JPS62207276A - N,n'-dialkyldihydropyrrolopyrrole compound and production thereof - Google Patents
N,n'-dialkyldihydropyrrolopyrrole compound and production thereofInfo
- Publication number
- JPS62207276A JPS62207276A JP5094486A JP5094486A JPS62207276A JP S62207276 A JPS62207276 A JP S62207276A JP 5094486 A JP5094486 A JP 5094486A JP 5094486 A JP5094486 A JP 5094486A JP S62207276 A JPS62207276 A JP S62207276A
- Authority
- JP
- Japan
- Prior art keywords
- group
- alkyl
- alkyl group
- trialkylsilyl
- formula
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 title abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 35
- 125000004665 trialkylsilyl group Chemical group 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 3
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000012776 electronic material Substances 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 2
- 229940100198 alkylating agent Drugs 0.000 abstract 1
- 239000002168 alkylating agent Substances 0.000 abstract 1
- 239000002305 electric material Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- -1 puwapyr group Chemical group 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PLUBXMRUUVWRLT-UHFFFAOYSA-N Ethyl methanesulfonate Chemical compound CCOS(C)(=O)=O PLUBXMRUUVWRLT-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000160 carbon, hydrogen and nitrogen elemental analysis Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 150000005452 ethyl sulfates Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003459 sulfonic acid esters Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は一般式（２）
（式中、Ｒ１はアルキル基を表わし、Ｒ３はＲ１がメチ
ル基の場合はアルキル基またはトリアルキルシリル基を
、Ｒｘがエチル基以上のアルキル基の場合は水素原子、
アルキル基またはトリアルキルシリル基を表わす。）で
示される新規なＮ、ｄ−シアｐキ〃ジヒドロピロロビロ
ーρ類およびその製造方法に関する。Detailed Description of the Invention <Industrial Application Field> The present invention is based on the general formula (2) (wherein, R1 represents an alkyl group, and when R1 is a methyl group, R3 represents an alkyl group or a trialkylsilyl group). , if Rx is an alkyl group greater than or equal to ethyl group, a hydrogen atom,
Represents an alkyl group or a trialkylsilyl group. ) and a method for producing the same.
〈従来の技術〉
Ｎ、侵−ジアルキ〃ジヒドロピロロピローμ類としては
前記構造式（１）においてＲ８がメチル基、Ｒ８が水素
原子である化合物が知られている（Ａｎｇ＠ｗ、 Ｃｈ
ｓｒｎ、 Ｉｎｔ、 Ｅｄ、 Ｅｎｇｌ、、 １４．８
４７（１９７５） ＊Ｔ＠ｔｒａｈ＠ｄｒｏｎ Ｌｕｔ
ｔ、、 ２５ ｅ５６６９（１９８４） ）。<Prior art> As N, invasive dialkyldihydropyrrolopyrro μ compounds, compounds in which R8 is a methyl group and R8 is a hydrogen atom in the above structural formula (1) are known (Ang@w, Ch
srn, Int, Ed, Engl, 14.8
47 (1975) *T@trah@dron Lut
T., 25 e5669 (1984)).
〈発明が解決しようとする問題点〉 しかしながら、前記一般式（１）で示されるＮ。<Problem that the invention seeks to solve> However, N represented by the general formula (1).
ｄ−シア〃キ〃ジヒドロピロロビローｙ類については全
く知られていなかった。Nothing was known about d-cya〃ki〃dihydropyrrolobilo y.
〈問題点を解決するための手段〉
本発明者らはジヒドロピロロビローρ類についてこれを
種々合成し、研究を重ねた結果、新規なＮ、ｄ−シアル
キルピロロビロール類カポリマーの、特に電気電子材料
用ポリマーの原料として有用であることを見出すととも
に種々の検討を加え本発明を完成した。<Means for Solving the Problems> The present inventors have synthesized various dihydropyrrolobirolles ρ and have conducted repeated research. The present invention was completed after discovering that the present invention is useful as a raw material for polymers for electronic materials and after various studies.
すなわち本発明は一般式（Ｉ）
（式中、Ｒ□はアルキル基を表わし、Ｒ８はＲｏがメチ
ル基の場合はアルキル基またはトリアルキルシリル基を
、Ｒ１がメチル基 以上のアルキル基の場合は水素原子
、アルキル基またはトリアルキルシリル基を表わす０）
で示されるＮ、ｄ−シア〃キ〃ジヒドロピロロビローμ
類およびその製造方法を提供するものである。That is, the present invention is based on the general formula (I) (wherein R□ represents an alkyl group, R8 represents an alkyl group or a trialkylsilyl group when Ro is a methyl group, and when R1 is an alkyl group of methyl or more, 0) representing a hydrogen atom, an alkyl group or a trialkylsilyl group
N, d-sia〃ki〃dihydropyrrolobilo μ represented by
and a method for producing the same.
本発明の対象化合物は上記一般式＋１）で示されるＮ、
ｄ−シア〃キ／Ｉ／！／ヒドロピロロビローμ類である
が、Ｒ１の具体例としては例えば、メチ／Ｖ基、メチル
基、プワピル基、ブチル基、ベンチｙ基、ヘキシル基、
ヘプチル基、オクチル基などが挙げられる。The target compound of the present invention is N represented by the above general formula +1),
d-sia〃ki/I/! /Hydropyrrolobilow μ, specific examples of R1 include methyl/V group, methyl group, puwapyr group, butyl group, benchy group, hexyl group,
Examples include heptyl group and octyl group.
またＲ１のアルキル基の具体例としては例えば上記Ｒ８
と同様なアルキル基が例示される０トリアルキルシリル
基としては例えばトリメチルシリμ基、トリエチルシリ
μ基、トリプロピ〃シリル基、トリブチルシリル基など
が例示される０次に本発明化合物の製造方法について説
明する〇
一般式（１）で示される本願発明の化合物は例えば、一
般式（６）
（式中、Ｒ１は水素原子、アルキル基またはトリアルキ
）ｖｙすｙ基を表わす。）
で示されるジヒドロピロロビローμ類に塩基の存在下、
一般式（２）
％式％
（式中、Ｘはハロゲン原子、スルフォン酸エステ／Ｉ／
残基または硫酸エステ／Ｌ／残基を表わし、Ｒ１は前記
のＲ１が水素の場合はエチル基以上のアルキル基を、Ｒ
８がアルキル基またはトリフルキルシリρ基の場合はア
ルキル基を表わす。）
で示されるア〃キ〃化剤を作用せしめるととＫよシ製造
することができる。Further, specific examples of the alkyl group of R1 include the above-mentioned R8
Examples of the trialkylsilyl group include alkyl groups similar to the following: trimethylsiliμ group, triethylsiliμ group, tripropysilyl group, tributylsilyl group, etc. Next, regarding the method for producing the compounds of the present invention The compound of the present invention represented by the general formula (1) to be explained is, for example, a vysy group represented by the general formula (6) (wherein R1 is a hydrogen atom, an alkyl group, or a trialkyl group). ) in the presence of a base,
General formula (2) % formula % (wherein, X is a halogen atom, sulfonic acid ester/I/
Represents a residue or a sulfuric acid ester/L/residue, and when R1 is hydrogen, R1 represents an alkyl group greater than or equal to ethyl group;
When 8 is an alkyl group or a triflukylsilyl ρ group, it represents an alkyl group. ) can be produced by using an oxidizing agent shown in the following formula.
ここで一般式（６）で示される化合物として、具体的に
は例えばＲ８が水素原子、前記のような７μキル基また
はトリアｙＪＩｒルＶリル基等であるジヒドロピロロピ
ローμ類が挙げられ、かかる化合物は例えばＣｈｅｍ、
Ｌｅｔｔ、、 １９８４２０８８．などに記載の方法
を参考にして得ることができる〇−一般式３）で示され
るアルキル他剤としては例えば、Ｒ１として前記のよう
なアルキル基を有するアルキルハフイド類、スルフォン
酸エステμ類、硫酸エヌテル類が例示でき、よシ具体的
にはアルキル基がエチル基の場合で示せば、塩化エチ〃
、臭化エチル、沃化エチルなどのハロゲン化７ｙキμ、
ｐ−）／ｌ／エンスルフをン酸エチｙ１メタンスルフォ
ン酸エチルなどのスルフをン酸アルキ〃、硫酸ジエチル
などの硫酸エステ〃が挙げられる０７μキ〃化剤はジヒ
ドロヒロロビロール類（２）に対し２倍モル以上使用さ
れ、通常は８〜１０モル倍迄の過剰量が用いられる０ま
た塩基としては例えば、ナトリウムメトキサイド、ナト
リウムニドキサイド、カリウムを一ブトキサイドのよう
なアルカリ金属アμコキサイド、ナトリウムアミド、リ
チウムジイソプロピルアミドのようなアルカリ金属アミ
ド、水素化ナトリウムのような水素化アルカリ金属が用
いられ、特に水素化ナトリウムを用いることが好ましい
。Here, specific examples of the compound represented by the general formula (6) include dihydropyrrolopyros μ, in which R8 is a hydrogen atom, the above-mentioned 7μ kyl group, triyJIrylVlyl group, etc. The compound is, for example, Chem,
Lett, 19842088. Examples of the alkyl other agents represented by 〇-general formula 3) which can be obtained with reference to the method described in 1. Examples include ethyl sulfates, and more specifically, when the alkyl group is an ethyl group, ethyl chloride
, 7y halides such as ethyl bromide and ethyl iodide,
p-)/l/Ensulfonate y1 Alkyl sulfonates such as ethyl methanesulfonate, sulfuric acid esters such as diethyl sulfate, etc.07μ Quenching agents include dihydrohirorobilols (2) The base is used in an excess amount of 8 to 10 moles or more, and is usually used in an excess of 8 to 10 moles. , sodium amide, alkali metal amide such as lithium diisopropylamide, and alkali metal hydride such as sodium hydride, and it is particularly preferable to use sodium hydride.
また反応溶媒としてはジエチルエーテル、テトラヒドロ
フランなどのエーテル系化合物が用いられ、これうｔ−
ベンゼン、トルエン、ヘキサンなどの炭化水素系化合物
で希釈して用いることも可能である◎反応温度は通常θ
℃から用いる溶媒の沸点までの間で選定される０反応時
間は原料である一般式（ＩＩ）の消滅速度と目的物であ
る一般式（１）の化合物の生成速度を測定しながら決定
することができ、通常はジアニオン化に８０分以上、シ
アμキ〜化に８０分以上を要し、１時間以上を要する０
目的物は反応混合物から抽出、蒸留などの通常の操作に
よシ分離することができ、再結晶、各種クロマトグラフ
ィー等の操作によシさらに精製することもできる０
〈発明の効果〉
かくして得られた本発明の化合物は、例えばポリマー等
の原料として有用であるＯポリマー用としては例えば本
発明の化合物を電気化学的に酸化することによシ得られ
、下記式四で示されるポリＮ−ア〜キμジヒドロピロロ
ビローμ類が挙げられる０
かかるポリマーは電気電子材料、例えば導電材料、エレ
クトロクロミックグイバイス、修飾電極などに有用であ
る０
次に実施例を示し本発明をさらに詳細に説明するが、本
発明は何らこれらに限定されるものではない。Ether compounds such as diethyl ether and tetrahydrofuran are used as reaction solvents, and these
It can also be used diluted with hydrocarbon compounds such as benzene, toluene, hexane, etc. ◎Reaction temperature is usually θ
The zero reaction time selected from °C to the boiling point of the solvent used should be determined while measuring the extinction rate of the raw material, general formula (II), and the production rate of the target compound, general formula (1). The target product is separated from the reaction mixture by normal operations such as extraction and distillation. The compound of the present invention thus obtained is useful as a raw material for polymers, for example, and can be further purified by operations such as recrystallization and various chromatography. Examples of such polymers include polyN-dihydropyrrolobylols obtained by electrochemically oxidizing the compound of the present invention and represented by the following formula 4.Such polymers can be used for electrical and electronic materials, For example, the invention is useful for conductive materials, electrochromic vices, modified electrodes, etc. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
〈実施例〉
実施例１
（８，６−ジーｔ−ブチ／ｌ／−１，４−ジメチルジヒ
ドロピロロ（８，２−ｂ）ピロー／Ｌ／）無水テトラヒ
ドロフフン６０ｍｊ中に、バフフィンで固めた含量６０
％の水素化ナトリウム８．７ｔ（１２ミリモ／Ｉ／）を
懸濁させ、これへ２．５−ジ−ｔ−ブチル−ジヒドロピ
ロロ（８、２−ｂ）ピロー／Ｉ１５１８ｍＦ（２，８７
ミリモ／Ｌ／）を加え、アルゴン雰囲気下、６０〜６８
℃で４０分間加熱攪拌した０得られた溶液にミラ化メチ
ｌ’６Ａ８ｆ（４８，２ミリモ／Ｉ／）を加え、６０℃
で７０分間加熱した〇
放冷した反応混合物にメタノ−／ｌ／２０ｍＪをゆっく
シと加えた後、減圧下で濃縮した０残渣に水１５ｆｆｌ
Ｊを加えると結晶が析出し、これを戸別した後、乾燥し
てｍｐ、 １９９〜２０８℃の結晶８５９ ｍ？（収率
６２＊）を得られた０エタノールよシ再結晶してｍｐ２
０２〜２０８℃の無色板状晶８．６−ジーｔ−ブチ／Ｉ
／ −１、４−ジメチルジヒドロピロロ（８，２−ｂ）
ピロー〃を得た０
元素分析値（Ｃ，Ｈｌ。馬として）
ＣＨＮ
分析値（＠ ７７．７Ｂ １０．４５ １１．８
２計算値（（転） ７８．００ １０．８６ １１．
８７マス分析ｍ／＊ ： ２４６（Ｍ”、５９％）ｐｍ
ｒ（ＣＤＣＪｓ） δｐｐｍ： １．８８ （１８Ｈ
，Ｓ ）、８．７８（６Ｈ，Ｓ ）。<Example> Example 1 (8,6-di-t-buty/l/-1,4-dimethyldihydropyrrolo(8,2-b) pillow/L/) solidified with buffine in 60 mj of anhydrous tetrahydrofufun Content 60
% of sodium hydride (12 mm/I/) was suspended, and 1518 mF (2,87
Add Milimo/L/), under argon atmosphere, 60-68
Miranated methyl l'6A8f (48.2 mm/I/) was added to the resulting solution which was heated and stirred at 60°C for 40 minutes.
After heating for 70 minutes at
When J is added, crystals are precipitated, which are separated from each other and then dried to give 859 m of crystals at a temperature of 199 to 208°C. (yield 62*) was obtained by recrystallizing from 0 ethanol and mp2
Colorless plate crystals 8.6-di-t-buty/I at 02-208°C
/ -1,4-dimethyldihydropyrrolo(8,2-b)
Pillow obtained 0 Elemental analysis value (C, Hl. As a horse) CHN Analysis value (@ 77.7B 10.45 11.8
2 Calculated value ((transformation) 78.00 10.86 11.
87 mass analysis m/*: 246 (M”, 59%) pm
r(CDCJs) δppm: 1.88 (18H
, S ), 8.78 (6H, S ).
６．０２（２Ｈ，５）
ＵＶ（シクロヘキサン）λｍａｘ：２６０ ｎｍ（ｔ
１４．ＴＯＯ）〈参考例〉
実施例１で得られた８、６−ジーｔ−ブチル−１，４−
ジメチルジヒドロピロロピロールのアセトニトリ／ｌ／
溶液（０，０１モＩＶ／ ｊ ）５０ｍｊおよび過塩素
酸ナトリウムのア七ト二トリ！溶液（０，１モ／ｌ’／
Ｊ ） ５０ｍＪを混合して電解酸化重合反応液とし
た〇
電極として作用電極（１４極）には白金板を、対極（陰
極）ＫはＰＥＴフィ〃ムに金を蒸着させた透明導電フィ
ルムを用いた◇反応溶液に窒素ガスを８０分間通気した
後、窒素ガス流通下、Ａｔ／ＡｆＣＪ比較［極に対しチ
ー１０Ｖ 〜＋１．５Ｖまでの間を５０ ｍＶ／ｓ・Ｃ
の走査速度で電位走査して２０時間電解酸化を行ったと
ころ作用電極上に重合体が析出した。6.02 (2H, 5) UV (cyclohexane) λmax: 260 nm (t
14. TOO) <Reference example> 8,6-di-t-butyl-1,4- obtained in Example 1
Dimethyldihydropyrrolopyrrole acetonitrile/l/
Solution (0,01 mo IV/j) 50 mj and sodium perchlorate acetonitri! Solution (0,1 mo/l'/
J) 50mJ was mixed to make an electrolytic oxidation polymerization reaction solution〇A platinum plate was used as the working electrode (14 electrodes), and a transparent conductive film made of PET film with gold vapor-deposited was used as the counter electrode (cathode) K. ◇ After bubbling nitrogen gas into the reaction solution for 80 minutes, under nitrogen gas flow, At/AfCJ comparison [50 mV/s・C between 10 V and +1.5 V with respect to the pole]
When electrolytic oxidation was performed for 20 hours by scanning the potential at a scanning speed of , a polymer was deposited on the working electrode.
このようにして得られた重合体を電極上から取υ出し粉
末を得た０これを加圧成型し電導度を測定したところ、
６． Ｉ Ｘ １０−＠Ｓ／ｃｌｌＩの良好な半導性を
示した０電導度は空気中に１週間放置しても殆ど変化を
示さず、重合体は安定性に優れることをも確認された０The polymer obtained in this way was taken out from the electrode to obtain a powder.The powder was molded under pressure and the electrical conductivity was measured.
6. The conductivity of I
Claims (2)
がメチル基の場合はアルキル基またはトリ アルキルシリル基を、Ｒ＿１がエチル基以上のアルキル
基の場合は水素原子、アルキル基 またはトリアルキルシリル基を表わす。） で示されるＮ，Ｎ′−ジアルキルジヒドロピロロピロー
ル類。(1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents an alkyl group, R_2 is R_1
When R_1 is a methyl group, it represents an alkyl group or a trialkylsilyl group, and when R_1 is an alkyl group greater than or equal to an ethyl group, it represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. ) N,N'-dialkyldihydropyrrolopyrroles represented by:
キルシリル基を表わす。） で示されるジヒドロピロロピロール類に塩基の存在下、
一般式（III） Ｒ＿１−Ｘ（III） （式中、Ｘはハロゲン原子、スルフォン酸 エステル残基または硫酸エステル残基を表 わし、Ｒ＿１は前記のＲ＿２が水素の場合はエチル基以
上のアルキル基を、Ｒ＿２がアルキル基またはトリアル
キルシリル基の場合はアルキ ル基を表わす。） で示されるアルキル化剤を作用せしめることを特徴とす
る一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１はアルキル基を表わし、Ｒ＿２はＲ＿１
がメチル基の場合はアルキル基またはトリ アルキルシリル基を、Ｒ＿１がエチル基以上のアルキル
基の場合は水素原子、アルキル基 またはトリアルキルシリル基を表わす。） で示されるＮ，Ｎ′−ジアルキルジヒドロピロロピロー
ル類の製造方法。(2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_2 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group.) A base is added to dihydropyrrolopyrroles represented by In the presence of
General formula (III) R_1-X(III) (wherein, , when R_2 is an alkyl group or a trialkylsilyl group, it represents an alkyl group.) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I ) (In the formula, R_1 represents an alkyl group, R_2 is R_1
When R_1 is a methyl group, it represents an alkyl group or a trialkylsilyl group, and when R_1 is an alkyl group greater than or equal to an ethyl group, it represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. ) A method for producing N,N'-dialkyldihydropyrrolopyrroles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5094486A JPS62207276A (en) | 1986-03-07 | 1986-03-07 | N,n'-dialkyldihydropyrrolopyrrole compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5094486A JPS62207276A (en) | 1986-03-07 | 1986-03-07 | N,n'-dialkyldihydropyrrolopyrrole compound and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62207276A true JPS62207276A (en) | 1987-09-11 |
Family
ID=12872930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5094486A Pending JPS62207276A (en) | 1986-03-07 | 1986-03-07 | N,n'-dialkyldihydropyrrolopyrrole compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62207276A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014070029A1 (en) * | 2012-11-05 | 2014-05-08 | Instytut Chemii Organicznej Polskiej Akademii Nauk | Strongly fluorescent heterocycles and a method for their synthesis |
-
1986
- 1986-03-07 JP JP5094486A patent/JPS62207276A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014070029A1 (en) * | 2012-11-05 | 2014-05-08 | Instytut Chemii Organicznej Polskiej Akademii Nauk | Strongly fluorescent heterocycles and a method for their synthesis |
| KR20150084811A (en) * | 2012-11-05 | 2015-07-22 | 인스티투트 헤미이 오르가니치네이 폴스키에이 아카데미이 나우크 | Strongly fluorescent heterocycles and a method for their synthesis |
| CN104870447A (en) * | 2012-11-05 | 2015-08-26 | 波兰科学院有机化学研究所 | Strongly fluorescent heterocycles and a method for their synthesis |
| JP2015536944A (en) * | 2012-11-05 | 2015-12-24 | インスト ケミー オーガニッチネイ ポルスキエイ アカデミー ナウク | Strong fluorescent luminescent heterocyclic compound and method for producing the same |
| US9988385B2 (en) | 2012-11-05 | 2018-06-05 | Instytut Chemii Organicznej Polskiej Akademii Nauk | Strongly fluorescent heterocycles and a method for their synthesis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Seyferth et al. | The Preparation of Organolithium Compounds by the Transmetalation Reaction. I. Vinyllithium1, 2 | |
| TW201602069A (en) | Zwitterionic compound and ion conductor | |
| Younus et al. | Synthesis and characterisation of mono-acetylide and unsymmetrical bis-acetylide complexes of ruthenium and osmium: X-ray structure determinations on [(dppe) 2Ru (Cl)(C C–C6H4-p-NO2)],[(dppe) 2Ru (Cl)(C C–C6H3-o-CH3-p-NO2)] and [(dppm) 2Os (C C–C6H4-p-CH3)(C C–C6H4-p-NO2)] | |
| Otsubo et al. | Syntheses, Structures, and Properties of 2, 3, 6, 7-Tetrathiabenzo (1, 3-cd: 4, 6-c'd') dipentalene and Its Methyl, Ethyl, Methylthio, and Ethylthio Derivatives: Novel Fused Polynuclear Heteroarenes. | |
| Teimuri-Mofrad et al. | Synthesis of new binuclear ferrocenyl compounds by hydrosilylation reactions | |
| Bruce et al. | The series of carbon-chain complexes {Ru (dppe) Cp∗} 2 {μ-(CC) x}(x= 4–8, 11): Synthesis, structures, properties and some reactions | |
| Atzkern et al. | Intramolecular Magnetic and Electrostatic Interactions in Stepwise Stacked Trinuclear Paramagnetic Metallocenes with the Metal Sequences FeM'Fe and NiM'Ni (M'= V, Cr, Co, Ni) and CoCrCo | |
| Tárraga et al. | Synthesis and electrochemical study of novel oxazolo-ferrocene derivatives displaying redox-switchable character | |
| Wong et al. | Carbon-rich organometallic materials derived from 4-ethynylphenylferrocene | |
| Glass et al. | Neighboring tin effect in electron transfer from thio ethers | |
| Höcher et al. | Novel [3] ferrocenophanes: Syntheses, redox properties and molecular structures of [Fe {(η5-C5H4) CMe2} 2PR](R= Ph, Cy) | |
| CN104817583B (en) | Carbon bridging bisamide base ytterbium and its preparation and the application in catalysis aldehyde and amine amide are combined to react | |
| JPS62207276A (en) | N,n'-dialkyldihydropyrrolopyrrole compound and production thereof | |
| Kupchik et al. | Reactions of triphenyltin hydride with certain acid chlorides and carboxylic acids | |
| Sakano et al. | Preparation and characterization of various N-substituted-2-aza-[3]-ferrocenophanes and their chemical and electrochemical properties | |
| Takimiya et al. | Improved Synthesis of Double‐Bridged Tetraselenafulvalenophanes and Formation of Their Conductive Radical Cation Salts | |
| Takao et al. | Redox-Induced Reversible Rearrangement of a Dimetallaallyl Ligand on the Trinuclear Cluster of Ruthenium. Mechanistic Aspects of Formation of the Face-Capping μ3-C3 Ring on the Triruthenium Plane | |
| Rømrning et al. | Oxidation of ruthenium hydrides (η5-C5H4R) Ru (PPh3) 2H (R= H, tBu, CH2Ph, CTol3). X-ray crystal structure determination of (η5-C5H4 (CTol3)) Ru (PPh3) 2H and an electrochemical study of its stable cation radical | |
| JP3969970B2 (en) | Diferrocenodithiin compound and method for producing the same | |
| JPH0421676A (en) | Thiophene derivative | |
| Pannell et al. | Bis (ferrocenylsilyl) thiophenes and ferrocenylene (silylene) thiophene oligomers | |
| JPS62212389A (en) | N-alkyldihydropyrrolopyrrole compound and production thereof | |
| JP2991818B2 (en) | Condensed 2-membered cyclic disilanilene-acetylene compound and method for producing the same | |
| JPH04108784A (en) | Thiophene derivative of polyethylene and thiophene derivative of ethylene | |
| JPS63135393A (en) | Production of alkylsilyl cyanide |