JPH01254662A - N-substituted-2,3'-bipyridyl 7,7,8,8-tetracyanoquinodimethane complex salts and production thereof - Google Patents

N-substituted-2,3'-bipyridyl 7,7,8,8-tetracyanoquinodimethane complex salts and production thereof

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Publication number
JPH01254662A
JPH01254662A JP8357388A JP8357388A JPH01254662A JP H01254662 A JPH01254662 A JP H01254662A JP 8357388 A JP8357388 A JP 8357388A JP 8357388 A JP8357388 A JP 8357388A JP H01254662 A JPH01254662 A JP H01254662A
Authority
JP
Japan
Prior art keywords
formula
bipyridyl
tetracyanoquinodimethane
substituted
complex salts
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
Application number
JP8357388A
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Japanese (ja)
Inventor
Hiroyuki Kurihara
博之 栗原
Kozo Shirai
白井 孝三
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Elna Co Ltd
Original Assignee
Elna Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Elna Co Ltd filed Critical Elna Co Ltd
Priority to JP8357388A priority Critical patent/JPH01254662A/en
Publication of JPH01254662A publication Critical patent/JPH01254662A/en
Pending legal-status Critical Current

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  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

NEW MATERIAL:N-Substituted-2,3'-bipyridyl 7,7,8,8-tetracyanoquinodimethane complex salts expressed by formula I [R is 1-6C alkyl or benzyl; m is a positive number (0.5-1.5) corresponding to the number of mol of neutral 7,7,8,8- tetracyanoquinodimethane contained in 1 mol complex salts]. EXAMPLE:N-Methyl-2,3'-bipyridyl-quaternary ammonium 7,7,8,8- tetracyanoquinodimethane complex salts. USE:An organic semiconductor, solid electrolyte, etc., of solid electrolytic capacitors. PREPARATION:N-Substituted-2,3'-bipyridyl-quaternary ammonium salts expressed by formula II are reacted with 7,7,8,8-tetracyanoquinodimethane expressed by formula III to afford the aimed compounds expressed by formula I.

Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は、電子機器分野あるいは電子材料分野などにお
ける導電性材料として注目されている有機半導体に関す
るもので、特に新規物質としてのN−置換−2,3′−
ビピリジル・7,7,8.8−テトラシアノキノジメタ
ン錯塩類およびその製造力l去に関するものである。
Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an organic semiconductor that is attracting attention as a conductive material in the field of electronic equipment or electronic materials, and in particular, relates to an organic semiconductor that is attracting attention as a conductive material in the field of electronic devices or electronic materials. 2,3'-
This invention relates to bipyridyl 7,7,8.8-tetracyanoquinodimethane complex salts and their manufacturing capabilities.

[9,明の概要] 更に詳しくは、下記の式[1]で表わされる新規有機f
導体(新規化合物)としてのN−置換−2,3′−ビピ
リジル・7.7,8.8−テトラシアノキノジメタン錯
塩類およびその製造方法を提供するものである。
[9, Overview of Ming] More specifically, the novel organic f expressed by the following formula [1]
The present invention provides N-substituted-2,3'-bipyridyl 7.7,8.8-tetracyanoquinodimethane complex salts as conductors (new compounds) and a method for producing the same.

ただし、式[1]中、RはC1〜C6のアルキル基また
はベンジル基を示す。mは1モルの錯塩に含まれる中性
?、7,8.8−テトラシアノキノジメタンのモル数に
対応する正の数(0,5〜1.5)を意味する。
However, in formula [1], R represents a C1-C6 alkyl group or a benzyl group. Is m the neutral contained in 1 mole of complex salt? , means a positive number (0.5 to 1.5) corresponding to the number of moles of 7,8.8-tetracyanoquinodimethane.

なお、説明の便宜上、7,7,8.8−テトラシアノキ
ノジメタンを以下、TCNQと称す。
In addition, for convenience of explanation, 7,7,8.8-tetracyanoquinodimethane is hereinafter referred to as TCNQ.

次に、」―記の式[1]で示した化合物は、下記の式[
2]で表ねされるN装置PA−2,3−ビピリジル・第
四アンモニウム塩類を 下記の式[3]で表わされるTCNQと反応させること
により製造することができるものである。
Next, the compound represented by the formula [1] shown in "-" is obtained by the following formula [
N device PA-2,3-bipyridyl quaternary ammonium salt represented by [2] can be produced by reacting with TCNQ represented by the following formula [3].

を記の式[1Fの化合物において1式中のRのアルキル
基の例としては、メチル、エチル、プロピル、ブチル、
ペンチル、ヘキシルのような炭素数がC,〜Caのアル
キル基(n−,1so−などの全ての異性体を含む。)
を例示することができる。また、式[11中のRとして
ベンジル基を例示することができる。式[1]中のmは
O15〜1.5が好ましく、より好ましくは約1である
In the compound of formula [1F], examples of the alkyl group of R in formula 1 include methyl, ethyl, propyl, butyl,
Alkyl groups with carbon numbers of C to Ca, such as pentyl and hexyl (including all isomers such as n- and 1so-)
can be exemplified. Moreover, a benzyl group can be exemplified as R in formula [11]. m in formula [1] is preferably O15 to 1.5, more preferably about 1.

また、式[2]中のRは式[1]と同様に01〜CI、
のアルキル基またはベンジル基であり、Xはハロゲンで
ある。
Further, R in formula [2] is 01 to CI, as in formula [1],
is an alkyl group or a benzyl group, and X is a halogen.

[合成方法] 1−述したように、本発明に係る式[1]の新規化合物
であるN−置換−2,3′−ビピリジル・TCNQCN
類は、式[2]のN−置換−2,3′−ビピリジル・第
四アンモニウム塩類を式[3]のTCNQに反応させる
ことによって容易に好ましい収率で製造することができ
る。以下に、その製造方法について述べる。
[Synthesis method] 1-As mentioned above, N-substituted-2,3'-bipyridyl TCNQCN, which is a novel compound of formula [1] according to the present invention
can be easily produced in a preferred yield by reacting N-substituted-2,3'-bipyridyl quaternary ammonium salts of formula [2] with TCNQ of formula [3]. The manufacturing method will be described below.

式[2]のN−置換−2,3−ビピリジル・第四アンモ
ニウム塩類は既に公知の化合物であって、2.3’−ビ
ピリジルからそれ自体公知のf法を利用して容易に合成
することができる。このN−置換−2,3′−ビピリジ
ル・第四アンモニウム塩類の合成例を第1表に示す。2
.3′−ビピリジルを1とした場合の反応モル比は1:
1〜3が好ましく、本例ではt:i、sとした。
The N-substituted-2,3-bipyridyl quaternary ammonium salts of formula [2] are already known compounds, and can be easily synthesized from 2,3'-bipyridyl using the per se known f method. Can be done. Synthesis examples of these N-substituted-2,3'-bipyridyl quaternary ammonium salts are shown in Table 1. 2
.. When 3'-bipyridyl is 1, the reaction molar ratio is 1:
1 to 3 are preferred, and in this example, t:i,s.

式[3]のTCNQおよびその種々の塩ならびにその製
造方法についても既に公知であって、例えばり、R,M
elbyらのJ、Am、Chem、Soc、、84.3
374 (1962)および昭和58(「特許出願公開
第191414号公報に明示されている。
TCNQ of formula [3] and various salts thereof and methods for producing the same are already known, for example, R, M
J, Am, Chem, Soc, 84.3 of elby et al.
No. 374 (1962) and Showa 58 (as clearly disclosed in Patent Application Publication No. 191414).

次に、式[2]の化合物と式[3]のTCNQとから式
[1]の化合物を製造するー・態様につい−(詳述する
と、例えば式[2]中の一例としてのN−メチル−2,
3′−ビピリジル・第四アンモニウム塩類の熱アセトニ
トリル溶液と式[3]のTCNQの熱アセトニトリル溶
液を熱時混合した後に放冷し、析出した結晶を濾過する
。この際1反応6イ液に大過剰のエーテルを注加し、反
応生成物を析出せしめても良い。反応生成物は熱アセト
ニトリルで+1結晶するか、または冷無水エタノールで
同エタノールの着色か無くなるまで洗浄すれば、無機塩
類を含有しない式[IJ中の一例としてのN−メチル−
2,3−ビピリジル・TCNQ錯塩を高収率で得ること
ができる。
Next, regarding the mode of producing the compound of formula [1] from the compound of formula [2] and TCNQ of formula [3] (in detail, for example, N-methyl in formula [2]) -2,
A hot acetonitrile solution of 3'-bipyridyl quaternary ammonium salts and a hot acetonitrile solution of TCNQ of formula [3] are mixed while hot, then allowed to cool, and the precipitated crystals are filtered. At this time, a large excess of ether may be added to the first reaction solution to precipitate the reaction product. The reaction product can be crystallized by +1 with hot acetonitrile or washed with cold absolute ethanol until the color of the ethanol disappears, resulting in a product of the formula [N-methyl- as an example in IJ] containing no inorganic salts.
2,3-bipyridyl/TCNQ complex salt can be obtained in high yield.

ところで、式[2]の化合物と式[3]のTCNQとの
反応において、同反応は例えば常圧下、好ましくは窒素
ガス、アルゴンガスのような不活性ガス雰囲気中で、ア
セトニトリル、ジメチルホルムアミド、テトラヒドロフ
ラン、アルキルセロソルブなと、あるいはそれらの’l
!i ”Faな混合物のような不活性有機溶媒の沸点ト
ーで行なうと良い。反応に使用する式[3]のTCNQ
の使用量は、式[2コの混合物1モルに対して約1〜3
モルの如き使用量を例示1−ることができる。また、不
活性有機溶媒の使用はも適宜選択することができ、式[
2]の化合物に対して約10〜20倍、式[3]のTC
NQに対して約50〜120倍の如き使用量を例示する
ことができる。
By the way, in the reaction between the compound of formula [2] and TCNQ of formula [3], the reaction is carried out, for example, under normal pressure, preferably in an inert gas atmosphere such as nitrogen gas or argon gas, using acetonitrile, dimethylformamide, or tetrahydrofuran. , alkyl cellosolve, or their
! It is preferable to carry out the reaction at the boiling point of an inert organic solvent such as a mixture of Fa.
The amount used is approximately 1 to 3 per mol of the mixture of formula [2].
Examples of amounts used include moles. In addition, the use of an inert organic solvent can be selected as appropriate, and the formula [
TC of formula [3] about 10 to 20 times as much as the compound of formula [2]
For example, the usage amount may be about 50 to 120 times that of NQ.

[実施例] 更に、本発明に係る式[1]のN−置換−2,3′−ビ
ピリジル・TCNQCN類の具体的な合成方法の実施例
について述べる。
[Example] Furthermore, an example of a specific method for synthesizing N-substituted-2,3'-bipyridyl TCNQCN of formula [1] according to the present invention will be described.

実施例I N−メチル−2,3″−ビピリジル・第四アンモニウム
・TCNQ錯塩の合成について述べる。
Example I The synthesis of N-methyl-2,3''-bipyridyl/quaternary ammonium/TCNQ complex salt will be described.

N−メチル−2,3′−ビピリジル・第四アンモニウム
・沃化水素酸塩o、otooモルをアセトニトリル50
m1に熱時溶解し、これにTCNQO,015モルをア
セトニトリル300m1に熱時溶解して注加し、混合し
た後に室温で約5時間放冷する。場合によってはこの放
冷後に大過剰のエーテルを加えて完全に結晶を析出させ
、析出した工、μ色針状結晶を濾別する。この結晶を熱
アセトニトリルにより再結晶を繰返し行ない、場合によ
っては引続きエタノールで同濾液が着色しなくなるまで
洗浄した後、エーテルで洗浄し、さらに乾燥させると、
沃素イオンを全く含有しない純粋なN−メチル−2,3
′−ビピリジル・第四アンモニウム・TCNQ錯塩、融
点216.5〜220゜0℃の黒色針状結晶を収率65
%の高収率で得ることができる。
50 moles of N-methyl-2,3'-bipyridyl quaternary ammonium hydroiodide in acetonitrile
0.15 mol of TCNQO dissolved in 300 ml of acetonitrile while hot was added thereto, mixed, and then allowed to cool at room temperature for about 5 hours. In some cases, after this cooling, a large excess of ether is added to completely precipitate the crystals, and the precipitated micro-colored needle crystals are filtered off. The crystals are repeatedly recrystallized using hot acetonitrile, and in some cases, the filtrate is washed with ethanol until the filtrate is no longer colored, then washed with ether, and further dried.
Pure N-methyl-2,3 containing no iodide ions
'-Bipyridyl quaternary ammonium TCNQ complex salt, black needle-like crystals with melting point 216.5-220° 0°C, yield 65
It can be obtained with a high yield of %.

実施例2〜4 」二足実施例1ではN−メチル−2,3−ビピリジル・
第四アンモニウム・TCNQ錯塩の合成について述べた
が、式[2]中の化合物Rがエチル、n−プロピルおよ
びペンシルに置換された式[2]の化合物(Ii*掲第
1表中2〜4)を用い、実施例1と同様の手法・手順に
準じて合成した結果、第2kに示すようにN−エチル−
2,3−ビピリジル・第四アンモニウム・TCNQ錯塩
(実施例2)、N−プロピル−2,3−ビピリジル・第
四アンモニウム・TCNQ錯塩(実施例3)、N−ヘン
シル−2,3−ビピリジル・第四アンモニウム・TCN
Q錯塩(実施例4)を1うtた。
Examples 2 to 4 In Example 1, N-methyl-2,3-bipyridyl
The synthesis of quaternary ammonium/TCNQ complex salts has been described, and compounds of formula [2] in which compound R in formula [2] is substituted with ethyl, n-propyl, and pencil (Ii * 2 to 4 in Table 1) ) using the same method and procedure as in Example 1. As a result, N-ethyl-
2,3-bipyridyl quaternary ammonium TCNQ complex salt (Example 2), N-propyl-2,3-bipyridyl quaternary ammonium TCNQ complex salt (Example 3), N-hensyl-2,3-bipyridyl Quaternary ammonium/TCN
1 t of Q complex salt (Example 4) was added.

第2表にN−アルキル−2,3−ビピリジル・第四アン
モニウム・沃化水素酸塩のモル数とアセトニトリルの量
、TCNQのモル数とアセトニトリルの!ニジ収率およ
び融点について、実施例2〜4に実施例1を追加して記
す。
Table 2 shows the number of moles of N-alkyl-2,3-bipyridyl quaternary ammonium hydroiodide and the amount of acetonitrile, the number of moles of TCNQ and the amount of acetonitrile! Regarding the rainbow yield and melting point, Example 1 is added to Examples 2 to 4.

[応用例] 上述のようにして得た式[1]のN−置換−2,3′−
ビピリジル・TCNQCN類の用途について述べると、
このTCNQCN類は例えば2枚のアルミニウム箔をセ
パレータを介して巻回したコンデンサ素子からなる固体
電解コンデンサの固体電解質として、あるいはタンタル
粉末焼結体のコンデンサ素子からなる固体電解コンデン
サの固体電解質として利用し得る乙のである。
[Application example] N-substituted -2,3'- of formula [1] obtained as described above
Regarding the uses of bipyridyl/TCNQCN,
These TCNQCNs can be used, for example, as the solid electrolyte of a solid electrolytic capacitor consisting of a capacitor element made of two sheets of aluminum foil wound with a separator in between, or as the solid electrolyte of a solid electrolytic capacitor consisting of a capacitor element of tantalum powder sintered body. It's up to you to get it.

Claims (2)

【特許請求の範囲】[Claims] (1)下記の式[1]で表わされるN−置換−2,3′
−ビピリジル・7,7,8,8−テトラシアノキノジメ
タン錯塩類。 ▲数式、化学式、表等があります▼[1] 式[1]中、RはC_1〜C_6のアルキル基またはベ
ンジル基を示す。mは1モルの錯塩に含まれる中性7,
7,8,8−テトラシアノキノジメタンのモル数に対応
する正の数(0.5〜1.5)を意味する。
(1) N-substituted-2,3' represented by the following formula [1]
-Bipyridyl 7,7,8,8-tetracyanoquinodimethane complex salts. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] In formula [1], R represents an alkyl group of C_1 to C_6 or a benzyl group. m is the neutral 7 contained in 1 mol of complex salt,
It means a positive number (0.5 to 1.5) corresponding to the number of moles of 7,8,8-tetracyanoquinodimethane.
(2)下記の式[2]で表わされるN−置換−2,3′
−ビピリジル・第四アンモニウム塩類を▲数式、化学式
、表等があります▼[2] 下記の式[3]で表わされる7,7,8,8−テトラシ
アノキノジメタンと反応させ、 ▲数式、化学式、表等があります▼[3] 下記の式[1]で表わされるN−置換−2,3−ビピリ
ジル・7,7,8,8−テトラシアノキノジメタン錯塩
類を ▲数式、化学式、表等があります▼[1] 得ることを特徴としたN−置換−2,3′−ビピリジル
・7,7,8,8−テトラシアノキノジメタン錯塩類の
製造方法。 式[2]中、RはC_1〜C_6のアルキル基またはベ
ンジル基を示し、Xはハロゲンを示す。 式[1]中、RはC_1〜C_6のアルキル基またはベ
ンジル基を示す。mは1モルの錯塩に含まれる中性7,
7,8,8−テトラシアノキノジメタンのモル数に対応
する正の数(0.5〜1.5)を意味する。
(2) N-substituted-2,3' represented by the following formula [2]
-Bipyridyl quaternary ammonium salts are reacted with 7,7,8,8-tetracyanoquinodimethane represented by the following formula [3], ▲Mathematical formula, chemical formula, table, etc.▼[2] There are chemical formulas, tables, etc. ▼ [3] N-substituted-2,3-bipyridyl 7,7,8,8-tetracyanoquinodimethane complex salts represented by the following formula [1] ▲ Numerical formulas, chemical formulas, There are tables etc. ▼ [1] A method for producing N-substituted-2,3'-bipyridyl 7,7,8,8-tetracyanoquinodimethane complex salts, characterized by obtaining them. In formula [2], R represents a C_1 to C_6 alkyl group or a benzyl group, and X represents a halogen. In formula [1], R represents a C_1 to C_6 alkyl group or a benzyl group. m is the neutral 7 contained in 1 mol of complex salt,
It means a positive number (0.5 to 1.5) corresponding to the number of moles of 7,8,8-tetracyanoquinodimethane.
JP8357388A 1988-04-05 1988-04-05 N-substituted-2,3'-bipyridyl 7,7,8,8-tetracyanoquinodimethane complex salts and production thereof Pending JPH01254662A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8357388A JPH01254662A (en) 1988-04-05 1988-04-05 N-substituted-2,3'-bipyridyl 7,7,8,8-tetracyanoquinodimethane complex salts and production thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8357388A JPH01254662A (en) 1988-04-05 1988-04-05 N-substituted-2,3'-bipyridyl 7,7,8,8-tetracyanoquinodimethane complex salts and production thereof

Publications (1)

Publication Number Publication Date
JPH01254662A true JPH01254662A (en) 1989-10-11

Family

ID=13806249

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8357388A Pending JPH01254662A (en) 1988-04-05 1988-04-05 N-substituted-2,3'-bipyridyl 7,7,8,8-tetracyanoquinodimethane complex salts and production thereof

Country Status (1)

Country Link
JP (1) JPH01254662A (en)

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