Neste trabalho foram sintetizados cinco compostos aza-heterociclos alquilados derivados dos núcleos quinoxalina, benzimidazol e fenazina. Todos os compostos foram funcionalizados com cadeias laterais alquilicas com doze átomos de carbono. No tocante à etapa sintética as metodologias empregadas associadas à infraestrutura de nosso laboratório se mostraram satisfatórias de se realizar. Os rendimentos para as etapas de obtenção dos derivados alquilados estiveram entre 55-90%. Todos os derivados alquilados foram submetidos a analises de Microscopia Óptica de Luz Polarizada (MOLP). Apenas para o derivado 2-(4-(dodeciloxi)fenil)-1H- benzo[d]imidazol (48) pode-se observar a presença de textura que é compatível com comportamento liquido cristalino, sendo este composto então, o que se mostrou promissor para investigações futuras de suas propriedades como provável semicondutor orgânico. Pelas medidas de DSC ficou claro para o derivado (48) que outras fases existem em uma temperatura, um pouco superior a ambiente (onde o composto está na fase cristalina) e a temperatura de fusão do composto 177 °C, onde o composto está na fase de liquido isotrópico. Para o derivado dodecilquinoxalina-2,3 (1H)-diona (45) outras modificações estruturais devem ser feitas para que o composto venha a apresentar comportamento liquido cristalino. A medida de DSC para o derivado (45) mostrou não existirem realmente fases intermediarias entre a fase cristalina e a fase de liquido isotrópico para tal composto.
REFERÊNCIAS BIBLIOGRÁFICAS
A. R. Barron and Changsheng Xiang. 2014. “The Analysis of Liquid Crystal Phases Using Polarized Optical Microscopy.” Physical Methods in Chemistry and Nanoscience (smectic C):2–10.
Alaqeel, Shatha Ibrahim. 2017. “Synthetic Approaches to Benzimidazoles from O- Phenylenediamine: A Literature Review.” Journal of Saudi Chemical Society 21(2):229–37. Retrieved (http://dx.doi.org/10.1016/j.jscs.2016.08.001).
Anand, Siddeswaran, Athianna Muthusamy, Sengottuvelu Dineshkumar, and J. Chandrasekaran. 2017. “Oxidative Polycondensation of Benzimidazole Using NaOCl: Synthesis, Characterization, Optical, Thermal and Electrical Properties of Polybenzimidazoles.” Journal of Molecular Structure 1147:351–63. Retrieved (http://dx.doi.org/10.1016/j.molstruc.2017.06.113).
Ananth Reddy, M. et al. 2011. “Synthesis of Novel Twisted Carbazole-Quinoxaline Derivatives with 1,3,5-Benzene Core: Bipolar Molecules as Hosts for Phosphorescent OLEDs.” Tetrahedron Letters 52(51):6942–47. Retrieved (http://dx.doi.org/10.1016/j.tetlet.2011.10.074).
Arikainen, Ekaterina 0. et al. 1995. “Effects of Side-Chain Length on the Charge Transport Properties of Discotic Liquid Crystals and Their Implications for the Transport Mechanism.” J. Mater. Chem 5(12):2161–65.
Arts, Kongunadu, Tamil Nadu, and Tamil Nadu. 2014. “Kirubavathy et Al.,.” 5(6):2508–17.
Bansal, Yogita and Om Silakari. 2012. “The Therapeutic Journey of Benzimidazoles: A Review.” Bioorganic and Medicinal Chemistry 20(21):6208–36. Retrieved (http://dx.doi.org/10.1016/j.bmc.2012.09.013).
Bushby, Richard J. and Ken Kawata. 2011. “Liquid Crystals That Affected the World: Discotic Liquid Crystals.” Liquid Crystals 38(11–12):1415–26.
Bushey, M. L., A. Hwang, P. W. Stephens, and C. Nuckolls. 2001. “Enforced Stacking in Crowded Arenes [21].” Journal of the American Chemical Society 123(33):8157–
58.
Carcanague, D., Y. K. Shue, and M. A. Wuonola. 2002. “Novel Structures Derived from 2-[[(2-Pyridyl) Methyl]Thio]-1H- Benzimidazole as Anti-Helicobacter Pylori Agents, Part 2.” Journal of Medicinal Chemistry 45:4300–4309.
Chandrashekhar, N., Bejoy Thomas, V. Gayathri, K. V. Ramanathan, and N. M. Nanje Gowda. 2008. “Synthesis and NMR Spectral Assignments of Novel Nitrogen and Sulfur Heterocyclic Compounds.” Magnetic Resonance in Chemistry 46(8):769–74.
Cimmino, A. et al. 2012. “Phenazines and Cancer.” Natural Product Reports 29(4):487. Retrieved (http://xlink.rsc.org/?DOI=c2np00079b).
Claire Seillan, Hugues Brisset, and Olivier Siri. 2008. “Efficient Synthesis of Substituted Dihydrotetraazapentacenes.” Organic Letters 2010(09):1431–32.
Clayden, Jonathan; Greeves, Nick; Warren, Stuart; Wothers, Peter, Jonathan Clayden, Nick Greeves, Stuart Warren, and Peter Wothers. 2001. “Organic Chemistry.” Structure 32:1345–1412.
Danel, Andrzej, Ewa Gondek, and Iwan Kityk. 2009. “1H-Pyrazolo[3,4-b]Quinoline and 1H-Pyrazolo[3,4-b]Quinoxaline Derivatives as Promising Materials for Optoelectronic Applications.” Optical Materials 32(2):267–73. Retrieved (http://dx.doi.org/10.1016/j.optmat.2009.09.008).
Demirayak, Seref, Ahmet C. Karaburun, Ismail Kayagil, Umit Uçucu, and Rana Beis. 2005. “Synthesis and Analgesic Activities of Some 2-(Benzazolylacetyl) Amino-3- Ethoxycarbonylthiophene Derivatives.” Phosphorus, Sulfur, and Silicon and the Related Elements 180(8):1841–48.
Dierking, Ingo. 2003. Ferroelectric and Antiferroelectric Liquid Crystals.
Ecologia, Mestrado E. M. 2009. “Universidade Federal De Santa Catarina Programa De Pós-Graduação.” Ecologia 1–100.
Facchetti, Antonio. 2013. “Made to Order.” Nature Publishing Group 1–2. Retrieved (http://dx.doi.org/10.1038/nmat3686).
Gao, Baoxiang et al. 2008. “Pyrazine-Containing Acene-Type Molecular Ribbons with up to 16 Rectilinearly Arranged Fused Aromatic Rings.” Journal of the American Chemical Society 130(26):8297–8306.
Hu, Mingming et al. 2018. “Bipolar Carbazole/Quinoxaline-Based Host Materials for Efficient Red PhOLEDs.” Dyes and Pigments 150:185–92. Retrieved (http://dx.doi.org/10.1016/j.dyepig.2017.08.040).
Huang, Wei-sheng, Jiann T. Lin, Chin-hsing Chien, and Yu-tai Tao. 2004. “Highly Phosphorescent Bis-Cyclometalated Iridium Complexes Containing Benzoimidazole- Based Ligands.” (7):2480–88.
Inokuchi, Hiroo. 2006. “The Discovery of Organic Semiconductors. Its Light and Shadow.” Organic Electronics: Physics, Materials, Applications 7(2):62–76.
Itaya, Tomoyuki, Masahiro Ichihara, Makiko Sugibayashi, Lin Hwa Tai, and Kazuchika Ohta. 2009. “Very Unique Liquid Crystalline Phase Structures Having Two- Dimensional Silver Sheet for the Adducts of Phenazine and Silver Alkylsulfonates.” Molecular Crystals and Liquid Crystals 503(1):69–80.
Jaung, Jae Yun, Masaru Matsuoka, and Koushi Fukunishi. 1998. “Syntheses and Spectral Properties of New Dicyanopyrazine-Related Heterocycles from Diaminomaleonitrile.” Journal of Chemical Research - Part S (6):284–85.
Koden, Mitsuhiro. 2017. “OLED Displays and Lighting.”
Kokunov, Yu. V., Yu. E. Gorbunova, V. V. Kovalev, and S. a. Kozyukhin. 2013. “Synthesis, Crystal Structure, and Luminescent Properties of a Silver(I) Perrhenate Complex with Phenazine.” Russian Journal of Inorganic Chemistry 58(5):523–26. Retrieved (http://link.springer.com/10.1134/S0036023613050124).
Laursen, Jane Buus and John Nielsen. 2004. “Phenazine Natural Products: Biosynthesis, Synthetic Analogues, and Biological Activity.” Chemical Reviews 104(3):1663–85.
Lee, Ching K., Kuang-Mei Hsu, Chun-Hsien Tsai, Chung K. Lai, and Ivan J. B. Lin. 2004. “Liquid Crystals of Silver Complexes Derived from Simple 1-Alkylimidazoles.” Dalton Transactions (Cambridge, England : 2003) (8):1120–26. Retrieved
(http://www.ncbi.nlm.nih.gov/pubmed/15252650).
Lezcano, M., W. Al-Soufi, M. Novo, E. Rodríguez-Núñez, and J. Vázquez Tato. 2002. “Complexation of Several Benzimidazole-Type Fungicides with α- and β- Cyclodextrins.” Journal of Agricultural and Food Chemistry 50(1):108–12.
Liu, Qing Xiang, Zhao Quan Yao, Xiao Jun Zhao, Zhi Xiang Zhao, and Xiu Guang Wang. 2013. “NHC Metal (Silver, Mercury, and Nickel) Complexes Based on Quinoxaline-Dibenzimidazolium Salts: Synthesis, Structural Studies, and Fluorescent Chemosensors for Cu2+ by Charge Transfer.” Organometallics 32(12):3493–3501.
Liu, Xu Ying, Takayuki Usui, and Junichi Hanna. 2014. “Self-Directed Orientation of Molecular Columns Based on n-Type Hexaazatrinaphthylenes (HATNAs) for Electron Transport.” Chemistry - A European Journal 20(44):14207–12.
Lu, Yuanyuan et al. 2017. “Design, Facile Synthesis and Biological Evaluations of Novel Pyrano[3,2-a]Phenazine Hybrid Molecules as Antitumor Agents.” European
Journal of Medicinal Chemistry 127:928–43. Retrieved
(http://dx.doi.org/10.1016/j.ejmech.2016.10.068).
Lugger, Jody A. M. and Rint P. Sijbesma. 2016. “Easily Accessible Thermotropic Hydrogen-Bonded Columnar Discotic Liquid Crystals from Fatty Acid??? Tris- Benzoimidazolyl Benzene Complexes.” ChemistryOpen 5(6):580–85.
Martins, Assis Farinha. 1991. “Os Cristais Líquidos.” Independent 7:253.
Matsui, Masaki et al. 2008. “Reaction, Identification, and Fluorescence of Aminoperfluorophenazines.” Tetrahedron 64(37):8830–36.
Meier, Gerhard, Erich Sackmann, and Josef G. Grabmaier. 1975. Applications of Liquid Crystals.
MENEZES. 2010. “Hexabromoacetona Na Preparação De Amidas. Síntese E Reatividade De Derivados De Benzimidazol E Quinoxalina.”
Moris, Marc Antoine et al. 2015. “2,3-Dialkoxyphenazines as Anticancer Agents.”
Tetrahedron Letters 56(21):2695–98. Retrieved
Murthy, Sabbavarapu Narayana, Bandaru Madhav, and Yadavalli Venkata Durga Nageswar. 2010. “Revisiting the Hinsberg Reaction: Facile and Expeditious Synthesis of 3-Substituted Quinoxalin-2(1H)-Ones under Catalyst-Free Conditions in Water.” Helvetica Chimica Acta 93(6):1216–20.
P, Mehendale Nitin and Pramila T. Gowda. 2012. “Issn 2230 – 8407 Synthesis and Antifungal Activity of Some Substituted Benzimidazole Analogues.” 3(7):189–94.
Panda, Siva S. and Subhash C. Jain. 2011. “Synthesis of 2-Arylbenzimidazoles in Water.” Synthetic Communications 41(5):729–35.
Park, Yoon Sun et al. 2018. “Molecular and Cellular Toxicological Profiling of DNA Bis-Intercalator, Quinoxaline Compounds: Echinomycin as the Versatile Lead.” Molecular and Cellular Toxicology 14(1):9–18.
Perrin, Leah C. et al. 2000. “DNA Targeted Platinum Complexes: Synthesis, Cytotoxicity and DNA Interactions of Cis-Dichloroplatinum(II) Complexes Tethered to Phenazine-1- Carboxamides.” Journal of Inorganic Biochemistry 81(1–2):111–17.
Pisula, Wojciech, Marcel Kastler, Daniel Wasserfallen, Tadeusz Pakula, and Klaus Mu. 2004. “Exceptionally Long-Range Self-Assembly of Hexa-Peri-Hexabenzocoronene with Dove-Tailed Alkyl Substituents.” 8074–75.
Przybylski, Piotr, Katarzyna Pyta-Klich, Krystian Pyta, and Anna Janas. 2018. “Cascade Reactions as Efficient and Universal Tools for Construction and Modification of 6-, 5-, 4- and 3-Membered Sulfur Heterocycles of Biological Relevance.”
Tetrahedron. Retrieved
(https://linkinghub.elsevier.com/retrieve/pii/S0040402018310913).
Ramalingam, P., S. Ganapaty, and Ch Babu Rao. 2010. “In Vitro Antitubercular and Antimicrobial Activities of 1-Substituted Quinoxaline-2,3(1H,4H)-Diones.” Bioorganic
and Medicinal Chemistry Letters 20(1):406–8. Retrieved
(http://dx.doi.org/10.1016/j.bmcl.2009.10.026).
Reddy, M. Rajeshkumar, Si Hyun Han, Jun Yeob Lee, and Sung Yong Seo. 2018. “Synthesis and Characterization of Quinoxaline Derivative for High Performance Phosphorescent Organic Light-Emitting Diodes.” Dyes and Pigments 153:132–36.
Retrieved (https://doi.org/10.1016/j.dyepig.2018.02.020).
Rivera, Ricardo and Ingrid Teixeira. 2014. “Perspectivas Para a Eletrônica OrgâNica No Brasil.” Biblioteca Digital BNDES 40:427–80.
Savić, Nada D. et al. 2016. “A Comparative Antimicrobial and Toxicological Study of Gold( Iii ) and Silver( i ) Complexes with Aromatic Nitrogen-Containing Heterocycles: Synergistic Activity and Improved Selectivity Index of Au( Iii )/Ag( i ) Complexes
Mixture.” RSC Adv. 6(16):13193–206. Retrieved
(http://www.scopus.com/inward/record.url?eid=2-s2.0- 84956902390&partnerID=tZOtx3y1).
Shen, Chao et al. 2018. “Incorporating Quinoxaline Unit as Additional Acceptor for Constructing Efficient Donor-Free Solar Cell Sensitizers.” Dyes and Pigments 149:65– 72. Retrieved (https://doi.org/10.1016/j.dyepig.2017.09.055).
Shen, Yuqiang et al. 2017. “Novel Benzimidazole-Containing Heterocyclic Compounds: Synthesis, Physical Properties and OLED Application.” ChemistrySelect 2(34):11206–10. Retrieved (http://doi.wiley.com/10.1002/slct.201701977).
Shi, Da Qing, Guo L. Dou, Sai N. Ni, Jing W. Shi, and Xiao Y. Li. 2008. “An Efficient Synthesis of Quinoxaline Derivatives Mediated by Stannous Chloride.” Journal of Heterocyclic Chemistry 45(6):1797–1801.
Shigehiro, Tatsuya et al. 2005. “Novel 10,13-Disubstituted Dipyrido[3,2-a:2′,3′- c]Phenazines and Their Platinum(II) Complexes: Highly Luminescent ICT-Type Fluorophores Based on D-A-D Structures.” Tetrahedron Letters 55(37):5195–98. Retrieved (http://dx.doi.org/10.1016/j.tetlet.2014.07.069).
Singh, Shri. 2002. Liquid Crystals: Fundamentals. Retrieved (http://books.google.com/books?hl=en&lr=&id=eAso5CIN44MC&oi=fn d&pg=PR5&dq=LIQUID+CRYSTALS+Fundamentals&ots=A2GckpR8 oP&sig=myu_mtVLlJv64yF_9U9NtcLQJYo).
Song, Ho Jun et al. 2015. “Conjugated Polymer Consisting of Benzothiadiazole and Phenazine as Donor Materials for Organic Photovoltaics.” Journal of Industrial and
(http://dx.doi.org/10.1016/j.jiec.2014.08.037).
Song, Ho Jun et al. 2013. “Enhancement of External Quantum Efficiency through Steric Hindrance of Phenazine Derivative for White Polymer Light-Emitting Diode
Materials.” Synthetic Metals 181:98–103. Retrieved
(http://dx.doi.org/10.1016/j.synthmet.2013.08.017).
Spiess, H. and V. Vill. n.d. Of Liquid Crystals 6B WILEYVCH.
Sun, Yongduo et al. 2009. “Derivative with High Electron and Hole Mobilities.” Organic Letters 11(10):2–6.
Tang, C. W. and S. A. Vanslyke. 1987. “Organic Electroluminescent Diodes.” Applied Physics Letters 51(12):913–15.
Tanimori, Shinji, Takeshi Nishimura, and Mitsunori Kirihata. 2009. “Synthesis of Novel Quinoxaline Derivatives and Its Cytotoxic Activities.” Bioorganic and
Medicinal Chemistry Letters 19(15):4119–21. Retrieved
(http://dx.doi.org/10.1016/j.bmcl.2009.06.007).
Tariq, Sana, K. Somakala, and Mohd Amir. 2018. “Quinoxaline: An Insight into the Recent Pharmacological Advances.” European Journal of Medicinal Chemistry 143:542–57. Retrieved (https://doi.org/10.1016/j.ejmech.2017.11.064).
Tonzola, Christopher J., Maksudul M. Alam, Werner Kaminsky, and Samson A. Jenekhe. 2003. “New N-Type Organic Semiconductors: Synthesis, Single Crystal Structures, Cyclic Voltammetry, Photophysics, Electron Transport, and Electroluminescence of a Series of Diphenylanthrazolines.” Journal of the American Chemical Society 125(44):13548–58.
Tsujimura, Takatoshi. 2012. “OLED Display Fundamentals and Application.” 1–5.
Tsutsui, Y., T. Sakurai, K. Kato, M. Takata, and S. Seki. 2015. “Side Chain-Directed Assembly of Large Discotic π-Conjugated Molecules: Toward Tuning and Stabilization of Mesophases.” Journal of Photopolymer Science and Technology 28(4):583–87.
Ughetto, Giovanni et al. 1985. “A Comparison of the Strucutre of Echinomycin and Tristin: A Complexed to a DNA Fragment.” Nucleic Acids Research 13(7):2305–23.
Venkateswarlu, Yekkirala, Sudhagani Kumar, and Panuganti Leelavathi. 2013. “Facile and Efficient One-Pot Synthesis of Benzimidazoles Using Lanthanum Chloride.”
Organic and Medicinal Chemistry Letters 3(1):7. Retrieved
(http://orgmedchemlett.springeropen.com/articles/10.1186/2191-2858-3-7).
Viault, Guillaume, Danielle Grée, Saibal Das, Jhillu Singh Yadav, and René Grée. 2011. “Synthesis of a Focused Chemical Library Based on Derivatives of Embelin, a Natural Product with Proapoptotic and Anticancer Properties.” European Journal of Organic Chemistry (7):1233–41.
Wang, Haiying et al. 2009. “The Synthesis and Characterization of Novel Dipolar Fluorescent Materials Based on a Quinoxaline Core.” Dyes and Pigments 83(3):269– 75. Retrieved (http://dx.doi.org/10.1016/j.dyepig.2009.03.007).
Wei, Bingzhuo, Shuai Tan, Ting Liang, Siyu Cao, and Yong Wu. 2017. “Synthesis , Structural and Electrochemical Characterization of Benzimidazole Compounds Exhibiting a Smectic C Liquid Crystal Phase.” Journal of Molecular Structure 1133:392–97. Retrieved (http://dx.doi.org/10.1016/j.molstruc.2016.12.042).
Wöhrle, Tobias et al. 2016. “Discotic Liquid Crystals.” Chemical Reviews 116(3):1139–1241.
Yellol, Gorakh S. et al. 2015. “Synthesis of 2-Pyridyl-Benzimidazole Iridium(III), Ruthenium(II), and Platinum(II) Complexes. Study of the Activity as Inhibitors of Amyloid-β Aggregation and Neurotoxicity Evaluation.” Inorganic Chemistry 54(2):470–75.
Zhang, Hai Li et al. 2017. “Phenazine-Based Colorimetric and Fluorescent Sensor for the Selective Detection of Cyanides Based on Supramolecular Self-Assembly in Aqueous Solution.” Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy 175:117–24. Retrieved (http://dx.doi.org/10.1016/j.saa.2016.12.022).