JPS62255460A - Diphenyldiacetylene derivative - Google Patents
Diphenyldiacetylene derivativeInfo
- Publication number
- JPS62255460A JPS62255460A JP9595686A JP9595686A JPS62255460A JP S62255460 A JPS62255460 A JP S62255460A JP 9595686 A JP9595686 A JP 9595686A JP 9595686 A JP9595686 A JP 9595686A JP S62255460 A JPS62255460 A JP S62255460A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- diacetylene
- dissolved
- acid
- 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
- HMQFJYLWNWIYKQ-UHFFFAOYSA-N 1,4-diphenylbutadiyne Chemical group C1=CC=CC=C1C#CC#CC1=CC=CC=C1 HMQFJYLWNWIYKQ-UHFFFAOYSA-N 0.000 title claims description 17
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 239000002253 acid Substances 0.000 abstract description 15
- 230000003287 optical effect Effects 0.000 abstract description 14
- 239000007790 solid phase Substances 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 13
- -1 diacetylene compound Chemical class 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 6
- LRMWMXRDZNLVIO-UHFFFAOYSA-N 1-(2-bromoethynyl)-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C#CBr LRMWMXRDZNLVIO-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- VMXAIJCDNKFKPO-UHFFFAOYSA-N n-ethynylaniline Chemical compound C#CNC1=CC=CC=C1 VMXAIJCDNKFKPO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 239000013078 crystal Substances 0.000 description 19
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 17
- 230000001186 cumulative effect Effects 0.000 description 17
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- ALQPJHSFIXARGX-UHFFFAOYSA-N 2-ethynylaniline Chemical compound NC1=CC=CC=C1C#C ALQPJHSFIXARGX-UHFFFAOYSA-N 0.000 description 2
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical compound NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 2
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical compound NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- HBUSBKFSYRSPBT-UHFFFAOYSA-N 1-(2-bromoethynyl)-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(C#CBr)=C1 HBUSBKFSYRSPBT-UHFFFAOYSA-N 0.000 description 1
- OBUPEYCFDRLOFR-UHFFFAOYSA-N 1-(2-bromoethynyl)-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C#CBr)C=C1 OBUPEYCFDRLOFR-UHFFFAOYSA-N 0.000 description 1
- ANSWQXDFGSOUBK-UHFFFAOYSA-N 2-buta-1,3-diynylaniline Chemical compound NC1=CC=CC=C1C#CC#C ANSWQXDFGSOUBK-UHFFFAOYSA-N 0.000 description 1
- FNSQLRFCKJEMPN-UHFFFAOYSA-N 3-[4-(3-nitrophenyl)buta-1,3-diynyl]aniline Chemical compound NC1=CC=CC(C#CC#CC=2C=C(C=CC=2)[N+]([O-])=O)=C1 FNSQLRFCKJEMPN-UHFFFAOYSA-N 0.000 description 1
- JPMLPKFDMDSLJT-UHFFFAOYSA-N 9-chloro-9-oxononanoic acid Chemical compound OC(=O)CCCCCCCC(Cl)=O JPMLPKFDMDSLJT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ジフェニルジアセチレン誘導体、詳しくは、
固体重合性を有し、且つ、累積膜化ができ、しかも、構
造的に非対称型であって置換基がンアセナレン三重合と
共役するジフェニルジアセチレン誘導体に関するもので
ある。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to diphenyl diacetylene derivatives, specifically,
The present invention relates to a diphenyl diacetylene derivative that has solid polymerizability, can be formed into a cumulative film, is structurally asymmetric, and has a substituent conjugated with ancenalene tripolymerization.
本発明に係るジフェニルジアセチレン誘導体は、固相重
合性を有することにより、非線形光学材料、ノ、4光材
料及び尚分子半導体結晶として用いられる。The diphenyl diacetylene derivative according to the present invention has solid phase polymerizability and can be used as a nonlinear optical material, a four-optical material, and a molecular semiconductor crystal.
近年、非線形光学材料、感光材料及び商分子半4体結晶
等を形成する為の単量体であるジアセチレン類の研究が
盛んに行われている。In recent years, research has been actively conducted on diacetylenes, which are monomers for forming nonlinear optical materials, photosensitive materials, semi-tetratram crystals, and the like.
非線形光学材料、感光材料及び商分子半逅体結晶等を形
成する為には、ジアセチレン類のji屋体が固相重合性
を有することが必要であり、分子が配向した商性能素子
を得る為には、累積膜化ができることが重要である。ま
た、非線形光学材料として非線形光学効果の向上の為に
は、周知の通り、単量体が構造的に非対称型であり、し
かも、玉鎖−側鎖が共役していることによって電子的効
果の大きいことが必要である。In order to form nonlinear optical materials, photosensitive materials, commercial molecular semi-animal crystals, etc., it is necessary that the diacetylene compound has solid phase polymerizability, and it is necessary to obtain commercial performance devices with oriented molecules. Therefore, it is important to be able to form a cumulative film. In addition, in order to improve the nonlinear optical effect as a nonlinear optical material, as is well known, the monomer is structurally asymmetric, and the ball chain and side chain are conjugated, so that the electronic effect can be improved. It needs to be big.
従来、一般式
%式%
で表されるジアセチレン類のうちいくつかの化合物が同
相重合性を有することが知られている。It has been known that some compounds among diacetylenes represented by the general formula % have homopolymerizability.
固相重合性を有し、且つ、累積膜化ができ、しかも構造
的に非対称型であって置換基がジアセチレン三重合結合
と共役するジアセチレン類は現在量も要求されていると
ころであるが、friI述した既知の固相重合性を有す
るジフェニルジアセチレン類は、一般式fi+で、R,
=Rbの様にジアセチレン部分の両端に同一の置換基を
有し、対称分子を形成しているために、偶数次の非線形
光学効果かまった(期待できない。There is currently a demand for diacetylenes that have solid phase polymerizability, can be formed into cumulative films, are structurally asymmetric, and have substituents conjugated with diacetylene triple bonds. , friI The diphenyl diacetylenes having known solid phase polymerizability described above have the general formula fi+, R,
Since the diacetylene moiety has the same substituent at both ends like =Rb, forming a symmetrical molecule, an even-order nonlinear optical effect occurs (unexpected).
しかも、置a、Mとジアセチレン部分との共役が切れた
構造のものが大半を占めている。この様に玉鎖−側鎮の
共役が切れた重合物では置換基R1、R2の電子的効果
がほとんどなくなってしまい、いずれの置換基であって
も類似の性質を呈する傾向がある。Moreover, most of them have a structure in which the conjugation between a and M and the diacetylene moiety is broken. In a polymer in which the chain-side chain conjugation is broken in this manner, the electronic effects of the substituents R1 and R2 are almost eliminated, and any substituents tend to exhibit similar properties.
これに対し、一般式(1)で表されるジアセチレン化合
物で置換5R,及びRhが芳香族であるような化合物は
、同式中の三重結合と共役する為、形成される結晶性高
分子は優れた電子的性質が期待されるが、この様なジア
セチレン類は大半が同相重合性をzくさないものである
。On the other hand, in the diacetylene compound represented by the general formula (1) in which the substituted 5R and Rh are aromatic, the crystalline polymer formed is conjugated with the triple bond in the formula (1). are expected to have excellent electronic properties, but most of these diacetylenes do not impair homopolymerizability.
ジフェニルジアセチレンの2つのフェニル基の各オルト
又はメタ位にアセチルアミノ基を存するものや、同フェ
ニル基の、2. 4−;2. 5−;3、(j−の位置
にトリフルオロメチル基ををするもの等、固相重合性を
有するものも若干あるが、これらは、累Mi膜化が出来
ず、また、各々の分子が対称構造をとっているため、偶
数次の非線形光学効果は発現しない。diphenyl diacetylene with an acetylamino group at each ortho or meta position of the two phenyl groups; 4-;2. 5-;3, (There are some products that have solid phase polymerizability, such as those with a trifluoromethyl group at the j-position, but these cannot be formed into a cumulative Mi film, and each molecule is Since it has a symmetrical structure, even-order nonlinear optical effects do not occur.
上述した通り、固相重合性を有し、且つ、累積膜化がで
き、しかも、構造的に非対称型であって置換基がジアセ
チレン三重結合と共役する芳香族であることによって電
子的効果が大きいジアセチレン化合物体は、現在、最も
要求されているところである。As mentioned above, it has solid phase polymerizability and can be formed into a cumulative film, and is structurally asymmetric and has an aromatic substituent conjugated with a diacetylene triple bond, so it has an electronic effect. Large diacetylenic compounds are currently in greatest demand.
本発明者は、固相重合性を有し、且つ、累積膜化ができ
、しかも、構造的に非対称型であって置換基がジアセチ
レン三重結合と共役する芳香族であることによって電子
的効果が大きいジアセチレン類tt体を得るべく種々検
討を行った結果、本発明に到達したのである。The present inventor has discovered that it has solid phase polymerizability and can be formed into a cumulative film, and that it is structurally asymmetric and the substituent is an aromatic group conjugated with a diacetylene triple bond, thereby producing an electronic effect. The present invention was achieved as a result of various studies aimed at obtaining a tt-form of diacetylenes with a large .
即ち、本発明は一般式
で表され、R1、R2のうちいずれか1つがニトロ基、
残りが水素であって、R:〜P−のうちいずれか1つが
−NHCO−4CHz)T−COtH(但しn m 6
〜18)、残りが水素であるジフェニルジアセチレン誘
導体である。That is, the present invention is represented by a general formula, in which either one of R1 and R2 is a nitro group,
The remainder is hydrogen, and any one of R: ~P- is -NHCO-4CHz)T-COtH (however, nm 6
~18) are diphenyl diacetylene derivatives in which the remainder is hydrogen.
先ず、本発明において最も重要な点は、本発明に係るジ
フェニルジアセチレン誘導体が固相重合性を存し、且つ
、累積膜化ができることに起因して、高性能の非線形光
学材料、感光材料及び高分子半導体結晶を形成すること
ができ、また、構造的に非対称型であり、置換基がジア
セチレン三重結合と共役する芳香族であることによって
電子的効果が大きいことに起因して非線形光学効果が大
きい点である。First, the most important point in the present invention is that the diphenyl diacetylene derivative according to the present invention has solid phase polymerizability and can be formed into a cumulative film, so that it can be used as a high-performance nonlinear optical material, a photosensitive material, and a photosensitive material. It can form polymer semiconductor crystals, and it is structurally asymmetric, and the substituent is an aromatic group that is conjugated with a diacetylene triple bond, resulting in a large electronic effect, resulting in nonlinear optical effects. This is a big point.
また、本発明に係るジフェニルアセチレン誘導体は、電
子吸引性基であるニトロ基と電子供与性基である −〜
lIC0+CHz汁C0zll基を有していることによ
り分子の分極が大きく、その結果、大きな非線形光学効
果が期待できる為、非線形光学材料としての応用に際し
て極めて有利なものである。Further, the diphenylacetylene derivative according to the present invention has a nitro group which is an electron-withdrawing group and an electron-donating group.
The presence of the C0zll group results in large molecular polarization, and as a result, a large nonlinear optical effect can be expected, making it extremely advantageous when applied as a nonlinear optical material.
次に、本発明に係るジフェニルジアセチレン誘4体の合
成方法について述べる。Next, a method for synthesizing diphenyl diacetylene derivative 4 according to the present invention will be described.
本発明のジフェニルジアセチレン誘導体はいずれも文献
未載の新規化合物であって
)IH
(但しRt、Rtのうちいずれか1つがニトロ基で残り
が水素)
で表されるブロモエチニルニトロベンゼンと式
Rz R+
H)l
(但しRI′〜R,1のうらいずれか1つがアミノ基で
残りが水素)
で表されるエチニルアニリンを非対称カップリングし得
られた
で表されるジフェニルジアセチレン誘導体にC1−C→
C1ot +r−C−0H
(但しn = 6〜1B)
で表されるアルキルジカルボン酸モノクロライドを、ア
ミン存在下で反応させることによって製造下ることがで
きる。The diphenyl diacetylene derivatives of the present invention are all new compounds not yet described in literature, and are combined with bromoethynylnitrobenzene represented by IH (where either one of Rt and Rt is a nitro group and the remainder is hydrogen).
C1 to the diphenyl diacetylene derivative obtained by asymmetric coupling of ethynylaniline represented by Rz R+ H)l (where one of RI' to R, 1 is an amino group and the rest is hydrogen) -C→
It can be produced by reacting an alkyldicarboxylic acid monochloride represented by C1ot +r-C-0H (where n = 6 to 1B) in the presence of an amine.
先の非対称カップリング反応は種々の反応条件ドでti
うことかできるが、いずれの場合にも銅塩の触媒作用が
必要である。具体的には、エチニルアニリンの78液に
アミン水溶液と塩化銅(11を加えた後、撹拌しながら
ブロモエチニルニトロベンゼンをゆっくりと加えるごと
によって非対称カップリング反応は進行する。The above asymmetric coupling reaction was performed under various reaction conditions.
However, in both cases the catalytic action of the copper salt is required. Specifically, after adding an amine aqueous solution and copper chloride (11) to ethynylaniline solution 78, the asymmetric coupling reaction proceeds by slowly adding bromoethynylnitrobenzene while stirring.
ン容媒としては、メタノール、エタノール、テトラハイ
ドロフラン、ジメチルホルムアミド、ジメチルアセトア
ミドなどの極性溶媒が好ましい。アミン水溶液としては
一船にエチルアミン水溶液が用いられるが、他のアミン
水溶液も用いることができる。塩化wA(I)はエチニ
ルアニリンに対して1〜50…o1%の範囲内で用いる
。As the solvent, polar solvents such as methanol, ethanol, tetrahydrofuran, dimethylformamide, and dimethylacetamide are preferred. As the amine aqueous solution, an ethylamine aqueous solution is used, but other amine aqueous solutions can also be used. The wA(I) chloride is used in an amount of 1 to 50...o1% based on ethynylaniline.
この反応はアルゴン又は窒素等の不活性ガス雰囲気ド、
0〜50℃の条件で行い、場合によっては1i (I+
イオンの酸化を防止するために、ヒドロキシルアミン塩
酸塩を適量加えながら、数時間ないし1〜2日間攪拌を
続けることによって行う。This reaction is carried out under an inert gas atmosphere such as argon or nitrogen.
The temperature is 0 to 50℃, and in some cases 1i (I+
In order to prevent oxidation of ions, stirring is continued for several hours to 1 to 2 days while adding an appropriate amount of hydroxylamine hydrochloride.
反応終−r後、反応混合物から溶媒を留去し、希塩酸水
?8液により中和希釈し、エーテル、ベンゼン等の溶媒
により抽出する。この溶液に硫酸ナトリウム、硫酸マグ
ネシウム等の乾燥剤を加えて脱水し、乾燥剤及び溶媒を
除去し、シリカゲルカラムクロマトグラフィーによって
精製することにより、式(5)で表されるジフェニルジ
アセチレン誘導体が黄色ないし赤色の結晶として得られ
る0次に得られた式(5)で表されるジフェニルジアセ
チレン誘4体をジメチルホルムアミド、ジメチルアセト
アミド等の溶媒に溶解し、アミン存在下、式(4)で示
したアルキルジカルボン酸モノクロライドを加え、加勢
下、10〜24時間撹拌する。反応混合物から溶媒を留
去、シリカゲルカラムクロマトグラフィーにより精製す
ることにより、一般式(2)で表されるジフェニルジア
セチレン誘4体が淡黄色結晶として得られる。After the end of the reaction, the solvent was distilled off from the reaction mixture, and diluted hydrochloric acid water was added. Neutralize and dilute with 8 liquid and extract with a solvent such as ether or benzene. This solution is dehydrated by adding a desiccant such as sodium sulfate or magnesium sulfate, the desiccant and solvent are removed, and the diphenyl diacetylene derivative represented by formula (5) is purified by silica gel column chromatography. The diphenyl diacetylene derivative represented by the formula (5) obtained as zero-order or red crystals is dissolved in a solvent such as dimethylformamide or dimethylacetamide, and in the presence of an amine, the diphenyl diacetylene derivative represented by the formula (4) is dissolved. Add the alkyl dicarboxylic acid monochloride and stir under pressure for 10 to 24 hours. By distilling off the solvent from the reaction mixture and purifying it by silica gel column chromatography, diphenyl diacetylene derivative 4 represented by general formula (2) is obtained as pale yellow crystals.
次に実施例および応用例並びに参考例により本発明を説
明する。Next, the present invention will be explained with reference to Examples, Application Examples, and Reference Examples.
実施例1
^「雰囲気ド、塩化銅m 50+mgをエチルアミン7
0%水溶液10 mlに溶解し、ここに2−エチニルア
ニリン930Bをジメチルアセトアミド5mlにを審問
したものを加え30分間室温付近で攪拌する。ここに3
−(1−ブロモエチニル)ニトロベンゼン18001I
Igをジメチルアセトアミド5mlに溶解したものを約
5時間かけて滴下、以後12時間室温で撹拌する。Example 1 Atmosphere, copper chloride m 50+mg ethylamine 7
Dissolve in 10 ml of 0% aqueous solution, add 2-ethynylaniline 930B mixed with 5 ml of dimethylacetamide, and stir at room temperature for 30 minutes. here 3
-(1-bromoethynyl)nitrobenzene 18001I
A solution of Ig in 5 ml of dimethylacetamide was added dropwise over about 5 hours, followed by stirring at room temperature for 12 hours.
(途中、塩化14OOの生成により緑色を呈した場合、
゛ 連着のエチルアミン塩酸塩を加え還元する。)反応
混合物から溶媒を留去し、■規定塩酸水溶液200m1
により中和、希釈しエーテル150m1により3回抽出
する。有機層を硫酸ナトリウムで乾燥後、溶媒を留去し
、シリカゲルカラムクロマトグラフィーによりベンゼン
を展開溶媒として分離、精製することにより1−(3−
ニトロフェニル)−4=(2−アミノフェニル)−1,
3−ブタジイン830軒を得た。このものは黄色結晶で
あった。次に得られたジアセチレン化合物soo mg
をジメチルホルムアミド20m1に溶解し、ここにトリ
エチルアミン]Qml、エイコサンニ酸モノクロライド
750+mgを加え、12時間還流する。これを室温ま
で空冷し溶媒を留去、希塩酸により酸性を示すまで希釈
する。(If it turns green due to the formation of 14OO chloride,
゛ Add ethylamine hydrochloride and reduce. ) The solvent was distilled off from the reaction mixture, and 200 ml of normal aqueous hydrochloric acid solution was added.
Neutralize, dilute, and extract three times with 150 ml of ether. After drying the organic layer with sodium sulfate, the solvent was distilled off, and 1-(3-
nitrophenyl)-4=(2-aminophenyl)-1,
3-830 butadiin houses were obtained. This substance was yellow crystal. Next obtained diacetylene compound soo mg
was dissolved in 20 ml of dimethylformamide, to which were added Qml of triethylamine and 750+ mg of eicosanniic acid monochloride, and the mixture was refluxed for 12 hours. The mixture is air-cooled to room temperature, the solvent is distilled off, and the mixture is diluted with dilute hydrochloric acid until it becomes acidic.
クロロホルム100n+1で3回抽出し、有機層を硫酸
ナトリウムで乾燥した後、溶媒を留去、シリカゲルカラ
ムクロマトグラフィーにより、クロロホルム、酢酸エチ
ル混合溶媒で展開し精製することにより、2−(4−(
3−ニトロフェニル)−1゜3−ブタシイニル)フェニ
ルカルバモイルノナデカンInI 230n+gを得た
。このものは淡黄色結晶であった・
元素分析値(C,、I(、、N、0.として)計算値(
%) ; C73,69、H7,90、N 4.77実
測値(%) ; C73,92、H7,75、N 4.
86実施例2
Ar雰囲気下、塩化銅fIl 51)++gをエチルア
ミン70%水溶液1抛lに溶解し、ここに3−エチニル
アニリン93(llIlgをジメチルアセトアミド5*
1に溶解したものを加え、30分間室温で攪拌する。さ
らに3−(ブロモエチニル)ニトロベンゼン1800
mgをシメナルアセトアミト5mlに7容解したものを
6時間かけて浦トし、室温で12時間撹拌する。以ド実
施例1と同様な操作により、1−(3−ニトロフェニル
)−4−(3−アミノフェニル)−1,3−ブタジイン
1230mgを得た。このものは黄色結晶で融点は17
1〜172℃であった。次に得られたジアセチレン化合
物500剛gをジメチルアセトアミド20IIIIに溶
解し、ここにトリエチルアミン101、エイコサンニ酸
モノクロライド750n+gを加え、10時間、120
℃で加熱攪拌する。以下、実施例1と同様な操作により
、3− (4−(3−ニトロフェニル)−1,3−ブタ
シイニル)フェニルカルバモイルノナデカン酸320+
mgを得た。After extracting three times with chloroform 100n+1 and drying the organic layer with sodium sulfate, the solvent was distilled off and purified by silica gel column chromatography developed with a mixed solvent of chloroform and ethyl acetate.
230n+g of 3-nitrophenyl)-1°3-butacyinyl)phenylcarbamoylnonadecane InI was obtained. This substance was a pale yellow crystal. Elemental analysis value (C,, I (,, N, 0.) Calculated value (
%) ; C73,69, H7,90, N 4.77 Actual value (%); C73,92, H7,75, N 4.
86 Example 2 Under an Ar atmosphere, 51)++ g of copper chloride was dissolved in 1 liter of a 70% aqueous solution of ethylamine, and 3-ethynylaniline 93 (lllg) was dissolved in dimethylacetamide 5*.
Add the solution dissolved in 1 and stir at room temperature for 30 minutes. Furthermore, 3-(bromoethynyl)nitrobenzene 1800
A solution of 7 mg in 5 ml of cymenal acetamide was poured over 6 hours and stirred at room temperature for 12 hours. By the same operation as in Example 1, 1230 mg of 1-(3-nitrophenyl)-4-(3-aminophenyl)-1,3-butadiyne was obtained. This substance is a yellow crystal with a melting point of 17.
The temperature was 1-172°C. Next, 500g of the obtained diacetylene compound was dissolved in 20g of dimethylacetamide, 101g of triethylamine and 750n+g of eicosanniic acid monochloride were added thereto, and
Heat and stir at ℃. Hereinafter, by the same operation as in Example 1, 3-(4-(3-nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecanoic acid 320+
mg was obtained.
このものは淡黄色結晶であった。This substance was pale yellow crystal.
元素分析値(C1hH4hNzosとして)計算値(%
) ; C73,69、H7,90、N 4.77実測
値(%) : C73,41、H8,10、N 5.0
1実施例3
Ar雰囲気下、塩化W(Il 50mgをエチルアミン
70%水溶液101に溶解し、ここに4−エチニルアニ
リン930+gをジメチルアセトアミド51に溶解した
ものを加え、30分間室温で撹拌する。さらに3−(ブ
ロモエチニル)ニトロベンゼン1800mgヲシメチル
アセトアミド5Illに溶解したものを6時間かけて滴
ドし、室温で12時間攪拌する。以下実施例1と同様な
操作により、1−(3−ニトロフェニル)−4−(4−
アミノフェニル)−1,3−ブタジイン950mgを得
た。このものは橙色結晶であった0次に得られたジアセ
チレン化合物500■gをジメチルアセトアミド20m
lに溶解し、ここにトリエチルアミン10鴎監、エイ
コサンニ酸モノクロライド750mgを加え、12時間
、120℃で加熱攪拌する。Elemental analysis value (as C1hH4hNzos) Calculated value (%
); C73,69, H7,90, N 4.77 Actual value (%): C73,41, H8,10, N 5.0
1 Example 3 Under an Ar atmosphere, 50 mg of W chloride (Il) was dissolved in 70% ethylamine aqueous solution 101, to which was added 930+ g of 4-ethynylaniline dissolved in dimethylacetamide 51, and stirred at room temperature for 30 minutes.Furthermore, 3 1800 mg of (bromoethynyl)nitrobenzene dissolved in 5 Ill of oxymethylacetamide was added dropwise over 6 hours and stirred at room temperature for 12 hours. 4-(4-
950 mg of (aminophenyl)-1,3-butadiine was obtained. This product was prepared by adding 500 g of the diacetylene compound obtained as orange crystals to 20 m of dimethylacetamide.
10 g of triethylamine and 750 mg of eicosanniic acid monochloride were added thereto, and the mixture was heated and stirred at 120° C. for 12 hours.
以下二実施例1と同様な操作により、4− (4−(3
−ニトロフェニル)−1,3−ブタシイニル)フェニル
カルバモイルノナデカン酸280mgを得り。By the same operation as in Example 1, 4- (4-(3
280 mg of -nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecanoic acid was obtained.
このものは淡黄色結晶であった。This substance was pale yellow crystal.
元素分析41t CC5hHaJtOsとして)計算値
(%) ; C73,69、H7,90、N 4.7?
実η1Hii (%) ; C73,51、H8
,15□N 4.62実施例4
静雰囲気ド、塩化銅[1150mgをエチルアミン70
%水溶液101m1に溶解し、ここに2−エチニルアニ
リン930s+gをジメチルアセトアミド5n+Iに溶
解したものを加え、30分間室温で攪拌する。さらに4
−(ブロモエチニル)ニトロベンゼン1800+gをジ
メチルアセトアミド5mlに溶解したものを6時間かけ
て滴下し、室温で12時間撹拌する。以下実施例1と同
様な操作により、1−(4−ニトロフェニル)−4−(
2−アミノフェニル)−1,3−ブタジイン1080+
agを得た。このものは橙色結晶であった。次に得られ
たジアセチレン化合物500mgをジメチルアセトアミ
ド20Illに熔解し、ここにトリエチルアミン10+
sl、エイコサンニ酸モノクロライド750Bを加え、
15時間、130℃で加熱攪拌する。Elemental analysis 41t CC5hHaJtOs) Calculated value (%); C73,69, H7,90, N 4.7?
Actual η1Hii (%); C73,51, H8
, 15□N 4.62 Example 4 Static atmosphere, copper chloride [1150 mg to ethylamine 70
% aqueous solution, to which a solution of 930s+g of 2-ethynylaniline dissolved in 5n+I dimethylacetamide was added, and the mixture was stirred at room temperature for 30 minutes. 4 more
A solution of 1800+ g of -(bromoethynyl)nitrobenzene dissolved in 5 ml of dimethylacetamide was added dropwise over 6 hours, and the mixture was stirred at room temperature for 12 hours. Hereinafter, by the same operation as in Example 1, 1-(4-nitrophenyl)-4-(
2-aminophenyl)-1,3-butadiyne 1080+
I got ag. This substance was an orange crystal. Next, 500 mg of the obtained diacetylene compound was dissolved in 20 Ill of dimethylacetamide, and triethylamine 10+
sl, add eicosanniic acid monochloride 750B,
Heat and stir at 130° C. for 15 hours.
以下、実施例1と同様な操作により、2−(4−(4−
ニトロフェニル)−1,3−ブタシイニル)フェニルカ
ルバモイルノナデカン酸310vagを得り。Hereinafter, by the same operation as in Example 1, 2-(4-(4-
310 vag of (nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecanoic acid were obtained.
このものは淡黄色結晶であった。This substance was pale yellow crystal.
元素分析値(C3JtJzO−、として)計3に[イd
!(%);C73,69,H7,90,N4.77実測
値(%) ; C73,50、H8,05、N 4.9
8実施例5
Ar雰囲気下、塩化ifI+ 5On+gをエチルアミ
ン70%水>8M10m1に溶解し、ここに3−エチニ
ルアニリン930II+gをジメチルアセトアミド5m
lに溶解したものを加え、30分間室温で攪拌する。さ
らに4−(ブロモエチニル)ニトロベンゼン180kg
をジメチルアセトアミド5mlに溶解したものを6時間
かけて滴下し、室温で12時間撹拌する。以下実施例1
と同様な操作により、1−(4−ニトロフェニル)−4
−(3−アミノフェニル)−1,3−ブタジイン113
0mgを得た。このものは黄色結晶であった。次に得ら
れたジアセチレン化合物500mgをジメチルアセトア
ミド20m1に溶解し、ここにトリエチルアミン101
、エイコサンニ酸モノクロライド750IIIgを加え
、15時間、130℃で加熱攪拌する。Elemental analysis value (as C3JtJzO-) in total 3 [Id
! (%); C73,69, H7,90, N4.77 Actual value (%); C73,50, H8,05, N4.9
8 Example 5 Under Ar atmosphere, ifI+ chloride 5On+g was dissolved in ethylamine 70% water>8M10ml, and 3-ethynylaniline 930II+g was dissolved in dimethylacetamide 5ml.
1 and stirred at room temperature for 30 minutes. In addition, 180 kg of 4-(bromoethynyl)nitrobenzene
A solution of 5 ml of dimethylacetamide was added dropwise over 6 hours, and the mixture was stirred at room temperature for 12 hours. Example 1 below
By the same operation as above, 1-(4-nitrophenyl)-4
-(3-aminophenyl)-1,3-butadiyne 113
0 mg was obtained. This substance was yellow crystal. Next, 500 mg of the obtained diacetylene compound was dissolved in 20 ml of dimethylacetamide, and 10 ml of triethylamine was added.
, 750III g of eicosanniic acid monochloride were added, and the mixture was heated and stirred at 130° C. for 15 hours.
以下、実施例1と同様な操作により、3− (4−(4
−ニトロフェニル)−1,3−ブタシイニル)フェニル
カルバモイルノナデカン酸300I1gG得り。Hereinafter, by the same operation as in Example 1, 3- (4-(4
-Nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecanoic acid 300I1gG obtained.
このものは淡黄色結晶であった。This substance was pale yellow crystal.
元素分析値(Ozbl14JhOsとして)計算値(%
) ; C73,69、H7,90、N 4.77実A
(す(+ff(%);c73.88.H7,69,N4
.73実施例6
Ar雰囲気F1塩化a4[+ 50mgをエチルアミン
70%水溶液101に溶解し、ここに4−エチニルアニ
リン930a+gをジメチルアセトアミド5mlに熔解
したものを加え、30分間室温で撹拌する。さらに4−
(ブロモエチニル)ニトロベンゼン1800mgヲンメ
チルアセトアミド51に溶解したものを8時間かけて滴
下し、室温で12時間攪拌する。以下実施例1と同様な
操作により、1−(4−ニトロフェニル)−4−(4−
アミノフェニル)−1,3−ブタジイン920mgを得
た。このものは赤色結晶であった。次に得られたジアセ
チレン化合物500mgをジメチルアセトアミド20m
lに溶解し、ここにトリエチルアミン10m+1、エ
イコサンニ酸モノクロライド750a+gを加え、20
時間、130℃で加熱撹拌する。Elemental analysis value (as Ozbl14JhOs) Calculated value (%
); C73,69, H7,90, N 4.77 Real A
(su(+ff(%);c73.88.H7,69,N4
.. 73 Example 6 Ar atmosphere F1 A4[+ chloride 50 mg is dissolved in ethylamine 70% aqueous solution 101, 4-ethynylaniline 930a+g dissolved in dimethylacetamide 5 ml is added thereto, and the mixture is stirred for 30 minutes at room temperature. Furthermore 4-
1800 mg of (bromoethynyl)nitrobenzene dissolved in methylacetamide 51 was added dropwise over 8 hours, and the mixture was stirred at room temperature for 12 hours. Hereinafter, by the same operation as in Example 1, 1-(4-nitrophenyl)-4-(4-
920 mg of (aminophenyl)-1,3-butadiyne was obtained. This substance was a red crystal. Next, 500 mg of the obtained diacetylene compound was added to 20 m of dimethylacetamide.
To this, add 10 m+1 triethylamine and 750 a+g eicosanniic acid monochloride.
Heat and stir at 130°C for an hour.
以下、実施例1と同様な操作により、4− (4−(4
−ニトロフェニル)−1,3−ブタシイニル)フェニル
カルバモイルノナデカンM 220+mgを得た。Hereinafter, by the same operation as in Example 1, 4- (4-(4
-Nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecane M 220+mg was obtained.
このものは黄色結晶であった。This substance was yellow crystal.
元素分析値(CibHabNtOsとして)計算値(%
) ; C73,69、H7,90、N 4.77実測
値(%) ; C73,64、H8,11、N 5.0
7実施例7
実施例2で得た、1−(3−ニトロフェニル)−4−(
3−アミノフェニル)−1,3−フ゛タジイン500m
gをジメチルアセトアミド20m lに溶解し、ここに
、トリエチルアミン101、アゼライン酸モノクロライ
ド490ffigを加え5時間、室温で攪拌する。以下
、実施例1と同様な操作により、3− (4−(3ニト
ロフエニル)−1,3−ブタシイニル)フェニルカルバ
モイルオクタン酸220mgを得た。このものは淡黄色
結晶であった。Elemental analysis value (as CibHabNtOs) Calculated value (%
); C73,69, H7,90, N 4.77 Actual value (%); C73,64, H8,11, N 5.0
7 Example 7 1-(3-nitrophenyl)-4-( obtained in Example 2)
3-aminophenyl)-1,3-phtadiyne 500m
g was dissolved in 20 ml of dimethylacetamide, 101 g of triethylamine and 490 ffig of azelaic acid monochloride were added thereto, and the mixture was stirred at room temperature for 5 hours. Thereafter, 220 mg of 3-(4-(3nitrophenyl)-1,3-butacyinyl)phenylcarbamoyl octanoic acid was obtained by the same operation as in Example 1. This substance was pale yellow crystal.
元素分析値(CzsH□autosとして)計算値(%
) ; C69,44、H5,59、N 6.48実/
I!I(+σ (%) ; C69,18、H5−
80、N 6.42〔応用例〕
次に添付図面に従って、本発明化合物の累積膜を製造す
る方法を説明する。第1図は累積膜を製造する装置の1
例を示す斜視図、第2図はその側方断面図であって、内
側に枠2を配置した水槽lの中に金属塩を含む水溶液例
えば塩化カドミウム水溶液を満たし、この中に表面を十
分に清浄化したガラス基板11を支持アーム12に把持
させ、ガラス平面と水面とが垂直になるように浸漬させ
る。Elemental analysis value (as CzsH□autos) Calculated value (%
); C69,44, H5,59, N 6.48 fruit/
I! I(+σ (%); C69,18, H5-
80, N 6.42 [Application Example] Next, a method for producing a cumulative film of the compound of the present invention will be explained according to the attached drawings. Figure 1 shows one of the devices for producing a cumulative film.
A perspective view showing an example, and FIG. 2 is a side sectional view thereof, in which an aqueous solution containing a metal salt, such as a cadmium chloride aqueous solution, is filled in a water tank l with a frame 2 arranged inside, and the surface is sufficiently covered with the aqueous solution containing a metal salt. The cleaned glass substrate 11 is held by the support arm 12 and immersed in the glass so that the plane of the glass is perpendicular to the water surface.
次に、この水面上に、本発明化合物を揮発性溶媒例えば
クロロホルムに溶かして展開させたのち、溶媒を完全に
蒸発させる。Next, the compound of the present invention is dissolved and developed in a volatile solvent such as chloroform on the water surface, and then the solvent is completely evaporated.
次いで、枠2の左右より滑動可能に接触し、かつ滑i5
を介して重り4により引張力を加えられている浮子3に
より所定の表面圧を加えながら、ガラス基板を引き上げ
るとガラス表面に単分子膜の第1の層が形成される0次
に引き上げたガラス基板を十分に乾燥させたのち、これ
を同様に表面圧を加えながら下降させると、先に形成さ
れた単分子膜の上に、さらに第2の層が累積される。こ
のようにして、ガラス基板の上界と下降を繰り返すこと
により、同じ成分組成をもつ単分子膜の累積膜が得られ
る。Next, it comes into sliding contact with the left and right sides of the frame 2, and slides i5.
A first layer of monomolecular film is formed on the glass surface when the glass substrate is pulled up while applying a predetermined surface pressure by the float 3 which is applied with tensile force by the weight 4 through the 0-order pulled glass. After sufficiently drying the substrate, it is lowered while applying surface pressure in the same manner, and a second layer is further accumulated on the previously formed monomolecular film. In this way, by repeating the upward and downward movement of the glass substrate, a cumulative monomolecular film having the same component composition can be obtained.
図中の6は浮子上に取り付けられた磁石で、この対磁石
7の作用により浮子6の元の位置への移動が行われる。6 in the figure is a magnet attached to the float, and the action of this pair of magnets 7 moves the float 6 to its original position.
上記方法に従って、添付図面に示す装置を用いて累積膜
を形成した。According to the above method, a cumulative film was formed using the apparatus shown in the attached drawings.
すなわち、lXl0−”M塩化カドミウム水溶液に、表
面が十分に清浄で親水性となっているガラス基板をガラ
ス平面と水面とが垂直になるように浸しておく。この水
溶液上に、実施例2で得た、3−(4−(3−ニトロフ
ェニル)−1,3−ブタシイニル)フェニルカルバモイ
ルノナデカン酸、1XIO−’Mのクロロホルム溶液を
水面上に展開する。That is, a glass substrate whose surface is sufficiently clean and hydrophilic is immersed in a lXl0-''M cadmium chloride aqueous solution so that the glass plane and the water surface are perpendicular. The obtained chloroform solution of 3-(4-(3-nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecanoic acid, 1XIO-'M is spread on the water surface.
クロロホルムを完全に蒸発させた後、表面圧を20dy
n/amに保ちながら浸してあったガラス基板を水面に
垂直に0.7 cm/winで上昇させる。引き上げた
基板を十分に乾燥させた後、今度は1.Oc+w/si
nで下降させる。この上昇及び下降の操作を繰り返すこ
とによって3− (4−(3−二トロフェニル)−1,
3−フタシイニル)フェニルカルバモイルノナデカン酸
の累積膜が得られた。After completely evaporating the chloroform, the surface pressure was increased for 20 days.
The glass substrate that had been immersed in the water was raised perpendicularly to the water surface at a rate of 0.7 cm/win. After sufficiently drying the pulled up substrate, 1. Oc+w/si
Lower it with n. By repeating this rising and falling operation, 3-(4-(3-nitrophenyl)-1,
A cumulative film of 3-phthacyinyl)phenylcarbamoylnonadecanoic acid was obtained.
その他の実施例で得られた誘導体についても、同様の操
作により累積膜が得られた。For the derivatives obtained in other Examples, cumulative films were obtained by the same operation.
(参考例〕
参考例1
粉末状の本発明化合物各試料をガラス管に真空封入しコ
バルト60ガンマ−線を用いて、50MRADの線量を
照射し、固相重合させた。開封後、テトラハイドロフラ
ン不溶のポリマーの重重から重合収率を求めた0次表に
アルキル鎖炭素数n=18のものについて結果を示した
。(Reference Example) Reference Example 1 Each sample of the compound of the present invention in powder form was vacuum sealed in a glass tube and irradiated with cobalt 60 gamma rays at a dose of 50 MRAD to undergo solid phase polymerization.After opening the package, tetrahydrofuran The results are shown in the 0-dimensional table, in which the polymerization yield was determined from the weight of the insoluble polymer, for those in which the number of carbon atoms in the alkyl chain was n=18.
(ニ)u基の置換位置) (7ミF基の置換位置)
(%)バラ パラ 60
いずれの化合物もかなりの固相重合性を存していること
は明らかである。また他の炭素鎖長の化合物についても
かなりの重合性を示すことがわかヮた。(d) Substitution position of u group) (Substitution position of 7miF group)
(%)Rose Para 60
It is clear that both compounds have considerable solid phase polymerizability. It was also found that compounds with other carbon chain lengths exhibit considerable polymerizability.
参考例2
本発明の化合物を累積膜化し、その固相重合性を観察し
た。応用例に示した方法で各々の化合物を11層累積し
、UV光(Xeランプ、500 W)を5時間照射し固
相重合させたところ、青色を呈するポリマー異積膜が得
られた0重合は、可視吸収スペクトルにより、630
nm近傍の吸収が照射時間に比例して増加することによ
って確認した。Reference Example 2 The compound of the present invention was formed into a cumulative film, and its solid phase polymerizability was observed. When 11 layers of each compound were accumulated using the method shown in the application example and irradiated with UV light (Xe lamp, 500 W) for 5 hours to perform solid phase polymerization, a blue-colored polymer heterolaminar film was obtained. is 630 according to the visible absorption spectrum.
This was confirmed by the fact that the absorption near nm increased in proportion to the irradiation time.
本発明に係るジフェニルジアセチレン誘4体は、前出実
施例に示した通り、構造的に非対称型であり、置換基が
ジアセチレン三重結合と共役する芳香族であることによ
って非線形光学効果を有し、また前出参考例並びに応用
例に示した通り、固相重合性を有し、且つ、累積膜化で
きることによって高性能素子化が容易である為、非線形
光学材料、感光材料及び高分子半導体材料を形成する為
のジアセチレン類の単量体として好適である。As shown in the above example, the diphenyl diacetylene derivative according to the present invention is structurally asymmetric, and has a nonlinear optical effect because the substituent is an aromatic group conjugated with a diacetylene triple bond. In addition, as shown in the reference examples and application examples above, it has solid phase polymerizability and can be formed into a cumulative film, making it easy to make high-performance devices. It is suitable as a diacetylene monomer for forming materials.
本発明に係るジフェニルジアセチレン誘導体を累積膜化
したものは、特に分子の配向がその性能に反映される非
線形光学材料として高性能素子への応用が可能なもので
ある。The cumulative film of the diphenyl diacetylene derivative according to the present invention can be applied to high-performance devices, especially as a nonlinear optical material in which the molecular orientation is reflected in its performance.
第1図は累積膜を製造するための装置の1例を示す斜視
図、第2図はその側方断面図である。
図中符号1は水槽、2は枠、3は浮子、4は重り、lO
は液面、11はガラス基板である。FIG. 1 is a perspective view showing an example of an apparatus for producing a cumulative film, and FIG. 2 is a side sectional view thereof. In the figure, 1 is the water tank, 2 is the frame, 3 is the float, 4 is the weight, lO
is a liquid level, and 11 is a glass substrate.
Claims (1)
基、残りが水素であって、R_1′〜R_3′のうちい
ずれか1つが−NHCO−(CH_2)−_nCO_2
H(但しn=6〜18)、残りが水素であるジフェニル
ジアセチレン誘導体。(1) It is represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where one of R_1 and R_2 is a nitro group, the rest is hydrogen, and any one of R_1' to R_3' is - NHCO-(CH_2)-_nCO_2
A diphenyl diacetylene derivative in which H (where n=6 to 18) and the remainder being hydrogen.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9595686A JPS62255460A (en) | 1986-04-25 | 1986-04-25 | Diphenyldiacetylene derivative |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9595686A JPS62255460A (en) | 1986-04-25 | 1986-04-25 | Diphenyldiacetylene derivative |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62255460A true JPS62255460A (en) | 1987-11-07 |
JPS6365659B2 JPS6365659B2 (en) | 1988-12-16 |
Family
ID=14151692
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9595686A Granted JPS62255460A (en) | 1986-04-25 | 1986-04-25 | Diphenyldiacetylene derivative |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62255460A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019520317A (en) * | 2016-04-25 | 2019-07-18 | デューク ユニバーシティ | Benzoyl glycine derivatives and methods of making and using the same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03107454U (en) * | 1990-02-21 | 1991-11-06 |
-
1986
- 1986-04-25 JP JP9595686A patent/JPS62255460A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019520317A (en) * | 2016-04-25 | 2019-07-18 | デューク ユニバーシティ | Benzoyl glycine derivatives and methods of making and using the same |
Also Published As
Publication number | Publication date |
---|---|
JPS6365659B2 (en) | 1988-12-16 |
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