JPH0131512B2 - - Google Patents
Info
- Publication number
- JPH0131512B2 JPH0131512B2 JP55144135A JP14413580A JPH0131512B2 JP H0131512 B2 JPH0131512 B2 JP H0131512B2 JP 55144135 A JP55144135 A JP 55144135A JP 14413580 A JP14413580 A JP 14413580A JP H0131512 B2 JPH0131512 B2 JP H0131512B2
- Authority
- JP
- Japan
- Prior art keywords
- tcnq
- complex
- present
- crown
- tetracyanoquinodimethane
- 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
Links
- 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 33
- 229920000570 polyether Polymers 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 239000011575 calcium Chemical group 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 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 claims 3
- 150000003839 salts Chemical class 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003983 crown ethers Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- JKCQOMAQPUYHPL-UHFFFAOYSA-N dibenzo-21-crown-7 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 JKCQOMAQPUYHPL-UHFFFAOYSA-N 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 238000002265 electronic spectrum Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Description
本発明は新規なテトラシアノキノジメタン錯体
に関するものである。詳しくは、特定の２価金
属、テトラシアノキノジメタン（TCNQ）及び
環状ポリエーテルから成るテトラシアノキノジメ
タン錯体に関するものである。
近年、TCNQのアルカリ金属塩や電子供与性
化合物との錯体が、有機化合物として高い電導性
を有することが見い出され、その物性や応用に関
する研究が盛んに行なわれている。一方、1967年
にペーダーソン（C.J.Pederson）の発見した一般
にクラウンエーテルと称される環状ポリエーテル
は、種々の金属塩と錯体を形成し、有機溶媒に対
する溶解性が著しく高いことは広く知られてい
る。（化学増刊74「クラウンエーテルの化学」：小
田良平、庄野利之、田伏岩夫共編：化学同人参
照）
本発明者等は、環状ポリエーテルの特異な性質
に注目し、TCNQの２価金属塩と反応させたと
ころ、高い電導性を有し、しかも、安定な錯体が
得られることを知得し本発明を完成するに到つ
た。
すなわち、本発明の要旨は、一般式
（CR）o〔M++（TCNQ-）2〕p（TCNQ）q
…（）
（式中、CRは環状ポリエーテルを示し、Ｍはマ
グネシウム、カルシウム、ストロンチウムまたは
鉛を示し、TCNQはテトラシアノキノジメタン
を示し、ｎは１、２または３を示し、ｐは１また
は２を示し、ｑは０、１または２を示す）で表わ
されるテトラシアノキノジメタン錯体に存する。
以下本発明を説明するに、本発明のテトラシア
ノキノジメタン錯体（TCNQ錯体）は、前記一
般式（）で表わされる。
環状ポリエーテルとしては、クラウンエーテル
として知られている種々の大きさの環を有するも
のが使用できるが、本発明においては、２価の金
属イオンを捕捉しやすい大きさのものが好まし
い。例えば、環の大きさが、12、14、15、18、
21、24、30員環のものが挙げられ、特に、12、
15、18員環のものが好ましい。
これら環状ポリエーテルの具体例としては、15
―クラウン―５（以下15CR5と略す）、ベンゾ―15
―クラウン―５、18―クラウン―６（以下18CR6
と略す）、ジベンゾ―18―クラウン―６、ジシク
ロヘキシル―18―クラウン―６（以下DCH18CR6
と略す）、ジベンゾ―21―クラウン―７、ジベン
ゾ―24―クラウン―８、12―クラウン―４（以下
12CR4と略す）等が挙げられる。
本発明のTCNQ錯体は、例えば、TCNQの２
価金属塩と過剰の環状ポリエーテル、更に必要に
応じてTCNQを有機溶媒中で、50℃〜溶媒の沸
点の温度範囲に加熱下反応させ、次いで、不溶分
のあるときは熱時過し、必要に応じて溶液を濃
縮した後、冷却して析出する結晶を別すること
によつて容易に得ることができる。
有機溶媒としては、メタノール、エタノール、
イソプロパノール等のアルコール類、ベンゼン、
トルエン、キシレン等の芳香族炭化水素、アセト
ン、メチルエチルケトン等のケトン類、テトラヒ
ドロフラン、ジオキサン等のエーテル類、塩化メ
チレン、クロロホルム、ジクロルエタン等のハロ
ゲン化炭化水素、アセトニトリル、ジメチルホル
ムアミド等の非プロトン性極性溶媒等が使用でき
る。
かくして得られる本発明のTCNQ錯体は、環
状ポリエーテルを有しているのでTCNQの金属
塩に比べ有機溶媒に対する溶解性が著しく向上し
た。また、TCNQの金属塩は難溶性のため、中
性のTCNQとの複雑塩を形成させようとしても
単純塩の形でのみ析出し、複雑塩の形成が困難で
あつたが、本発明のTCNQ錯体では、環状ポリ
エーテルと２価金属塩との相互作用により安定な
複雑塩が形成される。従つて、適用溶媒などの条
件選択の力が広がり、本発明のTCNQ錯体を反
応中間体として新規なTCNQ錯体を有利に合成
することが可能である。
更に、本発明のTCNQ錯体の電導度は、
TCNQの単純塩に比べ101〜104倍高く、有機電導
材料としての用途が期待される。
以下に実施例を挙げて更に本発明を具体的に説
明する。
実施例
所定のTCNQの２価金属塩と環状ポリエーテ
ルを、モル比で１：2.2〜2.4となるようにメタノ
ール中に加えて65℃に加熱し、溶解させた。表１
の化合物No.７〜12の複雑塩を得る場合には、更
に、所定量のTCNQのアセトニトリル溶液を加
えた。引き続き65℃で15分間反応させた後、反応
液を冷却し、析出した結晶を別し、少量のメタ
ノールで洗浄した。目的錯体が析出しない場合
は、反応液を適宜濃縮した後冷却して結晶を析出
させた。得られたTCNQ錯体を表１に示した。
得られたTCNQ錯体のうち、化合物No.10につ
いてその電子スペクトルを測定したところ、図１
に示すような結果が得られた。また、化合物No.
７、10および12についてそれらの比抵抗値を測定
したところ表２に示すような結果が得られた。表
２から明らかなように、本発明のTCNQ錯体は、
比較として示したTCNQ単純塩（化合物No.13お
よび14）に比べ電導度が向上しており、101Ω・
cmの値を示す錯体も得られていることが判つた。
The present invention relates to novel tetracyanoquinodimethane complexes. Specifically, the present invention relates to a tetracyanoquinodimethane complex consisting of a specific divalent metal, tetracyanoquinodimethane (TCNQ), and a cyclic polyether. In recent years, complexes of TCNQ with alkali metal salts and electron-donating compounds have been found to have high electrical conductivity as organic compounds, and research on their physical properties and applications has been actively conducted. On the other hand, it is widely known that cyclic polyethers, commonly called crown ethers, discovered by CJPederson in 1967, form complexes with various metal salts and have extremely high solubility in organic solvents. (See Kagaku Supplement 74 “Chemistry of Crown Ethers” co-edited by Ryohei Oda, Toshiyuki Shono, and Iwao Tabuse: Kagaku Doujin) The present inventors focused on the unique properties of cyclic polyethers, and reacted with divalent metal salts of TCNQ. As a result, they found that a complex with high conductivity and stability could be obtained, leading to the completion of the present invention. That is, the gist of the present invention is the general formula (CR) o [M ++ (TCNQ - ) 2 ] p (TCNQ) q
...() (wherein CR represents cyclic polyether, M represents magnesium, calcium, strontium or lead, TCNQ represents tetracyanoquinodimethane, n represents 1, 2 or 3, p represents 1 or 2, and q represents 0, 1 or 2). To explain the present invention below, the tetracyanoquinodimethane complex (TCNQ complex) of the present invention is represented by the above general formula (). As the cyclic polyether, those having rings of various sizes known as crown ethers can be used, but in the present invention, polyethers having a size that easily captures divalent metal ions are preferred. For example, if the ring size is 12, 14, 15, 18,
Those with 21-, 24-, and 30-membered rings are mentioned, especially those with 12-, 24-, and 30-membered rings.
A 15- or 18-membered ring is preferred. Specific examples of these cyclic polyethers include 15
-Crown-5 (hereinafter abbreviated as 15CR5), Benzo-15
-Crown-5, 18-Crown-6 (hereinafter referred to as 18CR6)
), dibenzo-18-crown-6, dicyclohexyl-18-crown-6 (hereinafter referred to as DCH18CR6)
), dibenzo-21-crown-7, dibenzo-24-crown-8, 12-crown-4 (hereinafter referred to as
12CR4). The TCNQ complex of the present invention is, for example, 2 of TCNQ.
The valent metal salt, excess cyclic polyether, and if necessary TCNQ are reacted in an organic solvent under heating at a temperature range of 50°C to the boiling point of the solvent, and then heated if there are insoluble components, It can be easily obtained by concentrating the solution if necessary, cooling it, and separating the precipitated crystals. Examples of organic solvents include methanol, ethanol,
Alcohols such as isopropanol, benzene,
Aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, aprotic polar solvents such as acetonitrile and dimethylformamide. etc. can be used. Since the thus obtained TCNQ complex of the present invention has a cyclic polyether, it has significantly improved solubility in organic solvents compared to metal salts of TCNQ. In addition, since the metal salt of TCNQ is poorly soluble, even if an attempt was made to form a complex salt with neutral TCNQ, it would precipitate only in the form of a simple salt, making it difficult to form a complex salt. In the complex, a stable complex salt is formed by the interaction between the cyclic polyether and the divalent metal salt. Therefore, the ability to select conditions such as applicable solvents is expanded, and it is possible to advantageously synthesize a novel TCNQ complex using the TCNQ complex of the present invention as a reaction intermediate. Furthermore, the electrical conductivity of the TCNQ complex of the present invention is
It is 10 1 to 10 4 times higher than the simple salt of TCNQ, and is expected to be used as an organic conductive material. EXAMPLES The present invention will be further explained in detail by giving examples below. Example A predetermined divalent metal salt of TCNQ and a cyclic polyether were added to methanol at a molar ratio of 1:2.2 to 2.4 and heated to 65°C to dissolve. Table 1
When obtaining complex salts of Compounds No. 7 to 12, a predetermined amount of an acetonitrile solution of TCNQ was further added. After a subsequent reaction at 65° C. for 15 minutes, the reaction solution was cooled, and the precipitated crystals were separated and washed with a small amount of methanol. When the target complex did not precipitate, the reaction solution was appropriately concentrated and then cooled to precipitate crystals. The obtained TCNQ complex is shown in Table 1. Among the TCNQ complexes obtained, the electronic spectrum of compound No. 10 was measured, and the results are shown in Figure 1.
The results shown are obtained. Also, compound no.
When the specific resistance values of Samples 7, 10 and 12 were measured, the results shown in Table 2 were obtained. As is clear from Table 2, the TCNQ complex of the present invention is
Compared to the TCNQ simple salts (compounds No. 13 and 14) shown for comparison, the conductivity is improved to 10 1 Ω・
It was found that complexes exhibiting cm values were also obtained.
【表】【table】
第１図は、実施例で得られた本発明のTCNQ
錯体である（12CR4）3〔Ca++（TCNQ-）2〕2
（TCNQ）2の電子スペクトルのグラフであり、横
軸は波数（Ｋcm-1）、縦軸は吸光度を表わす。
Figure 1 shows the TCNQ of the present invention obtained in the example.
It is a complex (12CR4) 3 [Ca ++ (TCNQ - ) 2 ] 2
(TCNQ) 2 is a graph of the electron spectrum, where the horizontal axis represents the wave number (Kcm -1 ) and the vertical axis represents the absorbance.
Claims (1)
グネシウム、カルシウム、ストロンチウムまたは
鉛を示し、TCNQはテトラシアノキノジメタン
を示し、ｎは１、２または３を示し、ｐは１また
は２を示し、ｑは０、１または２を示す）で表わ
されるテトラシアノキノジメタン錯体。[Claims] 1 General formula (CR) o [M ++ (TCNQ - ) 2 ] p (TCNQ) q (wherein, CR represents a cyclic polyether, and M represents magnesium, calcium, strontium or lead. , TCNQ represents tetracyanoquinodimethane, n represents 1, 2 or 3, p represents 1 or 2, and q represents 0, 1 or 2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14413580A JPS5767576A (en) | 1980-10-15 | 1980-10-15 | Tetracyanoquinodimethane complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14413580A JPS5767576A (en) | 1980-10-15 | 1980-10-15 | Tetracyanoquinodimethane complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5767576A JPS5767576A (en) | 1982-04-24 |
| JPH0131512B2 true JPH0131512B2 (en) | 1989-06-26 |
Family
ID=15355026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14413580A Granted JPS5767576A (en) | 1980-10-15 | 1980-10-15 | Tetracyanoquinodimethane complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5767576A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5545641A (en) * | 1978-09-27 | 1980-03-31 | Mitsubishi Chem Ind Ltd | Alkali metal-tetracyanoquinodimethane crown compound complex |
-
1980
- 1980-10-15 JP JP14413580A patent/JPS5767576A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5545641A (en) * | 1978-09-27 | 1980-03-31 | Mitsubishi Chem Ind Ltd | Alkali metal-tetracyanoquinodimethane crown compound complex |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5767576A (en) | 1982-04-24 |
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