JPH0421676A - Thiophene derivative - Google Patents
Thiophene derivativeInfo
- Publication number
- JPH0421676A JPH0421676A JP12400990A JP12400990A JPH0421676A JP H0421676 A JPH0421676 A JP H0421676A JP 12400990 A JP12400990 A JP 12400990A JP 12400990 A JP12400990 A JP 12400990A JP H0421676 A JPH0421676 A JP H0421676A
- Authority
- JP
- Japan
- Prior art keywords
- salt
- formula
- tetramer
- compound
- prepared
- 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
- 150000003577 thiophenes Chemical class 0.000 title claims abstract description 5
- -1 anionic radical salt Chemical class 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 7
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 abstract description 7
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 abstract description 6
- 239000004020 conductor Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 abstract description 3
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical compound BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 abstract description 2
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 abstract 2
- 230000004048 modification Effects 0.000 abstract 2
- 238000012986 modification Methods 0.000 abstract 2
- RNBVPNGWDHUVLV-UHFFFAOYSA-N C1(=CC=CC=C1)[Si](C1=CC=C(C=C1)[Zn])(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[Si](C1=CC=C(C=C1)[Zn])(C1=CC=CC=C1)C1=CC=CC=C1 RNBVPNGWDHUVLV-UHFFFAOYSA-N 0.000 abstract 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 abstract 1
- 159000000000 sodium salts Chemical class 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- NJFQTNXYFOEFJU-UHFFFAOYSA-N [2-[4-[4-(2-azanidylidene-1-cyanoethenyl)phenyl]phenyl]-2-cyanoethenylidene]azanide;tetrabutylazanium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.C1=CC(C(C#N)=C=[N-])=CC=C1C1=CC=C(C(C#N)=C=[N-])C=C1 NJFQTNXYFOEFJU-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- UKTSSJJZFVGTCG-UHFFFAOYSA-N (4-bromophenyl)-trimethylsilane Chemical compound C[Si](C)(C)C1=CC=C(Br)C=C1 UKTSSJJZFVGTCG-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VFHDCDDYMMQCBF-UHFFFAOYSA-M [Cl-].[Zn+]C1=CC=CC=C1 Chemical compound [Cl-].[Zn+]C1=CC=CC=C1 VFHDCDDYMMQCBF-UHFFFAOYSA-M 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- BINRQGPOCBVYMH-UHFFFAOYSA-N 2,5-dihydrothiophene Chemical compound C1SCC=[C]1 BINRQGPOCBVYMH-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- ZSDNRQGRRJEJGW-UHFFFAOYSA-M [Cl-].C[Si](C1=CC=C(C=C1)[Zn+])(C)C Chemical compound [Cl-].C[Si](C1=CC=C(C=C1)[Zn+])(C)C ZSDNRQGRRJEJGW-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001787 chalcogens Chemical group 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 1
- PZDGFIQCGRQOFR-UHFFFAOYSA-N trimethyl-[4-[5-(4-trimethylsilylphenyl)thiophen-2-yl]phenyl]silane Chemical compound C1=CC([Si](C)(C)C)=CC=C1C1=CC=C(C=2C=CC(=CC=2)[Si](C)(C)C)S1 PZDGFIQCGRQOFR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、有機電導体として有用なチオフェン誘導体に
関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to thiophene derivatives useful as organic conductors.
（従来の技術）
テトラチアフルバレン・テトラシアノキノジメタン（Ｔ
ＴＦ −ＴＣＮＱ）の電荷移動錯体が金属的性質を示す
ことが見い出されて以来、さらに優れた有機分子性金属
や高電導体の開発を目ざして、その構成成分となる電子
受容体や電子供与体かいろいろと分子設計され、合成さ
れ、その錯体やラジカル塩の電導性が研究の対象となっ
ている。(Prior art) Tetrathiafulvalene/tetracyanoquinodimethane (T
Since it was discovered that the charge transfer complex of TF-TCNQ) exhibits metallic properties, efforts have been made to develop even better organic molecular metals and high conductors, including the electron acceptors and electron donors that are their constituent components. A variety of molecules have been designed and synthesized, and the conductivity of their complexes and radical salts is the subject of research.
従来までの研究の結果、高電導性を発現させるために、
次に示すようないくつかの重要な分子設計上の要請があ
る。As a result of previous research, in order to achieve high conductivity,
There are several important molecular design requirements as follows.
（１）中性、アニオンラジカルまたはカチオンラジカル
、およびジアニオンまたはシカチオン状態で分子の平面
性が良いこと、
（２）イオンラジカル状態が安定であること、（３）ジ
アニオン状態またはシカチオン状態におけるクーロン斥
力が小さいこと、
（４）硫黄原子のようなカルコゲン原子を導入して、Ｓ
・・・Ｓコンタクトにより分離積層カラム内における分
子間相互作用を強めること
（３）の要請を受けて、テトラシアノキノジメタン（Ｔ
ＣＮＱ）よりもさらにジアニオン状態におけるクーロン
斥力を小さくする目的で、すでにテトラシアノジフェノ
キノン（以下、ＴＣＮＤＱという）が合成されている。(1) Good planarity of the molecule in the neutral, anion radical or cation radical, dianion or scation state; (2) stability in the ion radical state; (3) Coulomb repulsion in the dianion or scation state. (4) By introducing a chalcogen atom such as a sulfur atom, S
...In response to the request (3) to strengthen the intermolecular interaction in the separation stack column by S contact, we developed tetracyanoquinodimethane (T
Tetracyanodiphenoquinone (hereinafter referred to as TCNDQ) has already been synthesized for the purpose of making the Coulombic repulsion in the dianion state even smaller than that of CNQ).
ＴＣＮＱ ＴＣＮＤＱしかしＴ
ＣＮＤＱにおいては、二つの６員環上のオルソ水素原子
相互の立体反発が大きいために、これを解消しようとし
て、二つの６員環がねしれて非平面構造をとりやすく、
（１）の要請が満足されないという欠点があった。TCNQ TCNDQ But T
In CNDQ, there is a large steric repulsion between the ortho hydrogen atoms on the two six-membered rings, so in an attempt to eliminate this, the two six-membered rings tend to twist and form a non-planar structure.
There was a drawback that requirement (1) was not satisfied.
（発明が解決しようとする課題）
本発明者は、ＴＣＮＤＱにおけるこのような非平面性を
改良して平面性の良い分子を合成し、さらに電子移動の
過程で立体配座の変化を伴わず、さらに二つのジシアノ
メチレン基の間により長い共役系を導入して、ジアニオ
ン状態におけるクーロン斥力を小さくし、さらに（４）
の要請に応えるために分子の中央部に硫黄原子を導入す
ることを検討した結果、２．５−ビス（４−ジシアノメ
チレン−２，５−シクロへキサジエン−１−イリデン）
−２，５−ジヒドロチオフェンがその四量体、アニオン
ラジカル塩、およびジアニオン塩として安定に合成され
るとともに、とくにアニオンラジカル塩が高電導性を示
すことを見い出し、本発明に到達した。(Problems to be Solved by the Invention) The present inventors have synthesized a molecule with good planarity by improving such non-planarity in TCNDQ, and furthermore, the present inventors have synthesized a molecule with good planarity without changing the conformation in the process of electron transfer. Furthermore, by introducing a longer conjugated system between two dicyanomethylene groups, the Coulomb repulsion in the dianion state is reduced, and further (4)
As a result of considering introducing a sulfur atom into the center of the molecule in order to meet the demands of
The inventors have discovered that -2,5-dihydrothiophene can be stably synthesized as its tetramer, anion radical salt, and dianion salt, and that the anion radical salt in particular exhibits high conductivity, thereby achieving the present invention.
（課題を解決するための手段）
本発明は、構造式
で表される２、５−ビス（４−ジシアノメチレン−２，
５−シクロへキサジエン−１−イリデン）＝２．５−ジ
ヒドロチオフェン、別名、テトラシアノチエニル−拡張
型−ジフェノキノン（以下ＴＣＮＴＤＱという）の四量
体、アニオンラジカル塩及びジアニオン塩を提供するこ
とにある。(Means for Solving the Problems) The present invention provides 2,5-bis(4-dicyanomethylene-2,
An object of the present invention is to provide a tetramer, anion radical salt, and dianion salt of 5-cyclohexadien-1-ylidene)=2,5-dihydrothiophene, also known as tetracyanothienyl-extended-diphenoquinone (hereinafter referred to as TCNTDQ). .
以下、本発明について詳細に記述する。The present invention will be described in detail below.
本発明のチオフェン誘導体は、式（Ｉ）のＴＣＮＴＤＱ
の四量体、アニオンラジカル塩、ジアニオン塩として得
られる。The thiophene derivatives of the present invention are TCNTDQ of formula (I)
Obtained as a tetramer, anion radical salt, and dianion salt.
その製法は、１，４−ジブロモベンゼンを１モル当量の
ブチルリチウムと反応させ、リチウム化したのち、これ
をトリメチルクロロシランと反応させて、４−トリメチ
ルシリルブロモベンゼンを得る。これをブチルリチウム
でリチウム化した後、塩化亜鉛を加えてメタル交換を行
い、塩化ｐ−トリメチルシリルフェニル亜鉛とした後、
これに触媒としてＯ価パラジウム錯体の存在下に、２．
５−ジブロモチオフェンを作用させ、を得る。Its production method involves reacting 1,4-dibromobenzene with 1 molar equivalent of butyllithium to lithiate it, and then reacting it with trimethylchlorosilane to obtain 4-trimethylsilylbromobenzene. After lithiation of this with butyllithium, metal exchange was performed by adding zinc chloride to make p-trimethylsilylphenylzinc chloride, and then
In the presence of an O-valent palladium complex as a catalyst, 2.
5-dibromothiophene is applied to obtain.
得られた生成物（ＩＩ）に２モル当量のＮ−ヨウ化コハ
ク酸イミドを反応させて、ショート体である
を得る。The obtained product (II) is reacted with 2 molar equivalents of N-iodinosuccinimide to obtain a short product.
得られた生成物 （ＩＩ＋ ）にＰｄＣβ（ＰＰｈＳ）。the product obtained (II+) PdCβ (PPhS).
触媒の存在下に、 マロン酸ニトリルのＮａ塩を反 応させて、 ＴＣＮＴＤＱのジヒドロ体である を得る。In the presence of a catalyst, Reacting the Na salt of malonic acid nitrile Let me respond, It is a dihydro form of TCNTDQ. get.
得られた生成物 （ＩＶ）にＮ−ヨウ化コハク酸 イミドを反応させて、 ＴＣＮＴＤＱの四量体 を得る。the product obtained (IV) N-iodinosuccinic acid By reacting imide, Tetramer of TCNTDQ get.
またＴＣＮＤＱのジヒドロ体（ＩＶ）を水酸化ナトリウ
ム水溶液に溶解させ、テトラブチルアンモニウムヒドロ
キシド水溶液を作用させると、ジアニオン塩であるビス
（テトラブチルアンモニウム）塩
を得る。Further, when the dihydro form (IV) of TCNDQ is dissolved in an aqueous sodium hydroxide solution and treated with an aqueous tetrabutylammonium hydroxide solution, a bis(tetrabutylammonium) salt, which is a dianion salt, is obtained.
さらに、ＴＣＮＴＤＱの四量体（Ｖ）にヨウ化ナトリウ
ムを反応させると、ＴＣＮＴＤＱのアニオンラジカル塩
である
を得る。Furthermore, when the tetramer (V) of TCNTDQ is reacted with sodium iodide, an anion radical salt of TCNTDQ is obtained.
このＮａアニオンラジカル塩（■）は良好な電導性を示
す。This Na anion radical salt (■) exhibits good electrical conductivity.
ＴＣＮＴＤＱのアニオンラジカル塩が
ＴＣＮＤＱのアニオンラジカル塩に比べて高い電導性を
示す理由として、次のことが挙げられる。The reason why the anion radical salt of TCNTDQ exhibits higher conductivity than the anion radical salt of TCNDQ is as follows.
■ ＴＣＮＴＤＱはＴＣＮＤＱに比べて分子の平面性が
良いこと、
■ ＴＣＮＴＤＱはＴＣＮＤＱに比べてジアニオン状態
［ＴＣＮＴＤＱ］ ”−におけるクーロン斥力が減少し
ていること、
■ ＴＣＮＴＤＱは分子の中心部に硫黄原子を有してお
り、この硫黄原子がアニオンラジカルやジアニオン状態
を電子的に安定化していること、■ 結晶状態でＳ・・
・Ｓコンタクトにより分子間相互作用を高めていること
、
［実施例］
以下、実施例及び比較例により本発明を具体的に説明す
る。■ TCNTDQ has better molecular planarity than TCNDQ, ■ TCNTDQ has a reduced Coulomb repulsion in the dianion state [TCNTDQ] ``- compared to TCNDQ, ■ TCNTDQ has a sulfur atom in the center of the molecule. This sulfur atom electronically stabilizes the anion radical and dianion state;
- Intermolecular interaction is enhanced by S contact. [Examples] The present invention will be specifically explained below using Examples and Comparative Examples.
実施例１
［２，５−ビス（４−トリメチルシリルフェニル）チオ
フェンの合成］
１．４−ジブロモベンゼン４０．０ｇ（１７０，０ｍｍ
ｏｆ）を無水ジエチルエーテル２００−に溶解させた溶
液をＯ′Ｃに保ち、これに、ブチルリチウムの１４９Ｍ
ヘキサン溶液１１４ｍ１’ （１７０，０ｍｍｏｆ）を
滴下し、さらにＯ″Ｃで１時間撹拌した。これに、トリ
メチルクロロシラン４３２−（３４０，０ｍｍｏｆ）を
滴下し、さらに室温で３０分間撹拌した。反応液に水を
加え、ジエチルエテルで抽出した。ジエチルエーテル層
を水、ついて飽和食塩水で洗浄し、無水硫酸ナトリウム
を加えて乾燥した。溶媒を減圧で留去し、ヘキサンを用
いるシリカゲルカラムクロマトグラフィーにより残渣を
分離精製すると、無色液体の４−トリメチルシリルブロ
モベンゼンが３８．６８ｇ（１６８、８ｍｍｏｆ）得ら
れた。収率は理論量に対して９９．３％であった。Example 1 [Synthesis of 2,5-bis(4-trimethylsilylphenyl)thiophene] 40.0 g of 1,4-dibromobenzene (170.0 mm
of) in anhydrous diethyl ether was kept at O'C, and to this was added 149M of butyllithium.
114 ml of hexane solution (170,0 mmof) was added dropwise and further stirred for 1 hour at O''C. To this, trimethylchlorosilane 432-(340,0 mmof) was added dropwise and further stirred for 30 minutes at room temperature. Water was added and extracted with diethyl ether.The diethyl ether layer was washed with water and then with saturated brine, and dried by adding anhydrous sodium sulfate.The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using hexane. Upon separation and purification, 38.68 g (168.8 mmof) of 4-trimethylsilylbromobenzene was obtained as a colorless liquid.The yield was 99.3% based on the theoretical amount.
この化合物２、ＯＯｇ（８，７２６ｍｍｏｆ）を無水ジ
エチルエーテル１２１１１に溶解させて得た溶液を０℃
に保ち、アルゴン気流下で、ブチルリチウムの１５０Ｍ
ヘキサン溶液５８ｌ−（８、７２６ｍｍｏｆ）を滴下し
、さらに、１時間撹拌した。これを、無水塩化亜鉛１１
９ｇ（８、７２６ｍｍｏｆりを無水テトラヒドロフラン
１２−に溶解させて得た溶液中に滴下し、さらに、１時
間撹拌して、相当するフェニル塩化亜鉛を得た。他方、
ＰｄＣｊ２ａ（ＰＰｈｓ）ｚ ２４５ｍｇ（０、３４９
ｍｍｏｆ）を無水テトラヒドロフラン１２−に懸濁させ
て得た懸濁液にジイソブチルアルミニウムハイドライド
（ＤＩＢＡＨ）の１Ｍヘキサン溶液０．６９８ｍ／ （
０，６９８ｍｍｏｆ）を加え、１０分間撹拌して、Ｐｄ
（０）触媒を調製した。この中に、２．５−ジブロモ
チオフェン８４４ｍｇ（３，４９１１０１）を、無水テ
トラヒドロフラン１０．７部に溶解させて得た溶液と、
先に調製したフェニル塩化亜鉛のテトラヒドロフラン溶
液を滴下し、さらに１時間撹拌した。ついで反応液を水
に注ぎ、ジエチルエーテルで抽出した。ジエチルエーテ
ル層を水、ついで飽和食塩水で洗浄し、無水硫酸ナトリ
ウムを加えて乾燥した。溶媒を減圧留去したのち、ヘキ
サンを用いるシリカゲルカラムクロマトグラフィーによ
り残渣を分離精製すると、１２６〜７°Ｃの白色結晶が
７１４ｍｇ得られた。A solution obtained by dissolving this compound 2, OOg (8,726 mmof) in anhydrous diethyl ether 12111 was heated at 0°C.
150M of butyllithium under a stream of argon.
58 l of hexane solution (8,726 mmof) was added dropwise, and the mixture was further stirred for 1 hour. Add this to anhydrous zinc chloride 11
9 g (8,726 mmof) was added dropwise to a solution obtained by dissolving 12-g of anhydrous tetrahydrofuran, and the mixture was further stirred for 1 hour to obtain the corresponding phenylzinc chloride.
PdCj2a (PPhs)z 245 mg (0, 349
A 1M hexane solution of diisobutylaluminum hydride (DIBAH) (0.698 m/(
0,698 mmof) and stirred for 10 minutes.
(0) A catalyst was prepared. In this, a solution obtained by dissolving 844 mg (3,491101) of 2,5-dibromothiophene in 10.7 parts of anhydrous tetrahydrofuran,
The previously prepared tetrahydrofuran solution of phenylzinc chloride was added dropwise, and the mixture was further stirred for 1 hour. The reaction solution was then poured into water and extracted with diethyl ether. The diethyl ether layer was washed with water and then with saturated brine, and dried by adding anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was separated and purified by silica gel column chromatography using hexane to obtain 714 mg of white crystals with a temperature of 126 to 7°C.
得られた白色結晶の’ ＨＮＭＲ（ＣＤＣｆｆ 、、２
００ＭＨｚ）スペクトルを測定したところ、０．２９ｐ
ｐｍ （１８Ｈ，ｓ）にメチル基のシグナル、７．３
１ｐｐｍ （２Ｈ，ｓ）にチオフェン環上の水素のシ
グナル、７．５３ｐｐｍ （４Ｈ，ｄ、Ｊ＝８．２Ｈ
ｚ）と７．６２ｐｐｍ （４Ｈ，ｄ、Ｊ＝８．２Ｈｚ
）にベンゼン環上の水素のシグナルが現われることから
、この白色結晶は２．５−ビス（トリメチルシリルフェ
ニル）チオフェン（ＩＩ）（１、８７５ｍｍｏｆ）であ
ることが確認された。収率は理論量に対して５３．７％
であった。'HNMR of the obtained white crystals (CDCff, 2
00MHz) spectrum was measured and found to be 0.29p.
Methyl group signal at pm (18H,s), 7.3
Signal of hydrogen on the thiophene ring at 1 ppm (2H, s), 7.53 ppm (4H, d, J = 8.2H
z) and 7.62ppm (4H, d, J=8.2Hz
), this white crystal was confirmed to be 2,5-bis(trimethylsilylphenyl)thiophene (II) (1,875 mmof). Yield is 53.7% based on the theoretical amount
Met.
実施例２
［２，５−ビス（４−ヨウ化フェニル）チオフェンの合
成
実施例１で得られた２、５−ビス（４−トリメチルシリ
ルフェニル）チオフェン３．２０ｇ（８，４０６闘ｏｆ
）をクロロホルム８０−に溶解させ、この溶液に酢酸８
０−とＮ−ヨウ化コハク酸イミド３．７８ｇ （１６
，８１ｍｍｏｉ’）を加えて、室温で２時間攪拌した。Example 2 Synthesis of 2,5-bis(4-iodide phenyl)thiophene 3.20 g (8,406 g of 2,5-bis(4-trimethylsilylphenyl)thiophene obtained in Example 1)
) is dissolved in chloroform 80-, and acetic acid 8-8 is added to this solution.
3.78 g of 0- and N-iodinated succinimide (16
, 81 mmoi') and stirred at room temperature for 2 hours.
生成した沈殿を濾過し、水で洗浄すると、融点２８０−
２８５°Ｃの白色結晶が３．９０１ｇ得られた。When the formed precipitate is filtered and washed with water, the melting point is 280-
3.901 g of white crystals at 285°C were obtained.
得られた白色結晶の’ ＨＮＭＲ（ＣＤＣｆｆ 、、２
００ＭＨｚ）スペクトルを測定したところ、７．２８ｐ
ｐｍに水素２個分のやき幅広い一重線が現われ、チオフ
ェン環上の水素のシグナルと考えられた。また７、３５
ｐｐｍ （４Ｈ，ｄ、Ｊ＝８．８Ｈｚ）と７．７１ｐ
ｐｍ （４Ｈ，ｄ、Ｊ＝８．８Ｈｚ）にベンゼン環上
の水素のシグナルが現われた。また、マススペクトルを
測定したところ、ｍ／ｅ４８８に分子イオンビークがベ
ースビークとして現われた。これらの結果から、この白
色結晶は２．５−ビス（４−ヨウ化フェニル）チオフェ
ン（ＩＩＩ） （７、９９２ｍｍｏｆ）であることが
確認された。収率は理論量に対して９５１％であった。'HNMR of the obtained white crystals (CDCff, 2
00MHz) spectrum was measured and found to be 7.28p.
A broad singlet line corresponding to two hydrogen atoms appeared at pm, which was considered to be a signal of hydrogen on the thiophene ring. 7, 35 again
ppm (4H, d, J=8.8Hz) and 7.71p
A hydrogen signal on the benzene ring appeared at pm (4H, d, J=8.8Hz). Furthermore, when the mass spectrum was measured, a molecular ion peak appeared as a base peak at m/e 488. From these results, it was confirmed that this white crystal was 2,5-bis(4-iodide phenyl)thiophene(III) (7,992 mmof). The yield was 951% of the theoretical amount.
実施例３
［２，５−ビス（４−ジシアノメチルフェニル）チオフ
ェンの合成コ
アルゴン気流下、水素化ナトリウム１．１８ｇ（４９，
１７ｍｍｏｆ）を無水テトラヒドロフラン１２０Ｗｄ！
に懸濁させて懸濁液を得た。マロン酸ニトリル２．１７
ｇ （３２，７８ｍｍｏＪ）をテトラヒドロフラン４
０ｄに溶解させて得た溶液を上記の懸濁液に滴下し、室
温で、１０分間撹拌した。これに、ＰｄＣｆＰｄＣｆｆ
−１ＰＰｈ−）２５７５． ８１９ｍｍｏ１）及び実施
例２で得られた２、５−ビス（４−ヨウ化フェニル）チ
オフェン４、 ００ｇ （８，１９５ｍｍｏｆ）を加え
、２１時間還流した。反応液を水に注ぎ、ＩＮ塩酸で酸
性にした後、塩化メチレンで抽出し、塩化メチレン層を
水、次いで飽和食塩水で洗浄し、無水硫酸ナトリウムを
加えて乾燥した。Example 3 Synthesis of 2,5-bis(4-dicyanomethylphenyl)thiophene 1.18 g of sodium hydride (49,
17mmof) to anhydrous tetrahydrofuran 120Wd!
to obtain a suspension. Malonic acid nitrile 2.17
g (32,78 mmoJ) in tetrahydrofuran 4
The solution obtained by dissolving the solution in 0d was added dropwise to the above suspension, and the mixture was stirred at room temperature for 10 minutes. In addition, PdCfPdCff
-1PPh-)2575. 819 mmol) and 4,00 g (8,195 mmof) of 2,5-bis(4-iodide phenyl)thiophene obtained in Example 2 were added, and the mixture was refluxed for 21 hours. The reaction solution was poured into water, acidified with IN hydrochloric acid, extracted with methylene chloride, and the methylene chloride layer was washed with water and then with saturated brine, and dried by adding anhydrous sodium sulfate.
溶媒を減圧留去し、塩化メチレン 酢酸エチル２１の混
合溶媒を用いるシリカゲルカラムクロマトグラフィーに
より残渣を分離し、クロロホルムを用いる再結晶により
精製すると、融点１９４−１９５°Ｃの黄土色結晶が２
．９００ｇ得られた。 得らハだ黄土色結晶の ’ＨＮ
ＭＲ（ＣＤＣＩ２３．２００ＭＨｚ）スペクトルを測定
したところ、５．１０ｐｐｍ （２Ｈ，ｓ）にジシア
ノメチン水素によるシグナル、また７、３９ｐｐｍ（２
Ｈ，Ｓ）にチオフェン環上の水素のシグナル、７．５４
ｐｐｍ （４Ｈ，ｄ、Ｊ＝８．３Ｈｚ）と７．７５ｐ
９ｒｎ （４Ｈ，ｄ、Ｊ＝８．３Ｈｚ）にベンゼン環
上の水素のシグナルが現われた。The solvent was distilled off under reduced pressure, and the residue was separated by silica gel column chromatography using a mixed solvent of methylene chloride and ethyl acetate, and purified by recrystallization using chloroform.
．． 900g was obtained. 'HN of yellow ocher crystals
When the MR (CDCI23.200MHz) spectrum was measured, there was a signal due to dicyanomethine hydrogen at 5.10 ppm (2H,s), and a signal at 7.39 ppm (2H,s).
H, S) is the hydrogen signal on the thiophene ring, 7.54
ppm (4H, d, J=8.3Hz) and 7.75p
A hydrogen signal on the benzene ring appeared at 9rn (4H, d, J=8.3Hz).
このことから、この黄土色結晶は２．５−ビス（４−ジ
シアノメチルフェニル）チオフェン（ｒＶ） （７，
９５３ｍｍｏｆ）であることが確認された。収率は理論
量に対して９７１％であった。From this, this ocher crystal is 2,5-bis(4-dicyanomethylphenyl)thiophene (rV) (7,
953 mmof). The yield was 971% based on the theoretical amount.
実施例４
［ＴＣＮＴＤＱの四量体の合成］
実施例３で得られた２、５−ビス（４−ジシアノメチル
フェニル）チオフェン４０ｍｇ（０，１１０ｍｍｏｎ’
）を無水アセトニトリル４ｉに溶解し、アルゴン気流下
にＮ−ヨウ化コハク酸ニトリル３９ｍｇ （０、１７６
ｍｍｏｉ’）を加え、室温で１時間撹拌した。沈殿をｉ
濾過し、残渣をアセトニトリルで洗浄すると、融点３０
０℃以上の黄土色結晶が得られた。Example 4 [Synthesis of tetramer of TCNTDQ] 40 mg (0,110 mmon') of 2,5-bis(4-dicyanomethylphenyl)thiophene obtained in Example 3
) was dissolved in 4i of anhydrous acetonitrile, and 39 mg of N-iodinosuccinitrile (0,176
mmoi') and stirred at room temperature for 1 hour. Precipitate i
Filtration and washing of the residue with acetonitrile give a melting point of 30
Ocher crystals with a temperature of 0° C. or higher were obtained.
得られた黄土色結晶のＩＲスペクトル（ＫＢｒセル）を
測定したところ、２２０５ｃｍ−’に共役していないＣ
Ｎ基の吸収が現われた。またゲル浸透カラムクロマトグ
ラフィーにかけ、その保持容量から分子量を求めたとこ
ろ、分子量は４００〜１．５００であった。これらのこ
とより、この黄土色結晶はＴＣＮＴＤＱの四量体（Ｖ）
であることが確認された６収率は理論量に対して８０．
３％であった。When the IR spectrum (KBr cell) of the obtained ocher crystal was measured, it was found that C
Absorption of N groups appeared. The molecular weight was determined from the retention capacity by gel permeation column chromatography, and the molecular weight was 400 to 1.500. From these facts, this ocher crystal is a tetramer (V) of TCNTDQ.
The yield of 6 was confirmed to be 80% based on the theoretical amount.
It was 3%.
実施例５
［ＴＣＮＴＤＱのナトリウムアニオンラジカル塩の合成
］
実施例４で得られたＴＣＮＴＤＱの四量体１０ｍｇ （
０，０２７６ｍｍｏりを無水アセトニトリル４−に溶解
した。アルゴン気流下に、これに無水ヨウ化ナトリウム
１２ｍｇ （０，０８０ｍｍｏＩ）を加え、さらに３０
分間還流した。生成した沈殿をン濾過し、無水アセトニ
トリルで洗浄すると、融点３００℃以上の濃緑色固体が
１０ｍｇ得られた。Example 5 [Synthesis of sodium anion radical salt of TCNTDQ] 10 mg of the tetramer of TCNTDQ obtained in Example 4 (
0.0276 mmol was dissolved in anhydrous acetonitrile. Under an argon stream, 12 mg (0,080 mmol) of anhydrous sodium iodide was added to this, and an additional 30 mg
Refluxed for minutes. The generated precipitate was filtered and washed with anhydrous acetonitrile to obtain 10 mg of a dark green solid with a melting point of 300° C. or higher.
得られた緑色固体のＩＰスペクトル（ＫＢｒセル）を測
定したところ、２１８０ｃｍ−’に共役シアノ基の伸縮
振動が現われた。このことと、元素分析においてＴＣＮ
ＴＤＱ ： Ｎａの組成比がほぼ１：１であることから
、得られた濃緑色固体はＴＣＮＴＤＱのアニオンラジカ
ル塩（ＶＴ）と確認された。収率は理論量に対して９４
０％であった。When the IP spectrum (KBr cell) of the obtained green solid was measured, stretching vibration of the conjugated cyano group appeared at 2180 cm-'. In addition to this, in elemental analysis TCN
Since the composition ratio of TDQ:Na was approximately 1:1, the obtained dark green solid was confirmed to be an anion radical salt (VT) of TCNTDQ. The yield is 94% based on the theoretical amount.
It was 0%.
ＴＣＮＴＤＱ
・Ｎａアニオンラジカル塩の
遍１ヱコ肚定
得られた［ＴＣＮＴＤＱ］ ・Ｎａアニオンラジカル
塩の微結晶をまとめて乾燥し、加圧可能な電導度測定装
置に入れ、圧力を２０ ｋｇ／ ｃｍ２かけて加圧成形
し、二端子法で非抵抗値を測定したところ、１．５Ｘ１
０”Ω・ｃｍの値を示した。TCNTDQ ・Metal measurement of Na anion radical salt The microcrystals of the obtained [TCNTDQ] ・Na anion radical salt were dried together, placed in a pressurizable conductivity measuring device, and the pressure was set to 20 kg/cm2. When the non-resistance value was measured using the two-terminal method, it was found to be 1.5X1.
The value was 0''Ω·cm.
実施例６
［［ＴＣＮＴＤＱ］ ト・２ （Ｂｕ ４Ｎ”）、ジア
ニオン塩の合成］
実施例３で合成した２、５−ビス（４−ジシアノメチル
フェニル）チオフェン１００ｍｇ（０，２７４ｍｍｏｆ
）をアルゴンを通しながら１゜％ＮａＯＨ水溶液４−中
に加え、室温で１ｏ分間撹拌した。これに１０％テトラ
ブチルアンモニウムヒドロキシド水溶液１−を加え、生
成した沈殿をγ濾過した。沈殿を無水ベンゼンで洗浄す
ると、融点１３３〜１３５℃の黄土色粉末１６２ｍｇが
得られた。Example 6 [Synthesis of [TCNTDQ] 2 (Bu 4N”), dianion salt] 100 mg (0,274 mmof) of 2,5-bis(4-dicyanomethylphenyl)thiophene synthesized in Example 3
) was added to a 1% NaOH aqueous solution 4- while passing argon, and the mixture was stirred at room temperature for 10 minutes. A 10% aqueous solution of tetrabutylammonium hydroxide 1- was added to this, and the resulting precipitate was gamma-filtered. The precipitate was washed with anhydrous benzene to obtain 162 mg of an ocher powder with a melting point of 133-135°C.
得られた黄土色粉末のＩＰスペクトルを測定したところ
、２１１５ｃｍ−’に共役シアノ基による伸縮振動が現
われた。 ’ＨＮＭＲ（ＣＤ 、ＣＮ、２００ ＭＨｚ
）スペクトルを測定したところ、７．Ｏ８ｐｐｍ （
２Ｈ，ｓ）にチオフェン環上水素によるシグナルが現わ
れ、６．８４１）Ｉ）ｍ（４Ｈ、ｄ 、 Ｊ ＝ ８
、８ Ｈｚ）と７．３３ｐｐｍ（４Ｈ，ｄ、Ｊ＝８．８
Ｈｚ）にベンゼン環上水素によるシグナルが現われた。When the IP spectrum of the obtained ocher powder was measured, stretching vibration due to the conjugated cyano group appeared at 2115 cm-'. 'HNMR (CD, CN, 200 MHz
) When the spectrum was measured, 7. O8ppm (
A signal due to the hydrogen on the thiophene ring appears in 2H,s), and 6.841)I)m(4H,d, J = 8
, 8 Hz) and 7.33 ppm (4H, d, J = 8.8
Hz), a signal due to hydrogen on the benzene ring appeared.
元素分析値もＴＣＮＴＤＱのビス（テトラブチルアンモ
ニウム）塩と良く一致していた。以上のことから、この
黄土色粉末はＴＣＮＴＤＱのビス（テトラブチルアンモ
ニウム塩（ＶＩ）であることが確認された。収率は理論
量の７０６％であった。The elemental analysis values were also in good agreement with the bis(tetrabutylammonium) salt of TCNTDQ. From the above, it was confirmed that this ocher powder was bis(tetrabutylammonium salt (VI)) of TCNTDQ. The yield was 706% of the theoretical amount.
この化合物は強い蛍光を呈することが見出された。This compound was found to exhibit strong fluorescence.
サイク
ラックポルタモグラムの測定
このようにして得られたビス
（テトラブチル
アンモニウム）塩をｔ Ｂ ｕ ４ Ｎ Ｃ氾０４の
０．１Ｍアセトニトリル溶液に溶解させ、作用極と対極
に白金電極を、参照極に飽和カロメル電極を使用してサ
イクリックポルタモグラムを測定したところ、可逆性の
よい二電子−段階の酸化還元波が得られた。Measurement of Cyclic Portammogram The bis(tetrabutylammonium) salt thus obtained was dissolved in a 0.1 M acetonitrile solution of t B u 4 N C Flood 04, and platinum electrodes were used as the working and counter electrodes. When a cyclic portamogram was measured using a saturated calomel electrode, a highly reversible two-electron-stage redox wave was obtained.
この測定結果より、ＴＣＮＴＤＱの第１半波還元電位と
して＋〇 、 ０８ Ｖ（ｖｓ ５ＣＥ）を得た。From this measurement result, +0.08 V (vs. 5CE) was obtained as the first half-wave reduction potential of TCNTDQ.
比較例Ｉ
ＴＣＮＱのＮａアニオンラジカル塩を合成し、実施例５
と同様に加圧成形して二端子法で比抵抗値を測定したと
ころ、３．０ＸＩＯ’Ω・ａｍであり、実施例５のＴＣ
ＮＴＤＱのＮａアニオンラジカル塩の方が高電導性であ
った。結果を比較して第１表に示す。Comparative Example I Synthesis of Na anion radical salt of TCNQ, Example 5
When the specific resistance value was measured by the two-terminal method after pressure molding in the same manner as in Example 5, it was 3.0XIO'Ω・am, and the TC
The Na anion radical salt of NTDQ had higher conductivity. The results are compared and shown in Table 1.
比較例２
ＴＣＮＤＱのＮａアニオンラジカル塩を合成し、実施例
５と同様に加圧成形して二端子法で比抵抗値を測定した
ところ７．８Ｘ１０”Ω・ｃｍであり、実施例５のＴＣ
ＮＴＤＱのＮａアニオンラジカル塩の方が高電導性であ
った。Comparative Example 2 A Na anion radical salt of TCNDQ was synthesized, pressure molded in the same manner as in Example 5, and the specific resistance value was measured by the two-terminal method, and it was found to be 7.8 x 10" Ωcm, which was 7.8 x 10" Ωcm, which was TCNDQ of Example 5.
The Na anion radical salt of NTDQ had higher conductivity.
て第１表に示す６
第 １ 表
結果を比較し
く発明の効果）
以上述べたように、本発明の化合物はそのＮａラジカル
塩が高電導性であるので、単結晶化すれば、優れた高電
導体が得られる。また各種の電子受容体と錯体を形成さ
せ、電荷移動型錯体を生成することもできる。また本発
明の化合物は、そのジアニオン塩が強い蛍光発光を呈す
る６以上のことより、本発明の化合物は、有機電導体及
びエレクトロクロミズムを利用した電気・電子材料への
応用が可能である６6 Compare the results in Table 1 and see the effect of the invention) As mentioned above, the compound of the present invention has a high conductivity as its Na radical salt, so if it is made into a single crystal, it will have an excellent high conductivity. A conductor is obtained. It is also possible to form a complex with various electron acceptors to generate a charge transfer type complex. Furthermore, since the dianion salt of the compound of the present invention exhibits strong fluorescence, the compound of the present invention can be applied to electrical and electronic materials that utilize organic conductors and electrochromism.6
Claims (1)
ル塩及びジアニオン塩。[Claims] A tetramer, anion radical salt, and dianion salt of a thiophene derivative represented by the structural formula ▲ Numerical formula, chemical formula, table, etc. ▼.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12400990A JPH0421676A (en) | 1990-05-14 | 1990-05-14 | Thiophene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12400990A JPH0421676A (en) | 1990-05-14 | 1990-05-14 | Thiophene derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0421676A true JPH0421676A (en) | 1992-01-24 |
Family
ID=14874767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12400990A Pending JPH0421676A (en) | 1990-05-14 | 1990-05-14 | Thiophene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0421676A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036723A (en) * | 2004-07-29 | 2006-02-09 | Sharp Corp | pi-ELECTRON-CONJUGATED MOLECULE-CONTAINING SILICON COMPOUND AND METHOD FOR PRODUCING THE SAME |
| WO2006067497A3 (en) * | 2004-12-24 | 2006-11-30 | Cambridge Display Tech Ltd | Optical devices and their manufacture |
-
1990
- 1990-05-14 JP JP12400990A patent/JPH0421676A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036723A (en) * | 2004-07-29 | 2006-02-09 | Sharp Corp | pi-ELECTRON-CONJUGATED MOLECULE-CONTAINING SILICON COMPOUND AND METHOD FOR PRODUCING THE SAME |
| WO2006067497A3 (en) * | 2004-12-24 | 2006-11-30 | Cambridge Display Tech Ltd | Optical devices and their manufacture |
| GB2435181A (en) * | 2004-12-24 | 2007-08-15 | Cambridge Display Tech Ltd | Optical devices and their manufacture |
| JP2008525564A (en) * | 2004-12-24 | 2008-07-17 | ケンブリッジ ディスプレイ テクノロジー リミテッド | Optical device and manufacturing method thereof |
| GB2435181B (en) * | 2004-12-24 | 2009-08-19 | Cambridge Display Tech Ltd | Optical devices and their manufacture |
| JP2011153307A (en) * | 2004-12-24 | 2011-08-11 | Cambridge Display Technology Ltd | Optical device and method for production thereof |
| US8410241B2 (en) | 2004-12-24 | 2013-04-02 | Cambridge Display Technology Limited | Optical devices and their manufacture |
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