JPH0377923A - Organic nonlinear optical material - Google Patents
Organic nonlinear optical materialInfo
- Publication number
- JPH0377923A JPH0377923A JP21398389A JP21398389A JPH0377923A JP H0377923 A JPH0377923 A JP H0377923A JP 21398389 A JP21398389 A JP 21398389A JP 21398389 A JP21398389 A JP 21398389A JP H0377923 A JPH0377923 A JP H0377923A
- Authority
- JP
- Japan
- Prior art keywords
- nonlinear optical
- optical material
- stable
- crystal
- hydroxyphenyl
- 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 34
- 239000000463 material Substances 0.000 title claims abstract description 26
- KDLWVYJOFARPRV-UHFFFAOYSA-N 4-(2-pyrazin-2-ylethenyl)phenol Chemical compound OC1=CC=C(C=C1)C=CC1=NC=CN=C1 KDLWVYJOFARPRV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 19
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 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
- 239000000047 product Substances 0.000 description 4
- YVXDRFYHWWPSOA-BQYQJAHWSA-N 1-methyl-4-[(e)-2-phenylethenyl]pyridin-1-ium Chemical class C1=C[N+](C)=CC=C1\C=C\C1=CC=CC=C1 YVXDRFYHWWPSOA-BQYQJAHWSA-N 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 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000990 laser dye Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- 101100353042 Mycobacterium bovis (strain BCG / Pasteur 1173P2) lnt gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 101150028022 ppm1 gene Proteins 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は、２− ［２−（４−ヒドロキシフェニル）ビ
ニル］ピラジンからなる有機非線形光学材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an organic nonlinear optical material comprising 2-[2-(4-hydroxyphenyl)vinyl]pyrazine.
非線形光学材料は、レーザー光の周波数変換、増幅、発
振、スイッチングなどの現象を生じ、第２高調波発生（
ＳＨＧ）、第３高調波発生（ＴＨＧ）、高速度シャッタ
ー、光メモリ−、光演算素子などへの応用が可能である
。また、非線形光学材料は、電場によって屈折率が変化
する特質を生かした光スィッチなどへの応用が可能であ
る。Nonlinear optical materials produce phenomena such as frequency conversion, amplification, oscillation, and switching of laser light, and generate second harmonics (
It can be applied to SHG), third harmonic generation (THG), high-speed shutter, optical memory, optical arithmetic element, etc. In addition, nonlinear optical materials can be applied to optical switches and the like that take advantage of the property that their refractive index changes depending on an electric field.
従来、非線形光学材料として、ＫＨ，ＰＯ，、ＮＨ４Ｈ
ａ ＰＯ４、Ｌｉ ＮｂＯ＊ ％ ＫＮｂＯｓなどの無
機系の単結晶材料が知られているが、最近では、尿素や
ｐ−ニトロアニリン、２−メチル−４−ニトロアニリン
（ＭＮＡ） 、４− （Ｎ、Ｎ−ジメチルアミノ）−４
′−二トロスチルベン（ＤＡＮＳ） 、スチルバゾリウ
ム塩などの非線形光学有機材料の開発が進められている
。Conventionally, KH, PO, NH4H have been used as nonlinear optical materials.
Inorganic single crystal materials such as aPO4, LiNbO*% KNbOs are known, but recently, urea, p-nitroaniline, 2-methyl-4-nitroaniline (MNA), 4-(N, N-dimethylamino)-4
Development of nonlinear optical organic materials such as '-nitrostilbene (DANS) and stilbazolium salts is progressing.
非線形光学有機材料は、一般に、非線形性の起源が分子
内π電子であるため、光応答に対して格子振動を伴わず
、したがって無機材料に比べ応答が速く、また、非線形
光学定数が大きいものや吸収領域が変化できるものなど
を合成することが可能である。しかも、材料素子化の方
法も、単結晶化によるだけではなく、ＬＢ膜、蒸着法、
液晶化、高分子化などの各種の方法が考えられる。Nonlinear optical organic materials generally have nonlinearity originating from intramolecular π electrons, so they do not involve lattice vibration in response to light, and therefore have faster response than inorganic materials, and they also have large nonlinear optical constants. It is possible to synthesize a material whose absorption region can be changed. Moreover, the methods of making materials into devices are not limited to single crystallization, but also include LB film, vapor deposition, etc.
Various methods such as liquid crystal formation and polymerization are possible.
ところで、非線形光学材料には、次のような特性を有す
ることが求められる。By the way, nonlinear optical materials are required to have the following characteristics.
（１）非線形光学効果のうち、特に第２高調波発生（Ｓ
ＨＧ）は、変換の効率が高い等の理由から波長変換の基
本技術として位置付けられておりＳＨＧ効率（尿素を１
とする）の高いことが求められる。(1) Among nonlinear optical effects, especially second harmonic generation (S
HG) is positioned as a basic technology for wavelength conversion due to its high conversion efficiency, and SHG efficiency (1
) is required.
（２）材料が光学的非線形性を示すには、空間反転の対
称性を持たないこと、特に、その結晶が対称中心を持た
ないことが求められる。(2) For a material to exhibit optical nonlinearity, it is required that it has no spatial inversion symmetry, and in particular, that its crystal does not have a center of symmetry.
（３）室温で安定でかつ出来るだけ大きな単結晶を形成
するものであることが望まれる。(3) It is desired that the material be stable at room temperature and form a single crystal as large as possible.
（４）現在の半導体レーザーの波長は８００ｎｍ程度で
あるので、極大波長（λｆｆ１ａｘ ）またはカットオ
フ波長（λｃｕｔｏｆｆ）はできるだけ短波長領域にあ
ることが実用上重要である。(4) Since the wavelength of current semiconductor lasers is about 800 nm, it is practically important that the maximum wavelength (λff1ax) or cutoff wavelength (λcutoff) be in the shortest wavelength region as possible.
ところが、公知の非線形光学無機材料は、純度の高い単
結晶が高価であり、潮解性を有し、しかも一般にＳＨＧ
効率が小さいという欠点がある。However, known nonlinear optical inorganic materials are expensive to produce single crystals with high purity, have deliquescent properties, and are generally SHG-based.
It has the disadvantage of low efficiency.
一方、非線形光学有機材料には、一般にＳＨＧ効率の大
きいものがあることは知られているが、室温で安定かつ
大きな結晶を調製するのが困難である。例えば、ＭＮＡ
は高いＳＨＧ効率を有するけれども、大きな単結晶が得
られにくい。On the other hand, although it is known that some nonlinear optical organic materials generally have high SHG efficiency, it is difficult to prepare stable and large crystals at room temperature. For example, MNA
Although it has high SHG efficiency, it is difficult to obtain large single crystals.
尿素は、大きな単結晶を得やす（、白色・透明で、カッ
トオフ波長も２００ｎｍと短波長であるけれども、耐湿
性に劣るという欠点がある。Although urea is white and transparent and has a short cutoff wavelength of 200 nm, it has the disadvantage of poor moisture resistance.
また、スチルベン誘導体のＤＡＮＳ
は、分子レベルでは２次の非線形分極率βは非常に大き
い値を示すが、結晶になると分子の配列に反転対称を持
つに至るため非線形光学効果を示さない。Further, the stilbene derivative DANS exhibits a very large value of second-order nonlinear polarizability β at the molecular level, but when crystallized, it exhibits no nonlinear optical effect because the molecular arrangement has inversion symmetry.
さらに、スチルバゾリウム塩
は、ＳＨＧ効率が約２５０と大きな非線形光学効果を有
しているが、カットオフ波長が４７３（λｍａｘ ）〜
５８８ｎｍと長波長側にあり、実用上問題がある。また
、一般に、非線形光学材料は、π電子共役系の構造に起
因して黄色ないしはオレンジ色に着色した結晶を与える
が、そのためもありカットオフ波長は、通常、４００ｎ
ｍを越える長波長領域に位置しているものが多い。Furthermore, stilbazolium salt has a large nonlinear optical effect with an SHG efficiency of about 250, but the cutoff wavelength is 473 (λmax) ~
It is on the long wavelength side of 588 nm, which poses a practical problem. In addition, nonlinear optical materials generally give yellow or orange colored crystals due to the structure of the π-electron conjugated system, and for this reason, the cutoff wavelength is usually 400 nm.
Many of them are located in the long wavelength region exceeding m.
このように、ＳＨＧ効率が大きく、安定でかつ大きな単
結晶に成長させやす（、しかも透明性に優れ、λＩＩＩ
ａＸまたはλｃｕｔｏｆｆが短い非線形光学材料が求め
られているが、いまだ充分な性能を有する材料は提供さ
れていない。In this way, the SHG efficiency is high, and it is stable and easy to grow into large single crystals (in addition, it has excellent transparency, and
Although there is a demand for a nonlinear optical material with a short aX or λcutoff, no material with sufficient performance has yet been provided.
〔発明が解決しようとする問題点１
本発明の目的は、前記従来技術の有する問題点を克服し
、室温で安定で、対称中心を持たない単結晶を形成し、
必要に応じて大きな単結晶に成長させることができ、Ｓ
ＨＧ活性が太き（、しかも透明性に優れた有機非線形光
学材料を提供することにある。[Problem to be Solved by the Invention 1] The purpose of the present invention is to overcome the problems of the prior art and form a single crystal that is stable at room temperature and does not have a center of symmetry;
It can be grown into a large single crystal if necessary, and S
The purpose of the present invention is to provide an organic nonlinear optical material with high HG activity (and excellent transparency).
本発明者らは鋭意研究した結果、２− ［２−（４−ヒ
ドロキシフェニル）ビニル］ピラジンが安定かつ結晶性
の良い化合物であり、そしてＳＨＧ活性の大きな透明の
有機結晶を形成し、λｍａｘも３３９ｎｍと短波長領域
にあることを見出した。As a result of intensive research by the present inventors, we found that 2-[2-(4-hydroxyphenyl)vinyl]pyrazine is a stable and highly crystalline compound, forms transparent organic crystals with high SHG activity, and has a low λmax. It was found that the wavelength is in the short wavelength region of 339 nm.
この化合物は、非線形光学材料として有用であるが、そ
れ以外にも、蛍光増白剤やレーザー色素などとして使用
可能性を有している。This compound is useful as a nonlinear optical material, but it also has the potential to be used as a fluorescent whitening agent, laser dye, etc.
本発明は、これらの知見に基づいて完成するに至ったも
のである。The present invention has been completed based on these findings.
（以下余白）
〔課題を解決するための手段〕
すなわち、本発明によれば、下記化学式で表わされる２
−（２−（４−ヒドロキシフェニル）ビニル］ピラジン
から成る有機非線形材料が提供される。(Hereinafter in the margin) [Means for solving the problem] That is, according to the present invention, 2 expressed by the following chemical formula
An organic nonlinear material comprising -(2-(4-hydroxyphenyl)vinyl]pyrazine is provided.
以下、本発明の構成要素について詳述する。Hereinafter, the constituent elements of the present invention will be explained in detail.
本発明の化合物は、２つのπ電子系（芳香族環）が炭素
−炭素二重結合を介して結合されており、かつ、トラン
ス異性体である点では、前記のＤＡＮＳやスチルバゾリ
ウム塩などのスチルベン誘導体と類似している。The compound of the present invention has two π-electron systems (aromatic rings) bonded via a carbon-carbon double bond, and is a trans isomer. Similar to derivatives.
しかしながら、ＤＡＮＳの結晶が対象中心をもち非線形
光学効果を有しないのに対して、本発明の化合物は、そ
の結晶が対称中心をたないため、優れた非線形光学効果
を示し、微結晶粉末のＳＨＧ効率は尿素の３．４倍であ
る。また、スチルバゾリウム塩のカットオフ波長が長波
長側にあるのに対して１本発明の化合物のλｍａｘ４ｆ
３３９ｎｍと比較的短波長領域にあり、半導体レーザー
光を用いる非線形光学材料として実用的な性能を有する
。However, whereas the DANS crystal has a center of symmetry and does not have a nonlinear optical effect, the compound of the present invention exhibits an excellent nonlinear optical effect because its crystal does not have a center of symmetry, and the SHG of microcrystalline powder The efficiency is 3.4 times that of urea. Moreover, whereas the cutoff wavelength of the stilbazolium salt is on the long wavelength side, the λmax4f of the compound of the present invention is
It has a relatively short wavelength of 339 nm, and has practical performance as a nonlinear optical material using semiconductor laser light.
本発明の化合物は、その結晶が室温で安定であり、結晶
性もよく、透明性に優れている。そして、その化学構造
から明らかなように、蛍、光増白剤あるいは蛍光性を利
用したレーザー色素などの用途にも好適である。The compound of the present invention has stable crystals at room temperature, good crystallinity, and excellent transparency. As is clear from its chemical structure, it is also suitable for applications such as fireflies, optical brighteners, and laser dyes that utilize fluorescence.
本発明の２− ［２−（４−ヒドロキシフェニル）ビニ
ル］ピラジンは、クネーフエナーゲル（Ｋｎｏｅｖｅｎ
ａｇｅｌ）縮合（ＯＲＧＡＮＩＣＲＥＡＣＴＩＯＮＳ
ＶＯＬ、１５゜ｐ、 ２０４）を利用して合成すること
ができる。クネーフェナーゲル縮合は、ピペリジンを触
媒として、活性メチレンとアルデヒドを縮合させる反応
であり、オレフィン合成に汎用されている。The 2-[2-(4-hydroxyphenyl)vinyl]pyrazine of the present invention is manufactured by Knoeven Gel.
agel) condensation (ORGANIC CREATIONS)
VOL, 15°p, 204). Knoevenagel condensation is a reaction in which active methylene and aldehyde are condensed using piperidine as a catalyst, and is widely used in olefin synthesis.
〔実施例］
以下、実施例を挙げて本発明を具体的に説明するが、本
発明は、これらの実施例のみに限定されるものではない
。[Examples] The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.
［実施例１］
ｐ−ヒドロキシベンズアルデヒド５．２４ｇ （４３，
０ｍｍｏｌ）と、メチルピラジン４．００ｇ （４３，
０ｍｍｏ ｌ）を無水酢酸１２．１ｒｒＪ２に溶解し、
１５０℃で２４時間リフラックスさせた。その後、６規
定の塩酸を２０ｍｊ２加え、１２５℃で１時間リフラッ
クスさせ、放冷後アンンモニア水で中和した０次いで、
４時間撹拌し、生じた沈殿を真空乾燥した。[Example 1] 5.24 g of p-hydroxybenzaldehyde (43,
0 mmol) and 4.00 g of methylpyrazine (43,
0mmol) was dissolved in acetic anhydride 12.1rrJ2,
Reflux was performed at 150°C for 24 hours. Thereafter, 20mj2 of 6N hydrochloric acid was added, refluxed at 125°C for 1 hour, and after cooling, neutralized with aqueous ammonia.
After stirring for 4 hours, the resulting precipitate was vacuum dried.
メタノールを１％含有する塩化メチレンを展開液とし、
カラムクロマトグラフィーでＲｔ”０゜２７のフラクシ
目ンをとった。このフラクシ目ンから溶媒を留去して、
黄色固体の生成物１．２０ｇを得た。Using methylene chloride containing 1% methanol as a developing solution,
A fraction with an Rt of 0°27 was collected by column chromatography. The solvent was distilled off from this fraction.
1.20 g of yellow solid product was obtained.
この生成物を４０ｍＩ２のメタノールで再結晶させ、生
成した目的物０．８８ｇ （再結晶収率７３％）を得た
。この化合物の融点は、１９２．５〜１９４．０℃であ
った。This product was recrystallized with 40 mI2 of methanol to obtain 0.88 g of the desired product (recrystallization yield: 73%). The melting point of this compound was 192.5-194.0°C.
生成物の ’Ｈ−ＮＭＲスペクトルと帰属について第１
図に、また、ＩＲスペクトルを第２図に示す。About 'H-NMR spectrum and attribution of the product, Part 1
In addition, the IR spectrum is shown in FIG.
なお、ＩＲスペクトルのピーク値、ＮＭＲスペクトルの
δ値およびＵｖ測定値を以下に示す。Note that the peak value of the IR spectrum, the δ value of the NMR spectrum, and the measured Uv value are shown below.
Ｉ Ｒ（Ｋ Ｂ ｒ ） ： １６００，１５ｇ０，１
４００，９７０，８２０［ｃａ＋−’］
’ Ｈ−Ｎ Ｍ Ｒ（ＤＭＳＯ−ｄ６） ： ９．８１
（ＩＨ）、８゜７４（ＩＨ）。I R (K B r ): 1600,15g0,1
400,970,820[ca+-']' H-NMR (DMSO-d6): 9.81
(IH), 8°74 (IH).
８、５７ （ＩＨ） 、 ８．４３ （ＩＨ） 、 ７
．７０ （ＬＨ） 。8, 57 (IH), 8.43 (IH), 7
．． 70 (LH).
７、５３ （２Ｈ） 、 ７．１５ （ＩＨ） 、６．
８２ （２Ｈ）［ｐｐｍ１
ＵＶ （Ｅｌｏｈ） ：λｍａｘ＝３３９ｎｍこれら
の測定結果の分析から得られた化合物（生成物）が２−
［２−（４−ヒドロキシフェニル）ビニル］ピラジン
であることが確認できた。7, 53 (2H), 7.15 (IH), 6.
82 (2H) [ppm1 UV (Eloh): λmax = 339 nm The compound (product) obtained from the analysis of these measurement results is 2-
It was confirmed that it was [2-(4-hydroxyphenyl)vinyl]pyrazine.
チ ・と ての
上記で得られた２−［２−（４−ヒドロキシフェニル）
ビニル］ピラジンの微粉末結晶にＮｄ： ＹＡＧレーザ
−（波長＝１．０６４μｍ、出力１０ｍＪ／パルス）を
照射すると、第２次高調波が発生（ＳＨＧ）Ｌ／、入射
光の１／２の波長（５３２ｎｍ）の緑色光が観測された
。2-[2-(4-hydroxyphenyl) obtained above
When a fine powder crystal of vinyl]pyrazine is irradiated with a Nd:YAG laser (wavelength = 1.064 μm, output 10 mJ/pulse), a second harmonic is generated (SHG) L/, a wavelength of 1/2 of the incident light. (532 nm) green light was observed.
また、ＳＨＧ効率は、尿素の３．４倍であることが確認
された。Furthermore, it was confirmed that the SHG efficiency was 3.4 times that of urea.
さらに、この結晶は室温で安定であり、結晶性も良く、
透明性に優れていることが明らかになった。Furthermore, this crystal is stable at room temperature and has good crystallinity.
It has been found that transparency is excellent.
これらの測定結果から、この化合物が非線形光学材料と
して有用性をもっていることが分かる。These measurement results demonstrate that this compound is useful as a nonlinear optical material.
本発明によれば、２− ［２−（４−ヒドロキシフェニ
ル）ビニル］ピラジンから成る有機非線形光学材料が提
供される。According to the present invention, an organic nonlinear optical material comprising 2-[2-(4-hydroxyphenyl)vinyl]pyrazine is provided.
本発明の化合物は、室温で安定かつ結晶性が良好で、Ｓ
ＨＧ活性が太き（、しかも透明性に優れており、特に、
非線形光学材料として有用であり、レーザーの波長変換
素子としての使用が可能であるなど実用上重要な意義を
有する。The compound of the present invention is stable at room temperature and has good crystallinity, and S
High HG activity (and excellent transparency, especially
It is useful as a nonlinear optical material and has important practical significance, such as being able to be used as a wavelength conversion element for lasers.
第１図は、実施例１で製造した化合物のＩＨ−ＮＭＲス
ペクトルと帰属を示す図であり、第２図は該化合物のＩ
Ｒスペクトルを示す図である。FIG. 1 is a diagram showing the IH-NMR spectrum and assignment of the compound produced in Example 1, and FIG. 2 is a diagram showing the IH-NMR spectrum and assignment of the compound produced in Example 1.
It is a figure showing an R spectrum.
Claims (1)
ニル］ピラジンから成ることを特徴とする有機非線形光
学材料。(1) An organic nonlinear optical material comprising 2-[2-(4-hydroxyphenyl)vinyl]pyrazine represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21398389A JPH0377923A (en) | 1989-08-18 | 1989-08-18 | Organic nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21398389A JPH0377923A (en) | 1989-08-18 | 1989-08-18 | Organic nonlinear optical material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0377923A true JPH0377923A (en) | 1991-04-03 |
Family
ID=16648305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21398389A Pending JPH0377923A (en) | 1989-08-18 | 1989-08-18 | Organic nonlinear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0377923A (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693659A (en) * | 1994-06-23 | 1997-12-02 | Celltech Therapeutics Limited | Substituted oxime derivatives and processes for their preparation |
| US5723460A (en) * | 1993-03-10 | 1998-03-03 | Celltech Therapeutics Limited | Cyclo (alkyl and alkenyl) phenyl-alkenylyl heteroaryl compounds and pharmaceutical compositions containing same |
| US5739144A (en) * | 1993-03-10 | 1998-04-14 | Celltech Therapeutics Limited | Trisubstituted phenyl derivatives |
| US5776958A (en) * | 1993-12-22 | 1998-07-07 | Celltech Therapeutics, Limited | Trisubstituted phenyl derivatives and processes for their preparation |
| US5780478A (en) * | 1994-06-22 | 1998-07-14 | Celltech Therapeutics, Limited | Tetra-substituted phenyl derivatives |
| US5780477A (en) * | 1994-06-22 | 1998-07-14 | Celltech Therapeutics, Limited | Trisubstituted phenyl derivatives and processes for their preparation |
| US5786354A (en) * | 1994-06-21 | 1998-07-28 | Celltech Therapeutics, Limited | Tri-substituted phenyl derivatives and processes for their preparation |
| US5798373A (en) * | 1995-12-21 | 1998-08-25 | Celltech Therapeutics, Limited | Tri-substituted phenyl derivatives useful as PDE IV inhibitors |
| US5849770A (en) * | 1995-12-21 | 1998-12-15 | Celltech Therapeutics Ltd. | Tri-substituted phenyl derivatives useful as PDE IV inhibitors |
| US5859034A (en) * | 1996-12-04 | 1999-01-12 | Celltech Therapeutics, Limited | Tri-substituted phenyl compounds which have useful pharmaceutical activity |
| US5866593A (en) * | 1993-12-22 | 1999-02-02 | Celltech Therapeutics Ltd. | Trisubstituted phenyl derivatives and processes for their preparation |
| US5922741A (en) * | 1996-04-24 | 1999-07-13 | Celltech Therapeutics Ltd. | 5-aminopyrazoles useful as tyrosine kinase inhibitors |
| US5958935A (en) * | 1995-11-20 | 1999-09-28 | Celltech Therapeutics Limited | Substituted 2-anilinopyrimidines useful as protein kinase inhibitors |
| US6057329A (en) * | 1996-12-23 | 2000-05-02 | Celltech Therapeutics Limited | Fused polycyclic 2-aminopyrimidine derivatives |
| US6080790A (en) * | 1992-10-23 | 2000-06-27 | Celltech Therapeutics, Limited | Tri-substituted phenyl derivatives and processes for their preparations |
| US6093716A (en) * | 1996-09-16 | 2000-07-25 | Celltech Therapeutics, Limited | Substituted 2-pyrimidineamines and processes for their preparation |
| US6096747A (en) * | 1992-06-15 | 2000-08-01 | Celltech Therapeutics Limited | Phenylaminocarbonyl derivatives and processes for their preparation |
| US6114333A (en) * | 1996-10-28 | 2000-09-05 | Celltech Therapeutics Ltd. | 2-Pyrimidineamine derivatives and processes for their preparation |
| US6133257A (en) * | 1997-06-20 | 2000-10-17 | Celltech Therapeutics Limited | Fused polycyclic 2-aminopyrimidine derivatives |
| US6245774B1 (en) | 1994-06-21 | 2001-06-12 | Celltech Therapeutics Limited | Tri-substituted phenyl or pyridine derivatives |
| US6337335B1 (en) | 1997-03-14 | 2002-01-08 | Celltech Therapeutics Limited | Substituted 2-anilinopyrimidines useful as protein kinase inhibitors |
| US6579983B1 (en) | 1999-06-18 | 2003-06-17 | Celltech R&D Limited | 5-cyano-2-aminopyrimidine derivatives |
| US6600037B1 (en) | 1999-10-20 | 2003-07-29 | Celltech R & D Limited | 4,5-disubstituted-2-aminopyrimidines |
-
1989
- 1989-08-18 JP JP21398389A patent/JPH0377923A/en active Pending
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6096747A (en) * | 1992-06-15 | 2000-08-01 | Celltech Therapeutics Limited | Phenylaminocarbonyl derivatives and processes for their preparation |
| US6080790A (en) * | 1992-10-23 | 2000-06-27 | Celltech Therapeutics, Limited | Tri-substituted phenyl derivatives and processes for their preparations |
| US5962483A (en) * | 1993-03-10 | 1999-10-05 | Celltech Therapeutics, Limited | Trisubstituted phenyl derivatives and processes for their preparation |
| US5723460A (en) * | 1993-03-10 | 1998-03-03 | Celltech Therapeutics Limited | Cyclo (alkyl and alkenyl) phenyl-alkenylyl heteroaryl compounds and pharmaceutical compositions containing same |
| US5739144A (en) * | 1993-03-10 | 1998-04-14 | Celltech Therapeutics Limited | Trisubstituted phenyl derivatives |
| US5962492A (en) * | 1993-03-10 | 1999-10-05 | Celltech Therapeutics Limited | 2 cyclo(alkyl and alkenyl) phenyl-alkenylyl heteroaryl compounds and pharmaceutical compositions containing same |
| US5776958A (en) * | 1993-12-22 | 1998-07-07 | Celltech Therapeutics, Limited | Trisubstituted phenyl derivatives and processes for their preparation |
| US5866593A (en) * | 1993-12-22 | 1999-02-02 | Celltech Therapeutics Ltd. | Trisubstituted phenyl derivatives and processes for their preparation |
| US6077854A (en) * | 1994-06-21 | 2000-06-20 | Celltech Therapeutics, Limited | Tri-substituted phenyl derivatives and processes for their preparation |
| US5786354A (en) * | 1994-06-21 | 1998-07-28 | Celltech Therapeutics, Limited | Tri-substituted phenyl derivatives and processes for their preparation |
| US6245774B1 (en) | 1994-06-21 | 2001-06-12 | Celltech Therapeutics Limited | Tri-substituted phenyl or pyridine derivatives |
| US6297264B1 (en) | 1994-06-22 | 2001-10-02 | Celltech Therapeutics Limited | Trisubstituted phenyl derivatives and process for their preparation |
| US6197792B1 (en) | 1994-06-22 | 2001-03-06 | Celltech Therapeutics Limited | Tetra-substituted phenyl derivatives and processes for their preparation |
| US5780477A (en) * | 1994-06-22 | 1998-07-14 | Celltech Therapeutics, Limited | Trisubstituted phenyl derivatives and processes for their preparation |
| US5780478A (en) * | 1994-06-22 | 1998-07-14 | Celltech Therapeutics, Limited | Tetra-substituted phenyl derivatives |
| US5693659A (en) * | 1994-06-23 | 1997-12-02 | Celltech Therapeutics Limited | Substituted oxime derivatives and processes for their preparation |
| US5958935A (en) * | 1995-11-20 | 1999-09-28 | Celltech Therapeutics Limited | Substituted 2-anilinopyrimidines useful as protein kinase inhibitors |
| US6235746B1 (en) | 1995-11-20 | 2001-05-22 | Celltech Therapeutics, Limited | Substituted 2-anilinopyrimidines useful as protein kinase inhibitors |
| US5798373A (en) * | 1995-12-21 | 1998-08-25 | Celltech Therapeutics, Limited | Tri-substituted phenyl derivatives useful as PDE IV inhibitors |
| US5849770A (en) * | 1995-12-21 | 1998-12-15 | Celltech Therapeutics Ltd. | Tri-substituted phenyl derivatives useful as PDE IV inhibitors |
| US5922741A (en) * | 1996-04-24 | 1999-07-13 | Celltech Therapeutics Ltd. | 5-aminopyrazoles useful as tyrosine kinase inhibitors |
| US6093716A (en) * | 1996-09-16 | 2000-07-25 | Celltech Therapeutics, Limited | Substituted 2-pyrimidineamines and processes for their preparation |
| US6114333A (en) * | 1996-10-28 | 2000-09-05 | Celltech Therapeutics Ltd. | 2-Pyrimidineamine derivatives and processes for their preparation |
| US6552029B1 (en) | 1996-10-28 | 2003-04-22 | Celltech R&D Limited | 2-pyrimidineamine derivatives and processes for their preparation |
| US5859034A (en) * | 1996-12-04 | 1999-01-12 | Celltech Therapeutics, Limited | Tri-substituted phenyl compounds which have useful pharmaceutical activity |
| US6057329A (en) * | 1996-12-23 | 2000-05-02 | Celltech Therapeutics Limited | Fused polycyclic 2-aminopyrimidine derivatives |
| US6599908B1 (en) | 1996-12-23 | 2003-07-29 | Celltech R & D Limited | Fused polycyclic 2-aminopyrimidine derivatives |
| US6337335B1 (en) | 1997-03-14 | 2002-01-08 | Celltech Therapeutics Limited | Substituted 2-anilinopyrimidines useful as protein kinase inhibitors |
| US6133257A (en) * | 1997-06-20 | 2000-10-17 | Celltech Therapeutics Limited | Fused polycyclic 2-aminopyrimidine derivatives |
| US6579983B1 (en) | 1999-06-18 | 2003-06-17 | Celltech R&D Limited | 5-cyano-2-aminopyrimidine derivatives |
| US6600037B1 (en) | 1999-10-20 | 2003-07-29 | Celltech R & D Limited | 4,5-disubstituted-2-aminopyrimidines |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0377923A (en) | Organic nonlinear optical material | |
| JPH0377872A (en) | 2-(2-(2-hydroxyphenyl)vinyl)pyrazine and its production | |
| JPH0381744A (en) | Organic nonlinear optical material | |
| JPH0377871A (en) | 2-(2-(3-hydroxyphenyl)vinyl)-pyrazine and its production | |
| JPH02187734A (en) | Nonlinear optical organic material | |
| JP2530725B2 (en) | Organic nonlinear optical material | |
| JPH0356448A (en) | 1-(4-methylstyryl)-3-(4-nitrostyryl)benzene and production thereof | |
| JPH0356449A (en) | 1-(4-methoxystyryl)-3-(4-nitrostyryl)benzene and production thereof | |
| JPH03181919A (en) | Organic nonlinear optical material | |
| JPH03140927A (en) | Organic nonlinear optical material | |
| JPH0381746A (en) | Organic nonlinear optical material | |
| JPH03140928A (en) | Organic nonlinear optical material | |
| JP2533660B2 (en) | Organic nonlinear optical material | |
| JP2725929B2 (en) | Organic nonlinear optical material | |
| JPH07107012B2 (en) | Novel organic compound | |
| JPH02196759A (en) | New organic compound | |
| JPH08119914A (en) | Cyclobutendione derivative, its production and nonlinear optical element using the same | |
| JPH02113226A (en) | Organic nonlinear optical material | |
| JPH03142419A (en) | Nonlinear optical element | |
| JPH0616611A (en) | Alpha-cyanocinnamic acid ester compound and organic nonlinear optical material comprising the compound | |
| JPH0511291A (en) | Organic nonlinear optical material and nonlinear optical element formed by using this material | |
| JPH0558980A (en) | Alpha-cyanocinnamic acid ester-based compound and organic nonlinear optical material composed of the same compound | |
| JPH083125A (en) | Malondiamide derivative, optically functional element and production thereof | |
| JPH03179329A (en) | Nonlinear optical material and nonlinear optical element | |
| JPH03287139A (en) | Organic nonlinear optical material |