JP2764570B2 - Diacetylene derivative having tetrathiafulvalenyl group and method for producing the same - Google Patents
Diacetylene derivative having tetrathiafulvalenyl group and method for producing the sameInfo
- Publication number
- JP2764570B2 JP2764570B2 JP4274896A JP4274896A JP2764570B2 JP 2764570 B2 JP2764570 B2 JP 2764570B2 JP 4274896 A JP4274896 A JP 4274896A JP 4274896 A JP4274896 A JP 4274896A JP 2764570 B2 JP2764570 B2 JP 2764570B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- group
- compound
- represented
- formula
- 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.)
- Expired - Lifetime
Links
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title description 3
- -1 aromatic aminocarboxylic acid ester Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229940126062 Compound A Drugs 0.000 description 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LZXXNPOYQCLXRS-UHFFFAOYSA-N methyl 4-aminobenzoate Chemical compound COC(=O)C1=CC=C(N)C=C1 LZXXNPOYQCLXRS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は新規なジアセチレン
誘導体、さらに詳しくは、固相重合性を有し、非線形光
学材料、感光材料、高分子半導体結晶などの機能材料の
原料として有用なテトラチアフルバレニルを有するジア
セチレン誘導体及びその製造方法に関するものである。[0001] The present invention relates to a novel diacetylene derivative, more specifically, tetrathiafuran which has a solid phase polymerizability and is useful as a raw material for functional materials such as nonlinear optical materials, photosensitive materials, and polymer semiconductor crystals. The present invention relates to a diacetylene derivative having valenyl and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、非線形光学材料、感光材料、高分
子半導体結晶などを形成するための単量体として、ジア
セチレン化合物の研究が盛んに行われている。非線形光
学材料、感光材料、高分子半導体結晶などの形成にジア
セチレン化合物を用いるには、ジアセチレン化合物は固
相重合性を有することが必要であり、また、高分子半導
体結晶に用いる場合には、このジアセチレン化合物は、
テトラチアフルバレンなどの電子供与性が高く、電子求
引的なパイ共役系と電荷移動錯体を形成する置換基をも
つことが望ましいが、テトラチアフルバレニル基を有す
るジアセチレン誘導体は、これまで見出されていない。2. Description of the Related Art In recent years, diacetylene compounds have been actively studied as monomers for forming nonlinear optical materials, photosensitive materials, polymer semiconductor crystals, and the like. In order to use a diacetylene compound for forming a non-linear optical material, a photosensitive material, or a polymer semiconductor crystal, the diacetylene compound needs to have solid phase polymerizability. , This diacetylene compound is
It is desirable to have a substituent having a high electron donating property such as tetrathiafulvalene and forming a charge transfer complex with an electron-withdrawing pi-conjugated system. Not issued.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、テトラチア
フルバレニル基を有する新規なジアセチレン誘導体及び
その製造方法を提供することをその課題とする。An object of the present invention is to provide a novel diacetylene derivative having a tetrathiafulvalenyl group and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、新規なア
セチレン誘導体を開発するために鋭意研究を重ねた結
果、本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted intensive studies to develop a novel acetylene derivative, and as a result, have completed the present invention.
【０００５】すなわち、本発明によれば、一般式That is, according to the present invention, the general formula
【化１】 （式中、Ａｒは二価芳香族基であり、ｍ及びｎは１〜１
２の整数である）で表わされるジアセチレン誘導体が提
供される。また、本発明によれば、一般式Embedded image (Wherein, Ar is a divalent aromatic group, and m and n are 1 to 1)
A diacetylene derivative represented by the formula: Further, according to the present invention, the general formula
【化１】 （式中、Ａｒは二価芳香族基であり、ｍ及びｎは１〜１
２の整数である）で表わされるジアセチレン誘導体の製
造方法において、（ｉ）一般式Embedded image (Wherein, Ar is a divalent aromatic group, and m and n are 1 to 1)
A diacetylene derivative represented by the general formula (i):
【化２】 （式中、Ｒ1は水素又はハロゲン原子を示す）で表わさ
れる１，３−アルカジインカルボン酸化合物に、一般式Embedded image (Wherein, R 1 represents a hydrogen atom or a halogen atom)
【化３】 （式中、Ｒ2は炭化水素基を示し、Ａｒは前記と同じ意
味を有する）で表わされる芳香族アミノカルボン酸エス
テルを反応させて、一般式Embedded image (Wherein, R 2 represents a hydrocarbon group, and Ar has the same meaning as described above).
【化４】 （式中、Ａｒ、Ｒ2、ｍ及びｎは前記と同じ意味を有す
る）で表わされる１，３−アルカジインカルボン酸アミ
ド化合物を生成させる工程、（ii）前記１，３−アルカ
ジインカルボン酸アミド化合物中に含まれるエステル結
合を加水分解して、一般式Embedded image (Wherein, Ar, R 2 , m and n have the same meanings as described above), and (ii) the 1,3-alkadiyne carboxylic acid Hydrolyzing the ester bond contained in the amide compound, the general formula
【化５】 （式中、Ａｒ、ｍ及びｎは前記と同じ意味を有する）で
表わされるカルボキシル基を有する１，３−アルカジイ
ンカルボン酸アミド化合物を生成させる工程、（iii）
前記１，３−アルカジインカルボン酸アミド化合物又は
その酸ハライドに、式Embedded image (Wherein, Ar, m and n have the same meanings as described above), producing a 1,3-alkadiynecarboxylic acid amide compound having a carboxyl group, (iii)
The 1,3-alkadiynecarboxylic acid amide compound or an acid halide thereof has a formula
【化６】 で表わされるヒドロキシメチルテトラチアフルバレンを
反応させる工程、からなることを特徴とするジアセチレ
ン誘導体の製造方法が提供される。Embedded image And reacting hydroxymethyltetrathiafulvalene represented by the formula:
【０００６】[0006]
【発明の実施の形態】前記一般式（１）で表わされるジ
アセチレン誘導体は、文献未載の新規な化合物である。
式中のＡｒは、フェニレン基やナフチレン基等の二価芳
香族基（アリーレン基）である。また、ｍは１〜１８、
好ましくは１０〜１２の整数である。ｎは、１〜８、好
ましくは６〜８の整数である。BEST MODE FOR CARRYING OUT THE INVENTION The diacetylene derivative represented by the general formula (1) is a novel compound which has not been published in any literature.
Ar in the formula is a divalent aromatic group (arylene group) such as a phenylene group or a naphthylene group. Also, m is 1 to 18,
Preferably it is an integer of 10-12. n is an integer of 1 to 8, preferably 6 to 8.
【０００７】本発明の前記一般式（１）で表わされるジ
アセチレン誘導体は、前記一般式（２）で表わされる
１，３−アルカジインカルボン酸化合物を出発原料とし
て用いて製造することができる。前記一般式（２）にお
いて、ハロゲンとしては塩素又は臭素が挙げられる。The diacetylene derivative represented by the general formula (1) of the present invention can be produced by using a 1,3-alkadiynecarboxylic acid compound represented by the general formula (2) as a starting material. In the general formula (2), examples of the halogen include chlorine and bromine.
【０００８】本発明による一般式（１）のジアセチレン
誘導体を製造するには、前記一般式（２）で表わされる
１，３−アルカジインカルボン酸化合物を、前記一般式
（３）の芳香族アミノカルボン酸エステルと反応させ
る。前記一般式（３）におけるＲ2は炭化水素基であ
る。炭化水素基としては、メチル基、エチル基、プロピ
ル基、シクロヘキシル基等の鎖状又は環状のアルキル
基；フェニル基、トリル基等のアリール基；ベンジル基
等のアルアルキル基等が挙げられる。好ましい炭化水素
基は、炭素数１〜６、好ましくは１〜３の低級アルキル
基である。前記反応は、塩化メチレンのような非プロト
ン性溶媒中において、好ましくはアルゴンや窒素等の不
活性ガスの雰囲気中で、通常、常圧下において、０〜５
０℃、好ましくは２５〜４０℃範囲の温度で撹拌するこ
とによって実施される。前記反応によって、前記一般式
（４）で表わされる１，３−アルカジインカルボン酸ア
ミド化合物が得られる。In order to produce the diacetylene derivative of the general formula (1) according to the present invention, the 1,3-alkadiynecarboxylic acid compound represented by the general formula (2) is converted to an aromatic compound of the general formula (3). React with aminocarboxylic acid esters. R 2 in the general formula (3) is a hydrocarbon group. Examples of the hydrocarbon group include a chain or cyclic alkyl group such as a methyl group, an ethyl group, a propyl group, and a cyclohexyl group; an aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group. Preferred hydrocarbon groups are lower alkyl groups having 1 to 6, preferably 1 to 3 carbon atoms. The reaction is carried out in an aprotic solvent such as methylene chloride, preferably in an atmosphere of an inert gas such as argon or nitrogen, usually under normal pressure, from 0 to 5%.
It is carried out by stirring at a temperature of 0 ° C., preferably 25-40 ° C. By the reaction, a 1,3-alkadiynecarboxylic acid amide compound represented by the general formula (4) is obtained.
【０００９】次に前記で得た前記一般式（４）の１，３
−アルカジインカルボン酸アミド化合物に含まれるエス
テル結合を加水分解する。この反応は、塩基性触媒の保
存下で、０〜５０℃、好ましくは２５〜４０℃の範囲の
温度で実施される。塩基性触媒としては、水酸化リチウ
ムや水酸化カリウム等の水酸化アルカリの使用が好まし
い。また、この反応は、メタノール等のプロトン性溶媒
の存在下で好ましく実施される。前記の反応によって、
前記一般式（５）で表わされるカルボキシル基を有する
１，３−アルカジインカルボン酸アミド化合物が得られ
る。Next, 1,3 of the above-mentioned general formula (4) is obtained.
-Hydrolyze the ester bond contained in the alkadiyne carboxylic acid amide compound. This reaction is carried out at a temperature ranging from 0 to 50 ° C, preferably from 25 to 40 ° C, under storage of the basic catalyst. As the basic catalyst, use of an alkali hydroxide such as lithium hydroxide or potassium hydroxide is preferable. This reaction is preferably performed in the presence of a protic solvent such as methanol. By the above reaction,
A 1,3-alkadiynecarboxylic acid amide compound having a carboxyl group represented by the general formula (5) is obtained.
【００１０】次に、前記一般式（５）で表わされるカル
ボキシル基を有する１，３−アルカジインカルボン酸ア
ミド化合物又はその酸ハライドに、前記式（６）で表わ
されるヒドロキシメチルテトラチアフルバレンを反応さ
せる。これによって、前記一般式（１）の目的化合物を
得ることができる。前記反応は、好ましくはアルゴンや
窒素のような不活性ガスの雰囲気中で、通常、常圧下に
おいて、０〜５０℃、好ましくは２５〜５０℃で行われ
る。また、この反応は、塩化メチレンのような非プロト
ン性溶媒の存在下で好ましく行われる。Next, hydroxymethyltetrathiafulvalene represented by the above formula (6) is reacted with a 1,3-alkadiynecarboxylic acid amide compound having a carboxyl group represented by the above formula (5) or an acid halide thereof. Let it. Thereby, the target compound of the general formula (1) can be obtained. The reaction is preferably carried out in an atmosphere of an inert gas such as argon or nitrogen, usually at normal pressure, at 0 to 50 ° C, preferably 25 to 50 ° C. This reaction is preferably performed in the presence of an aprotic solvent such as methylene chloride.
【００１１】前記一般式（５）で表わされるカルボキシ
ル基を有する１，３−アルカジインカルボン酸アミド化
合物に含まれるカルボキシル基を酸ハライド（−ＣＯ
Ｘ、Ｘ：ハロゲン）に変換する方法としては、慣用の方
法が使用され、例えば、ハロゲン化剤として、シュウ酸
ジハライドを用いて行うことができる。The carboxyl group contained in the carboxyl group-containing 1,3-alkadiynecarboxylic acid amide compound represented by the general formula (5) is replaced with an acid halide (-CO
X, X: halogen) can be converted by a conventional method, for example, by using oxalic acid dihalide as a halogenating agent.
【００１２】本発明においては、前記一般式（４）の化
合物に式（６）のヒドロキシメチルテトラチアフルバレ
ンをエステル交換触媒の存在下で直接エステル交換反応
させることによって、一般式（１）の目的物を得ること
もできる。この場合、エステル交換触媒として、慣用の
アルカリ触媒、例えば、水酸化ナトリウム等を用いるこ
とができる。In the present invention, the compound of the general formula (1) is directly transesterified with the compound of the general formula (4) with hydroxymethyltetrathiafulvalene of the formula (6) in the presence of a transesterification catalyst. You can also get things. In this case, a conventional alkali catalyst, for example, sodium hydroxide or the like can be used as the transesterification catalyst.
【００１３】[0013]
【実施例】次に本発明を実施例によってさらに詳細に説
明する。Next, the present invention will be described in more detail with reference to examples.
【００１４】実施例１ （１）アミド化工程 次式で表わされる化合物Ａを反応原料として用いた。 ＣＨ3−(ＣＨ2)m−Ｃ≡Ｃ−Ｃ≡Ｃ−(ＣＨ2)n−ＣＯＯ
Ｈ （式中、ｍ：１１、ｎ：８） この化合物Ａ ２５ｇ、とシュウ酸二塩化物３５ｇを反
応溶媒としての塩化メチレン５００ｍｌ中で、窒素ガス
雰囲気下で、常圧において、２５℃で１２時間撹拌しな
がら反応を行った。溶媒を留去して、前記化合物Ａの酸
塩化物２７ｇが得られた。次に、この化合物Ａの酸塩化
物２７ｇと、ｐ−アミノ安息香酸メチル１３ｇを、反応
溶媒としての塩化メチレン５００ｍｌ中で、窒素ガス雰
囲気下で、常圧において、２５℃で１２時間撹拌しなが
ら反応を行った。溶媒を留去した後、シリカゲルカラム
クロマトグラフィーによりヘキサン−酢酸エチルを展開
溶媒として分離、精製することにより、次式で表わされ
る化合物Ｂ １７ｇが得られた。 ＣＨ3−(ＣＨ2)m−Ｃ≡Ｃ−Ｃ≡Ｃ−(ＣＨ2)nＣＯＮＨ
−Ｐｈ−ＣＯＯＣＨ3 （式中、ｍ及びｎは前記と同じ意味を有し、Ｐｈはフェ
ニレン基を示す）Example 1 (1) Amidation step Compound A represented by the following formula was used as a reaction raw material. CH 3 - (CH 2) m -C≡C-C≡C- (CH 2) n-COO
H (in the formula, m: 11, n: 8) 25 g of this compound A and 35 g of oxalic acid dichloride were added in 500 ml of methylene chloride as a reaction solvent under a nitrogen gas atmosphere at normal pressure and 25 ° C. for 12 hours. The reaction was performed with stirring for hours. The solvent was distilled off to obtain 27 g of the acid chloride of the compound A. Next, 27 g of the acid chloride of the compound A and 13 g of methyl p-aminobenzoate were stirred in 500 ml of methylene chloride as a reaction solvent under a nitrogen gas atmosphere at normal pressure and 25 ° C. for 12 hours. The reaction was performed. After the solvent was distilled off, the residue was separated and purified by silica gel column chromatography using hexane-ethyl acetate as a developing solvent to obtain 17 g of a compound B represented by the following formula. CH 3 - (CH 2) m -C≡C-C≡C- (CH 2) nCONH
-Ph-COOCH 3 (wherein m and n have the same meaning as described above, and Ph represents a phenylene group)
【００１５】（２）エステル基の加水分解 前記化合物Ｂ １５ｇを、メタノール５００ｍｌ中にお
いて、水酸化リチウム３ｇ及び水５０ｇの存在下、常圧
で、３０℃で１２時間撹拌しながら加水分解反応を行っ
た。このようにして、次式で表わされる化合物Ｃ １３
ｇが得られた。 ＣＨ3−(ＣＨ2)m−Ｃ≡Ｃ−Ｃ≡Ｃ−(ＣＨ2)nＣＯＮＨ
−Ｐｈ−ＣＯＯＨ （ｍ：１１、ｎ：８、Ｐｈ：フェニレン基）(2) Hydrolysis of Ester Group 15 g of the compound B was hydrolyzed in 500 ml of methanol in the presence of 3 g of lithium hydroxide and 50 g of water at 30 ° C. for 12 hours under stirring at normal pressure. Was. Thus, the compound C 13 represented by the following formula:
g was obtained. CH 3 - (CH 2) m -C≡C-C≡C- (CH 2) nCONH
-Ph-COOH (m: 11, n: 8, Ph: phenylene group)
【００１６】（３）エステル化工程 前記化合物Ｃをシュウ酸二塩化物を用いて塩素化して、
その塩化物を合成した。この化合物Ｃの塩化物１３ｇ
と、ヒドロキシメチルテトラチアフルバレン１２ｇを、
塩化メチレン３０ｍｌ中で、常圧で、窒素ガスの雰囲気
中で３０℃で１２時間撹拌しながら反応を行った。溶媒
を留去した後、シリカゲルカラムクロマトグラフィーに
よりヘキサン−酢酸エチルを展開溶媒として分離、精製
することにより、次式で表わされる目的化合物４ｇを得
た。(3) Esterification step The compound C is chlorinated with oxalic acid dichloride,
The chloride was synthesized. 13 g of the chloride of this compound C
And 12 g of hydroxymethyltetrathiafulvalene
The reaction was carried out in 30 ml of methylene chloride at normal pressure and in a nitrogen gas atmosphere at 30 ° C. with stirring for 12 hours. After evaporating the solvent, the residue was separated and purified by silica gel column chromatography using hexane-ethyl acetate as a developing solvent, to obtain 4 g of the desired compound represented by the following formula.
【化７】 （式中、ｍは１１、ｎは８を示し、Ｐｈはフェニレン基
を示す） このジアセチレン誘導体は、黄白色結晶であり、その融
点は約１１２℃であった。 元素分析値として、 計算値（％）； Ｃ ６５．９７ Ｈ ７．２４ Ｎ １．９７ 実測値（％）； Ｃ ６５．９５ Ｈ ７．２０ Ｎ ２．０３Embedded image (In the formula, m represents 11, n represents 8, and Ph represents a phenylene group.) This diacetylene derivative was a yellow-white crystal, and its melting point was about 112 ° C. Calculated value (%); C 65.97 H 7.24 N 1.97 Actual value (%); C 65.95 H 7.20 N 2.03
【００１７】[0017]
【発明の効果】本発明のジアセチレン誘導体は、電子供
与性の高いテトラチアフルバレニル基を有し、かつ固相
重合性を有することから、非線形光学材料、感光材料、
高分子半導体結晶等の機能性材料の原料として極めて有
用である。The diacetylene derivative of the present invention has a tetrathiafulvalenyl group having a high electron-donating property and has a solid-phase polymerization property.
It is extremely useful as a raw material for functional materials such as polymer semiconductor crystals.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中西 八郎 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (58)調査した分野(Int.Cl.6，ＤＢ名) C07D 339/06 C08F 38/02 G02B 1/04 G03C 1/73 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＷＰＩＤＳ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hachiro Nakanishi 1-1-1 Higashi, Tsukuba-shi, Ibaraki Pref. National Institute of Industrial Science and Technology (58) Field surveyed (Int. Cl. 6 , DB name) C07D 339 / 06 C08F 38/02 G02B 1/04 G03C 1/73 CA (STN) REGISTRY (STN) WPIDS (STN)
Claims (2)
２の整数である）で表わされるジアセチレン誘導体。1. A compound of the general formula (Wherein, Ar is a divalent aromatic group, and m and n are 1 to 1)
A diacetylene derivative represented by the formula:
２の整数である）で表わされるジアセチレン誘導体の製
造方法において、（ｉ）一般式 【化２】 （式中、Ｒ1は水素又はハロゲン原子を示す）で表わさ
れる１，３−アルカジインカルボン酸化合物に、一般式 【化３】 （式中、Ｒ2は炭化水素基を示し、Ａｒは前記と同じ意
味を有する）で表わされる芳香族アミノカルボン酸エス
テルを反応させて、一般式 【化４】 （式中、Ａｒ、Ｒ2、ｍ及びｎは前記と同じ意味を有す
る）で表わされる１，３−アルカジインカルボン酸アミ
ド化合物を生成させる工程、（ii）前記１，３−アルカ
ジインカルボン酸アミド化合物中に含まれるエステル結
合を加水分解して、一般式 【化５】 （式中、Ａｒ、ｍ及びｎは前記と同じ意味を有する）で
表わされるカルボキシル基を有する１，３−アルカジイ
ンカルボン酸アミド化合物を生成させる工程、（iii）
前記１，３−アルカジインカルボン酸アミド化合物又は
その酸ハライドに、式 【化６】 で表わされるヒドロキシメチルテトラチアフルバレンを
反応させる工程、からなることを特徴とするジアセチレ
ン誘導体の製造方法。2. A compound of the general formula (Wherein, Ar is a divalent aromatic group, and m and n are 1 to 1)
A diacetylene derivative represented by the general formula: (Wherein R 1 represents a hydrogen atom or a halogen atom) to a 1,3-alkadiynecarboxylic acid compound represented by the general formula: (Wherein R 2 represents a hydrocarbon group and Ar has the same meaning as described above) by reacting an aromatic aminocarboxylic acid ester represented by the general formula: (Wherein, Ar, R 2 , m and n have the same meaning as described above), and (ii) the 1,3-alkadiyne carboxylic acid The ester bond contained in the amide compound is hydrolyzed to give the general formula: (Wherein, Ar, m and n have the same meanings as described above), producing a 1,3-alkadiynecarboxylic acid amide compound having a carboxyl group, (iii)
The 1,3-alkadiynecarboxylic acid amide compound or an acid halide thereof has the formula: Reacting hydroxymethyltetrathiafulvalene represented by the following formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4274896A JP2764570B2 (en) | 1996-02-29 | 1996-02-29 | Diacetylene derivative having tetrathiafulvalenyl group and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4274896A JP2764570B2 (en) | 1996-02-29 | 1996-02-29 | Diacetylene derivative having tetrathiafulvalenyl group and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09227552A JPH09227552A (en) | 1997-09-02 |
| JP2764570B2 true JP2764570B2 (en) | 1998-06-11 |
Family
ID=12644643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4274896A Expired - Lifetime JP2764570B2 (en) | 1996-02-29 | 1996-02-29 | Diacetylene derivative having tetrathiafulvalenyl group and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2764570B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5728777B2 (en) * | 2008-02-15 | 2015-06-03 | 国立研究開発法人物質・材料研究機構 | Organic compounds, organic semiconductor compounds, semiconductor elements, and solar cells |
| WO2020065321A1 (en) * | 2018-09-28 | 2020-04-02 | Datalase Ltd. | Colour forming compositions |
-
1996
- 1996-02-29 JP JP4274896A patent/JP2764570B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09227552A (en) | 1997-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6322350B1 (en) | New trityl protecting agent | |
| JP2005336155A (en) | Method for producing cyclic disulfonic acid ester | |
| JP2007533727A (en) | Method for producing valsartan and its precursor | |
| JP2764570B2 (en) | Diacetylene derivative having tetrathiafulvalenyl group and method for producing the same | |
| JP2000212185A (en) | Production of para-boronophenylalanine derivative | |
| JPS6148830B2 (en) | ||
| JP4397550B2 (en) | Method for producing aromatic carboxylic acid | |
| JP2006104169A (en) | Method for producing tertiary cycloalkyl (meth) acrylate | |
| JP2002037759A (en) | Method for producing acrylic acid ester or methacrylic acid ester | |
| JP4172200B2 (en) | Ether compound and process for producing the same | |
| JP4929663B2 (en) | Method for producing polymerizable compound | |
| JP5177374B2 (en) | (Meth) acrylic acid ester and method for producing the same | |
| JPH06279433A (en) | 6-membered carbonic acid ester derivative | |
| JP2727243B2 (en) | Method for producing 2-acylaminocinnamic acid derivatives | |
| JP4070297B2 (en) | New (meth) acrylic ester compounds | |
| JP2979138B2 (en) | Acrylamide compounds with amino acid residues | |
| JP3509421B2 (en) | Method for producing diaryl carbonate | |
| JPH06306040A (en) | Photopolymerizable diacetylene compound | |
| JPH1171335A (en) | Production of aromatic carboxylic amides | |
| JP3013760B2 (en) | Method for producing 4-hydroxy-2-pyrrolidone | |
| JP2015518014A (en) | Synthesis of diamide gelling agents by using Dane salts of amino acids | |
| JP2560242B2 (en) | Diacetylene derivative and method for producing the same | |
| JPS5935369B2 (en) | Stereoselective synthesis method for optically active compounds | |
| JP2002097181A (en) | Method for producing n-(vinylphenyl) carbazole analogue | |
| JPS5837324B2 (en) | Method for producing 6-vinylindolo[2,3-b]quinoxaline polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |