JP2522342B2 - Dibenzo-1,6,7,8,13-pentathia [5.5.5] quinalene derivative - Google Patents
Dibenzo-1,6,7,8,13-pentathia [5.5.5] quinalene derivativeInfo
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- JP2522342B2 JP2522342B2 JP63040310A JP4031088A JP2522342B2 JP 2522342 B2 JP2522342 B2 JP 2522342B2 JP 63040310 A JP63040310 A JP 63040310A JP 4031088 A JP4031088 A JP 4031088A JP 2522342 B2 JP2522342 B2 JP 2522342B2
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- complex
- quinalene
- pentathia
- dibenzo
- iodine
- Prior art date
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- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明はジベンゾ−1,6,7,8,13−ペンタチア［5.5.
5］キナレン誘導体（2,5−ビス（1,3−ペンゾジチオ−
２−イリデン）−2,5−ジヒドロチオフェン誘導体）に
関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to dibenzo-1,6,7,8,13-pentathia [5.5.
5] quinalene derivative (2,5-bis (1,3-benzodithio-
2-ylidene) -2,5-dihydrothiophene derivative).
〈従来の技術〉 最近、テトラチアフルバレン（TTF）やテトラメチル
テトラセレナフルバレン（TMTSF）、ジベンゾ−1,6,7,
8,13−ペンタチア［5.5.5］キナレン（特開昭60−25818
0号公報）などの電子供与性の有機低分子化合物とテト
ラシアノキノジメン（TCNQ）や過塩素酸イオンなどとの
電荷移動錯体が導電性あるいは超伝導を示すことが知ら
れ、電子供与性の有機化合物の研究が盛んである。高電
導性や超伝導の機構を解析する過程でこれら分子は結晶
中でスタックしたカラムを形成し、伝導はカラムを通し
て起こり、かつ、硫黄を始めとするカルコゲン原子を介
して分子間の相互作用が重要な役割を果していることが
明らかにされている。有機π分子で、かつカルコゲン原
子を多く含む化合物が電子供与性や分子間相互作用の観
点から望まれており、種々の分子設計上のアプローチが
なされてきた。<Prior art> Recently, tetrathiafulvalene (TTF), tetramethyltetraselenafulvalene (TMTSF), dibenzo-1,6,7,
8,13-Pentathia [5.5.5] quinalene (JP-A-60-25818)
It is known that a charge transfer complex of an electron-donating organic low-molecular compound (eg, No. 0) and tetracyanoquinodimene (TCNQ) or perchlorate ion shows conductivity or superconductivity. Research on organic compounds is active. In the process of analyzing the mechanism of high conductivity and superconductivity, these molecules form a column stacked in the crystal, conduction takes place through the column, and interactions between molecules occur through chalcogen atoms such as sulfur. It is revealed that it plays an important role. A compound which is an organic π molecule and contains many chalcogen atoms has been desired from the viewpoint of electron donating property and intermolecular interaction, and various molecular design approaches have been taken.
〈本発明が解決しようとする課題〉 しかしながら、合成された多くの電子供与性化合物、
例えばTTFなどは１分子中に硫黄原子を４個持っている
化合物であり、また本発明者等が特開昭60−258180号公
報で提案したジベンゾ−1,6,7,8,13−ペンタチア［5.5.
5］キナレンは硫黄原子を５個有するものであるが、電
子受容体との電荷移動錯体は電気伝導度において必ずし
も満足できるものではなかった。<Problems to be Solved by the Present Invention> However, many synthesized electron-donating compounds,
For example, TTF and the like are compounds having four sulfur atoms in one molecule, and the dibenzo-1,6,7,8,13-pentathiae proposed by the present inventors in JP-A-60-258180. [5.5.
5] Quinalene has five sulfur atoms, but the charge transfer complex with an electron acceptor was not always satisfactory in electric conductivity.
本発明者等は上記の事情に鑑み、種々検討の結果、ジ
ベンゾ−1,6,7,8,13−ペンタチア［5.5.5］キナレンの
ベンゼン環に置換基として１個以上のメチル基を有する
新規な化合物であるジベンゾ−1,6,7,8,13−ペンタチア
［5.5.5］キナレン（DBPTQ）誘導体の合成に成功し、さ
らにその化合物とヨウ素、2,3−ジクロル−5,6−ｐ−ベ
ンゾキノン（DDQ）等の電子受容体との電荷移動錯体が
優れた電気電導度を示すことを見出し本発明に到達し
た。As a result of various investigations in view of the above circumstances, the present inventors have one or more methyl groups as substituents on the benzene ring of dibenzo-1,6,7,8,13-pentathia [5.5.5] quinalene. We succeeded in synthesizing a new compound, dibenzo-1,6,7,8,13-pentathia [5.5.5] quinalene (DBPTQ) derivative, and the compound and iodine, 2,3-dichloro-5,6- The inventors have found that a charge transfer complex with an electron acceptor such as p-benzoquinone (DDQ) exhibits excellent electric conductivity, and thus arrived at the present invention.
〈課題を解決するための手段〉 すなわち、本発明は一般式 n:0〜４の整数 m:0〜４の整数 ただしｎ＋ｍは１以上 で示される新規なジベンゾ−1,6,7,8,13−ペンタチア
［5.5.5］キナレン誘導体を提供するものである。<Means for Solving the Problems> That is, the present invention has the general formula n is an integer of 0 to 4 m is an integer of 0 to 4, provided that n + m is 1 or more and a novel dibenzo-1,6,7,8,13-pentathia [5.5.5] quinalene derivative is provided. .
本発明の化合物の製造例は後述の実施例に記載した
が、ジオチールとして1,2,3,4−テトラメチルベンゼン
−5,6−ジチオール、1,2,3−トリメチルベンゼン−4,5
−ジチオール、1,3−ジメチルベンゼン−4,5−ジチオー
ル等を使用することにより、種々のメチル基置換化合物
の合成が可能である。The production examples of the compound of the present invention are described in the examples below, but 1,2,3,4-tetramethylbenzene-5,6-dithiol and 1,2,3-trimethylbenzene-4,5 as diotile.
By using -dithiol, 1,3-dimethylbenzene-4,5-dithiol and the like, various methyl group-substituted compounds can be synthesized.
本発明のジベンゾペンタチアキナレンのメチル基置換
誘導体はすぐれた電子供与体であり、ヨウ素や2,3−ジ
クロル−5,6−ジシアノ−ｐ−ベンゾキノン（DDQ）のよ
うな電子受容体と電子対を形成し、安定な錯体として存
在する。これらの錯体は常圧常温において無置換のDBPT
Qより高い誘導性を示す。これはメチル基など置換基の
立体障害で電導度は低下するとの予想に反するものであ
り、予想出来ない結果であった。また、ジメチルジベン
ゾペンタチアキナレンのメチル基置換誘導体はサイクリ
ックボルタムグラムにおいて一電子二段階酸化還元波を
与え、安定なカチオンラジカル種を生成することも見出
された。これらの結果からも、DBPTQのメチル基置換誘
導体は導電性材料として、また表示素子用の有機材料と
して有用である。The methyl-substituted derivatives of dibenzopentathiaquinalene of the present invention are excellent electron donors, and have electron pairs with electron acceptors such as iodine and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ). And exists as a stable complex. These complexes are non-substituted DBPTs at normal pressure and normal temperature.
It shows higher inducibility than Q. This was contrary to the expectation that the conductivity would decrease due to the steric hindrance of the substituent such as methyl group, and it was an unexpected result. It was also found that a methyl group-substituted derivative of dimethyldibenzopentathiaquinalene gives a one-electron two-step redox wave in cyclic voltamgram and forms a stable cation radical species. From these results also, the methyl group-substituted derivative of DBPTQ is useful as a conductive material and as an organic material for display devices.
〈発明の効果〉 以上説明したとおり、本発明の化合物は種々の電子受
容体と錯体を形成し、またその錯体は高い電気伝導度を
与えるので、導電性や電子放出あるいは電子捕獲による
エレクトロクロミズムを利用した電気、電子材料への種
々の応用が可能である。<Effects of the Invention> As described above, the compound of the present invention forms a complex with various electron acceptors, and since the complex provides high electric conductivity, electrochromism due to conductivity, electron emission, or electron trapping may occur. Various applications to the used electric and electronic materials are possible.
〈実施例〉 以下に本発明を実施例によってさらに具体的に説明す
るが本発明はこれら実施例によって何ら限定されるもの
ではない 実施例１ （3,10−ジメチルジベンゾ−1,6,7,8,13−ペンタチア
［5,5,5］キナレン（DMDBPTQ）の合成） 30mlの無水ベンゼン中でトルエン−3,4−ジチオール
1.23g（7.85mmol）と2,5−チオフェンカルボキサアルデ
ヒド0.55g（3.92mmol）を触媒量のｐ−トルエンスルホ
ン酸0.020gの存在下、１時間加熱還流し、反応させ、収
率74.9％で下式の化合物 1.45gを得た。次に、この化合物1.45g（3.47mmol）を塩
化メチレン25ml中に溶解させて得られる溶液中にトリフ
ェニルメチルボロンテトラフロライド1.15g（3.47mmo
l）を塩化メチレン20ml中に溶解させた溶液を滴下し、
室温で１時間撹拌し、反応させ、下式の構造のフッ化ホ
ウ素塩1.49g得た。<Examples> The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 (3,10-Dimethyldibenzo-1,6,7, Synthesis of 8,13-pentathia [5,5,5] quinalene (DMDBPTQ)) Toluene-3,4-dithiol in 30 ml of anhydrous benzene
1.23 g (7.85 mmol) and 2,5-thiophene carboxaldehyde 0.55 g (3.92 mmol) were heated and refluxed for 1 hour in the presence of a catalytic amount of p-toluenesulfonic acid 0.020 g to react with a yield of 74.9%. Compound of formula 1.45g was obtained. Next, 1.45 g (3.47 mmol) of this compound was dissolved in 25 ml of methylene chloride to obtain a solution of triphenylmethylboron tetrafluoride (1.15 g, 3.47 mmo).
l) was added dropwise to a solution of methylene chloride in 20 ml,
The mixture was stirred at room temperature for 1 hour and reacted to obtain 1.49 g of a boron fluoride salt having the structure shown below.
収率は85.2％であった。このフッ化ホウ素塩0.90g（1.7
9mmol）を160mlの塩化メチレンに溶解させて得られる溶
液をトリエチルアミン0.543g（5.37mmol）を6.0mlの塩
化メチレン中に溶解させた溶液中に撹拌しながら室温で
2.5時間かけてゆっくり滴下し、滴下後、さらに、1.5時
間撹拌し、反応させ、生成物を濾過し、0.657gの橙色針
状晶を得た。収率は89％であった。この結晶をキシレン
より再結晶し精製した。 The yield was 85.2%. This boron fluoride salt 0.90 g (1.7
9 mmol) in 160 ml of methylene chloride and the resulting solution in 0.543 g (5.37 mmol) of triethylamine in 6.0 ml of methylene chloride at room temperature with stirring.
The mixture was slowly added dropwise over 2.5 hours, and after the addition, the mixture was stirred for 1.5 hours to cause a reaction, and the product was filtered to obtain 0.657 g of orange needle crystals. The yield was 89%. The crystals were recrystallized from xylene and purified.
この化合物の構造を解析するために、赤外スペクト
ル、マススペクトル、元素分析、プロトンNMRの測定を
行なった。In order to analyze the structure of this compound, infrared spectrum, mass spectrum, elemental analysis and proton NMR were measured.
高分解能マススペクトルからこの化合物の分子量は41
3.9739であることがわかり、この値は理論値413.9699と
良い一致を示した。From the high-resolution mass spectrum, the molecular weight of this compound is 41.
It was found to be 3.9739, which was in good agreement with the theoretical value of 413.9699.
元素分析値は炭素が58.20％、水素が3.40％、硫黄が3
9.04％であり、下記の構造として計算した理論値である
炭素57.93％、水素3.40％、硫黄39.67％と良い一致を示
した。Elemental analysis values are 58.20% for carbon, 3.40% for hydrogen, and 3 for sulfur.
It was 9.04%, which was in good agreement with the theoretical values calculated as the following structure: carbon 57.93%, hydrogen 3.40%, and sulfur 39.67%.
赤外吸収スペクトルでは3030と2900cm-1にそれぞれ芳
香族水素とメチル基の伸縮振動による吸収がみられ、15
34、1455cm-1に共役二重結合の伸縮振動による吸収がみ
られ、840、805、752cm--1に芳香族水素の面外変角振動
による吸収が認められた。また、Ｈ−NMR測定で2.35お
よび2.42ppmにメチル基のプロトンに基づくシグナルが
観測された。In the infrared absorption spectrum, absorption due to stretching vibration of aromatic hydrogen and methyl group was observed at 3030 and 2900 cm -1 , respectively.
Absorption by the stretching vibration of the conjugated double bond was observed at 34,1455cm -1, absorption by out-of-plane deformation vibration of aromatic hydrogens was observed 840,805,752cm- -1. In addition, a signal based on the proton of the methyl group was observed at 2.35 and 2.42 ppm by H-NMR measurement.
これらの実験事実からこの結晶の構造は以下の如くであ
ると断定した。From these experimental facts, it was concluded that the structure of this crystal was as follows.
実施例２ （3,4,10,11−テトラメチルジベンゾ−1,6,7,8,13−
ペンタチア［5.5.5］キナレン（TMDBPTQ）の合成） 40mlの無水ベンゼン中でオルソキシレン−4,5−ジチ
オール1.385g（8.13mmol）と2,5−チオフェンカルボキ
サアルデヒド0.60g（4.28mmol）触媒量のｐ−トルエン
スルホン酸0.020gの存在下１時間加熱還流し、反応さ
せ、収率84％で下式の構造の化合物を1.61g得た。 Example 2 (3,4,10,11-tetramethyldibenzo-1,6,7,8,13-
Synthesis of pentathia [5.5.5] quinalene (TMDBPTQ)) Ortho-xylene-4,5-dithiol 1.385 g (8.13 mmol) and 2,5-thiophene carboxaldehyde 0.60 g (4.28 mmol) catalytic amount in 40 ml of anhydrous benzene. Was heated to reflux for 1 hour in the presence of 0.020 g of p-toluenesulfonic acid and reacted to obtain 1.61 g of a compound having the following structure in a yield of 84%.
次に、この化合物0.5g（1.124mmol）を塩化メチレン70m
l中に溶解させて得られる溶液中にトリフェニルメチル
ボロンテトラフロライド0.371g（1.124mmol）を塩化メ
チレン10ml中に溶解させた溶液を加熱還流下に30分間要
して滴下し、さらに１時間還流し、反応させ、次のよう
な構造のフッ化ホウ素塩を0.573g得た。 Next, 0.5 g (1.124 mmol) of this compound was added to 70 m of methylene chloride.
A solution prepared by dissolving 0.371 g (1.124 mmol) of triphenylmethylboron tetrafluoride in 10 ml of methylene chloride was added dropwise to the resulting solution by heating under reflux for 30 minutes, and further for 1 hour. The mixture was refluxed and reacted to obtain 0.573 g of boron fluoride salt having the following structure.
収率は96％であった。このフッ化ホウ素塩0.3g（0.566m
mol）を50mlの塩化メチレンに溶解させて得られる溶液
をトリエチルアミン0.286g（2.83mmol）を3mlの塩化メ
チレンに溶解させた溶液中に激しく撹拌しながら、室温
で1.5時間を要してゆっくり滴下し、滴下終了後、さら
に室温で１時間反応させ、生成物を濾過し、0.211gの淡
橙色針状晶を得た。収率は85％であった。この結晶をキ
シレンより再結晶し、精製した。 The yield was 96%. 0.3g of this boron fluoride salt (0.566m
mol) in 50 ml of methylene chloride and slowly added dropwise to the solution of 0.286 g (2.83 mmol) of triethylamine in 3 ml of methylene chloride at room temperature over 1.5 hours with vigorous stirring. After the dropwise addition, the reaction was further continued at room temperature for 1 hour, and the product was filtered to obtain 0.211 g of pale orange needle crystals. The yield was 85%. This crystal was recrystallized from xylene and purified.
この化合物の構造を解析するために、マススペクト
ル、元素分析、赤外吸収スペクトル、プロトンNMRスペ
クトルを測定した。In order to analyze the structure of this compound, mass spectrum, elemental analysis, infrared absorption spectrum, and proton NMR spectrum were measured.
マススペクトルでは、m/e442に本発明のTMDBPTQがイ
オン化した分子イオンピーク（m/e422）に相当するシグ
ナルが認められた。In the mass spectrum, a signal corresponding to the molecular ion peak (m / e422) in which TMDBPTQ of the present invention was ionized was observed at m / e442.
元素分析値は、炭素が59.43％、水素が4.08％、硫黄
が30.98％を示し、理論値である炭素59.69％、水素4.10
％、硫黄31.21％とよい一致を示した。Elemental analysis shows that carbon is 59.43%, hydrogen is 4.08%, sulfur is 30.98%, and the theoretical values are carbon 59.69% and hydrogen 4.10.
%, Sulfur 31.21%, showing good agreement.
赤外吸収スペクトルでは3030、2970および2900cm-1に
それぞれ芳香族水素およびメチル基の伸縮振動による吸
収がみられ、また1533と1400cm−１に共役二重結合の伸
縮振動に基づく吸収がみられ、860、840および750cm-1
に芳香族水素の面外変角振動による吸収が認められた。
また、Ｈ−NMR測定で2.28および2.30ppmにメチル基のプ
ロトンに基づくシグナルが観測された。In the infrared absorption spectrum, absorptions due to stretching vibrations of aromatic hydrogen and a methyl group were observed at 3030, 2970, and 2900cm -1 , respectively, and absorptions due to stretching vibrations of the conjugated double bond were observed at 1533 and 1400cm -1 , respectively. 860, 840 and 750 cm -1
The absorption of aromatic hydrogen by out-of-plane bending vibration was observed.
In addition, a signal based on the proton of the methyl group was observed at 2.28 and 2.30 ppm by H-NMR measurement.
これらの実験事実から、以下の構造であると断定し
た。From these experimental facts, it was concluded that the structure is as follows.
参考例１ （ヨウ素との錯体とその導電性） 実施例１で得た0.04gのDMDBPTQを60mlのキシレンに溶解
した溶液と0.122gのヨウ素を50mlのキシレンに溶解した
溶液を混合するとDMDBPTQのヨウ素錯体が黒褐色結晶
（分解点267〜268℃）として得られた。元素分析よりDM
DBPTQとヨウ素の組成比は1:3.5であった。 Reference Example 1 (Complex with iodine and its conductivity) When the solution obtained by dissolving 0.04 g of DMDBPTQ obtained in Example 1 in 60 ml of xylene and the solution obtained by dissolving 0.122 g of iodine in 50 ml of xylene are mixed, iodine of DMDBPTQ is mixed. The complex was obtained as dark brown crystals (decomposition point 267-268 ° C). DM from elemental analysis
The composition ratio of DBPTQ and iodine was 1: 3.5.
実施例２で得た0.025gのTMDBPTQを200mlのキシレンに溶
解した溶液と0.071gのヨウ素を30mlのキシレンに溶解し
た溶液を混合するとTMDBPTQのヨウ素錯体が黒褐色結晶
（分解点300℃以上）として得られた。この錯体の元素
分析値よりTMDBPTQとヨウ素の組成比は1:4.5であった。
このようにして得た結晶粒をまとめてとりだし、乾燥
し、加圧可能な電導度測定装置に入れて、圧力を20kg/c
m2かけて電導度を測定した。A solution of 0.025 g of TMDBPTQ obtained in Example 2 in 200 ml of xylene and a solution of 0.071 g of iodine in 30 ml of xylene were mixed to obtain an iodine complex of TMDBPTQ as dark brown crystals (decomposition point: 300 ° C. or higher). Was given. From the elemental analysis value of this complex, the composition ratio of TMDBPTQ and iodine was 1: 4.5.
The crystal grains thus obtained are collectively taken out, dried, put in a pressurizable conductivity measuring device, and the pressure is 20 kg / c.
The electrical conductivity was measured by applying m 2 .
測定結果を第１表に示す。The measurement results are shown in Table 1.
参考例２ （DDQとの電荷移動錯体の生成とその導電性） 実施例１で得たDMDBPTQおよび実施例２で得たTMDBPTQ
を熱キシレン中でDDQと接触させると直ちにそれぞれ安
定なCT錯体を生成した。DMDBPTQとDDQとの電荷移動CT錯
体は黒紫色結晶で、分解点205〜209℃であった。TMDBPT
QとDDQとの電荷移動錯体は黒紫色結晶で分解点220〜225
℃であった。これらの錯体は参考例１と同様に電導度を
測定した。Reference Example 2 (Formation of charge transfer complex with DDQ and its conductivity) DMDBPTQ obtained in Example 1 and TMDBPTQ obtained in Example 2
When each of them was contacted with DDQ in hot xylene, a stable CT complex was formed immediately. The charge transfer CT complex of DMDBPTQ and DDQ was a black-purple crystal with a decomposition point of 205-209 ℃. TMDBPT
The charge transfer complex of Q and DDQ is a black-purple crystal and the decomposition point is 220-225.
° C. The electric conductivity of these complexes was measured in the same manner as in Reference Example 1.
測定結果を第１表に示す。The measurement results are shown in Table 1.
比較例１ 下式の構造のジベンゾ−1,6,7,8,13−ペンタチア［5.
5.5］キナレン（DBPTQ） のキシレン溶液とヨウ素のキシレン溶液を混合するとBT
TFのヨウ素錯体が黒褐色結晶として得られた。また、DB
PTQとDDQを熱キシレン中で接触させるとDBPTQのDDQ錯体
が黒褐色結晶として得られた。錯体は参考例１と同様に
電導度を測定した。測定結果を第１表に示す。Comparative Example 1 Dibenzo-1,6,7,8,13-pentathia [5.
5.5] Quinarene (DBPTQ) When a xylene solution of iodine and a xylene solution of iodine are mixed, BT
The iodine complex of TF was obtained as dark brown crystals. Also, DB
When PTQ and DDQ were contacted in hot xylene, DDPT complex of DBPTQ was obtained as blackish brown crystals. The conductivity of the complex was measured as in Reference Example 1. The measurement results are shown in Table 1.
比較例２ 下式の構造のベンゾテトラチアフルバレン（DBTTF） のキシレン溶液とヨウ素のキシレン溶液を混合するとDB
TTFのヨウ素錯体が黒褐色結晶として得られた。錯体は
参考例１と同様に電導度を測定した。測定結果を第１表
に示す。Comparative Example 2 Benzotetrathiafulvalene (DBTTF) having the following structure When xylene solution of iodine and xylene solution of iodine are mixed, DB
The iodine complex of TTF was obtained as dark brown crystals. The conductivity of the complex was measured as in Reference Example 1. The measurement results are shown in Table 1.
参考例３ （DMDBPTQのサイクリックボルタモグラムの測定） 実施例１で得たDMDBPTQをテトラエチルアンモニウム
パークロレートの0.1Mプロピオニトリル溶液に溶解させ
た。白金電極を作用極と対極に、また参照極に飽和カロ
メル電極を使用してサイクリックボルタモグラムを測定
したところ、0.3V（vs.SEC）と0.54V（vs.SEC）に２つ
の酸化波が観測された。 Reference Example 3 (Measurement of cyclic voltammogram of DMDBPTQ) The DMDBPTQ obtained in Example 1 was dissolved in a 0.1M propionitrile solution of tetraethylammonium perchlorate. Cyclic voltammograms were measured using a platinum electrode as the working electrode and the counter electrode, and a saturated calomel electrode as the reference electrode, and two oxidation waves were observed at 0.3V (vs.SEC) and 0.54V (vs.SEC). Was done.
参考例４ （TMDBPTQのサイクリックボルタモグラムの測定） 実施例２で得たTMDBPTQをテトラエチルアンモニウム
パークロレートの0.1Mプロピオニトリル溶液に溶解させ
た。参考例３と同様にサイクリックボルタモグラムを測
定したところ0.28V（vs.SEC）と0.52V（vs.SEC）に２つ
の酸化波が観測された。Reference Example 4 (Measurement of cyclic voltammogram of TMDBPTQ) TMDBPTQ obtained in Example 2 was dissolved in a 0.1 M propionitrile solution of tetraethylammonium perchlorate. When the cyclic voltammogram was measured in the same manner as in Reference Example 3, two oxidation waves were observed at 0.28 V (vs.SEC) and 0.52 V (vs.SEC).
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63040310A JP2522342B2 (en) | 1988-02-22 | 1988-02-22 | Dibenzo-1,6,7,8,13-pentathia [5.5.5] quinalene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63040310A JP2522342B2 (en) | 1988-02-22 | 1988-02-22 | Dibenzo-1,6,7,8,13-pentathia [5.5.5] quinalene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01213281A JPH01213281A (en) | 1989-08-28 |
| JP2522342B2 true JP2522342B2 (en) | 1996-08-07 |
Family
ID=12577044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63040310A Expired - Fee Related JP2522342B2 (en) | 1988-02-22 | 1988-02-22 | Dibenzo-1,6,7,8,13-pentathia [5.5.5] quinalene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2522342B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2722625B2 (en) | 1989-03-13 | 1998-03-04 | 住友化学工業株式会社 | 2,2 '-(2,5-dihydrothiophene-2,5-diylidene) bis (1,3-dithiol) derivative |
| US6682243B2 (en) | 2000-06-22 | 2004-01-27 | Kanebo, Ltd. | Bar-like paint delivering container |
-
1988
- 1988-02-22 JP JP63040310A patent/JP2522342B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2722625B2 (en) | 1989-03-13 | 1998-03-04 | 住友化学工業株式会社 | 2,2 '-(2,5-dihydrothiophene-2,5-diylidene) bis (1,3-dithiol) derivative |
| US6682243B2 (en) | 2000-06-22 | 2004-01-27 | Kanebo, Ltd. | Bar-like paint delivering container |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01213281A (en) | 1989-08-28 |
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