JPH0459764A - N-substituted-2,2'-dipyridylamine-7,7,8,8-tetracyanoquinodimethane complex salts and production thereof - Google Patents
N-substituted-2,2'-dipyridylamine-7,7,8,8-tetracyanoquinodimethane complex salts and production thereofInfo
- Publication number
- JPH0459764A JPH0459764A JP16899490A JP16899490A JPH0459764A JP H0459764 A JPH0459764 A JP H0459764A JP 16899490 A JP16899490 A JP 16899490A JP 16899490 A JP16899490 A JP 16899490A JP H0459764 A JPH0459764 A JP H0459764A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- dipyridylamine
- tetracyanoquinodimethane
- substituted
- complex 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
- 150000003839 salts Chemical class 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims abstract 8
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 27
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 3
- 239000012776 electronic material Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- 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 20
- 238000000034 method Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000004455 differential thermal analysis Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- JOZYBUSXAGFNKN-UHFFFAOYSA-N N-pyridin-2-ylpyridin-2-amine Chemical compound N(c1ccccn1)c1ccccn1.N(c1ccccn1)c1ccccn1 JOZYBUSXAGFNKN-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl cellosolve Chemical compound 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
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−２，２゛−
ジピリジルアミン・７．７８．８−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. 2,2゛-
The present invention relates to dipyridylamine/7.78.8-tetracyanoquinodimethane complex salts and a method for producing the same.
［発明の概要］
更に詳しくは、下記の式［１］で表わされる新規有機半
導体（新規化合物）としてのＮ−置換−２，２°−ジピ
リジルアミン・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。[Summary of the invention] More specifically, N-substituted-2,2°-dipyridylamine/7,7,8.8-tetracyanoquino as a novel organic semiconductor (new compound) represented by the following formula [1] Dimethane complex salts and a method for producing the same are provided.
下記の式［３］で表わされるＴＣＮＱとただし、式［１
］中、ＲはＣ３〜Ｃ＋ａ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。TCNQ expressed by the following formula [3] and formula [1]
], R represents a C3 to C+a alkyl group or a benzyl group. m is neutral 7, 7, 8. contained in 1 mol of complex salt.
It means a positive number (0.5 to 1.5) corresponding to the number of moles of 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、上記の式［１］で示した化合物は、下記の式［２
］で表わされるＮ−置換−２，２°−ジピリジルアミン
・第四アンモニウム塩類な反応させることにより製造す
ること力Ｓできるものである。Next, the compound shown by the above formula [1] can be converted to the compound shown by the following formula [2].
] N-substituted-2,2°-dipyridylamine quaternary ammonium salts can be produced by reacting them.
上記の式［１］の化合物において、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０１〜Ｃ３，のア
ルキル基（ｎ−，１ｓｏ−などの全ての異性体を含む。In the compound of formula [1] above, examples of the alkyl group for R in the formula include methyl, ethyl, propyl, butyl,
Alkyl groups having 01 to C3 carbon atoms such as pentyl and hexyl (including all isomers such as n- and 1so-).
）を例示すること力Ｓできる。また、式［１］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０．５〜１．５が好ましく、より好ましくは約１で
ある。さらに、式［２］中のＲは式［１］と同様にＣ０
〜Ｃｌ＋ｔ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。) can be exemplified by force S. Moreover, a benzyl group can be exemplified as R in formula [1]. m in formula [1] is preferably 0.5 to 1.5, more preferably about 1. Furthermore, R in formula [2] is C0 as in formula [1].
~Cl+t is an alkyl group or a benzyl group, and X is a halogen.
［合成方法１
上述したように、本発明に係る式［１］の新規化合物で
あるＮ−置換−２，２°−ジピリジルアミンを式［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。[Synthesis method 1] As described above, N-substituted-2,2°-dipyridylamine, which is a novel compound of formula [1] according to the present invention, is synthesized by formula [3]
It can be easily produced in a preferred yield by reacting with TCNQ.
式［２］のＮ−置換−２，２°−ジピリジルアミン・第
四アンモニウム塩類は既に公知の化合物であって、２，
２°−ジピリジルアミンからそれ自体公知の手法を利用
して容易に合成することができる。The N-substituted-2,2°-dipyridylamine quaternary ammonium salts of formula [2] are already known compounds, and 2,
It can be easily synthesized from 2°-dipyridylamine using a method known per se.
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年特許出願公開第
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 Patent Application Publication No. 191414 of 1988.
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一態様について詳述すると、
例えば式［２］中の一例としてのＮ−メチル−２，２°
−ジビーリジルアミンヨーダイド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
、反応溶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。反応生成物はアセトニトリル、メ
タノール、エーテルで洗浄しアセトニトリルで再結晶す
ると、無機塩類を含有しない式［１］中の一例としての
Ｎ−メチル−２，２゛−ジピリジルアミン・ＴＣＮＱ錯
塩を高収率で得ることができる。Next, one embodiment of producing the compound of formula [1] from the compound of formula [2] and TCNQ of formula [3] will be detailed.
For example, N-methyl-2,2° as an example in formula [2]
- A hot acetonitrile solution of dibyridylamine iodide and a hot acetonitrile solution of TCNQ of formula [3] are mixed while hot, and then allowed to cool, and the precipitated crystals are filtered. At this time, a large excess of ether may be added to the reaction solution to precipitate the reaction product. When the reaction product is washed with acetonitrile, methanol, and ether and recrystallized with acetonitrile, a high yield of N-methyl-2,2゛-dipyridylamine/TCNQ complex salt as an example of formula [1] containing no inorganic salts is obtained. You can get it at
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、あるいはそれらの適当
な混合物のような不活性有機溶媒の沸点下で行なうと良
い。反応に使用する式［３］のＴＣＮＱの使用量は、式
［２］の混合物１モルに対して約１〜３モルの如き使用
量を例示することができる。また、不活性［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. The reaction is preferably carried out at the boiling point of an inert organic solvent such as alkyl cellosolve, or a suitable mixture thereof. The amount of TCNQ of formula [3] used in the reaction may be about 1 to 3 moles per mole of the mixture of formula [2]. In addition, inert [3] TC
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゜２−ジピ
リジルアミン・ＴＣＮＱＣＮ類の具体的な合成方法の実
施例について述べる。[Example] Further, an example of a specific method for synthesizing N-substituted-2°2-dipyridylamine TCNQCN of formula [1] according to the present invention will be described.
〈実施例１〉
Ｎ−メチル−２，２“−ジピリジルアミン・ＴＣＮＱ錯
塩の合成について述べる。<Example 1> Synthesis of N-methyl-2,2''-dipyridylamine/TCNQ complex salt will be described.
２．２−ジピリジルアミン０．８６ｇ （５ｍｍｏｌ）
と、溶媒としてエチレングリコールジメチルエーテル５
ｍｌを撹拌溶解した後、ヨウ化メチル（１５ｍｍｏｌ、
３ｅｑ）を加え撹拌しながら室温で２４時間反応させ、
反応物を吸引濾過した後エチレングリコールジメチルエ
ーテルで洗浄してＮ−メチル−２，２°−ジピリジルア
ミンヨーダイト（融点１９３〜１９６℃）を４９％の収
率で得た。2.2-dipyridylamine 0.86g (5mmol)
and ethylene glycol dimethyl ether 5 as a solvent.
After dissolving ml with stirring, add methyl iodide (15 mmol,
Add 3 eq) and react at room temperature for 24 hours with stirring,
The reaction product was suction filtered and washed with ethylene glycol dimethyl ether to obtain N-methyl-2,2°-dipyridylamine iodite (melting point 193-196°C) in a yield of 49%.
こうして得たＮ−メチル−２，２°−ジピリジルアミン
ヨーダイト２ｍｍｏ ｌをアセトニトリル４ｍｍｏｌ、
１．２ｅｑ）を沸騰状態で溶解し１時間還流した溶液と
熱時混合した。さらに３０分間還流した後、５℃で２４
時間放置した。析出した結晶を濾過した後、アセトニト
リル、メタノール、エーテルの順で洗浄し、アセトニト
リルにより２回再結晶を行ない、Ｎ−メチル−２，２゜
ジピリジルアミン・ＴＣＮＱ錯塩、融点２０３〜２３６
℃の黒色結晶を収率６６％で得ることができた。2 mmol of N-methyl-2,2°-dipyridylamine iodite thus obtained was mixed with 4 mmol of acetonitrile,
1.2 eq) was dissolved in a boiling state and mixed with a solution that was refluxed for 1 hour while hot. After refluxing for an additional 30 min, 24 min at 5°C
I left it for a while. After filtering the precipitated crystals, they were washed with acetonitrile, methanol, and ether in that order, and recrystallized twice with acetonitrile to obtain N-methyl-2,2° dipyridylamine/TCNQ complex salt, melting point 203-236.
C. black crystals could be obtained in a yield of 66%.
得られたＮ−メチル−２，２°−ジピリジルアミン・Ｔ
ＣＮＱ錯塩（ＣｓａＨｚａＮ Ｉ＋）の元素分析、の結
果は次の通りである。The obtained N-methyl-2,2°-dipyridylamine T
The results of elemental analysis of the CNQ complex salt (CsaHzaN I+) are as follows.
ＨＣＮ
実測値（１３，４１７１，６０２５，３８計算値ｃ％ｌ
３．３９ ７０．７０ ２５．９１ＴＡ）し
た結果を第２図に示す。また分解点および融解前及び融
解後における比抵抗の四端子法による測定結果を表２に
示す。なお、四端子法はＴＣＮＱ塩約０．１ｇを錠剤成
型器に入れ３００ｋｇ／ｍ”の圧力で直径１０ｍｍのベ
レットを作り、これにＡ％Ｂ％Ｃ％Ｄの４箇のリード線
ペレットの周囲に順に取り付け、定電流発生装置により
４０ｕＡの直流電流をＡＢ間に流し、そのときのＣＤ間
の電位差を電圧計で測定し、次にＢＣ間にも同様に電流
を流してＤＡ間の電位差を測定する方法である。HCN actual value (13,4171,6025,38 calculated value c%l
3.39 70.70 25.91TA) The results are shown in Figure 2. Further, Table 2 shows the measurement results of the decomposition point and the specific resistance before and after melting using the four-terminal method. In addition, in the four-terminal method, approximately 0.1 g of TCNQ salt is placed in a tablet molding machine and a pellet with a diameter of 10 mm is made at a pressure of 300 kg/m'', and around the pellets of four lead wires A%B%C%D is formed. 40uA of DC current is passed between AB using a constant current generator, and the potential difference between CD is measured with a voltmeter. Next, a current is similarly passed between BC and the potential difference between DA is measured. It is a method of measurement.
〈実施例２〜５〉
上記実施例１ではＮ−メチル−２，２゛−ジピリジルア
ミン・ＴＣＮＱ錯塩について述べたが、実施例１と同様
の手法・手順に準じて表１のような条件で合成した結果
、式［２］中のＲがエチルｎ−プロピル、ブチル、ベン
ジルにそれぞれ置換されたＮ−置換−２，２°−ジピリ
ジルアミンヨーダイトを得、さらに実施例１と同様の手
法・手順に準じて、第２表に示すようにＮ−エチル−ジ
ルアミン・ＴＣＮＱ錯塩（実施例３）、Ｎ−ブチル−２
，２°−ジピリジルアミン・ＴＣＮＱ錯塩（実施例４）
、Ｎ−ベンジル−２，２°−ジピリジルアミン・ＴＣＮ
Ｑ錯塩（実施例５）を得た。これらの分解点ならびに比
抵抗値を表２に示す。なおＮ−エチル−２，２′−ジピ
リジルアミン−ＴＣＮＱ錯塩（実施例２）、Ｎ−ｎ−プ
ロピル−２，２゛−ジピリジルアミン・ＴＣＮＱ錯塩（
実施例３］のそれぞれの赤外吸収スペクトル、および熱
重量測定（ＴＧ）、示差熱分析（ＤＴＡ）した結果を第
２〜５図に示す。さらにＮ−ブチル−２，２°−ジピリ
ジルアミン・ＴＣＮＱ錯塩（実施例４）、Ｎ−ベンジル
−２，２°−ジピリジルアミン・ＴＣＮＱ錯塩（実施例
５）の赤外吸収スペクトルを第６〜７図に示す。<Examples 2 to 5> In Example 1 above, N-methyl-2,2'-dipyridylamine/TCNQ complex salt was described, but according to the same method and procedure as in Example 1, under the conditions shown in Table 1. As a result of the synthesis, N-substituted-2,2°-dipyridylamine iodite in which R in formula [2] was substituted with ethyl n-propyl, butyl, and benzyl, respectively, was obtained, and the same method as in Example 1 was obtained. According to the procedure, as shown in Table 2, N-ethyl-zylamine TCNQ complex salt (Example 3), N-butyl-2
, 2°-dipyridylamine/TCNQ complex salt (Example 4)
, N-benzyl-2,2°-dipyridylamine・TCN
Q complex salt (Example 5) was obtained. Table 2 shows these decomposition points and specific resistance values. In addition, N-ethyl-2,2'-dipyridylamine-TCNQ complex salt (Example 2), N-n-propyl-2,2'-dipyridylamine-TCNQ complex salt (
The infrared absorption spectra, thermogravimetry (TG), and differential thermal analysis (DTA) results of Example 3 are shown in FIGS. 2 to 5. Furthermore, the infrared absorption spectra of N-butyl-2,2°-dipyridylamine/TCNQ complex salt (Example 4) and N-benzyl-2,2°-dipyridylamine/TCNQ complex salt (Example 5) were measured at Nos. 6 to 7. As shown in the figure.
実施例２および４のＴＣＮＱ錯塩の元素分析の結果は次
の通りである。The results of elemental analysis of the TCNQ complex salts of Examples 2 and 4 are as follows.
Ｎ−エチル−２，２°−ジピリジルアミン・ＴＣＮＱ錯
塩（ＣｓｓＨｚａＮ １１）
ＨＣＮ
実測値（％ｌ ３．８７ ７１．６４ ２５．
１７計算値（％ｌ ３．４４ ７１．０４ ２
５．３２Ｎ−ｎ−プロピル−２，２°−ジピリジルアミ
ン・ＴＣＮＱ錯塩（Ｃ，ｔＨ１４Ｎ１１）ＨＣＮ
実測値（％１ ３．５１ ７０．８２ ２５．２
１計算値（％） ３．８９ ７１．３７ ２４
．７５Ｎ−ブチル−２，２°−ジピリジルアミン・ＴＣ
ＮＱ錯塩（Ｃ，。Ｈａ−Ｎ＋＋）
ＨＣＮ
実測値（％１ ４．０１ ７１．２７ ２４．４
６計算値（％＋ ４．１２ ７１．６８ ２４
．２ＯＮ−ベンジル−２，２°−ジピリジルアミン・Ｔ
ＣＮＱ錯塩（Ｃ４，Ｈａ、Ｎ、、）
ＨＣＮ
実測値（％１ ３．９１ ？３．３７ ２３．
３５計算値（％＋ ３．ｆｉｌ ７３．４２
２２．９８［応用例］
上述のようにして得た式［１］のＮ−置換−２，２°−
ジピリジルアミン・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
ンタル粉末第１図はこの発明の実施例１の錯塩の赤外吸
収スペクトル図、第２図は実施例１のＴＧ、ＤＴＡの測
定結果を示す図、第３〜６図は実施例２および３の赤外
線吸収スペクトル図およびＴＧ、ＤＴＡの測定結果を示
す図、第７および８図は実施例４．５の赤外線吸収スペ
クトル図である。N-Ethyl-2,2°-dipyridylamine/TCNQ complex salt (CssHzaN 11) HCN Actual value (%l 3.87 71.64 25.
17 Calculated value (%l 3.44 71.04 2
5.32N-n-propyl-2,2°-dipyridylamine/TCNQ complex salt (C,tH14N11)HCN Actual value (%1 3.51 70.82 25.2
1 Calculated value (%) 3.89 71.37 24
．． 75N-butyl-2,2°-dipyridylamine・TC
NQ complex salt (C,.Ha-N++) HCN Actual value (%1 4.01 71.27 24.4
6 Calculated value (%+ 4.12 71.68 24
．． 2ON-benzyl-2,2°-dipyridylamine T
CNQ complex salt (C4, Ha, N,...) HCN Actual value (%1 3.91 ?3.37 23.
35 calculated value (% + 3.fil 73.42
22.98 [Application example] N-substitution -2,2°- of formula [1] obtained as above
Regarding the uses of dipyridylamine/TCNQCN, for example, TCNQCN can be used as a solid electrolyte in a solid electrolytic capacitor consisting of a capacitor element made of two aluminum foils wound together with a separator in between, or as a solid electrolyte in a solid electrolytic capacitor, or tantalum powder in Fig. 1 according to the present invention. FIG. 2 is a diagram showing the measurement results of TG and DTA of Example 1. FIGS. 3 to 6 are infrared absorption spectra and TG of Examples 2 and 3. Figures 7 and 8 showing the DTA measurement results are infrared absorption spectra of Example 4.5.
Claims (2)
−ジピリジルアミン・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＿１＿８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-2,2' represented by the following formula [1]
-Dipyridylamine/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_1_8 or a benzyl group. m means a positive number (0.5 to 1.5) corresponding to the number of moles of neutral 7,7,8,8-tetracyanoquinodimethane contained in 1 mole of complex salt.
−ジピリジルアミン・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−２，２’−ジピ
リジルアミン・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−２，２’−ジピリジル
アミン・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、ｘはハロゲンを示す。 式［１］中、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。 式［１］および式［２］中、ＲはＣ＿１〜Ｃ＿１＿８の
アルキル基またはべンジル基を示す。(2) N-substituted-2,2' represented by the following formula [2]
- Dipyridylamine quaternary ammonium salts are reacted with 7,7,8,8-tetracyanoquinodimethane represented by the following formula [3] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ [3] N-substituted-2,2'-dipyridylamine/7,7,8,8-tetracyanoquinodimethane complex salts represented by the following formula [1]▲ There are mathematical formulas, chemical formulas, tables, etc.▼ [1] A method for producing N-substituted-2,2'-dipyridylamine/7,7,8,8-tetracyanoquinodimethane complex salts. In formula [2], x represents halogen. In formula [1], m is neutral 7,7, contained in 1 mol of complex salt.
It means a positive number (0.5 to 1.5) corresponding to the number of moles of 8,8-tetracyanoquinodimethane. In formula [1] and formula [2], R represents an alkyl group of C_1 to C_1_8 or a benzyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16899490A JPH0459764A (en) | 1990-06-27 | 1990-06-27 | N-substituted-2,2'-dipyridylamine-7,7,8,8-tetracyanoquinodimethane complex salts and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16899490A JPH0459764A (en) | 1990-06-27 | 1990-06-27 | N-substituted-2,2'-dipyridylamine-7,7,8,8-tetracyanoquinodimethane complex salts and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0459764A true JPH0459764A (en) | 1992-02-26 |
Family
ID=15878383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16899490A Pending JPH0459764A (en) | 1990-06-27 | 1990-06-27 | N-substituted-2,2'-dipyridylamine-7,7,8,8-tetracyanoquinodimethane complex salts and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0459764A (en) |
-
1990
- 1990-06-27 JP JP16899490A patent/JPH0459764A/en active Pending
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