JPH04321643A - Diacetylene-containing benzoic acid derivative - Google Patents
Diacetylene-containing benzoic acid derivativeInfo
- Publication number
- JPH04321643A JPH04321643A JP647291A JP647291A JPH04321643A JP H04321643 A JPH04321643 A JP H04321643A JP 647291 A JP647291 A JP 647291A JP 647291 A JP647291 A JP 647291A JP H04321643 A JPH04321643 A JP H04321643A
- Authority
- JP
- Japan
- Prior art keywords
- benzoic acid
- formula
- reaction
- diacetylene
- acid derivative
- 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
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 title claims abstract description 14
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 25
- 239000005711 Benzoic acid Substances 0.000 abstract description 13
- 235000010233 benzoic acid Nutrition 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 230000003287 optical effect Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 229920000015 polydiacetylene Polymers 0.000 abstract description 4
- 229920002994 synthetic fiber Polymers 0.000 abstract description 4
- 230000002862 amidating effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- -1 diacetylene compound Chemical class 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 8
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BAYUSCHCCGXLAY-UHFFFAOYSA-N 1-(3-methoxyphenyl)ethanone Chemical compound COC1=CC=CC(C(C)=O)=C1 BAYUSCHCCGXLAY-UHFFFAOYSA-N 0.000 description 2
- RMMRRRLPDBJBQL-UHFFFAOYSA-N 1-(3-methoxyphenyl)propan-2-one Chemical compound COC1=CC=CC(CC(C)=O)=C1 RMMRRRLPDBJBQL-UHFFFAOYSA-N 0.000 description 2
- WTPHVMQZKICGOH-UHFFFAOYSA-N 1-methoxy-3-prop-1-en-2-ylbenzene Chemical compound COC1=CC=CC(C(C)=C)=C1 WTPHVMQZKICGOH-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DHEWVQLPVBAYCQ-UHFFFAOYSA-N 1-bromooct-1-yne Chemical compound CCCCCCC#CBr DHEWVQLPVBAYCQ-UHFFFAOYSA-N 0.000 description 1
- GBWSKNOEQYRIGE-UHFFFAOYSA-N 1-butyl-4-(1-chloroethenyl)benzene Chemical compound CCCCC1=CC=C(C(Cl)=C)C=C1 GBWSKNOEQYRIGE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- SYYKCFBWTUNHHL-UHFFFAOYSA-N BrC1(CC=C(C=C1)CCCC)C#C Chemical group BrC1(CC=C(C=C1)CCCC)C#C SYYKCFBWTUNHHL-UHFFFAOYSA-N 0.000 description 1
- 241001288214 Brickellia diffusa Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000009815 homocoupling reaction Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- SIAMQZSXLMKZBY-UHFFFAOYSA-N hydroxylamine;dihydrochloride Chemical compound Cl.Cl.ON.ON SIAMQZSXLMKZBY-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- UMIPWJGWASORKV-UHFFFAOYSA-N oct-1-yne Chemical compound CCCCCCC#C UMIPWJGWASORKV-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 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
【０００１】0001
【産業上の利用分野】この発明は、非線形光学材料とし
て有望なポリジアセチレン合成材料であるジアセチレン
基を含有する新規な安息香酸誘導体に関する。FIELD OF THE INVENTION This invention relates to a novel benzoic acid derivative containing a diacetylene group, which is a polydiacetylene synthetic material that is promising as a nonlinear optical material.
【０００２】0002
【従来の技術】従来から、対称型のジアセチレン化合物
として、例えば、次式２で表されるビストシル体が代表
的なポリアセチレン合成材料として用いられている。BACKGROUND OF THE INVENTION Hitherto, as a symmetrical diacetylene compound, for example, a bistosil compound represented by the following formula 2 has been used as a typical polyacetylene synthetic material.
【０００３】0003
【化２】[Case 2]
【０００４】また、Ｓｃｈｕｌｚらは次式３で表される
ジアセチレンを合成した（Ｍａｃ−ｒｏｍｏｌ．Ｃｈｅ
ｍ．，Ｒａｐｉｄ Ｃｏｍｍｕｎ．，３，２４９−２
５４（１９８２））。Schulz et al. also synthesized diacetylene represented by the following formula 3 (Mac-romol.
m. , Rapid Commun. ,3,249-2
54 (1982)).
【０００５】[0005]
【化３】[Chemical formula 3]
【０００６】（式中、Ｒはアルキル基等を示す。）一方
、非対称型のジアセチレン化合物としては、例えば、Ｇ
ａｒｉｔｏ ｅｔ，ａｌ，ＡＣＳ Ｓｙｍｐｏｓｉ
ｕｍ Ｓｅｒｉｅｓ，２２３，１（１０８３）には次
式４で表される化合物が、特開昭６１−１３４３４５号
公報には次式５で現れる化合物が、特開昭６２−２５５
４７５号公報或いは特開昭６２−２８８６１２号公報に
は次式６で表されるジアセチレン化合物が、特開昭６１
−４３１４９号公報には次式７で表される化合物が、ま
た、特開昭６１−４３１４９号公報には次式８で表され
る化合物がそれぞれ提案されている。(In the formula, R represents an alkyl group, etc.) On the other hand, as an asymmetric diacetylene compound, for example, G
arito et, al, ACS Symposia
um Series, 223, 1 (1083) contains a compound represented by the following formula 4, and JP-A No. 61-134345 contains a compound represented by the following formula 5.
475 or JP-A-62-288612, a diacetylene compound represented by the following formula 6 is disclosed in JP-A-62-288612.
A compound represented by the following formula 7 is proposed in Japanese Patent Publication No. 43149-43149, and a compound represented by the following formula 8 is proposed in JP-A-61-43149.
【０００７】[0007]
【化４】[C4]
【０００８】[0008]
【化５】[C5]
【０００９】[0009]
【化６】[C6]
【００１０】0010
【化７】[C7]
【００１１】[0011]
【化８】[Chemical formula 8]
【００１２】0012
【発明が解決しようとする課題】上記の化合物は、電気
的、光学的な機能が改善されているが、さらに高次の電
気的、光学的な機能が発現される非線形光学材料用モノ
マーが要望されてきている。この発明の目的は、上記の
点に鑑み、一方にカルボニル基、カルボキシル基等の電
子吸引性の置換基を持ち、他方にフェニル基等の電子供
与性置換基を持つことにより、より高次の電気的、光学
的機能が発現し、ポリジアセチレン合成材料として有用
なジアセチレン含有安息誘導体を提供しようとするもの
である。[Problems to be Solved by the Invention] The above compounds have improved electrical and optical functions, but there is a need for monomers for nonlinear optical materials that exhibit even higher-order electrical and optical functions. It has been done. In view of the above points, an object of the present invention is to have an electron-withdrawing substituent such as a carbonyl group or a carboxyl group on one side and an electron-donating substituent such as a phenyl group on the other side, thereby achieving a higher order. The present invention aims to provide a diacetylene-containing ben derivative that exhibits electrical and optical functions and is useful as a material for synthesizing polydiacetylene.
【００１３】[0013]
【課題を解決するための手段】この発明のジアセチレン
含有安息香酸誘導体は、次式（１）で表される。[Means for Solving the Problems] The diacetylene-containing benzoic acid derivative of the present invention is represented by the following formula (1).
【００１４】[0014]
【化９】[Chemical formula 9]
【００１５】式中、Ｘ−ＣＯ−の置換位置は、オルト、
メタまたはパラのいずれでもよく、Ｘは、ＯＲ２（Ｒ２
は水素もしくはアルキル基）またはＮＲ３ Ｒ４ （
Ｒ３ 、Ｒ４ はそれぞれ水素もしくはアルキル基）
を示し、Ｒ１ はアルキル基、フェニル基もしくは置
換フェニル基を示す。置換フェニル基としては、アルキ
ル基もしくはアルコキシ基で置換されたフェニル基があ
げられる。In the formula, the substitution position of X-CO- is ortho,
It may be either meta or para, and X is OR2(R2
is hydrogen or alkyl group) or NR3 R4 (
R3 and R4 are each hydrogen or alkyl group)
and R1 represents an alkyl group, a phenyl group or a substituted phenyl group. Examples of the substituted phenyl group include phenyl groups substituted with an alkyl group or an alkoxy group.
【００１６】この発明のジアセチレン含有安息香酸誘導
体は、基本的には、次の反応式（９）または反応式（１
０）で示されるような非対称カップリング反応により合
成することができる。The diacetylene-containing benzoic acid derivative of the present invention basically follows the following reaction formula (9) or reaction formula (1).
It can be synthesized by an asymmetric coupling reaction as shown in 0).
【００１７】[0017]
【化１０】[Chemical formula 10]
【００１８】なお、ＸがＯＨもしくはＯＲ（Ｒはアルキ
ル基）であるジアセチレン含有安息香酸誘導体を得るに
は、上記反応式（９）もしくは（１０）から得られたジ
アセチレン含有安息香酸誘導体をエステル化すればよい
。また、安息香酸アミド体に関しては、安息香酸誘導体
のアミド化によって合成できるし、非対称カップリング
反応に用いるアミンがそのままアミド化剤となるように
反応条件を選ぶことも可能である。Note that in order to obtain a diacetylene-containing benzoic acid derivative in which X is OH or OR (R is an alkyl group), the diacetylene-containing benzoic acid derivative obtained from the above reaction formula (9) or (10) is used. It can be esterified. Furthermore, the benzoic acid amide compound can be synthesized by amidation of a benzoic acid derivative, and it is also possible to select reaction conditions such that the amine used in the asymmetric coupling reaction directly serves as an amidating agent.
【００１９】この非対称カップリング反応は、Ｃｏｄｉ
ｏｔ−Ｃｈｏｄｋｉｅｗｉｃｓ反応と呼ばれるが、次の
条件下で行うことができる。すなわち、上記式中に示さ
れるような末端アセチレン化合物のアミン系水溶液に触
媒とヒドロキシルアミン塩酸塩を加えて調整された混合
溶液に、上記式中に示されるようなブロム化合物を徐々
に滴下することにより反応を進行させる。なお、アセチ
レン同士のホモカップリング反応を避けるため、系内は
不活性ガス置換をしておく。[0019] This asymmetric coupling reaction
It is called the ot-Chodkiewicz reaction and can be carried out under the following conditions. That is, a bromine compound as shown in the above formula is gradually dropped into a mixed solution prepared by adding a catalyst and hydroxylamine hydrochloride to an amine-based aqueous solution of a terminal acetylene compound as shown in the above formula. The reaction is allowed to proceed. In addition, in order to avoid a homocoupling reaction between acetylenes, the inside of the system should be replaced with an inert gas.
【００２０】上記の反応において、使用される触媒、ヒ
ドロキシルアミン溶液、アミン水溶液及び有機溶媒と、
その反応条件等については、次のとおりである。
触媒
触媒としては、各種の一価の銅化合物が好適に使用され
るが、塩化第一銅が特に好適に用いられる。その使用量
は用いるアセチレン化合物の０．５〜６０ｍｏｌ％の範
囲が望ましい。In the above reaction, the catalyst, hydroxylamine solution, amine aqueous solution and organic solvent used,
The reaction conditions, etc. are as follows. As the catalyst, various monovalent copper compounds are preferably used, and cuprous chloride is particularly preferably used. The amount used is preferably in the range of 0.5 to 60 mol% of the acetylene compound used.
【００２１】ヒドロキシルアミン塩酸塩ヒドロキシルア
ミン塩酸塩は、触媒の活性を保持させるために用いられ
ものであり、反応中に反応溶液が二価の銅イオンの色で
ある青色に着色してきたら、随時添加するようにするの
が好ましい。
アミン水溶液
メチルアミン、エチルアミン、プロピルアミン等のアミ
ン類のアミン類の水溶液が好適に用いられる。通常、反
応基質に対して過剰に用いる。Hydroxylamine hydrochloride Hydroxylamine hydrochloride is used to maintain the activity of the catalyst, and can be added at any time during the reaction when the reaction solution turns blue, which is the color of divalent copper ions. It is preferable to do so. Amine Aqueous Solution Aqueous solutions of amines such as methylamine, ethylamine, propylamine, etc. are preferably used. It is usually used in excess of the reaction substrate.
【００２２】有機溶媒
反応基質の溶解を助けるために、例えば、下記の極性溶
媒を用いる。すなわち、メタノール、エタノール、プロ
パノール等のアルコール溶媒、テトラヒドロフラン、ジ
オキサン、ジメチルホルムアルデヒド等の非プロトン性
極性溶媒等が好適に用いられる。Organic Solvent Reaction To assist in dissolving the substrate, for example, the following polar solvents are used. That is, alcohol solvents such as methanol, ethanol, and propanol, aprotic polar solvents such as tetrahydrofuran, dioxane, and dimethyl formaldehyde, and the like are preferably used.
【００２３】反応条件
反応温度としては０〜５０℃、滴下時間は系の温度が急
に上昇しないようにコントロールしながら加える。通常
は３０〜２０時間の範囲で適当に決めることができる。
また、反応時間としては、滴下終了後、数時間乃至２〜
３日攪拌を続けて反応を完了させる。Reaction conditions: The reaction temperature is 0 to 50°C, and the dropwise addition time is controlled to prevent the temperature of the system from rising suddenly. Usually, the time can be appropriately determined within the range of 30 to 20 hours. In addition, the reaction time ranges from several hours to 2 to 2 hours after the completion of the dropwise addition.
Continue stirring for 3 days to complete the reaction.
【００２４】反応終了後の処理
反応混合物に少量のシアン化カリウムまたはシアン化ナ
トリウムを加えることにより、銅系触媒を水に可溶な化
合物に変えた後、大過剰の酸性水溶液に注ぎ込んで目的
とする安息香酸誘導体を沈澱させる方法、または、反応
混合物から溶媒を留去して得られた残渣に、酸性水溶液
を注ぎ入れ、これをクロロホルムやベンゼン等の有機溶
媒により抽出する。この抽出液を無水硫酸マグネシウム
等の脱水剤で乾燥し、次いで溶媒を留去して目的物の安
息香酸誘導体を得る。Treatment after completion of the reaction By adding a small amount of potassium cyanide or sodium cyanide to the reaction mixture, the copper catalyst is converted into a water-soluble compound, and then poured into a large excess of acidic aqueous solution to obtain the desired benzoin. An acid derivative is precipitated, or an acidic aqueous solution is poured into the residue obtained by distilling off the solvent from the reaction mixture, and this is extracted with an organic solvent such as chloroform or benzene. This extract is dried with a dehydrating agent such as anhydrous magnesium sulfate, and then the solvent is distilled off to obtain the desired benzoic acid derivative.
【００２５】ここで、好適に用いられる酸は、塩酸、硫
酸等の無機酸や酢酸のような有機酸類である。
精製
粗生成物を適当な有機溶媒から再結晶することにより精
製する。
誘導体の合成
通常の方法によってエステル化反応を行い、安息香酸エ
ステルを得、また、通常の方法によってアミド化反応を
行い、安息香酸アミドを得ることができる。[0025] The acids preferably used here are inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Purification The crude product is purified by recrystallization from a suitable organic solvent. Synthesis of derivatives An esterification reaction can be performed to obtain a benzoic acid ester using a conventional method, and an amidation reaction can be performed using a conventional method to obtain a benzoic acid amide.
【００２６】なお、以上により得られたジアセチレン含
有安息香酸誘導体は、光、熱により容易に重合するもの
もあるので、遮光して冷暗所に保管するのが望ましい。
この発明のジアセチレン含有安息香酸誘導体は、次の実
施例において述べるとおり、核磁気共鳴分析（ＮＭＲ）
、赤外線吸収スペクトル分析（ＩＲ）等の機器分析手段
、及び元素分析によりその構造は確認されている。[0026] Some of the diacetylene-containing benzoic acid derivatives obtained above are easily polymerized by light or heat, so it is desirable to store them in a cool, dark place protected from light. The diacetylene-containing benzoic acid derivatives of this invention were analyzed by nuclear magnetic resonance analysis (NMR) as described in the following examples.
Its structure has been confirmed by instrumental analysis methods such as , infrared absorption spectroscopy (IR), and elemental analysis.
【００２７】[0027]
【実施例】以下、この発明の実施例を説明する。
実施例１
メタエチニル安息香酸１４．６ｇを水酸化ナトリウム５
ｇを含む水溶液１００ｍｌに溶解させてメタエチニル安
息香酸のナトリウム塩水溶液を得た。一方、水酸化ナト
リウム１３ｇを含む水溶液７０ｍｌを５〜１０℃の温度
域において、窒素気流下に、１６ｇの臭素を徐々に加え
、得られた溶液に上記メタエチニル安息香酸のナトリウ
ム塩溶液を窒素気流下に徐々に加えながら攪拌した。
５〜２０時間攪拌し、その後水２００〜５００ｍｌを加
えて溶解させ、不溶部を濾過して除き、濾液に５０％酢
酸を加えて酸性にし、沈澱物を濾過、水洗し、常温で減
圧乾燥させ、融点１５３〜１５５℃の黄色粉末結晶を収
率８８％で得た。[Embodiments] Examples of the present invention will be described below. Example 1 14.6 g of metaethynylbenzoic acid was added to 5 g of sodium hydroxide.
An aqueous solution of sodium salt of metaethynylbenzoic acid was obtained by dissolving it in 100 ml of an aqueous solution containing g. On the other hand, 16 g of bromine was gradually added to 70 ml of an aqueous solution containing 13 g of sodium hydroxide under a nitrogen stream at a temperature range of 5 to 10°C, and the above sodium salt solution of metaethynylbenzoic acid was added to the obtained solution under a nitrogen stream. was gradually added to the solution while stirring. Stir for 5 to 20 hours, then add 200 to 500 ml of water to dissolve, remove the insoluble portion by filtration, add 50% acetic acid to the filtrate to make it acidic, filter the precipitate, wash with water, and dry under reduced pressure at room temperature. , yellow powder crystals with a melting point of 153-155°C were obtained in a yield of 88%.
【００２８】このときの反応式は上記反応式１１で示す
とおりであり、得られたブロム体は、式１１に示すとお
りであった。The reaction formula at this time was as shown in Reaction Formula 11 above, and the obtained bromine product was as shown in Formula 11.
【００２９】[0029]
【化１１】[Chemical formula 11]
【００３０】このようにして得たブロム体１５ｇを１０
ｍｌの７０％エチルアミン水溶液に加えて、メタノール
またはテトラヒドロフラン（ＴＨＦ）を少量加えて溶解
させた。これを８ｇの１−オクチン、１０ｍｌの７０％
エチルアミン水溶液、２０ｍｌのＴＨＦ及び１０ｍｌの
メタノール、０．２ｇの塩化第１銅、０．５ｇのヒドロ
キシルアミン塩酸塩の混合液中に窒素気流下、攪拌しな
がら、温度が急上昇しなように徐々に添加した。反応系
が青色に変わった時には、ヒドロキシルアミン塩酸塩を
少量加えて黄色に保つようにしながら、５〜２０時間反
応させる。反応終了後、シアン化ナトリウムを１〜２ｇ
加えた後、反応物を５００〜１００ｍｌの水中に注ぎ、
沈澱した固体を濾過し、濾液がアンモニア水で青色を呈
しなくなる迄、十分に水洗する。得られた固体を２０％
酢酸中で処理して塩を酸に変えた。[0030] 15 g of the bromine compound thus obtained was
In addition to 70% ethylamine aqueous solution (ml), a small amount of methanol or tetrahydrofuran (THF) was added and dissolved. Add this to 8g of 1-octyne, 10ml of 70%
Add a mixture of ethylamine aqueous solution, 20 ml of THF, 10 ml of methanol, 0.2 g of cuprous chloride, and 0.5 g of hydroxylamine hydrochloride under a nitrogen stream while stirring to prevent the temperature from rising rapidly. Added. When the reaction system turns blue, add a small amount of hydroxylamine hydrochloride to maintain the yellow color and allow the reaction to proceed for 5 to 20 hours. After the reaction is complete, add 1 to 2 g of sodium cyanide.
After addition, pour the reaction into 500-100 ml of water,
The precipitated solid is filtered and thoroughly washed with aqueous ammonia until the filtrate no longer turns blue. 20% of the solid obtained
The salt was converted to acid by treatment in acetic acid.
【００３１】濾過、水洗して乾燥した。収率は６５％で
淡黄色結晶性粉末のメタ（オクタ−１，３−ジイニル）
安息香酸を得た。このときの反応式は次式（１２）で示
すとおりである。[0031] It was filtered, washed with water and dried. The yield was 65%, and the meta(octa-1,3-diynyl) was a pale yellow crystalline powder.
Benzoic acid was obtained. The reaction formula at this time is as shown in the following formula (12).
【００３２】[0032]
【化１２】[Chemical formula 12]
【００３３】このメタ（オクタ−１，３−ジイニル）安
息香酸（Ｃ１７Ｈ１８Ｏ２）の元素分析値と計算値は、
次のとおりであり両者は良く整合しており、また、赤外
線吸収スペクトル分析結果は図１に示すとおりであった
。
実施例２
パラエチニル安息香酸１４．６ｇをエチルアミン７０％
水溶液３０ｍｌと２０ｍｌのメタノールの混合溶液に溶
解させ、０．３ｇの塩化第１銅及び０．５ｇのヒドロキ
シルアミン塩酸塩を加えた後、１−ブロモ−１−オクチ
ン１９ｇを１０ｍｌのＴＨＦに溶解した溶液に窒素気流
下で徐々に加えながら攪拌した。滴下終了後、５〜１０
時間反応を続けた。反応終了後、反応混合物にシアン化
カリウム２ｇを加え、これを塩酸酸性水５００ｍｌ中に
加え、沈澱物を濾過、洗浄、乾燥させて白色乃至淡黄色
結晶性粉末のメタ（オクタ−１、３−ジイニル）安息香
酸を得た（収率約８０％）。The elemental analysis values and calculated values of this meta(octa-1,3-diynyl)benzoic acid (C17H18O2) are as follows:
The results are as follows, and the two are in good agreement, and the results of infrared absorption spectrum analysis are as shown in FIG. Example 2 14.6 g of paraethynylbenzoic acid was added to 70% ethylamine.
After dissolving in a mixed solution of 30 ml of aqueous solution and 20 ml of methanol and adding 0.3 g of cuprous chloride and 0.5 g of hydroxylamine hydrochloride, 19 g of 1-bromo-1-octyne was dissolved in 10 ml of THF. The mixture was gradually added to the solution with stirring under a nitrogen stream. After completion of dripping, 5 to 10
The reaction continued for hours. After the reaction is complete, 2 g of potassium cyanide is added to the reaction mixture, which is added to 500 ml of hydrochloric acid acidified water, and the precipitate is filtered, washed, and dried to obtain meta(octa-1,3-diynyl) as a white to pale yellow crystalline powder. Benzoic acid was obtained (yield about 80%).
【００３４】このときの反応式は次式（１３）で示すと
おりである。The reaction formula at this time is as shown in the following formula (13).
【００３５】[0035]
【化１３】[Chemical formula 13]
【００３６】得られたメタ（オクタ−１、３−ジイニル
）安息香酸（Ｃ１７Ｈ１８Ｏ２）の融点は１９４℃であ
り、元素分析値と計算値は、次のとおりであり両者は良
く整合しており、また、赤外線吸収スペクトル分析結果
は図２に示すとおりであった。
実施例３
パラ−ｎ−ブチルアセトフェノンと五塩化燐との反応で
得られたα−クロロ−パラ−ｎ−ブチルスチレンをジメ
チルスルホキシド（ＤＭＳＯ）中、苛性ソーダで処理し
、パラ−ｎ−ブチルフェニルアセチレンを得た。このパ
ラ−ｎ−ブチルフェニルアセチレンを次亜臭素酸ナトリ
ウム（ＮａＯＢｒ）によりブロム化して１−ブロモ−パ
ラ−ｎ−ブチルフェニルアセチレンを得た。The melting point of the obtained meta(octa-1,3-diynyl)benzoic acid (C17H18O2) is 194°C, and the elemental analysis values and calculated values are as follows, and they are in good agreement. Further, the results of infrared absorption spectrum analysis were as shown in FIG. Example 3 α-chloro-para-n-butylstyrene obtained by the reaction of para-n-butylacetophenone and phosphorus pentachloride was treated with caustic soda in dimethyl sulfoxide (DMSO) to form para-n-butylphenylacetylene. I got it. This para-n-butylphenylacetylene was brominated with sodium hypobromite (NaOBr) to obtain 1-bromo-para-n-butylphenylacetylene.
【００３７】このときの反応式は次式（１４）に示すと
おりである。The reaction formula at this time is as shown in the following formula (14).
【００３８】[0038]
【化１４】[Chemical formula 14]
【００３９】次いで、実施例２と同様の反応条件下で、
パラエチニル安息香酸１４．６ｇと、２４ｇの上記１−
ブロモ−パラ−ｎ−ブチルフェニルアセチレンとを反応
させ黄色結晶性粉末のパラ（パラブチルフェニルブタ−
１、３−ジイニル）安息香酸を得（収率８６％）、これ
をメタノール・ベンゼン混合溶媒より再結晶した。この
ときの反応式は次式（１５）で示すとおりである。Next, under the same reaction conditions as in Example 2,
14.6 g of paraethynylbenzoic acid and 24 g of the above 1-
By reacting with bromo-para-n-butylphenylacetylene, a yellow crystalline powder of para(para-butylphenylbutylene) was obtained.
1,3-diynyl)benzoic acid was obtained (yield: 86%), which was recrystallized from a mixed solvent of methanol and benzene. The reaction formula at this time is as shown in the following formula (15).
【００４０】[0040]
【化１５】[Chemical formula 15]
【００４１】得られたパラ（パラブチルフェニルブタ−
１、３−ジイニル）安息香酸（Ｃ２１Ｈ１８Ｏ２）は、
１３０℃で相変化を起こし花弁状結晶になり、更に昇温
すると２００℃以上で溶融し、同時に重合して褐色レジ
ン状（非晶化）となるものであった。そして、元素分析
値と計算値は、次のとおりであり両者は良く整合した。
実施例４
ｍ−メトキシアセトフェノン１００ｇを２５０ｍｌのベ
ンゼンに溶解し、１６０ｇの五塩化燐を徐々に加えて攪
拌すると塩化水素を発生しながら発熱的に反応が進行し
た。常温で２４時間反応させ、生成したオキシ塩化燐を
減圧蒸留で除き、その後反応物を１リットルの氷水中に
注ぎ、エーテルで抽出した。このエーテル相を飽和食塩
水で２回洗浄し、無水硫酸マグネシウムで乾燥し、溶媒
を留去すると、α−メチル−メタ−メトキシスチレンが
得られた。このα−メチル−メタ−メトキシスチレンを
そのまま８５％エタノールに溶解し、２倍当量の水酸化
カリウムを加えて攪拌下３０時間還流させた。その後、
エタノールを留去し、大量の氷中に注ぎ、生成物をエー
テルで抽出した。エーテルを留去した後、減圧蒸留で９
５〜１００℃（約７Ｔｏｒｒ）の留分を集めた。出発物
質のｍ−メトキシアセトフェノンに対し約５０％の収率
でｍ−メトキシフェニルアセトンが得られた。The obtained para (para-butylphenyl but-
1,3-diynyl)benzoic acid (C21H18O2) is
At 130°C, a phase change occurred to form petal-shaped crystals, and when the temperature was further increased, it melted at 200°C or higher, and at the same time polymerized to become a brown resin-like (amorphous) state. The elemental analysis values and calculated values were as follows, and they matched well. Example 4 When 100 g of m-methoxyacetophenone was dissolved in 250 ml of benzene and 160 g of phosphorus pentachloride was gradually added and stirred, the reaction proceeded exothermically while generating hydrogen chloride. The reaction was allowed to proceed at room temperature for 24 hours, and the produced phosphorus oxychloride was removed by vacuum distillation.Then, the reaction product was poured into 1 liter of ice water and extracted with ether. This ether phase was washed twice with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain α-methyl-meta-methoxystyrene. This α-methyl-meta-methoxystyrene was directly dissolved in 85% ethanol, two equivalents of potassium hydroxide was added, and the mixture was refluxed for 30 hours with stirring. after that,
The ethanol was distilled off, poured into a large amount of ice, and the product was extracted with ether. After distilling off the ether, 9
A fraction between 5 and 100°C (approximately 7 Torr) was collected. m-methoxyphenylacetone was obtained in a yield of about 50% based on the starting material m-methoxyacetophenone.
【００４２】このｍ−メトキシフェニルアセトンを、窒
素気流下で、ＮａＯＢｒ水溶液中に徐々に加えて攪拌し
た。なお、アセチレンとＮａＯＢｒのモル比は約１／２
とした。少量のグライムを加えて混合性をよくし、その
後室温で１５〜２０時間攪拌した。反応の進行に伴って
、生成物が下層に分離してきた。反応終了後、反応混合
物を水中に注ぎ生成物をエーテル抽出した。このエーテ
ル相を無水硫酸マグネシウムで乾燥後、エーテルを留去
して、目的物である１−ブロム−２−メトキシフェニル
アセチレンを約６３％の収率で得た。This m-methoxyphenylacetone was gradually added to the NaOBr aqueous solution under a nitrogen stream and stirred. The molar ratio of acetylene and NaOBr is approximately 1/2.
And so. A small amount of glyme was added to improve mixing, and then stirred at room temperature for 15-20 hours. As the reaction progressed, the product separated into the lower layer. After the reaction was completed, the reaction mixture was poured into water and the product was extracted with ether. After drying this ether phase over anhydrous magnesium sulfate, the ether was distilled off to obtain the target product, 1-bromo-2-methoxyphenylacetylene, in a yield of about 63%.
【００４３】この１−ブロム−２−メトキシフェニルア
セチレンを実施例２と同様の反応条件下で、パラエチニ
ル安息香酸１４．６ｇと反応させることにより、パラ（
メタメトキシフェニルブタ−１、３−ジイニル）安息香
酸を淡黄色結晶性粉末として得た（収率約６０％）。
このときの反応式は次式（１６）で示すとおりである。By reacting this 1-bromo-2-methoxyphenylacetylene with 14.6 g of paraethynylbenzoic acid under the same reaction conditions as in Example 2, para(
Metamethoxyphenylbut-1,3-diynyl)benzoic acid was obtained as a pale yellow crystalline powder (yield about 60%). The reaction formula at this time is as shown in the following formula (16).
【００４４】[0044]
【化１６】[Chemical formula 16]
【００４５】得られたパラ（メタメトキシフェニルブタ
−１、３−ジイニル）安息香酸（Ｃ１８Ｈ１２Ｏ３）の
元素分析値と計算値は、次のとおりであり両者は良く整
合しており、また、赤外線吸収スペクトル分析結果は図
３に示すとおりであり、核磁気共鳴分析（ＮＭＲ）結果
は下記のとおりであった（図４参照）。
ＮＭＲ結果
１Ｈ−ＮＭＲ（１００ＭＨｚ 、ＣＤＣｌ３ ）δ（
ｐｐｍ）：３．７５（Ｓ、３Ｈ、Ｏ−ＣＨ３ ）６．９
〜７．５（ｍ、４Ｈ、Ｈｃ、Ｈｄ、Ｈｅ、Ｈｆ）７．７
（ｄ、２Ｈ、Ｈｂ）
７．９５（ｄ、２Ｈ、Ｈａ）The elemental analysis values and calculated values of the obtained para(methoxyphenylbut-1,3-diynyl)benzoic acid (C18H12O3) are as follows, and both agree well. The spectrum analysis results were as shown in FIG. 3, and the nuclear magnetic resonance analysis (NMR) results were as follows (see FIG. 4). NMR results 1H-NMR (100MHz, CDCl3) δ(
ppm): 3.75 (S, 3H, O-CH3) 6.9
~7.5 (m, 4H, Hc, Hd, He, Hf) 7.7
(d, 2H, Hb) 7.95 (d, 2H, Ha)
【００４６】[0046]
【発明の効果】上記したとおり、この発明のジアセチレ
ン含有安息香酸誘導体は、非対称型であって、一方にカ
ルボニル基、カルボキシル基等の電子吸引性の置換基を
持ち、他方にフェニル基系の電子供与性置換基を持つこ
とにより、ポリジアセチレン合成材料として固相重合後
、より高次の電気的、光学的機能が発現し、非線形光学
材料として有用なものである。Effects of the Invention As described above, the diacetylene-containing benzoic acid derivative of the present invention is of an asymmetric type, and has an electron-withdrawing substituent such as a carbonyl group or a carboxyl group on one side, and a phenyl group on the other side. By having an electron-donating substituent, higher-order electrical and optical functions are exhibited after solid-phase polymerization as a polydiacetylene synthetic material, making it useful as a nonlinear optical material.
【図面の簡単な説明】[Brief explanation of drawings]
【図１】メタ（オクタ−１，３−ジイニル）安息香酸の
ＩＲスペクトル図である。FIG. 1 is an IR spectrum diagram of meta(octa-1,3-diynyl)benzoic acid.
【図２】メタ（オクタ−１、３−ジイニル）安息香酸の
ＩＲスペクトル図である。FIG. 2 is an IR spectrum diagram of meta(octa-1,3-diynyl)benzoic acid.
【図３】パラ（メタメトキシフェニルブタ−１、３−ジ
イニル）安息香酸のＩＲスペクトル図である。FIG. 3 is an IR spectrum diagram of para(methoxyphenylbut-1,3-diynyl)benzoic acid.
【図４】パラ（メタメトキシフェニルブタ−１、３−ジ
イニル）安息香酸の １Ｈ−ＮＭＲチャート図である。FIG. 4 is a 1H-NMR chart of para(methoxyphenylbut-1,3-diynyl)benzoic acid.
Claims (1)
息香酸誘導体。 【化１】 （式中、Ｘ−ＣＯ−の置換位置は、オルト、メタまたは
パラのいずれでもよく、Ｘは、ＯＲ２（Ｒ２ は水素も
しくはアルキル基）またはＮＲ３ Ｒ４ （ Ｒ３ 、
Ｒ４ はそれぞれ水素もしくはアルキル基） を示し、
Ｒ１ はアルキル基、フェニル基もしくは置換フェニル
基を示す。）1. A diacetylene-containing benzoic acid derivative represented by the following formula 1. embedded image (wherein, the substitution position of X-CO- may be ortho, meta or para, and X is OR2 (R2 is hydrogen or an alkyl group) or NR3 R4 (R3,
R4 each represents hydrogen or an alkyl group),
R1 represents an alkyl group, a phenyl group or a substituted phenyl group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP647291A JPH04321643A (en) | 1991-01-23 | 1991-01-23 | Diacetylene-containing benzoic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP647291A JPH04321643A (en) | 1991-01-23 | 1991-01-23 | Diacetylene-containing benzoic acid derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04321643A true JPH04321643A (en) | 1992-11-11 |
Family
ID=11639403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP647291A Pending JPH04321643A (en) | 1991-01-23 | 1991-01-23 | Diacetylene-containing benzoic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04321643A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056000A (en) * | 2005-07-29 | 2007-03-08 | Sumitomo Bakelite Co Ltd | Aromatic carboxylic acid and acid halide thereof |
-
1991
- 1991-01-23 JP JP647291A patent/JPH04321643A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056000A (en) * | 2005-07-29 | 2007-03-08 | Sumitomo Bakelite Co Ltd | Aromatic carboxylic acid and acid halide thereof |
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