JPH01242583A - Electrically conductive charge-transfer complex - Google Patents
Electrically conductive charge-transfer complexInfo
- Publication number
- JPH01242583A JPH01242583A JP63070309A JP7030988A JPH01242583A JP H01242583 A JPH01242583 A JP H01242583A JP 63070309 A JP63070309 A JP 63070309A JP 7030988 A JP7030988 A JP 7030988A JP H01242583 A JPH01242583 A JP H01242583A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- charge transfer
- transfer complex
- represent
- compound expressed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical group N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims description 3
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- XKHYPFFZHSGMBE-UHFFFAOYSA-N buta-1,3-diene-1,1,2,3,4,4-hexacarbonitrile Chemical compound N#CC(C#N)=C(C#N)C(C#N)=C(C#N)C#N XKHYPFFZHSGMBE-UHFFFAOYSA-N 0.000 claims description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims 2
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 19
- 239000002904 solvent Substances 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 abstract description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 abstract description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052711 selenium Inorganic materials 0.000 abstract description 2
- LWHDQPLUIFIFFT-UHFFFAOYSA-N 2,3,5,6-tetrabromocyclohexa-2,5-diene-1,4-dione Chemical compound BrC1=C(Br)C(=O)C(Br)=C(Br)C1=O LWHDQPLUIFIFFT-UHFFFAOYSA-N 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 125000002653 sulfanylmethyl group Chemical group [H]SC([H])([H])[*] 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 239000000370 acceptor Substances 0.000 description 9
- 239000011669 selenium Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical group [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 1
- ZXNVEXYJVODARP-UHFFFAOYSA-N 4,5-bis(methylsulfanyl)-1,3-dithiol-2-one Chemical compound CSC=1SC(=O)SC=1SC ZXNVEXYJVODARP-UHFFFAOYSA-N 0.000 description 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VOTNXLNTNMCSTJ-UHFFFAOYSA-N ethyl hydrogen sulfite Chemical compound CCOS(O)=O VOTNXLNTNMCSTJ-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IPLONMMJNGTUAI-UHFFFAOYSA-M lithium;bromide;hydrate Chemical compound [Li+].O.[Br-] IPLONMMJNGTUAI-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は高導電性を与える有機電荷移動釦体に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to organic charge transfer buttons that provide high conductivity.
［従来の技術１
有機高導電性物質は銅やアルミニウム等の金属材料に比
べ軽量であること、又は腐食性がないこと等の優れた利
点を持っていることから、近年特に注目されつつおる。[Prior art 1] Organic highly conductive substances have been attracting particular attention in recent years because they have excellent advantages such as being lighter than metal materials such as copper and aluminum, and being non-corrosive.
有機高導電性物質はまた金属類に比べて豊富に存在する
有機資源を原料にして製造できる点でも優れている。一
般に有機物質は電気絶縁体とじての性質を有しており、
これに導電性を付与するには電荷移動錯体を形成させる
のが良く、これまでに種々の電子供与体と電子受容体が
合成され、それらの組み合わせから多数の新しい導電性
の電荷移動錯体か提供されている。Organic highly conductive materials are also superior to metals in that they can be manufactured from abundant organic resources. Generally, organic substances have the properties of electrical insulators,
A good way to impart conductivity to this is to form a charge transfer complex, and various electron donors and electron acceptors have been synthesized so far, and many new conductive charge transfer complexes have been created from their combinations. has been done.
例えばり、 Ｊ、 Ｓａｎｄｍａｎ等（Ｊ、Ｃｈｅｍ、
Ｓｏｃ、、Ｃｈｅｍ。For example, J. Sandman et al. (J. Chem.
Soc,, Chem.
Ｃｏｍｍｕｎ、、１９７７．６７７、 ）は新規な電子
供与体である２−（チオピラン−４−イソデン）−１，
３−ジチオールを合成し、その７．７．８．８−テトラ
シアノキノジメタンとの電荷移動錯体を報告している。Commun., 1977.677, ) is a novel electron donor, 2-(thiopyran-4-isodene)-1,
have synthesized 3-dithiol and reported its charge transfer complex with 7,7,8,8-tetracyanoquinodimethane.
［発明が解決しようとする課題］
本発明はり、 Ｊ、 Ｓａｎｄｍａｎ等の合成した電荷
移動１１１体の電子供与体部分に改良を加え、それらを
適切な電子受容体と組み合わせることにより、改善され
た導電性を有する電荷移動錯体を提供することを目的と
する。[Problems to be Solved by the Invention] The present invention provides improved conductivity by improving the electron donor portion of the charge transfer 111 body synthesized by J. Sandman et al. and combining it with an appropriate electron acceptor. The purpose of the present invention is to provide a charge transfer complex having the following properties.
［課題を解決するための手段］
本発明はすなわち電子供与体と電子受容体とよりなる錯
体で市って、電子供与体成分として一般式（Ｉ＞
（式中Ｘ、ＹはＳ原子又はＳｅ原子を、Ｒ１，Ｒ２は水
素原子もしくはＣＨ：＋Ｓ！ｌｆｉを表わし、又はＲ１
とＲ２とは閉環して一３ＣＨ２Ｃｆ−１２Ｓ−基を形成
していてもよい。またＲ１．Ｒ２が水素原子のときはＸ
とＹとは同時にＳ原子であることはない）
で示される化合物を用いることを特徴とする導電性電荷
移動錯体である。[Means for Solving the Problems] The present invention consists of a complex consisting of an electron donor and an electron acceptor. atom, R1 and R2 represent a hydrogen atom or CH:+S!lfi, or R1
and R2 may be ring-closed to form a -3CH2Cf-12S- group. Also R1. When R2 is a hydrogen atom, X
and Y are not S atoms at the same time) This is a conductive charge transfer complex characterized by using a compound represented by
他方の電子受容体成分としては一般的には、７、７．８
．８−テトラシアノキノジメタンが使用されるが、他に
テトラフルオロテトラシアノキノジメタン、ヘキサシア
ノブタジェン、テトラシアノエヂレン、ジクロロジシア
ノベンゾギノン、クロラニル等を挙げることかできる。The other electron acceptor component is generally 7, 7.8
．． 8-tetracyanoquinodimethane is used, but other examples may include tetrafluorotetracyanoquinodimethane, hexacyanobutadiene, tetracyanoedylene, dichlorodicyanobenzoginone, chloranil and the like.
またこの錯体にお（ブる電子供与体成分と電子受容体成
分とのモル比は通常１：１である。Further, the molar ratio of the electron donor component and the electron acceptor component in this complex is usually 1:1.
本発明電荷移動錯体は次のようにして合成することがで
きる。The charge transfer complex of the present invention can be synthesized as follows.
Ａ： （Ｉ）式化合物の合成
（Ｉ＞式においてＲ１、Ｒ２が水素原子のものは下記（
ｉ）（ｉｉ）及び（ｉｉｉ）式の経路で合成することか
できる。A: Synthesis of compounds of formula (I) (I>For those in the formula in which R1 and R2 are hydrogen atoms, the following (
i) It can be synthesized by the routes of formulas (ii) and (iii).
＜１＞ ＜２＞
＜３＞＜３＞
（４＞（ｉ）〜（ｉｉｉ）式中、Ｘ
、Ｙは（Ｉ）式と同一の置換基を示し、Ｒ３は飽和のア
ルキル基である。<1><2>
<3><3>
(4>(i) to (iii) where X
, Y represents the same substituent as in formula (I), and R3 is a saturated alkyl group.
すなわち〈１〉及び〈２〉を亜リン酸トリアルキル又は
亜リン酸トリフェニルの存在下、溶媒中で加熱すると〈
３〉が１ｑられる。亜リン酸トリアルキルとしては亜リ
ン酸トリメチル、亜リン酸トリエチル、亜リン酸トリプ
ロピル、亜リン酸トリオクチル等を挙げることができる
。く３〉をキノイド化合物の存在下溶媒中で加熱すると
〈４〉が得られる。キノイド化合物としてはクロラニル
、ブロモアニル、ジシクロジシアノベンゾキノン等を挙
げることができる。〈４〉を臭化リチウムの存在下へキ
サメチルホスホリックトリアミド中で７ＪＯ熱すると〈
５〉が得られる。That is, when <1> and <2> are heated in a solvent in the presence of trialkyl phosphite or triphenyl phosphite, <
3〉 is reduced by 1q. Examples of the trialkyl phosphite include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, and trioctyl phosphite. When 3) is heated in a solvent in the presence of a quinoid compound, 4 is obtained. Examples of quinoid compounds include chloranil, bromoanil, dicyclodicyanobenzoquinone, and the like. When <4> is heated for 7JO in the presence of lithium bromide in xamethylphosphoric triamide, <
5> is obtained.
（１）式でＲ１、Ｒ２がＣＨ３Ｓ−基の場合、又はＲ１
、Ｒ２が次式のごとく閉環して一３ＣＨ２０Ｈ２Ｓ−基
を形成する場合は、（（■〉及び（Ｖ）式の経路で合成
することができる。In the formula (1), when R1 and R2 are CH3S- groups, or R1
, R2 is ring-closed to form a -3CH20H2S- group as shown in the following formula, it can be synthesized by the routes of formulas ((■) and (V)).
＜６＞ ＜２＞
＜７＞（１ｖ）及び（Ｖ）式中、Ｒ１，Ｒ２，Ｘ及
びＹは（Ｉ＞式と同一の置換基を示す。すなわら（１）
及び（ｉｉ）式と同様の方法で〈６〉と〈２〉から〈７
〉を、また〈７〉から〈８〉を合成することができる。<6><2>
<7> In formulas (1v) and (V), R1, R2, X and Y represent the same substituents as in formula (I). That is, (1)
And in the same way as formula (ii), from <6> and <2> to <7
> can be synthesized, and <7> to <8> can be synthesized.
Ｂ：（１）式化合物と電子受容体とより電荷移動錯体の
合成
通常、有機溶媒中で（Ｉ）式化合物と電子受容体成分と
を混ぎ合わすことにより電荷移動錯体を合成することが
できる。有機溶媒としてはベンゼン、トルエン、クロロ
ベンゼン、テトラヒドロフラン、アセトニトリル、ジク
ロロメタン等を挙げることかできる。またこの電荷移動
錯体は有機溶媒を用いずに、相当早の（Ｉ）式化合物と
電子受容体成分とを乳鉢等でよく混合することにより合
成することができる。B: Synthesis of a charge transfer complex from a compound of formula (1) and an electron acceptor Usually, a charge transfer complex can be synthesized by mixing a compound of formula (I) and an electron acceptor component in an organic solvent. . Examples of organic solvents include benzene, toluene, chlorobenzene, tetrahydrofuran, acetonitrile, and dichloromethane. Moreover, this charge transfer complex can be synthesized by thoroughly mixing the compound of formula (I) and the electron acceptor component in a mortar or the like without using an organic solvent.
以下本発明を実施例によって具体的に説明するか、本発
明は下記実施例に限定されるものではない。EXAMPLES The present invention will be specifically explained below with reference to examples, but the present invention is not limited to the following examples.
実施例１
窒素気流下ビス（メトキシカルボニル）−１，３−ジヂ
オール−２−チオン（＜１＞、Ｒ３＝ＣＨ３、Ｘ＝Ｓ）
１．３（Ｊ、テトラヒドロ−４Ｆ１−セレノピラン−
４−オン（＜２＞、Ｙ＝Ｓｅ）３．５（１゜トリエチル
ホスファイ１〜５ｍｌ、およびベンゼン４０ｄの混合物
を１２時間還流撹拌する。放冷少溶媒を留去し、残）査
をシリカゲルカラムタロマドグラフィーにより精製し、
ベンゼン溶出部よりクロスカップリング生成物（＜３＞
、Ｒ’ ＝Ｃ１−Ｒ３゜Ｘ ＝Ｓ、 Ｙ＝Ｓｅ）
４４４ｍａを得たく収率２３％）。Example 1 Bis(methoxycarbonyl)-1,3-didiol-2-thione (<1>, R3=CH3, X=S) under nitrogen stream
1.3 (J, tetrahydro-4F1-selenopyran-
A mixture of 4-one (<2>, Y=Se) 3.5 (1-5 ml of 1° triethylphosphite, and 40 ml of benzene is stirred under reflux for 12 hours. The small solvent is distilled off while the mixture is left to cool. Purified by silica gel column talomadography,
The cross-coupled product (<3>
, R' = C1-R3゜X = S, Y = Se)
444 ma (yield 23%).
得られたクロスカップリング生成物２９０ｍ（］、クク
ロユニ４４３０ｍｇおよびキシレン２５ｍ１の混合物を
１１時間還流撹拌した。反応後氷水で冷却し、析出した
黒色固体をン戸別し、ン戸液より溶媒を減圧留去する。A mixture of 290 m of the obtained cross-coupled product, 4430 mg of Kukurouni, and 25 ml of xylene was stirred under reflux for 11 hours. After the reaction, it was cooled with ice water, the precipitated black solid was separated, and the solvent was distilled from the liquid under reduced pressure. leave
残渣をシリカゲルカラムクロマトグラフィーにより精製
し、ベンビン溶出部をベンゼン−ヘキサン混合溶媒より
再結晶し、脱水素生成物（＜４＞、Ｒ３＝ＣＨ３、Ｘ＝
Ｓ、Ｙ＝Ｓｅ）２４１１１１ｇが１７られた（収率８４
％）。The residue was purified by silica gel column chromatography, and the benbin eluate was recrystallized from a benzene-hexane mixed solvent to obtain the dehydrogenated product (<4>, R3=CH3, X=
17 g of 241,111 g of S, Y=Se) were obtained (yield: 84
%).
窒素気流下、得られた脱水素生成物１９３ｍｇ 、臭化
リチウム１水和物２２３ｍｇ、およびヘキサメヂルホス
ホリックトリアミド１０ｍ１の混合物を１５５°Ｃで１
２時間撹拌した。敢冷後水を加えてベンゼンで抽出し、
抽出液を水１次いで飽和食塩水で洗浄し、無水硫酸マグ
ネシウムで乾燥した。溶媒を減圧下沼去し、残ｊ査をシ
リカゲルカラムクロマトグラフィーにより精製、ベンゼ
ン−ヘキサン（１：１）溶出部をヘキサンより再結晶し
、電子供与性化合物（＜５＞ 、Ｘ＝Ｓ、Ｙ＝Ｓｅ）９
１ｍｇを得た（収率７０％）。Under a nitrogen stream, a mixture of 193 mg of the obtained dehydrogenated product, 223 mg of lithium bromide monohydrate, and 10 ml of hexamethylphosphoric triamide was heated at 155°C.
Stirred for 2 hours. After cooling thoroughly, add water and extract with benzene.
The extract was washed with water, then with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, the residue was purified by silica gel column chromatography, and the fraction eluted with benzene-hexane (1:1) was recrystallized from hexane to obtain an electron-donating compound (<5>, X=S, Y= Se)9
1 mg was obtained (yield 70%).
得られた電子供与性化合物１３ｍｇをクロロベンゼン２
威に、７．７．８．８−テトラシアノキノジメタン（以
下ＴＣＮＱという）１０．８ｍｇをクロロベンゼン４ｄ
に溶かした後、固溶液を混合すると沈澱が生じる。これ
をン戸別すると２− （４Ｈ−ｔレノピラン−４−イリ
デン）−１，３−ジチオール（＜５＞。13 mg of the obtained electron-donating compound was mixed with chlorobenzene 2
10.8 mg of 7.7.8.8-tetracyanoquinodimethane (hereinafter referred to as TCNQ) was added to 4 d of chlorobenzene.
After dissolving in the solid solution, a precipitate forms when the solid solution is mixed. When this was separated, 2-(4H-tlenopyran-4-ylidene)-1,3-dithiol (<5>) was obtained.
Ｘ＝Ｓ、Ｙ＝Ｓｅ）とＴ ＣＮ Ｑとの１：１錯体２１
ｍｇが得られる。得られた電子供与体、および電荷移動
錯体の物性を第１表に示した。1:1 complex of X=S, Y=Se) and T CN Q 21
mg is obtained. Table 1 shows the physical properties of the electron donor and charge transfer complex obtained.
実施例２〜３
実施例１のビス（メトキシカルボニル）−１，３−ジチ
オール−２−ヂオン（＜１＞、Ｒ３＝Ｃｌ−１３、Ｘ＝
Ｓ）とテトラヒドロ−４１１−セレノピラン−４−オン
（＜２＞、Ｙ＝Ｓｅ）の組み合わじの替わりに実施例２
では＜Ｄ （Ｒ３＝ＣＨ３゜Ｘ＝Ｓｅ）と＜２＞
（Ｙ＝Ｓ）の組み合わせを、実施例３では＜１＞ （
Ｒ３＝ＣＨ３、Ｘ＝Ｓｅ）と＜２＞ （Ｙ＝Ｓｅ）の
組み合わせを出発原料として用いる他は実施例１と全く
同様にして電子供与体＜５＞ （Ｘ＝Ｓｅ、Ｙ＝３＞と
＜５＞ （Ｘ＝Ｓｅ、Ｙ＝Ｓ（３）を（ｑ、また実施例
１と同様にしてそれぞれのＴＣＮＱとの１：１の電荷移
動銘体を（ｑだ。）ｑられた化合物の物性値を第１表に
示した。Examples 2-3 Bis(methoxycarbonyl)-1,3-dithiol-2-dione (<1>, R3=Cl-13, X=
Example 2 instead of the combination of S) and tetrahydro-411-selenopyran-4-one (<2>, Y=Se)
Then <D (R3=CH3゜X=Se) and <2>
In Example 3, the combination of (Y=S) is <1> (
The electron donor <5> (X=Se, Y=3> and <5> (X = Se, Y = S (3) (q), and in the same manner as in Example 1, a 1:1 charge transfer index with each TCNQ (q). The physical property values are shown in Table 1.
実施例４
４．５−ビス（メチルチオ）−１，３−ジチオール−２
−チオン（＜６＞ 、Ｒ１，Ｒ２＝Ｃｔ−ｈ Ｓ−。Example 4 4.5-bis(methylthio)-1,3-dithiol-2
-thione (<6>, R1, R2=Ct-h S-.
Ｘ＝Ｓ） ２．１７ｇ、テ１〜ラヒドロー４１ドチオ
ピラン−４−オン（＜２＞、Ｙ＝３＞５．０（］、］亜
すン酸１−リエチル１２ｍ１，１３よびベンじン６５７
の混合物を１２１Ｆ、″Ｊ間還流撹拌した。放冷後、溶
媒を減圧上留去した１安、残）青をシリカゲルカラムク
ロマ１〜グラフイーで精製し、２０％ベンゼン−ヘキサ
ン溶出部をヘキサンより再結晶し、クロスカップリング
生成物（＜７＞ 、 Ｒ’ 、 Ｒ２＝ＣＨ３Ｓ−、Ｘ
＝Ｓ。X=S) 2.17g, Te1~Rahydro41 dothiopyran-4-one (<2>, Y=3>5.0(],] 1-ethylsulfite 12ml1,13 and benzine 657
The mixture was stirred under reflux for 121F and 200mm. After cooling, the solvent was distilled off under reduced pressure. Recrystallized and cross-coupled product (<7>, R', R2=CH3S-,
=S.
Ｙ＝Ｓ） １．２６（］を（ｑだ（収率４５％）。得
られたクロスカップリング生成物１．０句、クロラニル
１．９６！１１． トルエン７０ｄの混合物を２時間
速流１ｊ２拌した。水冷後、析出した固体をン戸別し、
炉液より溶媒を留去し、残漬をＧＰＣにて精製し、溶出
部をヘキサンより再結晶すると電子供与性化合物（＜８
＞ 、Ｒ’ 、Ｒ２＝ＣＨ３Ｓ＋、ｘ＝ｓ。Y=S) 1.26(] is (q (yield 45%). Obtained cross-coupled product 1.0, chloranil 1.96! 11. A mixture of 70d toluene is rapidly flowed 1j2 for 2 hours. After cooling with water, the precipitated solid was separated,
The solvent was distilled off from the furnace solution, the residue was purified by GPC, and the eluted portion was recrystallized from hexane to form an electron-donating compound (<8
> , R', R2=CH3S+, x=s.
Ｙ＝Ｓ） ７４４ｍｇかイアｊられた（収率７２％）
。Y=S) 744 mg was obtained (yield 72%)
.
ｊ７られた電子供与性化合物を実施例１と同様に、ＴＣ
ＮＱと反応ざｕ、１ ： １ ノｆｉ荷ｒ：ｌＱＪ鉗に
ヲ１’＃た。冑られた電荷移動路体の物性を第１表に示
した。In the same manner as in Example 1, the obtained electron-donating compound was treated with TC
I reacted with NQ, 1:1 no fi load r:lQJ forceps. Table 1 shows the physical properties of the crushed charge transfer path body.
実施例５〜６
実施例４の４，５−ビス（メチルチオ）−１，３−ジチ
オール−２−オンおＪζびテトラヒドロ−４）１−チオ
ピラン−４−オンの組み合わせの替わりに、実施例５で
は＜６＞ （Ｒ１，Ｒ２は閉環して、−３ＣＨ２ＣＨ
２５−ＬＬａ”形成、Ｘ＝Ｓ） と＜２＞（Ｙ＝Ｓ）、
実施例６では＜６＞ （Ｒ’ 、Ｒ２１ａ閉環して一３
Ｃｆｈ Ｃｔ−ｈ Ｓ−基を形成、Ｘ＝Ｓ＞と＜２＞
（Ｙ＝Ｓｅ）の組み合わ′ｔ！を原料として用いる以
外は実施例４と同様にして相当する電子供与体と電荷移
動路体を１ｑた。得られた生成物の物性を第１表に示し
た。Examples 5 to 6 In place of the combination of 4,5-bis(methylthio)-1,3-dithiol-2-one and Jζ and tetrahydro-4)1-thiopyran-4-one in Example 4, Example 5 Then <6> (R1 and R2 are ring-closed, -3CH2CH
25-LLa” formation, X=S) and <2>(Y=S),
In Example 6, <6>(R', R21a is ring-closed and -3
Cfh Ct-h Forms S- group, X=S> and <2>
(Y=Se) combination 't! 1 q of the corresponding electron donor and charge transfer path were prepared in the same manner as in Example 4 except that 1 q of the corresponding electron donor and charge transfer path were used as the raw materials. The physical properties of the obtained product are shown in Table 1.
比較例１
上記実施例に準じた方法で下式
に示される化合物を合成しその物性を第１表に併記する
。Comparative Example 1 A compound represented by the following formula was synthesized by a method similar to the above example, and its physical properties are also listed in Table 1.
［発明の効果］
本発明の一般式（１）で示される２−（カルコゲノピラ
ン−４−イリデン）−１，３−ジカルコゲノール誘導体
と電子受容体とよりなる電荷移動錯体は新規物質であっ
て、２−（チオビラン−４−イリデン）−１，３−ジヂ
オールの置換体、特にセレン原子を導入した電子供与体
を使用することにより、導電性を向上させることができ
る。[Effects of the Invention] The charge transfer complex of the present invention comprising a 2-(chalcogenopyran-4-ylidene)-1,3-dichalcogenol derivative represented by general formula (1) and an electron acceptor is a new substance. , 2-(thiopyran-4-ylidene)-1,3-didiol, particularly by using an electron donor into which a selenium atom is introduced, the conductivity can be improved.
図面は各実施例で得られた電荷移動錯体の赤外線吸収ス
ペクトルである。The drawings show infrared absorption spectra of charge transfer complexes obtained in each example.
Claims (4)
、電子供与体成分として一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中Ｘ、ＹはＳ原子又はＳｅ原子を、Ｒ＾１、Ｒ＾２
は水素原子もしくはＣＨ＿３Ｓ−基を表わし、又はＲ＾
１とＲ＾２とは閉環して−ＳＣＨ＿２ＣＨ＿２Ｓ−基を
形成していてもよい。またＲ＾１、Ｒ＾２が水素原子の
ときはＸとＹとは同時にＳ原子であることはない） で示される化合物を用いることを特徴とする導電性電荷
移動錯体。(1) It is a complex consisting of an electron donor and an electron acceptor, and the electron donor component has the general formula (I) ▲mathematical formula, chemical formula, table, etc.▼(I) (in the formula, X and Y are S atoms Or Se atoms, R^1, R^2
represents a hydrogen atom or a CH_3S- group, or R^
1 and R^2 may be ring-closed to form a -SCH_2CH_2S- group. Furthermore, when R^1 and R^2 are hydrogen atoms, X and Y are not S atoms at the same time.
キノジメタン、テトラフルオロテトラシアノキノジメタ
ン、ヘキサシアノブタジエン、テトラシアノエチレン、
ジクロロジシアノベンゾキノン、クロラニルのいずれか
である請求項１に記載の導電性電荷移動錯体。(2) The electron acceptor component is 7,7,8,8-tetracyanoquinodimethane, tetrafluorotetracyanoquinodimethane, hexacyanobutadiene, tetracyanoethylene,
The conductive charge transfer complex according to claim 1, which is either dichlorodicyanobenzoquinone or chloranil.
キノジメタンである請求項２に記載の導電性電荷移動錯
体。(3) The conductive charge transfer complex according to claim 2, wherein the electron acceptor component is 7,7,8,8-tetracyanoquinodimethane.
１である請求項１〜３のいずれかに記載の導電性電荷移
動錯体。(4) The molar ratio of electron donor component and electron acceptor component is 1:
4. The conductive charge transfer complex according to claim 1, wherein the conductive charge transfer complex is 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63070309A JPH01242583A (en) | 1988-03-23 | 1988-03-23 | Electrically conductive charge-transfer complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63070309A JPH01242583A (en) | 1988-03-23 | 1988-03-23 | Electrically conductive charge-transfer complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01242583A true JPH01242583A (en) | 1989-09-27 |
| JPH0465074B2 JPH0465074B2 (en) | 1992-10-16 |
Family
ID=13427733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63070309A Granted JPH01242583A (en) | 1988-03-23 | 1988-03-23 | Electrically conductive charge-transfer complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01242583A (en) |
-
1988
- 1988-03-23 JP JP63070309A patent/JPH01242583A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0465074B2 (en) | 1992-10-16 |
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