Dppz配体10,13-位由芳香基取代的新型单核钌配合物的合成
|
摘要
目的本论文以1,10-邻菲罗啉(1,10-phenanthroline,phen)为辅助配体,在主配体联吡啶类(3,2-a:2'-3'-c)吩嗪[pyrido-(3,2-a:2',3'-c) phenazine,dppz]的10,13-位分别引入噻吩、苯并噻吩、呋喃及苯并呋喃,设计并合成出对应4种新型单核二-(1,10-邻菲罗啉)-吡啶类(3,2-a:2'-3'-c)吩嗪合钌(Ⅱ)衍生物。方法首先通过Suzuki偶联反应得到4种苯并噻二唑中间体,然后经Co Cl2催化、Na BH4还原得到邻苯二胺类化合物,再经缩合反应得到对应的目标配合物。结果苯并噻二唑中间体及对应的4种目标配合物通过磁共振氢谱、碳谱及高分辨质谱表征,紫外-可见吸收光谱进一步验证了目标配合物结构的正确性。结论本论文通过多步反应合成出以1,10-邻菲罗啉为辅助配体,主配体dppz的10,13-位分别含有噻吩、苯并噻吩、呋喃及苯并呋喃的4种新型单核多吡啶钌配合物。紫外-可见吸收光谱实验表明尽管4种芳香取代基结构有差异,对应苯并噻二唑中间体和钌配合物的吸收光谱相似。
Objective Four new ruthenium complexes with 1,10-phenanthroline ancillary ligand and 10,13-position substituted[pyrido-( 3,2-a: 2',3'-c) phenazine,dppz]major ligands including thiophenyl,furanyl,[2-benzo( b) thienyl]-2,1,3-benzothiadiazole and[2-benzo( b) furanyl]-2,1,3-benzothiadiazole will be designed and synthesized. Methods Target complexes were made by condensation reaction of ruthenium complex with the appropriate 3,6-diaryl substituted benzene-1,2-diamine. The latter 3,6-diaryl substituted benzene-1,2-diamine was obtained by a Suzuki-coupling reaction,and subsequently by reduction with Na BH4 under catalysis of Co Cl2. Results Benzothiadiazole intermediates and corresponding target complexes are well characterized by1 H nuclear magnetic resonance( NMR),13 C NMR and TOF-Mass. UV-vis absorption spectra of all ruthenium complexes further verify the structures of the target complexes. Conclusion In this paper,we have synthesized four mononuclear ruthenium complexes with 1,10-phenanthroline ancillary ligand and 10,13-diaryl including thiophenyl,furanyl,[2-benzo( b) thienyl]-2,1,3-benzothiadiazole and [2-benzo( b) furanyl]-2,1,3-benzothiadiazole, substituted dppz as major ligand through multiple steps. Both four 4,7-position substituted 2,1,3-benzothiadiazole intermediates and corresponding ruthenium complexes exhibit substantially similar absorption spectra despite the structural difference.
Objective Four new ruthenium complexes with 1,10-phenanthroline ancillary ligand and 10,13-position substituted[pyrido-( 3,2-a: 2',3'-c) phenazine,dppz]major ligands including thiophenyl,furanyl,[2-benzo( b) thienyl]-2,1,3-benzothiadiazole and[2-benzo( b) furanyl]-2,1,3-benzothiadiazole will be designed and synthesized. Methods Target complexes were made by condensation reaction of ruthenium complex with the appropriate 3,6-diaryl substituted benzene-1,2-diamine. The latter 3,6-diaryl substituted benzene-1,2-diamine was obtained by a Suzuki-coupling reaction,and subsequently by reduction with Na BH4 under catalysis of Co Cl2. Results Benzothiadiazole intermediates and corresponding target complexes are well characterized by1 H nuclear magnetic resonance( NMR),13 C NMR and TOF-Mass. UV-vis absorption spectra of all ruthenium complexes further verify the structures of the target complexes. Conclusion In this paper,we have synthesized four mononuclear ruthenium complexes with 1,10-phenanthroline ancillary ligand and 10,13-diaryl including thiophenyl,furanyl,[2-benzo( b) thienyl]-2,1,3-benzothiadiazole and [2-benzo( b) furanyl]-2,1,3-benzothiadiazole, substituted dppz as major ligand through multiple steps. Both four 4,7-position substituted 2,1,3-benzothiadiazole intermediates and corresponding ruthenium complexes exhibit substantially similar absorption spectra despite the structural difference.
引文
[1] Gill M R,Thomas J A. Ruthenium(Ⅱ)polypyridyl complexes and DNA-from structural probes to cellular imaging and therapeutic[J]. Chem Soc Rev,2012,41(8):3179-3192.
[2] Zhu Z,Xu L,Li H,et al. A tetraphenylethene-based zinc complex as a sensitive DNA probe by coordination interaction[J]. Chem Commun,2014,50(53):7060-7062.
[3] Pothayee N,Pothayee N,Hu N,et al. Manganese graft ionomer complexes(MaGICs)for dual imaging and chemotherapy[J]. J Mater Chem B,2014,2(8):1087-1099.
[4] Chen Y,Lei W,Jiang G Y,et al. Fusion of photodynamic therapy and photoactivated chemotherapy:a novel Ru(Ⅱ)arene complex with dual activities of photobinding and photocleavage toward DNA[J]. Dalton Trans,2014,43(41):15375-15384.
[5] Alam P,Das P,Climent C,et al. Facile tuning of the aggregation-induced emission wavelength in a common framework of a cyclometalated iridium(Ⅲ)complex:micellar encapsulated probe in cellular imaging[J]. J Mater Chem C,2014,2(28):5615-5628.
[6] Banik B,Somyajit K,Nagaraju G,et al. Oxovanadium(IV)complexes of curcumin for cellular imaging and mitochondria targeted photocytotoxicity[J]. Dalton Trans,2014,43(35):13358-13369.
[7] Friedman A E,Chambron J C,Sauvage J P,et al. A molecular light switch for DNA:Ru(bpy)2(dppz)2+[J]. J Am Chem Soc,1990,112(12):4960-4962.
[8] Puckett C A,Barton J K. Targeting a ruthenium complex to the nucleus with short peptides[J]. Bioorg Med Chem,2010,18(10):3564-3569.
[9] Fox K R,Brassett C,Waring M J. Kinetics of dissociation of nogalamycin from DNA:comparison with other anthracycline antibiotics[J]. Biochim Biophys Acta,1985,840(3):383-392.
[10] Wilhelmsson L M,Westerlund F,Lincoln P,et al. DNABinding of semirigid binuclear ruthenium complexΔ,Δ-[μ-(11,11‘-bidppz)(phen)4Ru2]4+:extremely slow intercalation kinetics[J]. J Am Chem Soc,2002,124(41):12092-12093.
[11] Sato S,Nojima T,Waki M,et al. Supramolecular complex formation byβ-cyclodextrin and ferrocenylnaphthalene dⅡmide-intercalated double stranded DNA and improved electrochemical gene detection[J]. Molecules,2005,10(6):693-707.
[12] Nordell P,Westerlund F,Wilhelmsson L M,et al. Kinetic Recognition of AT-Rich DNA by ruthenium complexes[J].Angew Chem Int Ed,2007,46(13):2203-2207.
[13] Westerlund F,Nordell P,Blechinger J,et al. Complex DNA binding kinetics resolved by combined circular dichroism and luminescence analysis[J]. J Phys Chem B,2008,112(21):6688-6694.
[14] Andersson J,Li M N,Lincoln P. AT-Specific DNA binding of binuclear ruthenium complexes at the border of threading intercalation[J]. Chem Eur J,2010,16(36):11037-11042.
[15] Li M,Lincoln P. Synthesis and DNA threading properties of quaternary ammonium[Ru(phen)2(dppz)]2+derivatives[J]. J Inorg Biochem,2009,103(7):963-970.
[16] Li M,Lincoln P,Andersson J. Slow Threading intercalation of monomeric Ru(Ⅱ)complexes with 10,13-diarylsubstituted dppz ligands[J]. J Phys Chem B,2011,115(24):7923-7931.
[17] Li M N,Zhao M,Peng S Q. Synthesis of enantiomers of mononuclear Ru(Ⅱ)complexes with 10,13-diaryl substituted dppz ligands[J]. Inorg Chem Commun,2013,36:130-132.
[18] Sullivan B P,Salmon D J,Meyer T J. Mixed phosphine 2,2'-bipyridine complexes of ruthenium[J]. Inorg Chem,1978,17(12):3334-3341.
[19] Hiort C,Lincoln P,Norden B. DNA binding of DELTA and LAMBDA-[Ru(phen)2DPPZ]2+[J]. J Am Chem Soc,1993,115(9):3448-3454.
[20] Dasilveria Neto B A,Lopes A S,Wüst M,et al. Reductive sulfur extrusion reaction of 2,1,3-benzothiadiazole compounds:a new methodology using Na BH4/Co Cl2·6H2O as the reducing system[J]. Tetrahedron Lett,2005,46(40):6843-6846.
[2] Zhu Z,Xu L,Li H,et al. A tetraphenylethene-based zinc complex as a sensitive DNA probe by coordination interaction[J]. Chem Commun,2014,50(53):7060-7062.
[3] Pothayee N,Pothayee N,Hu N,et al. Manganese graft ionomer complexes(MaGICs)for dual imaging and chemotherapy[J]. J Mater Chem B,2014,2(8):1087-1099.
[4] Chen Y,Lei W,Jiang G Y,et al. Fusion of photodynamic therapy and photoactivated chemotherapy:a novel Ru(Ⅱ)arene complex with dual activities of photobinding and photocleavage toward DNA[J]. Dalton Trans,2014,43(41):15375-15384.
[5] Alam P,Das P,Climent C,et al. Facile tuning of the aggregation-induced emission wavelength in a common framework of a cyclometalated iridium(Ⅲ)complex:micellar encapsulated probe in cellular imaging[J]. J Mater Chem C,2014,2(28):5615-5628.
[6] Banik B,Somyajit K,Nagaraju G,et al. Oxovanadium(IV)complexes of curcumin for cellular imaging and mitochondria targeted photocytotoxicity[J]. Dalton Trans,2014,43(35):13358-13369.
[7] Friedman A E,Chambron J C,Sauvage J P,et al. A molecular light switch for DNA:Ru(bpy)2(dppz)2+[J]. J Am Chem Soc,1990,112(12):4960-4962.
[8] Puckett C A,Barton J K. Targeting a ruthenium complex to the nucleus with short peptides[J]. Bioorg Med Chem,2010,18(10):3564-3569.
[9] Fox K R,Brassett C,Waring M J. Kinetics of dissociation of nogalamycin from DNA:comparison with other anthracycline antibiotics[J]. Biochim Biophys Acta,1985,840(3):383-392.
[10] Wilhelmsson L M,Westerlund F,Lincoln P,et al. DNABinding of semirigid binuclear ruthenium complexΔ,Δ-[μ-(11,11‘-bidppz)(phen)4Ru2]4+:extremely slow intercalation kinetics[J]. J Am Chem Soc,2002,124(41):12092-12093.
[11] Sato S,Nojima T,Waki M,et al. Supramolecular complex formation byβ-cyclodextrin and ferrocenylnaphthalene dⅡmide-intercalated double stranded DNA and improved electrochemical gene detection[J]. Molecules,2005,10(6):693-707.
[12] Nordell P,Westerlund F,Wilhelmsson L M,et al. Kinetic Recognition of AT-Rich DNA by ruthenium complexes[J].Angew Chem Int Ed,2007,46(13):2203-2207.
[13] Westerlund F,Nordell P,Blechinger J,et al. Complex DNA binding kinetics resolved by combined circular dichroism and luminescence analysis[J]. J Phys Chem B,2008,112(21):6688-6694.
[14] Andersson J,Li M N,Lincoln P. AT-Specific DNA binding of binuclear ruthenium complexes at the border of threading intercalation[J]. Chem Eur J,2010,16(36):11037-11042.
[15] Li M,Lincoln P. Synthesis and DNA threading properties of quaternary ammonium[Ru(phen)2(dppz)]2+derivatives[J]. J Inorg Biochem,2009,103(7):963-970.
[16] Li M,Lincoln P,Andersson J. Slow Threading intercalation of monomeric Ru(Ⅱ)complexes with 10,13-diarylsubstituted dppz ligands[J]. J Phys Chem B,2011,115(24):7923-7931.
[17] Li M N,Zhao M,Peng S Q. Synthesis of enantiomers of mononuclear Ru(Ⅱ)complexes with 10,13-diaryl substituted dppz ligands[J]. Inorg Chem Commun,2013,36:130-132.
[18] Sullivan B P,Salmon D J,Meyer T J. Mixed phosphine 2,2'-bipyridine complexes of ruthenium[J]. Inorg Chem,1978,17(12):3334-3341.
[19] Hiort C,Lincoln P,Norden B. DNA binding of DELTA and LAMBDA-[Ru(phen)2DPPZ]2+[J]. J Am Chem Soc,1993,115(9):3448-3454.
[20] Dasilveria Neto B A,Lopes A S,Wüst M,et al. Reductive sulfur extrusion reaction of 2,1,3-benzothiadiazole compounds:a new methodology using Na BH4/Co Cl2·6H2O as the reducing system[J]. Tetrahedron Lett,2005,46(40):6843-6846.