JPS5862171A - Bis(1,3-dithiols) - Google Patents
Bis(1,3-dithiols)Info
- Publication number
- JPS5862171A JPS5862171A JP16168181A JP16168181A JPS5862171A JP S5862171 A JPS5862171 A JP S5862171A JP 16168181 A JP16168181 A JP 16168181A JP 16168181 A JP16168181 A JP 16168181A JP S5862171 A JPS5862171 A JP S5862171A
- Authority
- JP
- Japan
- Prior art keywords
- bis
- dithiol
- formula
- ethanediylidene
- formulai
- 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.)
- Granted
Links
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Abstract
Description
【発明の詳細な説明】 本発明は％／、Ｊ−ジチオー身―に−する。[Detailed description of the invention] The present invention is based on %/J-dithiol.
’Ｉ’ＴＩＦ（テトラチアツルバレン）−丁０ＭＣ４（
テトフシアノキノジメタン）一体が異常に大１１％Ａ電
気伝尋性を示すことが見めされて以来。'I'TIF (tetrathia tourvalen) - D0MC4 (
Tetofcyanoquinodimethane) was found to exhibit an abnormally high 11% A electroconductivity.
！テア１ＩＩＩ縁体に−する検討が活発に行なわｈてい
る。・
本発明者Ｏは、ＴＴＩＮＣ代わる新しいドナー化合物の
検討を種々性ない１本発明に到達１．た。! Studies on the Thea IIII derivative are being actively conducted. - The inventor O arrived at the present invention after various studies on new donor compounds to replace TTINC.1. Ta.
すなわち、本発明は、一般式（Ｉ）
（式中、Ｒ’＃Ｒ”ＪＲ”ＩＩｔびＲ４＃ｉ低級アルキ
ル基を表わすか、又は、Ｒ１とＶ、も歌〈はＲ３とＲ′
が結合して、ｔ＊されていてもよいベンゼン環を千り七
り形成して４よい）
で示されるエタンシイリゾシーλ、コｌ−ビス（／。That is, the present invention relates to the general formula (I) (where R'#R"JR"IIt and R4#i represent a lower alkyl group, or R1 and V, or
may be combined to form 1,700 benzene rings which may be t*).
３−ジチオール）ｌｉＫある。3-dithiol)liK.
以下、本発明を詳１１１１Ｋ説明する。The present invention will be explained in detail below.
ビル、 ｔｅｒｔ−ブチル勢の縦嵩数７＃４のアルキ
ル基でメヤ、互いに同一であって本よい−また。 Ｒ１
とＲ８、もしく ｔｉ Ｒ’とＲ４１ｊ、結合してそね
ぞわベンゼン環を形成して４よい。その場合において、
ベンゼン環は、側鎖が一換されてｔｓｊｔ、ては、例え
ば
等ｉ１１挙げられる。Bill and tert-butyl groups are alkyl groups with a vertical bulk number of 7 and #4, and may be the same as each other. R1
and R8, or ti R' and R41j may be combined to form a benzene ring. In that case,
The benzene ring has one side chain replaced, such as tsjt, and, for example, i11.
これらのビス（／、Ｊ−ジチオール）ｆｉｉｌ＃ｉ、例
えば次のような方法によって製造することができる。These bis(/, J-dithiol) fiil #i can be produced, for example, by the following method.
すなわち、トリエチルアミンあゐいはブチルリチウムの
塩基存在下、ホスホニウム塩１とアルデヒド２とのグイ
テイヒ（Ｗｉｔｔｉｇ ）反応な用いて製造することが
できる。That is, it can be produced using a Wittig reaction between phosphonium salt 1 and aldehyde 2 in the presence of a base such as triethylamine or butyllithium.
きるＯ
本発明で得られるビス（／、３−ジチオール）類は１強
い電子供与性を鳴するので、有−導電材料としての用途
が期待される。Since the bis(/,3-dithiol) obtained in the present invention exhibits strong electron-donating properties, it is expected to be used as a conductive material.
以下、実ｂ ｅｌｌ Ｋより本発明をさらに詳細に＠！
明するが、本発明はその資旨を超えないかぎり、これら
の実施例ＫＶ＆定されるものではない。Below, the present invention will be explained in more detail by Mr. Bell K!
It is to be understood that the present invention is not limited to these embodiments unless they depart from the spirit thereof.
実施例／
ａ
ホスホニウム塩３ （２，４０１，４ｍｍｏｌ ）
とグリオキサール（４’ＯＸ＊浴濠、／、２ダｇ、ｉａ
ｍｍｏｌ ） のＴＩ（ｙ（ｔｏｏｖｓｔ）溶液にト
リエチルアきン（７７ｍ）を加え、室温で一夜攪拌する
。ＴＨＦｆ留去１．た後、塩化メチレン抽出をＬ２、Ｍ
ａｍ ８０４で乾燥、ａｍこねをカラム（シリカゲル
ｓ ”ｍＣｔｘ＠出）処理するとアルテヒド九がｏ、ｒ
ａｔ得られた（収率ｚＪ％）。Example/a Phosphonium salt 3 (2,401,4 mmol)
and glyoxal (4'OX * bath moat, /, 2 dag, ia
Add triethyl aquine (77m) to a solution of TI(y(toovst) (mmol)) and stir at room temperature overnight.After distilling off THFf, methylene chloride extraction was carried out in L2, M
When dried with am 804 and treated with a column (silica gel s ” mCtx@), altehyde 9 is o, r
At was obtained (yield zJ%).
ホスホニウム塩ｓ （Ｊ、ｊ ｆ、 ／、／ ｍｍｏｌ
） Ｖｒ’＊ 響ＩＩＩｍ下ｄｒｙテＨＩＰ （ｊ
ｊａｒ）ｉｃ溶カ【７、−７＃Ｕ、攪拌下ｎ−ＢｕＬｉ
（ヘキナン浴ｉ１５．２ ｍ／。Phosphonium salt s (J, j f, /, / mmol
) Vr'* Hibiki IIIm lower dry HIP (j
jar) ic melter [7, -7#U, n-BuLi under stirring
(Hequinane bath i15.2 m/.
Ｊ’、／ ｍｎ＋ｏ］）を加えホスホランｆ発生させる
。J', / mn+o]) to generate phosphorane f.
こｆ′ＬＫアルデヒド４ （Ｌ！ ｆ ％／、／ ｍｍ
ｏｌ ）のＴｎｙ（３ｊｓｒ）溶液を−１する０反え温
度を徐りに室温にあける。反応混合物を′炉下し、水、
エタノールの顯で洗浄すると黄色固体としてテトラメチ
ル＠導体１ａが／、ｊ ｊ ｆ ｍらねた（収率４／Ｆ
、９６）。f′LK aldehyde 4 (L! f %/, / mm
Incubate the Tny (3jsr) solution by -1 and gradually bring the temperature to room temperature. The reaction mixture was taken down to the furnace, water,
When washed with ethanol, tetramethyl@conductor 1a was obtained as a yellow solid (yield 4/F).
, 96).
ｍ、ｐ、 Ｑ１０−ＪＱ２ （ｄｅｃ、）’Ｈ−ＮＭ
Ｒ（ＯＤＯ４、Ｊ）
／、ター（Ｅ３． ／ａＨ，Ｍｅ）
１．９７（Ｂ、 Ｊ）ｉ、 ａｘｏ−ｍａｔｈｉｎ
ｅ）土Ｒ（Ｋｊｌｒ、 ｔｘｉ−’ ）
−タ００． ／ｊｔ／Ｊ、 ／４ｔＪθ、 ／２
７０． １００元素分析（０，、Ｈ，４Ｂ、 ）
ＯＨＢ
ｊＯ０Ｊ／ ４ｔ、９３ ４ｔ４ｔ、７≦ （ｏａｌ
ｃａ、）ｊθ、＃ ４１．ｆＪ ４１４１．４１
（Ｆｏｕｎｄ、）実施例λ
エタンジイリデンーー、λＩ−ビス（／、Ｊ−ジチオー
ル）のジベンゾ誘導体の合成
Ｉｂ
＊ｘ、ｔ＝”＞Ａ塩ａ（４ｔ＃Ｊｑ、／ １１１１０１
） と！リオキサー４ （４ｔ０９６Ｉｑｓ −
タＯ＋＋ｙ、２１１１１０１ ）のＴＨｙ（ｔＯｓｙ）
浴液にトリエチルアミン（Ｊ−）を加え、呈温下７時間
攪拌する。m, p, Q10-JQ2 (dec,)'H-NM
R (ODO4, J) /, ter (E3. /aH, Me) 1.97 (B, J) i, axo-mathin
e) SatR(Kjlr, txi-') -ta00. /jt/J, /4tJθ, /2
70. 100 elemental analysis (0,, H, 4B, ) OHB jO0J/ 4t, 93 4t4t, 7≦ (oal
ca,)jθ, #41. fJ 4141.41
(Found,) Example Synthesis of dibenzo derivative of λ ethanediylidene, λI-bis(/, J-dithiol) Ib *x, t=">A salt a(4t#Jq,/111101
) and! Lyoxer 4 (4t096Iqs -
THy(tOsy) of taO++y, 2111101)
Triethylamine (J-) was added to the bath solution, and the mixture was stirred at a constant temperature for 7 hours.
テＨ１を留去またのち塩化メチレン抽出し。The H1 was distilled off and then extracted with methylene chloride.
）Ｉａ２８０．でａｈ、ｓ縮する。これをカラム（シリ
カ、ＯＨ，Ｏｔ、溶出）処鳳し、黄色の７ラクシ冒ン【
採ゐと、アルデヒド６が／７／ｑ／得らｔＩた（収率１
７ Ｘ ） 。)Ia280. So ah, s shrinks. This was applied to a column (silica, OH, Ot, elution) and a yellow 7-lactone
Upon sampling, aldehyde 6 was obtained in /7/q/tI (yield 1
7X).
ホスホニウム塩５（ダダλ岬、／ｍＬｏｌ）ｌ−雰囲気
下２〇−のｄｒｙＴＨＦ［とかし、−７１℃においてｎ
ＢｕＬｉ −ヘ４ サン（八ｊｚＭ）（０，６’ｌ Ｊ
’ ｄ、 ／ １１ｍ＋０１ ）を加え、ホスホランを
発生させておく。こねにアルデヒド６（／ｆ４を岬、／
ｍｎ＋ｏｌ）のＴａｙ（ｚｏｓｚ）ｅｉ＆を滴下する
。室温に戻ｌた後析出１、たＩｂをろかし、（３Ｈ２（
ｊ１２ ＃水、 １ｔＯＨの願で洗浄するとジベンゾ体
１ｂ （淡黄色針状）が−ｊＪｑ得られた（収率２０％
）。Phosphonium salt 5 (Dada λ, /mLol) in dry THF [combed, at -71 °C] under 1-atmosphere
BuLi -he4 Sun (8jzM) (0,6'l J
'd, / 11m+01) to generate phosphorane. Koneni aldehyde 6 (/f4 to the cape, /
Tay(zosz)ei& of mn+ol) is added dropwise. After returning to room temperature, precipitate 1, Ib was filtered and (3H2(
When washed with water and 1tOH, dibenzo compound 1b (pale yellow needles) was obtained (yield 20%).
).
ｍ、ｐ、 コ００−コｏｉ （ａ・ｃ、）’Ｈ−ＮＭ
Ｒ（ＯＤＣ！ｔ、、 Ｊ）
！、りｙ（Ｂ、 ２１１． ｅｘｏ−ｍｅｔｈｉｎ
ｅ）。m, p, ko00-kooi (a・c,)'H-NM
R(ODC!t,, J)! , riy(B, 211. exo-methin
e).
？、／２（Ｂ、Ｉｎ、 ａｒｏｍａｔｉｃ）工Ｒ（ＫＢ
ｒ、 ｔｓ−’ ）
３０６０、 ／１０１． ／４１４０．１０１元素分析
（ｃ、、ｎ、。８４）
ＯＨＢ? , /2 (B, In, aromatic) Engineering R (KB
r, ts-') 3060, /101. /4140.101 Elemental analysis (c,,n,.84) OHB
Claims (1)
ぞれ形成してもよい） で示されるエタンジイリデンーー、λ′−ビス（／、Ｊ
−ジチオール）ＩＩ。(1) Ethanediylidene, λ'-bis(/, J
-dithiol) II.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16168181A JPS5862171A (en) | 1981-10-09 | 1981-10-09 | Bis(1,3-dithiols) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16168181A JPS5862171A (en) | 1981-10-09 | 1981-10-09 | Bis(1,3-dithiols) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5862171A true JPS5862171A (en) | 1983-04-13 |
| JPH0158187B2 JPH0158187B2 (en) | 1989-12-11 |
Family
ID=15739816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16168181A Granted JPS5862171A (en) | 1981-10-09 | 1981-10-09 | Bis(1,3-dithiols) |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5862171A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991007397A1 (en) * | 1989-11-21 | 1991-05-30 | Idemitsu Kosan Co., Ltd. | Thia- and/or selenafulvalenyl compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3758503A (en) * | 1970-06-17 | 1973-09-11 | Du Pont | T least one electron-withdrawing group and carbon disulfide 1,3-dithiole derivatives from acetylenic compounds substituted with a |
| JPS4997780A (en) * | 1972-12-26 | 1974-09-17 |
-
1981
- 1981-10-09 JP JP16168181A patent/JPS5862171A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3758503A (en) * | 1970-06-17 | 1973-09-11 | Du Pont | T least one electron-withdrawing group and carbon disulfide 1,3-dithiole derivatives from acetylenic compounds substituted with a |
| JPS4997780A (en) * | 1972-12-26 | 1974-09-17 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991007397A1 (en) * | 1989-11-21 | 1991-05-30 | Idemitsu Kosan Co., Ltd. | Thia- and/or selenafulvalenyl compound |
| US5312913A (en) * | 1989-11-21 | 1994-05-17 | Idemitsu Kosan Co., Ltd. | Electrically conductive complex |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0158187B2 (en) | 1989-12-11 |
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