JP6016909B2 - パラジウム系触媒を使用した直接的chアリール化方法 - Google Patents
パラジウム系触媒を使用した直接的chアリール化方法 Download PDFInfo
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- JP6016909B2 JP6016909B2 JP2014520151A JP2014520151A JP6016909B2 JP 6016909 B2 JP6016909 B2 JP 6016909B2 JP 2014520151 A JP2014520151 A JP 2014520151A JP 2014520151 A JP2014520151 A JP 2014520151A JP 6016909 B2 JP6016909 B2 JP 6016909B2
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F234/00—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
- C08F234/04—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring in a ring containing sulfur
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- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
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- H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
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- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- B01J2531/82—Metals of the platinum group
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- C08G2261/1412—Saturated aliphatic units
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Description
<発明を実施するための形態>
3,4−ジメチル−TP,14,15及び単一アシル化化合物16の結果である2つがアシル化された化合物1H NMRスペクトルは、それぞれメチル基水素で(N=CCH3−CCH3=N)から発生したα−methine陽子及び単一ピーク2.66,2.57及び2.54ppmの不在を示す。
次に、TP基盤のπ−共役された共重合体を作るめの簡単な合成方法を紹介するために、TP残基の簡便なアシル化の長所について説明する(反応式5及び表1)。
多様な反応条件を試みた後、Pd(PPh3)4の存在下で15分間130℃DMFで4aと18又は20のCH−アシル化を行い、部分的に溶解された共重合体を形成した(それぞれP1’及びP2’)。しかし、長い反応時間及び/又は高い温度、一般的な極小量の有機溶媒で溶けるポリマーのための重合反応を実施した。
共重合体P1’及びP2’の溶解度部分の1H NMRスペクトルは、スチレ交差結合方式を介して得たP1及びP2と比較すると互いに異なることが分かった。P1’及びP2’に対する1H NMRは、それぞれN原子に隣接するα−methine陽子で発生した広範囲の単一ピークca.8.56及びca.8.50ppm(N=CH−C=N;積分値、1)、そしてピークの積分値の複写、図1で説明したP1’及びP2’構造の一致をそれぞれ示す。
面白くも、Heck反応条件において、3,4−ジメチル−TP 5aと18又は20のパラジウム触媒を利用したCHアシル化反応は高い歩留(92%及び94%、表1)の共重合体を提供し、スチレ交差結合方法を介して準備された共重合体P3及びP4と比較するとそれらの1H NMR及びUV−visスペクトルデータは同じであることが分かった。
即ち、本発明による製造方法は高級有機物質のようなものに潜在的に使用することができ、このような反応は様々なπ−共役されたオリゴ及び/又は二種高分子芳香族システムの強力な道具であり、チエノピラジンライブラリーを建設するために潜在的に効果的なものであって、アリール置換チエノピラジンの多様な組み合わせの合成に活用することができる。
<発明を実施するための形態>
<実施例>
<実験準備部分>
Potentiostate/Galvanostate(SP−150 OMA company);電解質はスキャン速度50mVs−1でアセト二トリル溶媒下でテトラブチルアルミニウムヘキサフルオロフォスフェート(TBAPF6)0.1M濃度で測定した。3電極セルを使用した;プラチナワイヤと銀/塩化銀(Ag in 0.1M KCl)がそれぞれカウンタ及び参照電極として使用された。電子測定のためのポリマーフィルムはITOガラススライドにポリマー−クロロベンゼン溶媒でスピンコーティングした(ca.10mg/mL)ゲル浸透クロマトグラフィ分析はシマヅ(LC−20A Prominence Series)機械で行い、クロロフォルムは運搬溶媒トして使用され(flow rate:1mL/min,at 30℃)、補正曲線はポリスチレン標準サンプルで処理した。マイクロ波補助重合反応はマイクロ波合成システムCEM(Discover S−class System)で行われた。低い温度反応は本質的に低温槽(PSL1810−SHANGHA EYELA)で行われた。KD Scientific注射器ポンプ(KDS−100)は精密に分配し、一滴ずつ追加するプロセスを行う間で正確な量の試薬を提供するために使用された。
5,7−ジブロモチエノ[3,4−b]ピラジン(5a,0.5g,1.70mmol)、2−(3−hexylthiophen−2−yl)−4,4−5,5−tetraメチル−1,3,2−dioxaborolane(12,1.25g,4.25mmol)及びPd(PPh3)4(0.5g,43.5mol%)の混合物をトルエン(35mL)に溶かして20分間窒素でガスを除去した後、K2CO3(2M,30mL)水溶液を添加する。反応混合物を激しく攪拌し、12時間100℃で還流させる。冷やしてから反応混合物をCH2Cl2で抽出し、有機層を収集して水で洗浄した後、無水硫酸ナトリウムで乾燥する。溶媒は減圧下で蒸留させ、精製前の化合物をフラッシュシリカゲルカラムクロマトグラフィー(n−hexane/EtOAc=10:2)で精製して紫色の8aを得た。(0.70g,89% yield)。
DMF(50mL)に4a(1 equiv)を入れた溶液にpotassium acetate(6 equiv),tert−butylammonium bromide(2 equiv),2−ブロモ−3−hexylthiophen(6a,2 equiv)と最後にPlladium acetate(0.2 equiv)を入れて攪拌した。生成された懸濁液を80℃で一晩攪拌した。反応が終了した後、混合物を室温に冷却させてCH2Cl2と水を入れた。有機層を分離して濃縮した。暗い色のオイル結果物をn−hexane/EtOAc(2%)の条件下でフラッシュシリカゲルクロマトグラフィで精製し、紫色の固体化合物8a(50% yield)と粘性のある紫色のオイル9a(22% yield)を得た。
DMF(50mL)に4a(1 equiv)を入れた溶液にpotassium acetate(6 equiv),tert−butylammonium bromide(2 equiv),2−ブロモ−3−メチルチオフェン(6b,5 equiv)と最後にPlladium acetate(0.2 equiv)を入れて攪拌した。生成された懸濁液を80℃で一晩攪拌した。反応が終了した後、混合物を室温に冷却させてCH2Cl2と水を入れた。有機層を分離して濃縮した。暗い色のオイル結果物をn−hexane/EtOAc(2%)の条件下でフラッシュシリカゲルクロマトグラフィで精製し、濃い紫色の固体化合物8b(77% yield)と紫色の固体9b(18% yield)を得た。
5a(0.5g,1.70mmol)、2−(4−hexylthiophen−2−yl)−4,4−5,5−tetraメチル−1,3,2−dioxaborolane(13,1.25g,4.25mmol)及びPd(PPh3)4(0.5g,43.5mol%)の混合物をトルエン(35mL)に溶かして20分間窒素でガスを除去した後、K2CO3(2M,30mL)水溶液を添加する。反応混合物を激しく攪拌し、12時間100℃で還流させる。冷やしてから反応混合物をCH2Cl2で抽出し、有機層を収集して水で洗浄した後、無水硫酸ナトリウムで乾燥する。溶媒は減圧下で蒸留させ、精製前の化合物をフラッシュシリカゲルカラムクロマトグラフィー(n−hexane/EtOAc=10:2)で精製して濃い紫色の固体10を得た。(0.67g,85% yield)。
DMF(50mL)に4a(1 equiv)を入れた溶液にpotassium acetate(6 equiv),tert−butylammonium bromide(2 equiv),2−ブロモ−4−hexylthiophen(7,3 equiv)と最後にPlladium acetate(0.2 equiv)を入れて攪拌した。生成された懸濁液を80℃で一晩攪拌した。反応が終了した後、混合物を室温に冷却させてCH2Cl2と水を入れた。有機層を分離して濃縮した。暗い色のオイル結果物をn−hexane/EtOAc(2%)の条件下でフラッシュシリカゲルクロマトグラフィで精製し、紫色の固体化10(60% yield)と粘性のある紫色のオイル11(33% yield)を得た。
5,7−ジブロモ−2,3−ジメチルチエノ[3,4−b]ピラジン(5b,0.5g,1.55mmol)、2−(3−hexylthiophen−2−yl)−4,4−5,5−tetraメチル−1,3,2−dioxaborolane(12,1.14g,3.88mmol)及びPd(PPh3)4(0.5g,43.5mol%)の混合物をトルエン(35mL)に溶かして20分間窒素でガスを除去した後、K2CO3(2M,30mL)水溶液を添加する。混合物を激しく攪拌し、12時間100℃で還流させる。冷やしてから反応混合物をCH2Cl2で抽出し、有機層を収集して水で洗浄した後、無水硫酸ナトリウムで乾燥する。溶媒は減圧下で蒸留させ、精製前の化合物をフラッシュシリカゲルカラムクロマトグラフィー(n−hexane/EtOAc=10:2)で精製して濃い赤色の固体化合物14を得た。(0.71g,92% yield)。
DMF(50mL)に4b(1 equiv)を入れた溶液にpotassium acetate(6 equiv),tert−butylammonium bromide(2 equiv),2−ブロモ−3−へキシルチオフェン(6a,3 equiv)と最後にPlladium acetate(0.2 equiv)を入れて攪拌した。生成された懸濁液を80℃で一晩攪拌した。反応が終了した後、混合物を室温に冷却させてCH2Cl2と水を入れた。有機層を分離して濃縮した。暗い色のオイル結果物をn−hexane/EtOAc(2%)の条件下でフラッシュシリカゲルクロマトグラフィで精製して濃い赤色の固体化合物14を得た。(93% yield)。1H NMR(CDCl3,400MHz,δ/ppm):7.39−7.38(d,J=4Hz,2H,CH−S)、7.05−7.04(d,J=4Hz,2H,CH−C−hexyl)、2.91−2.88(t,J=12Hz,4H,2XArCH2CH2−)、2.66(s,6H,2XN=C−CH3)、1.76−1.73(m,4H,2XArCH2CH−)、1.47−1.31(m,12H,2XCH3(CH2)3)、0.91−89(t,J=8Hz,6H,2XCH3)。13C NMR(CDCl3,100MHz,δ/ppm):152.82,141.13,138.37,135.67,126.34,125.46,124.17,31.67,30.45,29.99,29.36,23.53,22.59,14.05。C28H36N2S3(496.79):calcd.C67.69,H7.30,N5.64,S19.36;found C67.77,H7.39,N5.55,S19.30。
5n(0.5g,1.55mmol)、2−(4−hexylthiophen−2−yl)−4,4,5,5−tetraメチル−1,3,2−dioxaborolane(13,1.14g,3.88mmol)and Pd(PPh3)4(0.5g,43.5mol%)の混合物をトルエン(35mL)に溶かして20分間窒素でガスを除去した後、K2CO3(2M,30mL)水溶液を添加する。混合物を激しく攪拌し、12時間100℃で還流させる。冷やしてから反応混合物をCH2Cl2で抽出し、有機層を収集して水で洗浄した後、無水硫酸ナトリウムで乾燥する。溶媒は減圧下で蒸留させ、精製前の化合物をフラッシュシリカゲルカラムクロマトグラフィー(n−hexane/EtOAc=10:2)で精製して濃い紫色の固体15を得た。(0.68g,88% yield)。
Method B:CH−arylation
乾燥したTHF(65mL)に3,3’−dihexyl−2,2’−biチオフェン:(1.7g,5.08mmol)を入れて氷で冷たく冷却させた後、NBS(2.26g,12.70mmol)を追加する。0℃で30分間攪拌した後、追加に反応混合物を常温で一晩攪拌し、NH4Cl飽和水溶液で処理(quenching)する。反応混合物をエチルアセテートで抽出した後、有機層を水で洗浄する。有機層を収集して無水硫酸ナトリウムで乾燥し、真空下で残余有機溶媒を除去する。精製前の混合物をフラッシュシリカゲルカラムクロマトグラフィー(n−hexane/EtOAc=10:2)で精製して黄色のオイル化合物20を得た。(2.35g,94% yield)。1H NMR(400MHz,CDCl3):δ=6.90(s,2H,2XCH−Br)、2.44−2.40(t,J=16Hz,4H,2XArCH2)、1.66(m,4H,2XArCH2CH2)、1.25−1.22(m,12H,2XCH3(CH2)3)、and 0.87−0.84(t,J=12Hz,6H,2XArCH3)ppm。13C NMR(100MHz,CDCl3):δ=143.81,131.37,128.83,112.35,31.56,30.49,28.96,28.71,22.58,14.05ppm。C20H28Br2S2(492.37):calcd.C48.79,H5.73,Br32.46,S13.02;found C48.67,H5.81,Br32.29,S13.15。
よく乾燥されたねじ蓋型のガラス管に同モル比で望みのジブロモとdi−tributylstannyl誘導体(0.5mmol)を入れて乾燥されたDMFに溶かした後、30分間窒素を使用して混合物に内包されたガスを除去してから、Pd(PPh)4(5mol%,relative to Br)を入れる。蓋があるガラス管をマイクロ波反応機に入れ、以下の条件下で照査する:5min 100℃で5分、120℃で5分、150℃で30分。末端封鎖作業は2ステップで行われる。まず、phenylboronic acid pinacol esterを使用し、次にボロモbenzeneを使用した。末端封鎖条件:100℃で2分、120℃で2分、150℃で5分。次に、最後の末端封鎖方法として、マイクロ波ねじ蓋ガラス管を室温に上昇させてから反応混合物にメタノールを注ぐ。精製前のポリマーは濾過して収集し、続いてメタノールで洗浄した。残留固体を円筒濾紙にロードし、メタノールで24時間、続いてアセトンで24時間洗浄した後、真空で乾燥してからGPC及び1H NMR分析器を介して分析した。
よく乾燥されたねじ蓋型のガラス管に同モル比で望みのジブロモと不飽和EDOT誘導体(0.5mmol)を入れ、乾燥されたDMF(20mL)に溶かした後、20分間窒素を使用して混合物に内包されたガスを除去してから、Potassium acetate(6.0 equiv),tetrabutylammonium bromide(TBAB;2.0 equiv)及びPd(OAc)2(0.2 equiv)を窒素状態下で追加する。蓋があるガラス管をマイクロ波反応機に入れ、以下の条件下で照査する:5 min 100℃で5分、120℃で5分、100℃で30分。末端封鎖はphenylboronic acid pinacol esterを使用して1ステップで行った。末端封鎖条件は以下のようである:100℃で2分、120℃で2分、最後に150℃で5分。マイクロ波ねじ蓋ガラス管を室温に上昇させた後、反応混合物にメタノールを注ぐ。精製前のポリマーは濾過して収集し、続いてメタノールで洗浄した。残留固体を円筒濾紙にロードし、メタノールで48時間、続いてアセトンで48時間洗浄した後、真空で乾燥してからGPC及び1H NMR分析器を介して分析した。
1H NMR(CDCl3,400MHz,δ/ppm):7.52(br s,2H,2XCHC−hexyl)、2.65−2.63(br s,10H,2XAr−CH2CH2+2XN=CCH3)、1.67−1.59(br m,4H,2XAr−CH2CH2−)、1.35−1.29(br m,12H,2XCH3(CH2)3)、0.91−0.85(br m,6H,2XCH3)。(C28H34N2S3)n(494.78)n:calcd.C67.97,H6.93,N5.66,S19.44;found C68.13,H6.85,N5.77,S19.36。
Claims (4)
- 第1単量体及び第2単量体をPdを含む触媒下で反応させるステップを含む下記化10の共重合体の製造方法であって、
前記第1単量体は下記化3の化合物であり、
前記第2単量体は下記化5乃至9の化合物又はそれらの混合物のうちから選択され、
前記反応は酢酸カリウム(KOAc)及びt−Bu4NBrを含むN,N−ジメチルフォルムアミドの中で行われることを特徴とする前記化10の共重合体の製造方法。 - 前記第1単量体はチエノピラジン誘導体であることを特徴とする請求項1に記載の化10の共重合体の製造方法。
- 第1単量体及び第2単量体をPdを含む触媒下で反応させるステップを含む共重合体の製造方法であって、
前記第1単量体はS,N,Oのうちから選択された第1ヘテロ原子を含む第1ヘテロ環式化合物であって、前記第1ヘテロ原子と隣接した炭素原子に少なくとも一つ以上の水素原子が結合されている第1ヘテロ環式化合物であり、
前記第2単量体は下記化5の第2ヘテロ環式化合物であり、
下記化5においてYはS,O,Nのうちから選択され、R’’はフェニル基を示し、X,X’はそれぞれ独立的にBr,Cl,Iのうちから選択され、
前記第1単量体はチエノピラジン誘導体であることを特徴とする共重合体の製造方法。
- 前記Pdを含む触媒はPd(OAc)2であることを特徴とする請求項1または3に記載の共重合体の製造方法。
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