JPH0459767A - N-substituted-nitron-7,7,8,8-tetracyanoquinodimethane complex salts and production thereof - Google Patents
N-substituted-nitron-7,7,8,8-tetracyanoquinodimethane complex salts and production thereofInfo
- Publication number
- JPH0459767A JPH0459767A JP16899690A JP16899690A JPH0459767A JP H0459767 A JPH0459767 A JP H0459767A JP 16899690 A JP16899690 A JP 16899690A JP 16899690 A JP16899690 A JP 16899690A JP H0459767 A JPH0459767 A JP H0459767A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- tetracyanoquinodimethane
- substituted
- nitrone
- nitron
- 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 32
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 125000000217 alkyl group Chemical group 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
- 125000005843 halogen group Chemical group 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 6
- -1 N-substituted nitrone Chemical class 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 30
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 238000009835 boiling Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000012776 electronic material Substances 0.000 abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 238000002360 preparation method Methods 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 23
- 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- ADCROEZEFWMOOY-UHFFFAOYSA-N n-methylmethanimine oxide Chemical compound C[N+]([O-])=C ADCROEZEFWMOOY-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000000203 mixture Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- CWGBFIRHYJNILV-UHFFFAOYSA-N (1,4-diphenyl-1,2,4-triazol-4-ium-3-yl)-phenylazanide Chemical compound C=1C=CC=CC=1[N-]C1=NN(C=2C=CC=CC=2)C=[N+]1C1=CC=CC=C1 CWGBFIRHYJNILV-UHFFFAOYSA-N 0.000 description 2
- 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
- 241000679125 Thoron Species 0.000 description 2
- 238000000862 absorption spectrum Methods 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
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- DKJBIKWXVUAJDU-UHFFFAOYSA-N n-butylmethanimine oxide Chemical compound CCCC[N+]([O-])=C DKJBIKWXVUAJDU-UHFFFAOYSA-N 0.000 description 2
- HDTLUHLZJMWTTI-UHFFFAOYSA-N n-ethylmethanimine oxide Chemical compound CC[N+]([O-])=C HDTLUHLZJMWTTI-UHFFFAOYSA-N 0.000 description 2
- YEBMGLVAYKCPBH-UHFFFAOYSA-N n-propylmethanimine oxide Chemical compound CCC[N+]([O-])=C YEBMGLVAYKCPBH-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent 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
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- DCSRPHQBFSYJNN-UHFFFAOYSA-L disodium 4-[(2-arsonophenyl)diazenyl]-3-hydroxynaphthalene-2,7-disulfonate Chemical group [Na+].[Na+].Oc1c(N=Nc2ccccc2[As](O)(O)=O)c2ccc(cc2cc1S([O-])(=O)=O)S([O-])(=O)=O DCSRPHQBFSYJNN-UHFFFAOYSA-L 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
- 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
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- 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
- 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−ニトロン・
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. Nitron・
The present invention relates to 7,7,8.8-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−ニトロン・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-nitrone 7, as a novel organic semiconductor (new compound) represented by the following formula [1]
7,8.8-tetracyanoquinodimethane 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Ｃ，−Ｃ，ａのアルキル基を示す０ｍ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 an alkyl group of C, -C, a; 0m is a positive number corresponding to the number of moles of neutral 7.7,8.8-tetracyanoquinodimethane contained in 1 mole of the complex salt ( 0.5~1.
5) means.
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−ニトロン・第四アンモニウム
塩類を
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 shown by the above formula [1] can be converted to the compound shown by the following formula [2].
] It can be produced by reacting N-substituted-nitrone/quaternary ammonium salts represented by the following.
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Ｃ３〜Ｃ１，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 a carbon number of C3 to C1, such as pentyl and hexyl (including all isomers such as n- and 1so-).
）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Ｃ＋ ’＝ Ｃ＋
ａのアルキル基であり、Ｘはハロゲンである。) can be exemplified. m in formula [1] is 0.5~
1.5 is preferred, more preferably about 1. Furthermore, R in formula [2] is C+ '= C+ as in formula [1]
a is an alkyl group, and X is a halogen.
〔合成方法］
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ｍ＝トロン・ＴＣＮＱＣＮ類は、式［２］
のＮ−置換ｍ＝トロン・第四アンモニウム塩類を式［３
コの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] As described above, the N-substituted m=throne/TCNQCN, which is a novel compound of formula [1] according to the present invention, has the formula [2]
N-substituted m = thoron quaternary ammonium salts of formula [3
It can be easily produced in a desirable yield by reacting with TCNQ.
式［２］のＮ−置換ｍ＝トロン・第四アンモニウム塩類
は既に公知の化合物であって、ニトロンからそれ自体公
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 m=throne quaternary ammonium salt of formula [2] is a known compound and can be easily synthesized from a nitrone 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１式［２コの化合物と式［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−ニトロン
ヨーダイトの熱アセトニトリル溶液と式［３］のＴＣＮ
Ｑ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。Next, one embodiment of producing the compound of formula [1] from the compound of formula [2] and TCNQ of formula [3] will be described in detail,
For example, a hot acetonitrile solution of N-methyl-nitron iodite as an example in formula [2] and TCN of formula [3]
After hot mixing the hot acetonitrile solution of Q, let it cool,
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.
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−メチル一二トロン
・ＴＣＮＱ錯塩を高収率で得ることができる。When the reaction product is washed with acetonitrile, methanol, and ether and recrystallized with acetonitrile, an N-methyl-dithrone/TCNQ complex salt as an example of formula [1] containing no inorganic salts 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、ジメチルボルムアミド、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コの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、不活性有機溶媒の使
用量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ＴＣＮＱに対して約５
０〜１２０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, dimethylbormamide, This is preferably carried out at the boiling point of an inert organic solvent such as tetrahydrofuran, 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]. Further, the amount of the inert organic solvent to be used can be appropriately selected, and is about 10 to 20 times the amount of the compound of formula [2], and about 5 times the amount of TCNQ of the formula [3].
An example of the usage amount is 0 to 120 times.
［実施例］
更に、本発明に係る式［１］のＮ−置換−ニトロン・Ｔ
ＣＮＱＣＮ類の具体的な合成方法の実施例について述べ
る。[Example] Furthermore, N-substituted-nitrone T of formula [1] according to the present invention
An example of a specific method for synthesizing CNQCNs will be described.
〈実施例１〉
Ｎ−メチル−ニトロン・ＴＣＮＱ錯塩の合成について述
べる。<Example 1> Synthesis of N-methyl-nitrone/TCNQ complex salt will be described.
ニトロン１ 、５６ ｇ （５、０ｍ ｍ ｏ １ ）
と、溶媒としてエチレングリコールジメチルエーテル４
５ｍ１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−ニトロンヨーダイト（融
点１８５〜１８７℃）を６９％の収率で得た。Nitron 1,56 g (5,0 m m o 1)
and ethylene glycol dimethyl ether 4 as a solvent.
After stirring and dissolving 5 ml of methyl iodide (15 mmol,
Add 3 eq) and react at room temperature for 24 hours with stirring,
The reaction product was filtered under suction and washed with ethylene glycol dimethyl ether to obtain N-methyl-nitron iodite (melting point 185-187°C) in a yield of 69%.
こうして得たＮ−メチル−ニトロンヨーダイト２．５ｍ
ｍｏｌをアセトニトリル４０ｍ１に沸騰状態で溶解し、
別に用意したアセトニトリル４１ｍ１にＴＣＮＱｏ、６
１ｇ （３，０ｍｍｏｌ、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−ニトロン・ＴＣＮＱ錯塩、融点２００
〜２３５℃の黒緑色結晶を収率４６％で得ることができ
た。2.5 m of N-methyl-nitrone iodite thus obtained
Dissolve mol in 40 ml of acetonitrile in boiling state,
Add 6 TCNQo to 41ml of acetonitrile prepared separately.
1 g (3.0 mmol, 1.2 eq) was dissolved in a boiling state and mixed hot with a solution that was refluxed for 1 hour. After refluxing for an additional 30 minutes, the mixture was left at 5° C. for 24 hours. 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-nitrone/TCNQ complex salt, melting point 200.
Black-green crystals of ~235°C could be obtained in a yield of 46%.
得られたＮ−メチル−ニトロン・ＴＣＮＱ錯塩（Ｃ４ｓ
Ｈ＊ｔＮ ｒ□）の元素分析の結果は次の通りである。The obtained N-methyl-nitrone/TCNQ complex salt (C4s
The results of elemental analysis of H*tN r□) are as follows.
ＨＣＮ
実測値（％ｌ ３．２０ ７３．４２ ２３．
１８計算値（％ｌ ３．７０ ７３．４６ ２
３．１８赤外吸収スペクトルを第１図に示す。また示差
熱分析の結果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のペレットを作り、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４０μＡ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 (%l 3.20 73.42 23.
18 Calculated value (%l 3.70 73.46 2
The 3.18 infrared absorption spectrum is shown in Figure 1. Further, Table 2 shows the results of differential thermal analysis and the measurement results of specific resistance before and after melting using the four-terminal method. For the four-terminal method, approximately 0.1 g of TCNQ salt is placed in a tablet molding machine and 300 kg is used.
Pellets with a diameter of 10 mm were made under a pressure of 1/m'', and the lead wires A%B, C, and D were attached to the pellets in order around the pellets, and a direct current of 40 μA was passed between AB using a constant current generator. In this method, the potential difference between CD at that time is measured with a voltmeter, and then a current is similarly passed between BC and the potential difference between DA is measured.
〈実施例２〜４〉
上記実施例１ではＮ−メチル−ニトロン・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、ブチルにそれぞれ置換されたＮ
−置換ｍ：トロンヨーダイトを得、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−ニトロン・ＴＣＮＱ錯塩（実施例２）、Ｎ−ｎ−プ
ロピル−ニトロン・ＴＣＮＱ錯塩（実施例３）、Ｎ−ブ
チル−ニトロン・ＴＣＮＱ錯塩（実施例４）を得た。こ
れらの示差熱分析結果ならびに比抵抗値を表２に示す。<Examples 2 to 4> In Example 1 above, N-methyl-nitrone/TCNQ complex salt was described, but as a result of synthesis under the conditions shown in Table 1 according to the same method and procedure as in Example 1, the formula [ 2] in which R is substituted with ethyl, n-propyl, or butyl, respectively
-Substitution m: Toroniodite was obtained, and according to the same method and procedure as in Example 1, as shown in Table 2, N-ethyl-nitrone/TCNQ complex salt (Example 2), N-n-propyl -Nitrone/TCNQ complex salt (Example 3) and N-butyl-nitrone/TCNQ complex salt (Example 4) were obtained. These differential thermal analysis results and specific resistance values are shown in Table 2.
なおＮ−エチル−ニトロン−ＴＣＮＱ錯塩（実施例２）
、Ｎ−ｎ−プロピル−ニトロン・ＴＣＮＱ錯塩（実施例
３）、Ｎ−ブチル−ニトロン・ＴＣＮＱ錯塩（実施例４
）のそれぞれの赤外吸収スペクトルを第２〜４図に示す
。Note that N-ethyl-nitrone-TCNQ complex salt (Example 2)
, N-propyl-nitrone/TCNQ complex salt (Example 3), N-butyl-nitrone/TCNQ complex salt (Example 4)
) are shown in Figs. 2 to 4.
実施例２および４のＴＣ，ＮＱ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 TC, NQ complex salts of Examples 2 and 4 are as follows.
Ｎ−エチル−ニトロン・ＴＣＮＱ錯塩（ｃ４６Ｈ□Ｎ１
．）
ＨＣＮ
実測値（％ｌ ３．４３ ７３．４９ ２２．
９８計算値（％） ３．９０ ７３．６９ ２
３．４２Ｎ −ｎ−プロピル−ニトロン・ＴＣＮＱ錯塩
（Ｃ４アＨ□Ｎ１□）
ＨＣＮ
実測値（％） ３．８４ ７４．１８ ２２．
２３計算値（％） ４．０９ ７３．９０ ２
２．０ＯＮ−ブチル−ニトロン・ＴＣＮＱ錯塩（Ｃ４゜
Ｈ−−Ｎ、＊）
実測値（％ｌ ３．７６
７３．９４
２１．７６
計算値ｃ％１ ４．２８
７４．１１
２１．６１
第１
ヌ収（ｃｍ−’）
第２
スｖ１（ｃｍ−１）
［応用例〕
上述のようにして得た式［１］のＮ−置換ｍ＝トロン・
ＴＣＮＱＣＮ類の用途について述べると、このＴＣＮＱ
ＣＮ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ものである。N-ethyl-nitrone/TCNQ complex salt (c46H□N1
．． ) HCN Actual value (%l 3.43 73.49 22.
98 calculated value (%) 3.90 73.69 2
3.42N -n-propyl-nitrone/TCNQ complex salt (C4AH□N1□) HCN Actual value (%) 3.84 74.18 22.
23 Calculated value (%) 4.09 73.90 2
2.0ON-Butyl-nitrone/TCNQ complex salt (C4°H--N, *) Actual value (%l 3.76 73.94 21.76 Calculated value c%1 4.28 74.11 21.61 1st Nu yield (cm-') 2nd su v1 (cm-1) [Application example] N-substitution m = thoron in formula [1] obtained as above
Regarding the uses of TCNQCN, this TCNQ
CNs 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 is something.
第１〜４図はこの発明の実施例１〜４の錯塩の赤外吸収
スペクトルである。1 to 4 are infrared absorption spectra of the complex salts of Examples 1 to 4 of the present invention.
Claims (2)
・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 nitrone/7,7,8,8-tetracyanoquinodimethane complex salts represented by the following formula [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] In formula [1], R represents an alkyl group of C_1 to C_1_8. m is the neutral 7,7,8,8- contained in 1 mol of complex salt
A positive number corresponding to the number of moles of tetracyanoquinodimethane (
0.5 to 1.5).
・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−ニトロン・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−ニトロン・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
アルキル基を示す。(2) N-substituted-nitrone quaternary ammonium salts represented by the following formula [2] ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [2] 7, 7, expressed by the following formula [3] By reacting with 8,8-tetracyanoquinodimethane, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [3] N-substituted-nitrone 7, represented by the following formula [1]
7,8,8-tetracyanoquinodimethane complex salts ▲Mathematical formulas, chemical formulas, tables, etc.▼ [1] N-substituted-nitrone 7,7,8 characterized by obtaining
, 8-tetracyanoquinodimethane complex salts manufacturing method. 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16899690A JPH0459767A (en) | 1990-06-27 | 1990-06-27 | N-substituted-nitron-7,7,8,8-tetracyanoquinodimethane complex salts and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16899690A JPH0459767A (en) | 1990-06-27 | 1990-06-27 | N-substituted-nitron-7,7,8,8-tetracyanoquinodimethane complex salts and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0459767A true JPH0459767A (en) | 1992-02-26 |
Family
ID=15878421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16899690A Pending JPH0459767A (en) | 1990-06-27 | 1990-06-27 | N-substituted-nitron-7,7,8,8-tetracyanoquinodimethane complex salts and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0459767A (en) |
-
1990
- 1990-06-27 JP JP16899690A patent/JPH0459767A/en active Pending
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