JPS62212389A - N-alkyldihydropyrrolopyrrole compound and production thereof - Google Patents
N-alkyldihydropyrrolopyrrole compound and production thereofInfo
- Publication number
- JPS62212389A JPS62212389A JP5308386A JP5308386A JPS62212389A JP S62212389 A JPS62212389 A JP S62212389A JP 5308386 A JP5308386 A JP 5308386A JP 5308386 A JP5308386 A JP 5308386A JP S62212389 A JPS62212389 A JP S62212389A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- group
- formula
- alkyl group
- general 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 5
- 150000001875 compounds Chemical class 0.000 title abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 8
- 125000004665 trialkylsilyl group Chemical group 0.000 claims abstract description 8
- 150000003459 sulfonic acid esters Chemical group 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000002148 esters Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 3
- 239000013043 chemical agent Substances 0.000 claims 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 8
- -1 sulfuric acid ester Chemical group 0.000 abstract description 8
- 229940100198 alkylating agent Drugs 0.000 abstract description 4
- 239000002168 alkylating agent Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000012776 electronic material Substances 0.000 abstract description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 2
- 229940030966 pyrrole Drugs 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 3
- 229940008406 diethyl sulfate Drugs 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- PLUBXMRUUVWRLT-UHFFFAOYSA-N Ethyl methanesulfonate Chemical compound CCOS(C)(=O)=O PLUBXMRUUVWRLT-UHFFFAOYSA-N 0.000 description 1
- 241001534756 Mungos Species 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 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
- 238000011097 chromatography purification Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration 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
- 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
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-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
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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α）
（式中、損はアルキル基を表わし、Ｒｚ Ｒ４はそれぞ
れ水素原子、アルキル基またはトリアルキルシリル基を
、Ｒａは槓と相異なるアｌレキル基またはアルコキシカ
ルボニル基を表わす。）
で示される新規なＮ−アルキルジヒドロピロロピロール
類およびその製造方法に関するつ〈従来の技術〉
Ｎ−アルキルジヒドロピロロピロール類としては前記構
造式（１）においてＲ１およびＲ３がメチル基であり、
Ｒ２およびＲ４が水素原子である化合物が知られている
（例えばムｎｇａｗ、 Ｃｈｅｍ、 Ｉｎむ。Detailed Description of the Invention <Industrial Application Field> The present invention relates to the general formula α Represents an alkyl group or an alkoxycarbonyl group different from the above structure. In formula (1), R1 and R3 are methyl groups,
Compounds in which R2 and R4 are hydrogen atoms are known (eg, Mungos, Chem, In.).
Ｅｄ、 Ｅｎｇ／、＋−１４＋８４７ （１９７５）
、ＴｅｔｒａｈｅｄｒｏｎＬｅｃｉ、、２５．５６６９
（１９８４））。Ed, Eng/, +-14+847 (1975)
, TetrahedronLeci, , 25.5669
(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α）で示されるＮ−アルキル
ジヒドロピロロピロール類については全く知られていな
かった。<Problems to be Solved by the Invention> However, the N-alkyldihydropyrrolopyrroles represented by the general formula α) have not been known at all.
〈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ピロール類についてこれを
種々合成し、研究を重ねた結果、新規なＮ−アルキルピ
ロロピロール類がポリマーの、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 synthesized various dihydropyrrolopyrroles, and as a result of repeated research, discovered that novel N-alkylpyrrolopyrroles can be used as polymers, especially polymers for electrical and electronic materials. The present invention was completed after discovering that it is useful as a raw material for
すなわち本発明は一般式α）
（式中、 Ｒｔはアルキル基を表わし、Ｒ２、Ｒ４はそ
れぞれ水素原子、アルキル基またはトリアルキルシリル
基を、ＲａはＲ１と相異なるアルキル基またはアルコキ
シカルボニル基を表わす。）
で示される新規なＮ−アルキルジヒドロピロロピロール
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 α) (wherein, Rt represents an alkyl group, R2 and R4 each represent a hydrogen atom, an alkyl group, or a trialkylsilyl group, and Ra represents an alkyl group or an alkoxycarbonyl group different from R1) The present invention provides novel N-alkyldihydropyrrolopyrroles represented by the following formula and a method for producing the same.
本発明の対象化合物、は上記一般式（ｐで示されるＮ−
フルキルジヒドロピロロビロール頬テあるが、Ｒ１の具
体例としては例えば、メチル基、エチル基、プロピル基
、ブチル基、ペンチル基。The target compound of the present invention is the general formula (N-
Examples of R1 include methyl group, ethyl group, propyl group, butyl group, and pentyl group.
ヘキシル基、ヘプチル基、オクチル基などのアルキル基
が挙げられる。Examples include alkyl groups such as hexyl, heptyl, and octyl groups.
またＢｋ２ 、 Ｒ４のアルキル基の具体例としては例
えば上記Ｒ１と同様なアルキル基が例示される。トリア
ルキルシリル基としては例えばトリメチルシリル基、ト
リエチルシリル基、トリプロピルシリル基、トリブチル
シリル基などが例示される。Specific examples of the alkyl groups for Bk2 and R4 include the same alkyl groups as those for R1 above. Examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, and tributylsilyl group.
Ｒ３のアルキル基の具体例としては、例えば上記ＩＬ１
と同様なアルキル基が例示されろが、Ｒ３とＲ＞ と
は同時に同一のフルキル基であることはない。アルコキ
シカルボニル基のＡ 体ｆ％Ｊとしては例えば、メトキ
シ、エトキシ、プロポキシ、ブトキシ、ペントキシ、ヘ
キソキシ、ヘプトキシ、オクトキシなどのアルコキシ基
を有するカルボニル基が挙げられる。Specific examples of the alkyl group for R3 include the above-mentioned IL1.
Examples include alkyl groups similar to , but R3 and R> are never the same furkyl group at the same time. Examples of the A-form f%J of the alkoxycarbonyl group include carbonyl groups having an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, and octoxy.
次に本発明化合物の製造方法について説明する。Next, a method for producing the compound of the present invention will be explained.
一般式α）で示される本願発明の化合物は例えば一般式
σ）
（式中、Ｒ２、Ｒ４はそれぞれ水素原子、アルキル基ま
たはトリアルキルシリル基を、Ｒａはアルキル基または
アルコキシカルボニル基を表わす。）
で示されるジヒドロピロロピロール類に塩基ノ存在下、
一般式（ＩＩＩ）
Ｒｔ−ｘ（Ｉｌｌ）
（式中、Ｒ１は前記Ｒ３とは相異なるアルキルｍを、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す。）で示されるアルキル化剤を作
用せしめることにより製造することができる。The compound of the present invention represented by general formula α) is, for example, general formula σ) (wherein R2 and R4 each represent a hydrogen atom, an alkyl group or a trialkylsilyl group, and Ra represents an alkyl group or an alkoxycarbonyl group). In the presence of a base, dihydropyrrolopyrroles represented by
General formula (III) Rt-x(Ill) (wherein, R1 represents an alkyl m different from R3, x
represents a halogen atom, a sulfonic acid ester residue or a sulfuric ester residue. ) can be produced by reacting with an alkylating agent shown in
ここで一般式（ｎ）で示される化合物として、具体的に
は例えば、Ｒ２、Ｒ４が水素原子、前記のようなアルキ
ル基またはトリアルキルシリル基等であり、Ｒａが前記
のようなアルキル基またはアルコキシカルボニル基等で
あるジヒドロピロロビロール類が挙げられ、かかる化合
物は例えばＣｈｅｍ、Ｌｅｔｔ、、 １９８４ ２０８
８ 、などに記載の方法を参考にして得ることができる
。Specifically, for the compound represented by the general formula (n), for example, R2 and R4 are a hydrogen atom, an alkyl group or a trialkylsilyl group as described above, and Ra is an alkyl group as described above or a trialkylsilyl group as described above. Examples include dihydropyrrolobyloles which are alkoxycarbonyl groups, and such compounds are, for example, Chem, Lett, 1984 208
It can be obtained by referring to the method described in 8.
一般式（ＩＩＩ）で示されるアルキル化剤としては例え
ば、Ｒ１として前記のよりなアルキル基を有するアルキ
ルハライド類、スルフォン酸エステル類、硫酸エステル
類が例示でき、より具体的にはアルキル基がエチル基の
場合で示せば、塩化エチル、具化エチル、沃化エチルな
どのハロゲン化アルキル、ｐ−トルエンスルフオン酸エ
チル、メタンスルフオン酸エチルなどのスルフオン酸ア
ルキル、硫酸ジエチルなどの硫酸エステルが挙げられる
。Examples of the alkylating agent represented by the general formula (III) include alkyl halides, sulfonic acid esters, and sulfuric acid esters having the above-mentioned alkyl group as R1, and more specifically, the alkyl group is ethyl. Examples of groups include alkyl halides such as ethyl chloride, ethyl iodide, alkyl sulfonates such as ethyl p-toluenesulfonate and ethyl methanesulfonate, and sulfuric esters such as diethyl sulfate. It will be done.
アルキル化剤はジヒドロピロロビロール類■に対し通常
、等モル以上使用され、一般的には１．１〜１０モル倍
程度の過剰蹟が用いられる。The alkylating agent is usually used in an amount equal to or more than the molar amount of the dihydropyrrolobyrolles (1), and is generally used in an excess of about 1.1 to 10 times the mole.
また塩基としては例えば、ナトリウムメトキサイド、ナ
トリウムエトキサイド、カリウム−１−ブトキサイドの
ようなアルカリ金属アルコキサイド、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【ド、また反応溶媒としては例えば、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、アセ
トン、メチルエチルゲドンなどのゲトン系化合物等が用
いられ、これらをベンゼン、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。Examples of the base include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium-1-butoxide, and alkali metal alkoxides such as sodium amide and lithium diisopropylamide.As the reaction solvent, examples include diethyl ether. , ether compounds such as tetrahydrofuran, getone compounds such as acetone and methyl ethylgedone, etc., and these may be diluted with hydrocarbon compounds such as benzene, toluene, hexane, etc. and used.
反応温度は通常ＯＣから用いる溶媒の沸点までの間で選
定される。反応時間は原料である一般式Ｄ）の消滅速度
と目的物である一般式（Ｉ）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る。The reaction temperature is usually selected between OC and the boiling point of the solvent used. The reaction time can be determined while measuring the rate of disappearance of the raw material, general formula D), and the production rate of the compound of general formula (I), which is the target product.
目的物は反応混合物から抽出、蒸留などの通常の操作に
より分離することができ、再結晶、各種クロマトグラフ
ィー等の操作にぶりさらに精製することもできる。The target product can be separated from the reaction mixture by conventional operations such as extraction and distillation, and can be further purified by operations such as recrystallization and various chromatography.
〈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。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り得られ
、下記式（ＩＴ）で示されるポリＮ−アルキルジヒドロ
ピロロピロ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ディバイス、修飾電極など
に有用である。<Effects of the Invention> The thus obtained compound of the present invention is useful, for example, as a raw material for polymers and the like. For polymers, for example, poly N-alkyl dihydropyrrolopyro obtained by electrochemically oxidizing the compound of the present invention and represented by the following formula (IT) can be used for electrical and electronic materials, such as conductive materials and electrochromic devices. , useful for modified electrodes, etc.
〈実施例〉
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。<Examples> Next, the present invention will be explained in more detail by showing Examples, but the present invention is not limited to these in any way.
実施例１
（８，６−ジーｔ−ブチル−１−メトキシカルボニル−
４−メチルジヒドロピロロ（８，２−ｂ）ピロール）
アセトン１０Ｍｔ中に粉末状の水酸化カリウム２９０岬
（５，２ミリモル）および８．６−ジーｔ−フチルー１
−メトキシカルボニルジヒドロピｏｏ（８，２−ｂ）ピ
ｏ−ル１８８ ”Ｐ（０，４９９モル）を加え窒素雰囲
気下に室温で１０分間激しく攪拌した。茨部これにヨウ
化メチル４２２ｑ（２，９８ｔリモル）を加えて１時間
、加熱還流させた。Example 1 (8,6-di-t-butyl-1-methoxycarbonyl-
4-Methyldihydropyrrolo(8,2-b)pyrrole) Powdered potassium hydroxide 290 capes (5,2 mmol) and 8,6-di-t-phthyl in 10 Mt acetone
-methoxycarbonyldihydropyroo(8,2-b)pyro-188''P (0,499 mol) was added and stirred vigorously at room temperature under nitrogen atmosphere for 10 minutes. , 98 tremol) was added thereto, and the mixture was heated under reflux for 1 hour.
次に反応ｎ合物にベンゼン１００ ｍｌを加え、不溶物
を濾過により除去した後、飽和食塩水で洗浄し、得られ
た有機ＷＪを芒硝で乾燥した。これを減圧濃縮して、ｍ
ｐ１０８〜１３０の淡褐色の結晶１５８岬−動勢零零存
＃を得た。この結晶は純度的７０％の８．６−ジーｔ−
ブチル−１−メトキシカルボニル−４−メチルジヒドロ
ピロロ（８，２−ｂ）ピロールであることがｐｍｒで確
認された。収ｅｌｆ ＴＡＸと襲ヱな丸ち。Next, 100 ml of benzene was added to the reaction n compound, and after removing insoluble matter by filtration, the mixture was washed with saturated brine, and the obtained organic WJ was dried with Glauber's salt. This was concentrated under reduced pressure, m
158 light brown crystals of p108-130 were obtained. This crystal is 70% pure 8.6-T-
PMR confirmed that it was butyl-1-methoxycarbonyl-4-methyldihydropyrrolo(8,2-b)pyrrole. Collection elf TAX and Asoenamaruchi.
尚、構造の確認は上記の結晶をメタノールより再結晶し
て得られたｍｐ１４８．５〜１４４．５℃の無色針状の
結晶を用いて行った。The structure was confirmed using colorless needle-like crystals with a mp of 148.5 to 144.5°C obtained by recrystallizing the above crystals from methanol.
ｐｍｒ （ＣＤＯ／ａ） ｊｐｐｍ
ｌ、８７（９Ｈ，８）、１．４２（９Ｈ，８）、８．７
９（８Ｈ，８）８．９０（８Ｈ，８）、６．８８（ＩＨ
，ｄ 、Ｊ＝１．４Ｈｚ ＞６．９８（１１−ｔ、ｄ、
Ｊ＝１．４８Ｚ）マス分析ｍ／ｅ：２９０ ＣＭ＋、
７４％）実ｍ例２
（１−エチル−８，６−ジーｔ−ブチル−４−メトキシ
カルボニルジヒドロピロロ〔８゜２−ｂ〕ビロール）
実施例１においてヨウ化メチル４２２ｑの代りにジエチ
ル硫酸４５８ｓｐ（２，９７ｔリモル）を用いた他は実
施例１と同様な操作を行った。pmr (CDO/a) jppm l, 87 (9H, 8), 1.42 (9H, 8), 8.7
9 (8H, 8) 8.90 (8H, 8), 6.88 (IH
, d , J = 1.4 Hz > 6.98 (11-t, d,
J=1.48Z) Mass analysis m/e: 290 CM+,
74%) Example 2 (1-ethyl-8,6-di-t-butyl-4-methoxycarbonyldihydropyrrolo[8°2-b]virol) In Example 1, 458sp of diethyl sulfate was substituted for 422q of methyl iodide. The same operation as in Example 1 was performed except that (2,97 t remol) was used.
減圧濃縮後の残渣として７８（ｌｖの黄色油状物が得ら
れた。これをシリカゲルのカラムクロマトに付し、偽を
酸を１７％含むヘキサン溶液で溶出した留分を減圧濃縮
して、ｍ９１２１〜１２６℃の淡黄色結晶１−エチル−
８，６−ジーｔ −フチルー４−メトキシカルボニルジ
ヒドロピロロ（８，２−ｂ）ピロール９６．８岬（収率
６８％）を得た。After concentration under reduced pressure, a yellow oil of 78 lv was obtained as a residue. This was subjected to silica gel column chromatography, and the fraction eluted with a hexane solution containing 17% acid was concentrated under reduced pressure. Pale yellow crystals of 1-ethyl at 126℃
96.8 capes of 8,6-di-t-phthyl-4-methoxycarbonyldihydropyrrolo(8,2-b)pyrrole (68% yield) were obtained.
構造の確認は上記結晶をメタノールより再結晶して得ら
れたｍｐ１８０〜１８１℃の無色プリズム状の結晶を用
いて行った。The structure was confirmed using colorless prismatic crystals with a mp of 180 to 181°C obtained by recrystallizing the above crystals from methanol.
ｐｍｒ（ＯＤＯｌａ）δｐｐｍ
１．８７（９Ｈ，８）、１．４８（９Ｈ，８）、１．４
８（８Ｈ。pmr (ODOla) δppm 1.87 (9H, 8), 1.48 (9H, 8), 1.4
8 (8H.
’１Ｊ＝７．２Ｈｚ）、８．９０（８）１，８）、４．
１８（２Ｈ。'1J=7.2Hz), 8.90(8)1,8), 4.
18 (2H.
ｑ、Ｊ＝７．２Ｈｚ）、６．４５（ＩＨ，ｄ、Ｊ ＝１
．５Ｈｚ）、６．９８（２Ｈ，ｄ 、Ｊ ＝１．５Ｈｚ
）マス分析ｍ／ｅ ： ８０４ （Ｍ＋、 １００％）
実施例８
実施例２においてジエチル硫酸４５８ｑの代りに臭化エ
チル８２４１ＩＦ（２，９７ミリモル）を用いた他は実
施例２と同様に操作を行った。カラムクロマト精製する
ことによりｌ−エチル−８，６−ジーｔ−ブチル−４−
メトキシカルボ・ニルジヒドロピロロ（８，２−ｂ）ビ
ロールがｍｐＨ９〜１２２℃の淡黄色結晶として得られ
た。収量９６．８ ’ＩＦ （収率６４形）く参考例１
〉
実施例１で得られた８、６−ジーｔ−ブチル−１−メト
キシカルボニル−４−メチルジヒドロピロロビロールの
アセトニトリル溶液（０，０１モル／ｊ）Ｓｏｗｔおよ
び過塩素酸ナトリウムのアセトニトリル溶液（０，１モ
ル／ｌ）５０ｍｌを混合して電解酸比重合反応液とした
。q, J = 7.2Hz), 6.45 (IH, d, J = 1
．． 5Hz), 6.98 (2H, d, J = 1.5Hz
) Mass analysis m/e: 804 (M+, 100%)
Example 8 The same procedure as in Example 2 was carried out except that ethyl bromide 8241IF (2.97 mmol) was used instead of diethyl sulfate 458q. By column chromatographic purification, l-ethyl-8,6-di-t-butyl-4-
Methoxycarbo-nyldihydropyrrolo(8,2-b)virol was obtained as pale yellow crystals with mpH 9-122°C. Reference example 1 with a yield of 96.8' IF (yield 64 type)
> An acetonitrile solution (0.01 mol/j) of 8,6-di-t-butyl-1-methoxycarbonyl-4-methyldihydropyrrolobyrol obtained in Example 1 and an acetonitrile solution of sodium perchlorate ( 0.1 mol/l) were mixed to prepare an electrolytic acid specific polymerization reaction solution.
電極として作用電極（陽極）には白金板を、対碓（陰画
）にはＰＥＴフィルムに金を蒸着させた透明導電フィル
ムを用いた。反応ｆＢ液に窒素ガスを８０分間通気した
後、窒素ガス流通下、Ａｆ／ムｔｅｘ比較ｆＨ，ｍニ対
シテ−１，０Ｖ 〜＋１．５Ｖまでの間を５９ ｍＶ／
ｓｅａ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ｗＬ補極上重合体が析出した。As the electrodes, a platinum plate was used as the working electrode (anode), and a transparent conductive film made by vapor-depositing gold on PET film was used as the counter electrode (negative). After bubbling nitrogen gas into the reaction fB solution for 80 minutes, Af/mtex comparison fH,m was applied at 59 mV/m from -1.0V to +1.5V under nitrogen gas flow.
When electrolytic oxidation was performed for 20 hours by potential scanning at a scanning speed of sea, a working wL co-electrode polymer was precipitated.
このようにして得られた重合体をｗｔ画上から取り出し
粉末を得た。これを加圧成型し電導度を測定したところ
、６．５Ｘ１Ｇ’８／ｃｆ１１の良好な半導性を示した
。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も確認された。The thus obtained polymer was taken out from the wt image to obtain a powder. When this was pressure molded and its conductivity was measured, it showed good semiconductivity of 6.5X1G'8/cf11. The conductivity showed almost no change even after being left in the air for one week, confirming that the polymer had excellent stability.
Claims (2)
はそれぞれ水素原子、アルキル基またはト リアルキルシリル基を、Ｒ＿３はＲ＿１と相異なるアル
キル基またはアルコキシカルボニル基 を表わす。） で示されるＮ−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, R_4
each represents a hydrogen atom, an alkyl group or a trialkylsilyl group, and R_3 represents an alkyl group or an alkoxycarbonyl group different from R_1. ) N-alkyldihydropyrrolopyrroles represented by:
基またはトリアルキルシリル基を、 Ｒ＿３はアルキル基またはアルコキシカルボニル基を表
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、Ｒ＿１は前記Ｒ＿３とは相異なるアルキル基を
、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▼ （式中、Ｒ＿１ 、Ｒ＿２、Ｒ＿３、Ｒ＿４はそれぞれ
前記と同じ意味を表わす。） で示されるＮ−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) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_2 and R_4 are each a hydrogen atom, an alkyl group, or a trialkylsilyl group, and R_3 is an alkyl group or an alkoxycarbonyl group. ) in the presence of a base,
Alkyl represented by the general formula (III) R_1-X(III) (wherein R_1 represents an alkyl group different from the above R_3, and X represents a halogen atom, a sulfonic acid ester residue, or a sulfuric ester residue) General formula (I) characterized by the action of a chemical agent ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3, and R_4 each represent the same meaning as above.) - A method for producing alkyl dihydropyrrolopyrroles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5308386A JPS62212389A (en) | 1986-03-11 | 1986-03-11 | N-alkyldihydropyrrolopyrrole compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5308386A JPS62212389A (en) | 1986-03-11 | 1986-03-11 | N-alkyldihydropyrrolopyrrole compound and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62212389A true JPS62212389A (en) | 1987-09-18 |
Family
ID=12932899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5308386A Pending JPS62212389A (en) | 1986-03-11 | 1986-03-11 | N-alkyldihydropyrrolopyrrole compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62212389A (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
- 1986-03-11 JP JP5308386A patent/JPS62212389A/en active Pending
Cited By (4)
| 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 |
| 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 |
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