JPH03112950A - Squarylium derivative and production thereof - Google Patents
Squarylium derivative and production thereofInfo
- Publication number
- JPH03112950A JPH03112950A JP24810989A JP24810989A JPH03112950A JP H03112950 A JPH03112950 A JP H03112950A JP 24810989 A JP24810989 A JP 24810989A JP 24810989 A JP24810989 A JP 24810989A JP H03112950 A JPH03112950 A JP H03112950A
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- Japan
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- mathematical
- chemical formulas
- chemical
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 3
- 150000007514 bases Chemical class 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 37
- -1 amino compound Chemical class 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 34
- 239000000463 material Substances 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000002894 organic compounds Chemical class 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- RGBVWCQARBEPPW-UHFFFAOYSA-N cyclobut-3-ene-1,2-dione Chemical group O=C1C=CC1=O RGBVWCQARBEPPW-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XTTIQGSLJBWVIV-UHFFFAOYSA-N 2-methyl-4-nitroaniline Chemical compound CC1=CC([N+]([O-])=O)=CC=C1N XTTIQGSLJBWVIV-UHFFFAOYSA-N 0.000 description 1
- SXOQOOQUBDERIZ-UHFFFAOYSA-N 3,4-dichlorocyclobut-3-ene-1,2-dione Chemical compound ClC1=C(Cl)C(=O)C1=O SXOQOOQUBDERIZ-UHFFFAOYSA-N 0.000 description 1
- DNJNUCYAVRRVMW-UHFFFAOYSA-N 3-chlorocyclobut-3-ene-1,2-dione Chemical class ClC1=CC(=O)C1=O DNJNUCYAVRRVMW-UHFFFAOYSA-N 0.000 description 1
- XJCVRTZCHMZPBD-UHFFFAOYSA-N 3-nitroaniline Chemical compound NC1=CC=CC([N+]([O-])=O)=C1 XJCVRTZCHMZPBD-UHFFFAOYSA-N 0.000 description 1
- 230000005374 Kerr effect Effects 0.000 description 1
- 229910003327 LiNbO3 Inorganic materials 0.000 description 1
- 230000005697 Pockels effect Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCVBBVTZZJFVLA-NSHDSACASA-N [(2s)-1-(4-nitrophenyl)pyrrolidin-2-yl]methanol Chemical compound OC[C@@H]1CCCN1C1=CC=C([N+]([O-])=O)C=C1 HCVBBVTZZJFVLA-NSHDSACASA-N 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- DWKPPFQULDPWHX-VKHMYHEASA-N l-alanyl ester Chemical compound COC(=O)[C@H](C)N DWKPPFQULDPWHX-VKHMYHEASA-N 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NVLSIZITFJRWPY-ONEGZZNKSA-N n,n-dimethyl-4-[(e)-2-(4-nitrophenyl)ethenyl]aniline Chemical compound C1=CC(N(C)C)=CC=C1\C=C\C1=CC=C([N+]([O-])=O)C=C1 NVLSIZITFJRWPY-ONEGZZNKSA-N 0.000 description 1
- TZSQCGFTOHIDIB-UHFFFAOYSA-N n-[2-(dimethylamino)-5-nitrophenyl]acetamide Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=C1NC(C)=O TZSQCGFTOHIDIB-UHFFFAOYSA-N 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000008832 photodamage Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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、非線形光学材料として有用な新規なスクェア
リリウム誘導体及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel square aryllium derivative useful as a nonlinear optical material and a method for producing the same.
従来の技術
光通信や光情報処理の分野では、非線形光学素子が重要
な役割を果たす。非線形光学素子に使用する非線形光学
材料は、周波数の異なる２種の入射光の和の周波数を発
生する光混合、周波数の異なる２種の光となる光パラメ
トリック、また、光媒体の屈折率を変化させるポッケル
ス効果やカー効果、或いは入射光の二次高調波（ＳＨＧ
）又は三次高調波（ＴＨＧ）への変換など、光信号処理
の上で極めて重要な作用を行う物質であるが、従来、こ
の様な非線形光学材料としては、無機系のものと有機系
のものとが見出だされている。BACKGROUND OF THE INVENTION Nonlinear optical elements play an important role in the fields of optical communication and optical information processing. The nonlinear optical materials used in nonlinear optical elements can be used for light mixing that generates a frequency that is the sum of two types of incident light with different frequencies, optical parametric that produces two types of light that have different frequencies, and changing the refractive index of the optical medium. The Pockels effect, the Kerr effect, or the second harmonic of the incident light (SHG)
) or third harmonic (THG), which perform extremely important functions in optical signal processing. Conventionally, such nonlinear optical materials have been classified into inorganic and organic types. It has been discovered that
無機系の非線形光学材料については、ＫＤＰ（ＫＨ２Ｐ
Ｏ４）およびニオブ酸リチウム（ＬｉＮｂＯ３）などの
無機化合物の結晶が知られているが、要求を十分に満足
するに足るものではなかった。Regarding inorganic nonlinear optical materials, KDP (KH2P
Although crystals of inorganic compounds such as O4) and lithium niobate (LiNbO3) are known, they have not been sufficient to fully satisfy the requirements.
一方、有機系の非線形光学材料については、近年、オプ
トエレクトロニクス分野における新光学素子用材料とし
て注目され、年々研究が盛んになってきている。特に、
π電子共役系を有する有機化合物は、その分子単体の性
能の大きさと高速の応答性から、材料探索のための研究
が数多くなされている。On the other hand, organic nonlinear optical materials have recently attracted attention as materials for new optical elements in the field of optoelectronics, and research is increasing year by year. especially,
Organic compounds with a π-electron conjugated system have been extensively studied for material exploration due to their high performance as a single molecule and high-speed response.
一般に、有機非線形光学材料の結晶は、無機非線形光学
材料の結晶に比べて、ＳＨＧの係数が１０〜１００倍大
きく、光応答速度も１０００倍程度速く、また、光損傷
に対する閾値も大きいことが知られている。In general, it is known that crystals of organic nonlinear optical materials have a SHG coefficient 10 to 100 times larger, a photoresponse speed of about 1000 times faster, and a higher threshold for photodamage than crystals of inorganic nonlinear optical materials. It is being
従来知られている有機非線形光学材料としては、２−メ
チル−４−ニトロアニリン、ｍ−ニトロアニリン、Ｎ−
（４−ニトロフェニル）−Ｌ−プロリノール、２−アセ
チルアミノ−４−ニトロ−Ｎ、Ｎ−ジメチルアニリン、
４−ジメチルアミノ−４′−二トロスチルベン、４′−
ジメチルアミノ−Ｎ−メチル−４−スチルバゾリウムメ
チルスルフェート及び４′−メチルベンジリデン−４−
ニトロアニリンなどの有機化合物があげられる。Conventionally known organic nonlinear optical materials include 2-methyl-4-nitroaniline, m-nitroaniline, and N-
(4-nitrophenyl)-L-prolinol, 2-acetylamino-4-nitro-N, N-dimethylaniline,
4-dimethylamino-4'-nitrostilbene, 4'-
Dimethylamino-N-methyl-4-stilbazolium methyl sulfate and 4'-methylbenzylidene-4-
Examples include organic compounds such as nitroaniline.
これらπ電子共役系を有する有機化合物の非線形性は、
電磁波としてのレーザー光と有機化合物のπ電子との相
互作用に起因するものであって、この相互作用は、π電
子共役系に電子吸引性、電子供与性の置換基を導入する
ことにより、更に大きくすることができる。The nonlinearity of organic compounds with these π-electron conjugated systems is
This is caused by the interaction between laser light as an electromagnetic wave and π electrons of organic compounds, and this interaction can be further enhanced by introducing electron-withdrawing or electron-donating substituents into the π-electron conjugated system. Can be made larger.
ところが、この様な有機化合物においては、股に双極子
モーメントが大きくなり、結晶時の双極子−双極子相互
作用が強くなって、２分子の双極子が互いに打ち消し合
う構造である中心対称性の結晶を形成し易くなる。応用
面で重要な２次の非線形光学効果については、この様な
中心対称性結晶では発現しないという問題がある。結晶
状態で非線形性を発現させる上で問題となる中心対称性
を崩すために、水素結合能を有する置換基や不斉炭素を
有する光学活性な置換基を、π電子共役系を有する有機
化合物に分子設計時に導入するという工夫がなされてい
る。However, in such organic compounds, the dipole moment increases in the crotch, and the dipole-dipole interaction during crystallization becomes stronger, resulting in a centrosymmetric structure in which the dipoles of two molecules cancel each other out. It becomes easier to form crystals. There is a problem in that the second-order nonlinear optical effect, which is important in practical applications, does not occur in such centrosymmetric crystals. In order to break the central symmetry, which is a problem in developing nonlinearity in the crystalline state, substituents with hydrogen bonding ability and optically active substituents with asymmetric carbon atoms are added to organic compounds with π-electron conjugated systems. An effort has been made to introduce it during molecular design.
発明が解決しようとする課題
一般に非線形光学素子用材料として必要とされる特性は
、光非線形性の大きさ、光の透過性、耐レーザ損傷強度
、結晶性、位相整合性、加工性、機械的強度、吸湿性等
があげられる。Problems to be Solved by the Invention In general, the properties required for materials for nonlinear optical elements include the magnitude of optical nonlinearity, optical transparency, laser damage resistance, crystallinity, phase matching, processability, and mechanical properties. Examples include strength and hygroscopicity.
従来から知られている有機非線形光学素子用材料の中か
ら、以上のような実用上必要とされる諸性性を満足する
ものを選択することは極めて困難であった。It has been extremely difficult to select from conventionally known materials for organic nonlinear optical elements that satisfy the various properties required for practical use as described above.
本発明は、従来の技術における上記のような実状に鑑み
てなされたものである。The present invention has been made in view of the above-mentioned actual situation in the prior art.
したがって、本発明の目的は、従来より知られている非
線形光学素子用材料における問題点を改善し、大きな非
線形光学効果を有し、保存安定性及び加工性の改良され
た実用的な有機非線形光学材料を提供することにある。Therefore, an object of the present invention is to improve the problems in the conventionally known materials for nonlinear optical elements, to provide a practical organic nonlinear optical device that has a large nonlinear optical effect, and has improved storage stability and processability. The purpose is to provide materials.
課題を解決するための手段
本発明者は、分子の双極子モーメントが大きく、結晶時
に中心対称性を形成しやすい化合物系であっても、分子
に適切な置換基を導入することにより、特に２次の非線
形光学効果の大きい有機非線形光学材料が得られること
を見出し、本発明を完成した。Means for Solving the Problems The present inventor has proposed that even if the molecular dipole moment is large and the compound system is likely to form central symmetry during crystallization, by introducing an appropriate substituent into the molecule, especially 2 The present invention was completed by discovering that an organic nonlinear optical material with the following large nonlinear optical effect can be obtained.
本発明の上記目的は、下記一般式（Ｉ）で示される新規
なスクェアリリウム誘導体によって達成される。The above objects of the present invention are achieved by a novel square lylium derivative represented by the following general formula (I).
ＨＲ
（式中、Ｘは水素原子、メチル基、エチル基又はメトキ
シ基を表わし、Ｒは、
−ＣＨ，ＣＨ２０Ｈ。HR (wherein, X represents a hydrogen atom, a methyl group, an ethyl group, or a methoxy group, and R is -CH, CH20H.
ＣＨ３ＣＨＣＨｉ、 “オ ＣＨ３ＣＨＣＨ２０Ｈ。CH3CHCHi, “O CH3CHCH20H.
Ｃ２Ｈ５ＣＨＣＨ２０Ｈ。C2H5CHCH20H.
量 Ｃ６Ｈ５ＣＨ２ＣＨＣＨ２０Ｈ。amount C6H5CH2CHCH20H.
ＣＨ３ＣＨＣＯ２ＣＨＩ、 ＣＨ３ＣＨＣＯ２ＣＨ２Ｃ６Ｈ！、 ＣＨ３ＣＨＣＯ２−ｔ−Ｃ４Ｈ９、 ＣＨ３０２ＣＣＨ２ＣＨＣＯ２ ＣＨ。CH3CHCO2CHI, CH3CHCO2CH2C6H! , CH3CHCO2-t-C4H9, CH302CCH2CHCO2 CH.
２ Ｈ５ Ｈ Ｃ”ＨＣＨ２ ／ ＣＨ。2 H5 H C”HCH2 / CH.
／ ＣＨ。/ CH.
を表わす。なお、Ｃは不斉炭素原子を意味する。）
本発明の上記一般式（Ｉ）で示されるスクェアリリウム
誘導体中に含まれるシクロブテンジオン環は、後記実施
例中で示す極大吸収波長からも分かるように、ニトロ基
並の強い電子吸引性を６すると共に、長いπ電子共役系
を持つ。そのため、分子全体が電子的に大きく分極した
構造を取り品くなり、高い非線形性発現の原因になって
いる。represents. In addition, C means an asymmetric carbon atom. ) The cyclobutenedione ring contained in the squareylium derivative represented by the above general formula (I) of the present invention has a strong electron-withdrawing property comparable to that of a nitro group, as can be seen from the maximum absorption wavelength shown in the examples below. 6 and has a long π-electron conjugated system. As a result, the entire molecule has a highly electronically polarized structure, which is a cause of high nonlinearity.
また、上記一般式（１）で示されるスクェアリリウム誘
導体においては、不斉炭素原子を有する置換基が導入さ
れている場合には、分子自体の双極子モーメントが大き
い場合であっても、バルク構造における分子の配向を制
御し、中心対称性を崩すことにより、大きな光非線形性
を発現させることになる。In addition, in the squarelylium derivative represented by the above general formula (1), when a substituent having an asymmetric carbon atom is introduced, even if the dipole moment of the molecule itself is large, the bulk structure By controlling the orientation of molecules in the center and breaking the central symmetry, large optical nonlinearity can be developed.
本発明の上記一般式（１）で示されるスクェアリリウム
誘導体は、次に示す反応式によって容易に、かつ収率よ
く合成することができる。The squarylium derivative represented by the above general formula (1) of the present invention can be easily synthesized in good yield according to the reaction formula shown below.
（ＩＩ）
（ｍ）
ＨＲ
（１）
（式中、Ｙは塩素原子、臭素原子、メトキシ基又はエト
キシ基を表わし、Ｘ及びＲはそれぞれ上記した定義と同
じものを意味する）
すなわち、一般式（ｎ）で示されるスクェアリリウム誘
導体をアセトン、テトラヒドロフラン、メタノール、エ
タノール等の溶媒に懸濁或いは溶解させ、次いで、得ら
れた懸濁液又は溶液中に、」二記スクェアリリウム誘導
体に対して当量以上の一般式（ＩＩＩ）で示されるアミ
ノ化合物を、撹拌しながら徐々に加えて反応させる。反
応は、通常、速やかに進行するが、必要に応じて加熱す
ることも可能である。反応の進行に伴い、生成物が析出
してくる場合は、濾過し、また、生成物が析出してこな
い場合は、濃縮するか、或いは適当な貧溶媒を加えて析
出させればよい。得られた結晶は、必要によりアルコー
ル、アセトン等の溶媒により再結晶させ、或いは昇華に
より精製する。(II) (m) HR (1) (In the formula, Y represents a chlorine atom, a bromine atom, a methoxy group or an ethoxy group, and X and R each have the same meaning as defined above.) That is, the general formula ( The squareylium derivative represented by n) is suspended or dissolved in a solvent such as acetone, tetrahydrofuran, methanol, ethanol, etc., and then, in the resulting suspension or solution, an amount equivalent to or more than the squareylium derivative described in 2. While stirring, an amino compound represented by the general formula (III) is gradually added and reacted. The reaction usually proceeds rapidly, but it is possible to heat the reaction if necessary. If the product precipitates as the reaction progresses, it may be filtered, and if the product does not precipitate, it may be concentrated or may be precipitated by adding an appropriate poor solvent. The obtained crystals are recrystallized from a solvent such as alcohol or acetone, or purified by sublimation, if necessary.
上記一般式（ｍ）で示されるアミノ化合物の代わりに、
その酸付加塩、例えば、塩酸塩、臭素酸塩、ｐ−トルエ
ンスルホン酸塩等を原料として使用し、トリエチルアミ
ン、Ｎ−メチルモルホリン等の塩基性化合物の共存下に
、一般式（ＩＩ）で示されるスクェアリリウム誘導体と
上記した方法と同様にして反応させることもできる。Instead of the amino compound represented by the above general formula (m),
Using the acid addition salt thereof, such as hydrochloride, bromate, p-toluenesulfonate, etc., as a raw material, and in the coexistence of a basic compound such as triethylamine, N-methylmorpholine, etc., it is expressed by the general formula (II). The reaction can also be carried out in the same manner as the above-mentioned method.
なお、上記一般式（■）で示されるスクェアリリウム誘
導体は、例えばジメチルアニリン化合物とジクロロシク
ロブテンジオンを、塩化アルミニウムの存在下フリーデ
ルクラフッ溶剤（例えば２硫化炭素、ニトロベンゼン、
塩化メチレン等）中で混合、撹拌することによって、ク
ロロシクロブテンジオン誘導体を得る方法、或いは、ジ
アルコキシシクロブテンジオンを、トリアルキルオキソ
ニウム塩及びハロゲン化溶剤と共に、ジメチルアニリン
化合物と反応させてアルコキシシクロブテンジオン誘導
体を得る方法、等によって製造することができる。The squarylium derivative represented by the above general formula (■) can be obtained by, for example, dimethylaniline compound and dichlorocyclobutenedione in a Friedelkraff solvent (e.g. carbon disulfide, nitrobenzene, etc.) in the presence of aluminum chloride.
(e.g. methylene chloride) to obtain a chlorocyclobutenedione derivative, or by reacting dialkoxycyclobutenedione with a dimethylaniline compound together with a trialkyloxonium salt and a halogenated solvent to form an alkoxycyclobutenedione derivative. It can be produced by a method of obtaining a cyclobutenedione derivative, etc.
実施例 以下、本発明を実施例によって説明する。Example Hereinafter, the present invention will be explained by examples.
実施例１
４−（４’−ジメチルアミノフェニル）−３−（２’−
ヒドロキシプロピルアミノ）−シクロブテン−１，２−
ジオンの合成
下記（Ｒ造式（ｌｌ−１）で示される化合物２ｇ（８，
４１０１）のアセトン溶液１００ ｍｇに、Ｉ
Ｓ−（＋）−１−アミノ−２−プロパツール２Ｋを添加
し、約２時間加熱攪拌を続けた。反応液中に黄色結晶が
析出した。反応液を静置した後、黄色結晶を捕集するこ
とにより、下記構造式（１−１）で示される４−（４’
−ジメチルアミノフェニル）−３−（２’−ヒドロキシ
プロピルアミノ）−シクロブテン−１，２−ジオン２．
１ ｇ （７，７ｍｍｏｌ）を黄色の結晶として得た。Example 1 4-(4'-dimethylaminophenyl)-3-(2'-
Hydroxypropylamino)-cyclobutene-1,2-
Synthesis of dione 2g of compound (8,
IS-(+)-1-amino-2-propatol 2K was added to 100 mg of an acetone solution of 4101), and the mixture was heated and stirred for about 2 hours. Yellow crystals were precipitated in the reaction solution. After the reaction solution was allowed to stand still, yellow crystals were collected to obtain 4-(4') represented by the following structural formula (1-1).
-dimethylaminophenyl)-3-(2'-hydroxypropylamino)-cyclobutene-1,2-dione2.
1 g (7.7 mmol) was obtained as yellow crystals.
収率９２％。Yield 92%.
ｗ点：２４５℃
極大吸収波長λｍａｘ
： ４００ｎｍ
（Ｃ１０ＣＩ□
［１す
元素分析
Ｓ１算値
６５．６７
６．６１
１０．２１
ａＰＩ定値
８５．５６
２
ｔｏ、ｔｅ
Ｈ
実施例２
４−（４’−ジメチルアミノフェニル）−３−（２’ヒ
ドロキ
シエチルアミノ）−シクロブテン−■、２−ジオンの合
成
下記構造式
％式％）
で示される化合物０．５
（２，０ｍＩＩｏｌ）
に
エタノールアミン２１−を加え、
約２時間加熱し
ながら攪拌した。反応終了後、約６０ ｍＭの水中に注
ぎ、反応生成物を黄色結晶として析出させた。W point: 245°C Maximum absorption wavelength λmax: 400 nm (C10CI□ [1 elemental analysis S1 calculated value 65.67 6.61 10.21 aPI constant value 85.56 2 to, te H Example 2 4-(4'- Synthesis of dimethylaminophenyl)-3-(2'hydroxyethylamino)-cyclobutene-■,2-dione Ethanolamine 21- was added to 0.5 (2,0 mIIol) of a compound represented by the following structural formula (% formula %). , and stirred while heating for about 2 hours. After the reaction was completed, it was poured into approximately 60 mM water to precipitate the reaction product as yellow crystals.
黄色結晶を捕集することにより、下記構造式（Ｉ−２）
で示される４−（４”−ジメチルアミノフェニル）−３
−（２’−ヒドロキシエチルアミノ）−シクロブテン−
１，２−ジオン０．３２ｓ−（１，２ｍｍｏｌ）を黄色
の結晶として得た。収率Ｂ０９６゜
融点：２４０℃
極大吸収波長λ１ＩｌａＸ ： ４０１ｎｍ （ＣＩ
ＩＣＩ３中）元素分析
ＣＨＮ
計算値 Ｂ４．８１ Ｂ、２０ １０．７８
測定値 ６４．５８ Ｂ、１２ １０．５８
実施例３
４−（４’−ジメチルアミノフェニル）−４−（１’−
メトキシカルボニルエチルアミノ）−シクロブテン−１
，２−ジオンの合成
Ｌ−アラニンメチルエステルの塩酸塩０．７ｇ（５ｇａ
ｏｌ）とトリエチルアミン０．Ｅｌ ｇ （５，８ｍｍ
ｏｌ）を含むアセトン溶液２０−に、上記構造式（■−
１）で示される化合物１−Ｏｇ （４，２ｍｍ＋ｏｌ）
のアセトン溶液２０ ｔｉｌｌを徐々に加え、反応させ
た。約２時間反応させた後、水を添加した。析出した黄
色の微結晶を捕集することにより、下記構造式（１−３
）で示される４−（４’−ジメチルアミノフェニル）−
３−（１’−メトキシカルボニルエチルアミノ）−シク
ロブテン−１，２−ジオン０．８６ｇ （２，２ｏ＋ｍ
ｏｌ）を得た。収率５２％。By collecting the yellow crystals, the following structural formula (I-2) is obtained.
4-(4”-dimethylaminophenyl)-3 represented by
-(2'-hydroxyethylamino)-cyclobutene-
0.32s-(1,2 mmol) of 1,2-dione was obtained as yellow crystals. Yield B096° Melting point: 240°C Maximum absorption wavelength λ1IlaX: 401 nm (CI
ICI3) Elemental analysis CHN Calculated value B4.81 B, 20 10.78
Measured value 64.58 B, 12 10.58
Example 3 4-(4'-dimethylaminophenyl)-4-(1'-
methoxycarbonylethylamino)-cyclobutene-1
, 2-Dione Hydrochloride of L-alanine methyl ester 0.7g (5ga
ol) and triethylamine 0. El g (5,8mm
The above structural formula (■-
1) Compound 1-Og (4,2mm+ol)
20 till of an acetone solution was gradually added to react. After reacting for about 2 hours, water was added. By collecting the precipitated yellow microcrystals, the following structural formula (1-3
) 4-(4'-dimethylaminophenyl)-
3-(1'-methoxycarbonylethylamino)-cyclobutene-1,2-dione 0.86g (2,2o+m
ol) was obtained. Yield 52%.
融点：２１７℃
極大吸収波長λｗａｘ ： ４０１ｎＩＩｌ（Ｃｔｌ、
ＣＩ２中）元素分析
ＨＮ
計算値 ８３．５８ ８．００ ９．２７測
定値 ６３．３２ ５．８２ ９．３５ＣＨ
３−ＣＨ−Ｃ０２ＣＨｉ
ＮＨ
実施例４〜３３
原料物質として、第１表の一般式（ｎ）の欄に記載のス
クェアリリウム誘導体と一般式（ｍ）の欄に記載のアミ
ノ化合物とを使用する以外は、実施例１に記載の場合と
同様にして第１表の一般式（Ｉ）の欄に記載の目的生成
物を合成した。Melting point: 217°C Maximum absorption wavelength λwax: 401nIIl (Ctl,
CI2) Elemental analysis HN Calculated value 83.58 8.00 9.27 Measured value 63.32 5.82 9.35CH
3-CH-C02CHi NH Examples 4 to 33 Other than using the square lium derivative described in the general formula (n) column of Table 1 and the amino compound described in the general formula (m) column as raw materials synthesized the target product described in the column of general formula (I) in Table 1 in the same manner as described in Example 1.
得られた生成物について、元素分析値、極大吸収波長λ
ｎ＋ａｘ及び融点をＪｌｌｌ定した。その結果を第２表
に示す。Regarding the obtained product, elemental analysis value, maximum absorption wavelength λ
n+ax and melting point were determined. The results are shown in Table 2.
第２表
第２表（続き）
応用例
実施例１に記載の上記構造式（１−１）で示される化合
物を、ガラスセル中に充填した粉末のサンプルに、Ｎｄ
： ＹＡＧレーザ（波長１．０８４虜、出力１８０ｓ
Ｊ／パルス）を照射すると、ＳＨＧに起因する５３２ｎ
ｌｌの緑色散乱光が発生した。その強度をｎ１定したと
ころ、尿素の粉末を同様の条件で測定した値の約７０倍
であった。Table 2 Table 2 (Continued) Application Examples The compound represented by the above structural formula (1-1) described in Example 1 was added to a powder sample filled in a glass cell.
: YAG laser (wavelength 1.084mm, output 180s
J/pulse), 532n caused by SHG
11 green scattered light was generated. When the intensity was determined by n1, it was about 70 times the value measured for urea powder under similar conditions.
発明の効果
本発明の上記一般式で示されるスクェアリリウム誘導体
は、新規な化合物であって、高い非線形性を示し、また
、耐熱性、耐光性、保存安定性及び加工性に優れた物質
であるので、非線形光学素子、例えば、光波長変換素子
、光シヤツター、高速光スイッチング素子、光論理ゲー
ト、光トランジスター等の作製に使用することができる
。Effects of the Invention The squarylium derivative represented by the above general formula of the present invention is a novel compound, exhibits high nonlinearity, and is a substance with excellent heat resistance, light resistance, storage stability, and processability. Therefore, it can be used for producing nonlinear optical elements such as optical wavelength conversion elements, optical shutters, high-speed optical switching elements, optical logic gates, optical transistors, etc.
Claims (3)
誘導体。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｘは、水素原子、メチル基、エチル基又はメト
キシ基を表わし、Ｒは、 −ＣＨ＿２ＣＨ＿２ＯＨ、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 又は▲数式、化学式、表等があります▼ を表わす。なお、Ｃ＾＊は不斉炭素原子を意味する。）(1) A squarylium derivative represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents a hydrogen atom, methyl group, ethyl group, or methoxy group, and R is -CH_2CH_2OH, ▲There are mathematical formulas, chemical formulas, tables, etc.) , ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼.C^* means an asymmetric carbon atom.)
シ基を表わし、Ｙは塩素原子、臭素原子、メトキシ基又
はエトキシ基を表わす） で示されるスクエアリリウム誘導体と、下記一般式（I
II） ＮＨ＿２Ｒ（III） （式中、Ｒは、−ＣＨ＿２ＣＨ＿２ＯＨ、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼ 又は▲数式、化学式、表等があります▼ を表わす。なお、Ｃ＾＊は不斉炭素原子を意味する。） で示されるアミノ化合物を反応させることを特徴とする
特許請求の範囲第１項に記載のスクエアリリウム誘導体
の製造方法。(2) General formula (II) below ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, X represents a hydrogen atom, methyl group, ethyl group, or methoxy group, Y represents a chlorine atom, a bromine atom, methoxy group or ethoxy group) and the following general formula (I
II) NH_2R(III) (In the formula, R is -CH_2CH_2OH, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas , chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ mathematical formulas, chemical formulas, tables, etc. The method for producing a squarylium derivative according to claim 1, characterized by reacting an amino compound represented by ▼ (in which C^* means an asymmetric carbon atom).
導体と、前記一般式（III）で示されるアミノ化合物の
酸付加塩を、塩基性化合物の存在下で反応させることを
特徴とする特許請求の範囲第１項に記載のスクエアリリ
ウム誘導体の製造方法。(3) A patent claim characterized in that the squarylium derivative represented by the general formula (II) and the acid addition salt of the amino compound represented by the general formula (III) are reacted in the presence of a basic compound. A method for producing a squarylium derivative according to item 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24810989A JP2762610B2 (en) | 1989-09-26 | 1989-09-26 | Squarylium derivative and method for producing the same |
| US07/586,980 US5106997A (en) | 1989-09-26 | 1990-09-24 | Squarylium derivatives and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24810989A JP2762610B2 (en) | 1989-09-26 | 1989-09-26 | Squarylium derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03112950A true JPH03112950A (en) | 1991-05-14 |
| JP2762610B2 JP2762610B2 (en) | 1998-06-04 |
Family
ID=17173365
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24810989A Expired - Fee Related JP2762610B2 (en) | 1989-09-26 | 1989-09-26 | Squarylium derivative and method for producing the same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210302A (en) * | 1990-11-29 | 1993-05-11 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative and process for preparing the same |
| JPH07309819A (en) * | 1994-05-20 | 1995-11-28 | Fuji Xerox Co Ltd | Cyclobutene dione derivative, production thereof and nonlinear optical element using the same |
| EP0761643A2 (en) | 1995-09-05 | 1997-03-12 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative, manufacturing method thereof and non-linear optical device containing the same |
| US5616802A (en) * | 1994-10-19 | 1997-04-01 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative, process for preparing the same, and nonlinear optical element |
| US5659085A (en) * | 1994-05-20 | 1997-08-19 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative, process for preparing the same, and nonlinear optical element |
| KR100752036B1 (en) * | 2001-07-27 | 2007-08-28 | 주식회사유한양행 | 4-Amino-3-cyclobutene-1,2-dione derivatives and processes for the preparation thereof |
-
1989
- 1989-09-26 JP JP24810989A patent/JP2762610B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210302A (en) * | 1990-11-29 | 1993-05-11 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative and process for preparing the same |
| JPH07309819A (en) * | 1994-05-20 | 1995-11-28 | Fuji Xerox Co Ltd | Cyclobutene dione derivative, production thereof and nonlinear optical element using the same |
| US5659085A (en) * | 1994-05-20 | 1997-08-19 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative, process for preparing the same, and nonlinear optical element |
| US5811552A (en) * | 1994-05-20 | 1998-09-22 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative, process for preparing the same, and nonlinear optical element |
| US5872256A (en) * | 1994-05-20 | 1999-02-16 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative, process for preparing the same, and nonlinear optical element |
| US5616802A (en) * | 1994-10-19 | 1997-04-01 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative, process for preparing the same, and nonlinear optical element |
| EP0761643A2 (en) | 1995-09-05 | 1997-03-12 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative, manufacturing method thereof and non-linear optical device containing the same |
| EP0761643A3 (en) * | 1995-09-05 | 1997-07-30 | Fuji Xerox Co Ltd | Cyclobutenedione derivative, manufacturing method thereof and non-linear optical device containing the same |
| US5726317A (en) * | 1995-09-05 | 1998-03-10 | Fuji Xerox Co., Ltd. | Cyclobutenedione compounds |
| US5948915A (en) * | 1995-09-05 | 1999-09-07 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative, manufacturing method thereof and non-linear optical device containing the same |
| US6118004A (en) * | 1995-09-05 | 2000-09-12 | Fuji Xerox Co., Ltd. | Cyclobutenedione derivative, manufacturing method thereof and non-linear optical device containing the same |
| KR100752036B1 (en) * | 2001-07-27 | 2007-08-28 | 주식회사유한양행 | 4-Amino-3-cyclobutene-1,2-dione derivatives and processes for the preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2762610B2 (en) | 1998-06-04 |
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