl-4-nitroaniline represented by the chemical formula ▲ Numerical formula, chemical formula, table, etc. ▼.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21966988A JPH0267527A (en) | 1988-09-02 | 1988-09-02 | Organic nonlinear optical material |
| US07/373,131 US5110988A (en) | 1988-08-23 | 1989-06-29 | Nonlinear optical material |
| EP89111875A EP0355326B1 (en) | 1988-08-23 | 1989-06-29 | Nonlinear optical material |
| DE89111875T DE68910224T2 (en) | 1988-08-23 | 1989-06-29 | Material for nonlinear optics. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21966988A JPH0267527A (en) | 1988-09-02 | 1988-09-02 | Organic nonlinear optical material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0267527A true JPH0267527A (en) | 1990-03-07 |
Family
ID=16739122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21966988A Pending JPH0267527A (en) | 1988-08-23 | 1988-09-02 | Organic nonlinear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0267527A (en) |
-
1988
- 1988-09-02 JP JP21966988A patent/JPH0267527A/en active Pending
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