JPH03202818A - Nonlinear optical material - Google Patents
Nonlinear optical materialInfo
- Publication number
- JPH03202818A JPH03202818A JP34466489A JP34466489A JPH03202818A JP H03202818 A JPH03202818 A JP H03202818A JP 34466489 A JP34466489 A JP 34466489A JP 34466489 A JP34466489 A JP 34466489A JP H03202818 A JPH03202818 A JP H03202818A
- Authority
- JP
- Japan
- Prior art keywords
- group
- nonlinear optical
- crystals
- substituents
- compound
- 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 26
- 239000000463 material Substances 0.000 title claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 21
- 125000003277 amino group Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 239000002904 solvent Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- -1 chalcone compound Chemical class 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000004566 IR spectroscopy Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 7
- 235000005513 chalcones Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000003993 interaction Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002085 enols Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 2
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- 229930194542 Keto Natural products 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 230000008832 photodamage Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- QPRQEDXDYOZYLA-YFKPBYRVSA-N (S)-2-methylbutan-1-ol Chemical compound CC[C@H](C)CO QPRQEDXDYOZYLA-YFKPBYRVSA-N 0.000 description 1
- JYPGOBDETCKKKV-UHFFFAOYSA-N 1-(3-bromo-4-methoxyphenyl)ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1Br JYPGOBDETCKKKV-UHFFFAOYSA-N 0.000 description 1
- QILWOKAXHOAFOF-UHFFFAOYSA-N 1-(3-chloro-4-methoxyphenyl)ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1Cl QILWOKAXHOAFOF-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000005374 Kerr effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- XIFJZJPMHNUGRA-UHFFFAOYSA-N n-methyl-4-nitroaniline Chemical compound CNC1=CC=C([N+]([O-])=O)C=C1 XIFJZJPMHNUGRA-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- QPRQEDXDYOZYLA-UHFFFAOYSA-N sec-pentyl alcohol Natural products CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は光情報、光通信等に用いられる非線形光学材料
に関するものであり、更に詳しくは１゜３−ジケトン誘
導体からなる有機非線形光学材料に関する。例えば半導
体レーザー用波長変換素子、計測機器、光ファイバーに
よる情報伝送等に用いることができる。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a nonlinear optical material used for optical information, optical communication, etc., and more particularly to an organic nonlinear optical material comprising a 1°3-diketone derivative. . For example, it can be used in wavelength conversion elements for semiconductor lasers, measuring instruments, information transmission through optical fibers, and the like.
（従来の技術）
レーザー光は単色性、指向性、すなわちコヒーレント性
を有するため物質に特異的な相互作用を及ぼす。この相
互作用は非線形光学効果として知られており、高調波発
生、カー効果、光混合、パラメトリック増幅等の現象を
起こす。特に二次及び三次非線形光学効果は比較的大き
な非線形感受率が期待できるため情報処理、光通信等へ
の応用が可能である。(Prior Art) Laser light is monochromatic and directional, that is, coherent, and therefore exerts a specific interaction with substances. This interaction is known as a nonlinear optical effect, and causes phenomena such as harmonic generation, the Kerr effect, optical mixing, and parametric amplification. In particular, second-order and third-order nonlinear optical effects can be expected to have relatively large nonlinear susceptibilities, so they can be applied to information processing, optical communications, etc.
従来、非線形光学材料としてＫ Ｄ Ｐ （ＫＨ２ＰＯ
４）。Conventionally, KDP (KH2PO
4).
Ａ Ｄ Ｐ （ＮＨ４Ｈ３ＰＯ４） 、 Ｌ ｉ Ｎ
ｂ ０３等の無機材料が使用され一部の測定機器に応
用されてきた。ADP (NH4H3PO4), L i N
Inorganic materials such as b03 have been used and applied to some measuring instruments.
しかし純度の高い単結晶が得に＜＜、又高価であること
、耐光損傷性に劣ること、潮解性であること、非線形光
学感受率が小さいこと等の理由から光関連への応用は困
難であった。However, it is difficult to apply it to light-related applications due to reasons such as high purity single crystals, high price, poor light damage resistance, deliquescent property, and low nonlinear optical susceptibility. there were.
近年になって、無機材料に比べ有機材料が優れた非線形
光学効果を有することが見出されて以来、分子設計の点
で自由度の高い有機材料が注目を浴びている。特に、２
−メチル−４−ニトロ−アニリンに代表されるようなπ
電子が共役し、分子内に電子供与性置換基及び電子吸引
性置換基を有したＣ −Ｔ （Ｃｈａｒｇｅ−Ｔｒａｎ
ｓｆｅｒ）型有機化合物が大きな分子超分極率を誘起す
るため大きな非線形感受率が期待できると考えられてき
た。In recent years, since it has been discovered that organic materials have superior nonlinear optical effects compared to inorganic materials, organic materials, which have a high degree of freedom in molecular design, have attracted attention. In particular, 2
-π such as methyl-4-nitro-aniline
C-T (Charge-Tran), which has electrons conjugated and has an electron-donating substituent and an electron-withdrawing substituent in the molecule.
It has been thought that large nonlinear susceptibility can be expected because sfer) type organic compounds induce large molecular hyperpolarizability.
しかし、有機化合物の結晶構造は分子間の相互作用即ち
水素結合、ファンデルワールス相互作用等の分子間力に
よって決定される。上記のような強い電子吸引性置換基
及び電子供与性置換基を有するＣ−Ｔ型分子の場合、分
子間の強い双極子−双極子相互作用か働き結晶を安定さ
せる構造、即ち二分子の双極子を打ち消し合う結晶構造
をとりやすい。このような結晶構造は分子集合体として
中心対称性結晶であり、従って非線形光学的に不活性で
ある。However, the crystal structure of an organic compound is determined by intermolecular interactions, ie, intermolecular forces such as hydrogen bonds and van der Waals interactions. In the case of C-T type molecules having strong electron-withdrawing substituents and electron-donating substituents as described above, the structure stabilizes the crystal due to strong dipole-dipole interactions between molecules, that is, bimolecular dipoles. It is easy to form a crystal structure in which the children cancel each other out. Such a crystal structure is a centrosymmetric crystal as a molecular assembly, and is therefore nonlinearly optically inactive.
そこで、このような結晶構造の中心対称性を崩壊させる
手段として次のような手法が用いられている。即ち、ヒ
ドロキシル基、カルボキシル基、アミノ基等の分子配向
を制御できる水素結合性の大きな置換基、立体的な障害
によって分子構造を大きく変化させうるバルキーな置換
基、アミノ酸又はアミノ酸誘導体等の光学活性な置換基
（Ｄ又はＬ体）等の他、包接化合物との錯体等、複合化
によって非中心対称性を誘起させる方法が実施されてい
る。Therefore, the following method is used as a means of disrupting the central symmetry of such a crystal structure. In other words, substituents with large hydrogen bonding properties that can control molecular orientation such as hydroxyl groups, carboxyl groups, and amino groups, bulky substituents that can significantly change the molecular structure due to steric hindrance, and optical activities such as amino acids or amino acid derivatives. In addition to substituents (D or L-form), methods of inducing non-centrosymmetric properties have been implemented by conjugation, such as complexes with clathrates.
又二次非線形光学材料が非線形光学素子として適用でき
る必要十分な条件として以下の点が挙げられる。Further, the following points are necessary and sufficient conditions for the application of the second-order nonlinear optical material as a nonlinear optical element.
■ 非線形光学感受率が極めて大きい
■ 光応答速度が早い
■ レーザー光の透過性に優れている
■ 耐光損傷性
■ 位相整合性
■ 結晶性（単結晶育成の可能性等）
■ 機械的強度
■ 加工が容易である
■ 耐湿性など化学的に安定である
＠１１１昇華性
（発明が解決しようとする課題）
超分極率が大きく、水素結合性置換基導入及び光学活性
な置換基導入によって達成された中心対称性のないＮＰ
ＰのようなＣ−Ｔ型化合物及びπ電子共役の長い分子の
場合、大きな二次非線形感受率は期待できるが透明性に
欠ける等の欠点を有している。そのため使用波長範囲が
限られてしまうという欠点があった。■ Extremely high nonlinear optical susceptibility ■ Fast optical response speed ■ Excellent laser light transparency ■ Light damage resistance ■ Phase matching ■ Crystallinity (possibility of single crystal growth, etc.) ■ Mechanical strength ■ Processing ■ Chemically stable, such as moisture resistance @111 Sublimation (problem to be solved by the invention) High hyperpolarizability, achieved by introducing hydrogen-bonding substituents and optically active substituents NP without central symmetry
In the case of C-T type compounds such as P and molecules with long π-electron conjugation, large second-order nonlinear susceptibility can be expected, but they have drawbacks such as lack of transparency. Therefore, there was a drawback that the usable wavelength range was limited.
（課題を解決するための手段）
本発明は上記問題点を解決するために行われたちのてあ
り、大きな非線形光学感受率を有し、透明性に優れた何
機化合物を提供するものである。(Means for Solving the Problems) The present invention was carried out to solve the above-mentioned problems, and provides a multifunctional compound having a large nonlinear optical susceptibility and excellent transparency. .
に記］］的を４成するため、本発明は下記の構成を有す
る。すなわち、本発明は下記一般式〔１〕で表わされる
１、３−ジケトン誘導体からなることを特徴とする非線
形光学材料である。] In order to achieve the four objectives, the present invention has the following configuration. That is, the present invention is a nonlinear optical material characterized by comprising a 1,3-diketone derivative represented by the following general formula [1].
（式中、置換基Ｘ１〜Ｘ４は、水素またはハロゲンであ
り、Ｘ５は炭素数１〜１８のアルコキシ基またはメルカ
プトアルコキシ基である。置換基Ｘ６〜ＸＩＯは、水素
、アミノ基、炭素数１〜１２の置換アミノ基、環状アミ
ノ基、炭素数１〜１８（７） ７ ｋキル基、炭素数１
〜１８のアルコキシ基、炭素数ｌ〜１８のメルカプトア
ルコキシ基、シアノ基、ハロゲン加ら選ばれた１種であ
り、おたがいに同一でもよく異種でもよいものである。(In the formula, substituents X1 to X4 are hydrogen or halogen, and X5 is an alkoxy group or mercaptoalkoxy group having 1 to 18 carbon atoms. Substituents X6 to XIO are hydrogen, an amino group, and 1 to 18 carbon atoms. 12 substituted amino groups, cyclic amino group, carbon number 1 to 18 (7) 7k kill group, carbon number 1
-18 alkoxy groups, mercaptoalkoxy groups having 1 to 18 carbon atoms, cyano groups, and halogens, and they may be the same or different.
）本発明の１，３−ジケトン誘導体は、ケト型とエノー
ル型の平衡状態によるがエノール型に大きく片寄ってい
る。) The 1,3-diketone derivative of the present invention is largely biased toward the enol type, although it depends on the equilibrium state between the keto type and the enol type.
この分子内エノール性水酸基は結晶状態においてＳＨＧ
活性の十分条件である非中心対称性を誘起させつる機能
性有機置換基（配向制御基）としての特徴を有しており
、又分子内に電子供与性基及び電子吸引性基を有してい
るため光非線形性を増大せしめることができる。特に電
子供与性基を芳香環のオルト位又はパラ位に導入する事
によって電荷移動相互作用による共鳴効果が大きくなる
ので効果的である。This intramolecular enolic hydroxyl group is SHG in the crystalline state.
It has the characteristics of a functional organic substituent (orientation control group) that induces non-centrosymmetric properties, which is a sufficient condition for activity, and also has an electron-donating group and an electron-withdrawing group in the molecule. Therefore, optical nonlinearity can be increased. Introducing an electron-donating group at the ortho or para position of the aromatic ring is particularly effective because it increases the resonance effect due to charge transfer interaction.
本発明で用いる置換基Ｘ、〜ＸｔＯにおいて、Ｘ、−Ｘ
４はハロゲンであるが特に塩素、臭素が好ましい。又置
換基Ｘ５はアルコキシ基、メルカプトアルコキシ基であ
るが炭素数５以内の長鎖アルキル基、分岐状アルキル基
もくしは不斉炭素を有するアルキル基が好ましい。置換
基Ｘ６〜Ｘ Ｉ（１において、アルキルを有する置換基
の場合好ましくは炭素数５以内のアルキル基もしくは不
斉炭素を有するアルキル基が好ましい。In the substituent X used in the present invention, ~XtO, X, -X
4 is a halogen, with chlorine and bromine being particularly preferred. The substituent X5 is an alkoxy group or a mercaptoalkoxy group, but preferably a long-chain alkyl group having up to 5 carbon atoms, a branched alkyl group, or an alkyl group having an asymmetric carbon. In the case of substituents X6 to X I (1), in the case of a substituent having an alkyl, an alkyl group having up to 5 carbon atoms or an alkyl group having an asymmetric carbon is preferable.
本発明の有機非線形光学材料の合成方法として、例えば
（３）式及び（４）式が考えられる。For example, formulas (3) and (4) can be considered as methods for synthesizing the organic nonlinear optical material of the present invention.
即ち、〈３）式において（ａ）クライゼンーシ二ミント
脱水縮合反応によるカルコン化合物の合成過程（ｂ）ブ
ロム化の過程（Ｃ）メトキシ化次いで脱メチル化の過程
によって合成することができる。（２）式において（ａ
）ベンゾイルアセトンの合成過程（ｂ）安息香酸エステ
ルとベンゾイルアセトン誘導体との反応過程によって合
成することができる。That is, in formula <3), it can be synthesized by (a) a process for synthesizing a chalcone compound by a dehydration condensation reaction of Claisen-cydimint, (b) a process of bromination, and (C) a process of methoxylation and then demethylation. In equation (2), (a
) Synthesis process of benzoylacetone (b) It can be synthesized by a reaction process between a benzoic acid ester and a benzoylacetone derivative.
（実施例）
以下、実施例に従って本発明を更に詳しく説明するが、
本発明はこれら実施例に限定されるものではない。(Example) Hereinafter, the present invention will be explained in more detail according to Examples.
The present invention is not limited to these examples.
第二次高調波発生（ＳＨＧ）の測定は粉末法（Ｓ、に、
Ｋｕｒｚ、Ｔ、Ｔ、ＰｅｒｒＹ、 ＬＬ３７９８ （１
９８Ｂ））に従って行った。測定に用いた光源はＮｄ；
ＹＡＧレーザーであり、基本波長１０８４ｔｕｎのレー
ザー光を粉末試料へ照射し、発生する二倍波（５３２ｎ
ｉ）を分光器で検出した。第二次高調波発生装置の概略
図を第２図に示す。Second harmonic generation (SHG) is measured using the powder method (S).
Kurz, T., PerrY, LL3798 (1
98B)). The light source used for measurement was Nd;
It is a YAG laser, which irradiates a powder sample with a laser beam with a fundamental wavelength of 1084 tun, and generates a double wave (532 nm).
i) was detected using a spectrometer. A schematic diagram of the second harmonic generator is shown in FIG.
使用した粉末試料はトルエン（ａ）、酢酸エチル（ｂ）
、アセトン（Ｃ）、エタノール（ｄ）、ヘキサン（ｅ）
、メタノール（ｆ）で再結晶して精製したものを用いた
。The powder samples used were toluene (a) and ethyl acetate (b).
, acetone (C), ethanol (d), hexane (e)
, purified by recrystallization with methanol (f) was used.
３００ ｘＱ−ロナスフラスコにＥｔＯＨ２００ｄを加
え、４−メトキシアセトフェノン８．４８ｇ（４３，０
８１ｍＭ）を加えて完全に溶解させた。Add 200d of EtOH to a 300 x Q-ronas flask and add 8.48g of 4-methoxyacetophenone (43,0
81 mM) was added and completely dissolved.
ＮａＯＨ水溶液（１，７２ｇ／Ｈ２０；４０ｍｆｆ）を
加えた後、室温下ｐ−クロロベンズアルデヒド６．０５
ｇ （４３，０８１ｍＭ）／ＥｔＯＨ溶液を少しずつ滴
下した。析出した沈殿物を減圧下分取し、蒸溜水５０ｉ
＋ｌ！で三回よく洗浄した後減圧加熱乾燥した。得られ
たカルコン化合物はシリカゲルカラムクロマトで精製し
た。After adding NaOH aqueous solution (1,72 g/H20; 40 mff), 6.05 g of p-chlorobenzaldehyde was added at room temperature.
g (43,081 mM)/EtOH solution was added dropwise little by little. The deposited precipitate was collected under reduced pressure and poured into 50 liters of distilled water.
+l! After washing thoroughly three times with The obtained chalcone compound was purified by silica gel column chromatography.
収量は１１．３ｇ （９６％）であった。この生成物は
エタノールで再結晶した。生成物の確認は核磁気共鳴ス
ペクトル、赤外吸収スペクトルを用いて行った。Yield was 11.3g (96%). This product was recrystallized from ethanol. The product was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.
過」し工」」−
過程（Ａ）で得られたカルコン化合物１０ｇ（３６，７
０４ｍＭ）を二硫化炭素中に懸濁しておき、冷却下（０
℃）臭素溶液１．７ｃｃを少しずつ滴下した。０℃で３
時間、室温に戻して２５℃で１時間反応させた後、減圧
下分取しＭ ｅ ＯＨで洗浄した。得られた粗白色結晶
１４．５ｇ（収率９１％）をトルエン展開溶媒でカラム
クロマト精製した後、溶媒で再結晶精製を行った。- 10g of chalcone compound obtained in process (A) (36,7
04mM) was suspended in carbon disulfide and cooled (04mM).
℃) 1.7 cc of bromine solution was added dropwise little by little. 3 at 0℃
After returning to room temperature and reacting at 25° C. for 1 hour, the mixture was fractionated under reduced pressure and washed with M e OH. 14.5 g (yield: 91%) of the obtained crude white crystals was purified by column chromatography using a toluene developing solvent, and then purified by recrystallization using a solvent.
化合物の確認は核磁気共鳴スペクトル及び赤外吸収スペ
クトルを用いて行った。The compound was confirmed using nuclear magnetic resonance spectrum and infrared absorption spectrum.
走乱工仁り
過程（Ｂ）で得られたジブロム体１０．０ｇ（２３，１
２４ｍＭ）をＥｔＯＮａ／ＥｔＯＨ溶液（Ｎａ／ＥｔＯ
Ｈ）へ加え、２時間加熱環流した後室温に戻し濃塩酸４
．０−を加え３０分加熱環流を行った。室温に戻した後
析出した粗結晶を減圧下分取した。この１．３−ジケト
ン誘導体の粗結晶８．３ｇ（収率９４％）を活性アルミ
ナ／シリカゲルでカラムクロマト精製した後、各種溶媒
によって再結晶精製した。化合物の確認は核磁気共鳴ス
ペクトル、赤外吸収スペクトルで行った。10.0 g of dibrome compound (23,1
24mM) in EtONa/EtOH solution (Na/EtO
H) and heated under reflux for 2 hours, then returned to room temperature and added concentrated hydrochloric acid 4
．． 0- was added and heated under reflux for 30 minutes. After the temperature was returned to room temperature, the precipitated crude crystals were collected under reduced pressure. 8.3 g (yield: 94%) of this crude crystal of the 1,3-diketone derivative was purified by column chromatography using activated alumina/silica gel, and then purified by recrystallization using various solvents. The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.
■
得られた１、３−ジケトン誘導体（Ｎｕ １ ）を上記
方法によりＳＨＧ強度の測定を行ったところ、尿素に対
して３８．９（アセトン）、４９．６（ＥｔＯＨ）、４
８．０ （）ルエン）、５１．３（酢酸エチル）、１．
１（ｎ−へキサン）のＳＨ６発生を確認することができ
た。(2) When the SHG intensity of the obtained 1,3-diketone derivative (Nu 1 ) was measured by the above method, it was found to be 38.9 (acetone), 49.6 (EtOH), 4
8.0 () toluene), 51.3 (ethyl acetate), 1.
It was possible to confirm the generation of SH6 in 1(n-hexane).
３−クロロ−４−メトキシアセトフェノン１０ｇ （５
４，２１５ｍＭ）を５００ ＊Ｑ−ロナスフラスコに入
れ、ＥｔＯＨ３００−を加えて完全に溶解させた。室温
下、ＮａＯＨ水溶液（ＮａＯＨ２、４ｇ ／ Ｈ２０５
０ｖａＱ ）を加え、さらに０−クロロベンズアルデヒ
ド７．６１ｇ
（５４，２１５ｍＭ）を少しづつ滴下した。析出した沈
殿物１８．５ｇ（収率；９９％）を減圧下分取し、蒸溜
水５０１Ｑで４回洗浄した後、ヘキサンで再結晶精製し
た。化合物の確認は核磁気共鳴スペクトル、赤外吸収ス
ペクトルで行った。3-chloro-4-methoxyacetophenone 10g (5
4,215mM) was placed in a 500*Q-ronas flask, and EtOH 300- was added to completely dissolve it. At room temperature, NaOH aqueous solution (NaOH2, 4g / H205
0 vaQ) was added thereto, and 7.61 g (54,215 mM) of 0-chlorobenzaldehyde was added dropwise little by little. 18.5 g (yield: 99%) of the precipitated precipitate was collected under reduced pressure, washed four times with distilled water 501Q, and then purified by recrystallization with hexane. The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.
過」Ｌ工」９一
過程（Ａ）で得られたカルコン化合物１５．０ｇ （４
８，８７６ｍＭ）を二硫化炭素１００−に溶解し、窒素
気流下、３℃で臭素５−を少しづつ滴下した。３℃〜５
℃で２時間反応させた後、室温（２６℃）に戻して１時
間反応させた。蒸溜水１’ ＯＯ＊Ｑ及びＨ２ＣＱ２７
０−を加え、ＣＨ２ＣＱ２５０．Ｑで３回抽出した。15.0 g of chalcone compound obtained in step (A) (4
8,876 mM) was dissolved in 100-carbon disulfide, and 5-bromine was added dropwise little by little at 3°C under a nitrogen stream. 3℃～5
After reacting at °C for 2 hours, the mixture was returned to room temperature (26 °C) and reacted for 1 hour. Distilled water 1' OO*Q and H2CQ27
0- and CH2CQ250. Extracted with Q three times.
ＣＨ２Ｃ９２抽出溶液は熱水硫酸マグネシウムで乾燥し
た。The CH2C92 extract solution was dried with hot water magnesium sulfate.
ＣＨ２ＣＱ２及び無水硫酸マグネシウムを除去した後、
白色結晶２２．８ｇ（収率９９％）を得た。得ろれた化
合物は十分に乾燥した後、次の反応に用いた。化合物の
確認は核磁気共鳴スペクトツメ、赤外吸収スペクトルで
行った。After removing CH2CQ2 and anhydrous magnesium sulfate,
22.8 g (yield 99%) of white crystals were obtained. The obtained compound was thoroughly dried and then used in the next reaction. The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.
過Ｘ
過程（Ｂ）で得られたジブロム体２０ｇ（４８，４０４
ｍＭ）を窒素気流下、事前に用意したＮａ０ＣＨａ ／
ＣＨ３０Ｈ（Ｎａ ；２．０７２ｇ／ＣＨａ ０Ｈ３０
０■Ｑ）溶液へ加えた後、２時間加熱環流を行った。室
温に戻した後、濃塩酸７−を加え、さらに１時間加熱環
流を行った。反応溶液を５℃に冷却し、析出した結晶を
減圧下分取した。得られた粗結晶（白色）はトルエンを
展開溶媒としてカラムクロマト精製した（１５．１ｇ（
収率９７％）後、各種溶媒で再結晶精製を行った。20 g (48,404
Na0CHa/mM) prepared in advance under a nitrogen stream
CH30H (Na; 2.072g/CHa 0H30
0■Q) After adding it to the solution, it was heated under reflux for 2 hours. After the temperature was returned to room temperature, concentrated hydrochloric acid 7- was added, and the mixture was further heated under reflux for 1 hour. The reaction solution was cooled to 5°C, and the precipitated crystals were collected under reduced pressure. The obtained crude crystals (white) were purified by column chromatography using toluene as a developing solvent (15.1 g (
After that (yield: 97%), recrystallization purification was performed using various solvents.
実施例１と同様の方法によりＮａ２の化合物のＳＨＧ強
度の測定を行ったところ、２８．５（Ｔｏｌｕｅｎｅ）
、３０．１ （酢酸エチル）、１０．８ （ＥｔＯＨ）
、２９．８ （アセトン）、３．４（ヘキサン）のＳＨ
Ｇ活性を確認することができた。When the SHG intensity of the Na2 compound was measured by the same method as in Example 1, it was found to be 28.5 (Toluene).
, 30.1 (ethyl acetate), 10.8 (EtOH)
, 29.8 (acetone), 3.4 (hexane) SH
G activity could be confirmed.
３−ブロモ−４−メトキシアセトフェノン１０ｇ （４
１，１５２２ｍＭ）を５００ ＊Ｑ−ロナスフラスコに
加え、Ｅ ｔ ＯＨ４００ｍＱで溶解させた。3-Bromo-4-methoxyacetophenone 10g (4
1,1522mM) was added to a 500*Q-ronas flask and dissolved with 400mQ of EtOH.
蒸溜水４０ ｗａＱに溶解させたＮａＯＨ水溶液（Ｎａ
ＯＨ； ２．１８ｇ／Ｈａ Ｏ； ３０ｍＱ）を加えた
後、４−メトキシベンズアルデヒド５．４３ｇ （４１
，１５２２ｍＭ）Ｅ ｔＯＨ溶液を滴下した。室温で３
時間反応させた後、析出したクリーム色結晶を減圧下分
取した後、ＣＨ２ＣＱ２を展開溶媒としてカラムクロマ
ト精製を行い、１４．１ｇ（収率９９％）のクリーム色
結晶を得た。さらにヘキサンで再結晶精製し、減圧下側
熱乾燥した後そのまま次の反応に用いた。Aqueous NaOH solution (Na
After adding OH; 2.18 g/HaO; 30 mQ), 5.43 g of 4-methoxybenzaldehyde (41
, 1522mM) E tOH solution was added dropwise. 3 at room temperature
After reacting for a period of time, the precipitated cream-colored crystals were collected under reduced pressure, and then purified by column chromatography using CH2CQ2 as a developing solvent to obtain 14.1 g (yield: 99%) of cream-colored crystals. The product was further purified by recrystallization using hexane, dried under reduced pressure under heat, and then used as it was in the next reaction.
化合物の確認は核磁気共鳴スペクトル、赤外吸収スペク
トルで行った。The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.
過」Ｌ工１９−
過程（Ａ）で得られたカルコン化合物１２．０ｇ （３
４，６８２ｍＭ）を窒素気流下二硫化炭素１５０−中に
加え、３〜５℃に冷却した後、臭素４．５−を滴下した
。３〜５℃で２．５時間、室温（約２６℃）で１時間撹
拌した後、結晶を減圧下分取し、冷Ｍ ｅ ＯＨで洗浄
した後Ｍ ｅ ＯＨで再結晶精製し白色結晶１６．９ｇ
（９８％）を得た。Process 19- 12.0 g of chalcone compound obtained in step (A) (3
4,682mM) was added into 150-carbon disulfide under a nitrogen stream, and after cooling to 3 to 5°C, 4.5-bromine was added dropwise. After stirring at 3-5°C for 2.5 hours and at room temperature (approximately 26°C) for 1 hour, the crystals were collected under reduced pressure, washed with cold MeOH, and recrystallized with MeOH to obtain white crystals 16. .9g
(98%).
化合物の確認は核磁気共鳴スペクトル、赤外吸収スペク
トルで行った。The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.
過」しエエ９一
過程（Ｂ）で得られたジブロム体１６．０ｇ（３１，８
２０５ｍＭ）を事前に用意したＮ ａ ＯＣＨ３／ Ｃ
Ｈ３０Ｈ溶液（Ｎａ；１．５３ｇ／４００ｗ１ｉ’ＣＨ
３０Ｈ）へ加え２時間加熱環流を行った。２時間後室温
に戻して濃塩酸６ ｗａＱを加えた後さらに１時間加熱
環流を行い、蒸溜水７〇−及びＣＨ２Ｃ（！２８０ｍＱ
を加え２０分間攪拌後、ＣＨ２（、Ｑ２５０−を用いて
４回抽出した。16.0 g (31,8
205mM) prepared in advance
H30H solution (Na; 1.53g/400w1i'CH
30H) and heated under reflux for 2 hours. After 2 hours, the temperature was returned to room temperature, 6 waQ of concentrated hydrochloric acid was added, and the mixture was further heated under reflux for 1 hour.
was added and stirred for 20 minutes, followed by extraction four times using CH2 (, Q250-).
ＣＨ２ＣＱ２抽出溶液は無水硫酸マグネシウムで乾燥後
溶媒を除去し、粗結晶１２．１ｇを得た。The CH2CQ2 extraction solution was dried over anhydrous magnesium sulfate and the solvent was removed to obtain 12.1 g of crude crystals.
これをトルエン展開溶媒としてカラムクロマト精製を行
い、白色結晶１１．１ｇ（９７％）を得た。This was purified by column chromatography using toluene as a developing solvent to obtain 11.1 g (97%) of white crystals.
これを各種溶媒で再結晶精製を行った。This was recrystallized and purified using various solvents.
得られた再結晶精製物Ｎｆｉ３は実施例１と同様の方法
でＳＨＧ強度の測定を行ったところ、５．８（Ｔｏ １
ｕｅｎｅ）、６．１ （酢酸エチル）、４．２ （Ｅｔ
ＯＨ）８．９ （ヘキサン）のＳＨＧ活性を確認するこ
とができた。When the SHG intensity of the obtained recrystallized purified product Nfi3 was measured in the same manner as in Example 1, it was found to be 5.8 (To 1
uene), 6.1 (ethyl acetate), 4.2 (Et
The SHG activity of OH)8.9 (hexane) could be confirmed.
４−メルカプトメトキシアセトフェノン１０ｇ（５４，
９４５１ｍＭ）を３００ ｍＱ−ロナスフラスコに入れ
、Ｅ ｔ ＯＨ３００ｖａＱを加えて完全に溶解させた
。10 g of 4-mercaptomethoxyacetophenone (54,
9451mM) was placed in a 300 mQ-ronas flask, and 300 vaQ of EtOH was added to completely dissolve it.
Ｎ ａ ＯＨ水溶液（Ｎ ａ ＯＨ； １ 、７５ ｇ
／ Ｈ２０；３０ｉｄ）を加えたあと、４−クロロベ
ンズアルデヒド７．７ｇ （５４，９４５ｍＭ）のＥｔ
ＯＨ溶液を滴下した。３時間、室温下撹拌した後析出し
た結晶を減圧下分取した。さらにトルエンを展開溶媒と
してカラムクロマト精製を行ない、１５．２ｇ（収率９
６％）のクリーム色結晶を得た。これを減圧加熱乾燥し
、そのまま次の反応に用いた。NaOH aqueous solution (NaOH; 1, 75 g
/H20; 30id) and then 7.7 g (54,945 mM) of 4-chlorobenzaldehyde in Et.
OH solution was added dropwise. After stirring for 3 hours at room temperature, the precipitated crystals were collected under reduced pressure. Furthermore, column chromatography purification was performed using toluene as a developing solvent, and 15.2 g (yield: 9
6%) of cream-colored crystals were obtained. This was dried by heating under reduced pressure and used as it was in the next reaction.
化合物の確認は核磁気共鳴スペクトル、赤外吸収スペク
トルで行った。The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.
過」し工ｆｉｌ
過程（Ａ）で得たカルコン化合物１４．０ｇ（４８，５
３５２ｍＭ）を３００−三〇フラスコへ入れ、二硫化炭
素を加えて懸濁液とした。窒素雰囲気下、３〜５℃に冷
却した後、臭素５−を少しづつ滴下した。３〜５℃で２
時間、室温下で１時間反応させた後結晶を減圧下分取し
た。結晶はへキチンで洗浄した後、Ｍｅｎ）（で再結晶
精製し２０．８７ｇ（収率９６％）の白色板状結晶を得
た。14.0 g (48.5 g) of the chalcone compound obtained in step (A)
352mM) was placed in a 300-30 flask, and carbon disulfide was added to form a suspension. After cooling to 3 to 5°C under a nitrogen atmosphere, bromine 5- was added dropwise little by little. 2 at 3-5℃
After reacting for 1 hour at room temperature, the crystals were collected under reduced pressure. The crystals were washed with hechitin and then purified by recrystallization using Men) to obtain 20.87 g (yield 96%) of white plate-like crystals.
過」Ｌエエ」一
過程（Ｂ）で得たジブロム体２０．０ｇ（４４，５９８
ｍＭ）を事前に用意したＮａＯＭｅ／ＭｅＯＨ溶ｌ＆（
Ｎａ ； ０．７８ｇ／Ｅ ｔ ＯＨ４００ｍＱ ）へ
加え３時間加熱環流を行った。次いで室温に戻した後、
濃塩酸８ ｖｓＱを加えさらに１時間加熱環流を行った
。反応の終点を薄層クロマトグラフィーで確認した後、
蒸溜水８０ＩＩＱ及びＣＨ２ＣＱ２１００■２を加え１
時間撹拌した。20.0 g of dibrome compound obtained in step (B) (44,598
mM) in previously prepared NaOMe/MeOH solution &(
Na; 0.78g/EtOH400mQ) and heated under reflux for 3 hours. Then, after returning to room temperature,
Concentrated hydrochloric acid (8 vs. Q) was added and the mixture was further heated under reflux for 1 hour. After confirming the end point of the reaction by thin layer chromatography,
Add distilled water 80IIQ and CH2CQ2100■2
Stir for hours.
ＣＨ２ＣＱ２７０■Ｑで３回抽出した後、無水硫酸マグ
ネシウムで乾燥した。乾燥剤及び溶媒を除去し、１４．
９ｇの粗結晶を得た。これをＴｏｌｕｅｎｅを溶媒とし
てカラムクロマト精製を行い、１３．１４ｇ（収率θ７
％）のクリーム色結晶を得た。これを各種有機溶媒で再
結晶精製を行い８８０強度測定の試料とした。After extraction three times with CH2CQ270Q, it was dried over anhydrous magnesium sulfate. Remove desiccant and solvent; 14.
9 g of crude crystals were obtained. This was purified by column chromatography using Toluene as a solvent, and 13.14 g (yield θ7
%) of cream-colored crystals were obtained. This was recrystallized and purified using various organic solvents and used as a sample for 880 intensity measurement.
化合物Ｎａ４の確認は核磁気共鳴スペクトル、赤外吸収
スペクトルで行った。Compound Na4 was confirmed by nuclear magnetic resonance spectrum and infrared absorption spectrum.
得られた各種結晶の８８０強度測定を行ったところ、３
９．９ （Ｔｏ Ｉｕｅｎｅ）４８．５ （酢酸エチル
） 、１８．４ （ＥｔＯＨ）、１１．１（ＭｅＯＨ）
、２９．６（Ａｃｅｔｏｎｅ）のＳＨＧ活性を確認す
ることができた。When the 880 intensity measurement of the various crystals obtained was performed, 3
9.9 (To Iuene) 48.5 (Ethyl acetate), 18.4 (EtOH), 11.1 (MeOH)
, 29.6 (Acetone) could be confirmed.
光学活性な（Ｓ）−（−）−２−メチル−１−ブタノー
ルから誘導した３−ブロモ４−（（Ｓ）−（−）−２−
メチル−１−ブトキシ）アセトフ、／７１０．０ｇ （
３５，０８７７ｍＭ）をＥｔＯＨ３００ｍＱに溶解させ
、ＮａＯＨ水溶液（ＮａＯＨ； １．９４ｇ／Ｈ２Ｏ４
０＋ｍ（ｉ’）を加えた。次いで室温下、４−メルカプ
トメトキシベンズアルデヒド５．３３ｇ （３５，０８
７７ｍＭ）を滴下した。室温下４時間撹拌した後、析出
した結晶を減圧下分取し蒸留水で十分に洗浄し、クリー
ム色結晶１３．９ｇ （９５％）を得た。3-Bromo4-((S)-(-)-2- derived from optically active (S)-(-)-2-methyl-1-butanol)
Methyl-1-butoxy)acetoph, /710.0g (
35,0877mM) was dissolved in EtOH300mQ, and NaOH aqueous solution (NaOH; 1.94g/H2O4
0+m(i') was added. Next, at room temperature, 5.33 g of 4-mercaptomethoxybenzaldehyde (35,08
77mM) was added dropwise. After stirring at room temperature for 4 hours, the precipitated crystals were collected under reduced pressure and thoroughly washed with distilled water to obtain 13.9 g (95%) of cream-colored crystals.
十分に減圧加熱乾燥した後、つぎの反応に使用した。After sufficient heating and drying under reduced pressure, it was used in the next reaction.
化合物の確認は核磁気共鳴スペクトル、赤外吸収スペク
トルで行った。The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.
過」し工」」一
過程（ａ）で得られたカルコン化合物１３．０ｇ （３
１，０２８２ｍＭ）を二硫化炭素３００１１ＩＱに懸濁
させ、窒素気流下Ｏ℃に冷却した後臭素７、Ｑを少しづ
つ滴下した。０℃で３時間、室温（２５℃）で１時間撹
拌した後、減圧下結晶を分取しヘキサンで十分に洗浄し
た。得られた結晶はへキサンで再結晶精製し、白色綿状
結晶１７．４ｇ（収率９７％）を得た。13.0 g of chalcone compound obtained in step (a) (3
1,0282mM) was suspended in carbon disulfide 30011IQ, and after cooling to 0°C under a nitrogen stream, bromine 7 and Q were added dropwise little by little. After stirring at 0°C for 3 hours and at room temperature (25°C) for 1 hour, the crystals were collected under reduced pressure and thoroughly washed with hexane. The obtained crystals were purified by recrystallization with hexane to obtain 17.4 g of white flocculent crystals (yield 97%).
得られた結晶は十分に減圧加熱乾燥を行い次の反応に用
いた。The obtained crystals were sufficiently dried by heating under reduced pressure and used for the next reaction.
Ｌ監工こと
過程（ｂ）で得られたジブロム体１７．４ｇ（３０，０
５１８ｍＭ）を事前に用意したＮａＯＭｅ／ＭｅＯＨ（
Ｎａ ； ０． ９ｇ／Ｍ ｅ ＯＨ４００ｄ ９
溶液へ加え、３時間加熱環流を行った。室温に戻した後
濃塩酸１２１Ｑを加え１時間加熱環流を行った。蒸溜水
８０−及びＣＨ２ＣＱ２１００−を加えて３０分間撹拌
した後、ＣＨ２Ｃｔ１２５０ｗ＋ｔ！で４回抽出した。17.4 g (30,0
NaOMe/MeOH (518mM) prepared in advance
Na; 0. 9g/M e OH400d 9
It was added to the solution and heated under reflux for 3 hours. After returning to room temperature, concentrated hydrochloric acid 121Q was added and heated under reflux for 1 hour. After adding distilled water 80- and CH2CQ2100- and stirring for 30 minutes, CH2Ct1250w+t! Extracted 4 times.
無水硫酸マグネシウムで乾燥後、乾燥剤及び溶媒を除去
し黄色粗結晶を得た。これをＴｏｌｕｅｎｅを展開溶媒
としてカラムクロマト精製し、白色結晶１２．８ｇ（収
率９８％）を得た。これを各種有機溶媒で再結晶精製し
、８８０強度測定のサンプルとした。After drying over anhydrous magnesium sulfate, the desiccant and solvent were removed to obtain crude yellow crystals. This was purified by column chromatography using Toluene as a developing solvent to obtain 12.8 g of white crystals (yield 98%). This was recrystallized and purified using various organic solvents to obtain a sample for 880 intensity measurement.
化合物ｍ５の確認は核磁気共鳴スペクトル、赤外吸収ス
ペクトルで行った。Compound m5 was confirmed by nuclear magnetic resonance spectrum and infrared absorption spectrum.
各種溶媒で調製したサンプルの８８０強度測定を行った
ところ、２９．８ （Ｔｏｌｕｅｎｅ）、４５．５（酢
酸エチル）、６．１ （ＥｔＯＨ）、３． ９ （Ｍ
ｅＯＨ） 、３７． ８（Ａｃｅｔｏｎｅ）、８．１
（ヘキサン）のＳＨＧ活性を確認することができた。880 intensity measurements of samples prepared with various solvents showed 29.8 (Toluene), 45.5 (Ethyl acetate), 6.1 (EtOH), 3. 9 (M
eOH), 37. 8 (Acetone), 8.1
The SHG activity of (hexane) could be confirmed.
（発明の効果）
本発明の化合物はケト型とエノール型の平衡関係にある
が、構造上安定なエノール型の含有率が大きく、それゆ
え大きくひろがったπ電子共役型構造になっている。従
って適当な双極子モーメントを有する置換基を付与する
ことで分子内共鳴を誘起させることができるため、大き
な非線形感受率が期待できる。(Effects of the Invention) The compound of the present invention has an equilibrium relationship between the keto type and the enol type, but has a large content of the structurally stable enol type, and therefore has a greatly expanded π-electron conjugated structure. Therefore, by adding a substituent having an appropriate dipole moment, intramolecular resonance can be induced, and a large nonlinear susceptibility can be expected.
また分子内エノール性水酸基を有しているため、これが
分子配向制御基として働きバルク構造を変化させうる。Furthermore, since it has an intramolecular enolic hydroxyl group, this acts as a molecular orientation control group and can change the bulk structure.
即ちＳＨＧ活性に必要な非中心対称性構造を誘起させう
る有効な機能性置換である。That is, it is an effective functional substitution that can induce the non-centrosymmetric structure required for SHG activity.
またＭＮＡ等のＣ−Ｔ型分子に比べて、本発明の化合物
は長波長領域に吸収を有していないため二倍波の吸収に
よる化合物の劣化が小さい。Furthermore, compared to CT type molecules such as MNA, the compound of the present invention does not have absorption in the long wavelength region, so that the compound is less likely to deteriorate due to absorption of the second harmonic.
本発明の化合物は高融点を有し、昇華性も低く、吸水性
も低いため保存安定性に優れており、且つ極めて大きな
非線形感受率を有し、レーザー耐性にも優れた有機非線
形光学材料を提供することができる。従って、半導体レ
ーザー用波長変換素子を初めとする光情報、光通信に有
効である。The compound of the present invention has a high melting point, low sublimation property, and low water absorption, so it has excellent storage stability. It also has extremely high nonlinear susceptibility and excellent laser resistance. can be provided. Therefore, it is effective for optical information and optical communication including wavelength conversion elements for semiconductor lasers.
第１図は本発明の実施例において使用した第二高長波発
生装置を示す外機略図である。
１；ＱスイッチＮｄ ： ＹＡＧレーザ−２： １０８
４ ｎｍレーザー反射ミラー３；シャッター ４；試
料（粉末状）５；集光レンズ ６；赤外カットフィル
ター７；ポリクロメーター
８°マルチチャンネルフォトダイオード９；ＭＣＰＤ駆
動回路FIG. 1 is a schematic diagram of a second high-frequency wave generator used in an embodiment of the present invention. 1; Q switch Nd: YAG laser-2: 108
4 nm laser reflection mirror 3; Shutter 4; Sample (powder) 5; Condenser lens 6; Infrared cut filter 7; Polychromator 8° multi-channel photodiode 9; MCPD drive circuit
Claims (1)
誘導体を含むことを特徴とする非線形光学材料。 ▲数式、化学式、表等があります▼・・・〔１〕 （式中、置換基Ｘ＿１〜Ｘ＿４は、水素またはハロゲン
であり、Ｘ＿５は炭素数１〜１８のアルコキシ基または
メルカプトアルコキシ基である。置換基Ｘ＿６〜Ｘ＿１
＿０は、水素、アミノ基、炭素数１〜１２の置換アミノ
基、環状アミノ基、炭素数１〜１８のアルキル基、炭素
数１〜１８のアルコキシ基、炭素数１〜１８のメルカプ
トアルコキシ基、シアノ基、ハロゲンから選ばれた１種
であり、おたがいに同一でもよく異種でもよいものであ
る。）(1) A nonlinear optical material characterized by containing a 1,3-diketone derivative represented by the following general formula [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[1] (In the formula, substituents X_1 to X_4 are hydrogen or halogen, and X_5 is an alkoxy group or mercaptoalkoxy group having 1 to 18 carbon atoms. Substituents X_6 to X_1
_0 is hydrogen, an amino group, a substituted amino group having 1 to 12 carbon atoms, a cyclic amino group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a mercaptoalkoxy group having 1 to 18 carbon atoms, It is one type selected from a cyano group and a halogen, and they may be the same or different. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34466489A JPH03202818A (en) | 1989-12-28 | 1989-12-28 | Nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34466489A JPH03202818A (en) | 1989-12-28 | 1989-12-28 | Nonlinear optical material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03202818A true JPH03202818A (en) | 1991-09-04 |
Family
ID=18371026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34466489A Pending JPH03202818A (en) | 1989-12-28 | 1989-12-28 | Nonlinear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03202818A (en) |
-
1989
- 1989-12-28 JP JP34466489A patent/JPH03202818A/en active Pending
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