JPH04261524A - Nonlinear optical material - Google Patents
Nonlinear optical materialInfo
- Publication number
- JPH04261524A JPH04261524A JP2244391A JP2244391A JPH04261524A JP H04261524 A JPH04261524 A JP H04261524A JP 2244391 A JP2244391 A JP 2244391A JP 2244391 A JP2244391 A JP 2244391A JP H04261524 A JPH04261524 A JP H04261524A
- Authority
- JP
- Japan
- Prior art keywords
- nonlinear optical
- optical material
- pyrrolyl
- methyl
- phenylpropen
- 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
- 230000003287 optical effect Effects 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims description 12
- 239000000126 substance Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- NZFLWVDXYUGFAV-UHFFFAOYSA-N 1-methyl-2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1C NZFLWVDXYUGFAV-UHFFFAOYSA-N 0.000 abstract description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- 125000000168 pyrrolyl group Chemical group 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001321 pyrrole-3,4-diyl group Chemical group N1C=C(C(=C1)*)* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910003327 LiNbO3 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- -1 methanol or ethanol Chemical compound 0.000 description 1
- 239000012046 mixed solvent 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
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、１−（２’−（１’−
メチル）ピロリル）−３−フェニルプロペン−１−オン
から成る非線形光学材料に関する。[Industrial Field of Application] The present invention provides 1-(2'-(1'-
The present invention relates to a nonlinear optical material comprising methyl)pyrrolyl)-3-phenylpropen-1-one.
【０００２】0002
【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、一般に下記数１により示される２次の項
以上のものにより生ずる。[Prior Art] A nonlinear optical material refers to a material that has a so-called nonlinear optical effect, in which induced polarization of electrons induced by the electric field of light in a substance produces a nonlinear response to the electric field. This is caused by more than the quadratic term shown by the following equation 1.
【０００３】0003
【数１】[Math 1]
【０００４】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。In particular, according to a phenomenon known as second harmonic generation (SHG) that utilizes the second-order effect, incident light becomes a second harmonic, a light wave with twice the frequency, or Since the refractive index changes depending on the voltage, this phenomenon can be used to perform various optical processing such as wavelength conversion, signal processing, and laser light modulation, and is known to be extremely useful. There is.
【０００５】従来の非線形光学材料としてはＫＨ２ＰＯ
４（ＫＤＰ）、ＬｉＮｂＯ３（ＬＮ）、ＮＨ４Ｈ２ＰＯ
４（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る。KH2PO is a conventional nonlinear optical material.
4 (KDP), LiNbO3 (LN), NH4H2PO
Inorganic crystals such as 4 (ADP) have been used, but single crystals with high optical purity are extremely expensive, are deliquescent and inconvenient to handle, and have low nonlinear susceptibility. There are problems such as.
【０００６】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
や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、前記有機化合物は未だ十分
な非線形光学効果を示しておらず、また化合物自身の光
吸収端が長波長側へ相当シフトしており、使用波長範囲
が極めて限定されるという問題がある。On the other hand, since the usefulness of organic materials was suggested at the 1983 American Chemical Society Symposium, organic crystals such as urea and aniline compounds have been announced as nonlinear optical materials. However, the above-mentioned organic compounds do not yet exhibit sufficient nonlinear optical effects, and the light absorption edge of the compounds themselves has shifted considerably toward longer wavelengths, resulting in the problem that the usable wavelength range is extremely limited.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、透明
性に優れ、高い非線形光学効果を有し、また青色光領域
の波長の光に対しても高い透過性を有する非線形光学材
料を提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide a nonlinear optical material that has excellent transparency, a high nonlinear optical effect, and also has high transparency for light with wavelengths in the blue light region. It's about doing.
【０００８】[0008]
【課題を解決するための手段】本発明によれば、下記構
造式化２で表される１−（２’−（１’−メチル）ピロ
リル）−３−フェニルプロペン−１−オンから成る非線
形光学材料が提供される。[Means for Solving the Problems] According to the present invention, a nonlinear compound composed of 1-(2'-(1'-methyl)pyrrolyl)-3-phenylpropen-1-one represented by the following structural formula 2 is provided. An optical material is provided.
【０００９】[0009]
【化２】[Case 2]
【００１０】以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
【００１１】本発明の非線形光学材料は、前記構造式化
２で表わされる１−（２’−（１’−メチル）ピロリル
）−３−フェニルプロペン−１−オンにより構成される
。The nonlinear optical material of the present invention is composed of 1-(2'-(1'-methyl)pyrrolyl)-3-phenylpropen-1-one represented by the above structural formula 2.
【００１２】前記１−（２’−（１’−メチル）ピロリ
ル）−３−フェニルプロペン−１−オンを製造するには
、例えば、ベンズアルデヒド１モルと２−アセチル−１
−メチルピロ−ル１モルとを水酸化ナトリウム、水酸化
カリウム、４級ナトリウム塩等の塩基性触媒存在下にて
好ましくはメタノ−ル、エタノ−ル等のアルコ−ル類な
どの溶媒を用い、好ましくは、０〜５０℃にて、１〜２
４時間反応させるなどして、容易に得ることができる。
前記反応温度が０℃未満の場合には、反応に長時間を要
し、５０℃を超えると副反応による生成物が多量に生成
するため好ましくない。To produce the 1-(2'-(1'-methyl)pyrrolyl)-3-phenylpropen-1-one, for example, 1 mole of benzaldehyde and 2-acetyl-1
-1 mol of methylpyrrole in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, or quaternary sodium salt, preferably using a solvent such as an alcohol such as methanol or ethanol, Preferably, at 0 to 50°C, 1 to 2
It can be easily obtained by reacting for 4 hours. If the reaction temperature is less than 0°C, the reaction takes a long time, and if it exceeds 50°C, a large amount of products due to side reactions will be produced, which is not preferable.
【００１３】本発明の１−（２’−（１’−メチル）ピ
ロリル）−３−フェニルプロペン−１−オンは、そのま
ま、若しくはカラムクロマトグラフィー、再結晶等公知
の方法により精製することによって、非線形光学材料と
して使用することができる。The 1-(2'-(1'-methyl)pyrrolyl)-3-phenylpropen-1-one of the present invention can be purified as it is or by purification by known methods such as column chromatography and recrystallization. It can be used as a nonlinear optical material.
【００１４】[0014]
【発明の効果】本発明の非線形光学材料は、１−（２’
−（１’−メチル）ピロリル）−３−フェニルプロペン
−１−オンにより構成されるので、高い非線形光学効果
を呈する。また、波長４００ｎｍ以上の可視光に対して
、極めて高い透過性を示し、且つ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 has a 1-(2'
Since it is composed of -(1'-methyl)pyrrolyl)-3-phenylpropen-1-one, it exhibits a high nonlinear optical effect. In addition, it exhibits extremely high transmittance to visible light with a wavelength of 400 nm or more and has excellent transparency, so it can be used for various optical purposes.
【００１５】[0015]
【実施例】本発明を実施例及び比較例により更に詳細に
説明するが、本発明はこれらに限定されるものではない
。EXAMPLES The present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
【００１６】[0016]
【合成例１】ベンズアルデヒド０．８６ｇ（８．１ｍｍ
ｏｌ）と、２−アセチル−１−メチルピロ−ル１．００
ｇ（８．１ｍｍｏｌ）と、エタノ−ル１０ｍｌとを反応
容器に仕込み、０℃にて撹拌しながら、１０重量％水酸
化ナトリウム水溶液１０ｍｌを適下した。適下終了後、
２５℃にて２４時間反応を行い、析出した固体を蒸留水
で数回洗浄した後、乾燥を行い粗結晶物を得た。得られ
た粗結晶物をアセトン：エタノ−ル＝２：１（重量比）
の混合溶媒を用いて再結晶し、１．２１ｇ（収率７０％
）の生成物を得た。各種分析を行った結果１−（２’−
（１’−メチル）ピロリル）−３−フェニルプロペン−
１−オンであった。分析結果を以下に示す。
分子量２１１
融点１１１．０℃
ＩＲ（ｃｍ￣１） １６４０（Ｃ＝Ｏ）１Ｈ−ＮＭＲ
（ＴＭＳ／ＣＤＣｌ３）
σ ４．０ｐｐｍ（Ｓ，３Ｈ，Ｎ−ＣＨ３）６．２ｐ
ｐｍ（ｄ−ｄ，１Ｈ，Ｃ４Ｈ３Ｎ）６．９ｐｐｍ（ｄ−
ｄ，１Ｈ，Ｃ４Ｈ３Ｎ）７．１ｐｐｍ（ｄ−ｄ，１Ｈ，
Ｃ４Ｈ３Ｎ）Ｊ３４＝２．６Ｈｚ，Ｊ３５＝１．７Ｈｚ
，Ｊ４５＝４．１Ｈｚ，
７．３〜７．８（ｍ，７Ｈ，Ｃ６Ｈ５−ＣＨ＝ＣＨ）[Synthesis Example 1] Benzaldehyde 0.86g (8.1mm
ol) and 2-acetyl-1-methylpyrrole 1.00
g (8.1 mmol) and 10 ml of ethanol were placed in a reaction vessel, and 10 ml of a 10% by weight aqueous sodium hydroxide solution was added dropwise while stirring at 0°C. After the proper procedure is completed,
The reaction was carried out at 25° C. for 24 hours, and the precipitated solid was washed several times with distilled water and then dried to obtain a crude crystal. The obtained crude crystals were mixed with acetone:ethanol=2:1 (weight ratio)
Recrystallized using a mixed solvent of 1.21 g (yield 70%)
) product was obtained. As a result of various analyses, 1-(2'-
(1'-methyl)pyrrolyl)-3-phenylpropene-
1-on. The analysis results are shown below. Molecular weight 211 Melting point 111.0℃ IR (cm￣1) 1640 (C=O)1H-NMR
(TMS/CDCl3) σ 4.0ppm (S, 3H, N-CH3) 6.2p
pm (dd, 1H, C4H3N) 6.9 ppm (d-
d, 1H, C4H3N) 7.1 ppm (dd, 1H,
C4H3N) J34=2.6Hz, J35=1.7Hz
, J45=4.1Hz, 7.3~7.8 (m, 7H, C6H5-CH=CH)
【
００１７】[
0017
【実施例１】合成例１で得られた１−（２’−（１’−
メチル）ピロリル）−３−フェニルプロペン−１−オン
の第２高調波発生（以下ＳＨＧ強度と称す）の測定を行
なった。測定方法は直径１０６〜１５０μｍに粒状化し
た試料をスライドガラスに挟み、前記試料にＱスイッチ
付のＮｄ＋ −ＹＡＧレーザー（波長１０６４ｎｍ）に
より１０ｎ 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。前記測
定法は当該業者には公知の方法であり、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３
７９８頁〜３８１３頁、１９６８年を参考にすることが
できる。また前記化合物の０．１ｍｍｏｌ／ｌエタノ−
ル溶液を調製し、最大吸収波長λｍａｘ、吸収波長端λ
ｃｕｔ ｏｆｆの測定も行った。結果を表１に示す。[Example 1] 1-(2'-(1'-
The second harmonic generation (hereinafter referred to as SHG intensity) of methyl)pyrrolyl)-3-phenylpropen-1-one was measured. The measurement method is to sandwich a granulated sample with a diameter of 106 to 150 μm between slide glasses, and irradiate the sample with a pulse of 10 n sec using a Q-switched Nd+ -YAG laser (wavelength 1064 nm) to detect the second harmonic generated by the sample. was detected. Similarly, granulated urea was used as a standard sample, and the SHG intensity ratio of the sample was determined when the SHG intensity of urea was set to 1. The above measurement method is a method known to those skilled in the art, for example, as described in Journal of Applied Physics, Vol. 36, No. 8, No. 3.
Reference may be made to pages 798 to 3813, 1968. Also, 0.1 mmol/l ethanol of the above compound
Prepare a solution with maximum absorption wavelength λmax, absorption wavelength edge λ
Cut off was also measured. The results are shown in Table 1.
【００１８】[0018]
【比較例】表１に示す構造式を有する化合物を用いた以
外は、実施例１と同様にして各測定を行った。結果を表
１に示す。また尿素、ＫＤＰのＳＨＧ強度についても表
１に示す。[Comparative Example] Each measurement was carried out in the same manner as in Example 1, except that a compound having the structural formula shown in Table 1 was used. The results are shown in Table 1. Table 1 also shows the SHG intensities of urea and KDP.
【００１９】[0019]
【表１】[Table 1]
Claims (1)
’−（１’−メチル）ピロリル）−３−フェニルプロペ
ン−１−オンから成る非線形光学材料。 【化１】[Claim 1] 1-(2
A nonlinear optical material comprising '-(1'-methyl)pyrrolyl)-3-phenylpropen-1-one. [Chemical formula 1]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2244391A JPH04261524A (en) | 1991-02-16 | 1991-02-16 | Nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2244391A JPH04261524A (en) | 1991-02-16 | 1991-02-16 | Nonlinear optical material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04261524A true JPH04261524A (en) | 1992-09-17 |
Family
ID=12082854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2244391A Pending JPH04261524A (en) | 1991-02-16 | 1991-02-16 | Nonlinear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04261524A (en) |
-
1991
- 1991-02-16 JP JP2244391A patent/JPH04261524A/en active Pending
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