JPH0719003B2 - Non-linear optical material - Google Patents
Non-linear optical materialInfo
- Publication number
- JPH0719003B2 JPH0719003B2 JP1249219A JP24921989A JPH0719003B2 JP H0719003 B2 JPH0719003 B2 JP H0719003B2 JP 1249219 A JP1249219 A JP 1249219A JP 24921989 A JP24921989 A JP 24921989A JP H0719003 B2 JPH0719003 B2 JP H0719003B2
- Authority
- JP
- Japan
- Prior art keywords
- optical material
- dithienylpropenone
- linear optical
- present
- linear
- 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.)
- Expired - Lifetime
Links
- 230000003287 optical effect Effects 0.000 title claims description 19
- 239000000463 material Substances 0.000 title claims description 15
- 230000009021 linear effect Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- -1 for example Substances 0.000 description 3
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 3
- 230000009022 nonlinear effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XTTIQGSLJBWVIV-UHFFFAOYSA-N 2-methyl-4-nitroaniline Chemical compound CC1=CC([N+]([O-])=O)=CC=C1N XTTIQGSLJBWVIV-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は、1,3−ジチエニルプロペノンからなる非線形
光学材料に関する。TECHNICAL FIELD The present invention relates to a nonlinear optical material composed of 1,3-dithienylpropenone.
〈従来の技術〉 非線形光学材料とは、物質の中の光の電界によって誘起
される電子の誘発分極が、電界に対して非線形な応答を
生じる、いわゆる非線形光学効果を有する材料をさし、
一般に下式により示される２次の項以上のものにより生
じる。<Prior Art> A non-linear optical material refers to a material having a so-called non-linear optical effect, in which induced polarization of electrons induced by an electric field of light in a substance causes a non-linear response to the electric field,
Generally, it is caused by one or more quadratic terms represented by the following equation.
Ｐ＝κ(1)Ｅ＋κ(2)Ｅ・Ｅ＋κ(3)Ｅ・Ｅ・Ｅ＋……＋
κ(n)Ｅ・ｎ （式中、Ｐは物質の分極率、Ｅは電界、κ(n)はｎ次の
非線形感受率を表わす。） 特に２次の効果を利用した第２高調波発生（SHG）とし
て知られている現象によれば、入射光は第２高調波であ
る２倍の周波数を有する光波となったり、また電圧によ
って屈折率が変化するので、この現象を利用して、波長
変換、信号処理、レーザー光の変調等の種々の光学的処
理を行うことが可能であり、極めて有用であることが知
られている。P = κ (1) E + κ (2) E ・ E + κ (3) E ・ E ・ E + ……
κ (n) E · n (where P is the polarizability of the substance, E is the electric field, and κ (n) is the n-th order nonlinear susceptibility.) Especially the second harmonic generation using the second-order effect According to a phenomenon known as (SHG), the incident light becomes a light wave having a frequency twice as high as the second harmonic, and the refractive index changes depending on the voltage. It is known that various optical processes such as wavelength conversion, signal processing, laser light modulation, etc. can be performed, and they are extremely useful.
従来の非線形光学材料としてはKH2PO4（KDP），LiNb
O3，NH4H2PO4（ADP）などの無機結晶が使用されていた
が、光学的純度の高い単結晶が非常に高価であることや
潮解性を示し取り扱いに不便であること、また非線形感
受率があまり高くないことなどの問題があった。一方、
1983年アメリカ化学会シンポジウムにおいて有機材料の
有用性が示唆されて以来、尿素、アニリン化合物等の有
機結晶が非線形光学材料として発表されている。ところ
が、これらの有機化合物はいまだ充分満足される非線形
効果を示しておらず、また比較的高い非線形効果を示す
ものは化合物自身の光吸収端が長波長側へ相当シフトし
ており使用波長範囲が極めて限定されてしまうという欠
点がある。Conventional non-linear optical materials include KH 2 PO 4 (KDP) and LiNb
Inorganic crystals such as O 3 and NH 4 H 2 PO 4 (ADP) have been used, but single crystals with high optical purity are very expensive and deliquescent, which makes them inconvenient to handle. There was a problem that the nonlinear susceptibility was not so high. on the other hand,
Organic crystals such as urea and aniline compounds have been announced as nonlinear optical materials since the usefulness of organic materials was suggested at the American Chemical Society 1983 symposium. However, these organic compounds do not yet exhibit a satisfactory non-linear effect, and those exhibiting a relatively high non-linear effect show that the light absorption edge of the compound itself has shifted considerably to the long wavelength side and the operating wavelength range is It has the drawback of being extremely limited.
〈発明が解決しようとする課題〉 本発明の目的は、透過性、透明性に優れ、極めて高い非
線形効果を呈する、1,3−ジチエニルプロペノンからな
る非線形光学材料を提供することにある。<Problem to be Solved by the Invention> An object of the present invention is to provide a non-linear optical material composed of 1,3-dithienylpropenone, which has excellent transparency and transparency and exhibits an extremely high non-linear effect.
〈課題を解決するための手段〉 本発明によれば、下記構造式（Ｉ） で表わされる1,3−ジチエニルプロペノンからなる非線
形光学材料が提供される。<Means for Solving the Problems> According to the present invention, the following structural formula (I) A non-linear optical material comprising 1,3-dithienylpropenone represented by
以下本発明を更に詳細に説明する。The present invention will be described in more detail below.
本発明に用いられる1,3−ジチエニルプロペノンは、下
記構造式（Ｉ）で表わすことができる。The 1,3-dithienylpropenone used in the present invention can be represented by the following structural formula (I).
前記構造式（Ｉ）で表わされる1,3−ジチエニルプロペ
ノンを製造するには、例えば、２−アセチルチオフェン
と２−チオフェンカルバルデヒドとを塩基性触媒または
酸性触媒存在下で脱水縮合反応を行なうことにより得る
ことができる。前記塩基性触媒としては、例えば水酸化
ナトリウム、水酸化カリウム又は種々の４級アンモニウ
ム塩等を用いることができ、また酸性触媒としては、例
えば三フッ化ホウ素、オキシ塩化リン、三フッ化ホウ素
エーテラート等を用いることができる。更に具体的に
は、前記２−アセチルチオフェンと前記２−チオフェン
カルバルデヒドとを前記触媒の存在下、必要に応じて、
適当な溶媒、例えばメタノール、エタノール等のアルコ
ール類を用いて、好ましくは０℃〜50℃の温度範囲内で
30分〜50時間反応を行なうことにより前記1,3−ジチエ
ニルプロペノンを得ることができる。反応温度が50℃よ
り高いと熱による様々な副反応が生じ、また０℃より低
温では、反応時間が極めて長くなり、不経済であるので
好ましくない。 To produce 1,3-dithienylpropenone represented by the structural formula (I), for example, 2-acetylthiophene and 2-thiophenecarbaldehyde are subjected to dehydration condensation reaction in the presence of a basic catalyst or an acidic catalyst. It can be obtained by doing. As the basic catalyst, for example, sodium hydroxide, potassium hydroxide or various quaternary ammonium salts can be used, and as the acidic catalyst, for example, boron trifluoride, phosphorus oxychloride, boron trifluoride etherate. Etc. can be used. More specifically, in the presence of the catalyst, the 2-acetylthiophene and the 2-thiophenecarbaldehyde are optionally added,
Using a suitable solvent, for example, alcohols such as methanol and ethanol, preferably within a temperature range of 0 ° C to 50 ° C.
The 1,3-dithienylpropenone can be obtained by carrying out the reaction for 30 minutes to 50 hours. When the reaction temperature is higher than 50 ° C., various side reactions due to heat occur, and when the temperature is lower than 0 ° C., the reaction time becomes extremely long and it is uneconomical, which is not preferable.
本発明の非線形光学材料は、前記1,3−ジチエニルプロ
ペノンを、そのまま若しくは公知の方法により精製する
ことによって得ることができる。The nonlinear optical material of the present invention can be obtained by purifying the 1,3-dithienylpropenone as it is or by a known method.
〈発明の効果〉 本発明の非線形光学材料は、極めて高い非線形光学効果
を呈する。また波長400nm以上の可視光線に対し、極め
て高い透過性を示し透明性に優れているため、種々の光
学的用途等に利用することができる。<Effects of the Invention> The nonlinear optical material of the present invention exhibits an extremely high nonlinear optical effect. Further, since it has extremely high transparency to visible light having a wavelength of 400 nm or more and is excellent in transparency, it can be used for various optical applications and the like.
〈実施例〉 本発明を実施例及び比較例により更に詳細に説明する。<Examples> The present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例１ ２−アセチルチオフェン1.26g（0.01mol）と２−チオフ
ェンカルバルデヒド1.28g（0.01mol）とを、エタノール
20mlとともに反応容器中に仕込み、25℃にて撹拌しなが
ら、40wt％水酸化ナトリウム水溶液1gとエタノール10ml
との混合溶液を滴下した。反応後0.5N塩酸水溶液20mlを
加え反応を停止させた後、析出した固体を蒸留水で数回
洗浄し、乾燥を行なった。Example 1 1.26 g (0.01 mol) of 2-acetylthiophene and 1.28 g (0.01 mol) of 2-thiophenecarbaldehyde were mixed with ethanol.
Charge into a reaction vessel with 20 ml, stir at 25 ° C, 1 g of 40 wt% sodium hydroxide aqueous solution and 10 ml of ethanol.
A mixed solution of and was added dropwise. After the reaction, 20 ml of 0.5N hydrochloric acid aqueous solution was added to stop the reaction, and the precipitated solid was washed several times with distilled water and dried.
得られた粗生成物をエタノール溶媒で再結晶したとこ
ろ、1,3−ジチエニルプロペノンの精製物2.08gを得た。
収率は88％であった。また融点は97.8℃であった。また
元素分析値を以下に示す。When the obtained crude product was recrystallized with an ethanol solvent, 2.08 g of a purified product of 1,3-dithienylpropenone was obtained.
The yield was 88%. The melting point was 97.8 ° C. The elemental analysis values are shown below.
元素分析値（C11H8S2O1として） Ｃ Ｈ Ｓ 計算値（％）62.04 3.47 27.60 実測値（％）62.17 3.41 26.97 また、1H−NMRスペクトルの測定結果を第１図に、光透
過スペクトルを第２図に夫々示す。Elemental analysis value (as C 11 H 8 S 2 O 1 ) C H S calculated value (%) 62.04 3.47 27.60 Measured value (%) 62.17 3.41 26.97 Moreover, the measurement result of 1 H-NMR spectrum is shown in FIG. The transmission spectra are shown in FIG. 2, respectively.
次に本発明の化合物の第２高調波発生（SHG）の測定を
行なった。測定方法は直径50〜150μｍの粒状化した試
料をスライドガラスに挟み、この試料にＱスイッチ付の
Nd+−YAGレーザー（波長1064nm）により15n secのパル
ス照射を行ない、試料より発生した第２高調波を検知し
た。標準試料には同様に粒状化した尿素を用い、尿素の
SHG強度を１とした時の試料のSHG強度比を求めることに
より行なった。この測定法は当該業者には良く知られて
いる方法であり、例えばジャーナル・オブ・アプライド
・フィジックス36巻、８号3798頁〜3813頁、1968年を参
考にすることができる。Next, the second harmonic generation (SHG) of the compound of the present invention was measured. The measurement method is to insert a granulated sample with a diameter of 50 to 150 μm into a slide glass and attach this sample with a Q switch.
The Nd + -YAG laser (wavelength 1064 nm) was used for pulse irradiation for 15 nsec, and the second harmonic generated from the sample was detected. For the standard sample, similarly granulated urea was used.
It was carried out by obtaining the SHG intensity ratio of the sample when the SHG intensity was 1. This measuring method is a method well known to those skilled in the art, and for example, Journal of Applied Physics 36, No. 8, pp. 3798 to 3813, 1968 can be referred to.
上記方法により測定した本発明の1,3−ジチエニルプロ
ペノンのSHG強度比は30.0であった。The SHG intensity ratio of the 1,3-dithienylpropenone of the present invention measured by the above method was 30.0.
比較例１ 公知の非線形光学材料である２−メチル−４−ニトロア
ニリンを用いて、光吸収スペクトルを測定した。結果を
第２図に示す。Comparative Example 1 A light absorption spectrum was measured using 2-methyl-4-nitroaniline, which is a known nonlinear optical material. Results are shown in FIG.
第２図により明らかなように、波長400nm以上の可視光
線に対してほぼ100％の透過率を示し、実質上透明であ
る。これに対して公知の非線形光学材料である２−メチ
ル−４−ニトロアニリンは、波長500nm以下の可視光は
吸収されて透過しない。As is clear from FIG. 2, it shows almost 100% transmittance for visible light having a wavelength of 400 nm or more, and is substantially transparent. On the other hand, the known non-linear optical material, 2-methyl-4-nitroaniline, absorbs visible light having a wavelength of 500 nm or less and does not transmit it.
第１図は1,3−ジチエニルプロペノンの1H−NMRスペクト
ルを示すチャート、第２図は本発明の非線形光学材料の
光吸収スペクトルと公知の非線形光学材料との光吸収ス
ペクトルとを示すチャートである。FIG. 1 is a chart showing a 1 H-NMR spectrum of 1,3-dithienylpropenone, and FIG. 2 shows a light absorption spectrum of a nonlinear optical material of the present invention and a light absorption spectrum of a known nonlinear optical material. It is a chart.
Claims (1)
形光学材料。1. The following structural formula (I) A non-linear optical material composed of 1,3-dithienylpropenone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1249219A JPH0719003B2 (en) | 1989-09-27 | 1989-09-27 | Non-linear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1249219A JPH0719003B2 (en) | 1989-09-27 | 1989-09-27 | Non-linear optical material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03112981A JPH03112981A (en) | 1991-05-14 |
| JPH0719003B2 true JPH0719003B2 (en) | 1995-03-06 |
Family
ID=17189691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1249219A Expired - Lifetime JPH0719003B2 (en) | 1989-09-27 | 1989-09-27 | Non-linear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0719003B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4930850B2 (en) * | 2007-10-04 | 2012-05-16 | Ｎｅｃカシオモバイルコミュニケーションズ株式会社 | Waterproof structure and housing of electronic equipment |
-
1989
- 1989-09-27 JP JP1249219A patent/JPH0719003B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| TETRAHEDRON LETTERS=1986 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03112981A (en) | 1991-05-14 |
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