Page  1 hv (UV) hv (Vis.)

Synthesis of spironaphthoxazine derivative having potential applications in Smart Polymers. Presented by: Sampath Weerasinghe Supervised by: Dr. Thilini Gunasekara Department of Chemistry, University of Sri Jayewardenepura 18/02/2014

Page  3 What are Smart Polymers?  Learn and self-correct over time  Respond to external stimuli Chen,M.; Wang,X.; Cheng,F. Light-driven mobile robot based on light-induced bending polymer film, J. of Mech. Engineering Research, 2011,03,114 Smart polymer Response External stimuli pH Heat Light Stress Chemicals Shape Colour Solubility Sol-to-gel transition physical or chemical changes Introduction

Page  4 Introduction Photochromic polymer Yu, Y.; Ikedaa, T., Alignment modulation of azobenzene-containing liquid crystal systems by photochemical reactions. J. Photochem. and Photobiol. 2004, 5, 247–265. hv Photoresponsive chromophore Polymer system Synthesis Incorporate

Page  5 Introduction Spironaphthoxazine  Photoresponsive chromophore Nishikiori, H.; Takamura, T.; Shimamura, S.; Fujii, T., Photochromic behavior of spironaphthoxazine in metal ion-containing solutions, J. Photo.chem. Photo.biol. Chem. 2001, 222, hv(UV) hv(Vis) 1,3,3-Trimethylspiroindolinenaphthoxazine hv (UV) hv (Vis.) hv (Vis) hv (UV)

Page  6  Synthesise 1,3,3-Trimethyl-9’- hydroxyspiroindolinenaphthoxazine pendant group which could be used in future to develop novel smart polymers.  Research objectives I.Develop and optimize simple synthesis pathway to produce 1,3,3-Trimethyl-9’-hydroxyspiroindolinenaphthoxazine. II.Identify suitable purification methods. III.Analyse and characterize the products. Objectives

Page  7 Proposed synthesis pathway Experimental methodology Step 1 Step 2 2,7-Dihydroxynaphthalene2,7-Dihydroxy-1-nitrosonaphthalene 1,3,3-Trimethyl-9’-hydroxyspiroindolinenaphthoxazine

Page  8 Synthesis of 2,7-Dihydroxy-1-nitrosonaphthalene Experimental methodology (step 1) 1.00 g, 6.25 mmol 0.6M NaOH 15 ml 0 0 C NaNO 0.43 g, 6.25 mmol Conc. H 2 SO ml Stir 1h low temperature

Page  9 Analysis of the crude product 1 S – starting material R – reaction mixture Mobile phase - 6 : 1, v/v mixture of Chloroform : Methanol Results and Discussion (step 1) R S Stir for 1 hour

Page  10 Characterization of product 1 by GC-MS Results and Discussion (step 1) Gas chromatogram Stir for 1 hour

Page  Results and Discussion (step 1) Mass Spectrum Stir for 1 hour

Page  12 Analysis of the crude product 2 Results and Discussion (step 1) SR S – starting material R – reaction mixture Mobile phase - 6 : 1, v/v mixture of Chloroform : Methanol Stir for 2 hours

Page  13 Characterization of product 2 by GC-MS Results and Discussion (step 1) Gas chromatogram Stir for 2 hours

Page  Results and Discussion (step 1) Mass Spectrum Stir for 2 hours

Page  15 Characterization of product 2 by IR spectrum Nishikiori, H.; Takamura, T.; Shimamura, S.; Fujii, T., Photochromic behavior of spironaphthoxazine in metal ion-containing solutions, J. Photo.chem. Photo.biol. Chem. 2001, 222, Results and Discussion (step 1) OH NO

Page  16 Experimental methodology (step 2) Synthesis of 1,3,3-Trimethyl-9’- hydroxyspiroindolinenaphthoxazine 1.6 ml (drop vice) 1,3,3,-trimethyl-2-methyleneindoline 2,7-dihydroxy-1-nitrosonaphthalene 1.88 g, 6.210mmol anhydrous CH 3 OH 50 ml Step 2

Page  17 Experimental methodology (step 2) 1,3,3,-trimethyl-2- methyleneindoline 2,7-dihydroxy-1-nitrosonaphthalene in anhydrous methanol Anhydrous Silica N 2 gas

Page  18 Purification of crude product by column chromatography  Determination of solvents/ solvent system for column chromatography Results and Discussion (step 2) Solvent systems Ratio of volume used in the solvent system 1 Methanol 1 2 Ethanol 1 3 Ethyl acetate : Hexane 3 :1 4 Ethyl acetate : Hexane 1 : 1 5 Ethyl acetate : Hexane 1 : 2 6 Ethyl acetate : Hexane1 : Rf–0.90 Rf–0.83 Rf–0.91 Rf–0.40

Page  19 Characterization of the purified product Results and Discussion (step 2) Gas chromatogram

Page  20 Characterization of the purified product Results and Discussion (step 2) Mass Spectrum 1,2-Benzenedicarboxylic acid

Page  21 Characterization of the purified product Results and Discussion (step 2) Gas chromatogram

Page  Results and Discussion (step 2) Mass Spectrum

Page  23 Characterization of the purified product Nishikiori, H.; Takamura, T.; Shimamura, S.; Fujii, T., Photochromic behavior of spironaphthoxazine in metal ion- containing solutions, J. Photo.chem. Photo.biol. Chem. 2001, 222, Results and Discussion (step 2) IR spectroscopy OH C-O C=N =C-H

Page  24 Results and Discussion (step 2) Characterization of the purified product Nishikiori, H.; Takamura, T.; Shimamura, S.; Fujii, T., Photochromic behavior of spironaphthoxazine in metal ion-containing solutions, J. Photo.chem. Photo.biol. Chem. 2001, 222, UV-Vis spectrophotometry

Page  25 hv (UV) hv (Vis.)

Page  26  Optimized the 1 st synthesis step and successfully able to synthesize 2,7-Dihydroxy-1-nitrosonaphthalene.  Peaks at 189.0, 172.0, and in the GC-MS spectrum, we can conclude that the targeted product 2,7- Dihydroxy-1-nitrosonaphthalene was successfully synthesized.  IR spectroscopy, UV-Vis spectroscopy and Gas Chromatography- Mass Spectrometry the final product was characterized and identified. Conclusion

Page  27  From the peaks at 344.1, 329.2, 314.1, 299.1, 172.1, 159.1, in the GC-MS spectrum, we can conclude that the targeted product 1,3,3-Trimethyl-9’- hydroxyspiroindolinenaphthoxazine was successfully synthesized.  Finally, we can confirm that we have successfully able to synthesised a photo and electro sensitive chromophore. Conclusion

Page  28  NMR spectrum analysis, can confirm the structure of 1,3,3- Trimethyl-9’-hydroxyspiroindolinenaphthoxazine.  Carry out photochromic studies of 1,3,3-Trimethyl-9’- hydroxyspiroindolinenaphthoxazine.  Incorporate into a polymer matrix to develop a novel smart polymer material. Future work

Page  29  Analytical thinking  Creativity  Problem solving  Technical skills  Patience Skills developed

Page  30 Memories of my research

Page  31  Dr. Thilini Gunasekara, Lecturer, Department of Chemistry  Prof. P. M. Jayaweera, Head - Department of Chemistry  Dr. S. D. M. Chinthaka, Coordinator of Central Instrumentation Facility  Mr. J. G. R. P. S. Ubesena, Central Instrumentation Facility  Dr. U. Weerasuriya and Dr. Sujeewa at University of Texas at Austin, USA for their precious support of this research.  Dr. M. N. Kaumal and Dr. Ashani Thilakarathne Department of Chemistry, University of Colombo.  Mr. W. Senadeera and other non academic staff.  My parents, colleagues and to my friends. Acknowledgement

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Page  33 Appendix IR spectrum of 2,7-Naphthalenediol

Page  34 Appendix UV-Vis spectrum of literature reported 1,3,3-Trimethyl-9’ hydroxyspiroindolinenaphthoxazine Nishikiori, H.; Takamura, T.; Shimamura, S.; Fujii, T., Photochromic behavior of spironaphthoxazine in metal ion-containing solutions, J. Photo.chem. Photo.biol. Chem. 2001, 222,

Page  35  The oven temperature was initially programmed at C and hold for 5minutes. Then the temperature was increased at the rate of 10 0 Cmin -1 to C and hold for 20minutes.

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