JPS63233976A - Novel tcnq complex - Google Patents
Novel tcnq complexInfo
- Publication number
- JPS63233976A JPS63233976A JP62015778A JP1577887A JPS63233976A JP S63233976 A JPS63233976 A JP S63233976A JP 62015778 A JP62015778 A JP 62015778A JP 1577887 A JP1577887 A JP 1577887A JP S63233976 A JPS63233976 A JP S63233976A
- Authority
- JP
- Japan
- Prior art keywords
- tcnq
- complex
- tcnq complex
- synthesis
- salt
- 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
- 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 abstract description 42
- -1 N-substituted isoquinolinium cation Chemical class 0.000 claims abstract description 21
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 abstract description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 150000004820 halides Chemical class 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012230 colorless oil Substances 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RIYFONBSYWACFF-UHFFFAOYSA-N 2-bromoethylcyclopropane Chemical compound BrCCC1CC1 RIYFONBSYWACFF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- LUNMJRJMSXZSLC-UHFFFAOYSA-N 2-cyclopropylethanol Chemical compound OCCC1CC1 LUNMJRJMSXZSLC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-O isoquinolin-2-ium Chemical compound C1=[NH+]C=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-O 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- AODPICOFZRYWKI-UHFFFAOYSA-N ethyl 2-cyclopropylacetate Chemical compound CCOC(=O)CC1CC1 AODPICOFZRYWKI-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、導電性材料等として有用な新規ＴＣＮＱ錯体
に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel TCNQ complex useful as a conductive material or the like.
（発明の背景）
ＴＣＮＱ錯体は、有機半導体として知られる電荷移動型
錯化合物であり、その構成成分であるＴＣＮＱが電子を
受は入れやすく、陽イオンと極めて安定なラジカル塩を
作り、ＴＣＮＱ自身が独自に積み爪なるという構造的特
徴を有することに起因して高導電性を示す。(Background of the invention) TCNQ complex is a charge-transfer type complex compound known as an organic semiconductor, and its component TCNQ easily accepts electrons, forms extremely stable radical salts with cations, and TCNQ itself It exhibits high electrical conductivity due to its unique structural feature of stacked claws.
ＴＣＮＱ錯体は、軽量、電導の異方性、溶融性、フィル
ム形成性、加工及び成形の容易さ等、有機化合物のもつ
特徴的性質と金属の性質を併せ有するという存利な点を
有し、このため、高機能導電性分子膜、非線形光学材料
、帯電防止剤、分子素子、生物素子への応用、電子機能
をもつ高秩序分子集合体の設計に、或は電解コンデンサ
や電池の固体電解質等、様々な有機半導体分野に、その
利用が大いに期待されている化合物である。TCNQ complexes have the advantage of having both the characteristic properties of organic compounds and the properties of metals, such as light weight, anisotropy of conductivity, meltability, film-forming properties, and ease of processing and molding. Therefore, it is useful for applications in high-performance conductive molecular films, nonlinear optical materials, antistatic agents, molecular devices, biological devices, the design of highly ordered molecular aggregates with electronic functions, or solid electrolytes for electrolytic capacitors and batteries. , is a compound that is highly expected to be used in various organic semiconductor fields.
ＴＣＮＱ錯体に関しては、これまでに多数の含望素＃ｉ
素環化合物カチオンＴＣＮＱ錯体が合成されているが、
本来ＴＣＮＱ錯体は有機化合物であり、置換基や構成し
ている元素を代えることによってわずかずつ構造や性質
を変化させていくことができるので、これによって導電
体とじて要求される様々な性質の最適化を目的に応じて
はかることが可能なため、それら各種ニーズに対応しく
：Ｉる更に新たなＴＣＮＱ錯体の開発が望まれている。Regarding TCNQ complexes, a large number of desired elements #i
A cationic TCNQ complex of a ring compound has been synthesized,
Originally, TCNQ complex is an organic compound, and its structure and properties can be changed little by little by changing substituents and constituent elements. Since it is possible to measure the TCNQ complex according to the purpose, it is desired to develop a new TCNQ complex that can meet these various needs.
本発明は、上記した如き現状に鑑みなされたもので、有
機導電性化合物であり、種々の電子化学的、或は光化学
的成果が期待できる新規なＴＣＮＱ錯体を提供すること
を目的とする。The present invention was made in view of the current situation as described above, and an object of the present invention is to provide a novel TCNQ complex, which is an organic conductive compound and is expected to have various electrochemical or photochemical results.
（但し、Ｒ１はシクロプロピル基、シクロペンチル基又
はシクロヘキシル基を示し、ｎは１〜３の整数を示す。(However, R1 represents a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group, and n represents an integer of 1 to 3.
）で表わされるＮ−置換イツキノリニウムカチオンと、
７，７，８．８−テトラシアノキノジメタンアニオンラ
ジカル（ＴＣＮＱつ及び中性ＴＣＮＱ （ＴＣＮＱつと
を構成成分とするＴＣＮＱ錯体の発明である。) an N-substituted quinolinium cation represented by
This is an invention of a TCNQ complex comprising a 7,7,8.8-tetracyanoquinodimethane anion radical (TCNQ) and a neutral TCNQ (TCNQ) as constituent components.
本発明のＴＣＮｄ錯体は、例えば下記の如く表ねされる
。The TCNd complex of the present invention is represented, for example, as follows.
（式中、ｋは０．５≦に≦２．０なる任意の数を表わす
。）
本発明のＴＣＮＱ錯体に於て、ドナ一部の式キノリニウ
ムカチオンのＲ１は、シクロプロピル基、シクロペンチ
ル基又はシクロヘキシル基を示し、ｎはＬ〜３の任意の
整数を示す。(In the formula, k represents an arbitrary number ranging from 0.5≦≦2.0.) In the TCNQ complex of the present invention, R1 of the quinolinium cation of the formula of the donor part is a cyclopropyl group, a cyclopentyl group, group or a cyclohexyl group, and n represents an arbitrary integer of L to 3.
本発明のＴ ＣＮ Ｑ ｊｆｆ体は、自体公知の方法、
例えばＮ−置換イツキノリニウムカチオンのハロゲン化
物とＴＣＮＱσ月、ｉ塩とを反応させてＮＱをドーピン
グさせる方法により容易に合成し得る。Ｎ−置換イツキ
ノリニウムカチオンのハロを、要すれば適当な溶媒の存
在下イソキノリンと反応させることにより容易に得るこ
とがてきるので、この様にして得たものを用いることで
足りる。また、本発明のＴＣＮＱ錯体は、ヨードイオン
１−の還元力を利用し、Ｎ−置換イソキノリン３：４
で反応させる方法によっても同様に合成し得ることは言
うまでもない。The T CN Q jff body of the present invention can be obtained by a method known per se,
For example, it can be easily synthesized by a method of doping NQ by reacting a halide of an N-substituted quinolinium cation with TCNQ σ, i salt. Since the halo of the N-substituted quinolinium cation can be easily obtained by reacting it with isoquinoline in the presence of a suitable solvent if necessary, it is sufficient to use the product obtained in this way. In addition, the TCNQ complex of the present invention utilizes the reducing power of iodo ion 1- to produce N-substituted isoquinoline 3:4
Needless to say, it can be synthesized in the same manner by a reaction method.
合成された本発明のＴＣＮＱ錯体は、電荷移動錯体特有
の色や電荷移動吸収帯の出現によって識別することがで
き、錯体組成比は元素分析及び紫外線吸収スペクトルの
測定から決定することができる。電気的性質、例えば比
抵抗値は、試料粉末をベレットに成型し二端子法で電流
電圧を測定して抵抗値Ｒを算出し、次式から求めること
ができる。ρ＝ Ｒ−Ａ ／ ｎ。但し、ρは比抵抗値
（Ω・ｃｍ）、 Ｒは抵抗（Ω）、Ａは電極接触面積（
ｃｍ″）、 ｉＬは試料の厚さくｃｍ）である。また、
熱的性質は、示差走査熱量（ＤＳＣ）測定等の熱分析で
測定することができる。The synthesized TCNQ complex of the present invention can be identified by the appearance of the color and charge transfer absorption band characteristic of charge transfer complexes, and the complex composition ratio can be determined from elemental analysis and measurement of ultraviolet absorption spectra. Electrical properties, for example, specific resistance value, can be determined from the following equation by molding the sample powder into a pellet, measuring the current and voltage using the two-terminal method, and calculating the resistance value R. ρ=R−A/n. However, ρ is the specific resistance value (Ω・cm), R is the resistance (Ω), and A is the electrode contact area (
cm''), iL is the thickness of the sample (cm).
Thermal properties can be measured by thermal analysis such as differential scanning calorimetry (DSC) measurements.
本発明の新規なＴＣＮＱ錯体は、特にその単独又は混合
品の導電性、加工及び成形性及び耐熱性に優れているの
で、これを高機能導電性分子膜、非線形光学材料、これ
らの分子素子、生物素子への応用など電子機能をもつ高
秩序分子集合体の設計に、或は電解コンデンサや電池の
固体電解質として笠様々な有機半導体分野に於て有効に
用い得ることが期待できる。The novel TCNQ complex of the present invention is particularly excellent in electrical conductivity, processing and moldability, and heat resistance when used alone or as a mixture. It is expected that it can be effectively used in various organic semiconductor fields, such as in the design of highly ordered molecular aggregates with electronic functions, such as applications in biological devices, or as solid electrolytes in electrolytic capacitors and batteries.
以下に実施例を示すが、本発明はこれら実施例により何
等制約を受けるものではない。Examples are shown below, but the present invention is not limited in any way by these examples.
参考例１．２−シクロプロピルエチルブロマイドの合成
（１）２−シクロプロピルアセトニトリルの合成シクロ
プロピルメチルブロマイド〔アルドリッチ社製） １５
ｇ （Ｉ１１ミリモル）をＤＭＳＯ（ジメチルスルホキ
シド）中、シアン化ソーダ６．１ｇ （１２４ミリモル
）と７０℃で３時間撹拌反応させた後、水中に注入した
。次いでエチルエーテルで抽出し、エーテル層を希塩酸
次いで水で洗浄後無水Ｍｇ５Ｏ。Reference Example 1. Synthesis of 2-cyclopropylethyl bromide (1) Synthesis of 2-cyclopropylacetonitrile Cyclopropylmethyl bromide (manufactured by Aldrich) 15
g (I11 mmol) was reacted with 6.1 g (124 mmol) of sodium cyanide in DMSO (dimethyl sulfoxide) at 70° C. for 3 hours with stirring, and then poured into water. Next, extraction was performed with ethyl ether, and the ether layer was washed with diluted hydrochloric acid and then with water, followed by anhydrous Mg5O.
で乾燥した。Ｉ陀燥削枦去後、溶媒留去し、残渣を減圧
蒸留してｂｐ５６〜５７℃／２７ｍｍ１１ｇの留分５．
９ｇを無色油状物として得た（収率 ６５．６％）。It was dried. After drying and removing the residue, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain a fraction 5.
9 g was obtained as a colorless oil (yield 65.6%).
Ｉ Ｒ（Ｎｅａｔ） ： ２２００ｃｍ−’ （−Ｃ
＝Ｎ）。I R (Neat): 2200cm-' (-C
=N).
（２）２−シクロプロピル酢酸エチルの合成（１）で得
た２−シクロプロピルアセトニトリル５．９３ （７：
１ミリモル）をエタノール３．７ｇ及びエチルエーテル
３０ｍｊに溶解させ、１０℃以下て゛塩化水素カス２．
９ｇを導入した。導入後ｌＯ〜！５℃で２時間撹拌した
後、減圧濃縮し、残渣に水及びエーテルを注入した。室
温で３０分撹拌した後、静置、分液してエーテル層を分
取し、水洗後無水Ｍｇ５Ｏ。(2) Synthesis of ethyl 2-cyclopropylacetate 2-cyclopropylacetonitrile obtained in (1) 5.93 (7:
1 mmol) was dissolved in 3.7 g of ethanol and 30 mj of ethyl ether, and the hydrogen chloride gas was dissolved at 10°C or below.
9g was introduced. After introduction! After stirring at 5° C. for 2 hours, the mixture was concentrated under reduced pressure, and water and ether were poured into the residue. After stirring at room temperature for 30 minutes, the ether layer was separated by standing and separated, and washed with water, followed by anhydrous Mg5O.
で乾燥した。乾燥剤枦去後、溶媒留去し、残渣を減圧蒸
留してｂｐ５５〜５７℃／３０ｍｍＨｇの留分４．Ｏｇ
を無色油状物として得たく収率 ４２．７％）。It was dried. After removing the desiccant, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain a fraction 4. with a BP of 55-57°C/30mmHg. Og
was obtained as a colorless oil (yield: 42.7%).
Ｉ Ｒ（Ｎｅａｔ、） ： １７３０ｃｍ−’
（−ＧＯ（Ｈ：２］１５）。IR (Neat,): 1730cm-'
(-GO(H:2]15).
（３）２−シクロプロピルエタノールの合成（２）で得
た２−シクロプロピル酢酸エチル４．０ｇ（３１ミリモ
ル）のエーテル溶液をＬｉＡ１０４７１０ｍｇを懸濁さ
せたエーテル溶液中に滴下し、次いで室温で１時間撹拌
を行った。反応液を水中に注入後、エーテル層を分取し
、エーテル層を濃縮後残渣を減圧蒸留してｂｐ７２℃／
６５＋ｎｍＨｇの留分１．５ｇを無色油状物として得た
（収率 ６６．７％）。(3) Synthesis of 2-cyclopropylethanol An ether solution of 4.0 g (31 mmol) of ethyl 2-cyclopropylacetate obtained in (2) was added dropwise to an ether solution in which 710 mg of LiA was suspended, and then 1 Stirring was performed for hours. After injecting the reaction solution into water, separate the ether layer, concentrate the ether layer, and distill the residue under reduced pressure.
1.5 g of a 65+nmHg fraction was obtained as a colorless oil (yield 66.7%).
Ｉ Ｒ（Ｎｅａｔ） ： ３３００ｃｍ−’ （−０
１１）。I R (Neat): 3300cm-' (-0
11).
（４）２−シクロプロピルエチルブロマイドの合成（３
）で得た２−シクロプロピルエタノール１．４ｇ（１９
，４ミリモル）を塩化メチレン中三臭化リン２．７ｇと
０〜５℃で１時間反応させ、反応液を水中に注入後、塩
化メチレンで抽出した。塩化メチレン層をＮａ１ｌＧＯ
，、水溶液洗浄及び水洗浄の後、無水Ｍｇ５Ｏ，で乾燥
した。乾燥剤枦去後、溶媒留去し、残１ｈを蒸留してｂ
ｐ１２７〜１２９℃の留分１．３ｇを無色油状物として
得た（収率 ４９，６％）。(4) Synthesis of 2-cyclopropylethyl bromide (3
) 1.4 g of 2-cyclopropyl ethanol (19
, 4 mmol) was reacted with 2.7 g of phosphorus tribromide in methylene chloride at 0 to 5° C. for 1 hour, and the reaction solution was poured into water and extracted with methylene chloride. Na1lGO methylene chloride layer
, After washing with an aqueous solution and washing with water, it was dried with anhydrous Mg5O. After removing the desiccant, the solvent was distilled off, and the remaining 1 h was distilled to
1.3 g of a fraction of 127-129° C. was obtained as a colorless oil (yield 49.6%).
参考例２．２−シクロへキシルメチルイソキノリニウム
ブロマイドの合成
イソキノリン（和光純薬工Ｘ＠製） ７４ｇ（６０ミリ
モル）と臭化シクロヘキシルメチル（アルドリッチ社製
） ＩＯ，６ｇを１１０〜１２０℃で４時間反応させた
後、アセトン及びエタノールを加えて還流溶解させた。Reference Example 2. Synthesis of 2-cyclohexylmethylisoquinolinium bromide 74 g (60 mmol) of isoquinoline (manufactured by Wako Pure Chemical Industries, Ltd. After reacting for 4 hours, acetone and ethanol were added and dissolved under reflux.
反応液を冷却し５析出晶を枦取、洗浄、乾燥して、淡黄
色結晶７．８ｇを得た（収率 ４２．４％）。The reaction solution was cooled, and 5 precipitated crystals were collected, washed, and dried to obtain 7.8 g of pale yellow crystals (yield: 42.4%).
ｍ ｐ １９９〜２０３℃。mp 199-203℃.
元素分析値（Ｇ＋５ＨｚｏＢｒＮ）
理論値Ｃ％） Ｃ：６２．７５． Ｈ：６．５８．
Ｎ： ４．５７実測値（９６） Ｃ：６２．５４． Ｈ
：６．７９． Ｎ： ４．６６゜’ＨＮ Ｍ Ｒ
δρρ信 （ＣＤα３ン ： ０．５２〜２．２２
（１０１１゜ｒｎ、 ｃｙｃｌｏｈｅｘｙｌ−Ｃ２
〜Ｇ、）、 １．８５〜２．４５ （ＩＩＩ、 ｍ。Elemental analysis value (G+5HzoBrN) Theoretical value C%) C: 62.75. H:6.58.
N: 4.57 actual value (96) C: 62.54. H
:6.79. N: 4.66゜'HN M R
δρρ (CDα3n: 0.52~2.22
(1011゜rn, cyclohexyl-C2
~G,), 1.85~2.45 (III, m.
ｃｙｃｌｏｈｅｘｙｌ−Ｃ，）、５．０２（２Ｈ，ｄ、
、１−６１１ｚ、；Ｎ”（Ｉｆ、−）。cyclohexyl-C,), 5.02 (2H, d,
, 1-611z,;N"(If,-).
７．７８〜９．２２ （６Ｈ，ｍ、１ｓｏｑｕｉｎｏｌ
ｉｎｅ −Ｃ３〜Ｃ，ｌ）。7.78-9.22 (6H, m, 1soquinol
ine-C3~C,l).
１１．１４ （ＩＨ，ｓ、 １ｓｏｑｕｉｎｏｌｉｎｅ
−Ｇ、）。11.14 (IH,s, 1soquinoline
-G,).
参考例３〜７．イソキノリニウムハライド化合物の合成
市販品或は参考例１で得られた種々のシクロアルキルハ
ライドとイソキノリンとを原料として参考例２と同様に
反応及び後処理を行い、対応するイソキノリニウムハラ
イド化合物を得た。結果を表−１に示す。Reference examples 3 to 7. Synthesis of isoquinolinium halide compounds Using commercially available products or various cycloalkyl halides obtained in Reference Example 1 and isoquinoline as raw materials, reaction and post-treatment were carried out in the same manner as in Reference Example 2 to obtain the corresponding isoquinolinium halide. The compound was obtained. The results are shown in Table-1.
以下余白
参考例８． ＴＣＮＱ−Ｌｉ塩の合成ＴＣＮＱ ［和
光紬薬工業＠製］ ２０．４ｇ （０，１モル）をアセ
トニトリル１．５！に加温溶解し、これにヨウ化リチウ
ム２６．８ｇ （０，２モル）をアセトニトリル２００
ｍｊに溶解した溶液を滴下して還流下１時間反応させた
。反°応後、冷却して結晶を枦取し、乾燥して、紫色粉
末品２０．０ｇを得た（収率９４．８％）。Margin reference example 8 below. Synthesis of TCNQ-Li salt 20.4g (0.1 mol) of TCNQ [manufactured by Wako Tsumugi Kogyo @] was added to 1.5 g of acetonitrile! 26.8 g (0.2 mol) of lithium iodide was dissolved in 200 g of acetonitrile.
A solution dissolved in mj was added dropwise and reacted under reflux for 1 hour. After the reaction, the mixture was cooled and the crystals were collected and dried to obtain 20.0 g of a purple powder (yield: 94.8%).
実施例１． ２−シクロへキシルメチルイソキノリニウ
ムＴＣＮＱ単塩の合成
参考例２で得られた２−シクロへキシルメチルイソキノ
リニウムブロマイド４．６ｇを参考例８で得られたＴＣ
ＮＱのＬｉ塩：１．１７ｇ（１５ミリモル）のメタノー
ル１５０ｍｊ溶液に加え、還流下２時間反応させた。反
応後、反応液を冷却して結晶を枦取し、洗浄、乾燥して
２−シクロへキシルメチルイソキノソニウムＴ ＣＮ
Ｑ ＩＦ塩５．２ｇを青紫色粉末として得た（収率 ８
０．５％）。Example 1. Synthesis of 2-cyclohexylmethylisoquinolinium TCNQ single salt 4.6 g of 2-cyclohexylmethylisoquinolinium bromide obtained in Reference Example 2 was mixed with TC obtained in Reference Example 8.
Li salt of NQ: It was added to a solution of 1.17 g (15 mmol) in 150 mj of methanol and reacted under reflux for 2 hours. After the reaction, the reaction solution is cooled and the crystals are collected, washed and dried to give 2-cyclohexylmethylisoquinosonium TCN.
5.2 g of Q IF salt was obtained as a blue-purple powder (yield: 8
0.5%).
元素分析値（ＣｚａＨ２４Ｎｓ）
理論値（！ｌｉ） Ｃニア８．１１． Ｈ： ５．６２
． Ｎ：Ｉ８．２７実測値（％） Ｃニア７．８２．
Ｈ： ５．８＋、 Ｎ ：Ｉ６．３７゜ＤＳＣ：吸熱点
２′０１℃９発熱分解点２４８℃。Elemental analysis value (CzaH24Ns) Theoretical value (!li) C near 8.11. H: 5.62
．． N: I8.27 Actual value (%) C near 7.82.
H: 5.8+, N: I6.37° DSC: Endothermic point 2'01°C 9 Exothermic decomposition point 248°C.
実施例２〜６．各種イソキノリニウムＴＣＮＱ単塩の合
成
参考例３〜７で得られたイソキノリニウムハライド化合
物と参考例８で得られたＴＣＮＱのＬｉ塩を用いて実施
例１と同様に反応及び後処理を行い、対応するイソキノ
リニウムＴＣＮＱ単塩を得た。結果を表−２に示す。Examples 2-6. Synthesis of various isoquinolinium TCNQ single salts Using the isoquinolinium halide compounds obtained in Reference Examples 3 to 7 and the Li salt of TCNQ obtained in Reference Example 8, reaction and post-treatment were carried out in the same manner as in Example 1. The corresponding isoquinolinium TCNQ single salt was obtained. The results are shown in Table-2.
実ｊＭ例７ 、 Ｔ ＣＮ Ｑ ′Ｊｒｆ体の合成実施
例１で１１られたＴＣＮＱ単塩２．１５ｇ（５ミリモル
）とＴＣＮＱ １．０２ｇ （５ミリモル）をアセト
ニトリル２００ｍ１に加温溶解し、還流ド２時間反応さ
せた。反応後、冷却して結晶を枦取し、アセトニトリル
より再結晶して２．７０ｇの黒紫色プリズム晶を得た（
収率 ８５．２％）。Practical Example 7, Synthesis of TCNQ'Jrf Formation 2.15 g (5 mmol) of the TCNQ single salt prepared in Example 1 and 1.02 g (5 mmol) of TCNQ were dissolved in 200 ml of acetonitrile under heating, and the solution was heated under reflux. The reaction was allowed to proceed for 2 hours. After the reaction, the crystals were collected by cooling and recrystallized from acetonitrile to obtain 2.70 g of black-purple prism crystals (
Yield 85.2%).
元素分析値（０４ｏ１１ｚ８ＮＪ
理論値（和Ｃニア５．６’ｌ、 Ｈ：４．４５． Ｎ
：１９．８６実測値（＄） Ｃニア５．４９． Ｈ：
４．５！ｌ、 Ｎ ：１９．９１゜比抵抗値：１４０
Ω−ｃｍ。Elemental analysis value (04o11z8NJ theoretical value (sum C near 5.6'l, H: 4.45.N
:19.86 Actual value ($) C near 5.49. H:
4.5! l, N: 19.91° Specific resistance value: 140
Ω-cm.
ＤＳＣ：吸熱点 ２３４℃：発熱分解点２７３℃。DSC: Endothermic point 234°C: Exothermic decomposition point 273°C.
’Ｉ’ＧＮＱ ’／Ｔｌ；ＮＱ ’比：１．０２実施例
８〜１２．各種ＴＣＮＱ錯体の合成実施例２〜６でＮら
れたＴＣＮＱ単塩を用いて実施例７と同様に反応及び後
処理を行い、対応するＴＣＮＱ錯体を得た。結果を表−
３に示す。'I'GNQ'/Tl;NQ' ratio: 1.02 Examples 8-12. Synthesis of various TCNQ complexes Using the TCNQ single salts prepared in Examples 2 to 6, reactions and post-treatments were carried out in the same manner as in Example 7 to obtain corresponding TCNQ complexes. Display the results -
Shown in 3.
尚、中性ＴＣＮＱ（ＴＣＮＱ＠と表示）とアニオンラジ
カルＴＣＮＱ（ＴＣＮＱ’と表示）との錯体構成比（’
ｒにＮＱ ’／Ｔｌｌ：ＮＱ” ）は文献（八、Ｒｅｍ
ｂａｕｍ Ｃｔ ａｌ、。In addition, the complex composition ratio ('
r to NQ'/Tll:NQ'') is based on the literature (8, Rem
baum Ctal,.
Ｊ、八ｍ、 ＣｈｅＬＩｌ、 Ｓｏｃ、、 ９３．２５
：１２ （＋９７１））に従い紫外線吸収スペクトル測
定方法で求めた。また、吸熱点及び発熱分解点について
は示差走査熱量（ＯＳＣ）測定で求めた。電気的特性値
については錯体をベレットとし、以上常法に従って試料
作製の後２５℃で電流電圧測定（二端子法）を行い、面
記計算式に基づいて比抵抗値ρ（Ω・ｃｍ ）を求めた
。J, 8m, CheLIl, Soc,, 93.25
:12 (+971)) by ultraviolet absorption spectrum measurement method. In addition, the endothermic point and exothermic decomposition point were determined by differential scanning calorimetry (OSC) measurement. Regarding the electrical property values, the complex was made into a pellet, and after preparing the sample according to the above conventional method, current and voltage measurements were carried out at 25°C (two-terminal method), and the specific resistance value ρ (Ω cm ) was calculated based on the surface calculation formula. I asked for it.
（発明の効果〕
以上述べた如く、本発明は、これまでＴＣＮＱ錯体に用
いられていなかったＮ−置換イツキノリニウムカチオン
をドナーとして用いた点に特徴を有する発明であり、従
来にない蛙々の電子化学的或は光学的成果が期待できる
新規なＴＣＮＱ錯体を提供し得るものである点に顕著な
効果を奏するものであり、斯業に貞献するところ大なる
発明である。(Effects of the Invention) As described above, the present invention is characterized in that an N-substituted quinolinium cation, which has not been used in TCNQ complexes, is used as a donor. This invention has a remarkable effect in that it can provide a new TCNQ complex from which electrochemical or optical results can be expected, and it is a great invention that is dedicated to this industry.
Claims (1)
又はシクロヘキシル基を示し、ｎは１〜３の整数を示す
。）で表わされるＮ−置換イソキノリニウムカチオンと
、７，７，８，８−テトラシアノキノジメタンアニオン
ラジカル（ＴＣＮＱ）及び中性ＴＣＮＱ（ＴＣＮＱ°）
とを構成成分とするＴＣＮＱ錯体。[Claims] Represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. N-substituted isoquinolinium cation and 7,7,8,8-tetracyanoquinodimethane anion radical (TCNQ) and neutral TCNQ (TCNQ°)
A TCNQ complex consisting of and.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61-238587 | 1986-10-07 | ||
| JP23858786 | 1986-10-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63233976A true JPS63233976A (en) | 1988-09-29 |
Family
ID=17032418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62015778A Pending JPS63233976A (en) | 1986-10-07 | 1987-01-26 | Novel tcnq complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63233976A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0395426A2 (en) * | 1989-04-28 | 1990-10-31 | Fujitsu Limited | Method of forming pattern by using an electroconductive composition |
| WO2003042145A1 (en) * | 2001-11-12 | 2003-05-22 | Kuraray Co.,Ltd. | Processes for preparation of cyclopropylethanol, cyclo- propylacetonitrile and intermediates of both |
-
1987
- 1987-01-26 JP JP62015778A patent/JPS63233976A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0395426A2 (en) * | 1989-04-28 | 1990-10-31 | Fujitsu Limited | Method of forming pattern by using an electroconductive composition |
| WO2003042145A1 (en) * | 2001-11-12 | 2003-05-22 | Kuraray Co.,Ltd. | Processes for preparation of cyclopropylethanol, cyclo- propylacetonitrile and intermediates of both |
| US7164047B2 (en) | 2001-11-12 | 2007-01-16 | Kuraray Co., Ltd. | Processes for preparation of cyclopropylethanol, cyclopropylacetonitorile and intermediates of both |
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